KR100622214B1 - Composition for low refractive layer and anti-refraction film using the same - Google Patents

Abstract

The present invention relates to a composition for coating a low refractive index layer and an antireflection film using the same, and more particularly, to an amorphous fluorine resin, a fluorine-containing resin containing an alcohol group, a fluorine-containing resin containing an acrylic ester group, and a solvent. It relates to a composition for coating a low refractive index layer and an antireflection film prepared using the same. According to the present invention, it is possible to provide an antireflection film having a low reflectance and a high transmittance while showing sufficient antifouling properties and improved durability.

Antireflection film, amorphous fluorine-containing resin, alcohol group, acrylic acid ester group, fluorine-containing solvent, hard coat layer, high refractive index layer, low refractive layer, reflectance, transmittance, hardness, adhesion

Description

Composition for Low Refractive Layer Coating and Anti-Reflective Film Using the Same {Composition for Low Refractive Layer and Anti-Refraction Film using the Same}

1 is a cross-sectional schematic view of an antireflective film according to an embodiment of the present invention;

Figure 2 shows the reflectance spectrum of the antireflective film obtained by Example 2 of the present invention.

Explanation of symbols on the main parts of the drawings

1. Base material 2. Hard coat layer

3. High refractive layer 4. Low refractive layer

The present invention relates to a composition for coating a low refractive index layer and an antireflection film using the same, and more particularly, to an amorphous fluorine resin, a fluorine-containing resin containing an alcohol group, a fluorine-containing resin containing an acrylic ester group, and a solvent. It relates to a composition for coating a low refractive index layer and an antireflection film prepared using the same.

As the use of display devices such as liquid crystal displays (LCDs), plasma display panels (PDPs), cathode ray tubes (CRTs), or electroluminescent displays (ELDs) has become commonplace, these display devices have been used in addition to When used outdoors and under bright lighting, the performance of preventing external light such as sunlight or fluorescent light from being reflected on the display surface is required.

In order to provide such an antireflection function, a method of initially forming one or more layers having different refractive indices on a plastic substrate by a vapor deposition method has been mainly used. However, the vapor deposition method is extremely expensive and cannot be coated on a large area. There is this. Accordingly, a method of forming a low refractive film using a fluorine-containing resin which is an organic resin having a low refractive index has been proposed. Fluorine-containing polymers are generally insoluble in solvents, but WO96 / 22356 proposes a method for dissolving amorphous tetrafluoroethylene copolymers in fluorine-containing solvents. A method of forming an antireflection film by a general coating method such as a dip coat or a gravure coat has been proposed. Japanese Patent Application Laid-Open No. Hei 8-22929 introduces a fluorine-containing polymer having a fluorine-containing aliphatic ring structure in the ring, which is amorphous due to the steric effect of the ring structure, and thus, a low refractive index can be expected to provide excellent antireflection effect. In addition, excellent antifouling properties due to sufficient fluorine content can be expected. However, when the film is formed only with amorphous fluorine-containing resin, there is a lack of adhesion and hardness, so durability is a problem. Therefore, a method of blending an fluorine-containing copolymer containing an acrylate group, an acrylic acid group, and an alcohol group with an amorphous fluorine resin to enable crosslinking reaction has been proposed (US Pat. No. 5,139,879). It is not clearly stated. On the other hand, a method of pretreatment of the surface of the substrate (Japanese Patent Laid-Open No. 4-326965) or overcoat of an ultra-thin film made of a silicone oil having lubricity on the upper layer of the anti-radiation layer is also proposed. It is possible to increase the manufacturing cost and to lower the production yield.

An object of the present invention to solve the problems of the prior art as described above is to provide an antireflection film excellent in antifouling properties and hardness without deterioration of antireflection performance.

That is, in order to achieve the above object, an aspect of the present invention relates to an amorphous fluorine-containing resin, a fluorine-containing resin containing an alcohol group, a fluorine-containing resin containing an acrylic ester group, and a composition for coating a low refractive index layer containing a solvent. will be.

Another aspect of the invention relates to a method for producing an antireflection film using the composition for coating the low refractive index layer.

Another aspect of the invention relates to an antireflective film produced by the method.

Another aspect of the present invention relates to an image display apparatus using the antireflection film.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail with reference to an accompanying drawing.

1 shows the structure of an antireflective film produced by the method of the present invention. The antireflection film produced by the method of the present invention includes a hard coat layer (2) giving scratch resistance on the substrate (1), a high refractive index layer (3) and a low refractive index layer (4) giving antireflection performance. It is a film of a structure coated in order.

Hereinafter, each layer of the antireflection film of the present invention will be described in more detail.

The substrate 1 of the antireflection film of the present invention is not particularly limited as long as it has transparency, but it is preferable to use a plastic film from the viewpoint of processability. Examples of the material commonly used as the substrate include cellulose esters such as acetyl cellulose, diacetyl cellulose, propionyl cellulose, acetyl propionyl cellulose and nitrocellulose; Or polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, cyclohexane Polyesters such as dimethylene terephthalate; Or polyolefins such as polyethylene, polypropylene, polymethylpentane, and the like, in addition, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, polycarbonate, polyamide, polyether Sulfone, polyether ketone, polysulfone, polyimide, nylon and the like can be used. Among these, acetyl cellulose, polyethylene terephthalate or polycarbonate is excellent in transparency and is more suitable as a substrate of an optical film. In addition, acetyl cellulose can also be used that is sensitized by an alkaline substance.

As resin which can be used for the hard-coat layer 2 of the antireflection film of this invention, the compound which has two or more functional groups as an ultraviolet curable resin is preferable. Such compounds include monomers, oligomers or polymers having unsaturated functional groups capable of polymerization reaction such as methacryloyl group and methacryloyloxy group or functional groups capable of cationic polymerization reaction such as epoxy group in the molecule. It can be used as a composition or by mixing two or more kinds. The composition should be a liquid at the time of uncuring, it is preferable to include an ethylene group in the molecule so as to form a crosslinking at the time of curing.

Specific examples of the monomers include 2-hydroxy ethyl methacrylate, 2-hydroxy propyl methacrylate, tetra hydroperryl acrylate, glycidyl methacrylate, acryloyl morpholine and 2-cyano methacrylate. , N, N-dimethyl acrylamide, N-vinyl pyrrolidone, N-vinyl-caprolactam, phenoxy diethylene glycol methacrylate, pentaerythritol tetramethacrylate, dipentaerythritol trimethacrylate, trimeme Tyrolpropane trimethacrylate, trimetholethane trimethacrylate, dipentaerythritol tetramethacrylate, erythritol dimethacrylate, pentaerythritol trimethacrylate, 1,2,3-cyclohexane tetra Methacrylate and the like.

Specific examples of the oligomer include polyester methacrylate or urethane methacrylate. The polyester methacrylate can be obtained according to the reaction of the polyester polyol and methacrylic acid, the urethane methacrylate is bisphenol-type epoxy resin and methacrylate, organic polyisocyanate and hydroxy methacrylate, or polyol It can be obtained according to the reaction of organic polyisocyanate and hydroxymethacrylate compound.

On the other hand, in order to harden the said liquid composition using ultraviolet-ray, a photoinitiator is needed. Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorerotone, 4,4'-dimethoxybenzophenone, 4,4'-dia Minobenzophenone, mihiraketone, benzoin propylether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy 2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2-methyl-1- [4- (methyl Thio) phenyl] -2-morpholino-propane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphineoxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethyl 1 type, or 2 or more types of combination is mentioned among pentyl phosphine oxide.

It is preferable that it is 0.5-10 weight%, and, as for the addition amount of the said photoinitiator, it is more preferable that it is 0.5-5 weight%. If the amount is less than 0.5% by weight, the hardness is insufficient when the curable composition is cured. If the amount is more than 10% by weight, the photopolymerization initiator itself may react with radicals to inhibit polymerization.

In addition, inorganic fine particles may be added to the hard coat layer in order to adjust the refractive index or increase the curing strength of the film. As the inorganic fine particles, the average particle size is preferably 0.5 micrometer or less. As the inorganic fine particles, silicon dioxide, titanium dioxide, aluminum oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin or calcium lactate particles can be used. The amount of the inorganic fine particles added is preferably 10 to 90% by weight and more preferably 30 to 60% by weight based on the total weight of the coating liquid for hard coat formation.

The solvent is not particularly limited, but alcohols such as methyl alcohol, ethyl alcohol, propanol and isopropanol; Or ketones such as methyl isobutyl ketone and methyl ethyl ketone; Or esters such as methyl acetate and ethyl acetate; Or aromatic compounds such as toluene, xylene, benzene; Or ethers such as diethyl ether can be used. When the content of the solvent is less than 20% by weight, it is difficult to uniformly apply due to the high viscosity, and when the content of the solvent exceeds 90% by weight, it is difficult to form a coating layer of a desired thickness, so the content is preferably 20 to 90% by weight, More preferably, you may be 50 to 90 weight%.

In the present invention, the thickness of the hard coat layer 2 is preferably 0.5 to 15 micrometers. If the thickness of the hard coat layer is too thin, the hardness is not sufficient, and if the thickness is too thick, curling is likely to occur in the film and the transmittance is low.

The coating method is not particularly limited, and general wet coating such as roll coating, die coating, bar coating, and spin coating can be used. After coating, the solvent is dried at 50 to 130 ° C. and energy is 100 to 700 mJ / UV curing at cm ² .

The coating liquid for forming the high refractive layer (3) of the present invention is prepared by dispersing the metal oxide fine particles (a) dispersed in an organic solvent in a resin (b) and an organic solvent (c) having at least two functional groups capable of ultraviolet curing.

The metal oxide fine particles (a) are not particularly limited, but zinc oxide, tin oxide, antimony-containing tin oxide, indium-containing tin oxide, indium oxide, antimony oxide, zirconium oxide, titanium oxide, tungsten oxide, zinc antimonate, and oxidation Vanadium and the like can be used, and it is preferable to select in consideration of the dispersibility of the particles and the ease of adjusting the refractive index. The metal oxide fine particles are difficult to disperse when the particle size is finer than necessary, and the haze may increase when the particle size is large, so that the average particle size may be in the range of 0.01 to 0.5 micrometer to achieve the object of the present invention. desirable. When the surfaces of these metal oxide fine particles are treated with a coupling agent, the dispersibility of the fine particles is improved and the dispersion stability of the coating liquid for forming the high refractive index is also increased. Examples of coupling agents include isopropyl triisostearoyl titanate, titanium n-butoxide, titanium ethoxide, titanium 2-ethylhexoxide, titanium isobutoxide, titanium stearyloxide, triisopropoxy hepta Desiccated titanium etc. are mentioned.

The resin (b) having at least two functional groups capable of ultraviolet curing is the same kind as the resin used for hard coating and cationic polymerization such as unsaturated bonds or epoxy groups capable of polymerization reaction such as methacryloyl group and methacryloyloxy group in the molecule. It is a monomer, oligomer, or polymer which has a functional group which can react.

The organic solvent (c) used in the coating liquid for forming the high refractive index is also the same as the solvent used for the hard coating, and the solid content is preferably 1 to 20% by weight in order to form a thin film during coating.

The coating method of the high refractive coating liquid is not particularly limited, and general wet coating such as roll coating, die coating, bar coating, and spin coating can be used. After coating, the solvent is dried at 50 to 130 ° C. and 300 to 1000 mJ. Ultraviolet curing at / cm ² to form a coating layer.

If necessary, the high refractive index layer can be provided in a two-layer form in the order of the medium refractive layer and the high refractive layer by adjusting its refractive index. At this time, the refractive index is controlled by the content of the metal oxide fine particles.

Characteristic of the low refractive index layer (4) coating composition of the present invention is an amorphous fluorine-containing resin (d), a fluorine-containing resin (e) containing an alcohol group, and a fluorine-containing resin (f) containing an acrylic acid ester group as a solvent ( It is prepared by dissolving in g).

The amorphous fluorine-containing resin (d) is generally in the form of a copolymer of tetrafluoroethylene with another comonomer containing fluorine. Examples of the fluorine-containing monomer reacting with tetrafluoroethylene include CH ₂ = CHF, CH ₂ = CF ₂ , CF ₂ = CHF, CH ₂ = CF-OC _n F _{2n + 1} ( n is an integer of 1 to 10); CF ₂ = CF-CF ₃ ; CF ₂ = CF-O-CF ₂ CF ₂ COOCH ₃ ; Or 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxol having the formula (1) below.

Among the amorphous fluorine-containing resins described above, amorphous fluorine-containing resins polymerized using 2,2-bistrifluoromethyl-4,5-difluoro-1,3-diosol as comonomer are Teflon-AF in DuPont. It is sold under the brand name.

The fluorine-containing resin (e) containing the alcohol group can be obtained by copolymerizing a monomer (component A) containing a fluorine atom with a monomer (component B) containing an alcohol group or an epoxy group. As the monomer (component A) containing the fluorine atom, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene, (fluoroalkyl) vinyl ether, (fluoroalkoxyalkyl) vinyl Ether, perfluoro (alkyl vinyl ether), perfluoro (alkoxy vinyl ether), fluorine-containing methacrylic acid ester and the like. As the monomer (component B) containing the alcohol group or the epoxy group, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl allyl ether, allyl glycidyl ether, methacrylic acid glycidyl ester, and crotonic acid glycine One kind or a combination of two or more kinds of diester, methylglycidyl ester and the like can be used. The said A component and B component can be superposed | polymerized into a copolymer using the solution polymerization method, suspension polymerization method, emulsion polymerization method, block polymerization method, etc. using a radical polymerization initiator. The preferred content range of the fluorine-containing resin containing an alcohol group is 20 to 50 parts by weight with respect to the total solids, when less than 20 parts by weight may reduce the hardness and adhesion of the anti-reflection film produced, if it exceeds 50 parts by weight Implementing anti-reflection performance can be difficult.

The fluorine-containing resin (f) containing the acrylic acid ester group can be produced by condensation polymerization of a fluorine-containing resin having an alcohol group in the molecular chain and a fluorine-containing resin having a carboxyl group in the molecular chain.

As a method of introducing a carboxyl group into the molecular chain, 1) polymerization is carried out in the presence of an carboxyl group or an initiator or chain transfer agent having such a precursor group (for example, an acyl group) in the molecule to introduce a carboxyl group to the terminal of the fluorinated polymer. 2) a method of oxidatively decomposing side chains or ends of the fluorine-containing polymer by heating the fluorine-containing polymer at high temperature in the presence of oxygen and introducing a carboxyl group by treating it with water or alcohol, or 3) a carboxylic acid derivative such as methyl felfluor The method etc. which introduce | transduce a functional group into the side chain of a fluorine-containing polymer by copolymerizing the monomer which has a group are mentioned.

 The preferred content range of the fluorine-containing copolymer including the acrylic ester group is 10 to 35 parts by weight based on the total solids, when less than 10 parts by weight, the adhesion of the antireflection film is not sufficient, and when more than 35 parts by weight includes an acrylic ester group An unreacted material of the fluorine-containing resin may be included in the coating film to decrease the hardness of the anti-reflection film.

The solvent used in the composition for coating the low refractive index layer of the present invention is not particularly limited, but includes an amorphous fluorine-containing resin (d), a fluorine-containing resin (e) containing an alcohol group, and a fluorine-containing resin (f) containing an acrylic ester group (f). It is more preferable to use the fluorine-containing solvent which can melt | dissolve (). Specific examples of the solvent include F (CF ₂ ) ₆ OCH ₃ , F (CF ₂ ) ₇ OCH ₃ , F (CF ₂ ) ₈ OCH ₃ , F (CF ₂ ) ₉ OCH ₃ or F (CF ₂ ) ₁₀ OCH ₃ Etc. 3M markets commercial fluorine-containing solvents, such as FC-40, FC-43, FC-75, FC-77, FC-84, FC-87, FC-104, FC-3283, FC-5312, FC-5320, HFE-7200, HFE-7100 and the like. The fluorine-containing solvent as described above may be used alone or in combination of two or more kinds.

It is preferable that the fluorine-containing resin (e) containing the alcohol group dissolved in the composition for coating the low refractive index layer is equivalent to or greater than the fluorine-containing resin (f) containing an acrylic ester group. In addition, the amorphous fluorine-containing resin (d) is a total solid It is preferable that it is 30 weight part or more with respect to. A preferable content range of the amorphous fluorine-containing resin (i) is 30 to 70 parts by weight based on the total solids, if less than 30 parts by weight may not be sufficient antifouling properties of the prepared antireflection film, if it exceeds 70 parts by weight The hardness of can be lowered.

On the other hand, the solid content of the low refractive index layer coating composition is preferably 0.5 to 5% by weight relative to the total composition. If the solid content is too small, it is impossible to form a coating film having a thickness capable of obtaining sufficient anti-reflection performance, and when the solid content exceeds 5% by weight, the fluorine-containing resin is difficult to dissolve uniformly.

In manufacturing the antireflection film using the composition for coating a low refractive index layer of the present invention,

The low refractive index coating composition is applied on a substrate by a general wet coating method, it is possible to form a coating film by drying the coating composition. The drying temperature of the coating composition is preferably 50 to 150 ° C, more preferably 70 to 140 ° C, and the drying time is preferably 15 to 120 minutes. If the drying temperature is less than 50 ° C, the solvent may not be sufficiently volatilized to form a coating film having excellent hardness. If the drying temperature exceeds 150 ° C, deformation of the base film and yellowing of the hard coat layer may occur.

If necessary, the durability of the coating film may be improved by adding a photopolymerization initiator capable of inducing ultraviolet curing to the low refractive coating solution by irradiating ultraviolet rays. In this case, the photopolymerization initiator is preferably soluble in the fluorine-containing solvent in the same kind as the photopolymerization initiator used for hard coating.

Another aspect of the invention relates to an antireflective film obtained by the above production method. As shown in FIG. 1, the antireflection film according to the present invention has a structure in which a hard coat layer 2 is formed on a substrate 1 and a high refractive index layer 3 and a low refractive index layer 4 are formed thereon. When the high refractive layer is formed from the coating liquid for forming the high refractive layer by the above method, the refractive index is 1.6 or more, preferably 1.6 to 2, and the thickness thereof is more preferably 60 nm to 600 nm. This is because it is necessary to finely adjust the layer thickness according to the refractive index of the coating film in order to exhibit anti-reflection performance by using the interference of light. The refractive index of the low refractive index layer is 1.5 or less, preferably 1.3 to 1.5, and the thickness thereof is more preferably 60 nm to 600 nm similarly to the high refractive layer. It is more preferable to achieve the object of the present invention that the difference between the refractive index of the high refractive index layer and the refractive index of the low refractive layer is 0.05 to 0.7.

The antireflection film formed by the manufacturing method has a transmittance of 92% or more, that is, a visible light region, that is, 380 to 750 nm. The average reflectance at is less than 3% and the pencil hardness is at least 3H and the contact angle to water is at least 100 ^° .

Yet another aspect of the present invention is an image display device manufactured using the anti-reflection film, and examples thereof include a PDP, an LCD, a touch panel, and the like.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Example 1

1) description

A 100 μm thick PET film (A4300, Toyobo) was used as the substrate.

2) Formation of Hard Coat Layer

30% by weight of urethane acrylate oligomer (Ebecryl 5129, SK-UCB), 20% by weight of zipa erythritol acrylate (A-400, Gunpowder) and 25% by weight of methyl ethyl ketone and toluene as solvent As an initiator, 1 part by weight of Igacure 184 (Ciba-geigy) was used based on the solid content.

After the coating film was formed using the bar coater # 12 bar, the solvent was dried at 80 ° C. for 2 minutes, and the coating film was cured by irradiating with UV light of 300 mJ / cm ² .

3) Formation of High Refractive Layer

Tin oxide fine particles having an average particle diameter of 25 nm were dispersed in an ultraviolet curable resin and ethanol and isopropanol in a tin oxide dispersion (catalyzed) to 8% by weight using isopropanol.

After the coating film was formed using the bar coater # 4 bar, the solvent was evaporated by drying at 80 ° C. for 2 minutes, and the coating film was cured by irradiating with UV light of 500 mJ / cm ² .

4) Formation of Low Refractive Layer

100 parts by weight of amorphous fluorine-containing resin (Teflon-AF 1600), 15 parts by weight of perfluoropolyethylene diol (FC-2202, 3M), 15 parts by weight of fluorinated polyfunctional acrylic acid ester (ART-4, Co., Ltd.) fluorine-containing solvent It melt | dissolved in (FC-77) so that it might become 2 weight% of solid content.

After the coating film was formed using the bar coater # 4 bar, the coating film was formed by drying at 130 ° C. for 30 minutes to volatilize the solvent.

The average reflectance, transmittance, pencil hardness, cross-cut test, and contact angle of the formed coating film were measured, and the results are shown in Table 1.

The physical property evaluation method of a coating film is as follows.

Average reflectance: The reflectance was measured using a UV / VIS / NIR spectrometer (Lambda 950, Perkin-Elmer). The back side of the sample was rubbed with sandpaper and coated with matt paint (CL440F-1999, Goryeo Paint) to remove the reflected light from the back side of the film. In the reflectance measurement, the sum of the specular reflectance value and the diffuse reflectance value was measured using an integrating sphere. The incident angle was set at 8 degrees and the reflectance average in the range of 380 to 750 nm was calculated.

Permeability: Measured using a haze and permeability meter (Nippon Denshoku Kogyo Co.).

Pencil hardness: The pencil hardness was measured by applying a load of 1 kg / cm ² with a slope of 45.

Cross-cut test: 100 checkers (1 mm × 1 mm) were scratched with a knife and then peeled off using cellophane tape. The pattern was not peeled off at all, and the 1-10 peeled off was indicated by Δ, and the peeling off of 10 or more peeled off was marked with x.

Contact angle: The contact angle to water was measured using a contact angle measuring instrument (Phoenix300, SEO).

Example 2

After coating the composition for coating the low refractive index coating to produce an antireflection film in the same manner as in Example 1, except that the drying temperature was 80 ℃, the physical properties were evaluated in the same manner as in Example 1 to the results It is shown together in Table 1. In addition, the reflectance spectrum of the antireflection film according to the present embodiment is shown in FIG. 2.

Example 3

100 parts by weight of amorphous fluorine-containing resin (Teflon-AF 2400), 15 parts by weight of perfluoropolyethylene diol (FC-2202, 3M), a fluorine-containing polyfunctional acrylic acid ester (ART-4, Co., Ltd.) 15 parts by weight was dissolved in a fluorine-containing solvent (FC-77) so as to have a solid content of 1.8% by weight.

The formation of the coating film and the evaluation of physical properties were the same as in Example 1, and the results of the physical properties were shown in Table 1 together.

Comparative Example 1

A low-reflection layer coating composition was prepared in the same manner as in Example 1 except that the amorphous fluorine-containing resin (Teflon-AF 1600) was dissolved in the fluorine-containing solvent (FC-77) to 2% by weight of solids. And the physical properties were evaluated in the same manner as in Example 1 and the results are shown in Table 1 together.

Comparative Example 2

As a composition for coating the low refractive index layer, 100 parts by weight of amorphous fluorine-containing resin (Teflon-AF 1600) and 30 parts by weight of perfluoropolyethylene diol (FC-2202, 3M) were added in a fluorine-containing solvent (FC-77). Except for dissolving as much as possible, an antireflection film was prepared in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 1 together.

Comparative Example 3

100 parts by weight of amorphous fluorine-containing resin (Teflon-AF 1600) and 15 parts by weight of fluorine-containing polyfunctional acrylic acid ester (ART-4, Co., Ltd.) as a composition for coating the low refractive index layer 2 weights of solids in fluorine-containing solvent (FC-77) Except for dissolving to a%, an antireflection film was prepared in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 1 together.

Comparative Example 4

An antireflection film was prepared in the same manner as in Example 1 except that the drying temperature was coated at 155 ° C. after coating the composition for coating the low refractive index layer. It was confirmed that the hard coating of the prepared antireflection film was yellowed.

Comparative Example 5

After coating the composition for coating the low refractive index coating except that the drying temperature was 40 ℃ to prepare an antireflection film in the same manner as in Example 1, and the physical properties in the same manner as in Example 1 to evaluate the results It is shown together in Table 1.

Comparative Example 6

As the composition for coating the low refractive index layer, 1.8 parts by weight of 100 parts by weight of amorphous fluorine-containing resin (Teflon-AF 2400) and 30 parts by weight of perfluoropolyethylene diol (FC-2202, 3M) were added to the fluorine-containing solvent (FC-77). Except for dissolving, the antireflection film was prepared in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 1 together.

Comparative Example 7

As a composition for coating the low refractive index layer, 100 parts by weight of amorphous fluorine-containing resin (Teflon-AF 2400) and 30 parts by weight of fluorine-containing polyfunctional acrylic acid ester (ART-4, Co., Ltd.), 1.8 parts by weight of solids in fluorine-containing solvent (FC-77). Except for dissolving to a%, an antireflection film was prepared in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1, and the results are shown in Table 1 together.

Average reflectance (%) Transmittance (%) Pencil hardness Cross-cut Exam Contact angle Example 1 1.9 94.3 5H ○ 105 Example 2 2.1 94.3 5H ○ 105 Example 3 2.0 94.2 4H ○ 107 Comparative Example 1 1.9 94.5 H ○ 116 Comparative Example 2 2.0 94.2 3H Δ 115 Comparative Example 3 1.8 94.1 3H × 109 Comparative Example 5 2.0 94.3 2B × 100 Comparative Example 6 1.8 93.9 H × 107 Comparative Example 7 1.9 94.2 3H × 110

From the results of Table 1, the average reflectance of the antireflection films of Examples 1,2 and 3 according to the production method of the present invention is 1.9% to 2.1%, the pencil hardness of 4H to 5H, of Comparative Examples 1 to 7 Compared with the antireflection film, it can be seen that the films of Examples 1 and 2 show excellent hardness without deterioration of the antireflection performance.

As described above, the antireflective film prepared by using the composition for coating the low refractive index layer of the present invention can produce an antireflection film having low reflectivity and high transmittance and excellent durability.

Claims (11)

Amorphous fluorine-containing resin (30) 30-70 parts by weight relative to the total solids; Fluorine-containing resin containing an alcohol group (ii) 20-50 parts by weight relative to the total solids; Fluorine-containing resin containing an acrylic ester group (iii) 10-35 parts by weight based on the total solids; And a low refractive index coating composition comprising a solvent. The method of claim 1, wherein the solvent is F (CF ₂ ) ₆ OCH ₃ , F (CF ₂ ) ₇ OCH ₃ , F (CF ₂ ) ₈ OCH ₃ , F (CF ₂ ) ₉ OCH ₃ and F (CF ₂ ) A composition for coating a low refractive index layer, characterized in that at least one fluorine-containing solvent selected from the group consisting of ₁₀ OCH ₃ . delete Base material, hard coat layer, high refractive index layer, and In manufacturing the antireflection film in which the low refractive layers are laminated in order, The method of manufacturing an anti-reflection film, characterized in that the low refractive layer is formed by applying a coating solution according to claim 1 and drying. The method of claim 4, wherein the drying temperature of the composition for coating the low refractive index layer is 50 to 150 ℃. Anti-radiation film prepared according to the method of claim 4 or 5. The antireflection film according to claim 6, wherein a thickness of the high refractive index layer or the low refractive index layer of the antireflection film is 60 nm to 600 nm. The antireflection film according to claim 6, wherein the high refractive index layer has a refractive index of 1.6 to 2 and the low refractive layer has a refractive index of 1.3 to 1.5. The antireflection film according to claim 6, wherein a difference between the refractive index of the low refractive index layer and the refractive index of the high refractive layer is 0.05 to 0.7. The antireflection film according to claim 6, wherein the antireflection film has a transmittance of 92% or more and an average reflectance of 380 nm to 750 nm of 3% or less. An image display device comprising the antireflection film of claim 6.

Images