KR101784002B1 - Hard Coating Composition, Hard Coating Film, Polarizing Plate and Image Display Device Using the Same - Google Patents

Abstract

The present invention relates to a hard coating composition, a hard coating film using the same, a polarizing plate and a display. Since the hard coating composition according to the present invention contains silicon (meth) acrylate having a predetermined structure, it has excellent leveling property and does not cause a problem of surface irregularity due to leakage to the outside in an environment of high temperature and high humidity, And the resulting hard coating film exhibits excellent releasability when attached to other substrates. Therefore, the hard coating composition is useful for a polarizing plate having a hard coating film, a polarizing plate having the hard coating film, and a display device .

Description

Technical Field [0001] The present invention relates to a hard coating composition, a hard coating film using the same, a polarizing plate,

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

The hard coating film is widely used for various display panels such as a liquid crystal display (LCD), a plasma display (PDP), a cathode ray tube (CRT), an electroluminescence display (EL) The hard coating film can also provide a hard coating property, resistance to display by fingerprints, markers, and / or ease of removal (i.e., antifouling property).

Such hardcoat films are formed using various types of hardcoat compositions. To the hard coating composition, a wetting agent or the like is added as an additive in order to generally add a leveling agent or impart surface lubricity in order to improve coatability

Since the additives added to the hard coating composition have specific performance, various kinds of additives must be added in order to realize various properties at the same time. However, when two or more kinds of additive are added in order to realize various physical properties at the same time, blocking properties between additives may be generated, so that not only the desired physical properties are obtained but also the surface of the hard coat layer may be uneven. In particular, the leveling agent generally added to the hard coating composition for improving the leveling has an advantage of improving the leveling property by floating on the surface, but it has a problem that the leveling agent flows out from the environment such as high temperature and high humidity and acts as a stain.

An object of the present invention is to provide a hard coat film which is superior in leveling property when applied to the production of a hard coat film, has no problem of surface unevenness even in an environment of high temperature and high humidity, Which is excellent in releasability in use and can be usefully used as an optical film.

Another object of the present invention is to provide a hard coating film which is excellent in removability of pen markers formed by using the hard coating composition and is excellent in releasability when used on other substrates.

It is still another object of the present invention to provide a polarizing plate having excellent removability of a pen marker equipped with the hard coating film.

It is still another object of the present invention to provide a display device having excellent removability of a pen marker equipped with the hard coating film.

In order to accomplish the above object, the present invention provides a hard coating composition comprising a silicon (meth) acrylate compound (F) represented by the following general formula (1).

[Chemical Formula 1]

(Wherein, a and b are each independently an integer of 1 to 10, n is an integer of 1 to 20, and each R ₁ is independently hydrogen or an alkyl group having 1 to 10 carbon atoms and may include a heteroatom And R ₂ is independently an aliphatic or aromatic hydrocarbon having 1 to 20 carbon atoms and may contain a hetero atom, and Y may be a divalent hydrocarbon group containing 0 to 30 (meth) acrylates having 1 to 10 (meth) acrylate groups The number of carbon atoms in the group may be excluded) may contain hetero atoms as aliphatic or aromatic hydrocarbons.

The hard coating composition may include a (meth) acrylate monomer (B), a photoinitiator (D), and a solvent (E).

The hard coating composition may further comprise at least one member selected from the group consisting of urethane (meth) acrylate oligomer (A) and silica particles (C) coated with a silane coupling agent.

The silicone (meth) acrylate compound (F) may be contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the entire hard coating composition.

The hard coat composition is prepared by mixing 5 to 70 parts by weight of the urethane (meth) acrylate oligomer (A), 5 to 70 parts by weight of the (meth) acrylate monomer (B) 1 to 50 parts by weight of the silicone (meth) acrylate compound (C), 0.1 to 10 parts by weight of the photoinitiator (D), 1 to 80 parts by weight of the solvent (E) Can

In order to accomplish another object of the present invention, there is provided a hard coating film comprising a hard coating layer formed by applying the hard coating composition on one side or both sides of a transparent substrate and then curing the hard coating composition.

According to another aspect of the present invention, there is provided a polarizing plate comprising the hard coating film.

According to another aspect of the present invention, there is provided a display device including the hard coating film.

Since the hard coating composition according to the present invention includes a silicon (meth) acrylate compound having a predetermined structure, it is excellent in leveling property and can not flow out to the outside in an environment of high temperature and high humidity, It is excellent in removability of pen markers, and the prepared hard coating film is attached to another substrate and exhibits excellent releasability when used. Accordingly, the hard coating film of the present invention has an effect of exhibiting excellent physical properties such as excellent releasability and pen marker removal property when applied to a polarizing plate and a display device.

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

The hard coating composition according to the present invention comprises a silicone (meth) acrylate compound (F). The hard coating composition may comprise a urethane (meth) acrylate oligomer (A), a (meth) acrylate monomer (B), a photoinitiator (D) and a solvent (E). The hard coating composition may further comprise silica particles (C) coated with a silane coupling agent.

The urethane (meth) acrylate oligomer (A)

The urethane (meth) acrylate oligomer (A) may be optionally added to ensure sufficient hardness and scratch resistance.

The urethane (meth) acrylate oligomer (A) may be any of those used in the art without limitation, but preferably includes a compound having at least one isocyanate group in the molecule and a (meth) acrylate having at least one hydroxyl group in the molecule A compound prepared by reacting a compound can be used.

Examples of the compound having at least one isocyanate group in the molecule include 4,4'-dicyclohexyldiisocyanate, hexamethylene diisocyanate trimer, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1 Diisocyanatohexane, 1,8-diisocyanatohexane, 1,8-diisocyanatohexane, 1,8-diisocyanatohexane, 1,8-diisocyanatohexane, Methylene) cyclohexane, trans-1,4-cyclohexene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, 1,3-diisocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenyl) Isocyanate), 4,4'-oxybis (phenyl isocyanate), hexamethylene diisocyanate A trifunctional isocyanate derived from isophorone diisocyanate, a hexamethylene diisocyanate burette type isocyanate group derived from trimethylolpropane adduct, toluene diisocyanate, acryloylethyl isocyanate, methacryloyl ethyl isocyanate, isophorone diisocyanate, May be used.

The (meth) acrylate compound having at least one hydroxyl group in the molecule specifically includes 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, dipentaerythritol penta / hexa (meth) acrylate, and mixtures thereof.

Examples of the urethane (meth) acrylate oligomer (A) include commercially available products such as EB1290 (6-functional urethane acrylate, SK CYTEC), SUO1700B (10-functional urethane acrylate, Functional urethane acrylate, H-eschemtron), and the like.

The amount of the urethane (meth) acrylate oligomer (A) to be used is not limited, but is preferably 5 to 70 parts by weight based on 100 parts by weight of the entire hard coating composition. When the content of the urethane (meth) acrylate oligomer (A) is less than 5 parts by weight, it is difficult to secure sufficient hardness. When the content of the urethane (meth) acrylate oligomer exceeds 70 parts by weight, cracks may be generated on the surface of the hard coat layer.

(Meth) acrylate monomer (B)

The (meth) acrylate monomer (B) is included to improve the hardness of the cured layer.

The (meth) acrylate monomer (B) may be any of those generally used in the art. Preferably, the (meth) acrylate monomer (B) is at least one monomer selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra Acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate, dipropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di Hydroxypropyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, iso At least one selected from the group consisting of (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate and isobonol Can be used.

The amount of the (meth) acrylate monomer (B) to be used is not limited, but is preferably 5 to 70 parts by weight based on 100 parts by weight of the entire hard coating composition. If the content of the (meth) acrylate monomer (B) is less than 5 parts by weight or exceeds 70 parts by weight, it is difficult to obtain sufficient hardness improving effect.

The silica particles (C)

The silica particles (C) may be optionally added to improve the hardness of the hard coat layer.

The silica particles (C) may preferably be powdery or colloidal silica having an average particle diameter of 0.001 to 20 mu m. When the hard coating composition of the present invention is used in the production of a transparent hard coat film, it is preferable that the particle diameter of the silica particles (C) is 0.001 to 2 탆, preferably 0.005 to 0.05 탆 in consideration of transparency.

The form of the silica particles (C) may be spherical, hollow, porous, rod-shaped, plate-like, fibrous or intangible. Of these, spherical silica particles are preferable. The specific surface area of the silica particles (C) is preferably from 0.1 to 3,000 m ² / g, particularly preferably from 10 to 1,500 m ² / g.

The silica particles (C) may be coated with a silane coupling agent. Examples of the silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldi Vinyltris (? -Methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltris 3,3,3-trifluoropropyldimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Glycidoxymethyltrimethoxysilane,? -Glycidoxymethyltriethoxy Silane,? -Glycidoxyethyltrimethoxysilane,? -Glycidoxyethyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? - (? -Glycidoxymethoxy) propyltrimethoxysilane,? - (meth) acrylooxymethyltrimethoxysil , γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (Meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, hexyltriethoxysilane, hexyltriethoxysilane, hexyltriethoxysilane, Hexyltriethoxysilane, octyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylsilane, perfluorooctyltrimethoxysilane, hexyltriethoxysilane, perfluorooctyltrimethoxysilane, perfluorooctyltrimethoxysilane, (Aminoethyl) gamma -aminopropylmethyldimethoxysilane, N-beta (aminoethyl) gamma -propyltrimethoxysilane, tri- Aminopropyltrimethoxysilane, N-phenyl-gamma -aminophen Peel-trimethoxysilane, γ- mercaptopropyl trimethoxysilane, trimethyl silanol, it is possible to use at least one selected from the group consisting of a silane with methyltrichlorosilane.

The silica particles (C) can be used in the form of dry powder or dispersed in water or an organic solvent. Preferably, the silica particles (C) may be dispersions of fine silica particles known in the art as colloidal silica. If high transparency is required for the hard coating film to be produced, colloidal silica may be preferably used as the silica particles (C). When the dispersion medium of the colloidal silica is water, colloidal silica preferably having a pH of 2 to 10, particularly preferably a pH of 3 to 7 can be used. When the dispersion medium of the colloidal silica is an organic solvent, examples of the organic solvent include methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and dimethylformamide And at least one selected from the group consisting of The organic solvent may be used in admixture with water. A preferred dispersing medium for the colloidal silica is methanol, isopropyl alcohol, methyl ethyl ketone or xylene.

Commercially available products of the silica particles (C) may be used. Among the commercially available products, colloidal silica includes methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST- 40, ST-C, ST-N, ST-O, ST-50 and ST-OL (manufactured by Nissan Chemical Industries Co., Ltd.). Among the commercially available products, AEROSIL 130, 300, 380, TT600 and OX50 (manufactured by Japan Aerosil Co., Ltd.), Sildex H31, H32, H51, H52, H121, H122 E220A, E220 (manufactured by Nippon Silica Industrial Co., Ltd.), Silicia 470 (manufactured by Fuji Silycia Chemical Co.), SG flake (manufactured by Nippon Sheet Glass Co., Ltd.) Ltd.), and the like.

The silica particles may be used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the entire hard coating composition. If the content of the silica particles is less than 1 part by weight, it is difficult to obtain sufficient hardness improving effect. If the content of the silica particles exceeds 50 parts by weight, cracks may be generated in the hard coating layer.

Photoinitiator (D)

The photoinitiator (D) is not limited as long as it is generally used in the art. The photoinitiator (D) may be selected from the group consisting of benzene ethers, benzyl ketals, alpha hydroxyalkylphenones, aminoalkylphenones, and phosphine oxides.

Preferably, the photoinitiator (D) is selected from the group consisting of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- Butanone-1, diphenylketone benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4- hydroxycyclophenyl ketone, dimethoxy- But are not limited to, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-quinoloacetophenone, 4,4-dimethoxyacetophenone, 4, 4- diaminobenzophenone, 1- hydroxycyclohexylphenylketone, Trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,9-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) - phenylphosphine oxide can be used.

The photoinitiator (D) may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the entire hard coating composition. If the content of the photoinitiator (D) is less than 0.1 parts by weight, the hardening speed of the hard coating composition is slow. If the content of the photoinitiator is more than 10 parts by weight, cracks may occur in the hard coating layer.

Solvent (E)

The solvent (E) may be used without limitation as long as it is known as a solvent in hard coating compositions of the technical field.

Examples of the solvent (E) include alcohols (methanol, ethanol, isopropanol, butanol, methylcellulose, ethylsorbox and the like), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, Ketone, cyclohexanone, etc.), hexane (hexane, heptane, octane etc.), benzene (benzene, toluene, xylene and the like). The above-exemplified solvents (E) can be used singly or in combination of two or more.

The solvent (E) may be added in an amount of 1 to 80 parts by weight based on 100 parts by weight of the entire hard coating composition. If the amount of the solvent (E) is less than 1 part by weight, the viscosity is high and the workability is poor. When the amount of the solvent (E) is more than 80 parts by weight, the curing process takes a long time.

The silicone (meth) acrylate compound (F)

The silicone (meth) acrylate compound (F) is added in order to impart sufficient leveling properties and releasability and pen marker removability.

The silicone (meth) acrylate compound (F) is represented by the following formula (1).

[Chemical Formula 1]

(Wherein, a and b are each independently an integer of 1 to 10, n is an integer of 1 to 20, and each R ₁ is independently hydrogen or an alkyl group having 1 to 10 carbon atoms and may include a heteroatom And R ₂ is independently an aliphatic or aromatic hydrocarbon having 1 to 20 carbon atoms and may contain a hetero atom, and Y may be a divalent hydrocarbon group containing 0 to 30 (meth) acrylates having 1 to 10 (meth) acrylate groups The number of carbon atoms in the group may be excluded) may contain hetero atoms as aliphatic or aromatic hydrocarbons.

In the silicone (meth) acrylate compound (F) represented by Formula 1, Y may contain 1 to 10 (meth) acrylate groups, preferably 3 to 10 acrylate groups, It can be more free from stains in the environment.

The polysiloxane, which is the main chain in the above formula (1), improves the leveling property and plays the role of imparting releasability.

The silicone (meth) acrylate compound (F) represented by the formula (1) is prepared by reacting a poly (dialkylsiloxane) having a hydroxy group at its terminal end with a compound having an isocyanate group to prepare a silicone isocyanate compound having an isocyanate group at the terminal, (Meth) acrylate having a hydroxy group in order to impart photo-curing properties to the polymerizable monomer.

As the polydialkylsiloxane in which both terminals are substituted with a hydroxyl group, polydimethylsiloxane having both terminal ends thereof substituted with a hydroxyl group is preferably used. Particularly, the polydimethylsiloxane having the terminal end thereof substituted with a hydroxy group has a number average molecular weight of 500 to 10,000, preferably 1,000 to 5,000. If the number average molecular weight is less than 1000, the mold releasing property is deteriorated. If the number average molecular weight is more than 5000, compatibility of silicone (meth) acrylate (F) represented by Formula 1 with other materials may be deteriorated and transparency may be lowered.

The compound having an isocyanate group which reacts with the above-mentioned hydroxyl group-bearing polydialkylsiloxane is preferably a compound containing at least two isocyanate groups. Preferably the compound having an isocyanate group is selected from the group consisting of toluene diisocyanate, xylene diisocyanate, methylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrocinnamate methylene diisocyanate, naphthalene diisocyanate and tetramethyl xylene diisocyanate At least one selected can be used.

(Meth) acrylate having a hydroxy group is reacted to give a photocuring property when a polydialkylsiloxane in which both terminals are substituted with a hydroxy group and a compound having an isocyanate group are reacted to produce a silicone isocyanate compound having an isocyanate group at the terminal .

The (meth) acrylate having a hydroxy group may preferably be a (meth) acrylate having three or more functional groups, and the (meth) acrylate having three or more functional groups may be selected from the group consisting of pentaerythritol triacrylate and dipentaerythritol pentaacrylate May be used.

The silicone (meth) acrylate compound (F) is preferably contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the entire hard coating composition. If the content of the silicone (meth) acrylate compound (F) is less than 0.1 parts by weight, the leveling property, releasability and pen marker removability are poor. If the content is more than 30 parts by weight, have.

The hard coating composition according to the present invention may contain, in addition to the above-mentioned components, a photostimulant, an antioxidant, a UV absorber, a light stabilizer, a thermal polymerization inhibitor and the like commonly used in the art within the range not lowering the effect of the present invention .

In the present invention, there is provided a hard coat film produced using the composition for hard coating described above. That is, the hard coating film according to the present invention has a hard coating layer formed by applying the above-mentioned composition for hard coating to one side or both sides of a transparent substrate and then curing.

The hard coating film prepared using the hard coating composition according to the present invention exhibits excellent releasability from other substrates and excellent pen marker removability.

Any film can be used as long as the transparent substrate is a plastic film having transparency. Examples of the transparent substrate include a cycloolefin-based derivative having a unit of a monomer including a cycloolefin such as norbornene or a polycyclic norbornene monomer, diacetylcellulose, triacetylcellulose, acetylcellulose butyrate, isobutyl Cellulose acetate, vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyethersulfone, polyether sulfone, polyether sulfone, polyether sulfone, Polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyethersulfone, polymethylmethacrylate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate , Polybutyl Terephthalate, may be used polyethylene naphthalate, polycarbonate, polyurethane, may be used one selected from among epoxy, non-stretched uniaxially or biaxially stretched film.

Of these, preferred are monoaxially or biaxially oriented polyester films which are excellent in transparency and heat resistance, cycloolefin-based derivative films which are excellent in transparency and heat resistance and capable of coping with the enlargement of the film, transparency and optical anisotropy, An acetylcellulose film may suitably be used.

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

The application of the hard coating composition can be carried out in a suitable manner such as die coater, air knife, reverse roll, spray, blade, casting, gravure and spin coating.

The preferable coating thickness of the hard coating composition is 3 to 200 탆. After application, the hard coating composition is dried by evaporation of volatiles at a temperature of 30 to 150 DEG C for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes. The hard coating composition is then cured by irradiation with UV light. The irradiation amount of the UV light is about 0.01 to 10 J / cm ² , preferably 0.1 to 2 J / cm ² .

The thickness of the hard coat layer is not limited, but is preferably in the range of 5 to 30 mu m, more preferably in the range of 10 to 25 mu m. When the thickness of the hard coating layer is within the above range, a hard coating film hardly causing the curling phenomenon can be obtained.

Since the hard coating film according to the present invention includes a silicone (meth) acrylate compound having a predetermined structure, it has excellent pen marker removability and exhibits excellent releasability when used on various other substrates. In addition, the silicone (meth) acrylate compound does not flow out to the outside in an environment of high temperature and high humidity, thereby preventing surface unevenness. Accordingly, the hard coating film according to the present invention can be effectively used as various kinds of optical films.

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

The polarizing plate is not particularly limited, but various types may be used. As the polarizing plate, for example, a hydrophilic polymer film such as a polyvinyl alcohol film and a partially saponified film of an ethylene-vinyl acetate copolymerization system may be produced by adsorbing a dichroic substance such as iodine or a dichroic dye to a uniaxially stretched film poly A polyene-based oriented film such as a dehydrated product of vinyl alcohol or a dehydrochlorinated product of polyvinyl chloride can be exemplified. Among them, a polarizing plate comprising a polyvinyl alcohol-based film and a dichroic substance such as iodine can be preferably used. The thickness of these polarizing plates is not particularly limited, but is generally about 5 to 80 탆.

The polarizing plate on which the hard coating film is laminated may further include a protective film on the upper surface of the hard coating film.

The protective film is usually formed of a transparent substrate such as polypropylene (PP), polyethylene terephthalate (PET), polycarbonate (PC), polymethylmethacrylate (PMMA) The adhesive layer is formed by applying the adhesive layer. As the pressure-sensitive adhesive, an acrylic resin, an ultraviolet curable resin, or the like is usually used. At this time, the hard coating film according to the present invention has excellent releasability from the adhesive layer due to the inclusion of the silicone (meth) acrylate compound represented by the general formula (1). Accordingly, when the releasability of the pressure-sensitive adhesive layer is poor, the problem that the pressure-sensitive adhesive component of the pressure-sensitive adhesive layer is transferred to the hard-coated surface or that peeling is not easily caused can be solved. As a result, when the hard coating film according to the present invention is used, workability or yield can be improved.

The present invention also provides a display device to which the above-mentioned hard coating film is applied.

For example, an image display apparatus to which the hard coating film according to the present invention is applied can be provided by incorporating the polarizing plate on which the hard coating film of the present invention is formed in an image display apparatus. It is also possible to provide an image display apparatus to which the hard coating film according to the present invention is applied by attaching the hard coating film of the present invention to a window of an image display apparatus.

The hard coating film of the present invention can be preferably used for reflective, transmissive, semi-transmissive LCD or LCDs of various driving types such as TN type, STN type, OCB type, HAN type, VA type and IPS type. In addition, the hard coating film of the present invention can be preferably used for various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and an electronic paper.

The present invention will be further illustrated by the following examples, which should not be construed as limiting or limiting the scope of protection of the present invention.

[Synthesis Example 1] Synthesis of silicone acrylate

To a heating apparatus connected to a mechanical stirrer, a temperature sensor and a temperature sensor was charged 101.6 g of toluene diisocyanate (Oriental Chemical), 145.8 g of dihydroxydimethylpolysiloxane (Teomo H-Si 2311, To 50 mg KOH / g, number average molecular weight: 2,500), 0.5 g of dibutyltin dilaurate, and the mixture was stirred at room temperature while maintaining the reaction temperature at 75 캜 and reacted for 3 hours. When the reaction was completed, the reaction temperature was cooled to room temperature, 750.2 g of pentaerythritol triacrylate (Viscot # 300, Osaka Uni) and 2 g of methoxyhydroquinone were added, and the reaction temperature was raised to 80 ° C to obtain 4 The completion of the reaction after the time reaction was regarded as the time point when the isocyanate characteristic peak of 2265 cm ^-1 in the infrared spectrum completely disappeared. The silicone-modified urethane acrylate synthesized was found to have a refractive index of 1.495 and a viscosity of 34,000 cps at 25 ° C.

[Synthesis Example 2] Synthesis of silicone acrylate

To a heating apparatus connected to a mechanical stirrer, a temperature sensor and a temperature sensor was charged 101.6 g of toluene diisocyanate (Oriental Chemical), 145.8 g of dihydroxydimethylpolysiloxane (Teomo H-Si 2311, To 50 mg KOH / g, number average molecular weight: 2,500), 0.5 g of dibutyltin dilaurate, and the mixture was stirred at room temperature while maintaining the reaction temperature at 75 캜 and reacted for 3 hours. After completion of the reaction, the reaction temperature was cooled to room temperature, and 1020 g of dipentaerythritol pentaacrylate (DPHA, produced by Japan) and 2 g of methoxyhydroquinone were added. The reaction temperature was raised to 80 ° C., The termination was made when the isocyanate characteristic peak of 2265 cm ^-1 in the infrared spectrum completely disappeared. The silicone-modified urethane acrylate synthesized had a refractive index of 1.495 and a viscosity of 110,000 cps at 25 占 폚.

[Synthesis Example 3] Synthesis of silicone acrylate

A three-necked reactor was charged with 79.6 g of isophorone diisocyanate (Oriental Chemical Industries), 145.8 g of dihydroxydimethylpolysiloxane (Teomo H-Si 2311, Teossa, hydroxyl value) in a heating device connected to a mechanical stirrer, 40 to 50 mg KOH / g, number average molecular weight: 2,500), 0.5 g of dibutyltin dilaurate, and the mixture was stirred at room temperature while maintaining the reaction temperature at 75 占 폚 for 3 hours. When the reaction was completed, the reaction temperature was cooled to room temperature, 750.2 g of pentaerythritol triacrylate (Viscot # 300, Osaka Uni) and 2 g of methoxyhydroquinone were added, and the reaction temperature was raised to 80 ° C to obtain 4 The completion of the reaction after the time reaction was regarded as the time point when the isocyanate characteristic peak of 2265 cm ^-1 in the infrared spectrum completely disappeared. The silicone-modified urethane acrylate synthesized was found to have a refractive index of 1.495 and a viscosity of 31,000 cps at 25 ° C.

[Synthesis Example 4] Synthesis of silicone acrylate

To a heating apparatus connected to a mechanical stirrer, a temperature sensor and a temperature sensor was charged with 101.6 g of toluene diisocyanate (Oriental Chemical Industries), 97.5 g of dihydroxydimethylpolysiloxane (Teomo H-Si 2700, To 70 mg KOH / g, number average molecular weight: 3,500) and 0.5 g of dibutyltin dilaurate were charged, and the mixture was stirred at room temperature while maintaining the reaction temperature at 75 캜 and reacted for 3 hours. When the reaction was completed, the reaction temperature was cooled to room temperature, 750.2 g of pentaerythritol triacrylate (Viscot # 300, Osaka Uni) and 2 g of methoxyhydroquinone were added, and the reaction temperature was raised to 80 ° C to obtain 4 The completion of the reaction after the time reaction was regarded as the time point when the isocyanate characteristic peak of 2265 cm ^-1 in the infrared spectrum completely disappeared. The silicone-modified urethane acrylate synthesized was found to have a refractive index of 1.495 and a viscosity of 68,000 cps at 25 占 폚.

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

A composition for hard coating was prepared from the components shown in Table 1 below

Composition Example Comparative Example One 2 3 4 5 6 7 8 9 One 2 3 Silicone Acrylate Compound Synthesis Example 1 3 5 0.09 Synthesis Example 2 3 10 Synthesis Example 3 3 15 Synthesis Example 4 3 21 BYK3570 0.5 BYK394 0.5 BYK388 0.5 EB1290 30 30 30 30 25 20 20 35 10 40 40 40 MIBK-ST 15 15 15 15 15 15 15 15 20 Acrylate monomer 17 17 17 17 20 20 15 15 7 10 10 10 menstruum MIBK 15 15 15 15 15 15 15 15 18 44 44 44 MEK 18 18 18 18 18 18 18 18 22 3 3 3 Photoinitiator I-184 One One One One One One One One One One One One TPO One One One One One One One 0.91 One 1.5 1.5 1.5

BYK3570: polyether-modified polydimethylsiloxane (BYK)

BYK394: polyacrylate copolymer (BYK)

BYK388: Fluorine-modified polyacrylate (BYK)

EB1290: 6-functional urethane acrylate (SK CYTEC)

MIBK-ST: Silica sol (10 nm particle diameter, 30% solids 30% methyl isobutyl ketone dispersion, Nissan Chemical Industries, Ltd.) surface-treated with? - (meth) acryloxymethyltrimethoxysilane

Acrylate monomer: dipentaerythritol penta / hexaacrylate (DPHA)

MIBK: Methylisobutyl ketone (purified gold)

MEK: Methyl ethyl ketone (purified water)

I-184: 1-hydroxycyclohexyl phenyl ketone (Ciba)

TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Ciba)

<Experimental Example>

The hard coating compositions prepared in the above Examples and Comparative Examples were stirred for 1 hour and then coated on a transparent base film (80 탆, TAC) with a Meyer bar (a kind of gravure coater) so as to have a thickness of 8 탆, minutes and dried, to prepare a hard coat film comprising a hard coat layer cured by formed of 720mJ / cm ^2. The prepared hard coating film was used as a protective layer of an iodine-based absorption dichroic polarizer.

The properties of the thus-prepared hard coating film were measured as follows. The results are shown in Table 2 below.

(1) Leveling property

The surface of the hard coating layer of the hard coating film is irradiated with the light of the lamp and observed in the direction of the inclination of 20 to 30 DEG to form irregularities or the like attributable to the uniformity of the surface of the hard coating layer The presence or absence of wrinkles was confirmed.

A: There is no microscopic agglomeration on the surface of the hard coat layer, and uniformity is not observed, and unevenness and wrinkles are not observed in the hard coat layer.

B: Micro-agglomeration appears on the surface of the hard coating layer, but it is very slight, and irregularities and wrinkles are not observed in the hard coating layer.

C: Micro-agglomeration appears on the surface of the hard coating layer, but unevenness and wrinkles are not observed in the hard coating layer.

D: Micro-agglomeration is remarkably seen on the surface of the hard coating layer, and the hard coating layer also has irregularities and wrinkles.

(2) Dysmorphism

The hard coating layer of the hard coating film was covered with a PET film (SKC Co.), compressed with rubber rolls, irradiated onto the PET film backside with a light amount of 500 mJ using a high-pressure mercury UV lamp, separated from the PET film, When it is separated, it is marked as bad.

(3) Pen marker removability

The hard coating layer of the hard coating film was marked with a greasy felt pen (made by Monamie), and rubbed five times using a Sabina cloth to measure the extent to which the mark of the pen marker was removed.

A: Scrubbing without marking. B: A little bit left. C: Some marks remain. D: Not removed.

(4) Surface stain

After coating the composition on the top of the TAC film, transparent glass (5 cm × 5 cm) was coated on the coated surface and fixed with a forceps. The glass surface was observed for 500 hours in a constant temperature and humidity chamber at 60 ° C. and 80% Respectively.

A: rough spot, B: little spot, C: spot

Example Comparative Example One 2 3 4 5 6 7 8 9 One 2 3 Leveling ability A A A A A A A A A B B C Dysplasia Good Good Good Good Good Good Good usually Good Bad Bad Bad Pen marker removability A A A A A A A B A D D D Surface stain A A A A A A A A A C C C

As shown in Table 2, the hard coating compositions of Examples 1 to 9 including the silicone (meth) acrylate compound according to the present invention were excellent in leveling and releasing properties as well as excellent in removing pen markers, It can be confirmed that the surface unevenness does not occur even in the environment.

Claims (8)

A hard coat composition comprising a silicone (meth) acrylate compound (F), a urethane (meth) acrylate oligomer (A) and a silica particle (C) coated with a silane coupling agent represented by the following formula (1).
[Chemical Formula 1]

(Wherein, a and b are each independently an integer of 1 to 10, n is an integer of 1 to 20, and each R ₁ is independently hydrogen or an alkyl group having 1 to 10 carbon atoms and may include a heteroatom And R ₂ is independently an aliphatic or aromatic hydrocarbon having 1 to 20 carbon atoms and may contain a hetero atom, and Y may be a divalent hydrocarbon group containing 0 to 30 (meth) acrylates having 1 to 10 (meth) acrylate groups The number of carbon atoms in the group may be excluded) may contain hetero atoms as aliphatic or aromatic hydrocarbons.
The hard coating composition of claim 1, wherein the hard coating composition comprises a (meth) acrylate monomer (B), a photoinitiator (D), and a solvent (E).
delete The hard coating composition according to claim 1, wherein the silicone (meth) acrylate compound (F) is contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the entire hard coating composition.
[5] The composition of claim 2, wherein 5 to 70 parts by weight of the urethane (meth) acrylate oligomer (A), 5 to 70 parts by weight of the (meth) acrylate monomer (B) 1 to 50 parts by weight of the silica particles (C), 0.1 to 10 parts by weight of the photoinitiator (D), 1 to 80 parts by weight of the solvent (E) and 0.1 to 30 parts by weight of the silicone (meth) &Lt; / RTI &gt;
A hardcoat film comprising a hardcoat layer formed by applying the hardcoat composition of any one of claims 1, 2, 4 and 5 on one or both sides of a transparent substrate and then curing.
A polarizing plate comprising the hard coating film of claim 6.
A display device comprising the hard coating film of claim 6.