KR20200050217A - Adhesive film for organic electronic device and encapsulation member comprising the same - Google Patents

Abstract

The present invention relates to an adhesive film for an organic electronic device and an encapsulant for an organic electronic device, comprising the same and, more specifically, to an adhesive film for an organic electronic device, which removes defective sources such as moisture and impurities to block access to the organic electronic device, does not cause interlayer delamination when moisture is removed, is excellent in moisture resistance and heat resistance while being excellent in processability by preventing overflow, and does not cause panel warpage, and to an encapsulant for an organic electronic device, comprising the same.

Description

Adhesive film for organic electronic devices and encapsulation material for organic electronic devices comprising the same {Adhesive film for organic electronic device and encapsulation member comprising the same}

The present invention relates to an adhesive film for an organic electronic device and an encapsulant for an organic electronic device including the same, and more specifically, to remove and block the organic electronic device from accessing a defective source of moisture, impurities, etc. There is no interlayer delamination that can occur when it is removed, excellent moisture resistance and heat resistance, and at the same time, overflow is prevented, processability is excellent, and the adhesive film for organic electronic devices that has the effect of not causing the warpage of the panel and containing the same It relates to a sealing material for an organic electronic device.

An organic light emitting diode (OLED) is a light emitting diode in which a light emitting layer is made of a thin film of an organic compound, and uses an electroluminescence phenomenon that generates light by passing a current through a fluorescent organic compound. These organic light-emitting diodes generally implement the main colors in the three-color (Red, Green, Blue) independent pixel method, bio-conversion method (CCM), and curly filter method, depending on the amount of organic material contained in the light emitting material used Accordingly, it is classified into a low molecular organic light emitting diode and a high molecular organic light emitting diode. In addition, it can be divided into a passive driving method and an active driving method according to the driving method.

The organic light emitting diode has characteristics such as high efficiency, low voltage driving, and simple driving by self-emission, and thus has an advantage of expressing a high-quality video. In addition, application to flexible displays and organic electronic devices using flexible properties of organic materials is also expected.

The organic light emitting diode is manufactured by stacking an organic compound as a light emitting layer 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 by external exposure or moisture and oxygen penetration. The deterioration of the organic material affects the light emission characteristics of the organic light emitting diode and shortens the life. In order to prevent this phenomenon, a thin film encapsulation process is required to prevent oxygen, moisture, etc. from entering the inside of the organic electronic device.

Conventionally, a metal can or glass is processed into a cap shape to have a groove, and a desiccant for water absorption is mounted in the groove in a powder form, but this method removes the sealed organic electronic device to a desired level for moisture permeation. It blocks organic and electronic devices from access to poor sources of moisture, impurities, etc., and does not cause interlayer delamination, which can occur when moisture is removed. , There was a problem in that it was difficult to achieve all the effects of not causing the panel warpage.

KR 10-2006-0030718 A

The present invention has been devised to solve the above problems, and the problem to be solved of the present invention is to prevent and remove the defective source material such as moisture and impurities from accessing the organic electronic device, and may occur when moisture is removed. There is no interlayer delamination, excellent moisture resistance and heat resistance, and at the same time, overflow is prevented, processability is excellent, and the adhesive film for organic electronic devices has the effect of not causing the bending of the panel and a bag for organic electronic devices including the same It is about ash.

In order to solve the above-described problems, the present invention includes an adhesive layer formed of a mixed resin including a first adhesive resin and a second adhesive resin, an adhesive agent including a first adhesive agent, and a hygroscopic agent, wherein the adhesive layer is It provides an adhesive film for an organic electronic device that satisfies both of the following conditions (1) and (2).

(1) After cutting the adhesive layer having a thickness of 50 µm into a circle with a diameter of 6 mm, the rate of change in diameter with respect to the initial diameter of ± 10 was measured after performing a hot press process for 60 seconds under the condition of a temperature of 50 ° C and a load of 4 kg. % Below,

(2) The rate of change in diameter with respect to the diameter of the adhesive layer before the heat treatment is ± 10% or less, measured during the heat treatment of the adhesive layer subjected to the hot press process at a temperature of 100 ° C. for 2.5 hours.

According to a preferred embodiment of the present invention, the adhesive layer may satisfy both of the following conditions (1) and (2).

(1) After cutting the adhesive layer having a thickness of 50 µm into a circle with a diameter of 6 mm, the rate of change in diameter with respect to the initial diameter of ± 8 was measured after performing a hot press process for 60 seconds at a temperature of 50 ° C and a load of 4 kg. % Below

(2) The rate of change in diameter with respect to the diameter of the adhesive layer before the heat treatment is ± 8% or less, measured during the heat treatment of the adhesive layer subjected to the hot press process at a temperature of 100 ° C. for 2.5 hours.

In addition, the first adhesive resin has a weight average molecular weight of 30,000 ~ 1,550,000, may include a random copolymer copolymerized with ethylene, propylene and diene compounds, the second adhesive resin is a compound represented by the formula (1) It can contain.

[Formula 1]

In Chemical Formula 1, R ¹ is a hydrogen atom or a C3 to C10 straight-chain alkenyl group or a C4 to C10 pulverized alkenyl group, and n is a compound satisfying the weight average molecular weight of 30,000 to 1,550,000 of Formula 1 It is rational.

In addition, the ethylene and propylene may be randomly copolymerized in a weight ratio of 1: 0.3 to 1.4, and the diene-based compound may be included in 2 to 15% by weight based on the total weight of the random copolymer.

In addition, the curing agent may further contain 2 to 50 parts by weight based on 100 parts by weight of the mixed resin.

In addition, the curing agent may include one or more selected from the group consisting of a urethane acrylate-based curing agent and an acrylate-based curing agent having a weight average molecular weight of 100 to 1500.

In addition, the UV initiator may further contain 0.1 to 10 parts by weight based on 100 parts by weight of the mixed resin.

In addition, the glass adhesive strength measured according to the following measurement method 1 may be 1500 gf / 25 mm or more, and the metal adhesive strength measured according to the measurement method 2 below may be 1000 gf / 25 mm or more.

[Measurement method 1]

The adhesive force measuring tape was laminated to the upper surface of the adhesive film, the sample was cut to a width of 25 mm and a length of 120 mm, and the lower surface of the adhesive film was laminated to glass at 80 ° C., and the prepared sample was left at room temperature for 30 minutes, and 300 mm / min. Measures the glass adhesion at speed.

[Measurement method 2]

The upper surface of the adhesive film was laminated to a Ni alloy having a thickness of 80 μm at 80 ° C., the adhesive force measuring tape was laminated to the lower surface of the adhesive film, the sample was cut 25 mm wide and 120 mm long, and the prepared sample was left at room temperature for 30 minutes, Metal adhesion is measured at a speed of 300 mm / min.

In addition, the mixed resin may include a first mixed resin and a second mixed resin, the adhesive layer is a first adhesive layer comprising a first mixed resin; And a second adhesive layer formed on one surface of the first adhesive layer and including a second mixed resin.

In addition, the first adhesive layer may further include a second adhesive agent.

Further, the first adhesive layer may include 50 to 300 parts by weight of an tackifier with respect to 100 parts by weight of the first mixed resin, and the second adhesive layer may contain 60 to 300 parts by weight of a tackifier with respect to 100 parts by weight of the second mixed resin. It may contain 300 parts by weight.

In addition, the first adhesive layer may further include 2 to 30 parts by weight of a curing agent with respect to 100 parts by weight of the first mixed resin, and the second adhesive layer 10 to 40 with a curing agent relative to 100 parts by weight of the first mixed resin. It may further include by weight.

In addition, the present invention provides a sealing material for an organic electronic device comprising the adhesive film for the organic electronic device.

In addition, the present invention is a substrate; An organic electronic device formed on at least one surface of the substrate; And a sealing material for the organic electronic device packaging the organic electronic device.

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

The hygroscopic agent, which is a term used in the present invention, can adsorb moisture by physical or chemical bonding such as the van der Waals force and the interface of the hygroscopic agent. It contains all of the water-absorbing material that absorbs moisture and changes into a new material.

The adhesive film for an organic electronic device of the present invention is removed and blocked to prevent access to a defective material such as moisture and impurities to the organic electronic device, and there is no interlayer peeling phenomenon that may occur when the moisture is removed, moisture resistance and heat resistance At the same time, the overflow is prevented, the processability is excellent, and there is an effect that the panel is not warped.

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

Hereinafter, the present invention will be described in more detail.

As described above, the substrate of the glass material used to encapsulate the organic electronic device has been in the trend of replacing with a substrate of a metal material due to its low strength, and this method removes the moisture to the desired level with the sealed organic element, It blocks organic and electronic devices from access to poor sources of moisture, impurities, etc., does not cause interlayer delamination that can occur when moisture is removed, has excellent moisture resistance and heat resistance, and is excellent in processability by preventing overflow. And, there is a problem that it is difficult to simultaneously have the effect of not causing the bending of the panel.

Accordingly, the present invention includes an adhesive layer formed of a mixed resin comprising a first adhesive resin and a second adhesive resin, an adhesive agent comprising a first adhesive agent and a hygroscopic agent, wherein the adhesive layer comprises the following conditions (1) and An adhesive film for an organic electronic device that satisfies all the conditions (2) was provided to find a solution to the above-described problem.

Through this, unlike the conventional invention, oxygen, impurities, and moisture can be blocked, and at the same time, moisture that is absorbed can be effectively removed to prevent the moisture from reaching the organic electronic device, thereby significantly improving the life and durability of the organic electronic device. It can be, and when the moisture is removed, the interlayer peeling phenomenon that does not occur, the moisture resistance and heat resistance is excellent, the overflow is prevented, the processability is excellent, and the effect of not causing the warpage of the panel can be simultaneously achieved. .

Specifically, Figure 1 is a cross-sectional view of an adhesive film for an organic electronic device according to a preferred embodiment of the present invention, the organic electronic device adhesive film 10 is a mixed resin (15b) comprising a first adhesive resin and a second adhesive resin ), An adhesive layer 15 formed of a tackifier containing a first adhesive agent and a hygroscopic agent 15a, a release film for supporting and protecting the adhesive film 10 for the organic electronic device, etc. The base films 13 and 14 may be further included.

In addition, according to a preferred embodiment of the present invention, the adhesive film 10 for an organic electronic device of the present invention has a multi-layer structure, as shown in FIG. 2, a first adhesive layer 11 and one surface of the first adhesive layer 11 It may include a second adhesive layer (12) formed on, the first adhesive layer (11) and the second adhesive layer 12 to support and protect the base film (13, 14), such as a release film for the first adhesive layer ( 11) may be further included in the lower portion or the upper portion of the second adhesive layer 12. In this case, the first adhesive layer 11 is a layer that directly contacts an organic electronic device (not shown), and includes a first adhesive resin and a second adhesive resin, including a first mixed resin 11b and a first adhesive agent. It may include a tackifier and a first absorbent (11a) comprising, the second adhesive layer 12 may be formed on one surface of the first adhesive layer 11, the first adhesive resin and the second adhesive resin It may include a second mixed resin (12b), a tackifier comprising a first adhesive and a second absorbent (12a).

Before explaining each component included in the adhesive film 10 for an organic electronic device according to the present invention, the reason why the adhesive layer 15 included in the adhesive film for an organic electronic device of the present invention should satisfy the following conditions First explained.

If the diameter increase is large after the hot press process is performed on the adhesive film 10 for an organic electronic device, air bubbles may be generated and / or reliability may decrease as overflow occurs, and processability such as equipment contamination may deteriorate. Problems can occur. In addition, when the diameter reduction of the adhesive layer is large after performing the hot press process, the panel may be warped. In addition, if the diameter of the adhesive layer is large when heat-treating the adhesive layer that has undergone the hot press process, air bubbles may be generated and / or reliability may be deteriorated as overflow occurs, and curing density may be low. In addition, when the diameter of the adhesive layer is largely reduced during heat treatment, reliability may be deteriorated and warpage of the panel may occur.

Accordingly, the adhesive layer included in the adhesive film for the organic electronic device should exhibit an appropriate diameter change rate as in the following conditions (1) and (2). The adhesive film for an organic electronic device according to the present invention satisfies both of the following conditions (1) and (2) in order to solve this problem.

As condition (1), the adhesive layer having a thickness of 50 µm was cut into a circle with a diameter of 6 mm, and after performing a hot press process for 60 seconds under a condition of 50 ° C and a load of 4 kg, the rate of change in diameter with respect to the initial diameter was ± 10% or less, preferably, the rate of change of diameter may be ± 8% or less, and as condition (2), the diameter of the adhesive layer before heat treatment, measured during heat treatment of the adhesive layer subjected to the hot press process at a temperature of 100 ° C. for 2.5 hours The rate of change of the diameter with respect to is ± 10% or less, preferably, the rate of change of the diameter may be ± 8% or less.

If, under the condition (1), after performing the hot press process, if the diameter change rate exceeds + 10%, bubbles may be generated and / or reliability may be deteriorated as overflow occurs, and equipment may be contaminated. A problem such as deterioration in fairness may occur, and when the rate of change in diameter is less than -10%, warping of the panel may occur. In addition, if the rate of change in diameter with respect to the diameter of the adhesive layer before heat treatment exceeds 10%, measured during heat treatment under the condition (2), bubbles may be generated and / or reliability may decrease as overflow occurs. The curing density may be low, and if the rate of change in diameter is less than -10%, reliability may be deteriorated, and panel warpage may occur.

On the other hand, the hot press process may be performed by applying a load to the upper and lower surfaces of the adhesive layer having a diameter of 6 mm and cut into a circle with a thickness of 50 μm, and the heat treatment is performed for 2.5 hours in an oven at a temperature of 100 ° C. Heat treatment may be.

Hereinafter, each configuration included in the adhesive film for an organic electronic device will be described in detail.

First, a single layer comprising an adhesive film 10 for an organic electronic device comprising a first adhesive resin and a second adhesive resin, a mixed resin 15b, a first adhesive agent, and an adhesive agent and a hygroscopic agent 15a. The case where the adhesive layer 15 of a structure is provided is demonstrated.

First, the mixed resin 15b included in the adhesive layer 15 according to the present invention has a first adhesive resin and a second adhesive resin in a weight ratio of 1: 0.1 to 10, preferably in a weight ratio of 1: 1 to 9 It can contain. If the weight ratio of the first adhesive resin and the second adhesive resin is less than 1: 0.1, reliability may be deteriorated. If the weight ratio exceeds 1: 10, elasticity of the adhesive layer may decrease.

The first adhesive resin includes a random copolymer in which ethylene, propylene and diene compounds are copolymerized. The ethylene and propylene may be randomly copolymerized in a weight ratio of 1: 0.3 to 1.4, preferably in a weight ratio of 1: 0.5 to 1.2. If the weight ratio of the copolymerized ethylene and propylene 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 results in deterioration of adhesion at a low temperature and adhesion to a substrate and elasticity decreases It may adversely affect the volume expansion of the absorbent according to, and if the weight ratio exceeds 1: 1.4, panel deflection may occur due to a decrease in modulus and hardness, and the deterioration of mechanical properties leads to a decrease in mechanical properties of the product. The problem of reliability decreases due to the difficulty of high filling.

In addition, the diene-based compound may be included in 2 to 15% by weight, preferably 7 to 11% by weight relative to the total weight of the random copolymer. If the diene-based compound is less than 2% by weight, it may cause a panel sagging problem due to a lower modulus due to a low curing rate and a curing density, heat resistance may deteriorate, and it is described by volume expansion of a moisture absorbent due to a decrease in elasticity. Wake-up may occur, and if it exceeds 15% by weight, the lack of wettability due to high cure density leads to a decrease in adhesive strength with the substrate, a decrease in compatibility between resins, and a decrease in panel adhesion due to high modulus, and yellowing by heat It may cause phenomenon.

Meanwhile, the first adhesive resin may have a weight average molecular weight of 30,000 to 1,550,000, 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, adhesion to the substrate may be reduced due to a decrease in wettability, adhesion to a panel may be deteriorated, reliability may be deteriorated, and panel warpage may occur. Can occur. In addition, if the weight average molecular weight exceeds 1,550,000, panel sagging may occur, heat resistance may deteriorate, reliability may deteriorate as the filling property of the hygroscopic agent decreases, mechanical properties may deteriorate, and over As the flow (Over Flow) occurs, air bubbles may be generated and / or reliability may be reduced, processability such as equipment contamination may be deteriorated, and curing density may be low.

In addition, the second adhesive resin includes a compound represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1, R ¹ may be a hydrogen atom or a C3 to C10 straight alkenyl group or a C4 to C10 pulverized alkenyl group, preferably R ¹ is a hydrogen atom or a C4 to C8 straight alkenyl group Or it may be a C4 ~ C8 pulverized alkenyl group. Reliability may be more excellent as R ¹ is a hydrogen atom or a C3 to C10 straight-chain alkenyl group or C4 to C10 a pulverized alkenyl group.

In addition, the n may be a rational number that satisfies the weight average molecular weight of 30,000 to 1,550,000 of the compound represented by Formula 1, preferably a rational number that satisfies the weight average molecular weight of 40,000 to 1,500,000 of the compound represented by Formula 1. If the weight average molecular weight of the compound represented by Formula 1 is less than 30,000, adhesion to a substrate may be reduced due to a decrease in wettability, adhesion to a panel may be reduced, reliability may be reduced, and Warpage may occur. When the weight average molecular weight exceeds 1,550,000, panel sagging may occur, heat resistance may decrease, reliability may deteriorate as the filling property of the hygroscopic agent decreases, mechanical properties may deteriorate, and overflow (Over As flow occurs, air bubbles may be generated and / or reliability may be deteriorated, processability such as equipment contamination may be deteriorated, curing density may be low, and excitation with a substrate due to volume expansion of a moisture absorbent due to elasticity deterioration may occur. Symptoms may occur.

Next, the tackifier containing the first tackifier is described.

The tackifier may be used without limitation as long as it is a pressure-sensitive resin commonly used in adhesive films for organic electronic devices, and preferably each independently hydrogenated petroleum resin, hydrogenated rosin resin, hydrogenated rosin ester resin, hydrogenated terpene resin, hydrogenated terpene One or more selected from phenol resin, polymerized rosin resin and polymerized rosin ester resin can be used.

The adhesive layer 15 may include 50 to 300 parts by weight, preferably 80 to 280 parts by weight, of the tackifier with respect to 100 parts by weight of the aforementioned mixed resin. If the tackifier is less than 50 parts by weight with respect to 100 parts by weight of the first mixed resin, a problem with poor moisture resistance may occur, and if the tackifier exceeds 300 parts by weight, durability and resistance to brittleness of the adhesive layer The problem of deteriorating wetness may occur.

Next, the hygroscopic agent 15a will be described.

The hygroscopic agent may be a hygroscopic agent contained in an encapsulant that is commonly used for packaging organic electronic devices, preferably a single or two types of absorbents, metal salts, metal oxides, etc., composed of zeolite, titania, zirconia, or montmorillonite. It can be used by mixing, and more preferably, a metal oxide can be used, and more preferably, calcium oxide can be used among the metal oxides.

The metal oxide is 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) ) Or an organic metal oxide or phosphorus pentoxide (P ₂ O ₅ ), alone or in combination of two or more.

In addition, the metal salt is 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 ), sulfates such as titanium sulfate (Ti (SO ₄ ) ₂ ) or nickel sulfate (NiSO ₄ ), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium chloride (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 ), Metal halide or barium perchlorate (Ba (ClO ₄ ) ₂ ) such as selenium bromide (SeBr ₄ ), vanadium bromide (VBr ₃ ), magnesium bromide (MgBr ₂ ), barium iodide (BaI ₂ ) or magnesium iodide (MgI ₂ ), etc. Alternatively, a metal chlorate such as magnesium perchlorate (Mg (ClO ₄ ) ₂ ) or the like may be used alone or in combination of two or more.

The second hygroscopic agent 15a may preferably have a purity of 95% or more. If the purity is less than 95%, not only the water absorption function is lowered, but also the substance contained in the hygroscopic agent 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 adhesive layer 15 may include 10 to 550 parts by weight of the hygroscopic agent 15a, preferably 20 to 520 parts by weight based on 100 parts by weight of the above-mentioned mixed resin. If the hygroscopic agent is less than 10 parts by weight based on 100 parts by weight of the mixed resin, the durability of the organic electronic device is lowered, and the desired adhesive film cannot be implemented such as the water removal effect is remarkably reduced. If the hygroscopic agent exceeds 550 parts by weight, wettability Due to the lack of adhesion between the adhesive film and the organic electronic device, poor adhesion, such as adhesion, the reliability of the organic electronic device decreases, and when moisture is absorbed, the life of the organic electronic device is shortened due to the lifting phenomenon due to excessive volume expansion. Problems may arise.

On the other hand, as the average particle size and shape of the hygroscopic agent 15a may be the same as the commonly used hygroscopic agent in the art, the present invention is not particularly limited.

According to a preferred embodiment of the present invention, the adhesive layer 15 may further include 2 to 50 parts by weight of the curing agent, preferably 5 to 40 parts by weight based on 100 parts by weight of the mixed resin. If the curing agent is included in an amount of less than 2 parts by weight, elasticity may deteriorate, mechanical properties may deteriorate, and bubble generation and / or reliability may deteriorate as overflow occurs. Process may be deteriorated, such as contamination of equipment, and curing density may be low. In addition, if the content of the curing agent exceeds 50 parts by weight, there may be a problem of poor adhesion of the panel, poor adhesion due to deterioration of wettability, reliability may be deteriorated, and bending of the panel may occur.

The curing agent may be used without limitation as long as it can be used as a curing agent, preferably, a material capable of securing a sufficient crosslinking density of the adhesive film by acting as a crosslinking agent, more preferably urethane acrylate System curing agents and acrylate-based curing agents.

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 may decrease due to an increase in hardness, and an outgas problem of the unreacted curing agent may occur, and if the weight average molecular weight exceeds 1500, softenability The problem of deteriorating mechanical properties may occur due to an increase in (Softness).

In addition, according to a preferred embodiment of the present invention, the adhesive layer 15 may further include 0.1 to 10 parts by weight of UV initiator, 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, a problem may arise in that heat resistance is poor due to poor UV curing, and when it is included in excess of 10 parts by weight, a problem in heat resistance due to deterioration in curing density may occur. .

 The UV initiator can be used without limitation, as long as it is commonly used as a UV initiator, preferably mono acyl phosphine, bis acyl phosphine, α-hydroxyketone ), α-amino ketone (α-Aminoketone), phenyl glyoxylate (Phenylglyoxylate), benzyl dimethyl-ketal (Benzyldimethyl-ketal) can be used at least one selected from.

On the other hand, the adhesive layer 15 included in the adhesive film 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 a viscosity of 120,000 to 280,000 Pa · s (50 ° C). ). If the viscosity of the adhesive layer 15 is less than 100,000 Pa · s (50 ° C.), the processability becomes poor due to an increase in the tack, and a problem that the release film cannot be peeled off may occur, and the viscosity is 300,000 Pa · s If it exceeds (50 ° C), a problem in that the adhesive strength with the substrate decreases may occur due to a decrease in tack.

The viscosity may be a viscosity measured by a conventional viscosity measuring method, preferably, the samples are laminated to a thickness of 800 to 900 μm, and after being punched into a circle having a diameter of 8 mm, viscosity measuring equipment (ARES-G2, TA) The sample can be placed on a plate and measured. At this time, the measurement conditions are 5% strain (strain), axial force (Axial Force) 0.05N, Sensitivity (Sensitivity) 0.005N, 1 rad / s, -5 ℃ ~ 130 ℃ can be measured, the axial direction before measurement Measurement may 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.

On the other hand, when the adhesive layer 15 of a single-layer structure is provided, the adhesive film 10 for an organic electronic device of the present invention has a glass adhesive strength measured according to the following measuring method 1 of 1500 gf / 25 mm or more, preferably 1600 gf / 25mm or more.

[Measurement method 1]

After laminating the adhesive force measuring tape (7475, TESA) on the top of the adhesive film through a hand roller (2Kg Hand Roller), cutting the sample to a width of 25 mm and a length of 120 mm, and laminating the bottom 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 layer 15 having a single-layer structure is provided, the adhesive film 10 for an organic electronic device of the present invention has a metal adhesive strength measured according to the following measurement method 2 of 1000 gf / 25 mm or more, preferably 1100 gf / 25mm or more.

[Measurement method 2]

The upper surface of the adhesive film was laminated to a Ni alloy having a thickness of 80 μm at 80 ° C., and the adhesive force measuring tape (7475, TESA) was laminated to the lower surface of the adhesive film through a hand roller (2Kg Hand Roller) to sample 25 mm in width and 120 in length. After ㎜ cutting, the prepared sample was left at room temperature for 30 minutes, and 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 remarkably lowered when applied to the organic electronic device.

Next, a case where the adhesive film 10 for an organic electronic device is provided with a multi-layered adhesive layer including a first adhesive layer 11 and a second adhesive layer 12 formed on one surface of the first adhesive layer will be described. .

At this time, the description of the same content as the case of providing the above-described single layer adhesive layer will be omitted and described.

First, the first adhesive layer 11 in direct contact with the organic light emitting device will be described.

The tackifier included in the first adhesive layer 11 may include a first adhesive tackifier. In addition, the tackifier included in the first adhesive layer 11 may further include a second adhesive.

The first adhesive agent and the second adhesive agent may be used without limitation as long as they are adhesive agents commonly used in adhesive films for organic electronic devices. Preferably, adhesive agents capable of improving trust can be used. , More preferably, each independently, one or more 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 can be used, and further Preferably, a hydrogenated petroleum resin having a different softening point can be used. For example, when a hydrogenated petroleum resin having a different softening point is used, the softening point of the first adhesive agent may be smaller than the softening point of the second adhesive agent, but is not limited thereto.

The tackifier may include the first tackifier and the second tackifier in a weight ratio of 1: 0.5 to 1.5, preferably 1: 0.6 to 1.4. If the weight ratio of the first adhesive agent and the second adhesive agent is less than 1: 0.5, a problem in that the heat-resistance retention force may decrease, and when the weight ratio exceeds 1: 1.5, the adhesive force with the substrate due to adhesion and wettability decrease Degradation problems may occur.

Meanwhile, the first adhesive layer 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. If the tackifier is less than 50 parts by weight with respect to 100 parts by weight of the first mixed resin, a problem with poor moisture resistance may occur, and if the tackifier exceeds 300 parts by weight, durability due to brittleness of the first adhesive layer And a problem in that moisture resistance is lowered.

The hygroscopic agent of the first adhesive layer 11 included in the adhesive film according to the present invention, that is, the first hygroscopic agent 11a, can be used without limitation as long as it is a material that can be used as a hygroscopic agent, and preferably silica. As silica is used as the first absorbent 11a, water removal performance is excellent, separation of the organic electronic device from the encapsulant can be prevented, and durability of the organic electronic device can be significantly increased.

On the other hand, according to a preferred embodiment of the present invention, the first absorbent (11a) contained in the first adhesive layer is 1 to 40 parts by weight based on 100 parts by weight of the first mixed resin, preferably 5 to 35 parts by weight can do. If the first absorbent (11a) is contained in less than 1 part by weight, there is a problem that the durability of the organic electronic device may be deteriorated because it is impossible to achieve a moisture removal effect in the desired first adhesive layer, and it exceeds 40 parts by weight. If included, there may be a problem that reliability of the organic electronic device is deteriorated due to poor adhesion such as adhesion and adhesion between the adhesive film and the organic electronic device due to lack of wettability.

On the other hand, since the average particle size and shape of the first absorbent 11a may be the same as a commonly used absorbent, a detailed description thereof will be omitted.

Meanwhile, according to a preferred embodiment of the present invention, the first adhesive layer 11 may further include 0.1 to 5 parts by weight of UV initiator, preferably 0.5 to 4 parts by weight, with respect to 100 parts by weight of the first mixed resin. have. If the UV initiator is included in an amount of less than 0.1 parts by weight, a problem may arise in that heat resistance is poor due to poor UV curing, and when it is included in an amount exceeding 5 parts by weight, a problem in heat resistance due to deterioration in curing density may occur. .

 The UV initiator can be used without limitation, as long as it is commonly used as a UV initiator, preferably mono acyl phosphine, bis acyl phosphine, α-hydroxyketone ), α-amino ketone (α-Aminoketone), phenyl glyoxylate (Phenylglyoxylate), benzyl dimethyl-ketal (Benzyldimethyl-ketal) can be used at least one selected from.

According to a preferred embodiment of the present invention, the first adhesive layer 11 may further include 2 to 30 parts by weight, preferably 5 to 25 parts by weight, with respect to 100 parts by weight of the first mixed resin. If the curing agent is included in an amount of less than 2 parts by weight, elasticity may deteriorate, mechanical properties may deteriorate, and bubble generation and / or reliability may deteriorate as overflow occurs. Process may be deteriorated, such as contamination of equipment, and curing density may be low. In addition, if it exceeds 30 parts by weight, there may be a problem of deterioration of adhesion due to poor adhesion of panels and deterioration of wettability, reliability may be deteriorated, and bending of the panel may occur.

The curing agent may be used without limitation as long as it can be used as a curing agent, preferably, a material capable of securing a sufficient crosslinking density of the adhesive film by acting as a crosslinking agent, more preferably urethane acrylate System curing agents and acrylate-based curing agents.

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 may decrease due to an increase in hardness, and an outgas problem of the unreacted curing agent may occur, and if the weight average molecular weight exceeds 1500, softenability The problem of deteriorating mechanical properties may occur due to an increase in (Softness).

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

The viscosity may be a viscosity measured by a conventional viscosity measuring method, preferably, the samples are laminated to a thickness of 800 to 900 μm, and after being punched into a circle having a diameter of 8 mm, viscosity measuring equipment (ARES-G2, TA) The sample can be placed on a plate and measured. At this time, the measurement conditions are 5% strain (strain), axial force (Axial Force) 0.05N, Sensitivity (Sensitivity) 0.005N, 1 rad / s, -5 ℃ ~ 130 ℃ can be measured, the axial direction before measurement Measurement may 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.

Next, the second adhesive layer 12 formed on one surface of the first adhesive layer 11 described above will be described.

The tackifier included in the second adhesive layer 12 may include a first tackifier. Specific types of the first adhesive additive are omitted in the same manner as described above.

Meanwhile, 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. If the tackifier is less than 60 parts by weight with respect to 100 parts by weight of the second mixed resin, a problem with poor moisture resistance may occur, and if the tackifier exceeds 300 parts by weight, durability due to brittleness of the second adhesive layer And a problem in that moisture resistance is lowered.

The hygroscopic agent of the second adhesive layer 12 included in the adhesive film according to the present invention, that is, the second hygroscopic agent 12a, may be a hygroscopic agent included in a sealing material used for packaging organic electronic devices, preferably A zeolite, titania, zirconia, or montmorillonite as a component, a hygroscopic agent, a metal salt, or a metal oxide can be used alone or in combination of two or more, more preferably a metal oxide can be used, more preferably oxidation of the metal oxide Calcium can be used.

The metal oxide is a metal oxide such as silica (SiO ₂ ), alumina (Al ₂ O ₃ ), sodium oxide (Na ₂ O), barium oxide (BaO), calcium oxide (CaO) or magnesium oxide (MgO), or organic Metal oxide or phosphorus pentoxide (P ₂ O ₅ ) or the like may be used alone or in combination of two or more.

In addition, the metal salt is 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 ), sulfates such as titanium sulfate (Ti (SO ₄ ) ₂ ) or nickel sulfate (NiSO ₄ ), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium chloride (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 ), Metal halide or barium perchlorate (Ba (ClO ₄ ) ₂ ) such as selenium bromide (SeBr ₄ ), vanadium bromide (VBr ₃ ), magnesium bromide (MgBr ₂ ), barium iodide (BaI ₂ ) or magnesium iodide (MgI ₂ ), etc. Alternatively, a metal chlorate such as magnesium perchlorate (Mg (ClO ₄ ) ₂ ) or the like may be used alone or in combination of two or more, preferably calcium oxide. The second absorbent (12a) is preferably a purity of 95% or more, if the purity is less than 95%, as well as the water absorption function is lowered, the substance contained in the absorbent acts as an impurity may cause a defect in the adhesive film , As it can affect the organic electronic device, it is preferable to use a hygroscopic agent having a purity of 95% or more.

The second absorbent included in the second adhesive layer may be included in 50 to 450 parts by weight based on 100 parts by weight of the second mixed resin (12b), preferably 70 to 430 parts by weight. If the second absorbent is contained in less than 50 parts by weight with respect to 100 parts by weight of the second mixed resin, there may be a problem that a desired adhesive film cannot be realized, such as a significant reduction in moisture removal effect, and in excess of 450 parts by weight If the adhesive performance of the second adhesive layer 12 is significantly reduced, the first adhesive layer 11 and the second adhesive layer 12 and / or the second adhesive layer 12 and the first adhesive layer due to excessive volume expansion during moisture absorption There may be a problem in that the adhesive layer containing (11) floats on the organic electronic device and moisture rapidly penetrates therebetween to shorten the life of the organic electronic device.

Since the average particle size and shape of the second absorbent 12a may be the same as the absorbent generally used in the art, the present invention is not particularly limited.

Meanwhile, according to a preferred embodiment of the present invention, the second adhesive layer 12 may further include 0.1 to 8 parts by weight of UV initiator, preferably 0.5 to 6 parts by weight, based on 100 parts by weight of the second mixed resin. have. If the UV initiator is included in an amount of less than 0.1 parts by weight, a problem may arise in that heat resistance is poor due to poor UV curing, and when it is included in an amount exceeding 8 parts by weight, a problem in heat resistance due to deterioration in curing density may occur. .

 The UV initiator can be used without limitation, as long as it is commonly used as a UV initiator, preferably mono acyl phosphine, bis acyl phosphine, α-hydroxyketone ), α-amino ketone (α-Aminoketone), phenyl glyoxylate (Phenylglyoxylate), benzyl dimethyl-ketal (Benzyldimethyl-ketal) can be used at least one selected from.

According to a preferred embodiment of the present invention, the second adhesive layer 12 may further include 10 to 40 parts by weight, preferably 12 to 35 parts by weight, with respect to 100 parts by weight of the second mixed resin. If the curing agent is included in an amount of less than 10 parts by weight, elasticity may be deteriorated, mechanical properties may be deteriorated, and bubble generation and / or reliability may be deteriorated as overflow occurs. Process may be deteriorated, such as contamination of equipment, and curing density may be low. In addition, when the content exceeds 40 parts by weight, the adhesion of the panel may be deteriorated, the adhesive strength may decrease due to the decrease in wettability, reliability may be deteriorated, and the panel may be warped.

The curing agent may be used without limitation as long as it can be used as a curing agent, preferably, a material capable of securing a sufficient crosslinking density of the adhesive film by acting as a crosslinking agent, more preferably urethane acrylate System curing agents and acrylate-based curing agents.

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 may decrease due to an increase in hardness, and an outgas problem of the unreacted curing agent may occur, and if the weight average molecular weight exceeds 1500, softenability The problem of deteriorating mechanical properties may occur due to an increase in (Softness).

On the other hand, the second adhesive layer 12 included in the adhesive film 10 for an organic electronic device according to the present invention has a viscosity of 200,000 Pa · s (50 ° C.) or higher, preferably a viscosity of 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), the processability becomes poor due to an increase in the tack, which may cause a problem that the release film cannot be peeled off.

The viscosity may be a viscosity measured by a conventional viscosity measuring method, preferably, the samples are laminated to a thickness of 800 to 900 μm, and after being punched into a circle having a diameter of 8 mm, viscosity measuring equipment (ARES-G2, TA) The sample can be placed on a plate and measured. At this time, the measurement conditions can be measured with 5% strain, axial force 0.05N, sensitivity 0.005N, 1 rad / s, -5 ° C to 130 ° C, and axial direction before measurement Measurement may 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.

On the other hand, the first adhesive layer and the second adhesive layer may be an adhesive layer of a thickness that can be commonly applied when a multi-layered adhesive layer is included, and preferably, the first adhesive layer and the second adhesive layer are from 1: 0.3 to 17. As a thickness ratio, it may be preferably provided at a thickness ratio of 1: 0.33 to 15. If the thickness ratio of the first adhesive layer and the second adhesive layer is less than 1: 0.3, the reliability of the adhesive film for organic electronic devices may decrease, and when the thickness ratio exceeds 1: 17, the adhesive film for organic electronic devices A problem that the adhesion is lowered may occur.

When the adhesive film 10 for an organic electronic device according to the present invention is provided with an adhesive layer having a multi-layer structure including a first adhesive layer 11 and a second adhesive layer 12, the adhesive film for an organic electronic device of the present invention 10 ) May have an adhesive strength measured according to the following measurement method 1 of 1500 gf / 25 mm or more, and preferably 1600 gf / 25 mm or more.

[Measurement method 1]

After laminating the adhesive force measuring tape (7475, TESA) on the top of the adhesive film through a hand roller (2Kg Hand Roller), cutting the sample to a width of 25 mm and a length of 120 mm, and laminating the bottom 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 layer comprising a first adhesive layer 11 and a second adhesive layer 12 is provided, the adhesive film 10 for an organic electronic device of the present invention is a metal adhesive force measured according to the following measurement method 2 This may be 1000 gf / 25 mm or more, preferably 1100 gf / 25 mm or more.

[Measurement method 2]

The upper surface of the adhesive film was laminated to a Ni alloy having a thickness of 80 μm at 80 ° C., and the adhesive force measuring tape (7475, TESA) was laminated to the lower surface of the adhesive film through a hand roller (2Kg Hand Roller) to sample 25 mm in width and 120 in length. After ㎜ cutting, the prepared sample was left at room temperature for 30 minutes, and 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 remarkably lowered when applied to the organic electronic device.

On the other hand, when including the adhesive layer of the multi-layer structure including the above-described single-layer structure of the adhesive layer 15, the first adhesive layer 11 and the second adhesive layer 12, specifications such as size and thickness may vary depending on the purpose Accordingly, the present invention is not particularly limited to this.

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

In this case, the UV exposure may be performed using a mercury lamp under conditions of a light amount of 600 to 1000 mJ.

On the other hand, the present invention includes an encapsulant for an organic electronic device including an adhesive film for an organic electronic device according to the present invention, and includes a light emitting device including the 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 formed by providing a single layer structure adhesive layer 115 including a mixed resin 115b and a hygroscopic agent 115a as shown in FIG. 3. According to another preferred embodiment of the present invention, the light emitting device 100 of the present invention includes a first mixed resin 111b and a first absorbent 111a as illustrated in FIG. 4. It may be formed by providing an adhesive layer of a multi-layered structure including an adhesive layer 111 and a second adhesive layer 112 including a second mixed resin 112b and a second absorbent 112a.

Contents to be described below will be described based on the light emitting device 100 having the adhesive layer of the multilayer structure of FIG. 4.

In the light emitting device 100 according to the present invention, an organic electronic device 102 is formed on a substrate 101, at least one surface of the substrate 101, and organic electrons are formed on the substrate 101 and the organic electronic device 102. Device encapsulants 111 and 112 are formed. The organic electronic device encapsulant includes a first adhesive layer 111 including a first mixed resin 111b including a first adhesive resin and a second adhesive resin and a first absorbent 111a containing silica; And a second adhesive layer 112 formed on one surface of the first adhesive layer, the second adhesive resin 112b including the first adhesive resin and the second adhesive resin and the second absorbent 112a.

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 thins the lower electrode on the substrate 101 and sequentially stacks an n-type semiconductor layer, an active layer, a p-type semiconductor layer, and an upper electrode thereon. It can be formed by etching or after being manufactured through a separate substrate and then disposed on the substrate 101. The specific method of forming the organic electronic device 102 on the substrate 101 can be by a method commonly known in the art, and is not particularly limited in the present invention, and the organic electronic device 102 is organic It may be a light emitting diode.

Next, the encapsulation material 111, 112 for an organic electronic device according to the present invention for packaging the organic electronic device 102, the specific method of the packaging can be by a known conventional method, the present The invention is not particularly limited. As a non-limiting example of this, the first adhesive layer 111 of the encapsulants 111 and 112 for the organic electronic device to the organic electronic device 102 formed on the substrate 101 is directly in contact with the organic electronic device 102 In contact, it can be performed by applying heat and / or pressure using a vacuum press or a vacuum laminator. In addition, heat may be applied for curing of the adhesive layer, and in the case of an adhesive including a photo-cured adhesive resin, the curing process may be further performed by moving it to a chamber to which light is irradiated.

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 ]

Example  1: Preparation of adhesive films for organic electronic devices

 (1) First adhesive layer formation

To form the first adhesive layer, ethylene and propylene monomers were copolymerized in a weight ratio of 1: 0.85, the diene-based compound was copolymerized at 9% by weight relative to the total weight of the random copolymer, and the diene-based compound was ethylidene norbornene ( ethylidene norbornene) to prepare a first mixed resin by mixing a random copolymer having a weight average molecular weight of 500,000 and a compound represented by the following Chemical Formula 1 in a weight ratio of 1: 2.33, and then 100 parts by weight of the first mixed resin Regarding, 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), acrylate with a weight average molecular weight of 226 as a curing agent (M200, Miwon Specialty) Chemical) 11 parts by weight, UV initiator (irgacure TPO, Ciba) 3 parts by weight and average particle size of 0.5 µm silica 24 parts by weight were added and stirred. After the stirring is completed, the mixture is passed through a capsule filter to remove foreign substances, and then applied to a medium peel antistatic release PET (RT81AS, SKCHass) having a thickness of 75 μm using a slot die coater, and then dried at 120 ° C. to remove the solvent. After removing the result, a first adhesive layer having a final thickness of 20 μm was prepared.

[Formula 1]

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

(2) Second adhesive layer formation

To form the second adhesive layer, ethylene and propylene monomers were copolymerized in a weight ratio of 1: 0.85, the diene-based compound was copolymerized at 9% by weight relative to the total weight of the random copolymer, and the diene-based compound was ethylidene norbornene ( ethylidene norbornene) to prepare a second mixed resin by mixing a random copolymer having a weight average molecular weight of 500,000 and a compound represented by the following formula 1 in a weight ratio of 1: 2.33, and then 100 parts by weight of the second mixed resin About the first adhesive agent (SU-90, Kolon Industries) 150 parts by weight, 17 parts by weight of acrylate (M200, Miwon Specialty Chemicals) with 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 It was stirred.

After the agitation is completed, the viscosity is adjusted to 800 cps at 20 ° C., the foreign matter is removed by passing through the capsule filter, and then coated with a thin film release PET (RF02, SKCHass) having a thickness of 38 μm using a slot die coater. After drying at 120 ° C. to remove the solvent, a second adhesive layer having a final thickness of 30 μm was prepared.

[Formula 1]

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

After the second adhesive layer was laminated on the first adhesive layer prepared to pass through the 70 ° C lamy roll, an 800 mJ / cm ² ultraviolet ray was irradiated using a mercury lamp to prepare an adhesive film as shown in FIG. 2.

Example  2 to 14 and Comparative example  1 to 14

Prepared in the same manner as in Example 1, the adhesive films as shown in Tables 1 to 6 were prepared by varying the weight average molecular weight, content of curing agent, and number of adhesive layers of the first adhesive resin and the second adhesive resin.

< Experimental Example  1>

The physical properties of the adhesive films prepared through the above Examples and Comparative Examples were measured and are shown in Tables 1 to 6.

One. Hot press  evaluation

The adhesive layer comprising the first adhesive layer and the second adhesive layer was cut into a circle of 6 mm in diameter, and subjected to a hot press process for 60 seconds by applying a load in the upper and lower directions of the adhesive layer under conditions of temperature 50 ° C and load 4 kg, and then performing the first adhesive layer for 60 seconds. The diameter change ratio of the adhesive layer to the diameter of was measured.

2. Oven evaluation

The adhesive layer subjected to the hot press process was heat treated in an oven at a temperature of 100 ° C. for 2.5 hours to measure the rate of change in diameter with respect to the diameter of the adhesive layer before heat treatment.

< Experimental Example  2>

The following physical properties of the adhesive films prepared through the above Examples and Comparative Examples were measured and are shown in Tables 1 to 6.

1. Evaluation of moisture penetration of adhesive film

After cutting the specimen to the size of 95㎜ Х 95㎜, the top of the adhesive film on 100㎜ Х 100㎜ alkali-free glass After removing the base film, it was well-aligned so that the specimen could be positioned 2.5 mm inward from the edge of the four sides of the alkali-free glass, and then attached using a roll laminator heated to 65 ° C. After removing the remaining base film on the attached specimen, another 100mm x 100mm alkali-free glass is covered and laminated with a vacuum laminator at 65 ° C for 1 minute to produce a bonded sample without bubbles. The sample that has been cemented is In a reliability chamber set at 85 ° C relative humidity of 85%, the length of water infiltration in a unit of 1000 hours was observed under a microscope.

2. Evaluation of volume expansion of adhesive film

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

As a result of observation, when the height change in the moisture-absorbing area is less than 1 μm, ◎, when the height change in the moisture-absorbing area is less than 1 to 3 μm, ○ when the height change in the moisture-absorbing area is less than 3 to 5 μm, △, height at the moisture-absorbing site When the change is 5 µm or more, it is represented by Х.

3. Evaluation of heat resistance of adhesive film

The adhesive film was cut to a size of 50 mm x 80 mm, and after removing the upper base film of the cut adhesive film, it was attached to a 60 mm x 150 mm 0.08T Ni alloy using a laminator under conditions of 80 ° C, Gap 1mm, and Speed 1. Subsequently, after removing the other base film of the attached adhesive film, it was attached to a 30mm x 70mm 5T alkali-free glass using a laminator under conditions of 80 ° C, Gap 1mm, and Speed 1. After the specimen attached to the glass was vertically fixed to a chamber at 130 ° C., the presence or absence of adhesive flow was determined by hanging a 1 kg weight.

At this time, in the case of no abnormality as a result of the evaluation, it is indicated by Х when it flows even a little.

4. Glass  Adhesive evaluation

For the adhesive film prepared according to Examples and Comparative Examples, the adhesive force measuring tape (7475, TESA) was laminated on the upper surface of the adhesive film from which the base film was removed through a 2 kg hand roller, and the sample width was 25. After cutting to ㎜ and 120 mm in length, the bottom of the adhesive film was laminated to an alkali-free glass at 80 ° C., and then the sample was left at room temperature for 30 minutes and glassed at a speed of 300 mm / min through a universal material tester (UTM). The adhesive force was measured.

5. Metal adhesion evaluation

For the adhesive films prepared according to Examples and Comparative Examples, the upper surface of the adhesive film from which the base film was removed was laminated to a Ni alloy having a thickness of 80 μm at 80 ° C., and the adhesive force measuring tape (7475, TESA) was laminated to the lower surface of the adhesive film. , After cutting the sample to a width of 25 mm and a length of 120 mm, the prepared sample was left at room temperature for 30 minutes, and metal adhesion was measured at a speed of 300 mm / min through a universal material tester (UTM).

6. Evaluation of panel warpage prevention

For the adhesive films prepared according to Examples and Comparative Examples, the upper surface of the adhesive film from which the upper base film was removed was laminated to a Ni alloy having a width x length of 100 cm x 100 cm and a thickness of 80 µm at 80 ° C. After removing the remaining base film, a specimen was prepared by vacuum laminating at 100 ° C x 100cm 5T alkali-free glass at 50 ° C, and evaluating the warpage of the panel before / after vacuum lamination and before / after leaving the oven at 2.5 ° C for 2.5 hours. Did. At this time, when the panel was not warped-○, when the panel was warped-x was evaluated as the panel warpage.

< Experimental Example  3>

After depositing and depositing 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 1,000 A) on a substrate with an ITO pattern, the produced device was After laminating the adhesive films according to Examples and Comparative Examples at room temperature, an OLED unit specimen emitting green light was produced. Then, the following physical properties of the specimens were evaluated and are shown in Tables 1 to 6.

1. Durability evaluation of organic light-emitting device due to moisture penetration of adhesive film

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

At this time, when the pixel reduction occurs more than 50% and the dark spot generation time is more than 1,000 hours ◎, when the pixel reduction occurs more than 50% and the dark spot generation time is less than 1000 hours ~ 800 hours or more ○, the pixel reduction 50% △ is indicated when an abnormality occurs and the time required to generate a dark spot is less than 800 hours to more than 600 hours, and △ when a pixel reduction occurs more than 50% and the time required to generate a dark spot is less than 600 hours.

2. Evaluation of durability of adhesive film

The specimen was observed for 1,000 hours at 100-hour intervals in a reliability chamber set at 85 ° C and a relative humidity of 85% to observe the optical microscope for interfacial separation between the organic electronic device and the adhesive film, generation of bubbles in the crack or adhesive film, separation between the adhesive layers, and the like. Through observation, physical damage was evaluated. When there was no abnormality in the evaluation results, it was represented by × when any abnormality occurred, such as interfacial separation, cracks or bubbles in the adhesive film, or separation between adhesive layers.

division Example 1 Example 2 Example 3 Example 4 Example 5 The first
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight 500,000 40,000 1,500,000 500,000 500,000 2nd
Adhesive resin Weight average
Molecular Weight 400,000 400,000 400,000 40,000 1,500,000 Hardener Content (parts by weight) 11 11 11 11 11 2nd
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight 500,000 40,000 1,500,000 500,000 500,000 2nd
Adhesive resin Weight average
Molecular Weight 400,000 400,000 400,000 40,000 1,500,000 Hardener Content (parts by weight) 17 17 17 17 17 Hot press evaluation, diameter change rate (%) +6.6 -2.4 +7.9 -3.2 +7.7 Oven evaluation, diameter change rate (%) -3.1 -7.7 +3.6 -6.9 +4.3 adhesion
film Moisture penetration length (㎛) 1.7 1.7 2.0 1.8 2.1 Volume expansion evaluation ◎ ◎ ○ ◎ ○ Heat resistance evaluation ○ ○ ○ ○ ○ Glass adhesion (gf / 25㎜) 2659 2128 2311 2090 2326 Metal adhesion (gf / 25㎜) 2174 1942 2026 1937 2057 Evaluation of panel warpage prevention ○ ○ ○ ○ ○ OLED
Psalter Organic light emitting device durability evaluation ◎ ◎ ◎ ◎ ◎ Evaluation of durability of adhesive film ○ ○ ○ ○ ○

division Example 6 Example 7 Example 8 Example 9 Example 10 The first
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight 500,000 500,000 - - - 2nd
Adhesive resin Weight average
Molecular Weight 400,000 400,000 - - - Hardener Content (parts by weight) 25 11 - - - 2nd
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight 500,000 500,000 500,000 40,000 1,500,000 2nd
Adhesive resin Weight average
Molecular Weight 400,000 400,000 400,000 400,000 400,000 Hardener Content (parts by weight) 17 35 17 17 17 Hot press evaluation, diameter change rate (%) -2.0 -3.1 +5.4 -3.6 +7.2 Oven evaluation, diameter change rate (%) -7.1 -7.8 -4.1 -7.9 +3.3 adhesion
film Moisture penetration length (㎛) 1.7 1.7 2.3 2.6 2.4 Volume expansion evaluation ◎ ◎ ◎ ○ ◎ Heat resistance evaluation ○ ○ ○ ○ ○ Glass adhesion (gf / 25㎜) 1971 2021 2617 2139 1938 Metal adhesion (gf / 25㎜) 1556 1626 2098 1716 1427 Evaluation of panel warpage prevention ○ ○ ○ ○ ○ OLED
Psalter Organic light emitting device durability evaluation ○ ○ ◎ ○ ○ Evaluation of durability of adhesive film ○ ○ ○ ○ ○

division Example 11 Example 12 Example 13 Example 14 The first
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight - - - - 2nd
Adhesive resin Weight average
Molecular Weight - - - - Hardener Content (parts by weight) - - - - 2nd
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight 500,000 500,000 500,000 500,000 2nd
Adhesive resin Weight average
Molecular Weight 40,000 1,500,000 400,000 400,000 Hardener Content (parts by weight) 17 17 12 35 Hot press evaluation, diameter change rate (%) -4.8 +7.0 +7.8 -4.2 Oven evaluation, diameter change rate (%) -7.7 +4.2 +4.0 -7.6 adhesion
film Moisture penetration length (㎛) 2.6 2.5 2.5 2.4 Volume expansion evaluation ○ ◎ ○ ◎ Heat resistance evaluation ○ ○ ○ ○ Glass adhesion (gf / 25㎜) 2267 2015 2109 1923 Metal adhesion (gf / 25㎜) 1750 1521 1687 1388 Evaluation of panel warpage prevention ○ ○ ○ ○ OLED
Psalter Organic light emitting device durability evaluation ○ ○ ○ ○ Evaluation of durability of adhesive film ○ ○ ○ ○

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 The first
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight 20,000 1,700,000 500,000 500,000 500,000 2nd
Adhesive resin Weight average
Molecular Weight 400,000 400,000 20,000 1,700,000 400,000 Hardener Content (parts by weight) 11 11 11 11 0.5 2nd
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight 20,000 1,700,000 500,000 500,000 500,000 2nd
Adhesive resin Weight average
Molecular Weight 400,000 400,000 20,000 1,700,000 400,000 Hardener Content (parts by weight) 17 17 17 17 17 Hot press evaluation, diameter change rate (%) -8.2 +13.1 -10.4 +15.1 +14.0 Oven evaluation, diameter change rate (%) -12.3 +8.4 -15.5 +10.6 +8.2 adhesion
film Moisture penetration length (㎛) 1.8 4.1 1.8 4.2 1.8 Volume expansion evaluation ◎ Х ◎ Х Х Heat resistance evaluation ○ ○ ○ ○ ○ Glass adhesion (gf / 25㎜) 1465 2421 1483 2472 2335 Metal adhesion (gf / 25㎜) 966 2088 918 2013 1843 Evaluation of panel warpage prevention Х ○ Х ○ ○ OLED
Psalter Organic light emitting device durability evaluation ○ ○ ○ ○ △ Evaluation of durability of adhesive film Х Х Х Х ○

division Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 The first
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight 500,000 500,000 500,000 - - 2nd
Adhesive resin Weight average
Molecular Weight 400,000 400,000 400,000 - - Hardener Content (parts by weight) 36 11 11 - - 2nd
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight 500,000 500,000 500,000 20,000 1,700,000 2nd
Adhesive resin Weight average
Molecular Weight 400,000 400,000 400,000 400,000 400,000 Hardener Content (parts by weight) 17 5 46 17 17 Hot press evaluation, diameter change rate (%) -8.8 +15.9 -10.4 -10.9 +14.8 Oven evaluation, diameter change rate (%) -13.4 +8.8 -16.5 -16.7 +8.3 adhesion
film Moisture penetration length (㎛) 1.7 1.8 1.7 2.5 4.7 Volume expansion evaluation ○ Х ◎ Х ○ Heat resistance evaluation ○ ○ ○ Х Х Glass adhesion (gf / 25㎜) 1437 2601 2021 1263 2180 Metal adhesion (gf / 25㎜) 913 2109 1626 730 1629 Evaluation of panel warpage prevention Х ○ Х Х ○ OLED
Psalter Organic light emitting device durability evaluation ○ △ ○ ○ ○ Evaluation of durability of adhesive film Х ○ ○ Х Х

division Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 The first
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight - - - - 2nd
Adhesive resin Weight average
Molecular Weight - - - - Hardener Content (parts by weight) - - - - 2nd
Adhesive layer The first
Adhesive resin Weight average
Molecular Weight 500,000 500,000 500,000 500,000 2nd
Adhesive resin Weight average
Molecular Weight 20,000 1,700,000 400,000 400,000 Hardener Content (parts by weight) 17 17 5 46 Hot press evaluation, diameter change rate (%) -10.7 +15.6 +16.8 -10.7 Oven evaluation, diameter change rate (%) -16.6 +10.6 +11.1 -16.9 adhesion
film Moisture penetration length (㎛) 2.4 4.6 4.6 2.5 Volume expansion evaluation Х ○ Х ○ Heat resistance evaluation Х Х Х Х Glass adhesion (gf / 25㎜) 1368 2027 2193 1358 Metal adhesion (gf / 25㎜) 889 1523 1677 785 Evaluation of panel warpage prevention Х ○ ○ Х OLED
Psalter Organic light emitting device durability evaluation ○ ○ ○ ○ Evaluation of durability of adhesive film Х Х Х Х

As can be seen from Tables 1 to 6, the conditions (1) and (2) of the present invention and preferred weight average molecular weight of the first adhesive resin and the second adhesive resin, the content of the curing agent, the content of the UV initiator and the number of adhesive layers, etc. Examples 1 to 14 satisfying all of them, compared to Comparative Examples 1 to 14 in which any of them is omitted, the water removal and blocking are more efficient, resulting in a shorter water penetration length, little volume expansion of the adhesive film, and heat resistance, The glass adhesive strength, the metal adhesive strength, and the durability evaluation result of the organic light emitting device were good, the panel was not warped, and the adhesive film was excellent in durability.

Although one embodiment of the present invention has been described above, the spirit of the present invention is not limited to the embodiments presented herein, and those skilled in the art to understand the spirit of the present invention may add elements within the scope of the same spirit. However, other embodiments may be easily proposed by changing, deleting, adding, or the like, but this will also be considered to be within the scope of the present invention.

10: adhesive film 11: first adhesive layer
11a: First absorbent 11b: First mixed resin
12: second adhesive layer 12a: second absorbent
12b: 2nd mixed resin 13, 14: base film
15: adhesive layer 15a: absorbent
15b: mixed resin 100: light emitting device
101: substrate 102: organic electronic device
111: first adhesive layer 111a: first absorbent
111b: first mixed resin 112: second adhesive layer
112a: second absorbent 112b: second mixed resin
115: adhesive layer 115a: absorbent
115b: mixed resin

Claims (14)

It includes an adhesive layer formed of a mixed resin comprising a first adhesive resin and a second adhesive resin, a tackifier comprising a first adhesive and a moisture absorbent,
The adhesive layer is an adhesive film for an organic electronic device satisfying both of the following conditions (1) and (2):
(1) After cutting the adhesive layer having a thickness of 50 µm into a circle with a diameter of 6 mm, the rate of change in diameter with respect to the initial diameter of ± 10 was measured after performing a hot press process for 60 seconds under the condition of a temperature of 50 ° C and a load of 4 kg. % Below,
(2) The rate of change in diameter with respect to the diameter of the adhesive layer before the heat treatment is ± 10% or less, measured during the heat treatment of the adhesive layer subjected to the hot press process at a temperature of 100 ° C. for 2.5 hours. According to claim 1,
The adhesive layer is an adhesive film for an organic electronic device satisfying both of the following conditions (1) and (2):
(1) After cutting the adhesive layer having a thickness of 50 µm into a circle with a diameter of 6 mm, the rate of change of diameter with respect to the initial diameter measured after performing a hot press process for 60 seconds under a condition of temperature 50 ° C. and load 4 kg is ± 8%. Below
(2) The rate of change in diameter with respect to the diameter of the adhesive layer before the heat treatment is ± 8% or less, measured during the heat treatment of the adhesive layer subjected to the hot press process at a temperature of 100 ° C. for 2.5 hours. According to claim 1,
The first adhesive resin has a weight average molecular weight of 30,000 ~ 1,550,000, and includes a random copolymer in which ethylene, propylene and diene compounds are copolymerized,
The second adhesive resin is an adhesive film for an organic electronic device comprising a compound represented by the formula (1):
[Formula 1]

In Chemical Formula 1, R ¹ is a hydrogen atom or a C3 to C10 straight-chain alkenyl group or a C4 to C10 pulverized alkenyl group, and n is a compound satisfying the weight average molecular weight of 30,000 to 1,550,000 of Formula 1 It is rational. According to claim 3,
The ethylene and propylene are randomly copolymerized in a weight ratio of 1: 0.3 to 1.4,
The diene-based compound is an adhesive film for an organic electronic device contained in 2 to 15% by weight relative to the total weight of the random copolymer. According to claim 1,
An adhesive film for an organic electronic device further comprising 2 to 50 parts by weight of a curing agent relative to 100 parts by weight of the mixed resin. The method of claim 5,
The curing agent is an adhesive film for an organic electronic device comprising at least one selected from the group consisting of a urethane acrylate-based curing agent and an acrylate-based curing agent having a weight average molecular weight of 100 to 1500. According to claim 1,
An adhesive film for an organic electronic device further comprising 0.1 to 10 parts by weight of a UV initiator with respect to 100 parts by weight of the mixed resin. According to claim 1,
The glass adhesion measured according to the following measurement method 1 is 1500 gf / 25 mm or more,
Adhesive film for organic electronic devices having a metal adhesive strength of 1000 gf / 25 mm or more measured according to the following measurement method 2.
[Measurement method 1]
The adhesive force measuring tape was laminated to the upper surface of the adhesive film, the sample was cut to a width of 25 mm and a length of 120 mm, and the lower surface of the adhesive film was laminated to glass at 80 ° C., and the prepared sample was left at room temperature for 30 minutes, and 300 mm / min. Measures the glass adhesion at speed.
[Measurement method 2]
The upper surface of the adhesive film was laminated to a Ni alloy having a thickness of 80 μm at 80 ° C., the adhesive force measuring tape was laminated to the lower surface of the adhesive film, the sample was cut 25 mm wide and 120 mm long, and the prepared sample was left at room temperature for 30 minutes, Metal adhesion is measured at a speed of 300 mm / min. According to claim 1,
The mixed resin includes a first mixed resin and a second mixed resin,
The adhesive layer may include a first adhesive layer comprising a first mixed resin; And a second adhesive layer formed on one surface of the first adhesive layer and including a second mixed resin. The method of claim 9,
The first adhesive layer is an adhesive film for an organic electronic device further comprising a second adhesive agent. The method of claim 9,
The first adhesive layer contains 50 to 300 parts by weight of an tackifier with respect to 100 parts by weight of the first mixed resin,
The second adhesive layer is an adhesive film for an organic electronic device comprising 60 to 300 parts by weight of a tackifier with respect to 100 parts by weight of the second mixed resin. The method of claim 9,
The first adhesive layer further comprises 2 to 30 parts by weight of a curing agent with respect to 100 parts by weight of the first mixed resin,
The second adhesive layer is an adhesive film for an organic electronic device further comprising 10 to 40 parts by weight of a curing agent with respect to 100 parts by weight of the first mixed resin. An encapsulant for an organic electronic device comprising the adhesive film for an organic electronic device according to any one of claims 1 to 12. Board;
An organic electronic device formed on at least one surface of the substrate; And
A light emitting device comprising a; encapsulation material for an organic electronic device according to claim 13 for packaging the organic electronic device.

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