KR102473646B1 - Method of fabricating barrier film, polarization plate and display device - Google Patents

Abstract

In the present invention, a barrier film made of a polymer in which inorganic particles are cross-linked is provided.
Therefore, it is possible to provide a barrier film having a simple manufacturing method and having a moisture barrier property, and a display device using the same can reduce manufacturing cost and minimize damage caused by moisture while manufacturing a simple manufacturing process.

Description

Manufacturing method of barrier film, polarization plate and display device {Method of fabricating barrier film, polarization plate and display device}

The present invention relates to a display device, and more particularly, to a barrier film capable of preventing damage to a display device due to external moisture, a polarizing plate, and a manufacturing method of the display device.

As the information society develops, demands for display devices for displaying images are increasing in various forms. Compared to the conventional cathode ray tube display (CRT), flat panel display devices such as liquid crystal display (LCD) devices and organic light emitting diode (OLED) displays, which are thinner and lighter, are being actively developed. research and commercialization.

1 is a schematic cross-sectional view of a conventional liquid crystal display device.

As shown in FIG. 1, the liquid crystal display device 1 includes a liquid crystal panel 10, first and second polarizing plates 20 and 30 positioned on both sides of the liquid crystal panel 10, and the first polarizing plate (20) It may include a backlight unit 40 positioned below.

Although not shown, the liquid crystal panel 10 may include a first substrate on which a pixel electrode and a common electrode are formed, a second substrate facing the first substrate, and a liquid crystal layer positioned between the first and second substrates. can

Each of the first and second polarizers 20 and 30 may include a polarizer and first and second base films positioned on both sides of the polarizer. An absorption axis (or transmission axis) of the first polarizer 20 may be perpendicular to an absorption axis (or transmission axis) of the second polarizer 30 .

Light from the backlight unit 40 is supplied to the liquid crystal panel 10 through the first polarizer 20, and the liquid crystal molecules of the liquid crystal layer are driven by an electric field formed between the pixel electrode and the common electrode. , light is selectively transmitted through the second polarizing plate 30 . Thus, the liquid crystal display device 1 can implement images.

Meanwhile, in recent years, the first and second substrates of the liquid crystal panel 10 have flexible characteristics like polyimide, thereby providing a flexible liquid crystal display device 1 .

However, since the flexible substrate has a low moisture barrier property, external moisture penetrates into the liquid crystal panel 10 and the display quality deteriorates.

2 is a schematic cross-sectional view of a conventional organic light emitting diode display.

As shown in FIG. 2 , the organic light emitting diode display device 50 includes a base substrate 60, a light emitting diode 70 disposed on the base substrate 60, and a light emitting diode 70 disposed on the organic light emitting diode 70. It includes an encapsulation film 80 located on.

Since the organic light emitting diode 70 is very vulnerable to moisture, the encapsulation film 80 covers the light emitting diode 70 and serves to block moisture.

For example, the encapsulation film 80 has a triple layer structure of a first inorganic layer 82 , an organic layer 84 , and a second inorganic layer 86 .

Although moisture permeation can be prevented by such an encapsulation film 80, the manufacturing process is complicated and the manufacturing cost increases because of the multi-layer structure. In addition, a problem in that the thickness of the organic light emitting diode display device 50 is increased by the multi-layer encapsulation film 80 occurs.

In the present invention, it is intended to solve problems such as an increase in manufacturing cost and an increase in the thickness of a display device due to a moisture barrier film while preventing damage to the display element due to external moisture.

In order to solve the above problems, the present invention provides a barrier film made of a polymer in which inorganic particles are crosslinked by crosslinking a low molecular weight polymer, replacing the crosslinked core with inorganic particles, and then polymerizing the polymer.

In addition, the present invention provides a barrier film made of a polymer in which inorganic particles are cross-linked by reacting a low-molecular polymer with an inorganic cross-linking agent to form an inorganic particle-cross-linked polymer and then polymerizing the polymer.

In addition, the present invention provides a method for manufacturing a polarizing plate using the barrier film formed by the above method as a base substrate.

In addition, the present invention provides a method for manufacturing a liquid crystal display device using the polarizing plate described above.

In addition, the present invention provides a method of manufacturing an organic light emitting diode display using the polarizing plate or barrier film described above.

Since the barrier film according to the present invention has a structure in which inorganic particles are cross-linked in a polymer, it is possible to provide a single-layered barrier film having desired moisture barrier properties.

Thus, the manufacturing process of the barrier film is simplified and the manufacturing cost is reduced.

In addition, by using the barrier film as a base film of the polarizing plate, it is possible to provide a polarizing plate having moisture barrier properties. By using such a polarizing plate in a liquid crystal display device, it is possible to provide a flexible liquid crystal display device without damage to the liquid crystal panel (display panel).

In addition, by using the barrier film as an encapsulation film covering the organic light emitting diode, it is possible to provide an organic light emitting diode display device capable of reducing manufacturing costs and preventing damage to the organic light emitting diode. In addition, since the encapsulation film can be omitted when the polarizing plate including the barrier film is attached to the top of the organic light emitting diode, manufacturing cost is further reduced.

1 is a schematic cross-sectional view of a conventional liquid crystal display device.
2 is a schematic cross-sectional view of a conventional organic light emitting diode display.
3 is a schematic diagram for explaining a barrier film according to an embodiment of the present invention.
4 is a flow chart for explaining the manufacturing process of the barrier film according to the first embodiment of the present invention.
5 is a flow chart for explaining a manufacturing process of a barrier film according to a second embodiment of the present invention.
6A and 6B are schematic cross-sectional views of polarizers according to third and fourth embodiments of the present invention, respectively.
7 is a schematic diagram for explaining a manufacturing process of a polarizing plate according to a fourth embodiment of the present invention.
8 is a schematic cross-sectional view of an organic light emitting diode display device according to a fifth embodiment of the present invention.
9 is a schematic cross-sectional view showing one pixel of an organic light emitting diode display device according to a fifth embodiment of the present invention.
10 is a schematic cross-sectional view of a liquid crystal display according to a sixth embodiment of the present invention.

The present invention comprises the steps of polymerizing a monomer at a first temperature to form a low molecular weight polymer, crosslinking the low molecular weight polymer at a second temperature to form a crosslinked polymer, and adding inorganic particles at a third temperature to form a low molecular weight polymer. Forming an inorganic particle-crosslinked polymer by substituting the crosslinked core of the crosslinked polymer with the inorganic particles, and forming a polymer by polymerizing the inorganic particle-crosslinked polymer at a fourth temperature. to provide.

From another point of view, the present invention provides the steps of polymerizing monomers at a first temperature to form a low molecular weight polymer, substituting inorganic particles for the core of the crosslinking agent at a second temperature to form an inorganic crosslinking agent, and forming an inorganic crosslinking agent at a third temperature. Forming an inorganic particle-crosslinked polymer by crosslinking the low molecular weight polymer with the inorganic crosslinking agent, and forming a polymer by polymerizing the inorganic particle-crosslinked polymer at a fourth temperature. do.

In the method for manufacturing a barrier film according to an embodiment of the present invention, the second temperature may be lower than the first temperature.

In the method for manufacturing a barrier film according to an embodiment of the present invention, the third temperature may be lower than the first temperature.

In the method of manufacturing a barrier film according to an embodiment of the present invention, the third temperature may be greater than the first and second temperatures.

In the method for manufacturing a barrier film according to an embodiment of the present invention, the fourth temperature may be higher than the first to third temperatures.

In the method for manufacturing a barrier film according to an embodiment of the present invention, the step of forming the inorganic crosslinking agent is performed before the step of forming the low-molecular polymer, concurrently with the step of forming the low-molecular polymer, or after the step of forming the low-molecular polymer. can proceed to

In the method for manufacturing a barrier film according to an embodiment of the present invention, the inorganic particles may have a weight ratio of 10 to 50% with respect to the polymer.

In the method for manufacturing a barrier film according to an embodiment of the present invention, the crosslinking agent is selected from Si, alkyl, epoxy, acryl, ether, ester, and peroxide materials, and the inorganic particles are metal, metal It may be selected from oxides, metal nitrides, metal fluorides, and silicon-based materials.

In the method for manufacturing a barrier film according to an embodiment of the present invention, the low molecular weight polymer includes N monomers, and N may be 4 or more and 20 or less.

In another aspect, the present invention includes forming a polarizing film, and attaching first and second barrier films to both sides of the polarizing film, wherein at least one of the first and second barrier films Provides a method for manufacturing a polarizing plate manufactured by the method of claim 1 or 2.

In another aspect, the present invention provides a method for manufacturing a liquid crystal display device comprising forming a liquid crystal panel and attaching a polarizing plate manufactured by the method of claim 11 to one side of the liquid crystal panel.

In another aspect, the present invention provides the steps of forming an organic light emitting diode on a substrate, and attaching a barrier film prepared by the method of claim 1 or 2 on the organic light emitting diode to cover the organic light emitting diode. It provides a method for manufacturing an organic light emitting diode display comprising the step of doing.

In another aspect, the present invention includes forming an organic light emitting diode on a substrate, and attaching a polarizing plate manufactured by the method of claim 11 on the organic light emitting diode to cover the organic light emitting diode. A manufacturing method of an organic light emitting diode display is provided.

Hereinafter, preferred embodiments according to the present invention will be described with reference to the drawings.

3 is a schematic diagram for explaining a barrier film according to an embodiment of the present invention.

As shown in FIG. 3, the barrier film of the present invention includes a polymer chain and inorganic particles cross-linked to the polymer chain.

That is, the barrier film of the present invention is an organic-inorganic hybrid film, and has high dispersion uniformity by cross-linking inorganic particles to polymer chains.

In the barrier film of the present invention, moisture barrier properties can be implemented by inorganic particles cross-linked to polymer chains, and can have a film form by polymer.

For example, the polymer chain may be any one of a cellulose-based polymer, an acryl-based polymer, an ester-based polymer, an ethylene-based polymer, and an olefin-based polymer. Specifically, the polymer chain is trieaceytyl cellulose (TAC), polymethyl metacrylate (PMMA), polyethylene terephthalate (PET), polyethylene naphthalate, (PEN), polybutylene terephthalate (PBT), high-density polyethylene (HDPE), low-density It may be any one of polyethylene (LDPE), cyclo-olefin polymer, polyimide, and ethylene vinyl alcohol (EVOH).

In addition, the inorganic particles include aluminum (Al), magnesium (Mg), indium (In), tin (Sn), lead (Pb), gold (Au), copper (Cu), titanium (Ti), nickel (Ni) , metals such as germanium (Ge), calcium (Ca), iron (Fe), and cesium (Ce), their oxides, nitrides, and fluorides, or silicon-based materials such as silica, silane, and silicon nitride (SiN) can be one of the substances.

The inorganic particles may have a weight ratio of about 10 to 50%, preferably about 15 to 20%, based on the polymer. If the weight ratio of the inorganic particles is smaller than the above-mentioned weight ratio, desired moisture barrier properties cannot be realized, and if the inorganic particles are larger than the weight ratio, the optical properties of the barrier film, such as transmittance, deteriorate.

On the other hand, when inorganic particles are simply mixed with a polymer to form an organic-inorganic hybrid barrier film, optical properties such as transmittance are deteriorated because the dispersion uniformity of the inorganic particles is low. In addition, when aggregation of the inorganic particles occurs, the reflectance of the barrier film increases and the optical properties deteriorate.

Even if a dispersant is used to improve the dispersion of inorganic particles, there is a limit to implementing dispersion uniformity that satisfies desired optical properties.

As described above, in the barrier film of the present invention, the inorganic particles are cross-linked to the polymer chain, thereby satisfying the optical properties due to high dispersion uniformity while having desired water barrier properties.

The manufacturing method of such a barrier film is demonstrated.

4 is a flow chart for explaining the manufacturing process of the barrier film according to the first embodiment of the present invention.

As shown in FIG. 4, the barrier film of the present invention includes forming a low-molecular polymer (ST110), crosslinking a low-molecular polymer (ST120), replacing the core of a crosslinking agent with inorganic particles (ST130), polymer It may be manufactured by a process including a forming step (ST140) and a film manufacturing step (ST150).

First, in the low-molecular polymer forming step (ST110), a low-molecular polymer is formed by polymerizing monomers. For example, a low-molecular polymer is formed by adding a monomer, which is a unit capable of forming an entire polymer chain, to a polymerization initiator and a solvent and then reacting.

Initiators can be radicals, acids or bases. For example, when a radical is used as an initiator, the radical is formed by irradiation with heat or light before being added to a solvent.

For example, about 70 to 90 wt% of the monomer and about 0.01 to 1 wt% of the initiator may be added relative to the solvent.

The low molecular weight polymer prepared in the low molecular weight polymer forming step (ST110) includes N polymerized monomers, and may be 4≤N≤20. For example, the molecular weight of the low molecular weight polymer may be less than 40000.

When N is less than 4, dispersion uniformity of inorganic particles may be deteriorated, and when N is greater than 20, substitution of inorganic materials becomes difficult.

That is, when N is less than 4, inorganic particles are substituted with the core of the crosslinking agent, but since the substitution of inorganic particles can occur at random locations, the dispersion uniformity of inorganic particles in the final polymer is lowered and the barrier film such as transmittance is substituted. Optical properties may deteriorate. In addition, when N is greater than 20, since the length and size of the low molecular weight polymer are too large, substitution of the inorganic particles is difficult to occur and the inorganic particles are simply mixed with the polymer. Accordingly, optical properties such as transmittance and reflectance of the barrier film are deteriorated.

In order to adjust the number (N) of monomers of the low molecular weight polymer, the low molecular polymer forming step (ST110) may be performed at a first temperature of 40 to 100°C.

When the low-molecular-weight polymer forming step (ST110) proceeds at a temperature lower than the first temperature, N may be less than 4 because the polymerization reaction of the monomer is difficult. In addition, when the low-molecular polymer forming step (ST110) is performed at a temperature higher than the first temperature, the polymerization rate of the monomers increases and N may become greater than 20.

Next, the low-molecular polymer crosslinking step (ST120) proceeds, and crosslinking proceeds by a heating process after adding a crosslinking agent.

As the crosslinking agent, Si, alkyl, epoxy, acryl, ether, ester, and peroxide materials may be used. For example, crosslinking agents include dimethylsiloxane, silicilic acid, dimethylacrylate, butadiene acrylate, trimethylolpropane trimethacrylate, isobutylene, butadiene, ethylene glycol, trimethylene oxide, caprolactone, valerolactone, dibenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5di(t It may be selected from -butylperoxy)-hexane and t-butylcumylperoxide.

The crosslinking agent may be added in an amount of about 15 to 50 wt% based on the total weight of the low molecular weight polymer. If the cross-linking agent is less than 15 wt% relative to the low-molecular polymer, the cross-linking degree of the low-molecular polymer is low, and the barrier properties and durability may deteriorate. If the cross-linking agent is greater than 15 wt%, the cross-linking degree is too high, and the barrier film breaks It becomes easy to lose. (brittle)

The low molecular weight polymer crosslinking step (ST120) is performed at a second temperature lower than the first temperature. For example, the second temperature may be 40 to 100 °C.

When the second temperature is higher than the first temperature, the polymerization reaction of the low molecular weight polymer proceeds (N>20), which may cause a problem in that the uniformity of substitution or dispersion of inorganic particles is lowered, and when the second temperature is lower than 30°C. The progress of the crosslinking reaction becomes difficult.

Next, a step of substituting the core of the crosslinking agent with inorganic particles (ST130) proceeds, thereby forming an inorganic particle-crosslinked polymer.

Based on the crosslinked polymer, about 10 to 50 wt% of inorganic particles are added to replace the core of the crosslinking agent in which the low molecular weight polymer is crosslinked with the inorganic particles. The inorganic particles preferably have a weight ratio of about 15 to 20% based on the crosslinked crosslinked polymer.

The inorganic particles include aluminum (Al), magnesium (Mg), indium (In), tin (Sn), lead (Pb), gold (Au), copper (Cu), titanium (Ti), nickel (Ni), germanium Among metals such as (Ge), calcium (Ca), iron (Fe), and cesium (Ce), their oxides, nitrides, and fluorides, or silicon-based materials such as silica, silane, and silicon nitride (SiN) can be one

When the weight ratio of the inorganic particles to the crosslinked polymer is smaller than the above conditions, the barrier film has degraded moisture barrier properties, and when it is greater than the above conditions, the barrier film has degraded optical properties such as transmittance.

At this time, about 1 to 5 wt% of a dispersant and about 1 to 5 wt% of an antioxidant may be further added based on the crosslinked polymer. The dispersion uniformity of the inorganic particles is increased by the dispersant, so that the dispersion uniformity of the inorganic particles is further increased even after being substituted. In addition, an antioxidant may be used to prevent deterioration of optical properties of the barrier film due to oxidation of inorganic particles such as metal.

When the weight ratio of the dispersant and the antioxidant is greater than the above range, the dispersant and the antioxidant act as impurities, and thus optical properties of the barrier film may be deteriorated.

Substituting the core of the crosslinking agent with inorganic particles (ST130) is performed at a third temperature lower than the first temperature. For example, the third temperature may be about 10 to 40°C.

When the third temperature is lower than 10°C, substitution of the inorganic particles is difficult to occur. On the other hand, when the third temperature is higher than the first temperature, the polymerization reaction of the low molecular weight polymer takes precedence over the substitution reaction of the inorganic particles, or the substitution reaction of the inorganic particles and the polymerization reaction of the low molecular weight polymer proceed competitively. Accordingly, the substitution ratio of the inorganic particles is reduced, and the inorganic particles are simply dispersed, and thus the properties of the barrier film may be deteriorated.

Since elements such as oxygen, silicon, and nitrogen located in the core of the crosslinking agent have low electronegativity, they are highly reactive with inorganic particles such as metal ions and metal oxides with high oxidation numbers, and become chemically more stable through substitution reactions. Therefore, a core substitution reaction of the crosslinking agent occurs by a heating process after adding the inorganic particles.

Next, the polymer forming step (ST140) proceeds to further polymerize the inorganic particle-crosslinked polymer to form a polymer.

The polymer forming step (ST140) is performed at a fourth temperature higher than the first temperature. For example, the fourth temperature may be about 100 to 150°C.

The polymer may have a molecular weight of 40000 to 600000. When the molecular weight of the polymer is less than 40000, the barrier film becomes soft and durability decreases, and when the molecular weight is greater than 600000, the barrier film becomes brittle. (brittle)

Next, the film manufacturing step (ST150) proceeds. For example, the barrier film can be obtained by performing the extrusion process under the fifth temperature condition of about 140 to 190°C.

5 is a flow chart for explaining a manufacturing process of a barrier film according to a second embodiment of the present invention.

As shown in FIG. 5, the barrier film of the present invention includes forming a low-molecular polymer (ST210), forming an inorganic crosslinking agent (ST220), crosslinking a low-molecular polymer (ST230), forming a polymer (ST240), It may be manufactured by a process including a film manufacturing step (ST250).

First, in the low-molecular polymer forming step (ST210), a low-molecular polymer is formed by polymerizing monomers. For example, a low-molecular polymer is formed by adding a monomer, which is a unit capable of forming the above-mentioned polymer chain, to a polymerization initiator and a solvent and then reacting.

Initiators can be radicals, acids or bases. For example, when a radical is used as an initiator, the radical is formed by irradiation with heat or light before being added to a solvent.

For example, about 70 to 90 wt% of the monomer and about 0.01 to 1 wt% of the initiator may be added relative to the solvent.

The low-molecular polymer prepared in the low-molecular polymer forming step (ST210) includes N polymerized monomers, and may be 4≤N≤20. For example, the molecular weight of the low molecular weight polymer may be less than 40000.

When N is less than 4, dispersion uniformity of inorganic particles may be deteriorated, and when N is greater than 20, substitution of inorganic materials becomes difficult.

That is, when N is less than 4, inorganic particles are substituted with the core of the crosslinking agent, but since the substitution of inorganic particles can occur at random locations, the dispersion uniformity of inorganic particles in the final polymer is lowered and the barrier film such as transmittance is substituted. Optical properties may deteriorate. In addition, when N is greater than 20, since the length and size of the low molecular weight polymer are too large, substitution of the inorganic particles is difficult to occur and the inorganic particles are simply mixed with the polymer. Accordingly, optical properties such as transmittance and reflectance of the barrier film are deteriorated.

In order to adjust the number of monomers (N) of the low molecular polymer, the low molecular weight polymer forming step (ST210) may be performed at a first temperature of 40 to 100 °C.

If the low-molecular polymer forming step (ST210) is performed at a temperature lower than the first temperature, N may be less than 4 because the polymerization reaction of the monomer is difficult. In addition, when the low-molecular polymer forming step (ST210) is performed at a temperature higher than the first temperature, the polymerization rate of the monomers increases and N may become greater than 20.

Next, the step of forming the inorganic crosslinking agent (ST220) proceeds.

By adding and reacting about 30 to 70 wt% of a crosslinking agent and about 10 to 50 wt% of inorganic particles based on a solvent, an inorganic crosslinking agent in which the core of the crosslinking agent is replaced with inorganic particles is formed.

The step of forming the inorganic crosslinking agent (ST220) may be performed at a second temperature of about 10 to 40° C., preferably at room temperature, and after forming the inorganic crosslinking agent, a drying process is performed to remove the solvent. (About 80~100℃ conditions)

The step of forming the inorganic crosslinking agent (ST220) may be performed before, simultaneously with, or after the step of forming the low molecular weight polymer (ST210).

Next, the low molecular weight polymer crosslinking step (ST230) proceeds. That is, the low molecular weight polymer formed in the step of forming the low molecular weight polymer (ST210) and the inorganic crosslinking agent formed in the step of forming the inorganic crosslinking agent (ST220) are mixed and reacted at a third temperature higher than the first and second temperatures. By crosslinking, an inorganic particle-crosslinked polymer is formed. Thus, the inorganic particles are bound between the crosslinked low molecular weight polymers.

The third temperature may be about 70 to 110 °C. Since the third temperature is greater than the first and second temperatures, particularly the first temperature, a polymerization reaction of the low molecular weight polymer proceeds along with a crosslinking reaction, thereby shortening the manufacturing process time of the barrier film. However, if the third temperature is too high (third temperature > 110° C.), the polymerization reaction proceeds too quickly rather than the crosslinking reaction, and thus the dispersion uniformity of the inorganic particles may deteriorate.

At this time, based on the low molecular weight polymer, about 1 to 5 wt% of the dispersant and about 1 to 5 wt% of the antioxidant may be further added. The dispersion uniformity of the inorganic particles is increased by the dispersant, so that the dispersion uniformity of the inorganic particles is further increased even after being substituted. In addition, an antioxidant may be used to prevent deterioration of optical properties of the barrier film due to oxidation of inorganic particles such as metal.

When the weight ratio of the dispersant and the antioxidant is greater than the above range, the dispersant and the antioxidant act as impurities, and thus optical properties of the barrier film may be deteriorated.

Next, the polymer forming step (ST240) proceeds.

In the polymer formation step (ST240), the inorganic particle-crosslinked polymer is further polymerized to form a polymer. The polymer forming step (ST240) is performed at a fourth temperature higher than the first to third temperatures. For example, the fourth temperature may be about 100 to 150°C.

The polymer may have a molecular weight of 40000 to 600000. When the molecular weight of the polymer is less than 40000, the barrier film becomes soft and durability decreases, and when the molecular weight is greater than 600000, the barrier film becomes brittle. (brittle)

Next, the film manufacturing step (ST250) proceeds. For example, the barrier film can be obtained by performing the extrusion process under the fourth temperature condition of about 140 to 190°C.

barrier manufacture of film

0.1wt% of azobisisobutyronitrile (AIBN) is irradiated with UV (50W 15min) to generate radicals, and 0.1 wt% of AIBN and 90wt% of MMA monomer are added to the cyclohexane solvent based on the solvent and reacted at 70 ° C. A molecular polymer was formed.

Next, an inorganic crosslinking agent was synthesized by adding 60 wt% of ethylene glycol dimethacrylate and 20 wt% of inorganic particles (AlO ₂ ) to an isopropanol solvent based on the isopropanol solvent and reacting at room temperature. Then, it was dried for 1 hour at 80 ℃ temperature conditions.

Next, based on the synthesized low molecular weight polymer, 25 wt% inorganic crosslinking agent, 0.2 wt% Irganox 1010, and 3 wt% dispersing agent were mixed and stirred at 85° C. to crosslink the low molecular weight polymer. The mixture was heated to 110°C, stirred, extruded at 170°C, and then dried at 50°C for 3 hours to obtain a barrier film. (thickness 80μm)

comparative example

A barrier film was obtained by sequentially stacking a first inorganic layer (AlO ₂ , 500 nm), an organic layer (cyclo-olefin polymer, 50 μm), and a second inorganic layer (AlO ₂ , 500 nm).

The transmittance and moisture permeability of the barrier films of Experimental Example and Comparative Example were measured and listed in Table 1.

As shown in Table 1, the barrier film of the present invention having a single-layer structure has a higher transmittance than the conventional barrier film (encapsulation film) of a triple-layer structure and has a similar water vapor transmission rate.

Accordingly, the present invention provides a moisture barrier film having a simple manufacturing process and excellent optical properties.

6A and 6B are schematic cross-sectional views of polarizers according to third and fourth embodiments of the present invention, respectively.

As shown in FIG. 6A, the polarizing plate 100 according to the third embodiment of the present invention includes a polarizer (polarizing film, 110), a first base substrate 120 positioned on one side of the polarizer 110, A second base substrate 130 positioned on the other side of the polarizer 110 is included.

The polarizer 110 may be a polyvinyl alcohol (PVA) film to which iodine ions or a dichroic dye are dyed.

The first base substrate 120 is the barrier film of the present invention described above, and the second base substrate 130 may be made of a material such as PET or TAC.

Meanwhile, as shown in FIG. 6B, the polarizing plate 200 according to the fourth embodiment of the present invention includes a polarizer (polarizing film, 210) and a first base substrate 220 positioned on one side of the polarizer 210. and a second base substrate 230 positioned on the other side of the polarizer 210.

The polarizer 210 may be a polyvinyl alcohol (PVA) film to which iodine ions or a dichroic dye are dyed.

Each of the first and second base substrates 220 and 230 may be the above-described barrier film of the present invention.

As described above, since the barrier film of the present invention has a single layer structure and inorganic particles are cross-linked to polymer chains, the polarizers 100 and 200 having water barrier properties can be obtained with a simple manufacturing process.

7 is a schematic diagram for explaining a manufacturing process of a polarizing plate according to a fourth embodiment of the present invention.

As shown in FIG. 7, the polarizing plate (200 in FIG. 6B) according to the third embodiment of the present invention includes a first supply unit 212, a dyeing unit 213, a stretching unit 214, and a drying unit 215. ), the first and second coating units 216a and 216b, the second supply unit 222, the third supply unit 232, the attachment unit 240, the curing unit 250, and the recovery roll 260 It can be made by equipment.

First, the polarizer 210 is supplied from the first supply unit 212 . The first supply unit 212 may be a supply roll on which the polarizer 210 is wound, and may further include a moving means (not shown) for moving the polarizer 210 . Here, the moving means may be a motor that provides rotational force to the supply roll, and the moving means may be directly connected to the rotation shaft of the supply roll or connected to the rotation shaft of the supply roll through a pulley and a belt.

The polarizer 210 may be formed of polyvinyl alcohol (PVA).

The polarizer 210 supplied from the first supply unit 212 is transferred to the dyeing unit 213, and in the dyeing unit 213, iodine ions are dyed in the polarizing film 210. At this time, a potassium iodide solution may be used for dyeing iodine ions. Alternatively, a dichroic dye may be dyed into the polarizer 210 .

On the other hand, the polarizing film 210 may undergo a water washing process using de-ionized water or the like before being transferred to the dyeing unit 213, and the polarizer 210 swells so that iodine ions can be easily complexed through the water washing process It can be.

Subsequently, the polarizer 210 dyed with iodine ions is transferred to the stretching unit 210, and the polarizing film 210 is stretched in the stretching unit 214. At this time, the iodine ions are aligned in the stretching direction so that the stretched polarizer 210 has an absorption axis in the stretching direction. Accordingly, the stretched polarizer 210 absorbs light vibrating in a direction parallel to the absorption axis and transmits light vibrating in a direction perpendicular to the absorption axis. For example, the polarizer 210 may be stretched in a longitudinal direction, that is, a machine direction (MD) of a process.

Meanwhile, a crosslinking step may be performed together by stretching the dyed polarizer 210 in an aqueous solution of boric acid. That is, by immersing the dyed polarizer 210 in an aqueous solution of boric acid and stretching, the boric acid crosslinks between the polymer and the polymer of the polarizer 210 dyed with iodine ions to prevent sublimation of iodine ions. The crosslinking step may be performed separately from the stretching step.

Next, the stretched polarizer 210 is transferred to the drying unit 215 and dried. At this time, the drying unit 215 may include an oven.

Next, the dried polarizer 210 is transferred to the first and second coating units 216a and 216b. The first and second coating units 216a and 216b face each other with respect to the polarizer 210 and are spaced apart, and the first and second coating units 216a and 216b are both sides of the polarizer 210 passing therebetween. Each is coated with adhesive. At this time, the adhesive may be a water-based adhesive or an ultraviolet (UV) curable adhesive.

Subsequently, the polarizer 210 coated with the adhesive is transferred to the attachment unit 240 .

On the other hand, the second supply unit 222 is disposed apart from the first supply unit 212, and the first base substrate 220 is supplied from the second supply unit 222. The second supply unit 222 may be a supply roll on which the first base substrate 220 is wound, and may further include a moving means (not shown) for moving the first base substrate 220 . Here, the moving means may be a motor that provides rotational force to the supply roll, and the moving means may be directly connected to the rotation shaft of the supply roll or connected to the rotation shaft of the supply roll through a pulley and a belt.

The first base substrate 220 may be the barrier film of the present invention. That is, by cross-linking the inorganic particles to the polymer chain, the optical properties are satisfied with high dispersion uniformity while having desired water barrier properties.

Next, the first base substrate 220 is transferred to the attachment unit 240 .

On the other hand, on the opposite side of the second supply unit 222 based on the first supply unit 212, a third supply unit 232 is disposed spaced apart from the first supply unit 212, and the second base substrate is removed from the third supply unit 232. (230) is supplied. The third supply unit 232 may be a supply roll on which the second base substrate 230 is wound, and may further include a moving unit (not shown) for moving the second base substrate 230 . Here, the moving means may be a motor that provides rotational force to the supply roll, and the moving means may be directly connected to the rotation shaft of the supply roll or connected to the rotation shaft of the supply roll through a pulley and a belt.

The second base substrate 230 may be the barrier film of the present invention. That is, by cross-linking the inorganic particles to the polymer chain, the optical properties are satisfied with high dispersion uniformity while having desired water barrier properties.

Next, the second base substrate 230 is transferred to the attachment unit 240 .

Meanwhile, the first base substrate 220 and the second base substrate 230 may undergo a cleaning step before being transferred to the attachment unit 240 .

The attachment unit 240 includes first and second attachment rolls 242 and 244 . The first and second attachment rolls 242 and 244 may be spaced apart from each other and face each other. Alternatively, the first and second attachment rolls 242 and 244 may be offset from each other.

The polarizer 210 delivered to the attachment unit 240, the first base substrate 220 on one side of the polarizer 210, and the second base substrate 230 on the other side of the polarizer 210 are the first and second attachment rolls ( 242 and 244 are pressed while passing between, and the polarizer 210 is attached to the first and second base materials 220 and 230 and each other by the adhesive coated on both sides of the polarizer 210 .

Meanwhile, although it has been described that the adhesive is coated on both sides of the polarizer 210 in the embodiment of the present invention, the adhesive may be coated on the first base substrate 220 and the second base substrate 230 .

Next, the attached polarizer 210 and the first and second base substrates 220 and 230 are transferred to the curing unit 250, and the curing unit 250 cures the adhesive. If the adhesive is a water-based adhesive, it is cured by heat, and if it is a UV curable adhesive, it is cured by UV. Subsequently, the polarizer 210 and the first and second base substrates 220 and 230 may be transferred to a drying unit (not shown) and subjected to a drying step.

Next, the polarizing film 210 and the first and second base substrates 220 and 230 may be transferred to the recovery roll 260 and wound around the recovery roll 260 .

Meanwhile, in the previous embodiment, the case where the polarizer 210 was made of polyvinyl alcohol was described, but the polarizer 210 may be made of liquid crystal.

That is, the polarizer 210 may be formed by coating one of the first and second base substrates 220 and 230 with a liquid crystal, for example, reactive mesogen, along with a dye. At this time, an alignment film may be formed between the polarizer 210 and one of the first and second base substrates 220 and 230, and between the polarizer 210 and the other of the first and second base substrates 220 and 230. An adhesive may be formed.

Meanwhile, in the polarizer 100 shown in FIG. 6A , one of the first and second base substrates 120 and 130 may be a barrier film and the other may be manufactured by using a TAC film or the like.

Since the first and second base substrates 220 and 230 of the polarizing plate 200 formed as described above are barrier films having moisture blocking characteristics, the present invention may provide the polarizing plate 200 having moisture blocking characteristics.

8 is a schematic cross-sectional view of an organic light emitting diode display device according to a fifth embodiment of the present invention.

As shown in FIG. 8, the organic light emitting diode display device 300 of the present invention includes a substrate 310, an organic light emitting diode D positioned on the substrate 310, and the organic light emitting diode D It includes a barrier film 320 covering the.

As shown in FIG. 3 , the barrier film 320 is an organic-inorganic hybrid barrier film in which inorganic particles are cross-linked to polymer chains. Accordingly, the barrier film 320 has a single-layer structure and has sufficient moisture penetration characteristics.

That is, the barrier film 320 of the present invention is manufactured by the method described with reference to FIG. 4 or 5, and after forming the organic light emitting diode (D) on the substrate 310, the organic light emitting diode (D) It is attached to the substrate 310 so as to cover it.

Although not shown, an adhesive layer such as pressure sensitive adhesive may be formed between the organic light emitting diode D and the encapsulation film 320 .

Referring to FIG. 9, which is a schematic cross-sectional view showing one pixel of an organic light emitting diode display device, a thin film transistor Tr is formed on a substrate 310, and an organic light emitting diode connected to the thin film transistor Tr is formed on top of the thin film transistor Tr ( D) is formed, and an encapsulation film 320 covering the organic light emitting diode D is attached to the substrate 310 while covering the organic light emitting diode D.

A semiconductor layer 330 is formed on the substrate 310 . For example, the substrate 310 may be a flexible substrate such as a glass substrate or polyimide, and the semiconductor layer 330 may be made of an oxide semiconductor material or polycrystalline silicon.

Although not shown, a buffer layer may be formed on the substrate 310 and a semiconductor layer 330 may be formed on the buffer layer.

When the semiconductor layer 330 is made of an oxide semiconductor material, a light blocking pattern (not shown) may be formed under the semiconductor layer 330, and the light blocking pattern prevents light from entering the semiconductor layer 330. Thus, the semiconductor layer 122 is prevented from being deteriorated by light.

A gate insulating layer 332 made of an insulating material is formed on the semiconductor layer 330 . The gate insulating layer 332 may be made of an inorganic insulating material such as silicon oxide or silicon nitride.

A gate electrode 340 made of a conductive material such as metal is formed on the gate insulating layer 332 corresponding to the center of the semiconductor layer 330 .

An interlayer insulating film 342 made of an insulating material is formed on the gate electrode 340 . The interlayer insulating layer 342 may be formed of an inorganic insulating material such as silicon oxide or silicon nitride, or an organic insulating material such as benzocyclobutene or photo-acryl.

A mask process is performed on the interlayer insulating layer 342 and the gate insulating layer 332 to form first and second contact holes 344 and 346 in the semiconductor layer exposing both sides of the semiconductor layer 330 . The first and second contact holes 344 and 346 are spaced apart from the gate electrode 340 on both sides of the gate electrode 340 .

A source electrode 350 and a drain electrode 352 made of a conductive material such as metal are formed on the interlayer insulating layer 342 .

The source electrode 350 and the drain electrode 352 are spaced apart from each other around the gate electrode 340, and both sides of the semiconductor layer 330 through the first and second contact holes 344 and 346, respectively. come into contact with

The semiconductor layer 330, the gate electrode 340, the source electrode 350, and the drain electrode 352 constitute the thin film transistor Tr, and the thin film transistor Tr is a driving element. ) function as

The thin film transistor Tr has a coplanar structure in which the gate electrode 340 , the source electrode 350 and the drain electrode 352 are positioned on the semiconductor layer 330 .

Alternatively, the thin film transistor Tr may have an inverted staggered structure in which a gate electrode is positioned below the semiconductor layer and a source electrode and a drain electrode are positioned above the semiconductor layer. In this case, the semiconductor layer may be made of amorphous silicon.

Although not shown, a gate line and a data line cross each other to define a pixel area, and a switching element connected to the gate line and the data line is further formed. The switching element is connected to the thin film transistor Tr, which is a driving element.

In addition, a power line is formed to be spaced apart in parallel with the data line or the data line, and a storage capacitor for maintaining a constant voltage of the gate electrode of the thin film transistor (Tr), which is a driving element, for one frame is further provided. can be configured.

A protective layer 354 having a drain contact hole 356 exposing the drain electrode 352 of the thin film transistor Tr is formed to cover the thin film transistor Tr.

On the protective layer 354, a first electrode 370 connected to the drain electrode 352 of the thin film transistor Tr through the drain contact hole 356 is formed separately for each pixel area. The first electrode 370 may be an anode and may be made of a conductive material having a relatively high work function value. For example, the first electrode 370 may be made of a transparent conductive material such as indium-tin-oxide (ITO) or indium-zinc-oxide (IZO). .

Meanwhile, when the organic light emitting diode display device 300 of the present invention is a top-emission type, a reflective electrode or a reflective layer may be further formed below the first electrode 370 . For example, the reflective electrode or the reflective layer may be made of an aluminum-palladium-copper (APC) alloy.

In addition, a bank layer 376 covering an edge of the first electrode 370 is formed on the passivation layer 354 . The bank layer 376 exposes the center of the first electrode 370 corresponding to the pixel area.

An organic emission layer 372 is formed on the first electrode 370 . The organic light emitting layer 372 may have a single layer structure of an emitting material layer made of a light emitting material. In addition, in order to increase the luminous efficiency, the organic light emitting layer 372 includes a hole injection layer, a hole transporting layer, a light emitting material layer, and an electron transporting layer sequentially stacked on the first electrode 370. It may have a multilayer structure of an electron transporting layer and an electron injection layer.

A second electrode 374 is formed on the substrate 310 on which the organic emission layer 372 is formed. The second electrode 374 is located on the front surface of the display area and is made of a conductive material having a relatively low work function value and can be used as a cathode. For example, the second electrode 374 may be formed of any one of aluminum (Al), magnesium (Mg), and an aluminum-magnesium alloy (AlMg).

The first electrode 370, the organic light emitting layer 372, and the second electrode 374 form an organic light emitting diode (D).

A barrier film 320 is formed on the second electrode 374 to prevent penetration of external moisture into the light emitting diode (D). The barrier film 320 is an organic-inorganic hybrid barrier film in which inorganic particles are cross-linked to polymer chains. As described above, the barrier film 320 may be attached to the organic light emitting diode D through an adhesive layer (not shown).

In the barrier film 320, the inorganic particles are cross-linked to the polymer chain, so that the optical properties are satisfied with high uniformity of dispersion while having desired water barrier properties.

Therefore, compared to a conventional organic light emitting diode display having an encapsulation in which an inorganic layer, an organic layer, and an inorganic layer are stacked, the organic light emitting diode display 300 can be provided with a simple manufacturing process.

Although not shown, a polarizer (not shown) may be attached to the barrier film 320 or to the outside of the substrate 310 to reduce reflection of external light. For example, the polarizing plate may be a circular polarizing plate.

As shown in FIG. 6A or 6B, in the polarizers 100 and 200, at least one of the first base substrates 120 and 220 and the second base substrates 130 and 230 is made of the barrier film of the present invention.

Accordingly, the organic light emitting diode display device 300 including the barrier film 320 and the polarizing plates 100 and 200 can minimize damage to the organic light emitting diode caused by external moisture.

Meanwhile, since the polarizers 100 and 200 have moisture barrier properties, a polarizer using a barrier film as a base material may be attached to the organic light emitting diode D without the barrier film 320 .

10 is a schematic cross-sectional view of a liquid crystal display according to a sixth embodiment of the present invention.

As shown in FIG. 10, the liquid crystal display device 400 of the present invention includes a liquid crystal panel 410, a first polarizing plate 420 positioned below the liquid crystal panel 410, and the liquid crystal panel 410. It includes a second polarizing plate 430 located on top of. Although not shown, the liquid crystal display device 400 may further include a backlight unit (not shown) positioned below the first polarizing plate 420 .

The liquid crystal panel 410 includes first and second substrates 440 and 480 facing each other, and a liquid crystal layer interposed between the first and second substrates 440 and 480 and including liquid crystal molecules 492. (490).

Each of the first and second substrates 440 and 480 may be a flexible substrate such as a glass substrate or polyimide.

A thin film transistor Tr is formed on the first substrate 440 . Although not shown, a buffer layer may be formed on the first substrate 410, and a thin film transistor Tr may be formed on the buffer layer.

A gate electrode 442 is formed on the first substrate 410 , and a gate insulating layer 444 is formed covering the gate electrode 442 . In addition, a gate wire (not shown) connected to the gate electrode 442 is formed on the first substrate 410 .

A semiconductor layer 446 is formed on the gate insulating layer 444 to correspond to the gate electrode 442 . The semiconductor layer 446 may be made of an oxide semiconductor material. Meanwhile, the semiconductor layer 446 may include an active layer made of amorphous silicon and an ohmic contact layer made of impurity amorphous silicon.

A source electrode 450 and a drain electrode 452 spaced apart from each other are formed on the semiconductor layer 446 . In addition, a data line (not shown) connected to the source electrode 450 is formed crossing the gate line to define a pixel area.

The gate electrode 442, the semiconductor layer 446, the source electrode 450, and the drain electrode 452 constitute a thin film transistor Tr.

A protective layer 454 having a drain contact hole 456 exposing the drain electrode 452 is formed on the thin film transistor Tr.

On the protective layer 454, a pixel electrode 470 connected to the drain electrode 452 through the drain contact hole 456 and a common electrode 472 alternately arranged with the pixel electrode 470 are formed. is formed

A black matrix (not shown) is formed on the second substrate 480 to cover non-display areas such as the thin film transistor Tr, the gate wiring, and the data wiring. In addition, a color filter layer 482 is formed corresponding to the pixel area.

The first and second substrates 440 and 480 are bonded with the liquid crystal layer 490 therebetween, and the liquid crystal layer 490 is formed by an electric field generated between the pixel electrode 470 and the common electrode 472. ) of the liquid crystal molecules 492 are driven.

Although not shown, an alignment layer may be formed on each of the first and second substrates 440 and 480 in contact with the liquid crystal layer 490 .

The first polarizing plate 420 may be attached to the outside of the first substrate 440 , and the second polarizing plate 430 may be attached to the outside of the second substrate 480 . For example, the first and second polarizers 420 and 430 may be attached to the first and second substrates 440 and 480 through an adhesive layer (not shown), respectively.

An absorption axis (or transmission axis) of the first polarizer 420 may be perpendicular to an absorption axis (or transmission axis) of the second polarizer 430 .

As shown in FIG. 6A or 6B, in the first and second polarizers 420 and 430, at least one of the first base substrates 120 and 220 and the second base substrates 130 and 230 is viewed. It consists of the barrier film of the invention.

That is, the base substrates of the first and second polarizers 420 and 430 are formed of organic-inorganic hybrid barrier films in which inorganic particles are cross-linked to polymer chains, thereby having desired moisture barrier properties and high dispersion uniformity. satisfy the optical properties.

Therefore, even if the first and second substrates 420 and 430 are made of a flexible substrate such as polyimide that is weak to moisture permeation, damage to the liquid crystal panel 410 due to external moisture can be prevented.

As described above, the barrier film of the present invention is formed by cross-linking inorganic particles to a polymer chain, so that it has a single layer structure and can have desired moisture barrier properties.

Therefore, when using the barrier film, it is possible to provide a polarizing plate and a display device in which manufacturing costs are reduced and damage due to moisture permeation is prevented.

Although the above has been described with reference to preferred embodiments of the present invention, those skilled in the art can variously modify and change the present invention within the scope not departing from the technical spirit and scope of the present invention described in the claims below. You will understand that it can be done.

100, 200, 420, 430: polarizing plate 110, 210: polarizing film
120, 130, 220, 230: base film
300: organic light emitting diode display
320: barrier film 400: liquid crystal display

Claims (16)

polymerizing the monomers at a first temperature to form a low molecular weight polymer;
adding a crosslinking agent and crosslinking the low molecular weight polymer at a second temperature to form a crosslinked polymer;
forming an inorganic particle-crosslinked polymer by adding inorganic particles at a third temperature to replace the crosslinking agent of the crosslinked polymer with the inorganic particles;
Forming a polymer by polymerizing the inorganic particle-crosslinked polymer at a fourth temperature;
The second temperature is a method of manufacturing a barrier film smaller than the first temperature.

delete delete According to claim 1,
The third temperature is a method of manufacturing a barrier film lower than the first temperature.
delete delete delete According to claim 1,
The method of manufacturing a barrier film wherein the inorganic particles have a weight ratio of 10 to 50% with respect to the polymer.
According to claim 1,
The crosslinking agent is selected from Si-based, alkyl-based, epoxy-based, acryl-based, ether-based, ester-based, and peroxide-based materials, and the inorganic particles are a barrier film selected from metals, metal oxides, metal nitrides, metal fluorides, and silicon-based materials. manufacturing method.
According to claim 1,
The low molecular weight polymer includes N monomers, and N is 4 or more and 20 or less.
forming a polarizing film;
Attaching first and second barrier films to both sides of the polarizing film,
At least one of the first and second barrier films is a method of manufacturing a polarizing plate manufactured by the method of claim 1.
forming a liquid crystal panel;
Attaching the polarizing plate manufactured by the method of claim 11 to one side of the liquid crystal panel.
Method for manufacturing a liquid crystal display device comprising a.
forming an organic light emitting diode on a substrate;
attaching a barrier film prepared by the method of claim 1 onto the organic light emitting diode so as to cover the organic light emitting diode;
Method of manufacturing an organic light emitting diode display device comprising a.
forming an organic light emitting diode on a substrate;
Attaching the polarizing plate manufactured by the method of claim 11 onto the organic light emitting diode so as to cover the organic light emitting diode.
Method of manufacturing an organic light emitting diode display device comprising a.
polymerizing the monomers at a first temperature to form a low molecular weight polymer;
adding a crosslinking agent and crosslinking the low molecular weight polymer at a second temperature to form a crosslinked polymer;
forming an inorganic particle-crosslinked polymer by adding inorganic particles at a third temperature to replace the crosslinking agent of the crosslinked polymer with the inorganic particles;
Forming a polymer by polymerizing the inorganic particle-crosslinked polymer at a fourth temperature;
The third temperature is a method of manufacturing a barrier film lower than the first temperature.
According to claim 1 or 15,
The fourth temperature is a method of manufacturing a barrier film greater than the first temperature.

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