KR102750795B1 - Photocurable composition, photocurable layer formed from the same, and image display device including the photocurable layer - Google Patents

Abstract

The present invention relates to a photocurable composition, a photocurable film formed therefrom, and an image display device including the same. More specifically, the present invention relates to a photocurable composition including a fluorine-containing (meth)acrylate compound having a fluorinated hydrocarbon group, an ester group, and at least two (meth)acryloyl groups. By using the above-described photocurable composition, a photocurable film having optical characteristics such as low reflectivity and high transmittance, and excellent mechanical properties such as antifouling properties, hardness, surface abrasion resistance, and flexibility, and an image display device including the same can be provided.

Description

Photocurable composition, photocurable layer formed therefrom, and image display device including the same {PHOTOCURABLE COMPOSITION, PHOTOCURABLE LAYER FORMED FROM THE SAME, AND IMAGE DISPLAY DEVICE INCLUDING THE PHOTOCURABLE LAYER}

The present invention relates to a photocurable composition, a photocurable film formed therefrom, and an image display device including the same. More specifically, the present invention relates to a photocurable composition including a (meth)acrylate compound, a photocurable film formed therefrom, and an image display device including the same.

Recently, as the information society has developed, demands for the display field have been presented in various forms. For example, liquid crystal display devices, plasma display panel devices, electroluminescent display devices, and organic light-emitting diode display devices with features such as thinness, weight reduction, and low power consumption are being studied.

In order to protect the above-mentioned image display device from external environments such as scratches, impacts from falling, external moisture, oil, etc., a window film made of, for example, tempered glass may be formed on the display panel. However, the window film is disadvantageous in reducing the weight of the display panel or image display device due to the characteristics of tempered glass, and is easily broken by external impact. In addition, there is a limit to implementing flexible characteristics through bendable or foldable functions.

In addition, when a polymer film is used as a window film, the image quality of the image display device may deteriorate due to the high refractive index and low anti-reflection properties of the polymer film. In this case, the reflection of external light occurring on the surface of the window film cannot be prevented, so the outdoor visibility of the image display device may deteriorate.

Accordingly, research is being conducted recently on window films made of optical plastic or resin materials that can secure flexibility and impact resistance and have excellent optical properties and can replace window films made of the above-mentioned reinforced glass material.

Korean Patent Publication No. 10-2015-0145141 discloses a composition for forming a hard coating layer including a mixture of (meth)acrylate series monomers.

Korean Patent Publication No. 10-2015-0145141

One object of the present invention is to provide a photocurable composition capable of forming a photocurable film having low refractive index and low reflection characteristics and high hardness.

An object of the present invention is to provide a photocurable film having high light transmittance and improved mechanical properties and improved outdoor visibility, and an image display device including the same.

A photocurable composition according to exemplary embodiments comprises a photopolymerizable compound comprising a fluorine-containing (meth)acrylate compound, and a solvent. The fluorine-containing (meth)acrylate compound may have a fluorinated hydrocarbon group, an ester group, and at least two (meth)acryloyl groups.

For example, the fluorine-containing (meth)acrylate compound may have a polymerizable functional group including at least two (meth)acryloyl groups, a fluorinated hydrocarbon group, and an ester group connecting the polymerizable functional group and the fluorinated hydrocarbon group.

According to exemplary embodiments, the fluorinated hydrocarbon group may be an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is replaced with a fluorine atom. In one embodiment, the fluorinated hydrocarbon group may be an alkyl group having 1 to 12 carbon atoms in which all hydrogen atoms are replaced with fluorine atoms.

According to exemplary embodiments, the fluorine-containing (meth)acrylate compound may include a compound represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1, R ₁ may be an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aliphatic hydrocarbon group having 1 to 10 carbon atoms in which at least one carbon atom is substituted with an oxygen atom. Ay may each independently be a functional group represented by the following chemical formula 2.

[Chemical formula 2]

In the above chemical formula 2, R ₂ can be a hydrogen atom or a methyl group, and * can be a bond.

Ay can be independently linked to at least one of the carbon atoms of R ₁ . For example, * in the above chemical formula 2 can be linked to at least one of the carbon atoms of R ₁ in the above chemical formula 1.

In the above chemical formula 1, n can be an integer from 1 to 10, and m can be an integer from 2 to 5.

In some embodiments, the fluorine-containing (meth)acrylate compound may include at least one of the compounds represented by the following chemical formulas 3 to 9.

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical formula 6]

[Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]

In some embodiments, the content of the fluorine-containing (meth)acrylate compound may be 10 to 90 wt% of the total weight of the photocurable composition.

In some embodiments, the photopolymerizable compound may further comprise a fluorine-free (meth)acrylate compound.

According to exemplary embodiments, the photocurable composition may further comprise a photopolymerization initiator or inorganic nanoparticles.

In some embodiments, the inorganic nanoparticle may comprise a core particle comprising a metal oxide. In one embodiment, a photopolymerizable functional group may be bonded to at least a portion of a surface of the core particle.

For example, the photopolymerizable functional group may include at least one of an acryloyl group, a methacryloyl group, a vinyl ether group, a glycidyl group, and a hydroxy group.

In some embodiments, the content of the photopolymerization initiator may be 0.1 to 5 wt%, and the content of the inorganic nanoparticles may be 5 to 40 wt%, of the total weight of the photocurable composition.

The photocurable film according to exemplary embodiments may include a cured product of the photocurable composition described above.

In some embodiments, the photocurable film may include a substrate film, and a hard coating layer disposed on the substrate film and including the cured product. For example, the photocurable film may be used as a hard coating film in an image display device.

In some embodiments, the refractive index of the hard coating layer may be 1.5 or less.

An image display device according to exemplary embodiments may include the photocurable film described above.

In some embodiments, the image display device may include a display panel, a polarizing layer disposed on the display panel, and a hard coating film disposed on the polarizing layer and including the photocuring film.

According to exemplary embodiments, a photocurable composition includes a fluorine-containing (meth)acrylate compound having a fluorinated hydrocarbon group and a plurality of (meth)acryloyl groups. Since the fluorine-containing (meth)acrylate compound has a photopolymerizable functional group of two or more functional groups, the polymerization reactivity of the photocurable composition can be improved, and the crosslinking density and curing degree of a photocurable film can be improved. In addition, the formation of a crosslinking network of the photocurable composition is promoted, so that a cured product formed thereby can have a dense structure, and the photocurable film can have a low refractive index and low reflectivity.

In addition, since the fluorine-containing (meth)acrylate compound has a fluorinated hydrocarbon group at the terminal of the molecular structure, the refractive index and light reflectance of the photocurable film can be lowered. Therefore, a photocurable film having high light transmittance can be formed from the photocurable composition. In one embodiment, the fluorinated hydrocarbon group may have all hydrogen atoms substituted with fluorine atoms. In this case, the content of fluorine atoms in the photocurable film increases, so that the optical properties of the photocurable film can be improved, and the anti-fingerprint and anti-stain properties can be further enhanced.

In addition, the fluorine-containing (meth)acrylate compound may include an ester bond in its molecular structure. Accordingly, the flexibility of the photopolymerizable compound may be improved, and the photocured film may have excellent bending properties and flexural properties.

For example, the fluorine-containing (meth)acrylate compound may include a compound represented by a given chemical formula. In this case, a photocurable film having excellent mechanical properties such as wear resistance and abrasion resistance and optical properties such as high transmittance can be provided.

The cured product formed by the above-described curable composition has excellent mechanical properties such as hardness and flexibility and excellent optical properties such as light transmittance, and thus can be applied as a protective layer or coating layer in an image display device. For example, when applied to a flexible display, it can maintain improved mechanical durability even when repeatedly folded or bent, and can improve outdoor visibility by preventing diffuse reflection of external light.

FIG. 1 is a schematic cross-sectional view illustrating a hard coating film according to exemplary embodiments.
FIGS. 2 and 3 are schematic cross-sectional views each illustrating an image display device according to exemplary embodiments.

Embodiments of the present invention provide a photocurable composition comprising a photopolymerizable compound including a fluorine-containing (meth)acrylate compound, and a solvent. The fluorine-containing (meth)acrylate compound may have a fluorinated hydrocarbon group, an ester group, and at least two (meth)acryloyl groups.

A photocurable film including a cured product of the above photocurable composition can have excellent mechanical properties and optical properties, and can be applied as an organic film protective layer, a hard coating layer, an overcoating layer, a window, etc. of an image display device.

Hereinafter, the present invention will be described in detail.

<Photocurable composition>

The photocurable composition according to exemplary embodiments may include a photopolymerizable compound including a fluorine-containing (meth)acrylate compound. The term "(meth)acrylate" as used herein is used to encompass acrylates or methacrylates. The term "(meth)acryloyl group" as used herein is used to encompass acryloyl groups or methacryloyl groups.

According to exemplary embodiments, the fluorine-containing (meth)acrylate compound may have a fluorinated hydrocarbon group, an ester group, and at least two (meth)acryloyl groups.

For example, the fluorine-containing (meth)acrylate compound may have a polymerizable functional group including at least two (meth)acryloyl groups, a fluorinated hydrocarbon group, and an ester group connecting the polymerizable functional group and the fluorinated hydrocarbon group.

Since the above-mentioned fluorine-containing (meth)acrylate compound has a polymerizable functional group including two or more (meth)acryloyl groups, the photocured product can have a high degree of crosslinking and curing. For example, the above-mentioned (meth)acryloyl group can cause a polymerization reaction in response to light irradiated to the photocurable composition, and can form a crosslinking network with an adjacent photopolymerizable compound.

In this case, since the cured product formed from the photocurable composition has a high crosslinking density and a low curing shrinkage, the surface hardness can be excellent, and the occurrence of curls and cracks can be suppressed. In addition, since the cured product has a dense crosslinking structure, the refractive index can be lowered, and a photocurable film having low reflection characteristics and high transmittance can be provided.

Since the above-mentioned fluorine-containing (meth)acrylate compound has a fluorinated hydrocarbon group, a photocured film formed therefrom can have optical properties of low reflectivity and high transmittance, and the structural stability of the photocured film can be excellent.

For example, fluorine atoms have a strong covalent bond with carbon atoms, and the interatomic bond stability may be superior to carbon-carbon bonds and carbon-hydrogen bonds. In addition, the fluorinated hydrocarbon group may have, for example, a helical twisted structure due to the repulsion between adjacent fluorine atoms. In this case, the carbon-carbon bond of the fluorinated hydrocarbon group may have a structure in which it is surrounded by fluorine atoms, and the main chain of the molecule composed of carbon atoms may be protected by the fluorine atoms. Therefore, the crosslinked molecule in the photocurable film may be structurally stable, and the durability and chemical stability of the photocurable film may be improved.

The term "backbone" as used herein may mean the longest portion of a chain of atoms within any molecular structure.

In addition, since the fluorine-containing (meth)acrylate compound has the fluorinated hydrocarbon group at one terminal, the optical properties can be improved while preventing the hardness of the photocured film from decreasing. For example, in this case, the polymer formed by crosslinking the fluorine-containing (meth)acrylate compound can include a fluorinated hydrocarbon group having low refractive index properties as a functional group. Accordingly, the light transmittance of the photocured film can be increased, and reflection of outdoor light can be suppressed, so that, for example, the visibility of an image display device can be improved.

In addition, the content of fluorine atoms on the surface of the photocured film can be increased by the fluorinated hydrocarbon group, and accordingly, the surface energy of the surface of the photocured film can be lowered. Accordingly, the photocured film can have a high surface water contact angle and excellent antifouling and antifingerprint properties.

In some embodiments, the fluorinated hydrocarbon group may be an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is replaced with a carbon atom. Preferably, the fluorinated hydrocarbon group may be an alkyl group having 1 to 12 carbon atoms in which all hydrogen atoms are replaced with carbon atoms.

In this case, the content of fluorine atoms included in the photocurable composition may increase, and the refractive index of the photocurable film may decrease due to the high concentration of fluorine atoms. Accordingly, a photocurable film having high transmittance, low reflectivity, and anti-fingerprint properties can be provided from the photocurable composition.

Since the above fluorine-containing (meth)acrylate compound has an ester group, the flexibility of the molecule can be improved. For example, the above fluorine-containing (meth)acrylate compound can have a structure in which a (meth)acryloyl group and a fluorinated hydrocarbon group are connected via an ester bond.

The flexibility of a photopolymerizable compound can be improved by an ester group, and a photocurable film formed from the photocurable composition can have excellent bending and flexural properties. Accordingly, it can have excellent durability and shape reliability even in repeated bending or folding operations.

According to exemplary embodiments, the fluorine-containing (meth)acrylate compound may include a compound represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1, R ₁ may be an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aliphatic hydrocarbon group having 1 to 10 carbon atoms in which at least one carbon atom is replaced by an oxygen atom. For example, R ₁ may be an m+1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms or an m+1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms in which at least one carbon atom is replaced by an oxygen atom.

For example, the R ₁ may be a straight-chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a branched-chain aliphatic hydrocarbon group having 3 to 10 carbon atoms. For example, the R ₁ may be a straight-chain aliphatic hydrocarbon group having 1 to 10 carbon atoms and containing an ether bond, or a branched-chain aliphatic hydrocarbon group having 3 to 10 carbon atoms and containing an ether bond.

In the chemical formula 1 above, n can be an integer from 1 to 10. As described above, since the fluorine-containing (meth)acrylate compound has a fluorinated hydrocarbon group in which all hydrogen atoms are replaced with fluorine atoms, a photocurable film formed from the photocurable composition can have optical properties of low refractive index and high transmittance.

Ay may be a functional group represented by the following chemical formula 2.

[Chemical formula 2]

In the above chemical formula 2, R ₂ can be a hydrogen atom or a methyl group, and * can be a bond.

A plurality of Ay can be independently linked to at least one of the carbon atoms of R ₁ . For example, * in the above chemical formula 2 can be linked to at least one of the carbon atoms of R ₁ in the above chemical formula 1.

In the chemical formula 1, m can be an integer from 2 to 5. As described above, since the fluorine-containing (meth)acrylate compound has two or more (meth)acryloyl groups, the crosslinking sites in the photocurable composition can increase, and the photocurable film can have a high crosslinking density. Accordingly, the structural stability and optical properties of the photocurable film can be excellent.

In some embodiments, the fluorine-containing (meth)acrylate compound may include at least one of the compounds represented by the following chemical formulas 3 to 9.

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical formula 6]

[Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]

Since the fluorine-containing (meth)acrylate compound includes at least one of the compounds represented by the chemical formulae 3 to 9, a high crosslinking density can be provided by a plurality of photopolymerizable functional groups, for example, a (meth)acryloyl group. In addition, due to the fluorinated hydrocarbon group located at the terminal of the molecular structure, the refractive index of the photocurable film can be lowered, and a coating layer having high transmittance can be provided.

In some embodiments, the content of the fluorine-containing (meth)acrylate compound may be 10 to 90 wt% of the total weight of the photocurable composition, and preferably 30 to 80 wt%. When the content of the fluorine-containing (meth)acrylate compound is less than 10 wt%, a low refractive index may not be provided, and the reflectivity of the photocurable film may increase. When the content of the fluorine-containing (meth)acrylate compound exceeds 90 wt%, the flexibility of the photocurable film may excessively increase, and mechanical properties such as hardness and scratch resistance may deteriorate.

In some embodiments, the photopolymerizable compound may further comprise another photopolymerizable monomer in addition to the fluorine-containing (meth)acrylate compound.

For example, the photopolymerizable compound may further include a fluorine-free (meth)acrylate compound that does not contain a fluorine atom in its molecular structure. In this case, the crosslinking density of the photocuring film may be increased, and curling may be suppressed. Accordingly, the photocuring film may have excellent durability, surface hardness, and scratch resistance.

For example, the fluorine-free (meth)acrylate compound may be dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, (meth)acrylic ester, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol (meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, It may include neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, isooctyl (meth)acrylate, iso-dexyl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate or isoborneol (meth)acrylate. These may be used alone or in combination of two or more.

In some embodiments, the content of the fluorine-free (meth)acrylate compound may be 5 to 70 wt% of the total weight of the photocurable composition. Within this range, the hardness and scratch resistance of the photocurable film may be excellent without deteriorating the optical properties.

In one embodiment, when the photopolymerizable compound further includes another photopolymerizable monomer, for example, a fluorine-free (meth)acrylate compound, in addition to the fluorine-containing (meth)acrylate compound, the content of the fluorine-containing (meth)acrylate compound may be 30 wt% or more of the total weight of the photopolymerizable compound, preferably 50 wt% or more, and more preferably 80 wt% or more. For example, the content of the fluorine-containing (meth)acrylate compound may be 50 to 95 wt% of the total weight of the photopolymerizable compound.

Within the above range, the content of fluorine atoms in the photocurable composition may increase, thereby lowering the refractive index of the photocurable film. Accordingly, the photocurable film may have high light transmittance, and external light reflection on the surface of the photocurable film may be prevented.

According to exemplary embodiments, the photocurable composition may include a photopolymerization initiator. For example, the photopolymerization initiator has a photoactive group in its molecular structure and can exhibit activity in response to light to initiate a polymerization reaction of the photocurable composition.

In some embodiments, the photopolymerization initiator may include acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, anthracene-based, anthraquinone-based, phosphine oxide-based, and biimidazole-based compounds. These may be used alone or in combination of two or more.

For example, as the photopolymerization initiator, 2-methyl-1-(4-methylsulfanyl-phenyl)-2-morpholin-4-yl-propan-1-one, 1-[4-(2-hydroxy-ethylsulfanyl)-phenyl]-2-methyl-2-morpholin-4-yl-propan-1-one, 2-methyl-2-morpholin-4-yl-1-(4-pentylsulfanyl-phenyl)-propan-1-one, 2-methyl-2-morpholin-4-yl-1-(4-phenylsulfanyl-phenyl)-propan-1-one, 1-(4-ethylsulfanylphenyl)-2-methyl-2-morpholin-4-yl-propan-1-one, 2-ethyl-1-(4-methylsulfanyl-phenyl)-2-morpholin-4-yl-hexan-1-one, Examples thereof include 2-methyl-2-morpholin-4-yl-1-(4-p-toylsulfanyl-phenyl)-propan-1-one and 1-(4-cyclohexylsulfanyl-phenyl)-2-methyl-2-morpholin-4-yl-propan-1-one, diphenyl ketone benzyldimethyl ketal, dimethoxy-2-phenylatetophenone, triphenylamine, benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, phosphine oxide phenylbis(2,4,5-trimethylbenzoyl) or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

In some embodiments, the content of the photopolymerization initiator may be 0.1 to 5 wt% of the total weight of the photocurable composition, and preferably 1 to 3 wt%. When the content of the photopolymerization initiator is less than 0.1 wt%, the crosslinking degree of the photocured film may be reduced, and mechanical properties such as hardness and wear resistance may be reduced. When the content of the photopolymerization initiator exceeds 5 wt%, the shrinkage rate of the photocured film may be increased due to excessive crosslinking, and cracks, curls, and surface unevenness may occur in the photocured film.

In one embodiment, a polymerization initiation aid may be additionally included to improve the sensitivity of the photocurable composition. The polymerization initiation aid may increase the polymerization reactivity of the photocurable composition upon light irradiation, and the productivity of the photocured film may be improved. Examples of the polymerization initiation aid include amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group.

According to exemplary embodiments, the photocurable composition may include inorganic nanoparticles. For example, the inorganic nanoparticles may lower the refractive index of the photocurable film and improve wear resistance and surface hardness.

In some embodiments, the inorganic nanoparticle may comprise a core particle comprising a metal oxide. For example, the metal oxide may include Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO, or MgO.

Since the above-described inorganic nanoparticles include the above-described metal oxide, the refractive index of light irradiated into the photocuring film can be lowered, and the photocuring film can have low reflection characteristics and high transmittance. In addition, the curing shrinkage rate can be lowered by the core particles including the metal oxide, the surface uniformity of the photocuring film can be excellent, and curling can be suppressed.

In some embodiments, the inorganic nanoparticle may include a photopolymerizable functional group bonded to at least a portion of the surface of the core particle. For example, the inorganic nanoparticle may form a crosslinking network with an adjacent photopolymerizable compound or other inorganic nanoparticle by the photopolymerizable functional group. In this case, a decrease in the crosslinking density of the photocurable composition may be prevented, and a photocurable film having a low refractive index, high light transmittance, and hardness may be provided.

In one embodiment, the photopolymerizable functional group may include at least one of an acryloyl group, a methacryloyl group, a vinyl ether group, a glycidyl group, and a hydroxy group.

In some embodiments, the average particle diameter of the inorganic nanoparticles may be 1 to 100 nm, and preferably 10 to 50 nm. For example, the average particle diameter may mean the longest diameter at a volume fraction of 50% in a volume distribution curve of the inorganic nanoparticles.

For example, when the average particle diameter of the inorganic nanoparticles is less than 1 nm, agglomeration of the inorganic nanoparticles may occur within the composition, and the uniformity and coatability of the photocurable film may deteriorate. For example, when the average particle diameter of the inorganic nanoparticles is more than 100 nm, the refractive index of the photocurable film may increase and the transmittance may decrease. In addition, as the volume ratio of the inorganic nanoparticles within the photocurable composition increases, the mechanical properties of the photocurable film may deteriorate.

In some embodiments, the content of the inorganic nanoparticles may be 5 to 40 wt% of the total weight of the photocurable composition, and preferably 10 to 30 wt%. When the content of the inorganic nanoparticles is less than 5 wt% of the total weight of the photocurable composition, the wear resistance or scratch resistance may not be sufficiently provided by the inorganic nanoparticles. When the content of the inorganic nanoparticles is more than 40 wt% of the total weight of the photocurable composition, the inorganic nanoparticles may excessively aggregate within the photocurable composition, and the durability and mechanical properties of the photocurable film may deteriorate.

The solvent may include a compound capable of dissolving or dispersing the components of the composition described above or the additives described below. For example, the solvent may lower the viscosity of the photocurable composition and improve the coating uniformity, adhesion, and application properties of the photocurable film.

For example, the solvent may be an alcohol such as methanol, ethanol, isopropanol, butanol, methylcellusob, ethylsolusob, etc.; a ketone such as methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone, etc.; a hexane such as hexane, heptane, etc., etc.; an aromatic hydrocarbon such as benzene, toluene, xylene, etc., mesitylene, etc.; an ester such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, etc., methyl 2-hydroxy-3-methylbutanoate, etc.; a cyclic ether such as tetrahydrofuran, pyran, etc.; a cyclic ester such as γ-butyrolactone, etc.; an ethylene glycol monoalkyl ether, etc.; a diethylene glycol dialkyl ether, etc. It may include ethylene glycol alkyl ether acetates; alkylene glycol alkyl ether acetates; propylene glycol monoalkyl ethers; propylene glycol dialkyl ethers; propylene glycol alkyl ether propionates; butyldiol monoalkyl ethers; butanediol monoalkyl ether acetates; butanediol monoalkyl ether propionates; dipropylene glycol dimethyl ether, dipropylene glycol dialkyl ethers, etc. These may be used alone or in combination of two or more.

In one embodiment, the content of the solvent may be 5 to 90 wt% of the total weight of the photocurable composition. When the content of the solvent is less than 5 wt%, the viscosity of the photocurable composition may be high, thereby reducing the applicability, workability, and coatability. When the content of the solvent is more than 90 wt%, the crosslinking density of the photocurable film may be reduced, and it may be difficult to control the thickness, thereby reducing the yield and productivity of the photocurable film.

The photocurable composition according to the exemplary embodiments may further include additives generally used in the art, in addition to the above components, as needed, within a range that does not impair the properties of the above components. For example, the photocurable composition may further include a leveling agent, an ultraviolet stabilizer, a surfactant, an antistatic agent, an ultraviolet absorber, a light stabilizer, a light stimulant, a chain transfer agent, a lubricant, an anti-coagulant, a colorant such as a pigment or a dye, etc., within a range that does not impair the effect of the above-described fluorine-containing (meth)acrylate compound. The content of the additive may be 0.01 to 5 wt% of the total weight of the photocurable composition.

<Photographic Curing Screen>

The photocurable film according to exemplary embodiments may include a cured product of the photocurable composition described above. For example, the photocurable composition described above may be applied onto a base film and then cured to produce a photocurable film.

In some embodiments, the photocurable film has excellent wear resistance, hardness, and optical properties, and thus can be usefully used in image display devices such as liquid crystal displays and organic light emitting diode displays. For example, it can function as an organic protective film on a substrate or a lower substrate of an image display device, and can be used as a hard coating layer, an overcoating layer, a window, etc.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the drawings. However, the following drawings attached to this specification illustrate preferred embodiments of the present invention, and serve to further understand the technical idea of the present invention together with the contents of the invention described above, so the present invention should not be interpreted as being limited to matters described in such drawings.

FIG. 1 is a schematic cross-sectional view showing a photocurable film according to exemplary embodiments.

Referring to FIG. 1, the photocurable film may include a substrate (100) and a hard coating layer (110) formed on the substrate (100). For example, the hard coating layer (100) may include a cured product of the photocurable composition described above. For example, the photocurable film may function as a hard coating film of an image display device.

The above substrate (100) may use a transparent polymer film so that it can be applied to a flexible display. For example, the substrate may include a polymer film such as triacetyl cellulose, acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, polyester, polystyrene, polyamide, polyetherimide, polyacrylic, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or polycarbonate. These may be used alone or in combination of two or more.

In some embodiments, surface treatment such as plasma treatment or corona treatment may be performed on the substrate (100) to improve adhesion with the hard coating layer (110).

In some embodiments, the hard coating layer (110) may be manufactured by applying the photocurable composition described above on a substrate (100) and then curing it by irradiating it with light. For example, the photocurable composition may be applied on a substrate (100) or a separate release film to form a coating film, and then a drying and exposure process may be performed to form the hard coating layer (100).

Examples of the above coating method include spin coating, flexible coating, roll coating, slit and spin coating, slit coating, die coater, air knife, reverse roll, spray, etc. After this, a pre-baking process can be performed to remove volatile components such as solvents.

Thereafter, an exposure process may be performed on the coating film to form a hard coating layer (110). In the exposure process, an ultraviolet light source such as a high-pressure mercury lamp may be used. In one embodiment, a development process may be further performed to pattern the photocuring film.

For example, in order to form a pattern having a desired shape during an exposure process, an exposure mask having a predetermined shape can be placed on the coating film. For example, ultraviolet rays can be irradiated to a portion of the coating film where the exposure mask is not placed, and a curing reaction can occur in the portion irradiated with ultraviolet rays, for example, the exposed portion. As the ultraviolet rays, g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), i-line (wavelength: 365 nm), etc. can be used.

In one embodiment, after the exposure process, a development process may be performed to form a desired pattern. For example, a cured pattern may be formed by removing an unexposed portion using an alkaline developer. The development process may include a liquid addition method, a dipping method, a spray method, etc. After the exposure process or the development process, a post-baking process may be further performed.

The hard coating layer (110) according to exemplary embodiments includes a cured product of the photocurable composition described above, so that shrinkage due to the curing process is suppressed, and the adhesion is excellent so that curling can be suppressed. In addition, since the hardness and durability are improved, the occurrence of yellowing and whitening can be minimized even when exposed to harsh conditions of high temperature and high humidity for a long time.

In addition, by including the fluorine-containing (meth)acrylate compound described above as a photopolymerizable compound, it can have low refractive index, high light transmittance, and excellent antifouling properties. Therefore, the photocurable film can function as an anti-reflection film in an image display device.

In one embodiment, the hard coating layer (110) may have a light transmittance of 80% or more, and preferably 90% or more, in the visible light range. For example, the light transmittance may be measured using a BYK Gardner transmittance meter for a hard coating layer (110) having a thickness of 5 μm.

In one embodiment, the refractive index of the hard coating layer (110) may be 1.5 or less, and preferably 1.4 or less. Specifically, the refractive index of the hard coating layer (110) may be 1.2 to 1.5. For example, the refractive index of the hard coating layer (110) may be 1.5 or less. For example, the refractive index may be a value measured using a reflectometer for a hard coating layer (110) having a thickness of 5 μm.

Since the photocurable film has the low refractive index described above, for example, light reflection at the interface between structures in an image display device can be reduced, and optical interference due to the difference in refractive index of adjacent structures can be prevented. Accordingly, when the photocurable film is applied as, for example, a hard coating layer or a window, excellent transparency and visual characteristics can be realized.

In some embodiments, the thickness of the hard coating layer (110) may be 5 to 100 μm. Within the thickness range, the cured film may have excellent hardness, wear resistance, and flexibility, and may prevent shrinkage or curling after curing.

<Video display device>

The image display device according to the exemplary embodiments may include the photocuring film described above. For example, the photocuring film may be applied as an outermost protective layer or an outermost window of the image display device. In this case, the photocuring film or the hard coating layer may be positioned toward the user's viewing side.

In this specification, the “viewing side” may refer to a side adjacent to the direction in which the user is looking when the photocuring film is used in an image display device.

FIG. 2 is a schematic cross-sectional view showing an image display device according to exemplary embodiments.

Referring to FIG. 2, it may include a display panel (200), a polarizing layer (210) disposed on the display panel (200), and a hard coating film disposed on the polarizing layer (210). The hard coating film may be disposed such that the hard coating layer (230) faces the user's viewing side, and may function as a display window.

The above hard coating film has excellent surface hardness, flexibility and optical properties, is lighter than glass and has excellent impact resistance, so it can be applied to a display device to secure excellent wear resistance and bending properties without deterioration of light transmittance and image quality.

In some embodiments, the hard coating layer (230) may be formed by directly applying and curing the photocurable composition described above on the polarizing layer (210).

The polarizing layer (210) may include a polyvinyl alcohol-based polarizer or a polarizing plate including a protective film attached to at least one surface of the polarizer. Alternatively, the polarizing layer (210) may include a liquid crystal layer including a liquid crystal compound, and may include an alignment layer for imparting alignment to the liquid crystal layer.

At least one phase difference film may be formed on the polarizing layer.

FIG. 3 is a schematic cross-sectional view showing an image display device according to exemplary embodiments.

Referring to FIG. 3, the image display device may include a display panel (200), a phase difference film disposed on the display panel (200), a polarizing layer (210) disposed on the phase difference film, and a hard coating film disposed on the polarizing layer (210).

For example, the phase difference film may include a half-wave (λ/2) phase difference layer (214). For example, the phase difference film may have a multi-layer structure of a quarter-wave (λ/4) layer (212) and a half-wave phase difference layer (214). In this case, the quarter-wave phase difference layer (212) and the quarter-wave phase difference layer (214) may be sequentially laminated from the display panel (200). When the quarter-wave phase difference film (212) and the half-wave phase difference film (214) are used together, a phase delay effect can be substantially implemented over the entire visible light region, so that phenomena such as light leakage can be improved.

For example, the image display device may include a display panel (200), a quarter-wave phase difference layer (212) disposed on the display panel (200), a dihedral phase difference layer (214) disposed on the quarter-wave phase difference layer (214), a polarizing layer (210) disposed on the half-wave phase difference layer (214), and a hard coating film disposed on the polarizing layer (210).

The display panel (200) may include a liquid crystal display element or an organic light emitting diode (OLED) element, and may be used as a flat panel display, a flexible display, or a foldable display. For example, the display panel (200) may include a pixel electrode, a pixel defining film, a display layer, a counter electrode, and an encapsulation layer arranged on a panel substrate.

The above image display device may include various image display devices such as a liquid crystal display device, an electroluminescent display device, a plasma display device, a field emission display device, and the like, and may be, for example, a flexible display device or a foldable display device having flexibility and bending characteristics.

Hereinafter, in order to help understanding of the present invention, experimental examples including specific examples and comparative examples are presented; however, these are only illustrative of the present invention and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications to the examples are possible within the scope and technical idea of the present invention, and it is natural that such changes and modifications fall within the scope of the appended claims.

Synthetic example: (meth)acrylate compound

Synthesis Example 1: A-1

In a flask equipped with a reflux device, 73 g (0.25 mol) of pentaerythritol triacrylate, 80 g (0.61 mol) of diisopropyl ethyl amine, and 250 mL of dichloromethane were added and mixed. 30 g (0.2 mol) of 3,3,3-trifluoropropanoyl chloride was dissolved in 50 mL of dichloromethane, and then slowly added to the flask. After this, the mixture was stirred and reacted at room temperature for 5 hours. When the reaction was complete, 300 mL of distilled water was added to extract the organic layer, and 10 g of anhydrous magnesium sulfate was added to the extracted organic layer to remove moisture. The solid in the organic layer was removed by filtering, and the collected organic layer was concentrated under reduced pressure. Purification was performed using silica gel column chromatography (dichloromethane/hexane, gradient elution 0-50% dichloromethane]. Accordingly, 20 g of a (meth)acrylate compound represented by the following chemical formula 3 was obtained.

[Chemical Formula 3]

NMR analysis was performed on the compound of chemical formula 3 obtained above, and the NMR data measured thereby are as follows.

¹ H-NMR (400 MHz, CDCl ₃ ): δ= 2.77 (2H, m), 3.94 (2H, m), 4.01 (6H, m), 5.83 (3H, dd, J = 16 Hz), 6.12 (3H) , dd, J = 16 Hz), 6.41(3H, dd, J = 16 Hz).

LRMS (ESI): [M + H]+ 409.33.

Synthesis Example 2: A-2

The synthesis was carried out in the same manner as in Synthesis Example 1, except that 40 g (0.1 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanoyl chloride was used instead of 3,3,3-trifluoropropanoyl chloride as a reaction monomer. Accordingly, 23 g of a (meth)acrylate compound (A-2) represented by the following chemical formula 5 was obtained.

[Chemical Formula 5]

NMR analysis was performed on the compound of chemical formula 5 obtained above, and the NMR data measured accordingly are as follows.

¹ H-NMR (400 MHz, CDCl ₃ ): δ= 2.58 (2H, m), 3.93 (2H, m), 4.03 (6H, m), 5.85 (3H, dd, J = 16 Hz), 6.15 (3H) , dd, J = 16 Hz), 6.43(3H, dd, J = 16 Hz).

LRMS (ESI): [M + H]+ 659.09.

Synthesis Example 3: A-3

Except that 19 g (0.1 mol) of 2-hydroxypropane-1,3-diyl diacrylate was used instead of pentaerythritol triacrylate as a reaction monomer, and 30 g (0.08 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanoyl chloride was used instead of 3,3,3-trifluoropropanoyl chloride, the synthesis was carried out using the same method as in Synthesis Example 1. Accordingly, 21 g of a (meth)acrylate compound (A-3) represented by the following chemical formula 6 was obtained.

[Chemical formula 6]

NMR analysis was performed on the compound of chemical formula 6 obtained above, and the NMR data measured thereby are as follows.

¹ H-NMR (400 MHz, CDCl ₃ ): δ= 2.57 (2H, m), 4.44 (4H, m), 5.86 (1H, m), 5.87 (2H, m), 6.12 (2H, dd, J = 16 Hz), 6.41(2H, dd, J = 16 Hz).

LRMS (ESI): [M + H]+ 561.05.

Synthesis Example 4: A-4

The synthesis was carried out in the same manner as in Synthesis Example 1, except that 50 g (0.1 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecanoyl chloride was used instead of 3,3,3-trifluoropropanoyl chloride as a reaction monomer. Accordingly, 25 g of a (meth)acrylate compound (A-4) represented by the following chemical formula 8 was obtained.

[Chemical formula 8]

NMR analysis was performed on the compound of chemical formula 8 obtained above, and the NMR data obtained thereby are as follows.

¹ H-NMR (400 MHz, CDCl ₃ ): δ= 2.65 (2H, m), 4.01 (2H, m), 4.05 (6H, m), 5.85 (3H, dd, J = 16 Hz), 6.15 (3H) , dd, J = 16 Hz), 6.45 (3H, dd, J = 16 Hz).

LRMS (ESI): [M + H]+ 759.08.

Synthesis Example 5: A-5

Instead of pentaerythritol triacrylate as a reactive monomer, 2-((3-(acryloyloxy)-2,2-bis((acryloyloxy)methyl)propyloxy)methyl)-2-(hydroxymethyl)propane-1,3-diyl diacrylate (66 g, 0.13 mol) was used, and instead of 3,3,3-trifluoropropanoyl chloride, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanoyl chloride (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanoyl chloride) The synthesis was carried out in the same manner as in Synthesis Example 1, except that 40 g (0.1 mol) was used. Accordingly, 32 g of a (meth)acrylate compound (A-5) represented by the following chemical formula 9 was obtained.

[Chemical formula 9]

NMR analysis was performed on the compound of chemical formula 9 obtained above, and the NMR data obtained thereby are as follows.

¹ H-NMR (400 MHz, CDCl ₃ ): δ= 2.62 (2H, m), 3.85 (4H, m), 4.08 (2H, m), 4.10 (10H, m), 5.87 (5H, dd, J = 16 Hz), 6.15 (5H, dd, J = 16 Hz), 6.47 (5H, dd, J = 16 Hz).

LRMS (ESI): [M + H]+ 885.17.

Examples and Comparative Examples

(1) Preparation of photocurable composition

A photocurable composition was prepared by mixing the components listed in Table 1 below in the corresponding contents (weight %).

division
(weight%) Photopolymerizable compound
(A) Photopolymerization initiator
(B) Inorganic Nanoparticles
(C) menstruum
(D) Example 1 40(A-1)
20(A-7) 5 - 35 Example 2 40(A-2)
20(A-7) 5 - 35 Example 3 40(A-3)
20(A-7) 5 - 35 Example 4 40(A-4)
20(A-7) 5 - 35 Example 5 40(A-5)
20(A-7) 5 - 35 Example 6 10(A-2)
50(A-7) 5 - 35 Example 7 30(A-2)
30(A-7) 5 - 35 Example 8 50(A-2)
10(A-7) 5 - 35 Example 9 40(A-2)
20(A-8) 5 - 35 Example 10 10(A-2)
50(A-8) 5 - 25 Example 11 40(A-2)
20(A-7) 5 10 25 Example 12 40(A-2)
20(A-8) 5 10 25 Comparative Example 1 40(A-6)
20(A-7) 5 - 35 Comparative Example 2 40(A-7)
20(A-8) 5 - 35 Comparative Example 3 60
(A-7) 5 - 35 Comparative Example 4 60
(A-8) 5 - 35 Comparative Example 5 40(A-6)
20(A-7) 5 10 25 Comparative Example 6 40(A-7)
20(A-8) 5 10 25

The specific ingredient names listed in Table 1 above are as follows.

Photopolymerizable compound (A)

A-1) (Meth)acrylate compound manufactured by the above synthesis example 1

A-2) (Meth)acrylate compound manufactured by the above synthesis example 2

A-3) (Meth)acrylate compound manufactured by the above synthesis example 3

A-4) (Meth)acrylate compound manufactured by the above synthesis example 4

A-5) (Meth)acrylate compound manufactured by the above synthesis example 5

A-6) (Meth)acrylate compound represented by the following chemical formula 10

[Chemical Formula 10]

A-7) Pentaerythritol tetraacrylate

A-8) Tetraethylene glycol pentaerythritol tetraacrylate (M4004, Miwonsa)

Photopolymerization initiator (B)

2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide (TPO, Ciba)

Inorganic nanoparticles (C)

MEK-AC-2140 (solids concentration 40%, Nissan Chemical)

Solvent (D)

Methyl ethyl ketone (MEK, Daejung Chemical)

(2) Manufacturing of photocuring film

The photocurable compositions of the above-mentioned manufactured examples and comparative examples were dried by bar coating on a transparent substrate film (TAC) having a thickness of 80 μm, applied to a thickness of 5 μm, and then dried at 100°C for 1 minute. Thereafter, an ultraviolet light source was used to irradiate light of a wavelength of 365 nm at a light amount of 500 mJ/cm ³ in an air atmosphere using an ultrahigh-pressure mercury lamp (USH-250D, manufactured by Ushio Denki Co., Ltd.) to manufacture a photocurable film.

Experimental example

(1) Pencil hardness evaluation

For the photocured films of the examples and comparative examples, a pencil hardness test was performed at a load of 500 g and an angle of 45° using a pencil hardness tester in accordance with JIS K5600. A Mitsubishi product was used as the pencil, and the test was performed five times for each pencil hardness, and the maximum pencil hardness at which two or fewer scratches appeared was expressed as the pencil hardness of the corresponding photocured film.

The evaluation results are shown in Table 2 below.

(2) Scratch resistance evaluation

The surface scratch evaluation was performed on the photocuring films of the examples and comparative examples using a steel wool tester (WT-LCM100, Korea Protec). Steel wool of level #0000s was used, and the scratch resistance was tested by applying a load of 1 kg/(2 cm × 2 cm) to the upper surface of the photocuring film and performing 10 reciprocating movements.

After evaluation, the photocured film was exposed to fluorescent light in a darkroom and the number of scratches on the surface was measured. The evaluation results are shown in Table 2 below.

The evaluation criteria are as follows.

<Evaluation criteria>

ⓞ: Less than 10

○: 10 or more and less than 20

△: 20 to 40

×: More than 40

(3) Refractive index measurement

The photocurable compositions according to the examples and comparative examples described above were applied to 100 ㎛ thick tempered glass (EAGLE X, Corning), and then dried at 70° C. for 1 minute. Thereafter, light having a wavelength of 365 nm was irradiated at a light dose of 500 mJ/cm ³ in an air atmosphere using an ultra-high pressure mercury lamp (USH-250D, Ushio Denki Co., Ltd.) to produce a 10 ㎛ thick photocurable film.

The refractive index of the photocuring film manufactured above was measured using a reflectometer (ST4000-DLX, manufactured by K-MAC) at a temperature of 25°C.

The evaluation results are shown in Table 2 below.

(4) Water contact angle evaluation

The water contact angle of the surface of the photocured films of the examples and comparative examples was measured using a contact angle measuring device (DSA 100, manufactured by KRUSS). Specifically, the photocured films of the examples and comparative examples were washed with ultrapure water for 30 seconds and then dried with nitrogen. Thereafter, 1 ㎕ of a drop of ultrapure water was dropped on the surface of the photocured film at room temperature, and the contact angle was measured.

The evaluation results are shown in Table 2 below.

(5) Evaluation of water resistance

A 5 cm straight line was drawn on the surface of the photocuring film of the examples and comparative examples with the same black oil-based pen, and then the stain resistance was evaluated by counting the number of times the straight line was erased by wiping it with clean paper (ULTIMA Ⅱ, Hansong). The evaluation results are shown in Table 2 below.

The evaluation criteria are as follows.

<Evaluation criteria>

○: Erased after wiping 10 times or less

△: Erased after 11 to 20 wipes

×: Erased or not erased after wiping 21 or more times

division Pencil hardness Scratch resistance Refractive index Water contact angle (°) Waterproofing Example 1 2H ⓞ 1.45 103.5 ○ Example 2 1H ○ 1.40 105.3 ○ Example 3 1H ○ 1.38 108.7 ○ Example 4 1H ○ 1.38 108.9 ○ Example 5 2H ⓞ 1.42 104.5 ○ Example 6 3H ⓞ 1.48 101.1 ○ Example 7 2H ⓞ 1.44 103.7 ○ Example 8 1H ○ 1.38 109.1 ○ Example 9 1H ○ 1.40 106.5 ○ Example 10 1H ○ 1.48 103.2 ○ Example 11 1H ○ 1.36 109.3 ○ Example 12 1H ○ 1.37 109.1 ○ Comparative Example 1 1B X 1.40 109.1 ○ Comparative Example 2 3H ⓞ 1.53 93.5 X Comparative Example 3 4H ⓞ 1.52 94.1 X Comparative Example 4 2H ⓞ 1.54 93.2 X Comparative Example 5 2B △ 1.38 107.1 ○ Comparative Example 6 1H ○ 1.47 95.5 X

It can be confirmed that the photocuring film according to the exemplary embodiments has excellent pencil hardness, scratch resistance, and light transmittance overall. Since the photopolymerizable compound includes a fluorine-containing (meth)acrylate compound having a fluorinated hydrocarbon group, the refractive index of the photocuring film can be lowered, and a photocuring film having low reflection characteristics and excellent antifouling properties can be provided. In addition, since the fluorine-containing (meth)acrylate compound has a (meth)acryloyl group having two or more functional groups, the crosslinking density of the photocuring film can be increased, and the surface hardness and scratch resistance can be excellent.

It can be confirmed that the photocuring films according to the comparative examples have overall worse mechanical properties such as hardness and scratch resistance, and optical properties such as transmittance and antifouling properties compared to the examples.

In the case of a comparative example containing a monofunctional fluorine-containing (meth)acrylate compound as a photopolymerizable compound, it can be confirmed that the hardness and scratch resistance deteriorate as the crosslinking density of the photocured film decreases.

In the case of a comparative example in which the photopolymerizable compound does not contain a fluorinated hydrocarbon group, it can be confirmed that the transmittance and antireflection properties are deteriorated because the photocured film has a high refractive index. In addition, it can be confirmed that the photocured film has a low water contact angle and that the antifouling properties are reduced.

100: Base film 110: Hard coating layer
200: Display panel 210: Polarizing layer
212: Bi-wave phase difference layer 214: Quarter-wave phase difference layer
220: Base layer 230: Hard coating layer

Claims (16)

A photopolymerizable compound comprising a fluorine-containing (meth)acrylate compound having a polymerizable functional group including at least two (meth)acryloyl groups, a fluorinated hydrocarbon group, and an ester group connecting the polymerizable functional group and the fluorinated hydrocarbon group; and
Containing a solvent,
The above fluorine-containing (meth)acrylate compound is a photocurable composition comprising a compound represented by the following chemical formula 1:
[Chemical Formula 1]

(In the above chemical formula 1, R ₁ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aliphatic hydrocarbon group having 1 to 10 carbon atoms in which at least one carbon atom is substituted with an oxygen atom,
Ay is a functional group independently represented by the following chemical formula 2 and is connected to at least one of the carbon atoms of R ₁ ,
m is an integer from 2 to 5, and n is an integer from 1 to 10)
[Chemical formula 2]

(In the above chemical formula 2, R ₂ is a hydrogen atom or a methyl group, and * is a bond.)
delete delete delete In claim 1, the fluorine-containing (meth)acrylate compound is a photocurable composition comprising at least one of the compounds represented by the following chemical formulas 3 to 9:
[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical formula 6]

[Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]
.
A photocurable composition according to claim 1, wherein the content of the fluorine-containing (meth)acrylate compound is 10 to 90 wt% of the total weight of the photocurable composition.
A photocurable composition according to claim 1, wherein the photopolymerizable compound further comprises a fluorine-free (meth)acrylate compound.
A photocurable composition according to claim 1, further comprising a photopolymerization initiator or inorganic nanoparticles.
A photocurable composition according to claim 8, wherein the inorganic nanoparticle comprises a core particle comprising a metal oxide, and a photopolymerizable functional group bonded to at least a portion of a surface of the core particle.
A photocurable composition according to claim 9, wherein the photopolymerizable functional group comprises at least one of an acryloyl group, a methacryloyl group, a vinyl ether group, a glycidyl group, and a hydroxy group.
In claim 8, among the total weight of the photocurable composition,
The content of the above photopolymerization initiator is 0.1 to 5 wt%,
A photocurable composition having a content of the above inorganic nanoparticles of 5 to 40 wt%.
A photocurable film comprising a cured product of the photocurable composition according to claim 1.
In claim 12,
substrate film; and
A photocurable film comprising a hard coating layer including the cured material and disposed on the above-described substrate film.
A photocurable film according to claim 13, wherein the refractive index of the hard coating layer is 1.5 or less.
An image display device comprising a photocurable film according to claim 12.
In claim 15,
display panel;
a polarizing layer disposed on the above display panel; and
An image display device comprising a hard coating film disposed on the polarizing layer and including the photocuring film.