ADHESIVE COMPOSITION

Abstract

The present invention relates to an adhesive composition and an organic electronic device comprising the same, and provides an adhesive composition which can form a encapsulating structure capable of effectively blocking moisture or oxygen introduced from the outside into the organic electronic device, thereby securing the lifetime of the organic electronic device, and can improve processability by being easily applied in the process of forming the encapsulating structure of the organic electronic device, thereby preventing problems that air bubbles flow into the inside of the encapsulating structure or application nozzles are clogged, and an organic electronic device comprising the same.

Claims

1. An adhesive composition for encapsulating an organic electronic element comprising: an olefin compound, wherein the adhesive composition has a zero shear viscosity .sub.0 in a range of 200 Pa.Math.s to 18,000 Pa.Math.s at any one shear rate of 0.02 to 50s.sup.1 and ata temperature of 25 C.

2. The adhesive composition for encapsulating an organic electronic element according to claim 1, wherein a shear thinning slope constant n in Equation 1 below is in a range of 0.36 to 0.83. $\begin{array}{cc}\frac{\left(\right)-{}_{}}{{}_0-{}_{}}={\left[1+{\left(.Math..Math.\right)}^a\right]}^{\frac{n-1}{a}}& \left[\mathrm{Equation}.Math..Math.1\right]\end{array}$ wherein, () is a viscosity function with the shear rate, .sub.0 is the zero shear viscosity, .sub. is an infinite shear viscosity, n is the shear thinning slope constant, is a time variable, a is a shear thinning approximate shape constant and is a shear rate variable.

3. The adhesive composition according to claim 2, wherein , is in a range of 10 to 230.

4. The adhesive composition according to claim 1, wherein the olefin compound has at least one reactive functional group.

5. The adhesive composition according to claim 1, wherein the olefin compound has a weight average molecular weight of 100,000 or less.

6. The adhesive composition according to claim 4, wherein the reactive functional group comprises an acid anhydride group, a carboxyl group, an epoxy group, an amino group, a hydroxyl group, an isocyanate group, an oxazoline group, an oxetane group, a cyanate group, a phenol group, a hydrazide group or an amide group.

7. The adhesive composition of claim 1, further comprising an inorganic filler.

8. The adhesive composition according to claim 7, wherein the inorganic filler has a BET specific surface area in a range of 35 m.sup.2/g to 500 m.sup.2/g.

9. The adhesive composition according to claim 7, wherein the inorganic filler is comprised in an amount of 0.1 to 20 parts by weight relative to 100 parts by weight of the olefin compound.

10. The adhesive composition of claim 1, further comprising a curable compound and a reactive diluent.

11. The adhesive composition according to claim 10, wherein the curable compound is a resin comprising at least one curable functional group.

12. The adhesive composition according to claim 10, wherein the curable compound is a reactive oligomer compound.

13. The adhesive composition of claim 10, wherein the curable compound has a weight average molecular weight in a range of from 400 to 100,000.

14. The adhesive composition according to claim 10, wherein the curable compound is comprised in an amount of 10 to 70 parts by weight relative to 100 parts by weight of the olefin compound.

15. The adhesive composition according to claim 10, wherein the reactive diluent has a weight average molecular weight of less than 400.

16. The adhesive composition according to claim 10, wherein the reactive diluent is comprised in an amount of 10 to 100 parts by weight relative to 100 parts by weight of the olefin compound.

17. The adhesive composition according to claim 10, wherein the reactive diluent comprises an epoxy compound or a multifunctional active energy ray polymerizable compound.

18. The adhesive composition according to claim 1, further comprising an initiator or a curing agent.

19. The adhesive composition according to claim 1, further comprising a moisture adsorbent.

20. The adhesive composition according to claim 19, wherein the moisture adsorbent comprises a moisture-reactive adsorbent or a physical adsorbent.

21. An organic electronic device comprising: a substrate; an organic electronic element formed on the substrate; and a side encapsulating layer formed on the outer peripheral portion of said substrate so as to surround the side of said organic electronic element and comprising the adhesive composition according to claim 1.

22. The organic electronic device according to claim 21, further comprising a top encapsulating layer covering the entire surface of the organic electronic element, wherein said top encapsulating layer and said side encapsulating layer are present on the same plane.

23. A method for manufacturing an organic electronic device comprising steps of: applying the adhesive composition of claim 1 on an outer peripheral portion of a substrate, on which an organic electronic element is formed, so as to surround a side of said organic electronic element; and curing said adhesive composition.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0093] FIG. 1 is a cross-sectional view showing an organic electronic device according to one example of the present invention.

EXPLANATION OF REFERENCE NUMERALS

[0094] 1: adhesive

[0095] 10: side encapsulating layer

[0096] 11: top encapsulating layer

[0097] 21: substrate

[0098] 22: cover substrate

[0099] 23: organic electronic element

BEST MODE

[0100] Hereinafter, the present invention will be described in more detail with reference to 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

[0101] An acid anhydride modified polyisobutylene resin (BASF, Mn 1000 g/mol, Glissopal SA) as an olefin compound; an alicyclic epoxy resin (Kukdo Chemical, ST-3000, epoxy equivalent 230 g/eq, viscosity 3000 cPs), epoxy acrylate (Sartomer, CN110) and urethane acrylate (Sartomer, CN307) as curable compounds; and an alicyclic epoxy compound (Celloxide 2021P, Mw: 250, Daicel corporation, hereinafter, often referred to as C2021P) and 1,6-hexanediol diacrylate (HDDA) as reactive diluents were introduced as the main component into a mixing vessel in a weight ratio of 70:5:10:5:5:5 (GlissopalSA: ST-3000: CN110: CN307: Celloxide2021P: HDDA) at room temperature. A photo-cationic initiator (San-apro, CPI-101A) was introduced into the vessel in an amount of 10 parts by weight relative to 100 parts by weight of the main component, 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651, Ciba) as a radical initiator was introduced into the vessel in an amount of 5 parts by weight relative to 100 parts by weight of the main component and an imidazole curing agent (Adeka, EH-4357S), a latent curing agent, as a thermosetting agent was introduced thereto in an amount of 5 parts by weight relative to 100 parts by weight of the main component. In addition, fumed silica (Aerosil, Evonik, R805, particle size of 10 to 20 nm, BET=150 m.sup.2/g) as an inorganic filler was introduced into the vessel in an amount of 4 parts by weight relative to 100 parts by weight of the main component. On the other hand, calcium oxide (CaO, Aldrich) as a moisture adsorbent was further introduced into the vessel in an amount of 15 parts by weight relative to 100 parts by weight of the main component.

[0102] In the mixing vessel, a uniform composition solution was prepared using a planetary mixer (Kurabo, KK-250s).

EXAMPLE 2

[0103] An acid anhydride modified polyisobutylene resin (BASF, Mn 1000 g/mol, Glissopal SA) as an olefin compound; an alicyclic epoxy resin (Kukdo Chemical, ST-3000, epoxy equivalent 230 g/eq, viscosity 3000 cPs) and urethane acrylate (Sartomer, CN307) as curable compounds; and an alicyclic epoxy compound (Celloxide 2021P, Mw: 250, Daicel corporation) and 1,6-hexanediol diacrylate (HDDA) as reactive diluents were introduced as the main component into a mixing vessel in a weight ratio of 55:10:15:6:4 (GlissopalSA: ST-3000: CN307: Celloxide2021P: HDDA) at room temperature. 2,2-Dimethoxy-1,2-diphenylethane-1-one (Irgacure 651, Ciba) as a radical initiator was introduced into the vessel in an amount of 5 parts by weight relative to 100 parts by weight of the main component and a photo-cationic initiator (San-apro, CPI-101A) was introduced into the vessel in an amount of 5 parts by weight relative to 100 parts by weight of the main component. In addition, fumed silica (Aerosil, Evonik, R805, particle size of 10 to 20 nm, BET=150 m.sup.2/g) as an inorganic filler was introduced into the vessel in an amount of 8 parts by weight relative to 100 parts by weight of the main component. On the other hand, calcium oxide (CaO, Aldrich) as a moisture adsorbent was further introduced into the vessel in an amount of 15 parts by weight relative to 100 parts by weight of the main component.

[0104] In the mixing vessel, a uniform composition solution was prepared using a planetary mixer (Kurabo, KK-250s).

EXAMPLE 3

[0105] An acid anhydride modified polyisobutylene resin (BASF, Mn 1000 g/mol, Glissopal SA) as an olefin compound; epoxy acrylate (Sartomer, CN110) as a curable compound; and 1,6-hexanediol diacrylate (HDDA) as a reactive diluent were introduced as the main component into a mixing vessel in a weight ratio of 60:30:10 (GlissopalSA: CN110: HDDA) at room temperature. 2,2-Dimethoxy-1,2-diphenylethane-l-one (Irgacure 651, Ciba) as a radical initiator was introduced into the vessel in an amount of 5 parts by weight relative to 100 parts by weight of the main component and an imidazole curing agent (Adeka, EH-4357S) as a thermosetting agent was introduced thereto in an amount of 10 parts by weight relative to 100 parts by weight of the main component. In addition, fumed silica (Aerosil, Evonik, R805, particle size of 10 to 20 nm, BET=150 m.sup.2/g) as an inorganic filler was introduced into the vessel in an amount of 10 parts by weight relative to 100 parts by weight of the main component. On the other hand, calcium oxide (CaO, Aldrich) as a moisture adsorbent was further introduced into the vessel in an amount of 15 parts by weight relative to 100 parts by weight of the main component.

[0106] In the mixing vessel, a uniform composition solution was prepared using a planetary mixer (Kurabo, KK-250s).

EXAMPLE 4

[0107] An acid anhydride modified polyisobutylene resin (BASF, Mn 1000 g/mol, Glissopal SA) as an olefin compound; an alicyclic epoxy resin (Kukdo Chemical, ST-3000, epoxy equivalent 230 g/eq, viscosity 3000 cPs) and urethane acrylate (Sartomer, CN307) as curable compounds; and an alicyclic epoxy compound (Celloxide 2021P, Mw: 250, Daicel corporation) and 1,6-hexanediol diacrylate (HDDA) as reactive diluents were introduced as the main component into a mixing vessel in a weight ratio of 55:5:30:5:5 (GlissopalSA: ST-3000: CN307: Celloxide2021P: HDDA) at room temperature. A photo-cationic initiator (San-apro, CPI-101A) was introduced into the vessel in an amount of 5 parts by weight relative to 100 parts by weight of the main component and 2,2-dimethoxy-1,2-diphenylethane- 1-one (Irgacure 651, Ciba) as a radical initiator was introduced into the vessel in an amount of 5 parts by weight relative to 100 parts by weight of the main component. In addition, fumed silica (Aerosil, Evonik, R805, particle size of 10 to 20 nm, BET=150 m.sup.2/g) as an inorganic filler was introduced into the vessel in an amount of 7 parts by weight relative to 100 parts by weight of the main component. On the other hand, calcium oxide (CaO, Aldrich) as a moisture adsorbent was further introduced into the vessel in an amount of 15 parts by weight relative to 100 parts by weight of the main component.

[0108] In the mixing vessel, a uniform composition solution was prepared using a planetary mixer (Kurabo, KK-250s).

COMPARATIVE EXAMPLE 1

[0109] A polyisobutylene resin (BASF, B14, Mw=60,000) as an olefin compound; an alicyclic epoxy resin (Kukdo Chemical, ST-3000, epoxy equivalent 230 g/eq, viscosity 3000 cPs) and epoxy acrylate (Sartomer, CN110) as curable compounds; and an alicyclic epoxy compound (Celloxide 2021P, Mw: 250, Daicel corporation) and 1,6-hexanediol diacrylate (HDDA) as reactive diluents were introduced as the main component into a mixing vessel in a weight ratio of 70:15:5:8:2 (B14: ST-3000: CN110: Celloxide2021P: HDDA) at room temperature. 2,2-Dimethoxy-1,2-diphenylethane- 1-one (Irgacure 651, Ciba) as a radical initiator was introduced into the vessel in an amount of 5 parts by weight relative to 100 parts by weight of the main component and an imidazole curing agent (Adeka, EH-4357S) as a thermosetting agent was introduced thereto in an amount of 5 parts by weight relative to 100 parts by weight of the main component. In addition, fumed silica (Aerosil, Evonik, R805, particle size of 10 to 20 nm, BET=150 m.sup.2/g) as an inorganic filler was introduced into the vessel in an amount of 6 parts by weight relative to 100 parts by weight of the main component. On the other hand, calcium oxide (CaO, Aldrich) as a moisture adsorbent was further introduced into the vessel in an amount of 15 parts by weight relative to 100 parts by weight of the main component.

[0110] In the mixing vessel, a uniform composition solution was prepared using a planetary mixer (Kurabo, KK-250s).

COMPARATIVE EXAMPLE 2

[0111] An acid anhydride modified polyisobutylene resin (BASF, Mn 1000 g/mol, Glissopal SA) as an olefin compound; an alicyclic epoxy resin (Kukdo Chemical, ST-3000, epoxy equivalent 230 g/eq, viscosity 3000 cPs) and epoxy acrylate (Sartomer, CN110) as curable compounds; and an alicyclic epoxy compound (Celloxide 2021P, Mw: 250, Daicel corporation) and 1,6-hexanediol diacrylate (HDDA) as reactive diluents were introduced as the main component into a mixing vessel in a weight ratio of 50:10:10:20:10 (GlissopalSA: ST-3000: CN110: Celloxide2021P: HDDA) at room temperature. 2,2-Dimethoxy-1,2-diphenylethane-1-one (Irgacure 651, Ciba) as a radical initiator was introduced into the vessel in an amount of 5 parts by weight relative to 100 parts by weight of the main component. In addition, fumed silica (Aerosil, Evonik, R805, particle size of 10 to 20 nm, BET=150 m.sup.2/g) as an inorganic filler was introduced into the vessel in an amount of 2 parts by weight relative to 100 parts by weight of the main component. On the other hand, calcium oxide (CaO, Aldrich) as a moisture adsorbent was further introduced into the vessel in an amount of 15 parts by weight relative to 100 parts by weight of the main component.

[0112] In the mixing vessel, a uniform composition solution was prepared using a planetary mixer (Kurabo, KK-250s).

COMPARATIVE EXAMPLE 3

[0113] An acid anhydride modified polyisobutylene resin (BASF, Mn 1000 g/mol, Glissopal SA) as an olefin compound; an alicyclic epoxy resin (Kukdo Chemical, ST-3000, epoxy equivalent 230 g/eq, viscosity 3000 cPs), epoxy acrylate (Sartomer, CN110) and urethane acrylate (Sartomer, CN307) as curable compounds; and an alicyclic epoxy compound (Celloxide 2021P, Mw: 250, Daicel corporation) and 1,6-hexanediol diacrylate (HDDA) as reactive diluents were introduced as the main component into a mixing vessel in a weight ratio of 30:20:20:10:5:15 (GlissopalSA: ST-3000: CN110: CN307: Celloxide2021P: HDDA) at room temperature. 2,2-Dimethoxy-1,2-diphenylethane-l-one (Irgacure 651, Ciba) as a radical initiator was introduced into the vessel in an amount of 5 parts by weight relative to 100 parts by weight of the main component and an imidazole curing agent (Adeka, EH-4357S) as a thermosetting agent was introduced thereto in an amount of 10 parts by weight relative to 100 parts by weight of the main component. In addition, fumed silica (Aerosil, Evonik, R805, particle size of 10 to 20 nm, BET=150 m.sup.2/g) as an inorganic filler was introduced into the vessel in an amount of 3 parts by weight relative to 100 parts by weight of the main component. On the other hand, calcium oxide (CaO, Aldrich) as a moisture adsorbent was further introduced into the vessel in an amount of 15 parts by weight relative to 100 parts by weight of the main component.

[0114] In the mixing vessel, a uniform composition solution was prepared using a planetary mixer (Kurabo, KK-250s).

COMPARATIVE EXAMPLE 4

[0115] An acid anhydride modified polyisobutylene resin (BASF, Mn 1000 g/mol, Glissopal SA) as an olefin compound; an alicyclic epoxy resin (Kukdo Chemical, ST-3000, epoxy equivalent 230 g/eq, viscosity 3000 cPs), epoxy acrylate (Sartomer, CN110) and urethane acrylate (Sartomer, CN307) as curable compounds; and 1,6-hexanediol diacrylate (HDDA) as a reactive diluent were introduced as the main component into a mixing vessel in a weight ratio of 30:20:30:10:10 (GlissopalSA: ST-3000: CN110: CN307: HDDA) at room temperature. 2,2-Dimethoxy-1,2-diphenylethane- 1-one (Irgacure 651, Ciba) as a radical initiator was introduced into the vessel in an amount of 5 parts by weight relative to 100 parts by weight of the main component and an imidazole curing agent (Adeka, EH-4357S), a latent curing agent, as a thermosetting agent was introduced thereto in an amount of 5 parts by weight relative to 100 parts by weight of the main component. In addition, fumed silica (Aerosil, Evonik, R805, particle size of 10 to 20 nm, BET=150 m.sup.2/g) as an inorganic filler was introduced into the vessel in an amount of 3 parts by weight relative to 100 parts by weight of the main component. On the other hand, calcium oxide (CaO, Aldrich) as a moisture adsorbent was further introduced into the vessel in an amount of 15 parts by weight relative to 100 parts by weight of the main component.

[0116] In the mixing vessel, a uniform composition solution was prepared using a planetary mixer (Kurabo, KK-250s).

[0117] The compositions of Examples and Comparative Examples above were shown in Table 1 below, and the respective compositions were blended in the weight ratios shown in Table 1 below.

TABLE-US-00001 TABLE 1 Example Comparative Example 1 2 3 4 1 2 3 4 PIBSA 70 55 60 55 50 30 30 PIB 70 ST-3000 5 10 5 15 10 20 20 CN110 10 30 5 10 20 30 CN307 5 15 30 10 10 C2021P 5 6 5 8 20 5 HDDA 5 4 10 5 2 10 15 10 R805 4 8 10 7 6 2 3 3 CaO 15 15 15 15 15 15 15 15 CPI-101A 10 5 5 Irgacure651 5 5 5 5 5 5 5 5 EH-4357S 5 10 5 10 5

[0118] Hereinafter, the physical properties in Examples and Comparative Examples were evaluated in the following manner.

[0119] 1. Measurement of Viscosity

[0120] The viscosity according Equation 1 for each adhesive composition prepared in Examples and Comparative Examples was measured in a cone and plate mode using ARES (Advanced Rheometric Expansion System)-G2 from TA Corporation as follows. Specifically, an angle of the cone was 0.1002 rad and after loading the adhesive composition sample at a gap of 0.1 mm, the viscosity was measured at any one shear rate of 0.02 to 505.sup.-1 and a temperature of 25 C. Through the viscosity measured above, the respective variables were calculated according to Equation 1 below.

[00002]$\begin{array}{cc}\frac{\left(\right)-{}_{}}{{}_0-{}_{}}={\left[1+{\left(.Math..Math.\right)}^a\right]}^{\frac{n-1}{a}}& \left[\mathrm{Equation}.Math..Math.1\right]\end{array}$

[0121] 2. Application Characteristics

[0122] The application characteristics were observed while side-applying each adhesive composition solution prepared in Examples or Comparative Examples on a 0.7 T Soda-Lime glass using a Musashi 200DS instrument to form a square having a size of 150 mm150 mm (needle number: #18, dispensing speed: 10 mm/sec). When there was no inflow of air bubbles and no nozzle clogging of the instrument during application, it was represented by 0; when air bubbles were introduced during application or the original shape was lost after application and the solution spread widely, it was represented by A; and when a large amount of air bubbles were introduced during application or the nozzle was clogged and the application was cut off, it was represented by X.

[0123] 3. Sedimentation Stability

[0124] The sedimentation stability of the adhesive compositions of Examples and Comparative Examples was evaluated as follows. The adhesive composition prepared above was compounded and defoamed, then injected into a syringe and allowed to stand at 25 C. for 3 days. Thereafter, it was evaluated whether or not the inorganic filler settled in the bottom part of the syringe through application. When the upper and lower layers were applied with a uniform amount of inorganic filler and there was no nozzle clogging, it was represented by 0; and when the nozzle was clogged during application and the upper layer was transparent as compared to the lower layer, it was represented by X.

[0125] 4. Heat Resistance and Moisture Resistance

[0126] Each adhesive composition solution prepared in Examples or Comparative Examples was side-applied on a 0.7 T Soda-Lime glass using a Musashi 200DS instrument to form a square having a size of 150 mm150 mm Thereafter, a sample was prepared by laminating it with the same glass, and the adhesive composition was irradiated with light (metal halide lamp) having a wavelength range of the UV-A region band at a light quantity of 3 J/cm.sup.2, and then heated in an oven at 100 C. for 3 hours. The sample was then maintained in a constant temperature and humidity chamber at 85 C. and 85% relative humidity for about 1000 hours.

[0127] The heat resistance measurement was represented as O in the case where there was no change in the inside and the side of the application area, and as X in the case where voids occurred inside the application area.

[0128] The moisture resistance measurement was represented as O when there was no lifting of the area to which moisture was penetrated, and as X when the moisture penetration site was lifted from the glass.

[0129] 4. Compatibility

[0130] The compatibility of the adhesive compositions of Examples and Comparative Examples was evaluated as follows. The prepared adhesive composition was allowed to stand in a container at 25 C. for 3 days, and then the presence of phase-separation was observed. When no phase separation occurred in the composition, it was represented by O; when the phase separation occurred partially, it was represented by ; and when the phase separation occurred in the two layers, it was represented by X.

TABLE-US-00002 TABLE 2 Heat resistance/ .sub.0 Application Sedimentation moisture (Pas) n (sec) characteristics stability resistance Compatibility Example 1 607 0.77 19 O O O/O O 2 1730 0.64 26 O O O/O O 3 1871 0.49 50 O O O/O O 4 6058 0.42 120 O O O/O O Comparative 1 22890 0.30 250 X O X/O X Example 2 165 0.88 90 X O/X O 3 117 0.91 39 O O O/X 4 18854 0.23 203 X O O/X