KR20200016797A - Composition for forming hard coating layer, method of preparing hard coating film and hard coating film prepared by using the same - Google Patents

Abstract

The present invention relates to a composition for forming a hard coating layer, which comprises: an epoxy siloxane resin; a cross-linking agent containing a compound having an alicyclic epoxy group; a thermal initiator including a compound represented by chemical formula 2; and a photo-initiator, thereby reducing the curl of a hard coating film and increasing the hardness.

Description

A composition for forming a hard coat layer, a method of manufacturing a hard coat film, and a hard coat film manufactured using the same. {COMPOSITION FOR FORMING HARD COATING LAYER, METHOD OF PREPARING HARD COATING FILM AND HARD COATING FILM PREPARED BY USING THE SAME}

The present invention relates to a composition for forming a hard coat layer, a method for producing a hard coat film, and a hard coat film manufactured using 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 a composition for forming a hard coat layer that improves the mechanical properties, hardness, and curl inhibition properties of the hard coat layer.

One object of the present invention is to provide a method for producing a hard coat film having improved mechanical properties, hardness and curl inhibition properties.

One object of the present invention is to provide a hard coat film with improved mechanical properties, hardness and curl suppression properties.

The composition for forming a hard coat layer according to the exemplary embodiments of the present invention includes an epoxy siloxane resin, a crosslinking agent including a compound having an alicyclic epoxy group, a thermal initiator including a compound represented by the following Chemical 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. N is 1-4, R ⁵ is an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 7 to 15 carbon atoms which may be substituted with 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 some embodiments, the epoxy siloxane resin may have a weight average molecular weight of 1,000 to 20,000.

In some embodiments, the compound having an alicyclic epoxy group may be represented by the following 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.

Method for producing a hard coat film according to an exemplary embodiment of the present invention, an epoxy siloxane resin, a crosslinking agent comprising a compound having an alicyclic epoxy group, a thermal initiator comprising a compound represented by the formula (2), and a photoinitiator Preparing a composition for forming a hard coating layer; Applying the composition for forming a hard coat layer on a substrate; Irradiating ultraviolet rays to the applied composition for forming a hard coat layer; And thermosetting the UV-coated hard coating layer-forming composition to form a composite hardened hard coat 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. N is 1-4, R ⁵ is an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 7 to 15 carbon atoms which may be substituted with 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 some embodiments, the epoxy siloxane resin may have a weight average molecular weight of 1,000 to 20,000.

In some embodiments, the compound having an alicyclic epoxy group may be represented by the following 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 some embodiments, the thermal curing may be performed for 5 to 20 minutes at a temperature of 100 to 200 ℃.

In some embodiments, the method may further include heating and pretreating the composition for forming the hard coating layer before the ultraviolet irradiation.

In some embodiments, the pretreatment may be performed at a lower temperature than the thermal curing.

In some embodiments, further comprising applying the composition for forming a hard coat layer on the surface of the substrate is not formed with the composite cured hard coating layer; And UV curing the additionally applied composition for forming a hard coat layer to form a photocurable hard coat layer.

In some embodiments, the thickness ratio of the composite cured hard coat layer and the photocured hard coat layer may be 1.1: 1 to 8: 1.

The hard coat film according to the exemplary embodiments of the present invention may be manufactured by the method of manufacturing the hard coat film.

Hard coating film according to an exemplary embodiment of the present invention, the substrate; And a composite cured hard coat layer formed by complex curing a composition comprising a crosslinking agent comprising a compound having an epoxy siloxane resin and an alicyclic epoxy group on the substrate.

In exemplary embodiments, the complex curing may be curing including a thermal initiator and a photoinitiator.

In exemplary embodiments, the thermal initiator may include a compound represented by the following Formula 2.

[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. N is 1-4, R ⁵ is an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 7 to 15 carbon atoms which may be substituted with 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 compound having an alicyclic epoxy group may be represented by the following 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 hard coat film may further include a photocurable hard coat layer formed by photocuring the composition on a surface on which the composite cured hard coat layer of the substrate is not formed.

In example embodiments, the thickness ratio of the composite cured hard coat layer and the photocured hard coat layer may be 1.1: 1 to 8: 1.

In some embodiments, the hard coating film, the length of each side is 10cm, the amount of curl at each vertex of the square sample cut to be inclined at an angle of 45 ° to the MD direction of the film is less than 5mm Can be.

The composition for forming a hard coat layer according to the exemplary embodiments of the present invention may include a thermal initiator represented by the formula (2) to reduce the curing half-life of the composition so that the composition may be quickly thermally cured at a low temperature. Accordingly, physical defects such as cracks or curls generated by excessively exposing the composition for forming the hard coat layer to light in the curing process can be prevented. In addition, the composition may be uniformly cured for a short time to suppress curling of the hard coat layer and increase hardness.

In addition, the curing process of the composition for forming a hard coating layer including a thermal initiator may be sequentially performed as two steps of photocuring and thermosetting, thereby improving the hardness and curl suppression properties of the hard coating layer.

In some embodiments, a hardening layer of the hard coating layer formed by photocuring the composition for forming the hard coating layer on the surface of the substrate is disposed, and a photocured hard coating layer on which the hard coating layer forming composition is photocured on the other surface of the substrate. , The curl suppressing properties and shape restoring force of the hard coat film can be further improved.

1 and 2 are schematic flow charts illustrating a method of manufacturing a hard coat film according to exemplary embodiments of the present invention.
3 and 4 are schematic diagrams illustrating a hard coat film according to exemplary embodiments of the present invention.

Embodiments of the present invention, including an epoxy siloxane resin, a crosslinking agent, a thermal initiator and a photoinitiator, to provide a composition for forming a hard coating layer that can reduce the curl and increase the hardness of the hard coating film. The present invention also provides a method for producing a hard coat film using the composition for forming a hard coat layer and a hard coat film produced thereby.

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.

In exemplary embodiments, the composition for forming a hard coating layer of the present invention includes an epoxy siloxane resin, a crosslinking agent including a compound having an alicyclic epoxy group, a thermal initiator including a compound represented by the following Chemical 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. N is 1-4, R ⁵ is an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 7 to 15 carbon atoms which may be substituted with 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.

In the present invention, the epoxy siloxane resin may be a siloxane (Siloxane) resin containing 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.

The epoxy siloxane resin may be, for example, 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-described 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.

The epoxy siloxane resin according to the present invention may be prepared by the alkoxy silane having an epoxy group alone or in the presence of water through hydrolysis and condensation reaction between the alkoxy silane having an epoxy group and a heterogeneous alkoxy silane.

According to exemplary embodiments, the alkoxy silane having the epoxy group may be exemplified by the following formula (12).

[Formula 12]

R ⁷ _n Si (OR ⁸ ) _4-n

In Formula 12, R ⁷ is a linear or branched alkyl group having 1 to 6 carbon atoms substituted with an epoxycycloalkyl group or oxiranyl group having 3 to 6 carbon atoms, wherein the alkyl group may include an ether group, and R ⁸ may be linear or It is a branched alkyl group of 1 to 7 carbon atoms, n may be an integer of 1 to 3.

The alkoxy silane represented by the formula (12) 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 an amount of 10 to 80 parts by weight based on 100 parts by weight of the total composition. More preferably, it may be included in 20 to 70 parts by weight, even more preferably 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.

In the present invention, for example, the crosslinking agent may form a crosslink with the epoxy siloxane resin to solidify the composition for forming a hard coat layer and improve the hardness of the hard coat layer.

In the present invention, the crosslinking agent may be one containing a compound having an alicyclic epoxy group.

According to exemplary embodiments, the compound having an alicyclic epoxy group, two 3,4-epoxycyclohexyl group may be connected. More specifically, the compound having the alicyclic epoxy group may be represented by the following formula (1). The compound having an alicyclic epoxy group 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 for forming the hard coat layer 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.

Specific examples of the compound represented by Formula 1 include, but are not limited to, the compounds of Formulas 3 to 11 below. The compounds represented by the following Chemical Formulas 3 to 11 may be used alone or in combination of two or more thereof.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

In Formula 8, R is a linear or branched alkylene group having 1 to 8 carbon atoms, l is an integer of 1 to 30, m in the formula (10) is an integer of 1 to 30.

The content of the crosslinking agent according to the present invention is not particularly limited. For example, the crosslinking agent may be included 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 within the above range, the viscosity of the composition for forming a hard coat layer may be maintained in an appropriate range, and the coating property and curing reactivity may be improved.

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 the present invention, the thermal initiator may promote the crosslinking reaction of the epoxy siloxane resin or the crosslinking agent when heat is applied to the composition for forming a hard coat layer. Cationic thermal initiator may be used as the thermal initiator, but is not limited thereto.

In addition, by using a combination of thermal curing using the thermal initiator and photocuring using a photoinitiator described later, it is possible to improve the degree of curing, hardness, flexibility and the like 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.

That is, the composition for forming the hard coating layer may be semi-cured or partially cured by the photocuring, and the composition for forming the semi-curing or partially-cured hard coating layer may be substantially completely cured by the thermal curing. Can be.

When the hard coating layer-forming composition is cured only by photocuring, the curing time may be excessively long or partially may not be completely cured. 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 is performed, the hard coating layer may lose flexibility or mechanical defects such as curl 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, the hardness can be improved, and curl generation can be suppressed.

Although the method of photocuring and further thermosetting the composition for forming the hard coating layer was described above, the order of photocuring and thermosetting is not particularly limited thereto. That is, in some embodiments, the thermal curing may be performed first, followed by the photocuring.

In exemplary embodiments, the thermal initiator may include a compound represented by the following Formula 2. The compound of formula 2 may, for example, act as a cationic thermal initiator. By using the compound represented by the following formula (2) as a thermal initiator, the curing half life can be shortened. Thus, heat 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.

 [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. N is 1-4, R ⁵ is an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 7 to 15 carbon atoms which may be substituted with 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 some embodiments, the thermal initiator may be included in an amount of 0.1 to 60 parts by weight, more preferably 0.5 to 45 parts by weight, even more preferably 1 to 30 parts by weight based on 100 parts by weight of the epoxy siloxane resin. . When the content of the thermal initiator is in the above range, the thermal curing reaction may proceed at a more effective rate, the content of the other components of the composition for forming the hard coat layer is reduced, so that the mechanical properties (eg, hardness, flexibility, curl) It is possible to effectively prevent deterioration of the suppressing characteristics and the like).

In addition, for example, the thermal initiator may be included in 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, even more preferably 0.5 to 10 parts by weight based on 100 parts by weight of the total composition. In this case, excellent hardness and curl suppression characteristics can be exhibited. In particular, when included in 0.5 to 10 parts by weight based on 100 parts by weight of the total composition, it can exhibit a remarkably excellent hardness and curl suppression properties.

According to exemplary embodiments, the composition for forming a hard coating layer may further include a thermosetting agent.

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

The content of the thermosetting agent is not particularly limited. For example, the thermosetting agent may be included in an amount of 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 to form a hard coating layer having excellent hardness.

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

As the photocationic initiator, for example, an onium salt and / or an organometallic salt may be used, but is not limited thereto. For example, diaryl iodonium salt, triarylsulfonium salt, aryldiazonium salt, 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, and, for example, 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 excellently, and to prevent the degradation of physical properties due to the remaining components after curing.

In addition, for example, the photoinitiator may be included as 0.01 to 10 parts by weight, more preferably 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 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 500 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 can secure a proper level of viscosity, it may be more excellent workability at the time of forming the hard coat layer. In addition, it is easy to control the thickness of the hard coating layer, it is possible to ensure a fast 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 composition for forming a hard coat layer 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 hard coating layer-forming composition 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, levling agents, surfactants, lubricants, antifouling agents, and the like.

Moreover, this invention is a base material; And a composite cured hard coat layer formed by complex curing a composition comprising an epoxy siloxane resin and a crosslinking agent comprising a compound having an alicyclic epoxy group on the substrate.

Here, complex curing may mean curing using a curing method having a different curing mechanism, for example, photocuring and thermosetting in combination.

In exemplary embodiments, the complex curing may include curing the photoinitiator and the thermal initiator. This has been described above and will also be described later, and the detailed description thereof will be omitted.

In example embodiments, the hard coat film may further include a photocurable hard coat layer formed by photocuring the composition on a surface on which the composite cured hard coat layer of the substrate is not formed.

In exemplary embodiments, the thickness ratio of the composite cured hard coat layer and the photocured hard coat layer is 1: 1 to 10: 1, more preferably 1.1: 1 to 8: 1, even more preferably 2: 1 to 6: 1.

In the hard coat film of the present invention, the epoxy siloxane resin, the crosslinking agent containing the compound having the alicyclic epoxy group, the photoinitiator and the thermal initiator may be the same as described above, here, the specific description thereof Omit. In addition, a detailed description of the description will be described later.

The present invention provides an exemplary method of making the hard coat film.

In exemplary embodiments, a hard coat film may be manufactured using the composition for forming a hard coat layer according to the present invention. Hereinafter, a method of manufacturing a hard coat film and a hard coat film manufactured thereby will be described with reference to the drawings.

1 is a schematic flowchart illustrating a method of manufacturing a hard coat film according to exemplary embodiments of the present invention.

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

Referring to FIG. 1, after preparing a composition for forming a hard coating layer (for example, step S10), applying it onto a substrate (for example, step S20), irradiating ultraviolet light (for example, step S30) ), A hard coating film may be manufactured by thermal curing (for example, step S40).

Referring to FIG. 3, the hard coat film 10 may include a substrate 100 and a composite cured hard coat layer 110.

The hard coating layer-forming composition may include an epoxy siloxane resin, a crosslinking agent including a compound having an alicyclic epoxy group, a thermal initiator including the compound represented by Formula 2, and a photoinitiator.

The thermal initiator including the compound represented by Formula 2 may have a short curing half life. For example, thermal curing can be performed quickly even at low temperature conditions. Thus, damage and deformation that occur when long-term heat treatment under high temperature conditions can be prevented.

According to some embodiments, the epoxy siloxane resin may have a weight average molecular weight of 1,000 to 20,000.

In some embodiments, the compound having an alicyclic epoxy group may be represented by Formula 1.

The hard coat layer-forming composition may be applied onto the substrate 100 (for example, step S20).

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, ethylene propylene copolymer; Polyimide resin; Polyaramid resins; Polyamideimide resin; Polyether sulfone resin; It may be made of a sulfone resin or the like. 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 application (for example, step S20) may be performed by a die coater, air knife, reverse roll, spray, blade, casting, gravure, spin coating, or the like.

According to some embodiments, ultraviolet rays may be irradiated to the applied composition for forming a hard coat layer (for example, step S30). The hard coating layer-forming composition may be at least partially photocured by the ultraviolet irradiation.

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

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

In example embodiments, the UV cured composition for forming a hard coat layer may be thermoset to form a composite hardened hard coat layer 110 (for example, step S40).

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 to form a crosslink evenly. In addition, while maintaining the hardness of the composite curing hard coating layer 110, flexibility can be maintained, and the curl of the hard coating film 10 can be significantly reduced.

In some embodiments, the thermosetting may be performed at 100 to 200 ° C. for 5 to 20 minutes. More preferably, it may be carried out at a temperature of 120 to 180 ℃. In the above temperature range, the thermal curing may proceed at an effective speed, and each component in the composition for forming a hard coating layer may be thermally decomposed, a side reaction may occur, or the hard coating layer may be excessively hardened to prevent cracking.

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.

The thickness of the composite curing hard coating layer 110 is not particularly limited, and may be, for example, 5 to 100 μm. More preferably, it may be 5-50 micrometers. When the thickness is in the above range, it may have excellent hardness and maintain flexibility, so that curling may not occur substantially.

According to the exemplary embodiments, the hard coating film 10, the length of each side 10cm, the amount of curl at each vertex of the square sample cut so that each side is inclined at an angle of 45 ° to the MD direction of the film It may be 5 mm or less.

The curl is the vertical height from the lowest point (e.g., the center) to the vertex of the film for each vertex of the sample in which the hard-coated film is inclined at an angle of 45 ° relative to the MD direction and each side is cut to 10 cm square. It may mean. In the present specification, the MD direction may mean a direction in which the film is moved along the automated machine when the film is stretched or laminated in the automated process as the machine direction. As curls are measured for a sample 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.

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

2 is a schematic flowchart illustrating a method of manufacturing a hard coat film according to exemplary embodiments of the present invention.

4 is a schematic diagram illustrating a hard coat film according to exemplary embodiments of the present invention.

Referring to Figure 2, after forming the composite curing hard coating layer (for example, step S40), the composition for forming a hard coating layer is further applied to the opposite side of the surface on which the composite curing hard coating layer of the substrate is formed (for example , Step S50), and ultraviolet curing (eg, step S60) may be performed.

The hard coat film manufactured according to this, with reference to FIG. 4, may include a substrate 100, a composite cured hard coat layer 110, and a photocurable hard coat layer 120.

The additional coating may be performed in the same manner as the coating of the hard coating layer forming composition (for example, step S20).

The ultraviolet curing (for example, step S60) may be performed to have a higher degree of curing than the ultraviolet irradiation (for example, step S30). Accordingly, even if only the photocuring for the photocurable hard coating layer 120 can be secured an appropriate hardness.

For example, the formation of the photocurable hard coating layer 120 may be performed by omitting the thermosetting step in the process of forming the composite curing hard coating layer 110.

Therefore, the composite hardened hard coat layer 110 may be formed on one surface of the substrate 100, and the photocured hard coat layer 120 may be formed on the other surface of the substrate 100. By forming hard coating layers having different mechanical properties on both sides of the substrate 100 so that the warp in the top direction and the warp in the bottom direction of the hard coat film are at least partially canceled, the curl of the hard coat film can be further suppressed. Can be. In addition, even when the hard coating film is deformed to be bent in various directions, it is possible to secure the shape restoring force, and even if repeated deformation is performed, it is possible to suppress the formation of physical defects such as cracks.

According to exemplary embodiments, but not limited thereto, the ratio of the thickness of the composite hardened hard coat layer 110 and the photocured hard coat layer 120 may be 1: 1 to 10: 1.

According to example embodiments, the composite cured hard coat layer 110 may be thicker than the photocured hard coat layer 120. For example, the thickness of the composite hardened hard coat layer 110 and the photocured hard coat layer 120 may be 1.1: 1 to 8: 1. More preferably, it may be 2: 1 to 6: 1. The difference in thickness in the ratio range of the thickness is adjusted to an appropriate range to further improve curl suppression characteristics, shape restoring force, etc. of the hard coat film.

For example, the thickness of the composite curing hard coating layer 110 may be 5 to 100㎛. More preferably, it may be 10-50 micrometers. When the thickness is in the above range, it may have excellent hardness and maintain flexibility, so that curling may not occur substantially.

In addition, for example, the thickness of the photocurable hard coating layer 120 may be 1 to 20㎛. More preferably, it may be 2-10 micrometers. Within the thickness range, the composite hardened hard coat layer 110 and the photocured hard coat layer 120 satisfy an appropriate thickness ratio, thereby ensuring an effect of canceling warpage and shape restoring force by both hard coat layers. In some embodiments, since the hard coating film 10 has a high surface hardness and excellent flexibility, the hard coating film 10 may be preferably used as a window substrate on the outermost surface of the display panel because it is light and excellent in impact resistance compared to tempered glass.

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

The 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 device, an electroluminescent display device, a plasma display device, and a field emission display device.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims. 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.

Production Example

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. Thereafter, 0.1 mL of tetramethylammonium hydroxide (Aldrich) and 100 mL of tetrahydrofuran (Aldrich) were added to the mixture, followed by stirring at 25 ° C. for 36 hours. Thereafter, the layers were separated and the product layer was extracted with methylene chloride (Aldrich), the extract was removed with magnesium sulfate (Aldrich), and the solvent was dried in vacuo 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.

Examples 1 to 14, Comparative Examples 1 and 2

The epoxy siloxane resin, the crosslinking agent, the thermal initiator, the photoinitiator, and the solvent prepared in the preparation example were mixed at a weight ratio of the following Table 1 to the total weight of the composition to prepare a composition for forming a hard coat layer.

The hard coating layer-forming composition was applied on a cPI film (colorless polyimide) 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, a hard coating film having a composite hardened hard coating layer having a thickness of 30 μm was prepared by curing at 120 ° C. for 15 minutes.

Example 15 and Comparative Example 3

Each component was mixed according to the following Table 1 to prepare a hard coating layer-forming composition.

The composition for forming the hard coat layer was applied on the upper surface of the cPI film of 80 μm thickness by a Meyer bar method, and allowed to stand at 60 ° C. for 5 minutes.

UV irradiation was performed at 1 J / cm ² using a high pressure metal lamp, and then cured at 120 ° C. for 15 minutes to form a composite cured hard coating layer having a thickness of 20 μm.

The composition for forming a hard coat layer was applied on the bottom surface of the cPI film on which the composite cured hard coat layer was not formed by a Meyer bar method, and allowed to stand at 60 ° C. for 5 minutes. Thereafter, UV was irradiated at 1 J / cm ² using a high pressure metal lamp to form a photocurable hard coat layer having a thickness of 5 μm, thereby preparing hard coat films of Example 15 and Comparative Example 3.

division Epoxysiloxane resin Crosslinking agent Ten initiators Photoinitiator menstruum Other Kinds content Kinds content Kinds content Kinds content Example 1 35 A-1 10 B-1 One C-1 One 53 Example 2 35 A-1 10 B-1 5 C-1 One 49 Example 3 35 A-1 10 B-1 0.1 C-1 One 53.9 Example 4 35 A-1 10 B-1 0.2 C-1 One 53.8 Example 5 35 A-1 10 B-1 0.5 C-1 One 53.5 Example 6 35 A-1 10 B-1 10 C-1 One 44 Example 7 35 A-1 10 B-1 15 C-1 One 39 Example 8 35 A-1 10 B-1 20 C-1 One 34 Example 9 30 A-1 15 B-1 0.5 C-1 One 53.5 Example 10 15 A-1 10 B-1 One C-1 One 73 Example 11 20 A-1 10 B-1 One C-1 One 68 Example 12 50 A-1 10 B-1 One C-1 One 38 Example 13 70 A-1 10 B-1 One C-1 One 18 Example 14 80 A-1 10 B-1 One C-1 One 8 Example 15 30 A-1 15 B-2 One C-1 One 52 D One Comparative Example 1 35 A-2 10 B-1 One C-1 One 53 Comparative Example 2 35 A-1 10 - - C-1 One 54 Comparative Example 3 - - - - - C-2 One 59 E 40

(Daicel社, Celloxide 2021P)
A-2:

B-1:

B-2: 4-아세톡시페닐디메틸설포늄 헥사플루오로안티모네이트(Sanshin社, Si-60)
C-1: (4-메틸페닐)[4-(2-메틸프로필)페닐]아이오도늄 헥사플루오로포스페이트
C-2: 1-히드록시사이클로헥실페닐케톤
용매: 메틸에틸케톤(Aldrich社)
D: 불소폴리머(센트럴글라스社, cc-04)
E(광중합성 화합물): 펜타에리스리톨테트라아크릴레이트Epoxy siloxane resin: preparation example
A-1:

(Daicel, Celloxide 2021P)
A-2:

B-1:

B-2: 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate (Sanshin, Si-60)
C-1: (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate
C-2: 1-hydroxycyclohexylphenyl ketone
Solvent: Methyl ethyl ketone (Aldrich)
D: Fluoropolymer (Central Glass, cc-04)
E (photopolymerizable compound): pentaerythritol tetraacrylate

Examples 16-21

To prepare a hard coating film in the same manner as in Example 15, the thickness of the composite cured hard coating layer and the photocurable hard coating layer was changed according to Table 2.

division Thickness of Composite Curing Hard Coating Layer (㎛) Thickness of the photocured hard coating layer (㎛) Example 15 20 5 Example 16 5 5 Example 17 5.5 5 Example 18 10 5 Example 19 30 5 Example 20 40 5 Example 21 50 5

Experimental Example

Pencil hardness and curl inhibition properties were evaluated for the hard coat films of Examples and Comparative Examples.

1. Pencil hardness measurement

According to ASTM D3363, the pencil hardness on the surface of the composite hardened hard coat layer of the hard coat film was measured using a pencil by hardness (Mistubishi) at a load of 1 Kg using a pencil hardness tester (Gigi Engineering Co., Ltd.). The measured pencil hardness is shown in Table 3 below.

2. Curling amount measurement

After the hard coating film was cut into 10 cm X 10 cm, which became a square inclined at 45 ° with respect to the MD direction, the curl degree of each vertex was measured using a ruler after standing for 12 hours at a constant temperature and humidity of 25 ° C and 50%. The amount of curl measured is shown in Table 3 below.

division Pencil hardness Curl sheep Example 1 8H 0.2mm Example 2 8H 0.5mm Example 3 5H 3 mm Example 4 7H 2 mm Example 5 8H 0.1mm Example 6 8H 0.5mm Example 7 7H 2 mm Example 8 5H 3 mm Example 9 8H 1 mm Example 10 5H 3 mm Example 11 8H 0.5mm Example 12 8H 1 mm Example 13 6H 2 mm Example 14 5H 3 mm Example 15 8H 0.5mm Example 16 6H 1 mm Example 17 7H 0.5mm Example 18 8H 0.5mm Example 19 8H 0.5mm Example 20 8H 1 mm Example 21 8H 3 mm Comparative Example 1 4H 6 mm Comparative Example 2 4H 10 mm Comparative Example 3 5H 50mm or more

Referring to Table 3, the composition for forming a hard coat layer according to the embodiments of the present invention, it can be seen that to form a hard coat film significantly improved hardness and curl inhibition properties compared to the comparative examples.

In addition, after the composite cured hard coating layer is formed on one surface of the substrate according to the embodiments of the present invention, when the photocured hard coating layer is formed on the other surface, it can be seen that the hardness and curl suppression characteristics are further improved.

10: hard coating film
100: base material 110: composite curing hard coating layer
120: photocuring hard coating layer

Claims (18)

A composition for forming a hard coat layer comprising an epoxy siloxane resin, a crosslinking agent comprising a compound having an alicyclic epoxy group, 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. N is 1-4, R ⁵ is an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 7 to 15 carbon atoms which may be substituted with 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 1,
The epoxy siloxane resin has a weight average molecular weight of 1,000 to 20,000, the composition for forming a hard coating layer. The method according to claim 1,
Compound having an alicyclic epoxy group is represented by the following formula (1), a hard coating layer forming composition:
[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. Preparing a composition for forming a hard coating layer comprising an epoxy siloxane resin, a crosslinking agent comprising a compound having an alicyclic epoxy group, a thermal initiator comprising a compound represented by the following Formula 2, and a photoinitiator;
Applying the composition for forming a hard coat layer on a substrate;
Irradiating ultraviolet rays to the applied composition for forming a hard coat layer; And
A method of manufacturing a hard coating film, comprising: forming a complex hardened coating layer by thermosetting the composition for forming a UV-coated hard coating 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. N is 1-4, R ⁵ is an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 7 to 15 carbon atoms which may be substituted with 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 4,
The epoxy siloxane resin has a weight average molecular weight of 1,000 to 20,000, a method for producing a hard coat film. The method according to claim 4,
The compound having an alicyclic epoxy group is represented by the following formula (1), a method for producing a hard coat 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 4,
The thermosetting is carried out for 5 to 20 minutes at a temperature of 100 to 200 ℃, method of producing a hard coat film. The method according to claim 4,
The method of manufacturing a hard coat film further comprising the step of pretreatment by heating the composition for forming the hard coat layer before the ultraviolet irradiation. The method according to claim 8,
Wherein said pretreatment is carried out at a lower temperature than said thermosetting. The method according to claim 4,
Further applying the composition for forming a hard coat layer on a surface of the substrate on which the complex hard coat layer is not formed; And
UV curing the additionally applied composition for forming a hard coating layer to form a photocurable hard coating layer; further comprising, the method of manufacturing a hard coating film. The method according to claim 10,
Thickness ratio of the composite cured hard coating layer and the photocurable hard coating layer is 1.1: 1 to 8: 1, the method of producing a hard coat film. materials; And
A hard coat film comprising; a composite cured hard coat layer formed by complex curing a composition comprising a crosslinking agent comprising a compound having an epoxy siloxane resin and an alicyclic epoxy group on the substrate. The method according to claim 12,
The composite curing is a hard coating film, including a thermal initiator and a photoinitiator to cure. The method according to claim 13,
The thermal initiator is a hard coating film comprising a compound represented by the following formula (2):
[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. N is 1-4, R ⁵ is an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 7 to 15 carbon atoms which may be substituted with 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 12,
The compound having an alicyclic epoxy group is represented by the following formula 1, a 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 12,
And a photocurable hardcoat layer formed by photocuring the composition on a surface where the composite cured hardcoat layer of the substrate is not formed. The method according to claim 16,
The thickness ratio of the composite curing hard coating layer and the photocurable hard coating layer is 1.1: 1 to 8: 1, the hard coating film. The method according to claim 12,
The hard-coating film whose length of each side is 10 cm, and the amount of curl at each vertex of the square sample cut | disconnected so that it inclines at 45 degrees with respect to MD direction of each side film is 5 mm or less.

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