KR102152247B1 - encapsulation member of organic electronic device - Google Patents

Abstract

The present invention relates to a sealing material for an organic electronic device, and more particularly, to a sealing material for an organic electronic device capable of improving the reliability of a product by excellent adhesion and adhesion.

Description

Encapsulation member of organic electronic device}

The present invention relates to a sealing material for an organic electronic device, and more particularly, to an sealing material for an organic electronic device capable of improving the reliability of a product by excellent adhesion and adhesion.

An organic light emitting diode (OLED) is a light emitting diode in which a light emitting layer is made of a thin organic compound, and uses an electroluminescence phenomenon in which light is generated by passing an electric current through a fluorescent organic compound. These organic light-emitting diodes generally implement major colors in a three-color (Red, Green, Blue) independent pixel method, a bioconversion method (CCM), and a curly filter method, and the amount of organic substances contained in the used light emitting materials Accordingly, it is classified into a low-molecular organic light-emitting diode and a high-molecular organic light-emitting diode. In addition, according to the driving method, it may be classified into a passive driving method and an active driving method.

Such an organic light emitting diode has features such as high efficiency, low voltage driving, and simple driving by self-luminescence, and thus has an advantage of expressing high-quality video. In addition, applications to flexible displays and organic electronic devices using the flexible properties of organic materials are also expected.

The organic light emitting diode is manufactured in a form in which an organic compound, which is a light emitting layer, is stacked on a substrate in the form of a thin film. However, the organic compound used in the organic light emitting diode is very sensitive to impurities, oxygen, and moisture, and thus has a problem that properties are easily deteriorated due to external exposure or penetration of moisture or oxygen. This deterioration of the organic material affects the luminescence characteristics of the organic light emitting diode and shortens the lifespan. In order to prevent such a phenomenon, a thin film encapsulation process is required to prevent oxygen, moisture, etc. from flowing into the organic electronic device.

Conventionally, a metal can or glass was processed into a cap shape to have a groove, and a desiccant for moisture absorption was mounted in the groove in the form of a powder. However, this method removes the desired level of moisture permeation with a sealed organic electronic device. There is a problem in that it is difficult to block the organic electronic device from accessing substances that are cause of defects such as moisture and impurities, do not cause delamination, which may occur when moisture is removed, and have excellent effects in moisture resistance and heat resistance at the same time.

In addition, there is a problem in that the reliability of the product is deteriorated because the adhesion and adhesion to the organic electronic device are not excellent.

Korean Patent Application Publication No. 10-2006-0030718 (Publication date: 2006.04.11)

The present invention has been devised to solve the above problems, and an object to be solved of the present invention is to provide a sealing material for an organic electronic device capable of improving the reliability of a product by having excellent adhesion and adhesion.

In addition, the present invention is an organic electronic device having excellent moisture resistance and heat resistance at the same time that the organic electronic device is removed and blocked from access to substances that cause bad materials such as moisture and impurities, and the delamination phenomenon that may occur when moisture is removed does not occur. It is to provide an encapsulant for use.

In order to solve the above-described problems, the encapsulant for an organic electronic device of the present invention includes a metal sheet and an adhesive film formed on one surface of the metal sheet, and both conditions (1) and (2) below may be satisfied.

≤ 1.07 mN/cm·°(1) 0.93 mN/cm°≤

≤ 1.07 mN/cm°

(2) 32 mN/cm ≤ X ≤ 65 mN/cm

In the above conditions (1) and (2), X is the surface energy (mN/cm) of the metal sheet, and Y is the contact angle of deionized water (°) of the adhesive film.

In a preferred embodiment of the present invention, the metal sheet may have a surface roughness of Ra of 2.0 μm or less, Rsm of 200 μm or less, and Rz of 6.0 μm or less.

As a preferred embodiment of the present invention, the metal sheet is iron (Fe), bismuth (Bi), tin (Sn), indium (In), silver (Ag), copper (Cu), zinc (Zn), antimony ( It may contain at least one selected from Sb), nickel (Ni), and alloys thereof.

As a preferred embodiment of the present invention, the adhesive film may include a mixed resin, a tackifier and a hygroscopic agent, and the mixed resin may contain a first adhesive resin and a second adhesive resin in a weight ratio of 1: 0.1 to 10. .

As a preferred embodiment of the present invention, the first adhesive resin comprises a random copolymer having a weight average molecular weight of 30,000 to 1,550,000 copolymerized with ethylene, propylene and diene compounds, and the second adhesive resin is represented by the following formula (1). It may contain a compound.

[Formula 1]

In Formula 1, R ¹ is a straight chain alkenyl group of C3 to C10 or a pulverized alkenyl group of C4 to C10, and n is a rational number that satisfies the weight average molecular weight of the compound represented by Formula 1 30,000 to 1,550,000.

As a preferred embodiment of the present invention, ethylene and propylene are randomly copolymerized in a weight ratio of 1: 0.3 to 1.4, and the diene-based compound may contain 2 to 15% by weight based on the total weight of the random copolymer.

As a preferred embodiment of the present invention, the adhesive film may include a first adhesive layer and a second adhesive layer formed on one surface of the first adhesive layer.

In a preferred embodiment of the present invention, the first adhesive layer includes a first mixed resin, a tackifier and a first absorbent, and the first mixed resin is a first adhesive resin and a second adhesive resin of 1: 0.1 to 10 Included in a weight ratio, the tackifier may include 50 to 300 parts by weight based on 100 parts by weight of the first mixed resin, and the first absorbent may include 1 to 40 parts by weight based on 100 parts by weight of the first mixed resin.

As a preferred embodiment of the present invention, the tackifier comprises a first tackifier and a second tackifier in a weight ratio of 1: 0.5 to 1.5, and the softening point of the first tackifier is the second tackifier It is smaller than the softening point of, and the first desiccant may include silica (SiO ₂ ).

As a preferred embodiment of the present invention, the first adhesive layer further comprises at least one of a curing agent and a UV initiator, the curing agent comprises 2 to 30 parts by weight based on 100 parts by weight of the first mixed resin, and the UV initiator is the first Based on 100 parts by weight of the mixed resin, it may contain 0.1 to 5 parts by weight.

As a preferred embodiment of the present invention, the viscosity of the first adhesive layer may be 150,000 Pa·s (50° C.) or less.

As a preferred embodiment of the present invention, the second adhesive layer includes a second mixed resin, a tackifier and a second absorbent, and the second mixed resin is a first adhesive resin and a second adhesive resin of 1: 0.1 to 10. It includes in a weight ratio, the tackifier may include 60 to 300 parts by weight based on 100 parts by weight of the second mixed resin, and the second absorbent may include 50 to 450 parts by weight based on 100 parts by weight of the second mixed resin.

As a preferred embodiment of the present invention, the tackifier may include a first tackifier, and the second absorbent may include calcium oxide (CaO).

As a preferred embodiment of the present invention, the second adhesive layer further comprises at least one of a curing agent and a UV initiator, the curing agent comprises 10 to 40 parts by weight based on 100 parts by weight of the second mixed resin, and the UV initiator is a second Based on 100 parts by weight of the mixed resin, 0.1 to 8 parts by weight may be included.

In a preferred embodiment of the present invention, the viscosity of the second adhesive layer may be 200,000 Pa·s (50° C.) or more.

Meanwhile, the light emitting device of the present invention includes a substrate, an organic electronic device formed on at least one surface of the substrate, and the aforementioned encapsulant for an organic electronic device packaging the organic electronic device.

Hereinafter, terms used in the present invention will be described.

The term desiccant used in the present invention can adsorb moisture through a physical or chemical bond such as van der Waals' force with the interface of the desiccant, and absorbs moisture and chemical reactions in which the component of the material does not change due to adsorption of moisture. It contains all of the moisture-absorbing materials that absorb moisture and change into a new material.

The encapsulant for an organic electronic device of the present invention blocks oxygen, impurities, and moisture and at the same time effectively removes moisture permeating to prevent moisture from reaching the organic electronic device, thereby significantly improving the life and durability of the organic electronic device. I can make it. In addition, there is an effect of excellent moisture resistance and heat resistance at the same time that the delamination phenomenon that may occur when moisture is removed does not occur. In addition, it has excellent adhesion and adhesion, which can improve product reliability.

In addition, the encapsulant for an organic electronic device of the present invention has remarkably excellent adhesion between the metal sheet and the adhesive film constituting the encapsulant, thereby improving the reliability of the product.

1 and 2 are cross-sectional views of an encapsulant for an organic electronic device according to an embodiment of the present invention.
3 and 4 are cross-sectional schematic diagrams of a light emitting device according to a preferred embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art can easily implement the present invention. The present invention may be implemented in various different forms, and is not limited to the embodiments described herein. In the drawings, parts not related to the description are omitted in order to clearly describe the present invention, and the same reference numerals are added to the same or similar components throughout the specification.

Specifically, FIG. 1 is a cross-sectional view of an organic electronic device encapsulant according to a preferred embodiment of the present invention. The organic electronic device encapsulant 10 of the present invention is a metal sheet 13 and an adhesive film formed on one surface of the metal sheet 13 (15) may be included.

In addition, a base film 14 such as a release film may be formed on the other surface of the adhesive film 15 on which the metal sheet 13 is not formed to further include. The base film 14 serves to support and protect the encapsulant 10 for an organic electronic device.

The organic electronic device encapsulation material 10 of the present invention may satisfy both the following conditions (1) and (2).

≤ 1.07 mN/cm·°, 바람직하게는 0.96 mN/cm·° ≤

≤ 1.04 mN/cm·°, 더욱 바람직하게는 0.99 mN/cm·° ≤

≤ 1.01 mN/cm·°(1) 0.93 mN/cm° ≤

≤ 1.07 mN/cm°, preferably 0.96 mN/cm° ≤

≤ 1.04 mN/cm°, more preferably 0.99 mN/cm° ≤

≤ 1.01 mN/cm°

(2) 32 mN/cm ≤ X ≤ 65 mN/cm, preferably 35 mN/cm ≤ X ≤ 63 mN/cm, more preferably 50 mN/cm ≤ X ≤ 62 mN/cm

In the above conditions (1) and (2), X represents the surface energy (mN/cm) of the metal sheet 13, and Y represents the contact angle of deionized water (°) of the adhesive film 15 (purified water contact angle), and specifically, Y represents the contact angle of deionized water on the surface of the adhesive film 15 that contacts the metal sheet 13.

At this time, the surface energy is the value measured with Accu Dyne Test Pens of DIVERSIFIED ENTERPRISES, and the contact angle of deionized water is the value measured with the Phoenix 150 equipment of Surface Electro Optics.

이 0.93 mN/cm·° 미만이거나, 1.07 mN/cm·°을 초과하게 된다면 기재와의 점착력 및/또는 밀착력 저하로 인해 신뢰성이 저하되는 문제가 있을 수 있다.If, in condition (1),

If the value is less than 0.93 mN/cm·° or exceeds 1.07 mN/cm·°, there may be a problem of deteriorating reliability due to lower adhesion and/or adhesion to the substrate.

In addition, in condition (2), if X is less than 32 mN/cm or exceeds 65 mN/cm, there may be a problem in that reliability is deteriorated due to a decrease in adhesion and/or adhesion to the substrate.

Meanwhile, the metal sheet 13 may have a surface roughness of Ra, Rsm, and Rz as follows.

Ra may have a value of 2.0 μm or less, preferably 1.0 μm or less, more preferably 0.1 μm ≤ Ra ≤ 0.5 μm, and if Ra exceeds 2.0 μm, the plugging property of the adhesive film deteriorates and reliability is reduced. There may be a problem.

Rsm may have a value of 200 μm or less, preferably 150 μm or less, more preferably 30 μm ≤ Rsm ≤ 100 μm, and if the Rsm exceeds 200 μm, vacuum between products may be formed during storage and there may be a problem during pickup during the process. have.

Rz may have a value of 6 μm or less, preferably 5 μm or less, more preferably 0.5 μm ≤ Rz ≤ 3 μm, and if Rz exceeds 6 μm, there may be a problem of poor reliability due to poor plugability of the adhesive film. have.

Metal sheet 13 is iron (Fe), bismuth (Bi), tin (Sn), indium (In), silver (Ag), copper (Cu), zinc (Zn), antimony (Sb), nickel (Ni) And it may include one or more selected from these alloys, preferably may include an alloy containing iron and nickel.

Meanwhile, specifications such as the size or thickness of the metal sheet 13 may vary according to the purpose, and thus the present invention is not particularly limited thereto. However, as an example, the metal sheet 13 may have a thickness of 60 to 120 μm, preferably 70 to 110 μm, and more preferably 80 to 100 μm.

Next, the adhesive film 15 may be formed by including a mixed resin (15b), a tackifier and a desiccant (15a).

First, the mixed resin (15b) may include a first adhesive resin and a second adhesive resin, the first adhesive resin and the second adhesive resin in a weight ratio of 1: 0.1 to 10, preferably 1: 1 to 9 It may be included in a weight ratio, more preferably in a weight ratio of 1: 1.1 to 5. If the weight ratio of the first adhesive resin and the second adhesive resin is less than 1:0.1, reliability may deteriorate, and if the weight ratio exceeds 1:10, the elasticity of the adhesive layer may decrease.

The first adhesive resin may include a random copolymer in which ethylene, propylene, and a diene-based compound are copolymerized. At this time, ethylene and propylene may be randomly copolymerized in a weight ratio of 1: 0.3 to 1.4, preferably 1: 0.5 to 1.2. If the weight ratio of ethylene and propylene to be copolymerized is less than 1:0.3, it may cause a defect in panel adhesion due to an increase in modulus and hardness, and a problem that causes adhesion to the substrate and decreases in properties at low temperatures occurs, and decreases the elastic modulus. Accordingly, it may adversely affect the volume expansion of the desiccant. If the weight ratio exceeds 1:1.4, panel sag may occur due to a decrease in modulus and hardness, and a decrease in mechanical properties leads to a decrease in the mechanical properties of the product. Due to the difficulty in high filling, there may be a problem that the reliability is deteriorated.

In addition, the diene-based compound may be included in an amount of 2 to 15% by weight, preferably 7 to 11% by weight, based on the total weight of the random copolymer copolymerized with ethylene, propylene, and the diene-based compound. If the diene-based compound is less than 2% by weight, it may cause a problem of panel sagging due to a decrease in modulus due to a low curing rate and curing density, and heat resistance may be lowered. If it exceeds 15% by weight, adhesion to the substrate decreases due to lack of wettability due to high curing density, compatibility between resins decreases, panel adhesion decreases due to high modulus, and yellowing due to heat Can lead to

The first adhesive resin may have a weight average molecular weight of 30,000 to 1,550,000, and preferably, a weight average molecular weight of 40,000 to 1,500,000. If the weight average molecular weight of the first adhesive resin is less than 30,000, panel sagging may occur due to a decrease in gelation rate and modulus, heat resistance may decrease, and reliability may decrease as the filling property of the desiccant decreases. Mechanical properties may deteriorate. In addition, if the weight average molecular weight exceeds 1,550,000, adhesion to the substrate may decrease due to a decrease in wettability, and adhesion to the panel may decrease according to an increase in gelation rate and modulus.

The second adhesive resin may include a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R ¹ is a hydrogen atom, a straight chain alkenyl group of C3 to C10 or a ground alkenyl group of C4 to C10, and preferably R ¹ is a straight alkenyl group of C4 to C8 or a straight chain alkenyl group of C4 to C8. It may be a ground alkenyl group.

Since R ^{1 in} Formula 1 is a hydrogen atom, a straight chain alkenyl group of C3 to C10 or a pulverized alkenyl group of C4 to C10, reliability may be more excellent.

In addition, in Formula 1, n is a rational number that satisfies the weight average molecular weight of 30,000 to 1,550,000, and preferably may be a rational number that satisfies the weight average molecular weight of 40,000 to 1,500,000. If the weight average molecular weight is less than 30,000, panel sagging may occur due to a decrease in modulus, heat resistance may decrease, reliability may decrease as the filling property of the desiccant decreases, and mechanical properties may decrease. , Lifting with the substrate may occur due to the volume expansion of the desiccant due to the decrease in elasticity. In addition, when the weight average molecular weight exceeds 1,550,000, adhesion to the substrate may decrease due to a decrease in wettability, and adhesion to the panel may decrease as the modulus increases.

Next, the tackifier may be included without limitation, as long as it is an adhesive resin commonly used in an organic electronic device encapsulant, and preferably hydrogenated petroleum resin, hydrogenated rosin paper, hydrogenated rosin ester resin, hydrogenated terpene resin, hydrogenated terpene It may include at least one selected from a phenol resin, a polymerized rosin resin, and a polymerized rosin ester resin.

The tackifier included in the adhesive film 15 may include 50 to 300 parts by weight, preferably 80 to 280 parts by weight, based on 100 parts by weight of the mixed resin 15b. If the tackifier is less than 50 parts by weight with respect to 100 parts by weight of the mixed resin, a problem of poor moisture resistance may occur. If the tackifier exceeds 300 parts by weight, durability and moisture resistance due to the brittle of the adhesive layer decrease. Problems may occur.

Next, the desiccant 15a may be included without limitation, as long as it is an encapsulant typically used for packaging organic electronic devices, and desirably, a desiccant, metal salt, and metal oxide including zeolite, titania, zirconia or montmorillonite as a component. It may include at least one of, more preferably, a metal oxide, and even more preferably, calcium oxide (CaO) among the metal oxides.

Metal oxides include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), barium oxide (BaO), calcium oxide (CaO), or magnesium oxide (MgO). It may include at least one of metal oxides, organic metal oxides, and phosphorus pentoxide (P ₂ O ₅ ).

Metal salts include lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga ₂ (SO ₄ ) ₃ ), titanium sulfate (Ti(SO ₄ ) ₂ ) or nickel sulfate (NiSO ₄ ), such as sulfate, calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium salt (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 ( Metal halides such as SeBr ₄ ), vanadium bromide (VBr ₃ ), magnesium bromide (MgBr ₂ ), barium iodide (BaI ₂ ) or magnesium iodide (MgI ₂ ), and barium perchlorate (Ba(ClO ₄ ) ₂ ) or magnesium perchlorate (Mg(ClO ₄ ) ₂ ) It may contain one or more of metal chlorate.

It may be desirable that the moisture absorbent 15a has a purity of 95% or more. If the purity is less than 95%, not only the moisture absorption function is lowered, but also the material contained in the desiccant acts as an impurity, which may cause a defect in the adhesive film, and may affect the organic electronic device, but is not limited thereto.

The desiccant 15a included in the adhesive film 15 may include 10 to 550 parts by weight, preferably 20 to 520 parts by weight, based on 100 parts by weight of the mixed resin 15b. If the desiccant is less than 10 parts by weight per 100 parts by weight of the mixed resin, the durability of the organic electronic device is deteriorated and the moisture removal effect is remarkably reduced. If the desiccant exceeds 550 parts by weight, the desired encapsulant cannot be implemented. As a result, the reliability of the organic electronic device is lowered due to poor adhesion such as adhesion between the adhesive film and the organic electronic device, adhesion, etc., and the life of the organic electronic device is shortened as a phenomenon of lifting occurs due to excessive volume expansion when moisture is absorbed. Can occur.

On the other hand, the adhesive film 15 of the present invention may further include one or more of a curing agent and a UV initiator.

When including the curing agent in the adhesive film 15 of the present invention, the curing agent may include 2 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the mixed resin. If less than 2 parts by weight of the curing agent is included, the desired gelation rate and modulus cannot be achieved, and elasticity may be deteriorated. If it contains more than 50 parts by weight, panel bonding is defective due to high modulus and hardness. , A problem of lowering adhesion due to lowering of wettability may occur.

The curing agent may be included without limitation as long as it is a material that can be used as a curing agent in general, and preferably may include a material capable of securing a sufficient crosslinking density of the encapsulant by serving as a crosslinking agent, and more preferably, urethane acrylate It may include at least one selected from the group consisting of a curing agent and an acrylate curing agent.

In addition, the curing agent may have a weight average molecular weight of 100 to 1500, preferably a weight average molecular weight of 200 to 1300. If the weight average molecular weight of the curing agent is less than 100, the adhesion of the panel and adhesion to the substrate decreases due to the increase in hardness, and outgas of the unreacted curing agent may occur. If the weight average molecular weight exceeds 1500, the softening property There may be a problem that mechanical properties are deteriorated due to an increase in (Softness).

When including the UV initiator in the adhesive film 15 of the present invention, the UV initiator may include 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the mixed resin. If the UV initiator is included in an amount of less than 0.1 parts by weight, heat resistance may be poor due to poor UV curing, and if it is included in an amount exceeding 10 parts by weight, heat resistance may be poor due to a decrease in curing density.

The UV initiator may be included without limitation as long as it is commonly used as a UV initiator, and preferably mono acyl phosphine, bis acyl phosphine, α-hydroxyketone (α-Hydroxyketone) ), α-aminoketone (α-Aminoketone), phenylglyoxylate (Phenylglyoxylate), and benzyldimethyl-ketal (Benzyldimethyl-ketal) may include at least one selected from.

On the other hand, the adhesive film 15 included in the encapsulant 10 for an organic electronic device according to the present invention has a viscosity of 100,000 to 300,000 Pa·s (50°C), preferably 120,000 to 280,000 Pa·s (50 ℃). If the viscosity of the adhesive film 15 is less than 100,000 Pa·s (50°C), the processability becomes poor as the tack increases, resulting in a problem that the release film cannot be peeled off, and the viscosity is 300,000 Pa·s. If it exceeds (50°C), the problem of lowering the adhesive strength with the substrate may occur due to the lowering of the tack.

The viscosity may be a viscosity measured by a conventional viscosity measuring method, and preferably, a sample is laminated to a thickness of 800 to 900 μm, punched into a circle having a diameter of 8 mm, and then a viscosity measuring device (ARES-G2, TA) is used. The sample can be placed on a plate and measured. At this time, the measurement conditions can be measured at 5% strain, axial force 0.05N, sensitivity 0.005N, 1 rad/s, -5℃ ~ 130℃. Measurement can be started under the above conditions after adjusting the gap and stabilizing the sample with 0.5N of Axial Force and 0.05N of Sensitivity, but is not limited thereto.

On the other hand, when provided with the adhesive film 15 of a single-layer structure, the adhesive film 15 of the sealing material 10 for an organic electronic device of the present invention has a glass adhesion measured according to the following Measurement Method 1 of 1500 gf/25 mm It may be above, preferably 1600 gf/25mm or more, more preferably 1700 to 3000 gf/25mm.

[Measurement Method 1]

Laminate the adhesive strength measuring tape (7475, TESA) on the upper surface of the adhesive film through a 2Kg Hand Roller, cut the sample into 25 mm width and 120 mm length, and laminate the lower surface of the adhesive film to glass at 80°C. , The prepared sample was left at room temperature for 30 minutes, and the glass adhesion was measured at a speed of 300 mm/min.

In addition, when the adhesive film 15 of a single-layer structure is provided, the adhesive film 15 of the sealing material 10 for an organic electronic device of the present invention has a metal adhesive force of 1000 gf/25 mm measured according to Measurement Method 2 below. It may be more than, preferably 1100 gf/25mm or more, more preferably 1200 to 2500 gf/25mm.

[Measurement method 2]

At 80℃, the upper surface of the adhesive film is laminated on a Ni alloy having a thickness of 80㎛, and an adhesive force measuring tape (7475, TESA) is laminated to the lower surface of the adhesive film through a 2Kg Hand Roller, and the sample is 25mm in width and 120 in length. After cutting by mm, the prepared sample was left at room temperature for 30 minutes, and the metal adhesion was measured at a speed of 300 mm/min.

In addition, the adhesive film 15 of the present invention may have a deionized water contact angle of 75° or less, preferably 50 to 73°. If the contact angle with deionized water of the adhesive film 15 exceeds 75°, there may be a problem in that reliability is deteriorated due to a decrease in adhesive strength with the substrate.

The contact angle of deionized water of the adhesive film 15 is formed by coating a solution of about 15% by weight of a solid content prepared by dissolving the component of the adhesive layer 15 in an appropriate solvent on glass and drying it to form a film. It is a contact angle measured by dropping deionized water on the coating film, and may be an average of the contact angle measured by repeating the above process 10 times.

Further, according to a preferred embodiment of the present invention, as shown in FIG. 2, the sealing material 10 for an organic electronic device of the present invention has a multilayer structure, and the first adhesive layer 11 and the first adhesive layer 11 ) It may include a second adhesive layer 12 formed on one side.

At this time, the encapsulant 10 for an organic electronic device of the present invention may further include a base film 14 such as a release film formed under the first adhesive layer 11, and a metal on the second adhesive layer 12 The sheet 13 may be formed.

The first adhesive layer 11 is a layer that directly contacts an organic electronic device (not shown) and may be formed including a first mixed resin 11b, a tackifier, and a first absorbent 11a. In this case, the first mixed resin 11b may include a first adhesive resin and a second adhesive resin, and the tackifier may include a first adhesive agent, and further include a second adhesive agent. I can.

The second adhesive layer 12 is a layer in direct contact with the metal sheet 13 and may be formed including a second mixed resin 12b, a tackifier and a second absorbent 12a. In this case, the second mixed resin 12b may include a first adhesive resin and a second adhesive resin, and the tackifier may include a first adhesive agent.

First, a description of the first adhesive layer 11 is as follows.

The first mixed resin 11b of the first adhesive layer may include a first adhesive resin and a second adhesive resin, and the first adhesive resin and the second adhesive resin are those of the aforementioned mixed resin (15b, FIG. 1). It may contain the same material as the first adhesive resin and the second adhesive resin.

The first adhesive resin and the second adhesive resin of the first mixed resin 11b are included in a weight ratio of 1: 0.1 to 10, preferably in a weight ratio of 1: 1 to 9, more preferably in a weight ratio of 1: 1.1 to 5 can do. If the weight ratio of the first adhesive resin and the second adhesive resin is less than 1:0.1, reliability may be deteriorated, and if the weight ratio exceeds 1:10, the elasticity of the adhesive film may be lowered.

The tackifier of the first adhesive layer 11 may include a first adhesive agent, and may further include a second adhesive agent. The first tackifier and the second tackifier may each independently contain, without limitation, any tackifier commonly used in an adhesive film for an organic electronic device, and preferably a tackifier capable of improving reliability. It may include, and more preferably, hydrogenated petroleum resin, hydrogenated rosin paper, hydrogenated rosin ester resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, polymerized rosin resin, and polymerized rosin ester resin. , More preferably, hydrogenated petroleum resins having different softening points may be included. For example, when a hydrogenated petroleum resin having a different softening point is included, the softening point of the first tackifying agent may be smaller than that of the second tackifying agent, but is not limited thereto.

When the first adhesive layer 11 contains a hydrogenated petroleum resin and the first adhesive layer 11 contains a hydrogenated petroleum resin smaller than the softening point of the second adhesive layer, 1 : It may be included in a weight ratio of 0.5 to 1.5, preferably 1: 0.6 to 1.4. If the weight ratio of the first tackifier and the second tackifier is less than 1:0.5, heat resistance retention may be deteriorated, and if the weight ratio exceeds 1:1.5, adhesion with the substrate decreases due to reduced adhesion and wettability. Problems can arise.

The tackifier of the first adhesive layer 11 may include 50 to 300 parts by weight, preferably 80 to 280 parts by weight, based on 100 parts by weight of the first mixed resin 11b of the first adhesive layer 11. If less than 50 parts by weight of the tackifier is included with respect to 100 parts by weight of the first mixed resin, a problem of poor moisture resistance may occur. If the tackifier exceeds 300 parts by weight, the elasticity of the first adhesive layer is reduced (Brittle ), the durability and moisture resistance may be deteriorated.

The first desiccant 11a of the first adhesive layer 11 may be used without limitation, as long as it is a material that can be used as a conventional desiccant, and silica may be preferably used. As silica is used as the first absorbent 11a, moisture removal performance is excellent, separation of the organic electronic device and the encapsulant may be prevented, and durability of the organic electronic device may be significantly increased.

The first desiccant 11a of the first adhesive layer 11 has a BET specific surface area of 2 to 20 m ² /g, preferably a BET specific surface area of 3 to 14 m ² /g, more preferably a BET specific surface area of 4 It may be ~ 8 m ² /g. The specific surface area was measured using the BET method, and specifically, it can be measured using ASAP2020 (Micromeritics, USA) without pretreatment at -195°C by adding a sample of 1 g of the first absorbent to the tube. The average value can be obtained by measuring three times for the same sample. If the BET specific surface area of the first moisture absorbent 11a exceeds 20 m ² /g, not only the adhesive strength with the substrate decreases, but also the resin flow decreases, resulting in poor adhesion. In addition, when the surface is rough or porous, the BET specific surface area may increase, and panel damage may occur due to the roughness of the surface. Therefore, the first moisture absorbent of the present invention can exhibit a high sphericity by having a low BET specific surface area.

The first desiccant 11a of the first adhesive layer 11 may be included in an amount of 1 to 40 parts by weight, preferably 5 to 35 parts by weight, based on 100 parts by weight of the first mixed resin 11b of the first adhesive layer 11. have. If the first moisture absorbent (11a) is contained in an amount of less than 1 part by weight, there is a problem that the durability of the organic electronic device may be deteriorated because the moisture removal effect from the desired first adhesive layer cannot be achieved. If included, there may be a problem in that the reliability of the organic electronic device is deteriorated due to poor adhesion such as adhesion between the encapsulant and the organic electronic device due to insufficient wettability.

Meanwhile, the first adhesive layer 11 of the present invention may further include at least one of a curing agent and a UV initiator.

When including the curing agent in the first adhesive layer 11 of the present invention, the curing agent may include 2 to 30 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the first mixed resin. If less than 2 parts by weight of the curing agent is included, the desired gelation rate and modulus cannot be achieved, and elasticity may be deteriorated.If it contains more than 30 parts by weight, panel bonding is defective due to high modulus and hardness , A problem of lowering adhesion due to lowering of wettability may occur.

The curing agent may be included without limitation as long as it is a material that can be used as a curing agent in general, and preferably may include a material capable of securing sufficient crosslinking density of the adhesive film by serving as a crosslinking agent, and more preferably, urethane acrylic It may include at least one selected from the group consisting of a rate-based curing agent and an acrylate-based curing agent.

In addition, the curing agent may have a weight average molecular weight of 100 to 1500, preferably a weight average molecular weight of 200 to 1300. If the weight average molecular weight of the curing agent is less than 100, the adhesion of the panel and adhesion to the substrate decreases due to the increase in hardness, and outgas of the unreacted curing agent may occur. If the weight average molecular weight exceeds 1500, the softening property There may be a problem that mechanical properties are deteriorated due to an increase in (Softness).

When including a UV initiator in the first adhesive layer 11 of the present invention, the UV initiator may include 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the first mixed resin. If the UV initiator is included in an amount of less than 0.1 part by weight, heat resistance may be poor due to poor UV curing, and if it is included in an amount exceeding 5 parts by weight, heat resistance may be poor due to a decrease in curing density.

The UV initiator may be included without limitation as long as it is commonly used as a UV initiator, and preferably, mono acyl phosphine, bis acyl phosphine, α-hydroxyketone (α-Hydroxyketone) ), α-aminoketone (α-Aminoketone), phenylglyoxylate (Phenylglyoxylate), and benzyldimethyl-ketal (Benzyldimethyl-ketal) may include at least one selected from.

On the other hand, the first adhesive layer 11 included in the encapsulant 10 for an organic electronic device according to the present invention has a viscosity of 150,000 Pa·s (50°C) or less, preferably 10,000 to 130,000 Pa·s (50 ℃). If the viscosity of the first adhesive layer 11 exceeds 150,000 Pa·s (50°C), there may be a problem that the adhesive strength with the substrate decreases due to the decrease in tack.

The viscosity may be a viscosity measured by a conventional viscosity measuring method, and preferably, a sample is laminated to a thickness of 800 to 900 μm, punched into a circle having a diameter of 8 mm, and then a viscosity measuring device (ARES-G2, TA) is used. The sample can be placed on a plate and measured. At this time, the measurement conditions can be measured in 5% strain, axial force 0.05N, sensitivity 0.005N, 1 rad/s, -5℃~130℃, and the axial direction before measurement Measurement can be started under the above conditions after adjusting the gap and stabilizing the sample with 0.5N of Axial Force and 0.05N of Sensitivity, but is not limited thereto.

Next, a description will be given of the second adhesive layer 12 formed on one surface of the first adhesive layer 11 of the present invention.

The second mixed resin 12b of the second adhesive layer 12 may include a first adhesive resin and a second adhesive resin, and the first adhesive resin and the second adhesive resin are the aforementioned mixed resin (15b). It may contain the same material as the first adhesive resin and the second adhesive resin of 1).

The first adhesive resin and the second adhesive resin of the second mixed resin 12b are included in a weight ratio of 1: 0.1 to 10, preferably in a weight ratio of 1: 1 to 9, more preferably in a weight ratio of 1: 1.1 to 5 can do. If the weight ratio of the first adhesive resin and the second adhesive resin is less than 1:0.1, reliability may be deteriorated, and if the weight ratio exceeds 1:10, the elasticity of the adhesive film may be lowered.

The tackifier of the second adhesive layer 12 may include a first tackifier. The first tackifier may be included without limitation, as long as it is an adhesive resin commonly used in an adhesive film for organic electronic devices, and preferably hydrogenated petroleum resin, hydrogenated rosin paper, hydrogenated rosin ester resin, hydrogenated terpene resin, hydrogenated terpene phenol It may include at least one selected from resin, polymerized rosin resin, and polymerized rosin ester resin.

The first adhesive imparting agent of the second adhesive layer 12 may include 60 to 300 parts by weight, preferably 90 to 280 parts by weight, based on 100 parts by weight of the second mixed resin 12b of the second adhesive layer 12 . If less than 60 parts by weight of the first adhesive agent is included with respect to 100 parts by weight of the second mixed resin, a problem of poor moisture resistance may occur. If the first adhesive agent is included in an amount exceeding 300 parts by weight, the second adhesive layer There may be a problem in that durability and moisture resistance are deteriorated due to brittle.

The second desiccant 12a of the second adhesive layer 12 can be used without limitation, as long as it is a material that can be used as a conventional desiccant, and desirably, a desiccant, metal salt and metal containing zeolite, titania, zirconia or montmorillonite as components. One or more of the oxides may be included, more preferably a metal oxide may be included, and even more preferably calcium oxide (CaO) may be included in the metal oxide.

Metal oxides include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), barium oxide (BaO), calcium oxide (CaO), or magnesium oxide (MgO). It may include at least one of metal oxides, organic metal oxides, and phosphorus pentoxide (P ₂ O ₅ ).

Metal salts include lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga ₂ (SO ₄ ) ₃ ), titanium sulfate (Ti(SO ₄ ) ₂ ) or nickel sulfate (NiSO ₄ ), such as sulfate, calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium salt (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 ( Metal halides such as SeBr ₄ ), vanadium bromide (VBr ₃ ), magnesium bromide (MgBr ₂ ), barium iodide (BaI ₂ ) or magnesium iodide (MgI ₂ ), and barium perchlorate (Ba(ClO ₄ ) ₂ ) or magnesium perchlorate (Mg(ClO ₄ ) ₂ ) It may contain one or more of metal chlorate.

The second desiccant 12a may preferably have a purity of 95% or more. If the purity is less than 95%, not only the moisture absorption function is deteriorated, but also the material contained in the desiccant acts as an impurity, which may cause defects of the encapsulant, and may affect the organic electronic device, but is not limited thereto.

The second moisture absorbent 12a of the second adhesive layer 12 may be included in an amount of 50 to 450 parts by weight, preferably 70 to 430 parts by weight, based on 100 parts by weight of the second mixed resin 12b of the second adhesive layer 12. have. If the second moisture absorbent (12a) is included in an amount of less than 50 parts by weight, there may be a problem in that the intended encapsulant may not be implemented, such as a remarkable decrease in the moisture removal effect. If it is included in an amount exceeding 450 parts by weight, the second adhesive layer 12 ) Significantly deteriorates, and an adhesive layer including the first adhesive layer 11 and the second adhesive layer 12 and/or the second adhesive layer 12 and the first adhesive layer 11 due to excessive volume expansion upon moisture absorption There may be a problem in that the lifespan of the organic electronic device is shortened due to excitement in the organic electronic device and moisture rapidly penetrates therebetween.

On the other hand, the second moisture absorbent 12a of the second adhesive layer 12 is not limited in shape or particle diameter, but preferably, in order to improve dispersibility in the second adhesive layer, it may be a spherical shape having an average particle diameter of 5 nm to 8 µm. , Preferably, it may be a spherical shape having an average particle diameter of 10 nm to 6 µm. This is preferable for thinning the encapsulant while having a desired moisture removal function.

On the other hand, the second adhesive layer 12 of the present invention may further include at least one of a curing agent and a UV initiator.

When including a curing agent in the second adhesive layer 12 of the present invention, the curing agent may include 10 to 40 parts by weight, preferably 12 to 35 parts by weight, based on 100 parts by weight of the second mixed resin. If the curing agent is included in less than 10 parts by weight, the desired gelation rate and modulus cannot be achieved, and elasticity may be deteriorated.If it contains more than 40 parts by weight, panel bonding is defective due to high modulus and hardness , A problem of lowering adhesion due to lowering of wettability may occur.

The curing agent may be included without limitation as long as it is a material that can be used as a curing agent in general, and preferably may include a material capable of securing sufficient crosslinking density of the adhesive film by serving as a crosslinking agent, and more preferably, urethane acrylic It may include at least one selected from the group consisting of a rate-based curing agent and an acrylate-based curing agent.

In addition, the curing agent may have a weight average molecular weight of 100 to 1500, preferably a weight average molecular weight of 200 to 1300. If the weight average molecular weight of the curing agent is less than 100, the adhesion of the panel and adhesion to the substrate decreases due to the increase in hardness, and outgas of the unreacted curing agent may occur. If the weight average molecular weight exceeds 1500, the softening property ( There may be a problem that mechanical properties are deteriorated due to an increase in softness).

When including a UV initiator in the second adhesive layer 12 of the present invention, the UV initiator may include 0.1 to 8 parts by weight, preferably 0.5 to 6 parts by weight, based on 100 parts by weight of the second mixed resin. If the UV initiator is included in an amount of less than 0.1 parts by weight, heat resistance may be poor due to poor UV curing, and if it is included in an amount exceeding 8 parts by weight, heat resistance may be poor due to a decrease in curing density.

The UV initiator may be included without limitation as long as it is commonly used as a UV initiator, and preferably, mono acyl phosphine, bis acyl phosphine, α-hydroxyketone (α-Hydroxyketone) ), α-aminoketone (α-Aminoketone), phenylglyoxylate (Phenylglyoxylate), and benzyldimethyl-ketal (Benzyldimethyl-ketal) may include at least one selected from.

On the other hand, the second adhesive layer 12 included in the encapsulant 10 for an organic electronic device according to the present invention has a viscosity of 200,000 Pa·s (50°C) or more, preferably 220,000 to 1,000,000 Pa·s (50 ℃). If the viscosity of the second adhesive layer 12 is less than 200,000 Pa·s (50°C), there may be a problem in that the adhesive strength with the substrate decreases due to the decrease in tack.

The viscosity may be a viscosity measured by a conventional viscosity measuring method, and preferably, a sample is laminated to a thickness of 800 to 900 μm, punched into a circle having a diameter of 8 mm, and then a viscosity measuring device (ARES-G2, TA) is used. The sample can be placed on a plate and measured. At this time, the measurement conditions can be measured in 5% strain, axial force 0.05N, sensitivity 0.005N, 1 rad/s, -5℃~130℃, and the axial direction before measurement Measurement can be started under the above conditions after adjusting the gap and stabilizing the sample with an axial force of 0.5N and a sensitivity of 0.05N, but is not limited thereto.

Further, when a multi-layered adhesive film including the first adhesive layer 11 and the second adhesive layer 12 is provided, the adhesive film of the sealing material 10 for an organic electronic device of the present invention is measured according to the following measurement method 1. The measured adhesive strength may be 1500 gf/25mm or more, preferably 1600 gf/25mm or more, and more preferably 1700 to 3000 gf/25mm.

[Measurement Method 1]

Laminate the adhesive strength measuring tape (7475, TESA) on the upper surface of the adhesive film through a 2Kg Hand Roller, cut the sample into 25 mm width and 120 mm length, and laminate the lower surface of the adhesive film to glass at 80°C. , The prepared sample was left at room temperature for 30 minutes, and the glass adhesion was measured at a speed of 300 mm/min.

In addition, when a multi-layered adhesive film including the first adhesive layer 11 and the second adhesive layer 12 is provided, the adhesive film of the encapsulant 10 for an organic electronic device of the present invention is determined according to Measurement Method 2 below. The measured metal adhesion may be 1000 gf/25 mm or more, preferably 1100 gf/25 mm or more, and more preferably 1200 to 2500 gf/25 mm.

[Measurement method 2]

At 80℃, the upper surface of the adhesive film is laminated on a Ni alloy having a thickness of 80㎛, and an adhesive force measuring tape (7475, TESA) is laminated to the lower surface of the adhesive film through a 2Kg Hand Roller, and the sample is 25mm in width and 120 in length. After cutting by mm, the prepared sample was left at room temperature for 30 minutes, and the metal adhesion was measured at a speed of 300 mm/min.

When the adhesive force measured according to the measurement method 1 and the measurement method 2 satisfies the above range, peeling of the adhesive film may be significantly reduced when applied to an organic electronic device.

On the other hand, in the case of including the above-described single-layered adhesive film 15, a multi-layered adhesive film including the first adhesive layer 11 and the second adhesive layer 12, specifications such as size and thickness will vary depending on the purpose. As it may be, the present invention does not specifically limit this.

In addition, the adhesive film 15 of the single-layer structure, the multi-layered adhesive film including the first adhesive layer 11 and the second adhesive layer 12 may be an adhesive film in a dried state or an adhesive film in a cured state.

Meanwhile, as mentioned above, when the adhesive film of the present invention includes the first adhesive layer 11 and the second adhesive layer 12 formed on one surface of the first adhesive layer 11, the contact angle of deionized water of the first adhesive layer 11 is It may be 75° or less, preferably 50 to 73°. In addition, the contact angle of deionized water of the second adhesive layer 12 may be 75° or less, and preferably 50 to 73°.

If the contact angle of deionized water between the first adhesive layer 11 and the second adhesive layer exceeds 75°, there may be a problem in that reliability is deteriorated due to a decrease in adhesive strength with the substrate.

The contact angle of deionized water of the adhesive film is obtained by dissolving the components of the first adhesive layer 11 and the second adhesive layer 12 in an appropriate solvent to form a film by coating a solution of about 15% by weight solid content on glass and drying it. And, it is a contact angle measured by dropping deionized water on the coating film at about 25°C, and may be an average of the contact angle measured by repeating the above process 10 times.

Specifically, the contact angle of deionized water is to prepare a solution having a solid content of 15% by weight by dissolving the component to be measured in a dilutable solvent, and after coating the prepared solution on glass, drying to form a film, and coating to a thickness of 10㎛. Drying to form a coating film can be measured for the coating film. More specifically, the contact angle can be measured with the KRUSS DSA100 by dropping deionized water at about 25° C. on the coating film, and the same process can be repeated 10 times to make the average contact angle.

In addition, as mentioned above, when the adhesive film of the present invention includes the first adhesive layer 11 and the second adhesive layer 12 formed on one surface of the first adhesive layer 11, the first adhesive layer 11 is ( It may have a tensile modulus of 210 to 390) × 10 ³ Pa, preferably a tensile modulus of (240 to 360) × 10 ³ Pa, more preferably (270 to 330) × 10 ³ Pa. If the tensile modulus of the first adhesive layer 11 is less than 210×10 ^3, durability may be deteriorated. If it exceeds 390×10 ³ Pa, the substrate (glass, metal, etc.) ) And/or cracking may occur.

In addition, the second adhesive layer 12 has a tensile modulus of (1,400 to 2,600) × 10 ³ Pa, preferably (1,600 to 2,400) × 10 ³ Pa, more preferably (1,800 to 2,200) It can have a tensile modulus of 10 ³ Pa. If the tensile modulus of the second adhesive layer 12 is less than 1,400×10 ^{3, the} durability may be deteriorated, and if it exceeds 2,600×10 ³ Pa, the substrate (glass, metal, etc.) ) And/or cracking may occur.

In addition, the first adhesive layer 11 and the second adhesive layer 12 of the present invention have a variation in tensile modulus of 2,390×10 ³ Pa or less at 25°C, preferably 1,010×10 ³ Pa to 2,040×10 ³ Pa, further Preferably, it may be 1,530×10 ³ Pa to 1,870×10 ³ Pa. If the deviation exceeds 2,390×10 ³ Pa, partial film breakage and cracking may occur due to shrinkage and/or expansion of the adhesive film.

Meanwhile, as mentioned above, when the adhesive film of the present invention includes the first adhesive layer 11 and the second adhesive layer 12 formed on one surface of the first adhesive layer 11, the first adhesive layer 11 is represented by the following equation 1 The measured value according to may be 8.4 to 15.8%, preferably 9.68 to 14.52%, more preferably 10.89 to 13.31%. If the measured value of the first adhesive layer 11 according to Equation 1 is less than 8.4%, heat resistance may deteriorate and resin over flow may occur, and if it exceeds 15.8%, it may cause a material (glass, metal, etc.) There may be a problem that the adhesive strength is lowered.

[Equation 1]

Measured value (%) = 100 × S ₂ /S ₁

S ₁ is a vertical force of 200 gf at 85°C using a parallel plate with a diameter of 8 mm in the stress relaxation test mode with ARES (Advanced Rheometric Expansion System) in the state of manufacturing an adhesive layer with a thickness of 600 μm. normal force) is the maximum stress value measured when a 30% strain is applied to the adhesive film, and S ₂ is the stress measured after maintaining the state of applying the strain to the adhesive film for 180 seconds Value.

In addition, the second adhesive layer 12 of the present invention may have a measured value according to Equation 1 of 1 to 20%, preferably 7.32 to 10.98%, and more preferably 8.23 to 10.07%. If the measured value according to Equation 1 of the second adhesive layer 12 is less than 1%, heat resistance may deteriorate and resin overflow may occur, and if it exceeds 20%, adhesion with a substrate (glass, metal, etc.) This deterioration problem may occur.

In addition, in the first adhesive layer 11 and the second adhesive layer 12 of the present invention, the deviation of the measured value according to Equation 1 is 11.6% or less, preferably 0.39 to 6.29%, more preferably 2.36 to 3.54%. I can. If the deviation exceeds 11.6%, there may be a problem of deteriorating reliability due to shrinkage and/or expansion of the adhesive layer during the thermal process.

Furthermore, the adhesive film of the present invention may satisfy both the following conditions (3) and (4).

, 바람직하게는

일 수 있다.As condition (3),

, Preferably

Can be

, 바람직하게는

일 수 있다.In addition, as condition (4),

, Preferably

Can be

In the above conditions (3) and (4), a ₁ and a ₂ are the storage modulus (Pa) and loss modulus (Pa) at 25°C, respectively, and b ₁ and b ₂ are the storage modulus (Pa) at 50°C, respectively. ) And loss modulus (Pa).

이 5.28 미만이면 패널 처짐현상이 발생함에 따라 부피 팽창을 방지할 수 없는 문제가 발생할 수 있고, 7.16을 초과하면 외부충격에 의한 완충효과가 저하됨에 따라 내구성이 저하될 수 있다. If, in the above condition (3)

If it is less than 5.28, a problem that cannot prevent volume expansion may occur as the panel sag occurs, and if it exceeds 7.16, the durability may be deteriorated as the buffering effect due to external shock is lowered.

이 4.22 미만이면 합착공정 중 오버 플로우(Over Flow)가 발생함에 따라 기포 발생 및/또는 신뢰성이 저하될 수 있고, 5.6을 초과하면 패널의 단차를 매꾸지 못함에 따라 점착력 저하 및/또는 층간 박리현상이 발생할 수 있다.In addition, if in the above condition (4)

If this value is less than 4.22, bubbles may occur and/or reliability may decrease as overflow occurs during the bonding process, and if it exceeds 5.6, adhesive strength decreases and/or interlayer peeling occurs due to failure to fill the level of the panel. This can happen.

In addition, the adhesive film of the present invention may satisfy the following condition (5).

, 바람직하게는

일 수 있다.As condition (5),

, Preferably

Can be

In the above condition (5), c ₁ and c ₂ are storage modulus (Pa) and loss modulus (Pa) at 100°C, respectively.

이 3.46 미만이면 점착제의 흐름성으로 인해 내열성이 저하되는 문제가 발생할 수 있고, 5.02를 초과하면 젖음성 부족에 따른 점착력 저하 및 내열성이 저하되는 문제가 발생할 수 있다.If, in the above condition (5)

If it is less than 3.46, heat resistance may be deteriorated due to the flowability of the pressure-sensitive adhesive, and if it exceeds 5.02, adhesive strength and heat resistance may be deteriorated due to insufficient wettability.

In addition, the adhesive film of the present invention may have a storage elastic modulus at 25° C. of 7×10 ⁶ to 1.5×10 ⁸ Pa, preferably 8×10 ⁶ to 1×10 ⁸ Pa, so as to satisfy the condition (3), The loss modulus at 25° C. may be 10 ⁷ ~ 2×10 ⁸ Pa, preferably 1.2×10 ⁷ ~ 1.5×10 ⁸ Pa. If the storage modulus at 25°C is less than 7×10 ⁶ Pa, a problem that cannot prevent volume expansion may occur as the panel sag occurs, and if it exceeds 1.5×10 ⁸ Pa, the buffering effect due to external impact is reduced. As it deteriorates, durability may decrease. In addition, if the loss modulus at 25°C is less than 10 ⁷ Pa, a problem that cannot prevent volume expansion may occur as the panel sag occurs, and if it exceeds 2×10 ⁸ Pa, the buffering effect due to external impact is lowered. Accordingly, durability may decrease.

In addition, the adhesive film of the present invention may have a storage elastic modulus at 50° C. of 10 ⁶ to 1.5×10 ⁷ Pa, preferably 1.2×10 ⁶ to 9×10 ⁶ Pa to satisfy condition (4), and 50° C. The loss modulus at may be 8×10 ⁵ to 1.5×10 ⁷ Pa, preferably 9×10 ⁵ to 1×10 ⁷ Pa. If the storage modulus at 50°C is less than 10 ⁶ Pa, bubbles may be generated and/or reliability may be deteriorated as an overflow occurs during the bonding process. If it exceeds 1.5×10 ⁷ Pa, the step of the panel is reduced. Due to the failure to fill, adhesion may decrease and/or delamination may occur. In addition, if the loss modulus at 50°C is less than 8×10 ⁵ Pa, bubbles may occur and/or reliability may decrease as an overflow occurs during the bonding process. If it exceeds 1.5×10 ⁷ Pa, the panel's Failure to fill in the steps may cause a decrease in adhesive strength and/or delamination between layers.

In addition, the adhesive film of the present invention may have a storage elastic modulus at 100° C. of 2×10 ⁵ to 8×10 ⁶ Pa, preferably 3×10 ⁵ to 6×10 ⁶ Pa, so as to satisfy the condition (5), The loss modulus at 100° C. may be 5×10 ⁴ to 2×10 ⁶ Pa, preferably 6×10 ⁴ to 1.5×10 ⁶ Pa. If the storage modulus at 100°C is less than 2×10 ⁵ Pa, heat resistance may decrease due to the flowability of the adhesive, and if it exceeds 8×10 ⁶ Pa, adhesive strength and heat resistance decrease due to insufficient wettability. Problems can arise. In addition, if the loss modulus at 100°C is less than 5×10 ⁴ Pa, heat resistance may decrease due to the flowability of the pressure-sensitive adhesive, and if it exceeds 2×10 ⁶ Pa, adhesive strength and heat resistance may decrease due to insufficient wettability. Problems can arise.

Meanwhile, the adhesive film of the present invention may have a gel content of 45 to 95%, preferably 50 to 90%, as measured by Equation 2 below.

[Equation 2]

The weight of the adhesive film dried in Equation 2 is: The adhesive layer is cut into 100 mm × 25 mm horizontally × vertically, put the cut adhesive layer in a vial bottle containing 5 g of toluene, and allowed to stand for 15 minutes, and then the adhesive layer is filtered through a filter. , The filtered adhesive layer is hot air dried at 160° C. for 30 minutes to completely remove toluene, and the measured weight is shown.

If the gelation rate of the adhesive film is less than 45%, panel sagging occurs, expansion due to moisture absorption cannot be prevented, and bubbles occur and/or reliability due to overflow during the bonding process. This may be reduced, and the heat resistance may be decreased due to the flowability of the adhesive film. In addition, if the gelation rate of the adhesive film exceeds 95%, the durability may decrease as the buffering effect due to external impact decreases, and the adhesion decrease and/or interlayer peeling phenomenon due to failure to fill the level difference of the panel. It may occur, and there may be a problem of lowering of adhesion and heat resistance due to insufficient wettability.

Further, the adhesive film of the present invention may satisfy both of the following conditions (6) and (7) in order to solve such a problem.

, 바람직하게는

일 수 있고, 조건 (7)로써,

, 바람직하게는

일 수 있다.As condition (6),

, Preferably

Can be, and as condition (7),

, Preferably

Can be

However, d denotes the thickness (㎛) of the adhesive film, and e denotes the average particle diameter (㎛) of the desiccant.

이 8 미만이면 유기전자장치 봉지재의 접착필름의 합착성이 저하될 수 있고, 접착필름 표면에 흡습제가 돌출되는 문제가 발생할 수 있으며, 접착필름 표면에서 묻어나오는 흡습제로 인하여 신뢰성이 저하될 수 있다. 또한, 만일 상기 조건 (7)에서

가 0.01 미만이면 접착필름 표면에 흡습제가 묻어나오는 문제가 발생할 수 있고, 신뢰성 및 합착성이 저하될 수 있으며,

가 0.9를 초과하면 유기전자장치용 봉지재의 접착필름의 합착성이 저하될 수 있고, 접착필름 표면에 흡습제가 돌출되는 문제가 발생할 수 있다.If, under condition (6) above

If the value is less than 8, the adhesion of the adhesive film of the organic electronic device encapsulant may be deteriorated, a problem of protruding a desiccant on the surface of the adhesive film may occur, and reliability may be deteriorated due to the desiccant oozing from the surface of the adhesive film. In addition, if in the above condition (7)

If is less than 0.01, there may be a problem that a moisture absorbent is adhered to the surface of the adhesive film, and reliability and adhesion may be deteriorated.

When is greater than 0.9, adhesion of the adhesive film of the encapsulant for an organic electronic device may be deteriorated, and a problem in which the moisture absorbent protrudes from the surface of the adhesive film may occur.

At this time, the adhesive film of the present invention may have a thickness of 8 to 85 μm, preferably 10 to 80 μm, so as to satisfy the above conditions (6) and (7). If the thickness of the adhesive film is less than 8㎛, the adhesion of the adhesive film of the encapsulant for organic electronic devices may be deteriorated, and there may be a problem that the moisture absorbent protrudes on the surface of the adhesive film. If the thickness exceeds 85㎛, the organic electronics There may be a problem that the reliability of the adhesive film of the device encapsulant is deteriorated.

On the other hand, the present invention includes a light emitting device including the aforementioned encapsulant for an organic electronic device.

The light emitting device includes a substrate, an organic electronic device formed on at least one surface of the substrate, and an encapsulant for an organic electronic device according to the present invention for packaging the organic electronic device.

According to a preferred embodiment of the present invention, the light emitting device 100 of the present invention is provided with a single-layered adhesive film 115 including a mixed resin 115b and a moisture absorbent 115a as shown in FIG. According to another preferred embodiment of the present invention, the light emitting device 100 of the present invention comprises a first mixed resin 111b and a first absorbent 111a as shown in FIG. It may be formed by having a multi-layered adhesive film including the first adhesive layer 111 and the second adhesive layer 112 including the second mixed resin 112b and the second absorbent 112a.

Details to be described below will be described based on the light emitting device 100 including the multilayer adhesive film of FIG. 4.

In the light emitting device 100 according to the present invention, a substrate 101, an organic electronic device 102 is formed on at least one surface of the substrate 101, and an organic electronic device 102 is formed on the substrate 101 and the organic electronic device 102. Device encapsulants 111, 112, 130 are formed. The organic electronic device encapsulant includes a first adhesive layer 111, a second adhesive layer 112, and a metal sheet 130 sequentially stacked, and the first adhesive layer matches the substrate 101 and the organic electronic device 102. Is formed by touching.

The first adhesive layer 111 may include a first mixed resin 111b containing a first adhesive resin and a second adhesive resin, and a desiccant 111a containing silica, and the second adhesive layer 112 is a first adhesive resin. A second mixed resin 112b including an adhesive resin and a second adhesive resin, and a moisture absorbent 112a may be included.

The substrate 101 may be preferably any one of a glass substrate, a crystal substrate, a sapphire substrate, a plastic substrate, and a flexible polymer film that can be bent.

The organic electronic device 102 formed on at least one surface of the substrate 101 includes a thin film of a lower electrode on the substrate 102 and an n-type semiconductor layer, an active layer, a p-type semiconductor layer, and an upper electrode sequentially stacked thereon. It may be formed by etching after, or may be formed by placing it on the substrate 101 after being manufactured through a separate substrate. A specific method of forming the organic electronic device 102 on the substrate 101 may be a method known in the art and is not particularly limited in the present invention, and the organic electronic device 102 is It may be a light-emitting diode.

Next, a specific method of packaging may be performed by a known conventional method, and the present invention is not particularly limited. As a non-limiting example of this, the first adhesive layer 111 of the organic electronic device 102 formed on the substrate 101 and the organic electronic device 102 and the first adhesive layer 111 of the organic electronic device encapsulant 111, 112, 130 It can be performed by applying heat and/or pressure using a vacuum press or a vacuum laminator in a state in direct contact. In addition, heat may be applied to cure the adhesive layer, and in the case of an adhesive including an adhesive resin that is photo-cured, it may be moved to a chamber to which light is irradiated to undergo a curing process.

Hereinafter, the present invention will be described through the following examples. At this time, the following examples are only presented to illustrate the invention, and the scope of the present invention is not limited by the following examples.

Example 1: Preparation of sealing material for organic electronic devices

(1) Formation of the first adhesive layer

1 To form an adhesive layer, a random copolymer (first adhesive resin) in which ethylene, propylene and diene-based compounds are copolymerized and a compound represented by the following formula (1) (second adhesive resin) are mixed in a weight ratio of 1: 2.33 1 After preparing the mixed resin, 80 parts by weight of the first adhesive agent (SU-90, Kolon Industries) and 50 parts by weight of the second adhesive agent (SU-100, Kolon Industries) based on 100 parts by weight of the first mixed resin. Parts, 11 parts by weight of acrylate (M200, Miwon Specialty Chemical) having a weight average molecular weight of 226 as a curing agent, 3 parts by weight of UV initiator (irgacure TPO, Ciba), and 24 parts by weight of silica having an average particle diameter of 0.5 µm were added and stirred.

After removing foreign substances by passing through a capsule filter, the mixture after stirring was applied to a heavy peeling antistatic release PET (RT81AS, SKCHass) having a thickness of 75㎛ using a slot die coater, and then dried at 120℃ to remove the solvent. A first adhesive layer having a final thickness of 20 μm was prepared.

The first adhesive resin was prepared by copolymerizing ethylene and propylene monomers in a weight ratio of 1:0.85, and copolymerizing a diene-based compound at 9% by weight based on the total weight of the random copolymer, and the diene-based compound was ethylidene norbornene ( ethylidene norbornene) is a random copolymer with a weight average molecular weight of 500,000.

[Formula 1]

In Formula 1, R ¹ is isoprene, and n is a rational number that satisfies the weight average molecular weight of 400,000 of the compound represented by Formula 1.

(2) Formation of the second adhesive layer

To form the second adhesive layer, a random copolymer (first adhesive resin) in which ethylene, propylene, and diene-based compounds are copolymerized and a compound represented by the following formula (1) (second adhesive resin) are mixed in a weight ratio of 1: 2.33. After preparing the second mixed resin, the first adhesive imparting agent (SU-90, Kolon Industries) based on 100 parts by weight of the second mixed resin 150 parts by weight, 17 parts by weight of acrylate (M200, Miwon Specialty Chemical) having a weight average molecular weight of 226 as a curing agent, 3 parts by weight of UV initiator (irgacure TPO, Ciba), and 100 parts by weight of calcium oxide having an average particle diameter of 3 µm are added And then stirred.

After stirring is completed, the mixture is set to 800 cps at 20℃, and then passed through a capsule filter to remove foreign substances, and then applied to a 38um thin release PET (RF02, SKCHass) using a slot die coater, and then dried at 120℃. To remove the solvent to prepare a second adhesive layer having a final thickness of 30 μm.

The first adhesive resin was prepared by copolymerizing ethylene and propylene monomers in a weight ratio of 1:0.85, and copolymerizing a diene-based compound at 9% by weight based on the total weight of the random copolymer, and the diene-based compound was ethylidene norbornene ( ethylidene norbornene) is a random copolymer with a weight average molecular weight of 500,000.

[Formula 1]

In Formula 1, R ¹ is isoprene, and n is a rational number that satisfies the weight average molecular weight of 400,000 of the compound represented by Formula 1.

(3) Manufacture of adhesive film

The prepared first adhesive layer was laminated to face the second adhesive layer and passed through a 70° C. lami roll to prepare an adhesive film.

(4) Manufacture of sealing materials for organic electronic devices

The release PET attached to the second adhesive layer of the adhesive film was removed, and the second adhesive layer and the metal sheet were laminated to face to each other, and then passed through a lami roll at 80° C. to prepare an organic electronic device encapsulant. At this time, the used metal sheet had a surface energy of 60mN/cm, a surface roughness of Ra = 0.27μm, Rsm = 50μm, Rz = 2.0μm, and a contact angle of deionized water of the second adhesive layer laminated with the metal sheet was 53.4°. .

Examples 2 to 46

Manufactured in the same manner as in Example 1, but the weight average molecular weight of the first adhesive resin and the second adhesive resin used to prepare the adhesive sheet, the content of the curing agent, the content of the UV initiator and the number of adhesive layers were varied in Table 1 to An encapsulant for organic electronic devices as shown in Table 8 was prepared.

<Experimental Example 1>

In order to measure the physical properties of the adhesive film of the encapsulant for an organic electronic device of the present invention, before laminating the metal sheet, the following physical properties were measured for the adhesive film of the encapsulant for an organic electronic device prepared through Examples 1 to 46. It is shown in Tables 1 to 8 below.

1. Evaluation of moisture penetration of the adhesive film of the encapsulant for organic electronic devices

After cutting the specimen into a size of 95mm × 95mm, remove the protective film on the 100mm × 100mm alkali-free glass, align the specimen so that it can be placed 2.5mm inside the edge of the four sides of the alkali-free glass, and heat it at 65℃. It was attached using a rolled laminator. After removing the release film remaining on the attached specimen, another 100mm × 100mm alkali-free glass is covered and laminated at 65℃ with a vacuum laminator for 1 minute to prepare a bonded sample without bubbles. Samples that have been cemented together In a reliability chamber set at 85° C. and 85% relative humidity, the length of moisture penetration was observed with a microscope in units of 1000 hours.

2. Evaluation of volume expansion of the adhesive film of the encapsulant for organic electronic devices

After removing the release film of the specimen to a 50 μm-thick SUS plate cut into 30 mm × 20 mm, it was attached using a roll laminator heated to about 65. The attached specimen was cut with a knife according to the size of SUS, and then attached to 40mm × 30mm 0.7T alkali free glass using a roll laminator heated at 65℃. After confirming that the specimen is well adhered between the glass and SUS without voids, observe the specimen for 1,000 hours at 100 hour intervals in a reliability chamber set at 85°C and 85% relative humidity. The height change of was observed through an optical microscope.

As a result of observation, if the height change at the moisture absorption site is less than 1㎛ ◎, if the height change at the moisture absorption site is less than 1 ~ 3㎛ ○, if the height change at the moisture absorption site is less than 3 ~ 5㎛ △, the height at the moisture absorption site When the change is 5 μm or more, it is indicated by ×.

3. Evaluation of heat resistance of adhesive film for organic electronic device encapsulant

The specimen was cut into a size of 50 mm × 80 mm, and the protective film of the specimen was removed, and then attached to a 60 mm × 150 mm 0.08T Ni alloy at 80° C., Gap 1 mm, and Speed 1 using a roll laminator. After removing the liner film of the attached specimen, it was attached to 30mm x 70mm 5T alkali free glass at 80℃, Gap 1mm, Speed 1 using a roll laminator. The specimen attached to the glass was vertically fixed to a chamber at 130° C., and then a 1 kg weight was suspended to determine the presence or absence of an adhesive.

At this time, when there is no abnormality in the evaluation result, it is indicated as ○, and when even a little flows, ×.

4. Evaluation of adhesion between adhesive film and glass of encapsulant for organic electronic devices

For the adhesive film prepared according to the embodiment, an adhesive force measuring tape (7475, TESA) was laminated on the upper surface of the adhesive film through a 2 kg hand roller, and the sample was cut into 25 mm in width and 120 mm in length. After that, after laminating the lower surface of the adhesive film at 80° C. on an alkali-free glass, the sample was left at room temperature for 30 minutes, and the glass adhesion was measured at a rate of 300 mm/min through a universal testing machine (UTM).

5. Evaluation of adhesion between adhesive film and metal of encapsulant for organic electronic devices

For the adhesive film prepared according to the Example, the upper surface of the adhesive film was laminated to a Ni alloy having a thickness of 80 μm at 80° C., and an adhesive force measuring tape (7475, TESA) was laminated to the lower surface of the adhesive film, and the sample was 25 mm wide and After cutting to a length of 120 mm, the prepared sample was allowed to stand at room temperature for 30 minutes, and the metal adhesion was measured at a rate of 300 mm/min through a universal testing machine (UTM).

<Experimental Example 2>

On the substrate with the ITO pattern, an organic light emitting device (hole transport layer NPD/thickness 800A, light emitting layer Alq3/thickness 300A, electron injection layer LiF/thickness 10A, cathode Al + Liq/thickness 1,000A) was deposited and stacked on the fabricated device. After laminating the adhesive film according to Examples 1 to 46 (the adhesive film before the metal sheet was laminated when manufacturing an organic electronic device encapsulant) was laminated at room temperature, an OLED unit specimen emitting green light was prepared. Thereafter, the following physical properties were evaluated for the specimen and are shown in Tables 1 to 8.

1. Durability evaluation of organic light emitting devices according to moisture penetration of the adhesive film of the encapsulant for organic electronic devices

Pixel shrinkage and generation and/or growth of dark spots in the light-emitting area by time in an environment of 85°C and 85% relative humidity are observed with a digital microscope of X100 every 100 hours. The time taken for the reduction to occur by 50% or more and/or to generate a dark spot was measured.

At this time, if 50% or more of pixel reduction occurs and the time required for dark spot generation is 1,000 hours or more ◎, When 50% or more of pixel reduction occurs and the time required for dark spot generation is less than 1000 to 800 hours ○, 50% pixel reduction When an abnormality occurs and the time required to generate a dark spot is less than 800 hours to over 600 hours, it is expressed as △, and a case where the pixel reduction occurs more than 50% and the time required to generate dark spots is less than 600 hours.

2. Durability evaluation of the adhesive film of the encapsulant for organic electronic devices

The specimen was observed in a reliability chamber set at 85°C and 85% relative humidity for 1,000 hours at 100-hour intervals to determine the interface separation between the organic electronic device and the adhesive film, the occurrence of cracks or bubbles in the adhesive film, and the separation between the adhesive layers. Through observation, the physical damage was evaluated. If there is no abnormality as a result of the evaluation, ○, if any abnormalities such as interfacial separation, cracks or bubbles in the adhesive film, and separation between adhesive layers occur, are indicated as x.

As can be seen from Tables 1 to 8,

Preferred first adhesive resin, the second adhesive resin molecular weight, R ^1, the first adhesive resin and a second adhesive resin weight ratio of the monomer content, the tackifier in the random copolymer of Formula 1 of claim content, moisture absorbent content of the curing agent of the present invention Examples 1 to 7, Example 9, Example 10, Example 13, Example 14, Example 17, Example 18, Example 21, Example 22, which satisfy all of the content, the molecular weight of the curing agent and the number of adhesive layers, etc. Example 25, Example 26, Example 29, Example 30, Example 33, Example 36, Example 39, and Example 41 were omitted in Example 8, Example 11, Example 12 , Example 15, Example 16, Example 19, Example 20, Example 23, Example 24, Example 27, Example 28, Example 31, Example 32, Example 34, Example 35, Example Compared to Examples 37, 38, 40, and Comparative Examples 42 to 46, moisture removal and blocking were more efficient, so that the water penetration length was short, there was little volume expansion of the adhesive film, and the heat resistance and durability of the organic light emitting device were evaluated. The result was good, the durability of the adhesive film was excellent, and the adhesive strength was excellent.

Specifically, Examples 1, 9, and 10 satisfying the weight ratio of the first adhesive resin and the second adhesive resin are more efficient in removing and blocking moisture compared to Example 8, which does not satisfy this, and the moisture penetration length Was short, and moisture removal and blocking were more efficient than in Example 11, so that the moisture penetration length was short, and the durability of the adhesive film was excellent.

In addition, Examples 1, 13, and 14 satisfying the copolymerization ratio of ethylene and propylene were more efficient in removing and blocking moisture compared to Example 12, which did not satisfy the copolymerization ratio, and thus the moisture penetration length was short. There was almost no volume expansion, excellent heat resistance and durability of the adhesive film, excellent adhesion, and more efficient moisture removal and blocking compared to Example 15, resulting in a shorter water penetration length, and almost no volume expansion of the adhesive film. , The durability of the adhesive film was excellent.

In addition, Examples 1, 17, and 18 satisfying the content and weight ratio of the first and second tackifiers are more efficient in removing and blocking moisture compared to Example 16, which is not satisfied. The moisture permeation length was short, the heat resistance was excellent, and the moisture permeation length was shorter because the moisture removal and blocking were more efficient than in Example 19, and the durability of the adhesive film was excellent, and the adhesive strength was excellent.

In addition, Example 1, Example 21, and Example 22 satisfying the content of the tackifier in the second adhesive layer were more efficient in removing and blocking moisture compared to Example 20, which did not satisfy this, and the moisture penetration length was short, Compared to Example 23, moisture removal and blocking were more efficient, so that the moisture penetration length was short, there was little volume expansion of the adhesive film, and the durability of the adhesive film was excellent.

In addition, Example 1, Example 25, and Example 26 satisfying the content of the first absorbent were more efficient in removing and blocking moisture compared to Example 24, which did not satisfy the content, and thus the moisture penetration length was short. The durability evaluation result was good, the durability of the adhesive film was excellent, there was almost no volume expansion of the adhesive film compared to Example 27, and the durability of the adhesive film was excellent.

In addition, Examples 1, 29, and 30 satisfying the content of the second absorbent were more efficient in removing and blocking moisture compared to Example 28, which did not satisfy the content, and thus the moisture penetration length was short, and the durability of the adhesive film. This was excellent, and moisture removal and blocking were more efficient than in Example 31, so that the moisture penetration length was short, there was little volume expansion of the adhesive film, the durability evaluation result of the organic light emitting device was good, and the durability of the adhesive film was excellent, The adhesion was excellent.

In addition, Examples 1 and 33 satisfying the content of the curing agent in the first adhesive layer showed little volume expansion of the adhesive film compared to Example 32, which did not satisfy this, and the durability evaluation result of the organic light emitting device was good. Compared to Example 34, the adhesive film had excellent durability and excellent adhesive strength.

In addition, Example 1 and Example 36 satisfying the content of the curing agent in the second adhesive layer showed little volume expansion of the adhesive film compared to Example 35, which did not satisfy this, and the durability evaluation result of the organic light emitting device was good. Compared to Example 37, the adhesive film had excellent durability and excellent adhesion.

In addition, Examples 1 and 39, which satisfy the weight average molecular weight of the curing agent, are more efficient in removing and blocking moisture than in Example 38, which does not satisfy this, so that the moisture permeation length is short, and the durability of the adhesive film is excellent, The adhesive strength was excellent, and there was almost no volume expansion of the adhesive film compared to Example 40, and the durability of the adhesive film was excellent compared to that of Example 40.

In addition, Example 1 including a multi-layered adhesive layer and Example 41 including a single-layered adhesive layer efficiently removed and blocked moisture, resulting in a short water penetration length, little volume expansion of the adhesive film, and heat resistance and The durability evaluation result of the organic light emitting device was good, the durability of the adhesive film was excellent, and the adhesive strength was excellent.

In addition, Examples 1 to 3, which satisfy the weight average molecular weight of the first adhesive resin, were more efficient in removing and blocking water than in Example 42, which did not satisfy this, so that the moisture penetration length was short, and the volume expansion of the adhesive film was almost There was no, the durability of the adhesive film was excellent, compared to Example 43, the durability of the adhesive film was excellent, and the adhesive strength was excellent.

In addition, Examples 1, 4 and 5 satisfying the weight average molecular weight of the second adhesive resin. Compared to Example 44, which did not satisfy this, moisture removal and blocking were more efficient, so that the moisture penetration length was short, there was little volume expansion of the adhesive film, and the durability of the adhesive film was excellent, and the durability of the adhesive film compared to Example 45. This was excellent and the adhesion was excellent.

In addition, Examples 1, 6, and 7 satisfying R ¹ of the second adhesive resin of the present invention were more efficient in removing and blocking water than in Example 46, which did not satisfy this, and thus the moisture penetration length was short. , There was almost no volume expansion of the adhesive film.

Example 47

An organic electronic device was prepared in the same manner as in Example 1, but unlike Example 1, a metal sheet having a surface energy of 40 mN/cm and a second adhesive layer laminated with the metal sheet had a contact angle of 74.8° with deionized water. An encapsulant for use was prepared.

Example 48

An organic electronic device was prepared in the same manner as in Example 1, but unlike Example 1, a metal sheet having a surface energy of 38 mN/cm and a second adhesive layer laminated with the metal sheet had a contact angle of 76.4° with deionized water. An encapsulant for use was prepared.

Comparative Example 1

An organic electronic device was prepared in the same manner as in Example 1, but unlike Example 1, a metal sheet having a surface energy of 30 mN/cm and a second adhesive layer laminated with the metal sheet had a contact angle of 79.3° with deionized water. An encapsulant for use was prepared.

<Experimental Example 3>

Evaluation of adhesion between the adhesive film of the encapsulant for organic electronic devices and the metal sheet of the encapsulant for organic electronic devices

The encapsulants for organic electronic devices prepared in Examples 1, 47, 48 and Comparative Example 1 were cut into a width of 30 mm and a length of 100 mm. Thereafter, the back side PET film attached to the adhesive film of the organic electronic device encapsulant was removed, and the adhesive film side from which the back side PET film was removed was laminated to a glass at 50. Then, it was allowed to stand for 30 minutes, and the adhesion between the adhesive film of the sealing material for organic electronic devices and the metal sheet of the sealing material for organic electronic devices was evaluated through a universal material testing machine (UTM), and is shown in Table 9 below. The glass is fixed to the jig, and the metal sheet of the encapsulant for organic electronic devices is bitten into the upper jig and held with a force of 5mm/sec.)

As can be seen in Table 9, the sealing material for an organic electronic device prepared in Example 1 was prepared in Examples 47 and 48 and Comparative Example 1 in terms of adhesion between the adhesive film of the sealing material for an organic electronic device and the metal sheet of the sealing material for an organic electronic device. It was confirmed that it is significantly better than the organic electronic device encapsulant.

A simple modification or change of the present invention can be easily implemented by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (16)

Metal sheet; And an adhesive film formed on one surface of the metal sheet. Including,
An encapsulant for an organic electronic device, characterized in that it satisfies both the following conditions (1) and (2);
(1) 0.93 mN/cm° ≤

≤ 1.07 mN/cm°
(2) 32 mN/cm ≤ X ≤ 65 mN/cm
In the above conditions (1) and (2), X is the surface energy (mN/cm) of the metal sheet, and Y is the contact angle of deionized water (°) of the adhesive film.
The method of claim 1,
The metal sheet has a surface roughness of 0.1 μm to 2.0 μm Ra, 30 μm to 200 μm Rsm, and 0.5 μm to 6.0 μm Rz.
The method of claim 1,
The metal sheet is iron (Fe), bismuth (Bi), tin (Sn), indium (In), silver (Ag), copper (Cu), zinc (Zn), antimony (Sb), nickel (Ni), and these An encapsulant for an organic electronic device comprising at least one selected from among the alloys of.
The method of claim 1,
The adhesive film includes a mixed resin, a tackifier and a moisture absorbent,
The mixed resin comprises a first adhesive resin and a second adhesive resin in a weight ratio of 1: 0.1 to 10. An encapsulant for an organic electronic device.
The method of claim 4,
The first adhesive resin comprises a random copolymer having a weight average molecular weight of 30,000 to 1,550,000 copolymerized with ethylene, propylene and a diene-based compound,
The second adhesive resin is an encapsulant for an organic electronic device, characterized in that it contains a compound represented by the following formula (1);
[Formula 1]

In Formula 1, R ¹ is a straight chain alkenyl group of C3 to C10 or a pulverized alkenyl group of C4 to C10, and n is a rational number that satisfies the weight average molecular weight of the compound represented by Formula 1 30,000 to 1,550,000.
The method of claim 5,
The ethylene and propylene are randomly copolymerized in a weight ratio of 1: 0.3 to 1.4,
The diene-based compound is an encapsulant for an organic electronic device comprising 2 to 15% by weight based on the total weight of the random copolymer.
The method of claim 1,
The adhesive film includes a first adhesive layer; And a second adhesive layer formed on one surface of the first adhesive layer.
The method of claim 7,
The first adhesive layer includes a first mixed resin, a tackifier and a first absorbent,
The first mixed resin contains the first adhesive resin and the second adhesive resin in a weight ratio of 1: 0.1 to 10,
The tackifier contains 50 to 300 parts by weight based on 100 parts by weight of the first mixed resin,
The first moisture absorbent is an organic electronic device encapsulant comprising 1 to 40 parts by weight based on 100 parts by weight of the first mixed resin.
The method of claim 8,
The tackifier comprises a first tackifier and a second tackifier in a weight ratio of 1: 0.5 to 1.5,
The softening point of the first tackifier is smaller than that of the second tackifier,
The first moisture absorbent is a sealing material for an organic electronic device, characterized in that it contains silica (SiO ₂ ).
The method of claim 8,
The first adhesive layer further comprises at least one of a curing agent and a UV initiator,
The curing agent contains 2 to 30 parts by weight based on 100 parts by weight of the first mixed resin,
The UV initiator is an encapsulant for an organic electronic device comprising 0.1 to 5 parts by weight based on 100 parts by weight of the first mixed resin.
The method of claim 8,
The first adhesive layer has a viscosity of 10,000 to 150,000 Pa·s (50° C.).
The method of claim 7,
The second adhesive layer comprises a second mixed resin, a tackifier and a second absorbent,
The second mixed resin includes the first adhesive resin and the second adhesive resin in a weight ratio of 1: 0.1 to 10,
The tackifier contains 60 to 300 parts by weight based on 100 parts by weight of the second mixed resin,
The second moisture absorbent is an organic electronic device encapsulant comprising 50 to 450 parts by weight based on 100 parts by weight of the second mixed resin.
The method of claim 12,
The tackifier comprises at least one selected from hydrogenated petroleum resin, hydrogenated rosin resin, hydrogenated rosin ester resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, polymerized rosin resin, and polymerized rosin ester resin,
The second absorbent is an organic electronic device encapsulant, characterized in that it contains calcium oxide (CaO).
The method of claim 12,
The second adhesive layer further comprises at least one of a curing agent and a UV initiator,
The curing agent contains 10 to 40 parts by weight based on 100 parts by weight of the second mixed resin,
The UV initiator is an encapsulant for an organic electronic device, comprising 0.1 to 8 parts by weight based on 100 parts by weight of the second mixed resin.
The method of claim 12,
The second adhesive layer has a viscosity of 200,000 to 1,000,000 Pa·s (50° C.).
Board;
An organic electronic device formed on at least one surface of the substrate; And
A light emitting device comprising a; encapsulant for an organic electronic device according to any one of claims 1 to 15 for packaging the organic electronic device.

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