KR102258294B1 - barrier film - Google Patents

Abstract

This application relates to a barrier film. The barrier film of the present application includes a base layer; An undercoat layer formed on the base layer and having a static friction coefficient of 0.5 or less with respect to the stainless steel substrate under a vertical load of 200 g; And a barrier layer formed on the undercoat layer, wherein the moisture permeability is 1x10 ^-2 g/m ² /day or less.

Description

Barrier film {barrier film}

This application relates to a barrier film and a use thereof.

A barrier film formed by forming a thin film of metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide on the surface of a plastic substrate or film is used for packaging of items requiring blocking of water vapor or oxygen, food, industrial supplies, and pharmaceuticals, etc. It has been widely used for packaging purposes to prevent deterioration. In addition to packaging, it is used to secure gas barrier properties for liquid crystal displays, solar cells, and electroluminescent (EL) substrates.

Such a barrier film may be formed by, for example, a roll-to-roll process. In the manufacture of a barrier film according to such a roll-to-roll process, There may be problems such as occurrence of scratches due to friction between the barrier layer exhibiting gas barrier properties and the guide roll and deterioration of gas barrier properties accordingly.

(Patent Literature)

(Patent Document 0001) Patent Document 1: Republic of Korea Patent Publication No. 2013-0134477

(Patent Document 0002) Patent Document 2: Japanese Laid-Open Patent Publication No. 2006-88538

An object of the present application is to provide a high-quality barrier film by preventing problems such as scratches that may occur during the manufacturing process of the barrier film.

All of the above and other objects of the present application can be achieved by the present application described in detail below.

In one example related to the present application, the present application relates to a barrier film.

The barrier film according to the present invention is to prevent the occurrence of scratches and friction between the barrier layer and the guide roll that may occur during the manufacturing process of the barrier film, for example, a roll-toroll process, The barrier film includes an undercoat layer having a predetermined coefficient of static friction on the base layer, and through this, the above-described problem can be overcome.

In addition, the undercoat layer of the present application includes two regions having different surface roughness values and has a predetermined aspect ratio of surface irregularities, thereby maintaining high productivity while maintaining the inherent gas barrier properties of the barrier film.

The barrier film of the present application includes: a base layer; An undercoat layer formed on the base layer; And a barrier layer formed on the undercoat layer. The undercoat layer has a static friction coefficient of 0.5 or less with respect to the stainless steel substrate under a vertical load of 200 g.

Specifically, as shown in FIG. 1, the barrier film 1000 includes a base layer 100; An undercoat layer 200 sequentially formed on the base layer 100; And a barrier layer 300.

As described above, the barrier film of the present application includes an undercoat layer having a static friction coefficient of 0.5 or less with respect to a stainless steel substrate under a vertical load of 200 g, thereby preventing damage to the barrier layer during the manufacturing process of the barrier film.

The barrier layer, which is an essential component of the barrier film for barrier properties such as water vapor or oxygen, is advantageously formed on a flat undercoat layer having a low surface roughness to secure barrier properties. For example, a barrier layer is deposited on the undercoat layer. In this process, if the surface of the undercoat layer is not flat, the possibility of occurrence of defects on the deposition surface increases.

On the other hand, when manufacturing the barrier film, the guide roll used in the roll-to-roll process is made of, for example, a stainless steel plate, which forms a smooth surface. When a guide roll having a smooth surface and an undercoat layer having a low surface roughness come into contact with each other, blocking is well performed and the coefficient of friction increases, which acts as a cause of the occurrence of scratches.

Accordingly, an object of the present invention is to prevent the occurrence of defects in the barrier layer deposited on the undercoat layer, and to keep the coefficient of friction at the contact surface with the guide roll used in the roll-to-roll process low. To this end, the barrier film according to the present application basically has a very flat surface and includes an undercoat layer partially formed with large and smooth irregularities by adding a particulate component. It is preferable that the particle diameter of the particulate component is larger than the thickness of the undercoat layer.

The barrier film of the present application may overcome the above-described problem by forming an undercoat layer having a static friction coefficient of 0.5 or less on a base layer and forming a barrier layer on the undercoat layer. For example, in the present application, a particulate component having a relatively large particle diameter is dispersed in an undercoat layer having a very high flatness, thereby forming a large and smooth shape of irregularities. Through this, defects that may occur during the deposition of the barrier layer are minimized, and blocking with the guide roll is prevented by securing a low coefficient of friction, thereby preventing scratches occurring during the process. That is, the present application provides a barrier film in which the ^{water permeability is controlled to 1x10 -2} g/m ² /day or less while preventing surface scratches generated during the process.

For example, FIG. 2 schematically shows a cross-sectional structure of a barrier film according to an embodiment of the present application.

2, a structure in which an undercoat layer 201 is formed on the base layer 101, and a spherical particulate component 211 is dispersed in the undercoat layer 201, and the spherical particulate component 211 is Accordingly, the undercoat layer 201 forms an uneven structure. A structure in which the barrier layer 301 is deposited again is formed on the undercoat layer 201 having the uneven structure formed thereon. In the present application, it is preferable that the diameter of the particulate component 211 is greater than the thickness of the undercoat layer 201. In addition, by controlling the content of the particulate component 211 to a relatively low level, the undercoat layer 201 has a first region in which irregularities are formed by the particulate component 211 and a flat surface in which the particulate component 211 does not exist. The formed second regions coexist.

The barrier film of the present application includes an undercoat layer having a static friction coefficient of 0.5 or less. The coefficient of static friction of the undercoat layer is, for example, a shear force at the time when the undercoat layer moves by applying a shear force to the undercoat layer in a state where the undercoat layer is laminated to a stainless steel substrate and then a vertical load of 200g is applied. Can be calculated from the measurement of. Another example of the static friction coefficient may be 0.45 or less, 0.4 or less, or 0.35 or less. The lower limit of the static friction coefficient is not particularly limited, and may be, for example, 0.01 or more, 0.05 or more, 0.1 or more, or 0.2 or more.

The undercoat layer of the present application satisfies the aforementioned static friction coefficient and may include two regions having different surface roughness values at the same time. In one example, the undercoat layer of the present application may include a first region and a second region having different centerline surface roughness (Ra) or roughness maximum (Rpv) values.

The first region and the second region are for separating two regions formed on the undercoat layer having different surface roughnesses. For example, the undercoat layer contains a particulate component therein, the first region is a region in which unevenness is formed by particulate components contained in the undercoat layer, and the second region is an unevenness due to particulate components contained in the undercoat layer. It is an unformed area.

In the present application, the area range occupied by the first area per total unit area obtained by adding the first area and the second area may be 5% or less. This means that, based on the total area of the barrier film, the first region in which the irregularities are formed is formed in a very small area fraction. For example, the area range occupied by the first area per total unit area of the sum of the first area and the second area may be 0.05% or more, 0.1% or more, 0.5% or more, or 1% or more, and 5% or less, 4% or more. It may be less than or equal to 3.5%.

The barrier film according to the present invention may have an average centerline roughness (Ra) of 310 µm x 232 µm including the first region in a range of 4 nm to 50 nm on average.

The centerline average roughness (Ra) of an area of 310 µm x 232 µm including the first area means the average roughness of the center line (Ra) measured in an area of 310 µm x 232 µm including one or more irregularities formed by particulate components. do.

The centerline average roughness (Ra) of an area of 310 µm x 232 µm including the first region may be 5 nm or more, 6 nm or more, or 8 nm or more, 45 nm or less, or 40 nm or less in the above range. Within this range, the desired coefficient of static friction can be achieved.

In addition, the barrier film according to the present invention may have a maximum roughness value (Rpv) of 310 µm x 232 µm including the first region in a range of 50 nm to 1000 nm. The highest and lowest roughness value (Rpv) refers to the difference between the highest value and the lowest value of the measured surface roughness in the measurement area.

The highest roughness value (Rpv) of an area of 310 µm x 232 µm including the first region refers to the highest roughness value (Rpv) measured in an area of 310 µm x 232 µm including one or more irregularities formed by particulate components. do.

In another example, the maximum roughness (Rpv) of an area of 310 µm x 232 µm including the first region may be 100 nm or more, 150 nm or more, or 200 nm or more, and 950 nm or less, 900 nm or more in the above range. It may be less than or equal to 800 nm. By controlling the maximum roughness (Rpv) of an area of 310 µm x 232 µm including the first region within the above range, damage to the barrier layer during the barrier film manufacturing process can be minimized, and productivity can be increased.

In one example, the first region in the undercoat layer may have, for example, a predetermined aspect ratio of surface irregularities. The term "aspect ratio of surface irregularities" refers to a ratio (width/height) of the width to the height of the surface irregularities in the measurement area of the first region.

In one example, the aspect ratio of the surface irregularities measured in the first area may be in the range of 100 to 4,000. By including the first region having such an aspect ratio in the undercoat layer, a desired static friction coefficient value of the undercoat layer may be achieved, and ultimately, damage to the barrier layer may be prevented. In another example, the aspect ratio may be 300 or more, 400 or more, or 500 or more, 3,500 or less, or 3,000 or less in the above range.

The undercoat layer may include a second region present inside the first region or a region other than the first region. In addition, the second region is a region having a different surface roughness value from the first region, and may mean, for example, a flat surface compared to the first region.

In one example, a centerline average roughness (Ra) of 5 μm x 5 μm in the second area may be in a range of 0.2 nm to 0.5 nm. Centerline average roughness (Ra) of the area of 5㎛ x 5㎛ in the second area is the average roughness of the centerline measured in the area of 5㎛ x 5㎛ in the area not including the first area, that is, the unevenness of the undercoat layer is not formed Means (Ra).

In another example, the centerline average roughness (Ra) of an area of 5 μm x 5 μm in the second region may be 0.25 nm or more, or 0.3 nm or more, and 0.45 nm or less, or 0.4 nm or less in the above range. Within this range, the desired coefficient of static friction can be achieved.

In one example, a roughness maximum (Rpv) of an area of 5 µm x 5 µm in the second region may be in a range of 2 nm to 6 nm. The maximum roughness value (Rpv) of the area of 5µm x 5µm in the second area is the highest roughness measured in the area of 5µm x 5µm in the area that does not include the first area, that is, where the unevenness of the undercoat layer is not formed. It means low value (Rpv).

By including the second region having the lowest roughness value (Rpv) within the above range in the undercoat layer, damage to the barrier layer during the manufacturing process of the barrier film can be minimized, and productivity can be increased. In another example, the lowest roughness value (Rpv) in the second region may be 2.2 nm or more, or 2.5 nm or more, and may be 5.5 nm or less, or 5.0 nm or less in the above range.

In one example, the undercoat layer according to the present invention may have an average thickness in the range of 200 nm to 1500 nm, and the average particle diameter of the particulate component may be in the range of 250 nm to 2500 nm. In addition, the average particle diameter of the particulate component may be in the range of 1.2 to 2 times the average thickness of the undercoat layer. By controlling the average thickness of the undercoat layer and the particle diameter of the particulate component within the above range, it is possible to secure a desired coefficient of static friction and obtain a scratch prevention effect without deteriorating the physical properties of the barrier film.

In one example, the undercoat layer includes a resin and a particulate component dispersed in the resin.

In one example, the resin included in the undercoat layer may be an acrylic resin, and the acrylic resin may include a polymerization unit of a (meth)acrylate monomer and/or a (meth)acrylate oligomer.

In the present application, the (meth)acrylate monomer may be, for example, a polyfunctional (meth)acrylate compound. The term "polyfunctional (meth)acrylate compound" may mean a (meth)acrylate compound having two or more polymerizable functional groups.

In a specific example, the polyfunctional (meth)acrylate is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol (meth) acrylate, hexanediol di (meth) acrylate, nonandi Oldy(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tri Propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, acrylate neopentyl glycol di(meth)acrylate, epoxidized neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth) Acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate or hydroxypival acid neo It may be a bifunctional acrylate compound such as pentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri( Meth)acrylate, tris2-hydroxyethyl isocyanurate tri(meth)acrylate or glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate Or a trifunctional acrylate compound such as ditrimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth) Acrylate, dipentaerythritol penta (meth) acrylate, di-methylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate or ditrimethylolpropane hexa (meth) acrylate, etc. It may also be a trifunctional or higher polyfunctional acrylate compound.

The (meth)acrylate oligomer is, for example, epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, polybutadiene (meth)acrylate, silicone (meth)acrylate, or Alkyl (meth) acrylate may be exemplified, but is not limited thereto.

In one example, the particulate component may be inorganic particles, organic particles, or organic-inorganic particles. The particulate component may be dispersed in a resin forming an undercoat layer.

The inorganic particles may be, for example, one or more selected from the group consisting of silica particles, titanium particles, aluminum particles, antimony oxide particles, zinc oxide particles, and zirconia particles, but are not limited thereto. Further, although the refractive index of the inorganic particles is not particularly limited, inorganic particles having a predetermined refractive index value may be adopted within a range that does not impair the optical properties of the barrier film.

The organic particles included in the undercoat layer may be polymethacrylate particles or polystyrene particles, but are not limited thereto, and various organic particles known in the art may be used.

In addition, the organic-inorganic particles that may be included in the undercoat layer may include, for example, inorganic particles surface-modified with organic silane, etc., but are not limited thereto.

In one example, the undercoat layer may include a particulate component in the range of 0.005 to 2 parts by weight based on 100 parts by weight of the acrylic resin. In another example, within the above range, the particulate component may be 0.01 or more, 0.02 or more, or 0.03 or more, and 1.7 or less, 1.4 or less, or 1.2 or less. When an excessive amount of particulate components is added, the area fraction occupied by the first region increases, which causes defects in the barrier layer. Conversely, if an excessively small amount of particulate component is added, the coefficient of friction with the guide roll increases, causing surface scratches.

In one example, the particulate component may satisfy Equation 1 below.

[Equation 1]

|A-B|≤≤0.1

In Equation 1, A is a refractive index of the undercoat layer with respect to light having a wavelength of 633 nm, and B is a refractive index of the particulate component with respect to light having a wavelength of 633 nm.

That is, the particulate component may have a refractive index and a difference of 0.1 between the undercoat layer. Within this refractive index range, properties required for the barrier film, such as transparency, can be achieved.

In one example, the undercoat layer may include nanoparticles having an average particle diameter of 20 nm to 150 nm. The nanoparticles may be included in the range of 10 parts by weight to 60 parts by weight based on 100 parts by weight of the acrylic resin.

The kind of the nanoparticles may be included without limitation as long as they do not damage the physical properties of the undercoat layer, for example, silica, alumina, zirconia, indium tin oxide (ITO), antimony tin oxide. , ATO) or a mixture thereof. When the undercoat layer includes the nanoparticles, the refractive index can be adjusted, the coating properties can be improved to improve hardness, and scratch resistance can be improved. In addition, it is possible to improve the adhesion between each layer.

In one example, the undercoat layer may include a polymerization initiator. The polymerization initiator is an initiator for polymerizing a monomer or oligomer for forming an acrylic resin, and may be, for example, a photo initiator.

The kind of the photoinitiator is not particularly limited as long as it can generate a radical by irradiation with ultraviolet rays or the like and initiate a curing reaction.

Specific photoinitiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylanino acetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1one, 1-hydroxycyclohexylphenylketone, 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzo Phenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2 -Methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino Benzoic acid ester, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. In addition, one or two or more photoinitiators may be appropriately selected and included in a predetermined ratio.

The undercoat layer may contain a solvent as necessary. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, cyclohexane or cyclohexyl benzene; hydrocarbons such as n-hexane; Ethers such as dibutyl ether, dimethoxy methane, dimethoxy ethane, diethoxy ethane, propylene oxide, dioxane, dioxolane, trioxane or tetrahydrofuran; Ketones such as methyl isobutyl ketone, methyl butyl ketone, acetone, methyl ethyl ketone, diethyl ketone, zipurophil ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone or methyl cyclohexanone; Esters such as ethyl formate, propyl formate, n-pentyl methyl formate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate or γ-phthyrolactone; Cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, or cellosolve acetate; Alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, or ethylene glycol; Alternatively, it may be appropriately selected from water, etc. in consideration of the method of the coating process.

The undercoat layer has various known additives, such as a silane coupling agent, an antistatic agent, a near-infrared absorber, a curing agent, an ultraviolet stabilizer, an antioxidant, a toning agent, a reinforcing agent, a filler, an antifoaming agent, It may further include a surfactant or a plasticizer.

The undercoat layer may be formed by coating the above-described components on a base layer, followed by heat or light curing. The method of coating the undercoat layer is not particularly limited, and known coating methods, such as bar coating, gravure coating, reverse roll coating, reverse gravure coating, slot die coating, comma coating, spray coating, knife coating, die Coating, dip coating, micro gravure coating, or wire bar coating may be used.

The substrate layer may be, for example, a metal oxide substrate, a semiconductor substrate, a glass substrate, or a polymer substrate. A single layer may be sufficient as the said base material layer, or two or more layers may be sufficient as it.

In one example, the base layer is a polyolefin such as polyethylene or polypropylene; Polyesters such as polyethylene terephthalate and polyethylene naphthalate; Cellulose such as triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyl cellulose or acetyl cellulose, and polyamides such as 6-nylon or 6,6-nylon; Acrylic polymers such as polymethyl methacrylate; Polystyrene, polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, or an organic polymer such as ethylene vinyl alcohol may be used, but the present invention is not limited thereto. The base layer may be formed of one or more mixtures or polymers of the above, or may have a structure in which a plurality of layers are laminated.

In addition, the base layer may contain known additives such as an antistatic agent, an ultraviolet absorber, an infrared absorber, a plasticizer, a lubricant, a colorant, an antioxidant, or a flame retardant.

In addition, the base layer may have a modified surface. The surface modification may employ a treatment method such as chemical treatment, corona discharge treatment, mechanical treatment, ultraviolet (UV) treatment, active plasma treatment, or glow discharge treatment, but is not limited thereto.

The thickness of the base layer may be set to an appropriate thickness in consideration of the purpose of minimizing the occurrence of wrinkles, etc. due to tension during thinning and processing of the barrier film film, and 10 µm to 80 µm, or 20 µm to 50 µm. It is preferable that it is ㎛, but is not limited thereto.

The base layer may have, for example, a refractive index of light having a wavelength of 550 nm in the range of 1.0 to 2.0. Within this range, the overall transparency of the barrier film may be ensured, and optical properties may be applied to an electronic device.

The barrier film of the present application includes a barrier layer formed on the undercoat layer. The barrier layer may play a role of securing a desired barrier property of the barrier film. Materials and methods of forming the barrier layer may be any known material within a range capable of achieving the above-described object without limitation.

In one example, the barrier layer may include any one material selected from the group consisting of oxides, nitrides, sulfides of groups IVB, VB, VIB, IIIA, IIB, IVA, VA and VIA of the periodic table, and combinations thereof. The present invention is not limited thereto, and a carbon-based thin film such as diamond carbon or amorphous carbon may also be used as a material for the barrier layer.

In a specific example, the barrier layer may be formed using a material such as _{SiO 2} , Al ₂ O ₃ , TiO ₂ , ZnO, HfO ₂ , HfON, AlN, or Si ₃ N _{4, but is not limited thereto.}

In addition, a known additive such as an oxygen remover or a moisture remover may be further included in the barrier layer. Such a barrier layer is, for example, sputtering (sputtering), PLD (pulsed laser deposition), electron beam evaporation (Electron beam evaporation), thermal evaporation (thermal evaporation) or L-MBE (Laser Molecular Beam Epitaxy) such as PVD (physical vapor epitaxy), etc. Deposition) method; Or CVD (Chemical Vapor Deposition) such as MOCVD (Metal Organic Chemical Vapor Deposition), HVPE (Hydride Vapor Phase Epitaxy), ALD (Atomic Layer Decomposition), PECVD (Plasma Enhanced Chemical Vapor Deposition) or iCVD (initiated Chemical Vapor Deposition), etc. Way of; Although it can be formed by using, etc., it is preferable to form the barrier layer using the ALD method.

The thickness of the barrier layer is not particularly limited, but may be in the range of 1 nm to 100 nm, or 5 nm to 70 nm.

In addition, the moisture permeability of the barrier layer may be 1x10 ^-2 g/m ² /day or less. In another example, the moisture permeability of the barrier layer may be 1x10 ^-3 g/m ² /day or less, or 1x10 ^-4 g/m ² /day or less. The barrier film according to the present application may particularly provide excellent barrier properties against water vapor and oxygen transmission by including the barrier layer.

The barrier layer in the barrier film of the present application can minimize damage to the barrier layer during the manufacturing process of the barrier film due to the low static friction coefficient of the undercoat layer formed on the lower surface thereof. Specifically, when forming a barrier film using a roll-to-roll process, the barrier film on which the barrier layer is formed may cause scratches on the barrier layer located at the outermost layer by a guide roll or the like. However, in the barrier film of the present application, by forming an undercoat layer having a predetermined surface roughness and a static friction coefficient, and then forming a barrier layer, such a phenomenon can be effectively prevented and productivity can be increased.

The barrier film of the present application may further include a protective coating layer on the barrier layer. That is, as shown in FIG. 3, the barrier film 1000 of the present application has a structure including the undercoat layer 200, the barrier layer 300, and the protective coating layer 400 sequentially on the substrate 100. I can have it.

Such a protective coating layer may include, for example, inorganic particles and a binder that may be included in the undercoat layer.

In one example, the binder included in the protective coating layer may include a polymerization unit of a radical polymerizable compound and/or a cationic polymerizable compound. Specifically, the radical polymerizable compound is acrylic acid, methacrylic acid, methyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl Acrylate, phenoxy ethyl acrylate, triloxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, phenoxydiethylene glycol acrylate, benzyl acrylate, butoxyethyl acrylate, cyclohexyl Monofunctional radical polymerizable monomers such as acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, carbitol acrylate, or isobornyl acrylate; 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, dicyclopentanyl diacrylate, butylene glycol diacrylate, pentarisritordi Acrylate, trimethylolpropane triacrylate, propion oxide modified trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol Polyfunctional radical polymerizable monomers such as hexaacrylate or tetramethylolmethane tetraacrylate; Alternatively, radical polymerizable oligomers such as polyester acrylate, polyether acrylate, urethane acrylate, epoxy acrylate, or polyol acrylate may be exemplified.

Specifically, the cationic polymerizable compound is a cationic polymerizable epoxy compound, a vinyl ether compound, an oxetane compound, an oxorane compound, a cyclic acetal compound, a cyclic lactone compound, a tyrane compound, a thiovinyl ether compound, a spiroso ester compound, and ethylene. A sexually unsaturated compound, a cyclic ether compound, or a cyclic thioether compound may be exemplified, but is not limited thereto. Preferably, a cationic polymerizable epoxy compound or an oxetane compound may be used.

The barrier film of the present application may further include an anti-blocking layer. The blocking prevention layer may be formed, for example, on a surface opposite to the surface on which the undercoat layer of the base layer is formed.

Specifically, as shown in FIG. 4, the barrier film 1000 of the present application includes an under coating layer 200, a barrier layer 300 and a protective coating layer 400 sequentially on the base layer 100, The base layer 100 may have a structure including an anti-blocking layer 500 formed on a surface opposite to a surface on which the undercoat layer 200 is formed.

The anti-blocking layer is a layer for improving blocking resistance, and the term ``blocking resistance'' refers to a property for improving the handling and winding properties of the film by preventing the undercoat layer from sticking to each other. .

Such an anti-blocking layer is a solution containing, for example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, polyarirate, cyclic olefin polymer, norbornene resin, acrylic resin, epoxy resin, etc. It can be formed by coating on one surface of the substrate layer by adding about 0.01 to 50% by mass of inorganic particles, organic particles, or organic-inorganic particles to the substrate layer, and a polyester film having a roughened surface can be used. have.

The anti-blocking layer may have a predetermined aspect ratio of surface irregularities within a range in which the above-described anti-blocking property can be secured.

In one example, the anti-blocking layer may have an aspect ratio of surface irregularities measured in a range of 310 µm x 232 µm in a range of 10 to 700 or 20 to 500. Within this range, it is possible to improve the above-described winding properties and handling properties of the film.

In yet another example of the present application, the present application relates to an electronic device including a barrier film. The electronic device may be, for example, a display device such as an LCD or OLED or a product that is susceptible to deterioration by moisture, such as a photovoltaic device such as a solar cell, but is not limited thereto. Structures of other electronic devices or configurations that may be additionally included are known according to the type of electronic device, and those of ordinary skill in the art may employ them without limitation.

In a specific example, by providing a conductive electrode layer on the outermost layer of the above-described barrier film, it is suitable for display elements such as liquid crystals, organic/inorganic electroluminescent elements, elements using electrochromic as a transparent conductive electrode substrate, and liquid crystal backlights or lighting. It can be suitably used for various uses, such as an area light-emitting body, a solar cell, a photoelectric conversion element, and an optical device using electroluminescence light. The conductive metal oxide electrode can be formed using conventional indium oxide, tin oxide, zinc oxide, titanium oxide, and mixtures thereof.

According to the present application, it is possible to provide a barrier film having excellent gas barrier properties and excellent productivity by preventing problems such as scratches that may occur during the manufacturing process.

The present application may also provide an electronic device including such a barrier film.

1, 3, and 4 respectively schematically illustrate a structure of a barrier film according to an embodiment of the present invention.
2 is a schematic diagram of a cross-sectional structure of a barrier film according to an embodiment of the present invention.

Hereinafter, the present application will be described in detail through examples. However, the scope of protection of the present application is not limited by the examples described below.

The physical properties of the barrier film were measured by the following method.

One. Under Measurement of the coefficient of static friction of the coating layer

The coefficient of static friction of the undercoat layer prepared according to Examples and Comparative Examples was determined by measuring the ASTMD1894 test method. Measurement conditions were carried out on a SUS plate with a weight of 200 g.

2. No. 1 Area included 310 μm X 232 μm Area center line surface roughness (Ra), roughness peak (Rpv) measurement

Using an optical profiler (Nano view E1000, Nanosystem, Korea), the average roughness of the center line (Ra) and the maximum roughness (Rpv) of an area of 310 µm X 232 µm including the first area where the unevenness was formed were measured.

3. Second Within the area 5 μm X 5 μm Area centerline surface roughness (Ra) and roughness Of the highest value (Rpv) Measure

The surface roughness of the center line surface roughness (Ra) and the highest-low roughness value (Rpv) were measured for an area of 5 µm x 5 µm in the second region without irregularities.

Specifically, AFM (Atomic Force Microscopy) was used, and the centerline average roughness (Ra) and the highest roughness value (Rpv) of an area of 5 µm X 5 µm were measured through a tapping mode in which the sample surface was tapped at a constant speed.

4. Barrier Measurement of moisture permeability of film

The moisture permeability of the barrier films prepared according to Examples and Comparative Examples was evaluated using AQUATRAN 1 (Mocon) under 30° C. and 100% relative humidity.

5. Under Measuring the thickness of the coating layer and Barrier layer scratch Confirm

The thickness of the undercoat layer formed on the base layer and the presence or absence of scratches on the barrier layer were measured by observing with an electron scanning microscope (Hitachi S4800).

Example One

COP base film (thickness 50㎛, refractive index 1.53) acrylic resin 100 parts by weight, silica nanoparticles 30 parts by weight, PMMA-PS organic particles (average particle diameter: 1.5μm) as a particulate component forming irregularities 0.05 parts by weight The composition was coated and cured to form an undercoat layer having a thickness of about 1.0 μm.

Zinc tin oxide having a thickness of about 20 nm was deposited on the undercoat layer by a sputtering method to form a barrier layer, thereby preparing a barrier film including a structure of a base layer/undercoat layer/barrier layer.

Physical properties were measured in the above manner for the prepared barrier film, and the results are as shown in Table 1.

Example 2 to 6 and Comparative example 1 to 3

When forming the undercoat layer, a barrier film was prepared in the same manner as in Example 1, except that the coating thickness and the particle diameter and content of the particulate component forming irregularities were different as shown in Tables 1 and 2.

Physical properties were measured in the above manner for the prepared barrier film, and the results are as shown in Tables 1 and 2.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Coating thickness 1000nm 1000nm 800nm 500nm 500nm 200nm Particle diameter 1500nm 1500nm 1500nm 800nm 800nm 300nm Particle content (parts by weight) 0.05 0.5 0.05 0.5 0.05 0.8 Ra(nm, OP) 25 35 38 30 40 15 Rpv(nm, OP) 450 550 600 280 290 210 Ra(nm, AFM) 0.3 0.3 0.4 0.4 0.4 0.3 Rpv(nm, AFM) 4 4 4 4 4 4 Static friction coefficient 0.30 0.25 0.27 0.31 0.35 0.35 Presence or absence of scratches radish radish radish radish radish radish Water permeability (g/m ² /day) 4 x 10 ^-3 6.0 x 10 ^-3 4.0 x 10 ^-3 6 x 10 ^-3 6 x 10 ^-3 7 x 10 ^-3

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Coating thickness 500nm 1000nm 500nm Particle diameter - 800nm 800nm Particle content (parts by weight) 0 0.05 5 Ra(nm) 3 8 60 Rpv(nm) 26 45 1100 Ra(nm) 0.3 0.3 0.5 Rpv(nm) 4 4 8 Static friction coefficient 0.5 or more 0.50 or more 0.25 Presence or absence of scratches U U radish Water permeability (g/m ² /day) 1 x10 ^-1 1 x10 ^-1 7 x 10 ^-2

Referring to Tables 1 and 2, the barrier films of Examples 1 to 5 can provide excellent barrier properties by controlling the diameter and content of particulate components in an appropriate range to prevent scratches and implement low moisture permeability. Confirmed that there is.

Referring to the comparative example of Table 2, Comparative Example 1 corresponds to the existing barrier film to which the particulate component was not added, and it can be seen that scratches are generated. In addition, the moisture permeability of the scratched portion and the non-scratched portion due to the scratch generated on the barrier film showed a large difference. That is, it was confirmed that the barrier film according to Comparative Example 1 had low uniformity and thus had no value as a product.

In Comparative Example 2, the diameter of the particulate component was small compared to the coating thickness, and in this case, it was confirmed that scratches occurred in the barrier film, and the moisture permeability between the scratched portion and the non-scratched portion was different. In addition, Comparative Example 3 is a case where the content of the particulate component is too high, and in this case, scratches do not occur, but it can be seen that the moisture permeability increases rapidly.

1000: barrier film
100, 101: base layer
200, 201: undercoat layer
211: particulate component
300, 301: barrier layer
400: protective coating layer
500: anti-blocking layer

Claims (19)

Base layer;
An undercoat layer formed on the base layer and having a static friction coefficient of 0.5 or less with respect to the stainless steel substrate under a vertical load of 200 g; And
Includes; a barrier layer formed on the under coating layer,
The undercoat layer includes a resin and a particulate component dispersed in the resin, and the particulate component is included in an amount of 0.005 to 2 parts by weight based on 100 parts by weight of the resin,
A barrier film with a moisture permeability of 1x10 ^-2 g/m ² /day or less.
The method of claim 1,
The undercoat layer is a barrier film including a first region and a second region having different centerline surface roughness (Ra) or roughness maximum (Rpv) values.
The method of claim 2,
The second region is a barrier film that is present inside the first region or in a region other than the first region.
The method of claim 2,
The undercoat layer contains a particulate component having an average particle diameter of 1.2 to 2 times the average thickness of the undercoat layer inside,
The first region is a region in which irregularities are formed by the particulate component,
The second region is a region in which unevenness due to the particulate component is not formed,
A barrier film, wherein an area range occupied by the first area per total unit area obtained by adding the first area and the second area is 5% or less.
The method of claim 4,
Barrier film, characterized in that the centerline average roughness (Ra) of an area of 310 µm x 232 µm including the first region is in the range of 4 nm to 50 nm on average.
The method of claim 4,
Barrier film, characterized in that the maximum roughness (Rpv) of an area of 310 µm x 232 µm including the first region is in a range of 50 nm to 1000 nm.
The method of claim 4,
The barrier film, characterized in that the aspect ratio of the irregularities formed in the first region is in the range of 100 to 4,000 on average.
The method of claim 4,
A barrier film having a centerline average roughness (Ra) of 5 µm x 5 µm in the second region in the range of 0.2 nm to 0.5 nm.
The method of claim 4,
A barrier film having a maximum roughness value (Rpv) of 5 µm x 5 µm in the second region in the range of 2 nm to 6 nm.
The method of claim 1,
The particulate component is a barrier film, characterized in that the inorganic particles, organic particles, or organic-inorganic particles.
The method of claim 1,
The resin included in the undercoat layer is an acrylic resin,
The acrylic resin is a barrier film comprising a polymerized unit of a (meth) acrylate monomer and/or (meth) acrylate oligomer.
The method of claim 4,
The undercoat layer,
The average thickness is in the range of 200 nm to 1500 nm,
Barrier film, characterized in that the average particle diameter of the particulate component is in the range of 250nm to 2500nm.
delete The method of claim 1,
The particulate component is a barrier film that satisfies the following Formula 1:
[Equation 1]
|AB|≤≤0.1
In Equation 1, A is a refractive index of the undercoat layer with respect to light having a wavelength of 633 nm, and B is a refractive index of the particulate component with respect to light having a wavelength of 633 nm.
The method of claim 1,
The barrier layer is a barrier film comprising any one material selected from the group consisting of oxides, nitrides, sulfides, and combinations of groups IVB, VB, VIB, IIIA, IIB, IVA, VA and VIA of the periodic table.
The method of claim 1,
A barrier film further comprising a protective coating layer on the barrier layer.
The method of claim 16,
A barrier film further comprising an anti-blocking layer formed on a surface opposite to the surface of the base layer on which the undercoat layer is formed.
The method of claim 17,
The anti-blocking layer is a barrier film having an aspect ratio of surface irregularities measured within an area of 310 µm x 232 µm in a range of 10 to 700.
An electronic device comprising the barrier film according to any one of claims 1 to 12 and 14 to 18.

Images