KR20200023192A - Antireflaction hard coating film and method of preparing the same - Google Patents

Abstract

According to an embodiment of the present invention, provided is a hard coating film which has excellent hardness and anti-reflection performance and of which curling is suppressed, as a low-refractive-index layer, a high-refractive-index layer, and a hard coating layer having a water contact angle of 90 degrees or less are laminated on a base material.

Description

Anti-reflection hard coating film and manufacturing method thereof {ANTIREFLACTION HARD COATING FILM AND METHOD OF PREPARING THE SAME}

The present invention relates to an antireflective hard coating film and a method of manufacturing the same.

Recently, a thin display device using a flat panel display device such as a liquid crystal display or an organic light emitting diode display has attracted much attention. In particular, these thin display devices are implemented in the form of a touch screen panel, and are characterized by portability not only to smart phones and tablet PCs, but also to various wearable devices. It is widely used in various smart devices.

Such portable touch screen panel-based display devices include a display protection window cover on the display panel to protect the display panel from scratches or external impacts, and in most cases, tempered glass for display is used as the window cover. Tempered glass for display is thinner than the general glass, but with a high strength and is characterized by being made resistant to scratches.

However, tempered glass has a disadvantage of not being suitable for light weight of a mobile device due to its heavy weight, and it is difficult to realize an unbreakable property because it is vulnerable to external shock, and is not bent over a certain level. It is not suitable as a flexible display material with a foldable function.

Recently, various studies have been conducted on an optical plastic cover having strength and scratch resistance corresponding to tempered glass while securing flexibility and impact resistance. In general, optically transparent plastic cover materials that are more flexible than tempered glass include polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyacrylate (PAR), and polycarbonate (PC). , Polyimide (PI), polyaramid (PA), polyamideimide (PAI) and the like.

However, these polymer plastic substrates exhibit not only poor physical properties in terms of hardness and scratch resistance, but also insufficient impact resistance compared to tempered glass used as a window cover for display protection. Therefore, various attempts have been made to compensate for the physical properties required by coating the composite resin composition on these plastic substrates. For example, there is a plastic substrate disclosed in Korean Patent Publication No. 10-2013-0074167.

Typical hard coatings use a composition comprising a resin containing a photocurable functional group such as (meth) acrylate or epoxy and a curing agent or curing catalyst and other additives, but corresponding to tempered glass. Not only is it hard to implement high hardness, but also a large amount of curl occurs due to shrinkage during curing, and there is a disadvantage that it is not suitable as a protective window substrate for application to a flexible display due to insufficient flexibility.

Korean Patent Publication No. 10-2013-0074167

One object of the present invention is to provide an antireflective hard coating film having improved mechanical properties, hardness, scratch resistance, curl suppression characteristics, and antireflection performance.

One object of the present invention is to provide a method for producing an antireflective hard coating film having improved mechanical properties, hardness, scratch resistance, curl suppression characteristics and antireflection performance.

Anti-reflective hard coating film according to an exemplary embodiment of the present invention, the substrate; A hard coating layer disposed on the substrate and having a water contact angle of 90 ° or less; A high refractive index layer disposed on the hard coating layer; And a low refractive index layer disposed on the high refractive index layer.

In example embodiments, the hard coating layer may include an epoxy siloxane resin, a thermal initiator including a compound represented by Formula 2, and a photoinitiator.

[Formula 2]

In Formula 2, R ³ is hydrogen, an alkoxycarbonyl group having 1 to 4 carbon atoms, an alkylcarbonyl group having 1 to 4 carbon atoms, or an arylcarbonyl group having 6 to 14 carbon atoms, and R ⁴ is each independently hydrogen, halogen or 1 to 4 carbon atoms. An alkyl group, n is 1 to 4, R ⁵ is an aralkyl group having 7 to 15 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and R ⁶ is an alkyl group having 1 to 4 carbon atoms , X is SbF ₆ , PF ₆ , AsF ₆ , BF ₄ , CF ₃ SO ₃ , N (CF ₃ SO ₂ ) ₂ or N (C ₆ F ₅ ) ₄ .

In exemplary embodiments, the hard coating layer may be a cured layer of a composition for forming a hard coating layer including an epoxy siloxane resin, a thermal initiator including the compound represented by Formula 2, and a photoinitiator.

In some embodiments, the cured layer may be formed by heat curing after the hard coating layer forming composition is photocured.

In exemplary embodiments, the hard coating layer-forming composition may further include a crosslinking agent including a compound represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 5 carbon atoms, and X is a direct bond; Carbonyl group; Carbonate group; Ether group; Thioether group; Ester group; Amide group; Linear or branched alkylene, alkylidene or alkoxylene groups having 1 to 18 carbon atoms; A cycloalkylene group or a cycloalkylidene group having 1 to 6 carbon atoms; Or a linking group thereof.

In example embodiments, the high refractive index layer may include a metal oxide or a metal nitride.

In example embodiments, the metal of the metal oxide or metal nitride may include at least one selected from niobium (Nb), zirconium (Zr), and indium (In).

In example embodiments, the low refractive index layer may include an inorganic oxide.

In example embodiments, the inorganic oxide may include silicon dioxide (SiO ₂ ).

In example embodiments, the refractive index of the high refractive index layer may be 1.6 to 2.6, and the refractive index of the low refractive index layer may be 1.38 to 1.45.

In example embodiments, the refractive index of the hard coat layer may be 1.49 to 1.54.

In example embodiments, when the high refractive index layer and the low refractive index layer are defined as an antireflective laminate, the antireflective laminate may be repeatedly stacked two to four times.

In example embodiments, the anti-reflection hard coating film may further include an antifouling layer disposed on the low refractive index layer and including a metal fluoride.

In example embodiments, the metal of the metal fluoride may include magnesium (Mg) or barium (Ba).

Method for producing an anti-reflective hard coating film according to an embodiment of the present invention, the composition for forming a hard coating layer comprising an epoxy siloxane resin, a thermal initiator comprising a compound represented by the following formula (2) on the substrate, and a photoinitiator Applying a; Hardening the composition for forming a hard coat layer to form a hard coat layer; Forming a high refractive index layer on the hard coating layer; And forming a low refractive index layer on the high refractive index layer.

[Formula 2]

In Formula 2, R ³ is hydrogen, an alkoxycarbonyl group having 1 to 4 carbon atoms, an alkylcarbonyl group having 1 to 4 carbon atoms, or an arylcarbonyl group having 6 to 14 carbon atoms, and R ⁴ is each independently hydrogen, halogen or 1 to 4 carbon atoms. An alkyl group, n is 1 to 4, R ⁵ is an aralkyl group having 7 to 15 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and R ⁶ is an alkyl group having 1 to 4 carbon atoms , X is SbF ₆ , PF ₆ , AsF ₆ , BF ₄ , CF ₃ SO ₃ , N (CF ₃ SO ₂ ) ₂ or N (C ₆ F ₅ ) ₄ .

In example embodiments, the curing may include photocuring and thermal curing performed sequentially.

In example embodiments, the formation of the high refractive index layer may be performed by sputtering a metal oxide or a metal nitride, or sputtering a metal element while supplying oxygen.

In example embodiments, the metal of the metal oxide or metal nitride may include at least one selected from niobium (Nb), zirconium (Zr), and indium (In).

In example embodiments, the formation of the low refractive index layer may be performed by sputtering an inorganic oxide.

In example embodiments, the inorganic oxide may include silicon dioxide (SiO ₂ ).

In example embodiments, the method of manufacturing the anti-reflection hard coating film may further include forming an antifouling layer on the low refractive index layer.

In example embodiments, the formation of the antifouling layer may be performed by sputtering a metal fluoride.

In example embodiments, the metal of the metal fluoride may include magnesium (Mg) or barium (Ba).

According to exemplary embodiments of the present invention, a hard coating layer, a high refractive index layer, and a low refractive index layer having a water contact angle of 90 ° or less are laminated. Thus, an antireflective hard coat film having improved interlayer adhesion between the hard coat layer and the high refractive index layer can be provided. In addition, the antireflection hard coating film can secure excellent hardness, curl suppression characteristics and antireflection characteristics.

According to some embodiments, the hard coating layer may include an epoxy siloxane resin, a specific thermal initiator, and a photoinitiator to further improve hardness and curl suppression properties of the antireflective hard coating film.

According to some embodiments, the hard coating layer-forming composition may be cured by sequentially photocuring and thermosetting to further improve the hardness and the curl suppression property of the antireflective hardcoat film.

In addition, by forming the high refractive index layer by sputtering a metal oxide or a metal nitride, it is possible to further improve the antireflection characteristics of the antireflective hard coat film.

In addition, by forming the low refractive index layer by sputtering the inorganic oxide, it is possible to further improve the antireflection characteristics of the antireflective hard coat film.

According to some embodiments, by further stacking an antifouling layer including a metal fluoride, the scratch resistance and the water contact angle of the antireflective hard coating film may be improved, and the antifouling function may be implemented.

1 to 3 are schematic diagrams illustrating an antireflective hard coating film according to exemplary embodiments of the present invention.
4 and 5 are schematic flowcharts illustrating a method of manufacturing an anti-reflective hard coating film according to exemplary embodiments of the present invention.

Embodiments of the present invention, a hard coating layer, a high refractive index layer and a low refractive index layer having a water contact angle of 90 ° or less on the substrate is laminated, to provide an antireflection hard coating film excellent in suppressing curl and excellent hardness and antireflection performance. In addition, it provides a method for producing the anti-reflection hard coating film.

Hereinafter, embodiments of the present invention will be described in detail. However, this is merely exemplary and the present invention is not limited to the specific embodiments described by way of example.

As used herein, the terms “curl” and “curling” refer to the warp-strain of the film, and “amount of curl” means that the film bends and rises from the lowest point of the film when the film on which the curl occurs is placed on a plane It can mean the vertical height to the point.

As used herein, the term "curl suppression characteristic" may refer to a characteristic in which the "amount of curl" appears less.

1 is a schematic diagram illustrating an antireflective hard coating film according to exemplary embodiments of the present invention.

Referring to FIG. 1, the antireflection hard coating film 10 may include a substrate 100, a hard coating layer 110, a high refractive index layer 120, and a low refractive index layer 130.

The substrate 100, the hard coating layer 110, the high refractive index layer 120, and the low refractive index layer 130 may be stacked in order while the respective layers directly contact each other. In addition, another layer may be interposed between each of the layers.

The substrate 100 is preferably excellent in transparency, mechanical strength, thermal stability, moisture shielding, isotropy and the like. The base material 100 may be, for example, polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate and the like; Cellulose resins such as diacetyl cellulose and triacetyl cellulose; Polycarbonate resins; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene resins such as polystyrene acrylonitrile-styrene copolymer; Polyolefin resins such as polyethylene, polypropylene, cycloolefin or polyolefin resin having a norbornene structure, an ethylene propylene copolymer; Polyimide resin; Polyaramid resins; Polyamideimide resin; Polyether sulfone resin; Sulfone resins; It may be prepared such as. These resins may be used alone or in combination of two or more thereof.

The thickness of the substrate 100 is not particularly limited, and may be, for example, 10 to 250 μm.

The hard coat layer 110 may be disposed on the substrate 100.

In some embodiments, the water contact angle of the hard coat layer 110 may be 90 ° or less. When the water contact angle of the hard coating layer 110 is 90 ° or less, the surface tension of the hard coating layer 110 is high, and the interlayer bonding force between the hard coating layer 110 and the high refractive index layer 120 may be improved. In addition, since the hard coating layer 110 and the high refractive index layer 120 to prevent the deformation of each other, the curl phenomenon of the entire anti-reflective hard coating film can be suppressed, durability can be improved. More preferably, the water contact angle of the hard coat layer 110 may be 80 ° or less or 50 ° or less, and 40 ° or more. In this case, the above effects can be further increased.

The water contact angle of the hard coat layer 110 may be adjusted by adding a leveling agent to the composition for forming a hard coat layer to be described later, or by performing a physical treatment such as corona and plasma discharge on the hard coat layer. However, a method of adding a leveling agent to the composition for forming a hard coat layer may be more easily performed in the process.

In some embodiments, the hard coating layer 110 may include an epoxy siloxane resin, a thermal initiator comprising a compound represented by the following formula (2), and a photoinitiator.

[Formula 2]

In Formula 2, R ³ is hydrogen, an alkoxycarbonyl group having 1 to 4 carbon atoms, an alkylcarbonyl group having 1 to 4 carbon atoms, or an arylcarbonyl group having 6 to 14 carbon atoms, and R ⁴ is each independently hydrogen, halogen or 1 to 4 carbon atoms. An alkyl group, n is 1 to 4, R ⁵ is an aralkyl group having 7 to 15 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and R ⁶ is an alkyl group having 1 to 4 carbon atoms , X is SbF ₆ , PF ₆ , AsF ₆ , BF ₄ , CF ₃ SO ₃ , N (CF ₃ SO ₂ ) ₂ or N (C ₆ F ₅ ) ₄ .

The alkoxycarbonyl group has 1 to 4 carbon atoms in the alkoxy moiety, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and the like.

The alkylcarbonyl group has 1 to 4 carbon atoms in the alkyl moiety, and examples thereof include an acetyl group and a propionyl group.

The arylcarbonyl group has 6 to 14 carbon atoms in the aryl moiety, and examples thereof include a benzoyl group, 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, and the like.

Examples of the aralkyl group include benzyl group, 2-phenylethyl group, 1-naphthylmethyl group and 2-naphthylmethyl group.

According to exemplary embodiments, the hard coating layer 110 may be formed by curing the epoxy siloxane resin, a thermal initiator comprising the compound represented by Formula 2, and a hard coating layer forming composition comprising the photoinitiator. . That is, the hard coat layer 110 may be a cured layer of the composition for forming a hard coat layer.

The epoxy siloxane resin may be, for example, a siloxane (Siloxane) resin including an epoxy group. The epoxy group may be any one or more selected from cyclic epoxy groups, aliphatic epoxy groups, and aromatic epoxy groups. The siloxane resin may mean a polymer compound in which a silicon atom and an oxygen atom form a covalent bond.

In some exemplary embodiments, the epoxy siloxane resin may be a Silsesquioxane resin substituted with an epoxy group. For example, an epoxy group may be directly substituted with a silicon atom of the silsesquioxane resin, or an epoxy group may be substituted with a substituent substituted with the silicon atom. As a non-limiting example, the epoxy siloxane resin may be a silsesquioxane resin substituted with a 2- (3,4-epoxycyclohexyl) ethyl group.

According to some embodiments, the epoxy siloxane resin may have a weight average molecular weight of 1,000 to 20,000, more preferably 1,000 to 18,000, even more preferably 2,000 to 15,000. When the weight average molecular weight is in the above range, the composition for forming a hard coat layer may have a more suitable viscosity. Thus, the flowability, coatability, curing reactivity of the composition for forming the hard coat layer may be further improved. In addition, the hardness of the hard coat layer can be further improved, the flexibility of the hard coat layer can be improved, the curl generation can be further suppressed.

Epoxy siloxane resins according to the present invention can be prepared either by alkoxy silanes having an epoxy group alone or in the presence of water through hydrolysis and condensation reactions between alkoxy silanes having epoxy groups and heteroalkoxy silanes.

According to exemplary embodiments, the alkoxy silane having an epoxy group used to prepare the epoxy siloxane resin may be exemplified by the following formula (3).

[Formula 3]

R ⁷ _n Si (OR ⁸ ) _4-n

In Formula 3, R ⁷ is a linear or branched alkyl group having 1 to 6 carbon atoms substituted with an epoxycycloalkyl group or an oxiranyl group having 3 to 6 carbon atoms, wherein the alkyl group may include an ether group, and R ⁸ may be linear or Branched chain alkyl group having 1 to 7 carbon atoms, n may be an integer of 1 to 3.

The alkoxy silane represented by the formula (3) is not particularly limited, and for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane And 3-glycidoxypropyltrimethoxysilane. These can be used individually or in mixture of 2 or more types.

In some embodiments, the epoxy siloxane resin may be included in 20 to 70 parts by weight based on 100 parts by weight of the total composition. More preferably, the epoxy siloxane resin may be included in 20 to 50 parts by weight based on 100 parts by weight of the total composition. When satisfying the above range, the composition for forming a hard coat layer can ensure more excellent flowability and coating properties. In addition, it is possible to uniformly harden during curing of the composition for forming a hard coat layer to more effectively prevent physical defects such as cracks caused by overcure. In addition, the hard coat layer may exhibit more excellent hardness.

The thermal initiator may form radicals, cations or anions by heat, and may initiate polymerization of the polymerizable compounds. The thermal initiator may promote crosslinking reaction of the epoxy siloxane resin or the crosslinking agent described later when heat is applied to the composition for forming a hard coat layer.

In exemplary embodiments, the thermal initiator may include a compound represented by Chemical Formula 2. The compound of Formula 2 may be provided, for example, as a cationic thermal initiator. By using the compound of Formula 2 as a thermal initiator, the curing half life can be shortened. Therefore, thermal curing can be performed quickly even at low temperature conditions, thereby preventing damages and deformations that occur when long-term heat treatment is performed under high temperature conditions.

In some embodiments, the thermal initiator may be included in an amount of 0.1 to 20 parts by weight, and more preferably 2 to 20 parts by weight, based on 100 parts by weight of the epoxy siloxane resin. When the content of the thermal initiator is within the above range, the thermosetting reaction may proceed at a more effective rate. In addition, the content of the other components of the composition for forming a hard coat layer may be reduced to effectively prevent the mechanical properties (eg, hardness, flexibility, curl properties, etc.) of the hard coat layer from being lowered.

In addition, for example, the thermal initiator may be included in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the total composition. More preferably, it may be included in an amount of 0.2 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total composition.

In some embodiments, the photoinitiator may include a photocationic initiator. The photocationic initiator may initiate polymerization of the epoxy siloxane resin and the epoxy monomer.

The photocationic initiator may be used, for example, onium salts and / or organometallic salts, but is not limited thereto. For example, a diaryl iodonium salt, a triarylsulfonium salt, an aryldiazonium salt, an iron-arene complex, etc. can be used. These may be used alone or in combination of two or more thereof.

The content of the photoinitiator is not particularly limited, for example, may be included in 0.1 to 15 parts by weight, more preferably 1 to 15 parts by weight based on 100 parts by weight of the epoxy siloxane resin. When the content of the photoinitiator is in the above range, it is possible to maintain the curing efficiency of the composition for forming the hard coating layer more excellent, and effectively prevent the degradation of physical properties due to the remaining components after curing.

In addition, for example, the photoinitiator may be included in 0.01 to 10 parts by weight based on 100 parts by weight of the total composition. More preferably, it may be included in 0.1 to 10 parts by weight, even more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the total composition.

In exemplary embodiments, the hard coating layer-forming composition may be cured by photocuring or thermosetting. Further, the photocuring may be performed by thermosetting after photocuring or photocuring after thermosetting, and photocuring and thermosetting may be simultaneously performed. However, in view of the hardness and the curl suppression of the hard coating layer 110, it is more preferable to thermally cured after photocuring.

In some embodiments, by using the thermal curing using the thermal initiator and photocuring using the photoinitiator in combination, it is possible to improve the degree of curing, hardness, flexibility, etc. of the hard coat layer, and to reduce curl.

For example, the composition for forming a hard coat layer may be applied to a substrate or the like and irradiated with ultraviolet light (photocuring) and at least partially cured, followed by additional heat (thermal curing), thereby substantially curing the composition. In this case, the partial curing may be performed until the pencil hardness of the cured layer by ultraviolet curing is about 1H.

That is, the hard coating layer-forming composition may be semi-cured or partially cured by the photocuring. The pencil hardness of the semi-cured or partially cured hard coat layer-forming composition may be about 1H. The semi-cured or part-cured hard coating layer-forming composition may be substantially completely cured by the thermosetting.

For example, when the hard coating layer-forming composition is cured only by photocuring, the curing time may be excessively long or partially hardened completely. On the other hand, when the thermosetting is performed after the photocuring, the portion not cured by the photocuring may be substantially completely cured by the thermosetting, and the curing time may also be reduced.

Also, in general, excessive curing may occur by providing excessive energy to a portion already cured to an appropriate degree with increasing curing time (eg, increasing exposure time). When the hardening proceeds, the hardened layer may lose flexibility or mechanical defects such as curls and cracks may occur. On the other hand, when the photocuring and the thermosetting are used in combination, the composition for forming the hard coat layer may be substantially completely cured for a short time. Thus, while maintaining the flexibility of the hard coating layer, it is possible to improve the hardness and suppress curling.

According to some embodiments, the hard coating layer-forming composition may further include a crosslinking agent. For example, the crosslinking agent may form a crosslink with the epoxy siloxane resin to solidify the composition for forming the hard coat layer and to improve the hardness of the hard coat layer.

According to some embodiments, the crosslinking agent may include a compound having an alicyclic epoxy group. For example, the crosslinking agent may include a compound in which two 3,4-epoxycyclohexyl groups are linked. For more specific example, the crosslinking agent may include a compound represented by the following formula (1). The crosslinking agent may be similar in structure and properties to the epoxy siloxane resin. In this case, crosslinking of the epoxy siloxane resin can be promoted and the composition can be maintained at an appropriate viscosity.

[Formula 1]

In Formula 1, R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 5 carbon atoms, and X is a direct bond; Carbonyl group; Carbonate group; Ether group; Thioether group; Ester group; Amide group; Linear or branched alkylene, alkylidene or alkoxylene groups having 1 to 18 carbon atoms; A cycloalkylene group or a cycloalkylidene group having 1 to 6 carbon atoms; Or a linking group thereof.

As used herein, "direct bond" may mean a structure directly connected without other functional groups. For example, in Formula 1, two cyclohexanes may be directly connected. In addition, in the present invention, the "linking group" may mean that two or more substituents described above are connected.

In addition, in Formula 1, the substitution position of R ¹ and R ² is not particularly limited, but when the carbon number X is connected to 1, the epoxy group is carbon 3, 4 is substituted at position 6 It is more preferable.

The above-mentioned compounds include a cyclic epoxy structure in the molecule, the epoxy structure of the linear structure as shown in Formula 1, it is possible to lower the viscosity of the composition to an appropriate range. Such a decrease in viscosity not only improves the applicability of the composition, but also further improves the reactivity of the epoxy group, thereby promoting a curing reaction. In addition, the hardness of the hard coat layer may be improved by forming crosslinks with the epoxy siloxane resin.

The content of the crosslinking agent according to the present invention is not particularly limited, and may be included, for example, in an amount of 5 to 150 parts by weight based on 100 parts by weight of the epoxy siloxane resin. When the content of the crosslinking agent is in the above range, it is possible to maintain the viscosity of the composition for forming a hard coat layer in a more suitable range, it is possible to further improve the coating properties and curing reactivity.

In addition, for example, the crosslinking agent may be included in 1 to 30 parts by weight based on 100 parts by weight of the total composition. More preferably, the crosslinking agent may be included in 5 to 20 parts by weight based on 100 parts by weight of the total composition.

In example embodiments, the hard coating layer-forming composition may further comprise a leveling agent.

As the leveling agent, an additive having high leveling property and high surface tension after curing may be used. For example, the leveling agent, BYK Chemie's BYK310, BYK322, BYK325, BYK347, BYK3530, BYK3560 and BYK-LPG21241; And Tego Glide100, Tego Glide406, Tego Glide415, Tego Glide420, Tego Glide450 and Tego Glide B1484 from Evonik; And at least one selected from the like.

The leveling agent may be included in 0.1 to 5 parts by weight based on 100 parts by weight of the total composition. In this case, generation of haze in the hard coat layer can be effectively prevented.

In example embodiments, the hard coating layer-forming composition may further include a thermosetting agent.

The thermosetting agent may include an amine-based, imidazole-based, acid anhydride-based, amide-based thermosetting agent, and the like, and more preferably, an acid anhydride-based thermosetting agent may be further used in view of prevention of discoloration and high hardness. . These can be used individually or in mixture of 2 or more types.

The content of the thermosetting agent is not particularly limited, and may be included, for example, 5 to 30 parts by weight based on 100 parts by weight of the epoxy siloxane resin. When the content of the thermosetting agent is in the above range, it is possible to further improve the curing efficiency of the composition for forming a hard coating layer to form a hard coating layer having excellent hardness.

In some embodiments, the hard coating layer-forming composition may further include a solvent. The solvent is not particularly limited and a solvent known in the art may be used.

Non-limiting examples of the solvent include alcohols (methanol, ethanol, isopropanol, butanol, methylcellulose, ethyl solusorb, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone , Dipropyl ketone, cyclohexanone, etc.), hexane type (hexane, heptane, octane etc.), benzene type (benzene, toluene, xylene etc.) etc. are mentioned. These may be used alone or in combination of two or more thereof.

The content of the solvent is not particularly limited, and for example, the solvent may be included in an amount of 10 to 200 parts by weight based on 100 parts by weight of the epoxy siloxane resin. When satisfying the above range, the composition for forming a hard coat layer may ensure a viscosity of an appropriate level, it may be more excellent workability when the hard coat layer is formed. In addition, it is easy to control the thickness of the hard coating layer, it is possible to ensure a faster process speed by reducing the solvent drying time.

Further, for example, the solvent may be included in the remaining amount excluding the amount occupied by the remaining components in the total weight of the predetermined total composition. For example, if the total weight of the predetermined total composition is 100 g and the sum of the weights of the remaining components excluding the solvent is 70 g, the solvent may include 30 g.

In some embodiments, the hard coating layer-forming composition may further include an inorganic filler. The inorganic filler may improve the hardness of the hard coat layer.

The said inorganic filler is not specifically limited, For example, Metal oxides, such as a silica, an alumina, a titanium oxide; Hydroxides such as aluminum hydroxide, magnesium hydroxide and potassium hydroxide; Metal particles such as gold, silver, copper, nickel, and alloys thereof; Conductive particles such as carbon, carbon nanotube, and fullerene; Glass; ceramic; And the like can be used. Preferably, silica may be used in terms of compatibility with other components of the composition for forming a hard coat layer. These may be used alone or in combination of two or more thereof.

In some embodiments, the composition for forming a hard coat layer may further include a lubricant. The lubricant may improve winding efficiency, blocking resistance, wear resistance, scratch resistance, and the like.

The type of the lubricant is not particularly limited, and examples thereof include waxes such as polyethylene wax, paraffin wax, synthetic wax or montan wax; Synthetic resins such as silicone resin and fluorine resin; And the like can be used. These may be used alone or in combination of two or more thereof.

In addition, the hard coating layer-forming composition may further include additives such as antioxidants, UV absorbers, light stabilizers, thermal polymerization inhibitors, surfactants, lubricants, antifouling agents, and the like.

The thickness of the hard coat layer 110 is not particularly limited, and may be, for example, 5 to 100 μm, more preferably 5 to 50 μm. When the thickness of the hard coating layer 110 is within the above range, the hard coating layer may have excellent hardness and maintain flexibility, so that curling may not occur substantially.

In some embodiments, the antireflective hard coating film 10 has a length of 10 cm on each side so that the amount of curl at each vertex of the square sample is cut so that each side is inclined at an angle of 45 ° with respect to the MD direction of the film. It may be less than 5mm.

The curls are perpendicular from the lowest point of the film (e.g., the center) to the vertex for each vertex of the sample which is inclined at an angle of 45 ° to the MD direction and squared at 10 cm on each side. It can mean height. In the present specification, the MD direction may mean a direction in which the film moves along the automated machine when the film is stretched or laminated in an automated process as a machine direction. As curls are measured for samples inclined at an angle of 45 ° with respect to the MD direction, curls at each vertex may mean curls in the MD direction and a direction perpendicular thereto, thereby distinguishing curls in each direction.

In some embodiments, the refractive index of the hard coat layer 110 may be 1.49 to 1.54.

According to some embodiments, the hard coat layer 110 may be formed on one surface of the substrate 100, and the hard coat layer 110 may be formed on both surfaces of the substrate 100.

The high refractive index layer 120 is disposed on the opposite side of the side where the base material 100 of the hard coating layer 110 is located.

In some embodiments, the refractive index of the high refractive index layer 120 may be higher than that of the hard coating layer 110 and the low refractive index layer 130.

In some embodiments, the high refractive index layer 120 may include a metal oxide or metal nitride. As the metal oxide or metal nitride, a material having high light transmittance and refractive index may be used.

For example, the metal of the metal oxide or metal nitride may include any one or more selected from niobium (Nb), zirconium (Zr), indium (In), and the like. More preferably, it may include niobium or zirconium. Oxides and nitrides of niobium or zirconium may be particularly effective for antireflection due to their high transparency and refractive index.

In some embodiments, the high refractive index layer 120 may be made of a single material of the metal oxide or metal nitride.

In some embodiments, the high refractive index layer 120 may be formed by sputtering the metal oxide or metal nitride. In this case, the high refractive index layer 120 may be uniform and thin in thickness, and may be more excellent in hardness and light transmittance than when the solvent is dried to form a film by wet. In addition, it is possible to implement an improved anti-reflection effect.

In addition, the high refractive index layer 120 may be formed by sputtering a metal element while supplying oxygen. For example, the metal element may include any one or more selected from niobium, zirconium, indium, and the like. More preferably, it may include niobium or zirconium.

In some embodiments, the refractive index of the high refractive index layer 120 may be 1.6 to 2.6.

The low refractive index layer 130 is disposed on the opposite side of the side where the hard coating layer 110 of the high refractive index layer 120 is located. The low refractive index layer 130 may have a refractive index lower than that of the high refractive index layer 120.

In some embodiments, the low refractive index layer 130 may include an inorganic oxide. As the inorganic oxide, a material having a high light transmittance and a refractive index lower than that of the metal oxide or metal nitride of the high refractive index layer 120 may be used. The inorganic oxide may be free of metal oxides. For example, the inorganic oxide may be an oxide of a metalloid element.

For example, the inorganic oxide may include silicon dioxide (SiO ₂ ). Silicon dioxide may have a lower light refractive index than the metal oxide or metal nitride of the high refractive index layer 120 and may be suitable for an antireflective coating.

In some embodiments, the low refractive index layer 130 may be made of a single material of the inorganic oxide.

In some embodiments, the low refractive index layer 130 may be formed by sputtering the inorganic oxide. In this case, the low refractive index layer 130 may have a uniform and thin thickness as compared to the case of forming a film by drying the solvent in a wet manner. In addition, the purity can be high without impurities such as solvent residues, and the light transmission can be better. In addition, it is possible to implement an improved anti-reflection effect.

In some embodiments, the refractive index of the low refractive index layer 130 may be 1.38 to 1.45.

In some embodiments, the antireflective hard coating film 10 may further include an antifouling layer on the low refractive index layer 130. In this case, the antireflective hard coat film can exhibit improved scratch resistance and water contact angle. In addition, antifouling functions can be implemented. Detailed description of the antifouling layer will be described later.

2 is a schematic diagram illustrating an antireflective hard coating film according to exemplary embodiments of the present invention.

Referring to FIG. 2, in some embodiments, the high refractive index layer 120 and the low refractive index layer 130 may be defined as an antireflective laminate 125, and the antireflective laminate 125 may be several times. Can be stacked repeatedly.

The antireflection effect of light incident on the low refractive index layer 130 may be implemented by the difference in refractive index between the high refractive index layer 120 and the low refractive index layer 130 in the antireflective laminate 125.

In example embodiments, the antireflective stack 125 may be stacked two to four times. In this case, an excellent antireflection effect can be realized. In addition, reduction in light transmittance and reduction in visibility on the bottom of the antireflective hard coating film can be effectively prevented.

In this case, the anti-reflection hard coating film may further include an antifouling layer on the outermost low refractive index layer. In this case, the antireflective hard coat film can exhibit improved scratch resistance and water contact angle. In addition, antifouling functions can be implemented. Detailed description of the antifouling layer will be described later.

3 is a schematic diagram illustrating an antireflective hard coating film according to exemplary embodiments of the present invention.

Referring to FIG. 3, in some embodiments, the outermost high refractive index layer 122 may be disposed on the low refractive index layer 130, and the antifouling layer 140 may be disposed on the outermost high refractive index layer 122. This can be arranged.

The outermost high refractive index layer 122 may have substantially the same configuration as the high refractive index layer 120.

In some embodiments, the antifouling layer 140 may include a metal fluoride. In this case, the antifouling layer 140 may ensure water repellent, waterproof and oilproof performance.

The metal of the metal fluoride may include, for example, magnesium (Mg) or barium (Ba). Magnesium or barium fluoride may be suitable as a material of the antifouling layer 140 because of good light transmittance and excellent water repellency.

In some embodiments, the antifouling layer 140 may be made of a single material of the metal fluoride.

In some embodiments, the antifouling layer 140 may be formed by sputtering the metal fluoride. In this case, the antifouling layer 140 may have a uniform thickness and thinness as compared with the case of forming a film by drying the solvent in a wet manner. In addition, the purity can be high without impurities such as solvent residues, and the light transmission can be better. In addition, it is possible to implement improved scratch resistance and antifouling effect.

In some embodiments, the refractive index of the antifouling layer 140 may be 1.30 to 1.60, and may have a value lower than the refractive index of the outermost high refractive index layer 122. Accordingly, the outermost high refractive index layer 122 and the antifouling layer 140 may perform a function similar to the antireflective laminate 125 to implement an antireflection effect.

4 is a schematic flowchart illustrating a method of manufacturing an anti-reflective hard coating film according to exemplary embodiments of the present invention.

Hereinafter, a method of manufacturing an antireflective hard coating film according to exemplary embodiments of the present invention will be described with reference to FIG. 4.

According to exemplary embodiments, a composition for forming a hard coat layer may be applied onto a substrate (eg, step S10).

The hard coating layer-forming composition may be a composition for forming a hard coat layer according to the above-described exemplary embodiments of the present invention.

The application (for example, step S10) may be performed by a die coater, air knife, reverse roll, spray, blade, casting, gravure, spin coating and the like.

According to some embodiments, the hard coating layer forming composition may be cured to form a hard coating layer (eg, step S20).

In exemplary embodiments, the hard coating layer-forming composition may be cured by photocuring or thermal curing. Further, the photocuring may be performed by thermosetting after photocuring or photocuring after thermosetting, and photocuring and thermosetting may be simultaneously performed. However, from the viewpoint of hardness and curl suppression of the hard coat layer, it is more preferable to thermally cure after photocuring. The photocuring may be performed by ultraviolet irradiation.

The hard coating layer-forming composition may be at least partially photocured by the ultraviolet irradiation.

In exemplary embodiments, the ultraviolet irradiation may be performed such that the curing degree of the composition for forming the hard coat layer is about 20 to 80%. When the degree of cure is within the above range, the hard coat layer may be primarily cured to secure hardness, and may prevent overcuring due to an extended exposure time.

For example, the ultraviolet irradiation may be performed so that the pencil hardness of the hardened coating layer is 1H or less. In other words, the UV irradiation may be terminated and the thermosetting may be performed before the pencil hardness of the hard coating layer is about 1H.

For example, it may be substantially completely cured by applying heat to the hard coat layer composition primarily cured by irradiation with ultraviolet rays. By using photocuring and thermosetting having different curing mechanisms together, the curing time can be shortened and the overcuring phenomenon can be suppressed as compared with the case where curing is performed by photocuring or thermosetting alone. In addition, it is possible to effectively induce a crosslinking reaction so that the crosslinking is uniformly formed. In addition, flexibility can be maintained while improving the hardness of the hard coat layer, and the curl of the antireflective hard coat film can be significantly reduced.

In some embodiments, the thermal curing may be performed for 5 to 20 minutes at a temperature of 100 to 200 ℃. More preferably, it may be carried out at a temperature of 120 to 180 ℃. In the above temperature range, thermal curing may proceed at a more effective rate. In addition, each component in the composition for forming a hard coat layer may effectively prevent cracking due to thermal decomposition, side reactions, or hardening of the hard coat layer.

According to exemplary embodiments, pretreatment may be performed by heating the hard coating layer-forming composition before the ultraviolet irradiation. In the pretreatment process, the highly volatile solvent may be evaporated before ultraviolet irradiation. Accordingly, it is possible to prevent bubbles from occurring during ultraviolet irradiation, or curing is performed unevenly.

The pretreatment may be performed at a lower temperature than the thermosetting, for example, it may be carried out at 40 to 80 ℃. In this temperature range, the solvent can be effectively evaporated without initiation reaction of the thermal initiator.

In example embodiments, a high refractive index layer is formed on the hard coat layer (eg, step S30).

In some embodiments, the formation of the high refractive index layer may be performed by sputtering a metal oxide or a metal nitride, or by sputtering a metal element while supplying oxygen.

The metal of the metal oxide or metal nitride may include, for example, any one or more selected from niobium (Nb), zirconium (Zr), indium (In), and the like. More preferably, it may include niobium or zirconium.

Similarly, the metal element may include any one or more selected from niobium, zirconium, indium, and the like. More preferably, it may include niobium or zirconium.

In some embodiments, the high refractive index layer may be made of only the metal oxide or metal nitride.

According to exemplary embodiments, a low refractive index layer is formed on the high refractive index layer (eg, step 40).

Formation of the low refractive index layer may be performed by sputtering an inorganic oxide. For example, the inorganic oxide may include silicon dioxide (SiO ₂ ).

In some embodiments, the low refractive index layer may be made of only the inorganic oxide.

The formation of the high refractive index layer and the formation of the low refractive index layer may be repeated several times, and may be performed to end with the formation of the low refractive index layer.

In some embodiments, the method may further include forming an antifouling layer on the low refractive index layer. In this case, an anti-reflection hard coating film having improved scratch resistance and water contact angle and antifouling function can be manufactured.

In some embodiments, the formation of the antifouling layer may be performed by sputtering metal fluoride.

The metal of the metal fluoride may include, for example, magnesium (Mg) or barium (Ba).

5 is a schematic flowchart illustrating a method of manufacturing an antireflective hard coating film according to exemplary embodiments of the present invention.

Hereinafter, a method of manufacturing an antireflective hard coating film according to exemplary embodiments of the present invention will be described with reference to FIG. 5. However, detailed description of the same process as the process described with reference to FIG. 4 may be omitted.

According to example embodiments, the outermost high refractive index layer may be formed on the low refractive index layer (eg, step S50).

The formation of the outermost high refractive index layer may be performed in the same manner as the formation of the high refractive index layer (for example, step 30).

According to example embodiments, an antifouling layer may be formed on the outermost high refractive index layer (eg, step S60).

In some embodiments, the anti-reflective hard coating film 10 has high surface hardness, excellent flexibility, light weight and excellent impact resistance compared to tempered glass, and thus may be preferably used as the window substrate on the outermost surface of the display panel. .

According to some embodiments, an image display device including the antireflective hard coating film 10 may be provided.

The antireflective hard coat film 10 may be used as the outermost window substrate of the image display device. The image display device may be various image display devices such as a conventional liquid crystal display, an electroluminescent display, a plasma display, a field emission display, and the like.

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

Preparation Example 1

2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECTMS, TCI) and water (H ₂ O, Sigma-Aldrich) at 24.64g: 2.70g (0.1mol: 0.15mol) Mix and put into 250mL 2-neck flask. Then, 0.1 mL of tetramethylammonium hydroxide (Sigma-Aldrich) catalyst and 100 mL of tetrahydrofuran (Sigma-Aldrich) were added to the mixture, followed by stirring at 25 ° C. for 36 hours. Thereafter, layer separation was performed, and the product layer was extracted with methylene chloride (Sigma-Aldrich), the extract was removed with magnesium sulfate (Sigma-Aldrich), and the solvent was vacuum dried to obtain an epoxy siloxane resin. The epoxy siloxane resin was measured using GPC (Gel Permeation Chromatography), and the weight average molecular weight was 2500.

Example 1

30 parts by weight of the epoxy siloxane resin prepared in Preparation Example 1, 15 parts by weight of (3 ', 4'-epoxycyclohexyl) methyl 3,4-epoxycyclohexanecarboxylate (Daicel, Celloxide 2021P), 4-ace 1 part by weight of oxyphenyldimethylsulfonium hexafluoroantimonate (Sansin, SI-60), 1 part by weight of (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate, 0.3 parts by weight of a silicone polymer (BYK, BYK3560, leveling agent) and 52.7 parts by weight of methyl ethyl ketone (Sigma-Aldrich) were mixed to prepare a composition for forming a hard coat layer.

The composition for forming the hard coat layer was applied on a cPI (colorless polyimide) film film having a thickness of 80 μm by a Meyer bar method, and allowed to stand at 60 ° C. for 5 minutes. After irradiating UV at 1J / cm ² using a high-pressure metal lamp, it was cured at 120 ° C. for 15 minutes to form a hard coating layer having a thickness of 10 μm, a refractive index of 1.51, and a water contact angle of 79 °.

Nb ₂ O ₅ was sputtered on the hard coat layer to form a high refractive index layer having a refractive index of 2.3.

SiO ₂ was sputtered on the upper surface of the high refractive index layer to form a low refractive index layer having a refractive index of 1.45.

The high refractive index layer and the low refractive index layer was repeated three times to form an antireflection hard coating film.

Example 2

In Example 1, an anti-reflection hard coat film was manufactured in the same manner as in Example 1, except that the high refractive index layer was replaced with a high refractive index layer having a refractive index of 2.2 formed by sputtering ZrO ₂ .

Example 3

In Example 1, a hard coat film was manufactured in the same manner as in Example 1, except that the high refractive index layer was replaced with a high refractive index layer having a refractive index of 2.6 formed by sputtering In ₂ O ₃ .

Example 4

In Example 1, an antireflective hard coat film was manufactured in the same manner as in Example 1, except that acrylic polymer (BYK, BYKLPG21241) was used as a leveling agent for the composition for forming a hard coat layer.

Example 5

In Example 1, MgF ₂ was sputtered on the uppermost outermost low refractive index layer of the antireflective hard coat film, thereby preparing an antireflective hard coat film having an antifouling layer having a refractive index of 1.38.

Example 6

In Example 2, BaF ₂ was sputtered on the uppermost outermost low refractive index layer of the antireflective hard coat film to prepare an antireflective hard coat film having an antifouling layer having a refractive index of 1.42.

Comparative Example 1

20 parts by weight of pentaerythritol tetraacrylate, 20 parts by weight of o-phenylphenoxyethyl acrylate, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, 0.3 part by weight of a silicone polymer (BYK, BYK3530, leveling agent), methyl 58.7 parts by weight of ethyl ketone (Sigma-Aldrich, Inc.) was mixed to prepare a hard coating composition.

The hard coating composition was applied by a Meyer bar method on an 80 μm thick cPI film, and allowed to stand at 60 ° C. for 5 minutes. UV was irradiated at 1 J / cm ² using a high-pressure metal lamp to form a hard coat layer having a thickness of 10 μm and a refractive index of 1.55.

SiO ₂ was sputtered on the upper surface of the hard coating layer to form a low refractive index layer having a refractive index of 1.45 to prepare an antireflection hard coating film.

Comparative Example 2

70 parts by weight of urethane acrylate (Shinakamura Chemical, U015HA), 30 parts by weight of pentaerythritol triacrylate (PE-3A, a public company), 3 parts by weight of a photoinitiator (Shiba, D-1173), silicone polymer ( BYK, BYK3570, leveling agent) 0.3 parts by weight, methyl ethyl ketone 150 parts by weight and toluene 100 parts by weight were mixed to prepare a hard coating composition.

3 parts by weight of a polyfunctional urethane acrylate UP111 (Entis), 10 parts by weight of a surface-treated zircon sol (40% solids), 57 parts by weight of propylene glycol monomethyl ether (Semielectric Chemical), and 29 parts by weight of methyl ethyl ketone (Samjeon Chemical) was mixed and completely dissolved, and then 1 part by weight of Irgacure 184 (BASF, photoinitiator) was added and stirred for 5 minutes to prepare a high refractive index layer composition.

1 part by weight of dipentaerythritol hexaacrylate (DPHA, Japan Synthetic), 0.03 part by weight of photoinitiator (BASF, IRG907), 3 parts by weight of hollow silicon nanotubes (inner diameter 45 nm, outer diameter 85 nm, length 150 nm, refractive index 1.28), 0.07 parts by weight of fluorine-based acrylate (chemoptics Co., Ltd.) and 95.9 parts by weight of methyl isobutyl ketone were mixed and stirred to prepare a low refractive index layer composition.

The hard coating composition was applied by a Meyer bar method on an 80 μm thick cPI film, and allowed to stand at 60 ° C. for 5 minutes. UV was irradiated at 1 J / cm ² using a high pressure metal lamp to form a hard coating layer having a thickness of 10 μm.

The high refractive index layer composition was applied to the top surface of the hard coating layer, and allowed to stand at 60 ° C. for 5 minutes. UV of 1 J / cm ² was irradiated with a high-pressure metal lamp to form a high refractive index layer having a refractive index of 2.0.

The low refractive index layer composition was applied to the upper surface of the high refractive index layer and allowed to stand at 60 ° C. for 5 minutes. UV irradiation of 1J / cm ² with a high-pressure metal lamp was performed to form a low refractive index layer having antifouling properties and a refractive index of 1.40, thereby preparing an anti-reflection hard coating film.

Experimental Example

Pencil hardness, curl suppression characteristics (amount of curl) and reflectance of the antireflective hard coat films of Examples and Comparative Examples were evaluated and shown in Table 1 below.

The water contact angles of the hard coat layers of Examples and Comparative Examples were measured by using a contact angle measuring instrument (MSA, KRUSS) and are shown in Table 1 below.

1. Pencil hardness measurement

According to ASTM D3363, the pencil hardness of the outermost layer surface of the antireflective hard coating film was measured using a pencil by hardness (Mitsubishi) at a load of 1 kg using a pencil hardness tester (GiB & T Co., Ltd.).

2. Curling amount measurement

The anti-reflective hard coating film was cut into a 10 cm x 10 cm square inclined at an angle of 45 ° in the MD direction, and left at 25 ° C. and 50% constant temperature and humidity for 12 hours, and the curl degree of each vertex was measured using a ruler.

3. Reflectance Measurement

Adapter MPC603 was attached to the spectrophotometer UV3600 (Shimadzu Co., Ltd.), and the specular reflectance with respect to the emission angle of 5 ° at the incident angle of 5 ° in the wavelength region of 380 to 780 nm was measured, and the average reflectance of 400 to 800 nm was calculated.

division Pencil hardness Curl sheep Hard Coating Layer Water Contact Angle (°) reflectivity(%) Example 1 7H 0.5mm 79 0.4 Example 2 7H 0.5mm 80 0.3 Example 3 7H 0.5mm 79 0.5 Example 4 7H 0.5mm 72 0.4 Example 5 7H 0.5mm 78 0.2 Example 6 7H 0.5mm 79 0.5 Comparative Example 1 4H 50 mm 73 1.8 Comparative Example 2 4H 50 mm 101 0.7

Referring to Table 1, in the case of the anti-reflection hard coating layer film according to the embodiments of the present invention, it can be seen that exhibits a significantly superior hardness and curl suppression characteristics than the comparative examples.

In addition, in the case of the examples, the antireflection property was significantly superior to the comparative examples.

In Example 5, 6 and Comparative Example 2, the following evaluation was further carried out and shown in Table 2 below.

4. Transmittance Measurement

The total light transmittance of the antireflective hard coat film was measured using a spectrophotometer (COH-400, Denshoku Co., Ltd.).

5. Water contact angle evaluation

The water contact angle of the outermost layer surface of the antireflective hard coat film was measured using a contact angle measuring instrument (MSA, KRUSS).

6. Scratch resistance evaluation

The anti-reflective hard coating film was cut to 7cm x 12cm and fixed to the wear resistance measuring instrument (Gay & T Co., Ltd.) jig. After setting the moving distance 100mm, the moving speed 60mm / sec and the load 0.5kg, the steel wool was rubbed 500 times on the outermost surface of the antireflective hard coating film, and the number of scratches on the surface was visually observed. .

division Transmittance (%) Water contact angle (°) Scratch resistance Example 5 94.3 118 5 Example 6 94 117 7 Comparative Example 2 93.5 105 Peeling

As can be seen in Table 2, in the case of the anti-reflection hard coating film according to the embodiments of the present invention, it showed excellent transmittance, water contact angle and scratch resistance compared to the comparative example. In particular, it showed remarkably excellent scratch resistance.

10: Anti-reflective hard coating film
100: base material 110: hard coating layer
120: high refractive index layer 122: outermost high refractive index layer
125: antireflective laminate 130: low refractive index layer
140: antifouling layer

Claims (23)

materials;
A hard coating layer disposed on the substrate and having a water contact angle of 90 ° or less;
A high refractive index layer disposed on the hard coating layer; And
And a low refractive index layer disposed on the high refractive index layer. The method according to claim 1,
The hard coating layer, an anti-reflection hard coating film comprising an epoxy siloxane resin, a thermal initiator comprising a compound represented by the following formula (2), and a photoinitiator:
[Formula 2]

In Formula 2, R ³ is hydrogen, an alkoxycarbonyl group having 1 to 4 carbon atoms, an alkylcarbonyl group having 1 to 4 carbon atoms, or an arylcarbonyl group having 6 to 14 carbon atoms, and R ⁴ is each independently hydrogen, halogen or 1 to 4 carbon atoms. An alkyl group, n is 1 to 4, R ⁵ is an aralkyl group having 7 to 15 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and R ⁶ is an alkyl group having 1 to 4 carbon atoms , X is SbF ₆ , PF ₆ , AsF ₆ , BF ₄ , CF ₃ SO ₃ , N (CF ₃ SO ₂ ) ₂ or N (C ₆ F ₅ ) ₄ . The method according to claim 2,
The hard coating layer is an anti-reflection hard coating film of the epoxy siloxane resin, a thermal initiator comprising a compound represented by the formula (2), and a hardened layer of the composition for forming a hard coating layer comprising a photoinitiator. The method according to claim 3,
The cured layer is an antireflection hard coating film that is formed by heat curing after the composition for forming the hard coating layer is photocured. The method according to claim 3,
The hard coating layer-forming composition further comprises a crosslinking agent containing a compound represented by the following formula (1), anti-reflection hard coating film:
[Formula 1]

In Formula 1, R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 5 carbon atoms, and X is a direct bond; Carbonyl group; Carbonate group; Ether group; Thioether group; Ester group; Amide group; Linear or branched alkylene, alkylidene or alkoxylene groups having 1 to 18 carbon atoms; A cycloalkylene group or a cycloalkylidene group having 1 to 6 carbon atoms; Or a linking group thereof. The method according to claim 1,
The high refractive index layer, a metal oxide or metal nitride, antireflection hard coating film. The method according to claim 6,
The metal of the metal oxide or metal nitride, at least one selected from niobium (Nb), zirconium (Zr) and indium (In), anti-reflective hard coating film. The method according to claim 1,
The low refractive index layer, an anti-reflection hard coating film containing an inorganic oxide. The method according to claim 8,
The inorganic oxide, silicon dioxide (SiO ₂ ), anti-reflective hard coating film. The method according to claim 1,
The refractive index of the high refractive index layer is 1.6 to 2.6, the refractive index of the low refractive index layer is 1.38 to 1.45, anti-reflective hard coating film. The method according to claim 1,
The refractive index of the hard coat layer, 1.49 to 1.54, anti-reflective hard coating film. The method according to claim 1,
When the high refractive index layer and the low refractive index layer is defined as an antireflective laminate, the antireflective laminate is laminated repeatedly two to four times. The method according to claim 1,
And an antifouling layer disposed on the low refractive index layer and comprising a metal fluoride. The method according to claim 13,
The metal of the metal fluoride, magnesium (Mg) or barium (Ba), antireflection hard coating film. Applying a composition for forming a hard coating layer comprising an epoxy siloxane resin, a thermal initiator comprising a compound represented by Formula 2, and a photoinitiator on the substrate;
Hardening the composition for forming a hard coat layer to form a hard coat layer;
Forming a high refractive index layer on the hard coating layer; And
Forming a low refractive index layer on the high refractive index layer; comprising a method of manufacturing an anti-reflection hard coating film comprising:
[Formula 2]

In Formula 2, R ³ is hydrogen, an alkoxycarbonyl group having 1 to 4 carbon atoms, an alkylcarbonyl group having 1 to 4 carbon atoms, or an arylcarbonyl group having 6 to 14 carbon atoms, and R ⁴ is each independently hydrogen, halogen or 1 to 4 carbon atoms. An alkyl group, n is 1 to 4, R ⁵ is an aralkyl group having 7 to 15 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and R ⁶ is an alkyl group having 1 to 4 carbon atoms , X is SbF ₆ , PF ₆ , AsF ₆ , BF ₄ , CF ₃ SO ₃ , N (CF ₃ SO ₂ ) ₂ or N (C ₆ F ₅ ) ₄ . The method according to claim 15,
The curing is a method of producing an anti-reflection hard coating film, including photocuring and thermal curing performed sequentially. The method according to claim 15,
The formation of the high refractive index layer is performed by sputtering a metal oxide or a metal nitride, or by sputtering a metal element while supplying oxygen. The method according to claim 17,
The metal of the metal oxide or metal nitride, at least one selected from niobium (Nb), zirconium (Zr) and indium (In), a method for producing an antireflective hard coating film. The method according to claim 15,
The formation of the low refractive index layer is performed by sputtering an inorganic oxide, a method for producing an antireflection hard coating film. The method according to claim 19,
The inorganic oxide, silicon dioxide (SiO ₂ ), a method for producing an antireflection hard coating film. The method according to claim 15,
The method of claim 1, further comprising forming an antifouling layer on the low refractive index layer. The method according to claim 21,
Formation of the antifouling layer is performed by sputtering a metal fluoride, the method of manufacturing an antireflection hard coating film. The method according to claim 22,
The metal of the metal fluoride, magnesium (Mg) or barium (Ba) comprises a method of producing an antireflective hard coating film.

Images