TW201819564A - OLED package tape, method for producing the same and using the same for packaging OLED - Google Patents

Abstract

The present invention is an OLED package tape, comprising a first releasing film and a moisture barrier layer, wherein the moisture barrier layer is formed on the releasing side of the first releasing film and comprises modified nano-monmorillonite and epoxy resin. The OLED package tape of the present invention not only blocks water vapor and oxygen effectively, but also provides characteristics of high mechanical strength, high thermal stability, gas barrier and solvent resistance, for proving the efficacy of packaging OLED and elongating the service life of OLED.

Description

 Film for OLED packaging, manufacturing method thereof and packaged OLED method using same  

The present invention relates to a film for OLED packaging that can be used to package OLEDs, particularly semiconductor devices.

OLED (Organic Light Emitting Diode) has long replaced the traditional CRT display because of its high luminous efficiency, high brightness, wide viewing angle and fast screen response. It is used as a lighting device for displays, such as mobile phones, computer monitors, TV screens, and others. Handheld device, or other device used to display information.

Today, the OLED industry has been committed to the development of OLED packaging technology. Due to the good packaging of OLED, it is often a key factor affecting the internal performance and service life of OLED. Poor packaging will cause moisture and oxygen to enter the OLED, causing problems such as electrode oxidation, delamination or material cracking.

Common OLED packaging methods, including UV glue and filler package, glass glue package or desiccant package, etc., which are most commonly used in UV glue and filler. However, when using UV glue and filling glue, due to the viscosity of the liquid filling glue, bubbles that are difficult to be removed are often stored in the encapsulation layer when poured into the sealing strip, so that there are bubbles remaining in the encapsulating layer, and in the bubbles There are moisture and oxygen, which affects the performance and life of the OLED.

In addition, there is also a desiccant with UV glue and filler to package to solve the problem of water vapor and oxygen in the bubble, but some of the desiccant is corrosive after filling, causing cracking of the material in the OLED, especially the liquid desiccant. .

In view of the above-mentioned general OLED packaging method, there is a problem that packaging effect such as bubble generation is not good, and the inventors intend to provide a film for OLED packaging which can be directly attached to an OLED to be packaged, and then cured by UV light and/or thermally hardened. That is, the package is completed, and the problem of residual bubbles in the package is effectively improved.

Since the film for OLED encapsulation of the present invention comprises a water vapor barrier layer, the material of the water vapor barrier layer is modified nano montmorillonite, which has high hydrophobicity and high heat in addition to hydrophobic properties to effectively block moisture. The stability, gas barrier and solvent resistance properties enhance the performance of OLED packages and extend the life of OLEDs.

That is, the present invention provides a film for OLED packaging, comprising a first release sheet and a moisture barrier layer, the moisture barrier layer being formed on the peelable surface of the first release sheet, wherein the moisture resists The layer contains modified nano montmorillonite and epoxy resin.

In a preferred embodiment, the modified nano-montmorillonite is modified with polyetheramine.

In a preferred embodiment, the polyetheramine has a molecular weight of from 200 to 5,000 and has repeating units of the following formula (I): Wherein n is an integer from 2 to 50.

In a preferred embodiment, the modified nano montmorillonite is added in an amount of 100% by weight of the epoxy resin, and 1 to 10 phr is added.

In a preferred embodiment, the moisture barrier layer further comprises a second release sheet on a side of the first release sheet.

The invention provides a method for preparing the above-mentioned film for OLED packaging, which comprises the following steps: (a) providing a first release sheet; (b) mixing modified nano montmorillonite and epoxy resin to obtain an epoxy a resin-modified nano montmorillonite slurry; (c) applying the epoxy resin-modified nano montmorillonite slurry to the peelable surface of the first release sheet to form a wet film and baking Bake to form a moisture barrier.

In a preferred embodiment, the baking conditions are at a temperature of from 70 to 120 ° C for a period of from 5 to 12 minutes.

In a preferred embodiment, the method further comprises attaching a peelable surface of a second release sheet to the moisture barrier layer.

The invention provides a method for packaging an OLED, comprising the above OLED packaging film, which is attached with a moisture barrier layer on an OLED component on a first substrate, tearing off the release sheet, and attaching a second substrate. On the moisture barrier layer, it is cured by UV light and/or thermally cured.

The present invention provides a packaged OLED obtained by encapsulation of claim 9.

1‧‧‧OLED packaging film

1'‧‧‧OLED packaging film

3‧‧‧Water and gas barrier

5‧‧‧The first release piece

5'‧‧‧Second release piece

7‧‧‧Epoxy resin-modified nano-montmorillonite slurry

7'‧‧‧ wet film

9‧‧‧Modified Nano-montmorillonite

11‧‧‧Epoxy resin

13‧‧‧First substrate

13'‧‧‧second substrate

15‧‧‧OLED

1 is a schematic view 1 of a film for OLED packaging according to the present invention.

2 is a schematic view 2 of a film for OLED packaging according to the present invention.

3 is a flow chart of a method for preparing a film for OLED packaging according to the present invention.

4 is a flow chart of a method of packaging an OLED of the present invention.

FIG. 5 is a schematic view showing the shape required for pre-cutting the film for OLED packaging of the present invention.

The OLED encapsulating film of the present invention comprises a first release sheet and a moisture barrier layer formed on the peelable surface of the first release sheet, wherein the moisture barrier layer comprises Modified nano montmorillonite and epoxy resin; in fact, as shown in FIG. 1, the film 1 for OLED packaging includes a first release sheet 5 and a moisture barrier layer 3, and the moisture barrier layer 3 is formed thereon. The peelable surface of the first release sheet 5.

The above-mentioned modified nano montmorillonite system can be modified by an amine group-containing polymer such as polyetheramine, polyamidolimine or polyamidamine. Among them, the modified nano-montmorillonite can be used for sodium montmorillonite or lithium-based nano-montmorillonite. The modification method uses a cation exchange method to replace the cation of the nano montmorillonite with a polymer having an amine group, as shown by the following reaction formula (MMT is montmorillonite, and the cation may be Na ⁺ or Li ⁺ ). : MMT-cation + polymer - NH ₃ ⁺ → MMT-NH ₃ ⁺ - polymer + cation.

Wherein, the above-mentioned modified nano montmorillonite is preferably modified with polyetheramine, and the polyetheramine may be a repeating unit having the following formula (I), and the molecular weight thereof is 200 to 5000: Wherein n is an integer from 2 to 50, such as 2, 3, 5, 6, 10, 15, 20, 25, 30, 33, 35, 40, 45 or 50.

The nanometer montmorillonite of the modified nano-montmorillonite may have a particle size of 1 to 1000 nm, for example, 1 nm, 5 nm, 10 nm, 30 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm. 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm or 1000 nm.

The modified nano montmorillonite is added in an amount of 100% by weight of the epoxy resin, and is added in an amount of 1 to 10 phr, for example, 1 phr, 1.5 phr, 2 phr, 2.5 phr, 3 phr, 3.5 phr, 4 phr, 4.5 phr, 5 phr, 5.5 phr, 6 phr, 6.5 phr, 7 pbr, 7.5 phr, 8 phr, 8.5 phr, 9 phr, 9.5 phr or 10 phr

The above epoxy resin may be a general-purpose epoxy resin such as triethoxypropyl isocyanurate, butadiene-acrylonitrile epoxy resin, phenoxy resin, bisphenol A epoxy resin, bromination Epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl amine type epoxy resin, ethyl urex type epoxy resin, alicyclic ring Oxygen resin, trishydroxyphenylmethane type epoxy resin, bis-xylenol type or bisphenol type epoxy resin or a mixture thereof, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, Tetraphenylphenol (PHENYLOL) ethane type epoxy resin, heterocyclic epoxy resin, diglycidyl benzoate resin, tetraglycidyl xylenyl ethane resin, epoxy resin containing naphthyl , nitrogen-containing epoxy resin, epoxy resin having a dicyclopentadiene skeleton, glycidyl methacrylate copolymerized epoxy resin, cyclohexylmaleimide and glycidyl methacrylate Copolymerized epoxy resin, CTBN modified epoxy resin, etc., but not limited to these, the epoxy trees It may be used alone or in combination of two or more.

The above-mentioned water gas barrier layer may be added with a common photoinitiator, including barium salts, organic metal salts, organic decanes, latent sulfonic acids, benzophenones, benzoin ethers, benzyl ketals, benzene. But not limited to, such as diaryl iodonium salts, triaryl sulfonium salts, aryl diazonium salts, iron aromatic hydrocarbons, phosphorus nitrobenzyl triaryl Base mercapto ether, triarylsulfonyl peroxide, mercaptodecane, α-sulfonyloxy ketone, α-hydroxymethylbenzoin sulfonate, benzophenone, N,N'-tetramethyl-4, 4'-Diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin Phenyl ether, isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-ethylhydrazine, etc. The photoinitiators may be used singly or in combination of two or more; the photoinitiator is added in an amount of 100% by weight of the epoxy resin, and added in an amount of 1 to 10 phr, for example, 1 phr, 1.5 phr, 2 phr, 2.5 phr, 3phr, 3.5phr, 4phr, 4.5phr, 5phr, 5 .5 phr, 6 phr, 6.5 phr, 7 phr, 7.5 phr, 8 phr, 8.5 phr, 9 phr, 9.5 phr or 10 phr.

The above-mentioned water vapor barrier layer may be added with a general thermal hardener, and includes, but is not limited to, polyamines, polythiols, imidazoles, etc., such as diethylenetriamine, triethylenetetramine, N -amino-ethylpyridazine, diamino-diphenylmethane, diammonium adipate, trioxane trimethylene thiol, benzyl-dimethylamine, 2,4,6-tris(dimethylamino) Methyl)phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2-phenyl-4,5-dimethylolimidazole, 2,4-diamino-6(2'-methylimidazolyl-(1'))ethyl-s -triazine, 2,4-diamino-6(2'-methylimidazolyl-(1'))ethyl-s-triazine, isocyanuric acid, triphenylphosphine, dicyandiamide, 3 -Phenyl-1,1-dimethylurea, 5-amino-1-naphthol or 8-hydroxyquinoline, etc., the thermosetting agent may be used singly or in combination of two or more kinds; The amount added is 100% by weight of epoxy resin, adding 1 to 10 phr, for example 1 phr, 1.5 phr, 2 phr, 2.5 phr, 3 phr, 3.5 phr, 4 phr, 4.5 phr, 5 phr, 5.5 phr, 6 phr, 6.5 phr, 7 phr, 7.5 phr, 8 phr, 8.5 Ph, 9 phr, 9.5 phr or 10 phr.

The above-mentioned water vapor barrier layer may be added with a general heat hardening accelerator, and may include dimethylurea or imidazole, but is not limited thereto and may be used alone or in combination of two or more kinds; the amount of the heat hardening accelerator added For 100% by weight of epoxy resin, 1 to 10 phr, for example 1 phr, 1.5 phr, 2 phr, 2.5 phr, 3 phr, 3.5 phr, 4 phr, 4.5 phr, 5 phr, 5.5 phr, 6 phr, 6.5 phr, 7 phr, 7.5 phr are added. , 8 phr, 8.5 phr, 9 phr, 9.5 phr or 10 phr.

The water vapor barrier layer may have a thickness of 5 to 300 μm, for example, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 70 μm, 100 μm, 130 μm, 150 μm, 180 μm, 200 μm, 230 μm, 250 μm. , 280 μm or 300 μm.

The first release sheet may be in the form of a roll, a sheet or a gel. The material may be composed of a film made of the following materials, such as polyethylene, polypropylene, polybutene, polybutadiene, polymethyl pentane. Alkene, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyurethane, ethylene - vinyl acetate, ionomer resin, ethylene / (methene) acrylic copolymer, ethylene / (methene) acrylate copolymer, polystyrene, polycarbonate, cellulose acetate, cellulose triacetate, Polyimine and fluorine resin. Among them, polymethylpentene, polyethylene naphthalate, cellulose triacetate and polyimide film are preferred because they have better heat resistance; the first release sheet has surface tension 400 millinewtons/meter or less, preferably 250 millinewtons/meter or less, more preferably 150 millinewtons/meter or less, the low surface tension can be achieved by selecting a sheet of a suitable material. The thickness of the release sheet 1 is usually 5 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 150 μm.

The water vapor barrier layer further comprises a second release sheet with respect to one side of the first release sheet, and a second release sheet 5' as shown in FIG. 2, the second release sheet having the same characteristics as described above The first release piece.

The method for preparing a film for OLED packaging according to the present invention comprises the steps of: (a) providing a first release sheet; (b) mixing modified nano montmorillonite and epoxy resin to obtain an epoxy a resin-modified nano montmorillonite slurry; (c) applying the epoxy resin-modified nano montmorillonite slurry to the peelable surface of the first release sheet to form a wet film, and Baking to form a moisture barrier layer; in fact, as shown in FIG. 3, a first release sheet 5 is provided, and the modified modified nano montmorillonite 9 and epoxy resin 11 are mixed to obtain an epoxy resin-modified nanometer. The montmorillonite slurry 7, the epoxy resin-modified nano montmorillonite slurry 7 is applied to the peelable surface of the first release sheet 5 to form a wet film 7', and baked to form a water. Gas barrier layer 3.

In the above method, the coating of the step (c) may be a general coating method such as spin coating, slit coating, cast coating, roll coating, rod coating or inkjet coating, A general coating machine, such as a coater, includes a roll coater, a gravure coater or a die coater.

In the above method, the baking condition has a temperature of 70 to 120 ° C and a time of 5 to 12 minutes. Wherein, the temperature may be, for example, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C, 95 ° C, 100 ° C, 105 ° C, 110 ° C, 115 ° C or 120 ° C; the time may be, for example, 5 minutes, 6 minutes, 7 Points, 8 points, 9 points, 10 points, 11 points or 12 points.

In the above method, the method further comprises attaching a peelable surface of a second release sheet to the moisture barrier layer, the second release sheet having the same characteristics as the first release sheet.

The method for packaging an OLED of the present invention comprises providing the film for OLED packaging described above, attaching a water vapor barrier layer to an OLED on a first substrate, tearing off the release sheet, and attaching a second substrate to the film. The water vapor barrier layer is further cured by UV light and/or thermally hardened; in fact, as shown in FIG. 4, the OLED encapsulating film 1' is first peeled off the second release sheet 5', and then the water vapor barrier layer is removed. 3 OLED 15 attached to the first substrate 13, tearing off the first release sheet 5, and attaching the second substrate 13' to the moisture barrier layer 3, and then curing by UV light and/or heat hardening That is, the package is completed.

In the above method, the OLED encapsulating film can be used after being pre-cut into a desired shape. For example, as shown in FIG. 5, the moisture barrier layer 3 can be pre-cut.

In the above method, the OLED encapsulating film is preheated before being applied, and the preheating temperature is about 70 to 100 ° C (for example, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C, 95 ° C or 100 ° C), heating time is 20 to 60 seconds (for example, 20 seconds, 25 seconds, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 55 seconds or 60 seconds).

In the above method, the irradiation wavelength and time of the UV curing, and the temperature and time of the thermal curing are adjusted according to the photoinitiator and the thermosetting agent to be used; in general, the UV curing is irradiated. The wavelength is about 330~400nm (for example, 330nm, 350nm, 380nm, or 400nm), and the irradiation time is about 30~60 seconds (for example, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 55 seconds, or 60 seconds), and the The temperature and time of heat hardening are 110~200°C (such as 110°C, 130°C, 150°C, 180°C or 200°C) and 20 minutes to 2.5 hours (20 minutes, 30 minutes, 50 minutes, 1 hour, 2 hours). Or 2.5 hours).

The method for packaging the OLED of the present invention can be disposed in an environment with an exhausting and exhausting device, which can reduce the airflow resistance of the packaging environment when the coating is applied, so as to increase the density of the OLED packaging film of the present invention when attached to the OLED. Synergy.

The packaged OLED of the present invention is obtained by using the film for OLED packaging of the present invention and the above OLED packaging method. The packaged OLED of the present invention can be used in display devices such as general purpose display devices such as cell phones, computers, televisions, or large screens.

[Specific embodiment]

In the following, the contents disclosed in the present invention will be specifically described using specific embodiments. However, the disclosure of the present invention is not limited to the following examples.

Preparation example. Modified nano-montmorillonite D2000/MMT

30g of sodium-nano-nine montmorillonite (purchased from Baikang Nai Technology) was dissolved in 100ml of deionized water at 90 ° C for four hours to prepare 1.15 milliequivalent aqueous solution of sodium-nine montmorillonite; 14.4g Jeffamine D2000 polyetheramine (structure of the formula (I), n is 33) is dissolved in 0.26 g (1.15 meq) of hydrochloric acid to prepare a 1.15 mol acidified Jeffamine D2000 polyetheramine solution; mixing the sodium-based montmorillonite The aqueous solution and the acidified Jeffamine D2000 polyetheramine solution were subjected to a cation exchange reaction at a temperature of 80 ° C for 30 minutes to obtain a modified nano montmorillonite D2000/MMT.

Example 1. OLED package film 1

68 g of triepoxypropyl isocyanurate (TEPIC-S sold by Nissan Chemical Co., Ltd.), 24 g of epoxy-terminated butadiene-acrylonitrile epoxy resin (Hypro 1300× sold by Emerald Performance Material, USA) 44 ETBN), 8 g of phenoxy resin (H360 sold by DIC, Japan Ink Chemical Industry Co., Ltd.), 6 g of dicyandiamide (sold by Degussa, Germany), and bis (dimethylurea) compound (U- sold by SANAPRO, Japan) CAT 3513N), photoinitiator (CPI-200S sold by SANAPRO, Japan) and 1g of modified nano-montmorillonite D2000/MMT of the preparation example are uniformly mixed, and the mixture is epoxy resin-modified nanometer Earth slurry.

The epoxy resin-modified nano montmorillonite slurry was precision coated onto a release sheet of polyethylene terephthalate to form a wet film having a thickness of 60 μm, and baked in a continuous oven at 90 ° C, 10 Minutes, and can be simultaneously assisted by ultraviolet light irradiation for at least 30 seconds (wavelength 365 nm) to form a water vapor barrier layer, and the OLED package film 1 is completed, as shown in Table 1.

Example 2. OLED package film 2

The manufacturing procedure of the same as in Example 1 is as shown in Table 1, except that the modified nano-montmorillonite D2000/MMT of the preparation example added by the epoxy resin/modified nano montmorillonite slurry was 2 g.

Example 3. OLED package film 3

The manufacturing procedure of Example 1 was as shown in Table 1, except that the modified nano-montmorillonite D2000/MMT of the preparation example added by the epoxy resin/modified nano-montmorillonite slurry was 4 g.

Comparative Example 1. OLED package film without modified nano-montmorillonite

The manufacturing steps of Example 1 are as shown in Table 1. The difference is that only the modified nano-montmorillonite D2000/MMT of the preparation example is not added to the mixture, and the completed packaged film does not have a moisture barrier layer, only For general packaging film.

Examples 4 to 6 and Comparative Example 2. Packaging OLED

The OLED package film of Examples 1 to 3 and the package film of Comparative Example 1 were preheated at 90 ° C for 30 seconds, respectively, and then attached to a glass substrate provided with an OLED and pressed to seal the OLED, and then torn. In addition to the release sheet of the OLED package film, another glass substrate is pasted on the moisture barrier layer and pressed by UV light at 365 nm for 40 seconds and then heated at 120 ° C for 2 hours to block the moisture. The layer hardening was completed, and the packaged OLEDs of Examples 4 to 6 and Comparative Example 2 were respectively packaged; after packaging, the moisture barrier layers of Examples 4 to 6 and the oxygen of the package film of Comparative Example 2 were tested using an oxygen permeability meter. The air permeability was measured as shown in Table 2.

As shown in Tables 1 and 2, since the moisture barrier layer of the OLED package film of Examples 1 to 3 contains modified nano montmorillonite, the moisture of the moisture barrier layer is lower than that of the general package film of Comparative Example 1. The low gas permeability means that the gas can be effectively blocked from entering the interior of the OLED package. Moreover, as the content of the modified nano montmorillonite increases, the oxygen permeability thereof also decreases.

Therefore, the OLED encapsulating film of the present invention can effectively block the passage of gas due to the modified nano-montmorillonite to reduce the entry of moisture and oxygen into the OLED, thereby effectively reducing the occurrence of oxidation such as electrodes. Problems such as peeling of the luminescent layer or cracking of the material, thereby improving the performance of the OLED package and prolonging the service life of the OLED.

Claims (10)

 An OLED encapsulating film comprising a first release sheet and a moisture barrier layer formed on the peelable surface of the first release sheet, wherein the moisture barrier layer comprises a modified naphthalene Mimontite and epoxy resin.    The film for OLED encapsulation of claim 1, wherein the modified nano montmorillonite is modified with polyetheramine.   The film for OLED encapsulation of claim 2, wherein the polyetheramine has a molecular weight of 200 to 5000 and has a repeating unit of the following formula (I): Wherein n is an integer from 2 to 50.  The film for OLED packaging according to claim 1, wherein the modified nano montmorillonite is added in an amount of 100% by weight of the epoxy resin, and 1 to 10 phr is added.    The OLED encapsulating film of claim 1, wherein the moisture barrier layer further comprises a second release sheet with respect to one side of the first release sheet.    A method of preparing a film for OLED encapsulation according to any one of claims 1 to 5, comprising the steps of: (a) providing a first release sheet; (b) mixing modified nano montmorillonite and epoxy Resin, obtaining an epoxy resin-modified nano montmorillonite slurry; (c) applying the epoxy resin-modified nano montmorillonite slurry to the peelable surface of the first release sheet to form A wet film is baked and formed into a moisture barrier layer.    The method of claim 6, wherein the baking condition has a temperature of 70 to 120 ° C and a time of 5 to 12 minutes.    The method of claim 7, further comprising attaching a peelable surface of a second release sheet to the moisture barrier layer.    A method of packaging an OLED, comprising: providing a film for OLED packaging according to any one of claims 1 to 5, attaching a moisture barrier layer to an OLED element on a first substrate, and tearing off the release sheet, and A second substrate is attached to the moisture barrier layer and then cured by UV light and/or thermally cured.    A packaged OLED obtained by the encapsulation method of claim 9.