WO2016032281A1 - Plastic substrate - Google Patents

Abstract

The present application relates to a plastic substrate, a method for producing same, an organic electronic device, and display light source and lighting apparatus. The plastic substrate according to the present application has superb light extraction efficiency and exhibits an excellent surface roughness characteristic. Furthermore, the method for producing the plastic substrate according to the present application can produce the plastic substrate by means of a process in which scattering components are added secondarily. Moreover, the plastic substrate according to the present application can be utilized as a substrate for an organic electronic device, and the organic electronic device can be utilized as display light source and lighting apparatus.

Description

Plastic substrate

Cross Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0112911 dated August 28, 2014 and Korean Patent Application No. 10-2015-0121560 dated August 28, 2015. All content disclosed in the literature is included as part of this specification.

Technical Field

The present application relates to a plastic substrate, a method of manufacturing the substrate, an organic electronic device, a light source and a lighting device.

An organic electronic device (OED) is, for example, a device including one or more layers of organic materials capable of conducting current, as disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 1996-176293). to be. The type of organic electronic device includes an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC), or an organic transistor.

An organic light emitting device, which is a representative organic electronic device, typically includes a substrate, a first electrode layer, an organic layer, and a second electrode layer sequentially. In a structure called a bottom emitting device, the first electrode layer may be formed of a transparent electrode layer, and the second electrode layer may be formed of a reflective electrode layer. In addition, in a structure called a top emitting device, the first electrode layer may be formed of a reflective electrode layer, and the second electrode layer may be formed of a transparent electrode layer. Electrons and holes injected by the electrode layer may be recombined in the emission layer existing in the organic layer to generate light. Light may be emitted to the substrate side in the bottom light emitting device and to the second electrode layer side in the top light emitting device.

The present application provides a plastic substrate, a method of manufacturing the substrate, an organic electronic device, a light source, and a lighting device.

The present application relates to a plastic substrate. Exemplary plastic substrates of the present application have a support layer comprising a polymeric binder and scattering components contained within the polymeric binder. 1 exemplarily shows a plastic substrate 1 having a polymeric binder 1011 and a support layer 101 comprising a scattering component 1012 contained in the polymeric binder.

As an example, as shown in FIG. 1, the plastic substrate may include the scattering component 1012 completely in the polymer binder 1011 so that the support layer 101 may have a flat surface. As another example, as illustrated in FIG. 2, the plastic substrate may have the scattering component 1012 exposed to the surface of the polymer binder 1011 so that the surface of the support layer 101 may have an uneven structure.

As used herein, the term "scattering component" has a refractive index different from that of a surrounding material such as a polymer binder and the like, and has an appropriate size to form an area capable of scattering, refracting, or diffracting incident light. It can mean a substance. The scattering component may be, for example, in the form of particles.

The content ratio of the scattering component in the polymer binder may be appropriately selected within a range that does not impair the purpose of the present application. In one example, the scattering component may be included in the polymer binder in a proportion within the range of 0.05% to 3.75% by weight. In the present specification, "the content ratio of the scattering component in the polymer binder is A wt%" may mean that the content ratio of the scattering component is 100% by weight of the polymer binder. In the present specification, 100% by weight of the polymer binder may mean a weight ratio based on the weight of the polymer binder excluding the solvent. The upper limit of the content ratio in the polymer binder of the scattering component is specifically 3.75 wt% or less, 3.5 wt% or less, 3.25 wt% or less, 3 wt% or less, 2.75 wt% or less, 2.5 wt% or less, 2.25 wt% or less, 2 wt% % Or less, 1.9% or less, 1.8% or less, or 1.7% or less, or 1.6% or less. The lower limit of the content ratio in the polymer binder of the scattering component is specifically 0.05% by weight, 0.1% by weight, 0.15% by weight, 0.2% by weight, 0.25% by weight, 0.3% by weight, 0.35% by weight, 0.4% by weight. % Or more, 0.45% or more, or 0.5% or more. When the content ratio of the scattering component in the polymer binder is within the above range, it is possible to provide a plastic substrate having excellent light extraction performance.

The content ratio of the scattering component in the polymer binder is not necessarily limited to the above range, and may be adjusted to be below or above the above range in consideration of the haze characteristics of the support layer and / or the plastic substrate to be implemented. However, as will be described later, considering that the plastic substrate of the present application is manufactured by superimposing the scattering component on the polymer binder precursor, the upper limit of the content ratio of the scattering component in the polymer binder may be about 10% by weight. have. When the content ratio of the scattering component in the polymer binder precursor exceeds about 10% by weight, the filter may be clogged in the filtering step, and sufficient filtering is not performed, thus including the polymer binder precursor and the scattering component. Since the surface of the coating layer is rough after coating the layer of the composition to be disadvantageous when manufacturing the device.

The thickness of the support layer may be appropriately selected within a range that does not impair the purpose of the present application. In one example, the thickness of the support layer may be in the range of about 10 μm to 130 μm. Specifically, the upper limit of the thickness of the support layer may be 130 μm or less, 120 μm or less, 110 μm or less, 100 μm or less, 90 μm or less, 80 μm or less, or 70 μm or less. In addition, the lower limit of the thickness of the support layer may be 10 µm or more, 20 µm or more, 30 µm or more, 40 µm or more, 50 µm or more, or 60 µm or more. When the thickness of the support layer is within the above range, it is possible to provide a plastic substrate having excellent light extraction performance.

In addition, the thickness of the support layer within the above range means that the support layer itself has a sufficient thickness to function as a substrate such as an organic electronic device. This results in a very thin thickness of the light extraction layer, for example, on a conventional plastic substrate (without light extraction capability) of sufficient thickness to function as a substrate in manufacturing a plastic substrate having conventional light extraction capability. It is different from the structure coated with a thickness of about 2 μm or less. According to the present application, the support layer is advantageous in terms of fabrication of the substrate since it can simultaneously perform the function of the substrate and the function of the light extraction layer.

The haze of the plastic substrate may be appropriately selected within a range that does not impair the purpose of the present application. In one example, the haze of the plastic substrate can range from about 5% to 80%. The upper limit of the haze of the plastic substrate is specifically 80% or less, 77.5% or less, 75% or less, 72.5% or less, 70% or less, 67.5% or less, 65% or less, 62.5% or less, 60% or less, 57.5% or less or 55 It may be less than or equal to%. Further, the lower limit of the haze of the plastic substrate is specifically 5% or more, 7.5% or more, 10% or more, 12.5% or more, 15% or more, 17.5% or more, 20% or more, 22.5% or more, 25% or more, 27.5% At least 30%, at least 32.5%, at least 35%, at least 37.%, at least 40%, at least 42.5%, at least 45%, at least 47.5%, at least 50% or at least 52.5%. When the haze of the plastic substrate is within the above range, it is possible to provide a plastic substrate having excellent light extraction performance.

In the present specification, the method of measuring the haze of the plastic substrate is not particularly limited, and haze may be measured by employing a haze measuring method known in the art. In one example, the haze can be measured using a D65 light source with a hazemeter known in the art, for example, the HM-150 device from MURAKAMI.

The plastic substrate may exhibit the haze range even in a state in which no haze-inducing element is included in addition to the scattering component of the support layer. In the present specification, that the plastic substrate does not include a haze-inducing element other than the scattering component of the support layer, the only haze-inducing component in the plastic substrate is a scattering component, and further includes a haze-inducing layer or a haze-inducing component in the polymerization of the polymer binder. It may mean that no additional addition.

For example, the plastic substrate of the present application may exhibit haze in the range of about 5% to 80% without including a haze causing element other than the scattering component of the support layer. The upper limit of the haze of the plastic substrate is specifically 80% or less, 77.5% or less, 75% or less, 72.5% or less, 70% or less, 67.5% or less, 65% or less, 62.5% or less, 60% or less, 57.5% or less or 55 It may be less than or equal to%. Further, the lower limit of the haze of the plastic substrate is specifically 5% or more, 7.5% or more, 10% or more, 12.5% or more, 15% or more, 17.5% or more, 20% or more, 22.5% or more, 25% or more, 27.5% At least 30%, at least 32.5%, at least 35%, at least 37.%, at least 40%, at least 42.5%, at least 45%, at least 47.5%, at least 50% or at least 52.5%. According to the present application, since the plastic substrate is manufactured by superimposing the scattering components before the conversion from the polymer binder precursor to the polymer binder, it is possible to ensure stable dispersibility of the scattering components in the polymer binder, and thus a haze-inducing element in addition to the scattering components Even if it does not include the excellent haze characteristics as shown above.

The plastic substrate of the present application also has excellent surface roughness characteristics. The excellent surface roughness characteristics of the substrate in the present specification may mean that the surface is flat because the surface roughness of the substrate is low. In the support layer including the polymer binder and the scattering component, it is generally expected that the higher the content ratio of the scattering component, the thicker the support layer, the higher the haze. According to the present application, although the content ratio of the scattering component is relatively low and the thickness of the support layer is relatively high, even if it exhibits similar haze characteristics, compared with the case where the ratio of the scattering component is relatively high and the thickness of the support layer is relatively low, It can exhibit excellent surface roughness characteristics. This may be attributed to the relatively low content of the scattering component. Furthermore, as will be described later, the plastic substrate of the present application is manufactured by superimposing the scattering component on the polymer binder precursor, in which case the dispersibility of the scattering component in the support layer can be stably secured, as compared to the method of post-adding. This is because scattering components at the surface can reduce aggregation. When scattering components are agglomerated on the surface of the plastic substrate, a short may occur, which is disadvantageous for device fabrication.

Therefore, as described above, in manufacturing a plastic substrate having light extraction performance, compared to the prior art of coating a light extraction layer in a very thin thickness on a general plastic substrate of sufficient thickness to perform a function as a substrate, The plastic substrate of the present application is more advantageous in terms of the dispersion stability of the scattering components in the support layer, the uniformity of the scattering components and the surface roughness characteristics.

In one example, the support layer may have a surface roughness (Ra) in a range of about 0.1 nm to 30 nm measured in a region of 20 μm × 20 μm or more. More specifically, the upper limit of the surface roughness Ra may be 30 nm or less, 27.5 nm or less, 25 nm or less, 22.5 nm or less, 20 nm or less, 17.5 nm or less, 15 nm or less, or 12.5 nm or less. Further, the lower limit of the surface roughness Ra is more specifically 0.1 nm or more, 1 nm or more, 2 nm or more, 3 nm or more, 4 nm or more, 5 nm or more, 6 nm or more, 7 nm or more, 8 nm or more. Or 9 nm or more. When the surface roughness of the support layer is within the above range, the plastic substrate may exhibit excellent surface roughness characteristics, and when the plastic substrate is applied to the substrate of the organic electronic device described later, it is advantageous in terms of device fabrication of the organic electronic device, and short Does not cause problems such as

In the present specification, the method of measuring the surface roughness is not particularly limited, and the surface roughness may be measured by employing a surface roughness measuring method known in the art. In one example, the surface roughness is AFM (atomic force microscope) equipment known in the art, for example, NS4 D3100 DEN P-4 Rev. A device can be used for non-contact (vibrating) measurements.

The plastic substrate of the present application also shows excellent light transmittance. For example, the plastic substrate has a transmittance of at least 80%, at least 82%, at least 84%, at least 86%, at least 88% for light of at least one wavelength in the visible region, for example, at a wavelength of 550 nm or at 638 nm. Or 90% or more. Plastic substrate of the present application includes a relatively small amount of scattering components in order to exhibit the haze characteristics and / or light extraction performance to be implemented, and because of using a relatively thick thickness of the support layer, it can exhibit such excellent light transmittance have. Since the plastic substrate of the present application has excellent light transmittance as described above, the plastic substrate may be suitable as a substrate of an organic electronic device of a bottom emission type, but is not limited thereto.

The plastic substrate of the present application may exhibit excellent durability, peeling resistance and the like even in the process of forming an organic electronic device requiring high temperature. For example, the thermal expansion coefficient of the plastic substrate may be in the range of 10 ppm / ° C. to 50 ppm / ° C., but is not limited thereto.

The plastic substrate of the present application may exhibit high refractive index. In one example, the plastic substrate may have a refractive index of at least about 1.5, at least about 1.6, at least about 1.65, or at least about 1.7 for light having a wavelength of 550 nm or 633 nm. The upper limit of the refractive index is not particularly limited, but may be, for example, 1.9 or less, 1.85 or less, 1.80 or less, or 1.75 or less. Such a refractive index range can be ensured by, for example, forming a plastic substrate from a polymer material having a high refractive index or by blending high refractive index particles with a material of the plastic substrate. When the refractive index of the plastic substrate satisfies the above range, the total reflection phenomenon may be solved or alleviated in the substrate, thereby realizing an organic electronic device having excellent light extraction performance.

In one example, the polymer binder may include polyimide, polyethylene naphthalate, polycarbonate, acrylic resin, polyethylene terephthalate, polysulfone, polyether sulfide, polypropylene, polyether ether ketone or polydimethylsilonic acid However, it is not limited thereto. In one specific example, polyimide may be selected and used as the polymer binder in terms of process temperature or light extraction performance. Such a polyimide can be manufactured using the monomer which introduce | transduced a halogen atom, a sulfur atom, a phosphorus atom, etc., for example.

In one example, the polymer binder may include a polyimide compound including a repeating unit of Formula 1 below.

[Formula 1]

In Formula 1, L is a single bond, an alkylene group, an alkylidene group, an alkynylene group, an arylene group, an alkenylene group, -S-, -S (= O)-, -S (= O) 2- or -SS And R ₁ to R ₂₀ are each independently a hydrogen, an alkyl group, an alkoxy group, an aryl group or a functional group containing a halogen atom, a sulfur atom or a phosphorus atom, and n is an integer of 1 or more. In addition, R ₁ to R ₂₀ There is no substituent substituted on a carbon atom connecting two of the ring structure. For example, R ₂ and R ₅ are not present when the carbon atom to which R ₂ is connected and the carbon atom to which R ₈ is connected connect the benzene ring.

As used herein, the term "single bond" may mean that no separate atom or atom group exists at the corresponding site. For example, in Formula 1, when -L- is a single bond, benzene on both sides of -L- may be directly connected to form a biphenyl structure.

In the present specification, the alkyl group may be, for example, a straight or branched chain alkyl group having 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. . The alkyl group may be optionally substituted with one or more substituents.

In the present specification, unless otherwise specified, for example, an alkoxy group may mean an alkoxy group having 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. The alkoxy group may be linear, branched or cyclic. The alkoxy group may be optionally substituted by one or more substituents.

The aryl group or the arylene group herein includes, unless otherwise specified, an aromatic compound comprising a benzene or a structure containing two or more benzene condensed or bonded while sharing two or one carbon atom or It may mean a monovalent residue or a divalent residue derived from a derivative. The aryl group or arylene group may be, for example, an aryl group or arylene group having 6 to 22 carbon atoms, 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 14 carbon atoms or 6 to 12 carbon atoms. , The aryl group or arylene group may be optionally substituted by one or more substituents.

In this specification, unless otherwise specified, the alkylene group or the alkylidene group may be, for example, an alkylene group having 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. It may mean a leaden group. The alkylene group or alkylidene group may be, for example, linear, branched or cyclic. In addition, the alkylene group or alkylidene group may be optionally substituted by one or more substituents.

In the present specification, unless otherwise specified, the alkenylene group or alkynyldene group includes, for example, an alkenylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. Or an alkynylidene group. The alkenylene group or alkynylidene group may be, for example, linear, branched or cyclic. In addition, the alkenylene group or alkynylidene group may be optionally substituted with one or more substituents.

In the present specification, unless otherwise specified, the alkenyl group may be, for example, an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. The alkenyl group may be, for example, linear, branched or cyclic. In addition, the alkenyl group may be optionally substituted with one or more substituents.

In the present specification, substituents that may be substituted with an alkyl group, an alkoxy group, an aryl group, an alkylene group, an alkylidene group, an alkenylene group, an alkynylene group, an arylene group, or the like include a halogen atom such as fluorine, chlorine, bromine or iodine, A functional group, a phenyl group, a benzyl group, a naphthyl group, or a thiophenyl group, including a sulfur atom or a phosphorus atom, etc. may be exemplified, but is not limited thereto.

The polymeric binder may be a homopolymer formed of only the repeating unit of Formula 1, or may be a block or random copolymer including other units other than the repeating unit of Formula 1. In addition, both ends of the polymer may be independently a hydrogen, an alkyl group, an alkoxy group aryl group or a functional group including a halogen atom, a sulfur atom or a phosphorus atom. In the case of a copolymer, the kind and ratio of another repeating unit can be suitably selected in the range which does not inhibit a desired refractive index, heat resistance, a light transmittance, etc., for example.

The polymer binder including the repeating unit of Chemical Formula 1 may be, for example, about 10,000 to 100,000 or about 10,000 to 50,000 in terms of weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). The polymeric binder having a repeating unit of formula (1) also has a light transmittance of 80% or more, 85% or more or 90% or more in the visible light region, and is excellent in heat resistance.

In the plastic substrate of the present application, the average particle diameter of the scattering component may be in the range of 150 nm to 300 nm. The lower limit of the average particle diameter of the scattering component may be 150 nm or more, 160 nm or more, 170 nm or more, 180 mm or more, 190 mm or 200 nm or more. In addition, an upper limit of the average particle diameter of the scattering component may be specifically 300 nm or less, 290 nm or less, 280 nm or less, 270 nm or less, 260 nm or less, or 250 nm or less. When the average particle diameter of the scattering component satisfies the above range, it is possible to provide a plastic substrate having excellent light extraction performance.

In the plastic substrate of the present application, the scattering component may have a higher or lower refractive index than the surrounding material, for example, a polymeric binder. For example, the absolute value of the difference in refractive index for the light of the wavelength of 550 nm or 633 nm of the polymeric binder and the scattering component may be in the range of 0.5 to 1.2. The lower limit of the absolute value of the difference in refractive index may be specifically 0.5 or more, 0.55 or more, 0.6 or more, 0.65 or more, or 0.7 or more. In addition, an upper limit of the absolute value of the difference in refractive index may be specifically 1.2 or less, 1.15 or less, 1.1 or less, 1.05 or less, or 1 or less. When the absolute value of the refractive index difference between the polymer binder and the binder of the scattering component satisfies the above range, an organic electronic device having excellent light extraction performance can be provided by appropriately scattering, refracting, or diffracting light incident on the plastic substrate.

In the plastic substrate of the present application, the shape of the scattering component may be appropriately selected within a range that does not impair the purpose of the present application. In one example, the scattering component may have a shape such as spherical, oval, polyhedron or amorphous, but is not limited thereto.

In the plastic substrate of the present application, as the scattering component, a material capable of forming a region capable of scattering, refracting, or diffracting light incident in a state contained in a polymer binder may be appropriately selected from known materials known in the art. Can be used. The scattering component may include, for example, an organic material and / or an inorganic material. Examples of the organic material include acrylic resins, styrene resins, olefin resins, nylon resins, melamine resins, formaldehyde resins, silicone resins, urethane resins, polyester resins, polycarbonate resins and derivatives thereof. An organic material including one or more may be exemplified, but is not limited thereto. The inorganic material may be a metal or an oxide of a metal, but is not limited thereto. Examples of the inorganic substance include TiO ₂ , HfO ₂ , BaTiO ₃ , SnO ₂ , ZrO ₂ , ZnO, Al ₂ O _3, and SiO _2. Minerals including one or more selected from the group consisting of may be exemplified, but are not limited thereto. The scattering component may be formed of only one of the above materials or two or more of the above materials. For example, hollow particles such as hollow silica or particles having a core / cell structure may be used as the scattering component.

In the exemplary plastic substrate of the present application, a barrier layer may be further formed on one or both surfaces of the support layer. As used herein, the term "barrier layer" may mean a layer having a function of preventing permeation of oxygen, moisture, nitrogen oxides, sulfur oxides, or ozone in the atmosphere. The barrier layer is not particularly limited as long as it has the above function, and may be appropriately selected depending on the intended use.

In one example, the barrier layer may be formed on one side or both sides of the plastic substrate via a buffer layer. That is, the plastic substrate may further include a buffer layer formed between the barrier layer and the support layer. The buffer layer may serve to improve adhesion between the barrier layer and the base layer. The buffer layer may be formed by, for example, depositing an inorganic layer such as SiO ₂ , SiONx or SiNx by a sputtering method or a known vacuum deposition method. If necessary, the buffer layer may be formed by a method of organic / inorganic coating.

The material of the barrier layer may be selected and used without limitation, a material having a function of preventing the substances that promote device degradation such as moisture and oxygen from entering the device.

In one example, the barrier layer may be formed of a metal such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni; TiO, TiO ₂ , Ti ₃ O _{3 ,} Al ₂ O ₃ , MgO, SiO, SiO ₂ , GeO, NiO, CaO, BaO, Fe ₂ O ₃ , Y2O ₃ , ZrO ₂ , Nb ₂ O ₃ and CeO ₂ and Metal oxides such as; Metal nitrides such as SiN; Metal oxynitrides such as SiON; Metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ ; Polyethylene, polypropylene, polymethylmethacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, or chlorotrifluoroethylene and dichlorodifluoroethylene Copolymers; Copolymers obtained by copolymerizing a comonomer mixture comprising at least one comonomer with tetrafluoroethylene; Fluorine-containing copolymer which has a cyclic structure in a copolymer main chain; An absorbent material having an absorption rate of 1% or more; And moisture proof materials having an absorption coefficient of 0.1% or less.

In another example, the material of the barrier layer may be a metal oxide. For example, the material of the barrier layer may be a high refractive index metal oxide. Accordingly, the refractive index of the barrier layer may be, for example, about 1.45 or more, about 1.5 or more, about 1.6 or more, about 1.65 or more, or about 1.7 or more with respect to a wavelength of 633 nm. In addition, the upper limit of the refractive index of the barrier layer can be appropriately adjusted according to the desired function, for example, the refractive index for the wavelength of 633 nm may be 2.6 or less, 2.3 or less, 2.0 or less or 1.8 or less. When the refractive index of the barrier layer satisfies the above range, the total reflection phenomenon may be solved or alleviated, so that an organic electronic device having excellent light extraction performance may be implemented.

In one example, the barrier layer may be a single layer structure or a multilayer structure. The single layer structure may include, for example, a material of one kind of barrier layer, or may include a mixture of two or more types of barrier layers. The multilayer structure may be, for example, a structure in which two or more layers of the single layer structure are stacked, and in one suitable example, the barrier layer may include a titanium oxide layer (eg, TiO ₂ layer) and an aluminum oxide layer (eg, For example, the Al ₂ O ₃ layer) may be a multilayer structure sequentially stacked.

The thickness of the barrier layer is not particularly limited and may be appropriately selected depending on the intended use. In one example, the thickness of the barrier layer can be 5 nm to 1000 nm, 7 nm to 750 nm or 10 nm to 500 nm.

The light transmittance of the barrier layer is not particularly limited and may be appropriately selected depending on the intended use. In one example, the light transmittance of the barrier layer may be at least about 80%, at least 85%, or at least 90%.

In one example, the barrier layer can have a refractive index that is comparable to the adjacent layer. For example, when the electrode layer is adjacent to the barrier layer, the barrier layer may have a refractive index of 1.5 or more for light having a wavelength of 550 nm or 633 nm. Accordingly, since the total reflection phenomenon at the interface between the barrier layer and the electrode layer can be solved or alleviated, an organic electronic device having excellent light extraction performance can be realized.

In one example, the barrier layer may have a water vapor transmission rate (WVTR) of 10 ⁻⁴ g / m ² · day or less. The water vapor transmission rate may be, for example, a value measured at a temperature of 40 ° C. and a relative humidity of 90%. The water vapor transmission rate can be measured using, for example, a water vapor transmission rate meter (manufactured by PERMATRAN-W3 / 31, manufactured by MOCON, Inc.). When the barrier layer satisfies the numerical range, curl does not occur due to the penetration of foreign substances such as moisture or oxygen even in a high temperature and high humidity environment. An electronic device can be implemented.

The barrier layer is, for example, ALD (Atomic Layer Deposition) method, vacuum deposition method, sputtering method, reactive sputtering method, MBE (molecular beam epitaxy) method, cluster ion beam method, ion plating method, plasma polymerization method (high frequency excitation ion plating method), It may be a layer formed by plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method or coating method, and may be an atomic layer deposition layer formed by ALD method as one suitable example.

The plastic substrate of the present application may further include a flat layer. The flat layer may be formed on one or both surfaces of the support layer, for example. In one example, the flat layer has such a concave-convex structure when the scattering component 1012 is exposed to the surface of the polymeric binder 1011 such that the surface of the support layer has a concave-convex structure, such as the plastic substrate illustrated in FIG. 2. It may be formed on the upper surface of the support layer. 3 exemplarily illustrates a plastic substrate 1 having a structure in which a flat layer 301 is formed on an upper surface of a support layer 101 having an uneven structure.

The planarization layer can include high refractive particles, for example, with a binder. The flat layer may be formed using a composition in which high refractive particles are mixed with a binder. The flat layer may provide a surface on which an organic electronic device including an electrode layer and the like may be formed, and have light scattering properties to improve light extraction performance of the device. The flat layer may have a refractive index that is equal to or greater than that of the adjacent electrode layer, and for example, the refractive index of light having a wavelength of 550 nm or 633 nm may be 1.5 or more.

As the binder of the flat layer, a known material can be used without particular limitation. As the binder, for example, various organic binders, inorganic binders or organic-inorganic binders known in the art can be used. The organic binder, the inorganic binder, or the organic / inorganic binder having excellent heat resistance and chemical resistance may be selected and used in consideration of excellent resistance to a high temperature process, a photo process or an etching process performed during the life of the device or the fabrication process. The binder may, for example, have a refractive index of at least about 1.4, at least about 1.45, at least about 1.5, at least about 1.6, at least about 1.65, or at least about 1.7. The upper limit of the refractive index of the binder may be selected in a range capable of satisfying the refractive index of the flat layer in consideration of the refractive index of the particles to be blended together. As the binder, for example, epoxy resin, polysiloxane or polyimide can be exemplified.

As a binder of a flat layer, a high refractive binder or a low refractive binder can be used, for example. As used herein, the term "high refractive index binder" means a binder having a refractive index of about 1.7 to 2.5 or about 1.7 to 2.0, and the term "low refractive binder" may mean a binder having a refractive index of about 1.4 or more and less than about 1.7. have. Such binders are variously known, and suitable binders may be selected and used among various kinds of binders described above or other known binders.

The flat layer may further comprise high refractive particles. In the flat layer, the term "high refractive particles" may mean, for example, particles having a refractive index of 1.8 or more, 2.0 or more, 2.2 or more, 2.5 or more, 2.6 or more, or 2.7 or more. The upper limit of the refractive index of the high refractive particles may be selected in a range capable of satisfying the refractive index of the flat layer, for example, in consideration of the refractive index of the binder and the like blended together. The high refractive particles may be, for example, about 1 nm to 100 nm, 10 nm to 90 nm, 10 nm to 80 nm, 10 nm to 70 nm, 10 nm to 60 nm, 10 nm to 50 nm or about 10 nm to 45 nm. It may have an average particle diameter of. As the high refractive particles, for example, alumina, aluminosilicate, titanium oxide or zirconium oxide and the like can be exemplified. As the high refractive particles, rutile titanium oxide can be used, for example, as particles having a refractive index of 2.5 or more. Titanium oxide of the rutile type has a high refractive index compared to other particles, and therefore can be adjusted to the desired refractive index in a relatively small proportion. The refractive index of the high refractive particles may be a refractive index measured for light of 550 nm wavelength or 633 nm. In one example, the flat layer may include high refractive particles having a refractive index of 1.8 or more and an average particle diameter of 50 nm or less for light having a wavelength of 633 nm.

The ratio of the high refractive particles in the flat layer is not particularly limited and may be adjusted within a range in which the refractive index of the flat layer described above can be secured. In consideration of the physical properties of the flat layer, for example, moisture or moisture permeability of the flat layer, outgassing, etc., the high refractive particles are 300 parts by weight or less, 250 parts by weight or less, 200 parts by weight or less relative to 100 parts by weight of the binder. It may be included in the flat layer in a ratio of 150 parts by weight or less or 120 parts by weight or less. In addition, the ratio of the high refractive particles may be, for example, 40 parts by weight or more, 60 parts by weight or more, 80 parts by weight or more, or 100 parts by weight or more. In the present specification, "unit weight part" means the ratio of weight between components, unless otherwise specified. By maintaining the ratio of the binder and the high refractive particles as described above, for example, to form an organic electronic device to increase the external quantum efficiency, to prevent the ingress of gas or water from the outside, and to reduce the outgasing A device having excellent performance and reliability can be provided.

The flat layer may be, for example, a wet coating method using a coating liquid containing a binder and high refractive particles, a deposition method such as a sol-gel method, a chemical vapor deposition (CVD) or a physical vapor deposition (PVD) method, or a micro It can be formed through an embossing method, but is not limited thereto.

In another example, the flat layer may be formed using a material in which a compound such as alkoxide or acylate of a metal such as zirconium, titanium or cerium is combined with a binder having a polar group such as a carboxyl group or a hydroxy group. Compounds such as alkoxides or acylates may be condensed with the polar groups in the binder, and the high refractive index may be realized by including the metal in the binder. Examples of the alkoxide or acylate compound include titanium alkoxides such as tetra-n-butoxy titanium, tetraisopropoxy titanium, tetra-n-propoxy titanium or tetraethoxy titanium, titanium stearate and the like. Zirconium such as zirconium alkoxides such as titanium acylate, titanium chelates, tetra-n-butoxy zirconium, tetra-n-propoxy zirconium, tetraisopropoxy zirconium or tetraethoxy zirconium and zirconium tributoxy stearate Acylate, zirconium chelates, etc. can be illustrated. The flat layer may also be formed by a sol-gel coating method in which a metal alkoxide, such as titanium alkoxide or zirconium alkoxide, and a solvent such as alcohol or water are prepared to prepare a coating liquid, and after the coating is applied, the coating solution is baked at an appropriate temperature.

The plastic substrate of the present application may further include a carrier substrate attached to one surface of the support layer. In one example, when the barrier layer or the flat layer is further formed on a plastic substrate, a surface opposite to the barrier layer or the flat layer may be in contact with the carrier substrate.

In one example, the carrier substrate may use a glass substrate or a rigid substrate, for example. As the glass substrate, an appropriate material can be used without particular limitation, and for example, a base layer such as soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, or quartz can be used. It may be illustrated, but is not limited thereto. In one example, the carrier substrate may be formed to be detachable from the plastic substrate.

The present application also relates to a method of manufacturing the plastic substrate. Exemplary plastic substrate manufacturing methods of the present application include forming a layer of a composition comprising a polymeric binder precursor and a scattering component, and converting the polymeric binder precursor into a polymeric binder in the layer.

In the manufacturing method, the composition including the polymer binder precursor and the scattering component may include the scattering component in a ratio within the range of about 0.05% to 3.75% by weight based on 100% by weight of the polymer binder precursor. In the present specification, "100 wt% polymer binder precursor" may refer to a weight ratio based on the weight of the polymer binder precursor except for the solvent. Specific matters regarding the content ratio of the scattering component may be equally applicable to the content ratio of the scattering component in the polymer binder described in the item of the plastic substrate.

In the above production method, the layer of the composition may be formed to a thickness within the range of about 10 μm to 130 μm. The layer of the composition may be the support layer described in the section of the plastic substrate by converting the polymeric binder precursor to a polymeric binder. Therefore, the details regarding the thickness of the layer of the composition may be equally applicable to the contents of the thickness of the support layer described in the item of the plastic substrate.

Since the manufacturing method relates to a manufacturing method of the plastic substrate, in the manufacturing method, the contents described in the items of the plastic substrate are equally applied to matters other than the content ratio of the scattering component and the thickness of the layer of the composition. Can be. Therefore, when manufacturing a plastic substrate by the said manufacturing method, the plastic substrate which exhibits the haze characteristic described in the item of the said plastic substrate can be manufactured.

The manufacturing method produces a plastic substrate by sintering the scattering component. As used herein, the term "addition" means that in the method of manufacturing a plastic substrate having a support layer comprising a polymer binder and a scattering component, the step of adding the scattering component is performed before the polymer binder precursor is converted into the polymer binder. can do. That is, the term "addition" in the present specification may mean that the scattering component is added to the polymer binder precursor in the manufacturing method of the plastic substrate. On the contrary, in the present specification, the term “post-addition” may mean that in the method of manufacturing the plastic substrate, the step of adding the scattering component is performed after the polymer binder precursor is converted into the polymer binder. That is, in the present specification, the term "post-addition" may mean that the scattering component is added to the polymer binder in the method of manufacturing the plastic substrate.

As used herein, the term "polymer binder precursor" may refer to a material that is a material required to form a polymer binder or a material of a previous stage of the polymer binder in a series of reactions forming the polymer binder.

The high molecular weight binder precursor may be appropriately selected depending on the type of the polymeric binder. For example, when the polymer binder is polyimide, the polymer binder precursor may mean a polyamic acid or a monomer compound for synthesizing the polyamic acid. In such a case, the production method may be said to be heavy when the scattering component is blended with the polyamic acid or the monomer compound for synthesizing the polyamic acid.

As in the manufacturing method, when the plastic substrate is manufactured by squeezing the scattering component, it is possible to secure stable dispersibility of the scattering component in the polymer binder precursor and / or the polymer binder, and thus exhibit a haze suitable for light extraction performance. The plastic substrate which is excellent in a roughness characteristic can be manufactured. On the contrary, when the plastic substrate is manufactured by post-scattering the scattering component, it is impossible to secure the dispersibility of the scattering component in the polymer binder. Therefore, aggregation of the scattering component may occur inside the polymer binder or on the surface of the layer of the composition. It is difficult to represent a haze suitable for the light extraction performance and the surface roughness characteristics are also lowered there is a disadvantage in manufacturing the device.

In the above production method, the composition may be prepared by dissolving the polymer binder precursor and the scattering component in a suitable solvent. As a solvent, well-known organic solvents, such as toluene, xylene, cyclopentanone, or cyclohexanone, can be used. If necessary, the composition may further include additives such as a polymerization initiator, a surfactant, and the like.

In the above production method, the layer of the composition can be formed by applying a composition comprising a polymeric binder precursor and a scattering component onto a suitable substrate. The substrate may use the carrier substrate described in the section of the plastic substrate. The coating method is not particularly limited and a known coating method can be applied. As the coating method, for example, a roll coating, a printing method, an inkjet coating, a slit nozzle method, a bar coating, a comma coating, a spin coating or a gravure coating may be exemplified.

In one example, when the polymeric binder is polyimide, the polymeric binder precursor may be polyamic acid. As a polyamic acid, the well-known polyamic acid which can form a polyimide can be used. For example, a polyamic acid including a repeating unit represented by the following Formula 2 may be used as the polyamic acid.

[Formula 2]

In Formula 2, L is a single bond, an alkylene group, an alkylidene group, an alkynylene group, an arylene group, an alkenylene group, -S-, -S (= O)-, -S (= O) ₂ -or- SS is, and R ₁ to R ₂₀ are each independently a hydrogen, an alkyl group, an alkoxy group, an aryl group, or a functional group including a halogen atom, a sulfur atom, or a phosphorus atom, and n is an integer of 1 or more. Details of R ₁ to R ₂₀ may be the same as those described in Chemical Formula 1 of the plastic substrate.

In Formula 2, R ₁ to R ₂₀ do not have a substituent substituted on a carbon atom connecting two ring structures to each other. For example if, when R ₂ is attached is a carbon atom and a carbon atom connected to R ₈ is connected, R ₂ and R ₈ is absent, -NH- group and R ₁₄ is a carbon atom connected to R ₁₄ is coupled from the formula (2) Does not exist.

In one example, when the polymer binder is polyimide, the step of converting the polymer binder precursor to the polymer binder in the layer of the composition may be performed by a step of imidizing the polyamic acid. The condition or method of the imidation reaction is not particularly limited, and conditions or methods of the imidation reaction for converting a polyamic acid known in the art to polyimide may be applied.

The present application also relates to the use of the plastic substrate. For example, the present application relates to an organic electronic device including the plastic substrate. The organic electronic device includes a polymer binder; And a scattering component contained in the binder at a ratio within the range of 0.05% to 3.75% by weight, the support layer having a thickness in the range of 10 μm to 130 μm, and having a haze in the range of 5% to 80%. Board; A first electrode layer formed on the substrate; It may include an organic layer formed on the first electrode layer and a second electrode layer formed on the organic layer. For the plastic substrate of the organic electronic device, the contents described in the items of the plastic substrate may be applied in the same manner.

The organic layer may include at least a light emitting layer. For example, when the first electrode layer is transparently implemented and the second electrode layer is a reflective electrode layer, a lower light emitting device in which light generated in the light emitting layer of the organic layer is emitted to the base layer side through the optical functional layer may be implemented.

The organic electronic device may be an organic light emitting device. In this case, the organic electronic device may have a structure in which an organic layer including at least the light emitting layer is interposed between the hole injection electrode layer and the electron injection electrode layer. For example, the first electrode layer formed on the plastic substrate may be a hole injection electrode layer, and the second electrode layer formed on the organic layer may be an electron injection electrode layer. The first electrode layer may be a transparent electrode layer.

The organic layer existing between the electron and the hole injection electrode layer may include at least one light emitting layer. The organic layer may include a plurality of light emitting layers of two or more layers. When two or more light emitting layers are included, the light emitting layers may have a structure divided by an intermediate electrode layer or a charge generating layer (CGL) having charge generation characteristics.

The light emitting layer can be formed using, for example, various fluorescent or phosphorescent organic materials known in the art. Examples of the material of the light emitting layer include tris (4-methyl-8-quinolinolate) aluminum (III) (tris (4-methyl-8-quinolinolate) aluminum (III)) (Alg3), 4-MAlq3 or Gaq3. Alq series materials, C-545T (C ₂₆ H ₂₆ N ₂ O ₂ S), DSA-amine, TBSA, BTP, PAP-NPA, Spiro-FPA, Ph ₃ Si (PhTDAOXD), PPCP (1,2,3 Cyclopenadiene derivatives such as, 4,5-pentaphenyl-1,3-cyclopentadiene), DPVBi (4,4'-bis (2,2'-diphenylyinyl) -1,1'-biphenyl), distyryl Benzene or derivatives thereof or DCJTB (4- (Dicyanomethylene) -2-tert-butyl-6- (1,1,7,7, tetramethyljulolidyl-9-enyl) -4H-pyran), DDP, AAAP, NPAMLI,; Or Firpic, m-Firpic, N-Firpic, bon ₂ Ir (acac), (C ₆ ) ₂ Ir (acac), bt ₂ Ir (acac), dp ₂ Ir (acac), bzq ₂ Ir (acac), bo _{2 Ir (acac), F 2} Ir (bpy), F 2 Ir (acac), op 2 Ir (acac), ppy 2 Ir (acac), tpy 2 Ir (acac), FIrppy (fac-tris [2- ( 4,5-difluorophenyl) pyridine-C'2, N] iridium (III)) or Btp ₂ Ir (acac) (bis (2- (2'-benzo [4,5-a] thienyl) pyridinato-N, Phosphorescent materials such as C3 ') iridium (acetylactonate)) and the like can be exemplified, but is not limited thereto. The light emitting layer includes the material as a host, and further includes perylene, distyrylbiphenyl, DPT, quinacridone, rubrene, BTX, ABTX, or DCJTB. It may have a host-dopant system including a dopant.

The light emitting layer can be formed by appropriately adopting a kind showing light emission characteristics among the electron-accepting organic compound or electron donating organic compound described later.

The organic layer may be formed in various structures further including other various functional layers known in the art, as long as it includes a light emitting layer. Examples of the layer that may be included in the organic layer may include an electron injection layer, a hole blocking layer, an electron transport layer, a hole transport layer, a hole injection layer, and the like.

The electron injection layer or the electron transport layer can be formed using, for example, an electron accepting organic compound. As the electron-accepting organic compound in the above, any compound known without particular limitation may be used. Such organic compounds include polycyclic compounds such as p-terphenyl or quaterphenyl or derivatives thereof, naphthalene, tetratracene, pyrene, coronene, and coronene. ), Polycyclic hydrocarbon compounds or derivatives thereof, such as chrysene, anthracene, diphenylanthracene, naphthacene or phenanthrene, phenanthroline, vasophenanthrol Heterocyclic compounds or derivatives thereof, such as lean (bathophenanthroline), phenanthridine, acridine (acridine), quinoline (quinoline), quinoxaline or phenazine (phenazine) and the like. In addition, fluoroceine, perylene, phthaloperylene, naphthaloperylene, naphthaloperylene, perynone, phthaloperinone, naphtharoferinone, diphenylbutadiene ( diphenylbutadiene, tetraphenylbutadiene, oxadiazole, ardazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene , Oxine, aminoquinoline, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyrane, thiopyrane, polymethine, mero Cyanine (merocyanine), quinacridone or rubrene, or derivatives thereof, JP-A-1988-295695, JP-A-1996-22557, JP-A-1996-81472, Japanese Patent Laid-Open Publication No. 1993-009470 or Japanese Patent Laid-Open Publication Metal chelate complex compounds disclosed in Japanese Patent Application Publication No. 017764, for example, tris (8-quinolinolato) aluminium, which is a metal chelated oxanoid compound, and bis (8-quinolin) Norato) magnesium, bis [benzo (f) -8-quinolinolato] zinc {bis [benzo (f) -8-quinolinolato] zinc}, bis (2-methyl-8-quinolinolato) aluminum, Tris (8-quinolinolato) indium, tris (5-methyl-8-quinolinolato) aluminum, 8-quinolinolatorium, tris (5-chloro- Metal complex having one or more 8-quinolinolato or derivatives thereof, such as 8-quinolinolato) gallium, bis (5-chloro-8-quinolinolato) calcium, as derivatives, Japanese Patent Application Laid-Open No. 1993-202011 Oxadiazole compounds disclosed in Japanese Patent Laid-Open No. 195-179394, Japanese Patent Laid-Open Publication No. 195-278124, or Japanese Patent Publication No. 195-228579, and Japanese Patent Publication Triazine compounds disclosed in Japanese Patent Application Laid-Open Nos. 195-157473, Stilbene Derivatives, Distyrylarylene Derivatives, and Japanese Patent Publication No. 194-132080 Styryl derivatives disclosed in Japanese Patent Application Laid-Open No. 1944-88072 and the like, diolefin derivatives disclosed in Japanese Patent Laid-Open No. 194-100857 and Japanese Patent Application Laid-Open No. 194-207170; Fluorescent brighteners such as a benzooxazole compound, a benzothiazole compound or a benzoimidazole compound; 1,4-bis (2-methylstyryl) benzene, 1,4-bis (3-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, distyrylbenzene, 1,4- Bis (2-ethylstyryl) benzyl, 1,4-bis (3-ethylstyryl) benzene, 1,4-bis (2-methylstyryl) -2-methylbenzene or 1,4-bis (2- Distyrylbenzene compounds such as methylstyryl) -2-ethylbenzene and the like; 2,5-bis (4-methylstyryl) pyrazine, 2,5-bis (4-ethylstyryl) pyrazine, 2,5-bis [2- (1-naphthyl) vinyl] pyrazine, 2,5- Distyryls such as bis (4-methoxystyryl) pyrazine, 2,5-bis [2- (4-biphenyl) vinyl] pyrazine or 2,5-bis [2- (1-pyrenyl) vinyl] pyrazine Pyrazine (distyrylpyrazine) compound, 1,4-phenylenedimethylidine, 4,4'-phenylenedimethylidine, 2,5-xylenedimethylidine, 2,6-naphthylenedimethylidine, 1,4-biphenylenedimethyl Lidine, 1,4-para-terphenylenedimethellidine, 9,10-anthracenediyldimethylidine or 4,4 '-(2,2-di-thi-butylphenylvinyl) biphenyl , Dimethylidine compounds or derivatives thereof, such as 4,4?-(2,2-diphenylvinyl) biphenyl, and the like described in JP-A-194-49079 or JP-A-1994-293778. Namin (silanamine) derivative, disclosed in Japanese Patent Laid-Open No. 194-279322 or Japanese Patent Laid-Open No. 194-279323 Polyfunctional styryl compound, an oxadiazole derivative disclosed in Japanese Patent Application Laid-Open No. 194-107648 or Japanese Patent Application Laid-Open No. 194-092947, an anthracene compound disclosed in Japanese Patent Application Laid-Open No. 194-206865, Japanese Patent Oxynate derivative disclosed in Japanese Patent Application Laid-Open No. 194-145146, tetraphenylbutadiene compound disclosed in Japanese Patent Application Laid-Open No. 1992-96990, organic trifunctional compound disclosed in Japanese Patent Application Laid-Open No. 1991-296595, Japanese Patent A coumarin derivative disclosed in Japanese Patent Application Laid-Open No. 1990-191694, a perylene derivative disclosed in Japanese Patent Application Laid-Open No. 1990-196885, a naphthalene derivative disclosed in Japanese Patent Application Laid-Open No. 1990-255789, and Japanese Patent Publication A phthaloperynone derivative disclosed in Japanese Patent Application Laid-Open No. 1990-289676 or Japanese Patent Application Laid-Open No. 1990-88689, or Japanese Patent Application Laid-Open No. 1990-25029 Styrylamine derivatives disclosed in Japanese Patent No. 2 and the like can also be used as the electron-accepting organic compound included in the low refractive layer. In addition, the electron injection layer may be formed using, for example, a material such as LiF or CsF.

The hole blocking layer is a layer capable of preventing the injected holes from entering the electron injection electrode layer through the light emitting layer to improve the life and efficiency of the device, and if necessary, using a known material, the light emitting layer and the electron injection electrode layer It can be formed in a suitable portion in between.

The hole injection layer or hole transport layer may comprise, for example, an electron donating organic compound. Examples of the electron donating organic compound include N, N ', N'-tetraphenyl-4,4'-diaminophenyl, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4, 4'-diaminobiphenyl, 2,2-bis (4-di-p-tolylaminophenyl) propane, N, N, N ', N'-tetra-p-tolyl-4,4'-diamino ratio Phenyl, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N , N, N ', N'-tetraphenyl-4,4'-diaminodiphenylether, 4,4'-bis (diphenylamino) quadriphenyl [4,4'-bis (diphenylamino) quadriphenyl], 4-N, N-diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminosteelbenzene, N-phenylcarbazole, 1,1-bis (4 -Di-p-triaminophenyl) cyclohexane, 1,1-bis (4-di-p-triaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane , N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, N, N, N ', N'-tetraphenyl-4,4'-diamino ratio Nyl N-phenylcarbazole, 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] biphenyl, 4,4'-bis [N- (1-naphthyl) -N- Phenylamino] p-terphenyl, 4,4'-bis [N- (2-naphthyl) -N-phenylamino] biphenyl, 4,4'-bis [N- (3-acenaphthenyl) -N -Phenylamino] biphenyl, 1,5-bis [N- (1-naphthyl) -N-phenylamino] naphthalene, 4,4'-bis [N- (9-anthryl) -N-phenylamino] Biphenylphenylamino] biphenyl, 4,4'-bis [N- (1-antryl) -N-phenylamino] -p-terphenyl, 4,4'-bis [N- (2-phenanthryl) -N-phenylamino] biphenyl, 4,4'-bis [N- (8-fluoranthenyl) -N-phenylamino] biphenyl, 4,4'-bis [N- (2-pyrenyl)- N-phenylamino] biphenyl, 4,4'-bis [N- (2-perylenyl) -N-phenylamino] biphenyl, 4,4'-bis [N- (1-coroneyl)- N-phenylamino] biphenyl (4,4'-bis [N- (1-coronenyl) -N-phenylamino] biphenyl), 2,6-bis (di-p-tolylamino) naphthalene, 2,6-bis [Di- (1-naphthyl) amino] naphthalene, 2,6-bis [N- (1-naphthyl) -N- (2-naphthyl) amino] naphthalene, 4,4'-ratio S [N, N-di (2-naphthyl) amino] terphenyl, 4,4'-bis {N-phenyl-N- [4- (1-naphthyl) phenyl] amino} biphenyl, 4,4 '-Bis [N-phenyl-N- (2-pyrenyl) amino] biphenyl, 2,6-bis [N, N-di- (2-naphthyl) amino] fluorene or 4,4'-bis Aryl amine compounds such as (N, N-di-p-tolylamino) terphenyl, and bis (N-1-naphthyl) (N-2-naphthyl) amine may be representatively exemplified, but are not limited thereto. It is not.

The hole injection layer or the hole transport layer may be formed by dispersing an organic compound in a polymer or using a polymer derived from the organic compound. Also, such as polyparaphenylene vinylene and derivatives thereof, so-called π-conjugated polymers, hole-transporting non-conjugated polymers such as poly (N-vinylcarbazole), or π-conjugated polymers of polysilane may also be used. Can be.

The hole injection layer is formed by using electrically conductive polymers such as metal phthalocyanine such as copper phthalocyanine, non-metal phthalocyanine, carbon film and polyaniline, or by reacting the aryl amine compound with Lewis acid as an oxidizing agent. You may.

By way of example, the organic light emitting device may include: (1) a hole injection electrode layer / organic light emitting layer / electron injection electrode layer formed sequentially; (2) the form of a hole injection electrode layer / hole injection layer / organic light emitting layer / electron injection electrode layer; (3) the form of a hole injection electrode layer / organic light emitting layer / electron injection layer / electron injection electrode layer; (4) the form of a hole injection electrode layer / hole injection layer / organic light emitting layer / electron injection layer / electron injection electrode layer; (5) the form of a hole injection electrode layer / organic semiconductor layer / organic light emitting layer / electron injection electrode layer; (6) the form of a hole injection electrode layer / organic semiconductor layer / electron barrier layer / organic light emitting layer / electron injection electrode layer; (7) the form of a hole injection electrode layer / organic semiconductor layer / organic light emitting layer / adhesion improvement layer / electron injection electrode layer; (8) the form of a hole injection electrode layer / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / electron injection electrode layer; (9) the form of a hole injection electrode layer / insulation layer / organic light emitting layer / insulation layer / electron injection electrode layer; (10) the form of a hole injection electrode layer / inorganic semiconductor layer / insulation layer / organic light emitting layer / insulation layer / electron injection electrode layer; (11) the form of a hole injection electrode layer / organic semiconductor layer / insulation layer / organic light emitting layer / insulation layer / electron injection electrode layer; (12) hole injection electrode layer / insulation layer / hole injection layer / hole transport layer / organic light emitting layer / insulation layer / electron injection electrode layer or (13) hole injection electrode layer / insulation layer / hole injection layer / hole transport layer / organic light emitting layer / electron It may have a form of an injection layer / electron injection electrode layer, and in some cases, an intermediate electrode layer or a charge generation layer (CGL) having at least two light emitting layers having charge generation characteristics between the hole injection electrode layer and the electron injection electrode layer It may have a form including an organic layer having a structure divided by, but is not limited thereto.

In this field, various materials for forming a hole or electron injection electrode layer and an organic layer, for example, a light emitting layer, an electron injection or transport layer, a hole injection or transport layer, and a method of forming the same are known. The same can all be applied.

The organic electronic device may further include an encapsulation structure. The encapsulation structure may be a protective structure to prevent foreign substances such as moisture or oxygen from flowing into the organic layer of the organic electronic device. The encapsulation structure may be, for example, a can such as a glass can or a metal can, or a film covering the entire surface of the organic layer.

FIG. 4 shows that the first electrode layer 401, the organic layer 402, and the second electrode layer 403 sequentially formed on the plastic substrate 1 are encapsulated in a can structure such as a glass can or a metal can. Illustrate the protected form. As shown in FIG. 4, the encapsulation structure 404 may be attached to the plastic substrate 1 by, for example, an adhesive. In this way it is possible to maximize the protective effect through the encapsulation structure.

The encapsulation structure may be, for example, a film covering the entire surface of the first electrode layer, the organic layer, and the second electrode layer. 5 exemplarily illustrates an encapsulation structure 501 in the form of a film covering the entire surface of the first electrode layer 401, the organic layer 402, and the second electrode layer 403. For example, the encapsulation structure 501 in the form of a film covers the entire surface of the first electrode layer 401, the organic layer 402, and the second electrode layer 403, as shown in FIG. The two substrates 502 may be bonded to each other. As the second substrate, for example, a glass substrate, a metal substrate, a polymer film or a barrier layer may be exemplified. The encapsulation structure in the form of a film is formed by applying, curing, and curing a liquid material that is cured by heat or ultraviolet (UV) irradiation or the like, for example, an epoxy resin, or by using the epoxy resin or the like beforehand It can be formed by laminating the substrate and the upper substrate using an adhesive sheet prepared in the form.

The encapsulation structure, if necessary, may include a metal oxide such as calcium oxide, beryllium oxide, a metal halide such as calcium chloride, or a water adsorbent such as phosphorus pentoxide, or a getter material. The moisture adsorbent or getter material may be included, for example, inside the encapsulation structure in the form of a film, or may be present at a predetermined position of the encapsulation structure in the can structure. The encapsulation structure may further include a barrier film, a conductive film, or the like.

The present application also relates to the use of such organic electronic devices, for example organic light emitting devices. In one example, the present application relates to a light source for a display including the organic electronic device. In another example, the present application relates to a lighting device including the organic electronic device. The light source for the display may be a backlight of a liquid crystal display (LCD), a light source, a light source of various sensors, a printer, a copier, a vehicle instrument light source, a signal lamp, an indicator light, a display device, a light source of an area light emitting body, a display, A decoration or various lights etc. can be illustrated.

In addition, when the organic electronic device is applied to the light source for the display, the lighting device, or other uses, other components constituting the light source for the display or the lighting device, or a configuration method thereof are not particularly limited, and the organic electronic device is applied. As far as possible, any material or method known in the art may be employed.

Plastic substrate of the present application is excellent in light extraction performance and surface roughness characteristics. In addition, the method of manufacturing a plastic substrate of the present application may produce the plastic substrate through a process of adding a scattering component. In addition, the plastic substrate of the present application may be used as a substrate of the organic electronic device, the organic electronic device may be used as a light source and a lighting device for a display.

1-3 show exemplary plastic substrates.

4 and 5 illustrate exemplary organic electronic devices.

6 shows an SEM cross-sectional image of the plastic substrate of Example 1. FIG.

7 shows an optical microscope surface image of a dark field mode of the plastic substrates of Example 4 and Comparative Examples 5 and 6 (scale bar: 20 μm).

8 shows SEM surface images of the plastic substrates of Example 4 and Comparative Examples 5 and 6. FIG.

9 is a graph showing the transmittance of the visible light region of the plastic substrate and the absolute quantum efficiency of the organic light emitting device.

Hereinafter, the substrate will be described in more detail through examples according to the present application, but the scope of the present application is not limited to the examples given below.

1. Measurement of transmittance of plastic substrate

The transmittance of the plastic substrate was measured using an integrating sphere. More specifically, the brightness of the integrating sphere is set to L ₀ while the self-absorption correction lamp in the integrating sphere is turned on. The brightness of the integrating sphere when the sample to be measured in the integrating sphere is centered is referred to as Ls. When the brightness of the integrating sphere when the complete absorber having the same size as is positioned at the center is L _D , the plastic substrate transmittance can be calculated by Equation 4 below.

[Equation 4]

Substrate transmittance (%) = (Ls-L _D ) / (L ₀ -L _D ) x 100

2. of plastic substrate Haze  Measure

The haze of a plastic substrate was measured using the D65 light source with the HM-150 apparatus of MURAKAMI.

3. Measurement of surface roughness of plastic substrate

The surface roughness of the plastic substrate is AFM (atomic force microscope) equipment, for example, Digital Instrument's NS4 D3100 DEN P-4 Rev. A-device was used for non-contact (vibrating) measurement.

4. Measurement of Absolute Quantum Efficiency of Organic Electronic Devices

Absolute quantum efficiency of the organic light emitting device was measured using an integrated hemisphere device of OTSUKA Corporation.

Example  One

Manufacture of Plastic Substrates

The glass substrate was used as a carrier substrate, and the plastic substrate which has a support layer was produced. Specifically, 3,3 ', 4,4'-biphenyltetracarboxylic acid di & hydride (3,3', 4,4'-biphenyl tetracarboxylic acid dianhydride) and 2,2'-bis (trifluoromethyl)- Scattering component in a polyamic acid polymer solution (polyimide precursor) synthesized in a known manner using 4,4'-diaminobiphenyl (2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl) as a monomer As a coating liquid, TiO ₂ (refractive index: 2.7) for light having a wavelength of 633 nm was mixed in an amount such that the content ratio of the scattering component to 100% by weight of polyimide in the finally prepared support layer may be about 0.1% by weight. (Polyamic acid: scattering component = 100: 0.1 weight ratio).

Subsequently, the coating solution was coated on the glass substrate in a range such that the thickness of the supporting layer finally prepared was about 30 μm, followed by imidization, and the refractive index of the light having a wavelength of 633 nm was about 1.6. The plastic substrate which has the support layer in which the said scattering component is disperse | distributed in the polyimide was manufactured.

The prepared plastic substrate had a transmittance of about 88% and a haze of about 5%.

Manufacture of Organic Electronic Devices

A hole injection electrode layer including ITO (Indium Tin Oxide) was formed on the manufactured plastic substrate by a known sputtering method. Subsequently, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and an electron injection electrode layer were formed using a known material and method. Thereafter, the structure was sealed with a glass can to manufacture an organic electronic device.

Example  2.

In the preparation of the plastic substrate, the coating solution is prepared by mixing in an amount such that the content ratio of the scattering component to 100 wt% of the polyimide may be about 0.5 wt% in the finally prepared support layer (polyamic acid: scattering component = 100: 0.5 Except for the weight ratio), a plastic substrate and an organic electronic device were manufactured in the same manner as in Example 1.

The prepared plastic substrate had a transmittance of about 84% and a haze of about 26%.

Example  3.

In the preparation of the plastic substrate, the coating solution is prepared by mixing in an amount such that the content ratio of the scattering component to 100 wt% of the polyimide may be about 1 wt% in the finally prepared support layer (polyamic acid: scattering component =: 100: A plastic substrate and an organic electronic device were manufactured in the same manner as in Example 1, except that 1 weight ratio) was used.

The prepared plastic substrate had a transmittance of about 81% and a haze of about 32%.

Example  4.

In the preparation of the plastic substrate, the coating solution is prepared by mixing in an amount such that the content ratio of the scattering component to 100 wt% of the polyimide may be about 0.5 wt% in the finally prepared support layer (polyamic acid: scattering component = 100: 0.5 weight ratio), and the plastic substrate and the organic electronic device by the same method as in Example 1 except that the coating solution was coated in a range that the thickness of the support layer finally produced on the glass substrate can be about 14 ㎛ Was prepared.

The haze of the prepared plastic substrate was about 33%. 7 (a) and 8 (a) show optical microscope surface images (dark field mode) and SEM surface images of the prepared plastic substrate, respectively.

Comparative example  One

In the manufacture of the plastic substrate, the plastic substrate and the organic electronic device were manufactured in the same manner as in Example 1 except that the polyamic acid polymerization liquid was changed so as not to include scattering particles.

The prepared plastic substrate had a transmittance of about 94% and a haze of about 1%.

Comparative example  2.

In the preparation of the plastic substrate, the coating solution is prepared by mixing in an amount such that the content ratio of the scattering component to 100 wt% of the polyimide may be about 5 wt% in the finally prepared support layer (polyamic acid: scattering component = 100: 5 Except for the weight ratio), a plastic substrate and an organic electronic device were manufactured in the same manner as in Example 1.

The prepared plastic substrate had a transmittance of about 78% and a haze of about 65%.

Comparative example  3.

In the preparation of the plastic substrate, the coating solution is prepared by mixing the content ratio of the scattering component to about 10 weight percent of the polyimide in the finally prepared support layer (polyamic acid: scattering component = 100: 10). Except for the weight ratio), a plastic substrate and an organic electronic device were manufactured in the same manner as in Example 1.

The prepared plastic substrate had a transmittance of about 72% and a haze of about 84%.

Comparative example  4

In the production of the plastic substrate, the content ratio of the scattering component to 100% by weight of the polyimide will be about 2% by weight in the support layer finally prepared in the polyimide subjected to the imidization reaction without adding the scattering particles to the polyamic acid polymerization liquid. A plastic substrate and an organic electronic device were manufactured in the same manner as in Example 1, except that the coating solution was prepared by mixing in an amount that can be used (polyimide: scattering component = 100: 2 weight ratio).

Comparative Example 4 has a higher content of the scattering component compared to Example 3, but is prepared by adding the scattering component after the completion of the polymerization of the polyamic acid, which ensures stable dispersibility in the polyimide by agglomeration of the scattering component Not so, local high haze was expressed. As a result of the haze measurement, the comparative example 4 did not show the haze characteristic of the grade suitable for the light extraction performance, and was confirmed to show the haze about 50% or more locally.

Comparative example  5.

In the preparation of the plastic substrate, the coating solution is prepared by mixing in an amount such that the content ratio of the scattering component to 100 wt% of the polyimide may be about 0.5 wt% in the finally prepared support layer (polyimide: scattering component = 100: 0.5 weight ratio), the plastic substrate and the organic electronic device by the same method as in Comparative Example 4 except that the coating liquid was coated in a range that the thickness of the support layer finally produced on the glass substrate can be about 10 ㎛ Was prepared.

The haze of the prepared plastic substrate was about 3%. 7 (b) and 8 (b) show optical microscope surface images (dark field mode) and SEM surface images of the prepared plastic substrate, respectively.

Comparative example  6.

In the preparation of the plastic substrate, the coating solution is prepared by mixing in an amount such that the content ratio of the scattering component to 100 wt% of the polyimide may be about 20 wt% in the finally prepared support layer (polyimide: scattering component = 100: 20) A plastic substrate and an organic electronic device were manufactured by the same method as Comparative Example 4, except that the coating solution was coated on the glass substrate in a range in which the thickness of the supporting layer finally prepared was about 2 μm. It was.

The haze of the prepared plastic substrate was about 51%. 7 (c) and 8 (c) show optical microscope surface images (dark field mode) and SEM surface images of the prepared plastic substrate, respectively.

Example  1 to 3 and Comparative example  1 to 3 characteristics comparison

The content, haze, and transmittance of the scattering components of the plastic substrates of Examples 1 to 3 and Comparative Examples 1 to 3 are summarized in Table 1 below, and the absolute quantum efficiencies of the organic electronic devices of Examples 1 to 3 and Comparative Examples 1 to 3 Was measured and shown in Table 1 and FIG.

	Comparative Example 1	Example 1	Example 2	Example 3	Comparative Example 2	Comparative Example 3
Scattering Particle Content (wt%)	0	0.1	0.5	One	5	10
Haze (%)	One	5	26	32	65	84
Permeability (%)	94	88	84	81	78	72
Absolute Quantum Efficiency (%)	44	51	54	53	42	38

[Description of the code]

1: plastic substrate

101: support layer

1011: polymer binder

1012 scattering component

301: flat layer

401: transparent electrode layer

402: an organic layer

403: second electrode layer

404: can-shaped bag structure

501: film type encapsulation structure

502: second substrate

Claims (22)

1. Polymeric binders; And a scattering component contained in the polymer binder at a ratio within the range of 0.05% to 3.75% by weight, having a support layer having a thickness in the range of 10 μm to 130 μm, and having a haze in the range of 5% to 80%. Plastic substrate.
2. The plastic substrate according to claim 1, wherein the transmittance for light of at least one wavelength in the visible light region is 80% or more.
3. The plastic substrate of claim 1, wherein the coefficient of thermal expansion is in the range of 10 ppm / ° C. to 50 ppm / ° C. 7.
4. The plastic substrate according to claim 1, wherein the refractive index of the light having a wavelength of 550 nm or 633 nm is 1.5 or more.
5. The plastic substrate according to claim 1, wherein the polymer binder is polyimide, polyethylene naphthalate, polycarbonate, acrylic resin, polyethylenetetephthalate, polysulfone, polyethersulfide, polypropylene, polyetherether ketone or polydimethylsilonic acid.
6. The plastic substrate of claim 1, wherein the polymer binder comprises a repeating unit represented by Formula 1 below:

   [Formula 1]

   

   In Formula 1, L is a single bond, an alkylene group, an alkylidene group, an alkynylene group, an arylene group, an alkenylene group, -S-, -S (= O)-, -S (= O) ₂ -or -SS R ₁ to R ₂₀ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group or a functional group including a halogen atom, a sulfur atom or a phosphorus atom, n is an integer of 1 or more, and 2 of R ₁ to R ₂₀ There are no substituents substituted on the carbon atoms connecting the two ring structures to each other.
7. The plastic substrate of claim 1, wherein the scattering component is scattering particles having an average particle diameter in a range of 150 nm to 300 nm.
8. The plastic substrate according to claim 1, wherein the absolute value of the difference in refractive index between the polymer binder and the scattering component is in the range of 0.5 to 1.2.
9. The plastic substrate of claim 1, wherein the scattering component comprises at least one selected from the group consisting of TiO ₂ , HfO ₂ , BaTiO ₃ , SnO ₂ , ZrO ₂ , ZnO, Al ₂ O _3, and SiO ₂ .
10. The plastic substrate of claim 1, wherein the plastic substrate exhibits haze in a range of 5% to 80% without including a haze-inducing element in addition to the scattering component of the support layer.
11. The plastic substrate of claim 1, wherein the support layer has a surface roughness Ra measured in a region of 20 μm × 20 μm or more in a range of 0.1 nm to 30 nm.
12. The plastic substrate according to claim 1, wherein a barrier layer having a refractive index of 1.5 or more for light having a wavelength of 550 nm or 633 nm is further formed on one or both surfaces of the support layer.
13. 13. The plastic substrate of claim 12, further comprising a buffer layer formed between the barrier layer and the support layer.
14. The plastic substrate of claim 1, further comprising a flat layer having a refractive index of at least 1.5 for light at a wavelength of 550 nm or 633 nm.
15. The plastic substrate of claim 1, further comprising a carrier substrate attached to one or both sides of the support layer.
16. A layer having a thickness in the range of 10 μm to 130 μm is formed by using a composition comprising a scattering component at a ratio within the range of 0.05 wt% to 3.75 wt% relative to 100 wt% of the polymer binder precursor and 100 wt% of the polymer binder precursor, wherein the layer The method of manufacturing the plastic substrate of claim 1, comprising converting the polymer binder precursor into a polymer binder therein.
17. The method of claim 16, wherein the polymeric binder precursor is a polyamic acid.
18. The method of claim 16, wherein the polymer binder precursor comprises a repeating unit represented by Formula 2 below:

    [Formula 2]

    

    In Formula 2, L is a single bond, alkylene group, alkylidene group, alkynylene group, arylene group, alkenylene group, -S-, -S (= O)-, -S (= O) ₂ -or -SS R ₁ to R ₂₀ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group or a functional group including a halogen atom, a sulfur atom or a phosphorus atom, n is an integer of 1 or more, and 2 of R ₁ to R ₂₀ There are no substituents substituted on the carbon atoms connecting the two ring structures to each other.
19. Claim 1 plastic substrate; A first electrode layer formed on the substrate; An organic electronic device comprising an organic layer formed on the first electrode layer and a second electrode layer formed on the organic layer.
20. The organic electronic device of claim 19, wherein the organic layer comprises a light emitting layer.
21. 20. A display light source comprising the organic electronic device of claim 19.
22. 20. A lighting device comprising the organic electronic device of claim 19.

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