KR101779647B1 - Antireflective composition and method of producing the same, and antireflective film - Google Patents

Abstract

A metal-containing organic oligosiloxane in which some of Si is substituted with a metal and contains a metal; Photo-curable acrylate-based compounds; A network-containing fluorinated organic oligosiloxane; And hollow silica particles, wherein the metal atom comprises at least one selected from the group consisting of titanium, zirconium, and combinations thereof. Also disclosed is an antireflection film formed by photo-curing the antireflection composition and a method for producing the antireflection film.

Description

TECHNICAL FIELD [0001] The present invention relates to an antireflective composition, a method of manufacturing the same, and an antireflection film.

An antireflective composition, a process for producing the same, and an antireflection film.

When the display is exposed to external light such as various lighting and natural light, the contrast is deteriorated due to the invisibility of the image formed in the display due to the reflected light to the eyes, which makes view of the screen difficult and the eyes feel fatigue Or headache. For this reason, the importance of reflection prevention is increasing.

In the conventional antireflection film, an antireflection layer is disposed on a transparent substrate. The antireflection layer has a three-layer structure in which a hard coating layer, a refractive index layer and a low refractive index layer are sequentially laminated on a transparent substrate.

In addition, although the high refractive index layer is generally formed of a binder resin such as a styrene-based or epoxy-based high-cost metal oxide fine particle, the cost of the metal oxide fine particles is high and the production cost is increased. Acrylic resin, and the like, but the compatibility between the acrylic resin and the silica particles is poor.

Also, since the antireflection film includes both the high refractive index layer and the low refractive index layer to realize the antireflection performance, the manufacturing process is complicated and the productivity is low due to the process of forming each layer.

In one embodiment of the present invention, there is provided an antireflective composition that provides excellent antireflective performance, good processability, and good economics.

In another embodiment of the present invention, there is provided an antireflection film which realizes excellent antireflection performance, excellent processability and excellent economical efficiency.

In another embodiment of the present invention, there is provided a process for preparing the antireflective composition.

In one embodiment of the present invention, a network-containing organo oligosiloxane having a network in which some of Si is substituted with a metal and contains a metal; Photo-curable acrylate-based compounds; A network-containing fluorinated organic oligosiloxane; And hollow silica particles, wherein the metal atom comprises at least one selected from the group consisting of titanium, zirconium, and combinations thereof.

The antireflective composition may comprise an upper layer and a lower layer that are phase separated.

The lower layer includes a network-containing organo oligosiloxane having a network structure; And a photo-curable acrylate-based compound.

The above-mentioned upper layer contains a fluorine-containing organic oligosiloxane having the network structure as a binder; And the hollow silica particles are present, and the network-containing fluorinated organic oligosiloxane may be attached to the surface of the hollow silica particles by chemical bonding.

The atomic ratio of Si to metal contained in the network-containing organo oligosiloxane of the network may be from about 1: 0.03 to about 1: 5.90.

The fluorine-containing organic oligosiloxane of the network structure may be connected to the surface of the hollow silica particles by a siloxane bond.

The weight ratio of the metal-containing organic oligosiloxane to the fluorine-containing organic oligosiloxane may be about 1: 0.1 to about 1: 2.

The content of the metal-containing organic oligosiloxane of the network structure may be about 10 parts by weight to about 1000 parts by weight based on 100 parts by weight of the photocurable (meth) acrylate compound.

The content of the fluorine-containing organic oligosiloxane having a network structure as the binder may be about 10 parts by weight to about 120 parts by weight based on 100 parts by weight of the hollow silica particles.

The network structure of the metal-containing organic oligosiloxane may partially include a structure opened by a substituent, and the substituent may include a (meth) acrylate functional group having 4 to 18 carbon atoms.

Wherein the network structure of the fluorine-containing organic oligosiloxane partially contains a structure opened by a substituent, the substituent is a fluoroalkyl group having 3 to 18 carbon atoms, a (meth) acrylate group having 4 to 18 carbon atoms, .

Wherein the metal-containing organic oligosiloxane is a titanium compound represented by the following formula (1), a zirconium compound represented by the following formula (2), or a mixture thereof; And a silane compound of formula (3): < EMI ID =

[Chemical Formula 1]

R ¹ _x Ti (OR ² ) _4-x

(2)

R ³ _y Zr (OR ⁴ ) _4-y

(3)

_{^{R 5 z Si (OR 6)}} 4-z

Each of R ¹ , R ³ and R ⁵ independently represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, (Meth) acrylate group, an aryl group having 6 to 18 carbon atoms, an acetonate group having 3 to 8 carbon atoms, or a halide group, and R ² , R ⁴ , R ⁶ Are each independently H or an alkyl group having 1 to 6 carbon atoms, and each of x, y and z is independently 0, 1 or 2.

The total amount of the titanium compound of Formula 1 and the zirconium compound of Formula 2 may be about 10 parts by weight to about 1000 parts by weight based on 100 parts by weight of the silane compound of Formula 3. [

The fluorine-containing organic oligosiloxane may be the reaction product of the second composition comprising the silane compound of Formula 3 and the fluorine-containing silane compound of Formula 4:

 [Chemical Formula 4]

R ⁷ _w Si (OR ⁸ ) _4-w

In Formula 4, R ⁷ is a fluoroalkyl group having 3 to 18 carbon atoms, R ⁸ is H or an alkyl group having 1 to 10 carbon atoms, and w is independently 0, 1 or 2.

The content of the fluorine-containing silane compound of Formula 4 may be about 0.1 part by weight to about 20 parts by weight based on 100 parts by weight of the silane compound of Formula 3.

The first composition, the second composition, or both may further include at least one selected from the group consisting of an acid catalyst, water, and an organic solvent.

In another embodiment of the present invention, there is provided an antireflective film formed by photocuring the antireflective composition and comprising an upper layer and a lower layer.

Chemical bonding is present at the interface between the upper layer and the lower layer, and the upper layer and the lower layer can be attached by the chemical bonding.

The chemical bond may include a siloxane bond, a crosslinking between compounds having an acrylate-based functional group, or both.

The thickness of the upper layer to the thickness of the lower layer may be from about 1: 1 to about 1: 4.

The water contact angle of the upper layer may be greater than the water contact angle of the lower layer and the difference in water contact angle between the upper and lower layers may be between about 20 ° and about 50 °.

The surface energy of the upper layer may be less than the surface energy of the lower layer and the difference in surface energy between the upper and lower layers may be between about 10 dyn / cm ² and about 30 dyn / cm ² .

In another embodiment of the present invention, a network-containing organo oligosiloxane having a network structure in which a part of Si is substituted with a metal and contains a metal; And a photo-curable acrylate-based compound, wherein the metal-containing organic oligosiloxane is prepared by preparing a high refractive index composition containing a metal atom by forming a chemical bond; A network-containing fluorinated organic oligosiloxane; And hollow silica particles; And preparing the antireflective composition by mixing the high refractive index composition and the low refractive index composition.

The phase separation may occur spontaneously in the anti-reflection composition so that upper and lower layers may be formed.

A titanium compound represented by the following formula (1), a zirconium compound represented by the following formula (2), or a mixture thereof; And a silane compound represented by the following formula (3) to form a metal-containing organic oligosiloxane having the network structure:

 [Chemical Formula 1]

R ¹ _x Ti (OR ² ) _4-x

(2)

R ³ _y Zr (OR ⁴ ) _4-y

(3)

_{^{R 5 z Si (OR 6)}} 4-z

Each of R ¹ , R ³ and R ⁵ independently represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, (Meth) acrylate group, an aryl group having 6 to 18 carbon atoms, an acetonate group having 3 to 8 carbon atoms, or a halide group, and R ² , R ⁴ , R ⁶ Are each independently H or an alkyl group having 1 to 6 carbon atoms, and each of x, y and z is independently 0, 1 or 2.

And then reacting the second composition containing the silane compound of Formula 3 and the fluorine-containing silane compound of Formula 4 to form the fluorine-containing organic oligosiloxane having the reticulated structure.

 [Chemical Formula 4]

R ⁷ _w Si (OR ⁸ ) _4-w

In Formula 4, R ⁷ is a fluoroalkyl group having 3 to 18 carbon atoms, R ⁸ is H or an alkyl group having 1 to 10 carbon atoms, and w is independently 0, 1 or 2.

The antireflective composition implements excellent antireflection performance while simultaneously achieving excellent processability and economy.

1 is a schematic cross-sectional view of an antireflection film according to another embodiment of the present invention.
Figure 2 is a schematic process flow diagram of a method of making an antireflective composition according to another embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. In the drawings, for the convenience of explanation, the thicknesses of some layers and regions are exaggerated.

Hereinafter, the formation of any structure in the "upper (or lower)" or the "upper (or lower)" of the substrate means that any structure is formed in contact with the upper surface (or lower surface) of the substrate However, the present invention is not limited to not including other configurations between the substrate and any structure formed on (or under) the substrate.

In one embodiment of the present invention, a network-containing organo oligosiloxane having a network in which some of Si is substituted with a metal and contains a metal; Photo-curable acrylate-based compounds; A network-containing fluorinated organic oligosiloxane; And hollow silica particles, wherein the metal atom comprises at least one selected from the group consisting of titanium, zirconium, and combinations thereof.

Generally, an antireflection film must include a high-refraction layer and a low-refraction layer, thereby forming a respective layer and a process for laminating them, so that the manufacturing process is complicated, and time and cost are considerably consumed.

In addition, the high refractive index composition for forming the high refractive index layer is manufactured by mixing metal oxide particles having high refractive index with high refractive index, for example, styrene-based or epoxy-based binder resin. However, these metal oxide particles are expensive There is a problem that the manufacturing cost remarkably increases.

As described below, the antireflective composition according to an embodiment of the present invention may be spontaneously phase separated due to different surface energies of the respective components included in the antireflective composition, and may be divided into an upper layer and a lower layer. The antireflection film formed by photo-curing the antireflection composition can form an upper layer as a low refractive layer and a lower layer as a high refractive layer at one time. As a result, it is possible to simplify the manufacturing process of the antireflection film, and to be effective in time and cost, so that the high-refraction layer and the low refractive layer are formed in separate processes and are formed in a single light- And an excellent economical efficiency.

In addition, since the lower layer of the antireflective composition contains a metal-containing organic oligosiloxane having a network structure in which Si is substituted with a metal, a high refractive index can be realized more uniformly overall without containing expensive metal oxide particles At the same time, the low refractive index can be realized by including the fluorine-containing organic oligosiloxane and the hollow silica particles in the upper layer, and the antireflection film formed from the antireflective composition can economically realize excellent antireflection performance.

Also, since the curing can be performed at a high speed including the photo-curable (meth) acrylate compound, the manufacturing time can be further shortened, and the processability and productivity can be further improved.

The antireflective composition may comprise an upper layer and a lower layer that are phase separated.

The antireflective composition may include an upper layer and a lower layer which are formed by spontaneous phase separation due to the surface energy of each component being different, as described later.

Specifically, the components forming the low refraction layer by the photo-curing are relatively low in surface energy as compared with the components forming the high refraction layer, so that the components forming the low refraction layer with low surface energy converge upward, And the components forming the high-refraction layer having a high surface energy can gather downward to form a lower layer.

Since the low refractive index layer and the high refractive index layer can be formed at one time by photocuring the anti-reflection composition phase-separated into the upper layer and the lower layer, the manufacturing process of the antireflection film can be simplified, and the time and cost can be effectively reduced have.

The thickness of the upper layer to the thickness of the lower layer may be from about 1: 1 to about 1: 4. The antireflection film formed by photo-curing the product by phase-splitting at a thickness ratio within the above range further improves the destructive interference phenomenon of light, thereby realizing excellent antireflection performance.

The fluorine-containing organic oligosiloxane may contain fluorine to impart hydrophobicity. As the degree of imparting hydrophobicity increases, the surface energy may be lowered. Thus, the fluorine-containing organic oligosiloxane having a fluorine- Of the metal-containing organic oligosiloxane and the photocurable acrylate-based compound.

Accordingly, the network-containing organic oligosiloxane and the photocurable acrylate compound may be present as a binder in the lower layer of the antireflective composition.

In the upper layer of the antireflective composition, the fluorine-containing organic oligosiloxane having the network structure as the binder; And the hollow silica particles may be present on the surface of the hollow silica particles, and the surface of the hollow silica particles surface-treated by attaching the network-containing fluorinated organic oligosiloxane to the surface of the hollow silica particles by chemical bonding may have low surface energy have. The chemical bond may include, for example, a siloxane bond, whereby the fluorine-containing organic oligosiloxane of the network structure may be connected to the surface of the hollow silica particles by a siloxane bond, i.e., a Si-O-Si bond.

That is, in the upper layer of the antireflective composition, the fluorine-containing organic oligosiloxane having the network structure as the binder; And a hollow silica particle on the surface of which the fluorine-containing organic oligosiloxane having the network structure is attached by chemical bonding.

The weight ratio of the metal-containing organo oligosiloxane to the fluorine-containing organo oligosiloxane included in the antireflective composition may be from about 1: 0.1 to about 1: 2. The refractive index of the high refractive index layer as a lower layer of the antireflection film formed from the antireflection film is increased to a high level and the refractive index of the low refractive index layer as the upper layer is reduced to improve the antireflection performance .

In one embodiment, the content of the network-containing organo oligosiloxane present in the lower layer of the antireflective composition is, for example, from about 10 parts by weight to about 100 parts by weight, based on 100 parts by weight of the photocurable (meth) About 1000 parts by weight, and specifically about 100 parts by weight to about 1000 parts by weight. By including it in the content within the above range, it is possible to uniformly realize a high refractive index as a whole without including expensive metal oxide particles, and at the same time, it can be cured at a high speed by appropriately performing a photo-curing reaction,

 The metal-containing organo-oligosiloxane of the network structure may be prepared by adjusting a degree of substitution of a part of Si in the organic oligosiloxane with a metal and substituting the metal with a metal according to the object and properties of the invention, Can be implemented.

For example, the atomic ratio of Si to metal contained in the network-containing organo oligosiloxane of the network may be, for example, from about 1: 0.03 to about 1: 5.90, and specifically from about 1: 0.3 to about 1: : 5.90. By including a metal at the atomic ratio of the above range, a high refractive index can be uniformly implemented as a whole and an economical efficiency can be realized without increasing the cost excessively.

The network structure of the metal-containing organic oligosiloxane may include a structure partially opened by a substituent. Specifically, the metal-containing organic oligosiloxane may include a substituent which breaks bonds of the network structure, and thus the structure of the network may be partially broken due to the substituent.

The substituent in the metal-containing organic oligosiloxane may include a (meth) acrylate-based functional group having 4 to 18 carbon atoms. By including a (meth) acrylate-based functional group having a carbon number within the above range, the length of the carbon chain is appropriate, and the photo-curing reaction by light irradiation proceeds appropriately, and the hydrolysis reaction and the condensation reaction described below can easily occur.

The substituent may be an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, an acetonate group having 3 to 8 carbon atoms, A halide group, and a combination thereof. The halide group may be F, Cl, Br, I.

Wherein the metal-containing organic oligosiloxane is selected from the group consisting of a titanium compound represented by the following formula (1), a zirconium compound represented by the following formula (2), or a mixture thereof; And a silane compound of formula (3): < EMI ID =

[Chemical Formula 1]

R ¹ _x Ti (OR ² ) _4-x

(2)

R ³ _y Zr (OR ⁴ ) _4-y

(3)

_{^{R 5 z Si (OR 6)}} 4-z

Each of R ¹ , R ³ and R ⁵ independently represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, (Meth) acrylate group, an aryl group having 6 to 18 carbon atoms, an acetonate group having 3 to 8 carbon atoms, or a halide group, and R ² , R ⁴ , R ⁶ Are each independently H or an alkyl group having 1 to 6 carbon atoms, and each of x, y and z is independently 0, 1 or 2.

The titanium compound may be, for example, tetraethoxy titanium, tetramethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetra tert-butoxy titanium, titanium 2-ethylhexyl oxide, titanium Tetrachlorotitanium, chlorotriethoxytitanium, chlorotrimethoxytitanium, chlorotriisopropoxytitanium, dichlorodimethoxytitanium, dichlorodiethoxytitanium, dichlorodiethoxytitanium, dichlorodiethoxytitanium, titanium dichloride, titanium tetrachloride, At least one selected from the group consisting of isopropoxy titanium, dichlorodibutoxy titanium, trichloromethoxy titanium, trichloroethoxy titanium, diethoxy diisopropoxy titanium, titanium bromide, titanium fluoride, titanium iodide, One can be included.

Also, the titanium compound may include a titanium compound in which at least one of an alkoxide group such as methoxy and ethoxy and a halide group is substituted by a (meth) acrylate-based functional group, whereby the reaction product of the first composition , The substituent in the metal-containing organic oligosiloxane may include a (meth) acrylate-based functional group to be photocured, shortening the manufacturing time and improving the processability and productivity.

Also, in the above-exemplified titanium compound, at least one of an alkoxide group such as methoxy, ethoxy and the like and a halide group may include a titanium compound substituted with an alkyl group, an alkenyl group, an aryl group or another halide group.

The zirconium compound may be, for example, tetramethoxy zirconium, tetraethoxy zirconium, tetrapropoxy zirconium, tetrabutoxy zirconium, tetra tert-butoxy zirconium, tetraisopropoxy zirconium, tetraacetylacetonate, zirconium chloride, zirconium At least one selected from the group consisting of bromide, zirconium fluoride, zirconium iodide, zirconium acrylate, zirconium carboxyethyl acrylate, and combinations thereof.

In addition, the zirconium compound may include a zirconium compound in which at least one of an alkoxide group such as methoxy, ethoxy, and a halide group is substituted with a (meth) acrylate-based functional group, , The substituent in the metal-containing organic oligosiloxane may include a (meth) acrylate-based functional group to be photocured, shortening the manufacturing time and improving the processability and productivity.

Further, in the illustrated zirconium compound, a zirconium compound in which at least one of an alkoxide group such as methoxy, ethoxy, and a halide group is substituted with an alkyl group, an alkenyl group, an aryl group, or another halide group may be included.

The silane compound may be, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra- Propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriethoxysilane, n-propyltriethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, , Dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trichloromethylsilane, trichlorochloromethylsilane, trichlorodichloromethylsilane, tetrachlorosilane, dimethoxydimene Silane, triacetoxyvinylsilane, trichlorooctadecylsilane trichlorooctylsilane, acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxy Silane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldimethoxysilane, methacryloxymethylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxy At least one selected from the group consisting of propyl methyldiethoxysilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropyldimethylethoxysilane, and combinations thereof.

Also, the silane compound in which at least one of alkoxide groups such as methoxy, ethoxy, and halide groups of the illustrated silane compound is substituted with a (meth) acrylate-based functional group may be included, , The substituent in the metal-containing organic oligosiloxane may include a (meth) acrylate-based functional group to be photocured, shortening the manufacturing time and improving the processability and productivity.

Also, in the exemplified silane compound, a silane compound in which at least one of an alkoxide group such as methoxy, ethoxy, and a halide group is substituted with an alkyl group, an alkenyl group, an aryl group, or another halide group may be included.

The reaction product of the first composition may specifically include a hydrolysis reaction, a condensation reaction, or a reaction product of both of them. For example, a hydrolysis reaction of a silane alkoxide or the like occurs first, and a condensation reaction may occur between the silane compounds having a hydroxy group thus formed. The hydrolysis reaction, the condensation reaction, and the like Can proceed.

The total content of the titanium compound of Formula 1 and the zirconium compound of Formula 2 may be, for example, about 10 parts by weight to about 1000 parts by weight, based on 100 parts by weight of the silane compound of Formula 3, About 100 parts by weight to about 1000 parts by weight. By incorporating the content within the above range, the refractive index of the high refractive index composition can be increased to a high value, and the gelation reaction can be suppressed by suitably adjusting the reaction rate, thereby improving the storage stability.

As described above, the high refractive index composition includes the photocurable (meth) acrylate compound, and the high refractive index composition can be cured at a high speed, thereby realizing excellent processability and productivity.

The photocurable (meth) acrylate compound may include at least one selected from the group consisting of a (meth) acrylate monomer, an oligomer, a resin, and a combination thereof.

Also, the photo-curable (meth) acrylate-based compound may include, for example, a polyfunctional (meth) acrylate-based monomer to improve the crosslinkability, and specifically, the polyfunctional (meth) For example, a trifunctional or higher (meth) acrylate monomer to effectively improve the crosslinking property, and the high refractive index layer formed by curing the high refractive index composition can increase the crosslinking density and hardness to realize excellent durability.

Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n- (Meth) acrylate, isooctyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl And combinations thereof.

The (meth) acrylate oligomer may be at least one monomer selected from the group consisting of alkyl (meth) acrylates, alkylene glycol (meth) acrylates, carboxyl groups and unsaturated double bonds (meth) acrylates, hydroxyl group- (Meth) acrylate oligomer having various kinds of functional groups such as acrylate and the like. However, it is not limited thereto.

The (meth) acrylate resin may be at least one selected from the group consisting of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane triacrylate, trimethanol Hexanediol diacrylate, polyethylene glycol diacrylate, diethylene glycol acrylate, triethylene glycol acrylate, tetraethylene glycol acrylate, hexaethylene glycol acrylate, propyl acrylate, butyl Bisphenol A diglycidyl acrylate, bisphenol A epoxy acrylate, ethylene oxide addition bisphenol A diacrylate, 2-phenoxy acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, bisphenol A diglycidyl diacrylate, Cy ethyl acrylate It may include at least one selected from the group consisting of, but not limited thereto.

The multifunctional (meth) acrylate monomer may be, for example, a (meth) acrylate monomer having a bifunctional or twelve functional group, and specifically, 1,2-ethylene glycol diacrylate, (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di Neopentylglycol adipate di (meth) acrylate, hydroxyl puivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, capro (Meth) acrylates such as lactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (meth) acryloxyethyl isocyanurate, allyl cyclohexyl di tree (Meth) acrylate, trimethylolpropane di (meth) acrylate, cyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentanedi (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (Meth) acrylate such as modified trimethyl propane di (meth) acrylate, adamantane di (meth) acrylate or 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene Bifunctional acrylates; (Meth) acrylates such as trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri Trifunctional acrylates such as modified trimethylolpropane tri (meth) acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethylisocyanurate; Tetrafunctional acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; Pentafunctional acrylates such as propionic acid-modified dipentaerythritol penta (meth) acrylate; And dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (e.g., an isocyanate monomer and trimethylolpropane tri Hexafunctional acrylates such as hexafunctional acrylates, hexafunctional acrylates and hexafunctional acrylates, and the like.

The first composition may further include at least one selected from the group consisting of an acid catalyst, water, and an organic solvent.

The acid catalyst may be, for example, an inorganic acid or an organic acid. Specifically, nitric acid, hydrochloric acid, sulfuric acid or acetic acid may be used.

The organic solvent includes, for example, alcohols such as methanol, isopropyl alcohol (IPA), ethylene glycol, and butanol; Ketones such as methyl ethyl ketone and methyl iso butyl ketone (MIBK); Esters such as ethyl acetate, butyl acetate and? -Butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; And a combination of these.

In one embodiment, the reticular structure of the fluorine-containing organic oligosiloxane may comprise a structure that is partially open by substituents. Specifically, the fluorine-containing organic oligosiloxane may include a substituent which disassociates the network structure, and thus the structure of the network may be partially broken by the substituent to open the structure.

The antireflective composition may include a network-containing fluorinated organic oligosiloxane as a binder, for example, in an amount of about 10 parts by weight to about 120 parts by weight per 100 parts by weight of the hollow silica particles, and may also include, for example, about 20 To about 100 parts by weight, and specifically about 40 parts by weight to about 80 parts by weight. By including it in the content within the above range, excellent antireflection performance can be realized without causing bleaching phenomenon.

The fluorine-containing organic oligosiloxane may have a weight average molecular weight of, for example, from about 1,000 g / mol to about 100,000 g / mol, for example from about 2,000 g / mol to about 50,000 g / mol, , From about 5,000 g / mol to about 20,000 g / mol. By having a weight average molecular weight within the above range, a low refractive index and excellent light transmittance can be realized at the same time.

The substituent in the fluorine-containing organic oligosiloxane may include a fluoroalkyl group having 3 to 18 carbon atoms, a (meth) acrylate group having 4 to 18 carbon atoms, or both of them.

Specifically, the substituent includes a fluoroalkyl group having 3 to 18 carbon atoms and a (meth) acrylate group having 4 to 18 carbon atoms, wherein the fluorine-containing organic oligosiloxane contains a fluoroalkyl group substituted with at least one fluorine (Meth) acrylate is present even when a low refractive index is present, so that a photo-curing reaction can be performed.

In addition, since at least one photocurable (meth) acrylate-based functional group exists in the fluorine-containing organic oligosiloxane, the photocuring reaction can proceed, and the curing can be performed at a high speed, shortening the manufacturing time, Can be further improved.

Wherein the fluorine-containing organic oligosiloxane is a reaction product of a second composition comprising the silane compound of Formula 3 and the fluorine-containing silane compound of Formula 4:

 [Chemical Formula 4]

R ⁷ _w Si (OR ⁸ ) _4-w

In Formula 4, R ⁷ is a fluoroalkyl group having 3 to 18 carbon atoms, R ⁸ is H or an alkyl group having 1 to 10 carbon atoms, and w is independently 0, 1 or 2.

The silane compound of the above formula (3) is as described above.

The fluorine-containing silane compound of Formula 4 may be, for example, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, nonafluoro But are not limited to, butylethyltrimethoxysilane, butylethyltrimethoxysilane, nonafluorobutylethyltriethoxysilane, nonafluorohexyltrimethoxysilane, nonafluorohexyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooxane Heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and combinations thereof. [0033] The term " a "

The content of the fluorine-containing silane compound of Formula 4 may be, for example, about 0.1 to about 20 parts by weight, and more preferably about 5 to about 10 parts by weight, based on 100 parts by weight of the silane compound of Formula 3 have. The upper layer as a low refraction layer formed by photocuring the antireflective composition within the above range has a low refractive index and is imparted with hydrophobicity and has a surface energy appropriately lowered so that excellent stain resistance and excellent adhesion can be realized. Panel or the like.

The first composition, the second composition, or both may further include at least one selected from the group consisting of an acid catalyst, water, and an organic solvent.

The acid catalyst may be, for example, an inorganic acid or an organic acid. Specifically, nitric acid, hydrochloric acid, sulfuric acid or acetic acid may be used.

The organic solvent includes, for example, alcohols such as methanol, isopropyl alcohol (IPA), ethylene glycol, and butanol; Ketones such as methyl ethyl ketone and methyl iso butyl ketone (MIBK); Esters such as ethyl acetate, butyl acetate and? -Butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; And a combination of these.

In one embodiment, the hollow silica particles may be, for example, silica particles formed from a silicone compound or an organosilicon compound, and voids may be present on the surface, interior, or both of the silica particles .

The hollow silica particles may be dispersed in, for example, a dispersion medium such as water or an organic solvent, and may be in the form of a colloid in which the solid content of the hollow silica particles is 5 to 40% by weight. Examples of the organic solvent usable as the dispersion medium include alcohols such as methanol, isopropyl alcohol (IPA), ethylene glycol, and butanol; Ketones such as methyl ethyl ketone and methyl iso butyl ketone (MIBK); Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethyl formamide, dimethyl acetamide and N-methyl pyrrolidone; Esters such as ethyl acetate, butyl acetate and? -Butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; Or a mixture thereof.

The number average diameter of the hollow silica particles may be, for example, from about 1 nm to about 1,000 nm, and may also be, for example, from about 5 nm to about 500 nm, and specifically from about 10 nm to about 100 nm. By having the number average diameter within the above range, the antireflection film can simultaneously realize excellent transparency and antireflection performance.

The antireflective composition may further comprise a photoinitiator, and without particular limitation, photoinitiators known in the art may be used.

In another embodiment of the present invention, an antireflection film 100 formed by photocuring an antireflective composition phase-separated into the upper layer and the lower layer to form an upper layer 120 as a low refractive layer and a lower layer 110 as a high refractive layer, . 2 schematically shows a cross-sectional view of an anti-reflection film 100 according to another embodiment of the present invention.

As a result, the low refractive index layer and the high refractive index layer can be formed in a single photo-curing process without having to be separately manufactured and laminated, thereby simplifying the manufacturing process, reducing time and cost, There is an advantage.

The antireflection film 100 may be formed by hot-air drying the antireflective composition and then curing the antireflective composition followed by an aging process.

The photocuring may be, for example, UV curing or the like, and may be performed using a conventional metal halide lamp or the like, but is not limited thereto.

  The hydrolysis reaction, the condensation reaction, and the like can be further progressed while removing the solvent by the hot air drying. For example, the hot air drying can be performed at a temperature of about 50 ° C to about 200 ° C for about 1 minute to about 10 minutes, But is not limited thereto. The aging step may be further followed by a hydrolysis reaction, a condensation reaction or the like between the unreacted compounds remaining in the antireflective composition, and aging may be performed at a temperature of about 40 캜 to about 100 캜 for about 10 hours to about 100 hours But are not limited thereto.

In another embodiment, a chemical bond exists at the interface of the upper layer 120 and the lower layer 110, and the upper layer 120 and the lower layer 110 may be attached by chemical bonding. Accordingly, in the anti-reflection film 100, the upper layer 120 as the low refractive index layer and the lower layer 110 as the high refractive index layer can firmly adhere to each other to realize excellent durability.

The chemical bond may include, for example, siloxane bonds, crosslinks between compounds having an acrylate-based functional group, or both.

The lower layer 110 as the high refractive index layer may have a refractive index of, for example, from about 1.40 to about 1.73, and specifically from about 1.51 to about 1.73. By having a high level of refractive index within the above range, it is possible to realize an excellent antireflection performance together with the low refractive layer described later.

The refractive index of the low refractive layer may be about 1.20 to about 1.25 at about 23 占 폚. By having a low refractive index within the above range, it is possible to realize an excellent antireflection performance together with the high refractive index layer described above.

The thickness of the upper layer 120 as the low refraction layer and the thickness ratio of the lower layer 110 as the high refraction layer may be about 1: 1 to about 1: 4. By having the thickness ratio within the above range, the antireflection film can further improve the destructive interference phenomenon of light and realize excellent antireflection performance.

The thickness of the lower layer 110 as the high refractive index layer may be, for example, from about 50 nm to about 200 nm. By having the thickness within the above range, the antireflection film 100 can be formed not to be excessively thick and an excellent antireflection performance can be realized together with the low refractive layer described later without increasing the cost.

The thickness of the upper layer 120 as the low refraction layer may be, for example, from about 50 nm to about 200 nm. By having the thickness within the above range, the antireflection film 100 can be formed with an excessively large thickness and an excellent antireflection performance can be realized together with the high refractive index layer without increasing the cost.

The water contact angle of the upper layer 120 is greater than the water contact angle of the lower layer 110 and the difference in water contact angle between the upper layer 120 and the lower layer 110 is between about 20 ° and about 50 ° . By having water contact angle differences within this range, the surface energies of the respective components included in the antireflective composition prior to photocuring can be different, and can be spontaneously phase separated into the upper and lower layers as described above in one embodiment.

The water contact angle of the upper layer 120 may be, for example, from about 90 degrees to about 110 degrees, and the water contact angle of the lower layer 110 may be, for example, from about 60 degrees to about 70 degrees.

The surface energy of the upper layer 120 may be less than the surface energy of the lower layer 110 and the difference in surface energy between the upper layer 120 and the lower layer 110 may be between about 10 dyn / cm ² and about 30 dyn / cm ^2. have. By having the surface energy difference within the above range, phase separation phenomenon between the components forming the low refractive index layer by photocuring and the components forming the high refractive index layer in the antireflection composition prior to the photocuring can be more easily occurred and the phase- The antireflection film 100 formed by photo-curing the composition can realize excellent antireflection performance.

The surface energy may be calculated in a manner known in the art without any particular limitation, but is calculated according to the Owen-Wendt model using the Young's formula herein.

The antireflective film 100 may have a luminous transmittance of about 93% to about 98% and a luminous reflectance measured at a temperature of 23 캜, for example, about 0.2 to about 1.5, 1.0, and excellent light transmittance and antireflection performance can be realized.

Figure 3 shows a schematic process flow diagram of a method of making an antireflective composition according to another embodiment of the present invention.

In another embodiment of the present invention, a metal-containing organo oligosiloxane and a photo-curable acrylate-based compound in which a part of Si is substituted with a metal and contain a metal, wherein the metal is titanium, zirconium and combinations thereof (S1) a high refractive index composition comprising at least one selected from the group consisting of (S2) preparing a low refractive composition comprising a fluorinated organic oligosiloxane having a network structure and hollow silica particles; (S3) mixing the high refractive index composition and the low refractive index composition to prepare an antireflective composition.

The components included in the high refractive index composition and the components included in the low refractive index are different in surface energy as described above in one embodiment, and the phase separation is spontaneously generated in the antireflective composition to separate the upper layer and the lower layer The antireflection film formed by photo-curing the phase-separated antireflection composition as described above can be formed as a low refractive index layer as a top layer and a high refractive index layer as a bottom layer at a time.

As a result, it is possible to simplify the manufacturing process of the antireflection film and to save time and cost, so that the high-refraction layer and the low refractive layer can be manufactured with separate processes, And economical efficiency can be realized.

According to the above manufacturing method, by preparing a high refractive index composition containing a metal-containing organo oligosiloxane in which a part of Si is substituted with a metal to contain a metal, it is possible to maintain a high refractive index while maintaining high refractive index without containing expensive metal oxide particles Economical efficiency can be realized.

In addition, it is possible to cure at a high speed including a photo-curable (meth) acrylate compound, shorten the manufacturing time, and thus, the processability can be improved and the productivity can be further improved.

A titanium compound represented by the following formula (1), a zirconium compound represented by the following formula (2), or a mixture thereof; And a silane compound represented by the following formula (3) to form a metal-containing organic oligosiloxane having the network structure:

[Chemical Formula 1]

R ¹ _x Ti (OR ² ) _4-x

(2)

R ³ _y Zr (OR ⁴ ) _4-y

(3)

_{^{R 5 z Si (OR 6)}} 4-z

Each of R ¹ , R ³ and R ⁵ independently represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, (Meth) acrylate group, an aryl group having 6 to 18 carbon atoms, an acetonate group having 3 to 8 carbon atoms, or a halide group, and R ² , R ⁴ , R ⁶ Are each independently H or an alkyl group having 1 to 6 carbon atoms, and each of x, y and z is independently 0, 1 or 2.

In the above production process, the titanium compound of Formula 1, the zirconium compound of Formula 2, and the silane compound of Formula 3 are as described above in one embodiment of the present invention.

The first composition may be stirred, for example, at about 20 [deg.] C to about 60 [deg.] C for about 3 hours to about 40 hours. By stirring under the temperature and time conditions within the above range, the hydrolysis reaction and the condensation reaction proceed sufficiently, and the metal-containing organic oligosiloxane having a network structure can be easily formed. The high refractive index composition can be prepared by mixing and stirring the photocurable acrylate compound in the first composition including the network-containing organo oligosiloxane having the network structure. The metal-containing organic oligosiloxane of the network structure is as described above in one embodiment of the present invention.

The photocurable (meth) acrylate compound may include at least one selected from the group consisting of a (meth) acrylate monomer, an oligomer, a resin and a combination thereof, and more specifically, a polyfunctional (meth) The crosslinking property can be improved. The specific kind of the photocurable acrylate compound is as described above in one embodiment of the present invention. In addition, the polyfunctional (meth) acrylate-based monomer specifically includes trifunctional or more (meth) acrylate-based monomers to further improve the crosslinking property, thereby realizing excellent crosslinking density and hardness.

The method may further include reacting the silane compound represented by Formula 3 and the fluorine-containing silane compound represented by Formula 4 to form a fluorine-containing organic oligosiloxane having the reticular structure.

[Chemical Formula 4]

R ⁷ _w Si (OR ⁸ ) _4-w

In Formula 4, R ⁷ is a fluoroalkyl group having 3 to 18 carbon atoms, R ⁸ is H or an alkyl group having 1 to 10 carbon atoms, and w is independently 0, 1 or 2. The fluorine-containing silane compound of Formula 4 is as described above in one embodiment of the present invention.

The second composition may be stirred, for example, at about 20 [deg.] C to about 60 [deg.] C for about 4 hours to about 80 hours. By stirring under the temperature and time conditions within the above range, the hydrolysis reaction and the condensation reaction proceed sufficiently, and the fluorine-containing organic oligosiloxane having a network structure can be easily formed. The above-mentioned fluorinated organic oligosiloxane of the network structure is as described above in one embodiment of the present invention. Thus, the hollow silica particles are mixed with the second composition containing the fluorine-containing organic oligosiloxane having the network structure and stirred at about 20 캜 to about 40 캜 for about 5 hours to about 50 hours to form the low refractive composition Can be prepared. By stirring under the temperature and time conditions within the above range, the fluorine-containing organic oligosiloxane can be appropriately attached to the surface of the hollow silica particles by chemical bonding, whereby the surface of the hollow silica particles has a low refractive index and a low surface energy . The chemical bond may be, for example, a siloxane bond, i.e., a Si-O-Si bond. Accordingly, the low refractive index composition is a fluorine-containing organic oligosiloxane having a network structure as a binder; And hollow silica particles to which a fluorine-containing organic oligosiloxane having a network structure is attached by chemical bonding.

The first composition, the second composition, or both may further include at least one selected from the group consisting of an acid catalyst, water, and an organic solvent, and the acid catalyst and the organic solvent are as described above in an embodiment.

The antireflective composition may be prepared by mixing the high refractive index composition and the low refractive index composition. The antireflective composition is as described above in one embodiment.

Specifically, the high refractive index composition and the low refractive index composition may be mixed and then stirred at about 20 ° C to about 40 ° C for about 30 minutes to about 2 hours. The antireflection film formed by photocuring the antireflection composition by stirring at the temperature and the time within the above range can realize more uniform antireflection performance as a whole.

In the antireflective composition, phase separation occurs spontaneously and upper and lower layers may be formed. Specifically, the antireflective composition has a composition that spontaneously phase separates due to a difference in surface energy between the components forming the low refraction layer and the components forming the high refraction layer, thereby forming a low refraction layer having a relatively low surface energy And the components forming the high refractive index layer with high surface energy can form the underlayer. As described above, the anti-reflection composition spontaneously undergo phase separation and can be divided into the upper layer and the lower layer.

The antireflective composition was coated on at least one side of the base film and photocured after the phase separation occurred in the antireflective composition applied to one side of the base film as described above to form an upper layer as a low refractive layer and a lower layer as a high refractive layer Can be produced.

The substrate may be any of various types of transparent substrates, transparent resin laminates, and the like known in the art without any particular limitation. For example, a PET (polyethylene terephthalate), a polyethylenenaphthalate (PEN), a polyethersulfone (PES) Poly carbonate, polypropylene (PP), norbornene resin, and the like may be used, but the present invention is not limited thereto.

For example, gravure coating, slot die coating, spin coating, spray coating, bar coating, and dip coating may be used for coating the antireflective composition. However, But is not limited thereto.

The antireflection film can be produced, for example, by hot air-drying the antireflective composition, then photocuring, and then applying an aging process to form an upper layer as a low refractive layer and a lower layer as a high refractive layer at a time.

The hydrolysis reaction, the condensation reaction, and the like can be further progressed while the solvent is evaporated by the hot air drying, and hot air drying can be performed at a temperature of, for example, about 50 ° C to about 200 ° C for about 1 minute to about 10 minutes But is not limited thereto.

The aging step may be further followed by a hydrolysis reaction, condensation reaction or the like between unreacted compounds remaining in the high refractive index composition, and the solution may be subjected to aging treatment at a temperature of about 40 캜 to about 80 캜 for about 10 hours to about 100 hours But is not limited thereto.

The photocuring may be, for example, UV curing or the like, and may be performed using a conventional metal halide lamp or the like, but is not limited thereto. The ultraviolet curing may be performed, for example, by irradiating ultraviolet light of about 100 mJ / cm ² to about 1000 mJ / cm ² to sufficiently cure, but is not limited thereto.

The antireflection film produced by the above production method is characterized in that the antireflection film has a weak light transmittance of about 94% to about 98% and a luminous reflectance measured at a temperature of about 23 캜, for example, about 0.2 to about 1.5 And can be specifically about 0.2 to about 1.0, so that excellent light transmittance and anti-reflection performance can be realized.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

Hereinafter, examples of the present invention will be described. The following embodiments are only examples of the present invention, and the present invention is not limited to the following embodiments.

 ( Example )

Example  One

100 parts by weight of tetraethoxyorthosilicate, 250 parts by weight of titanium tetraisopropoxide, 200 parts by weight of water, 200 parts by weight of ethanol and 1 part by weight of 1 M nitric acid were mixed and stirred at 25 DEG C for 48 hours to prepare a first composition Then, pentaerythritol triacrylate (PETA) was further added to the first composition and stirred to prepare a high refractive index composition. The content of the metal-containing organic oligosiloxane in the high refractive index composition was 100 parts by weight based on 100 parts by weight of PETA. 100 parts by weight of tetraethoxyorthosilicate, 40 parts by weight of 3,3,3-trifluoropropyltrimethoxysilane, 100 parts by weight of water, 100 parts by weight of isopropyl alcohol and 1 part by weight of 1 M nitric acid, Was added to the second composition as a binder solution to prepare a hollow silica particle-methyl isobutyl ketone dispersion sol (20% w / w) having a number average particle diameter of 60 nm on the basis of 100 parts by weight of the second composition, w, JGC C & C, Thrulya 4320), 20 parts by weight of acryloxypropyltrimethoxysilane and the photoinitiator Igacure 184 were further mixed and stirred at room temperature for 24 hours to prepare a low refractive composition.

The high refractive index composition and the low refractive index composition were mixed and stirred at 25 DEG C for 2 hours to prepare an antireflective composition. In the antireflective composition, the weight ratio of the metal-containing organic oligosiloxane to the fluorine-containing organic oligosiloxane was 1: 0.6.

Next, the antireflective composition was coated on one side of a PET film having a thickness of 50 μm, followed by hot air drying at 130 ° C. for 2 minutes, UV irradiation at 300 mJ / cm ² , and then aging treatment in an oven at 60 ° C. for 24 hours The total thickness of the anti-reflection film prepared above except for the PET film was 250 nm, the thickness of the upper layer was 100 nm, and the thickness of the lower layer was 150 nm.

evaluation

The refractive index, water contact angle and surface energy of each of the low refraction layer and the high refraction layer included in the antireflection film of Example 1 were measured and the light transmittance, luminous reflectance and minimum reflectance of the antireflection film of Example 1 were measured, .

(Refractive index)

How to measure:

Measurement method: The reflectance was measured at 532 nm, 632.8 nm and 830 nm wavelength with a prism coupler, and the optical constant of the cauchy dispersion formula was calculated by a least square curve fitting method using an approximate expression of refractive index wavelength dispersion using a cauchy dispersion formula The refractive index was measured at a wavelength of 550 nm and a temperature of 23 캜.

(Contact angle measurement)

Water contact angle and organic solvent contact angle were measured when distilled water (di water) and diiodomethane (CH ₂ I ₂ ) were used as a solvent.

Measurement method: A low refractive index layer and a high refractive index layer included in the antireflection film of Example 1 were prepared as a sample having a size of 50 mm x 60 mm. Then, a drop of solvent was dropped on each specimen using a syringe, The sample was magnified with a microscope equipped with a measuring instrument (KRUSS, DSA100, Germany), and the angle formed with the surface of the specimen at the critical point at the left and right ends was measured.

With respect to the above measurement method, five samples of the low refraction layer and the high refraction layer included in the antireflection film of Example 1 were prepared, and the contact angle was measured at three specific points per each sample to obtain a total of 15 measured values Refractive index layer and the high-refraction layer included in the antireflection film of Example 1, and each of the 15 measured values was averaged to evaluate the contact angle.

 (Surface energy)

Measurement method: Calculated according to Owen-Wendt mode using Young's formula, and distilled water (DI water) and diiodomethane (CH ₂ I ₂ ) were used as solvents.

(Light transmittance)

Measurement method: An antireflection film having a thickness of about 50 탆 was measured using a hazemeter (Nippon Denshoku, NDH 5000)

(Luminous reflectance and minimum reflectance)

Measurement method: A black tape for preventing the reflection of the back surface of the antireflection film was attached to the opposite surface, that is, the lower surface, of the PET substrate, on which the high refractive index layer was formed, and a spectrophotometer (Konica Minolta, CM-5) , The luminous reflectance (D65) of the surface of the low refractive index layer at the temperature of 23 占 폚 and the lowest reflectance were evaluated.

The smaller the luminous reflectance and the lowest reflectance, the better the antireflection performance of the antireflection film.

Refractive index Water contact angle (°) Surface energy
(dyn / cm ²⁾ Light transmittance
(%) Luminous reflectance
(%) Lowest reflectance
(%) Example 1 Low refraction layer: 1.28
High refractive index layer: 1.61 Low refraction layer: 107
High refractive index layer: 68 Low refraction layer: 19
High refractive index layer: 43 97 0.4 0.3

100: Antireflection film
110: upper layer as high refractive index layer
120: lower layer as a low refractive layer

Claims (26)

A metal-containing organic oligosiloxane in which some of Si is substituted with a metal and contains a metal; Photo-curable acrylate-based compounds; A network-containing fluorinated organic oligosiloxane; And hollow silica particles, wherein the metal atom comprises at least one selected from the group consisting of titanium, zirconium, and combinations thereof
Antireflective composition.
The method according to claim 1,
Wherein the antireflective composition comprises an upper layer and a lower layer which are phase separated
Antireflective composition.
3. The method of claim 2,
The lower layer includes a network-containing organo oligosiloxane having a network structure; And a photo-curable acrylate-based compound;
Antireflective composition.
3. The method of claim 2,
The above-mentioned upper layer contains a fluorine-containing organic oligosiloxane having the network structure as a binder; And the hollow silica particles are present on the surface of the hollow silica particles, and the fluorine-containing organic oligosiloxane having the network structure is attached to the surface of the hollow silica particles by chemical bonding
Antireflective composition.
The method according to claim 1,
The atomic ratio of Si to metal contained in the metal-containing organic oligosiloxane of the network structure is 1: 0.03 to 1: 5.90
Antireflective composition.
5. The method of claim 4,
The fluorine-containing organic oligosiloxane of the network structure is bonded to the surface of the hollow silica particles by a siloxane bond
Antireflective composition.
The method according to claim 1,
Wherein the weight ratio of the metal-containing organic oligosiloxane to the fluorine-containing organic oligosiloxane is from 1: 0.1 to 1: 2
Antireflective composition
The method of claim 3,
Wherein the content of the metal-containing organic oligosiloxane of the network structure is 10 parts by weight to 1000 parts by weight based on 100 parts by weight of the photocurable acrylate compound
Antireflective composition.
5. The method of claim 4,
The content of the fluorine-containing organic oligosiloxane having a network structure as the binder is 10 parts by weight to 120 parts by weight based on 100 parts by weight of the hollow silica particles
Antireflective composition.
The method according to claim 1,
Wherein the network structure of the metal-containing organic oligosiloxane partially contains a structure opened by a substituent, and the substituent includes a (meth) acrylate-based functional group having 4 to 18 carbon atoms
Antireflective composition.
The method according to claim 1,
Wherein the network structure of the fluorine-containing organic oligosiloxane partially contains a structure opened by a substituent, the substituent is a fluoroalkyl group having 3 to 18 carbon atoms, a (meth) acrylate group having 4 to 18 carbon atoms, Included
Antireflective composition.
The method according to claim 1,
Wherein the metal-containing organic oligosiloxane is a titanium compound represented by the following formula (1), a zirconium compound represented by the following formula (2), or a mixture thereof; And a silane compound represented by the following formula (3):
Antireflective composition:
[Chemical Formula 1]
R ¹ _x Ti (OR ² ) _4-x
(2)
R ³ _y Zr (OR ⁴ ) _4-y
(3)
_{^{R 5 z Si (OR 6)}} 4-z
Each of R ¹ , R ³ and R ⁵ independently represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, (Meth) acrylate group, an aryl group having 6 to 18 carbon atoms, an acetonate group having 3 to 8 carbon atoms, or a halide group, and R ² , R ⁴ , R ⁶ Are each independently H or an alkyl group having 1 to 6 carbon atoms, and each of x, y and z is independently 0, 1 or 2.
13. The method of claim 12,
The total amount of the titanium compound of Formula 1 and the zirconium compound of Formula 2 is 10 parts by weight to 1000 parts by weight based on 100 parts by weight of the silane compound of Formula 3
Antireflective composition.
13. The method of claim 12,
Wherein the fluorine-containing organic oligosiloxane is a reaction product of a second composition comprising the silane compound of Formula 3 and the fluorine-containing silane compound of Formula 4
Antireflective composition:
[Chemical Formula 4]
R ⁷ _w Si (OR ⁸ ) _4-w
In Formula 4, R ⁷ is a fluoroalkyl group having 3 to 18 carbon atoms, R ⁸ is H or an alkyl group having 1 to 10 carbon atoms, and w is independently 0, 1 or 2.
15. The method of claim 14,
The content of the fluorine-containing silane compound of Formula 4 is 0.1 part by weight to 20 parts by weight based on 100 parts by weight of the silane compound of Formula 3
Antireflective composition.
15. The method of claim 14,
Wherein the first composition, the second composition, or both all further comprise at least one selected from the group consisting of an acid catalyst, water and an organic solvent
Antireflective composition.
17. An antireflection film formed by photocuring an antireflective composition according to any one of claims 1 to 16 and comprising an upper layer and a lower layer.
18. The method of claim 17,
Wherein chemical bonding is present at the interface between the upper layer and the lower layer and the upper layer and the lower layer are bonded by the chemical bond
Antireflection film.
18. The method of claim 17,
The chemical bond includes a siloxane bond, a crosslinking between compounds having an acrylate-based functional group, or both
Antireflection film.
18. The method of claim 17,
Wherein the thickness of the upper layer to the thickness of the lower layer is from 1: 1 to 1: 4
Antireflection film.
18. The method of claim 17,
Wherein a water contact angle of the upper layer is larger than a water contact angle of the lower layer and a difference in water contact angle between the upper layer and the lower layer is 20 to 50
Antireflection film.
18. The method of claim 17,
Wherein a surface energy of the upper layer is smaller than a surface energy of the lower layer, and a difference in surface energy between the upper layer and the lower layer is 10 dyn / cm ² to 30 dyn / cm ²
Antireflection film.
A metal-containing organic oligosiloxane in which some of Si is substituted with a metal and contains a metal; And a photo-curable acrylate-based compound, wherein the metal-containing organic oligosiloxane is prepared by preparing a high refractive index composition containing a metal atom by forming a chemical bond;
A network-containing fluorinated organic oligosiloxane; And hollow silica particles; And
Mixing the high refractive index composition and the low refractive index composition to produce an antireflective composition;
≪ / RTI >
24. The method of claim 23,
The phase separation is spontaneously generated in the anti-reflection composition so that the upper layer and the lower layer are formed
≪ / RTI >
24. The method of claim 23,
A titanium compound represented by the following formula (1), a zirconium compound represented by the following formula (2), or a mixture thereof; And a silane compound represented by the following formula (3) to form a metal-containing organic oligosiloxane having the network structure
Method of preparing antireflective composition:
[Chemical Formula 1]
R ¹ _x Ti (OR ² ) _4-x
(2)
R ³ _y Zr (OR ⁴ ) _4-y
(3)
_{^{R 5 z Si (OR 6)}} 4-z
R ¹ , R ³ and R ⁵ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, (Meth) acrylate group, an aryl group having 6 to 18 carbon atoms, an acetonate group having 3 to 8 carbon atoms, or a halide group, and R ² , R ⁴ , R ⁶ Are each independently H or an alkyl group having 1 to 6 carbon atoms, and each of x, y and z is independently 0, 1 or 2.
26. The method of claim 25,
Further comprising reacting a second composition comprising the silane compound of Formula 3 and the fluorine-containing silane compound of Formula 4 to form the fluorine-containing organic oligosiloxane having the network structure
Method of preparing antireflective composition:
[Chemical Formula 4]
R ⁷ _w Si (OR ⁸ ) _4-w
In Formula 4, R ⁷ is a fluoroalkyl group having 3 to 18 carbon atoms, R ⁸ is H or an alkyl group having 1 to 10 carbon atoms, and w is independently 0, 1 or 2.

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