KR102159497B1 - Pressure-sensitive adhesive composition - Google Patents

Abstract

This application provides a 　adhesive 　 composition 　 and an adhesive film including the same, which can effectively block moisture or oxygen flowing into the organic electronic device from the outside, and can realize not only durability reliability under severe conditions such as high temperature and high humidity, but also excellent optical properties. .

Description

Adhesive composition {PRESSURE-SENSITIVE ADHESIVE COMPOSITION}

The present application relates to an adhesive composition, an adhesive film including the same, and an organic electronic device including the same.

An organic electronic device (OED) refers to a device including an organic material layer that generates an exchange of charges using holes and electrons, and examples thereof include a photovoltaic device, a rectifier, and And a transmitter and an organic light emitting diode (OLED).

Among the organic electronic devices, an organic light emitting diode (OLED) consumes less power, has a faster response speed, and is advantageous in reducing the thickness of a display device or lighting compared to a conventional light source. In addition, OLED has excellent space utilization, and is expected to be applied in various fields ranging from various portable devices, monitors, notebooks and TVs.

In the commercialization and expansion of OLED use, the most important problem is durability. Organic materials and metal electrodes included in OLEDs are very easily oxidized by external factors such as moisture. Therefore, products containing OLED are highly sensitive to environmental factors. Accordingly, various methods have been proposed to effectively block the penetration of oxygen or moisture from the outside into an organic electronic device such as OLED.

Recently, a technology using a PIB (polyisobutylene)-based resin has been attempted as an adhesive composition for sealing. PIB (polyisobutylene) resins are hydrophobic resins, and are superior in barrier properties to prevent the influence of moisture and active oxygen compared to acrylic resins, are transparent, and have little effect of corrosion. However, due to the restriction of the curing agent due to the compatibility problem and the decrease in crosslinking density accordingly, problems of heat resistance and chemical resistance occur.

Patent Document 1 is an adhesive encapsulation composition film and an organic electroluminescent device, which is an adhesive based on PIB (polyisobutylene), which has poor processability and poor reliability under high temperature and high humidity conditions.

Accordingly, there is a need to develop an encapsulant that can secure a required life in an organic electronic device and effectively block the penetration of moisture, maintain reliability under high temperature, high humidity conditions, and excellent optical properties.

Korean Patent Publication No. 2008-0088606

The present application provides a pressure-sensitive adhesive composition that can effectively block moisture or oxygen flowing into an organic electronic device from the outside, has excellent heat resistance, chemical resistance, and transparency, and an adhesive film including the same.

The present application relates to an adhesive composition. The pressure-sensitive adhesive composition may be applied to encapsulate or encapsulate an organic electronic device such as an OLED, for example. For example, the pressure-sensitive adhesive composition may be applied to encapsulate the entire surface of an organic electronic device, or may be applied to be positioned on a surface opposite to a surface on which the device is formed in a substrate on which the device is formed.

In the present specification, the term ``organic electronic device'' refers to an article or device having a structure including an organic material layer that generates an exchange of electric charges using holes and electrons between a pair of electrodes facing each other. Examples include, but are not limited to, a photovoltaic device, a rectifier, a transmitter, and an organic light-emitting diode (OLED). In one example of the present invention, the organic electronic device may be an OLED.

An exemplary pressure-sensitive adhesive composition may include a base resin and an acrylic compound. The base resin includes an olefin-based compound as a polymerization unit, and may have at least one reactive functional group. In addition, the acrylic compound may have a functional group bondable to the reactive functional group. In one example, in the present application, the base resin and the acrylic compound may exist in a bonded state. For example, an acrylic compound may be introduced into the base resin by reacting a reactive functional group present in the main chain constituting the base resin with the functional group of the acrylic compound. In the present application, by including the base resin and the acrylic compound together, excellent moisture barrier properties are implemented, and a crosslinked structure of the base resin derived from the acrylic group is provided, thereby achieving heat resistance at high temperature and high humidity.

In one example, the base resin may be a homopolymer derived from an olefinic compound or a copolymer in which other polymerizable monomers are polymerized together. In addition, as described above, the base resin may have at least one or more reactive functional groups. In one example, the reactive functional group may be at least one selected from a glycidyl group, an isocyanate group, a hydroxy group, a carboxyl group, an amide group, an epoxide group, a cyclic ether group, a sulfide group, an acetal group, and a lactone group. The kind of the reactive functional group is not particularly limited, and a person skilled in the art may appropriately select it according to the functional group of the acrylic compound.

In the embodiment of the present application, the base resin includes a resin derived from a mixture of monomers, and the mixture may include an olefin-based compound. The olefinic compound may have an isoolefin monomer component or a multiolefin monomer component having at least 4 to 7 carbon atoms. The isoolefin may be present, for example, in a range of 70 to 100% by weight, or 85 to 99.5% by weight, based on the total monomer weight. The multiolefin-derived component may be present in the range of 0.5 to 30% by weight, 0.5 to 15% by weight, or 0.5 to 8% by weight.

The isoolefin is, for example, isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butene, 2-butene, methyl, vinyl ether, indene , Vinyltrimethylsilane, hexene, or 4-methyl-1-pentene may be exemplified. The multiolefin may have 4 to 14 carbon atoms, for example isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-fulbene, hexadiene, cyclopentadiene, or Piperylene can be illustrated. Other polymerizable monomers such as styrene and dichlorostyrene may also be homopolymerized or copolymerized.

In one example, the isobutylene-based olefin-based resin or polymer may refer to an olefin-based resin or polymer comprising 70 mol% or more of repeating units from isobutylene or isoprene and one or more other polymerizable units.

In the present application, the base resin may be a butyl rubber or a branched butyl rubber. Exemplary, the base resin is an unsaturated butyl rubber such as an olefin or a copolymer of an isoolefin and a multiolefin. As the base resin included in the pressure-sensitive adhesive composition of the present invention, styrene-isoprene-styrene copolymer, poly(isobutylene-co-isoprene), polyisoprene, polybutadiene, polyisobutylene, poly(styrene-co-butadiene), Natural rubber, butyl rubber, and mixtures thereof may be exemplified.

In one example, the base resin may include a polymer in which a reactive functional group is side-chain bonded by grafting a compound having a polymerizable functional group to a polymer derived from an olefin-based compound. The polymerizable functional group may be, for example, a carbon-carbon double bond, an acryloyl group or a methacryloyl group.

In another embodiment, the reactive functional group may be in a form in which the unsaturated group of the base resin is epoxidized. The reactive functional group may be in a form in which the unsaturated group of the main chain of the base resin is epoxidized. The unsaturated group can be, for example, a carbon-carbon double bond. In one example, the epoxidation may refer to a reaction in which one atom of oxygen is added to an ethylene bond to generate 1,2-epoxide.

The epoxidation can be carried out using an oxidizing agent. The oxidizing agent may be a known oxidizing agent capable of epoxidation, and examples thereof include organic peroxides such as hydrogen peroxide, performic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid, metachloroperbenzoic acid (mCPBA), and dimethyldioxane; Oxo complexes such as salen complexes; Peroxide salts such as magnesium monoperoxyphthalate and oxone may be used, and in detail, from the viewpoint of reaction efficiency, peroxide salts may be used. In the present application, when the base resin is epoxidized using a peroxide salt, an epoxy group may be introduced into an unsaturated group even at a low acidity, thereby minimizing the problem of forming a hydroxyl group through a side reaction that may occur at a high acidity.

In one example, the epoxy conversion rate of the unsaturated group of the base resin may be 70 mol% or more. As the epoxy conversion rate increases, a curable compound and a dense crosslinking density may be formed, thereby increasing internal stress and providing a highly reliable encapsulant. In this respect, the upper limit of the epoxy conversion rate is not particularly limited, and may be, for example, 99 mol% or less, 95 mol% or less, or 90 mol% or less.

In another example, the base resin may have an epoxy equivalent in the range of 100g/eq to 20,000g/eq. As described above, the base resin may include a reactive functional group, and when the reactive functional group is an epoxy group, the epoxy equivalent may be controlled within the above range. The present application provides a highly reliable encapsulant by controlling the epoxy equivalent of the base resin within the above range, thereby controlling the introduction of an acrylic compound, forming a dense crosslinking density, increasing internal stress, and realizing excellent transparency.

In one example, in the present application, the base resin may have a weight average molecular weight such that the pressure-sensitive adhesive composition can be molded into a film shape. For example, the base resin may have a weight average molecular weight of about 100,000 to 1 million, more than 100,000 to less than 900,000, 150,000 to 800,000, 200,000 to 700,000, or 200,000 to 650,000. In the present application, by controlling the weight average molecular weight of the base resin within the above range, after being applied as an encapsulant, heat resistance, durability reliability, and optical properties can be simultaneously excellently maintained at high temperature and high humidity.

In addition, the base resin may have an integration ratio (R) of a hydroxyl group represented by the following General Formula 1 of 10% or less, 5% or less, or 1% or less.

[General Formula 1]

R=H/(E+H)×100

In the general formula 1, E represents the area (integration) of the peak resulting from the reactive functional group in ¹ H-NMR, and H represents the area of the peak resulting from the hydroxyl group (integration).

The lower limit of the hydroxyl group area ratio (integration ratio, R) may be 0%. The measurement method of ¹ H-NMR is not particularly limited, and may be performed in a known manner. For example, when the peaks derived from each of the reactive functional groups and hydroxyl groups do not overlap each other as a result of NMR measurement, it can be obtained through the area of the corresponding peak, and when the peaks overlap each other, the ratio can be calculated by taking the overlapping portions into account have. Various analysis programs that can obtain the area of a peak by analyzing ¹ H-NMR spectrum are known. For example, the area of the peak can be calculated using the MestReC program.

In the present application, by controlling the integration ratio of the hydroxyl groups of the base resin within the above range, the degree of bonding between the base resin and the acrylic compound is controlled by introducing a reactive functional group into the resin in a desired range, and thus moisture barrier properties. While excellently implemented, it can maintain excellent heat resistance, durability, reliability and optical properties at high temperature and high humidity at the same time. In addition, the present application does not require additional washing since the base resin is not obtained under acidic conditions.

In a specific example of the present application, the acrylic compound may satisfy Formula 1 below.

[Formula 1]

In Formula 1, R ₁ is hydrogen or an alkyl group, R ₂ is a single bond, an alkylene group or an alkylidene group, and X is a functional group capable of bonding with a reactive functional group. In the above, the case where R ₂ is a single bond may mean a case where the reactive functional group X is directly bonded to oxygen. The functional group bondable to the reactive functional group may be at least one selected from a glycidyl group, an isocyanate group, a hydroxy group, a carboxyl group, an amide group, an epoxide group, a cyclic ether group, a sulfide group, an acetal group and a lactone group. The functional group is not particularly limited, and may be appropriately selected in terms of binding properties with the reactive functional group of the base resin described above. For example, when the reactive functional group of the base resin is an epoxy group, a hydroxy group or a carboxyl group may be selected as a reactive group capable of bonding with the epoxy group.

In the present specification, the term "alkyl group" is 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. It may mean an alkyl group of. The alkyl group may have a straight chain, branched chain or cyclic structure, and may be optionally substituted by one or more substituents.

In the present specification, the term "alkylene group" or "alkylidene group" is 2 to 30 carbon atoms, 2 to 25 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, unless otherwise specified, It may mean an alkylene group or an alkylidene group having 2 to 10 carbon atoms or 2 to 8 carbon atoms. The alkylene group or alkylidene group may have a straight chain, branched chain or cyclic structure, and may be optionally substituted with one or more substituents.

The acrylic compound is not particularly limited as long as it satisfies Formula 1, but, for example, 2-carboxylethyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl meta Acrylate, 4-hydroxybutyl methacrylate, acrylic acid or glycidyl methacrylate.

In one example, the base resin and the acrylic compound may be included in a ratio of 70 to 90 parts by weight and 1 to 40 parts by weight, respectively. Or the acrylic compound is included in the range of 1 to 40 parts by weight, 2 to 35 parts by weight, 3 to 30 parts by weight, 3 to 25 parts by weight, 3 to 20 parts by weight, or 3 to 19 parts by weight based on 100 parts by weight of the base resin. I can. In the present application, by controlling the weight ratio of the base resin and the acrylic compound to the above range, the amount of the acryloyl group introduced into the base resin is adjusted to a desired range, thereby implementing a dense crosslinked structure of the base resin.

In one example, the pressure-sensitive adhesive composition of the present application may further include a crosslinking agent for bonding the base resin and the acrylic compound. The type of the crosslinking agent is not particularly limited, and one or more types such as an amine compound, an imidazole compound, a phenol compound, a phosphorus compound or an acid anhydride compound may be used, but the present invention is not limited thereto.

In one example, as the crosslinking agent, an imidazole compound having a solid state at room temperature and a melting point or decomposition temperature of 80° C. or higher may be used. Such compounds include, for example, 2-methyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole, or 1-cyanoethyl-2-phenyl imidazole. This may be illustrated, but is not limited thereto,

In the present application, as described above, the base resin and the acrylic compound may exist in a combined state. In addition, the pressure-sensitive adhesive composition may further include a curable compound. The curable compound may provide a specific crosslinked structure together with the base resin into which the acrylic compound is introduced.

In a specific example of the present application, the pressure-sensitive adhesive composition may have an annular structure after curing. The cyclic structure may be derived from a base resin or may be derived from the curable compound. In the present application, by implementing the adhesive having the above structure, even after crosslinking or curing, a crosslinked structure that is stable against external factors such as contraction and expansion can be implemented.

In one example, the curable compound may have a cyclic structure in which the cyclic atoms in the molecular structure are in the range of 3 to 20 or 4 to 15, but is not limited thereto. In addition, the curable compound may have the cyclic structure even after the pressure-sensitive adhesive is cured. The cyclic structure may be alicyclic. The curable compound having the above structure may implement a crosslinked structure that is stable against external factors such as shrinkage and expansion even after the adhesive is crosslinked or cured.

In one embodiment, the crosslinked structure derived from the curable compound may be a crosslinked structure formed by application of heat, a crosslinked structure formed by irradiation of active energy rays, or a crosslinked structure formed by aging at room temperature. In the above, the category of "active energy rays" includes microwaves, infrared rays (IR), ultraviolet rays (UV), X-rays and gamma rays, as well as alpha-particle beams and proton beams. , A particle beam such as a neutron beam or an electron beam may be included, and typically, it may be an ultraviolet ray or an electron beam.

For example, the pressure-sensitive adhesive composition of the present invention may include a polyfunctional active energy ray polymerizable compound that can be polymerized by irradiation with active energy rays together with a base resin. The active energy ray polymerizable compound is, for example, a functional group capable of participating in a polymerization reaction by irradiation of an active energy ray, for example, a functional group including an ethylenically unsaturated double bond such as an acryloyl group or a methacryloyl group. , It may mean a compound containing two or more functional groups such as an epoxy group or an oxetane group.

As the active energy ray polymerizable compound, for example, a multifunctional acrylate (MFA) may be used.

The curable compound may be included in an amount of 10 to 50 parts by weight, 10 to 40 parts by weight, 12 to 30 parts by weight, or 15 to 20 parts by weight based on 100 parts by weight of the base resin. The present application may implement a crosslinked structure of a desired range in the weight range, thereby providing an encapsulant having heat resistance and chemical resistance at high temperature and high humidity.

The kind of the polyfunctional active energy ray-polymerizable compound that can be polymerized by irradiation with the active energy ray is not particularly limited, but, for example, the compound is 1,4-butanediol di(meth)acrylate, 1, 3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,12-dodecanediol di( Meth)acrylate, neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclodecanedimethanol(meth)acrylate, dimethylol dicyclopentan di(meth)acrylate , Neopentyl glycol-modified trimethylpropane di(meth)acrylate, adamantane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, or a mixture thereof.

As the polyfunctional active energy ray polymerizable compound, for example, a compound having a molecular weight of less than 1,000 and containing two or more functional groups can be used. In this case, the molecular weight may mean a weight average molecular weight or a conventional molecular weight. The ring structure included in the polyfunctional active energy ray polymerizable compound may be a carbocyclic structure or a heterocyclic structure; Alternatively, any of a monocyclic or polycyclic structure may be used.

In an embodiment of the present invention, the pressure-sensitive adhesive composition may further include an initiator capable of inducing a polymerization reaction of the above-described curable compound. The initiator may be a radical initiator. The radical initiator can be a photoinitiator or a thermal initiator. The specific type of the photoinitiator may be appropriately selected in consideration of the curing rate and the possibility of yellowing. For example, benzoin-based, hydroxy ketone-based, amino ketone-based, or phosphine oxide-based photoinitiators can be used, and specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether , Benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylanino acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2 -Hydroxy-2-methyl-1-phenylpropan-1one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1- One, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4 -Dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoic acid ester, oligo[2-hydroxy-2-methyl-1-[4-(1-methyl Vinyl)phenyl]propanone] and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. can be used.

The initiator may be included in a ratio of 0.2 parts by weight to 20 parts by weight based on 100 parts by weight of the curable compound. Through this, it is possible to effectively induce the reaction of the active energy ray-polymerizable compound, and to prevent the physical properties of the pressure-sensitive adhesive composition from deteriorating due to residual components after curing.

In one example, the pressure-sensitive adhesive composition of the present application may further include a tackifier. The tackifier may be a resin produced by reacting a terpene compound and an aromatic compound. When the tackifier has an aromatic in the molecular structure, the compatibility between the above-described base resin having low polarity and the curable compound having high polarity can be improved. In addition, the aromatic compound may include a reactive functional group, and examples of the functional group include a hydroxy group, a carboxyl group, and an amine group. The present application may improve the crosslinking density of the entire pressure-sensitive adhesive due to the reactive functional group. Specifically, the aromatic compound may be phenol, and the tackifier may be a terpene phenolic resin. In this application, by using the terpene phenolic resin as a tackifier, it is possible to increase not only excellent adhesion but also the compatibility of the base resin and the curable compound, and accordingly, improve the crosslinking density to provide a pressure sensitive adhesive having excellent durability. I can.

The tackifier may be a resin produced by reacting a terpene compound and a phenol compound. The terpene compound may mean a compound having a basic skeleton (C ₅ H ₈ )n in which two or more isoprenes (C ₅ H ₈ ) are bound. In the above, n may be 2 or more. In the above, the terpene compound may be at least one selected from the group consisting of α-pinene, β-pinene, δ-3-karene, 3-karene, D-limonene and dipentene. In addition, the phenolic compound is phenol, 4-t-butylphenol (para-tert-butylphenol; PTBP), 4-t-octylphenol (para-tert-octhylphenol; PTOP), 4-n-pentylphenol (para-n -pentyl phenol; PNPP) and 4-n-hexyl phenol (para-n-hexyl phenol; PNHP) may be at least one selected from the group consisting of.

The tackifier is 10 to 100 parts by weight, 20 to 90 parts by weight, 30 to 90 parts by weight, 30 to 80 parts by weight, 35 to 70 parts by weight, 35 to 60 parts by weight or 38 to based on 100 parts by weight of the base resin. It may be included in 50 parts by weight. In the present specification, unless otherwise specified, the unit "parts by weight" means a weight ratio between each component.

In addition to the above-described configuration, the pressure-sensitive adhesive composition according to the present application may include various additives according to the use, the type of the resin component, and the manufacturing process of the pressure-sensitive adhesive layer to be described later within a range that does not affect the effects of the above-described invention. For example, the pressure-sensitive adhesive composition may include a moisture adsorbent, an inorganic filler, a coupling agent, a crosslinking agent, a curable material, an ultraviolet stabilizer, or an antioxidant in an appropriate range according to the desired physical properties.

In addition, the pressure-sensitive adhesive composition according to the present application may have a gel content of 65% or more according to the following General Formula 1.

[General Formula 1]

Gel content (% by weight) = B/A × 100

In the general formula 1, A represents the mass of the pressure-sensitive adhesive composition, and B is the pressure-sensitive adhesive composition is immersed in toluene at 25° C. for 24 hours and then filtered through a 200 mesh (pore size 74 μm) net, and does not pass through the net. It shows the dry mass of the insoluble part of an adhesive composition.

The gel content represented by the general formula 1 may be 65% to 95%, 70% to 90%, or 73 to 85%. That is, the present invention can provide an adhesive having an excellent crosslinking structure and degree of crosslinking by controlling the gel content within the above range.

The present application also relates to an adhesive film. The adhesive film may include an adhesive layer including the adhesive composition described above. The structure of the adhesive film of the present application is not particularly limited, but as an example, a base film or a release film (hereinafter, referred to as a "first film" in some cases); And it may have a structure including the pressure-sensitive adhesive layer formed on the base film or release film.

The pressure-sensitive adhesive film of the present application may further include a base film or a release film (hereinafter, referred to as “second film”) formed on the pressure-sensitive adhesive layer.

The specific type of the first film that can be used in the present application is not particularly limited. In the present application, as the first film, for example, a general polymer film in this field may be used. In the present application, for example, as the substrate or release film, a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a vinyl chloride copolymer film, a polyurethane film , An ethylene-vinyl acetate film, an ethylene-propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film may be used. In addition, an appropriate release treatment may be performed on one or both sides of the base film or release film of the present application. Examples of the releasing agent used in the release treatment of the base film may be alkyd-based, silicone-based, fluorine-based, unsaturated ester-based, polyolefin-based or wax-based, among which alkyd-based, silicone-based or fluorine-based release agents are used in terms of heat resistance. Although preferred, it is not limited thereto.

In addition, the type of the second film (hereinafter, referred to as “cover film” in some cases) that can be used in the present application is not particularly limited. For example, in the present application, as the second film, within the range exemplified in the above-described first film, the same or different types as the first film may be used. In addition, in the present application, an appropriate release treatment may also be performed on the second film and used.

The thickness of the pressure-sensitive adhesive layer included in the pressure-sensitive adhesive film of the present application is not particularly limited, and may be appropriately selected according to the following conditions in consideration of the application to which the film is applied. The thickness of the pressure-sensitive adhesive layer included in the pressure-sensitive adhesive film of the present application may be about 5 µm to 200 µm, preferably about 10 µm to 150 µm.

In addition, the adhesive film may have excellent light transmittance in a visible light region. In one example, the adhesive film of the present application may exhibit a light transmittance of 90% or more with respect to the visible light region. For example, the adhesive film may have a light transmittance of 92% or more or 95% or more with respect to the visible light region. Further, the adhesive film of the present application may exhibit excellent light transmittance and low haze. In one example, the adhesive film may exhibit a haze of 10% or less, 5% or less, 4% or less, 3% or less, or 2.5% or less. The optical properties may be measured at 550 nm using a UV-Vis Spectrometer.

The present application also includes a substrate 1; An organic electronic device 2 formed on one surface of the substrate 1; And it relates to an organic electronic device including the above-described adhesive film (3) for completely encapsulating the organic electronic device (2).

In the present application, the organic electronic device may be an organic light emitting diode.

The 　 organic electronic device may further include a protective film positioned on the electrode of the device to protect the electrode.

The 　 organic electronic device may further include a cover substrate 4 covering an upper end of the adhesive film 3 which is an encapsulant.

The present application also relates to a method of manufacturing an organic electronic device comprising the step of forming a pressure-sensitive adhesive film including the aforementioned pressure-sensitive adhesive composition on the entire surface of the organic electronic device of a substrate having an organic electronic device formed on one surface thereof.

The manufacturing method may further include crosslinking or curing the adhesive film.

In addition, the adhesive film exhibits excellent transparency, and may be formed as a stable adhesive film regardless of the shape of an organic electronic device, such as top emission or bottom emission.

In the present specification, the term "curing" may mean that the adhesive composition of the present invention forms a crosslinked structure through a heating or UV irradiation process and the like to form a pressure-sensitive adhesive.

Specifically, a transparent electrode is formed on a glass or polymer film used as a substrate by a method such as vacuum deposition or sputtering, and a light-emitting organic material composed of, for example, a hole transport layer, a light emitting layer, and an electron transport layer on the transparent electrode. After the layer of is formed, an electrode layer may be additionally formed thereon to form an organic electronic device.

Subsequently, the adhesive film is placed on one side of the substrate, and the adhesive film is heated using a laminating machine or the like to provide fluidity and press-bonding, thereby crosslinking the resin in the adhesive film.

The present application provides a pressure-sensitive adhesive composition that can effectively block moisture or oxygen flowing into an organic electronic device from the outside and has excellent durability and optical properties, and an adhesive film including the same.

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

Hereinafter, the present invention will be described in more detail through examples according to the present invention and comparative examples not according to the present invention, but the scope of the present invention is not limited by the examples presented below.

Example One

100 parts by weight of toluene and 15 parts by weight of isobutyl isoprene rubber (IIR, Lanxess RB301) were added to a sealed 500 mL reaction vessel, and stirred at room temperature until the resin was dissolved. In addition, 15 parts by weight of acetone, 8 parts by weight of sodium bicarbonate dissolved in water, and 15 parts by weight of potassium peroxomonosulfate were added to the reaction vessel, and the reaction was carried out by stirring at room temperature for about 20 hours. Then, it was separated by using the difference in density between the solvent toluene and water to obtain a modified base resin.

100 parts by weight of the modified base resin dissolved in toluene, 2 parts by weight of triethylamine and 4 parts by weight of 2-carboxylethyl acrylate were added to a 500 mL reaction vessel equipped with a reflux condenser and a nitrogen inlet, and then at 65° C. for 3 hours Stir and react. After the reaction was cooled to room temperature, an aqueous HCl solution was added to remove the catalyst, thereby obtaining a base resin 1 into which the acrylic compound was introduced. The solid content of the obtained resin was 15%.

100 g of the obtained base resin solution 1 was added to a mixing container, and tricyclodecane dimethanol diacrylate (Miramer M262, Miwon) as a curable compound was added to the container at 17 parts by weight based on 100 parts by weight of the solid content of the base resin. . In addition, a terpene phenolic tackifier (DERTOPHENE T 115, DRT) was added to the container in an amount of 40 parts by weight based on 100 parts by weight of the solid content of the base resin, and 2,2-dimethoxy-1,2-diphenylethane After adding 1.2 parts by weight of 1-one (Irgacure651, Ciba) based on 100 parts by weight of the solid content of the base resin, toluene was added so that the total solid content of the adhesive composition coating solution was 20%.

A uniform pressure-sensitive adhesive composition solution (solvent: toluene) was prepared using a conventional mechanical stirrer as the mixing container.

The prepared solution was applied to the release surface of the release PET and dried in an oven at 80° C. for 60 minutes (5 atm) to prepare an adhesive film including an adhesive layer having a thickness of 50 μm. Physical properties were measured for the sample obtained by irradiating the prepared film with ultraviolet rays at 2 J/cm ² under a nitrogen atmosphere (100 mW/cm ² based on area A).

Comparative example One

Instead of the base resin 1, an adhesive film was prepared in the same manner as in Example 1, except that isobutyl isoprene rubber (IIR, Lanxess RB301) was used.

For the base resin, the pressure-sensitive adhesive composition and the pressure-sensitive adhesive film prepared in Examples and Comparative Examples, physical properties were measured as follows.

One. Light transmittance And Haze Measure

For the adhesive film prepared above, light transmittance at 550 nm was measured using a UV-Vis Spectrometer, and haze was measured according to the JIS K7105 standard test method using a haze meter.

2. Gel content

Gel content (% by weight) = B/A × 100

In the above, A represents the mass of the pressure-sensitive adhesive composition, B is the pressure-sensitive adhesive composition is immersed in toluene at 25° C. for 24 hours and then filtered through a 200 mesh (pore size 74 μm) net, and the pressure-sensitive adhesive composition that does not pass through the net It represents the dry mass of the insoluble matter of.

3. Creep test

A base film in which an adhesive layer having a thickness of 30 μm including the adhesive compositions of Examples and Comparative Examples was formed on one side was attached to a glass plate with an adhesive area of 1 cm ² , aged for 24 hours, and then a load of 1.5 kg was applied at 25° C. for 1000 seconds. When, the pushed distance was measured. The base film was a polyethylene terephthalate (PET) film. If the pressure-sensitive adhesive layer is separated from the attached glass plate, it is classified as dropping.

4. Heat resistance and durability

After applying the pressure-sensitive adhesive layer prepared in Examples and Comparative Examples to a barrier film (3M), a sample was prepared in a laminated structure with glass (STN glass, 1.2T), and then 5 atm at 50°C using an autoclave. By heating under pressure to prepare a specimen.

The specimens were stored in an oven at 105° C. and after 500 hours, whether or not lifting, bubbles, or cracks of the adhesive occurred were visually checked, and if less than 5 occurred, it was classified as good, and if more than 5 occurred, it was classified as bad.

The measurement results are summarized and described in Table 1 below.

Example 1 Comparative Example 1 Haze (%) 2.11 3.05 Light transmittance (%) 90.26 91.63 Gel content (%) 75 60.6 Creep(㎛) 755 leaving out Heat resistance and durability Good Bad

1: substrate
2: organic electronic device
3: adhesive film
4: cover substrate

Claims (20)

A base resin containing an olefinic compound as a polymerization unit and having at least one reactive functional group, and an acrylic compound having a functional group bondable to the reactive functional group,
The reactive functional group is a pressure-sensitive adhesive composition in which the unsaturated group of the base resin is epoxidized. delete delete The pressure-sensitive adhesive composition of claim 1, wherein the unsaturated group has an epoxy conversion ratio of 70 mol% or more. The pressure-sensitive adhesive composition of claim 1, wherein the base resin has an epoxy equivalent of 100 g/eq to 20,000 g/eq. The pressure-sensitive adhesive composition of claim 1, wherein the base resin has a weight average molecular weight in the range of 100,000 to 1,000,000. The pressure-sensitive adhesive composition of claim 1, wherein the acrylic compound satisfies the following Chemical Formula 1:
[Formula 1]

In Formula 1, R ₁ is hydrogen or an alkyl group, R ₂ is a single bond, an alkylene group or an alkylidene group, and X is a functional group capable of bonding with a reactive functional group. The pressure-sensitive adhesive according to claim 1, wherein the functional group bondable to the reactive functional group is at least one selected from glycidyl group, isocyanate group, hydroxy group, carboxyl group, amide group, epoxide group, cyclic ether group, sulfide group, acetal group and lactone group. Composition. The pressure-sensitive adhesive composition of claim 1, wherein the base resin and the acrylic compound are included in a ratio of 70 to 90 parts by weight and 1 to 40 parts by weight, respectively. The pressure-sensitive adhesive composition of claim 1, wherein the base resin and the acrylic compound are present in a bonded state, and further comprises a curable compound. The pressure-sensitive adhesive composition of claim 10, wherein the curable compound comprises an active energy ray polymerizable compound. The pressure-sensitive adhesive composition of claim 10, wherein the curable compound comprises a polyfunctional acrylate. The pressure-sensitive adhesive composition of claim 10, wherein the curable compound has a cyclic structure in which the cyclic atoms are in the range of 3 to 20 in the molecular structure. The pressure-sensitive adhesive composition of claim 10, wherein the curable compound is contained in an amount of 10 to 50 parts by weight based on 100 parts by weight of the base resin. The pressure-sensitive adhesive composition according to claim 10, further comprising an initiator. The pressure-sensitive adhesive composition according to claim 1, further comprising a tackifier. The pressure-sensitive adhesive composition according to claim 16, wherein the tackifier comprises a terpene phenol-based tackifier. The pressure-sensitive adhesive composition of claim 16, wherein the tackifier is contained in an amount of 10 to 100 parts by weight based on 100 parts by weight of the base resin. An adhesive film having an adhesive layer comprising the adhesive composition according to claim 1. Board; An organic electronic device formed on one surface of the substrate; And an adhesive film according to claim 19 for sealing the entire surface of the organic electronic device.

Images