Adhesive composition, adhesive film comprising same, and organic electronic device comprising same

Abstract

The present application relates to an adhesive composition comprising a curable oligomer and a polymer derived from butylene, an adhesive film comprising same, an organic electronic device comprising same, and a lighting apparatus and a display device comprising same. The adhesive film comprising the adhesive composition shows excellent moisture-blocking properties and enables an organic electronic device to have flexibility as well as excellent and reliable durability at high temperature and high humidity.

Claims

1. An adhesive composition, comprising: a polymer derived from butylene, a curable oligomer which is an aromatic compound; and a curable monomer comprising one or more functional groups selected from among a glycidyl group, an isocyanate group, an amide group, an epoxide group, a cyclic ether group, a sulfide group, an acetal group, and a lactone group.

2. The adhesive composition according to claim 1, wherein the polymer derived from butylene is a homopolymer of a butylene monomer, a copolymer obtained by copolymerizing a second monomer polymerizable with a butylene monomer, a reactive oligomer using a butylene monomer, or a mixture thereof.

3. The adhesive composition according to claim 2, wherein the second monomer is isoprene, styrene or butadiene.

4. The adhesive composition according to claim 2, wherein the reactive oligomer using a butylene monomer comprises: a butylene polymer having a reactive functional group; or a butylene polymer bonded to another polymer having a reactive functional group.

5. The adhesive composition according to claim 1, wherein the polymer derived from butylene has a weight average molecular weight in a range of 10,000 to 2,000,000 g/mol.

6. The adhesive composition according to claim 1, wherein the curable oligomer is a hydrogenated compound.

7. The adhesive composition according to claim 1, wherein the curable oligomer has a weight average molecular weight in a range of 400 to 10,000 g/mol.

8. The adhesive composition according to claim 1, wherein the curable oligomer is a hydrogenated aromatic epoxy compound.

9. The adhesive composition according to claim 8, wherein the curable oligomer has an epoxy equivalent in a range of 100 to 1500 g/eq.

10. The adhesive composition according to claim 1, wherein the curable oligomer is included in an amount of 15 to 100 parts by weight, relative to 100 parts by weight of the polymer derived from butylene.

11. The adhesive composition according to claim 1, wherein the curable monomer has a weight average molecular weight of less than 400 g/mol.

12. The adhesive composition according to claim 1, wherein the curable monomer has a cyclic structure in which ring constituent atoms in the molecular structure are in a range of 3 to 10.

13. The adhesive composition according to claim 1, wherein the curable monomer is included in an amount of 20 to 80 parts by weight, relative to 100 parts by weight of the polymer derived from butylene.

14. The adhesive composition according to claim 1, wherein the curable monomer and the curable oligomer are included in proportions of 10 to 50 parts by weight and 20 to 70 parts by weight, respectively, relative to 100 parts by weight of the polymer derived from butylene.

15. The adhesive composition according to claim 1, comprising no tackifier.

16. An adhesive film having an adhesive layer comprising the adhesive composition of claim 1.

17. The adhesive film according to claim 16, wherein the adhesive layer has a storage elastic modulus, as measured under conditions of a temperature of 25 C., a strain of 5% and a frequency of 1 Hz after curing, in a range of 10.sup.5 Pa to 10.sup.9 Pa.

18. A flexible organic electronic device comprising a substrate in which an organic electronic element is formed on one surface, and the adhesive film according to claim 16 attached in a state covering the entire surface of said organic electronic element on said substrate.

19. The flexible organic electronic device according to claim 18, comprising at least one folding portion satisfying Equation 1 below:
X10%[Equation 1] wherein, X is a luminance change rate before and after a folding test in which a process of folding the folding portion of said organic electronic device to a curvature radius of 1R (1mm) at a temperature of 25 C. and a relative humidity of 50%, is repeated 100,000 times.

20. The flexible organic electronic device according to claim 18, further comprising a cover substrate, wherein the adhesive layer attaches said cover substrate to the surface of said substrate on which the organic electronic element exists.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIGS. 1 and 2 are cross-sectional views illustrating exemplary organic electronic devices.

EXPLANATION OF REFERENCE NUMERALS

(2) 1: substrate

(3) 2: organic electronic element

(4) 3: adhesive layer or adhesive film

(5) 4: cover substrate

BEST MODE

(6) Hereinafter, the present invention will be described in more detail with reference to Examples complying with 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

(7) A styrene-isobutylene copolymer (SIBS 062M, Mw: 60,000, Kaneka) as a polymer derived from butylene, a hydrogenated bisphenol A epoxy resin (YX8000, epoxy equivalent: 201 g/eq, Mitsubishi Chemical) as a curable oligomer, and an alicyclic epoxy compound (Celloxide 2021P, Mw: 250, Daicel corporation) as a curable monomer were introduced into a reaction vessel at a weight ratio of 50:30:20 (SIBS 062M: YX8000: Celloxide 2021P), respectively, and CXC1612 (King Industry) as a cationic photoinitiator was added thereto in an amount of 0.1 parts by weight, relative to 100 parts by weight of the polymer, and then diluted with toluene to a solid content of about 15% by weight to prepare an adhesive composition coating solution.

(8) An adhesive film was produced by coating the prepared solution on the releasing surface of the releasing PET and drying it in an oven at 100 C. for 15 minutes to form an adhesive layer having a thickness of 50 m.

EXAMPLE 2

(9) An adhesive composition and an adhesive film were produced in the same manner as in Example 1, except that a styrene-isobutylene copolymer (SIBS 102T, Mw: 100,000, Kaneka) as a polymer derived from butylene, a hydrogenated bisphenol A epoxy resin (YX8000, Mitsubishi Chemical) as a curable oligomer, and a silane-modified epoxy resin (KSR-177, Kukdo Chemical) as a curable monomer were introduced into a reaction vessel at a weight ratio of 60:15:25 (SIBS 102T: YX8000: KSR-177), respectively.

COMPARATIVE EXAMPLE 1

(10) Polyisobutylene (B50, BASF) as a polymer derived from butylene, a hydrogenated petroleum resin (SU90, Kolon), and 1,6-hexandediol diacrylate (M200, Miwon Commercial Co., Ltd.) were introduced into a reaction vessel at a weight ratio of 60:30:10 (B50: SU90: M200), respectively, and Irgacure654 (Ciba) as a radical initiator was added thereto in an amount of 0.1 parts by weight, relative to 100 parts by weight of the polymer, and then diluted with toluene to a solid content of about 15% by weight to prepare an adhesive composition coating solution.

(11) An adhesive film was produced by coating the prepared solution on the releasing surface of the releasing PET and drying it in an oven at 100 C. for 15 minutes to form an adhesive layer having a thickness of 50 m.

COMPARATIVE EXAMPLE 2

(12) An adhesive composition and an adhesive film were produced in the same manner as in Comparative Example 1, except that polyisobutylene (B50, BASF) as a polymer derived from butylene, a hydrogenated petroleum resin (SU90, Kolon), and 1,6-hexandediol diacrylate (M200, Miwon Commercial Co., Ltd.) were introduced into a reaction vessel at a weight ratio of 50:40:10 (B50: SU90: M200), respectively.

COMPARATIVE EXAMPLE 3

(13) An adhesive composition and an adhesive film were produced in the same manner as in Example 1, except that a silane-modified epoxy resin (KSR-277, Kukdo Chemical) and an alicyclic epoxy compound (Celloxide 2021P, Daicel corporation) were introduced into a reaction vessel at a weight ratio of 70:30 (KSR-277: Celloxide 2021P), respectively.

COMPARATIVE EXAMPLE 4

(14) An adhesive composition and an adhesive film were produced in the same manner as in Example 1, except that a bisphenol A type phenoxy resin (YP-50, Kukdo Chemical), a high molecular weight silane-modified epoxy resin (KSR-277, Kukdo Chemical) and a silane-modified epoxy resin (KSR-177, Kukdo Chemical) were introduced into a reaction vessel at a weight ratio of 40:30:30 (YP-50: KSR-277: KSR-177), respectively.

EXPERIMENTAL EXAMPLE 1

Storage Elastic Modulus after Curing

(15) After curing the adhesive film prepared in Examples and Comparative Examples with a UV dose of 1000 mJ/cm.sup.2 or at 110 C. for 1 hour, the film was laminated to a thickness of 600 m, and physical properties were measured using ARES equipment as follows.

(16) The storage elastic modulus was measured in conditions of a temperature of 25 C., a strain of 5% and a frequency of 1 Hz.

EXPERIMENTAL EXAMPLE 2

Viscosity Before Curing

(17) Before curing the adhesive film prepared in Examples and Comparative Examples, the film was laminated to a thickness of 600 m, and physical properties were measured using ARES equipment as follows. The viscosity was measured depending on shear stress in conditions of a temperature of 65 C., a strain of 5% and a frequency of 1 Hz.

EXPERIMENTAL EXAMPLE 3

Step Filling Property

(18) In a simple substrate on which steps of 10 m are formed, the adhesive film prepared in Examples and Comparative Examples was attached to the center portion by using a roll laminator. A glass having the same size as the prepared specimen is pressed in the vertical direction and bonded together by applying a vacuum of 100 pa and a pressure of 0.5 MPa under a temperature condition of 65 C. with a vacuum bonding machine. The cohesiveness was determined depending on looseness of the step forming region in the front side of the adhesive and classified as O when the loosed portion of the step formation region is 10% or less of the total area, when it is 30% or less and X when it is 50% or more.

EXPERIMENTAL EXAMPLE 4

Presence of Cracks

(19) A transparent electrode is formed on a polyimide substrate by a vacuum deposition method, and an organic material layer is formed on the transparent electrode. The organic material layer comprises a hole injecting layer, a hole transporting layer, a light emitting layer, an electron injecting layer and an electron transporting layer. Then, a reflective electrode is further formed on the organic material layer. Thereafter, the adhesive film prepared in Examples and Comparative Examples was sealed so as to encapsulate the entire surface of the organic electronic element on the substrate, a cover substrate was formed on the adhesive film, and then curing was carried out under the same conditions as Experimental Example 1.

(20) For the prepared organic electronic device, the presence or absence of cracks was visually observed after the folding test in which the process of folding the folding portion of the organic electronic device to a curvature radius of 1R (1 mm) under a temperature of 25 C. and a relative humidity of 50%, is repeated 100,000 times. It was classified as O without any crack or interface separation, A when at least one of crack or interface separation is observed and X when observed in large quantities.

EXPERIMENTAL EXAMPLE 5

Moisture Permeability

(21) The adhesive composition prepared in Examples or Comparative Examples was applied to a base film (release polyester film, RS-21G, manufactured by SKC) having a thickness of 38 m. Then, it was dried at 110 C. for 10 minutes to prepare a film-shaped layer having a thickness of 100 m. Thereafter, the base film was peeled off, and the moisture permeability of the film-shaped layer to the thickness direction was measured in a state where the film-shaped layer was positioned at 100 F. and a relative humidity of 100%. The moisture permeability was measured in accordance with the provisions of ASTM F1249.

(22) TABLE-US-00001 TABLE 1 Storage Viscosity at elastic 65 C. modulus before Step Presence after curing curing filling of (MPa) (Pa .Math. s) property cracks WVTR Example 1 1.0 1500 5 Example 2 2.1 5000 5 Comparative 0.3 20000 3 Example 1 Comparative 0.1 15000 3 Example 2 Comparative 2000 300 20 Example 3 Comparative 700 1000 15 Example 4