WO2018155784A1 - Hard coating film and image display device comprising same - Google Patents

Abstract

The present invention relates to a hard coating film and, more specifically, comprises a fluorine atom and/or a silicon atom, has a coefficient of skin friction on at least one side of 0.3 or less, and has a surface resistance of 10⁸-10¹² Ω/□, thereby having excellent slip and generating a remarkably low amount of static electricity.

Description

Hard coating film and image display device comprising the same

The present invention relates to a hard coat film and an image display device including the same.

The image display device may be composed of a liquid crystal cell containing a liquid crystal, a polarizing plate, and the like, which are mainly bonded by forming an adhesive layer on one surface of the polarizing plate. In addition, in order to improve the function of the image display device, a surface protective film such as a retardation plate, a wide viewing angle compensation plate, and brightness enhancement is additionally attached to the polarizing plate through an adhesive or the like.

Since the optical members such as the surface protection film and the polarizing plate are made of a plastic material, static electricity is generated during friction and peeling, and when voltage is applied to the liquid crystal while the static electricity remains, the orientation of the liquid crystal molecules is lost or the panel is defective. This can happen. Therefore, various antistatic treatments are performed to prevent such defects.

For example, there is a method of adding an at least one surfactant to the adhesive and transferring the surfactant to the adherend to perform an antistatic function, but in this case, the surfactant is easy to bleed on the surface of the adhesive, when applied to a protective film, There was a problem of contamination of the adherend.

In addition, there is a method of adding an antistatic agent composed of a polyether polyol and an alkali metal salt to the acrylic adhesive, but in this case, bleeding of the antistatic agent occurs, and the durability after the curing of the adhesive is significantly reduced, and when applied to a protective film, Bleed out easily occurs under high temperature conditions, and there is a problem that contamination occurs in the adherend.

Korean Patent Publication No. 2011-0112263 discloses a method of introducing a functional group having excellent compatibility with an antistatic agent in a monomer of the pressure-sensitive adhesive composition to suppress bleeding of the antistatic agent. However, durability is deteriorated under high temperature and high humidity conditions. Did not solve.

An object of the present invention is to provide a hard coating film having excellent slip properties and significantly less static electricity generation, and an image display device including the same.

1. A base film and a hard coating layer formed on at least one surface of the base film, the hard coating layer includes at least one of fluorine atoms and silicon atoms, the surface friction coefficient is 0.3 or less, the surface resistance is 10 ⁸ to 10 Hard coating film which is ¹² Ω / □.

2. In the above 1, wherein the hard coating layer is formed by hardening the composition for forming a hard coating layer comprising an antistatic agent, a translucent resin, a solvent and an initiator, a hard coating film.

3. In the above 2, the antistatic agent is lithium hexafluorophosphate (LiPF ₆ ), lithium hexafluoroalsenate (LiAsF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium bistrifluoromethanesulfonimide Date (LiTFSI), lithium bisfluorosulfonylimide superacid lithium salt system (LiSA: C _n F _{2n + 1} SO ₃ Li, n = 4,8,10), lithium poly anion salt system, 1,2,3- Dithiazolidine-4,4,5,5-tetrafluoro-1,1,3,3-tetraoxide (LiCTFSI), 1-ethyl-3-methylimidazolium tetrafluoroborate (C ₆ H ₁₁ BF ₄ N ₂ ), 1-butyl-3-methylimidazolium hexafluorophosphate (C ₈ H ₁₅ F ₆ N ₂ P), 1-butyl-3-methylimidazolium tetrafluoroborate (C ₈ H ₁₅ BF ₄ N ₂ ), 1-butyl-3-methylimidazolium hexafluoroantimonate (C ₈ H ₁₅ F ₆ N ₂ Sb), 1-butyl-2,3-dimethylimidazolium tetrafluoroborate _{(C 9 H 17 BF4N 2)} , 1- butyl-2,3-dimethyl-imidazole Fluoro help tree methane-sulfonate _{(C 8 H 13 F 3 N} 2 O 3 S), 1- ethyl-3-methyl imidazolium a microporous fluoro tree methane-sulfonate _{(C 7 H 11 F 3 N} 2 O 3 S), methyl-trioctylammonium bis (trifluoromethyl-sulfonyl) imide (C ₂₇ H ₅₄ F ₆ N ₂ O ₄ S ₂ ), tetraethylammonium trifluoromethanesulfonate (C ₉ H ₂₀ F ₃ NO ₃ S), triethylsulfonium bis (trifluoromethylsulfonyl) imide (C ₈ H ₁₅ F ₆ NO ₄ S ₂ ), tetrabutylphosphonium tetrafluoroborate (C ₁₆ H ₃₆ BF ₄ P), 1-butyl-3-methylimidazolium bis (trifluoromethyl-sulfonyl) imide (C ₁₀ H ₁₅ F ₆ N ₃ O ₄ S ₂ ), 1-butyl-3-methyl Pyridinium bis (trifluoromethylsulfonyl) imide (C ₁₂ H ₁₆ F ₆ N ₂ O ₄ S ₂ ), 1,2-dimethyl-3-propyllimidazolium bis (trifluoromethyl-sulfonyl ) imide _{(C 10 H 15 F 6 N} 3 O 4 S 2), 1,2- dimethyl-3-propyl imidazolium tris (trifluoromethyl-sulfonic Carbonyl) methide _{(C 12 H 15 F 9 N} 2 O 6 S 3), 1- ethyl-3-methylimidazolium bis (ethylsulfonyl pentafluorophenyl) imide _{(C 10 H 11 F 10 N} 3 O ₄ S ₂ ), 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) -imide (C ₈ H ₁₁ F ₆ N ₃ O ₄ S ₂ ), 1-butyl-3-methyl Imidazolium hexafluorophosphate (C ₈ H ₁₅ F ₆ N ₂ P), 1-butyl-4-methylpyridinium tetrafluoroborate (C ₁₀ H ₁₆ BF ₄ N), 1-hexyl-3-methyl Imidazolium tetrafluoroborate (C ₁₀ H ₁₉ BF ₄ N ₂ ), 1-methyl-3-octylimidazolium hexafluorophosphate (C ₁₂ H ₂₃ F ₆ N ₂ P), 1-methyl-3- Octylimidazolium tetrafluoroborate (C ₁₂ H ₂₃ BF ₄ N ₂ ), At least one selected from the group consisting of a hard coating film.

4. In the above 2, wherein the antistatic agent comprises a siloxane-based resin, hard coating film.

5. In the above 1, wherein the hard coating layer is cut in the direction in which the base film and the hard coating layer is laminated, the concentration of at least one of the fluorine atoms and silicon atoms is higher than the center side of the cross-section, Hard coated film.

6. In the above 2, wherein the light-transmitting resin comprises a dendrimer compound, hard coating film.

7. In the above 2, wherein the hard coating layer-forming composition comprises a nano silica sol, hard coating film.

8. Window film comprising any one of the hard coating film 1 to 7 above.

9. The image display device comprising the window film of the above eight.

Hard coating film according to the embodiments of the present invention, it is possible to implement a touch feeling similar to glass with a low friction coefficient and excellent slip properties.

In addition, the hard coating film according to the embodiments of the present invention is significantly less static electricity generation, it is possible to prevent the adhesion of dust, to ensure a high yield during the bonding process, it is possible to prevent the occurrence of fire during processing.

In addition, the hard coating film according to the embodiments of the present invention, may be excellent in flexibility and excellent hardness and scratch resistance.

Embodiments of the present invention include a base film and a hard coating layer formed on at least one surface of the base film, wherein the hard coating layer includes at least one of fluorine atoms and silicon atoms, and has a surface friction coefficient of 0.3 or less and a surface resistance. This 10 ⁸ to 10 ¹² Ω / □ relates to a hard coat film that can be excellent in slip properties and significantly less generation of static electricity.

Hereinafter, specific embodiments of the present invention will be described. However, this is only an example and the present invention is not limited thereto.

<Hard coating film>

Embodiments of the present invention, the hard coating layer includes at least one of fluorine atoms and silicon atoms, the surface friction coefficient is 0.3 or less, thereby improving the reliability, touch feeling and excellent slip properties to achieve a glass-like touch feeling It is possible to prevent the adhesion of dust due to the remarkably low static electricity generation, to ensure a high yield during the bonding process and to prevent the occurrence of fire during processing. If the surface friction coefficient exceeds 0.3, slip resistance is lowered and scratch resistance is lowered.

In addition, embodiments of the present invention, the surface resistance satisfies 10 ⁸ to 10 ¹² Ω / □, when the surface resistance is less than 10 ⁸ Ω / □ mechanical properties such as pencil hardness is lowered, the surface resistance is 10 ¹² If Ω / □ or more, the conductivity, anti-static properties are lowered due to the static electricity due to the inflow of foreign matter during the manufacturing process is significantly higher than the problem may occur such as yield.

Surface friction coefficient and surface resistance of a specific range according to an embodiment of the present invention, the content of fluorine atoms or silicon atoms included in the hard coating layer; It can be achieved by adjusting the composition of the composition for forming another hard coating layer or the content ratio of the composition, solvent change, drying and curing conditions, and the like.

Hard coating film according to an embodiment of the present invention, may include a hard coating layer formed by curing of the composition for forming a hard coating layer comprising an antistatic agent, a light-transmitting resin, a solvent and an initiator.

Antistatic Agent (A)

The antistatic agent (A) may include at least one selected from the group consisting of a fluorine antistatic agent and a silicon antistatic agent. Since the antistatic agent includes a compound having a fluorine atom or a silicon atom, embodiments of the present invention may include at least one of a fluorine atom and a silicon atom, and the surface friction coefficient of at least one side is 0.3 or less, thereby providing reliability, Improved touch feeling and excellent slipperiness can realize glass-like touch feeling, and due to the low static electricity generation, it prevents dust from attaching, secures high yield during the bonding process, and prevents fire during processing. .

For example, the fluorine-based antistatic agent may be lithium hexafluorophosphate (LiPF ₆ ), lithium hexafluoroalsenate (LiAsF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), or lithium bistrifluoromethanesulfonimide ( LiTFSI), lithium bisfluorosulfonylimide (LiFSI), superacid lithium salt system (LiSA: C _n F _{2n + 1} SO ₃ Li, n = 4,8,10), lithium poly anion salt system, 1,2, 3-dithiazolidine-4,4,5,5-tetrafluoro-1,1,3,3-tetraoxide (LiCTFSI), 1-ethyl-3-methylimidazolium tetrafluoroborate (C ₆ H ₁₁ BF ₄ N ₂ ), 1-butyl-3-methylimidazolium hexafluorophosphate (C ₈ H ₁₅ F ₆ N ₂ P), 1-butyl-3-methylimidazolium tetrafluoroborate (C ₈ H ₁₅ BF ₄ N ₂ ), 1-butyl-3-methylimidazolium hexafluoroantimonate (C ₈ H ₁₅ F ₆ N ₂ Sb), 1-butyl-2,3-dimethylimidazolium tetrafluor Roborate (C ₉ H ₁₇ BF ₄ N ₂ ), 1-butyl-2,3-dimethylimida Zolium trifluoromethane-sulfonate (C ₈ H ₁₃ F ₃ N ₂ O ₃ S), 1-ethyl-3-methylimidazolium trifluoromethane-sulfonate (C ₇ H ₁₁ F ₃ N ₂ O ₃ S), methyl-trioctylammonium bis (trifluoromethyl-sulfonyl) imide (C ₂₇ H ₅₄ F ₆ N ₂ O ₄ S ₂ ), tetraethylammonium trifluoromethanesulfonate (C ₉ H ₂₀ F ₃ NO ₃ S), triethylsulfonium bis (trifluoromethylsulfonyl) imide (C ₈ H ₁₅ F ₆ NO ₄ S ₂ ), tetrabutylphosphonium tetrafluoroborate (C ₁₆ H ₃₆ BF ₄ P), 1-butyl-3-methylimidazolium bis (trifluoromethyl-sulfonyl) imide (C ₁₀ H ₁₅ F ₆ N ₃ O ₄ S ₂ ), 1-butyl-3-methyl Pyridinium bis (trifluoromethylsulfonyl) imide (C ₁₂ H ₁₆ F ₆ N ₂ O ₄ S ₂ ), 1,2-dimethyl-3-propyllimidazolium bis (trifluoromethyl-sulfonyl Imide (C ₁₀ H ₁₅ F ₆ N ₃ O ₄ S ₂ ), 1,2-dimethyl-3-propylimidazolium tris (trifluoromethyl- Sulfonyl) methide (C ₁₂ H ₁₅ F ₉ N ₂ O ₆ S ₃ ), 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) -imide (C ₁₀ H ₁₁ F ₁₀ N ₃ O ₄ S ₂ ), 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) -imide (C ₈ H ₁₁ F ₆ N ₃ O ₄ S ₂ ), 1-butyl-3- Methylimidazolium hexafluorophosphate (C ₈ H ₁₅ F ₆ N ₂ P), 1-butyl-4-methylpyridinium tetrafluoroborate (C ₁₀ H ₁₆ BF ₄ N), 1-hexyl-3- Methylimidazolium tetrafluoroborate (C ₁₀ H ₁₉ BF ₄ N ₂ ), 1-methyl-3-octylimidazolium hexafluorophosphate (C ₁₂ H ₂₃ F ₆ N ₂ P), 1-methyl-3 -Octylimidazolium tetrafluoroborate (C ₁₂ H ₂₃ BF ₄ N ₂ ) and the like, preferably lithium hexafluorophosphate (LiPF ₆ ), lithium bifluorosulfonylimide (LiFSI). .

For example, the silicone antistatic agent may be a siloxane resin, or the like, and preferably, UVAS-364 (Jinbo), MORESTAT ES-4110 (Moire), or the like.

If necessary, on the cross section in which the hard coat layer is cut in the direction in which the base film and the hard coat layer are stacked, the concentration of at least one of the fluorine atom and the silicon atom according to the embodiment of the present invention is the center side of the cross section. May be higher outside.

At least one of the fluorine atom and the silicon atom may be preferable in terms of achieving a numerical range of the above-described effect coefficient of friction by having an outer side higher than the center side of the cross section. It is believed that this is because a large amount of fluorine atoms or silicon atoms contributes to the improvement of slip properties as they are disposed outside the hard coating layer.

Content of the antistatic agent according to an embodiment of the present invention is not particularly limited, for example, may be included in 1 to 20 parts by weight based on a total of 100 parts by weight of the composition for forming a hard coating layer, the present charging if the above range is satisfied The effect according to the inhibitor may be better.

Light transmitting resin (B)

Translucent resin (B) is photocurable resin, The said photocurable resin can be manufactured by condensation reaction of a photocurable (meth) acrylate oligomer and / or a monomer.

In the present invention, "(meth) acryl-" refers to "acryl-", "methacryl-", or both.

As said photocurable (meth) acrylate oligomer, epoxy (meth) acrylate, urethane (meth) acrylate, etc. can be used, for example, urethane (meth) acrylate is preferable. Urethane (meth) acrylate can be manufactured by condensation reaction of the polyfunctional (meth) acrylate which has a hydroxyl group in a molecule | numerator, and the compound which has an isocyanate group. Specific examples of the (meth) acrylate having a hydroxy group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and capro It may be selected from one or more selected from the group consisting of lactone ring-opened hydroxyacrylate, pentaerythritol tri / tetra (meth) acrylate mixture, and dipentaerythritol penta / hexa (meth) acrylate mixture. Specific examples of the compound having an isocyanate group include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanatododecane, 1, 5-diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) cyclohexane, trans-1,4-cyclohexene diisocyanate, 4,4 '-Methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethylxylene-1, 3-diisocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenylisocyanate), 4,4'-oxybis (phenylisocyanate), hexamethylene diisocyanate Trifunctional Isocyanates Derived from, and Trimethane Propanol Adduct Toluenediiso O it may be one or more selected from the group consisting of carbonate.

The monomer is usually used, having a unsaturated group such as a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, and the like in a photocurable functional group, and a (meth) acryloyl group is more preferred among them.

Specific examples of the monomer having a (meth) acryloyl group include neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, 1 , 2,4-cyclohexane tetra (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Yit, tripentaerythritol tri (meth) acrylate, tripentaerythritol hexatri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso-decyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth ) Acrylate, phenoxyethyl (meth) acrylate, isobornol (meth) acrylate may be selected from one or more kinds.

The translucent resin can be prepared using at least one selected from the group consisting of the photocurable (meth) acrylate oligomers and monomers exemplified above.

If necessary, the translucent resin according to an embodiment of the present invention may include a dendrimer compound. By adding the dendrimer compound to the composition for forming the hard coat layer, it is possible to further improve the flexibility and hardness of the hard coat film or the hard coat layer.

In the present application, the dendrimer compound may refer to a compound in which chains of molecules are regularly polymerized from the center to the outward direction. On the other hand, the "generation" of the dendrimer compound refers to the step of growing the dendrimer structure, it is understood that one generation increases each time a unit structure that is constantly repeated with respect to the center of the molecule is added. For example, when the first generation branch terminal formed is subjected to the polymerization reaction again, the second generation becomes a second generation, and the repeated polymerization reaction proceeds.

According to embodiments of the present invention, the dendrimer compound may have a plurality of (meth) acrylate end groups, and may have a structure of two or more generations.

For example, the end group of the dendrimer compound may be represented by the following formula (1).

[Formula 1]

In formula (1), for example, R ₅ may be a direct bond or an alkylene group having 1 to 6 carbon atoms, and R ₆ may be a hydrogen atom or a methyl group.

As a non-limiting example, the dendrimer compound may be prepared through the following reaction route. The following reaction route is provided to illustrate an example of a dendrimer compound having a (meth) acrylate end group of, for example, a third generation structure, and the dendrimer compound of the present invention should not be construed as being limited thereto.

[Reaction Path]

Referring to the reaction path, the first generation dendrimer structure of condensation of DMPA is formed with TMP as the center, and the generation of dendrimer can be increased by repeatedly condensation polymerization of DMPA as a branched structure. For example, condensation polymerization of acrylic acid on the end group after the third generation can yield a dendrimer compound having a polyfunctional acrylate group at the end.

According to embodiments of the present invention, a polymerizable functional group is formed at the branch terminal of the dendrimer compound, and may have a structure of two or more generations. Accordingly, compared with a general polymerizable compound, since more polymerizable functional groups are contained relative to the unit molecular weight of the polymer, excellent hardness characteristics can be realized.

In some embodiments, the dendrimer compound may have a second generation or third generation structure. When the dendrimer compound is 4 generations or more, the number of polymerizable functional groups may be excessively increased, thereby lowering flexibility and curling characteristics.

In addition, in the dendrimer compound, since the polymerizable functional group is included only at the branch end, the central portion of the polymer can secure appropriate flexibility and bending properties, thereby securing the hardness of the hard coating film or the hard coating layer and at the same time Properties and flexibility can be improved.

In some embodiments, the dendrimer compound may be included in an amount of about 10 to 60 parts by weight, preferably about 15 to 55 parts by weight, in 100 parts by weight of the total composition for forming the hard coating layer. When the content of the dendrimer compound is less than about 10 parts by weight, desired flexible properties (eg, flexibility and bending characteristics) of the hard coat film or the hard coat layer may not be secured. When the content of the dendrimer compound exceeds about 60 parts by weight, due to the above-described steric hindrance with the photocurable compound, the hardness may be reduced due to lack of curing.

In the present invention, when the compound or resin represented by the chemical formula has an isomer thereof, the chemical formula representing the compound or resin means a representative chemical formula including the isomer.

The content of the translucent resin is not particularly limited, but may be 5 to 60 parts by weight based on 100 parts by weight of the total composition for forming the hard coating layer. When the content is satisfied, the hardness of the formed hard coating layer may be improved and curling may be reduced.

Nano silica sol (C)

In addition, nano silica sol (C) may be added to further strengthen the hardness, and the content of the nano silica sol is not particularly limited, but is based on the nano silica sol having an average particle diameter (D ₅₀ ) of 10 to 100 nm and a solid content of 40% The hard coating layer may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the total composition.

Photoinitiator (D)

The photoinitiator (D) can be used without limitation as long as it is known in the art. For example, one or more selected from the group consisting of hydroxyketones, aminoketones, hydrogen decyclic photoinitiators, and combinations thereof can be used.

Specifically, the photoinitiator is 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenylketone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- Phenyl-1-one, 4-hydroxycyclophenyl ketone, 2,2-dimethoxy-2-phenyl-acetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-ke Noloacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone, benzophenone, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and One or more types selected from the group consisting of these combinations can be used.

Such photoinitiator is used in the range of 0.1 to 10% by weight, preferably 1 to 5% by weight, based on 100 parts by weight of the total composition for forming the hard coat layer. If the content is less than the above range, the curing rate of the composition is slow and uncured, so that mechanical properties are lowered. On the contrary, if the content exceeds the above range, cracks may occur in the coating due to overcuring.

Solvent (E)

The solvent (E) according to the present invention can be used without particular limitation as long as it can dissolve or disperse the above components.

Specific examples include alcohols (methanol, ethanol, isopropanol, butanol, propylene glycol methoxy alcohol, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, etc.), Acetate-based (methyl acetate, ethyl acetate, butyl acetate, propylene glycol methoxy acetate, etc.), cellosolve-based (methyl cellosolve, ethyl cellosolve, propyl cellosolve, etc.), hydrocarbon-based (normal hexane, normal heptane, benzene, toluene , Xylene, etc.), and these may be used alone or in combination of two or more thereof.

In the present invention, the content of the solvent (E) is not particularly limited, for example, it may be included in 30 to 90 parts by weight, preferably 40 to 70 parts by weight based on 100 parts by weight of the total composition for forming a hard coating layer. have. When included in the content range, it is preferable to implement the appropriate coatability. On the other hand, if less than 5 parts by weight, the viscosity is high, the coating property is lowered, if it exceeds 90 parts by weight, it is difficult to adjust the thickness of the coating film and dry stains may occur, appearance defects may occur.

Additive (F)

The composition for forming a hard coat according to the present invention may further include an additive (F) as necessary in addition to the above-described components, for example, a leveling agent, an ultraviolet stabilizer, a heat stabilizer, and the like.

The leveling agent is added to improve the smoothness and coatability of the coating film when the composition is applied, and a silicone leveling agent, a fluorine-based leveling agent, an acrylic leveling agent, and the like can be used. Commercially available products of the leveling agent include BYK-323, BYK-331, BYK-333, BYK-337, BYK-373, BYK-375, BYK-377, BYK-378, TEGO Glide 410, TEGO Glide 411, TEGO Glide 415, TEGO Glide 420, TEGO Glide 432, TEGO Glide 435, TEGO Glide 440, TEGO Glide 450, TEGO Glide 455, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, 3M FC-4430, FC-4432, etc. can be used.

The sunscreen agent is added to prevent discoloration or brittleness of the surface of the coating film by continuous UV exposure, and serves to block or absorb UV light. The UV stabilizers may be classified into absorbents, quenchers, and hindered amine light stabilizers (HALS) according to functional mechanisms. For example, phenyl salicylates (absorbers), Benzophenone (Benzophenone, absorbent), benzotriazole (Benzotriazole, absorbent), nickel derivative (quencher), radical scavenger, etc. are mentioned.

As the heat stabilizer, polyphenol-based, phosphite-based and lactone-based heat stabilizers may be used, and the UV stabilizer and the heat stabilizer may be used by mixing in an appropriate amount at a level that does not affect the UV curability.

The additives (F) is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total composition for forming a hard coat layer.

Base film

For example, the hard coating layer-forming composition may be cured by applying the hard-coat layer-forming composition onto a base film.

The material of the base film may be used without limitation as long as it is a transparent polymer resin, and the base film may be, for example, triacetyl cellulose, acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propy O'Neill cellulose, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, It may be a film formed of a polymer resin such as polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polycarbonate. These polymer resins can be used individually or in mixture of 2 or more types.

In the case of a crystalline polymer substrate film, an engineering plastic substrate, or a polymer substrate film whose surface has changed to hydrophilicity due to hydrolysis or saponification, it is difficult to increase adhesion when using a composition for forming a hard coating layer, For this purpose, mechanical properties may be lowered. However, the composition for forming a hard coating layer according to an embodiment of the present invention can realize excellent adhesion without deteriorating mechanical properties even for these substrate films.

The base film may be subjected to a surface treatment such as plasma treatment, corona treatment, etc. to improve adhesion to the hard coating layer.

When the hard coating film according to an embodiment of the present invention further includes a layer other than the hard coating layer, the hard coating layer is disposed closer to the viewer's side than the other layers.

The hard coating layer is formed by applying and curing the composition for forming a hard coating layer on the base film, the coating is a slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method , Roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, gravure printing method, flexographic printing method, offset printing method, inkjet coating method, dispenser printing method, nozzle coating method, capillary coating method Known methods such as these can be used.

The thickness of the hard coating layer is not particularly limited, and may be, for example, 5 to 100 μm. When the thickness is in the above range, it shows excellent hardness and flexibility, and can prevent the curling phenomenon.

Since the hard coat film of the present invention has excellent hardness, flexibility, and curl characteristics, it can be usefully applied to a window film of an image display device. In this case, the hard coating film alone or an additional layer known in the art may be laminated and used as the window film.

<Image display device>

Moreover, this invention provides the image display apparatus provided with the said hard coat film.

The hard coat film of the present invention is excellent in hardness and flexibility so that the hard coat film can be used, for example, as the outermost window film of the image display device, and particularly, can be preferably applied to the flexible image display device.

The image display device may be various image display devices such as a conventional liquid crystal display device, an electroluminescent display device, a plasma display device, and a field emission display device.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Examples and Comparative Examples

To prepare a composition for forming a hard coating layer having a composition and content (parts by weight) described in Table 1 below.

A-1: lithium bisfluorosulfonylimide (LiFSI)

A-2: UVAS-364 (Jinbo)

A-3: lithium hexafluorophosphate (LiPF ₆ )

A'-1: antimony tin oxide (ATO)

B-1: urethane acrylate (18 functional, Miwon specialty chemical, Miramer SP1106)

C-1: nano silica sol (12 nm, 40% solids)

D-1: 1-hydroxycyclohexylphenyl ketone (1-Hydroxy-cyclohexyl-phenyl-ketone)

E-1: Propylene Glycol Monomethyl Ether

E-2: methyl ethyl ketone

F-1: BYK307 (BYK Chemisa)

After hardening the composition for forming the hard coating layer on one side of the polyimide film (80um) and coating it to have a thickness of 10um, after drying the solvent and irradiating UV accumulated light amount 500mJ, the other side of the polyimide film In the same manner, the coating was hardened to a thickness of 0.5 μm and dried, followed by UV curing to prepare a hard coat film.

Experimental Example

The following experiments were performed on the prepared examples and comparative examples.

1. Friction Coefficient Measurement

After the base film was fixed to the glass so that the hard coating faced upwards, an initial reciprocating friction test was performed using steel wool having a contact area of 3 * 2.5 cm with a load of 3.75 kgf to evaluate the load applied.

 Initial coefficient of friction: value of horizontal load / vertical load in one round trip

2. Inclined  Ball tack tester

The angle was measured with a sloped ball tack tester to evaluate the slip and similarity of touch with glass.

The inclined ball tack tester holds the test piece to be tested on the inclined plate on the inclined plate that can adjust the angle from 10˚ to 40˚. Was measured to evaluate the slip properties of the test piece. In the case of glass, the data was evaluated with data of 18.5˚.

3. Antistatic property Surface resistivity , Ω / □)

Using a surface resistance measuring instrument (MCP-HT450, Mitsubishi Chemical, Probe: URS, UR100, Probe checker: URS, UR100), apply a voltage of 500V, measure each of the three points of the coating layer 10 times, and measure the average value. Calculated.

4. Pencil Hardness

After the pencil was set in the 45 ° direction under a load of 1 kg, the coating film was fixed on the glass, and after evaluating five times with a pencil having each pencil hardness, the pencil hardness was expressed by hardness not to be scratched more than four times.

As shown in Table 2, the examples are excellent in both the coefficient of friction and the antistatic effect, the comparative example was confirmed that one or more of the coefficient of friction or antistatic effect is not excellent.

Example 4, the content of the antistatic agent (A) is less than the other examples, the friction coefficient was found to be slightly higher, the sloped ball test angle is higher,

In Example 5, although the content of the light-transmissive resin (B) is less than other examples, the hardness of the hard coating layer is slightly lowered, although not shown in Table 2, it was confirmed that the HC film is relatively poor in appearance.

In Example 6, the content of the light-transmissive resin (B) is higher than in other examples, although it is not shown in Table 2, but it was confirmed that curling was relatively increased.

Example 7 is a case in which the nano silica sol (C) is not included, it was confirmed that the hardness of the hard coating layer compared to other examples.

Comparative Example 4 is a comparative example in which an excessive amount of the antistatic agent (A) was added, and it was confirmed that the hardness of the hard coating layer was significantly lowered compared to other examples.

Claims (9)

A base film and a hard coating layer formed on at least one surface of the base film, The hard coating layer includes at least one of fluorine atoms and silicon atoms, the surface friction coefficient is 0.3 or less, the surface resistance is 10 ⁸ to 10 ¹² Ω / □, a hard coating film. The hard coat film of claim 1, wherein the hard coat layer is formed by curing a composition for forming a hard coat layer including an antistatic agent, a translucent resin, a solvent, and an initiator. The method of claim 2, wherein the antistatic agent is lithium hexafluorophosphate (LiPF ₆ ), lithium hexafluoroalsenate (LiAsF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium bistrifluoromethanesulfonimide ( LiTFSI), lithium bisfluorosulfonylimide (LiFSI), superacid lithium salt system (LiSA: C _n F _{2n + 1} SO ₃ Li, n = 4,8,10), lithium poly anion salt system, 1,2, 3-dithiazolidine-4,4,5,5-tetrafluoro-1,1,3,3-tetraoxide (LiCTFSI), 1-ethyl-3-methylimidazolium tetrafluoroborate (C ₆ H ₁₁ BF ₄ N ₂ ), 1-butyl-3-methylimidazolium hexafluorophosphate (C ₈ H ₁₅ F ₆ N ₂ P), 1-butyl-3-methylimidazolium tetrafluoroborate (C ₈ H ₁₅ BF ₄ N ₂ ), 1-butyl-3-methylimidazolium hexafluoroantimonate (C ₈ H ₁₅ F ₆ N ₂ Sb), 1-butyl-2,3-dimethylimidazolium tetrafluor Robo rate _{(C 9 H 17 BF4N 2)} , 1- butyl-2,3-dimethyl A microporous fluoro imidazolium tree methane-sulfonate _{(C 8 H 13 F 3 N} 2 O 3 S), 1- ethyl-3-methyl imidazolium methane microporous fluoro tri-sulfonate _{(C 7 H 11 F 3 N} 2 O ₃ S), methyl-trioctylammonium bis (trifluoromethyl-sulfonyl) imide (C ₂₇ H ₅₄ F ₆ N ₂ O ₄ S ₂ ), tetraethylammonium trifluoromethanesulfonate (C ₉ H ₂₀ F ₃ NO ₃ S), triethylsulfonium bis (trifluoromethylsulfonyl) imide (C ₈ H ₁₅ F ₆ NO ₄ S ₂ ), tetrabutylphosphonium tetrafluoroborate (C ₁₆ H ₃₆ BF ₄ P), 1-butyl-3-methylimidazolium bis (trifluoromethyl-sulfonyl) imide (C ₁₀ H ₁₅ F ₆ N ₃ O ₄ S ₂ ), 1-butyl-3- Methylpyridinium bis (trifluoromethylsulfonyl) imide (C ₁₂ H ₁₆ F ₆ N ₂ O ₄ S ₂ ), 1,2-dimethyl-3-propyllimidazolium bis (trifluoromethyl-sul Ponyl) imide (C ₁₀ H ₁₅ F ₆ N ₃ O ₄ S ₂ ), 1,2-dimethyl-3-propylimidazolium tris (trifluoro Methyl-sulfonyl) methide (C ₁₂ H ₁₅ F ₉ N ₂ O ₆ S ₃ ), 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) -imide (C ₁₀ H ₁₁ F ₁₀ N ₃ O ₄ S ₂ ), 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) -imide (C ₈ H ₁₁ F ₆ N ₃ O ₄ S ₂ ), 1-butyl- 3-methylimidazolium hexafluorophosphate (C ₈ H ₁₅ F ₆ N ₂ P), 1-butyl-4-methylpyridinium tetrafluoroborate (C ₁₀ H ₁₆ BF ₄ N), 1-hexyl- 3-methylimidazolium tetrafluoroborate (C ₁₀ H ₁₉ BF ₄ N ₂ ), 1-methyl-3-octylimidazolium hexafluorophosphate (C ₁₂ H ₂₃ F ₆ N ₂ P), 1-methyl Hard coating film comprising at least one selected from the group consisting of -3-octylimidazolium tetrafluoroborate (C ₁₂ H ₂₃ BF ₄ N ₂ ). The hard coat film of claim 2, wherein the antistatic agent comprises a siloxane resin. The hard coating according to claim 1, wherein a concentration of at least one of the fluorine atom and the silicon atom is higher than the center side of the cross section on the cross section in which the hard coating layer is cut in the direction in which the base film and the hard coating layer are laminated. film. The hard coat film of claim 2, wherein the light transmissive resin comprises a dendrimer compound. The hard coating film of claim 2, wherein the hard coating layer forming composition comprises nano silica sol. A window film comprising the hard coat film of claim 1. An image display device comprising the window film of claim 8.