KR102168964B1 - Barrier film having anti-glare function and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a highly transparent barrier film having an anti-glare function and a method for manufacturing the same, wherein the barrier film according to an embodiment of the present invention comprises a polymer film substrate made of a polymer molded product, a first deposited on one surface of the polymer film substrate. An inorganic film layer and a second inorganic film layer deposited on one surface of the first inorganic film layer, wherein a refractive index (n1) of the first inorganic film layer is greater than a refractive index (ns) of the polymer film substrate, and the second inorganic film layer The refractive index (n2) of is characterized in that it is smaller than the refractive index (ns) of the polymer film substrate.
In addition, the barrier film manufacturing method according to the present invention is a film substrate preparation step of preparing a polymer film substrate, and a first inorganic film layer and a second inorganic film layer are sequentially vacuum deposited on one surface of the polymer film substrate prepared in the film substrate preparation step. In the film forming step, an organic film layer forming step of coating an organic film layer on one surface of the second inorganic film layer vacuum-deposited in the film forming step, and an anti-glare layer forming step of forming an anti-glare layer on the polymer base film or the organic film layer. It characterized in that it includes.
As described above, the barrier film having a continuous layered structure has the advantage of satisfying the functions of excellent moisture barrier properties and high transparent barrier film by controlling the refractive index of the first inorganic layer and the second inorganic layer, and the barrier film manufacturing method proceeds in the same order as above. Silver has the advantage of improving work efficiency by reducing process time and material loss through simplification of the process.

Description

Highly transparent barrier film with anti-glare function and its manufacturing method {BARRIER FILM HAVING ANTI-GLARE FUNCTION AND MANUFACTURING METHOD THEREOF}

The present invention relates to a highly transparent barrier film having an anti-glare function and a method of manufacturing the same, and more particularly, a first inorganic film and a second inorganic film are laminated to form a continuous layer to reduce the degree of moisture permeation and to reduce the overall thickness. It relates to a reduced barrier film and a method of manufacturing the same.

Recently, as portable devices adopting e-ink, OLED, and QD (Quantum Dot) Display have become popular and their scope of application has been expanded, interest and demand for moisture permeation prevention films, so-called barrier films, are increasing.

The barrier film is a type of technology for protecting internal electric devices of electronic devices such as displays, and conventionally, a technology for protecting internal electric devices by using a glass plate as a substrate material or a cover plate has been limited. However, in the case of glass, not only is it heavy, but also has a problem that is fragile, and in recent years, attempts to replace glass with plastics have been actively conducted. In the case of a film formed of plastic or the like, improvement in water resistance and gas barrier properties are required compared to the case of glass, and a barrier film having excellent gas barrier properties and light transmittance is required.

In addition, the gas barrier film to be attached to the front of the flexible display must be close to colorless, which is highly transparent and does not interfere with the color reproducibility of the OLED light source, as well as better blocking moisture, and anti-glare treatment is required to increase user readability. Can be. In particular, when electronic devices are used outdoors, the resolution of the display decreases due to the reflection of light and the battery efficiency decreases, so its preservation function is required. Research on a barrier film having an anti-glare (ANTI-GLARE) function and Development is required.

As a technology for such a barrier film, Korean Patent No. 10-1624829 discloses a barrier film including a base layer, a first dielectric layer, an inorganic material layer, and a second dielectric layer in sequence. In the above registered patent, the first dielectric layer and the second dielectric layer are formed as organic or organic-inorganic composite layers to prevent substances such as moisture or oxygen from penetrating into the interior. However, the above registered patent has a structure in which an inorganic layer is provided between the organic layer and the organic layer, so that the barrier film must be manufactured in the order of organic-inorganic-organic processes, so the production lead time is lengthened by repetition of the organic-inorganic process and the loss between operations is also increased. There is a big drawback.

On the other hand, the permeation of moisture and gas from a low-density organic polymer film substrate is difficult to use as a display protective layer because moisture and gas particles are easily diffused into the substrate by adsorption and absorption concentration gradient at the substrate interface. In order to have excellent gas and moisture barrier properties, inorganic film coating is required.Inorganic film such as silicon oxide (SiOx) through wet coating and dry coating on the substrate and organic film by wet coating on the surface of the inorganic film are formed. An existence-non-organic hybrid method can be applied. In the case of such a hybrid method, there is a problem that productivity is degraded due to the complexity of the process requiring the use of different coating facilities and loss between operations.

(Document 0001) Korean Patent Registration No. 10-1624829 (Registration Date: 16.05.20.) (Document 0002) Korean Patent Registration No. 10-1329218 (Registration Date: 13.11.07.) (Document 0003) Korean Laid-Open Patent No. 10-2016-0020834 (Publication Date: 16.02.24) (Document 0004) Japanese Laid-Open Patent No. 2004-056036 (Publication Date: 06.03.02.)

An object of the present invention invented in consideration of the above points is to provide an anti-glare function to a barrier film having excellent moisture barrier properties and high transmittance in visible light, thereby expanding its application and use to electronic devices such as displays. It is to provide a highly transparent barrier film having an anti-glare function with high production efficiency by increasing the production process and simplifying the manufacturing process.

The highly transparent barrier film having an anti-glare function according to the present invention for achieving the above object is a polymer film base made of a polymer molded material, a first inorganic film layer formed by deposition on one side of the polymer film base, and a first inorganic film layer deposited on one side of the first inorganic film layer. Including a second inorganic film layer, the refractive index (n1) of the first inorganic film layer is greater than the refractive index (ns) of the polymer film substrate, and the refractive index (n2) of the second inorganic film layer is less than the refractive index (ns) of the polymer film substrate Is formed.

Also, the total thickness of the first inorganic layer and the second inorganic layer may be 100 nm or more.

In addition, the optical thickness of the first inorganic layer is 0.14λ or more and 0.60λ or less, the physical thickness is 42 nm or more and 186 nm or less, the optical thickness of the second inorganic layer is 0.22λ or more and 0.29λ or less, and the physical thickness is 80 nm or more and 110 nm or less. And, as a material of the first inorganic layer, aluminum oxide (Al2O3) or silicon nitride oxide (SiON) having a refractive index of 1.8 or less may be used, and silicon oxide (SiO2) may be used as the material of the second inorganic layer.

In addition, the optical thickness of the first inorganic layer is 0.37λ or more and 0.57λ or less, the physical thickness is 99 nm or more and 153 nm or less, the optical thickness of the second inorganic layer is 0.22λ or more and 0.25λ or less, and the physical thickness is 80 nm or more and 95 nm or less. And, silicon nitride (SiN) having a refractive index of 1.8 or higher may be used as the material of the first inorganic layer, and silicon oxide (SiO2) may be used as the material of the second inorganic layer.

In addition, it may further include an organic film layer laminated on one side of the second inorganic film layer and an anti-glare layer laminated on one side of the organic film layer or the polymer base film to diffusely reflect light.

The barrier film manufacturing method according to an embodiment of the present invention is to sequentially vacuum a first inorganic film layer and a second inorganic film layer on one surface of the polymer film substrate prepared in the film substrate preparation step of preparing the polymer film substrate, and the film substrate preparation step. A film forming step of evaporation, an organic film layer forming step of coating an organic film layer on one side of the second inorganic film layer vacuum-deposited in the film forming step, and an anti-glare layer forming step of forming an anti-glare layer on the polymer base film or organic film layer. .

In addition, in the film forming step, the first inorganic film layer and the second inorganic film layer may be continuously deposited by using a roll-to-roll sputtering method or an evaporation method.

According to an embodiment of the present invention, it is possible to realize a high transparent barrier film by lowering the average reflectance in visible light while having excellent moisture barrier properties of 1.0X10 ^-2 g/m2/day or less in a predetermined optical thickness range.

In addition, it is possible to simplify the process by using only one organic layer, and there is an effect of reducing manufacturing cost.

1 is a cross-sectional view showing a highly transparent barrier film according to an embodiment of the present invention.
2 is a graph showing an optical thickness range of a first inorganic layer and a second inorganic layer according to an embodiment of the present invention.
3 is a graph comparing reflectance of each wavelength of a first inorganic film layer and/or a second inorganic film layer formed on a polymer film substrate according to an embodiment of the present invention.
4 and 5 are graphs showing changes in average reflectance in visible light according to an optical thickness of a first inorganic layer according to an embodiment of the present invention.
6 and 7 are cross-sectional views showing a highly transparent varistor film including an organic layer and an anti-barrier layer according to an embodiment of the present invention.
8 is a flow chart showing a method of manufacturing a highly transparent barrier film according to an embodiment of the present invention.

In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted.

Since the embodiments according to the concept of the present invention can apply various changes and have various forms, specific embodiments will be illustrated in the drawings and described in detail in the present specification or application. However, this is not intended to limit the embodiments according to the concept of the present invention to a specific form of disclosure, and it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

The terms used in the present specification are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise" or "have" are intended to designate the presence of a set feature, number, step, action, component, part, or combination thereof, but one or more other features or numbers It is to be understood that the possibility of addition or presence of, steps, actions, components, parts, or combinations thereof is not preliminarily excluded.

Hereinafter, the present invention will be described in detail.

The refractive index described in the present invention means the refractive index at the reference wavelength of 550 nm, which is the center wavelength of visible light.

When coating aluminum oxide (refractive index 1.67~1.78) and silicon nitride (refractive index 1.70~2.03), etc., which have good barrier properties in a dry type, it is greater than the refractive index of a polymer substrate, and the reflectance is high at a certain thickness to increase gas and moisture barrier properties. There is a problem with this falling.

When two inorganic film layers with different refractive indices are sequentially formed and the optical thickness of the inorganic film layer is 1/4 wavelength, the higher the optical thickness of the high refractive inorganic film layer than the low refractive inorganic film layer, the greater the reflectivity, and the high refractive inorganic film layer is 1/4 When the wavelength is approached, the reflectance is several times higher than that of the polymer substrate. On the contrary, when the low refractive inorganic layer approaches the optical thickness of 1/4 wavelength, the thickness of the high refractive inorganic layer decreases, and the moisture barrier effect decreases compared to the case where the high refractive inorganic layer is thick. Is done.

In addition, even if the barrier film is manufactured only from the low-refractive inorganic film, not only the moisture barrier effect is reduced, but also the optical properties are worse than when the high-refractive inorganic film and the low-refractive inorganic film are coated.

Optical design for minimizing reflectance for the purpose of enhancing optical properties can be obtained when the difference between the admittance of the incident medium (air) and the admittance of the thin film is minimized. At this time, admittance is a physical quantity of a magnetic field and an electric field ratio, and is calculated from Equation 1 through a 2X2 characteristic matrix as follows.

[Equation 1]

Here, δ is the phase thickness, ns is the refractive index of the substrate, n is the refractive index of the thin film, B is the electric field, C is the magnetic field, and i is the imaginary number.

In order to be an anti-reflective coating, the condition that the admittance of the thin film and the admittance of the incident medium must be the same, that is, the admittance of the thin film must be equal to the refractive index of air (about 1.0), so it can be solved by an equation satisfying Y=1.

[Equation 2]

The refractive index of the substrate is greater than 1, and the phase thickness δ is π/2, and thus the optical thickness (nd) must satisfy 1/4λ, and the thin film refractive index (n) must be equal to the square root of the refractive index (n _s ) of the substrate.

Since the refractive index of a typical polymer film substrate is in the range of 1.4 or more and 1.7 or less, non-reflective coating is possible only by forming a thin film with a material having a refractive index of 1.3 or less, but the refractive index of general silicon oxide (SiO2) is between 1.45 and 1.47. Considering that, it is impossible to have an anti-reflection coating with a single thin film.

In consideration of the above points, the highly transparent barrier film according to the present invention sequentially forms a first inorganic film layer 4 having a higher refractive index than a polymer film substrate and a second inorganic film layer 5 having a lower refractive index to a constant optical thickness, and Provides a barrier film with high transmittance and excellent moisture barrier properties of 1.0X10-2g/m2/day or less.

1 is a cross-sectional view showing a highly transparent barrier film according to an embodiment of the present invention.

1, the barrier film according to the present invention includes a polymer film base 10, a first inorganic film layer 4 formed by deposition on one surface of the polymer film base 10, and the first inorganic film layer 4 It includes a second inorganic film layer 5 deposited on one side, and the refractive index n1 of the first inorganic film layer 4 is greater than the refractive index ns of the polymer base film 10, and the second inorganic film layer The refractive index (n2) of (5) is characterized in that it is smaller than the refractive index (ns) of the polymer base film 10.

The first inorganic film layer 4 and the second inorganic film layer on one or both surfaces of the polymer film base 10 made of the organic polymer molded product in this embodiment, that is, at least one surface of the polymer film base 10 5) It is constructed by stacking in this order. The first inorganic film layer 4 and the second inorganic film layer 5 may be formed by sequentially vacuum deposition on the polymer film substrate 10.

The polymer film substrate 10 includes a first substrate film 1 made of an organic polymer molded product. As the first base film 1, various plastic films or sheets having transparency can be used. Plastic films and sheets can be used, for example, those containing polyester, polycarbonate, polyimide, polyolefin, polyamide or polyacrylate as a resin component. Among these, polyester is particularly preferable, and polyethylene terephthalate is more preferable among polyester.

The polymer film support 10 may include an undercoat layer 2 provided on one side of the first base film 1 and a back coat layer 3 provided on the other side.

The undercoat layer 2 and the back coat layer 3 are whitening phenomenon in which oligomers, which may be involved in the deposition process, are deposited on the surface, and charging of the film surface due to friction in roll-to-roll fixing and static electricity. It prevents damage to the first base film 1 due to adhesion of foreign substances or electric shock.

Conductive polymer resin with a refractive index of about 1.4 to 1.6 as undercoat layer (2) and back coat layer (3), urethane resin containing at least one functional group such as carboxyl group, hydroxy group, and N-methylol group, acrylic resin, melamine resin , Alkyd resins, siloxane-based polymers, organosilane livestock products, etc. can be used, and inorganic substances such as SiOx (x = 1 to 2), Al2O3, MaF2, CaF2, BaF2, LaF2, NaF, TiO2, Nb2O5, ZrO2, or the above organic substances Using a mixture material of a resin and the inorganic material, a film can be formed by dry coating or wet coating.

In addition, in order to increase the adhesion between the polymer film base 10 and the first inorganic film layer 4, before forming the first inorganic film layer 4, plasma treatment, corona discharge treatment, and ultraviolet rays are applied to the surface of the polymer film base 10. An appropriate adhesion treatment such as irradiation may be performed.

The thickness of the polymer film substrate 10 is 10 μm to 250 μm, and the refractive index (ns) is in the range of 1.49 or more and 1.7 or less at a center wavelength of 550 nm in visible light, and primer layers and hard coating layers on one and both sides of the film substrate, etc. Regardless of the presence or absence of.

2 is a graph showing the optical thickness range of the first inorganic film layer 4 and the second inorganic film layer 5 according to an embodiment of the present invention. Specifically, the first inorganic layer 4 simulated using the following equations 4 and 5 as a random number of the refractive indices of the first inorganic layer 4 and the second inorganic layer 5 at a center wavelength (550 nm). ) And the optical thickness range of the second inorganic film layer 5 are shown.

3 is a graph comparing the reflectance of each wavelength of the first inorganic layer 4 and/or the second inorganic layer 5 formed on the polymer film substrate 10 according to an exemplary embodiment of the present invention. In FIG. 3, a polymer film substrate 10 and a first inorganic film layer 4 and a second inorganic film layer 5 formed on one surface of the polymer film substrate 10 in a predetermined optical thickness range, and the polymer film substrate 10 When a single layer of the first inorganic film layer 4 or the second inorganic film layer 5 is formed on one surface of the film substrate 10, the reflectance of each wavelength in visible light was compared.

2 to 3, the first inorganic film layer 4 and the second inorganic film layer 5 of the present invention include a first inorganic film layer 4 having high refractive properties and a second inorganic film layer having low refractive properties ( By manufacturing the barrier film with the optical thickness of 5) in a predetermined range, the required transmittance and moisture barrier properties are satisfied.

To this end, in the present invention, aluminum oxide or silicon nitride having high gas and moisture barrier properties is used as the first inorganic film layer 4, and silicon oxide having a lower refractive index than the polymer base film 10 is used as the second inorganic film layer 5 It may be sequentially stacked.

In addition, the refractive index (n1) of the first inorganic film layer 4 should be greater than the refractive index (ns) of the polymer film substrate 10 and greater than the refractive index (n2) of the second inorganic film layer 5.

The material of the first inorganic film layer 4 may be aluminum oxide (Al2O3, n:1.66-1.78), silicon nitride (Si3N4, n:1.95-2.05), and silicon nitride oxide (SiON, n:1.66-1.95). The refractive index (n2) of the second inorganic film layer 5 should be less than the refractive index (ns) of the polymer base film 10 and less than the refractive index (n1) of the first inorganic film layer 4, and As a material, silicon oxide (SiO2, n:1.44-1.47) or silicon nitride oxide (SiON, n:1.48-1.5) may be used, and the refractive index should be different as shown in Equation 3 below.

[Equation 3]

n2 <ns <n1

(ns: refractive index of the polymer base film 10, n1: refractive index of the first inorganic film layer 4, n2: refractive index of the second inorganic film layer 5)

In the condition of having two different refractive indices n1 and n2, each having a phase thickness of δ1 and δ2, Y(=C/B) is the same as Equation 4, where the wheremittance of the thin film is the wheremittance of the incident medium The equation for calculating the thickness of each thin film under the condition of 1 is shown in Equation 5.

[Equation 4]

[Equation 5]

In the present invention, in order to determine the range of the refractive indices (n1, n2, ns), the refractive index is a random number within the refractive index range of each of the first inorganic layer 4, the second inorganic layer 5, and the polymer film substrate 10. Then, a Monte Carlo simulation was performed to obtain the required optical thickness (nd) range of the first inorganic film layer 4 and the second inorganic film layer 5, and the power distribution for the optical thickness of the inorganic material was obtained. .

Table 1 shows the first inorganic layer 4 and the second inorganic layer 4 when the first inorganic layer 4 is thick (case 1) and when the second inorganic layer 5 is thick (case 2) at a reference wavelength of 550 nm. 5) shows the optical thickness range, which is as shown in FIG.

division Refractive index range Case 1 Case 2 Optical thickness(nd) Optical thickness(nd) Ieast maximum Ieast maximum Average Ieast maximum Average First inorganic layer 1.66 2.45 0.25λ 0.45λ 0.40λ 0.09λ 0.25λ 0.15λ Second inorganic layer 1.44 1.50 0.17λ 0.25λ 0.25λ 0.25λ 0.33λ 0.29λ

As shown in Table 1, in order to improve the barrier properties when the first inorganic layer 4 having high refractive index is thick (case 1) and when the second inorganic layer 5 having low refractive index is thick (case 2), 1 When the inorganic film layer 4 is thick (case 1), the optical thickness range of the first inorganic film layer 4 and the second inorganic film layer 5 is 0.25λ or more and 0.45λ or less for the first inorganic film layer 4 When the second inorganic film layer 5 is 0.17λ or more and 0.25λ or less, and the second inorganic film layer 5 is thick (case 2), the optical of the first inorganic film layer 4 and the second inorganic film layer 5 The thickness range of the first inorganic film layer 4 is 0.07λ or more and 0.25λ or less, and the second inorganic film layer 5 is 0.25λ or more and 0.34λ or less.

4 and 5 are graphs showing changes in average reflectance in visible light according to an optical thickness of a first inorganic layer according to an embodiment of the present invention. In FIG. 4, when the refractive index of the first inorganic layer 4 is 1.8 or less, the average reflectance in visible light is shown, and in FIG. 5, when the refractive index of the first inorganic layer 4 is 1.8 or more, the average reflectance in visible light is shown.

Table 1 shows the optical thickness range at a single wavelength (550 nm) in visible light, and the conditions having an average reflectance in visible light (380 nm to 760 nm) lower than that in the case of forming a single layer were obtained. The optical thickness range of the second inorganic film layer 5 is 0.17λ or more and 0.25λ or less, which is narrower than the optical thickness range of the first inorganic film layer 4, and there is a continuity of the optical thickness range between Case 1 and Case 2. Based on the optical thickness of the film layer 5, a simulation according to the change in the optical thickness of the first inorganic film layer 4 was additionally performed.

Accordingly, as shown in FIGS. 4 and 5, depending on the range of the refractive index of the second inorganic layer 5, when the refractive index of the first inorganic layer 4 is 1.8 or less or the refractive index of the first inorganic layer 1 is 1.8 In the above case, the optical thickness range of the first inorganic film layer 4 and the second inorganic film layer 5 having a reflectance lower than the lowest average reflectance when formed of a single layer of SiO 2, which is a material of the low reflection coating, can be obtained.

In addition, as a result of the simulation, it was confirmed that even when the optical thickness of the first inorganic layer 4 is slightly thicker than the range of Table 1, there is an effect of lowering the average reflectance.

Referring to FIG. 4, Al2O3 (n:1.66-1.80) and SiO2 (n:1.70-1.80) having a refractive index of 1.8 or less in the optical thickness range of SiO2 (0.22λ ~ 0.29λ) are used as materials for the second inorganic layer 5. The average reflectance in visible light was calculated according to the optical thickness of the first inorganic film layer 4 when used as a material. It was confirmed that a film having a low average reflectance can be obtained when the optical thickness range of the second inorganic film layer 5 satisfies a predetermined range when compared with the case where the SiO2 single layer was deposited to have the lowest reflectance.

Silicon oxide (SiO2) is used as the material of the second inorganic film layer 5 and the optical thickness is in the range of 0.22λ or more and 0.29λ or less, and the material of the first inorganic film layer 4 is aluminum oxide (Al2O3) having a refractive index of 1.66 to 1.8. ) Or silicon nitride oxide (SiON) and the optical thickness is 0.14λ or more and 0.60λ or less, the average reflectance in visible light is lower than that of a SiO2 single layer. When the optical thickness is expressed in terms of physical thickness, Al2O3 (n: 1.80) satisfying 0.14λ is 42 nm, and Al2O3 (n: 1.80) satisfying 0.60λ is 186 nm.

If the first inorganic film layer 4 is thicker than the above range, the average reflectance may be lower than that of the case formed with a single SiO2 layer, but in this case, the total inorganic film layer thickness is 300 nm or more, so that cracking and damage due to stress during handling after deposition Can occur. In addition, when the thickness of the first inorganic layer 4 is thinner than the above range, there is a problem that the moisture barrier properties of 1.0X10-2g/m2/day or less cannot be guaranteed.

As shown in Fig. 5, when the refractive index of the first inorganic film layer 4 is 1.8 or more, it can be lower than the lowest average reflectance when formed with a single layer of SiO2, which is a low-reflective coating material, the first inorganic film layer 4 and the second inorganic film. The optical thickness range of the film layer 5 is formed narrower than that shown in FIG. 4.

Silicon oxide (SiO2) is used as the material of the second inorganic film layer 5, and silicon nitride having a refractive index of 1.8 or more is used as the material of the first inorganic film layer 4 in the range of 0.22λ or more and 0.25λ or less with an optical thickness. When it is 0.37λ or more and 0.57λ or less, an average reflectance in visible light that is lower than that formed with a single SiO2 film is obtained.

The optical thickness of SiO2 (n: 1.44-1.47), the material of the second inorganic film layer 4, has an optical thickness of 0.22λ or more and 0.29λ or less, and is 80 nm or more and 110 nm or less, and within this range, the refractive index of the material of the first inorganic layer 4 is 1.8 When the following Al2O3 or SiON is used, the optical thickness is 0.14λ or more and 0.60λ or less, and the physical thickness is 42nm or more and 186nm or less.

In addition, when silicon nitride (SiN) having a refractive index of 1.8 or higher is used as the material of the first inorganic film layer 4, the optical thickness is 0.37λ or more and 0.57λ or less, and the physical thickness must satisfy 99nm to 153nm. In this case, the second inorganic layer 4 When SiO2 is used as the material of the film layer 5, the optical thickness is 0.22λ or more and 0.25λ or less, and the physical thickness is 80nm to 95nm.

Whereas the optical thickness of the first inorganic layer 4 is thinner than the above range, the average reflectance can be lowered, but in this case, there is a problem in that it is difficult to stably secure the required barrier properties due to the thin thickness of the first inorganic layer 4. .

In the present invention, by limiting the refractive index and optical thickness of the first inorganic film layer 4 and the second inorganic film layer 5 as described above, the average reflectance in visible light is lower than that of the case where the inorganic film layer is formed as a single layer, thereby producing a highly transparent film. It has an excellent effect, and a barrier film with high moisture barrier properties of 1.0X10-2g/m2/day or less can be stably obtained. In addition, by appropriately limiting the thickness of the total inorganic film layer in which the first inorganic film layer 4 and the second inorganic film layer 5 are stacked, it is possible to prevent cracking and damage caused by stress during handling, and to secure required barrier properties stably. can do.

In addition, as a material for forming the first inorganic layer 4, aluminum, silicon, trivalent element B, etc., or pentavalent element P, etc., may be added in a small amount. Also, aluminum oxide, silicon nitride and silicon nitride oxide may be used. As a material for forming the second inorganic film layer 5, silicon, silicon or silicon nitride, and silicon nitride oxide to which a small amount of silicon, trivalent element B, or pentavalent element P is added may be used.

In order to provide excellent moisture barrier properties of 1.0X10-2g/m2/day or less, the total thickness of the first inorganic layer 4 and the second inorganic layer 5 must be 100 nm or more to be stably realized. For example, SiON (n1:1.89) is used as the material of the first inorganic layer 4 and SiO2 (n2:1.46) is used as the material of the second inorganic layer 5 in the range of the optical thickness of each layer. When each of the polymer substrate film 10 (ns:1.66) is sequentially formed by 116 nm and 80 nm, as shown in FIG. 4, it has an evenly low reflectance in the field of visible light, and a barrier with excellent transmittance of 90% or more and moisture barrier properties. Film can be realized.

Hereinafter, an embodiment according to the present invention will be described. Since Embodiments 1 and 2 to be described below are only examples according to the present invention, the scope of the present invention is not limited to Embodiments 1 and 2, and may be changed within the scope of the specification of the present invention.

[Example 1]

A polymer film substrate 10 made of a polyethylene terephthalate film having a thickness of 50 μm was put in a sputtering device and reduced to a vacuum degree of 1E-3 Pa or less, thereby sufficiently removing moisture and organic gas in the sputtering device and in the polymer film substrate 10. A mixed gas of argon gas and oxygen gas in the sputtering device was introduced, and aluminum oxide having a thickness of 118 nm having a refractive index of 1.77 was used as the first inorganic film layer 4 and oxidized with a thickness of 82 nm having a refractive index of 1.46 on one surface of the polymer film substrate 10. Silicon was sequentially formed as the second inorganic film layer 5.

[Example 2]

On one surface of the polymer film substrate 10 according to the conditions of Example 1, 70 nm of aluminum oxide was sequentially formed as the first inorganic film layer 4 and 83 nm of aluminum oxide was sequentially formed as the second inorganic film layer 5.

[Comparative Example 1]

The first inorganic film layer 4 was removed under the conditions of Example 1.

[Comparative Example 2]

The second inorganic film layer 5 was removed under the conditions of Example 1.

Table 2 shows the refractive index, transmittance, and moisture permeability of Example 1, Example 2, Comparative Example 1, and Comparative Example 2.

division First inorganic layer Second inorganic layer Transmittance WVTR material Refractive index thickness material Refractive index thickness % g/m2/day Example 1 Al2O3 1.77 118 SiO2 1.46 82 93.5 3.00E-03 Example 2 Al2O3 1.77 70 SiO2 1.46 83 92.5 8.00E-03 Comparative Example 1 SiO2 1.46 94 91.5 7.00E-02 Comparative Example 2 Al2O3 1.77 78 84.0 6.50E-02

As shown in Table 2, Examples 1 and 2 according to the present invention were compared with Comparative Examples 1 and 2 having a single-layer structure as the first inorganic film layer 4 or the second inorganic film layer 5 It can be seen that the transmittance is high and has more excellent moisture permeability.

6 and 7 are schematic views showing cross-sections of a highly transparent barrier film including an organic layer 20 and an anti-glare layer 30 according to an exemplary embodiment of the present invention.

6 and 7, a highly transparent barrier film according to an embodiment of the present invention includes an organic layer 20 stacked on one side of the second inorganic layer 5 and one of the organic layer 20. It may further include an anti-glare layer 30 that is laminated on the surface and diffusely reflects light. In this case, the highly transparent barrier film is sequentially composed of a polymer base film 10, a first inorganic film layer 4, a second inorganic film layer 5, an organic film layer 20, and an anti-glare layer 30.

In addition, the highly transparent barrier film is an organic film layer 20 laminated on one side of the second inorganic film layer 5 and an anti-glare layer laminated on one side of the polymer film substrate 10 to diffuse light ( 30) may be further included. In this case, the highly transparent barrier film is sequentially composed of an anti-glare layer 30, a polymer film substrate 10, a first inorganic layer 4, a second inorganic layer 5, and an organic layer 20.

The organic layer 20 includes carbon and may be formed by coating on the surface of the second inorganic layer 5. For example, the organic layer 20 may be formed of polysiloxane or polysilazane. polysilazane) system can be used. A prepolymer can be formed using the polysiloxane or polysilazane system, and a coating solution is prepared by adding an acid to a siloxane monomer and heating to a certain temperature to form a polysiloxane oligomer. After that, the coating solution may be coated on the surface of the second inorganic layer 5 to form the organic layer 20.

In addition to the above-described examples, the organic layer 20 may be formed of various materials and may have various structures.

The anti-glare layer 30 serves to prevent glare by inducing scattering of light from inside and out to induce diffuse reflection. For example, the anti-glare layer 30 may induce light scattering by implementing a porous film therein or forming a surface curvature.

In addition, the anti-glare layer 30 may include polyethyleneterephthalate (PET), polyethersulfone (PES), polycarbonate (PC), polyethylenenaphthalate (PEN), and polyimide; PI), polyarylate (polyarylate), may be formed on the second base film 32 formed of an epoxy resin, etc., the second base film 32 may be formed to a thickness of 15 to 400 μm.

The highly transparent barrier film according to the present invention having the above configuration has a high transmittance in visible light by adjusting the refractive index of the first inorganic film layer 4, the second inorganic film layer 5, and the polymer film substrate 10, and is 1.0X10-2g. It can have a moisture barrier property of less than /m2/day, and includes only one organic layer 20 to reduce the overall thickness and at the same time reduce the manufacturing cost, and include the anti-glare layer 30 to prevent glare. It works.

8 is a flow chart showing a method of manufacturing a barrier film according to an embodiment of the present invention.

Referring to Figure 8, the method of manufacturing a highly transparent barrier film according to the present invention, a film substrate preparation step (S110) of preparing a polymer film substrate 10, and a first inorganic film layer 4 on the polymer film substrate 10 And a film forming step S120 of sequentially forming the second inorganic film layer 5.

Film substrate preparation step (S110) according to the present invention is a step of forming a polymer film substrate 10, the polymer film substrate 10 formed in the film substrate preparation step (S110) is a first substrate film (1) single Although it may be formed as, the above-described undercoat layer 2 may be coated on one side of the first base film 1, and the above-described back coat layer 3 may be coated on the other side. The formation of the undercoat layer 2 and the back coat layer 3 may be independently performed, and in this case, the back coat layer 3 may be formed after performing the film forming step S120.

In addition, in the film substrate preparation step (S110), in order to increase the adhesion between the polymer film substrate 10 and the first inorganic film layer 4, plasma treatment, corona discharge treatment, ultraviolet irradiation, etc. Appropriate bonding treatment can be performed.

The thickness of the polymeric film substrate 10 formed in the film substrate preparation step (S110) may vary depending on the film forming conditions or use, but is generally preferably within the range of 10 μm to 250 μm, and 20 to 200 μm It is more preferable to be in the range of.

The film-forming step (S120) of the present invention is a step of sequentially vacuum-depositing the first inorganic film layer 4 and the second inorganic film layer 5 on one surface of the polymer film substrate 10. Evaporation, chemical Vapor deposition (CVD), sputtering, etc. may be used, and in the present invention, it is preferable to sequentially deposit the first inorganic film layer 4 and the second inorganic film layer 5 in a single process by sputtering. . In the film forming step S120, the first inorganic film layer 4 and the second inorganic film layer 5 may be deposited on both surfaces of the polymer film substrate 10.

When forming the first inorganic film layer 4 and the second inorganic film layer 5 using the above metal materials, oxygen or nitrogen, which is a reactive gas, must be introduced. It can be carried out by introducing oxygen and nitrogen as reactive gases.

In the film forming step (S120) of the present invention, the first inorganic film layer 4 and the second inorganic film layer 5 may be formed by a roll-to-roll sputter method, and the degree of vacuum reached in the sputtering device Is 1 Pa or less, preferably 1.0e-2Pa or less, and more preferably 1.0E-3Pa or less. In addition, roll-to-roll sputtering, evaporation, CVD (PE-CVD), etc. can be used.

In the film forming step (S120) performed by applying the sputtering method, vacuum deposition of the first inorganic film layer 4 and the second inorganic film layer 5 can be performed in a single process, thus simplifying the process and increasing work efficiency. It has the advantage of being.

In an embodiment of the present invention, the method of manufacturing the highly transparent barrier film is an organic film layer forming step of coating an organic film layer 20 on one surface of the second inorganic film layer 5 vacuum-deposited in the film forming step S120 (S300). ) And an anti-glare layer forming step (S300) of forming an anti-glare layer 30 on the polymer film base 10 or the organic film layer 20.

The organic layer forming step (S200) may be performed by coating an organic coating solution on the second inorganic layer 5, and the organic coating solution may have a thickness of about 0.5 to 5 μm by a method such as micro-gravure or slot die. It may be coated to form the organic layer 20. In addition, in the organic layer forming step (S200), the organic coating solution may be coated on the second inorganic layer 5 and then dried at 100 to 130°C.

The organic coating solution may be obtained by adding an acid to a siloxane monomer and heating at 20 to 60°C to form a poly-siloxane oligomer.

In the step of forming the anti-glare layer (S300), for example, after applying the anti-glare coating solution on the second base film 32, the second base film 32 and the organic film layer 20 or the second base film 32 It may be formed by bonding the film 32 and the polymer film substrate 10. In this case, it is preferable to use an optical adhesive as the adhesive 31, and the functionality may be increased by adding a UV blocking agent to the adhesive 31.

The anti-glare coating solution may be applied to any one or both sides of the second base film 32, and the anti-glare layer 30 includes the first base film 1, the polymer film base 10, and/or It may be formed by being stacked on the organic layer 20.

In addition, in the case where the anti-glare layer 30 is stacked on one surface of the organic layer 20 in the anti-glare layer forming step (S300), the process proceeds after the organic layer forming step (S300) is performed, and the anti-glare layer When (30) is laminated on one surface of the polymer film substrate 10, the organic layer forming step (S300) may be performed before, after, or at the same time.

The barrier film manufacturing method according to the present invention made in the above order has the advantage of improving work efficiency by reducing process time and material loss through simplification of the process.

1: first base film 2: undercoat layer
3: back coat layer 4: first inorganic film layer
5: second inorganic film layer
10: polymer film substrate
20: organic film layer
30: anti-glare layer 31: adhesive
32: second base film
S110: film substrate preparation step S120: film forming step
S200: organic layer forming step S300: anti-glare layer forming step

Claims (8)

A polymer film base made of a polymer molded product;
A first inorganic film layer deposited on one surface of the polymer film substrate; And
Including; a second inorganic film layer deposited on one surface of the first inorganic film layer,
The refractive index (n1) of the first inorganic film layer is greater than the refractive index (ns) of the polymer film substrate,
The refractive index (n2) of the second inorganic film layer is less than the refractive index (ns) of the polymer film substrate,
The first inorganic film layer and the second inorganic film layer is a highly transparent barrier film having an anti-glare function, characterized in that formed by sequentially vacuum deposition on the polymer film substrate.
The method of claim 1,
A highly transparent barrier film having an anti-glare function, characterized in that the total thickness of the first inorganic layer and the second inorganic layer is 100 nm or more.
The method of claim 1,
The optical thickness of the first inorganic layer is 0.14λ or more and 0.60λ or less, and the physical thickness is 42 nm or more and 186 nm or less,
The optical thickness of the second inorganic layer is 0.22λ or more and 0.29λ or less, and the physical thickness is 80 nm or more and 110 nm or less,
As the material of the first inorganic layer, aluminum oxide (Al2O3) or silicon nitride oxide (SiON) having a refractive index of 1.8 or less is used,
A highly transparent barrier film having an anti-glare function, characterized in that silicon oxide (SiO2) is used as the material of the second inorganic layer.
The method of claim 1,
The optical thickness of the first inorganic film layer is 0.37λ or more and 0.57λ or less, and the physical thickness is 99 nm or more and 153 nm or less,
The optical thickness of the second inorganic layer is 0.22λ or more and 0.25λ or less, and the physical thickness is 80 nm or more and 95 nm or less,
Silicon nitride (SiN) having a refractive index of 1.8 or more is used as a material for the first inorganic layer,
A highly transparent barrier film having an anti-glare function, characterized in that silicon oxide (SiO2) is used as the material of the second inorganic layer.
The method of claim 1,
The first inorganic film layer and the second inorganic film layer is a highly transparent barrier film having an anti-glare function, characterized in that provided on both sides of the polymer film substrate.
The method of claim 1,
An organic layer laminated on one surface of the second inorganic layer; And
An anti-glare layer laminated on one surface of the organic film layer or the polymer film substrate to diffusely reflect light; a highly transparent barrier film having an anti-glare function.
In the manufacturing method for manufacturing the highly transparent barrier film according to any one of claims 1 to 6,
Film substrate preparation step of preparing a polymer film substrate;
A film forming step of sequentially vacuum depositing a first inorganic film layer and a second inorganic film layer on one surface of the polymer film substrate prepared in the film substrate preparation step;
An organic film layer forming step of coating an organic film layer on one surface of the second inorganic film layer vacuum-deposited in the film forming step; And
And an anti-glare layer forming step of forming an anti-glare layer on the polymer film base material or the organic film layer.
The method of claim 7,
The film forming step,
A barrier film manufacturing method, characterized in that the first inorganic layer and the second inorganic layer are continuously deposited using a roll-to-roll sputtering or evaporation method.

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