TWI670340B - Hard coating film alternative to tempered glass - Google Patents

Abstract

The present invention discloses a hard coating film that replaces strengthened glass. The hard coat film includes a hard coat layer having a thickness of 10 to 80 ㎛ and including a polysilsesquioxane compound, a multifunctional methacrylic oligomer, and a methacrylic monomer. So that the hard coat film can have excellent transparency and the same surface hardness (7H or higher pencil hardness) as glass, and is therefore suitable as a substitute for strengthened glass.

Description

Replaces hard-coated film for tempered glass

The present invention relates to a hard coating film that replaces strengthened glass and has excellent surface hardness.

Due to the recent trend of thin, light and short mobile phones, an attempt has been made to remove the plastic plate arranged on the outermost layer, and the hard coat film disposed under the panel and the outermost layer of the polarizing film is exposed. However, because it has a roughness smaller than that of a plastic plate, the hard coating film cannot be practically used.

Recently, due to rolling scratches when manufacturing a polarizing film, many defects are generated in a polarizing plate, resulting in an increase in the defect rate of a panel. Hard coating films are used to solve these problems. However, despite the use of a hard coat film, defects due to scratches still exist. Like the outermost polarizing film described above, a hard coat film is also applied to the lower polarizing film to prevent scratches from being generated in the lower polarizing film during the panel manufacturing process.

In the related art, a hard coating film having a pencil hardness of about 3H has been commercialized. When the same hard coating composition used to make the related art hard coating film is applied to glass, the glass has a pencil hardness of about 7H to 9H. However, when the related art hard coating composition is applied to a plastic substrate, the plastic substrate is easily deformed by external pressure due to the small roughness. Since the hard coat film has a pencil hardness of only 3H, the hard coat layer formed on the plastic substrate also deforms with the plastic substrate.

In order to increase the pencil hardness of the hard coating layer in a plastic film, attempts have been made to form a hard coating layer that has a thickness of about 20 ㎛ or more. However, although the hard coat film obtained by the above method has improved hardness, it has weak impact resistance, which causes the hard coat film to crack or break even with a small impact, and the hard coat film is produced during the process. Will cause curling.

In order to solve these problems, a hard coat optical film including a rigid layer between a substrate and a hard coat layer is disclosed in Korean Patent Publication No. 2008-55698. However, although the above-mentioned application has excellent impact resistance and hardness, since a separation layer is present between the substrate and the hard coat layer, the workability, operability, and the like are reduced.

Therefore, the present invention is to solve the above-mentioned problems in the related art. One aspect of the present invention is to provide a hard coating film instead of strengthened glass, which can have excellent impact resistance and hardness, and excellent processability and operation No need to use separate functional layers.

Further, another aspect of the present invention is to provide a hard coat film instead of a strengthened glass, which can exert its effect when applied to the outermost layer of a display device.

In order to achieve this, a hard coat film is provided here instead of strengthened glass. The hard coat film includes a hard coat layer having a thickness of 10 to 80 ㎛ and containing a polysilsesquioxane compound, A multifunctional methacrylic oligomer and a methacrylic monomer.

According to another aspect of the present invention, there is provided a hard coat film instead of strengthened glass, the hard coat film includes a hard coat layer, the hard coat layer has a thickness of 10 to 80 ㎛ and includes a poly-half Siloxane compounds, monofluoromethacrylic oligomers and monomethacrylic monomers.

The thickness of the hard coating layer is 10 to 50 ㎛.

The polysilsesquioxane compound can be represented by the following Chemical Formula 1 or Chemical Formula 2:

[Chemical Formula 1]

[Chemical Formula 2]

Wherein, in Chemical Formula 1 or 2, R represents a C2-C80 aliphatic hydrocarbon or aromatic hydrocarbon, and contains 2 to 20 methacrylic groups, and the methacrylic group may or may not contain a hetero atom.

The hard coat film may further include a low refractive layer on the hard coat layer.

The hard coating film may be provided as an alternative to tempered glass for protecting display devices, or an alternative to tempered glass integrated in a polarizing plate.

The hard coating film may be provided on a display device selected from the group consisting of a mobile phone, a smart window, and a touch screen panel.

According to another aspect of the present invention, a polarizing plate having the hard coat film is provided here.

The present invention relates to a hard coating film that replaces strengthened glass and has excellent surface hardness.

Hereinafter, the present invention will be described in detail.

The hard coating film of the substitute tempered glass of the present invention includes a hard coating layer having a thickness of 10 to 80 ㎛ and including a polysilsesquioxane compound, a polyfunctional methacrylic oligomer, and Monomethacrylic monomer.

In addition, the hard coat film of the substitute tempered glass of the present invention includes a hard coat layer having a thickness of 10 to 80 ㎛ and including a polysilsesquioxane compound and a fluoromethacrylic oligomer物 和 monomethacrylic monomer.

The thickness of the hard coat layer is preferably 10 to 50 ㎛. The thickness of the hard coating layer is less than 10 裂缝 due to cracks and scratches caused by external impact, and it may not provide sufficient hardness. The thickness of the hard coating layer is greater than 80 ㎛, which may not provide sufficient flexibility and flexibility, resulting in deterioration of processability and operability.

The hard coat film of the present invention has excellent transparency and the same surface hardness as glass (pencil hardness of 7H or higher), and thus can be used as a substitute for strengthened glass. Further, the additional physical properties of the hard coat film vary depending on the kind of the methacrylic oligomer contained in the hard coat film.

The composition of the hard coat layer of the hard coat film according to the present invention will be described in detail below.

The included polysilsesquioxane compound is used to provide improved hardness and elasticity of the hard coat film. The polysilsesquioxane compound can be represented by the following chemical formula 1 or 2. In the structure of the polysilsesquioxane compound, an organic component is connected to a ceramic structure composed of silicon and oxygen. The organic component may be selected from organic molecules such as acrylate, aryl, alkyl, amino, ester, epoxy, vinyl, and fluorocarbon. Preferably, an acrylate group is used, which is the same as the polymerizable group of the aforementioned multifunctional methacrylic oligomer and methacrylic monomer.

[Chemical Formula 1]

[Chemical Formula 2]

Here, in Chemical Formula 1 or 2, R represents a C2-C80 aliphatic hydrocarbon or aromatic hydrocarbon, and contains 2 to 20 methacrylic groups, and the methacrylic group may or may not contain a hetero atom.

R preferably includes 5 to 15 methacrylic groups. If the methacrylic group is included in the above range, stains can be prevented from being generated in an environment of high temperature, high humidity, and the like.

The polysilsesquioxane represented by the above Chemical Formula 1 or 2 can be prepared by using, for example, a monomer having three hydrolyzable reactive groups, trichlorosilane, or trialkoxysilane. In addition to this, polysilsesquioxanes are known to be prepared from the use of silanetriols produced in intermediate reactions. Here, when the above-mentioned compound is used to prepare a polysilsesquioxane, heat polycondensation polymerization can also be used. The product suitable for the polysilsesquioxane represented by the above chemical formula 1 or 2 can be MA0736 (cage type, hybrid plastic company) or Vitolane® SF1000MA (step type, TWI company).

The content of the polysilsesquioxane compound is preferably from 0.1 to 50% by weight, more preferably from 5 to 20% by weight, based on 100% by weight of the entire composition for forming a hard coat layer. If the content of the polysilsesquioxane compound is less than 0.1% by weight, a hard coat film having sufficient hardness is difficult to manufacture. If the content of the polysilsesquioxane compound is higher than 50% by weight, this content is beneficial to hardness and curl, but may cause cracks in the hard coating in the subsequent process.

Regarding the polyfunctional methacrylic oligomer, any of them can be used in the art without limitation. For the improvement of hardness, at least one selected from the multifunctional methacrylic oligomer (A) (represented by the following Chemical Formula 3) may be used:

[Chemical Formula 3]

In Chemical Formula 3, where X represents a C2-C80 aliphatic or aromatic hydrocarbon, containing 2 to 20 methacrylic functional groups, with or without a heteroatom; R represents a linear, branched, or cyclic C3-C50 aliphatic hydrocarbon Or aromatic hydrocarbon, with or without a heteroatom; m represents an integer from 1 to 10.

The polyfunctional methacrylic oligomer represented by the above Chemical Formula 3 can be prepared by reacting a methacrylic monomer having a hydroxyl group with a compound having 2 or more isocyanate groups in its molecule.

Specific examples of compounds having two or more isocyanates based on their molecules may include at least one selected from the group consisting of 4,4'-dicyclohexyl diisocyanate, hexamethylene diisocyanate trimer, 1,4-diiso Butane cyanate, 1,6-diisocyanate, 1,8-diisocyanate octane, 1,12-diisocyanate dodecane, 1,5-diisocyanato-2-methylpentane, Trimethyl-1,6-diisocyanate hexane, 1,3-bis (isocyanatomethyl) cyclohexane, trans-1,4-cyclohexene diisocyanate, 4,4'- Methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylyl-1,4-diisocyanate, tetramethyl- 1,3-diisocyanate, 1-chloromethyl-1,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenyl isocyanate), 4,4'-oxybis ( Phenyl isocyanate), trifunctional isocyanate derived from hexamethylene diisocyanate, toluene diisocyanate of trimethylolpropane adduct, propylene ethyl isocyanate, and methyl ethyl isocyanate .

In addition, specific examples of the methacrylic monomer having a hydroxyl group may include at least one (meth) acrylate selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate Ester, 4-hydroxybutyl (meth) acrylate, caprolactone ring-opening hydroxy (meth) acrylate, pentaerythritol tri / tetra (meth) acrylate mixture, and dipentaerythritol penta / hexa (meth) acrylic acid A group of ester mixtures.

The content of the functional methacrylic oligomer is preferably included in the range of 0.1 to 65% by weight based on 100% by weight of the entire composition for forming a hard coat layer. If the content of the functional methacrylic oligomer is less than 0.1% by weight, the hard coat film may not have sufficient hardness. If the content of the functional methacrylic oligomer is more than 65% by weight, compatibility with the coating liquid may be deteriorated, resulting in a decrease in processability.

The addition of a fluoromethacrylic oligomer ensures excellent stain resistance and fingerprint resistance, which can be polymerized by a compound having 3 or more isocyanates based on its molecule, a fluoroalcohol represented by Chemical Formula 4 below, and 2 -Hydroxyethylmethacrylic acid to prepare:

[Chemical Formula 4]

In Chemical Formula 4, wherein Y represents H or F; n and m each represent an integer from 0 to 200.

Specific examples of compounds having 3 or more isocyanates based on the compounds in their molecules may include a compound selected from isocyanurate-type trifunctional isocyanates derived from 1,4-diisocyanate, from 1,6 -Diisocyanate-derived isocyanurate-type trifunctional isocyanate, isocyanurate-type trifunctional isocyanate derived from 1,8-diisocyanate octane, and 1,12-diisocyanate dodecane Isocyanurate type trifunctional isocyanate, Isocyanurate type trifunctional isocyanate derived from 1,5-diisocyanato-2-methylpentane, Trimethyl-1,6-diiso Isocyanurate-type trifunctional isocyanate derived from hexane cyanate, Isocyanurate-type trifunctional isocyanate derived from 1,3-bis (isocyanatomethyl) cyclohexane, trans-1 Isocyanurate-type trifunctional isocyanate derived from 1,4-cyclohexene diisocyanate, Isocyanurate-type trifunctional isocyanate derived from 4,4-methylenebis (cyclohexyl isocyanate), Isophor Keto diisocyanate-derived isocyanurate-type trifunctional isocyanate, isocyanate derived from toluene-2,4-diisocyanate Ester type trifunctional isocyanate, isocyanurate type trifunctional isocyanate derived from toluene-2,6-diisocyanate, isocyanurate type trifunctional isocyanate derived from xylyl-1,4-diisocyanate , Isocyanurate-type trifunctional isocyanate derived from tetramethyl-1,3-diisocyanate, isocyanurate-type trifunctional isocyanate derived from 1-chloromethyl-1,4-diisocyanate, from 4,4'-Methylenebis (2,6-dimethylphenyl isocyanate) -derived isocyanurate-type trifunctional isocyanate, derived from 4,4'-oxybis (phenyl isocyanate) Isocyanurate type trifunctional isocyanate, trifunctional isocyanate derived from hexamethylene diisocyanate, toluene diisocyanate of trimethylolpropane adduct, and 1,6-diisocyanate trifunctional biuret A group of compounds of type I.

Preferably, a trifunctional isocyanate selected from hexamethylene diisocyanate, toluene diisocyanate derived from trimethylolpropane adduct, and isocyanurate type trifunctional derived from isophorone diisocyanate. Isocyanates, and hexamethylene diisocyanate biuret-type isocyanates can be used as compounds having 3 or more isocyanates based on their molecules.

Specific examples of the fluoroalcohol represented by the above Chemical Formula 4 may include at least one compound selected from the group consisting of 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 2,3, 3,3-pentafluoro-1-propanol, 2,2,3,4,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,4-heptafluoro-1 -Butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 2,2,3,3,4,4,5,5,5-nonafluoro-1 -A group consisting of amyl alcohol and 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecfluoro-1-octanol.

The reaction of a fluoroalcohol having 2 or more isocyanates based on a compound in its molecule and represented by Chemical Formula 4 above with 2-hydroxyethyl (meth) acrylic acid is preferably performed in the presence of a solvent. The solvent is not particularly limited, but for compatibility reasons, it is preferable to use an ether-based solvent, a ketone-based solvent, or the like. As for the solvent, it is more preferable that the fluorine-based solvent may be mixed and used. In particular, hydrofluorocarbons and hydrofluoroethers can be used. Regarding commercial products, at least one selected from Vertrel XF (CF ₃ CHFCHFCF ₂ CF ₃ ) produced by DuPont, Zeorora H (Heptafluorocyclopentane) produced by Nippon Zeon, and HFE produced by 3M A group consisting of -7100 (C ₄ F ₉ OCH ₃ ) and 7200 (C4F9OC2H5) can be used.

Preferably, the fluoromethacrylic oligomer may include at least one compound selected from the following Chemical Formula 5 to Chemical Formula 12:

[Chemical Formula 5]

[Chemical Formula 6]

[Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 12]

In Chemical Formula 5 to Chemical Formula 12, wherein X represents a hydrogen atom or a C1-C10 alkyl group; Rf is represented by Chemical Formula 13, [Chemical Formula 13]

In Chemical Formula 13, wherein Y each independently represents H or F; each n and m represents an integer from 0 to 200.

The content of the fluoro (meth) acrylic acid is preferably contained in the range of 0.1 to 65% by weight, and more preferably 5 to 40% by weight based on 100% by weight of the entire composition for forming a hard coat layer. Less than 0.1% by weight of fluoro (meth) acrylic acid may not exhibit the effects of preventing contamination and eliminating fingerprints. A fluorinated (meth) acrylic acid in excess of 65% by weight may lead to poor compatibility and therefore reduce processability.

A (meth) acrylic monomer is included to improve the hardness and curl characteristics of the cured layer.

Regarding the (meth) acrylic monomer, any one which can be used in the art can be used without limitation. Preferably, the (meth) acrylic monomer may include at least one member selected from the group consisting of pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythr , Trimethylolpropane tri (meth) acrylic acid, glycerol tri (meth) acrylic acid, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylic acid, ethylene glycol di (meth) acrylic acid , Propylene glycol (meth) acrylic acid, 1,3-butanediol di (meth) acrylic acid, 1,4-butanediol di (meth) acrylic acid, 1,6-hexanediol di (meth) acrylic acid, Neopentyl glycol di (meth) acrylic acid, diethylene glycol di (meth) acrylic acid, triethylene glycol di (meth) acrylic acid, dipropylene glycol di (meth) acrylic acid, bis (2-hydroxyethyl) Isocyanuric acid di (meth) acrylic acid, hydroxyethyl (meth) acrylic acid, hydroxypropyl (meth) acrylic acid, hydroxybutyl (meth) acrylic acid, isooctyl (meth) acrylic acid, isodecyl (Meth) acrylic, stearic (meth) acrylic, tetrahydro (meth) acrylic, phenoxy (meth) acrylic , And groups isobornyl (meth) acrylate thereof.

The amount of the methacrylic monomer used is not limited, but the content of the methacrylic monomer is preferably contained in a range of 5 to 70% by weight based on 100% by weight of the entire composition for forming a hard coat layer, more preferably It is 10 to 40 weight percent. If the content of the methacrylic monomer is less than 5 weight percent or more than 70 weight percent, the effect of improving the hardness may not be effectively exhibited.

Further, in the hard coat film of the present invention, the composition for forming a hard coat layer is in addition to a polysilsesquioxane compound, a polyfunctional methacrylic oligomer or a fluoromethacrylic oligomer, and formazan In addition to the acrylic monomer, it is also prepared by including a photoinitiator and a solvent. The photoinitiator and solvent can be removed during a curing film formation process after the hard coat layer is formed. In particular, the solvent is preferably used when the composition prepared for the hard coating layer is diluted.

Regarding the photoinitiator, any one that can be used in the art can be used without limitation. As for the photoinitiator, at least one selected from the group consisting of a hydroxyketone-based photoinitiator, an aminoketone-based photopolymerization initiator, and a recapture hydrogen-type photoinitiator can be used.

Specific examples of the photoinitiator may be at least one selected from 2-methyl-1-4- (methylthio) phenyl] -2-morpholinylpropane-1, benzophenone benzyldimethylketal , 2-hydroxy-2-methyl-1-phenylpropane-1-one, 4-hydroxycyclohexylphenyl ketone, dimethoxy-2-phenylacetophenone, anthraquinone, hydrazone, triphenylamine, Carbazole, 3-methylacetophenone, 4-chloroacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenyl ketone And benzophenone.

The content of the photoinitiator is preferably included in the range of 0.1 to 10% by weight based on 100% by weight of the entire composition for forming a hard coat layer. If the content of the photoinitiator is less than 0.1% by weight, the curing speed of the composition for forming a hard coat layer may be reduced. If the content of the photoinitiator is higher than 10% by weight, cracks may be generated in the cured hard coating layer due to excessive curing.

As for the solvent, any known solvent, which can be used in the art for forming a hard coating composition, can be used without limitation.

Specific examples of the solvent may include alcohols (methanol, ethanol, isopropanol, butanol, methyl cellosolve, ethyl cellosolve, etc.), ketones (methylethylketone, methylbutylketone, methyl alcohol Isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone, etc.), hexanes (hexane, heptane, octane, etc.) and benzenes (benzene, toluene, xylene, etc.).

The solvent content may be added as 0.1 to 90% by weight based on 100% by weight of the entire composition for forming a hard coat layer. If the content of the solvent is less than 0.1% by weight, the viscosity of the composition may increase, resulting in deterioration of processability. If the content of the solvent is higher than 90% by weight, the curing process may be very time-consuming and the economic feasibility may deteriorate.

The composition for forming a hard coat layer according to the present invention may further include one or two or more selected from antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, surfactants, and The group consisting of stains is generally used in the art, as long as the effect of the present invention is not reduced.

According to the present invention, the composition for forming a hard coat layer is coated and cured on one or two surfaces of a transparent substrate, thereby producing a hard coat film having a hard coat layer formed on the transparent substrate.

As for the transparent substrate, any plastic film having transparency can be used. Specific examples of the transparent substrate may optionally include monomer units, including cyclic olefins, such as cycloolefin derivatives of norbornene ring or polycyclic norbornene-based monomers, selected from the group consisting of diethyl cellulose and triethyl cellulose Cellulose, cellulose acetate butyrate, cellulose isobutyrate, propyl cellulose, butyl cellulose, cellulose of ethyl acetate and propyl cellulose, ethylene-vinyl acetate copolymer, polyester , Polystyrene, polyimide, polyetherimide, polyacrylic acid, polyimide, polyetherimide, polyimide, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene Vinyl chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether fluorene, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, poly Naphthalate, polycarbonate, polyurethane and epoxy resin. Unstretched or unidirectional or biaxially stretched films can also be used.

Among these, unidirectional or biaxially stretched polyester films and rings having excellent transparency and heat resistance have excellent transparency and heat resistance, and can satisfy larger-sized olefin-based derivative films, or have transparency and A cellulose triacetate film having no optical anisotropy can be suitably used.

The thickness of the transparent substrate is preferably 8 to 1000 ㎛, and more preferably 40 to 100 ㎛.

The coating of the composition for forming a hard coat layer may be performed in an appropriate manner, such as die coating, air knife coating, reverse roll coating, spray coating, doctor blade coating, cast coating, gravure coating, and spin coating. cloth.

The composition for forming a hard coat layer is applied and then dried at a temperature of 30 to 150 ° C. for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes. Thereafter, the composition is cured by irradiation with ultraviolet light. The amount of ultraviolet light irradiation is about 0.01 J / cm ² to 10 J / cm ² , preferably 0.1 J / cm ² to 2 J / cm ² .

In addition, according to the present invention, after the hard coat layer is formed as described above, the composition for forming a low refractive layer is coated and cured on the hard coat layer to form a low refractive layer on the hard coat layer.

In the present invention, the low-refractive layer means that a reflective layer has a refractive index lower than the cured refractive index of the hard coat layer. The curing refractive index of the hard coat layer at 25 ° C is generally about 1.50 to 1.65, and the low refractive index layer is 1.20 to 1.49, preferably 1.30 to 1.44.

When the low-refractive layer is formed, a substrate having a high refractive index, such as polyethylene terephthalate, may cause interference defects due to a refractive index difference between the hard coat layer and the transparent substrate. To avoid the above-mentioned flaws, the refractive index of the hard coating layer can be increased. The refractive index of the hard coat layer can be increased by methods commonly used in the art, such as using an acrylate oligomer having a high refractive index or adding inorganic particles having a high refractive index.

As long as the refractive index range is satisfied, the low-refractive layer may be formed using any composition for forming a low-refractive layer, and the composition is generally used in the art. For example, a composition containing a fluorocopolymer, particles having pores, an initiator, and a solvent may be used.

According to the present invention, regarding a hard coat film having a low refractive layer on a hard coat layer containing a polyfunctional methacrylic oligomer, the hard coat has a pencil hardness of 7H or higher, and its reflectance is 380 to 780 1% or less in the nm wavelength range.

Further, regarding the hard coat film containing a fluoromethacrylic oligomer according to the present invention, the hard coat has a water-resistant contact angle (at 25 ° C) of 90 to 130 degrees, and its oil-resistant contact angle (at 25 ° C) ) Is 60 to 90 degrees, so the hard coat film has excellent stain resistance.

The present invention provides a polarizing plate with excellent physical properties, which is manufactured by laminating and combining the aforementioned hard coat film on at least one surface of a polarizing plate.

In addition, the present invention provides a display device using the aforementioned hard coat film. The hard coating film may be simply used as a substitute for strengthened glass, and more specifically, it may be used as a substitute for strengthened glass to protect a display device, or reinforced glass integrated into a polarizing plate.

For example, an image display device having a polarizing plate and the hard coat film of the present invention can be provided. Further, an image display device to which a hard coat film of the present invention is attached to its window may be provided.

The hard coat film of the present invention can be preferably used for liquid crystal displays of different driving types, such as reflective, transmissive, and transflective liquid crystal displays, and TN, STN, OCB, HAN, VA, and IPS liquid crystal displays. Further, the hard coat film of the present invention can be preferably used in different forms of display devices, such as plasma displays, field emission displays, organic EL displays, inorganic EL displays, and electronic paper.

In the following, although preferred embodiments are provided to help understand the present invention, the following embodiments are provided only to illustrate the present invention. Obviously, those skilled in the art can understand that various changes and modifications can be made within the scope and technical field of the present invention, and these changes and modifications are included in the appended claims.

[Hardcoat film containing polyfunctional (meth) acrylic oligomer]

Synthesis example: polyfunctional methacrylic oligomer

Synthesis Example 1-1: Oligomer A

As 4,4-dicyclohexyl diisocyanate (H12-MDI, Bayer) having two or more isocyanates based on compounds in its molecule, pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol / hexaacrylate as methacrylic acid monomer containing hydroxyl Mixture (KAYARAD, Nippon Kayaku) 906.27 g, dibutyltin dilaurate (FASCAT 4202, Akema) as a reaction catalyst, and methoxyhydroquinone (HQMME, Oriental) as a polymerization inhibitor 0.5 g was introduced at room temperature, and then stirred when the reaction temperature increased to 90 ° C. The reaction can be allowed to proceed at 90 ° C for 12 hours. When the characteristic peak of the ultraviolet spectrum is completely eliminated at 2260㎝-1, the reaction is terminated. As a result, a polyfunctional methacrylic acid oligomer containing 4,4'-dicyclohexyl diisocyanate was synthesized.

Synthesis example 1-2: oligomer B

75 g as a trimer (N3300, Bayer) derived from hexamethylene diisocyanate with two or more isocyanate-based organic compounds in the molecule, dipentaerythritol as a methacrylic acid monomer containing a hydroxyl group Penta / hexa (meth) acrylate mixture (KAYARAD, Nippon Kayaku) 425 g, dibutyltin dilaurate (FASCAT 4202, Akema) as a reaction catalyst, and a methoxy group as a polymerization inhibitor 0.25 g of hydroquinone (HQMME, Oriental Co., Ltd.) was introduced at room temperature, and then stirred when the reaction temperature increased to 110 ° C. The reaction can be allowed to proceed at 110 ° C for 10 hours. When the characteristic peak of the ultraviolet spectrum is completely eliminated at 2260㎝-1, the reaction is terminated. As a result, a polyfunctional methacrylic acid oligomer containing a trimer derived from hexamethylene diisocyanate was synthesized.

Example 1 and Comparative Examples 1 to 3: Compositions for forming a hard coat layer

The composition for forming a hard coat layer is prepared from the composition shown in Table 1 below. [Table 1]

Example 2: Hard coating film

Each of the compositions for forming a hard coat layer prepared in Example 1 and Comparative Examples 1 to 3 was stirred for 1 hour, and then a Meyer bar (a gravure coater) was used and dried at 70 ° C. 1 Minutes, coated on a transparent substrate film (80 ㎛, cellulose triacetate) to the thickness of Table 2. Thereafter, the coating was cured at 500 mJ / cm ² to form a hard coating.

A composition for forming a low-refractive layer, wherein an anti-reflection coating liquid (MB-1030SIC, curing refractive index: 1.36, Catalyst Chemical Co.) accounts for 95% by weight and vinyl methyl diacetate accounts for 5% by weight The methoxysilane was mixed, and was coated with a thickness of 0.1 至 to the prepared hard coat layer using a Mayer rod, and then dried at 70 ° C for 1 minute and cured at 1 mJ / cm ² , so the production included low refractive index. Layer (cured refractive index: 1.36). [Table 2]

Experimental example 1

The physical quality of Example 2 and Comparative Examples 4 to 6 were measured as follows, and the results are shown in Table 3 below.

1-1. Total light transmittance

When the cellulose triacetate surface is facing the light source (D65), the total light transmittance is measured by using a spectrophotometer (HZ-1, manufactured by Sga Corporation, Japan).

1-2. Pencil hardness

The surface of the low-refractive layer of the hard-coating film including the hard-coat layer and the low-refractive layer was measured for pencil hardness using a pencil hardness tester (PHT, manufactured by SukBo Science Co., Ltd., Korea) under a load of 500 g. Manufacturing pencil. Each pencil hardness measurement was performed 5 times. The number of defective scratches is determined to be two or more, and the pencil hardness level is marked based on the pencil used before the defect occurred. [Evaluation] No scratch: OK One scratch: OK Two or more scratches: NG

1-3. Scratch resistance

The surface of the low refractive layer of the hard coating film including the hard coating layer and the low refractive layer was tested for scratch resistance by using a steel wool tester (WT-LCM100, manufactured by Protec Corporation). The steel wool was moved back and forth 10 times under a load of 1kg / (2cm × 2cm), using # 0000 steel wool. [Evaluation] A: No scratches A ': 1 to 10 scratches B: 11 to 20 scratches C: 21 to 30 scratches D: 31 or more scratches

1-4. Adhesion

Eleven vertical and horizontal straight lines are each drawn on a surface spaced 1 mm apart, the surface being formed by applying a composition for forming a refractive layer on a hard coat layer, thereby creating 100 squares. Next, a peeling test was performed three times by using a tape (CT-24, manufactured by Nichiban). Test 100 squares 3 times and record the average. The adhesion record is as follows. Adhesion = n / 100 n: The number of unpeeled in all squares 100: The number of all squares Therefore, when no square is peeled off, 100/100 is recorded.

1-5. Reflectivity

The reflectance of the hard coat film was measured using an ultraviolet spectrometer (SHIMADZU, Japan). The measurement range is visible light within 380 ~ 780nm. The minimum reflectance (%) of the hard coat film is obtained from the reflectance spectrum. [table 3]

From Table 3 above, it can be confirmed that Examples 2-1 to 2-17 of the hard coating film according to the present invention have excellent pencil hardness, scratch resistance, and adhesion, and also have excellent properties compared to Comparative Examples 4 to 6. Low reflectivity.

[Hard coat film containing fluoromethacrylic oligomer]

Synthesis example: fluoromethacrylic oligomer

Synthesis example 2-1: oligomer A

20 weight percent of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 24 weight percent Trifunctional isocyanate derived from isophorone diisocyanate (Degussa), 6 weight percent 2-hydroxyethyl acrylate, 20 weight percent propylene glycol monomethyl ether (Aldrich), 30 weight percent sevoflurane Pentane (Aldrich) and 0.1% by weight of dibutyltin dilaurate were added to the reactor, and then the temperature of the reactor was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak of the infrared spectrum was completely eliminated at 2260 ㎝ ^-1 , the reaction was terminated, thereby obtaining a compound having 50% by weight of solids.

Synthesis Example 2-2: Oligomer B

10 weight percent of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 22 weight percent Trifunctional isocyanate derived from isophorone diisocyanate (Degussa), 18% by weight 2-hydroxyethyl acrylate, 20% by weight propylene glycol monomethyl ether (Aldrich), 30% by weight sevoflurane Pentane (Aldrich) and 0.1% by weight of dibutyltin dilaurate were added to the reactor, and then the temperature of the reactor was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak of the infrared spectrum was completely eliminated at 2260 ㎝ ^-1 , the reaction was terminated, thereby obtaining a compound having 50% by weight of solids.

Synthesis example 2-3: oligomer C

20 weight percent of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 24 weight percent Trifunctional isocyanate derived from hexamethylene diisocyanate (Basf), 6 weight percent 2-hydroxyethyl acrylate, 20 weight percent propylene glycol monomethyl ether (Aldrich), 30 weight percent sevoflurane Pentane (Aldrich) and 0.1% by weight of dibutyltin dilaurate were added to the reactor, and then the temperature of the reactor was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak of the infrared spectrum was completely eliminated at 2260 ㎝ ^-1 , the reaction was terminated, thereby obtaining a compound having 50% by weight of solids.

Synthesis example 2-4: oligomer D

13 weight percent of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 22 weight percent Trifunctional isocyanate derived from hexamethylene diisocyanate (Basf), 15% by weight 2-hydroxyethyl acrylate, 20% by weight propylene glycol monomethyl ether (Aldrich), 30% by weight sevoflurane Pentane and 0.1% by weight of dibutyltin dilaurate were added to the reactor, and then the temperature of the reactor was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak of the infrared spectrum was completely eliminated at 2260 ㎝ ^-1 , the reaction was terminated, thereby obtaining a compound having 50% by weight of solids.

Synthesis example 2-5: oligomer E

20 weight percent of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 18 weight percent Trimethylolpropane adduct toluene diisocyanate (AEKYUNG Chemical Co.), 6 weight percent 2-hydroxyethyl acrylate, 20 weight percent propylene glycol monomethyl ether (Aldrich), 30 weight percent heptafluoro Cyclopentane and 0.1% by weight of dibutyltin dilaurate were added to the reactor, and then the temperature of the reactor was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak of the infrared spectrum was completely eliminated at 2260 ㎝ ^-1 , the reaction was terminated, thereby obtaining a compound having 50% by weight of solids.

Synthesis example 2-6: oligomer F

15 weight percent of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 20 weight percent Trimethylolpropane adduct toluene diisocyanate (AEKYUNG Chemical Co.), 15% by weight 2-hydroxyethyl acrylate, 20% by weight propylene glycol monomethyl ether (Aldrich), 30% by weight heptafluoro Cyclopentane and 0.1% by weight of dibutyltin dilaurate were added to the reactor, and then the temperature of the reactor was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak of the infrared spectrum was completely eliminated at 2260 ㎝ ^-1 , the reaction was terminated, thereby obtaining a compound having 50% by weight of solids.

Synthesis example 2-7: oligomer G

20 weight percent of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 23 weight percent Hexamethylene diisocyanate biuret-type isocyanate (Basf), 7 weight percent hydroxyethyl acrylate, 20 weight percent propylene glycol monomethyl ether (Aldrich), 30 weight percent heptafluorocyclopentane, and 0.1 A weight percent of dibutyltin dilaurate was added to the reactor, and then the temperature of the reactor was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak of the infrared spectrum was completely eliminated at 2260 ㎝ ^-1 , the reaction was terminated, thereby obtaining a compound having 50% by weight of solids.

Synthesis Example 2-8: Oligomer H

12 weight percent of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), 23 weight percent Hexamethylene diisocyanate biuret-type isocyanate (Basf), 15% by weight hydroxyethyl acrylate, 20% by weight propylene glycol monomethyl ether (Aldrich), 30% by weight heptafluorocyclopentane, and 0.1 A weight percent of dibutyltin dilaurate was added to the reactor, and then the temperature of the reactor was raised to 50 ° C, followed by stirring for 2 hours. When the characteristic peak of the infrared spectrum was completely eliminated at 2260 ㎝ ^-1 , the reaction was terminated, thereby obtaining a compound having 50% by weight of solids.

Example 3 and Comparative Examples 7 to 9: Composition for forming a hard coat layer

The composition for forming a hard coat layer is prepared by using the composition shown in Table 4 below. [Table 4]

Example 4: Hard coating film

The hard coat layer was prepared in each of the compositions for forming a hard coat layer in Example 3 and Comparative Examples 7 to 9, and after stirring for 1 hour, a Meyer bar (a gravure coater) was used, and the temperature was 70 ° C. Dry for 1 minute and apply on a transparent substrate film (80㎛, cellulose triacetate) to the thickness of Table 5. Thereafter, the coating was cured at 500 mJ / cm ² to form a hard coating, resulting in the production of a hard coating film including the hard coating. [table 5]

Experimental example 2

The physical quality of Example 4 and Comparative Examples 10 to 12 were measured as follows, and the results are shown in Table 6 below.

2-1. Total light transmittance

When the cellulose triacetate surface is facing the light source (D65), the total light transmittance is measured by using a spectrophotometer (HZ-1, manufactured by Sga Corporation, Japan).

2-2. Pencil hardness

The surface of the low-refractive layer of the hard-coating film including the hard-coat layer and the low-refractive layer was measured for pencil hardness using a pencil hardness tester (PHT, manufactured by SukBo Science Co., Ltd., Korea) under a load of 500 g. Manufacturing pencil. Each pencil hardness measurement was performed 5 times. The number of defective scratches is determined to be two or more, and the pencil hardness level is marked based on the pencil used before the defect occurred. [Evaluation] No scratch: OK One scratch: OK Two or more scratches: NG

2-3. Scratch resistance

The scratch resistance was tested by using a steel wool tester (WT-LCM100, manufactured by Protec), in which the steel wool was moved back and forth 10 times under a load of 1 kg / (2cm × 2cm). For steel wool, use # 0000. [Evaluation] A: No scratches A ': 1 to 10 scratches B: 11 to 20 scratches C: 21 to 30 scratches D: 31 or more scratches

2-4. Water-resistant contact angle

Water droplets were dropped on the surface of the film at room temperature (25 ° C). After 1 minute, a contact angle measuring instrument (CAM100, manufactured by KSV) was used to measure the contact angle with respect to water droplets. This contact angle value is obtained by measuring the left and right contact angles with respect to a water droplet 5 times and taking an average measurement value.

2-5. Oil-resistant contact angle

Oleic acid droplets were dropped on the membrane surface at room temperature (25 ° C). After 1 minute, a contact angle measuring instrument (CAM100, manufactured by KSV) was used to measure the contact angle with respect to oleic acid. This contact angle value is obtained by measuring the left and right contact angles with respect to the oleic acid solution five times and taking an average measurement value.

2-6. Fingerprint removal characteristics

The fingerprint smears on the film-coated surface were cleaned with clean paper (ULTIMA II, Hansong) by 10 experimenters 10 times, and then the fingerprint removal characteristics were evaluated by the naked eye. [Evaluation] A: No stain remains. B: Some stains remain. C: Many stains remain. [TABLE 6]

From Table 6 above, it can be confirmed that Examples 4-1 to 4-16 of the hard coating film according to the present invention have excellent pencil hardness, scratch resistance, and fingerprint removal characteristics. Compared with Comparative Examples 10 to 12, they are also generally excellent. Water-resistant contact angle and oil-resistant contact angle. Here, the water-resistant contact angle and the oil-resistant contact angle can indicate the degree of stain resistance.

As described above, the hard coat film according to the present invention has the advantages of excellent transparency and the same surface hardness (pencil hardness of 7H or higher) as that of glass.

In particular, a hard coat film containing a fluorinated methacrylic oligomer is excellent in view of water contact angle, oil contact angle, and stain resistance, such as fingerprint removal characteristics.

Therefore, the present invention can prevent the damage of the conventional strengthened glass (the disadvantage of the strengthened glass) and produce lighter products, so that the present invention can perform various replacements of the strengthened glass and be applied to products using the strengthened glass.

In particular, the present invention can suitably replace tempered glass for protecting display devices, such as mobile phones, smart windows and touch screen panels, or tempered glass for integration into polarizing plates.

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Claims (9)

A hard coating film that replaces strengthened glass, the hard coating film includes a hard coating, the hard coating has a thickness of 10 to 80 μm, and includes a polysilsesquioxane compound and a fluoromethacrylic oligomeric And a methacrylic monomer, wherein the pencil hardness of the hard coat layer is 7H or higher, wherein the fluoromethacrylic acid oligomer includes at least one compound selected from the following Chemical Formula 5 to Chemical Formula 12:

[Chemical Formula 8]

In Chemical Formula 5 to Chemical Formula 12, wherein X represents a hydrogen atom or a C1-C10 alkyl group; Rf is represented by Chemical Formula 13,

In Chemical Formula 13, Y independently represents H or F; each n and m represent integers from 0 to 200. The hard coat film as described in item 1 of the patent application range, wherein the thickness of the hard coat layer is 10 to 50 μm. The hard coating film as described in item 1 of the patent application scope, wherein the polysilsesquioxane compound is represented by the following Chemical Formula 1 or Chemical Formula 2:

Among them, in Chemical Formula 1 or 2, R represents a C2-C80 aliphatic hydrocarbon or aromatic hydrocarbon, and contains 2 to 20 methacrylic groups, which may or may not contain a hetero atom. The hard coating film as described in item 1 of the patent application scope, wherein based on 100 weight percent of the composition for forming a hard coating layer, the hard coating film contains 0.1 to 50 weight percent of polysilsesquioxane Compound, 0.1 to 65 weight percent fluoromethacrylic acid oligomer and 5 to 70 weight percent methacrylic monomer. The hard coat film as described in item 1 of the patent application range, wherein the hard coat layer has a water-resistant contact angle of 90 to 130 degrees and an oil-resistant contact angle of 60 to 90 degrees at 25 ° C. The hard coat film as described in item 1 of the patent application scope further includes a low refractive layer on the hard coat layer. The hard coating film as described in item 1 of the patent application range, wherein the hard coating film is provided as an alternative to strengthened glass for protecting display devices, or an alternative to strengthened glass integrated in a polarizing plate. The hard coating film as described in item 7 of the patent application range, wherein the hard coating film is provided on a display device selected from the group consisting of a mobile phone, a smart window and a touch screen panel Group. A polarizing plate having a hard coating film as described in item 1 of the patent application scope.