Composition for encapsulating organic electronic element

Abstract

Provided is a composition for encapsulating an organic electronic element and an organic electronic device comprising the same, and an encapsulating composition that can form a structure capable of effectively blocking moisture or oxygen introduced from the outside into an organic electronic device, thereby securing a lifetime of the organic electronic device, and that can be applied to a top-emitting organic electronic device to prevent physical and chemical damage of organic electronic elements, while having excellent optical properties and processability, and an organic electronic device comprising the same.

Claims

1. A composition for encapsulating an organic electronic element, comprising: a curable compound comprising a compound having an oxetane group; a thermal initiator; and a hardening retarder, and satisfying Equation 1 below,
0.03<R/P<0.6  [Equation 1] wherein R is a part by weight of the hardening retarder relative to 100 parts by weight parts of the curable compound, and P is a part by weight of the thermal initiator relative to 100 parts by weight of the curable compound.

2. The composition according to claim 1, wherein the curable compound comprises at least one or more curable functional groups.

3. The composition according to claim 2, wherein the curable functional group is one or more selected from a glycidyl group, an isocyanate group, a hydroxyl group, a carboxyl group, an amide group, an epoxide group, a cyclic ether group, a sulfide group, an acetal group and a lactone group.

4. The composition according to claim 1, wherein the curable compound further comprises an epoxy compound having a cyclic structure in the molecular structure.

5. The composition according to claim 4, wherein the epoxy compound having a cyclic structure in the molecular structure has 3 to 10 ring constituent atoms.

6. The composition according to claim 4, wherein the epoxy compound having a cyclic structure in the molecular structure is an alicyclic epoxy compound.

7. The composition according to claim 4, wherein an amount of the compound having an oxetane group in the curable compound is in a range of 3 to 50 parts by weight relative to 100 parts by weight of the epoxy compound.

8. The composition according to claim 1, wherein the curable compound has a weight average molecular weight of 300 g/mol or less.

9. The composition according to claim 1, wherein the thermal initiator is a thermal cationic initiator.

10. The composition according to claim 1, wherein the thermal initiator comprises a sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt or a iodonium salt, which has BF.sub.4.sup.−, ASF.sub.6.sup.−, PF.sub.6.sup.−, SbF.sub.6.sup.−, or (BX.sub.4).sup.− as an anion, where X is a phenyl substituted with at least two fluorine or trifluoromethyl groups.

11. The composition according to claim 1, wherein the thermal initiator is included in an amount of 0.01 to 1 part by weight relative to 100 parts by weight of the curable compound.

12. The composition according to claim 1, wherein the hardening retarder comprises one or more selected from the group consisting of an amine-based compound, a polyether-based compound, boric acid, phenylboric acid, salicylic acid, hydrochloric acid, sulfuric acid, oxamic acid, tetraphthalic acid, isophthalic acid, phosphoric acid, acetic acid, and lactic acid.

13. The composition according to claim 1, wherein R/P is in a range of more than 0.1 and less than 0.5 when the hardening retarder is a polyether-based compound, and R/P is in a range of more than 0.03 and 0.1 or less when the hardening retarder is an amine-based compound.

14. The composition according to claim 1, wherein the hardening retarder is included in an amount of 0.002 to 0.12 parts by weight relative to 100 parts by weight of the curable compound.

15. An organic electronic device, comprising: a substrate; an organic electronic element formed on the substrate; and a top encapsulating layer which seals the top surface of the organic electronic element and comprises the composition for encapsulating an organic electronic element according to claim 1.

16. The organic electronic device according to claim 15, further comprising a side encapsulating layer formed so as to surround the side surfaces of the organic electronic element on the substrate, wherein the side encapsulating layer and the top encapsulating layer are present on the same plane.

17. A method for manufacturing an organic electronic device comprising steps of: applying the composition for encapsulating an organic electronic element of claim 1 on a substrate, on which the organic electronic element is formed, so as to seal the top surface of the organic electronic element; and curing the composition.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a cross-sectional diagram showing an organic electronic device according to one example of the present invention.

EXPLANATION OF REFERENCE NUMERALS

(2) 1: encapsulating structure 10: side encapsulating layer 11: top encapsulating layer 21: substrate 22: cover substrate 23: organic electronic element

BEST MODE

(3) Hereinafter, the present invention will be described in more detail with reference to examples according to the present invention and comparative examples not according to the present invention, but the scope of the present invention is not limited by the following examples.

(4) Example 1

(5) At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel Corporation, Mw 270 g/mol) and an oxetane compound (OXT-101 from TOAGOSEI Co., Ltd.) as a curable compound were introduced into a mixing vessel at a ratio by weight of 77:23 (Celloxide 2021P:OXT-101). 0.15 parts by weight of a thermal cationic initiator (King Industries, Inc., CXC-1612) and 0.050 parts by weight of 18-crown-6-ether as a hardening retarder were introduced to the vessel, relative to 100 parts by weight of the curable compound. The mixed solution was stirred to prepare a uniform composition solution.

(6) Example 2

(7) At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel Corporation, Mw 270 g/mol) and an alicyclic epoxy compound (Celloxide 8000 from Daicel Corporation) as a curable compound were introduced into a mixing vessel at a ratio by weight of 70:30 (Celloxide 2021P:Celloxide 8000). 0.06 parts by weight of a thermal cationic initiator (King Industries, Inc., CXC-1612) and 0.024 parts by weight of 18-crown-6-ether as a hardening retarder were introduced to the vessel, relative to 100 parts by weight of the curable compound. The mixed solution was stirred to prepare a uniform composition solution.

(8) Example 3

(9) At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel Corporation, Mw 270 g/mol), an alicyclic epoxy compound (Celloxide 8000 from Daicel Corporation) and an oxetane compound (OXT-221 from TOAGOSEI Co., Ltd., Mw 210 g/mol) as a curable compound were introduced into a mixing vessel at a ratio by weight of 30:65:5 (Celloxide 2021P:Celloxide 8000:OXT-221). 0.06 parts by weight of a thermal cationic initiator (King Industries, Inc., CXC-1612) and 0.024 parts by weight of 18-crown-6-ether as a hardening retarder were introduced to the vessel, relative to 100 parts by weight of the curable compound. The mixed solution was stirred to prepare a uniform composition solution.

(10) Example 4

(11) At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel Corporation, Mw 270 g/mol) and an alicyclic epoxy compound (Celloxide 8000 from Daicel Corporation) as a curable compound were introduced into a mixing vessel at a ratio by weight of 70:30 (Celloxide 2021P:Celloxide 8000). 0.06 parts by weight of a thermal cationic initiator (King Industries, Inc., CXC-1821) and 0.020 parts by weight of 18-crown-6-ether as a hardening retarder were introduced to the vessel, relative to 100 parts by weight of the curable compound. The mixed solution was stirred to prepare a uniform composition solution.

(12) Example 5

(13) At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel Corporation, Mw 270 g/mol) and an alicyclic epoxy compound (Celloxide 8000 from Daicel Corporation) as a curable compound were introduced into a mixing vessel at a ratio by weight of 70:30 (Celloxide 2021P:Celloxide 8000). 0.1 parts by weight of a thermal cationic initiator (King Industries, Inc., CXC-1612) and 0.021 parts by weight of 18-crown-6-ether as a hardening retarder were introduced to the vessel, relative to 100 parts by weight of the curable compound. The mixed solution was stirred to prepare a uniform composition solution.

(14) Example 6

(15) At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel Corporation, Mw 270 g/mol) and an oxetane compound (OXT-221 from TOAGOSEI Co., Ltd., Mw 210 g/mol) as a curable compound were introduced into a mixing vessel at a ratio by weight of 70:30 (Celloxide 2021P:OXT-221). 0.1 parts by weight of a thermal cationic initiator (King Industries, Inc., CXC-1821) and 0.049 parts by weight of 18-crown-6-ether as a hardening retarder were introduced to the vessel, relative to 100 parts by weight of the curable compound. The mixed solution was stirred to prepare a uniform composition solution.

(16) Example 7

(17) At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel Corporation, Mw 270 g/mol) and an oxetane compound (OXT-221 from TOAGOSEI Co., Ltd., Mw 210 g/mol) as a curable compound were introduced into a mixing vessel at a ratio by weight of 75:25 (Celloxide 2021P:OXT-221). 0.2 parts by weight of a thermal cationic initiator (King Industries, Inc., CXC-1821) and 0.0062 parts by weight of benzylamine as a hardening retarder were introduced to the vessel, relative to 100 parts by weight of the curable compound. The mixed solution was stirred to prepare a uniform composition solution.

(18) Comparative Example 1

(19) An encapsulating composition solution was prepared in the same manner as in Example 2, except that 0.0018 parts by weight of 18-crown-6-ether as a hardening retarder was introduced thereto, relative to 100 parts by weight of the curable compound.

(20) Comparative Example 2

(21) An encapsulating composition solution was prepared in the same manner as in Comparative Example 1, except that 0.04 parts by weight of 18-crown-6-ether as a hardening retarder was introduced thereto, relative to 100 parts by weight of the curable compound.

(22) Comparative Example 3

(23) An encapsulating composition solution was prepared in the same manner as in Example 1, except that no hardening retarder was introduced.

(24) Comparative Example 4

(25) An encapsulating composition solution was prepared in the same manner as in Example 4, except that no hardening retarder was introduced.

(26) Comparative Example 5

(27) At room temperature, an alicyclic epoxy compound (Celloxide 2021P from Daicel Corporation, Mw 270 g/mol) and an alicyclic epoxy compound (Celloxide 8000 from Daicel Corporation) as a curable compound were introduced into a mixing vessel at a ratio by weight of 70:30 (Celloxide 2021P:Celloxide 8000). 0.1 parts by weight of a photo cationic initiator (CPI-101A) and 0.049 parts by weight of 18-crown-6-ether as a hardening retarder were introduced to the vessel, relative to 100 parts by weight of the curable compound. The mixed solution was stirred to prepare a uniform composition solution.

(28) The physical properties in Examples and Comparative Examples were evaluated in the following manner.

(29) 1. Viscosity Measurement

(30) The viscosity of each of the compositions prepared in Examples and Comparative Examples was measured using a Brookfield viscometer (LV type) as follows.

(31) For the above-prepared curable compositions, the viscosity was measured at a temperature of 25° C. and a rotation speed of 100 rpm. Specifically, the viscosity was measured according to the torque at the RV-63 spindle of Brookfield viscometer.

(32) 2. Pot Life Measurement

(33) After 40 g of each of the compositions prepared in Examples and Comparative Examples was sealed in a glass bottle, it was allowed to stand in an oven at 35° C. to measure the viscosity every 24 hours. Specifically, the time at which the viscosity became 1.5 times the initial viscosity immediately before the sealing was recorded. It was classified as excellent for the case of 100 hours or more, good for the case of 60 hours or more and poor for the case of less than 60 hours.

(34) 3. Measurement of Light Transmittance and b*

(35) The compositions prepared in Examples and Comparative Examples were each applied between non-alkali glass (0.7 T) substrates and then heated at 100° C. for 30 minutes to form an encapsulating layer having a thickness of 50 μm.

(36) The light transmittance was measured as light transmittance at 550 nm using a UV-Vis spectrometer.

(37) On the other hand, the b* value was measured according to ASTM D 1003 standard using a COH 400 transmittance measuring instrument from Nippon Denshoku.

(38) 4. Out-Gas Measurement

(39) Measuring instrument: Purge & Trap sampler-GC/MSD system (P & T: JAI JTD-505111, GC/MS: Agilent 7890B/5977A)

(40) 300 g of each of the compositions prepared in Examples and Comparative Examples was cured by applying heat at 100° C. for 1 hour. The cured sample was immersed in a test tube and placed in the measuring instrument. In the instrument, the Purge and Trap was performed at 100° C. for 60 minutes, and then the total volatilization volume was measured using GC-MS.

(41) The area of each component of the sample was converted to the weight of toluene as the reference material, and then divided by the weight of the sample to calculate the out-gas content.

(42) It was classified as excellent for the case of 12 ppm or less, good for the case of 100 ppm or less and poor for the case of more than 100 ppm.

(43) TABLE-US-00001 TABLE 1 Light Viscos- Pot Trans- Out- ity Life mittance gas R/P (cP) (hour) (%) b* (ppm) Example 1 0.33 84 105 92.3 0.21 24 2 0.4 155 87 92.5 0.23 10 3 0.4 89 185 93.2 0.23 15 4 0.33 155 90 92.5 0.22 11 5 0.21 155 72 92.5 0.22 8 6 0.49 81 207 93.0 0.21 42 7 0.031 97 150 93.1 0.27 15 Comparative 1 0.03 155 10 92.7 0.21 9 Example 2 0.67 155 165 92.5 0.22 120 3 — 84 20 92.8 0.22 20 4 — 155 32 92.1 0.25 13 5 0.49 155 190 92.7 0.25 150