KR20090120546A - Flexible dispaly substrate using nano clay and flexible dispaly employed them - Google Patents

Abstract

PURPOSE: A flexible display substrate using nano clay and a flexible display including the same are provided to improve transparency and humidity preventing property by controlling a nano particle size. CONSTITUTION: A flexible display substrate using nano clay includes a polymer resin. The nano clay is formed with a chain shape of a nano size. The nano clay is made of a gas barrier coating layer. A particle size of the nano clay formed with the chain shape is 1~3nm. The nano clay formed with the chain shape has a fixed orientation under a current of 0.1~0.5mA.

Description

Flexible display substrate using nano clay and flexible display having same {FLEXIBLE DISPALY SUBSTRATE USING NANO CLAY AND FLEXIBLE DISPALY EMPLOYED THEM}

The present invention relates to a flexible display substrate having improved transparency and moisture permeability using nano clay and a flexible display having the same, and more preferably to a nano barrier having a chain shape manufactured using a porous silicate template as a gas barrier coating layer. The present invention relates to a flexible display substrate, and a flexible display having improved transparency and moisture permeability.

Background Art A glass substrate has conventionally been used for an image display device represented by a liquid crystal display.

However, in recent years, an image display device has been required to have a further thinner, lighter weight, larger screen, freedom of shape, curved display, and a high-transparent polymer film substrate has been studied as a material to replace a heavy and brittle glass substrate.

Since a liquid crystal display (hereinafter referred to as "LCD") must employ a backlight, many members must be used. In comparison, displays having a magnetic printing function using an electroluminescent (EL) display element, in particular an organic light emitting diode (hereinafter referred to as "OLED") such as an organic EL element, and an electronic ink such as electronic paper In terms of being able to cope with a smaller member than a liquid crystal display, development is progressing to a display excellent in thinning, portability, and flexibility.

Polymer films have been studied as substrate materials for such applications, and portable applications and flexible displays such as roll rolls have been actively developed using the flexibility of the polymer films.

In other words, a flexible display is a flat panel display made of a plastic-like substrate that can be bent or rolled while maintaining excellent display characteristics. Therefore, almost all IT products can be produced and utilized in various forms. Of course, it can be applied to household goods.

In general, a flexible display is composed of a substrate, a transparent electrode formed on the substrate, and a display material, and by replacing the substrate material with a plastic film on a glass substrate surrounding a liquid crystal in a conventional LCD or OLED, an LCD using a conventional glass substrate or Compared to OLED, it is thinner, lighter and more shock-resistant than ever.

Therefore, the flexible display substrate is required to have transparency so as not to impair mechanical strength, flexibility, gas barrier properties for enhancing durability of organic EL elements, electronic ink and the like, and visibility of the display.

Japanese Laid-Open Patent Publication No. 2003-17244 discloses polyethylene terephthalate, polycarbonate, polyolefin, polyether sulfone, and the like as the substrate material.

However, since the substrate material has a large thermal expansion rate, the flexible display used for the substrate has a problem of cracking in the transparent electrode due to ambient temperature change, thereby increasing resistance, or even disconnection.

In addition, the plastic film used as a substrate for flexible display is significantly weaker than the conventional glass, so additional gas barrier coating layer is required, and clay as a way to improve the performance of the gas barrier in recent years It is applied a lot.

However, since clay is an inherently colored material, there is a disadvantage in that transparency is lowered when coated on a flexible substrate, and the substrate is cracked or broken when the degree of warpage of the coated film due to rigidity due to clay is large. For this reason, a flexible display using a clay-coated flexible substrate has been pointed out that the displayed screen is blurred or has low flexibility.

Therefore, in order to commercialize the flexible display, the flexible display substrate having the gas barrier coating layer using the conventional clay should be assumed to have improved transparency and moisture permeability.

Accordingly, the present inventors intend to disclose a gas barrier coating layer technology using nano clay having superior transparency and flexibility as well as excellent moisture permeability for commercialization of a flexible display.

An object of the present invention is to provide a flexible display substrate with improved transparency and moisture permeability using nano clay.

Another object of the present invention is to provide a method of manufacturing a flexible display substrate having improved transparency and moisture permeability, wherein the nano clay is formed of a gas barrier coating layer.

Another object of the present invention is to provide a flexible display having a flexible display substrate having improved transparency and moisture permeability.

In order to achieve the above object, the present invention provides a flexible display substrate having improved transparency and moisture permeability of the nano clay formed in the polymer resin and nano-sized chain form of the gas barrier coating layer.

The nanoclays formed in the chain form have a particle size of 1 to 3 nm, and have a constant orientation under a current of 0.1 to 0.5 mA.

The polymer resin of the present invention uses at least one member selected from the group consisting of olefin copolymers, polyethylene terephthalates, polyethylene naphthalates, polyether sulfones, polyimides, polyacrylate barriers, polycarbonates and polyvinyl alcohols.

In addition, the clay may be kaolinite, smectite, kaolinite, dickite, nacrite, halosite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilylmica, sodium teniolite, white mica, pearl mica, At least one selected from the group consisting of talc, vermiculite, gold mica, zansopyrite and chlorite is used.

The present invention is 1) preparing a porous silicate template, 2) impregnating clay in a solution containing the prepared porous silicate template by the impregnation method, dried at 100 ± 20 ℃ and plastically processed, the chain-shaped nanoclay And 3) providing a method of manufacturing a flexible display substrate having improved transparency and moisture permeability by mixing the chain-shaped nanoclay with a polymer resin or coating the polymer resin on a surface of the polymer resin.

At this time, 1 to 10 parts by weight of clay is supported based on 100 parts by weight of the porous silicate template.

The particle size of the chain-shaped nanoclay depends on the particle size of the porous silicate template to be removed during plastic working, and thus has the same size as the porous silicate template. More preferably, in the production method of the present invention, the chain-shaped nanoclay has a particle size of 1 to 3 nm.

In addition, the manufacturing method of the present invention imparts a constant orientation to the nanoclay by flowing a current of 0.1 to 0.5mA when applied to the surface of the polymer resin.

Furthermore, the present invention provides a flexible display including a flexible display substrate and a transparent electrode (anode and cathode) in which a nano resin formed in a polymer resin and chain form is formed of a gas barrier coating layer.

At this time, the flexible display of the present invention is provided by the nano-clay formed in the chain form having a particle size of 1 to 3 nm, by having a flexible display substrate having a certain orientation under a current of 0.1 to 0.5mA, thereby improving moisture permeability and transparency.

The present invention is to modify the nano-clay formed in the form of a chain using a porous silicate template for a flexible display substrate having a gas barrier coating layer using a conventional clay, by controlling the nano-particle size, moisture resistance and transparency of the conventional problem It can be improved.

In addition, the nanoclay of the present invention can be effectively mass-produced through silicate.

Hereinafter, the present invention will be described in detail.

1 illustrates a structure of a flexible display substrate of the present invention. The present invention provides a flexible display substrate comprising a gas barrier coating layer comprising a nano resin formed in a polymer resin and a nano-sized chain.

"Nano clay" of the present invention refers to a clay formed in a long chain form by imparting a uniform pore structure from the porous silicate by being prepared from a porous silicate having a uniform nano-sized pore structure.

Since the nanoclay of the present invention is formed in a uniform pore structure and a long chain form, it improves the disorderly dispersity of ordinary clay, and suppresses water infiltration by the compact network structure of nano pore size. Therefore, the moisture permeability is improved to a degree comparable to the conventional glass substrate.

Furthermore, the nanoclay having a chain form of the present invention has a uniform arrangement by the interaction of the nanomaterial. Therefore, when coated on a film, when a current of 0.1 to 0.5 mA is applied to both axes of the film, the film has a constant orientation. At this time, the current is preferably 0.1 to 0.5mA. If the current is lower than 0.1 mA, it does not react to the clay, whereas if the current is higher than 0.5 mA, the interaction between the clays is strong and the chain structure may be broken.

In addition, the particle size of the nanoclay of the present invention is controlled to 1 to 3 nm, thereby improving transparency. In this case, when the particle size of the nanoclay is less than 1 nm, the structure may collapse during the film coating process, and when the particle size exceeds 3 nm, the clay becomes thick and the transparency decreases.

In the present invention, the polymer resin used in combination with the nano-clay formed in the chain form is a thermoplastic resin, and preferably used as long as it is transparent to visible light. Preferably the glass transition point (Tg) should be excellent in heat resistance as 150 degreeC or more, More preferably, it is 180 degreeC or more, More preferably, it is 200 degreeC or more. Examples thereof include low density polyethylene, high density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-norbornene copolymer, ethylene-dmonone copolymer, polypropylene Polyolefin copolymers such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer and ionomer resin; Polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Nylon-6, nylon-6,6, metaxylenediamine-adipic acid condensers; Amide resins such as polymethyl methacrylimide; Acrylic resins such as polymethyl methacrylate; Styrene-acrylonitrile resins such as polystyrene, styrene-acrylonitrile copolymers, styrene-acrylonitrile-butadiene copolymers, and polyacrylonitrile; Hydrophobized cellulose resins such as triacetic cellulose and diacetic cellulose; Halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and polytetrafluoroethylene; Hydrogen bond resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose derivatives; Polycarbonate; Polysulfones; Polyether sulfone; Polyether ether ketone; Polyphenylene oxide; Polymethylene oxide; Liquid crystal resin.

More preferably, at least one selected from the group consisting of an olefin copolymer, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyimide, polyacrylate, polycarbonate and polyvinyl alcohol as the polymer resin of the present invention To use.

Then, the clay used in the present invention is kaolinite, smectite, kaolinite, dickite, nacrite, halosite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilyl mica, sodium teniolite, At least one selected from the group consisting of dolomite, pearl mica, talc, vermiculite, gold mica, zansopyrite and chlorite, preferably kaolinai, smectite, vermiculite, and the like. Preferably kaolinite. In addition, the kaolinite clay may be natural kaolinite-based or synthetic kaolinite-based.

1 illustrates a flexible display substrate structure of the present invention, comprising: a substrate; A gas barrier coating layer; And made of a structure consisting of a transparent electrode, to protect the film between the transparent electrode and the layer, the overcoat layer or an undercoat layer can be further laminated for the wear resistance of the film. In addition, a primer layer may be further laminated to improve adhesion. The additional laminated overcoat layer, undercoat layer or primer layer can be easily modified by those skilled in the art according to the desired purpose.

The present invention is to prepare 1) a porous silicate template,

2) Impregnating clay in the solution containing the prepared porous silicate template by the impregnation method, dried at 100 ± 20 ℃ temperature and then plasticized to prepare a chain-shaped nanoclay,

3) The present invention provides a method of manufacturing a flexible display substrate having improved transparency and moisture permeability by mixing the chain-shaped nanoclay with a polymer resin or coating the polymer resin on a surface of the polymer resin.

In step 1), the porous material is preferably a pure silica material, and tetraethyl orthosilicate is added to a Pluronic copolymer surfactant solution in a strong acidic atmosphere of pH 3.0 or lower, and hydrothermal synthesis ), Filtered, and then calcined to prepare a porous silicate template having 1 to 3 nm pores (Mesoporous silicate Template). The porous silicate can control the size of the pores by controlling the temperature during hydrothermal synthesis, and can eliminate all impurities other than silica during the plastic working.

Step 2) is prepared by dissolving the prepared porous silicate template in an organic solution, and the clay is supported by an incipient wetness method, then dried at 100 ± 20 ℃ temperature and plastically processed to form a nano-sized chain form To prepare a nano clay having.

The nano-sized chain form in the nanoclay is produced by the particle size of the porous silicate template to be removed during plastic processing. Therefore, the particle size of the chain-shaped nanoclay depends on the particle size of the porous silicate template to be removed during plastic working, and thus has the same size as the porous silicate template used.

More preferably, in the production method of the present invention, the chain-shaped nanoclay has a particle size of 1 to 3 nm. In this case, if the particle size of the clay is less than 1 nm, the structure may collapse during the film coating process, and if it exceeds 3 nm, the clay becomes thick and transparency is lowered.

At this time, the clay is kaolinite, smectite, kaolinite, dickite, nacrite, halosite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilic mica, sodium teniolite, white mica, pearl mica, It is at least one selected from the group consisting of talc, vermiculite, gold mica, zansopyrite and chlorite, and preferably kaolini-based, smectite-based, vermiculite-based or the like.

The clay is preferably added in an amount of 1 to 10 parts by weight based on 100 parts by weight of the porous silicate template. At this time, if the clay is less than 1 part by weight, it is difficult to form a uniform chain form, and if it exceeds 10 parts by weight, the transparency of the film may be lowered.

Since the nanoclay modified into a uniform nano-sized long chain form of the present invention is synthesized from a porous silicate having nano-sized pores as a starting material, it is possible to efficiently mass-produce nanoclays through the silicate material.

Step 3) provides a method of manufacturing a flexible display substrate having a gas barrier coating layer prepared by mixing the chain-shaped nanoclay with a polymer resin or by coating the polymer resin on a surface of the polymer resin.

In addition, as a method of mixing the chain-shaped nanoclay with a polymer resin, a compounding may be prepared by feeding a twin screw extruder or a batch mixer using a syringe pump.

In this case, the polymer resin to be compounded is as described above, more preferably, olefin copolymer, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyimide, polyacrylate, polycarbonate and polyvinyl alcohol It is made of one or more selected from the group consisting of.

In addition, the manufacturing method of the present invention imparts a constant orientation to the nanoclay by flowing a current of 0.1 to 0.5mA when applied to the surface of the polymer resin. At this time, when the current is lower than 0.1mA, it does not react to the clay, on the other hand, if it exceeds 0.5mA, the interaction between the clay is a strong action can be broken chain structure is not preferable.

Furthermore, the present invention provides a flexible display including a flexible display substrate and a transparent electrode (anode and cathode) in which a nano resin formed in a polymer resin and chain form is formed of a gas barrier coating layer.

The flexible display of the present invention includes a flexible organic EL display or a flexible liquid crystal display.

At this time, the flexible display of the present invention is provided by the nano-clay formed in the chain form having a particle size of 1 to 3 nm, and having a flexible display substrate having a constant orientation under a current of 0.1 to 0.5mA, thereby improving moisture permeability and transparency.

Hereinafter, the present invention will be described in more detail with reference to Examples.

This embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

<Examples 1-3>

Tetraethyl orthosilicate was stirred in a pluronic copolymer surfactant solution in a strong acid atmosphere of pH 3 or less, hydrothermally synthesized at 60 ° C., filtered, and calcined at 550 ° C. to remove impurities other than silica. From this method, a template of porous silicate structure having pores of 3 nm was prepared.

100 g of the prepared porous material template-containing solution was loaded with 5 g of kaolinite for 5 minutes by an incipient wetness method. Thereafter, the porous material template was removed by drying at 100 ° C. and then plastically processing at 550 ° C. Then, a long chain nanoclay having a particle size of 3nm was obtained.

The nanoclay having the nano-sized chain form prepared above was coated on the polycarbonate surface to prepare a gas barrier coating layer having a thickness of 100 nm.

The thickness was changed to 200 nm and 300 nm, except that the gas barrier coating layer was manufactured.

<Example 4>

The same procedure as in Example 1 was carried out except that 10 g of kaolinite was supported on 100 g of the template containing solution of the porous material.

<Comparative Examples 1 to 3>

The same procedure as in Example 1 was carried out except that a gas barrier coating layer having a thickness of 100, 200, and 300 nm was manufactured using a conventional clay, not a nano clay having a nano-sized chain form.

<Comparative Example 4>

In the hydrothermal synthesis of the porous silicate, using a template of a porous silicate structure having a pore of 10nm by performing at 50 ℃, except for producing a chain-shaped nanoclay having a particle size of 10nm, Example 1 and The same was done.

Comparative Example 5

When hydrothermal synthesis of the porous silicate, using a template of a porous silicate structure having a pore of 15nm by performing at 35 ℃, except for producing a chain-shaped nanoclay having a particle size of 15nm, Example 1 and The same was done.

Experimental Example 1

For a flexible display substrate having a gas barrier coating layer prepared using nanoclay having a nano-sized chain form prepared in Examples 1 to 3, transparency and moisture permeability were measured, and the surface of the gas barrier coating layer was observed. It is shown in Table 1 .

division Film thickness Transparency (at 400 ~ 700nm) Permeability (at 40 ℃ 90% RH) Surface observation (SEM) Example 1 100 nm 87% 0.010 g / m ² [day] 3nm pore observation Example 2 200 nm 85% 0.007 g / m ² [day] 3nm pore observation Example 3 300 nm 72% 0.002 g / m ² [day] 3nm pore observation

On the other hand, with respect to a flexible display substrate having a gas barrier coating layer manufactured using a conventional general clay rather than a nano clay having a nano-sized chain form, the transparency and moisture permeability were measured, and the surface of the gas barrier coating layer was observed. It is shown in Table 2 .

division Film thickness Transparency (at 400 ~ 700nm) Permeability (at 40 ℃ 90% RH) Surface observation (SEM) Comparative Example 1 100 nm 83% 0.040 g / m ² [day] Bunch Comparative Example 2 200 nm 81% 0.015 g / m ² [day] Bunch Comparative Example 3 300 nm 75% 0.009 g / m ² [day] Bunch

As shown in Tables 1 and 2, the flexible display substrate having the gas barrier coating layer manufactured using the nanoclay having the nano-sized chain form of the present invention has the same thickness, transparency, and transparency compared with the case of conventional clay. Moisture resistance has been improved. In addition, micropores were confirmed without aggregation on the surface.

As described above, the present invention

First, a chain-shaped nanoclay prepared by supporting a conventional clay in a porous silicate template-containing solution, drying and plasticizing was prepared.

Second, the structure and particle size of the chain-shaped nanoclay was optimized, and the transparency and moisture permeability of the flexible display substrate including the chain-shaped nanoclay as a gas barrier coating layer were improved.

Third, since the chain-type nanoclay is manufactured from porous silicates, mass production is possible.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

1 illustrates the structure of a flexible display substrate of the present invention.

Claims (13)

Polymer resin and A flexible display substrate with improved transparency and moisture permeability, characterized in that the nano clay formed in a nano-sized chain form consists of a gas barrier coating layer. The flexible display substrate of claim 1, wherein the nanoclays formed in the chain form have a particle size of 1 to 3 nm. The flexible display substrate of claim 1, wherein the nanoclays formed in the chain form have a constant orientation under a current of 0.1 to 0.5 mA. The method of claim 1, wherein the polymer resin is at least one selected from the group consisting of an olefin copolymer, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyimide, polyacrylate barrier, polycarbonate and polyvinyl alcohol. The flexible display substrate. The method of claim 1, wherein the clay is kaolinite, smectite, kaolinite, dickite, nacrite, halosite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilyl mica, sodium teniolite, The flexible display substrate, characterized in that at least one selected from the group consisting of dolomite, pearl mica, talc, vermiculite, gold mica, zansopyrite and chlorite. 1) prepare a porous silicate template, 2) impregnating the clay in the solution containing the prepared porous silicate template by the impregnation method, dried at 100 ± 20 ℃ and plasticized to prepare a chain-shaped nanoclay, 3) A method of manufacturing a flexible display substrate with improved transparency and moisture permeability, characterized in that the chain-shaped nanoclay is mixed with a polymer resin or coated on the polymer resin surface. The method according to claim 6, wherein 1 to 10 parts by weight of clay is supported based on 100 parts by weight of the porous silicate template. The method according to claim 6, wherein the chain-shaped nanoclay has a particle size of the same size as that of the porous silicate template to be removed during plastic working. The method according to claim 6, wherein the chain-shaped nanoclay has a particle size of 1 to 3 nm. The method according to claim 6, wherein, when applied to the surface of the polymer resin, a current of 0.1 to 0.5 mA flows to impart a constant orientation to the nanoclay. A flexible display having improved moisture permeability and transparency, comprising a flexible display substrate of claim 1, wherein the nano clay formed in a chain form is formed of a gas barrier coating layer on a base film made of a polymer resin. The flexible display according to claim 11, wherein the nanoclays formed in the chain form have a particle size of 1 to 3 nm. The flexible display of claim 11, wherein the nanoclays formed in the chain form have a constant orientation under a current of 0.1 to 0.5 mA.

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