WO2013103282A1 - 봉지용 필름 - Google Patents
봉지용 필름 Download PDFInfo
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- WO2013103282A1 WO2013103282A1 PCT/KR2013/000108 KR2013000108W WO2013103282A1 WO 2013103282 A1 WO2013103282 A1 WO 2013103282A1 KR 2013000108 W KR2013000108 W KR 2013000108W WO 2013103282 A1 WO2013103282 A1 WO 2013103282A1
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- C—CHEMISTRY; METALLURGY
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L2924/0001—Technical content checked by a classifier
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
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- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/31855—Of addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present application relates to an encapsulation film, an electronic device, and a method of manufacturing the same.
- the encapsulation film may be used to protect devices or devices sensitive to external factors such as moisture or oxygen.
- An element or device that can be protected by a sealing film includes, for example, a secondary battery such as an organic electronic device, a solar cell, or a lithium secondary battery.
- a secondary battery such as an organic electronic device, a solar cell, or a lithium secondary battery.
- the organic electronic device of the device or device is vulnerable to external factors such as moisture or oxygen.
- the organic electronic device is a device containing a functional organic material.
- Examples of the organic electronic device or the organic electronic device included in the organic electronic device may include a photovoltaic device, a rectifier, a transmitter, an organic light emitting diode (OLED), and the like. have.
- an organic light emitting device typically includes a layer of functional organic material present between a pair of electrodes comprising a metal or metal oxide, wherein the layer of organic material is separated from the electrode by moisture that penetrates from the outside. Problems such as peeling under the influence of moisture at the interface of the electrode, oxidation of the electrode due to moisture, the resistance value increases, or the organic material itself is deteriorated, resulting in loss of luminescence function or decrease in luminance.
- the organic light emitting device is used to protect the organic light emitting device from an external environment such as moisture, and a sealing structure in which an organic light emitting device formed on a substrate is heated with a glass can or a metal can equipped with a getter or an absorbent or fixed with an adhesive.
- the present application provides an encapsulation film, an electronic device, and a method of manufacturing the same.
- One embodiment of the present application provides a sealing film including a first layer and a second layer.
- the encapsulation film may include one or more of the first layer and the second layer, and may further include a separate layer in addition to the first and second layers.
- the encapsulation film comprises a first layer and a second layer having different physical properties and / or different components, so that the film may cause bubbles or the like even when applied for protection of the device in a large-area device, for example. It can be stacked on the device without, and can effectively protect the device from external components, for example moisture, after the encapsulation process.
- the encapsulation film may have various structures. For example, as shown in FIG. 1, the second layer 11 is disposed on one surface of the first layer 12 or the first layer 12 as illustrated in FIG. 2. The structure in which the 2nd layer 11 is arrange
- the structure in which the second layer 11 is disposed on one or both surfaces of the first layer 12 may include a structure in which the second layer 11 is directly attached to the first layer 12; And a structure in which the second layer 11 is indirectly attached to the first layer 12 via another separate layer.
- the first layer may have a lower modulus of elasticity than the second layer.
- the tensile modulus of the first layer may be lower than the tensile modulus of the second layer.
- the tensile modulus is a tensile modulus measured at a temperature of 25 ° C.
- the tensile elasticity modulus with respect to the hardenable structure is the tensile elasticity modulus measured after hardening.
- the term "moisture scavenger” may mean, for example, a material capable of removing the above through a chemical reaction with moisture or moisture penetrated into the encapsulation film. Typically, when the water scavenger reacts with water in the film, the volume expands as much as it reacts with water, causing stress.
- the film when the elasticity does not have enough elasticity to relieve the expansion stress to the water removal, the film may be peeled from the adherend, in the case of a film of a multi-layer structure may cause the peeling between the layers.
- the elastic modulus of the film is adjusted to be low, peeling due to the stress can be prevented, but the moisture permeability of the film can be increased when the elastic modulus is controlled by lowering the glass transition temperature through simply adjusting the degree of curing.
- the moisture remover is mainly included in the layer having the low modulus of elasticity
- water penetrated through the relatively small layer of the moisture remover that is, the layer having the high modulus of elasticity
- It can diffuse into the layer with low modulus of elasticity to improve moisture barrier property.
- it can also meet various physical properties such as durability of the film.
- the tensile modulus of the first layer is 0.001 MPa to 400 MPa, 0.001 MPa to 300 MPa, 0.001 MPa to 200 MPa, 0.001 MPa to 100 MPa, 0.001 MPa to 80 MPa, 0.001 MPa to 60 MPa, 0.001 MPa to 40 MPa, 0.001 MPa to 20 MPa , 0.001 MPa to 10 Mpa, 0.001 MPa to 5 Mpa, 0.001 MPa to 3 Mpa, 0.001 MPa to 1 Mpa, 0.005 MPa to 100 Mpa, 0.01 MPa to 100 Mpa, 0.05 MPa to 100 Mpa, 0.1 MPa to 100 Mpa, 0.2 MPa to 100 Mpa, 0.3 MPa to 100 Mpa , 0.005 MPa to 80 MPa, 0.01 MPa to 60 MPa, 0.05 MPa to 40 MPa, 0.05 MPa to 20 MPa, 0.1 MPa to 10 MPa, 0.1 MPa to 5
- the second layer has a tensile modulus of 400 MPa to 1000 Mpa, 400 MPa to 900 Mpa, 400 MPa to 800 Mpa, 400 MPa to 700 Mpa, 400 MPa to 1000 Mpa, 500 MPa to 1000 Mpa, 550 MPa to 1000 Mpa, 400 MPa to 900 Mpa, 500 MPa to 550 MPa to 700 Mpa.
- the first layer may have a lower elastic modulus than the second layer.
- the ratio (M1 / M2) of the tensile modulus M1 of the first layer and the tensile modulus M2 of the second layer is 1 x 10 -6 to 0.5, 1 x 10 -6 to 0.4, 1 x 10 -6 to 0.3, 1 x 10 -6 to 0.2, 10 x 10 -6 to 0.5, 100 x 10 -6 to 0.5, 200 x 10 -6 to 0.5, 300 x 10 -6 to 0.5, 400 x 10 - 6 to 0.5, 500 x 10 -6 to 0.5, 10 x 10 -6 to 0.4, 100 x 10 -6 to 0.4, 200 x 10 -6 to 0.3, 300 x 10 -6 to 0.3, 400 x 10 -6 to 0.2 or 500 x 10 -6 to about 0.2.
- the encapsulation film can be effectively applied to, for example, a large-area device, and can easily perform the adjustment of the ratio of the water scavenger between the layers, which
- the encapsulation film may include a moisture remover.
- the first layer may comprise a greater amount of moisture scavenger than the second layer.
- the second layer may or may not comprise less water scavenger than the first layer.
- the first layer may include a resin component, 5 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight or 45 to 100 parts by weight of the resin component. It may include more than parts by weight of the water scavenger.
- the upper limit of the ratio of the water scavenging agent of the first layer is not particularly limited to be changed according to the desired moisture barrier properties, but, for example, 250 parts by weight or less, 230 parts by weight or less or 210 parts by weight with respect to 100 parts by weight of the resin component. Up to parts water scavenger may be included in the first layer.
- the second layer may not include a water scavenger, and may include a trace amount of a water scavenger even if it includes a water scavenger.
- the second layer may comprise, for example, less than 5 parts by weight or less than 3 parts by weight of water scavenger relative to 100 parts by weight of solids of the second layer. Since the second layer may not include a moisture remover, the lower limit of the content of the moisture remover of the second layer may be 0 parts by weight.
- unit parts by weight means a ratio of weight.
- the thickness of the first layer and the second layer can be controlled in consideration of the number of each layer included in the film or the use of the film.
- the thickness of the first layer may be about 5 to 100 ⁇ m
- the thickness of the second layer may be about 2 to 30 ⁇ m. Within this range, it is possible to provide a film having excellent moisture barrier property, workability and durability.
- the first layer may comprise a resin component having a contact angle for deionized water of at least 80 °, at least 85 °, at least 90 ° or at least 95 °.
- the contact angle is a solid content prepared by dissolving a resin component in a suitable solvent, after coating a glass of about 15% by weight of the solution on the glass and dried to form a film, the contact angle measured by dropping deionized water on the coating film at about 25 °C It may be an average of the contact angle measured by repeating the above procedure 10 times. It is possible to provide a film having excellent moisture barrier property and durability by including a component whose contact angle is adjusted as described above in the first layer.
- the upper limit of the contact angle of the resin component is not particularly limited, and may be, for example, 150 ° or less or 120 ° or less.
- the first layer may also include a resin component having a water vapor transmission rate (WVTR) of 50 g / m 2 ⁇ day or less or 45 g / m 2 ⁇ day or less.
- the moisture permeability may be a moisture permeability measured in the thickness direction of the film, prepared in the form of a film having a thickness of 100 ⁇ m thickness, relative humidity of 100 ° F and 100%.
- the moisture permeability of the resin component can be controlled as described above to provide a film exhibiting excellent moisture barrier properties.
- the lower limit of the water vapor transmission rate of the resin component may be 0 g / m 2 ⁇ day.
- the resin component included in the first layer may satisfy all of the above-described ranges of contact angle and moisture permeability.
- a component having a contact angle and moisture permeability in the above range can provide a film excellent in moisture barrier properties, water repellency and the like.
- the resin component any component known in the art can be used without particular limitation as long as it can satisfy the above-mentioned contact angle and moisture permeability or can provide the first layer satisfying the above-mentioned elastic modulus.
- the contact angle and the water vapor transmission rate may be used as a resin component by the combination.
- the term "resin component" may refer to a base resin forming the first layer.
- the base resin is a resin used to implement the main physical properties of the first layer, and means a configuration in which optional components such as additives are excluded. In one example, if an additive such as a tackifier is added to the first layer, the base resin may mean a configuration in which the tackifier is excluded.
- styrene resin for example, styrene resin, polyolefin resin, thermoplastic elastomer, polyoxyalkylene resin, polyester resin, polyvinyl chloride resin, polycarbonate resin, polyphenylene sulfide resin, hydrocarbon And mixtures thereof, polyamide resins, acrylate resins, epoxy resins, silicone resins, fluorine resins, or mixtures thereof.
- styrene resin for example, styrene-ethylene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), acrylonitrile-butadiene-styrene block copolymer (ABS ), Acrylonitrile-styrene-acrylate block copolymers (ASA), styrene-butadiene-styrene block copolymers (SBS), styrene-based homopolymers or mixtures thereof.
- SEBS styrene-ethylene-butadiene-styrene block copolymer
- SIS styrene-isoprene-styrene block copolymer
- ABS acrylonitrile-butadiene-styrene block copolymer
- ASA Acrylonitrile-styrene-acrylate block cop
- the olefin resin for example, a high density polyethylene resin, a low density polyethylene resin, a polypropylene resin or a mixture thereof may be exemplified.
- the thermoplastic elastomer for example, an ester thermoplastic elastomer, an olefin thermoplastic elastomer, a mixture thereof, or the like can be used.
- polybutadiene resin or polyisobutene resin may be used as the olefinic thermoplastic elastomer.
- the polyoxyalkylene resins include polyoxymethylene resins, polyoxyethylene resins, and mixtures thereof.
- polyester resins examples include polyethylene terephthalate resins, polybutylene terephthalate resins, and mixtures thereof.
- polyvinyl chloride-based resin for example, polyvinylidene chloride and the like can be exemplified.
- mixture of the hydrocarbons for example, hexatriacotane or paraffin may be exemplified.
- polyamide resin nylon etc. can be illustrated, for example.
- acrylate resin polybutyl (meth) acrylate etc. can be illustrated, for example.
- Bisphenol-type such as bisphenol A type, bisphenol F type, bisphenol S type, and these hydrogenated substances
- Novolak types such as phenol novolak type and cresol novolak type
- Nitrogen-containing cyclic types such as triglycidyl isocyanurate type and hydantoin type
- Alicyclic type Aliphatic type
- Aromatic types such as naphthalene type and biphenyl type
- Glycidyl types such as glycidyl ether type, glycidyl amine type and glycidyl ester type
- Dicyclo types such as dicyclopentadiene type; Ester type; Ether ester type or mixtures thereof and the like can be exemplified.
- silicone resins examples include polydimethylsiloxane and the like.
- fluorine-type resin polytrifluoroethylene resin, polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyhexafluoropropylene resin, polyvinylidene fluoride, polyvinylidene fluoride, polyfluoro Ethylene propylene propylene or mixtures thereof and the like can be exemplified.
- the above-listed resins may be used, for example, by grafting with maleic anhydride, or the like, or may be used after being copolymerized with other listed resins or monomers for preparing the resins, or may be modified with other compounds.
- the other compounds include carboxyl-terminated butadiene-acrylonitrile copolymers.
- the resins listed may include one or more functional groups or moieties that can be cured by heat such as glycidyl group, isocyanate group, hydroxy group, carboxyl group or amide group or the like to be cured and exhibit adhesiveness, or one or more functional groups or moieties that can be cured by irradiation of active energy rays such as (epoxide) groups, cyclic ether groups, sulfide groups, acetal groups, or lactone groups. Can be.
- one or more functional groups or moieties that can be cured by heat such as glycidyl group, isocyanate group, hydroxy group, carboxyl group or amide group or the like to be cured and exhibit adhesiveness
- one or more functional groups or moieties that can be cured by irradiation of active energy rays such as (epoxide) groups, cyclic ether groups, sulfide groups, acetal groups, or lactone groups.
- active energy rays such as
- the first layer may comprise a polyisobutene resin.
- Polyisobutene resins may have hydrophobicity and exhibit low water vapor permeability and low surface energy.
- a polyisobutene resin For example, Homopolymer of an isobutylene monomer; Or the copolymer which copolymerized the isobutylene monomer and the other monomer which can superpose
- the other monomers polymerizable with the isobutylene monomer may include, for example, 1-butene, 2-butene, isoprene or butadiene.
- a resin having a weight average molecular weight (Mw) that can be molded into a film shape may be used.
- the weight average molecular weight may be about 100,000 to 2 million, 100,000 to 1.5 million, or 100,000 to 1 million.
- weight average molecular weight means a conversion value with respect to standard polystyrene measured by gel permeation chromatography (GPC).
- 1 type may be used among the above-mentioned structures, and 2 or more types may be used.
- 2 or more types 2 or more types of resin from a different kind may be used, 2 or more types of resin from which a weight average molecular weight differs, or 2 or more types of resin from a both type and weight average molecular weight may be used.
- the first layer may further include a moisture remover in addition to the resin component described above. Thereby, the water barrier property of a 1st layer can be improved further.
- the water scavenger may be present evenly dispersed in the resin component.
- the evenly dispersed state may mean a state in which the water scavenger is present at the same or substantially the same density in any part of the resin component.
- the water scavenger which can be used above include metal oxides, sulfates or organic metal oxides.
- the metal oxide include magnesium oxide, calcium oxide, strontium oxide, barium oxide or aluminum oxide
- examples of the sulfate include magnesium sulfate, sodium sulfate, nickel sulfate, and the like.
- the organic metal oxides include aluminum oxide octylate and the like.
- 1 type of said structure may be used and 2 or more types may be used.
- calcined dolomite may be used.
- Such moisture remover may be controlled to an appropriate size depending on the use of the film.
- the average particle diameter of the moisture remover may be controlled to about 10 to 15000 nm.
- the moisture remover having the size of the above range is easy to store because the reaction rate with the moisture is not too fast, and can effectively remove moisture without damaging the device to be encapsulated.
- the content of the moisture remover may be controlled, for example, in the range of 5 parts by weight to 250 parts by weight relative to 100 parts by weight of the resin component as described above.
- the first layer may further include a dispersant such that the moisture scavenger can be uniformly dispersed in the resin component.
- a dispersing agent which can be used here, the nonionic surfactant which has affinity with the surface of a hydrophilic water removal agent, and is compatible with a resin component can be used, for example.
- a compound represented by Chemical Formula 1 may be used as the nonionic surfactant.
- R is a saturated or unsaturated hydrocarbon group
- X is a hydroxyl group, carboxyl group, amino group or carbohydrate moiety.
- R may be a saturated or unsaturated hydrocarbon group having 4 to 28 carbon atoms, 4 to 24 carbon atoms, 4 to 20 carbon atoms or 6 to 20 carbon atoms.
- X is a carbohydrate moiety, which may mean a compound in which any one of hydrogen of carbohydrates is replaced with R.
- examples of the carbohydrates include glucose and the like.
- Examples of the compound of Formula 1 include fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, and the like; Fatty alcohols such as cetyl alcohol, stearyl alcohol, cetostearyl alcohol or oleyl alcohol; Or alkyl glucosides such as octyl glucoside, decyl glucoside or lauryl glucoside.
- fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, and the like
- Fatty alcohols such as cetyl alcohol, stearyl alcohol, cetostearyl alcohol or oleyl alcohol
- alkyl glucosides such as octyl glucoside, decyl glucoside or lauryl glucoside.
- the content of such dispersants may be controlled according to the type and / or size of the water scavenger. Specifically, the smaller the size of the water scavenger, the wider the surface area of the water scavenger, so that a large amount of dispersant may be used to uniformly disperse the water scavenger.
- a moisture remover having an average particle diameter of about 40 nm about 5 parts by weight or more of a dispersant based on 100 parts by weight of the moisture remover may be used.
- about 0.05 part by weight or more of a dispersant based on 100 parts by weight of the moisture remover may be used.
- a dispersant of about 0.01 to 500 parts by weight based on 100 parts by weight of the moisture remover may be used. Within this range, the moisture scavenger can be uniformly dispersed without affecting the overall physical properties such as the adhesion of the film.
- the method of including the moisture remover and the dispersant in the resin component can be used without any limitation in the art, and is not particularly limited. However, the method of adjusting a compounding order and making it possible to disperse
- the dispersant is dispersed in a solvent to prepare a dispersion.
- the solvent may be selected based on coating properties, drying temperature or compatibility with the resin component. In one example, when the above-described polyisobutene resin is used as the resin component, an aromatic solvent such as toluene or xylene may be used as the solvent.
- a moisture remover Into the dispersion is added a moisture remover and mixed.
- the process of mixing the moisture remover with the dispersion may further use a physical dispersion method in order to increase the dispersion of the moisture remover.
- a physical dispersion method the method using a shaker, the sonication method, the bead milling method, etc. are mentioned, for example.
- the solution in which the moisture remover and the dispersant are dispersed can be added to a solution containing a resin component to obtain a composition for producing the first layer.
- the solution in which the water scavenger and the dispersant are dispersed may optionally be filtered so that the large particles are filtered out and added to the solution containing the resin component.
- the first layer in which the water scavenger and the dispersant are uniformly dispersed in the resin component can be prepared.
- the process is not limited to the described contents, and simple modifications may be made by those skilled in the art.
- the first layer can also include a moisture barrier.
- moisture blocker may refer to a material that has no or low reactivity with moisture that penetrates into the film, but may block or prevent movement of moisture or moisture within the film.
- the moisture barrier for example, one or two or more of clay, talc, acicular silica, plate silica, porous silica, zeolite, titania or zirconia can be used.
- the moisture barrier may be surface treated with an organic modifier or the like to facilitate penetration of organic matter.
- Such organic modifiers include, for example, dimethyl benzyl hydrogenated tallow quaternaty ammonium, dimethyl dihydrogenated tallow quaternary ammonium, methyl tallow bis-2-hydroxyethyl Methyl tallow bis-2-hydroxyethyl quaternary ammonium, dimethyl hydrogenated tallow 2-ethylhexyl quaternary ammonium, dimethyl dehydrogenated tallow quaternary ammonium ) Or mixtures thereof and organic modifiers may be used.
- the content of the moisture barrier which can be included in the first layer can be appropriately adjusted in relation to the matrix structure of the moisture scavenger and the resin component.
- the content of the moisture blocker may be adjusted to about 0 to 50 parts by weight or 1 to 30 parts by weight based on 100 parts by weight of the resin component. Within this range it can be provided a film having excellent moisture barrier properties and mechanical properties.
- the component blending order of the first layer may be controlled to uniformly disperse the moisture remover and the moisture blocker in the resin component.
- a first dispersion can be prepared by first adding a moisture barrier to the solvent.
- the first dispersion may be obtained as a uniformly dispersed dispersion through processes such as sonication, bead milling, ball milling, high speed dispersion, high pressure dispersion, and the like.
- a second dispersion in which a water scavenger and / or a dispersant is dispersed as described above is prepared.
- the prepared first and second dispersions are added to a solution containing a resin component and mixed.
- the solvent may be further added in consideration of viscosity control and coating properties of the resin composition during mixing.
- the first layer in which the water scavenger and the blocking agent are uniformly dispersed can be prepared.
- the manufacturing method of the said 1st layer can be changed freely within the obvious thing by a person skilled in the art.
- the first layer may comprise a tackifier.
- a tackifier the hydrogenated petroleum resin obtained by hydrogenating a petroleum resin can be used, for example. Hydrogenated petroleum resins may be partially or fully hydrogenated and may be a mixture of such resins. Such a tackifier can be selected from those having good compatibility with the resin component and excellent moisture barrier properties. Specific examples of the hydrogenated petroleum resin include hydrogenated terpene resins, hydrogenated ester resins, or hydrogenated dicyclopentadiene resins. The weight average molecular weight of the tackifier may be about 200 to 5,000. The content of the tackifier can be appropriately adjusted as necessary. For example, the tackifier may be included in the first layer in a ratio of 5 parts by weight to 100 parts by weight with respect to 100 parts by weight of the resin component.
- the first layer may include various additives depending on the use of the film and the manufacturing process of the film.
- the first layer may further include a curable material.
- the curable material may mean a material having a thermosetting functional group and / or an active energy ray curable functional group which are separately included in addition to the above-described resin component.
- the content of the curable material included in the first layer may be adjusted according to the desired physical properties of the film.
- the second layer may be, for example, a layer containing the curable resin composition.
- the second layer may be a hot melt adhesive layer.
- the term "hot melt type adhesive layer” is maintained at a solid or semi-solid state at room temperature, and when appropriate heat is applied, melts to show adhesiveness, After curing, it may mean a layer in a form capable of firmly fixing the object as an adhesive.
- the term "hardening of the adhesive” in the present specification may mean a chemical or physical action or reaction that changes so that the target material can exhibit adhesion.
- room temperature may mean a natural temperature that is not heated or reduced, for example, may mean a temperature of about 15 to 35 degrees, about 20 to 25 degrees, about 25 or 23 degrees.
- maintaining the solid or semi-solid state at room temperature in the above may mean that the target material exhibits a viscosity of about 10 6 poise or more or about 10 7 poise or more at room temperature.
- a viscosity is a viscosity measured using ARES (Advanced Rheometric Expansion System).
- ARES Advanced Rheometric Expansion System
- the upper limit of the viscosity is not particularly limited and may be, for example, about 10 9 poise or less.
- a 2nd layer can maintain a solid state or semi-solid state at normal temperature, even if the component contained in a 2nd layer like curable resin composition etc. is an uncured state. Therefore, the second layer may include the curable resin composition in the form of a film. Through this, it is possible to prevent the physical or chemical damage to the device when applied to the sealing process, such as excellent handling and smooth operation.
- Curable resin composition can contain curable resin, for example.
- curable resin thermosetting, active energy ray curable or hybrid curable resins known in the art can be used.
- thermosetting resin is a resin in which curing may occur through an appropriate heat application or aging step
- active energy ray curable resin is a resin in which curing may occur by irradiation of active energy rays
- Matable curable resin may mean a resin in which the curing mechanism of the thermosetting and active energy ray curable resins proceeds simultaneously or sequentially to be cured.
- the active energy rays are microwaves, infrared rays (IR), ultraviolet rays (UV), X-rays and gamma rays, alpha-particle beams, proton beams, and neutron beams.
- Particle beams such as neutron beams or electron beams may be exemplified.
- the curable resin may be, for example, a resin that is cured to exhibit adhesive properties, and includes one or more functional groups or moieties that can be cured by heat such as glycidyl, isocyanate, hydroxy, carboxyl, or amide groups, or the like.
- One or more functional groups or sites that can be cured by irradiation of an active energy ray such as an epoxide group, a cyclic ether group, a sulfide group, an acetal group or a lactone group Resin to be used can be used.
- an acrylic resin, a polyester resin, an isocyanate resin or an epoxy resin having at least one or more of the above functional groups or sites may be exemplified, but is not limited thereto.
- an epoxy resin may be used as the curable resin.
- the epoxy resin may be an aromatic or aliphatic epoxy resin.
- a thermosetting epoxy resin can be used, or the epoxy resin hardened
- Epoxy resin according to one example the epoxy equivalent may be 150 g / eq to 2,000 g / eq. Within the range of the epoxy equivalent, properties such as adhesion performance of the cured product and glass transition temperature can be maintained in an appropriate range.
- the epoxy resin may be an aromatic epoxy resin.
- aromatic epoxy resin may mean an epoxy resin containing at least one aromatic core, such as a phenylene structure, or an aromatic group, such as a phenyl group, in the main chain or side chain of the resin.
- an aromatic epoxy resin a biphenyl type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, a dicyclopentadiene modified phenol type epoxy resin, a cresol type epoxy resin, a bisphenol type epoxy resin, a xylox type epoxy resin , Polyfunctional epoxy resins, phenol novolac epoxy resins, triphenol methane-type epoxy resins and alkyl-modified triphenol methane epoxy resins, such as one or more types or more may be exemplified, but is not limited thereto.
- the epoxy resin may be a silane-modified epoxy resin.
- silane-modified epoxy resin for example, a reactant of at least one of the epoxy resins described above with the silane compound can be used.
- silane compound in the above for example, the compound represented by the following formula (2) can be exemplified.
- D is a vinyl group, an epoxy group, an amino group, an acryl group, a methacryl group, a mercapto group, an alkoxy group or an isocyanate group, or an alkyl group substituted with any one of the above functional groups
- Q is hydrogen or an alkyl group.
- n is a number of 1 to 3.
- functional group D may react with a functional group included in the epoxy resin to form a silane-modified epoxy resin.
- the silane compound may be introduced into the epoxy group while the amino group reacts with the epoxy group of the epoxy resin to form a "-CH (OH) -CH 2 -NH-" bond.
- an epoxy resin containing a hydroxy group for example, a bisphenol F type epoxy resin, a bisphenol F type novolak epoxy resin, a bisphenol A type epoxy resin or a bisphenol A type A silane compound may be introduced by reacting with a bisphenol type epoxy resin such as a novolac epoxy resin or the like.
- alkyl group in Formula 2 an 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 may be exemplified.
- the alkyl group may be a straight chain, branched chain or cyclic alkyl group.
- fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) may be exemplified.
- alkoxy group in Formula 2 an alkoxy group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms may be exemplified.
- the alkoxy group may be linear, branched or cyclic.
- aralkyl group may be included.
- the aryl group may mean a monovalent moiety derived from a compound or derivative thereof including one or more benzene rings or a structure in which two or more benzene rings are linked or condensed.
- the aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms.
- aryl group for example, a phenyl group, dichlorophenyl, chlorophenyl, phenylethyl group, phenylpropyl group, benzyl group, tolyl group, xylyl group or naphthyl group can be exemplified.
- an acyloxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, or 1 to 12 carbon atoms may be exemplified.
- an alkylthio group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, or 1 to 8 carbon atoms or 1 to 4 carbon atoms may be exemplified, and an alkyleneoxythio group.
- an alkyleneoxythio group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, or 1 to 8 carbon atoms or 1 to 4 carbon atoms may be exemplified, and an alkyleneoxythio group.
- an alkyleneoxythio group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, or 1 to 8 carbon atoms or 1 to 4 carbon atoms may be exemplified, and an alkyleneoxythio group.
- the alkyl group, alkoxy group, aryl group, acyloxy group, alkylthio group or alkyleneoxythio group may be optionally substituted with one or more substituents.
- substituents a hydroxy group, an epoxy group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an acyl group, a thiol group, an acryloyl group, a methacryloyl group, an aryl group or an isocyanate group may be exemplified, but is not limited thereto. It is not.
- the functional group D may be, for example, an alkoxy group, an amino group or an isocyanate group.
- At least one, two or more or three of the functional groups Q in Formula 2 may be, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group or an alkyleneoxythio group, or the like. It may be an alkoxy group.
- Examples of the silane-modified epoxy resin include about 0.1 part by weight to about 10 parts by weight, about 0.1 part by weight to about 9 parts by weight, about 0.1 part by weight to about 8 parts by weight, and about 0.1 part by weight based on 100 parts by weight of the epoxy resin. To about 7 parts by weight, about 0.1 to about 6 parts by weight, about 0.1 to about 5 parts by weight, about 0.1 to about 4 parts by weight, about 0.1 to about 3 parts by weight, about 0.3 Epoxy resins in which parts by weight to 2 parts by weight or about 0.5 parts by weight to about 2 parts by weight of the silane compound are introduced may be used.
- the epoxy resin into which the silane compound is introduced may be an aromatic epoxy resin.
- the aromatic epoxy resins include bisphenol epoxy resins such as bisphenol F epoxy resins, bisphenol F novolac epoxy resins, bisphenol A epoxy resins, and bisphenol A novolac epoxy resins.
- the epoxy resin modified with silane and including the silyl group in the structure may allow the encapsulation layer of the electronic device to exhibit excellent moisture barrier property, durability and reliability while exhibiting excellent adhesion to a substrate or the like.
- the second layer may further include a curing agent capable of reacting with the curable resin and forming a crosslinked structure or the like or an initiator capable of initiating a curing reaction of the resin, depending on the kind of the curable resin.
- An appropriate kind can be selected and used according to the kind of curable resin or the functional group contained in the resin for a hardening
- the curing agent may be a curing agent of an epoxy resin known in the art, for example, an amine curing agent, an imidazole curing agent, a phenol curing agent, a phosphorus curing agent or an acid anhydride curing agent.
- an epoxy resin known in the art, for example, an amine curing agent, an imidazole curing agent, a phenol curing agent, a phosphorus curing agent or an acid anhydride curing agent.
- One kind or more than one kind may be used, but is not limited thereto.
- an imidazole compound which is solid at room temperature and has a melting point or decomposition temperature of 80 C or more can be used.
- a compound for example, 2-methyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole or 1-cyanoethyl-2-phenyl imidazole, etc. This may be illustrated, but is not limited thereto.
- the content of the curing agent may be selected according to the composition of the composition, for example, the type or ratio of the curable resin.
- the curing agent may include 1 part by weight to 20 parts by weight, 1 part by weight to 10 parts by weight, or 1 part by weight to 5 parts by weight based on 100 parts by weight of the curable resin.
- the weight ratio may be changed depending on the type and ratio of the curable resin or functional group of the resin, or the crosslinking density to be implemented.
- curable resin is an epoxy resin which can be hardened by irradiation of an active energy ray
- a cationic photoinitiator can be used, for example.
- an onium salt or an organometallic salt-based ionizing cation initiator or an organosilane or a latent sulfuric acid-based or non-ionized cationic photopolymerization initiator may be used.
- the onium salt-based initiator include a diaryliodonium salt, a triarylsulfonium salt, an aryldiazonium salt, and the like.
- the zero, iron arene and the like can be exemplified.
- the organosilane-based initiator include o-nitrobenzyl triaryl silyl ether and triaryl silyl peroxide.
- the latent sulfuric acid-based initiator may be exemplified by ⁇ -sulfonyloxy ketone or ⁇ -hydroxymethylbenzoin sulfonate and the like, but is not limited thereto. .
- an ionized cationic photopolymerization initiator may be used as the cationic initiator.
- the content of the initiator may be changed according to the type and ratio of the curable resin or functional group of the resin, or the crosslinking density to be implemented, as in the case of the curing agent.
- the initiator may be blended in an amount of 0.01 to 10 parts by weight or 0.1 to 3 parts by weight with respect to 100 parts by weight of the curable resin.
- the second layer may further comprise a binder resin.
- the binder resin may serve to improve moldability when molding the second layer into a film or sheet shape.
- binder resin The kind of binder resin will not be restrict
- a phenoxy resin, an acrylate resin or a high molecular weight epoxy resin can be used.
- the high molecular weight epoxy resin may mean, for example, a resin having a weight average molecular weight of about 2,000 to 70,000 or about 4,000 to 6,000.
- a high molecular weight epoxy resin a solid bisphenol A epoxy resin, a solid bisphenol F epoxy resin, etc. can be illustrated.
- the binder resin rubber components such as high polarity functional group-containing rubber and high polarity functional group-containing reactive rubber may also be used.
- a phenoxy resin may be used as the binder resin.
- the ratio is not particularly limited to be adjusted according to the desired physical properties.
- the binder resin may be included in an amount of about 200 parts by weight, about 150 parts by weight or less, or about 100 parts by weight or less based on 100 parts by weight of the curable adhesive component.
- the ratio of the binder resin is 200 parts by weight or less, the compatibility with each component of the second layer can be effectively maintained, and it can also play a role as an adhesive layer.
- the second layer may further comprise a moisture blocker.
- Moisture removers cause chemical reactions with moisture, which can damage the device when it comes into contact with devices containing organic materials. Accordingly, the second layer may contain no moisture scavengers or may contain traces of moisture scavengers. If the second layer comprises a trace amount of water scavenger, the content of the water scavenger may be as described above. However, the moisture blocker blocks the moisture by lengthening the movement path of the moisture, and less likely to damage the device due to less reactivity than the moisture remover.
- the content of the moisture barrier that may be included in the second layer may be, for example, about 0.01 to about 50 parts by weight or about 1 to about 30 parts by weight based on 100 parts by weight of the curable resin.
- a method including the moisture barrier agent and the moisture barrier agent included in the first layer may be referred to.
- the second layer further includes a plasticizer in a range that does not affect the desired effect; It may further comprise additives such as ultraviolet stabilizers and / or antioxidants.
- the film may further comprise a substrate, for example.
- the substrate may be disposed, for example, on one or both sides of the film.
- the substrate may be, for example, a substrate subjected to a release treatment, and such substrate can be used in the art without limitation.
- the encapsulation film may be applied to encapsulation and protection of various objects.
- the film can be effective for the protection of an object comprising a device sensitive to external components, for example moisture or moisture.
- the object to which the encapsulation film can be applied include organic electronic devices such as photovoltaic devices, rectifiers, transmitters, or organic light emitting diodes (OLEDs); Solar cells; Or a secondary battery, but is not limited thereto.
- Another embodiment of the present application also includes an upper substrate; Lower substrate; And an encapsulation layer including a film encapsulating an element between the upper substrate and the lower substrate.
- the device may mean any one component of the electronic device.
- the device that can be protected by the film as described above may be an organic electronic device such as an organic light emitting device, but is not limited thereto.
- the film may be an encapsulation film including the first layer and the second layer described above.
- the film can be, for example, in an uncured state.
- the encapsulation layer including such a film may be a layer formed by curing the film.
- the upper substrate and the lower substrate may be disposed to face each other.
- the device may be formed on one surface of the lower substrate, and one surface of the lower substrate may be a surface facing the upper substrate.
- the film may be positioned between the upper and lower substrates, such that the second layer of the film is in contact with the lower substrate on which the device is formed. In this structure the film may cover substantially the entire surface of the device.
- the film may include a first layer 12 and a second layer 11, and the second layer 11 may be disposed to contact the device 23 and the lower substrate 22. have.
- FIG. 1 the film may include a first layer 12 and a second layer 11, and the second layer 11 may be disposed to contact the device 23 and the lower substrate 22. have.
- the film may include a second layer 11, a first layer 12, and a second layer 11, and any one of the second layers 11 may be a device ( 23) and the lower substrate 22.
- the second layer does not contain a small amount or no moisture scavenger which may damage the device, and thus the second layer does not affect the function of the device.
- the second layer has a step filling property, and thus, the second layer may be attached without lifting and / or bubbles to a surface having a height difference, such as the lower substrate 22 on which the element 23 is formed. Accordingly, an electronic device having excellent interface adhesion between the encapsulation layer and the element or the lower substrate can be provided.
- the second layer may have a glass transition temperature of 0 ° C. or higher, 50 ° C. or higher, 70 ° C. or higher, 85 ° C. or higher, or 100 ° C. or higher. Since the first layer may include a large amount of water scavenger, ions generated by the water scavenger react with water may migrate to the second layer. However, the second layer is in contact with the device, so that ions migrated from the first layer to the second layer can affect the device's performance. Therefore, the second layer can be sufficiently cured to prevent ions from moving from the first layer to the second layer and to prevent deterioration of the device performance. That is, the second layer may prevent the ions of the first layer having the glass transition temperature in the above range to be transferred to the second layer, thereby exhibiting the above-described effect.
- the electronic device may be an organic electronic device.
- the encapsulation layer can efficiently fix and support the upper substrate and the lower substrate while exhibiting excellent moisture barrier properties and optical properties in the organic electronic device.
- the encapsulation layer exhibits excellent transparency by, for example, preparing a moisture remover to a nano unit size and uniformly dispersing the resin in a resin, thereby providing organic electrons such as top emission or bottom emission. Regardless of the shape of the device, it can be formed into a stable encapsulation layer.
- the organic electronic device may be provided in a conventional configuration in the art, except that the encapsulation layer is formed of the above-described film.
- the organic electronic device may include, for example, a pair of electrodes and a layer of an organic material formed between the pair of electrodes.
- any one of the pair of electrodes may be composed of a transparent electrode.
- the layer of the organic material may include, for example, a hole transporting layer, a light emitting layer, an electron transporting layer, or the like.
- Another embodiment of the present application provides a method of manufacturing an electronic device, including laminating the aforementioned film on a substrate having an element formed thereon such that the second layer of the film contacts the element.
- the method of manufacturing the electronic device may be a method of manufacturing the above-described electronic device.
- the film is laminated to contact the device, for example, the film may be applied so that the film covers the entire surface of the device.
- laminating the second layer of the film in contact with the device may include, for example, contacting the second layer of the film and the device, and compressing the device while heating the second layer to impart fluidity.
- the second layer is solid or semi-solid at room temperature and heated to maintain a viscosity in the range of 10 3 to 10 5 Pa.s at 65 ° C. and 1 Hz of the second layer at the point of contact with the device. can do. If the second layer is, for example, the hot melt adhesive layer described above, it is possible to adhere without lifting and / or bubbles to a surface having a height difference, such as a substrate on which an element is formed. Therefore, even in a large area electronic device, it is possible to provide an electronic device without deteriorating the performance of the device due to bubbles or the like.
- the curing reaction may be excessive in the above process, and thus the adhesion or adhesion of the encapsulation layer may decrease, so that the process temperature is about 40 ° C. to 100 ° C., and the process time is 1 It can be controlled within minutes to 20 minutes.
- the pressing may be performed using a vacuum press or the like to prevent bubbles or the like from occurring between the device and the second layer.
- the manufacturing method may include curing the second layer after laminating the second layer of the film in contact with the device.
- the curing process may be carried out in an appropriate heating chamber or ultraviolet chamber, for example, depending on the curing method of the curable resin. Heating conditions or irradiation conditions of the active energy ray may be appropriately selected in consideration of the stability of the electronic device and the curability of the curable resin composition.
- curing may be performed such that the second layer has a glass transition temperature of at least 0 ° C, at least 50 ° C, at least 70 ° C, at least 85 ° C, or at least 100 ° C.
- the curing is performed so that the second layer has a glass transition temperature in the above range, it is possible to prevent the ions of the first layer from moving to the second layer, thereby exhibiting the above-described effects.
- the film may be previously transferred to the upper substrate of the electronic device before being laminated to the device.
- the first layer 12 of the film may be transferred to the upper substrate 21.
- the first layer 12 may be attached to the upper substrate 21 by a predetermined pressure. Accordingly, the transfer of the first layer may be performed by contacting the first layer and the upper substrate 21 and performing roll lamination.
- the transfer of the first layer 12 may be performed in a manner similar to the method of stacking the device with the second layer, 12) may include curing. Thereafter, as described above, the second layer 11 of film may be laminated with the element 23.
- the second layer 11 of the film may be transferred to the upper substrate 21. have. Transfer of the second layer 11 may be performed in the same manner as the method of stacking the second layer and the device, and may include curing the second layer.
- the manufacturing method of the electronic device is not limited thereto, and the manufacturing of the device is performed in the same manner as described above, but the order or conditions of the process may be changed. have.
- FIG. 1 is a view schematically showing a film according to one example.
- FIG. 2 is a view schematically showing a film according to another example.
- 3 is a schematic view of an organic electronic device according to an example.
- FIG. 4 is a schematic view of an organic electronic device according to another example.
- FIG. 5 is a view schematically illustrating a method of manufacturing an organic electronic device according to an example.
- FIG. 6 is a view schematically illustrating a method of manufacturing an organic electronic device according to another example.
- the resin composition was prepared by melt
- the said resin composition was apply
- Calcium (Ca) was deposited in a size of 10 mm ⁇ 10 mm (length ⁇ width) on a glass substrate having a size of 12 mm ⁇ 12 mm (length ⁇ width). Separately, the film produced in the Example or the comparative example was cut into the size of 12 mm x 12 mm (length x width). Then, the first layer or one side of the film was transferred to the cover glass. Then the opposite side of the side where the cover glass of the film is present is laminated onto the calcium of the glass substrate, heated and pressed at 80 ° C. for 2 minutes using a vacuum press, and at 100 ° C. for 3 hours. Curing to form an encapsulation layer to prepare a specimen.
- the calcium evaporated portion was oxidized and changed to a length that was transparent. Since the total length of calcium in one direction is 10 mm, all the calcium is oxidized when the length of the oxidized portion is 5 mm from one end of the calcium.
- the films prepared in Examples and Comparative Examples were laminated between soda-lime glass substrates, heated and pressed at 80 ° C. for 2 minutes using a vacuum press, and cured at 100 ° C. for 3 hours to form encapsulation layers. To form a specimen. Thereafter, while maintaining the specimen in a constant temperature and humidity chamber at 85 ° C. and 85% relative humidity for about 500 hours, it was observed whether the lifting occurred at the interface between the glass substrate and the encapsulation layer.
- the film produced by the Example or the comparative example was cut into the size of 90 mm x 90 mm (length x width), and the 1st layer or one side was transferred to the cover glass. . Then the opposite side of the surface where the cover glass of the film is present was heated and pressed at 80 ° C. for 2 minutes using a vacuum press on a glass of 100 mm ⁇ 100 mm (length ⁇ width), and 100 ° C. The panel was prepared by curing for 3 hours at and observed whether bubbles were generated inside.
- calcined dolomite as a water remover and 0.5 parts by weight of stearic acid as a dispersant were added to toluene at a concentration of 50% by weight of solids to prepare a water remover solution, and the solution was milled for 24 hours by a ball mill process.
- 70 parts by weight of a polyisobutene resin (trade name: B100, manufacturer: BASF) of a weight average molecular weight of 1.1 million as a first layer component was separately added to the reactor at room temperature, and a hydrogenated dicyclopentadiene-based resin ( 30 parts by weight of the product was added thereto, followed by dilution with toluene such that the solid content was about 20% by weight.
- the water removing agent solution prepared in advance in the homogenized solution was added so that the content of calcined dolomite was 50 parts by weight based on 100 parts by weight of the first component, and mixed to prepare a first layer solution.
- region prepared above was apply
- region prepared above was apply
- the first layer and the second layer were laminated to prepare a multilayer film.
- a first layer solution, a second layer solution, and a film were prepared in the same manner as in Example 1, except that the content of the calcined dolomite was 100 parts by weight based on 100 parts by weight of the first component.
- a first layer solution, a second layer solution, and a film were prepared in the same manner as in Example 1, except that the content of the calcined dolomite was 200 parts by weight based on 100 parts by weight of the first component.
- a second layer solution was prepared in the same manner as in Example 1.
- a film was prepared in the same manner as in Example 1, except that the first solution was prepared in Example 4.
- a first layer solution, a second layer solution, and a film were prepared in the same manner as in Example 4, except that 30 parts by weight were used.
- the second layer solution of Example 1 was used as the solution of the first layer, and the same water remover solution as that prepared in Example 1 was added to the solution so that the content of calcined dolomite was 10 parts by weight relative to 100 parts by weight of the epoxy resin.
- a second layer solution and a film were prepared in the same manner as in Example 1 except that a solution was used.
- a first layer solution, a second layer solution, and a film were prepared in the same manner as in Comparative Example 1 except that the content of the calcined dolomite was 50 parts by weight based on 100 parts by weight of the epoxy resin.
- a first layer solution, a second layer solution, and a film were prepared in the same manner as in Comparative Example 1 except that the content of the calcined dolomite was 70 parts by weight based on 100 parts by weight of the epoxy resin.
- a first layer solution, a second layer solution, and a film were prepared in the same manner as in Comparative Example 1 except that the content of the calcined dolomite was 100 parts by weight based on 100 parts by weight of the epoxy resin.
- a film was prepared in the same manner as in Comparative Example 3, except that the second layer solution prepared in Comparative Example 5 was used as the second layer solution.
- a first layer solution was prepared in the same manner as in Example 1, except that the moisture remover solution was added so that the content of calcined dolomite was 70 parts by weight based on 100 parts by weight of the first component.
- Nitrogen gas was refluxed, and 98 parts by weight of n-butyl acrylate (n-BA) and 2 parts by weight of 2-hydroxyethyl acrylate were added to a 1 L reactor equipped with a cooling device for easy temperature control, and ethyl acetate was used as a solvent. 100 parts by weight of (EAc; ethyl aceate) was added. Thereafter, nitrogen gas was purged for 1 hour for oxygen removal, and the temperature was maintained at 60 ° C. 0.05 parts by weight of azobisisobutyronitrile (AIBN) as a reaction initiator and 0.01 parts by weight of n-dodecyl mercaptan were further added and reacted.
- AIBN azobisisobutyronitrile
- the reaction mixture was diluted with ethyl acetate to prepare an acrylic resin solution having a weight average molecular weight of 1.3 million and a solid content concentration of 25% by weight.
- a tetrafunctional epoxy compound (trade name: BXX5627, manufacturer: Toyo Co., Ltd.) was added to the solution as 0.5 parts by weight based on 100 parts by weight of the acrylic resin solution solids, and mixed to prepare a first layer solution.
- a film was prepared in the same manner as in Example 1, except that the first layer solution prepared in Comparative Example 6 was used, and the second layer solution prepared in Comparative Example 6 was used.
- a first layer solution and a film were prepared in the same manner as in Comparative Example 6, except that the second layer solution was prepared in Comparative Example 5.
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Abstract
Description
M1a | M2b | M1/M2 | 수분 차단성c | 내구신뢰성 | 패널적용가능성 | ||
실시예 | 1 | 0.68 | 580 | 0.0012 | 2 | 양호 | 기포없음 |
2 | 0.68 | 580 | 0.0012 | 1.6 | 양호 | 기포없음 | |
3 | 0.68 | 580 | 0.0012 | 1.1 | 양호 | 기포없음 | |
4 | 120 | 580 | 0.0017 | 4.3 | 양호 | 기포없음 | |
5 | 98 | 580 | 0.1690 | 4.1 | 양호 | 기포없음 | |
비교예 | 1 | 580 | 580 | 1 | 5 이상 | 파괴 | 기포없음 |
2 | 580 | 580 | 1 | 5 이상 | 파괴 | 기포없음 | |
3 | 580 | 580 | 1 | 5 이상 | 파괴 | 기포없음 | |
4 | 580 | 580 | 1 | 5 이상 | 파괴 | 기포없음 | |
5 | 580 | 0.68 | 853 | 5 이상 | 파괴 | 기포발생 | |
6 | 0.68 | 0.45 | 1.5111 | 5 이상 | 양호 | 기포발생 | |
7 | 0.68 | 0.68 | 1 | 5 이상 | 양호 | 기포발생 | |
a: 제 1 층의 인장 탄성률(단위: MPa)b: 제 2 층의 인장 탄성률(단위: MPa)c: 칼슘의 일면에서 일 방향으로 산화된 길이(단위: mm) |
Claims (15)
- 제 1 층; 및 제 1 층의 25℃에서의 경화 후 인장 탄성률(M1)에 대한 25℃에서의 경화 후 인장 탄성률(M2)의 비율(M1/M2)이 1 x 10-6 내지 0.5인 제 2 층을 포함하는 봉지용 필름.
- 제 1 항에 있어서, 제 1 층의 25℃에서의 경화 후 인장 탄성률은 0.001MPa 내지 400MPa 인 필름.
- 제 1 항에 있어서, 제 2 층의 25℃에서의 경화 후 인장 탄성률은 400MPa 내지 1000MPa인 필름.
- 제 1 항에 있어서, 제 2 층은 제 1 층의 일면 또는 양면에 배치되는 필름.
- 제 1 항에 있어서, 제 1 층은 수지 성분을 포함하는 필름.
- 제 5 항에 있어서, 제 1 층은 수분 제거제를 추가로 포함하는 필름.
- 제 6 항에 있어서, 제 1 층은 수분 제거제를 수지 성분 100 중량부 대비 5 중량부 내지 250 중량부로 포함하는 필름.
- 제 1 항에 있어서, 제 2 층은 제 2 층의 고형분 100 중량부 대비 5 중량부 미만의 수분 제거제를 포함하는 필름.
- 제 1 항에 있어서, 제 2 층은 상온에서 고상 또는 반고상인 필름.
- 제 9 항에 있어서, 제 2 층은 미경화 상태인 필름.
- 제 1 항에 있어서, 제 2 층은 경화성 수지 조성물을 포함하는 필름.
- 제 11 항에 있어서, 제 2 층은 경화성 수지 조성물을 필름 형태로 포함하는 필름.
- 상부 기판; 하부 기판; 및 상기 상부 기판과 하부 기판의 사이에서 소자를 봉지하고 있는 제 1 항의 필름을 포함하는 봉지층을 가지는 전자장치.
- 제 13 항에 있어서, 소자는 하부 기판의 상부 기판과 대향하는 면에 형성되어 있고, 필름의 제 2 층이 상기 하부 기판과 접하고 있는 전자장치.
- 표면에 소자가 형성되어 있는 기판에 제 1 항의 필름을 상기 필름의 제 2 층이 상기 소자와 접하도록 적층하는 것을 포함하는 전자장치의 제조방법.
Priority Applications (4)
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EP13733915.6A EP2781571B1 (en) | 2012-01-06 | 2013-01-07 | Encapsulation film |
CN201380004696.9A CN104039910B (zh) | 2012-01-06 | 2013-01-07 | 封装薄膜 |
JP2014551197A JP6037576B2 (ja) | 2012-01-06 | 2013-01-07 | 封止用フィルム |
US14/323,867 US9698379B2 (en) | 2012-01-06 | 2014-07-03 | Encapsulation film |
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KR10-2012-0002170 | 2012-01-06 | ||
KR20120002170 | 2012-01-06 | ||
KR1020130001833A KR101474630B1 (ko) | 2012-01-06 | 2013-01-07 | 봉지용 필름 |
KR10-2013-0001833 | 2013-01-07 |
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US14/323,867 Continuation US9698379B2 (en) | 2012-01-06 | 2014-07-03 | Encapsulation film |
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PCT/KR2013/000109 WO2013103283A1 (ko) | 2012-01-06 | 2013-01-07 | 봉지용 필름 |
PCT/KR2013/000106 WO2013103281A1 (ko) | 2012-01-06 | 2013-01-07 | 봉지용 필름 |
PCT/KR2013/000108 WO2013103282A1 (ko) | 2012-01-06 | 2013-01-07 | 봉지용 필름 |
PCT/KR2013/000110 WO2013103284A1 (ko) | 2012-01-06 | 2013-01-07 | 전자장치의 제조방법 |
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PCT/KR2013/000106 WO2013103281A1 (ko) | 2012-01-06 | 2013-01-07 | 봉지용 필름 |
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US (4) | US9806293B2 (ko) |
EP (4) | EP2801476B1 (ko) |
JP (5) | JP5872068B2 (ko) |
KR (4) | KR101472199B1 (ko) |
CN (4) | CN104024360B (ko) |
TW (5) | TWI558566B (ko) |
WO (4) | WO2013103283A1 (ko) |
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