KR101546098B1 - Coating composition for low refractive layer anti-reflection film using the same and image displaying device comprising said anti-reflection film - Google Patents

Abstract

The present invention relates to a composition for forming a low-refractive-index layer, an antireflection film, a polarizing plate, and a display device using the same, wherein the composition for forming a low refractive index layer includes hollow silica particles and polyfunctional fluorine compounds, Excellent scratch resistance and adhesion, and can be effectively applied to an antireflection film, a polarizing plate and a display device.

Low refractive layer, hollow silica, polyfunctional fluorine compound

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for forming a low refractive index layer, an antireflection film using the same, a polarizing plate, and a display device. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

The present invention relates to a composition for forming a low refractive index layer, an antireflection film using the same, a polarizing plate and a display device.

Recently, displays such as CRT, LCD, and PDP have been developed and various devices using these displays have been used in various fields. In the case where these devices are used in a relatively bright place such as the outdoors, there is an increasing tendency that the external light such as sunlight or fluorescent light is not reflected to the display, thereby preventing the external light from being reflected on the display surface And the demand for it is becoming strong.

An anti-reflection film for preventing the external appearance of the display device from being reflected is widely developed. As the antireflection film, a multilayered antireflection film is known (PCT JP2003-008535). The antireflection film of the multi-layer structure has a three-layer structure composed of a two-layer structure composed of a high refractive index layer and a low refractive index layer, a middle refractive index layer, a high refractive index layer and a low refractive index layer, Layer structure and a low-refractive index layer are known.

In recent years, the antireflection film is required to have additional functions such as scratch resistance, abrasion resistance and antifouling property as well as antireflection function. To this end, an antireflection film using an antistatic property to the high refractive index layer or a substance having antifouling property to the low refractive index layer is used.

However, the above-mentioned antireflection film is limited in the materials that can be used, is expensive, raises the manufacturing cost, and the problem of deteriorating optical properties such as reflection characteristics, transmittance, haze and the like due to addition of such additional functions there was.

Disclosure of the Invention An object of the present invention is to provide a composition for forming a low refraction layer excellent in antireflection characteristics such as haze and reflectance when applied to an antireflection film and excellent in scratch resistance and adhesion There is.

Another object of the present invention is to provide an antireflection film formed using the composition for forming a low refractive index layer.

It is still another object of the present invention to provide a polarizing plate provided with the antireflection film.

It is still another object of the present invention to provide a display device provided with the antireflection film.

(B), a (meth) acrylate monomer (C), a photoinitiator (D) and a solvent (E) represented by the following general formula (1) The composition for forming a low refractive index layer.

[Chemical Formula 1]

(Wherein 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 is independently linear, branched branched or cyclic aliphatic or aromatic hydrocarbon containing 3 to 50 carbon atoms and containing no hetero atom and X is a hetero ring having 7 to 80 carbon atoms containing a (meth) acrylate group having 2 to 15 functional groups And R _f is a linear or branched alkyl group of 1 to 20 carbon atoms in which at least 50% of the hydrogen atom sites are substituted by F.)

The refractive index of the hollow silica particles is preferably 1.17 to 1.40.

Wherein the composition for forming a low refractive index layer comprises 0.1 to 20 parts by weight of the hollow silica particles (A), 0.1 to 30 parts by weight of the multifunctional fluorine compound (B), 0.1 to 30 parts by weight of the (meth) acrylate monomer (C), 0.05 to 5 parts by weight of the photoinitiator (D), and 50 to 98 parts by weight of the solvent (E).

According to another aspect of the present invention, there is provided an antireflection film comprising a transparent substrate and a low refractive layer formed on the transparent substrate using the composition for forming a low refractive layer according to the present invention. Film.

The reflective film may further include a hard coating layer formed between the transparent base and the low refractive layer.

The refractive index of the low refractive layer is preferably 1.2 to 1.49 at 25 캜.

According to another aspect of the present invention, there is provided a polarizing plate comprising the anti-reflection film according to the present invention.

In order to achieve still another object of the present invention, there is provided a display device comprising the anti-reflection film according to the present invention.

The composition for forming a low refractive index layer according to the present invention is excellent in antireflection characteristics such as haze and reflectance, and has excellent scratch resistance and adhesion properties by including hollow silica particles and a polyfunctional fluorine compound having a predetermined structure have. Accordingly, the antireflection film produced using the composition for forming a low refractive index layer has excellent scratch resistance and antireflection property, and can be applied to a polarizing plate and a display device.

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

The composition for forming a low refraction layer according to the present invention comprises a hollow silica particle (A), a polyfunctional fluorine compound (B), a (meth) acrylate monomer (C), a photoinitiator (D) .

The hollow silica particles (A)

The hollow silica particles are used to improve the anti-reflection property by lowering the refractive index and to improve the scratch resistance.

The refractive index of the hollow silica particles is preferably 1.17 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. Here, the refractive index does not mean the refractive index of the silica, that is, the refractive index of the outer periphery forming the hollow particle, but the refractive index of the whole particle.

The porosity in the hollow silica particles is preferably in the range of 10 to 60%, more preferably in the range of 20 to 60%, and most preferably in the range of 30 to 60%.

If the low refractive index of the hollow silica particles and their high porosity are to be achieved, the thickness of the shell is reduced and the strength of the particles is weakened. Therefore, from the viewpoint of scratch resistance, any particles having a refractive index of the hollow silica particles of less than 1.17 are undesirable because they have low scratch resistance. In addition, when the refractive index of the hollow silica particles exceeds 1.40, the refractive index is high and the antireflection characteristics are deteriorated. The refractive index of the hollow silica particles is measured using an Abbe refractive index meter (manufactured by ATAGO).

The above-mentioned hollow silica particles can be easily produced by a known production method. For example, hollow silica particles prepared by the method described in JP-A-2001-233611 and JP-A-2002-79616 can be used.

The average particle diameter of the hollow silica particles is preferably 30 to 150%, more preferably 35 to 80%, and particularly preferably 40 to 60% of the low refractive index layer. That is, when the thickness of the low refractive index layer is 100 nm, the average particle diameter of the hollow silica particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and particularly preferably 40 nm to 60 nm. When the hollow silica fine particles are within the range described above, the proportion of the hollow portion is increased, and a low refractive index can be achieved. Furthermore, it does not cause a problem of forming fine irregularities on the surface of the low refractive index layer to lower the reflectance. The hollow silica particles may be crystalline particles or amorphous particles, and monodisperse particles are preferable. In consideration of the shape, spherical particles are most preferable, but amorphous particles can be used without problems. The average particle diameter of the hollow silica fine particles is also measured by using an electron microscope photograph.

The content of the hollow silica is not limited, but is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total composition for forming a low refractive layer. If the content of the hollow silica is less than 0.1 parts by weight, a sufficient refractive index reduction effect can not be obtained. If the content is more than 20 parts by weight, scratch resistance is deteriorated.

The multifunctional fluorine compound (B)

The polyfunctional fluorine compound is used for improving the refractive index lowering effect and the scratch resistance. The composition for forming a low refractive layer according to the present invention includes a polyfunctional fluorine compound represented by the following formula (1).

[Chemical Formula 1]

(Wherein 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, and R ₁ is each independently a linear, branched ) Or cyclic aliphatic or aromatic hydrocarbons containing 3 to 50 carbon atoms and containing no hetero atoms and X is a hetero atom having 7 to 80 carbon atoms containing a (meth) acrylate group having 2 to 15 functional groups And R _f is a linear or branched alkyl group having 1 to 20 carbon atoms, in which at least 50% of the hydrogen atom sites are substituted by F.)

The multifunctional fluorine compound represented by the formula (1) can be easily produced by reacting a perfluoropolyether diol compound and a compound having two or more isocyanate groups in the molecule and a compound having two or more (meth) acrylate groups each having a hydroxyl group in the molecule Can be manufactured.

The perfluoropolyether diol compound is commercially available from Omnova Solutions, Inc. under the trade names of Polyox ^™ PF-636, Polyox ^™ PF-6320, Polyox ^™ PF-656, Polyox ^™ PF-6520 and Polyox ^™ PF- , And the molecular weight thereof is 1000 to 5000. The molecular weight of the polymer is preferably in the range of 1,000 to 5,000.

Further, the compound having two or more isocyanate groups in the molecule is specifically 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- 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, Diisocyanate, 1, -chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenylisocyanate), 4,4'-oxybis (phenylisocyanate) Trifunctional isocyanate derived from hexamethylene diisocyanate, trimethane propanol adduct tall From the group consisting of isocyanate-endian can be used at least one member selected.

The compound having a hydroxyl group in the molecule and having two or more (meth) acrylate groups specifically includes pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate may be used.

The content of the multifunctional fluorine compound represented by the formula (1) is not limited, but is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the low refractive layer forming composition. If the content of the polyfunctional fluorine compound is less than 0.1 part by weight, a sufficient refractive index reduction effect can not be obtained and scratch resistance is lowered. When the content of the polyfunctional fluorine compound exceeds 30 parts by weight, workability is poor due to poor compatibility.

(Meth) acrylate monomer (C)

The (meth) acrylate monomer is added to improve the hardness of the cured layer. The (meth) acrylate monomer is specifically exemplified by dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl (meth) acrylate, propylene glycol Acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di Hydroxypropyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, iso At least one member selected from the group consisting of styrene (meth) acrylate, stearyl (meth) acrylate, tetrahydroperfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, Can be used.

The content of the (meth) acrylate monomer is not limited, but is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the entire composition for forming a low refractive layer. When the content of the (meth) acrylate monomer is less than 0.1 part by weight, there is a problem in surface hardening of the low refraction layer. When the content is more than 30 parts by weight, the refraction index of the low refraction layer increases.

Photoinitiator (D)

The photoinitiator may be selected from the group consisting of 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenylketone benzyldimethylketal , 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenyl ketone, dimethoxy-2-phenylacetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3 At least one selected from the group consisting of methyl acetophenone, 4-quinolone acetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone and benzophenone is used .

The content of the photoinitiator is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the entire composition for forming a low refractive index layer. If the content of the photoinitiator is less than 0.05 part by weight, the curing rate of the composition for forming a low refractive index layer is slow. If the content of the photoinitiator exceeds 5 parts by weight, cracks may be generated in the low refractive layer.

Solvent (E)

The solvent is not limited as long as it is known as a solvent for the composition for forming a low refractive layer in the technical field.

For example, the solvent may be at least one selected from the group consisting of alcohols (methanol, ethanol, isopropanol, butanol, methylcellulose, ethylsulosorb), 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 solvents exemplified above may be used alone or in combination of two or more.

The content of the solvent may be 50 to 98 parts by weight based on 100 parts by weight of the entire composition for forming a low refractive index layer. When the amount of the solvent is less than 50 parts by weight, the viscosity of the solvent is too high to coat the thin film. When the amount of the solvent exceeds 98 parts by weight, the curing process takes a long time and the cost is low.

In addition to the above components, a light stimulant, an antioxidant, a UV absorber, a light stabilizer, a thermal polymerization inhibitor, a lubricant, a surfactant, a lubricant, and the like may be used in the composition for forming a low refractive index layer.

In the present invention, there is provided an antireflection film comprising a low refraction layer produced using the composition for forming a low refraction layer. More specifically, the antireflection film includes a transparent substrate and a low refractive layer formed on one or both surfaces of the transparent substrate using the composition for forming a low refractive layer according to the present invention.

At this time, the antireflection film of the present invention may further include a hard coat layer between the transparent material and the low refractive layer to impart the physical strength of the film. That is, a preferred example of the antireflection film according to the present invention includes a hard coating layer formed on an upper surface of a transparent substrate, and a low refractive index layer formed by curing the composition for forming a low refractive index layer on an upper surface thereof.

Any transparent plastic film may be used. For example, cycloolefin-based derivatives having units of monomers including cycloolefins such as norbornene and polycyclic norbornene monomers, diacetylcellulose Cellulose acetate, ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyvinyl alcohol, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyrrolidone, polyvinylpyrrolidone, polyvinylpyrrolidone, polyvinylpyrrolidone, polyvinylpyrrolidone, triacetylcellulose, acetylcellulosebutylate, isobutylestercellulose, propionylcellulose, butyrylcellulose or acetylpropionylcellulose. , Polyacrylic, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyetheretherketone, poly Ether sulfone, poly Polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, and epoxy. Non-stretched monoaxially or biaxially stretched films can be used.

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 base film is 8 to 1000 탆, preferably 40 to 100 탆.

From the optical design for obtaining a good antireflection film, the hard coat layer formed on the transparent substrate preferably has a refractive index in a range of 1.48 to 2.00 at 25 DEG C, more preferably 1.50 to 1.90, Is 1.50 to 1.80. Since the antireflection film according to the present invention includes at least one low refractive index layer on the hard coat layer, if the refractive index is less than the above range, the antireflection property is deteriorated. If the refractive index is larger than the above range, There are disadvantages.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a photo-curable compound. These compounds are not particularly limited. For example, a composition for forming a hard coating layer containing a photo-curable polyfunctional monomer or a polyfunctional oligomer is applied on a transparent support, and then the polyfunctional monomer or polyfunctional oligomer is crosslinked or polymerized And the like.

The functional group of the polyfunctional monomer or polyfunctional oligomer of the photocuring agent is preferably a polymer which is photo-polymerizable, electron-beam-polymerizable, or radiation-polymerizable. Of these, photopolymerizable functional groups are preferable.

Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group, and among them, a (meth) acryloyl group is preferable.

Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include (meth) acrylates such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate and propylene glycol di (meth) Meta) acrylic acid diesters; (Meth) acrylate such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate and polypropylene glycol di Esters; (Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; Propylene oxide adducts such as 2,2-bis {4- (acryloxy diethoxy) phenyl} propane, 2,2-bis {4- (acryloxypolypropoxy) Di (meth) acrylate, and the like. Also, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates can be preferably used as photopolymerizable polyfunctional monomers.

Of the photopolymerizable polyfunctional monomers exemplified above, esters of polyhydric alcohol and (meth) acrylic acid can be preferably used.

The photopolymerizable polyfunctional monomer is more preferably a polyfunctional monomer having three or more (meth) acryloyl groups in one molecule. Specific examples of the polyfunctional monomer having three or more (meth) acryloyl groups in the molecule include trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, 1,2,4-cyclo (Meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexa triacrylate, and the like.

The photopolymerizable multifunctional monomers described above may be used alone or in combination of two or more.

It is preferable to use a photoinitiator for the polymerization reaction of the photopolymerizable multifunctional monomer. As the photoinitiator, a photo radical initiator and a photo cation initiator are preferable, and a photo radical initiator is particularly preferable.

As the photo radical initiator, those generally used in the art can be applied, and examples thereof include acetophenones, benzophenones, benzoyl benzoates of Mihiller,? -Amyloxime esters, tetramethylthiurammonosulfur Fats and thioxanthones, and the like.

The hard coating layer and the low refractive layer sequentially formed on the transparent substrate in the antireflection film according to the present invention may be formed into a hard coating layer by an appropriate method such as die coater, air knife, reverse roll, spray, blade, casting, gravure, And a composition for forming a low refractive index layer according to the present invention.

The coating thickness of the composition for forming a hard coat layer is usually 3 to 50 占 퐉, preferably 5 to 40 占 퐉, and more preferably 5 to 35 占 퐉. The composition for forming a hard coat layer is coated and then dried at a temperature of 30 to 150 DEG C for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes. Upon completion of the drying, UV light is irradiated to cure the composition for forming a hard coating layer to form a hard coating layer. 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 coating thickness of the low refraction layer forming composition is 0.01 to 2 탆, preferably 0.05 to 0.3 탆. After the composition for forming a low refractive index layer is applied, the composition is dried at a temperature of 30 to 150 DEG C for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes. Upon completion of drying, UV light is irradiated to cure the composition for forming a low refractive layer to form a low refractive layer. The irradiation amount of the UV light is about 0.01 to 10 J / cm ² , preferably 0.1 to 2 J / cm ² .

When the coating thickness of the composition for forming a low refractive index layer is within the above range, more excellent antifouling characteristics can be obtained and good durability can be maintained.

From the optical design for obtaining the antireflection film, it is preferable that the refractive index at 25 캜 is in the range of 1.20 to 1.49. When the refractive index of the low refractive layer is less than the above range, the antireflection property is deteriorated. If the refractive index is higher than the above range, the color of the reflected light becomes strong.

The antireflection film produced as described above has excellent scratch resistance, antireflection properties, and excellent adhesion.

The present invention provides a polarizing plate comprising the above-mentioned antireflection film.

The polarizing plate is not particularly limited, but various types can be used. As the polarizing plate, for example, a hydrophilic polymer film such as a polyvinyl alcohol-based film and an ethylene-vinyl acetate copolymerization system partially saponified film may be produced by adsorbing a dichromatic substance such as iodine or a dichromatic 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 may be mentioned. Among them, a polarizing plate made of a dichromatic material such as a polyvinyl alcohol-based film and iodine is preferable. The thickness of these polarizing plates is not particularly limited, but is generally about 5 to 80 탆.

The present invention also provides a display device to which the above-described antireflection film is applied.

For example, by incorporating the polarizing plate on which the antireflection film of the present invention is formed in a display device, various display devices having excellent visibility can be manufactured. Further, the antireflection film of the present invention may be attached to a window of a display device. The antireflection 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. Further, the antireflection 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 multifunctional fluorine compound

, 30 parts by weight of a fluorine diol compound having an average molecular weight of 1,500 (Polyox ^™ PF-656, Omnova Solutions Inc.), 9 parts by weight of isophorone diisocyanate (IPDI, BASF Corp.), dipentaerythritol penta / hexaacrylate (FASCAT 4202, Akeema Co.) as a reaction catalyst, 0.05 part by weight of methoxyhydroquinone (HQMME, Eastman) as a polymerization inhibitor was added thereto at room temperature, and the mixture was stirred The reaction temperature was raised to 90 占 폚. The reaction was carried out at 90 DEG C for 12 hours, and the reaction was terminated when the characteristic peak of isocyanate of 2260 cm < ^-1 > in the infrared spectroscopic spectrum completely disappeared.

[Synthesis Example 2] Synthesis of polyfunctional fluorine compound

30 parts by weight of a fluorine diol compound having an average molecular weight of 1,500 (Polyox ^™ PF-656, Omnova Solutions Inc.), 9 parts by weight of isophorone diisocyanate (IPDI, BASF Corp.), pentaerythritol trie / tetraacrylate (M340, ), 0.1 part by weight of dibutyltin dilaurate (FASCAT 4202, Akema) as a reaction catalyst, 0.05 part by weight of methoxyhydroquinone (HQMME, Eastman) as a polymerization inhibitor was added thereto at room temperature, The temperature was raised to 90 占 폚. The reaction was carried out at 90 DEG C for 12 hours and the reaction was terminated when the characteristic peak of isocyanate of 2260 cm < ^-1 > in the infrared spectroscopic spectrum completely disappeared.

[Synthesis Example 3] Synthesis of multifunctional fluorine compound

60 parts by weight of a fluorine diol compound having an average molecular weight of 3200 (Polyox ^™ PF-6520, Omnova Solutions Inc.), 9 parts by weight of isophorone diisocyanate (IPDI, BASF Corp.), dipentaerythritol penta / hexaacrylate (FASCAT 4202, Akeema Co.) as a reaction catalyst, 0.05 part by weight of methoxyhydroquinone (HQMME, Eastman) as a polymerization inhibitor was added thereto at room temperature, and the mixture was stirred The reaction temperature was raised to 90 占 폚. The reaction was carried out at 90 DEG C for 12 hours, and the reaction was terminated when the characteristic peak of isocyanate of 2260 cm < ^-1 > in the infrared spectroscopic spectrum completely disappeared.

[Synthesis Example 4] Synthesis of polyfunctional fluorine compound

20 parts by weight of a fluorine diol compound having an average molecular weight of 1000 (Polyox ^™ PF-636, Omnova Solutions Inc.), 9 parts by weight of isophorone diisocyanate (IPDI, BASF Corp.), and 25 parts by weight of dipentaerythritol penta / hexaacrylate (FASCAT 4202, Akeema Co.) as a reaction catalyst, 0.05 part by weight of methoxyhydroquinone (HQMME, Eastman) as a polymerization inhibitor was added thereto at room temperature, and the mixture was stirred The reaction temperature was raised to 90 占 폚. The reaction was carried out at 90 DEG C for 12 hours, and the reaction was terminated when the characteristic peak of isocyanate of 2260 cm < ^-1 > in the infrared spectroscopic spectrum completely disappeared.

[Synthesis Example 5] Synthesis of multifunctional fluorine compound

, 54 parts by weight of a fluorine diol compound having an average molecular weight of 2800 (Polyox ^™ PF-6320, Omnova Solutions Inc.), 9 parts by weight of isophorone diisocyanate (IPDI, BASF Corp.), dipentaerythritol penta / hexaacrylate (FASCAT 4202, Akeema Co.) as a reaction catalyst, 0.05 part by weight of methoxyhydroquinone (HQMME, Eastman) as a polymerization inhibitor was added thereto at room temperature, and the mixture was stirred The reaction temperature was raised to 90 占 폚. The reaction was carried out at 90 DEG C for 12 hours, and the reaction was terminated when the characteristic peak of isocyanate of 2260 cm < ^-1 > in the infrared spectroscopic spectrum completely disappeared.

[Synthesis Example 6] Synthesis of multifunctional fluorine compound

, 20 parts by weight of a fluorine diol compound having an average molecular weight of 1,500 (Polyox ^™ PF-656, Omnova Solution Company), 7 parts by weight of 1,6-dihexane diisocyanate (HDI, TCI), 10 parts by weight of dipentaerythritol penta / (DPHA, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 0.1 part by weight of dibutyltin dilaurate (FASCAT 4202, Akeema Co.) as a reaction catalyst, 0.05 part by weight of methoxyhydroquinone (HQMME, Eastman) And the reaction temperature was raised to 90 DEG C while stirring. The reaction was carried out at 90 DEG C for 12 hours, and the reaction was terminated when the characteristic peak of isocyanate of 2260 cm < ^-1 > in the infrared spectroscopic spectrum completely disappeared.

[Synthesis Example 7] Synthesis of multifunctional fluorine compound

20 parts by weight of a fluorine diol compound having an average molecular weight of 1,500 (Polyox ^™ PF-656, Omnova Solutions Inc.), 7 parts by weight of 1,6-dihexane diisocyanate (HDI, TCI), and pentaerythritol penta / hexaacrylate 140 parts by weight as a reaction catalyst, and 0.1 part by weight of dibutyltin dilaurate (FASCAT 4202, Akeema Co.) as a polymerization inhibitor were added at room temperature to 0.05 parts by weight of methoxyhydroquinone (HQMME, Eastman) , And the reaction temperature was raised to 90 DEG C while stirring. The reaction was carried out at 90 DEG C for 12 hours, and the reaction was terminated when the characteristic peak of isocyanate of 2260 cm < ^-1 > in the infrared spectroscopic spectrum completely disappeared.

[Production Example of Composition for Hard Coat Layer]

70 parts by weight Urethane acrylate (Shin-Nakamura Chemical Co., U-15HA), 30 parts by weight pentaerythritol triacrylate (PE-3A), 3 parts by weight Photoinitiator (Cibasia, D-1173) Ethyl ketone, and 100 parts by weight of toluene were mixed to prepare a composition having a refractive index of 1.51.

[Examples 1 to 8 and Comparative Examples 1 to 3]

The above-prepared composition for a hard coat layer was coated on one side of a transparent substrate made of a triacetyl cellulose film having a thickness of 80 mu m, followed by drying by heating, followed by ultraviolet curing to form a hard coat layer having a thickness of 5 mu m.

A composition for forming a low refractive index layer having the composition shown in the following Table 1 was coated on the hard coating layer, and after heating and drying, a low refractive layer having a thickness of 0.1 占 퐉 was formed by ultraviolet curing.

Composition Example Comparative Example One 2 3 4 5 6 7 8 9 10 11 12 13 One 2 3 Multifunctional fluorine compound Synthesis Example 1 3 3 Synthesis Example 2 3 10 Synthesis Example 3 3 31 Synthesis Example 4 3 3 Synthesis Example 5 3 5 15 Synthesis Example 6 3 20 Synthesis Example 7 3 Fluoropolymer 3 10 Hollow silica particles 3 3 3 3 3 3 3 10 5 3 21 3 15 3 Acrylate
The monomer (a) 2 2 2 2 One 0.5 3 2 2 2 3 5 Acrylate
The monomer (b) 2 2 2 One menstruum MIBK 86 86 86 86 4 4 4 76 76 60 9 70 66 86 70 3 MEK 4 4 4 4 86 86 86 8 6 4 60 3 12 4 10 80 Photoinitiator I-184 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 One 1.5 1.5 1.5 1.5 1.5 1.5 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 0.5 0.5 The low-
Refractive index 1.37 1.36 1.38 1.37 1.39 1.37 1.36 1.32 1.34 1.4 1.31 1.39 1.32 1.38 1.45 1.48

Fluoropolymer: CC-04 (refractive index 1.41, solid content 50% in butyl acetate, central glass)

Hollow silica particles: refractive index 1.30, average particle diameter 40 nm,

Acrylate monomer (a): dipentaerythritol penta / hexaacrylate (refractive index: 1.476, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., DPHA)

Acrylate monomer (b): pentaerythritol tri / tetraacrylate (refractive index 1.47, M340, M340)

MIBK: Methylisobutyl ketone (purified gold)

MEK: Methyl ethyl ketone (purified water)

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

BYK-378: silicone modified oil (BYK)

<Experimental Example>

The antireflection film thus prepared was measured for physical properties as described below, and the results are shown in Table 2 below.

(1) scratch resistance

And scratch resistance was tested by reciprocating ten times under 1 kg / (2 cm x 2 cm) using a steel wool tester (WT-LCM100, Korea Protec Co.). Steel wool used # 0000.

A: 0 scratches

A ': 1 to 10 scratches

B: 11-20 scratches

C: 21 ~ 30 scratches

D: More than 31 scratches

(2) Adhesion

11 straight lines were drawn at intervals of 1 mm on the coated surface of the film to form 100 squares, and then peel test was performed three times using a tape (CT-24, manufactured by Nihon Nichiban Co., Ltd.). Three 100 squares were tested and the average was recorded.

The adhesion was recorded as follows.

Adhesion = n / 100

n: the number of rectangles that are not to be peeled out of the entire rectangle

100: total number of squares

Therefore, when one of them was not peeled off, it was recorded as 100/100.

(3) Surface reflectance

The adapter MPC2200 was attached to a spectrophotometer UV2450 (Shimadzu) to measure the specular reflectance at an angle of incidence of 5 deg. At an incident angle of 5 deg. In a wavelength range of 380 to 780 nm, and an average reflectance of 450 to 650 nm was calculated.

(4) Hayes

The haze was measured using a haze meter (Suga HZ-1).

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Comparative Example 1 Comparative Example 2 Comparative Example 3 Scratch resistance A A A A A A A A A A A A A C B C Adhesiveness 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 90 /
100 85 /
100 Haze (%) 0.2 0.2 0.3 0.3 0.2 0.3 0.2 0.2 0.3 0.3 0.4 0.2 0.3 0.3 0.5 0.7 reflectivity(%) 0.96 0.97 1.03 0.93 1.04 1.01 0.96 0.97 0.98 0.99 0.92 1.01 0.97 0.96 1.33 1.35

As shown in Table 2, in Examples 1 to 13 including the multifunctional fluorine compound represented by Formula 1 and the hollow silica particles according to the present invention, the scratch resistance was remarkably higher than that of Comparative Examples 1 to 3 You can see the results show. Also, it has excellent reflectance characteristics and excellent anti-reflection effect is realized.

Claims (8)

(B), (C) a photoinitiator (D), and (E) a solvent (E), wherein the hollow silica particles (A) / RTI &gt; [Chemical Formula 1]

(Wherein 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, and R ₁ is each independently a linear, branched ) Or cyclic aliphatic or aromatic hydrocarbons containing 3 to 50 carbon atoms and containing no hetero atoms and X is a hetero atom having 7 to 80 carbon atoms containing a (meth) acrylate group having 2 to 15 functional groups And R _f is a linear or branched alkyl group having 1 to 20 carbon atoms, in which at least 50% of the hydrogen atom sites are substituted by F.) The composition for forming a low refractive layer according to claim 1, wherein the refractive index of the hollow silica particles is 1.17 to 1.40. The composition for forming a low refractive index layer according to claim 1, wherein 0.1 to 20 parts by weight of the hollow silica particles (A), 0.1 to 30 parts by weight of the polyfunctional fluorine compound (B) 0.1 to 30 parts by weight of the acrylate monomer (C), 0.05 to 5 parts by weight of the photoinitiator (D), and 50 to 98 parts by weight of the solvent (E). An antireflection film comprising a transparent base material and a low refractive layer formed on the top surface of the transparent base material by using the composition for forming a low refractive layer according to any one of claims 1 to 3. 5. The antireflection film according to claim 4, wherein the antireflection film further comprises a hard coat layer formed between the transparent substance and the low refractive layer. The antireflection film according to claim 4, wherein the refractive index of the low refraction layer is 1.2 to 1.49 at 25 캜. A polarizing plate comprising the antireflection film of claim 4. A display device comprising the antireflection film of claim 4.