WO2019203558A1 - Light-diffusing barrier film - Google Patents

Abstract

The present application relates to a light-diffusing barrier film. The film is an integrated film comprising, in order, a barrier layer, a base layer and a light-diffusing layer. The film can prevent moisture ingress into a device such as an organic light emitting device, and also provides the device with a light-diffusing function. Particularly, the film can have excellent moisture barrier properties even after a roll-to-roll process.

Description

Light Diffusion Barrier Film

Cross Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0044337 dated April 17, 2018 and Korean Patent Application No. 10-2019-0044610 dated April 17, 2019, and the Korean patent All content disclosed in the literature of the application is included as part of this specification.

Technical Field

The present application relates to a light diffusing barrier film and a method of manufacturing the same. Specifically, the present application relates to an integrated film including a barrier layer and a light diffusing layer at the same time, and a method of manufacturing the same using a roll-to-roll process.

A device including a light source such as an organic light emitting material or a backlight unit has a problem of deterioration in durability when exposed to moisture or oxygen. Thus, barrier films can be used in such devices to protect them from the external environment. In addition, a light diffusion sheet is required to uniformly diffuse the light projected from the light source. When both the light diffusing function and the barrier property are required, it may be considered to use the barrier film and the light diffusing sheet attached by using an adhesive.

The film or sheet may be manufactured using dry coating or wet coating. For example, in the case of imparting barrier properties to a film mainly by an inorganic material such as metal, it may be possible to use a dry coating such as physical vapor deposition (PVD) or chemical vapor deposition (CVD). Barrier films can be made. In addition, when the imparting barrier property to the film is mainly made of an organic or organic / inorganic composite material, the barrier film may be manufactured by wet coating.

On the other hand, in accordance with the trend toward larger display areas, display barrier films are also required to be manufactured in large areas. When the barrier film is manufactured by a dry coating method such as deposition, there is an advantage in that the thin film uniformity is superior to the wet coating, but it is expensive and not easy to have a large area. In addition, dry and wet coating can be performed during a roll-to-roll process, during which a significant pressure is applied during the winding or unwinding of the transported film onto the roll. May damage the barrier material, resulting in a deterioration of the barrier properties of the film.

Therefore, there is a need for a barrier film providing technology that does not deteriorate in the manufacturing process, has light diffusibility, and can be mass produced in a large area.

One object of the present application is to provide an integrated film, that is, a light diffusing barrier film having excellent blocking properties against external environments (eg, moisture) and simultaneously having a light diffusing function.

Another object of the present application is to provide a large area light diffusing barrier film.

Another object of the present application is to provide an electronic or electrical device comprising the film.

Another object of the present application is to prevent damage to the barrier film during barrier film production using a roll-to-roll process.

Still another object of the present application is to manufacture a light diffusing barrier film according to a wet coating method so that a separate adhesive layer is not required, thereby thinning the barrier film and simplifying the manufacturing process.

The above and other objects of the present application can all be solved by the present application described in detail below.

In one example of the present application, the present application relates to a light diffusing barrier film. That is, the present application relates to an integrated film having not only barrier properties but also light diffusing functions.

The light diffusing barrier film includes a light diffusing layer, a base layer, and a barrier layer. Specifically, the film may include a light diffusion layer and a barrier layer, respectively, on both surfaces of the substrate layer facing each other. That is, the barrier film may sequentially include a light diffusion layer, a base layer, and a barrier layer as shown in FIG. 1.

Unless specifically defined otherwise, the terms "phase" or "phase" as used in this application with respect to the interlayer stacking position are not only used when a configuration is located directly above another configuration, It may be used to include even when the configuration is interposed.

The inventors of the present application have found that when the barrier film is prepared using a wet coating during the roll-to-roll process, there is damage to the barrier material. For example, in the case of forming the barrier layer on the substrate layer, the laminate including the barrier layer may be subjected to a process of being wound on or unrolled from a roll or roller. In particular, a considerable amount of static electricity may be generated as the interface of the thin laminate film is separated in the process of winding up the wound film, which causes damage to the barrier layer. In order to reduce the generation of static electricity, it is necessary that the interface between the barrier layer and the base material layer is not completely in contact even in the wound state. However, considering the tension applied to the film when winding up the roll, this is not easy. On the other hand, in order to reduce the generation of static electricity, it may be considered to form irregularities on the surface of any layer so that the interface between the barrier layer and the base layer is not in close contact. However, irregularities of the barrier layer itself may cause defects in the thin film stability and barrier properties of the barrier layer. In addition, when the unevenness of the layer (eg, the light diffusion layer) contacting the barrier layer in the wound state is too large, the barrier layer may be damaged by the tension applied during the winding.

In view of this, the inventor of the present application invented a light diffusing barrier film suitable for a roll-to-roll process, without degrading the properties of the barrier layer. The light-diffusion barrier film of this application improves a roll-to-roll process, while providing a predetermined | prescribed unevenness | corrugation to a light-diffusion layer, and ensures a light-diffusion function, and simultaneously prevents damage to a barrier layer.

In this regard, the light diffusing layer of the present application has a predetermined surface roughness Rt on one surface thereof.

As used herein, the term "surface roughness Rt" refers to the distance between the highest point H ₁ and the lowest point H ₂ when observing the surface roughness in the normal direction to the surface of the layer to be measured. It means a height difference (ΔH = H ₁ -H ₂ ). As will be described below, the light diffusing layer may include a resin component and a particle component which are matrix components, and the highest point H ₁ observed when measuring the surface roughness Rt is formed by one particle or by agglomeration of a plurality of particles. It may be a point, and the lowest point (H ₂ ) may be a point formed by the resin or particle component. Such surface roughness Rt can be measured using the equipment described in the Examples.

Specifically, in the light diffusing barrier film, one surface S ₁ opposite to one surface of the optical diffusion layer facing the substrate layer has irregularities having a surface roughness Rt of 6 μm or less. The surface S ₁ of the light diffusion layer having the unevenness is in contact with the barrier layer when wound on a roller. Therefore, through the unevenness, the degree of adhesion between the light diffusing layer and the barrier layer can be alleviated, and damage to the barrier layer due to static electricity can be prevented.

In one example, the surface roughness Rt is at least 0.01 μm, at least 0.02 μm, at least 0.03 μm, at least 0.04 μm, at least 0.05 μm, at least 0.06 μm, at least 0.07 μm, at least 0.08 μm, at least 0.09 μm, or at least 0.1 μm. It may be abnormal. Specifically, the surface roughness Rt may be 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, 0.6 μm or more, 0.7 μm or more, 0.8 μm or more, 0.9 μm or more, or 1.0 μm or more, more specifically. It may be at least 1 μm, at least 1.5 μm, at least 2.0 μm, at least 2.5 μm, at least 3.0 μm, at least 3.5 μm, at least 4.0 μm, at least 4.5 μm, or at least 5.0 μm.

When the surface roughness Rt exceeds 6 μm, one surface of the barrier layer in contact with the surface S ₁ of the light diffusion layer may be damaged by irregularities.

Although not particularly limited, the lower limit of the surface roughness Rt may be 0.02 μm or more. When the lower limit of the surface roughness is smaller than the lower limit, the possibility of generating static electricity when unwinding the film wound on the roller increases.

In one example, the number of particles observed on the uneven surface may be in the range of 0.8 to 3.0 / m ² . For example, the number of particles observed per unit area (μm ² ) on the uneven surface is 0.9 or more μm ² or more, 1.0 or more μm ² or more, 1.1 or more μm ² or more, 1.2 or more μm ² or more, or 1.3 / Μm ² or more, 1.4 pieces / μm ² or more, 1.5 pieces / μm ² or more, 1.6 pieces / μm ² or more, 1.7 pieces / μm ² or more, 1.8 pieces / μm ² or more, 1.9 pieces / μm ² or more, or 2.0 pieces / Μm ^{2 or} more, and 2.9 pieces / μm ² or less, 2.8 pieces / μm ² or less, 2.7 pieces / μm ² or less, or 2.6 pieces / μm ² or less. The number of particles may be obtained by obtaining an SEM image of magnification x 50,000 with respect to a predetermined area (width μm × length μm) of the layer and confirming the number of particles observed on the surface thereof. In one example, the determination of the number of particles may be made several times, for example three or five times, and the average value may be taken as the number of particles.

In one example, the light diffusing layer, the base layer, and the barrier layer may further include another layer between adjacent layers.

In another example, the light diffusion layer, the base layer, and the barrier layer may directly contact adjacent layers. Specifically, no separate adhesive may be used between adjacent layers. Thereby, the film which is thin and excellent in barrier property can be provided.

In one example, the surface roughness (Rt) of the light diffusing layer may range from 0.1 to 6 ㎛. If the above range is satisfied, the possibility of generating static electricity during film unwinding is relatively low. Specifically, the light diffusing barrier film comprises a light diffusing layer; Base layer; And a barrier layer in order, and one surface S1 opposite to one surface of the optical acid layer facing the substrate layer may have irregularities having a surface roughness Rt in a range of 0.1 to 6 μm.

In one example, when the surface roughness Rt of the light diffusing layer is less than 0.1 μm, for example, when 0.01 or more and less than 0.1 μm, the sheet resistance of one surface S ₁ having the surface roughness is 10 ¹⁰ Ω /. can be configured to satisfy sq or less. Specifically, the optically acidic barrier film comprises a light diffusion layer; Base layer; And a barrier layer in order, and one surface S1 opposite to one surface of the optical acid layer facing the substrate layer has a surface roughness Rt of 0.02 μm or more and less than 0.1 μm, and has one surface of the optical acid layer S1 having the surface roughness. ) May have a sheet resistance of 10 ¹⁰ Ω / sq or less.

In this regard, when the unevenness is present on one surface of the optical scattering layer S ₁ , the possibility of static electricity may be lowered at the time of peeling the interface between the light diffusing layer and the barrier layer. It is necessary to adjust the sheet resistance of one surface S ₁ to a certain level. Through this, despite the relatively low surface irregularities, it is possible to prevent damage to the barrier layer due to static electricity, which is a concern when unwinding the film.

In one example, the sheet resistance of the light diffusion layer one surface (S ₁ ) having a surface roughness (Rt) of less than 0.1 ㎛ is 1.0 x 10 ¹² Ω / sq or less, 1.0 x 10 ¹¹ Ω / sq or less, 1.0 x 10 ¹⁰ Ω / sq Or less than 1.0 x 10 ⁹ Ω / sq, or less than or equal to 1.0 x 10 ⁸ Ω / sq. The sheet resistance value defines a size capable of preventing damage to the barrier layer caused by static electricity in connection with the unevenness, and the lower limit thereof is not particularly limited. For example, the lower limit may be at least 1.0 × 10 ⁷ Ω / sq, at least 1.0 × 10 ⁸ Ω / sq, or at least 1.0 × 10 ⁹ Ω / sq.

The means for satisfying the sheet resistance of the light-diffusion layer whose surface roughness Rt is less than 0.1 micrometer in the said range is not specifically limited. For example, the light-diffusion layer forming material can be selected suitably. In one example, the light diffusion layer having a surface roughness Rt of less than 0.1 μm may include a predetermined amount of an antistatic agent.

In one example, the light diffusing barrier film may satisfy a moisture permeability change rate of 30% or less calculated by the following formula.

[Equation]

Moisture permeability change rate (%) = {(B-A) / A} × 100

In the above formula, A is the moisture permeability of the light diffusing barrier film (F ₁ ); B is a light diffusion barrier film (F ₁₎ of the barrier layer surface of the light diffusion barrier film (F _2), the light-diffusing layer uneven surface is flush to applying a constant load (or in contact with each other) the two films to each other in the ( F ₁ , F ₂ ) and the moisture permeability of the light diffusing barrier film F ₁ measured after maintaining the constant load for 24 hours; The light diffusing barrier films (F ₁ , F ₂ ) have the same configuration; Moisture permeability (A, B) may be measured using AQUATRAN 2 (MOCON Co., Ltd.) at 38 ℃ and 100% relative humidity conditions.

The light diffusing barrier films (F ₁ , F ₂ ) used for calculating the moisture permeability change rate are light diffusing barrier films according to the present application, and include a light diffusing layer, a base layer, and a barrier layer sequentially, and are defined in the present application. Each layer has the characteristics.

In one example, the constant load applied when calculating the moisture permeability change rate may be made before curing of the polysilazane layer of the film (F ₂ ). After the predetermined load is applied, curing may be performed on the polysilazane layer of the film F ₂ . In one example, the moisture permeability A and B may also be the moisture permeability of the film (F ₁ , F ₂ ) measured before curing to the polysilazane layer. Alternatively, the moisture permeability A and B may be the moisture permeability of the films (F ₁ , F ₂ ) measured after curing of the polysilazane layer.

In one example, the rate of change may be 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less.

Since the barrier layer may be damaged when the roll-to-roll process is performed for the aforementioned reason, the barrier property of the damaged film may be degraded. That is, moisture permeability can be increased. Therefore, in relation to the above formula, the change in moisture permeability (%) of 30% or less may mean that the increase in moisture permeability (%) of 30% or less. That is, in the present application, the moisture permeability change rate (%) may be used as the same meaning as the moisture permeability increase rate (%). However, the change rate is expressed in consideration of the mechanical error related to the measurement of the change rate of water permeability.

The moisture permeability change rate is a numerical change assuming that the film or a part thereof is unwound and wound on a roller in the process of manufacturing the optical barrier film using a roll-to-roll process. Specifically, the moisture permeability B is a water permeability of the barrier film when the film or part of its configuration is wound on a roll (or roller) while being given tension, and is unwound from the roll (or roller) after the winding state is maintained for a predetermined time. Is the value to check how much change (decrease) is. As confirmed through the following experimental example, the degree of decrease in moisture permeability (that is, the degree of damage of the barrier film) may vary depending on, for example, the degree of concavities and convexities of the light diffusion layer.

Although not particularly limited, the constant load or the predetermined pressure applied to the superposition of the two films F ₁ and F ₂ during water permeability B measurement may be about 10 to 35 kg load. In addition, the two films (F ₁ , F ₂ ) can be cut into a sheet shape when the moisture permeability B is measured, wherein the size of the contact surface of the sheet may be 10 cm × 10 cm in size.

The kind of the base material layer is not particularly limited. For example, the substrate layer may comprise a glass substrate or a plastic (polymer) material.

In one example, the base layer is a polyester film such as polyethylene terephthalate (PET) film, polycarbonate film, polyethylene naphthalate film or polyarylate film, polyether film film such as polyethersulfone film, cycloolefin polymer Cellulose resin films such as polyolefin films such as films, polyethylene films or polypropylene films, diacetyl cellulose films, triacetyl cellulose films or acetyl cellulose butyrate films, polyimide films, acrylic films or epoxy resin films and the like. . However, it is not limited to these.

The substrate layer may comprise one or more of the films listed above. That is, the base layer may be a single layer or a multilayer structure.

The thickness of the base material layer is not particularly limited. For example, it may be selected in the range of 2 to 200 μm, in the range of 5 to 190 μm, in the range of 10 to 180 μm, in the range of 20 to 180 μm, or in the range of 20 to 150 μm.

The thickness of the base layer may be measured by, for example, cross-sectional image observation by SEM (HR-SEM, S-4800, Hitachi, Inc.) or TEM (FE-TSEM, TITAN G2 ChemiSTEM 80-200, FEI, Inc.). . Alternatively, the thickness may be measured by analyzing an electron density difference between adjacent layers using XRR (X'Petr Pro MRD XRD, PANalytical Co., Ltd.), and inferring thickness oscillation. In this case, the thickness may be an average value of the thickness values measured at various points on the surface when observed in the normal direction to the surface of the substrate layer to be measured.

In one example, the substrate layer may have transparency or light transmission. In the present application, the term “transparent or translucent” means that visible light transmittance within a wavelength range of 380 to 780 nm of the predetermined layer or film, specifically, transmittance of light having a wavelength of 550 nm is 50% or more, 60% or more, 70% or more, It may mean a case of 80% or more, 90% or more, or 95% or more. The upper limit of the transmittance may be, for example, about 100%.

The substrate layer may include one or more additives selected from the group consisting of known additives, for example, antistatic agents, light blocking agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, crosslinking agents, and antioxidants. .

In one example, one or both surfaces of the substrate layer may be subjected to surface treatment such as primer treatment, corona discharge irradiation, plasma irradiation, ion irradiation, and the like, as necessary. For example, the substrate layer may be a layer on which at least one surface is primed to improve adhesion or adhesion with the light diffusion layer or the barrier layer.

In one example, the barrier layer may include one or more sub barrier layers. When two or more sub barrier layers are laminated to form a barrier layer, the types of each sub barrier layer may be the same or different. For example, as shown in FIG. 2, the light diffusing barrier film may sequentially include a light diffusing layer, a base layer, a first barrier layer, and a second barrier layer.

In one example, the barrier layer or sub-barrier layer may be a polysilazane layer or a cured layer of polysilazane.

In the present application, the polysilazane layer may be a layer formed by coating and drying the polysilazane-containing composition (coating composition) described below on one surface of the base layer as a state before curing. In addition, the cured layer of polysilazane may mean a layer formed by curing the polysilazane layer.

The polysilazane layer means a layer containing a polysilazane as a main component (a coating layer in a pre-cured state formed on a base layer). The main component is, for example, in the polysilazane layer or the polysilazane-containing composition, the proportion of polysilazane is 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80 by weight. It may mean when more than%, more than 85% or more than 90%. The weight ratio may be, for example, 100% or less, 99% or less, 98% or less, 97% or less, 96% or less, or 95% or less.

In the present application, the term "polysilazane" refers to a polymer in which a silicon atom (Si) and a nitrogen atom (N) are repeated to form a basic backbone. Such polysilazane may be modified through a predetermined treatment (eg, a plasma treatment described below) to form silicon oxide and / or silicon oxynitride having barrier properties. Accordingly, the cured product of the polysilazane layer, that is, the cured layer contains Si, N and / or O, and has barrier properties to the external environment.

In one example, the polysilazane used in the present application may include a unit represented by Formula 1 below.

[Formula 1]

R ¹ , R ² and R ³ in Formula 1 may each independently be a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsilyl group, an alkylamide group or an alkoxy group.

In the present application, the term "alkyl group" may mean an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkyl group may be linear, branched or cyclic. In addition, the alkyl group may be optionally substituted with one or more substituents.

As used herein, unless otherwise specified, the term "alkenyl group" may refer to an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. The alkenyl group may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

In the present specification, the term "alkynyl group" may mean an alkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, unless otherwise specified. The alkynyl group may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

As used herein, unless otherwise specified, the term “aryl group” includes a compound having a structure in which a benzene ring or two or more benzene rings are connected, or a structure condensed or bonded while sharing one or two or more carbon atoms. Or monovalent residues derived from the derivatives thereof. In the present specification, the range of the aryl group may include a so-called aralkyl group or an arylalkyl group as well as a functional group commonly referred to as an aryl group. The aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. Examples of the aryl group include phenyl group, dichlorophenyl, chlorophenyl, phenylethyl group, phenylpropyl group, benzyl group, tolyl group, xylyl group or naphthyl group.

In the present application, the term "alkoxy group" may mean an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkoxy group may be linear, branched or cyclic. In addition, the alkoxy group may be optionally substituted with one or more substituents.

If it includes the unit represented by the formula (1), specific types of polysilazane is not particularly limited.

In one example, in consideration of the densities of the modified polysilazane layer and the like, the polysilazane of the present application includes a polysilazane including a unit of Formula 1 wherein R ¹ to R ³ are all hydrogen atoms, for example, Perhydropolysilazane can be used.

Although not particularly limited, the number average molecular weight (Mn) of the polysilazane compound may be, for example, 100 to 50,000 or less.

In one example, the polysilazane layer may be formed by coating, for example, a composition prepared by dissolving polysilazane in a suitable organic solvent (coating solution containing polysilazane as a main component) on a base layer. have. If the solvent is not reactive with polysilazane and can dissolve it, the kind of solvent included in the coating liquid is not particularly limited. For example, ethers such as hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used. Specifically, hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, sorbetso, and taben, halogen hydrocarbons such as methylene chloride and tricholoethane, dibutyl ether, dioxane, tetra hybrido furan and the like Or the like can be used as the solvent.

In one example, a commercialized polysilazane or a composition comprising the same may be used to form the barrier layer. For example, AZ Electronic Materials, Inc. (trademark) NN120-10, NN120-20, NAX120-10, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, Polysilazane commercially available products such as NP140 or SP140 may be used, but are not limited thereto.

The polysilazane layer may include a polysilazane modification-promoting catalyst, that is, a compound that promotes modification of the polysilazane compound by mutual reaction with the polysilazane compound. Such catalysts include, but are not limited to, organic amine compounds, organic acids, inorganic acids, metal carboxylate salts, organic metal complex salts, and the like.

The barrier layer forming composition may include other additives as necessary. Examples of the additive include, but are not limited to, a viscosity modifier and a crosslinking accelerator.

When the thickness of the polysilazane layer coated on the base layer, that is, the sub-barrier layer is too thin, the coating process is not smooth, it is difficult to sufficiently secure the barrier property, and is likely to be damaged by the light diffusion layer irregularities. And, if the thickness is too thick, there is a fear that cracks (damage) due to shrinkage of the polysilazane layer occurs during the curing process. Although not particularly limited, the thickness of the polysilazane layer to be coated is considered as above, the lower limit thereof is, for example, about 20 nm or more, 30 nm or more, 40 nm or more, 50 nm or more, 60 nm or more, 70 nm or greater, 80 nm or greater, 90 nm or greater, or 100 nm or greater. And the upper limit may be, for example, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, or 200 nm or less. In this case, the thickness of the barrier layer may mean an average thickness of the resin component (eg, polysilicon) that forms the barrier layer or a thickness of the cured resin component.

The thickness of the barrier layer may be determined by a known method, for example, cross-sectional image observation by SEM (HR-SEM, S-4800, Hitachi) or TEM (FE-TSEM, TITAN G2 ChemiSTEM 80-200, FEI) Can be measured. Alternatively, the thickness may be measured by analyzing an electron density difference between adjacent layers using XRR (X'Petr Pro MRD XRD, PANalytical Co., Ltd.) and inferring thickness oscillation. In this case, the thickness may be an average value of the thickness values measured at various points of the surface formed by the resin component when observed in the normal direction to the surface of the layer to be measured.

In one example, the polysilazane layer may be applied on one surface of the substrate layer, dried, and present on the substrate layer in a state before curing.

In one example, the polysilazane layer may be cured on the substrate layer.

In one example, the thickness of the layer obtained by curing the polysilazane layer, ie the cured layer of polysilazane, may be determined according to the thickness of the polysilazane layer described above. In addition, the thickness of the barrier layer including two or more sub barrier layers may be appropriately adjusted according to the number of polysilazane cured layers or polysilazane layers in a range of 1,500 nm or less.

In one example, the barrier layer may be a stack of a first sub barrier layer and a second sub barrier layer. In this case, the thickness of each sub barrier layer may be, for example, 40 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more or 100 nm or more. And the upper limit of the thickness of each sub-barrier layer may be, for example, 250 nm or less, 240 nm or less, 230 nm or less, 220 nm or less, 210 nm or less, or 200 nm or less.

When a plurality of sub barrier layers are stacked, for example, when a second sub barrier layer is formed on the first sub barrier layer, when the cross section of the barrier layer is observed by SEM or TEM, each sub barrier layer may be divided. have.

In one example, the barrier layer may include only a polysilazane layer or a cured layer thereof. For example, the metal component containing layer formed by vapor deposition may not be included.

In one example, the barrier layer may comprise a particle component. The particle component is the same as described for the light diffusion layer.

In one example, the barrier layer may not contain particle components.

In one example, the barrier layer may have transparency or light transmission.

In one example, the barrier layer may be directly formed on one surface of the substrate layer. That is, there is no separate adhesive layer between them. Thereby, the film which is thin and excellent in barrier property can be provided.

In one example, the light diffusing layer having a surface roughness may include a matrix component forming a continuous phase in the light diffusing layer and a light diffusing agent which is a dispersed phase present in the continuous phase. In this case, the matrix component may be a curable resin (or a cured product thereof), and the light diffusing agent may be (light diffusing) particles that are known to perform a light diffusing function. Surface irregularities may be formed through the particles, and a unique light diffusion function may be performed.

In one example, the light diffusion layer having the surface roughness (Rt) may have a thickness of 20 ㎛ or less. Specifically, the upper limit of the thickness of the light diffusion layer is 19 μm or less, 18 μm or less, 17 μm or less, 16 μm or less, 15 μm or less, 14 μm or less, 13 μm or less, 12 μm or less, 11 μm or less, 10 μm or less, 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, or 1 μm or less. The lower limit of the thickness is, for example, 0.5 µm or more, 1 µm or more, 2 µm or more, 3 µm or more, 4 µm or more, 5 µm or more, 6 µm or more, 7 µm or more, 8 µm or more, or 9 µm. Or 10 μm or more. When the above range is satisfied, the light diffusion layer may be stably formed while having the above-described surface roughness Rt.

The thickness of the light diffusing layer does not consider light diffusing particles, but only a matrix component, that is, a resin component. The thickness of the light diffusing layer is a known method, for example, SEM (HR-SEM, S-4800, Hitachi) or TEM (FE- TSEM, TITAN G2 ChemiSTEM 80-200, FEI company) can be measured through cross-sectional image observation. Alternatively, the thickness may be measured by analyzing an electron density difference between adjacent layers using XRR (X'Petr Pro MRD XRD, PANalytical Co., Ltd.) and inferring thickness oscillation. In this case, the thickness may be an average value of the thickness values measured at various points of the surface formed by the resin component when observed in the normal direction to the surface of the layer to be measured.

In one example, the light diffusing layer may be formed from a coating composition (hereinafter referred to as a 'light diffusing layer coating composition') containing 0.1 parts by weight or more relative to 100 parts by weight of the curable resin. Specifically, the lower limit of the content of the particles may be, for example, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight or 0.5 parts by weight or more, and specifically, 1 part by weight, 2 parts by weight or more, and 3 parts by weight. It may be at least 4 parts by weight, at least 4 parts by weight or at least 5 parts by weight, specifically 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight. It may be at least 45 parts by weight, or at least 50 parts by weight. In addition, the upper limit of the content of the particles may be, for example, 100 parts by weight or less, 95 parts by weight or less, 90 parts by weight or less, 85 parts by weight or less, or 80 parts by weight or less.

In one example, low density particles may be used when preparing the light diffusing layer coating composition to form a surface having irregularities, that is, a light diffusing layer surface having a predetermined range of surface roughness (Rt). Specifically, in the case of mixing the resin, the solvent, and the particles to prepare the light diffusing layer coating composition, by using particles of relatively low density, the particles of the light diffusing layer coating composition coated on the substrate layer by buoyancy To protrude to the surface.

In another example, a method of adjusting the diameter of the particle may be used in consideration of the thickness of the light diffusing layer to be formed. Specifically, particles larger in diameter than the thickness (height) of the light diffusion layer formed after curing may be used in the light diffusion layer coating composition. When the particle size as described above is satisfied, the uneven structure can be formed more easily. For example, when the height of the light diffusion layer is about 20 μm, particles having a diameter of about 20 to 25 μm may be used. However, when the diameter of the particles is larger than the thickness of the layer, the interface between the particles and the light diffusing layer may act as a defect. Therefore, the content of the particles needs to be appropriately adjusted so that the amount of the particles is not excessively used.

In another example, another method of forming surface roughness is to use components having different degrees of hydrophobicity or hydrophilicity in the preparation of the light diffusing layer coating composition. Specifically, when particles having a diameter smaller than the thickness of the light diffusion layer are used, relatively hydrophobic particles or more hydrophilic particles may be used as compared to the solvent or resin component used in the light diffusion layer coating composition. When the hydrophobic or hydrophilic properties are different from each other as described above, the particles may be present in a floating state on the surface of the light diffusing layer (or the light diffusing layer coating composition layer applied on the substrate layer) formed after curing the resin (or the state Curing may take place). Whether the particles are hydrophobic or hydrophilic can be determined according to the properties (eg components) of the particles themselves. Alternatively, hydrophobicity or hydrophilicity may be imparted to the particles through surface treatment by a hydrophobic functional group or a hydrophilic functional group. At this time, whether hydrophobic or hydrophilic is not determined uniformly, and may be determined in relation to other components (eg, a solvent or a resin) in the composition used together, and whether or not the polarity of the compound or functional group forming the particle surface, or in the compound It can be judged relatively in consideration of the total length of the carbon chain. For example, when the thickness of the light diffusion layer is in the range of 15 to 17 μm, the diameter of the particle may be adjusted in the range of about 1 to 5 μm, and the particle surface characteristics may be adjusted to allow the particles to float on the surface S ₁ of the light diffusion layer. Can be present in a state.

The resin component used for forming the light diffusion layer is not particularly limited. Thermosetting resin, photocurable resin, etc. can be used as a resin component.

In one example, the light diffusion layer coating composition may include an acrylic resin, urethane resin, melamine resin, alkyd resin, epoxy resin, siloxane polymer or a condensate of the following organic silane compound.

Although not particularly limited, in consideration of weather resistance, scratch resistance, surface gloss characteristics and heat resistance, an acrylic resin may be used.

Specifically, acrylic resin can be obtained by copolymerizing the monomer which has acrylic acid and methacrylic acid derivative as a main component. As a monomer which can be used, it is (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t, for example. -Butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) Acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate and tetradecyl (meth) acrylate, and the like, but is not limited thereto.

In one example, the light diffusion layer composition may include a polyfunctional (meth) acrylate as a resin component. As a kind of the said polyfunctional acrylate, 1, 4- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene, for example Glycol di (meth) acrylate, neopentylglycol adipate di (meth) acrylate, hydroxyl puivalic acid neopentylglycol di (meth) acrylate, dicyclopentanyl di (Meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (meth) acryloxy ethyl isocyanurate, allylated cyclohexyl Di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, Tricyclodecane dimethanol (meth) acrylate, neopentylglycol modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylate or 9,9-bis [4- (2-acrylo) Bifunctional acrylates such as yloxyethoxy) phenyl] fluorine and the like; Trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide Trifunctional acrylates such as modified trimethylolpropane tri (meth) acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethyl isocyanurate; Tetrafunctional acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; 5-functional acrylates, such as propionic acid modified dipentaerythritol penta (meth) acrylate; And dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (ex. Isocyanate monomers and trimethylolpropane tri (meth) acrylate Six-functional acrylates such as reactants may be used, but is not limited thereto.

As the epoxy resin that can be used to form the light diffusion layer, at least one selected from the group consisting of an alicyclic epoxy resin and an aromatic epoxy resin may be used.

As an alicyclic epoxy resin, 1 or more types chosen from the group which consists of an alicyclic glycidyl ether type epoxy resin and an alicyclic glycidyl ester type epoxy resin can be used, for example. Also, for example, 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate (3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate), which is, for example, Celloxide 2021P (Daicel) Derivatives may be used, which are stable at high temperatures, are colorless, transparent, toughness, and have good adhesion and adhesion properties for lamination.

Examples of the aromatic epoxy resins include bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, fluorene-containing epoxy resins, and triglycidyl isocyanurates. One or more aromatic epoxy resins selected from the group may be used.

The kind of polymerization initiator which causes the resin to form a matrix of the light diffusion layer by polymerization is not particularly limited, and a known photopolymerization initiator or a thermal polymerization initiator may be used.

In addition, the light diffusion layer coating composition may further include a curing agent. These kinds are not particularly limited.

The kind of particles used for forming the light diffusion layer is not particularly limited. As the particle component, organic particles, inorganic particles, organic-inorganic hybrid particles, or mixtures thereof may be used without limitation. The shape of the particles is also not particularly limited. For example, the particles may be spherical, ellipsoidal, pyramidal, or amorphous.

In one example, when spherical particles are used in forming the light diffusing layer, the surface of the light diffusing layer having a predetermined surface roughness may have a shape in which a hemispherical protrusion is irregularly protruded or an irregular embossing shape.

The kind of inorganic particle which can be used for a light-diffusion layer is not specifically limited. In one example, it is selected from clay, talc, alumina, calcium carbonate, zirconia, silica, barium sulfate, titanium dioxide, aluminum hydroxide, glass, talc, unibo, white carbon, magnesium oxide, zinc oxide, indium oxide and tin oxide particles. Inorganic particles may be used. Compared with the organic particle component described below, since the inorganic particle component has better barrier properties to moisture and the like, it may be advantageous to use inorganic particles to improve the barrier property to the external environment of the film.

The kind of organic particle | grains which can be used for a light-diffusion layer is not specifically limited. The organic particles include a polymer component, and examples thereof include acrylic particles, siloxane particles, polycarbonate particles, styrene particles, and the like, but are not limited thereto.

In one example, the particles used in the light diffusion layer may be amphiphilic particles. Amphiphilic particles can be determined by the relative degree of hydrophilicity and hydrophobicity of the solvent or resin used together. Amphiphilicity can be achieved through surface treatment and the like.

In one example, the size of the particles included in the light diffusion layer may be 50 nm or more or 100 nm or more. Specifically, the particle size may be 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 450 nm or more, or 500 nm or more. In addition, considering the thickness or surface roughness of the light diffusion layer, for example, the upper limit of the size of the particles may be, for example, 25 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, 5 μm or less, or 1 μm or less. Can be. In this regard, "particle size" may be used in the same sense as "particle size" and means the length of the largest dimension among the shapes that the particles have. The particle diameter can be analyzed using a known particle size analyzer, for example, a dynamic light scattering system (DLS).

When the particle diameter is larger than the thickness of the light diffusion layer, the unevenness of the light diffusion layer may be formed by the particle diameter of the particles. In addition, when the particle diameter is small compared to the thickness of the light diffusion layer, the unevenness of the light diffusion layer may be formed by the aggregation of particles or a plurality of particles floating on the surface of the light diffusion layer.

In one example, the particle diameter may include particles having two or more kinds of particle diameters. In this case, the size of the particle may mean an average value, for example, an average particle diameter (D50). D50 means the particle size corresponding to 50% of the weight percentage in the particle size distribution curve.

The light diffusion layer coating composition may include a solvent. The solvent is, for example, toluene, xylene, propylene glycol monoethyl ether, cyclopentanone, cyclopentanone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO, Dimethyl sulfoxide), dibutyl ether Anisole or 1,2,4-trichlorobenzene may be used, but is not limited thereto.

The light diffusing layer coating composition is an antistatic agent, antibacterial agent, heat stabilizer, antioxidant, release agent, light stabilizer, surfactant, coupling agent, plasticizer, admixture, colorant, stabilizer, lubricant, colorant, flame retardant, weathering agent, ultraviolet absorber, sunscreen Or an additive of a combination thereof. The content of these additives is not particularly limited, but may be used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the resin component.

In one example, the light diffusion layer may be directly formed on one surface of the substrate layer. That is, there is no separate adhesive layer between the substrate layer and the light diffusion layer. Thereby, the film which is thin and excellent in barrier property can be provided.

In one example, the light diffusing layer may have transparency or light transmission.

In one example, the light diffusing barrier film may further include a hard coating layer. The hard coat layer is a layer that provides hardness or strength to the film. Specifically, as shown in FIG. 3, the light diffusing barrier film may sequentially include a light diffusing layer, a base layer, a hard coating layer, and a barrier layer.

In one example, the hard coating layer may be in direct contact with the substrate layer and the barrier layer, respectively. In this case, scratch resistance and solvent resistance of the substrate layer can be improved.

The specific composition of the hard coat layer forming composition is not particularly limited.

In one example, the hard coat layer forming composition may include a curable resin. In this case, the hard coat layer-forming composition may further include a polymerization initiator and the like. The kind of polymerization initiator is not particularly limited, and known thermal polymerization initiators or photopolymerization initiators may be used.

In one example, the curable resin included in the hard coating layer composition may be a photocurable resin. For example, urethane acrylate oligomers, polyester acrylates and the like can be used, but are not limited thereto.

In one example, in addition to the resin component, (meth) acrylates having a hydroxy group such as pentaerythritol acrylate and dipentaerythritol hexaacrylate may be used to form the hard coat layer.

In one example, the hard coat layer forming composition may further include particles. The specific kind of particles is not particularly limited, but for example, one or more of organic or inorganic particles that can be used in the light diffusion layer can be used.

In one example, the hard coat layer forming composition may further include a solvent. Known solvents can be used without limitation, for example, the solvents described above can be used.

In addition, the hard coat layer-forming composition may further comprise a curing agent. These kinds are not particularly limited.

In one example, the hard coating layer may have the same composition as described above with respect to the optical diffusion layer. For example, the hard coat layer composition may include the same resin component as the light diffusion layer composition. At this time, the composition for forming a hard coat layer may not contain particles.

In one example, the hard coating layer may have transparency or light transmission.

In one example, the light diffusion barrier film of the above configuration may have a water transmittance of 5.0 × 10 ^-3 g / m ² day or less. For example, the moisture permeability is 4.5 × 10 ^-3 g / m ² day or less, 4.0 × 10 ^-3 g / m ² day or less, 3.5 × 10 ^-3 g / m ² day or less, 3.0 × 10 ^-3 g / m ² day or less, 2.5 × 10 ^-3 g / m ² day or less, 2.0 × 10 ^-3 g / m ² day or less, 1.5 × 10 ^-3 g / m ² day or less or 1.0 × 10 ^-3 g / m ^It may be less than ² days. The lower limit of the moisture permeability may be, for example, 0.001 × 10 ⁻³ g / m ² day or more, 0.01 × 10 ⁻³ g / m ² day or more, or 0.1 × 10 ⁻³ g / m ² day or more.

In one example, the light diffusion barrier film of the above configuration may have light transmissivity or transparency.

In one example, the haze of the light diffusion barrier film of the configuration may be 60% or more, 80% or more, 85% or more or 88% or more. The haze may be a percentage of the transmittance of the diffused light to the transmittance of the total transmitted light passing through the measurement object.

The optically acidic barrier film of the present application is used in various applications such as various packaging materials, displays such as liquid crystal displays (LCDs), solar cell members, electronic papers, and substrates for organic light emitting diodes (OLEDs). It can be used as a sealing film.

In another example relating to the present application, the present application relates to an electrical or electronic device. The electronic or electrical device may be, for example, an optical device such as various display devices or lighting devices.

When used in this application, the light diffusing barrier film may be positioned such that the barrier layer is adjacent to a protective object, i.e., moisture vulnerable. For example, when the barrier film is attached to the OLED device, the stacking order may be a light diffusion layer, a base layer, a barrier layer, and an OLED device.

In another example of the present application, the present application is directed to a method of making a light diffusing barrier film.

The barrier film may be prepared through a roll-to-roll process. At this time, the film or the laminate may be wound on a roll (or roller) of the roll-to-roll equipment, and / or the process of being unwound from it.

The method may be performed by first forming a laminate of the base layer and the light diffusion layer and then forming a barrier layer. This is because the barrier layer may be damaged in the process of using the roll-to-roll process because the substrate layer does not have the unevenness and / or sheet resistance of the light diffusion layer described above.

The properties of the light diffusion layer, the base layer and the barrier layer, the materials constituting them, and the like are as described above.

In one example, the method comprises a laminate comprising a substrate layer and a light diffusion layer, the surface roughness (Rt) of one surface (S ₁ ) opposite to one surface of the optical diffusion layer facing the substrate layer is in the range of 0.1 to 6 μm. Preparing a first step; And a second step of forming a barrier layer by applying a barrier layer coating composition on one surface of the substrate layer on which the light diffusion layer is formed and then drying the coating layer. In this case, the barrier layer may be a polysilazane layer.

In one example, the method includes a substrate layer and a light diffusion layer, the surface roughness (Rt) of the opposite surface (S ₁ ) of one surface of the optical diffusion layer facing the substrate layer is 0.02 or more and less than 0.1 ㎛, A first step of providing a laminate having a surface roughness of one surface S ₁ having an optical roughness of 10 ¹⁰ Ω / sq or less; And a second step of forming a barrier layer by applying a barrier layer coating composition on one surface of the substrate layer on which the light diffusion layer is formed and then drying the coating layer. In this case, the barrier layer may be a polysilazane layer.

In one example, the light diffusing layer may be formed on one surface of the substrate layer by wet coating. That is, the light diffusing layer coating composition described above may be formed by coating on one surface of the base layer and then drying and / or curing.

The method of applying the light diffusion layer coating composition is not particularly limited. For example, gravure coating method, kiss coating method, die coating method, lip coating method, comma coating method, blade coating method, roll-to-roll coating method, knife coating method, spray coating method, bar coating method, spin coating method, or A dip coating method may be used, but is not limited thereto.

The drying method for the light diffusing layer coating composition is also not particularly limited. For example, hot air drying, infrared drying and microwave drying may be used.

The drying temperature may be adjusted in consideration of the boiling point of the liquid (eg, solvent) component included in the composition and the durability of the base layer. In one example, the temperature at which the drying is performed may be at least 50 ° C, at least 60 ° C, or at least 70 ° C, more specifically at least 80 ° C, at least 85 ° C, at least 90 ° C, at least 95 ° C, or at least 100 ° C. And the upper limit may be 150 degrees C or less, 140 degrees C or less, 130 degrees C or less, 120 degrees C or less, 110 degrees C or less, or 100 degrees C or less, for example.

The drying time is not particularly limited and may be in the range of several seconds to several tens of minutes or in the range of moisture. Although not particularly limited, drying may be performed, for example, for a time of 1 minute or more and 10 minutes or less, 5 minutes or less, or 3 minutes or less.

The method for curing the light diffusion layer coating composition is not particularly limited. For example, a method such as ultraviolet (UV) irradiation can be used. The wavelength, energy amount, and the like of the ultraviolet ray can be appropriately selected by those skilled in the art in consideration of the material to be used, and the like.

When the laminate in which the light diffusing layer is formed on one surface of the substrate layer is provided in the above manner, a roll-to-roll process may be used. A roll-to-roll process is a continuous process which transfers a process object using a some roll, and performs bonding, coating, etc. In this process, the object to be processed may have a thin sheet shape and undergo a process of being wound on or unrolled from a roll (or roller).

In the following, reference numerals R1, R2, R3, etc. used to describe winding and unwinding are for convenience of description, and they may be the same or different rolls.

In one example, the method may further comprise winding the laminate prepared in the first step onto a roll R1 before performing the second step. Since the wound laminate includes the light diffusing layer having the unevenness, static electricity can be suppressed at the time of peeling the substrate layer and the light diffusing layer even when the wound laminate is unwound. In addition, damage to the base layer may be minimized even in a wound state in which tension is applied through the surface roughness in the above range.

In one example, the state in which the laminate provided in the first step is wound on a roll R1 may be maintained for a predetermined time. In the case of a roll-to-roll process designed for mass production, the laminate can be wound up for several minutes, tens of minutes, hours or even days because of the need for continuous mass production of the laminate. The time for which the wound state is maintained is not particularly limited, and may be, for example, 5 minutes or more, 10 minutes or more, 30 minutes or more, or 1 hour or more, specifically 5 hours or more, 10 hours or more, 20 hours or more, It can be more than 24 hours, more than 48 hours.

In one example, the method may perform the second step by unwinding the wound laminate from the roll R1. That is, a process of applying the barrier layer coating composition on one side of the laminate opposite to one surface of the base layer on which the light diffusion layer is formed, and then drying the transferred laminate is carried out.

Drying for the barrier layer coating composition may be the same as described above for drying for forming the light diffusion layer.

In one example, the method may further include winding the light diffusing barrier film provided in the second step on a roll R2 and maintaining the wound state for a predetermined time. The roll-to-roll process, which is designed to be mass-produced, can remain wound on the roll for several minutes, tens of hours, hours or days, for example, due to the need for continuous mass production of the barrier film or its components. The time for which the wound state is maintained is not particularly limited and may be, for example, 5 minutes or more, 10 minutes or more, 30 minutes or more, or 1 hour or more, specifically 5 hours or more, 10 hours or more, 20 hours or more, It can be more than 24 hours, more than 48 hours. After winding, a process for curing the dried barrier layer (coating composition) is performed.

In one example, the method may further comprise unwinding the wound light diffusing barrier film from the roll R2 and curing the polysilazane layer. Through the curing, it is possible to secure the compactness of the barrier layer, and more excellent barrier properties may be realized.

Curing of the barrier layer may be performed by light irradiation (for example, UV light irradiation) or plasma treatment. UV irradiation can be done in the same manner as described above.

In one example, curing of the barrier layer, that is, curing of the polysilazane layer, may be accomplished by plasma treatment.

Plasma treatment generates a plasma in an atmosphere containing a plasma generating gas such as Ar, and injects cations in the plasma to the polysilazane layer. The plasma may be generated by, for example, an external electric field or a negative high voltage pulse. have. This plasma treatment can be performed using a known apparatus.

Plasma treatment for forming the cured layer may be performed while injecting discharge gas Ar and oxygen in a predetermined processing space. More specifically, the plasma treatment may be performed under the following conditions.

In one example, the plasma treatment may be performed under a predetermined power density. Specifically, the power density per unit area of the electrode during the plasma treatment may be about 0.05 W / cm ² or 0.10 W / cm ^{2 or} more. In another example, the power density is about 0.2 W / cm ² or more, about 0.3 W / cm ² or more, about 0.4 W / cm ² or more, about 0.5 W / cm ² or more, about 0.6 W / cm ² or more, about 0.7 W / cm ² or more, about 0.8 W / cm ² or more, or about 0.9 W / cm ^{2 or} more. Within the range of satisfying the power density, in the case of the positive electrode, as the power density increases, the degree of plasma treatment may be increased for a short time, and the degree of denaturation of polysilazane due to high voltage application may be increased. In the case of a negative electrode, an excessively high power density may cause damage to the substrate layer due to high voltage. In view of this, the upper limit of the power density may be about 2 W / cm ² or less, 1.5 W / cm ² or less, or 1.0 W It may be less than / cm ² .

In one example, when having the power density, the treatment energy during the plasma treatment, which is determined by the product of the power density and the treatment time, may be 50 J / cm ² or less. Specifically, the energy may be 45 J / cm ² or less, 40 J / cm ² or less, 35 J / cm ² or less, 30 J / cm ² or less, 25 J / cm ² or less, or 20 J / cm ² or less, The lower limit may be 5 J / cm ² or more, 10 J / cm ² or more, or 15 J / cm ² or more.

In one example, the plasma treatment may be performed under a predetermined process pressure. Specifically, the process pressure during the plasma treatment may be 350 mTorr or less. In the case of the positive electrode, the lower the process pressure, the easier the securing of the mean free path, and thus the plasma treatment can be performed without energy loss due to collision with gas molecules. For example, the process pressure is 340 mTorr or less, 330 mTorr or less, 320 mTorr or less, 310 mTorr or less, 300 mTorr or less, 290 mTorr or less, 280 mTorr or less, 270 mTorr or less, 260 mTorr or less, 250 mTorr or less, 240 mTorr or less 230 mTorr or less, 220 mTorr or less, 210 mTorr or less, or 200 mTorr or less. On the other hand, in the case of the negative electrode, the lower the process pressure, the less gas molecules, so a high voltage and power may be required to generate a plasma. Since the high voltage and the high power may cause damage to the substrate layer, for example, The lower limit is at least 50 mTorr, at least 60 mTorr, at least 70 mTorr, at least 80 mTorr, at least 90 mTorr, at least 100 mTorr, at least 110 mTorr, at least 120 mTorr, at least 130 mTorr, at least 140 mTorr, at least 150 mTorr, at least 160 mTorr, It may be at least 170 mTorr, at least 180 mTorr or at least 190 mTorr. The pressure may be a pressure at the start of the process and may be maintained within this range even during the process.

When using the discharge gas (Ar) and oxygen as the process gas, the vapor pressure of oxygen in the processing space may range from 20 to 80%. The oxygen vapor pressure refers to the injection flow rate percentage of the oxygen injected to the total flow rate of the gases injected into the processing space. For example, when the plasma treatment is performed while Ar and O ₂ are injected at a flow rate of A sccm and B sccm, the vapor pressure of oxygen may be calculated to be 100 × B / (A + B).

The plasma treatment time may be appropriately adjusted at a level that does not impede the barrier property of the film. For example, the plasma treatment may be performed for a time of about 10 seconds to about 10 minutes.

In addition, as described above, the light diffusing barrier film may further include a hard coating layer. The coating, drying, and / or drying for the light diffusion layer coating composition may be equally applied to hard coating layer formation.

In one example, the hard coat layer may be made simultaneously or upon coating with the light diffusing layer.

In another example, the method includes winding the laminate prepared in the first step onto a roll R1 'before performing the second step; The method may further include preparing a second laminate by forming a hard coat layer while unwinding the laminate from the roll R1 ′. Subsequently, the method may be performed by winding the second laminate having the hard coating layer on the roll R1 ″ and unwinding the laminate from the roll R1 ″.

In addition, as described above, the light diffusing barrier film may include a plurality of sub barrier layers. For example, the light diffusing barrier film may have a structure in which a first sub barrier layer and a second sub barrier layer are sequentially stacked. At this time, the first sub barrier layer is located closer to the base layer than the second sub barrier layer (see FIG. 2 or FIG. 4). In this case, as described above, the second sub-barrier layer coating composition is applied to the outer side of the first sub-barrier layer in the light-diffusion barrier film F ′ obtained after curing of the first sub-barrier layer. The step, and the step of curing it, may be further performed. The second sub-barrier layer formation may be made in a roll-to-roll manner. As described above, the barrier film F ′ may sequentially include a light diffusion layer, a base layer, and a first sub barrier layer, or may include a light diffusion layer, a base layer, a hard coating layer, and a first sub barrier layer. It may be included sequentially.

In one example, the barrier film F ′ may be wound on a roll R3 prior to application to the second sub barrier layer coating composition. In addition, coating, drying, and curing of the second sub-barrier layer coating composition may be performed on the barrier film F ′ unwound from the roll R3. As a result, a light diffusing barrier film F ″ including at least a light diffusing layer, a base layer, a first sub barrier layer, and a second sub barrier layer may be manufactured. As described above, the barrier film F ″ may further include a hard coat layer between the substrate layer and the first sub barrier layer, and the related process is as described above.

According to an example of the present application, since the damage of the barrier film can be prevented during the roll-to-roll process, a light diffusing barrier film having excellent barrier property against gas or moisture can be provided. In addition, according to an example of the present application, there is an advantage that the film manufacturing process is simplified, and the film is thinned and large in area.

1 to 4 schematically show the structure of a light diffusing barrier film according to an embodiment of the present application.

Reference numerals used in the drawings are as follows.

10: barrier layer

11: first sub barrier layer

12: second sub barrier layer

20: substrate layer

30: light diffusion layer

40: hard coating layer

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

<Measurement method>

The physical properties compared with respect to the following Examples and Comparative Examples films were measured as follows.

How to measure surface roughness

The surface roughness of the light diffusion layer surface was measured by a non-contact (vibrating) method using an AFM (atomic force microscope) equipment, for example, XE7 equipment from Park Science.

Sheet resistance measurement method

The prepared light-diffusion barrier film was cut to have a width of 10 cm and a length of 10 cm to prepare a specimen. Subsequently, using a sheet resistance meter (Hyresta-UP MCP-HT450, Mitsubishi Chemical Co., Ltd.), the electrode of the meter was pressed at a pressure of 2 kgf, and the sheet resistance was measured at an applied voltage of 500 V. The three points in the width direction of each specimen were measured for 10 seconds and the average value was taken.

How to measure moisture permeability

(1) Water permeability (10 ^-3 g / m ² day)

As a water permeability of the light diffusing barrier film finally prepared in Examples and Comparative Examples, it was measured using AQUATRAN 2 (MOCON) under 38 ℃ and 100% relative humidity.

(2) Moisture permeability change rate (%)

It was calculated according to the following formula.

[Equation]

Moisture permeability change rate (%) = {(B-A) / A} × 100

In the above formula, A omits the blocking procedure (see Examples 1 to 4) in each of Examples and Comparative Examples, and the moisture permeability of the finally prepared light diffusing barrier film (in Tables 1 and 2, ① moisture permeability) ), And B is the moisture permeability (in Tables 1 and 2, ② moisture permeability) of the light diffusing barrier film finally prepared according to each Example and Comparative Example. Each moisture permeability (A, B) is measured using AQUATRAN 2 (MOCON) at 38 ℃ and 100% relative humidity conditions.

How to measure haze and light transmittance

Haze and light transmittance of the prepared light diffusing barrier film were measured using a haze meter (hm-150, Murakami color research laboratory).

<Examples and Comparative Examples>

Example 1

1) forming a light diffusion layer on the base layer

A superdiffusion layer coating composition was prepared comprising 20 parts by weight of the photocurable resin relative to the solvent. Specifically, 80 parts by weight of pentaerythritol triacrylate (PETA) and 20 parts by weight of dipentaerythritol hexaacrylate (DPHA) were dissolved in a solvent (propylene glycol monomethyl ether). 4 parts by weight of a polymerization initiator (Irgacure 127, Ciba), 5 parts by weight of an antistatic agent (ELEC ME-2, Kao), and 10 parts by weight of particles (MX80, Soken) having an average particle diameter of 0.8 µm were added to the solution. The light diffusion layer composition was prepared.

A 50 μm-thick polyethylene terephthalate (PET) film (T600E50, Mitsubishi Co., Ltd.) was applied to one surface by a bar coat (using # 5 bar). Then, the obtained coating film was heat-dried at 100 degreeC for 2 minutes, and then irradiated with vacuum UV light using a UV light irradiation line, and formed the light-diffusion layer which has surface roughness (Rt) shown in the following table | surface.

2) Hard coating layer formation

80 parts by weight of pentaerythritol triacrylate (PETA) and 20 parts by weight of dipentaerythritol hexaacrylate (DPHA) were dissolved in a solvent (propylene glycol monomethyl ether) on the opposite side of the base film on which the light diffusion layer was formed. 4 parts by weight of a polymerization initiator (Irgacure 127, Ciba) was added to the solution to prepare a hard coating composition. After the coating film was formed on the surface where the light diffusion layer of the base film was not formed by the bar coat method, the film was heated and dried at 100 ° C. for 2 minutes, and then subjected to UV light irradiation to form a hard coating layer having a thickness of 1 μm.

3) barrier layer formation

After dissolving polysilazane (trade name NL120) in dibutyl ether, the solution was applied to the surface on which the base film of the hard coat layer was not formed by the bar coat method. The obtained coating film was heat-dried at 70 degreeC for 1 minute, and 130 degreeC for 2 minutes, and the barrier layer of thickness 150nm was formed (uncured barrier layer formation).

4) Blocking

The film having a lamination structure of 'light diffusion layer / substrate layer / hard coating layer / barrier layer' formed through the above-described processes 1) to 3) is called a first film F ₁ . In addition, a second film (F ₂ ) was further manufactured by the same process as the manufacturing of the first film (F ₁ ). The first and second films F ₁ and F ₂ are stacked by applying a load of 18 kg on the barrier layer surface of the first film F ₁ to abut the uneven surface of the light diffusion layer of the second barrier film F ₂ . The load was maintained for 24 hours. At this time, the first and second films (F ₁ , F ₂ ) is in the form of a sheet, the size of the area in contact is 10 cm x 10 cm. This process simulates the process when the light diffusing barrier film is wound in a roll-to-roll process.

5) Hardening of the barrier layer (first barrier layer)

The barrier layer was cured by performing a plasma treatment on the first film F ₁ . The plasma treatment was performed under about Ar: O 2 = 1: 1 flow rate (sccm basis), about 138 mTorr pressure, about 0.27 W / cm ² power and about 20 J / cm ² energy conditions. The light diffusable barrier film of Example 1 was prepared by finishing barrier layer hardening.

Example 2

An optical barrier film of Example 2 was prepared in the same manner as in Example 1, except that the coating bar was used differently when coating the light diffusion layer composition (using # 4 bar). Surface roughness (Rt) values of the light diffusion layer are shown in the following table.

Example 3

An optical barrier film of Example 3 was prepared in the same manner as in Example 1, except that no antistatic agent was used and a coating bar was used when coating the light diffusing layer composition (using # 3bar). Surface roughness (Rt) values of the light diffusion layer are shown in the following table.

Example 4

Example 1 except that no antistatic agent was used in the optical acid layer composition and particles having an average particle diameter of 5 μm (GB05S, manufactured by Aica Kogyo) instead of the particles used in Example 1 (coated with # 5 bar), In the same manner, the optical barrier film of Example 4 was prepared. Surface roughness (Rt) values of the light diffusion layer are shown in the following table.

Example 5

An optical barrier film of Example 5 was prepared in the same manner as in Example 4, except that the coating bar was used differently when using the light diffusing layer composition (using # 4bar). Surface roughness (Rt) values of the light diffusion layer are shown in the following table.

Example 6

The light diffusing barrier film of Example 6 was prepared in the same manner as in Example 4, except that the coating bar was used differently when coating the light diffusing layer composition (coating with # 3 bar). Surface roughness (Rt) values of the light diffusion layer are shown in the following table.

Example 7

3) The light diffusing barrier film of Example 7 was prepared in the same manner as in Example 6, except that the thickness of the heat-dried barrier layer was 80 nm instead of 150 nm. Surface roughness (Rt) values of the light diffusion layer are shown in the following table.

Example 8

The polysilazane composition was coated and dried in the same manner as 3) described in Example 1 on the cured barrier layer (first barrier layer) of the optical barrier film prepared in Example 3. Thereafter, the light diffusing barrier of Example 8 comprising the first barrier layer (cured) and the cured second barrier layer (cured) (thickness 150 nm) through 4) and 5) described in Example 1 A film was prepared. Surface roughness (Rt) values of the light diffusion layer are shown in the following table.

Comparative Example 1

Instead of the particles used in Example 1, particles having an average particle diameter of 20 μm (MX-2000, Soken) were used, a light diffusion layer coating composition containing 50 parts by weight of a photocurable resin relative to a solvent, and an antistatic agent were used. The light-diffusing barrier film of Comparative Example 1 was prepared in the same manner as in Example 1, except that no coating was performed and knife coating was used to coat the light-diffusion layer composition. Surface roughness (Rt) values of the light diffusion layer are shown in the following table.

Comparative Example 2

A light diffusing barrier film of Comparative Example 2 was prepared in the same manner as in Example 1, except that no antistatic agent was used in the light diffusing layer coating composition. Surface roughness (Rt) values of the light diffusion layer are shown in the following table.

Comparative Example 3

A light diffusing barrier film of Comparative Example 3 was prepared in the same manner as in Example 2, except that no antistatic agent was used in the light diffusing layer coating composition. Surface roughness (Rt) values of the light diffusion layer are shown in the following table.

Comparative Example 4

3) An optically acidic barrier film of Comparative Example 4 was prepared in the same manner as in Comparative Example 1, except that the thickness of the heat-dried barrier layer was 80 nm instead of 150 nm.

Light Diffusion Layer Rt (㎛) * Light Diffusion Layer Surface Resistance (Ω / sq) Moisture permeability Moisture Permeability Change (%) ** ① Without blocking (10 ^-3 g / m ² day) ② When performing blocking (10 ^-3 g / m ² day) Example 1 0.025 8.3 x 10 ⁹ 3.24 3.38 4.32 Example 2 0.08 7.3 x 10 ⁹ 3.31 2.95 10.9 Example 3 0.13 Not measurable *** 2.87 2.43 15.3 Example 4 1.34 Not measurable 3.16 3.56 12.7 Example 5 3.52 Not measurable 3.35 3.18 5.1 Example 6 5.13 Not measurable 2.95 3.64 23.4 Comparative Example 1 8.34 Not measurable 3.48 12 244.8 Comparative Example 2 0.025 Not measurable 3.72 14 276.3 Comparative Example 3 0.08 Not measurable 3.25 18 453.8 * The R (t) of the light diffusion layer is affected by particle size, coating thickness and particle aggregation. ** The percentage change in moisture permeability is based on the value of ①,% between ① and ② values. Rate of change *** Not measurable: The limit sheet resistance (10 ¹² Ω / sq) of the measuring instrument is exceeded.

Looking at Examples 3 to 6, it can be seen that the sheet resistance is large because no antistatic agent is used in forming the light diffusion layer. However, the rate of change in moisture permeability shows that the barrier layer is less damaged in these examples. This is because since the surface roughness of the light diffusion layer is sufficient, damage due to static electricity generation at the time of interfacial peeling can be avoided. In Comparative Example 1, since the surface unevenness is too large, the barrier layer is damaged by the unevenness, and the rate of change of moisture permeability is large.

On the other hand, when comparing the Examples 1 to 2 and Comparative Examples 2 to 3, even if the surface roughness of the light diffusing layer is 0.1 ㎛ or less, there is a limit in reducing the interface adhesion between the light diffusing layer and the barrier layer even if the surface irregularities Therefore, it can be seen that it is necessary to adjust the sheet resistance of the light diffusion layer to a predetermined range.

Light Diffusion Layer Rt (㎛) * Light Diffusion Layer Surface Resistance (Ω / sq) Moisture permeability Moisture Permeability Change (%) ** ① Without blocking (10 ^-3 g / m ² day) ② When performing blocking (10 ^-3 g / m ² day) Example 7 5.13 Not measurable 11.86 13.38 12.8 Comparative Example 4 8.34 Not measurable 11.86 347.74 2,832 * The R (t) of the light diffusion layer is affected by particle size, coating thickness and particle aggregation. ** The percentage change in moisture permeability is based on the value of ①,% between ① and ② values. Rate of change *** Not measurable: exceeding the limit sheet resistance (10 ¹² Ω / sq) of the measuring instrument

From Table 2, it is confirmed that Comparative Example 4 has a high moisture permeability (②) and a moisture permeability change rate (%). In particular, the moisture permeability change rate is very high compared to that of the embodiment. This means that when the surface roughness Rt of the light diffusion layer is too large, the barrier layer is damaged by the unevenness of the light diffusion layer in the wound state. In other words, the results of Example 7 and Comparative Example 4 suggest that the barrier layer damage prevention in the roll-to-roll process is important even if the thickness of the barrier layer which has the greatest influence on the moisture permeability of the film is the same. do.

Barrier layer Moisture permeability (10 ^-3 g / m ² day) Haze (%) Light transmittance (%) Example 3 fault 2.43 86.5 89.1 Example 8 Second floor 0.02 86.6 86.5

Table 3 shows that water permeability is lowered as a plurality of barrier layers are included (ie, sub barrier layer 2 or more), regardless of blocking. Specifically, even if the second barrier layer is further formed thereon after the blocking is performed on the first barrier layer, it can be confirmed that according to the embodiment of the present application, excellent moisture barrier property (low moisture permeability) is secured. .

Claims (22)

Sequentially including a light diffusion layer, a base layer, and a barrier layer, Opposite side (S ₁ ) of one surface of the optical diffusion layer facing the substrate layer has a surface roughness (Rt) has a concave-convex in the range of 0.1 to 6 ㎛. The light diffusing barrier film of claim 1, wherein a water permeability change rate calculated by the following formula satisfies 30% or less: [Equation] Moisture permeability change rate (%) = {(B-A) / A} × 100 In the above formula, A is the moisture permeability of the light diffusing barrier film (F ₁ ); B is a light diffusion barrier film (F ₁₎ of the two films (F _1, F ₂₎ was added to the light-diffusing layer constant load to uneven surface is flush with the light diffusion barrier film (F ₂₎ on the barrier layer surface of the The moisture permeability of the light diffusing barrier film F ₁ measured after the constant load is maintained for 24 hours; The light diffusing barrier films (F ₁ , F ₂ ) have the same configuration; The moisture permeability (A, B) is measured using AQUATRAN 2 (MOCON Co., Ltd.) at 38 ℃ and 100% relative humidity conditions.) Sequentially including a light diffusion layer, a base layer, and a barrier layer, One surface S ₁ opposite the one surface of the optical acid layer facing the substrate layer has a surface roughness Rt of 0.02 μm or more and less than 0.1 μm, and the sheet resistance of the optical acid layer one surface S ₁ having the surface roughness is 10 ¹⁰ Ω /. A light diffusing barrier film of less than or equal to sq. The light diffusing barrier film of claim 3, wherein the light diffusing layer comprises an antistatic agent. The light diffusing barrier film of claim 3, wherein a water permeability change rate calculated by the following formula satisfies 30% or less: [Equation] Moisture permeability change rate (%) = {(B-A) / A} × 100 In the above formula, A is the moisture permeability of the light diffusing barrier film (F ₁ ); B is a light diffusion barrier film (F ₁₎ of the two films (F _1, F ₂₎ was added to the light-diffusing layer constant load to uneven surface is flush with the light diffusion barrier film (F ₂₎ on the barrier layer surface of the The moisture permeability of the light diffusing barrier film F ₁ measured after the constant load is maintained for 24 hours; The light diffusing barrier films (F ₁ , F ₂ ) have the same configuration; The moisture permeability (A, B) is measured using AQUATRAN 2 (MOCON Co., Ltd.) at 38 ℃ and 100% relative humidity conditions.) 4. The light diffusing barrier film of claim 1 or 3, wherein the barrier layer comprises one or more sub barrier layers. The light diffusing barrier film of claim 6, wherein the sub barrier layer has a thickness in a range of 20 to 400 nm. The light diffusing barrier film according to claim 1 or 3, wherein the barrier layer or the sub barrier layer is a cured layer of a polysilazane layer or a polysilazane layer. The light diffusing barrier film of claim 8, wherein the polysilazane has a unit represented by Formula 1 below: [Formula 1]

R 1, R 2 and R 3 in Formula 1 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsilyl group, an alkylamide group or an alkoxy group. The light diffusing barrier film according to claim 1 or 3, wherein the light diffusing layer has a thickness of 20 µm or less. The light diffusing barrier film of claim 10, wherein the light diffusing layer is formed from a coating composition comprising 0.1 part by weight or more of particles with respect to 100 parts by weight of the curable resin. The light diffusing barrier film of claim 1, wherein the light diffusing layer, the base layer, and the barrier layer directly contact each other. An electrical or electronic device comprising the light diffusing barrier film of claim 1. A first step of providing a laminate including a substrate layer and a light diffusion layer, the surface roughness Rt of one surface S ₁ opposite to one surface of the optical diffusion layer facing the substrate layer being in the range of 0.1 to 6 μm; And And a second step of forming a polysilazane layer by applying a barrier layer coating composition on one surface of the substrate layer on which the light diffusion layer is formed and then drying the coating layer. An optical scattering layer including a substrate layer and a light diffusing layer, the surface roughness Rt of one surface S ₁ opposite to the optical scattering layer facing the substrate layer is 0.02 or more and less than 0.1 µm, and has one surface of the optical scattering layer (S). A first step of providing a laminate having a sheet resistance of ₁ ) of 10 ¹⁰ Ω / sq or less; And And a second step of forming a polysilazane layer by applying a barrier layer coating composition on one surface of the substrate layer on which the light diffusion layer is formed and then drying the coating layer. The method of claim 14 or 15, wherein the light diffusion layer coating composition comprising 0.1 parts by weight or more of particles relative to 100 parts by weight of the curable resin is applied on one surface of the substrate layer to prepare a light diffusion barrier film to form a light diffusion layer Way. The method of claim 14 or 15, wherein the barrier layer coating composition comprises a polysilazane represented by Formula 1 below: [Formula 1]

R 1, R 2 and R 3 in Formula 1 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsilyl group, an alkylamide group or an alkoxy group. The method of claim 16, wherein a roll-to-roll process is used, Before performing the second step, the method of manufacturing a light diffusing barrier film further comprising the step of winding the laminate prepared in the first step (roll: R1). 19. The method of claim 18, wherein the wound laminate is unwound from the roll (R1) to perform the second step. 20. The method of claim 19, further comprising winding the light diffusing barrier film provided in the second step on a roll R2 and maintaining the wound state for at least 1 hour. . 21. The method of claim 20, further comprising unwinding the wound light diffusing barrier film from the roll (R2) and curing the polysilazane layer. The method of claim 21, wherein the curing of the polysilazane layer is performed by plasma treatment or UV light irradiation.

Images