Encapsulating composition

Abstract

Provided is an encapsulating composition and an organic electronic device comprising the same. The encapsulating composition can effectively block moisture or oxygen from being introduced into an organic electronic device from the outside. The encapsulating composition can secure the lifetime of the organic electronic device, make it possible to realize a top emission type organic electronic device, is applicable to an inkjet method and can provide a thin display.

Claims

1. An organic electronic device, comprising: a substrate; an organic electronic element formed on the substrate; and an organic layer sealing the entire surface of the organic electronic element and comprising an encapsulating composition that comprises: an epoxy compound comprising: an alicyclic epoxy compound; and a linear or branched aliphatic epoxy compound having at least bifunctionality or more selected from among 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether, wherein the linear or branched aliphatic epoxy compound having at least bifunctionality or more is present in an amount of 20 to 60 parts by weight or 173 to 205 parts by weight relative to 100 parts by weight of the alicyclic epoxy compound; a compound having an oxetane group and a boiling point in a range of 110 to 300° C. present in an amount of 45 parts by weight to 145 parts by weight relative to 100 parts by weight of the total epoxy compounds present in the composition; a surfactant comprising a fluorine-based compound having a polar functional group which is present at the end of the surfactant, wherein the polar functional group is a carboxyl group, a hydroxyl group, a phosphate, an ammonium salt, a carboxylate group, a sulfate, or a sulfonate; and a photoinitiator comprising an iodonium salt, wherein the composition has a viscosity of 50 cP or less, as measured at a temperature of 25° C., a torque of 90% and a shear rate of 100 rpm.

2. The organic electronic device according to claim 1, wherein the alicyclic epoxy compound includes a ring having from 3 to 10 ring constituent atoms.

3. The organic electronic device according to claim 1, wherein the alicyclic epoxy compound or the linear or branched aliphatic epoxy compound has an epoxy equivalent in a range of 50 to 350 g/eq.

4. The organic electronic device according to claim 1, wherein the compound having an oxetane group has a weight average molecular weight in a range of 150 to 1,000 g/mol.

5. The organic electronic device according to claim 1, wherein the photoinitiator is present in an amount of 1 to 15 parts by weight relative to 100 parts by weight of the epoxy compound.

6. The organic electronic device according to claim 1, wherein the surfactant is present in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the epoxy compound.

7. The organic electronic device according to claim 1, wherein the composition is a solventless ink composition.

8. A method for manufacturing an organic electronic device of claim 1, comprising applying the encapsulating composition on the substrate on which the organic electronic element is formed, sealing the entire surface of the organic electronic element, and forming an organic layer.

9. The method of claim 8, wherein the applying comprises inkjet printing, gravure coating, spin coating, screen printing or reverse offset coating.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIGS. 1 and 2 are cross-sectional views showing an organic electronic device according to one example of the present invention.

EXPLANATION OF REFERENCE NUMERALS

(2) 3: organic electronic device 31: substrate 32: organic electronic element 33: organic layer 34: protective layer 35: inorganic layer 36: sealing structure 37: encapsulation film 38: cover substrate

BEST MODE

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

Example 1

(4) An alicyclic epoxy compound (Celloxide 2021P, Daicel Corp.) and an aliphatic epoxy compound (DE200, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator comprising an iodonium salt (TTA-UV694 from Tetrachem, hereinafter, UV694) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 23.8:28.7:37.5:5.0:1.0 (Celloxide2021P: DE200: OXT-221: UV694: F552) at room temperature.

(5) In the mixing vessel, a uniform encapsulating composition ink was prepared using a planetary mixer (Kurabo, KK-250s).

Example 2

(6) An encapsulating composition was prepared in the same manner as in Example 1, except that an alicyclic epoxy compound (Celloxide 2021P, Daicel Corp.) and an aliphatic epoxy compound (DE201, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-212 from TOAGOSEI), a photoinitiator comprising an iodonium salt (UV694) and a fluorine-based surfactant (FC-4430 from 3M) were each introduced into a mixing vessel in a weight ratio of 29.4:10.2:50.4:5.0:1.0 (Celloxide2021P: DE201: OXT-212: UV694: FC-4430) at room temperature.

Example 3

(7) An encapsulating composition was prepared in the same manner as in Example 1, except that an alicyclic epoxy compound (Celloxide 2021P, Daicel Corp.) and an aliphatic epoxy compound (DE203, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator comprising an iodonium salt (UV694) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 12.4:24.8:46.8:10.0:1.0 (Celloxide2021P: DE203: OXT-221: UV694: F552) at room temperature.

Example 4

(8) An encapsulating composition was prepared in the same manner as in Example 1, except that an alicyclic epoxy compound (Celloxide 2081, Daicel Corp.) and an aliphatic epoxy compound (DE203, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator comprising an iodonium salt (Irgacure 250 from BASF, hereinafter, 1250) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 24.8:24.2:40.9:5.0:1.0 (Celloxide 2081: DE203: OXT-221: I250: F552) at room temperature.

Example 5

(9) An encapsulating composition was prepared in the same manner as in Example 1, except that an alicyclic epoxy compound (Celloxide 3000, Daicel Corp.) and an aliphatic epoxy compound (DE207, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator comprising an iodonium salt (1250) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 30.0:7.2:52.8:5.0:1.0 (Celloxide 3000: DE207: OXT-221: I250: F552) at room temperature.

Example 6

(10) An encapsulating composition was prepared in the same manner as in Example 1, except that an alicyclic epoxy compound (Celloxide 2021P, Daicel Corp.) and an aliphatic epoxy compound (DE203, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator comprising an iodonium salt (UV694) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 37.5:7.0:45.5:5.0:1.0 (Celloxide2021P: DE203: OXT-221: UV694: F552) at room temperature.

Example 7

(11) An encapsulating composition was prepared in the same manner as in Example 1, except that an alicyclic epoxy compound (Celloxide 2081P, Daicel Corp.) and an aliphatic epoxy compound (DE203, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator comprising an iodonium salt (UV694) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 20.0:41.0:29.0:5.0:1.0 (Celloxide 2081P: DE203: OXT-221: UV694: F552) at room temperature.

Comparative Example 1

(12) An alicyclic epoxy compound (Celloxide 2021P, Daicel Corp.) and an aliphatic epoxy compound (DE213, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-121 from TOAGOSEI), a sulfonium salt-containing photoinitiator (Irgacure PAG 290 from BASF, hereinafter, 1290) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 2.3:23.4:64.3:5.0:1.0 (Celloxide2021P: DE213: OXT-121: I290: F552) at room temperature.

(13) In the mixing vessel, a uniform encapsulating composition ink was prepared using a planetary mixer (Kurabo, KK-250s).

Comparative Example 2

(14) An encapsulating composition was prepared in the same manner as in Comparative Example 1, except that an alicyclic epoxy compound (Celloxide 2021P, Daicel Corp.) and an aliphatic epoxy compound (DE201, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-221 from TOAGOSEI), a sulfonium salt-containing photoinitiator (TTA-UV692 from Tetrachem, hereinafter, UV692) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 23.8:30.0:36.2:5.0:1.0 (Celloxide2021P: DE201: OXT-221: UV692: F552) at room temperature.

Comparative Example 3

(15) An encapsulating composition was prepared in the same manner as in Comparative Example 1, except that an alicyclic epoxy compound (Celloxide 2021P, Daicel Corp.) and an aliphatic epoxy compound (DE201, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-212 from TOAGOSEI), a sulfonium salt-containing photoinitiator (GSID26-1 from BASF) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 29.4:10.2:50.4:5.0:1.0 (Celloxide2021P: DE201: OXT-212: GSID26-1: F552) at room temperature.

Comparative Example 4

(16) An encapsulating composition was prepared in the same manner as in Comparative Example 1, except that an alicyclic epoxy compound (Celloxide 2021P, Daicel Corp.) and an aliphatic epoxy compound (DE207, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-212 from TOAGOSEI), a non-ionic photoinitiator (Irgacure PAG 103 from BASF, hereinafter, PAG103) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 29.4:10.2:50.4:5.0:1.0 (Celloxide2021P: DE207: OXT-212: PAG103: F552) at room temperature.

Comparative Example 5

(17) An encapsulating composition was prepared in the same manner as in Comparative Example 1, except that an alicyclic epoxy compound (Celloxide 2021P, Daicel Corp.) and an aliphatic epoxy compound (DE207, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-212 from TOAGOSEI), a non-ionic photoinitiator (CGI725 from BASF) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 29.4:10.2:50.4:5.0:1.0 (Celloxide2021P: DE207: OXT-212: CGI725: F552) at room temperature.

Comparative Example 6

(18) An encapsulating composition was prepared in the same manner as in Comparative Example 1, except that an alicyclic epoxy compound (Celloxide 2021P, Daicel Corp.) and an aliphatic epoxy compound (DE203, HAJIN CHEM TECH) as epoxy compounds, an oxetane group-containing compound (OXT-221 from TOAGOSEI), a photoinitiator comprising an iodonium salt (UV694) and a fluorine-based surfactant (F552 from DIC) were each introduced into a mixing vessel in a weight ratio of 12.5:7.3:66.7:5.0:1.0 (Celloxide2021P: DE203: OXT-221: UV694: F552) at room temperature.

(19) Physical properties in Examples and Comparative Examples were evaluated in the following manner.

(20) 1. Viscosity Measurement

(21) Each viscosity of the encapsulating compositions prepared in Examples and Comparative Examples was measured using DV-3 as a Brookfield viscometer as follows.

(22) The viscosity of the prepared encapsulating composition was measured under conditions of a temperature of 25° C., a torque of 90% and a shear rate of 100 rpm. Specifically, 0.5 ml of a sample was injected using a cone/plate method of the Brookfield viscometer to measure the viscosity.

(23) 2. Curing Sensitivity Measurement

(24) The encapsulating compositions prepared in Examples and Comparative Examples were each irradiated with UV of 1 J/cm.sup.2 at an intensity of 1000 mW/cm.sup.2 and then the tack free time of each sealing material was measured. First, the encapsulating composition is applied by spin coating to a thickness of 10 μm and cured. A time until a tacky feeling disappears and there is no leakage of the sealing material when the surface of the sealing material has been touched immediately after curing, is defined as a tack free time and measured. It was measured by dividing the relative humidity at 5%, 25% and 50%. It was classified as ⊚ in the case where the tack free time was less than 1 second, as O in the case where it was less than 1 minute, as Δ in the case where it was 5 minutes or more and as X in the case where it was 30 minutes or more.

(25) 3. Upper Adhesion Measurement

(26) The encapsulating compositions prepared in Examples and Comparative Examples were each spin-coated on an LCD glass to a thickness of 5 μm. The coated encapsulating composition was irradiated with UV of 1 J/cm′ at an intensity of 1000 mW/cm.sup.2 under a condition of 5% relative humidity. An adhesive strength was measured using TA-/XT/PLUS as a texture analyzer from STABLE MICRO SYSTEMS. The adhesive strength was measured according to ASTM D-3330 standard. The measurement was performed ten times, where since there was a measurement error in the measured value, the ranges were set for each section and indicated in Table 1.

(27) 4. Lower Adhesive Strength

(28) The encapsulating compositions prepared in Examples and Comparative Examples were each spin-coated on an LCD glass to a thickness of 5 μm. The coated encapsulating composition was irradiated with UV of 1 J/cm′ at an intensity of 1000 mW/cm.sup.2 under a condition of 5% relative humidity. The cured encapsulating composition was subjected to a cross cut test according to ASTM D3359 standard.

(29) Specifically, a Nichiban Tape CT-24 (width 2 cm) was used, and a specimen was cut with a knife at a distance of 1 mm in transverse and longitudinal directions by 11 lines, respectively, to form 100 square lattices with a width of 1 mm and a length of 1 mm. Thereafter, when the CT-24 adhesive tape from Nichiban Co., Ltd. was attached to the cut surface and then peeled off, the state of the peeling faces together was measured and evaluated according to the following criteria.

(30) <Cross-Hatch Adhesive Force Evaluation Criteria> 5B: if there is no peeled face 4B: if the peeled faces are within 5% relative to the total area 3B: if the peeled faces are more than 5% and within 15% relative to the total area 2B: if the peeled faces are more than 15% and within 35% relative to the total area 1B: if the peeled faces are more than 35% and within 65% relative to the total area 0B: if the peeled faces are more than 60% relative to the total area

(31) TABLE-US-00001 TABLE 1 Curing sensitivity Upper Viscosity 5% 25% 50% adhesion Lower (cPs) RH RH RH (gf/inch) adhesion Example 1 33.6 ⊚ ⊚ ⊚  900~1000 5B Example 2 21.8 ⊚ ⊚ ⊚ 700~800 5B Example 3 17 ⊚ ⊚ ◯ 800~900 4B Example 4 35.8 ⊚ ⊚ ◯ 800~900 5B Example 5 10.9 ⊚ ⊚ ◯ 700~800 5B Example 6 70 ⊚ ⊚ ⊚ 700~800 5B Example 7 46 ⊚ ⊚ ⊚ 800~900 4B Comparative 90.3 ⊚ Δ Δ 500~600 3B Example 1 Comparative 33.8 ◯ Δ X 200~300 2B Example 2 Comparative 21.8 Δ X X 100~200 2B Example 3 Comparative 21.8 Δ Δ X 100~200 2B Example 4 Comparative 21.8 ◯ Δ X 200~300 1B Example 5 Comparative 14.2 Δ X X 100~200 0B Example 6