KR20110024985A - 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 surface smoothness, transmittance, adhesion, haze, hardness, and scratch resistance, and to obtain a hard coating film with excellent anti-finger printing and anti-fouling properties. CONSTITUTION: A hard coating composition comprises (A) fluro(meth)acrylate represented by chemical formula 1, (B) urthane(meth)acrylate oligomer, (C) (meth)acrylate monomer, (D) photoinitiator, and (E) solvent. In chemical formula 1, X is hydrogen atom or C1-10 alkyl group; R1 is C1-30 aliphatic or aromatic hydrocarbon which includes or does not include heterocycle; and Rf is C1-20 linear or branched alkyl group.

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) have been disclosed. have.

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 above problems and to produce a hard coating film having excellent physical properties such as surface smoothness, transmittance, hardness, adhesion, haze and scratch resistance, as well as excellent fingerprint and antifouling properties. It is to provide a hard coating composition that can be usefully used.

Another object of the present invention is to provide a hard coating film having excellent anti-fingerprint and antifouling properties 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.

Still another object of the present invention is to provide an image display device having the hard coating film.

The present invention for achieving the above object is a fluoro (meth) acrylate (A), urethane (meth) acrylate oligomer (B), (meth) acrylate monomer (C), photoinitiator represented by the following [Formula 1] It provides a hard coating composition comprising (D) and a solvent (E).

 [Formula 1]

(In Formula 1, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₁ is an aliphatic or aromatic hydrocarbon having 1 to 30 carbon atoms, with or without heterocycle, R _f is independently 1 to 20 carbon atoms A linear or branched alkyl group of at least 50% of the hydrogen atom sites are replaced by F.)

The hard coating composition is based on 100 parts by weight of the total composition, 0.1 to 30 parts by weight of the fluorine (meth) acrylate (A), 5 to 70 parts by weight of the urethane (meth) acrylate oligomer (B), (meth) 5 to 70 parts by weight of the acrylate monomer (C), 0.1 to 10 parts by weight of the photoinitiator (D) and 1 to 80 parts by weight of the solvent (E) are preferably included.

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 has excellent anti-fingerprint and antifouling properties as well as fluorine (meth) acrylate represented by Chemical Formula 1, as well as surface smoothness, transmittance, adhesiveness, haze hardness and scratch resistance. Excellent properties. 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 image display device.

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

The hard coating composition according to the present invention includes fluorine (meth) acrylate (A), urethane (meth) acrylate oligomer (B), (meth) acrylate monomer (C), photoinitiator (D) and solvent (E). do.

Fluorine (meth) acrylate (A)

The fluorine (meth) acrylate (A) is added to impart excellent antifouling properties and fingerprints to the hard coating composition, fluorine (meth) acrylate (A) according to the present invention is represented by the following formula (1).

[Formula 1]

(In Formula 1, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₁ is an aliphatic or aromatic hydrocarbon having 1 to 30 carbon atoms, with or without heterocycle, R _f is independently 1 to 20 carbon atoms A linear or branched alkyl group of at least 50% of the hydrogen atom sites are replaced by F.)

Fluorine (meth) acrylate (A) represented by Formula 1 is subjected to epoxidation reaction of fluorine alcohol and then ring-opened with (meth) acrylic acid to obtain fluoroepoxy (meth) acrylate, and the obtained fluoroepoxy (meth). ) Acrylate can be easily prepared by reacting a compound having at least one isocyanate group in a molecule.

The fluoroalcohol may be specifically 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,3-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, 3,3,4,4,5,5,6,6,7,7,8,8-tridecafluoro-1-octanol, 2,2,3 , 3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol, 1,1,1,3,3,3-hexafluoro-2-propanol And at least one selected from the group consisting of 1,1,1,3,3,4,4,4-octafluoro-2-butanol and the like.

The epoxidation reaction of the fluoroalcohol may be carried out by reacting the fluoroalcohol with epichlorohydrin or epibromohydrin at high temperature by using an alkali salt or a quaternary ammonium salt as a catalyst in an alcohol solvent.

In addition, the epoxy ring-opening reaction carried out after the epoxidation reaction may be carried out by performing an acrylate reaction with (meth) acrylic acid under heavy metal catalysts such as triphenylphosphine, quaternary ammonium salts, Cr, and Co. By carrying out the epoxy ring-opening reaction in this way it is possible to easily obtain fluoroepoxy (meth) acrylate.

Compounds having at least one isocyanate group in the molecule used in the reaction with the fluoroepoxy (meth) acrylate are specifically 4,4'-dicyclohexyl diisocyanate, hexamethylene diisocyanate trimer, 1,4-di Socianatobutane, 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), 4, At least one selected from the group consisting of 4'-oxybis (phenylisocyanate), trifunctional isocyanate derived from hexamethylene diisocyanate, trimethanepropanol adduct toluene diisocyanate, acryloylethyl isocyanate, methacryloylethyl isocyanate Can be used.

The fluorine (meth) acrylate (A) represented by Chemical Formula 1 is preferably used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the total hard coating composition. If the content of the fluorine (meth) acrylate (A) represented by the formula (1) is less than 0.1 parts by weight based on the above standard, it is difficult to produce an antifouling effect. There is a problem.

Urethane (meth) acrylate oligomer (B)

The urethane (meth) acrylate oligomer (B) is added to secure sufficient hardness and scratch resistance.

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

The compound having at least one isocyanate group in the molecule may use at least one selected from the group consisting of compounds exemplified for the synthesis of the fluoro (meth) acrylate (A).

The (meth) acrylate compound having at least one hydroxy group in the molecule includes 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, One or more selected from the group consisting of caprolactone ring-opening hydroxyacrylate, pentaerythritol tri / tetra (meth) acrylate mixture, dipentaerythritol penta / hexa (meth) acrylate mixture, and the like can be used.

The urethane (meth) acrylate oligomer (B) may be a commercially available one, for example, EB1290 (6-functional urethane acrylate, SK Cytec), SUO1700B (10-functional urethane acrylate, cinnatiC), UV9160 (15) Functional urethane acrylate, H. smtron, etc. can be used.

Although the amount of the urethane (meth) acrylate oligomer (B) is not limited, it is preferably included 5 to 70 parts by weight based on 100 parts by weight of the hard coating composition, the amount of the urethane (meth) acrylate oligomer (B) added If it is less than 5 weight part on the basis of said reference | standard, it will be hard to see sufficient hardness improvement effect, and when it exceeds 70 weight part, there exists a problem which curling becomes severe.

(Meth) acrylate monomer (C)

The (meth) acrylate monomer (C) is added in order to improve the hardness and the curling properties of the cured layer.

The (meth) acrylate monomer (C) is, for example, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) ) Acrylate, (meth) acrylic ester, trimethylolpropane 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) acrylic Latene, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydrate Hydroxyethyl) isocyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso At least one selected from the group consisting of dexyl (meth) acrylate, stearyl (meth) acrylate, tetrahydroperfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornol (meth) acrylate, and the like. One kind can be used.

The amount of the (meth) acrylate monomer (C) is not limited, but is preferably included 5 to 70 parts by weight based on 100 parts by weight of the hard coating composition. If the addition amount of the (meth) acrylate monomer (C) is less than 5 parts by weight or more than 70 parts by weight based on the above criteria, it is difficult to exhibit an effect on sufficient hardness improvement.

Photoinitiator (D)

The photoinitiator may be applied without limitation as long as it is generally used in the art. Specifically, the photoinitiator (D) is 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenylketonebenzyldimethylketal, 2-hydroxy-2-methyl-1 -Phenyl-1-one, 4-hydroxycyclophenylketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloacetophenone , 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone, benzophenone and the like can be selected and 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 hard coating composition. When the content of the photoinitiator (D) is less than 0.1 parts by weight based on the above standard, if the curing speed of the hard coating composition is slow and exceeds 10 parts by weight, cracking of the hard coating layer due to over curing may occur.

Solvent (E)

The solvent (E) can be used without limitation that known as a solvent of the hard coating composition in the art.

Examples of the solvent (E) include alcohols (methanol, ethanol, isopropanol, butanol, methyl cellulose, ethyl solusorb, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, and dipropyl). Ketone, cyclohexanone, etc.), hexane system (hexane, heptane, octane etc.), benzene system (benzene, toluene, xylene etc.) etc. can be illustrated.

The solvents (E) 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 properties of the fluorine compound.

Specific examples of the fluorine solvent include hydrofluorocarbon and hydrofluoroether, and commercially available Batrell XF (CF ₃ CHFCHFCF ₂ CF ₃ ) manufactured by DuPont, Zeolola H (heptafluorocyclopentane) manufactured by Nippon Zeon, and 3M One or more 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 (E) may be added 1 to 80 parts by weight based on 100 parts by weight of the hard coating composition. If the solvent (E) is less than 1 part by weight based on the above-mentioned standards, the viscosity is high and workability is inferior, and when it exceeds 80 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 selected from triacetyl cellulose, acetyl cellulose butyrate, isobutyl ester cellulose, propionyl cellulose, butyryl cellulose, or acetyl propionyl cellulose , Polyacryl, polyimide, polyether sulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, poly Ether 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, has no transparency and optical anisotropy. Acetylcellulose film can be suitably used.

8-1000 micrometers is preferable and, as for the thickness of the said 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 has a water resistance contact angle of 90 ° to 130 ° at 25 ° C, and oil contact angle of 60 ° to 90 ° at 25 ° C. 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 Fluorine Epoxy Compound

50 parts by weight of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (TCI), epichlorohydrin (Aldrich G) 320 parts by weight, 100 parts by weight of isopropyl alcohol (Aldrich) and the reactor temperature are raised to 50 ° C, and then 5 parts by weight of sodium hydroxide is dissolved in 10 parts by weight of purified water and slowly added thereto. After the addition is complete, the mixture is stirred for an additional 1 hour. After completion of the reaction, the upper water layer was removed, 50 wt% sodium hydroxide solution was added thereto, and the mixture was terminated by stirring at 40 ° C. for 2 hours. Remove the water layer, add 300 parts by weight of methyl isopropyl ketone, add 200 parts by weight of water to remove the extract layer, and remove the extract by adding twice more water in the field. The solvent layer was removed at 70 ° C. and 5 torr to obtain a fluorine epoxy compound having an epoxy equivalent of 90.

Synthesis Example 2 Fluorine Epoxy Compound

30 parts by weight of 1,1,1,3,3,3-hexafluoro-2-propanol (TCI), 320 parts by weight of epichlorohydrin (Aldrich), 100 parts by weight of isopropyl alcohol (Aldrich), reactor After the temperature was raised to 50 ° C, 5 parts by weight of sodium hydroxide (Aldrich) was dissolved in 10 parts by weight of purified water and slowly added thereto. After the addition is complete, the mixture is stirred for an additional 1 hour. After completion of the reaction, the upper water layer was removed, 50 wt% sodium hydroxide solution was added thereto, and the mixture was terminated by stirring at 40 ° C for 2 hours. The water layer was removed, and 300 parts by weight of methyl isopropyl ketone (Daejung Jingum Co., Ltd.) and 200 parts by weight of water were added to remove the extract layer, followed by extracting and removing water by adding twice a day. The solvent layer is removed at 70 ° C. and 5 torr to obtain a reaction product having an epoxy equivalent of 87.

Synthesis Example 3 Fluorine Epoxy (meth) acrylate Compound

30 parts by weight of the epoxy compound prepared in Synthesis Example 1, 5 parts by weight of acrylic acid (LG Chem.), 0.1 parts by weight of triphenylphosphine (TCI) as a catalyst, 0.05 parts by weight of 4-methoxyphenol (TCI) Inject and raise the temperature to 95 ℃ and stirred for 7 hours. A reaction product having an acid value of 0.2 was obtained.

Synthesis Example 4 Fluorine Epoxy (meth) acrylate Compound

30 parts by weight of the epoxy compound prepared in Synthesis Example 2, 7 parts by weight of acrylic acid (LG Chem.), 0.1 part by weight of triphenylphosphine (TCI) as a catalyst, 0.05 part by weight of 4-methoxyphenol (TCI) Inject and raise the temperature to 95 ℃ and stirred for 7 hours. A reaction product having an acid value of 0.1 was obtained.

Synthesis Example 5 Fluorine (meth) acrylate compound

25 parts by weight of the epoxy (meth) acrylate compound prepared in Synthesis Example 3, 9 parts by weight of isophorone diisocyanate (Aldrich), 0.1 part by weight of dibutyltin dilaurate (Aldrich) as a catalyst, polymerization inhibitor 4- 0.05 parts by weight of methoxy phenol (TCI) was added and the temperature was raised to 70 ° C and stirred for 2 hours. The reaction was terminated when 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

Synthesis Example 6 Fluoro (meth) acrylate Compound

25 parts by weight of the epoxy (meth) acrylate compound prepared in Synthesis Example 3, 10 parts by weight of 1,6-diisocyanatohexane (Aldrich), 0.1 part by weight of dibutyltin dilaurate (Aldrich) as a catalyst, and polymerization prohibited 0.05 part by weight of 4-methoxyphenol (TCI) was added thereto, and the mixture was heated to 70 ° C and stirred for 2 hours. The reaction was terminated when 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

Synthesis Example 7 Fluorine (meth) acrylate compound

25 parts by weight of the epoxy (meth) acrylate compound prepared in Synthesis Example 3, 13 parts by weight of 4,4'-methylenebis (cyclohexyl isocyanate) (Aldrich), 0.1 part by weight of dibutyltin dilaurate (Aldrich) In addition, 0.05 weight part of 4-methoxyphenol (TCI) polymerization inhibitors were added, the temperature was raised to 70 ° C and stirred for 2 hours. The reaction was terminated when 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

Synthesis Example 8 Fluorine (meth) acrylate compound

27 parts by weight of the epoxy (meth) acrylate compound prepared in Synthesis Example 4, 9 parts by weight of isophorone diisocyanate (Aldrich), 0.1 part by weight of dibutyltin dilaurate (Aldrich) as a catalyst, polymerization inhibitor 4- 0.05 parts by weight of methoxy phenol (TCI) was added and the temperature was raised to 70 ° C and stirred for 2 hours. The reaction was terminated when 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

Synthesis Example 9 Fluorine (meth) acrylate compound

26 parts by weight of the epoxy (meth) acrylate compound prepared in Synthesis Example 4, 9 parts by weight of 4,4'-methylenebis (cyclohexyl isocyanate) (Aldrich), 0.1 part by weight of dibutyltin dilaurate (Aldrich) In addition, 0.05 weight part of 4-methoxyphenol (TCI) polymerization inhibitors were added, the temperature was raised to 70 ° C and stirred for 2 hours. The reaction was terminated when 2260 cm ^-1 , the characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

[Examples 1-11 and Comparative Examples 1-3: 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.

Composition Example Comparative example One 2 3 4 5 6 7 8 9 10 11 One 2 3 Fluorine (meth) acrylate Synthesis Example 5 3 One 3 Synthesis Example 6 3 20 0.05 Synthesis Example 7 3 Synthesis Example 8 3 9 Synthesis Example 9 3 31 MCF 350-5 One 10 3 EB1290 25 25 25 25 25 27 10 30 40 45 5 40 25 30 Acrylate monomer 15 15 15 15 15 15 20 7 5 5 15 10 20 10 menstruum MIBK 15 15 15 15 15 15 24 28 30 19 23 44 36 43 MEK 40 40 40 40 40 40 24 24 20 29 24 3 7 12 Photoinitiator I-184 One One One One One One One One One One One One One One I-907 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 additive BYK-378 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

MCF 350-5: Fluoropolymer (Dainippon Ink)

EB1290: 6-functional urethane acrylate (SK Cytec)

Acrylate monomer: dipentaerythritol penta / hexa acrylate (Japanese synthetic, DPHA)

MIBK: methyl isobutyl ketone

MEK: methyl ethyl ketone

I-184: 1-hydroxycyclohexylphenyl 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 on a transparent substrate film (80㎛, TAC) to a thickness of 8㎛ and then dried at 70 ℃ for 2 minutes, 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 three peel tests were performed using a tape (CT-24, manufactured by Nichi Nippon Co., Ltd.), and the average value was recorded. .

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) waterproof 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.

(6) oil resistance 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.

(7) 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: A lot of wipe marks remain.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 practice
Example 9 practice
Example 10 practice
Example 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 Hard Coating Thickness (㎛) 8 8 8 8 8 8 8 8 8 8 8 8 8 8 Surface smoothness A A A A B B A B A A B B B A Total light transmittance (%) 90.8 91.3 91.1 91.3 92 91 90.5 90 91.2 91.1 90.7 87.5 82 76 Pencil hardness 4 H 5 H 5 H 2 H 5H 3H 4H 3H 4H 3H 4H 3H 3H 3H Scratch resistance A A A B A A A A A A A B B B Adhesion 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 99 /
100 99 /
100 100 /
100 Fingerprint Wipe A A A A A A A A A A A C B C Haze 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 Waterproof contact angle (°) 109 109 109 110 108 109 118 113 114 115 125 75 95 87 Oil contact angle (°) 77 76 77 77 75 77 86 81 77 78 90 50 63 59

As shown in Table 2, in the case of Examples 1 to 3 containing fluorine (meth) acrylate represented by Formula 1 according to the present invention, the fingerprint wiping resistance and the degree of contamination resistance were compared with those of Comparative Examples 1 to 3, which do not include the same. It can be confirmed that the internal contact angle and the oil contact angle can be confirmed in general. In addition, the hard coating film according to the present invention can be confirmed that the physical properties such as surface smoothness, total light transmittance, pencil hardness, scratch resistance, adhesion, haze and the like.

Claims (7)

Fluorine (meth) acrylate (A), urethane (meth) acrylate oligomer (B), (meth) acrylate monomer (C), photoinitiator (D), and solvent (E) represented by the following [Formula 1] Hard coating composition, characterized in that.  [Formula 1]

(In Formula 1, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₁ is an aliphatic or aromatic hydrocarbon having 1 to 30 carbon atoms, with or without heterocycle, R _f is independently 1 to 20 carbon atoms A linear or branched alkyl group of at least 50% of the hydrogen atom sites are replaced by F.) The method of claim 1, wherein the hard coating composition is based on 100 parts by weight of the total composition, 0.1 to 30 parts by weight of the fluorine (meth) acrylate (A), 5 to 70 parts by weight of the urethane (meth) acrylate oligomer (B) 5 to 70 parts by weight of the (meth) acrylate monomer (C), 0.1 to 10 parts by weight of the photoinitiator (D) and 1 to 80 parts by weight of the solvent (E). Hard coating film comprising a hard coating layer formed by applying the hard coating composition of claim 1 or 2 on one or both sides of the transparent substrate and then cured. The hard coating film of claim 3, wherein the hard coating layer has a water contact angle of 90 to 130 ° at 25 ° C. The hard coating film of claim 3, wherein the hard coating layer has an oil contact angle of 60 to 90 ° at 25 ° C. 5. The hard coating film of claim 3 is provided, characterized in that the polarizing plate. An image display device, comprising the hard coating film of claim 3.