KR20110013751A - Coating composition for low refractive layer, anti-reflection film using the same and image displaying device comprising said anti-reflection film - Google Patents

Abstract

PURPOSE: A coating composition for forming a low refractive layer is provided to ensure excellent anti-reflection properties such as haze and reflectivity as well as good scratch resistance and adhesion when applied to an anti-reflection film. CONSTITUTION: A coating composition for forming a low refractive layer includes, based on 100.0 parts by weight of a whole composition, (A) 0.1-20 parts by weight of hollow silica particles, (B) 0.1-30 parts by weight of multi-functional fluorine-containing compounds, (C) 0.1-30 parts by weight of (meth)acrylate, (D) 0.05-5 parts by weight of photoinitiator, and (E) 50-98 parts by weight of solvent.

Description

Composition for forming a low refractive index layer, anti-reflection film, polarizing plate and display device using the same {COATING COMPOSITION FOR LOW REFRACTIVE LAYER, ANTI-REFLECTION FILM USING THE SAME AND IMAGE DISPLAYING DEVICE COMPRISING SAID ANTI-REFLECTION FILM}

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.

Recently, displays such as CRT, LCD, PDP have been developed, and various devices using these displays have been used in various fields. When these devices are used in a relatively bright place, such as outdoors, the use of external light such as sunlight or fluorescent light is increasing to become a problem, and thus the display surface is prevented from reflecting external light, that is, preventing reflection. The demands are also growing.

Accordingly, antireflection films have been widely developed to prevent the external appearance of the display device from being easily reflected. As the antireflection film, an antireflection film having a multilayer structure is known (PCT JP2003-008535). The antireflection film of the multilayer structure is a two-layer structure consisting of a high refractive index layer and a low refractive index layer, a three-layer structure consisting of a middle refractive index layer, a high refractive index layer and a low refractive index layer, and a high refractive index layer, a low refractive index layer, a high refractive index Four-layer structures consisting of layers and low refractive index layers are known.

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

However, the above-described anti-reflection film has limited materials and is expensive, and thus the manufacturing cost is increased, and the addition of such additional functions reduces optical properties, for example, reflection properties, transmittance, and haze. there was.

An object of the present invention is to solve the conventional problems as described above when applied to the anti-reflection film excellent anti-reflection properties such as haze and reflectance, to provide a composition for forming a low refractive index layer 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.

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

Another object of the present invention is to provide a display device provided with the anti-reflection film.

The present invention for achieving the above object, the hollow silica particles (A), polyfunctional fluorine compound (B), (meth) acrylate monomer (C), photoinitiator (D) and solvent (E) represented by the following formula (1) It provides a composition for forming a low refractive index layer comprising a.

[Formula 1]

(In Formula 1, m is an integer of 1 to 100, n is an integer of 1 to 6, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₁ are each independently linear, branch ( branched) or an cyclic or cyclic aliphatic or aromatic hydrocarbon containing or not containing a hetero atom having 3 to 50 carbon atoms, X is a heterocyclic group having 7 to 80 carbon atoms containing a (meth) acrylate group having 2 to 15 functional groups An aliphatic or aromatic hydrocarbon, with or without atoms, 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 replaced by F.)

It is preferable that the refractive index of the said hollow silica particle is 1.17-1.40.

The composition for forming the low refractive index layer is 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), and the (meth) acrylate monomer ( C) 0.1 to 30 parts by weight, 0.05 to 5 parts by weight of the photoinitiator (D) and 50 to 98 parts by weight of the solvent (E).

In order to achieve the another object of the present invention, the present invention, the antireflection characterized in that it comprises a transparent substrate and a low refractive index layer formed on the upper surface of the transparent substrate using the composition for forming the low refractive index layer according to the present invention Provide a film.

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

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

In order to achieve another object of the present invention, the present invention provides a polarizing plate characterized in that the anti-reflection film according to the present invention is provided.

In order to achieve another object of the present invention, the present invention provides a display device characterized in that the anti-reflection film according to the present invention is provided.

The composition for forming a low refractive index layer according to the present invention has excellent anti-reflection properties such as haze and reflectance by including hollow silica particles and a polyfunctional fluorine compound having a predetermined structure, and can obtain an effect excellent in scratch resistance and adhesion. have. Accordingly, the antireflection film manufactured using the composition for forming the low refractive index layer has excellent scratch resistance and antireflection, and may be usefully 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 refractive index layer according to the present invention comprises hollow silica particles (A), a polyfunctional fluorine compound (B), a (meth) acrylate monomer (C), a photoinitiator (D), and a solvent (E) represented by the general formula (1). It includes.

Hollow Silica Particles (A)

The hollow silica particles are used to lower the refractive index to increase antireflection properties and to increase 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 portion forming the hollow particles, but rather the refractive index of the entire particle.

At this time, 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%.

When trying to achieve low refractive index and high porosity of hollow silica particles, the thickness of the outer edge is reduced and the strength of the particles is weakened. Therefore, from the viewpoint of scratch resistance, any particles having a refractive index of less than 1.17 of the hollow silica particles are not preferable because of their poor scratch resistance. In addition, when the refractive index of the hollow silica particles exceeds 1.40, the refractive index is high, and thus the antireflection property is not preferable. The refractive index of the hollow silica particles is measured using an Abbe refractive index meter (manufactured by ATAGO).

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

The average particle diameter of the hollow silica particles is preferably 30 to 150% of the low refractive index layer, more preferably 35 to 80%, particularly preferably 40 to 60%. 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 in the above-described range, the ratio of the cavities becomes high so that a low refractive index can be achieved. Moreover, the formation of fine unevenness on the surface of the low refractive index layer does not cause the problem of lowering the reflectance. The hollow silica particles may be crystalline particles or amorphous particles, with monodisperse particles being preferred. In consideration of the shape, spherical particles are most preferred, 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 micrograph.

The content of the hollow silica is not necessarily limited, but may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total composition for forming the low refractive index layer. If the content of the hollow silica is less than 0.1 parts by weight, a sufficient refractive index reduction effect cannot be obtained, and if it exceeds 20 parts by weight, there is a problem in that scratch resistance is lowered.

Polyfunctional Fluorine Compound (B)

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

[Formula 1]

(In Formula 1, m is an integer of 1 to 100, n is an integer of 1 to 6, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₁ is each independently linear, branched ) Or an aliphatic or aromatic hydrocarbon containing or not containing a cyclic C3-C50 hetero atom, X is a C7-C80 hetero atom containing a (meth) acrylate group having 2 to 15 functional groups Is an aliphatic or aromatic hydrocarbon containing or not containing, R _f is a linear or branched alkyl group having 1 to 20 carbon atoms, and at least 50% of the hydrogen atom sites are replaced by F.)

The polyfunctional fluorine compound represented by Chemical Formula 1 may be easily reacted with a perfluoropolyether diol compound, a compound having two or more isocyanate groups in a molecule, and a compound having two or more (meth) acrylate groups having a hydroxyl group in the molecule. It can manufacture.

The perfluoro polyether diol compounds are commercially available as ohmic Nova solution's Poly Fox ^TM PF-636, Poly Fox ^TM PF-6320, Poly Fox ^TM PF-656, Poly Fox ^TM PF-6520, Poly Fox ^TM PF-7002 product At least one selected from among those can be used and the molecular weight is 1000 to 5000.

In addition, 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-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), 4,4'-oxybis (phenylisocyanate), Trifunctional isocyanate derived from hexamethylene diisocyanate, trimethanepropanol adduct From the group consisting of isocyanate-endian can be used at least one member selected.

In addition, the compound having a hydroxyl group in the molecule and having two or more (meth) acrylate groups is specifically pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) At least one selected from the group consisting of acrylates can be used.

The content of the polyfunctional fluorine compound represented by Chemical Formula 1 is not necessarily limited, but may be included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the total composition for forming the low refractive index layer. If the content of the polyfunctional fluorine compound is less than 0.1 parts by weight, not only does not reduce the sufficient refractive index effect, but also scratch resistance is lowered, if it exceeds 30 parts by weight there is a problem in that the 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. Specific examples of the (meth) acrylate monomers include 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) acrylate, neopentyl Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydride) 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, and isobornol (meth) acrylate The compound of can be used.

Although the content of the (meth) acrylate monomer is not limited, it is preferably included 0.1 to 30 parts by weight based on 100 parts by weight of the total composition for forming the low refractive index layer. If the content of the (meth) acrylate monomer is less than 0.1 parts by weight, there is a problem in the surface hardening of the low refractive index layer, and if it exceeds 30 parts by weight, the antireflection effect may be reduced by increasing the refractive index of the low refractive layer.

Photoinitiator (D)

The photoinitiator may be used without limitation in the art, the photoinitiator is specifically 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenyl ketone benzyldimethyl ketal , 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenylketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3 At least one selected from the group consisting of -methylacetophenone, 4-knoloacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone and benzophenone Can be.

The photoinitiator is preferably contained in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the total composition for forming the low refractive index layer. When the content of the photoinitiator is less than 0.05 parts by weight, the curing rate of the composition for forming the low refractive index is slow, and when it exceeds 5 parts by weight, cracking may occur in the low refractive layer by over curing.

Solvent (E)

The solvent can be used without limitation as long as it is known as a solvent of the composition for forming a low refractive index layer in the art.

In one example, the solvent is alcohol-based (methanol, ethanol, isopropanol, butanol, methylcellulose, ethyl solusorb, etc.), ketone-based (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl Ketones, cyclohexanone and the like), hexane-based (hexane, heptane, octane and the like), benzene-based (benzene, toluene, xylene and the like) and the like can be preferably used. The solvents exemplified above may be used alone or in combination of two or more thereof.

The solvent may be included in an amount of 50 to 98 parts by weight based on 100 parts by weight of the total composition for forming the low refractive layer. If the solvent is less than 50 parts by weight based on the above standard, the viscosity is high, the coating is difficult, and when it exceeds 98 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 composition for forming a low refractive index according to the present invention may be used with photo-stimulating agents, antioxidants, UV absorbers, light stabilizers, thermal polymerisation inhibitors, levling agents, surfactants, lubricants, and the like.

The present invention provides an anti-reflection film including a low refractive layer manufactured by using the composition for forming a low refractive layer described above. More specifically, the anti-reflection film includes a transparent substrate and a low refractive layer formed by using the composition for forming a low refractive index layer according to the present invention on one or both surfaces of the transparent substrate.

In this case, the anti-reflection film of the present invention may further include a hard coating layer between the transparent substrate and the low refractive index layer to impart the physical strength of the film. That is, a preferred example of the anti-reflection film according to the present invention is a hard coating layer is formed on the upper surface of the transparent substrate, the low refractive index layer formed by curing the composition for forming the low refractive index layer on the upper surface.

The transparent substrate may be any film 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, or 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 sulfone, paul One selected from dimethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyurethane, and epoxy may be used, and an unstretched uniaxial or biaxially oriented film may be used.

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

The thickness of the transparent base film is 8 ~ 1000㎛, preferably 40 ~ 100㎛.

The hard coat layer formed on the transparent substrate preferably has a refractive index in the range of 1.48 to 2.00, more preferably 1.50 to 1.90, and more preferably from an optical design for obtaining a good antireflection film. 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 coating layer, when the refractive index is smaller than the above range, the antireflection property is lowered, and when the refractive index is larger than the above range, the color of the reflected light becomes stronger. There are disadvantages.

The hard coating layer is preferably formed by a crosslinking reaction or a polymerization reaction of the photocurable compound. These compounds are not particularly limited, and, for example, a hard coating layer-forming composition containing a photocurable polyfunctional monomer or a polyfunctional oligomer is applied onto a transparent support, and then the polyfunctional monomer or the polyfunctional oligomer is crosslinked or polymerized. It can form by making it react.

It is preferable that the functional group of the polyfunctional monomer and polyfunctional oligomer of the said photocuring agent is light, an electron beam, and radiation polymerization property, and a photopolymerizable functional group is especially preferable.

As said photopolymerizable functional group, unsaturated polymerizable functional groups, such as a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned, Especially, a (meth) acryloyl group is preferable.

Specific examples of the photopolymerizable polyfunctional monomer having the photopolymerizable functional group include alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, and propylene glycol di (meth) acrylate. Meta) acrylic acid diesters; Polyoxyalkylene glycol (meth) acrylic acid di, such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate Esters; (Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; Ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxydiethoxy) phenyl} propane and 2,2-bis {4- (acryloxypolypropoxy) phenyl} propane And meta) acrylic acid diesters. In addition, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates can also be preferably used as the photopolymerizable polyfunctional monomer.

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

As for the said photopolymerizable polyfunctional monomer, it is more preferable to use the polyfunctional monomer which has three or more (meth) acryloyl groups in 1 molecule. As a specific example of the polyfunctional monomer which has three or more (meth) acryloyl groups in the said molecule | numerator, a trimethyl all propane tri (meth) acrylate, a trimethylol ethane tri (meth) acrylate, and 1,2, 4- cyclo Hexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, and the like.

The photopolymerizable polyfunctional monomer mentioned above can be used individually or in combination of 2 or more types, respectively.

It is preferable to use a photoinitiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As said photoinitiator, an optical radical initiator and a photocationic initiator are preferable, and an optical radical initiator is especially preferable.

As the photoradical initiator, those generally used in the art can be applied, and examples thereof include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyl oxime ester and tetramethylthiuram monosulfur. Those selected from pits and thioxanthones can be used.

In the anti-reflection film according to the present invention, the hard coating layer and the low refractive layer, which are sequentially formed on the transparent substrate, may be formed in a suitable manner such as die coater, air knife, reverse roll, spray, blade, casting, gravure, and spin coating. It can form by apply | coating the composition for forming and the composition for low refractive layer formation which concerns on this invention.

The coating thickness of the composition for forming a hard coat layer is usually 3 to 50 µm, preferably 5 to 40 µm, and more preferably 5 to 35 µm. After applying the composition for forming the hard coat layer and dried for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes at a temperature of 30 ~ 150 ℃. When the drying is complete, UV light is irradiated to harden the composition for forming a hard coat layer to form a hard coat layer. The irradiation amount of UV light is about 0.01-10 J / cm ² , preferably 0.1-2 J / cm ² .

The coating thickness of the said composition for low refractive layer formation is 0.01-2 micrometers, Preferably it is 0.05-0.3 micrometers. After applying the composition for forming the low refractive layer is dried for 10 seconds to 1 hour, preferably 30 seconds to 10 minutes at a temperature of 30 ~ 150 ℃. When the drying is complete, UV light is irradiated to photocur the composition for forming the low refractive layer to form a low refractive layer. The irradiation amount of UV light is about 0.01-10 J / cm ² , preferably 0.1-2 J / cm ² .

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

It is preferable that the refractive index in 25 degreeC exists in the range of 1.20-1.49 from the optical design for obtaining the said low refractive layer from an antireflection film. If the refractive index of the low refractive index layer is smaller than the above range, the antireflection property is lowered. If the refractive index is higher than the above range, the color of the reflected light is strong.

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

In the present invention, a polarizing plate including the antireflection film described above is provided.

The polarizing plate is not particularly limited, but various kinds may be used. As said polarizing plate, the film poly which uniaxially stretched by adsorb | sucking dichroic substances, such as an 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 dehydration products of vinyl alcohol and dehydrochlorination products of polyvinyl chloride. 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 a display device to which the above-described antireflection film is applied.

For example, various display devices excellent in visibility can be manufactured by embedding the polarizing plate on which the antireflection film of the present invention is formed in the display device. In addition, the antireflection film of the present invention may be attached to a window of the display device. The antireflection film of the present invention can be suitably used in reflective, transmissive, transflective LCDs or LCDs of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, and IPS type. Moreover, the antireflection film of this invention can be used suitably also in various display apparatuses, such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, an electronic paper.

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

Synthesis Example 1 Synthesis of Multifunctional Fluorine Compound

30 parts by weight of a fluorine diol compound having an average molecular weight of 1500 (Polyfox ^TM PF-656, Ohm Nova Solutions), 9 parts by weight of isophorone diisocyanate (IPDI, BASF), dipentaerythritol penta / hexaacrylate (DPHA, Japan) Synthetic yarn) 170 parts by weight, and 0.1 parts by weight of dibutyl tin dilaurylate (FASCAT 4202, Akema) as a reaction catalyst was added 0.05 part by weight of methoxyhydroquinone (HQMME, Eastman) at a room temperature while stirring, The reaction temperature was raised to 90 ° C. The reaction was terminated when the reaction was carried out at 90 ° C. for 12 hours and 2260 cm ^{−1, which} is a characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

Synthesis Example 2 Synthesis of Multifunctional Fluorine Compound

30 parts by weight of a fluorine diol compound having an average molecular weight of 1500 (polyfox ^TM PF-656, Ohm Nova Solutions), 9 parts by weight of isophorone diisocyanate (IPDI, BASF), pentaerythritol tri / tetraacrylate (M340, Miwon Corporation) ) 148 parts by weight, and 0.1 parts by weight of dibutyltin dilaurylate (FASCAT 4202, Akema) as a reaction catalyst was added 0.05 part by weight of methoxyhydroquinone (HQMME, Eastman) as a polymerization inhibitor at room temperature, followed by stirring. The temperature was raised to 90 ° C. The reaction was terminated when the reaction was carried out at 90 ° C. for 12 hours and 2260 cm ^{−1, which} is a characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

Synthesis Example 3 Synthesis of Multifunctional Fluorine Compound

60 parts by weight of a fluorine diol compound having an average molecular weight of 3200 (polypox ^TM PF-6520, Ohm Nova Solution), 9 parts by weight of isophorone diisocyanate (IPDI, BASF), dipentaerythritol penta / hexaacrylate (DPHA, Japan) Synthetic yarn) 170 parts by weight, and 0.1 parts by weight of dibutyl tin dilaurylate (FASCAT 4202, Akema) as a reaction catalyst was added 0.05 part by weight of methoxyhydroquinone (HQMME, Eastman) at a room temperature while stirring, The reaction temperature was raised to 90 ° C. The reaction was terminated when the reaction was carried out at 90 ° C. for 12 hours and 2260 cm ^{−1, which} is a characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

Synthesis Example 4 Synthesis of Multifunctional Fluorine Compound

20 parts by weight of a fluorine diol compound having an average molecular weight of 1000 (Polyfox ^TM PF-636, Ohm Nova Solution), 9 parts by weight of isophorone diisocyanate (IPDI, BASF), dipentaerythritol penta / hexaacrylate (DPHA, Japan) Synthetic yarn) 170 parts by weight, and 0.1 parts by weight of dibutyl tin dilaurylate (FASCAT 4202, Akema) as a reaction catalyst was added 0.05 part by weight of methoxyhydroquinone (HQMME, Eastman) at a room temperature while stirring, The reaction temperature was raised to 90 ° C. The reaction was terminated when the reaction was carried out at 90 ° C. for 12 hours and 2260 cm ^{−1, which} is a characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

Synthesis Example 5 Synthesis of Multifunctional Fluorine Compound

54 parts by weight of a fluorine diol compound having an average molecular weight of 2800 (Polypox ^TM PF-6320, Ohm Nova Solutions), 9 parts by weight of isophorone diisocyanate (IPDI, BASF), dipentaerythritol penta / hexaacrylate (DPHA, Japan) Synthetic yarn) 170 parts by weight, and 0.1 parts by weight of dibutyl tin dilaurylate (FASCAT 4202, Akema) as a reaction catalyst was added 0.05 part by weight of methoxyhydroquinone (HQMME, Eastman) at a room temperature while stirring, The reaction temperature was raised to 90 ° C. The reaction was terminated when the reaction was carried out at 90 ° C. for 12 hours and 2260 cm ^{−1, which} is a characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

Synthesis Example 6 Synthesis of Multifunctional Fluorine Compound

20 parts by weight of a fluorine diol compound having an average molecular weight of 1500 (Polyfox ^TM PF-656, Ohm Nova Solutions), 7 parts by weight of 1,6-dihexane diisocyanate (HDI, TCI), dipentaerythritol penta / hexaacrylate (DPHA, Nippon Synthetic Co., Ltd.) 170 parts by weight, 0.1 parts by weight of dibutyltindilaurylate (FASCAT 4202, Akema) as a reaction catalyst was added 0.05 parts by weight of methoxy hydroquinone (HQMME, Eastman) at a room temperature as a polymerization inhibitor. And the reaction temperature was raised to 90 degreeC, stirring. The reaction was terminated when the reaction was carried out at 90 ° C. for 12 hours and 2260 cm ^{−1, which} is a characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

Synthesis Example 7 Synthesis of Multifunctional Fluorine Compound

20 parts by weight of a fluorine diol compound having an average molecular weight of 1500 (polyfox ^TM PF-656, OmNova Solution, Inc.), 7 parts by weight of 1,6-dihexane diisocyanate (HDI, TCI), pentaerythritol penta / hexaacrylate ( M340, Miwon Corporation) 140 parts by weight, 0.1 parts by weight of dibutyl tin dilaurylate (FASCAT 4202, Akema) as a reaction catalyst was added to 0.05 parts by weight of methoxy hydroquinone (HQMME, Eastman) at a room temperature as a polymerization inhibitor. The reaction temperature was raised to 90 ° C while stirring. The reaction was terminated when the reaction was carried out at 90 ° C. for 12 hours and 2260 cm ^{−1, which} is a characteristic peak of isocyanate in the infrared spectral spectrum, disappeared completely.

[Example of Manufacturing Composition for Hard Coating Layer]

70 parts by weight of urethane acrylate (Shin-Nakamura Chemical Co., U-15HA), 30 parts by weight of pentaerythritol triacrylate (public company, PE-3A), 3 parts by weight of photoinitiator (Shiba Corporation, D-1173), 150 parts by weight of methyl Ethyl ketone and 100 parts by weight of toluene were combined to prepare a composition having a refractive index of 1.51.

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

The hard coating layer composition prepared above was coated on one side of a transparent substrate made of a triacetyl cellulose film having a thickness of 80 μm to form a hard coating layer having a thickness of 5 μm by heat curing after heat drying.

The low refractive index layer-forming composition having the composition shown in Table 1 was applied on the hard coat layer to form a low refractive index layer having a thickness of 0.1 μm by heat curing after heat drying.

Composition Example Comparative example One 2 3 4 5 6 7 8 9 10 11 12 13 One 2 3 Polyfunctional fluorine compounds 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
Monomer (a) 2 2 2 2 One 0.5 3 2 2 2 3 5 Acrylate
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 Low refractive layer
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 40nm, catalyzed sand

Acrylate monomer (a): dipentaerythritol penta / hexa acrylate (refractive index 1.476, Japanese synthetic yarn, DPHA)

Acrylate monomer (b): pentaerythritol tri / tetra acrylate (refractive index 1.47, Miwon Corporation, M340)

MIBK: methyl isobutyl ketone

MEK: methyl ethyl ketone

I-184: 1-hydroxycyclohexylphenyl ketone (Shiba Corporation)

BYK-378: Silicone Modified Oil (BYK)

Experimental Example

The physical properties of the antireflective film prepared as described above were measured as follows, and the results are shown in Table 2 below.

(1) scratch resistance

The scratch resistance was tested by using a steel wool tester (WT-LCM100, manufactured by Protec Co., Ltd.) for 10 reciprocations at 1 kg / (2 cm × 2 cm). 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

(2) adhesion

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

The adhesion was recorded as follows.

Adhesion = n / 100

n: number of rectangles

100: total number of squares

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

(3) surface reflectance

The adapter MPC2200 was attached to the spectrophotometer UV2450 (Shishima Co., Ltd.), and the specular reflectance with respect to the exit angle of 5 ° at the incident angle of 5 ° in the wavelength region of 380 to 780 nm was measured, and the average reflectance of 450 to 650 nm was calculated.

(4) haze

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 Adhesion 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
100 100 /
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 the case of Examples 1 to 13 containing the polyfunctional fluorine compound and hollow silica particles represented by the formula (1) according to the present invention, scratchability is very excellent compared to Comparative Examples 1 to 3, which do not include the same. You can see the result. In addition, it has excellent reflectance characteristics to realize excellent anti-reflection effect.

Claims (8)

Hollow silica particles (A), polyfunctional fluorine compound (B) represented by the following formula (1), (meth) acrylate monomer (C), photoinitiator (D) and a solvent (E), characterized in that the low refractive layer formation Composition. [Formula 1]

(In Formula 1, m is an integer of 1 to 100, n is an integer of 1 to 6, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₁ is each independently linear, branched ) Or an aliphatic or aromatic hydrocarbon containing or not containing a cyclic C3-C50 hetero atom, X is a C7-C80 hetero atom containing a (meth) acrylate group having 2 to 15 functional groups Is an aliphatic or aromatic hydrocarbon containing or not containing, R _f is a linear or branched alkyl group having 1 to 20 carbon atoms, and at least 50% of the hydrogen atom sites are replaced by F.) The composition for forming a low refractive index layer according to claim 1, wherein the hollow silica particles have a refractive index of 1.17 to 1.40. The composition for forming a low refractive index layer is 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), and the (meth) A composition for forming a low refractive index layer comprising 0.1 to 30 parts by weight of an 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 substrate and a low refractive layer formed on the upper surface of the transparent substrate using the composition for forming a low refractive index layer according to any one of claims 1 to 3. The antireflection film according to claim 4, wherein the antireflection film further comprises a hard coating layer formed between the transparent substrate and the low refractive layer. The antireflection film according to claim 4, wherein the low refractive index layer has a refractive index of 1.2 to 1.49 at 25 ° C. The antireflection film of Claim 4 was provided, The polarizing plate characterized by the above-mentioned. Display device characterized in that the anti-reflection film of claim 4.