KR20100132784A - Hard coating composition, hard coating film, polarizing plate and image display device using the same - Google Patents

Abstract

PURPOSE: A hard coating composition is provided to ensure excellent anti-finger printing, anti-finger printing, and good hardness, scratch resistance, and productivity. CONSTITUTION: A hard coating composition comprises fluor(meth)acrylate represented by chemical formula 1, a (meth)acrylate monomer, a photoinitiator and a solvent. In chemical formula 1, m is an integer of 1-100; n is an integer of 1-6; R is hydrogen or C1-6 alkyl group; and R1 is aliphatic or aromatic hydrocarbon which contains or does not contain linear, branched or cyclic C3-50 hetero atom.

Description

Hard coating composition, hard coating film, polarizing plate and image display device using the same {Hard Coating Composition, Hard Coating Film, Polarizing Plate and Image Display Device Using the Same}

The present invention relates to a hard coating composition, a hard coating film, a polarizing plate and an image display device using the same.

Display devices, such as plasma display panels, electroluminescent displays, and liquid crystal displays, have attracted attention for their fast response speed, low power consumption, and excellent color reproduction. Such display devices have been used in various electronic products such as TVs, computer monitors, laptops, mobile phones, and display units of refrigerators.

Recently, display devices for inputting information using a touch screen, such as a personal digital assistant and an automated teller machine, have been widely used.

However, in a display device having a function of inputting information by using a hand or a pen on the surface of the display device such as a touch screen, the display device has excellent resistance to fingerprints or smudges caused by the touch of a hand or a pen, or There is a need for an optical film having a property of removing fingerprints and stains, that is, antifouling properties.

In order to improve the anti-fouling properties and the scratch resistance, it is effective to impart the rolling property to the surface of the optical film, such as to impart a fluorine compound and a silicon compound. However, fluorine-containing polymers and fluorine-containing olefin copolymers, which are compounds of low refractive index, exhibit extremely high water and oil repellency and thus exhibit good antifouling properties by -CF ₂ -or -CF ₃ groups derived from the film surface. Since it is difficult to dissolve in a solvent, it is difficult to obtain a film by coating.

There is also a method of improving the coating properties by introducing a polysilane component, such as a fluorine-containing olefin copolymer (JP-A-2000-313709), amino group-containing polysiloxane introduced into the polysiloxane block copolymer component by a silicone macro-azo initiator A polymer reaction of a fluorine-containing olefin copolymer containing an epoxy group (JP-A-56-28219) and a polymer reaction of a hydroxyl group-containing perfluoroolefin copolymer having a polysiloxane containing an epoxy group (WO 98/29505) are disclosed. There is a bar.

However, the above-described techniques have greatly improved film uniformity, but have a problem of deterioration of anti-fouling properties, and particularly, of long-term use of the film, a sudden deterioration of anti-fouling properties.

An object of the present invention is to solve the problems as described above, excellent in rubbing and anti-fouling properties, excellent durability of anti-fouling properties, as well as being useful in the production of hard coating film excellent in hardness and scratch resistance It is to provide a hard coating composition that can be.

Another object of the present invention is to provide a hard coating film formed using the hard coating composition.

Still another object of the present invention is to provide a polarizing plate provided with the hard coating film.

Another object of the present invention is to provide a display device provided with the hard coating film.

The present invention for achieving the above object comprises a fluorine (meth) acrylate (A), (meth) acrylate monomer (C), a photoinitiator (D), a solvent (E) represented by the following formula (1) It provides a hard coating composition.

 [Formula 1]

(In Formula 1, m is an integer of 1 to 100, n is an integer of 1 to 6, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₁ are each independently linear, branch ( branched) or an cyclic or cyclic aliphatic or aromatic hydrocarbon containing or not containing a hetero atom having 3 to 50 carbon atoms, X is a heterocyclic group having 7 to 80 carbon atoms including a (meth) acrylate group having 1 to 15 functional groups Aliphatic or aromatic hydrocarbons, with or without atoms, R _f is a linear or branched alkyl group having 1 to 20 carbon atoms independently, wherein at least 50% of the hydrogen atom sites are replaced by F; .)

Preferably, the hard coating composition further includes an organic-inorganic silica particle (B) coated with a polyfunctional silane compound represented by the following Chemical Formula 2.

 [Formula 2]

(In Formula 2, l is an integer of 1 to 3, R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms, R ₃ is an aliphatic having 1 to 15 carbon atoms containing or without a hetero atom Or an aromatic hydrocarbon, R ₄ and R ₅ each represent an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms, with or without hydrogen or a hetero atom, wherein R ₄ and R ₅ are connected to each other to form a cyclic structure. R ₆ may be an aliphatic or aromatic hydrocarbon containing or not containing a hetero atom having 1 to 20 carbon atoms, and G is a hetero atom having 7 to 80 carbon atoms containing a (meth) acrylate group having 2 to 10 functional groups. Aliphatic or aromatic hydrocarbons with or without))

The polyfunctional silane compound of Chemical Formula 2 is preferably represented by the following Chemical Formula 3.

(3)

(In the formula (3), l is an integer of 1 to 3, R ₁ and R ₂ each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, R ₃ is a carbon atom containing 1 to 10 atoms or not containing a hetero atom) 15 represents an aliphatic or aromatic hydrocarbon, and R ₄ and R ₅ each represent an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms, with or without hydrogen or hetero atoms, wherein R ₄ and R ₅ are linked to each other and are cyclic; It may form a structure, R ₇ is an aliphatic or aromatic hydrocarbon containing or not containing a hetero atom having 1 to 20 carbon atoms, G is a C7 to 80 containing a (meth) acrylate group having 2 to 10 functional groups Aliphatic or aromatic hydrocarbons with or without hetero atoms).

The hard coating composition is based on 100 parts by weight of the total composition, 0.1 to 20 parts by weight of the fluorine (meth) acrylate (A), 5 to 60 parts by weight of the (meth) acrylate monomer (C), the photoinitiator (D) It is preferable that 0.1-10 weight part and 0.1-50 weight part of said solvents (E) are included.

In addition, the organic-inorganic silica particles coated with the multifunctional silane compound may be included in an amount of 5 to 80 parts by weight based on 100 parts by weight of the total hard coating composition.

In order to achieve the other object of the present invention, the present invention provides a hard coating film comprising a hard coating layer formed by applying the hard coating composition on one or both surfaces of the transparent substrate and then curing.

The hard coat layer is preferably a water contact angle of 90 to 130 ° at 25 ° C.

The hard coat layer preferably has an oil contact angle of 60 to 90 ° at 25 ° C.

In order to achieve another object of the present invention the present invention provides a polarizing plate characterized in that the hard coating film is provided.

In order to achieve another object of the present invention, the present invention provides an image display device characterized in that the hard coating film is provided.

As described above, the hard coating composition according to the present invention, as well as fluorine (meth) acrylate represented by the general formula (1) not only has excellent anti-fingerprint and anti-fouling properties, but also exhibits excellent hardness, scratch resistance. In addition, the hard coating composition according to the present invention is excellent in productivity due to the fast curing speed in the production of the coating film, the film produced after curing hardly occurs, but also has excellent optical high transparency. Accordingly, the coating film of the invention has the effect of showing excellent physical properties and optical properties when applied to the polarizing plate and the display device.

Hereinafter, the present invention will be described in more detail.

The hard coating composition according to the present invention comprises a hard coating composition comprising a fluorine (meth) acrylate (A), a (meth) acrylate monomer (C), a photoinitiator (D) and a solvent (E). The hard coating composition may further include organic-inorganic silica particles (B) coated with a multifunctional silane compound.

Fluorine (meth) acrylate (A)

The hard coating composition according to the present invention contains fluorine (meth) acrylate represented by the following formula (1) for excellent antifouling properties and fingerprints.

 [Formula 1]

(In Formula 1, m is an integer of 1 to 100, n is an integer of 1 to 6, R is hydrogen or alkyl of 1 to 6 carbon atoms, R ₁ are each independently linear, branch ( branched) or an cyclic or cyclic aliphatic or aromatic hydrocarbon containing or not containing a hetero atom having 3 to 50 carbon atoms, X is a heterocyclic group having 7 to 80 carbon atoms including a (meth) acrylate group having 1 to 15 functional groups Aliphatic or aromatic hydrocarbons, with or without atoms, R _f is a linear or branched alkyl group having 1 to 20 carbon atoms independently, wherein at least 50% of the hydrogen atom sites are replaced by F; .)

Fluorine (meth) acrylate represented by Formula 1 reacts a polyfluorooxetane diol compound with a compound having at least one isocyanate group in the molecule, and then at least one hydroxyl group and at least one (meth) acrylate in the molecule Reaction of a compound having a group can be easily prepared.

As the polyfluorooxetane diol compound, at least one selected from PolyFox ^™ PF7002, PolyFox ^™ PF636, PolyFox ^™ PF6320, PolyFox ^™ PF656, and PolyFox ^™ PF6520 may be used as a commercially available product.

In addition, the compound having an isocyanate group is more specifically 4,4'-dicyclohexyl diisocyanate, hexamethylene diisocyanate trimer, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8 -Diisocyanatooctane, 1,12-diisocyanatodecane, 1,5-diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) Cyclohexane, trans-1,4-cyclohexene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, Xylene-1,4-diisocyanate, tetramethylxylene-1,3-diisocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenylisocyanate) From 4,4'-oxybis (phenylisocyanate), hexamethylene diisocyanate At least one selected from the group consisting of trifunctional isocyanate derived, trimethanepropanol adduct toluene diisocyanate, acryloylethyl isocyanate and methacryloylethyl isocyanate can be used.

In addition, the compound having at least one hydroxy group and at least one (meth) acrylate group in the molecule is more specifically 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxy 1 type from the group which consists of a hydroxybutyl (meth) acrylate, a caprolactone ring-opening hydroxy (meth) acrylate, a pentaerythritol tri / tetra (meth) acrylate mixture, a dipentaerythritol penta / hexa (meth) acrylate mixture, etc. The (meth) acrylate selected above can be used.

The fluorine (meth) acrylate represented by Chemical Formula 1 is preferably used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total hard coating composition. If the content of the fluorine (meth) acrylate is less than 0.1 parts by weight based on the above standards, it is difficult to produce a pollution prevention effect, and if it exceeds 20 parts by weight, there is a problem in that the compatibility with the coating liquid is poor and the workability is poor.

Organic-inorganic silica particles coated with polyfunctional silane compounds (B)

The hard coating composition according to the present invention may further include organic-inorganic silica particles coated with a chemically bonded polyfunctional silane compound represented by the following Chemical Formula 2 to the surface hydroxy group of the silica particles in order to ensure sufficient hardness and scratch resistance Can be.

[Formula 2]

(In Formula 2, l is an integer of 1 to 3, R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms, R ₃ is an aliphatic having 1 to 15 carbon atoms containing or without a hetero atom or An aromatic hydrocarbon, and R ₄ and R ₅ each represent an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms, with or without hydrogen or a hetero atom, wherein R ₄ and R ₅ are connected to each other to form a cyclic structure. R ₆ may be an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 20 carbon atoms, and G is a hetero atom having 7 to 80 carbon atoms including a (meth) acrylate group having 2 to 10 functional groups. Aliphatic or aromatic hydrocarbons with or without))

The polyfunctional silane compound of Chemical Formula 2 is preferably represented by the following Chemical Formula 3.

(3)

(In the formula (3), l is an integer of 1 to 3, R ₁ and R ₂ each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, R ₃ is a carbon atom containing 1 to 10 atoms or not containing a hetero atom) 15 represents an aliphatic or aromatic hydrocarbon, and R ₄ and R ₅ each represent an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms, with or without hydrogen or hetero atoms, wherein R ₄ and R ₅ are linked to each other and are cyclic; It may form a structure, R ₇ is an aliphatic or aromatic hydrocarbon containing or not containing a hetero atom having 1 to 20 carbon atoms, G is a C7 to 80 containing a (meth) acrylate group having 2 to 10 functional groups Aliphatic or aromatic hydrocarbons with or without hetero atoms)

Although not limited, it will be described in more detail as an example R ₁ and R ₂ may be a methyl group, ethyl group, isopropyl group, propyl group, butyl group, pentyl group, etc., R ₃ is methyl group, ethyl group, isopropyl group, propyl The structure in which hetero atoms, such as an ether bond, exist in group, a butyl group, a pentyl group, or these combination is possible. R ₄ and R ₅ may be a hydrogen group, a methyl group, an ethyl group, a propyl group, a cyclohexyl group, or the like. R ₆ and R ₇ may be an alkyl group derived from succinic acid, a phthalic acid derivative, an aromatic group, an aromatic group containing an alkyl group, and the like, and G is a C 7 to 80 carbon group containing a (meth) acrylate group having 2 to 10 functional groups. Aliphatic or aromatic hydrocarbons with or without hetero atoms.

Although not limited, G is preferably selected from polyfunctional (meth) acrylates which can be reacted by the presence of a hydroxyl group. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylic Rate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acrylonyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylic Latex, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate Etc. are possible.

The compound of Formula 2 may be synthesized by ring-opening reaction with a silane coupling agent containing a (meth) acrylate containing a carboxylic acid group and an oxirane.

At this time, the organic compound containing a carboxylic acid group can be synthesized on a simple condition by reacting the organic anhydride in the presence of a tertiary amine to (meth) atrylate containing a hydroxy group.

Examples of the (meth) acrylate containing the hydroxy group include dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, (meth) acrylic ester, Trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (Meth) acrylate, 1,3-butanediol mono (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol mono (meth) acrylate, bis (2-hydroxyethyl) isocy Nurate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso-decyl (meth) Acrylates and the like can be used.

The above-mentioned (meth) acrylate containing a hydroxyl group can react with organic anhydride to introduce carboxylic acid. Examples of the organic anhydride include succinic anhydride, methyl succinic anhydride, 2,2-dimethyl succinic anhydride, isobutenyl succinic anhydride, 2-octen-1-ylsuccinic anhydride, octadekenyl succinic anhydride, 2-oxabicyclo [ 3,1,0] hexane-2,4-dione, cis-1,2-cyclohexanedicarboxylic anhydride, trans-1,2-cyclohexanedicarboxylic anhydride, hexahydro-4-methylphthal anhydride, ita Gon anhydride, 2-dodecene-1-ylsuccinic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, endo- Bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, cantharidin, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy -1,2,3,6-tetrahydrophthalic anhydride, S-acetylmercaptosuccinic anhydride, maleic anhydride, citragonic anhydride, 2,3-dimethylmaleic anhydride, 1-cyclopentene-1,2-dica Levonic acid anhydride, 3,4,5,6, -tetra Drophthalic anhydride, bromomaleic anhydride, dichloromaleic anhydride, glutaric anhydride, 3-methylglutarate anhydride, 2,2-dimethylglutarate anhydride, 3,3-dimethylglutarate anhydride, 3-ethyl-3- Methylglutamic anhydride, 3,3-tetramethylene glutaric anhydride, hexafluoroglutarate anhydride, diglycolic acid anhydride, phenylsuccinic anhydride, phenylmaleic anhydride, 2,3-diphenylmaleic anhydride, 2-phenylglutal acid Anhydride, homophthalic anhydride, phthalic anhydride, 4-methylphthalic anhydride, 3,6-difluorophthalic anhydride, 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, tetrafluorophthalic anhydride, tetrachlorophthalic anhydride Anhydride, tetrabromophthalic anhydride, 3-hydroxyphthalic anhydride, 1,2,4-benzenetricarboxylic acid anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, diphenyl acid anhydride, 1,8-naphthalic acid anhydride 4-chloro-1,8-naphthalic anhydride, 4-bromo-1,8-naphthalic anhydride, 4-amino-1,8-naphthalic anhydride, 3-nitro-1,8-naphthalic anhydride, 4-nitro-1,8-naphthalic anhydride etc. are mentioned, Among these, succinic anhydride and a phthalic anhydride are the most preferable reaction compounds.

The silane coupling agent containing the oxirane is, for example, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, [(3-methyloxetan-3-yl) -methyloxypropyl] -tri Ethoxysilane, [(3-methyloxetan-3-yl) -methyloxypropyl] -trimethoxysilane, [(3-methyloxetan-3-yl) -propyloxypropyl] -methyltrimethoxysilane , [(3-methyloxetan-3-yl) -propyloxypropyl] -methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-gly Cydoxybutyl trimethoxysilane, γ-glycidoxy butyl triethoxysilane, γ-glycidoxy propyl dimethoxyethoxysilane, γ-glycidoxy propylmethyldimethoxysilane, γ-glycidoxy propyldimethyl Toxoxysilane, 3,4-epoxybutyltrimethoxysilane The most preferred compound is [(3-methyloxetan-3-yl) -methyloxypropyl] -triethoxysilane, β- (3,4-epoxycyclohexyl Ethyltrimethoxysilicone Column, γ-glycidoxypropyltrimethoxysilane and the like can be used.

Organic-inorganic silica particles (B) coated with the multifunctional silane compound according to the present invention are prepared by chemically bonding the multifunctional silane compound represented by Chemical Formula 2 to the surface hydroxy group of the silica particles.

At this time, the organic-inorganic silica particles (B) coated with the multifunctional silane compound (B) is not limited, but may be included 5 to 80 parts by weight based on 100 parts by weight of the total hard coating composition. When the content of the organic-inorganic silica particles (B) coated with the multifunctional silane compound is less than 5 parts by weight, it is difficult to secure sufficient hardness and scratch resistance of the hard coating film, and when the content exceeds 80 parts by weight, the hard coating film Curling may occur.

The silica particles used in the preparation of the organic-inorganic silica particles (B) coated with the multifunctional silane compound are not limited, but it is preferable to use an aqueous dispersion or an alcohol-based dispersion of a colloidal silica sol. Specific examples of commercially available colloidal silica sol include PURISOL-O series (manufactured by Gamatek, average particle size of 5-40 nm, silica content of 20-40%), and CATALOID-S series (catalyst, average particle size 5 ~ 80nm). , Silica content of 20 to 48%), YGS-series (Youngilization agent, average particle size of 10 to 80nm, silica content of 20 to 40%) and the like. Any one or more of these can be selected and used.

In addition, the average particle diameter of the colloidal silica particles is not limited, but may be used in the range of 5nm ~ 100nm and when used in the cured transparent film is preferably 5nm ~ 50nm. When the average particle diameter of the colloidal silica particles is more than 100 nm, the transparency of the hard coat film is reduced or the surface state of the hard coat film is not good. In addition, when the average particle diameter of the colloidal silica particles is less than 5nm, the hardness of the hard coat film may be worse.

(Meth) acrylate monomer (C)

In the present invention, (meth) acrylate monomers are included in order to improve the hardness and curling properties of the cured layer by using the polyfunctional organic-inorganic silica particles simultaneously. For example, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, (meth) acrylic ester, trimethyl All propane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol (meth ) Acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentylglycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) Acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso-decyl (meth) acrylate, stearyl ( At least 1 sort (s) of compound can be selected and used from the group which consists of a meta) acrylate, tetrahydroperfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, an isobornol (meth) acrylate, etc.

Although the amount of the (meth) acrylate monomer (C) is not limited, it is preferably included 5 to 60 parts by weight based on 100 parts by weight of the hard coating composition, and the addition amount of the (meth) acrylate monomer is less than 5 parts by weight When it exceeds 60 weight part, it is hard to show an effect on sufficient hardness improvement.

Photoinitiator (D)

The hard coating composition according to the present invention includes a photoinitiator. Examples of the photoinitiator include 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenyl ketone benzyl dimethyl ketal, 2-hydroxy-2-methyl-1- Phenyl-1-one, 4-hydroxycyclophenylketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloacetophenone, At least one selected from the group consisting of 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxy cyclohexylphenyl ketone, benzophenone and the like can be used.

The photoinitiator may be used from 0.1 to 10 parts by weight based on 100 parts by weight of the hard coating composition. When the content of the photoinitiator is less than 0.1 part by weight, the hardening composition may have a slow curing rate and may exceed 10 parts by weight of the hard coating layer due to over curing.

Solvent (E)

The hard coating composition according to the present invention contains a solvent. The solvent can be used without limitation to what is known as a solvent of the hard coating composition in the art.

In one example, the solvent is alcohol-based (methanol, ethanol, isopropanol, butanol, methylcellulose, ethyl solusorb, etc.), ketone-based (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl Ketones, cyclohexanone and the like), hexane-based (hexane, heptane, octane and the like), benzene-based (benzene, toluene, xylene and the like) and the like. The organic solvents exemplified above may be used in admixture of one or more, and in particular, a fluorine solvent may be used for sufficient dispersibility and coating slip property of the fluorine compound. As the fluorine solvent, more specifically, hydrofluorocarbon and hydrofluoroether may be used, and commercially available Bartrel XF (CF ₃ CHFCHFCF ₂ CF ₃ ) manufactured by DuPont, Zeolola H (heptafluorocyclopentane) manufactured by Nippon Zeon, and 3M At least one selected from the group consisting of HFE-7100 (C ₄ F ₉ OCH ₃ ), 7200 (C ₄ F ₉ OC ₂ H ₅ ), and the like may be used.

The solvent may be added 0.1 to 50 parts by weight based on 100 parts by weight of the hard coating composition. If the solvent is less than 0.1 parts by weight, the viscosity is high, the workability is lowered, and if it exceeds 50 parts by weight, it takes a long time in the curing process and there is a problem of low economic efficiency.

In addition to the above components, the hard coating composition according to the present invention may be used with photo-stimulating agents, antioxidants, UV absorbers, light stabilizers, thermal polymerization inhibitors, labelling agents, surfactants, lubricants and the like.

The present invention provides a hard coat film manufactured using the above-described hard coat composition.

The hard coating film according to the present invention is provided with a hard coating layer formed by applying the above-described hard coating composition on one or both sides of the transparent substrate and then curing.

The hard coat film manufactured using the composition according to the present invention can be improved by solving the wear resistance and anti-fouling properties.

As the transparent base material, any film can be used as long as it is a transparent plastic film. For example, a cycloolefin derivative having a unit of a monomer containing a cycloolefin such as norbornene or a polycyclic norbornene monomer and a diacetyl cellulose Cellulose, ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, Polyetherimide, polyacryl, polyimide, polyether sulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether Ketones, polyethersulf May be used polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, may be used one selected from among epoxy, non-stretched uniaxially or biaxially stretched film.

Among them, a monoaxial or biaxially stretched polyester film having excellent transparency and heat resistance, but a cycloolefin derivative film capable of coping with an enlargement of the film while being excellent in transparency and heat resistance, and having no transparency and optical anisotropy Acetylcellulose film can be suitably used.

8-1000 micrometers is preferable and, as for the thickness of a transparent base material, More preferably, it is 40-100 micrometers.

Application of the hard coat film in the present invention may be in a suitable manner such as die coater, air knife, reverse roll, spray, blade, casting, gravure and spin coating.

The preferred coating thickness of the hard coating composition is 3 ~ 200㎛. After application, the composition is dried by evaporation of the volatiles for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes at a temperature of 30 ~ 150 ℃. After curing by irradiation with UV light. The irradiation amount of UV light is about 0.01-10 J / cm ² , preferably 0.1-2 J / cm ² .

The thickness of the hard coating layer is not limited, but is preferably in the range of 5 to 30 μm, more preferably in the range of 10 to 25 μm, and when the curling property is adjusted to 15 mm or less, a hard coating film of high hardness can be obtained. have.

The hard coating layer is a water-resistant contact angle that can be evaluated for contamination resistance is 90 to 130 ° at 25 ℃, oil contact angle is preferably from 60 to 90 ° at 25 ℃. When the water-resistant contact angle of the hard coating layer is less than 90 °, it is vulnerable to moisture and when it exceeds 130 ° water resistance is too good, when manufacturing a polarizing plate, water stains are likely to occur during the safaction process. In addition, when the oil-resistant contact angle is less than 60 °, the fingerprint resistance is lowered, if larger than 90 ° problem of coating property is likely to occur.

The present invention provides a polarizing plate having excellent physical properties formed by laminating the above-described hard coating film on at least one surface.

The polarizing plate is not particularly limited, but various kinds may be used. As a polarizing plate, the film polyvinyl which uniaxially stretched by adsorb | sucking dichroic substances, such as iodine and a dichroic dye, to hydrophilic polymer films, such as a polyvinyl alcohol-type film and an ethylene-vinyl acetate copolymerization partial saponification film, for example. And polyene-based alignment films such as alcohol dehydration products and polyvinyl chloride dehydrochlorination products. Among these, the polarizing plate which consists of dichroic substances, such as a polyvinyl alcohol-type film and iodine, is preferable. Although the thickness of these polarizing plates is not specifically limited, Generally, it is about 5-80 micrometers.

The present invention also provides an image display device to which the above-mentioned hard coat film is applied.

For example, various image display devices excellent in visibility can be manufactured by embedding the polarizing plate on which the hard coat film of the present invention is formed in an image display device. Moreover, the hard coat film of this invention can also be attached to the window of an image display apparatus. The hard coat film of the present invention can be preferably used in reflective, transmissive, transflective LCD or LCD of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, IPS type, and the like. In addition, the hard coat film of the present invention can be preferably used in various image display devices such as plasma displays, field emission displays, organic EL displays, inorganic EL displays, electronic papers, and the like.

The present invention will be further illustrated by the following examples, which are only specific examples of the present invention, and are not intended to limit or limit the protection scope of the present invention.

Synthesis Example 1 Synthesis of Carbonic Acid Polyfunctional (Meta) acrylate

4.76 parts by weight of succinic anhydride (Aldrich) is slowly added to 100 parts by weight of dipentaerythritol penta / hexaacrylate (Nipon Kayaku Co., KAYARAD DPHA) and 1.5 parts by weight of triethylamine (Aldrich) at room temperature for one hour. After the addition, the temperature was raised to 80 ° C. and stirred for six hours.

Infrared absorption spectrum peak of the product may disappear and the carbonyl 1810cm ^-1 1710cm ^-1 of succinic anhydride determine the carbonyl absorption peak of carboxylic acid.

Synthesis Example 2 Synthesis of carboxylic acid polyfunctional (meth) acrylate

It carried out similarly to the synthesis example 1 except using pentaerythritol tri / tetra acrylate (Miwon Corporation, M340) as a polyfunctional (meth) acrylate.

Infrared absorption spectrum peak of the product may disappear and the carbonyl 1810cm ^-1 1710cm ^-1 of succinic anhydride determine the carbonyl absorption peak of carboxylic acid.

Synthesis Example 3 Synthesis of Polyfunctional Silane Compound Containing Polyfunctional (meth) acrylate

100 parts by weight of the organic compound prepared in Synthesis Example 1, 11.16 parts by weight of 3-glycidylpropyltrimethoxysilane (Shin-Etsu Corp., KBM-503), 1.67 parts by weight Tetrabutylammonium bromide (Aldrich), 1.1 parts by weight 4 Mix methoxyphenol (Eastman) and raise the temperature to 85 ° C. and stir for 9 hours.

The infrared spectral absorption peak of the product can be seen that the epoxy 910cm ^-1 disappears.

Synthesis Example 4 Synthesis of Polyfunctional Silane Compound Containing Polyfunctional (meth) acrylate

100 parts by weight of the organic compound prepared in Synthesis Example 2, 11.3 parts by weight of 3-glycidylpropyltrimethoxysilane (Shin-Etsu, KBM503), 1.64 parts by weight of tetrabutylammonium bromide (Aldrich), 1.1 parts by weight of 4-methoxy Phenol (Eastman) is mixed and the temperature is raised to 85 ° C. and stirred for 9 hours. The infrared spectral absorption peak of the product can be seen that the epoxy 910cm ^-1 disappears.

Synthesis Example 5 Fluoroacrylate Synthesis

60 parts by weight of a polyfluorooxetanediol compound having a repeating unit of 6 (PolyFox ^™ PF656, Ohm Nova), 20 parts by weight of isophorone diisocyanate (IPDI, Degussa), pentaerythritol tree / penta acrylate (M340, Miwon Co., Ltd.) 40 parts by weight, 0.1 parts by weight of dibutyl tin dilaurate (FASCAT 4202, Akema) as a reaction catalyst and 0.05 parts by weight of methoxy hydroquinone (HQMME, Eastman) as a polymerization inhibitor at room temperature, while stirring, the reaction temperature Was raised to 90 ° C. The reaction was terminated when reacted at 90 ° C. for 12 hours and completely disappeared when the characteristic peak of isocyanate in the infrared spectral spectrum, 2260 cm ⁻¹ . The reaction product is diluted to 20 parts by weight in 1,1,2,2,3,3,4-heptafluorocyclopentane solvent.

Synthesis Example 6 Fluoroacrylate Synthesis

50 parts by weight of a polyfluorooxetane diol compound having a repeating unit of 20 (PolyFox ^™ PF6520, Ohm Nova), 15 parts by weight of isophorone diisocyanate (IPDI, Degussa), pentaerythritol tri / penta acrylate (M340, Miwon Superior) 38 parts by weight, 0.1 parts by weight of dibutyltin dilaurate (FASCAT 4202, Akema) as a reaction catalyst and 0.05 parts by weight of methoxy hydroquinone (HQMME, Eastman) as a polymerization inhibitor are mixed at room temperature and stirred while the reaction temperature Was raised to 90 ° C. The reaction was terminated when reacted at 90 ° C. for 12 hours and completely disappeared when the characteristic peak of isocyanate in the infrared spectral spectrum, 2260 cm ⁻¹ . The reaction product is diluted to 20 parts by weight in 1,1,2,2,3,3,4-heptafluorocyclopentane solvent.

Preparation Example 1 Preparation of Colloidal IPA Dispersed Organic-Inorganic Silica Particles

10.22 parts by weight of polyfunctional silane compound prepared in Synthesis Example 3, 107.28 parts by weight of PURISOL-OIS (manufactured by Gamatek, IPA dispersion, 10 to 20 nm, solids 30% by weight), 0.2 parts by weight of methanol (Aldrich) at 80 ° C., nitrogen The mixture is stirred for 3 hours in a gas atmosphere. 1.4 weight part of methyl orthopermate (Aldrich) is added, and it stirred at 80 degreeC and nitrogen gas atmosphere for 1 hour.

[Production Example 2]

It carried out similarly to the manufacture example 1 except using the product manufactured by the synthesis example 4 as a polyfunctional silane compound compound containing a polyfunctional (meth) acrylate.

[Examples 1-12 and Comparative Examples 1-4: Preparation of the composition for hard coating]

To prepare a hard coating composition containing a solvent by combining the composition for hard coating with the components shown in Table 1 below.

MCF 350-5: Fluoropolymer (Dainippon Ink)

Acrylate monomer: pentaerythritol tri / penta acrylate (miwon Corporation, M340)

MIBK: methyl isobutyl ketone

MEK: methyl ethyl ketone

Zeolala H: Heptafluorocyclopentane

I-184: 1-hydroxycyclohexyl phenyl ketone (Shiba Corporation)

I-907: 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1 (Shiba Corporation)

BYK-378: Silicone Modified Oil (BYK)

Experimental Example

The hard coating composition prepared in Example and Comparative Example was applied for 1 hour after stirring for 1 hour to a thickness of 10㎛ on a transparent substrate film (80㎛, TAC) and then dried at 70 ℃ for 1 minute, 720mJ / cm ^It was cured to ² to prepare a high hardness hard coat film. The prepared hard coat film was used as a protective layer of the iodine-based absorption dichroic polarizing plate.

In this case, the physical properties of the hard coat film prepared as described above were measured as follows, and the results are shown in Table 2 below.

(1) surface smoothness

The coated surface of the film is observed in the direction of inclination of 20 to 30 degrees by shining with the electric light, and the presence or absence of wrinkles or wrinkles which is thought to be due to the uniformity of the surface layer (microscopic) or the surface property of the hard coating layer Confirmed.

A: There is no micro aggregation in the surface layer, and it is uniform, and unevenness | corrugation and a wrinkle are not recognized by a hard coat layer.

B: Although microscopic aggregation is seen in the surface layer, it is very mild and unevenness | corrugation and a wrinkle are not recognized by a hard coat layer.

C: Although micro aggregates are seen in the surface layer, irregularities and wrinkles are not observed in the hard coat layer.

D: Microscopic aggregation is remarkable in the surface layer, and irregularities and wrinkles are also seen in the hard coat layer.

(2) pencil hardness

Pencil hardness was measured using a pencil hardness tester (PHT, manufactured by Seokbo Science, Inc.) under a 500g load. The pencil was made 5 times per pencil hardness using Mitsubishi products. If there were two or more gases, it was determined to be defective, and pencil hardness was indicated by a pencil before the failure occurred.

Kiss: 0 OK

Kiss: 1 OK

Ges: 2 or more NG

(3) scratch resistance

Scratch resistance was tested by reciprocating 10 times under 1 kg / (2 cm × 2 cm) using a steel wool tester (WT-LCM100, manufactured by Korea Protec).

Steel wool used # 0000.

A: 0 scratches

A ': 1 to 10 scratches

B: 11-20 scratches

C: 21-30 scratches

D: 31 or more scratches

(4) adhesion

Eleven straight lines were drawn on the coated surface of the film at intervals of 1 mm each to make 100 squares, and then a peel test was conducted three times using a tape (CT-24, manufactured by Nichi Nippon Co., Ltd.). Three 100 squares were tested and averaged. The adhesion was recorded as follows.

Adhesion = n / 100

n: number of rectangles not peeled off

100: total squares

Therefore, when none of the peeling was recorded as 100/100.

(5) curling

The sample cut into the square shape of A4 size (29.7 X 21.0 cm) was placed on a flat glass plate with the coated surface of the film facing up, and the distance from the square glass plate was measured at 25 ° C. and 50% RH, and then averaged. Was taken as a measured value.

Very good: 0 to 15 mm or less, good: more than 15 mm to 30 mm or less, poor: more than 30 mm to 50 mm or less, very poor: more than 50 mm.

(6) male contact angle

After dropping water droplets onto the film surface at room temperature (25 ° C.), the contact angle with respect to the water droplets was measured 1 minute later using a contact angle measuring instrument (KSV Co., Ltd. CAM100). The contact angle was measured 5 times with the same sample to the left and right contact angle of the water droplets and used the average value.

(7) oil contact angle

After dropping oleic acid at the surface of the film at room temperature (25 ° C.), the contact angle with respect to oleic acid was measured after 1 minute using a contact angle measuring instrument (CAMV, KSV). The contact angle was measured 5 times with the same sample of the left and right contact angle of the oleic acid and used the average value.

(8) fingerprint wiping

Fingerprint marks on the coated surface of the film were gently wiped 10 times by ten testers with clean paper (ULTIMA II, Hansong), and the wiping property was visually evaluated.

A: No wipe marks remained. B: A little wipe left. C: Wipe marks remained.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Hard coating
Thickness (㎛) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 surface
Smoothness A A A A A B B A B A A B B B A B Light rays
Transmittance (%) 91.5 90.8 91.3 91.1 91.3 92 91 90.5 90 91.2 91.1 90.7 87.5 82 76 90 Pencil hardness 4 H 4 H 5 H 5 H 2 H 5H 3H 4H 3H 4H 3H 4H 3H 2H 3H H Scratch resistance A A A A B A B B A A A A A B A B Adhesion 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 99 /
100 95 /
100 100 /
100 99 /
100 curling Good Good Good Good Good Good Good Good Good Good Good Good Bad Good Bad Good Fingerprint Wipe A A A A A A A B A A A A C B C B Haze 0.2 0.2 0.3 0.3 0.2 0.4 0.2 0.3 0.2 0.2 0.2 0.4 0.5 0.4 0.5 0.2 Water contact angle
(°) 110 109 109 109 110 108 109 100 118 114 115 120 83 100 99 99 Contact angle
(°) 75 77 76 77 77 75 77 63 80 77 78 83 55 60 63 62

As shown in Table 2, in Examples 1 to 12 including the fluorine (meth) acrylate represented by the formula (1) according to the present invention, the water contact angle and the oil contact angle which can confirm the fingerprint wiping resistance and the degree of contamination resistance are overall. It can be confirmed that excellent.

Claims (10)

A hard coating composition comprising a fluorine (meth) acrylate (A), a (meth) acrylate monomer (C), a photoinitiator (D), and a solvent (E) represented by the following Chemical Formula 1.  [Formula 1]

(In Formula 1, m is an integer of 1 to 100, n is an integer of 1 to 6, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₁ are each independently linear, branch ( branched) or an cyclic or cyclic aliphatic or aromatic hydrocarbon containing or not containing a hetero atom having 3 to 50 carbon atoms, X is a heterocyclic group having 7 to 80 carbon atoms including a (meth) acrylate group having 1 to 15 functional groups Aliphatic or aromatic hydrocarbons, with or without atoms, R _f is a linear or branched alkyl group having 1 to 20 carbon atoms independently, wherein at least 50% of the hydrogen atom sites are replaced by F; .) The hard coating composition of claim 1, wherein the hard coating composition further comprises an organic-inorganic silica particle (B) coated with a multifunctional silane compound represented by the following Chemical Formula 2.  [Formula 2]

(In Formula 2, l is an integer of 1 to 3, R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms, R ₃ is an aliphatic having 1 to 15 carbon atoms containing or not containing a hetero atom or An aromatic hydrocarbon, and R ₄ and R ₅ each represent an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms, with or without hydrogen or a hetero atom, wherein R ₄ and R ₅ are connected to each other to form a cyclic structure. R ₆ may be an aliphatic or aromatic hydrocarbon containing or not containing a hetero atom having 1 to 20 carbon atoms, and G is a hetero atom having 7 to 80 carbon atoms including a (meth) acrylate group having 2 to 10 functional groups. Aliphatic or aromatic hydrocarbons) The hard coating composition of claim 1, wherein the polyfunctional silane compound of Formula 2 is represented by the following Formula 3. (3)

(In the formula (3), l is an integer of 1 to 3, R ₁ and R ₂ each independently represent an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, R ₃ is a carbon atom containing 1 to 10 atoms, or not containing a hetero atom) 15 aliphatic or aromatic hydrocarbons, and R ₄ and R ₅ each represent an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms with or without hydrogen or a hetero atom, wherein R ₄ and R ₅ are linked to each other and are cyclic; And may form a structure, R ₇ is an aliphatic or aromatic hydrocarbon containing or not containing 1 to 20 carbon atoms, and G is 7 to 80 carbon atoms containing 2 to 10 (meth) acrylate groups. Aliphatic or aromatic hydrocarbons with or without hetero atoms) The method of claim 1, wherein the hard coating composition is based on 100 parts by weight of the total composition, 0.1 to 20 parts by weight of the fluorine (meth) acrylate (A), 5 to 60 parts by weight of the (meth) acrylate monomer (C), Hard coating composition characterized in that it comprises 0.1 to 10 parts by weight of the photoinitiator (D) and 0.1 to 50 parts by weight of the solvent (E). The hard coating composition of claim 2, wherein the organic-inorganic silica particles (B) are included in an amount of 5 to 80 parts by weight based on 100 parts by weight of the total hard coating composition. A hard coat film comprising a hard coat layer formed by applying the hard coat composition of any one of claims 1 to 5 on one or both surfaces of a transparent substrate and then curing the hard coat composition. The hard coating film of claim 6, wherein the hard coating layer has a water resistance contact angle of 90 to 130 ° at 25 ° C. The hard coating film of claim 6, wherein the hard coating layer has an oil contact angle of 60 to 90 ° at 25 ° C. The hard coating film of claim 6 is provided. Display device, characterized in that the hard coating film of claim 6.