CN113733696A - Encapsulating material for organic electronic device and rollable organic electronic device including the same - Google Patents

Encapsulating material for organic electronic device and rollable organic electronic device including the same Download PDF

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Publication number
CN113733696A
CN113733696A CN202110599905.5A CN202110599905A CN113733696A CN 113733696 A CN113733696 A CN 113733696A CN 202110599905 A CN202110599905 A CN 202110599905A CN 113733696 A CN113733696 A CN 113733696A
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Prior art keywords
organic electronic
encapsulating
resin layer
electronic device
sealing
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CN202110599905.5A
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CN113733696B (en
Inventor
孔利盛
权男勋
李相圭
崔昌烜
赵宣镐
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Innox Corp
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Innox Corp
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Priority claimed from KR1020200065495A external-priority patent/KR20210148567A/en
Priority claimed from KR1020200065494A external-priority patent/KR20210148566A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/846—Passivation; Containers; Encapsulations comprising getter material or desiccants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

The present invention relates to an encapsulating material for an organic electronic device and a rollable organic electronic device including the same, and more particularly, to an encapsulating material for a rollable organic electronic device and a rollable organic electronic device including the same, as follows: removing and blocking undesirable substances such as moisture, impurities, etc., to prevent them from approaching, without causing interlayer peeling that may occur when moisture is removed, while having excellent moisture resistance and heat resistance, and low rate of change of peel strength and storage modulus with temperature change.

Description

Encapsulating material for organic electronic device and rollable organic electronic device including the same
Technical Field
The present invention relates to an encapsulating material for a crimpable organic electronic device and a crimpable organic electronic device including the same, and more particularly, to an encapsulating material for a crimpable organic electronic device and a crimpable organic electronic device including the same, as follows: removing and blocking undesirable substances such as moisture, impurities, etc., to prevent them from approaching, without causing interlayer peeling that may occur when moisture is removed, while having excellent moisture resistance and heat resistance, and low rate of change of peel strength and storage modulus with temperature change.
Background
An Organic Light Emitting Diode (OLED) is a Light Emitting Diode in which a Light Emitting layer is formed of a thin-film Organic compound, and utilizes an electroluminescence phenomenon that generates Light by flowing current through a fluorescent Organic compound. Such an organic light emitting diode generally realizes main colors in a three-color (Red), Green (Green), Blue (Blue)) independent pixel system, a biological conversion system (CCM), a curl filter system, and the like, and is classified into a low molecular organic light emitting diode and a high molecular organic light emitting diode according to the amount of organic substances contained in a light emitting material used. Further, the driving method may be classified into a passive driving method and an active driving method.
Such an organic light emitting diode has characteristics of high efficiency, low voltage driving, simple driving, etc. by self-luminescence, and thus has an advantage that high definition video can be expressed. Further, applications to flexible displays and organic electronic devices utilizing the flexibility of organic materials are expected.
An organic light emitting diode is manufactured by laminating an organic compound as a light emitting layer on a substrate in the form of a thin film. However, the organic compounds used in the organic light emitting diode are very sensitive to impurities, oxygen and moisture, and thus have a problem that their characteristics are easily deteriorated by external exposure or permeation of moisture and oxygen. Such a degradation phenomenon of the organic substance affects the light emitting characteristics of the organic light emitting diode and shortens the life span. In order to prevent this phenomenon, a Thin Film Encapsulation process (Thin Film Encapsulation) for preventing oxygen, moisture, and the like from flowing into the interior of the organic electronic device is required.
Conventionally, a metal can or glass is processed into a cap shape to have a groove, and a desiccant for absorbing moisture is loaded in the groove in the form of powder, but this method has a problem that the following effects cannot be simultaneously obtained: the organic electronic device is removed to the extent that the organic electronic device can be moisture-permeable and packaged, and substances causing defects such as moisture and impurities are blocked so that the substances cannot approach the organic electronic device, and an interlayer peeling phenomenon which may occur when moisture is removed does not occur, and the organic electronic device has excellent moisture resistance and heat resistance.
On the other hand, among organic electronic devices such as organic light emitting diodes, flexible (flexible) organic electronic devices, which are made of a flexible material and thus maintain performance as it is even if they are bent like paper, are rapidly developing into next-generation organic electronic devices according to market demands. A flexible organic electronic device comprising: a bendable organic electronic device fixed in a state having a specific curvature; a foldable organic electronic device that can be bent above a certain radius of curvature or can be folded based on a folding axis; and a rollable organic electronic device capable of being rolled at a specific radius of curvature. Among them, since a rollable organic electronic device has an advantage of excellent portability compared to a display area, many studies are being made thereon.
As described above, a flexible organic electronic device has a specific curvature to achieve bending performance, and thus, unlike a general rigid organic electronic device, requires stability against bending stress, which in turn requires high stability against external environmental changes. In particular, the total area of the rollable organic electronic device is rolled at a specific radius of curvature, and thus there is a problem in that it is difficult to have higher stability.
Documents of the prior art
Patent document
Patent document 1: korea publication authorization No. 10-2019-0093833 (publication date: 2019, 08 and 12)
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an encapsulating material for a crimpable organic electronic device and a crimpable organic electronic device including the same, as follows: removing and blocking undesirable substances such as moisture, impurities, etc., to prevent them from approaching, without causing interlayer peeling that may occur when moisture is removed, while having excellent moisture resistance and heat resistance, low rate of change of peel strength and storage modulus with temperature change, and high stability against bending stress.
In order to solve the above problems, the present invention includes a sealing resin layer containing a sealing resin and a moisture absorbent, wherein the sealing resin contains an epoxy resin.
The present invention is characterized in that the encapsulating resin layer of the encapsulating material for a crimpable organic electronic device of the present invention comprises: a first encapsulating resin layer; and a second sealing resin layer formed on one surface of the first sealing resin layer, wherein the sealing resin of the first sealing resin layer further contains a polymer resin having a weight average molecular weight of 10000 to 300000g/mol, the sealing resin of the second sealing resin layer contains a thermoplastic elastomer (thermoplastic elastomer) having a storage modulus of 0.01 to 1.0MPa as measured by the following measurement method 1, and the sealing resin layer satisfies the following relational expression 1.
Relation 1
1.0≤A/B≤15.0
In the above relational expression 1, A is the peel strength (gf/10mm) of the cured encapsulating resin layer measured by a universal material tester under a temperature condition of 25 ℃ and B is the peel strength (gf/10mm) of the cured encapsulating resin layer measured by a universal material tester under a temperature condition of 60 ℃.
Measurement method 1
After punching a thermoplastic elastomer cured at a thickness of 800 μm so as to have a circular diameter of 6mm, Storage Modulus (Storage Modulus) at 25 ℃ under conditions of a temperature range of 10 to 110 ℃, a temperature rise rate of 5 ℃/min, a frequency of 15rad/s, and an axial force (axial force) of 0.1N were measured, respectively.
In a preferred embodiment of the present invention, the A may be 700gf/10mm or more, and the B may be 500gf/10mm or more.
In a preferred embodiment of the present invention, the A may be 1400 to 2600gf/10mm, and the B may be 1260 to 2340gf/10 mm.
The present invention is characterized in that the encapsulating resin layer of the encapsulating material for a crimpable organic electronic device of the present invention further satisfies the following relational expression 2.
Relation 2
1.0≤A’/B’≤15.0
In the above relational expression 2, a 'is a Storage Modulus (MPa) of the encapsulating resin layer cured in a thickness of 800 μm measured by a dynamic thermo-mechanical analyzer under a temperature condition of 25 ℃, and B' is a Storage Modulus (MPa) of the encapsulating resin layer cured in a thickness of 800 μm measured by a dynamic thermo-mechanical analyzer under a temperature condition of 60 ℃.
In a preferred embodiment of the present invention, the above A' may be 500MPa or more, and a preferred range may be 1050 to 1950 MPa. In a preferred embodiment of the present invention, B' may be 300MPa or more, and preferably ranges from 910 to 1690 MPa.
In a preferred embodiment of the present invention, the polymer resin having a weight average molecular weight of 10000 to 300000g/mol may include at least one selected from phenoxy (phenoxy) resins, acrylic resins, nitrile rubber resins, and urethane resins.
In a preferred embodiment of the present invention, the polymer resin having a weight average molecular weight of 10000 to 300000g/mol may include a compound represented by the following chemical formula 1.
Chemical formula 1
Figure BDA0003092544270000041
In the above chemical formula 1, n is an integer of 12 to 330.
In a preferred embodiment of the present invention, the thermoplastic elastomer may include at least one selected from the group consisting of isobutylene-based thermoplastic elastomers, isoprene-based thermoplastic elastomers, urethane-based thermoplastic elastomers, styrene-based thermoplastic elastomers, butadiene-based thermoplastic elastomers, and ester-based thermoplastic elastomers.
In a preferred embodiment of the present invention, the thermoplastic elastomer may comprise styrene-isobutylene-styrene block copolymer (styrene-isobutylene-styrene block copolymer).
In a preferred embodiment of the present invention, the sealing resin of the second sealing resin layer may include the thermoplastic elastomer and the epoxy resin in a weight ratio of 1:0.7 to 1.3.
In a preferred embodiment of the present invention, the encapsulating resin of the first encapsulating resin layer may include the polymer resin and the epoxy resin having a weight average molecular weight of 10000 to 300000g/mol in a weight ratio of 1:0.7 to 1.3.
In a preferred embodiment of the present invention, the epoxy resin may include a first epoxy resin and a second epoxy resin different from each other in a weight ratio of 1:0.7 to 2.5, the first epoxy resin may include one or more selected from dicyclopentadiene (DCPD) solid epoxy resins, bisphenol-a solid epoxy resins, bisphenol-F solid epoxy resins, and novolac solid epoxy resins, and the second epoxy resin may include one or more selected from silicon-modified liquid epoxy resins, urethane-modified liquid epoxy resins, and rubber-modified liquid epoxy resins.
In a preferred embodiment of the present invention, the first encapsulating resin layer may include 2.0 to 4.0 parts by weight of a moisture absorbent with respect to 100 parts by weight of the encapsulating resin, and the second encapsulating resin layer may include 48 to 90 parts by weight of the moisture absorbent with respect to 100 parts by weight of the encapsulating resin.
In a preferred embodiment of the present invention, the first sealing resin layer and the second sealing resin layer may further include a curing agent, respectively.
In a preferred embodiment of the present invention, the curing agent may include one or more selected from the group consisting of an amine curing agent, an imidazole curing agent, an amide curing agent, a thioether curing agent, a phenol curing agent, a thiol (mecaptan) curing agent, an isocyanate curing agent, and an acid anhydride curing agent, and the amine curing agent may include an aliphatic amine, an aromatic amine, an alicyclic amine, a secondary amine, a tertiary amine, or BF3An amine.
In a preferred embodiment of the present invention, the first encapsulating resin layer may include 0.1 to 2.0 parts by weight of a curing agent with respect to 100 parts by weight of the encapsulating resin, and the second encapsulating resin layer may include 2.5 to 9.0 parts by weight of a curing agent with respect to 100 parts by weight of the encapsulating resin.
In a preferred embodiment of the present invention, a thickness ratio between the first encapsulating resin layer and the second encapsulating resin layer may be 1:1.0 to 8.0.
In a preferred embodiment of the present invention, the thickness of the first sealing resin layer may be 1 to 25 μm, and the thickness of the second sealing resin layer may be 25 to 60 μm.
Also, the present invention provides a rollable organic electronic device comprising: a substrate; a rollable organic electronic device formed on at least one surface of the substrate; and the packaging material for the rollable organic electronic device is used for packaging the rollable organic electronic device.
Hereinafter, terms used in the present invention will be described.
The term "moisture absorbent" used in the present invention can absorb moisture through an interface of the moisture absorbent and a physical or chemical bond such as van der waals force, and includes both a moisture absorbing substance which does not change a substance component by absorbing moisture and a moisture absorbing substance which becomes a new substance by absorbing moisture through a chemical reaction.
Also, the term "normal temperature" used in the present invention means a temperature of 10 to 40 ℃, preferably 15 to 35 ℃, and preferably 18 to 30 ℃.
The packaging material for the crimpable organic electronic device and the crimpable organic electronic device comprising the same can block oxygen, impurities and moisture, and simultaneously can remarkably prevent moisture from reaching the organic electronic device by effectively removing moisture which is permeable to moisture, thereby remarkably improving the service life and the durability of the organic electronic device. And, the interlayer peeling phenomenon which may occur when removing moisture does not occur, and excellent moisture resistance and heat resistance are provided. In addition, the rate of change in peel strength and storage modulus with temperature change is low.
Drawings
Fig. 1 is a cross-sectional view of an encapsulation material for a rollable organic electronic device in accordance with a preferred embodiment of the present invention.
Fig. 2 is a cross-sectional view of a rollable organic electronic device in accordance with a preferred embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains can easily carry out the embodiments. The invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Parts that are not relevant to the description are omitted in the drawings to clearly explain the present invention. Throughout the specification, the same or similar structural elements are given the same reference numerals.
Referring to fig. 1, the encapsulation material for a rollable organic electronic device of the present invention includes an encapsulation resin layer 10.
The encapsulating resin layer 10 of the present invention may contain an encapsulating material containing an epoxy resin, and may further contain moisture absorbents 40' and 40 ″.
Specifically, the encapsulating resin layer 10 of the present invention includes: a first encapsulating resin layer 11; and a second sealing resin layer 12 formed on one surface of the first sealing resin layer 11.
In this case, the encapsulating resin layer 10 of the present invention satisfies the following relational expression 1.
Relation 1
1.0≤A/B≤15.0
In relation 1, A is the peel strength (gf/10mm) of the cured encapsulating resin layer measured by a universal material tester under a temperature condition of 25 ℃, and B is the peel strength (gf/10mm) of the cured encapsulating resin layer measured by a universal material tester under a temperature condition of 60 ℃. In the above relational expression 1, the above A/B may preferably be 1.0. ltoreq. A/B.ltoreq.10.0, more preferably 1.0. ltoreq. A/B.ltoreq.5.0, still more preferably 1.0. ltoreq. A/B.ltoreq.2.5, and still more preferably 1.05. ltoreq. A/B.ltoreq.1.25.
In relation 1, if a/B is less than 1.0, there may be a problem of reliability degradation due to insufficient curing rate, and if it exceeds 15.0, there may be a problem of durability degradation of the encapsulating material due to insufficient resistance to deformation with temperature change.
In relation to formula 1, A may be 700gf/10mm or more, preferably 1400 to 2600gf/10mm, more preferably 1600 to 2400gf/10mm, still more preferably 1800 to 2200gf/10mm, and still more preferably 1900 to 2100gf/10mm, and if A is less than 700gf/10mm, there may be a problem of deterioration in moisture resistance and bonding quality.
In relation to formula 1, B may be 500gf/10mm or more, preferably 1260 to 2340gf/10mm, more preferably 1440 to 2160gf/10mm, still more preferably 1620 to 1980gf/10mm, and yet more preferably 1710 to 1890gf/10mm, and if B is less than 500gf/10mm, there is a possibility that the moisture resistance and durability may be deteriorated.
Preferably, the encapsulating resin layer 10 of the present invention also satisfies the following relational expression 2.
Relation 2
1.0≤A’/B’≤15.0
In the above relational expression 2, a 'is a Storage Modulus (MPa) of the encapsulating resin layer cured in a thickness of 800 μm measured by a dynamic thermo-mechanical analyzer under a temperature condition of 25 ℃, and B' is a Storage Modulus (MPa) of the encapsulating resin layer cured in a thickness of 800 μm measured by a dynamic thermo-mechanical analyzer under a temperature condition of 60 ℃.
In the above relational expression 2, preferably, 1.0. ltoreq. A '/B'. ltoreq.10.0, more preferably, 1.0. ltoreq. A '/B'. ltoreq.5.0, further preferably, 1.0. ltoreq. A '/B'. ltoreq.2.5, most preferably, 1.05. ltoreq. A '/B'. ltoreq.1.25 can be satisfied.
In relation 2, if a '/B' is less than 1.0, there is a possibility of a problem of reliability degradation due to insufficient curing rate, and if it exceeds 15.0, there is a possibility of durability degradation of the panel due to insufficient resistance to deformation caused by temperature change.
In relation 2, a 'may be 500MPa or more, preferably 1050 to 1950MPa, more preferably 1200 to 1800MPa, still more preferably 1350 to 1650MPa, and still more preferably 1425 to 1575MPa, and if a' is less than 500MPa, there is a problem that the panel quality is poor due to insufficient deformation resistance against external stress.
In relation 2, B 'may be 300MPa or more, preferably 910 to 1690MPa, more preferably 1040 to 1560MPa, still more preferably 1170 to 1430MPa, and still more preferably 1235 to 1365MPa, and if B' is less than 300MPa, there is a problem that the heat resistance is insufficient.
Preferably, the encapsulating resin layer 10 of the present invention also satisfies the following relational expression 3. When the following relational expression 3 is satisfied, the moisture resistance and the quality of the panel can be further prevented from being deteriorated.
Relation 3
C＜D
In the above relational expression 3, C is the content of the moisture absorbent 40 ″ contained in the first encapsulating resin layer 11, and D is the content of the moisture absorbent 40' contained in the second encapsulating resin layer 12.
The sealing material for a rollable organic electronic device according to the present invention may further include a release layer 30 formed on the other surface of the first sealing resin layer 11, and may further include a metal layer 20 formed on one surface of the second sealing resin layer 12.
First, the first encapsulating resin layer 11 is a layer in direct contact with a rollable organic electronic device (not shown), and may include an encapsulating resin and a moisture absorbent 40 ″.
The encapsulating resin contained in the first encapsulating resin layer 11 may contain a pressure-sensitive adhesive composition containing an epoxy resin, and preferably, may further contain a polymer resin having a weight-average molecular weight of 10000 to 300000 g/mol.
In this case, the encapsulating resin contained in the first encapsulating resin layer 11 may contain a polymer resin and an epoxy resin in a weight ratio of 1:0.7 to 1.3, preferably 1:0.8 to 1.2, more preferably 1:0.9 to 1.1, and further preferably 1:0.95 to 1.05, and if the weight ratio is less than 1:0.7, there may be a problem of a decrease in peel strength, and if it exceeds 1:1.3, there may be a problem in moisture resistance and coating quality.
Preferably, the weight average molecular weight of the polymer resin of the encapsulating resin contained in the first encapsulating resin layer 11 of the present invention may be 20000 to 150000g/mol, more preferably 30000 to 75000 g/mol.
If the weight average molecular weight is less than 10000g/mol, there may be a problem in heat resistance, and if it exceeds 300000g/mol, there may be a problem in peel strength and adhesiveness.
The polymer resin having a weight average molecular weight of 10000 to 300000g/mol, which is contained in the first sealing resin layer 11 of the present invention, may include one or more selected from phenoxy (phenoxy) resins, acrylic resins, nitrile rubber resins, and urethane resins, and preferably, may include phenoxy resins. The phenoxy resin has a functional group that reacts with an epoxy group, and thus has an advantage that a high storage modulus can be achieved after curing of the encapsulating resin layer.
Preferably, the polymer resin may include a compound represented by the following chemical formula 1.
Chemical formula 1
Figure BDA0003092544270000091
In the above chemical formula 1, n is an integer of 12 to 330.
Preferably, n may be an integer of 24 to 165, more preferably an integer of 36 to 80.
Preferably, the glass transition temperature (Tg) of the polymer resin having a weight average molecular weight of 10000 to 300000g/mol may be 84 ℃ or higher.
The epoxy resin of the encapsulating resin included in the first encapsulating resin layer 11 of the present invention may include a first epoxy resin and a second epoxy resin which are different from each other. In this case, the first epoxy resin and the second epoxy resin may be contained in a weight ratio of 1:0.7 to 2.5, preferably 1:1.0 to 2.0, more preferably 1:1.2 to 1.8, and further preferably 1:1.35 to 1.65, and if the weight ratio is less than 1:0.7, there may be a problem in adhesion to a base material of the sealing material, and if it is more than 1:2.5, there may be a problem in moisture resistance.
The first epoxy resin of the encapsulating resin contained in the first encapsulating resin layer 11 of the present invention may include one or more selected from the group consisting of dicyclopentadiene type solid epoxy resin, bisphenol-a type solid epoxy resin, bisphenol-F type solid epoxy resin, and novolac type solid epoxy resin, but is not limited thereto. Preferably, the first epoxy resin may include a dicyclopentadiene type solid epoxy resin. When the dicyclopentadiene type solid epoxy resin is used as the first epoxy resin, since it has a low softening point, an encapsulating material excellent in moisture resistance can be realized.
More preferably, the first epoxy resin may include a structure represented by the following chemical formula 2.
Chemical formula 2
Figure BDA0003092544270000101
Preferably, the softening point (s.p. softening point) of the first epoxy resin may be 80 ℃ or less. If the softening point is higher than 80 ℃, there may be a problem that the bonding property is lowered.
The second epoxy resin of the encapsulating resin contained in the first encapsulating resin layer 11 of the present invention may contain one or more selected from the group consisting of a silicon-modified liquid epoxy resin, a liquid bisphenol-type epoxy resin, a urethane-modified liquid epoxy resin, and a rubber-modified liquid epoxy resin, preferably, may contain a silicon-modified liquid epoxy resin, more preferably, may contain a silicon-modified liquid epoxy resin having a total chlorine content of 500ppm or less, in which a silicon intermediate containing a phenyl group is substituted. When the modified liquid epoxy resin is contained, superior peel strength can be achieved as compared with the case where other epoxy resins are used.
More preferably, the second epoxy resin may include a structure represented by the following chemical formula 3.
Chemical formula 3
Figure BDA0003092544270000102
The moisture absorbent 40 ″ contained as the first encapsulating resin layer 11 may be used without limitation as long as it is a moisture absorbent generally used for encapsulation of a crimpable organic electronic device, and preferably, may include one or more of a moisture absorbent containing zeolite, titanium dioxide, zirconium oxide, montmorillonite or the like as a component, a metal salt, and a metal oxide, and more preferably, may include a metal oxide.
The metal oxide may include, for example, silicon dioxide (SiO)2) Alumina (Al)2O3) Lithium oxide (Li)2O), sodium oxide (Na)2O), barium oxide (BaO), metal oxide such as calcium oxide (CaO) or magnesium oxide (MgO), organic metal oxide, and phosphorus pentoxide (P)2O5) More than one of them.
The metal salt may include, for example, lithium sulfate (Li)2SO4) Sodium sulfate (Na)2SO4) Calcium sulfate (CaSO)4) Magnesium sulfate (MgSO)4) Cobalt sulfate (CoSO)4) Gallium sulfate (Ga)2(SO4)3) Titanium sulfate (Ti (SO)4)2Or nickel sulfate (NiSO)4) Sulfates and the like; such as calcium chloride (CaCl)2) Magnesium chloride (MgCl)2) Strontium chloride (SrCl)2) Yttrium chloride (YCl)3) Copper chloride (CuCl)2) Cesium fluoride (CsF), tantalum fluoride (TaF)5) Niobium fluoride (NbF)5) Lithium bromide (LiBr), calcium bromide (CaBr)2) Cesium bromide (CeBr)3) Selenium bromide (SeBr)4) Vanadium bromide (VBr)3) Magnesium bromide (MgBr)2) Barium iodide (BaI)2) Or magnesium iodide (MgI)2) Metal halides such as; and barium perchlorate (Ba (ClO)4)2) Or magnesium perchlorate (Mg (ClO)4)2) Such as one or more metal chlorates.
It is preferable to use a moisture absorbent having a purity of 95% or more, and if the purity is less than 95%, not only the moisture absorption function is reduced, but also substances contained in the moisture absorbent may act as impurities to cause defects in the sealing material and may affect the rollable organic electronic device, but not limited thereto.
Also, most preferably, the moisture absorbent 40 ″ included in the first encapsulating resin layer 11 may include silicon dioxide (SiO)2) And thus has excellent moisture removal performance, can prevent separation between the rollable organic electronic device and the encapsulation material, and can significantly increase the durability of the rollable organic electronic device. Further, the shape or particle diameter of the moisture absorbent 40 ″ contained in the first encapsulating resin layer 11 is not limited, but preferably, the shape may be amorphous or spherical, and the average particle diameter may be 0.01 to 10 μm, preferably 0.1 to 5 μm, more preferably 0.2 to 1 μm, and if the average particle diameter is less than 0.01 μm, there is a problem that the peel strength with an adherend may be reduced due to an increase in specific surface area, and if it is more than 10 μm, there may be a direct physical damage to the organic electronic device.
On the other hand, the first encapsulating resin layer 11 of the present invention may contain the moisture absorbent 40 "in an amount of 2.0 to 4.0 parts by weight, preferably 2.4 to 3.6 parts by weight, more preferably 2.7 to 3.3 parts by weight, and further preferably 2.8 to 3.2 parts by weight, based on 100 parts by weight of the encapsulating resin, and if the content is less than 2.0 parts by weight, there may be the following problems: since the desired effect of removing moisture from the first encapsulating resin layer 11 cannot be achieved, resulting in a reduction in the durability of the rollable organic electronic device, if the contained amount is more than 4.0 parts by weight, there may be problems as follows: due to insufficient wettability, the reliability of the rollable organic electronic device is reduced because the adhesive force such as adhesion force and adhesive force between the rollable organic electronic device and the adhesive force is poor.
Further, the first encapsulating resin layer 11 of the present invention may contain a curing agent in addition to the encapsulating resin and the moisture absorbent 40 ″.
The curing agent contained as the first encapsulating resin layer 11 may be used without limitation as long as it is a substance that can be generally used as a curing agent, and preferably, a substance that can ensure a sufficient crosslinking density of the encapsulating resin layer by functioning as a crosslinking agent may be contained.
Specifically, the curing agent may include one or more selected from the group consisting of aliphatic amine (aliphatic amine), aromatic amine (aromatic amine), alicyclic amine (alicyclic amine), secondary amine (secondary amine), tertiary amine (tertiary amine), and BF3Amine-based curing agents such as amines; imidazole-based (imidazole) curing agents; amide-based curing agents such as dicyandiamide (dicyanamide); thioether (sulfide) curing agents; phenolic curing agents; thiol (mercaptan) curing agents; the curing agent may be one or more of an isocyanate (isocyanate) curing agent and an acid anhydride curing agent, and more preferably, an imidazole curing agent.
The first encapsulating resin layer 11 of the present invention may contain 0.1 to 2.0 parts by weight, preferably 0.7 to 1.3 parts by weight, more preferably 0.8 to 1.2 parts by weight, and still more preferably 0.9 to 1.1 parts by weight of a curing agent with respect to 100 parts by weight of the encapsulating resin, and if the content is less than 0.1 part by weight, a desired gel fraction and modulus may not be achieved, and there may be a problem of a decrease in elastic force, and if the content is more than 2.0 parts by weight, there may be a problem of poor panel adhesion due to high modulus and hardness, and a decrease in adhesive force due to a decrease in wettability.
The second sealing resin layer 12 of the present invention is a layer in direct contact with the metal layer 20, and may include a sealing resin and a moisture absorbent 40'.
The encapsulating resin contained in the second encapsulating resin layer 12 may contain a pressure-sensitive adhesive composition, and preferably, may further contain a thermoplastic elastomer having a storage modulus of 0.01 to 1.0MPa, preferably 0.05 to 0.5MPa, and more preferably 0.1 to 0.3MPa, as measured by the following measurement method 1. If the storage modulus of the thermoplastic elastomer is less than the numerical range, there may be a problem of defects such as looseness, and if it is greater than the numerical range, there may be a problem of panel damage due to insufficient peel strength and lack of cushioning effect.
Measurement method 1
After punching a thermoplastic elastomer cured at a thickness of 800 μm so as to have a circular diameter of 6mm, Storage Modulus (Storage Modulus) at 25 ℃ under conditions of a temperature range of 10 to 110 ℃, a temperature rise rate of 5 ℃/min, a frequency of 15rad/s, and an axial force (axial force) of 0.1N were measured, respectively. In this case, as the measuring apparatus, a Rheometer (Rheometer, ARES-G2, Ta Instruments) can be used.
Also, the thermoplastic elastomer of the present invention may include one or more selected from the group consisting of isobutylene-based thermoplastic elastomers, butadiene-based thermoplastic elastomers, isoprene-based thermoplastic elastomers, urethane-based thermoplastic elastomers, styrene-based thermoplastic elastomers, and ester-based thermoplastic elastomers, preferably, may include isobutylene-based thermoplastic elastomers, and more preferably, may include styrene-isobutylene-styrene block copolymers.
On the other hand, the encapsulating resin contained in the second encapsulating resin layer 12 may contain an epoxy resin in addition to the thermoplastic elastomer. In this case, the epoxy resin of the encapsulating resin contained in the second encapsulating resin layer 12 may include one or more selected from dicyclopentadiene type solid epoxy resin, bisphenol-a type solid epoxy resin, bisphenol-F type solid epoxy resin, and novolac type solid epoxy resin, and preferably, may include dicyclopentadiene type solid epoxy resin. The effect when the dicyclopentadiene type solid epoxy resin is used is as described in the above-mentioned first encapsulating resin layer.
The encapsulating resin contained in the second encapsulating resin layer 12 may contain the thermoplastic elastomer and the epoxy resin in a weight ratio of 1:0.7 to 1.3, preferably 1:0.8 to 1.2, more preferably 1:0.9 to 1.1, and further preferably 1:0.95 to 1.05, and when the weight ratio is less than 1:0.7, there is a problem that the peel strength may be reduced, and when it is more than 1:1.3, there may be a problem in the moisture resistance and the coating quality.
The moisture absorbent 40' contained in the second encapsulating resin layer 12 may be used without limitation as long as it is a moisture absorbent generally used for encapsulation of a crimpable organic electronic device, and preferably, may include one or more of a moisture absorbent containing zeolite, titanium dioxide, zirconium oxide, montmorillonite or the like as a component, a metal salt, and a metal oxide, and more preferably, may include a metal oxide.
The metal oxide may include, for example, silicon dioxide (SiO)2) Alumina (Al)2O3) Lithium oxide (Li)2O), sodium oxide (Na)2O), barium oxide (BaO), metal oxide such as calcium oxide (CaO) or magnesium oxide (MgO), organic metal oxide, and phosphorus pentoxide (P)2O5) More than one of them.
The metal salt may include, for example, lithium sulfate (Li)2SO4) Sodium sulfate (Na)2SO4) Calcium sulfate (CaSO)4) Magnesium sulfate (MgSO)4) Cobalt sulfate (CoSO)4) Gallium sulfate (Ga)2(SO4)3) Titanium sulfate (Ti (SO)4)2Or nickel sulfate (NiSO)4) Sulfates and the like; such as calcium chloride (CaCl)2) Magnesium chloride (MgCl)2) Strontium chloride (SrCl)2) Yttrium chloride (YCl)3) Copper chloride (CuCl)2) Cesium fluoride (CsF), tantalum fluoride (TaF)5) Niobium fluoride (NbF)5) Lithium bromide (LiBr), calcium bromide (CaBr)2) Cesium bromide (CeBr)3) Selenium bromide (SeBr)4) Vanadium bromide (VBr)3) Magnesium bromide (MgBr)2) Barium iodide (BaI)2) Or magnesium iodide (MgI)2) Metal halides such as; and barium perchlorate (Ba (ClO)4)2) Or magnesium perchlorate (Mg (ClO)4)2) Such as one or more metal chlorates.
It is preferable to use a moisture absorbent having a purity of 95% or more, and if the purity is less than 95%, not only the moisture absorption function is reduced, but also substances contained in the moisture absorbent may act as impurities to cause defects in the sealing material and may affect the rollable organic electronic device, but not limited thereto.
Also, most preferably, the moisture absorbent 40' contained in the second encapsulating resin layer 12 may contain calcium oxide (CaO), and thus has an advantage of improving moisture resistance. The shape or particle size of the moisture absorbent 40' contained in the second encapsulating resin layer 12 is not limited, but preferably, the shape may be amorphous or spherical, and the average particle size may be 0.1 to 20 μm, preferably 0.5 to 10 μm, and more preferably 1.5 to 4 μm.
If the average particle size is less than 0.1. mu.m, there is a problem that the peel strength with the adherend may be lowered due to an increase in the specific surface area, and if it exceeds 20. mu.m, there is a problem that a coating process failure may occur.
On the other hand, the second encapsulating resin layer 12 of the present invention may contain the moisture absorbent 40' in an amount of 48 to 90 parts by weight, preferably 54 to 83 parts by weight, more preferably 61 to 76 parts by weight, and further preferably 65 to 73 parts by weight, based on 100 parts by weight of the encapsulating resin, and if the content is less than 48 parts by weight, there may be the following problems: since the desired effect of removing moisture from the second encapsulating resin layer 12 cannot be achieved, resulting in a reduction in the durability of the rollable organic electronic device, if the contained amount is more than 90 parts by weight, there may be problems as follows: since the adhesive property is significantly reduced and excessive volume expansion occurs when moisture is absorbed, the interlayer and/or encapsulation resin layer 10 and the crimpable organic electronic device are lifted up to cause rapid permeation of moisture therebetween, thereby shortening the life span of the crimpable organic electronic device.
Further, the second encapsulating resin layer 12 of the present invention may contain a curing agent in addition to the encapsulating resin and the moisture absorbent 40'.
The curing agent contained as the second encapsulating resin layer 12 may be used without limitation as long as it is a substance that can be generally used as a curing agent, and preferably, a substance capable of ensuring a sufficient crosslinking density of the encapsulating resin layer by functioning as a crosslinking agent may be contained.
Specifically, the above curing agent may include one selected from the group consisting of aliphatic amine, aromatic amine, alicyclic amine, secondary amine, tertiary amine and BF3Amine-based curing agents such as amines; imidazole curing agents; amide-based curing agents such as dicyandiamide; a thioether-based curing agent; a phenolic curing agent; a thiol curing agent; the curing agent may be one or more selected from isocyanate curing agents and acid anhydride curing agents, and preferably, it may include imidazole curing agents. The effect caused thereby is as described in the curing agent of the first encapsulating resin layer.
The second encapsulating resin layer 12 of the present invention may contain 2.5 to 9.0 parts by weight, preferably 3.5 to 6.5 parts by weight, more preferably 4.0 to 6.0 parts by weight, and still more preferably 4.5 to 5.5 parts by weight of a curing agent with respect to 100 parts by weight of the encapsulating resin, and if the content is less than 2.5 parts by weight, a desired gel fraction and modulus may not be achieved, and there may be a problem of a decrease in elastic force, and if the content is more than 9.0 parts by weight, there may be a problem of poor panel adhesion due to high modulus and hardness, and a decrease in peel strength due to a decrease in wettability.
On the other hand, the thickness ratio between the first encapsulating resin layer 11 and the second encapsulating resin layer 12 may be 1:1.0 to 8.0, preferably 1:1.5 to 3.1, more preferably 1:1.8 to 2.8, still more preferably 1:2.1 to 2.6, and still more preferably 1:2.2 to 2.5. If the thickness ratio is less than 1:1.0, there is a possibility that the moisture resistance is lowered due to an insufficient absolute amount of the moisture absorbent, and if it exceeds 1:8.0, there is a possibility that the moisture resistance is lowered due to failure to effectively compensate for the swelling of the moisture absorbent due to moisture.
The thickness of the first sealing resin layer 11 of the present invention may be 1 to 25 μm, preferably 7 to 18 μm, more preferably 10 to 18 μm, and still more preferably 13 to 17 μm, and the thickness of the second sealing resin layer 12 of the present invention may be 25 to 60 μm, preferably 25 to 50 μm, more preferably 30 to 40 μm, and still more preferably 32 to 38 μm.
The first sealing resin layer 11 and the second sealing resin layer 12 may be a dry sealing resin layer or a cured sealing resin layer.
The metal layer 20 of the present invention may include one or more selected from iron (Fe), bismuth (Bi), tin (Sn), indium (In), silver (Ag), copper (Cu), zinc (Zn), antimony (Sb), nickel (Ni), chromium (Cr), and alloys thereof.
As a preferred example, the metal layer 20 includes a metal plate made of a stainless material including, for example, bismuth (Bi), tin (Sn), indium (In), silver (Ag), copper (Cu), zinc (Zn), antimony (Sb), nickel (Ni), and chromium (Cr), and more preferably, the metal plate may be a metal plate including an alloy (including inevitable impurities In addition to nickel and iron), the alloy including 34 to 38 wt% of nickel and the balance of iron (Fe).
The thickness of the metal layer 20 may be 60 to 150. mu.m, preferably 70 to 120. mu.m, and more preferably 75 to 105 μm.
As the release sheet (liner sheet) material of the release layer 30 of the present invention, a release sheet material generally used in the art may be used, and as a preferable example, one or more selected from polyethylene terephthalate (PET), Paper (Paper), polyimide (PI, Poly Imide), and polyester (PE, Poly Ester) may be included.
The thickness of the release layer 30 may be 15 to 75 μm, preferably 25 to 60 μm, and more preferably 35 to 55 μm.
Further, the following is explained with reference to fig. 2: the rollable organic electronic device of the present invention can include: a substrate 1; a rollable organic electronic device 2 formed on at least one surface of the substrate 1; and an encapsulating material 10 for a rollable organic electronic device of the present invention for encapsulating a rollable organic electronic device 2.
Preferably, the substrate 1 may use one of a glass substrate, a crystal substrate, a sapphire substrate, a plastic substrate, and a foldable flexible polymer film.
The rollable organic electronic device 2 formed on at least one surface of the substrate 1 may be formed by depositing a lower electrode on the substrate 1, and sequentially stacking an n-type semiconductor layer, an active layer, a p-type semiconductor layer, and an upper electrode on the lower electrode, followed by etching, or may be formed by fabricating a separate substrate and then disposing the substrate on the substrate 1. A specific method of forming such a rollable organic electronic device 2 on the substrate 1 may be a method known in the art, and the present invention is not particularly limited thereto, and the rollable organic electronic device 2 may be an organic light emitting diode.
Then, the rollable organic electronic device of the present invention encapsulates the rollable organic electronic device 2 with the encapsulation material 10, and a known conventional method may be used for a specific method of encapsulation, and the present invention is not particularly limited thereto. As a non-limiting example of this, the first encapsulating resin layer 11 of the wrapping material 10 for a crimpable organic electronic device may be directly contacted with the crimpable organic electronic device 2 formed on the substrate 1, and heat and/or pressure may be applied by using a vacuum press, a vacuum laminator, or the like. Also, heat may be applied to cure the encapsulation material 10 for the rollable organic electronic device, and in the case of an encapsulation material including a light-cured encapsulation resin, it may be moved into a chamber where light is irradiated to further perform a curing process.
The present invention is illustrated by the following examples. In this case, the following examples are presented only to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
Example 1: preparation of packaging material for crimpable organic electronic devices
(1) Preparation of first encapsulating resin layer
The first mixture was prepared by mixing a phenoxy resin (PKHB, Inchem) having a weight average molecular weight of 32000g/mol and an epoxy resin in a weight ratio of 1:1.
Among the above epoxy resins, as a first epoxy resin, a dicyclopentadiene type (DCPD) solid epoxy resin containing the structure of the following Chemical formula 2 was used, and as a second epoxy resin, a resin in which a silicon-modified liquid epoxy resin (KSR-177, Kukdo Chemical) was mixed in a weight ratio of 1:1.5 was used.
Chemical formula 2
Figure BDA0003092544270000171
With respect to 100 parts by weight of the above first mixture, 3 parts by weight of silica having an average particle diameter of 0.5 μm as a moisture absorbent was charged and mixed at a temperature of 25 ℃ for 2 hours to prepare a second mixture.
A third mixture was prepared by mixing 1 part by weight of an imidazole-based curing agent (2PZCNS-PW, Shikoku Chemical) with the above second mixture with respect to 100 parts by weight of the above first mixture, and mixing at a temperature of 25 ℃ for 1 hour.
The prepared third mixture was adjusted to a viscosity of 400cps at a temperature of 20 ℃, passed through a capsule filter to remove foreign substances, coated on a heavy-peel antistatic PET (RES751, Toray) having a thickness of 75 μm using a slit coater, dried at a temperature of 120 ℃ to remove a solvent, and then a first encapsulating resin layer having a final thickness of 15 μm was prepared.
(2) Preparation of second encapsulating resin layer
A Styrene-isoButylene-Styrene (SIBS) block copolymer having a storage modulus of 0.15MPa measured by the following measurement method 1 was used as the thermoplastic elastomer, a dicyclopentadiene type solid epoxy resin containing the structure of the above chemical formula 2 was used as the epoxy resin, and the thermoplastic elastomer and the epoxy resin were mixed in a weight ratio of 1:1 to prepare a first mixture.
Measurement method 1
After punching a thermoplastic elastomer cured at a thickness of 800 μm so as to have a circular diameter of 6mm, Storage Modulus (Storage Modulus) at 25 ℃ under conditions of a temperature range of 10 to 110 ℃, a temperature rise rate of 5 ℃/min, a frequency of 15rad/s, and an axial force (axial force) of 0.1N were measured, respectively.
Specifically, after punching a thermoplastic elastomer cured at a thickness of 800 μm so as to have a circular diameter of 6mm, the Storage Modulus (Storage Modulus) was measured using a Rheometer (Ares-G2, TA Instruments) under conditions of a temperature of 25 ℃, a frequency of 15rad/s, and an axial force (axial force) of 0.1N.
A second mixture was prepared by charging 69 parts by weight of calcium oxide (CaO) having an average particle size of 3 μm as a moisture absorbent with respect to 100 parts by weight of the first mixture and mixing at 25 ℃ for 2 hours.
A third mixture was prepared by further mixing 5 parts by weight of an imidazole-based curing agent (2PZCNS-PW, Shikoku Chemical) with the above second mixture, relative to 100 parts by weight of the above first mixture, and mixing at a temperature of 25 ℃ for 1 hour.
The third mixture was adjusted to a viscosity of 600cps at a temperature of 20 c, passed through a capsule filter to remove foreign substances, coated on a heavy-peel antistatic die PET (TG65R, SKC) having a thickness of 36 μm using a slit coater, and then dried at a temperature of 160 c to remove a solvent, thereby preparing a second encapsulating resin layer having a final thickness of 35 μm.
(3) Preparation of the encapsulating Material
The first encapsulating resin layer and the second encapsulating resin layer prepared as described above were laminated so as to face each other, and passed through a tenter roller at 70 ℃.
Example 2: preparation of packaging material for crimpable organic electronic devices
An encapsulating material was prepared in the same manner as in example 1. However, unlike example 1, a nitrile rubber (NBR) having a storage modulus of 0.11MPa was used as the thermoplastic elastomer of the encapsulating resin of the second encapsulating resin layer to prepare an encapsulating material.
Example 3: preparation of packaging material for crimpable organic electronic devices
An encapsulating material was prepared in the same manner as in example 1. However, unlike example 1, as the encapsulating resin of the second encapsulating resin layer, an encapsulating resin was prepared by mixing a thermoplastic elastomer and an epoxy resin at a weight ratio of 1:0.6, and an encapsulating material was prepared using the encapsulating resin.
Example 4: preparation of packaging material for crimpable organic electronic devices
An encapsulating material was prepared in the same manner as in example 1. However, unlike example 1, as the encapsulating resin of the second encapsulating resin layer, an encapsulating resin was prepared by mixing a thermoplastic elastomer and an epoxy resin at a weight ratio of 1:1.4, and an encapsulating material was prepared using the encapsulating resin.
Example 5: preparation of packaging material for crimpable organic electronic devices
An encapsulating material was prepared in the same manner as in example 1. However, unlike example 1, as the encapsulating resin of the first encapsulating resin layer, a phenoxy resin and an epoxy resin were mixed in a weight ratio of 1:0.6 to prepare an encapsulating resin, and an encapsulating material was prepared using the encapsulating resin.
Example 6: preparation of packaging material for crimpable organic electronic devices
An encapsulating material was prepared in the same manner as in example 1. However, unlike example 1, as the encapsulating resin of the first encapsulating resin layer, a phenoxy resin and an epoxy resin were mixed in a weight ratio of 1:1.4 to prepare an encapsulating resin, and an encapsulating material was prepared using the encapsulating resin.
Example 7: preparation of packaging material for crimpable organic electronic devices
An encapsulating material was prepared in the same manner as in example 1. However, unlike example 1, the epoxy resin as the encapsulating resin of the first encapsulating resin layer was mixed with the first epoxy resin and the second epoxy resin in a weight ratio of 1:4 to prepare an encapsulating material.
Example 8: preparation of packaging material for crimpable organic electronic devices
An encapsulating material was prepared in the same manner as in example 1. However, unlike example 1, the epoxy resin as the encapsulating resin of the first encapsulating resin layer was mixed with the first epoxy resin and the second epoxy resin in a weight ratio of 1:0.67 to prepare an encapsulating material.
Comparative example 1: preparation of packaging material for crimpable organic electronic devices
A sealing material was prepared in the same manner as in example 1, but in the following evaluation step, the physical properties of the test piece were changed by changing the curing conditions.
Comparative example 2: preparation of packaging material for crimpable organic electronic devices
A first encapsulating resin layer was prepared in the same manner as in example 1. Unlike example 1, a second encapsulating resin layer was prepared in the following manner: a mixture was prepared by further adding 25 parts by weight of a tackifier (R1010, Eastman) to 100 parts by weight of a thermoplastic elastomer, and mixing 6 parts by weight of various curing agents (M200, Miwon Specialty Chemical), 1 part by weight of Ultraviolet (UV) initiator (irgacure TPO, Ciba), and 88 parts by weight of calcium oxide having an average particle diameter of 3 μ M as a moisture absorbent. In this case, the same resin as in example 1 was used as the thermoplastic elastomer.
The prepared mixture was adjusted to a viscosity of 600cps at a temperature of 20 ℃ and passed through a capsule filter to remove foreign substances, and then coated on a heavy-peel antistatic die PET (TG65R, SKC) having a thickness of 36 μm using a slit coater, followed by drying at a temperature of 120 ℃ to remove the solvent, to prepare a second encapsulating resin layer having a final thickness of 35 μm.
Comparative example 3: preparation of packaging material for crimpable organic electronic devices
An encapsulating material was prepared in the same manner as in example 1. However, unlike example 1, an encapsulating material was prepared using only a phenoxy resin without using an epoxy resin as an encapsulating resin of the first encapsulating resin layer.
Comparative example 4: preparation of packaging material for crimpable organic electronic devices
An encapsulating material was prepared in the same manner as in example 1. However, unlike example 1, an encapsulating material was prepared using only a thermoplastic elastomer without using an epoxy resin as an encapsulating resin of the second encapsulating resin layer.
The compositions of each layer of the encapsulating material according to the above-described examples and comparative examples are shown in tables 1 to 3 below.
TABLE 1
Figure BDA0003092544270000211
Figure BDA0003092544270000221
Figure BDA0003092544270000222
Solid epoxy resin comprising structure represented by the above chemical formula 2
TABLE 2
Figure BDA0003092544270000223
Figure BDA0003092544270000231
Figure BDA0003092544270000232
Solid epoxy resin comprising structure represented by the above chemical formula 2
TABLE 3
Figure BDA0003092544270000233
Figure BDA0003092544270000241
Figure BDA0003092544270000242
Solid epoxy resin comprising structure represented by the above chemical formula 2
Figure BDA0003092544270000243
Miwon Specialty Chemical
Tackifier: r1010, Eastman
Uv initiator: irgacure TPO, Ciba
Experimental example 1
The following physical properties of the encapsulating materials prepared by the above examples and comparative examples were measured and are shown in the following tables 4 to 6.
1. Evaluation of glass adhesion
For the sealing materials prepared according to examples and comparative examples, an adhesive force measuring tape (7475, TESA) was laminated on the upper face of the second sealing resin from which the release PET was removed by a 2kg hand roller (2kg hand roller), and after cutting a sample (═ sealing material) into a width of 25mm and a length of 120mm, the first sealing resin layer from which the release PET was removed was roll-laminated on alkali-free glass at 50 ℃, followed by heat treatment at 100 ℃ for 2.5 hours to cure the sealing material. In this case, comparative example 1 was only thermally cured at 100 ℃ for 30 minutes, and in the case of comparative example 2, instead of heat, uv light was exposed to the encapsulating material to be replaced by photo-curing. The heat-treated sample was left to stand at normal temperature (═ 25 ℃ C.) for 30 minutes, and peeled off at a speed of 300mm/min by a universal material testing machine (UTM) and the glass adhesion was measured.
2. Evaluation of moisture permeation of encapsulating Material
After the sealing materials prepared according to examples and comparative examples were cut into a size of 95mm × 95mm, the protective film on the alkali-free glass of 100mm × 100mm was removed, and then the test piece was aligned so that it could be located inside 2.5mm from the edge portion of 4 faces of the alkali-free glass, and then attached using a roll laminator heated to 65 ℃. After removing the release film remaining on the attached test piece, another 100mm of the dry glass of 100mm, which was 100mm, was covered and laminated at 50 ℃ for 1 minute by a vacuum laminator without air bubbles, and heat-treated at 100 ℃ for 2 hours and 30 minutes. The length of water permeation of the heat-treated sample in a reliability chamber set at 85 ℃ and a relative humidity of 85% was observed in 100 hours under a microscope.
3. Evaluation of Heat resistance of encapsulating Material
The encapsulating materials prepared according to the examples and comparative examples were cut into a size of 50mm × 80mm, and the second encapsulating resin layer from which the release PET was removed was attached to a 60mm × 150mm 0.08T Ni alloy using a roll laminator under a condition of 80 ℃. After the first encapsulating resin layer from which the release PET remaining on the attached test piece was removed was attached to 30mm × 150mm 5T alkali-free glass using a roll laminator at 50 ℃, heat treatment was performed at 100 ℃ for 2 hours and 30 minutes. After the test piece attached to the glass was vertically fixed in a chamber at 100 ℃, a weight of 1kg was suspended to determine whether the test piece flowed. In this case, when there is no abnormality in the evaluation result, it is represented by ∘, and when there is little flow, it is represented by x.
4. Rolling (Rolling) appearance evaluation
The encapsulating materials prepared according to examples and comparative examples were cut into a size of 280mm × 500mm, and after attaching the second encapsulating resin layer from which the release PET was removed to a 0.08T Ni alloy of 300mm × 550mm using a roll laminator at 80 ℃, the release PET of the first encapsulating resin layer was removed, and the same size of PET which was not release-treated was attached using a roll laminator at 80 ℃, followed by heat treatment at 100 ℃ for 2 hours and 30 minutes. The heat-treated sample was wound and fixed in a circular (50R) Jig (Jig) in such a manner as to contact the PET surface, and after leaving it in a reliability chamber set at 60 ℃ and a relative humidity of 90% for 240 hours, the side surface of the sample was observed with a microscope.
In this case, when the evaluation result is no abnormality, it is represented by ≈ and when any abnormality such as interface separation, cracks, separation between the first and second encapsulating resin layers, or the like occurs, it is represented by ×.
Experimental example 2
After organic light emitting devices (hole transport layer NPD/thickness 800A, light emitting layer Alq 3/thickness 300A, electron injection layer LiF/thickness 10A, cathode Al + Liq/thickness 1000A) were evaporated and stacked on a substrate having an Indium Tin Oxide (ITO) pattern, the encapsulation materials according to examples and comparative examples were laminated on the prepared devices at room temperature, and then Organic Light Emitting Diode (OLED) unit test pieces emitting green light were prepared. The test pieces were then evaluated for the following physical properties and are shown in tables 4 to 6.
1. Durability evaluation of organic light emitting device according to moisture permeation of encapsulation material
In each of the above test pieces, generation and/or growth of Pixel shrinkage (Pixel shrinkage) and Dark spot (Dark spot) per one time period of the luminescent part was observed under an environment of 85 ℃ and 85% relative humidity in 100 hour units using an x 100 digital microscope, and the time until 50% or more of Pixel shrinkage and/or generation of Dark spot occurred was measured and shown in tables 4 to 6.
In this case, the time required for causing 50% or more of pixel shrinkage and generating a dark spot is 1000 hours or more, expressed as "excellent", the time required for causing 50% or more of pixel shrinkage and generating a dark spot is 800 hours or more and less than 1000 hours, expressed as "a", the time required for causing 50% or more of pixel shrinkage and generating a dark spot is 600 hours or more and less than 800 hours, expressed as "Δ", and the time required for causing 50% or more of pixel shrinkage and generating a dark spot is less than 600 hours, expressed as "x".
2. Evaluation of durability of encapsulating Material
The test pieces were observed in a reliability chamber set at 85 ℃ and a relative humidity of 85% at intervals of 100 hours for 1000 hours, and the occurrence of physical damage was evaluated by observing interfacial separation between the organic electronic device and the encapsulating material, cracks or bubbles in the adhesive film, separation between the adhesive layers, and the like through an optical microscope and is shown in tables 4 to 6. When there was no abnormality in the evaluation results, it is indicated by ≈ and when any abnormality such as interfacial separation, cracks, or bubbles in the encapsulating material, separation between the first and second encapsulating resin layers, or the like occurs, it is indicated by ×.
Experimental example 3: evaluation of storage modulus
16 sheets of the sealing materials having a thickness of 50 μm, from which the release PET was removed, prepared by the above-described examples and comparative examples were laminated (roll lamination, 50 ℃, gap of 2mm, speed of 1) to prepare sealing materials having a thickness of 800 μm, and heat-treated at 100 ℃ for 2.5 hours, respectively. The storage modulus of the samples subjected to the heat treatment was measured by a dynamic thermomechanical analyzer (Q850, TA Instruments) under the following measurement conditions and at temperatures of 25 ℃ and 60 ℃ and is shown in tables 4 to 6 below.
Inclined temperature rise (Ramp Up)
Initial temperature-40 deg.C
Final temperature 110 ℃ C
-a temperature rise rate of 5 ℃/min
Frequency 1Hz
Initial force 0.01N
Experimental example 4: evaluation of peeling Strength
The sealing materials prepared according to examples and comparative examples were cut into 40mm width and 60mm length, and the release PET of the second sealing resin layer of the sealing material was removed, and then laminated (roll lamination, 80 ℃, gap of 2mm, speed of 1) on a nickel alloy sheet having 50mm width, 150mm length and 0.08mm thickness. Then, the release PET was cut into a width of 10mm and a length of 150mm, and the first sealing resin layer of the sealing material was removed and laminated (roll-laminated, 50 ℃, gap of 2mm, speed of 1) on glass, and then heat-treated at 100 ℃ for 2 hours and 30 minutes. The peel strength of the heat-treated encapsulation material was measured by an universal material tester (OTT-0006, orental) under the following measurement conditions and at a temperature of 25 ℃ and 60 ℃ (measured after maintaining stability for 10 minutes) and is shown in tables 4 to 6 below.
Measurement conditions
-a peeling mode: 180 DEG peel
-measuring the speed: 10mm/sec
-peel length: 50mm (10sec)
TABLE 4
Figure BDA0003092544270000281
TABLE 5
Figure BDA0003092544270000282
TABLE 6
Figure BDA0003092544270000291
Simple modifications or changes to the present invention can be easily implemented by those of ordinary skill in the art to which the present invention pertains, and such modifications or changes can be considered to be included within the scope of the present invention.

Claims (20)

1. An encapsulating material for an organic electronic device, characterized in that the encapsulating material for an organic electronic device is rollable,
comprises an encapsulating resin layer containing an encapsulating resin and a moisture absorbent, the encapsulating resin layer containing an epoxy resin,
the encapsulating resin layer includes:
a first encapsulating resin layer; and
a second sealing resin layer formed on one surface of the first sealing resin layer,
the sealing resin of the first sealing resin layer also comprises a high molecular resin with the weight average molecular weight of 10000-300000 g/mol,
the encapsulating resin of the second encapsulating resin layer comprises a thermoplastic elastomer having a storage modulus of 0.01 to 1.0MPa as measured by the following measuring method 1,
the encapsulating resin layer satisfies the following relational expression 1:
relation 1:
1.0≤A/B≤15.0；
in the above relation 1, A is the peel strength of the cured sealing resin layer measured by a universal material tester under a temperature condition of 25 ℃, B is the peel strength of the cured sealing resin layer measured by a universal material tester under a temperature condition of 60 ℃, wherein the unit of the peel strength is gf/10mm,
measurement method 1:
after punching a thermoplastic elastomer cured at a thickness of 800 μm so as to have a circular diameter of 6mm, the storage modulus at 25 ℃ under conditions of a temperature range of 10 to 110 ℃, a temperature rise rate of 5 ℃/min, a frequency of 15rad/s, and an axial force of 0.1N were measured, respectively.
2. An encapsulating material for an organic electronic device according to claim 1, wherein A is 700gf/10mm or more and B is 500gf/10mm or more.
3. A sealing material for organic electronic device according to claim 2, wherein A is 1400 to 2600gf/10mm, and B is 1260 to 2340gf/10 mm.
4. The sealing material for organic electronic devices according to claim 1, wherein the sealing resin layer further satisfies the following relation 2:
relation 2:
1.0≤A’/B’≤15.0，
in the above relational expression 2, a 'is a storage modulus of the encapsulating resin layer cured in a thickness of 800 μm measured with a dynamic thermo-mechanical analyzer under a temperature condition of 25 ℃, and B' is a storage modulus of the encapsulating resin layer cured in a thickness of 800 μm measured with a dynamic thermo-mechanical analyzer under a temperature condition of 60 ℃.
5. An encapsulating material for an organic electronic device according to claim 4, wherein A 'is 500MPa or more and B' is 300MPa or more.
6. The sealing material for organic electronic device according to claim 5, wherein A 'is 1050 to 1950MPa and B' is 910 to 1690 MPa.
7. The sealing material for organic electronic device according to claim 1, wherein the polymer resin having a weight average molecular weight of 10000 to 300000g/mol comprises at least one selected from the group consisting of phenoxy resin, acrylic resin, nitrile rubber resin and urethane resin.
8. The sealing material for organic electronic devices according to claim 7, wherein the polymer resin having a weight average molecular weight of 10000 to 300000g/mol comprises a compound represented by the following chemical formula 1:
chemical formula 1:
Figure FDA0003092544260000021
in the above chemical formula 1, n is an integer of 12 to 330.
9. The sealing material for organic electronic devices according to claim 1, wherein the thermoplastic elastomer comprises at least one selected from the group consisting of isobutylene-based thermoplastic elastomers, isoprene-based thermoplastic elastomers, urethane-based thermoplastic elastomers, styrene-based thermoplastic elastomers, butadiene-based thermoplastic elastomers and ester-based thermoplastic elastomers.
10. The encapsulating material for an organic electronic device according to claim 9, wherein the thermoplastic elastomer comprises a styrene-isobutylene-styrene block copolymer.
11. The sealing material for organic electronic devices according to claim 1, wherein the sealing resin of the second sealing resin layer comprises the thermoplastic elastomer and an epoxy resin in a weight ratio of 1:0.7 to 1.3.
12. The encapsulating material for organic electronic device according to claim 1,
the encapsulating resin of the first encapsulating resin layer contains the polymer resin and the epoxy resin with the weight-average molecular weight of 10000-300000 g/mol in a weight ratio of 1: 0.7-1.3.
13. The encapsulating material for organic electronic device according to claim 1,
the epoxy resin includes a first epoxy resin and a second epoxy resin different from each other in a weight ratio of 1:0.7 to 2.5,
the first epoxy resin comprises at least one selected from dicyclopentadiene type solid epoxy resin, bisphenol-A type solid epoxy resin, bisphenol-F type solid epoxy resin and novolac type solid epoxy resin,
the second epoxy resin includes at least one selected from the group consisting of a silicon-modified liquid epoxy resin, a liquid bisphenol-type epoxy resin, a urethane-modified liquid epoxy resin, and a rubber-modified liquid epoxy resin.
14. The encapsulating material for organic electronic device according to claim 1,
the first sealing resin layer contains 2.0 to 4.0 parts by weight of a moisture absorbent per 100 parts by weight of the sealing resin,
the second sealing resin layer contains 48 to 90 parts by weight of a moisture absorbent with respect to 100 parts by weight of the sealing resin.
15. The sealing material for organic electronic device according to claim 1, wherein the first sealing resin layer and the second sealing resin layer each independently further comprise a curing agent.
16. The sealing material for organic electronic device according to claim 15, wherein the curing agent comprises one or more selected from the group consisting of amine curing agents, imidazole curing agents, amide curing agents, thioether curing agents, phenol curing agents, thiol curing agents, isocyanate curing agents, and acid anhydride curing agents, and the amine curing agent comprises aliphatic amine, aromatic amine, alicyclic amine, secondary amine, tertiary amine, or BF3An amine.
17. The encapsulating material for organic electronic device according to claim 1,
the first encapsulating resin layer contains 0.1 to 2.0 parts by weight of a curing agent per 100 parts by weight of the encapsulating resin,
the second encapsulating resin layer contains 2.5 to 9.0 parts by weight of a curing agent per 100 parts by weight of the encapsulating resin.
18. The sealing material for organic electronic device according to claim 1, wherein the thickness ratio between the first sealing resin layer and the second sealing resin layer is 1:1.0 to 8.0.
19. The encapsulating material for organic electronic device according to claim 18,
the thickness of the first sealing resin layer is 1 to 25 μm,
the thickness of the second sealing resin layer is 25 to 60 μm.
20. A rollable organic electronic device, comprising:
a substrate;
a rollable organic electronic device formed on at least one surface of the substrate; and
an encapsulating material for organic electronic devices selected from any one of claims 1 to 19, for encapsulating the above-mentioned rollable organic electronic device.
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