JP2023528503A - Easy adhesion layer forming composition and hard coating film using the same - Google Patents

Abstract

The present invention provides an easy-adhesion layer-forming composition containing a polysiloxane compound having a hydroxyl group in a side chain, a translucent resin, a photoinitiator, and a solvent, a hard coating film formed using the same, and an image display device provided with the hard coating film. The composition for forming an easy-adhesion layer according to the present invention contains a polysiloxane compound having a hydroxyl group in the side chain and a translucent resin, thereby improving the adhesion between the cycloolefin polymer substrate and the hard coating layer, thereby improving the bending resistance of the hard coating film.

Description

TECHNICAL FIELD The present invention relates to a composition for forming an easily adhesive layer and a hard coating film using the same, and more particularly, it can improve the adhesion between a cycloolefin polymer substrate and a hard coating layer. The present invention relates to an easily adhesive layer-forming composition capable of improving the flex resistance of a hard coating film along with a hard coating film, a hard coating film formed using the same, and an image display device provided with the hard coating film.

Hard coating films are used for the purpose of surface protection in image display devices such as liquid crystal displays, electroluminescence (EL) displays, plasma displays (PD), and field emission displays (FED). .

In recent years, flexible display devices that can maintain display performance even when bent like paper by using flexible materials such as plastic instead of existing inflexible glass substrates are the next generation. It is suddenly floating on the display device. Along with this, it not only has high hardness and excellent scratch resistance, but also does not curl at the edges of the film during the manufacturing process or during use, and has appropriate flexibility so that cracks do not occur. Research has been conducted on hard coating films.

On the other hand, cycloolefin polymer (COP) is excellent in transparency, heat resistance, dimensional stability, low hygroscopicity, low birefringence, and optical isotropy, and is used as a base material for hard coating films. is expected to be used. However, unlike an acrylic film or a polyester film, a cycloolefin polymer film has a small number of polar groups on the surface of the film, and thus is inferior in adhesion between the base film and the hard coating layer.

Accordingly, Korean Patent Laid-Open No. 10-2017-0107995 discloses a hard coating film produced by interposing an easy-adhesion layer containing a mixture of polyolefin resin and styrene-acrylic resin.

However, in the hard coating film, since the easy adhesion layer contains a resin component, the degree of cross-linking is inferior, so that it is difficult to achieve sufficient adhesion between the cycloolefin polymer substrate and the hard coating layer, and the hard coating film There was a problem that it was inferior in bending resistance when applied to.

An object of the present invention is to provide a composition for forming an easy-adhesion layer capable of improving the adhesion between a cycloolefin polymer substrate and a hard coating layer.

Another object of the present invention is to provide a hard coating film having improved bending resistance by being formed using the composition for forming an easily adhesive layer.

Still another object of the present invention is to provide an image display device provided with the hard coating film.

On the other hand, the present invention provides an easily adhesive layer-forming composition containing a polysiloxane compound having a hydroxyl group in a side chain, a translucent resin, a photoinitiator, and a solvent.

In one embodiment of the present invention, the polysiloxane compound having a hydroxyl group in the side chain may be contained in an amount of 10 to 90% by weight with respect to 100% by weight of the total solid content in the composition for forming an easy-adhesion layer. .

In one embodiment of the present invention, the translucent resin may include one or more selected from the group consisting of photocurable (meth)acrylate oligomers and monomers.

The easily adhesive layer-forming composition according to one embodiment of the present invention may be used between the cycloolefin polymer substrate and the hard coating layer.

On the other hand, the present invention provides
a cycloolefin polymer substrate,
A hard coating film comprising an easy-adhesion layer formed on at least one surface of the cycloolefin polymer substrate and a hard coating layer formed on the easy-adhesion layer,
Provided is a hard coating film in which the easy-adhesion layer is formed using the easy-adhesion layer-forming composition.

The hard coating film according to one embodiment of the present invention has a total light transmittance of 90% or more, and even after bending the hard coating film repeatedly 200,000 times with a radius of curvature of 1 mm with the hard coating layer surface facing inward. It may not cause breakage of the hard coating film or peeling of the hard coating layer.

In one embodiment of the present invention, the cycloolefin polymer substrate may be hydrophilically treated.

In one embodiment of the present invention, the hard coating layer may be formed using a hard coating composition including a translucent resin, a photoinitiator and a solvent.

In one embodiment of the present invention, the translucent resin may include one or more selected from the group consisting of photocurable (meth)acrylate oligomers and monomers.

On the other hand, the present invention provides an image display device provided with the hard coating film.

On the other hand, the present invention provides a flexible display window having the hard coating film.

On the other hand, the present invention provides a polarizing plate having the hard coating film.

On the other hand, the present invention provides a touch sensor provided with the hard coating film.

The easy-adhesion layer-forming composition according to the present invention contains a polysiloxane compound having a hydroxyl group in the side chain and a translucent resin, thereby improving the adhesion between the cycloolefin polymer substrate and the hard coating layer. It is possible to improve the bending resistance of the hard coating film.

The present invention will be described in more detail below.

One embodiment of the present invention relates to an easily adhesive layer-forming composition containing a polysiloxane compound having a hydroxyl group in a side chain, a translucent resin, a photoinitiator, and a solvent.

In one embodiment of the present invention, the polysiloxane compound having a hydroxyl group in the side chain is a component that provides adhesion between the cycloolefin polymer substrate and the hard coating layer, and is a side chain having a polysiloxane skeleton. It is a compound with a hydroxyl group in the chain.

In the polysiloxane compound having a hydroxyl group in the side chain, the hydroxyl group in the molecule forms a hydrogen bond with the hydroxyl group on the surface of the hydrophilically treated cycloolefin polymer substrate, thereby improving adhesion.

The polysiloxane compound having a hydroxyl group in the side chain is a condensation polymer of hydrolyzable trialkoxysilane or tetraalkoxysilane, and is not particularly limited as long as it has a hydroxyl group in the side chain. A polycondensation product of tetraalkoxysilane is preferred.

Examples of the hydrolyzable trialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane monoalkyltrialkoxysilanes such as silane, octadecyltrimethoxysilane and octadecyltriethoxysilane; monoaryltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; monovinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; Silanes; monoaminoalkyltrialkoxysilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane; monoepoxyalkylsilanes such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane trialkoxysilanes; mono(meth)acryloxyalkyltrialkoxysilanes such as γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane;

Examples of the hydrolyzable tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

The polysiloxane compound having a hydroxyl group in the side chain may be used after obtaining a commercially available product, or may be used after being produced according to a known polycondensation method.

Specifically, the polysiloxane compound having a hydroxyl group in the side chain can be prepared by adding water and an acid catalyst (hydrochloric acid, nitric acid, etc.) to a hydrolyzable trialkoxysilane or tetraalkoxysilane in an alcohol solvent (e.g., methanol, ethanol, etc.). may be obtained by condensation polymerization reaction in the presence of

Examples of commercially available polysiloxane compounds having hydroxyl groups in the side chains include Colcoat N-103X and Colcoat PX manufactured by Colcoat Co., Ltd.

The polysiloxane compound having a hydroxyl group in the side chain is contained in an amount of 10 to 90% by weight, preferably 15 to 80% by weight, based on 100% by weight of the total solid content in the composition for forming an easy adhesion layer. good. If the content of the polysiloxane compound having a hydroxyl group in the side chain is less than 10% by weight, a sufficient bond cannot be formed with the cycloolefin base material, resulting in poor adhesion. %, a sufficient bond with the hard coating layer cannot be formed, resulting in poor adhesion.

In one embodiment of the present invention, the translucent resin is a photocurable resin, and the photocurable resin may contain a photocurable (meth)acrylate oligomer and/or monomer.

As the photocurable (meth)acrylate oligomer, epoxy (meth)acrylate, urethane (meth)acrylate, etc. are usually used, and urethane (meth)acrylate is preferable. A urethane (meth)acrylate may be produced by reacting a (meth)acrylate having a hydroxyl group in the molecule with a compound having an isocyanate group in the presence of a catalyst. Specific examples of (meth)acrylates having a hydroxy group in the molecule include 2-hydroxyethyl (meth)acrylate, 2-hydroxyisopropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone ring-opening hydroxy acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like. Specific examples of the isocyanate group-containing compound include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, and 1,12-diisocyanate. dodecane, 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- Trifunctional isocyanate derived from 2,4-diisocyanate, 4,4'-methylenebis(2,6-dimethylphenyl isocyanate), 4,4'-oxybis(phenylisocyanate), hexamethylene diisocyanate, trimethanepropanol adduct toluene diisocyanate and so on.

The monomer may be used without particular limitation as long as it is commonly used, and as a photocurable functional group, a (meth)acryloyl group, a vinyl group, a styryl group, an unsaturated group such as an allyl group is included in the molecule. Among them, monomers having a (meth)acryloyl group are preferred.

Specific examples of the (meth)acryloyl group-containing monomer include neopentyl glycol acrylate, 1,6-hexanediol di(meth)acrylate, propylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. , dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaglycerol tri(meth) acrylates, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa( meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol hexa(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate , hydroxybutyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, and isoborneol (meth)acrylate It may be one or more selected from the group.

The photocurable (meth)acrylate oligomers and monomers that are translucent resins exemplified above may be used alone or in combination of two or more.

The translucent resin is not particularly limited, but may be contained in an amount of 1 to 80% by weight with respect to 100% by weight of the total solid content in the composition for forming an easy adhesion layer. If the content of the translucent resin is less than 1% by weight, it may not form a sufficient bond with the hard coating layer, resulting in poor adhesion. In addition, the content of the polysiloxane compound having a hydroxyl group in the side chain is insufficient to form a sufficient bond with the cycloolefin polymer substrate, resulting in poor adhesion.

In one embodiment of the present invention, the photoinitiator is not particularly limited as long as it can form radicals by light irradiation and is used in the technical field. For example, hydroxyketones, aminoketones, hydrogen abstraction photoinitiators, and the like may be used.

Specifically, the photoinitiators include 2-methyl-1-[4-(methylthio)phenyl]2-morpholinepropanone-1, diphenylketone, benzyldimethylketal, 2-hydroxy-2-methyl-1- Phenyl-1-one, 2,2-dimethoxy-2-phenyl-acetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-chloroacetophenone, 4,4-dimethoxyacetophenone, 4,4-diamino Benzophenone, 1-hydroxycyclohexylphenyl ketone, benzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and the like. The optical disclosure agents exemplified above may be used alone or in combination of two or more.

The content of the photoinitiator is not particularly limited. may be included. If the content of the photoinitiator is less than 0.1% by weight, the curing speed of the composition is slow and uncured, resulting in poor mechanical properties of the coating layer. Cracks may occur in the coating film.

The solvent may be used without particular limitation as long as it is used in the technical field. Specifically, alcohol-based (methanol, ethanol, isopropanol, butanol, methyl cellosolve, ethyl cellosolve, etc.), ketone-based (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone, etc.), acetate-based ( Ethyl acetate, propyl acetate, n-butyl acetate, tert-butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc.), hexane (hexane, heptane, octane, etc.), benzene (benzene, toluene, xylene, etc.), ether (diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, etc.) ) may be used. The solvents exemplified above may be used alone or in combination of two or more.

The solvent may be contained in an amount of 10 to 95% by weight with respect to 100% by weight of the composition for forming an easy adhesion layer. If the content of the solvent is less than 10% by weight, the viscosity is high, the workability is poor, and the swelling of the base film cannot be sufficiently progressed. However, there is a disadvantage that it takes a lot of time and is inferior in economic efficiency.

The easily adhesive layer-forming composition according to one embodiment of the present invention may further contain a leveling agent in order to impart smoothness and coatability to the coating film during coating.

As the leveling agent, commercially available silicone-based leveling agents, fluorine-based leveling agents, acrylic polymer-based leveling agents, and the like may be used. 310, BYK-313, BYK-323, BYK-331, BYK-333, BYK-337, BYK-371, BYK-373, BYK-375, BYK-377, BYK-378, BYK-3440, BYK-3570, BYK-UV3500, BYK-UV3530, BYK-UV3570, Degussa TEGO Glide 410, TEGO Glide 411, TEGO Glide 415, TEGO Glide 420, TEGO Glide 432, TEGO Glide 435, TEGO Glide e440, TEGO Glide 450, TEGO Glide 455, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, FC-4430, FC-4432 manufactured by 3M, etc. may be used. The leveling agent may be contained in the range of 0.1 to 3% by weight with respect to 100% by weight of the composition for forming an easy adhesion layer.

The easily adhesive layer-forming composition according to one embodiment of the present invention may be used between the cycloolefin polymer substrate and the hard coating layer. The composition for forming an easy-adhesion layer according to one embodiment of the present invention is a cycloolefin polymer substrate surface hydrophilically treated by containing a polysiloxane compound having a hydroxyl group in a side chain and a translucent resin. Adhesion can be ensured by hydrogen bonding between the hydroxyl groups of siloxane, and the unreacted translucent resin of the easy-adhesion layer participates in the UV curing reaction during the formation of the hard coating layer to form a bond with the hard coating layer. Adhesion can be secured. Along with this, it is possible to provide a hard coating film having excellent flex resistance by applying the easily adhesive layer-forming composition according to one embodiment of the present invention between the cycloolefin polymer substrate and the hard coating layer. can.

Accordingly, one embodiment of the present invention relates to a hard coating film formed using the easily adhesive layer-forming composition described above.

A hard coating film according to one embodiment of the present invention is
a cycloolefin polymer substrate,
A hard coating film comprising an easy-adhesion layer formed on at least one surface of the cycloolefin polymer substrate and a hard coating layer formed on the easy-adhesion layer,
The easy-adhesion layer is formed using the composition for forming an easy-adhesion layer described above.

A hard coating film according to an embodiment of the present invention has excellent transmittance characteristics and bending resistance. Specifically, the hard coating film according to one embodiment of the present invention has a total light transmittance of 90% or more, and the hard coating film is repeatedly formed with a curvature radius of 1 mm for 200,000 times with the hard coating layer surface facing inward. It may be one that does not cause breakage of the hard coating film or peeling of the hard coating layer even after being folded.

The total light transmittance (Tt, %) is calculated by measuring the incident light intensity (T ₀ ) to the hard coating film and the total transmitted light intensity (T ₁ ) transmitted through the hard coating film and using the following formula 1. .
[Mathematical formula 1]
Total light transmittance (Tt, %) = ( _T1 / _T0 ) x 100
The total light transmittance may be measured, for example, using a haze meter (manufactured by Murakami Color Laboratory) according to the method described in Experimental Examples below.

In one embodiment of the present invention, the cycloolefin polymer substrate serves as a base substrate of the hard coating film, and includes a cycloolefin polymer (COP) and has excellent transparency.

Said COP is a general term referring to resins produced by the polymerization of cyclic olefins as monomers, specific examples of which are ring-opening (co)polymers of cyclic olefins; addition polymers of cyclic olefins; copolymers (usually random copolymers) of α-olefins such as propylene; graft modifications, each modified with an unsaturated carboxylic acid or derivative thereof; and hydrides thereof. Specific examples of cyclic olefins include norbornene-based monomers.

Specifically, the COP is a polymer obtained by selectively hydrogenating one or more of the monomers represented by the following chemical formulas 1 to 3 by ring-opening metathesis polymerization. you can

The process of preparing COP from ring-opening metathesis polymerization reaction of one or more monomers represented by Formulas 1 to 3 can be easily carried out according to a conventional method.

For example, using palladium (II) acetylacetonate [Pd(acac) ₂ ] and tricyclohexylphosphine as a polymerization catalyst, and using dimethylanilinium tetrakiss(pentafluorophenyl)borate [dimethylanilinium tetrakiss(pentafluorophenyl)borate] as a cocatalyst. A polymerization step may be performed.

In one embodiment of the present invention, the COP may be produced by mixing ring-opening polymerizable cyclic olefins other than norbornene-based monomers without impairing the object of the present invention. Specific examples of such cyclic olefins include compounds with one reactive double bond, such as cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene, and the like.

The COPs may be further hydrogenated after the ring-opening metathesis polymerization reaction. Said hydrogenation may be carried out by reaction with hydrogen gas in the presence of a hydrogenation catalyst according to methods known in the art. The hydrogenation rate is preferably 90% or higher, more preferably 95% or higher, and even more preferably 99% or higher. A hydrogenation rate within the above range may provide excellent heat degradation resistance, light degradation resistance, and the like.

Various products are commercially available for the COPs. Specific examples of the COP include trade names "ZF-16", "ZEONEX" and "ZEONOR" manufactured by ZEON CORPORATION, trade names "Arton" manufactured by JSR Corporation, and trade names manufactured by TICONA Corporation. "TOPAS" and the trade name "APEL" manufactured by Mitsui Chemicals, Inc.

Any appropriate molding method may be employed as a method of forming a base film from the COP. Specific examples include compression molding, transfer molding, injection molding, extrusion, blow molding, powder molding, FRP molding, and casting. Extrusion and casting methods are preferred because the resulting films can have improved smoothness and good optical uniformity. Molding conditions may be appropriately set according to the composition or type of resin used, desired properties of the optical film, and the like.

The thickness of the cycloolefin polymer substrate is not particularly limited, but may be 10 to 1000 μm, specifically 20 to 150 μm. If the thickness of the transparent base material is less than 10 μm, the strength of the film is reduced and workability is deteriorated. occurs.

In one embodiment of the present invention, the cycloolefin polymer substrate may be hydrophilically treated.

The hydrophilic treatment may be performed by a surface treatment method such as corona or plasma treatment.

In one embodiment of the present invention, the easy-adhesion layer-forming composition is applied to at least one surface of the cycloolefin polymer substrate and cured to form an easy-adhesion layer.

The composition for forming an easy-adhesion layer according to one embodiment of the present invention is coated on a substrate by appropriately using a known method such as a die coater, air knife, reverse roll, spray, blade, casting, gravure, microgravure, and spin coating. may be coated (Coating Process).

After applying the easy-adhesion layer-forming composition to the base material, the solvent is evaporated to dry the composition, and then the composition is cured by irradiation with UV light. Specifically, the dose of the UV light may be about 10-500 mJ/cm ² , more specifically 50-400 mJ/cm ² .

At this time, the thickness of the easy adhesion layer to be formed may specifically be 0.1 to 5 μm, more specifically 0.3 to 3 μm. When the thickness of the easily bonding layer is within the above range, excellent adhesion and bending resistance can be obtained.

In one embodiment of the present invention, the hard coating layer may be formed using a hard coating composition including a translucent resin, a photoinitiator and a solvent.

The translucent resin is a photocurable resin, and the photocurable resin may contain a photocurable (meth)acrylate oligomer and/or monomer. The translucent resin preferably contains one or more selected from the group consisting of a photocurable (meth)acrylate oligomer and a (meth)acryloyl group-containing monomer from the viewpoint of adhesion with the easy adhesion layer.

Specific types of the photocurable (meth)acrylate oligomer and the (meth)acryloyl group-containing monomer may be the same as those used in the composition for forming an easy adhesion layer described above.

As the monomer having a (meth)acryloyl group, a dendrimer compound having a (meth)acrylate terminal group may be used.

The dendrimer compound having the (meth)acrylate terminal group may be used for UV curing by substituting the terminal of the branch structure with (meth)acrylate group, the center of which is completely aliphatic and tertiary ester. It has structural features consisting of bonds. Therefore, the dendrimer compound having the (meth)acrylate terminal group has a structural feature of having a larger number of functional groups with respect to the molecular weight as the generation increases compared to general polyfunctional acrylate monomers. With the functional groups distributed at the ends, the core portion can contribute to the improvement of bending properties during curing. As a result, a hard coating film with improved curl and flexibility can be obtained.

The dendrimer compounds with (meth)acrylate end groups may be obtained commercially or prepared according to methods known in the art. For example, after forming a first generation dendrimer structure by condensation reaction with dimethylolpropionic acid using a specific polyhydric alcohol as a central skeleton, the dimethylolpropionic acid is repeatedly condensed as a branched structure to form a second or higher generation After the structure is grown, the end groups are subjected to a condensation reaction with acrylic acid to obtain a highly branched dendrimer compound whose ends are substituted with a large number of (meth)acrylate groups.

The translucent resin is not particularly limited, but may be included in an amount of 1-80% by weight based on 100% by weight of the hard coating composition. If it is less than 1% by weight, it will be difficult to achieve a sufficient improvement in hardness, and if it exceeds 80% by weight, there will be a problem of severe curling.

As the photoinitiator, the same one as used in the composition for forming an easy adhesion layer may be used.

The photoinitiator may be included in an amount of 0.1 to 10 wt%, preferably 1 to 5 wt%, based on 100 wt% of the hard coating composition. If the content of the photoinitiator is less than 0.1% by weight, the curing speed of the composition is slow and uncured, resulting in poor mechanical properties. Cracks may occur.

As the solvent, the same solvent as that used in the composition for forming an easy-adhesion layer may be used.

Moreover, the solvent may include a fluorine-based solvent. The fluorine-based solvent not only increases the solubility of the fluorine-based UV-curable functional group-containing compound described later, and thereby maintains excellent wettability and film coating state of the hard coating film produced therefrom, It may serve to form a high-concentration fluorine component layer on the surface of the hard coat layer manufactured by orienting the fluorine-based UV curable functional group on the surface of the hard coat layer during the coating and drying process.

As the fluorine-based solvent, perfluorohexylethyl alcohol, perfluoroether, perfluorohexane, etc. may be used, and commercially available products are HFE-7100, HFE-7300, HFE-7500 and FC-3283 manufactured by 3M. , FC-40, FC-770, and C6FOH-BF manufactured by Nikka Corporation, but are not limited thereto.

The solvent may be included in an amount of 5-90 wt%, preferably 7-85 wt%, based on 100 wt% of the hard coating composition. If it is less than 5% by weight, the viscosity is high and the workability is poor.

In one embodiment of the present invention, the hard coating composition may further include a fluorine-based UV-curable functional group-containing compound.

The fluorine-based UV-curable functional group-containing compound is not particularly limited as long as it is a component that imparts antifouling properties and abrasion resistance, contains fluorine, and has a UV-curable functional group. .

The fluorine-based UV curable functional group-containing compound includes a (meth)acrylate containing a perfluoroalkyl group, a (meth)acrylate containing a perfluoropolyether group, and a perfluorocycloaliphatic group. One or more selected from the group consisting of (meth)acrylates and (meth)acrylates containing a perfluoro aromatic group may be used. It is preferable because it has the advantage of being excellent in durability to form a bond and maintain the antifouling performance for a long period of time even after repeated use.

The fluorine-based UV-curable functional group-containing compound may be contained in an amount of 0.01 to 30% by weight, preferably 0.01 to 30% by weight, based on 100% by weight of the total solid content in the hard coating composition. It may be included in an amount of 20% by weight, more preferably 0.01 to 10% by weight. When the fluorine-based UV-curable functional group-containing compound is contained within the above range, it is possible to impart excellent abrasion resistance and antifouling effect, which is preferable. If the content of the UV-curable functional group-containing compound is less than the above range, it may be difficult to achieve the desired abrasion resistance or antifouling property. It may decrease slightly.

In addition to the components described above, the hard coating composition contains components commonly used in the art, such as leveling agents, UV stabilizers, heat stabilizers, antioxidants, surfactants, lubricants, and antifouling agents. may further be included.

A hard coating film according to an embodiment of the present invention is formed by applying the hard coating composition onto an easy-adhesion layer formed on at least one surface of a cycloolefin polymer substrate and curing the hard coating composition to form a hard coating layer. can be manufactured by

The hard coating composition is coated on the easy-adhesion layer (Coating Process) by appropriately using a known method such as die coater, air knife, reverse roll, spray, blade, casting, gravure, microgravure, spin coating, and the like. good.

After the hard coating composition is applied to the easy adhesion layer, it is dried by evaporating volatiles at a temperature of 30 to 150° C. for 10 seconds to 1 hour, more specifically, 30 seconds to 30 minutes, It is cured by irradiation with UV light. Specifically, the dose of the UV light may be about 0.01-10 J/cm ² , more specifically 0.1-2 J/cm ² .

At this time, the thickness of the formed hard coating layer may specifically be 2 to 30 μm, more specifically 3 to 20 μm. When the thickness of the hard coating layer is within the range, excellent hardness and bending resistance can be obtained.

One embodiment of the present invention relates to an image display device provided with the hard coating film described above. As an example, the hard coating film of the present invention may be used as a window for image display devices, particularly flexible or foldable display devices. Moreover, the hard coating film of the present invention may be used by laminating it to a polarizing plate, a touch sensor, or the like.

The hard coating film according to one embodiment of the present invention can be applied to reflective, transmissive, transflective LCDs or LCDs of various drive systems such as TN type, STN type, OCB type, HAN type, VA type, and IPS type. may be used. Further, the hard coating film according to one embodiment of the present invention may also be used for various image display devices such as plasma displays, field emission displays, organic EL displays, inorganic EL displays, and electronic paper.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples, and Experimental Examples. It should be obvious to those skilled in the art that these Examples, Comparative Examples, and Experimental Examples are merely for the purpose of explaining the present invention, and that the scope of the present invention is not limited to these.

Production Example 1: Production of a composition for forming an easy-adhesion layer 60 parts by weight of a polysiloxane compound having a hydroxyl group in a side chain (Colcoat N-103X, solid content 2% by weight), 6 parts by weight of a trifunctional acrylate Monomer (Miramer M340, manufactured by Miwon), 33.4 parts by weight of methyl ethyl ketone, 0.3 parts by weight of 1-hydroxycyclohexylphenyl ketone, and 0.3 parts by weight of a leveling agent (BYK UV-3530, manufactured by BYK) were blended with a stirrer and filtered using a filter made of PP material to produce a composition for forming an easy-adhesion layer.

Production Example 2: Production of a composition for forming an easy adhesion layer 90 parts by weight of a polysiloxane compound having a hydroxyl group in a side chain (Colcoat N-103X, solid content 2% by weight), 6 parts by weight of a trifunctional acrylate Monomer (Miramer M340, manufactured by Miwon), 3.4 parts by weight of methyl ethyl ketone, 0.3 parts by weight of 1-hydroxycyclohexylphenyl ketone, and 0.3 parts by weight of a leveling agent (BYK UV-3530, manufactured by BYK) were blended with a stirrer and filtered using a filter made of PP material to produce a composition for forming an easy-adhesion layer.

Production Example 3: Production of a composition for forming an easy adhesion layer 60 parts by weight of a polysiloxane compound having a hydroxyl group in the side chain (Colcoat PX, solid content 2% by weight), 6 parts by weight of a trifunctional acrylate monomer ( Miwon Co., Miramer M340), 33.4 parts by weight of methyl ethyl ketone, 0.3 parts by weight of 1-hydroxycyclohexylphenyl ketone, and 0.3 parts by weight of a leveling agent (BYK, BYK UV-3530) are stirred. The mixture was blended using a machine and filtered using a filter made of PP material to produce a composition for forming an easy-adhesion layer.

Production Example 4: Production of a composition for forming an easy adhesion layer 90 parts by weight of a polysiloxane compound having a hydroxyl group in a side chain (Colcoat PX, solid content 2% by weight), 6 parts by weight of a trifunctional acrylate monomer ( Miwon Co., Ltd., Miramer M340), 3.4 parts by weight of methyl ethyl ketone, 0.3 parts by weight of 1-hydroxycyclohexylphenyl ketone, and 0.3 parts by weight of a leveling agent (BYK Co., BYK UV-3530) are stirred. The mixture was blended using a machine and filtered using a filter made of PP material to produce a composition for forming an easy-adhesion layer.

Production Example 5: Production of a composition for forming an easy-adhesion layer 100 parts by weight of a polysiloxane compound having a hydroxyl group in a side chain (Colcoat N-103X, solid content 2% by weight), using a PP material filter. It filtered and manufactured the composition for easily bonding layer forming.

Production Example 6: Production of a composition for forming an easy-adhesion layer 100 parts by weight of a polysiloxane compound having a hydroxyl group in its side chain (Colcoat PX, solid content 2% by weight) was filtered using a PP material filter. Thus, a composition for forming an easy-adhesion layer was produced.

Production Example 7: Production of a composition for forming an easy-adhesion layer 10 parts by weight of a polysiloxane compound having a hydroxyl group in a side chain (Colcoat N-103X, solid content 2% by weight), 6 parts by weight of a trifunctional acrylate Monomer (Miramer M340, manufactured by Miwon), 83.4 parts by weight of methyl ethyl ketone, 0.3 parts by weight of 1-hydroxycyclohexylphenyl ketone, and 0.3 parts by weight of a leveling agent (BYK UV-3530, manufactured by BYK) were blended with a stirrer and filtered using a filter made of PP material to produce a composition for forming an easy-adhesion layer.

Production Example 8: Production of a composition for forming an easy adhesion layer 10 parts by weight of a polysiloxane compound having a hydroxyl group in a side chain (Colcoat PX, solid content 2% by weight), 6 parts by weight of a trifunctional acrylate monomer ( Miwon, Miramer M340), 83.4 parts by weight of methyl ethyl ketone, 0.3 parts by weight of 1-hydroxycyclohexylphenyl ketone, and 0.3 parts by weight of a leveling agent (BYK, BYK UV-3530) are stirred. The mixture was blended using a machine and filtered using a filter made of PP material to produce a composition for forming an easy-adhesion layer.

Production Example 9: Production of hard coating composition 23 parts by weight of hexafunctional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., U-6LPA), 23 parts by weight of tetrafunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., VISCOAT #1000 ), 5 parts by weight of a fluorine-based solvent (C6FOH-BF manufactured by Nikka Co., Ltd.), 45 parts by weight of methyl ethyl ketone, 3.5 parts by weight of 1-hydroxycyclohexylphenyl ketone, and 0.5 parts by weight of a fluorine-based UV curable type A functional group-containing compound (KY-1203, manufactured by Shin-Etsu Chemical Co., Ltd.) was blended with a stirrer and filtered using a PP material filter to produce a hard coating composition.

Example 1: Production of easy-adhesive film A cycloolefin film (COP, ZF-14, 23 µm, manufactured by Nippon Zeon Co., Ltd.) was subjected to corona treatment to adjust the water contact angle of the surface to a level of 65 degrees. The composition for forming an easy-adhesion layer of Example 1 was coated so that the thickness after curing was 0.5 μm, and after drying the solvent, it was easily irradiated with an integrated UV light amount of 300 mJ/cm ² in a nitrogen atmosphere. An adhesive film was produced.

Example 2: Production of easy-adhesion film Same as Example 1 except that the composition for forming an easy-adhesion layer of Production Example 2 was used instead of the composition for formation of an easy-adhesion layer of Production Example 1. An easily adhesive film was produced by a method.

Example 3: Production of easy-adhesion film Same as Example 1 except that the composition for forming an easy-adhesion layer of Production Example 3 was used instead of the composition for formation of an easy-adhesion layer of Production Example 1. An easily adhesive film was produced by a method.

Example 4 Production of Easily Adhesive Film Same as Example 1 except that the easily adhesive layer-forming composition of Production Example 4 was used in place of the easily adhesive layer-forming composition of Production Example 1. An easily adhesive film was produced by a method.

Example 5: Production of hard coating film The hard coating composition of Production Example 9 was coated on the easily adhesive layer of the easily adhesive film produced in Example 1 so that the thickness after curing was 5 μm, After drying the solvent, a hard coating film was manufactured by irradiating UV light with an integrated amount of 600 mJ/cm ² in a nitrogen atmosphere.

Example 6 Preparation of Hard Coating Film The same method as in Example 5 was performed except that the easy-adhesion film prepared in Example 2 was used instead of the easy-adhesion film prepared in Example 1. A hard coating film was produced.

Example 7 Preparation of Hard Coating Film The same method as in Example 5 was performed except that the easy-adhesive film prepared in Example 3 was used instead of the easy-adhesive film prepared in Example 1. A hard coating film was produced.

Example 8 Preparation of Hard Coating Film The method of Example 5 was repeated except that the easy-adhesion film prepared in Example 4 was used instead of the easy-adhesion film prepared in Example 1. A hard coating film was produced.

Comparative Example 1: Production of easy-adhesion film Same as Example 1 except that the easy-adhesion layer-forming composition of Production Example 5 was used instead of the easy-adhesion layer-forming composition of Production Example 1. An easily adhesive film was produced by a method.

Comparative Example 2: Production of easy-adhesion film Same as Example 1 except that the composition for forming an easy-adhesion layer of Production Example 6 was used instead of the composition for formation of an easy-adhesion layer of Production Example 1. An easily adhesive film was produced by a method.

Comparative Example 3: Production of easy-adhesion film Same as Example 1 except that the composition for forming an easy-adhesion layer of Production Example 7 was used instead of the composition for formation of an easy-adhesion layer of Production Example 1. An easily adhesive film was produced by a method.

Comparative Example 4: Production of easy-adhesion film Same as Example 1 except that the composition for forming an easy-adhesion layer of Production Example 8 was used instead of the composition for formation of an easy-adhesion layer of Production Example 1. An easily adhesive film was produced by a method.

Comparative Example 5: Manufacture of Hard Coating Film The method of Example 5 was repeated, except that the easy-adhesive film produced in Comparative Example 1 was used instead of the easy-adhesive film produced in Example 1. A hard coating film was produced.

Comparative Example 6 Production of Hard Coating Film The method of Example 5 was repeated except that the easy-adhesive film produced in Comparative Example 2 was used instead of the easy-adhesive film produced in Example 1. A hard coating film was produced.

Comparative Example 7 Manufacture of Hard Coating Film The method of Example 5 was repeated except that the easy-adhesive film produced in Comparative Example 3 was used instead of the easy-adhesive film produced in Example 1. A hard coating film was produced.

Comparative Example 8 Preparation of Hard Coating Film The method of Example 5 was repeated except that the easy-adhesive film prepared in Comparative Example 4 was used instead of the easy-adhesive film prepared in Example 1. A hard coating film was produced.

Experimental example 1:
The physical properties of the films prepared in Examples and Comparative Examples were measured by methods described below, and the results are shown in Table 1 below.

(1) Adhesion After bonding the substrate film to the glass using a transparent adhesive so that the coated surface faces the front, cut the coated surface into a grid pattern of 100 horizontal and vertical pieces at 1 mm intervals with a cutter. After putting it in, Nichiban tape was pasted and an adhesion test was performed three times.

The evaluation results were expressed as "the number of squares that are OK after the adhesion test/100".

(2) Total light transmittance (Tt) and haze The total light transmittance (%) and haze (%) of the coating film were measured using a haze meter HM-150 manufactured by Murakami Color Laboratory.

(3) Water contact angle The contact angle of water was measured using a contact angle measuring device DSA100 manufactured by KRUSS. The droplet volume was 3 μl at room temperature.

(4) Abrasion Resistance Measured with an abrasion resistance measurement device manufactured by DAESUNG PRECISION. The contact angle was measured after the coating surface was rubbed 3000 times with an eraser for wear resistance test and a weight of 500 g. At this time, as an evaluation criterion, the case where the contact angle of water was 100° or more was selected as the wear resistance acceptance criterion.

<Evaluation Criteria>
○: Contact angle of 100° or more ×: Contact angle of less than 100° (5) Chemical resistance Measured with wear resistance measuring equipment manufactured by DAESUNG PRECISION. After dropping 99.9% ethanol on the coating surface, the area where the ethanol was dropped was rubbed 3000 times with an eraser for abrasion resistance test and a weight of 500 g, and then the contact angle was measured. The evaluation was performed while continuously dripping ethanol so that the ethanol would not volatilize during the evaluation. After completing the evaluation, the ethanol was removed and the water contact angle was measured. At this time, as an evaluation criterion, the case where the contact angle of water was 95° or more was selected as the chemical resistance acceptance criterion.

<Evaluation Criteria>
○: contact angle is 95° or more ×: contact angle is less than 95° (6) Scratch resistance #0000) was rubbed back and forth 10 times with a load of 500 g/cm ² , and the scratch was observed by transmitting and reflecting light from a three-wavelength lamp to the measuring portion. Scratch resistance was evaluated according to the following evaluation criteria.

<Evaluation Criteria>
○: No scratches or 10 or less scratches are visible ×: More than 10 scratches are visible (7) Flex resistance 200,000 times with a curvature radius of 1 mm with the hard coating layer surface facing inward A test of repeatedly bending the film was performed to observe whether the film was broken and whether the hard coating layer was peeled off. Flex resistance was evaluated according to the following evaluation criteria.

<Evaluation Criteria>
○: No breakage of the film or peeling of the hard coating layer ×: Breakage of the film or peeling of the hard coating layer

As shown in Table 1 above, examples produced using the easy-adhesion layer-forming compositions of Production Examples 1 to 4 containing a polysiloxane compound having a hydroxyl group in the side chain and a translucent resin according to the present invention It can be seen that the easily adhesive films of Nos. 1 to 4 are excellent in adhesion to the coating surface. In addition, the hard coating films of Examples 5 to 8, in which a hard coating layer was formed on the easily adhesive films of Examples 1 to 4, had not only adhesion but also water contact angle, abrasion resistance, chemical resistance, and scratch resistance. It was confirmed that it was excellent in flexibility and bending resistance.

On the other hand, the easy-adhesive films of Comparative Examples 1 and 2, which are produced using the easy-adhesive layer-forming compositions of Production Examples 5 and 6, which contain a polysiloxane compound having a hydroxyl group in a side chain but do not contain a translucent resin, Although the adhesion of the coating surface is good, the hard coating films of Comparative Examples 5 and 6, in which a hard coating layer is formed on the easy-adhesion film of Comparative Examples 1 and 2, have not only adhesion of the coating surface but also resistance. It could be confirmed that the bendability was also inferior. Furthermore, the easy-adhesion films of Comparative Examples 3-4 produced using the easy-adhesion layer-forming compositions of Production Examples 7-8, which have a low content of polysiloxane compounds having hydroxyl groups in their side chains, have excellent adhesion to the coating surface. is poor, and the hard coating films of Comparative Examples 7 and 8, in which a hard coating layer is formed on the easily adhesive films of Comparative Examples 3 and 4, are inferior not only in the adhesion of the coating surface but also in flex resistance. I was able to confirm.

Although specific portions of the present invention have been described in detail above, those of ordinary skill in the art to which the present invention pertains will appreciate that such specific descriptions are merely preferred examples of implementation. It is clear that they are not intended to limit the scope of the invention. A person having ordinary knowledge in the technical field to which the present invention belongs will be able to make various applications and modifications within the scope of the present invention based on the above contents.

Accordingly, the substantial scope of the invention will be defined by the claims appended hereto and their equivalents.

Claims (13)

A composition for forming an easy-adhesion layer, comprising a polysiloxane compound having a hydroxyl group in a side chain, a translucent resin, a photoinitiator, and a solvent. The easy-adhesion layer-forming composition according to claim 1, wherein the polysiloxane compound having a hydroxyl group in the side chain is contained in an amount of 10 to 90% by weight with respect to 100% by weight of the total solid content in the easy-adhesion layer-forming composition. composition. The composition for forming an easy adhesion layer according to claim 1, wherein the translucent resin contains at least one selected from the group consisting of photocurable (meth)acrylate oligomers and monomers. The composition for forming an easy-adhesion layer according to claim 1, which is used between the cycloolefin polymer substrate and the hard coating layer. a cycloolefin polymer substrate,
A hard coating film comprising an easy-adhesion layer formed on at least one surface of the cycloolefin polymer substrate and a hard coating layer formed on the easy-adhesion layer,
A hard coating film, wherein the easy-adhesion layer is formed using the easy-adhesion layer-forming composition according to any one of claims 1 to 4. Total light transmittance is 90% or more,
6. The hard coating film according to claim 5, wherein even after the hard coating film is repeatedly bent 200,000 times with a radius of curvature of 1 mm so that the hard coating layer surface faces inward, neither breakage of the hard coating film nor peeling of the hard coating layer occurs. 6. The hard coating film according to claim 5, wherein said cycloolefin polymer substrate is hydrophilically treated. 6. The hard coating film of claim 5, wherein the hard coating layer is formed using a hard coating composition containing a translucent resin, a photoinitiator and a solvent. The hard coating film of claim 8, wherein the translucent resin comprises at least one selected from the group consisting of photocurable (meth)acrylate oligomers and monomers. An image display device provided with the hard coating film according to claim 5 . A window of a flexible display device comprising the hard coating film of claim 5. A polarizing plate provided with the hard coating film according to claim 5 . A touch sensor provided with the hard coating film according to claim 5 .