KR102584191B1 - Curable composition for anti-glare flexible hard coat - Google Patents

Abstract

[Problem] To provide a material for forming a hard coat layer with excellent scratch resistance, elongation, and anti-glare properties.
[Solution] (a) 100 parts by mass of an active energy ray-curable oxyethylene-modified polyfunctional monomer, (b) a perfluoropolyether containing a poly(oxyperfluoroalkylene) group at both ends of the molecular chain. , a perfluoropolyether having an active energy ray polymerizable group via a urethane bond (however, a perfluoropolyether having a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond. (Excluding polyether) 0.05 parts by mass to 10 parts by mass, (c) 25 parts by mass to 65 parts by mass of silica particles surface-modified with a compound having a poly(oxyalkylene) group, (d) radicals by active energy rays It is a hard coat film comprising a curable composition containing 1 to 20 parts by mass of a polymerization initiator that generates and (e) an aprotic solvent, and a hard coat layer formed from this composition.

Description

Curable composition for anti-glare 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 touch panel display, and has excellent scratch resistance and anti-glare properties (anti-glare function), and has excellent stretchability. It relates to a curable composition capable of forming a hard coat layer comprising:

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. When a person operates these touch panel displays with their fingers, in order to prevent scratches on the surface of the touch panel due to fingernails, etc., a hard coat layer with scratch resistance to prevent damage is placed on the transparent plastic film as the base material. The provided hard coat film is provided on the outermost surface of this touch panel.

Meanwhile, recently, in order to improve the design of the above-mentioned electronic devices, a design in which the touch panel display portion of a mobile phone or the like 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, so this hard coat layer is also 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. Polyfunctional acrylate-based materials usually do not have stretchability due to their high crosslinking density, but by using polyfunctional acrylate and high-hardness silica fine particles together, a hard coat layer that achieves both a certain degree of scratch resistance and stretchability is achieved. The technology has been reported (Patent Document 1).

Furthermore, on the surface of these touch panel displays, there is a reflective glare (glare) of external light on the screen. ), a method of laminating an anti-glare hard coat film including 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 size of about several μm in the hard coat layer is generally used. For example, a hard coat layer technology that achieves both anti-glare properties and certain scratch resistance by adding 4 μm acrylic-styrene copolymerization (AS) microparticles to an acrylic ultraviolet curing resin as anti-glare particles has been reported (patent Document 2).

Japanese Patent Publication No. 2011-131409 Japanese Patent Publication No. 2013-257359

As described above, 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.

In the silica fine particle-added hard coat layer proposed so far and described in Patent Document 1, the physical interaction between the polyfunctional acrylate and the silica fine particles was weak, it was difficult to obtain sufficient scratch resistance, and the stretchability was not at a satisfactory level. In addition, in the AS fine particle-added hard coat layer described in Patent Document 2, the amount of AS fine particles added was suppressed in order to develop scratch resistance, and the problem was that the anti-glare property was not sufficient.

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. Perfluoropolyether having an active energy ray-polymerizable group through a urethane bond without intervening groups, an oxyethylene-modified polyfunctional monomer curable by active energy rays, and silica particles whose surfaces are modified with a poly(oxyethylene) group, It was discovered that a curable composition containing an aprotic solvent can improve both scratch resistance and stretchability and form a hard coat layer with excellent anti-glare properties, thereby completing the present invention.

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

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

(b) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray polymerizable group at both ends of its molecular chain 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) 25 to 65 parts by mass of silica particles surface-modified with a compound having a poly(oxyalkylene) group,

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

(e) Aprotic solvent

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

[Formula 1]

(In the above formula [1], n represents an integer of 5 to 30 as the total number of the number of repeating units - [OCF ₂ CF ₂ ] - and the number of repeating units - [OCF ₂ ] -, 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, some or all of the polyfunctional monomers (a) have at least three active energy polymerizable groups, and the average amount of oxyethylene modification is less than 3 mol per mol of the active energy polymerizable groups. It relates to the curable composition according to any one of the first to fifth aspects, which is a modified polyfunctional (meth)acrylate compound.

As a seventh aspect, the silica particles (c) are silica particles surface-modified with a silane coupling agent having a poly(oxyalkylene) group, and the silane coupling agent having a poly(oxyalkylene) group is subjected to gel permeation chromatography. It relates to the curable composition according to any one of the first to sixth aspects, which is a silane coupling agent having a molecular weight of 1,000 or more in terms of polystyrene conversion weight average molecular weight as measured by .

As an eighth aspect, it relates to the curable composition according to the seventh aspect, wherein the poly(oxyalkylene) group is a poly(oxyethylene) group.

As a ninth aspect, it relates to the curable composition according to any one of the first to eighth aspects, wherein the aprotic solvent (e) is a ketone solvent.

As a tenth aspect, it relates to the curable composition according to the ninth aspect, wherein the ketone-based solvent is methyl ethyl ketone.

As an 11th viewpoint, it relates to a cured film obtained from the curable composition according to any one of the 1st to 10th viewpoints.

As a twelfth 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 eleventh viewpoint.

As a 13th viewpoint, it relates to the hard coat film described in 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 tenth 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 fifteenth aspect, it relates to silica particles surface-modified with a silane coupling agent having a poly(oxyalkylene) group.

As a sixteenth aspect, it relates to the silica particles according to the fifteenth aspect, wherein the silane coupling agent is a silane coupling agent having a molecular weight of 1,000 or more in terms of polystyrene equivalent weight average molecular weight measured by gel permeation chromatography.

According to the present invention, it is possible to provide a curable composition useful for forming cured films and hard coat layers that have both excellent scratch resistance and high elongation properties even in thin films with a thickness of about 1 μm to 10 μm, and also have high anti-glare properties.

In addition, according to the present invention, it is possible to provide a hard coat film on the surface of which a cured film obtained from the curable composition or a hard coat layer formed therefrom is provided, and a hard coat film excellent in scratch resistance, stretchability, and anti-glare property is provided. can do.

<Curable composition>

The curable composition of the present invention is specifically,

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

(b) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray polymerizable group at both ends of its molecular chain 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) 25 to 65 parts by mass of silica fine particles surface-modified with a compound having a poly(oxyalkylene) group,

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

(e) Aprotic solvent

It relates to a curable composition containing.

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

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

In the present invention, as the component (a), an active energy ray-curable oxyethylene-modified polyfunctional monomer (hereinafter also simply referred to as “(a) polyfunctional monomer”) is used.

Component (a) is a polyfunctional monomer that has two or more active energy ray polymerizable groups that undergo a polymerization reaction and hardens by irradiating active energy rays such as ultraviolet rays, and also has an oxyethylene group. Examples of the active energy ray polymerizable group include (meth)acryloyl group and vinyl group.

In the present invention, known polyfunctional monomers (a) can be used without particular limitation.

For example, in the present invention, as the polyfunctional monomer (a), an oxyethylene-modified polyfunctional monomer having at least 3, preferably at least 4 active energy ray polymerizable groups can be used.

In the present invention, examples of the polyfunctional monomer (a) include monomers selected from the group consisting of oxyethylene-modified polyfunctional (meth)acrylate compounds, and examples include oxyethylene-modified polyfunctional urethane (meth)acrylate. A monomer selected from the group consisting of late compounds can be used. 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 oxyethylene-modified polyfunctional (meth)acrylate compound include (meth)acrylate compounds of polyol modified with oxyethylene.

Examples of this polyol include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc. You can.

In addition, in the polyfunctional monomer (a), the average amount of oxyethylene modification can be, for example, less than 3 mol per 1 mol of the active energy ray polymerizable group possessed by this monomer, and preferably, the active energy possessed by this monomer is It can be less than 2 mol per 1 mol of pre-polymerizable group. In addition, the average amount of oxyethylene modification is greater than 0 mol per 1 mol of active energy ray polymerizable groups of this monomer, preferably 0.1 mol or more, more preferably 0.5 mol of active energy ray polymerizable groups of this monomer. It can be done in mol or more.

Furthermore, in the polyfunctional monomer (a), the addition number of oxyethylene per molecule of this monomer can be 1 to 30, preferably 1 to 12.

In the present invention, a suitable polyfunctional monomer (a) is an oxyethylene-modified polyfunctional (meth) having at least three active energy ray polymerizable groups and an average oxyethylene modification amount of less than 3 mol per 1 mol of the active energy ray polymerizable groups. Acrylate compounds can be used.

Among them, (a) a suitable polyfunctional monomer is an oxyethylene-modified polyfunctional (meth)acrylate compound having at least four active energy ray polymerizable groups and an average oxyethylene modification amount of less than 2 mol per 1 mol of the active energy ray polymerizable groups. can be used.

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

[(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 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 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 ]-] It is preferable that it is a group included in a ratio of 2:1 to 1:2, and it is more preferable that it is a group 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 (hereinafter also referred to as GPC) is 1,000 to 5,000, preferably 1,500 to 3,000. am.

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 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.

(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 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, (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-described (a) active energy ray-curable oxyethylene-modified polyfunctional monomer. It is used in a ratio of 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 oxyethylene-modified polyfunctional monomer, A hard coat layer with less white cast 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, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, etc.) to form a urethane bond.

On the other hand, in the curable composition of the present invention, (b) a poly(oxyperfluoroalkylene) group is formed as a perfluoropolyether, and at both ends of the molecular chain, a purple polymerizable group is present through a urethane bond. In addition to the fluoropolyether (however, it does not have a poly(oxyalkylene) group between the poly(oxyperfluoroalkylene) group and the urethane bond), it contains a poly(oxyperfluoroalkylene) group. It is a perfluoropolyether, and has an active energy ray polymerizable group via a urethane bond at one end of its molecular chain (one end), and also has a hydroxy group at the other end of its molecular chain (another end). A perfluoropolyether (however, between the poly(oxyperfluoroalkylene) group and the urethane bond and between the poly(oxyperfluoroalkylene) group and the hydroxy group, poly(oxyalkylene) (does not have a group) or a perfluoropolyether containing a poly(oxyperfluoroalkylene) group as represented by the formula [3] above, and having hydroxy groups at both ends of the molecular chain. Low polyether (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] is included. There may be.

[(c) Silica particles surface-modified with a compound having a poly(oxyalkylene) group]

The component (c) is silica fine particles surface-modified with a compound having a poly(oxyalkylene) group described later (hereinafter also simply referred to as “(c) silica particles”).

In the curable composition of the present invention, the silica particles surface-modified with a compound having a poly(oxyalkylene) group (c) provide anti-glare properties by giving the surface of the hard coat layer formed from the curable composition an uneven shape. Together, (a) through interaction with the polyfunctional monomer, stretchability can be provided without impairing scratch resistance.

The shape of the silica particles themselves is not particularly limited, but for example, they may be roughly spherical in the form of beads, or may be in an irregular shape such as powder, but are preferably roughly spherical, and more preferably, have an approximately spherical shape with an aspect ratio of 1.5 or less. They are spherical particles, most preferably spherical particles.

The average particle diameter of the silica particles themselves used in the present invention is preferably in the range of 80 nm to 500 nm. Here, the average particle diameter (nm) is the 50% volume diameter (median diameter) obtained by measurement by a laser diffraction/scattering method based on Mie theory. By keeping the average particle diameter of the silica particles within the above numerical range, sufficient anti-glare properties can be provided, and a cured film with excellent scratch resistance and stretchability can be obtained.

Meanwhile, the silica particles are not particularly limited in terms of their particle size distribution, but have uniform particle diameters ( ) It is preferable that they are monodisperse fine particles.

In addition, the silica particles are selected so that their average particle diameter satisfies the range of average particle diameter b of silica fine particles/film thickness a = 0.02 to 1.0 with respect to the film thickness of the cured film obtained from the curable composition of the present invention described later. desirable.

As the silica particles, for example, colloidal silica having the above average particle diameter can be suitably used, and as this colloidal silica, silica sol can be used. As the silica sol, aqueous silica sol prepared by a known method using an aqueous sodium silicate solution as a raw material and organosilica sol obtained by replacing water, which is a dispersion medium for this aqueous silica sol, with an organic solvent can be used.

In addition, silica obtained by hydrolyzing and condensing an alkoxysilane such as methyl silicate or ethyl silicate in an organic solvent such as alcohol in the presence of a catalyst (e.g. ammonia, an organic amine compound, an alkali catalyst such as sodium hydroxide) Sol or organosilica sol obtained by solvent substitution of the silica sol with another organic solvent can also be used.

Examples of organic solvents in the above-mentioned organosilica sol include lower alcohols such as methanol, ethanol, and 2-propanol; Ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); Linear amides such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMAc); Cyclic amides such as N-methyl-2-pyrrolidone (NMP); esters such as γ-butyrolactone; Glycols such as ethyl cellosolve and ethylene glycol; Acetonitrile, etc. can be mentioned.

Replacement of water, which is a dispersion medium for aqueous silica sol, or replacement with another desired organic solvent can be performed by conventional methods such as distillation or ultrafiltration.

The viscosity of the above organosilica sol is about 0.6 mPa·s to 100 mPa·s at 20°C.

Examples of commercially available products of the aqueous silica sol and organo silica sol include, for example, Seahostar (registered trademark) KE series (made by Nippon Catalyst Co., Ltd.), Snowtex (registered trademark) series (manufactured by Nissan Chemical Co., Ltd.), etc. can be used.

In the present invention, as a compound having a poly(oxyalkylene) group used for surface modification of silica particles, a silane coupling agent having a poly(oxyalkylene) group can be used.

Examples of the poly(oxyalkylene) group include those in which the number of carbon atoms of the oxyalkylene group is 1 to 4, that is, poly(oxymethylene) group, poly(oxyethylene) group, and poly(oxyproprene) group. group, poly(oxybutylene) group, etc. Among them, poly(oxyethylene) group is suitable as the poly(oxyalkylene) group.

In addition, the silane coupling agent having the poly(oxyalkylene) group preferably has a molecular weight of 1,000 or more in terms of polystyrene conversion as measured by GPC.

Silica particles surface-modified with a compound having a poly(oxyalkylene) group can be prepared by mixing the silane coupling agent having the poly(oxyalkylene) group and the silica particles in the presence of moisture or alcohol. The silane coupling agent having a poly(oxyalkylene) group generates silanol groups through hydrolysis and bonds through a condensation reaction with the silanol group present on the surface of the silica particle. It is thought that silica particles whose surface is modified are formed.

Specifically, for example, silica particles surface-modified with a silane coupling agent having a poly(oxyalkylene) group by mixing a colloidal solution (silica sol) of silica particles with a silane coupling agent having a poly(oxyalkylene) group. can be prepared. Mixing of the colloidal solution and this silane coupling agent may be performed at room temperature or while heating. From the viewpoint of reaction efficiency, mixing is preferably performed while heating. When mixing is performed while heating, the heating temperature can be appropriately selected depending on the solvent, etc. The heating temperature can be, for example, 30°C or higher.

The mixing ratio of the silane coupling agent having a poly(oxyalkylene) group and the silica particles depends on the size of the silica particle and the type of oxyalkylene group, but for example, the silane coupling agent may be mixed per unit area (1 nm ² ) of the surface of the silica particle. The number of molecules can be 0.01 to 5, preferably 0.05 to 2, more preferably 0.1 to 1. Here, the surface area of the silica particles is calculated from the specific surface area measured by the nitrogen adsorption method (BET method).

In the present invention, the silica fine particles (c) are 25 parts by mass to 65 parts by mass, for example, 30 parts by mass to 50 parts by mass, based on 100 parts by mass of the above-described (a) active energy ray-curable oxyethylene-modified polyfunctional monomer. , Preferably it is used in a ratio of 35 parts by mass to 50 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, 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; Methyl phenylglyoxylate, etc. are mentioned.

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

[(e) Aprotic solvent]

The curable composition of the present invention contains an aprotic solvent as component (e).

(e) By the presence of an aprotic solvent, in the curable composition of the present invention, the silica particles surface-modified with the compound having a poly(oxyethylene) group (c) form an appropriate cluster structure, thereby contributing to the development of anti-glare properties. Contribute. That is, by combining (c) silica particles surface-modified with a compound having a poly(oxyethylene) group with (e) an aprotic solvent, component (c) can be fully used as an anti-glare imparting agent (low gloss agent). You can.

Examples of the aprotic solvent include 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); ethers such as diethyl ether, tetrahydrofuran (THF), and 1,4-dioxane; Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, and cyclohexanone; Nitriles such as acetonitrile, propionitrile, n-butyronitrile, and benzonitrile: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrroli amides such as NMP; Examples include sulfoxides such as dimethyl sulfoxide (DMSO), and solvents containing two or more of these aprotic solvents.

Among these aprotic solvents, aprotic polar solvents are preferable, and examples thereof include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); Cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; Nitriles such as acetonitrile; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); Sulfoxides such as dimethyl sulfoxide (DMSO) can be cited as suitable solvents, and ketones (ketone-based solvents) are particularly preferable, and among them, methyl ethyl ketone (MEK) can be used suitably.

(e) The amount of the aprotic solvent used is not particularly limited, but for example, 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. Use it as 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).

On the other hand, in the curable composition of the present invention, solvents other than the aprotic solvent may be used in addition to the aprotic solvent (e) above, as long as the effect of the present invention is not impaired.

Other solvents include methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and propylene glycol monoisopropyl. Ethers such as ether and propylene glycol mono-n-butyl ether, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, and ethylene. Alcohols such as glycol can be mentioned.

When the other solvents mentioned above are used, the other solvents are used in such an amount that the total amount of the other solvents and (e) the aprotic solvent is the solid content concentration in the curable composition of the present invention described above.

In addition, it is preferable that the amount of the other solvent used is such that the ratio of the other solvent is less than 50% by mass, for example, with respect to the total mass of the (e) aprotic solvent and the other solvent.

[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 is applied (coated) on a substrate to form a coating film, the coating film is dried to remove the solvent, and then the coating film is polymerized (cured) by irradiating active energy rays to form 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, 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. Meanwhile, when applying, a solvent may be additionally added to this curable composition as needed. Solvents in this case include various solvents (and other solvents) included in the above [(e) aprotic solvent].

After applying the curable composition on a substrate to form a coating film, 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 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 includes the steps of applying the above-described curable composition of the present invention on a film substrate to form a coating film, drying this coating film to remove the solvent, and, if necessary, It can be formed by a method including a step of removing the solvent by heating and a step of curing the coating film by irradiating it with active energy rays such as ultraviolet rays. A method for producing a hard coat film including a hard coat layer on at least one side of the 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), and polycarbonate. , polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, and triacetylcellulose (TAC).

In addition, the method of applying the curable composition on the film substrate (coating film forming process), the process of removing the solvent (solvent removal process), and the method of irradiating active energy rays to the coating film (curing process) are the above-described <cured film>. You can use the methods listed.

The layer thickness (film thickness) of the hard coat layer thus obtained is preferably set to be 1 to 50 times the thickness of the average particle diameter of the fine particles. For example, the thickness of the hard coat layer 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 #9)

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) Glossiness measurement

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

Measuring angle: 60 degrees

In addition, the abbreviated symbols indicate the following meanings.

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

A1: Pentaerythritol tri/tetraacrylate [Kayarad (registered trademark) PET-30 manufactured by Nippon Explosives Co., Ltd.]

Silica fine particles s-1: Silica fine particles with an average particle diameter of 200 nm [Snowtex (registered trademark) MP-2040 (solid concentration 40% by mass aqueous dispersion) manufactured by Nissan Chemical Co., Ltd.]

Silica fine particles s-2: Silica fine particles with an average particle diameter of 450 nm (Snowtex (registered trademark) MP-4540M (solid concentration 40% by mass aqueous dispersion) manufactured by Nissan Chemical Co., Ltd.)

Silane coupling agent: trimethoxysilane having a poly(oxyethylene) group (Shin-Etsu Silicone (registered trademark)

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 [Neostane (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]

MEK: Methyl ethyl ketone

MeOH: methanol

[Reference Example 1] Preparation of surface modifier SM

Into the screw tube, 1.19 g (0.5 mmol) of PFPE, 0.52 g (2.0 mmol) of BEI, 0.017 g of DOTDD (0.01 times the total mass of PFPE 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.

[Reference Example 2] Preparation of methanol dispersion of silica fine particles s-3 whose surface was modified with a compound having a poly(oxyalkylene) group

200 g of silica fine particles s-1 were passed through a column filled with 100 mL of a hydrogen-type strongly acidic cation exchange resin (Amberlight (registered trademark) IR120B, manufactured by Organo Co., Ltd.) for ion exchange. 363.8 g of the obtained water-dispersed silica fine particles were introduced into a glass reactor with an internal volume of 1 L equipped with a stirrer, condenser, thermometer, and two inlets. While the solvent in the glass reactor is kept boiling, methanol vapor generated by another boiler is continuously blown into the water in this reactor, and water is replaced by methanol while maintaining the liquid level at a substantially constant level, thereby dispersing methanol. Silica fine particles (solid concentration 40% by mass, average particle diameter 200nm) were obtained.]

Into the eggplant-shaped flask, 20 g of the methanol-dispersed silica fine particles, 0.18 g of silane coupling agent, and 0.14 g of water were added. This mixture was stirred for 3 hours at an oil bath temperature of 65°C using a stirrer chip, and the target compound, a methanol dispersion of silica fine particles s-3 with an average particle diameter of 200 nm modified with a silane coupling agent having a poly(oxyethylene) group ( solid concentration of 40% by mass) was obtained.

[Reference Example 3] Preparation of methanol dispersion of silica fine particles s-4 whose surface was modified with a compound having a poly(oxyalkylene) group

Methanol-dispersed silica fine particles were obtained by replacing the solvent in the same manner as in Reference Example 2, using silica fine particles s-2 instead of silica fine particles s-1.

Into the eggplant-shaped flask, 20 g of the methanol-dispersed silica fine particles, 0.08 g of silane coupling agent, and 0.14 g of water were added. This mixture was stirred for 3 hours at an oil bath temperature of 65°C using a stirrer chip, and a methanol dispersion of the target compound, silica fine particles s-4 with an average particle diameter of 450 nm modified with a silane coupling agent having a poly(oxyethylene) group ( solid concentration of 40% by mass) was obtained.

[Example 1 and Example 2, Comparative Examples 1 to 7]

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 using a bar coater on an A4 size double-sided adhesive PET film (Lumiror (trademark registered) U403, manufactured by Toray Co., Ltd., thickness 100 μm) to obtain a coating film. This coating film was dried in an oven at 50°C for 3 minutes to remove the solvent. The obtained film was exposed to UV light at an exposure dose of 300 mJ/cm ² under a nitrogen atmosphere to produce a hard coat film having a hard coat layer (cured film) having a layer thickness (film thickness) of approximately 3 μm.

The scratch resistance, stretchability, and anti-glare properties of the obtained hard coat film were evaluated. The order of evaluation of scratch resistance, stretchability, and anti-glare properties is 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 10 reciprocations by applying a load of 500 g/cm ² with steel wool (Born Star (registered trademark) #0000 (ultrafine) manufactured by Bone Star Sales Co., Ltd.) attached to the above reciprocating abrasion tester. It was rubbed, and the degree of scratches was visually confirmed. 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: Scratches less than 5 mm in length

C: Scratches over 5 mm in length

[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% to 5%, 7.5%, 10%. As shown, the tensile test was conducted at 2.5% intervals. The hard coat film after the tensile test was observed with an optical microscope to confirm the presence or absence of cracks, and the following A, B, and C were used as criteria for judgment. 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: The elongation rate at which cracks occur is greater than 22.5%.

B: Elongation at which cracks occur is 22.5%

C: Elongation at which cracks occur is less than 22.5%

[Bang Hyun-seong]

The glossiness Gs (60°) of the surface of the hard coat layer of the hard coat film was measured and evaluated according to the following standards 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: Gs(60°)≤100

B: 100<Gs(60°)≤130

C: 130<Gs (60°)

[Table 1]

[Table 2]

As shown in Table 2, oxyethylene-modified diglycerine tetraacrylate EOA1 as a polyfunctional monomer, and silica fine particles s-3 or s-4, the surface of which was modified with a silane coupling agent having a poly(oxyethylene) group, as the silica fine particles. From the curable compositions of Examples 1 and 2, which used perfluoropolyether SM, which has four acryloyl groups through urethane bonds at each end of the molecular chain as a modifier, and MEK, an aprotic solvent, as a solvent, respectively. It was shown that the obtained hard coat film provided with a hard coat layer was excellent in scratch resistance, stretchability, and anti-glare property, and was capable of achieving both these three properties.

On the other hand, the hard coat film provided with a hard coat layer obtained from the curable compositions of Comparative Examples 1 and 2 using surface unmodified silica fine particles s-1 or s-2, respectively, as silica fine particles is inferior in anti-glare property. appear. In addition, it was shown that the hard coat film provided with a hard coat layer obtained from the curable composition of Comparative Example 3 and Comparative Example 4 using methanol, a protic solvent, as the solvent was also inferior in anti-glare properties. Furthermore, it was shown that the hard coat film provided with a hard coat layer obtained from the curable composition of Comparative Example 5 using polyfunctional acrylate A1 not modified with oxyethylene as a polyfunctional monomer was inferior in stretchability and anti-glare properties. In addition, the hard coat film provided with a hard coat layer obtained from the curable composition of Comparative Example 6 without surface modifier SM showed poor scratch resistance. And, it was shown that the hard coat film provided with a hard coat layer obtained from the curable composition of Comparative Example 7 containing no silica fine particles was inferior in anti-glare properties.

As shown in the results of the examples above, oxyethylene-modified polyfunctional monomer, perfluoropolyether of a specific structure, silica particles surface-modified with a compound having a poly(oxyalkylene) group, and an aprotic solvent as a solvent. By using a curable composition combining the above, a hard coat film that satisfies all the performance of scratch resistance, stretchability, and anti-glare properties can be obtained.

Claims (16)

(a) 100 parts by mass of active energy ray-curable oxyethylene-modified polyfunctional monomer,
(b) A perfluoropolyether containing a poly(oxyperfluoroalkylene) group, which has an active energy ray polymerizable group at both ends of its molecular chain 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) 25 to 65 parts by mass of silica particles surface-modified with a compound having a poly(oxyalkylene) group,
(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, and
(e) Aprotic solvent
A curable composition containing. According to paragraph 1,
A curable composition in which the (b) perfluoropolyether has at least two active energy ray polymerizable groups at each end of its molecular chain through urethane bonds. According to paragraph 2,
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. 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 paragraph 4,
A curable composition in which the (b) perfluoropolyether has a partial structure represented by the following formula [1].

(In equation [1] above,
n represents an integer of 5 to 30 as the total number of repeat units - [OCF ₂ CF ₂ ] - and the number of repeat 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.) According to any one of claims 1 to 3,
Part or all of the polyfunctional monomer (a) has at least three active energy polymerizable groups, and the average amount of oxyethylene modification is less than 3 mol per mol of the active energy polymerizable group (meth). ) A curable composition that is an acrylate compound. According to any one of claims 1 to 3,
The (c) silica particles are surface-modified silica particles with a silane coupling agent having a poly(oxyalkylene) group, and the silane coupling agent having a poly(oxyalkylene) group is converted into polystyrene measured by gel permeation chromatography. A curable composition that is a silane coupling agent having a weight average molecular weight of 1,000 or more. In clause 7,
A curable composition wherein the poly(oxyalkylene) group is a poly(oxyethylene) group. According to any one of claims 1 to 3,
A curable composition wherein the (e) aprotic solvent is a ketone-based solvent. According to clause 9,
A curable composition wherein the ketone-based solvent is methyl ethyl ketone. 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 11. According to clause 12,
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. delete delete