KR102120989B1 - Resin composition for anti-glare and anti-glare film using the same - Google Patents

Abstract

The present invention can realize a high resolution through high image clarity, not only exhibits anti-glare properties by forming surface irregularities, but also easily controls the degree of surface irregularities to be applied to a display of high contrast ratio through excellent visibility. , It relates to an anti-glare resin composition having a high mechanical properties even in the coating thickness of the thin film and an anti-glare film using the same.

Description

Resin composition for anti-glare and anti-glare film using the same{RESIN COMPOSITION FOR ANTI-GLARE AND ANTI-GLARE FILM USING THE SAME}

The present invention relates to an anti-glare resin composition and an anti-glare film. In more detail, high resolution can be achieved through high image clarity, and surface irregularities are formed to exhibit anti-glare properties, and the degree of surface irregularities can be easily adjusted to be applied to a display of high contrast ratio through excellent visibility. And, it relates to an anti-glare resin composition having a high mechanical property even in a coating thickness of a thin film and an anti-glare film using the same.

In response to the recent high-speed and high-density transmission of information, diversification and multi-functionalization of the transmission medium, and as consumers demand high-quality products such as large-screen, high-definition, multi-functional and high-functionality, flat panel displays (FPD) of large screens Has appeared. 2. Description of the Related Art With the increase in the size and thickness of displays and the increase in demand for notebook PCs, various types of flat panel displays such as LCDs, PDPs, and rear-projection TVs have been developed and commercialized.

However, when such a display is exposed to external light such as natural light, the surface reflected light may cause fatigue or headache to the user's eyes, and a problem that the image created inside the display may not be recognized as a clear image occurs. have.

In order to solve this disadvantage, an anti-glare effect was implemented by forming irregularities on the display surface and scattering external light from the surface. However, this causes a problem in that the image clarity is deteriorated in a high-resolution display. In order to improve this, a method of inducing internal haze is used by adding particles that induce internal scattering to the coating layer, but has many problems.

In the Republic of Korea Patent No. 10-046782, the first particle having an average diameter of 0.05 to 1 µm with a difference in refractive index of 0.2 to 0.5 from the acrylate-based binder resin and the second particle having an average diameter of 0.5 to 3 µm with a difference in refractive index not exceeding 0.1 Although it has been described with respect to a high-resolution anti-glare coating layer, there is a disadvantage in that the difference in refractive index between the binder resin and the first particle is severe, resulting in poor contrast.

On the other hand, Korean Patent No. 10-0378340 contains at least two or more types of light-transmitting particles in the binder resin, and the refractive index of the light-transmitting particles is 0.03 or more and 0.2 or less, and each light-transmitting particle has a different refractive index. Although it has been described for an anti-coating layer, there is a disadvantage in that the anti-glare property is reduced compared to the same phase clarity and haze value, and the contrast is reduced due to haze of 10% or more, and the scratch resistance is poor due to organic particles.

In addition, Korean Patent Registration No. 10-0296369 includes a light-transmitting diffuser inside the binder resin, and has an external haze value of 7 to 30 due to surface irregularities and an internal haze value of 1 to 15 due to the translucent diffusion agent. Although it is described with respect to the anti-glare coating layer, there is a disadvantage that the contrast is lowered due to the high surface haze value.

Accordingly, there is a need to develop a resin composition for preventing glare that satisfies properties that can be applied to high-resolution and high-contrast display products.

The present invention can realize a high resolution through high image clarity, not only exhibits anti-glare properties by forming surface irregularities, but also easily controls the degree of surface irregularities to be applied to a display of high contrast ratio through excellent visibility. It is to provide a resin composition for preventing glare having high mechanical properties even in a coating thickness of a thin film.

In addition, the present invention is to provide an anti-glare film using the resin composition for preventing glare.

In the present specification, the core portion including the organic particles having a hydrophilic functional group on the surface and the composite particles having a core shell structure of a shell layer containing inorganic particles having a hydrophilic functional group on the surface; Reactive monomers, oligomers thereof or (co)polymers thereof; And a polar solvent, wherein the composite particle is provided with a resin composition for preventing glare dispersed alone or in an aggregate form of at least two or more composite particles.

Also in this specification, a binder resin; And a composite particle having a core shell structure of a shell layer including a core portion containing organic particles having a hydrophilic functional group on the surface and an inorganic particle having a hydrophilic functional group on the surface, dispersed in the binder resin, and the composite particle is alone or An anti-glare film is provided in the form of aggregates of at least two or more composite particles.

Hereinafter, a resin composition for preventing glare according to a specific embodiment of the present invention and an anti-glare film using the same will be described in more detail.

As used herein, "(co)polymer" is meant to include both polymers and copolymers.

In addition, in this specification, "(meth)acrylic" is meant to include both acrylic and methacrylic.

According to one embodiment of the invention, the composite particles having a core shell structure of a core layer including an organic particle having a hydrophilic functional group on the surface and a shell layer containing an inorganic particle having a hydrophilic functional group on the surface; Reactive monomers, oligomers thereof or (co)polymers thereof; And it includes a polar solvent, the composite particles alone or at least two or more composite particles may be provided with a resin composition for preventing glare dispersed in the form of aggregates.

When the present inventors use the above-mentioned anti-glare resin composition, they can easily form irregularities on the film surface by using a plurality of composite particles, as well as implement anti-glare properties, and control the degree of aggregation of the composite particles to the irregularities. It was confirmed through experiments that the surface roughness due to it can be reduced, thereby providing a soft vision, and the invention was completed.

Particularly, the anti-glare resin composition is composed of core-shell structured composite particles and composites using organic particles having a hydrophilic functional group on the surface in a polar solvent, and inorganic particles having a nano-level fine diameter in the surface. As the formation of aggregates between particles is easily achieved, the degree of aggregation within the composite particles and aggregates can be easily adjusted in the composition, thereby effectively controlling the uneven shape of the final anti-glare film surface.

Accordingly, the sol-gel method is used to form the core shell structure, and the efficiency of the process can be improved as compared to the conventional technique, which had to additionally perform a separate surface crosslinking process to form the uneven pattern, and it is possible to intersect a plurality of particles. While reducing the number of irregularities per unit area of the final anti-glare film due to the smooth formation of irregularities due to agglomeration, it is possible to implement an anti-glare effect equal to or higher than the prior art.

In addition, the composite particles are made of a composite having a core shell structure of a core made of organic particles and a shell made of inorganic particles, and a high resolution/high contrast ratio is required by lowering the Haze value and increasing the image clarity through the light scattering effect by the organic particles. The application range can be extended to products, and mechanical properties such as scratch resistance, crack resistance, and hardness can be improved by inorganic particles.

Specifically, the anti-glare resin composition includes composite particles having a core shell structure of a core layer including organic particles having a hydrophilic functional group on the surface and a shell layer containing inorganic particles having a hydrophilic functional group on the surface. can do.

The core portion of the core-shell-structured composite particle may include organic particles having a hydrophilic functional group on the surface. An example of the form of the organic particles may be spherical, and the average particle diameter may be 1 to 100 μm, or 1 to 50 μm, or 1 to 10 μm. When the average diameter of the organic particles is reduced to less than 1 μm, scattering characteristics of the composite particles may be lowered, and thus it may be difficult to obtain a sufficient haze value. When the average diameter of the organic particles increases to more than 100 μm, the anti-glare resin composition Since the thickness of the film to be produced is thick, it may exhibit cracked or broken properties.

The organic particles are polystyrene, polyacrylate-co-styrene, polymethylacrylate-co-styrene, polymethylmethacrylate-co-styrene, polycarbonate, polyvinyl chloride, polybutylene terephthalate, polyethylene terephthalate, Polyamide, polyimide, polysulfone, polyphenylene oxide, polyacetal, epoxy resin, phenol resin, melamine resin, benzoguanamine, polydivinylbenzene, polydivinylbenzene-co-styrene, polydivinylbenzene -co-acrylate, polydiallyl phthalate, and triallyl isocyanurate polymer, and may include one or more single substances or two or more copolymers.

The shell layer of the composite particle having the core shell structure may include organic particles having a hydrophilic functional group on the surface. Examples of the form of the inorganic particles include spherical, and the average particle diameter may be 1 nm to 500 nm, or 1 nm to 300 nm, or 1 nm to 200 nm. When the average diameter of the inorganic particles decreases to less than 1 nm, it is difficult to function as a shell in the composite particles, and the scattering properties are lowered, so that it is difficult to obtain a sufficient haze value, and the average diameter of the inorganic particles exceeds 500 nm. When it increases, the formation of the core-shell structured composite particles becomes difficult, and since the thickness of the final anti-glare film becomes thick, cracking or cracking characteristics may occur.

The inorganic particles are silica, silicon particles, aluminum hydroxide, magnesium hydroxide, titanium oxide, zirconium oxide, indium oxide, aluminum oxide, zinc oxide, cerium oxide, barium oxide, calcium carbonate, barium titanate, magnesium fluoride, calcium fluoride And it may include a single substance selected from the group consisting of barium sulfate or a complex of two or more.

Each of the organic particles and inorganic particles may be included in one or more. Each of the organic particles and the inorganic particles may have a hydrophilic functional group on the surface. The example of the hydrophilic functional group is not particularly limited, but may include, for example, at least one selected from the group consisting of an amino group, a carboxy group, a hydroxyl group, a ketone group, a sulfonic acid group and a phosphoric acid group.

Accordingly, each of the organic particles and the inorganic particles can be effectively dispersed without excessive agglomeration in the anti-glare resin composition containing a polar solvent, so that the organic particles and the inorganic particles are bonded through reaction between respective hydrophilic functional groups. To form a core-shell structure. That is, the organic particles and inorganic particles are composed of an ether group, an ester group, an amide group, a hemiacetal group, an acetal group, an imine group, an amine group, a sulfonic ester group, a sulfonic amide group, a phosphoric ester group and a phosphoric amide group It may bind via one or more functional groups selected from the group.

In addition, as the composite particles made of inorganic particles bound to the surface of the organic particles also have a hydrophilic functional group on the surface by the inorganic particles, they are effectively dispersed without excessive aggregation in the anti-glare resin composition containing a polar solvent, resulting in In the anti-glare film produced, it is possible to form a smooth and uneven surface having a small surface roughness.

On the other hand, when the inorganic particles have a hydrophobic functional group on the surface, as the inorganic particles are excessively aggregated in a polar solvent, the organic particles and the inorganic particles may be combined to make the core shell structure difficult, and the final glare is produced. Even in the prevention film, as the surface roughness of the surface is formed, black visibility may deteriorate.

The hydrophilic functional group on the surface of the inorganic particles may be 1/nm ² to 100/nm ² .

With respect to the total surface area of the organic particles, an area where the inorganic particles are bonded may be 70% or more.

On the other hand, the composite particles of the core-shell structure may have a particle diameter of 0.5 to 500㎛. When the diameter of the composite particles decreases to less than 0.5 µm, scattering properties of the composite particles are lowered to obtain a sufficient haze value, and when the diameter of the composite particles increases to 500 µm or more, per unit volume of the final anti-glare film Since the number of composite particles decreases, the internal scattering effect is reduced, and it may be difficult to obtain a sufficient haze value.

The thickness of the core portion included in the composite particles is 0.1 μm to 10 μm, and the thickness of the shell layer may be 1 nm to 1000 nm. When the thickness of the shell layer is reduced to less than 1 nm, the effect of improving physical properties such as fragile storage stability due to the thickness of the shell is insignificant, and when the thickness of the shell layer increases to more than 1000 nm, the core-shell structure is prepared. It is not easy, and since the overall particle diameter is increased, the internal scattering effect is lowered, it may be difficult to obtain a sufficient haze value.

The content of the inorganic particles may be in the range of 10 to 80 parts by weight with respect to 100 parts by weight of the organic particles. When the content of the inorganic particles is less than 10 parts by weight with respect to 100 parts by weight of the organic particles, the scratch resistance property of the anti-glare film finally produced by the organic particles projecting to the surface may decrease, and the content of the inorganic particles With respect to 100 parts by weight of the organic particles, if it is more than 80 parts by weight, the surface of the final anti-glare film produced may be rough and crack defects may occur.

The composite particles may be included in one or more in the anti-glare resin composition, and the composite particles may be dispersed alone or in an aggregate form of at least two or more composite particles.

The single form means a state in which one composite particle does not form an aggregate and exists alone, and the aggregate may mean a state in which at least two or more composite particles are aggregated through aggregation.

More specifically, in the at least two or more composite interparticle aggregates, at least two or more composite particles constituting the aggregate may satisfy the following Equation 1 as the minimum value of the distance between the particle centers.

[Equation 1]

R ≤ D ≤ 3R

In Equation 1, D denotes the minimum value between the particle centers of neighboring composite particles, and R denotes the average diameter of the composite particles.

That is, any one of the composite particles belonging to the agglomerate is in contact with the other adjacent adjacent composite particles (if D=R) or gathered at a distance within 2 times the average diameter of the composite particles (D ≤ 3R). Constant aggregates can be formed.

Therefore, when any of the composite particles contained in the anti-glare resin composition has a particle center distance with the other composite particles closest thereto is three times the average diameter of the composite particles (D> 3R), the composite particles alone It can be said to exist.

The aggregate includes a first aggregate comprising two or more and fewer than ten composite particles; And a second aggregate comprising 10 to 100 composite particles. That is, the first aggregate and the second aggregate may be distinguished according to the number of composite particles included in one aggregate.

At this time, the maximum diameter of the first aggregate may be 1 μm to 20 μm, and the maximum diameter of the second aggregate may be 2 μm to 100 μm.

More specifically, the ratio of the number of second aggregates to the number of first aggregates may be 0.01 to 2, or 0.1 to 1. The ratio of the number of second aggregates to the number of first aggregates means a value obtained by dividing the number of second aggregates by the number of first aggregates. When the ratio of the number of the second aggregates to the number of the first aggregates decreases to less than 0.01, the number of composite particles is 10 or more and the number of the second aggregates of 100 or less is excessively reduced, so that the black vision decreases and contrast decreases. Can be. In addition, when the ratio of the number of the second agglomerates to the number of the first agglomerates is increased to more than 2, the number of composite particles is 10 or more and the number of the 2nd agglomerates of 100 or less is excessively increased, so that the visibility of the surface appears rough and the screen is displayed. The image projected through may appear distorted.

In addition, the anti-glare resin composition may include a reactive monomer, an oligomer thereof or a (co)polymer thereof. The reactive monomer is not particularly limited in its kind, and any one known in the art may be used without particular limitation, for example, a (meth)acrylate-based monomer. The (meth)acrylate-based monomer may include at least one (meth)acrylate functional group capable of participating in the curing reaction.

Examples of the (meth)acrylate monomer include dipentaerythritol hexaacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated Glycerol triacrylate, trimethyllopropane ethoxy triacrylate, 1,6-hexanediol diacrylate, propoxylated glycero triacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate or mixtures thereof The like may be used, but is not necessarily limited to these examples.

As the acrylate oligomer, a urethane acrylate oligomer, an epoxy acrylate oligomer, a polyester acrylate, a polyether acrylate, or a mixture thereof may be used.

In addition, the anti-glare resin composition may include a polar solvent. Specifically, the polar solvent may be a single substance selected from the group consisting of alcohol, acetate, ketone, cellosolve, dimethylformamide, tetrahydrofuran and propylene glycol monomethyl ether, or a mixture thereof.

The alcohol is one selected from methanol, ethanol, isopropyl alcohol, butyl alcohol, isobutyl alcohol and diacetone alcohol, and the acetate is selected from methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate and cellosolve acetate. One material, and the ketone may be a material selected from methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, and acetone, but is not limited thereto.

More specifically, the polar solvent included in the anti-glare resin composition may be a mixture of alcohol and ketone. In this case, 50 to 90 parts by weight of ketone, or 60 to 80 parts by weight based on 100 parts by weight of the alcohol may be included. Accordingly, when the coating film is formed, the black visibility by the first aggregate and the second aggregate is excellent in the coating layer, and an anti-glare layer suitable for high resolution can be implemented.

The content of the reactive monomer, its oligomer or its (co)polymer relative to 100 parts by weight of the polar solvent may be 10 to 70 parts by weight, or 20 to 50 parts by weight. When the content of the reactive monomer, its oligomer or its (co)polymer is more than 70 parts by weight relative to 100 parts by weight of the polar solvent, the viscosity of the resin composition for preventing glare may be too large to reduce coating properties, and a polar solvent in the coating film. Lack of core-shell particles can make it difficult to form aggregates. When the content of the reactive monomer, its oligomer or its (co)polymer is less than 10 parts by weight with respect to 100 parts by weight of the polar solvent, the film strength of the anti-glare film decreases due to generation of residual solvent, and a coating film having a desired thickness is obtained. The coating may be too thick to form, making manufacturing difficult.

In addition, the anti-glare resin composition may further include at least one additive selected from the group consisting of UV curing initiators, leveling agents, wetting agents, antifoaming agents and dispersing agents.

The UV curing initiator, 1-hydroxy cyclohexylphenyl ketone, benzyl dimethyl ketal, hydroxydimethyl acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether It may be one single substance or a mixture of two or more selected, but is not limited thereto.

The leveling agent may make the surface of the coating film coated by using the anti-glare film composition uniform. As the wetting agent serves to lower the surface energy of the composition for anti-glare films, when the composition for anti-glare films is coated on a transparent substrate layer, uniform coating may be performed. The antifoaming agent may be added to remove air bubbles in the anti-glare film composition.

On the other hand, according to another embodiment of the invention, the binder resin; And a composite particle having a core shell structure of a shell layer including a core portion containing organic particles having a hydrophilic functional group on the surface and an inorganic particle having a hydrophilic functional group on the surface, dispersed in the binder resin, and the composite particle is alone or An anti-glare film in the form of aggregates of at least two or more composite particles may be provided.

The contents of the composite particle include the contents described above with respect to the embodiment.

Inside the anti-glare film, the composite particles may be dispersed alone or in at least two or more composite particle aggregates in a binder resin. Specifically, the composite particles 3 or aggregates are located inside the anti-glare film 2, as shown in FIG. 1 below, and can be dispersed to form a smooth shape of irregularities on the surface of the anti-glare film. have. The unevenness may scatter light incident from the outside at various angles, thereby providing an effect of reducing reflected light perceived by the user's perspective.

The single form means a state in which one composite particle does not form an aggregate and exists alone, and the aggregate may mean a state in which at least two or more composite particles are aggregated through aggregation.

More specifically, at least two or more composite particles constituting agglomerates in the aggregate between at least two or more composite particles may satisfy the following equation (1) as the minimum value of the distance between the particle centers.

[Equation 1]

R ≤ D ≤ 3R

In Equation 1, D denotes the minimum value between the particle centers of neighboring composite particles, and R denotes the average diameter of the composite particles.

That is, any one of the composite particles belonging to the agglomerate is in contact with the other adjacent adjacent composite particles (if D=R) or gathered at a distance within 2 times the average diameter of the composite particles (D ≤ 3R). Constant aggregates can be formed.

Therefore, when any of the composite particles included in the anti-glare film has a particle center distance with the other composite particles closest to it is three times the average diameter of the composite particles (D> 3R), the composite particles are present alone. It can be said.

The aggregate includes a first aggregate comprising two or more and fewer than ten composite particles; And a second aggregate comprising 10 to 100 composite particles. That is, the first aggregate and the second aggregate may be distinguished according to the number of composite particles included in one aggregate.

At this time, the maximum diameter of the first aggregate may be 1 μm to 20 μm, and the maximum diameter of the second aggregate may be 2 μm to 100 μm.

More specifically, the ratio of the number of second aggregates to the number of first aggregates may be 0.01 to 2. The ratio of the number of second aggregates to the number of first aggregates means a value obtained by dividing the number of second aggregates by the number of first aggregates. When the ratio of the number of the second aggregates to the number of the first aggregates decreases to less than 0.01, the number of composite particles is 10 or more and the number of the second aggregates of 100 or less is excessively reduced, so that the black vision decreases and contrast decreases. Can be. In addition, when the ratio of the number of the second agglomerates to the number of the first agglomerates is increased to more than 2, the number of composite particles is 10 or more and the number of the 2nd agglomerates of 100 or less is excessively increased, so that the visibility of the surface appears rough and the screen is displayed. The image projected through may appear distorted.

More specifically, the average surface roughness of the anti-glare film may be 0.4 μm or less. The average surface roughness may be obtained through Equation 2 below, and when the average surface roughness of the anti-glare film is excessively increased, image clarity may deteriorate and it may be difficult to realize high-resolution characteristics.

[Equation 2]

Average surface roughness =

In Equation 2, Ri is the height of each surface irregularity included in the anti-glare film, and n represents the number of surface irregularities.

The 60 ^o reflection gloss obtained by ASTM D523 of the anti-glare film may also be 80% or more, or 80 to 95%. In addition, it can be more specifically, 20 ^o reflection glossiness of the antiglare film is 40 to 75%, or 45 to 70%. The glossiness is a property of a material surface that reflects light, and means that the amount of light reflected from the incident light is compared with the gloss value of a black glass having a constant refractive index. Depending on the angle of incidence of the incident light beam, 20 ^o reflection glossiness and 60 ^o reflection glossiness may be respectively defined.

As an example of the method of measuring the glossiness, a method of measuring according to ASTM D523 standard by setting a measurement angle using a micro-TRI-gloss manufactured by BYK Gardner have.

As the 60 ^o reflection gloss obtained by ASTM D523 of the anti-glare film satisfies 80% or more, the anti-glare film may be excellent in blackness and may be applicable to high-resolution and high-contrast display devices.

In addition, a ratio of 60 ^o reflective gloss to 20 ^o reflective gloss of the anti-glare film may be 1.2 to 2. 20 ^o of the antiglare film 20 ^o reflection glossiness means 60 ^o reflection ratio is, 60 ^o reflection glossiness of 20 ^o reflection divided by gloss of the anti-glare film having a gloss on, and prevents the glare film of the As the ratio of the reflection gloss to 60 ^{o the} reflection glossiness satisfies 1.2 to 2, the anti-glare film may have excellent blackness and may be applicable to a display device having a high resolution and high contrast ratio.

The absolute value of the difference in average refractive index between the composite particles and the binder resin may be 0.1 or less, or 0.05 or less. When the absolute value of the difference in refractive index increases to more than 0.1, the internal scattering increases to increase the haze value, while the transmittance decreases and the contrast ratio may decrease. More specifically, the binder resin may have a refractive index of about 1.5 to 1.53.

As the binder resin, an acrylic binder resin may be used. The type of the acrylic binder resin is not particularly limited, and may be selected and used without particular limitation as long as it is known in the art. Examples of the acrylic binder resin may be acrylate monomers, acrylate oligomers, or mixtures thereof. In this case, it is preferable that the acrylate monomer or acrylate oligomer contains at least one acrylate functional group capable of participating in a curing reaction.

The acrylate monomers and acrylate oligomers are not particularly limited in their types, and can be selected and used without limitation in the art.

As the acrylate oligomer, a urethane acrylate oligomer, an epoxy acrylate oligomer, a polyester acrylate, a polyether acrylate, or a mixture thereof may be used. As the acrylate monomer, dipentaerythritol hexaacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate , Trimethyllopropane ethoxy triacrylate, 1,6-hexanediol diacrylate, propoxylated glycero triacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate, or mixtures thereof are preferred. It can be used, but is not necessarily limited to these examples.

The total content of the organic particles and inorganic particles may be included within a range of 1 to 30 parts by weight with respect to 100 parts by weight of the binder resin. That is, the total amount of particles composed of the organic particles and the inorganic particles may be summed to include 1 to 30 parts by weight based on 100 parts by weight of the binder resin. When the total content of the organic particles and the inorganic particles is less than 1 part by weight with respect to 100 parts by weight of the binder resin, haze value due to internal scattering may be difficult to implement, and when it is more than 30 parts by weight, coating properties become poor. Since the haze value due to internal scattering is turned on too much, the contrast ratio may be lowered.

The anti-glare film may have a thickness of 0.1 μm to 100 μm, or 1 μm to 10 μm. The thinner the anti-glare film, the lower the probability of cracking. However, in order to sufficiently realize the purpose as a coating layer for preventing glare, the thickness range may be appropriately adjusted by a person skilled in the art within the above range in consideration of this purpose.

At least one surface of the anti-glare film may further include a base layer. The configuration of the base layer is not particularly limited, and may be used commonly used in the art. For example, it may be formed of a material selected from triacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), and norbornene-based polymer. However, the present invention is not limited thereto, and other materials generally used in the art to which the present invention pertains may be used.

The anti-glare film may further include a separate layer in addition to the base layer. For example, an anti-pollution layer, a low-reflection layer, etc. for preventing contamination of the display surface may be further included, and layers for various other purposes may be further provided without limitation.

For example, the thickness of the low reflection layer may be 40 to 200 nm, and the refractive index of the low reflection layer may be 1.2 to 1.45. The low-refractive material for forming the low-reflection layer is a metal fluoride such as NaF, LiF, AlF ₃ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , MgF ₂ , YF ₃ having a refractive index of 1.40 or less, alone or 2 It may be used by mixing more than one species, and the size may be 1 to 100 nm.

In addition, the fluorine-based silane used in the low-reflection layer is tridecafluorooctyl triethoxysilane, heptadecafluorodecyl trimethoxysilane, heptadecafluorodecyl triisopropoxysilane, alone or by mixing two or more kinds Can be used. The material for forming the low reflection layer is not limited to the above.

The thickness of the anti-pollution layer may be 0.1 nm to 100 nm, and the anti-pollution layer may be formed using monofunctional and polyfunctional acrylates containing fluorine groups, but is not limited thereto.

The anti-glare film is interposed on the front of the high-resolution flat panel display and can be used for anti-glare applications, and is not limited to the type of display and can be applied to all. The structure of the display is not particularly limited, and may have a structure known in the art, for example, the anti-glare coating film may be disposed on the outermost side of the display in contact with the viewer.

An example of a method for manufacturing the anti-glare film is not particularly limited, but may include, for example, coating and curing the anti-glare composition of the embodiment on a substrate.

The coating method of the anti-glare composition may be a wet coating method, for example, a roll coating method, a bar coating method, a spray coating method, a dip coating method, and a spin coating method. The coating method is not limited to this, and various other coating methods used in the art may be used.

The curing step may be divided into a drying step and a curing step, or may be performed in one step. Curing conditions vary slightly depending on the blending ratio or components, but in general, in the case of electron beam or ultraviolet curing, the irradiation amount can be cured at 200 to 1,000 mJ/cm 2 for 1 second to 10 minutes.

In the case of electron beam or ultraviolet curing, when the curing time is less than 1 second, the binder resin may not be sufficiently cured and mechanical properties such as abrasion resistance may be poor, and when the curing time exceeds 10 minutes, yellowing occurs in the transparent base layer Can be.

According to the present invention, a high resolution can be realized through high image clarity, and surface irregularities are formed to exhibit anti-glare characteristics, and the degree of surface irregularities is easily adjusted to be applied to a display of high contrast ratio through excellent visibility. And, even in the coating thickness of the thin film, a resin composition for preventing glare having high mechanical properties and an anti-glare film using the same may be provided.

1 schematically shows a cross-section of an anti-glare film obtained in Examples.
Figure 2 shows an image of a cross-section of the composite particles obtained in the Examples.
Figure 3 shows the surface image of the anti-glare film obtained in Examples 1 and 2 and Comparative Example 2.

The invention is described in more detail in the following examples. However, the following examples are only illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

<Examples 1 to 3: Preparation of anti-glare film>

Example 1

30 g urethane acrylate oligomer; 70 g of pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha) as a polyfunctional acrylate monomer; 5 g of polyacrylate-co-styrene particles (TECHPOLYMER, manufactured by Sekisui) having an average diameter of 2 µm as an organic particle, a refractive index of 1.555, and having a hydroxyl group (-OH) on the surface; 2 g of silica sol having an average diameter of 12 nm as an inorganic particle and having a hydroxyl group (-OH) on the surface; 100 g of methyl ethyl ketone and 150 g of isopropyl alcohol as an organic solvent; As a UV curing initiator, 1-hydroxy-cyclohexylphenylketone (IRG-184, manufactured by BASF) was uniformly mixed to prepare a resin composition for producing an anti-glare film having fine particles having a core-shell structure as shown in FIG. It was prepared.

A composition for preparing a liquid anti-glare film prepared by the above method using a roll coating on a transparent base layer made of triacetyl cellulose (80 µm thick) was applied to a dry thickness of 4 µm, and then UV of 280 mJ/cm 2 was irradiated. And cured to obtain a film.

Example 2

In Example 1, except for changing the refractive index of the organic particles to 1.515 and the content of inorganic particles to 1 g, after preparing the resin composition for producing an anti-glare film as described in Example 1, it Cured in the same manner as in Example 1 to prepare an anti-glare film.

Example 3

In Example 1, except that a silica sol having an average diameter of 100 nm was used as the inorganic particles, and after preparing a resin composition for producing an anti-glare film as described in Example 1, it was the Example 1 It was cured in the same way as to prepare an anti-glare film.

<Comparative Examples 1 to 2: Preparation of anti-glare film>

Comparative Example 1

In Example 1, instead of the urethane acrylate oligomer, dipentaerythritol hexaacrylate (DPE-6A, manufactured by Kyoeisha) was used, and the inorganic particles were replaced with silica sol having an alkyl group on the surface. The anti-glare film was prepared in the same manner as described in Example 1.

Comparative Example 2

An anti-glare film was prepared in the same manner as described in Example 1, except that particles having an alkyl group on the surface were used as the organic particles in Example 1, and inorganic particles were not used.

<Experimental Example: Measurement of physical properties of anti-glare film obtained in Examples and Comparative Examples>

The properties of the anti-glare films prepared according to Examples 1 to 3 and Comparative Examples 1 to 2 were measured under the following conditions, and the respective results are shown in FIGS. 3 and 1 below.

1. Structural characteristics

(1) Particle

The structures of the particles included in the resin composition for anti-glare films prepared according to Examples 1 to 3 and Comparative Examples 1 to 2 were confirmed.

In the case of Example 1, it was confirmed that the particles contained in the resin composition for producing an anti-glare film have a core-shell structure in which the organic particles are the core and the inorganic particles are the shell layer, as shown in FIG. 2 below.

On the other hand, in the case of Comparative Example 1, as the surface of the inorganic particles was substituted with a hydrophobic group such as an alkyl group, it was confirmed that the formation of organic-inorganic core-shell particles in the resin composition for anti-glare film production.

(2) Anti-glare film

For the anti-glare films prepared according to Examples 1 to 3 and Comparative Examples 1 to 2, the surface structure was confirmed through an optical microscope (SEM), and the results are shown in FIG. 3.

As shown in FIG. 3, the anti-glare films of Examples 1 and 2 formed agglomerates through agglomeration of a plurality of particles, and formed surface irregularities, whereas the anti-glare films of Comparative Examples 1 to 2 each independently of the particles. It can be seen that the surface unevenness.

Accordingly, in the anti-glare film of the embodiment, it was confirmed that the core-shell particles contained in the anti-glare resin composition aggregated with each other to form aggregates and are dispersed, and the number of core-shell particles contained in each aggregate varies. Can be.

More specifically, according to the number of core-shell particles contained in the aggregate, the first aggregate (agglomerates consisting of 2 or more and less than 10 core-shell particles), the second aggregate (10 or more and 100 or less core-shell particles) Aggregate consisting of), and the results of measuring the number of aggregates within the range of 250 μm * 250 μm are summarized in Table 1 below.

Experimental Example 1 Results of Examples and Comparative Examples division 1st aggregate (number) 2nd aggregate (number) 2nd aggregate/first aggregate Example 1 36 20 0.55 Example 2 73 23 0.32 Comparative Example 1 120 0 0 Comparative Example 2 130 0 0

2. Transmittance (%)

The transmittance was measured according to JIS-K 7361 standard using HR-150 of Murakami Color Research Laboratory.

3. Haze value (%)

The haze value was measured according to JIS-K 7361 standard using HR-150 of Murakami Color Research Laboratory.

4. Reflection Gloss (%)

(1) 60 ^o reflective gloss

By using a micro-TRI-gloss manufactured by BYK Gardner, the measurement angle was set to 60°, and the 60 ^° reflective gloss was measured according to the ASTM D523 standard.

(2) 20 ^o reflective gloss

By using a micro-TRI-gloss manufactured by BYK Gardner, the measurement angle was set to 20°, and the 20 ^° reflective gloss was measured according to the ASTM D523 standard.

5. Merchant clarity (%)

The image clarity was measured using ICM-1T manufactured by Suga Test Instrument Co., Ltd.

6. Pencil hardness

According to ASTM D3363, hardness was measured by testing three times for each pencil hardness at 500 gf load.

7. Scratch resistance

Steel wool (#0000) It was observed after rubbing 10 times with the anti-glare film at 500 gf load.

◎: Number of scratches: 0

○: Number of scratches: 5 or less fine scratches of 1 cm or less

△: Number of scratches: 5 or more thin scratches of 1 cm or less, or 1 or more and 3 long scratches of 1 cm or more

×: number of scratches: more than 3 long scratches of 1 cm or more

8. Crack resistance

The length of the crack was observed through a mandrel test (1.0 mm).

9. Visual

The opposite side of the anti-glare treatment film is blacked, and the reflection from each anti-glare film observes the field of view from the specular reflection direction using the fluorescent lamp illumination having two rows of lamps as a light source to distinguish the image of the reflected image of the fluorescent lamp. Visibility was measured by the method.

◎: The boundary on the lamp reflected on the substrate is ambiguous, and the degree of visibility of the non-reflected part is black.

○: The boundary on the lamp reflected on the substrate is ambiguous, and the degree of visibility of the non-reflected portion is black.

△: The boundary on the lamp reflected on the substrate is not ambiguous, or the visibility of the non-reflected part is blurry.

×: The image of the lamp reflected on the substrate is still visible, or the visibility of the non-reflected part is very cloudy.

Experimental Examples 2 to 10 Results of Examples and Comparative Examples division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Transmittance (%) 93.6 94 93.6 93.5 93.5 Haze (%) 3 0.5 3 3 3 60 ^o Glossiness (%) 86 86 84 75 90 20 ^o Glossiness (%) 57 63 53 32 78 60 ^o gloss/20 ^o gloss 1.51 1.37 1.58 2.34 1.15 Merchant Clarity (%) 300 300 300 250 250 Scratch resistance
(500gf load) ◎ ◎ ◎ ◎ ◎ Pencil hardness
(500gf load) 3H 3H 3H 3H 3H Crack resistance 6Φ 6Φ 6Φ 6Φ 6Φ Sight ◎ ◎ ◎ × ×

As shown in Table 2, in the case where the surfaces of the organic particles and the inorganic particles are both substituted with hydroxyl groups, mechanical properties such as scratch resistance, pencil hardness, and crack resistance appear at the same level as those of the comparative example, and are dazzling. It can be seen that the prevention properties, the image clarity, and the visibility are improved.

On the other hand, in Comparative Example 1 in which the surface properties (hydrophilicity) of the organic particles and the surface properties (hydrophobicity) of the inorganic particles are different, and in Comparative Example 2 in which only the organic particles are used and no inorganic particles are used, the image clarity and visibility are high and the resolution is high. And it was confirmed that there is a difficulty in implementing the high contrast ratio.

1: description
2: Anti-glare film
3: Composite particles
4: Organic particles
5: inorganic particles

Claims (24)

The core portion and the surface including the organic particles having a hydrophilic functional group on the surface of the composite particles having a core-shell structure of the shell layer including an inorganic particle having a hydrophilic functional group in the 1 / ㎚ ² to 100 / ㎚ ^2;
Reactive monomers, oligomers thereof or (co)polymers thereof; And
A polar solvent,
The polar solvent includes at least one selected from the group consisting of alcohol, acetate, ketone, cellosolve, dimethylformamide, tetrahydrofuran and propylene glycol monomethyl ether,
The hydrophilic functional groups included in the organic particles and inorganic particles include at least one selected from the group consisting of amino groups, carboxy groups, hydroxyl groups, ketone groups, sulfonic acid groups and phosphoric acid groups,
The composite particles are dispersed in an aggregate form of at least two or more composite particles, the anti-glare resin composition.
According to claim 1,
In the aggregate of the at least two or more composite particles,
At least two or more composite particles constituting agglomerates, the minimum value of the distance between the particle centers satisfies the following equation (1), anti-glare resin composition:
[Equation 1]
R ≤ D ≤ 3R
In Equation 1,
D means the minimum distance between the particle centers of neighboring composite particles,
R means the average diameter of the composite particles.
According to claim 1,
The aggregate includes a first aggregate comprising two or more and fewer than ten composite particles; And a second aggregate comprising 10 to 100 composite particles.
According to claim 3,
The ratio of the number of the second aggregates to the number of the first aggregates is 0.01 to 2, the anti-glare resin composition.
According to claim 3,
A resin composition for preventing glare, wherein the first aggregate has a maximum diameter of 1 μm to 20 μm.
According to claim 3,
The maximum diameter of the second aggregate is 2 ㎛ to 100 ㎛, anti-glare resin composition.
delete According to claim 1,
The polar solvent is alcohol and ketone, a resin composition for preventing glare.
The method of claim 8,
A resin composition for preventing glare, comprising 50 to 90 parts by weight of ketone with respect to 100 parts by weight of the alcohol.
According to claim 1,
The resin composition for preventing glare, wherein the content of the reactive monomer, its oligomer or its (co)polymer is 10 to 70 parts by weight with respect to 100 parts by weight of the polar solvent.
According to claim 1,
Regarding the total surface area of the organic particles, the area where the inorganic particles are bonded is 70% or more, and the anti-glare resin composition.
According to claim 1,
The resin composition for preventing glare, wherein the inorganic particles have an average diameter of 1 nm to 500 nm.
delete According to claim 1,
In the composite particles, the thickness of the core portion is 0.1 μm to 10 μm, and the thickness of the shell layer is 1 nm to 1000 nm, the anti-glare resin composition.
According to claim 1,
The organic particles are polystyrene, polyacrylate-co-styrene, polymethylacrylate-co-styrene, polymethylmethacrylate-co-styrene, polycarbonate, polyvinyl chloride, polybutylene terephthalate, polyethylene terephthalate, Polyamide, polyimide, polysulfone, polyphenylene oxide, polyacetal, epoxy resin, phenol resin, melamine resin, benzoguanamine, polydivinylbenzene, polydivinylbenzene-co-styrene, polydivinylbenzene -Co-acrylate, polydiallyl phthalate and triallyl isocyanurate polymer comprising one single substance or two or more copolymers (copolymer) selected from the group consisting of, anti-glare resin composition.
According to claim 1,
The inorganic particles are silica, silicon particles, aluminum hydroxide, magnesium hydroxide, titanium oxide, zirconium oxide, indium oxide, aluminum oxide, zinc oxide, cerium oxide, barium oxide, calcium carbonate, barium titanate, magnesium fluoride, calcium fluoride And a single substance or two or more complexes selected from the group consisting of barium sulfate, the anti-glare resin composition.
According to claim 1,
The anti-glare resin composition further comprises at least one additive selected from the group consisting of UV curing initiators, leveling agents, wetting agents, anti-foaming agents and dispersants, anti-glare resin composition.
Binder resin; And is dispersed in the binder resin, having a core-shell structure of the shell layer including an inorganic particle having a hydrophilic functional group in the 1 / ㎚ ² to 100 / ㎚ ² to the core portion and the surface including the organic particles having a hydrophilic functional group on the surface Containing composite particles;
The composite particles are in the form of aggregates between single or at least two composite particles,
The hydrophilic functional groups included in the organic particles and inorganic particles include at least one selected from the group consisting of amino groups, carboxy groups, hydroxyl groups, ketone groups, sulfonic acid groups and phosphoric acid groups,
Anti-glare film, wherein the ratio of 60 ^o reflective gloss to 20 ^o reflective gloss obtained by ASTM D523 is 1.2 to 2.
The method of claim 18,
In the aggregate of the at least two or more composite particles,
At least two or more composite particles constituting agglomerates, the minimum value of the distance between the particle centers satisfies the following Equation 1:
[Equation 1]
R ≤ D ≤ 3R
In Equation 1,
D means the minimum distance between the particle centers of neighboring composite particles,
R means the average diameter of the composite particles.
The method of claim 18,
The aggregate includes a first aggregate comprising two or more and fewer than ten composite particles; And a second aggregate comprising 10 to 100 composite particles.
The method of claim 20,
The anti-glare film, wherein the ratio of the number of second aggregates to the number of first aggregates is 0.01 to 2.
The method of claim 20,
The anti-glare film, wherein the first aggregate has a maximum diameter of 1 μm to 20 μm.
The method of claim 20,
The anti-glare film, wherein the second aggregate has a maximum diameter of 2 μm to 100 μm.
delete

Images