WO2012148071A2 - Film adhésif pour dispositif el organique, composition comprise dans celui-ci et dispositif d'affichage el organique le comprenant - Google Patents

Film adhésif pour dispositif el organique, composition comprise dans celui-ci et dispositif d'affichage el organique le comprenant Download PDF

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Publication number
WO2012148071A2
WO2012148071A2 PCT/KR2012/000305 KR2012000305W WO2012148071A2 WO 2012148071 A2 WO2012148071 A2 WO 2012148071A2 KR 2012000305 W KR2012000305 W KR 2012000305W WO 2012148071 A2 WO2012148071 A2 WO 2012148071A2
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WIPO (PCT)
Prior art keywords
organic
film
substrate
weight
display device
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Ceased
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PCT/KR2012/000305
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English (en)
Korean (ko)
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WO2012148071A3 (fr
Inventor
이지연
김미선
이길성
조민행
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Cheil Industries Inc
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Cheil Industries Inc
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Priority claimed from KR1020110039178A external-priority patent/KR101374370B1/ko
Priority claimed from KR1020110039180A external-priority patent/KR101397692B1/ko
Application filed by Cheil Industries Inc filed Critical Cheil Industries Inc
Publication of WO2012148071A2 publication Critical patent/WO2012148071A2/fr
Publication of WO2012148071A3 publication Critical patent/WO2012148071A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

  • the present invention relates to an adhesive film for an organic EL device, a composition contained therein, and an organic EL display device including the same.
  • An organic EL element is a polycrystalline semiconductor device, is used in backlights of liquid crystals and the like to obtain high luminance light emission at low voltage, and is expected to be a thin flat display device.
  • the organic EL element is extremely weak in moisture, the interface between the metal electric field and the organic EL layer may be peeled off due to the influence of moisture, the metal may be oxidized and become highly resistant, and the organic material itself may be deteriorated by moisture. Therefore, there is a problem that light is not emitted and luminance is lowered.
  • the conventional method of encapsulating the organic EL device has a limitation in suppressing the occurrence and growth of dark spots, it cannot have sufficient adhesive force, and it cannot fully satisfy all the requirements for encapsulation of the organic EL device.
  • the organic EL device has a disadvantage in that it is very sensitive to moisture and easily decomposes, causing chemical reaction with moisture.
  • the curable composition used for the sealing application of the existing organic EL device has a limit in lowering the water transmittance.
  • thermosetting process during the encapsulation process of the organic EL element. Therefore, when the thermal expansion coefficient of the sealing composition is large, the adhesive layer may bend or peeling may occur between the organic EL element and the substrate.
  • An object of the present invention is to provide an adhesive film for an organic EL device comprising an adhesive layer having a low thermal expansion rate, a composition included therein, and an organic EL display device including the same.
  • Another object of the present invention is to provide an adhesive film for an organic EL device comprising an adhesive layer having a low water transmittance, a composition included therein, and an organic EL display device including the same.
  • An adhesive film for an organic EL device which is an aspect of the present invention, includes an adsorbent and may be cured at 90 ° C. for 2 hours, and then have a moisture transmittance of about 100 g / m 2 ⁇ day or less at 50 ° C. and 100% relative humidity. .
  • the adsorbent may be included in about 0.5-40% by weight based on solids in the adhesive film.
  • the adsorbent may include one or more selected from the group consisting of zeolite, calcium oxide, molecular sieve, activated carbon, silica gel and the like.
  • the adhesive film may further include an epoxy resin, a film former resin, and a curing agent having a weight average molecular weight of about 50-10,000 g / mol.
  • the film former resin may be included in an amount of about 50-240 parts by weight based on 100 parts by weight of an epoxy resin having a weight average molecular weight of about 50-10,000 g / mol.
  • the adhesive film may further include one or more selected from the group consisting of a silane coupling agent, a filler, a leveling agent, an antifoaming agent, a storage stabilizer, a plasticizer and a talc adjusting agent.
  • Another aspect of the present invention is an organic EL display device comprising: a first substrate having an organic EL element formed on one surface thereof; A second substrate spaced apart from the first substrate; And a substrate disposed between the first substrate and the second substrate to bond the first substrate and the second substrate, the cured at 90 ° C. for 2 hours, and then the water transmittance at about 50 ° C. and 100% relative humidity of about 100 g / It may include an adhesive layer that is m 2 ⁇ day or less.
  • Another aspect of the present invention is an organic EL display device comprising: a first substrate having an organic EL element formed on one surface thereof; A second substrate spaced apart from the first substrate; And an adhesive layer disposed between the first substrate and the second substrate to bond the first substrate and the second substrate and having a thermal expansion rate of about 0 ° C. to 100 ° C. of about 100 ppm / ° C. or less.
  • the adhesive layer may be cured for 2 hours at 90 °C and the water transmittance at about 50 °C and 100% relative humidity may be about 100g / m 2 ⁇ day or less.
  • the adhesive layer may include a plate-shaped filler.
  • the adhesive layer may further include an epoxy resin, a film former resin, and a curing agent having a weight average molecular weight of about 50-10,000 g / mol.
  • the adhesive layer may further include a silane coupling agent.
  • the adhesive composition for encapsulating an organic EL device includes (A) a plate-shaped filler, (B) an epoxy resin having a weight average molecular weight of about 50-10,000 g / mol, (C) a film-forming resin, and (D) It may include a curing agent.
  • the present invention provides an adhesive film for an organic EL device comprising an adhesive layer having a low water transmittance.
  • This invention provided the adhesive film for organic electroluminescent elements containing the adhesive layer in the state of a favorable coating film, and the adhesive force is high and usability is high.
  • the present invention provides an organic EL display device comprising an adhesive layer composed of the adhesive film for organic EL elements.
  • the present invention provides an organic EL display device including an adhesive layer having a low thermal expansion rate and a low water transmittance.
  • the present invention provides an organic EL display device having an adhesive layer having a good coating film state and having good adhesion and high usability.
  • FIG. 1 shows an organic EL display device according to an embodiment of the present invention.
  • One aspect of the present invention relates to an adhesive film for an organic EL device.
  • the film of the present invention may be cured at 90 ° C. for 2 hours, and then the water transmittance in the film thickness direction may be about 100 g / m 2 ⁇ day or less at 50 ° C. and 100% relative humidity. Within this range, the water barrier effect is high, and peeling of the glass or film substrate on which the organic EL element is formed and the organic EL element can be prevented.
  • Moisture permeability may preferably be greater than about 0 up to 100 g / m 2 ⁇ day at 50 ° C. and 100% relative humidity, more preferably greater than about 50 g / m 2 ⁇ day up to 50 ° C. and 100% relative humidity. have.
  • Moisture permeability can be measured with a film having a thickness of 20-30 ⁇ m.
  • the composition constituting the adhesive film is filmed to the thickness and cured at 90 ° C. for 2 hours, and then measured by MOCON test using carrier gas as nitrogen gas under 50 ° C., 100% relative humidity, and 760 mmHg pressure. This is not restrictive.
  • the adhesive film may have a thickness of about 20 ⁇ m-30 ⁇ m.
  • the adhesive film may include an adsorbent.
  • the adsorbent can block the contact between the organic EL element and water by providing hygroscopicity by physical adsorption.
  • the adsorbent preferably uses particles that are porous such that the surface area adsorbed per unit volume or unit weight is wide to provide effective hygroscopicity.
  • the adsorbent preferably has an average pore size of about 1 nm-20 nm.
  • the adsorbent preferably has a particle size (D50) of about 50 nm-5 ⁇ m. Within this range, the hygroscopic effect is good and the film formability does not deteriorate.
  • the adhesive film may comprise an adsorbent having two or more particle sizes.
  • the adsorbent may include one or more selected from the group consisting of zeolite, calcium oxide, molecular sieve, activated carbon, silica gel and the like, but is not limited thereto.
  • the adsorbent may be included in about 0.5-40% by weight of the adhesive film on a solids basis. Within this range, the hygroscopic effect is good and the film formability does not deteriorate. Preferably about 4-20% by weight.
  • the adsorbent may be included in an amount of about 10-150 parts by weight based on 100 parts by weight of an epoxy resin having a weight average molecular weight of about 50-10,000 g / mol described below. Within this range, the hygroscopic effect may be good and the film formability does not deteriorate and the adhesive force may have a high effect. Preferably about 15-50 parts by weight.
  • the adhesive film may further include, in addition to the adsorbent, an epoxy resin having a weight average molecular weight of about 50-10,000 g / mol, a film former resin, and a curing agent.
  • the epoxy resin may have a weight average molecular weight of about 50-10,000 g / mol. Within this range, the adhesion of the film may be enhanced and the coating properties may be imparted.
  • the weight average molecular weight may preferably be about 100-5,000 g / mol, more preferably about 200-4,000 g / mol.
  • the epoxy resin preferably has about 700 ppm or less of hydrolyzable chlorine ions. Within this range, there may be an effect that does not damage the device in the acceleration reliability test for long-term reliability evaluation.
  • the chlorine ion may preferably be about 0-500 ppm, more preferably about 0-300 ppm.
  • the epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol type epoxy resin, a cycloaliphatic epoxy resin, a naphthalene type epoxy resin, a phenol novolak type epoxy resin, an o-cresol novolak type epoxy It may include, but is not limited to, one or more selected from the group consisting of resins, disclopentadiene type epoxy resins, biphenyl type epoxy resins, biphenyl novolak type epoxy resins, and naphthalene novolak type epoxy resins. .
  • the epoxy resin may be included in about 20-80% by weight based on the solids of the adhesive layer. Within this range, coating film properties and film formability may be good. Preferably about 20-75% by weight, more preferably about 25-70% by weight, most preferably about 27-59% by weight.
  • the film-forming resin may be an aromatic resin including an epoxy resin having a weight average molecular weight of about 10,000-500,000 g / mol, a (meth) acrylate resin, a urethane (meth) acrylate resin, a polyimide, a styrene resin, And it may include one or more selected from the group consisting of rubber, including diene-based, silicone-based, urethane-based, fluorine-based rubber and the like.
  • the film former resin may be an epoxy resin having a weight average molecular weight of about 10,000-500,000 g / mol.
  • the epoxy resin has an effect of imparting adhesion and coating properties of the film with a room temperature tack within the weight average molecular weight range. Preferably about 70,000-500,000 g / mol.
  • the epoxy resin having a weight average molecular weight of about 10,000-500,000 g / mol may include a resin having a bisphenol A type or a bisphenol F type epoxy skeleton.
  • a resin having a bisphenol A type or a bisphenol F type epoxy skeleton may include, but is not limited to, one or more selected from the group consisting of a solid bisphenol A epoxy resin, a solid bisphenol F epoxy resin, and a phenoxy resin.
  • the film former resin may be included in about 10-70% by weight based on the solids of the adhesive layer. Within this range, the film formability may be good and the reliability may be good. Preferably about 20-70% by weight, more preferably about 25-70% by weight, most preferably about 25-67% by weight.
  • the film former resin may include about 40-240 parts by weight based on 100 parts by weight of the epoxy resin having the weight average molecular weight of about 50-10,000 g / mol. Within this range, the film formability may be good and the reliability may be good. Preferably about 50-240 parts by weight, more preferably about 100-150 parts by weight.
  • the curing agent may include an imidazole series curing agent.
  • the imidazole series curing agent may include an imidazole compound having at least one functional group selected from the group consisting of a phenyl group, 10 or more carbon atoms, preferably 10-20 alkenes, and a cyan group.
  • the imidazole-based curing agent may enable the curing of the film coating film stability, room temperature compatibility and low temperature, especially at a temperature of 90 ° C or less.
  • the curing agent may include an imidazole curing agent having a reaction initiation temperature of about 60-100 ° C. and an imidazole curing agent having a reaction initiation temperature of about 100-160 ° C.
  • the 'reaction start temperature' means a temperature at which the imidazole curing agent reacts with the epoxy resin to start curing.
  • an imidazole curing agent having a reaction initiation temperature of about 70-98 ° C. and an imidazole curing agent having a reaction initiation temperature of about 105-140 ° C. may be included.
  • Two or more kinds of imidazole curing agents having a reaction initiation temperature of about 60-100 ° C. may be included.
  • two or more kinds of imidazole curing agents having the reaction initiation temperature of about 100-160 ° C may be included.
  • the imidazole curing agent having a reaction initiation temperature of about 60-100 ° C. and the imidazole curing agent having a reaction initiation temperature of about 100-160 ° C. are a phenyl group, a benzyl group, one or more carbons, for example, one to twenty carbon alkanes. It may have a cyano group or an amine group.
  • Examples of the imidazole curing agent having a reaction start temperature of about 60-100 ° C. include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl Imidazole, 2-phenylimidazoline, and the like, but are not limited to these.
  • imidazole curing agents having a reaction initiation temperature of about 100-160 ° C. examples include 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium-trimelitate, 2,4- Diamino-6 [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 1-cyanoethyl-2-phenylimidazolium-trimelitate, 2-phenylimidazole isocyanuric acid adduct, 1-benzyl-2- Phenylimidazole hydrobromide and the like, but are not limited thereto.
  • the curing agent may be included in about 0.1-10% by weight based on the solids of the adhesive film. Within this range, the film formability may be good and the reliability may be good. Preferably about 1-10% by weight, more preferably about 1-5% by weight.
  • the curing agent is about 0.1-20 parts by weight, preferably about 0.5-10 parts by weight, more preferably about 1-7 parts by weight of 100 parts by weight of the epoxy resin having the weight average molecular weight of about 50-10,000 g / mol. It may be included in parts by weight.
  • the adhesive layer may further include one or more selected from the group consisting of a silane coupling agent and a filler.
  • the silane coupling agent and the filler may increase the properties and reliability of the film coating film.
  • the silane coupling agent may use a conventional coupling agent.
  • a conventional coupling agent For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyl Selected from the group consisting of trimethoxysilane, vinyltrimethoxysilane, N-2- (vinylbenzylamino) ethyl) -3-aminopropyltrimethoxysilane hydrochloride and 3- (meth) acryloxypropyl
  • the filler may be a conventional filler.
  • one or more selected from the group consisting of aluminum oxide, aluminum silicate, talc and plate silicates may be used, but is not limited thereto.
  • the filler may be included in about 1-150 parts by weight, preferably about 10-100 parts by weight, based on 100 parts by weight of the film-forming resin, based on solids.
  • the adhesive layer may further include one or more additives.
  • the additive can improve the leveling and coating properties on the surface.
  • the additive may be used, for example, but not limited to one or more selected from the group consisting of a leveling agent, an antifoaming agent, a storage stabilizer, a plasticizer and a talc adjusting agent.
  • the adhesive film can be produced by drying and laminating an adhesive composition for sealing an organic EL device described below. Drying and laminating methods are not particularly limited but may include a method of drying at about 20-80 ° C. to about 0.2 m / s-1.5 m / s.
  • the adhesive film may have a thickness of about 1-100 ⁇ m, more preferably about 10-50 ⁇ m. Within this range, the organic EL device and the sealing film can be adhered well.
  • Another aspect of the present invention relates to a resin composition for sealing an organic EL device.
  • composition is present in the form of a film exhibiting non-fluidity at 25 °C and when heated to 50-100 °C to express the fluidity and adhesiveness between the organic EL element formed on the glass or film substrate and the sealing glass or film substrate between can do.
  • an organic EL device consisting of a transparent electrode, a hole transport layer, an organic EL layer and a back electrode on a glass or film substrate, heat transfer the composition of the present invention thereon, and heat-transfer the non-permeable glass or film to bond and encapsulate it.
  • the composition of the present invention may be thermally transferred to a water-impermeable glass or film, and bonded and sealed while heating to a glass or film on which an organic EL element is formed.
  • a transparent electrode is formed to a thickness of about 0.1 mu m on a glass or film substrate.
  • a transparent electrode there is a method by vacuum deposition and sputtering.
  • a hole transporting layer and an organic EL layer are sequentially formed on the transparent electrode at a thickness of about 0.05 ⁇ m, respectively, and a back electrode is formed on the organic EL layer at a thickness of about 0.1-0.3 ⁇ m.
  • the composition of the present invention is transferred to a laminate or the like on top of the glass or film substrate which has finished film formation of the device. At this time, when the composition of the present invention is transferred to a release film to form a sheet can be easily transferred.
  • thermosetting resin is completely cured at a curing temperature, for example, about 90 ° C. or less. It is also possible to transfer the composition of the present invention to the above impervious glass or film substrate first and to polymerize the element substrate on which the organic EL layer is formed.
  • composition of the present invention may have a shelf life of at least about 7 days at about 25 °C.
  • the film or cured product layer prepared from the composition of the present invention preferably has a thickness of about 1-100 ⁇ m, more preferably about 10-50 ⁇ m. It is possible to easily bond between two sheets of glass or film within the above range.
  • the composition may include (A) an epoxy resin having a weight average molecular weight of about 50-10,000 g / mol, (B) film former resin, (C) adsorbent, and (D) hardener.
  • the content about said component (A)-(D) is as having mentioned above.
  • composition may further include one or more selected from the group consisting of the silane coupling agent and the filler described above, and may further include one or more of the additives described above.
  • the composition may include a solvent commonly used in the art, for example, methyl ethyl ketone. Solvents may be included in the balance in the composition.
  • the apparatus includes a first substrate having an organic EL element formed on one surface thereof;
  • an organic EL display device 1 may include a first substrate 2, an organic EL element 3, a second substrate 4, and an adhesive layer 5. Can be.
  • the moisture transmittance in the adhesive layer thickness direction may be about 100 g / m 2 ⁇ day or less at 50 ° C. and 100% relative humidity. Within this range, the water barrier effect is high and the peeling of the first substrate and the organic EL element can be prevented.
  • Moisture permeability may preferably be greater than about 0 and less than 50 g / m 2 ⁇ day at 50 ° C. and 100% relative humidity.
  • the adhesive layer may include the adhesive film for organic EL device or the adhesive composition for encapsulating the organic EL device described above.
  • the adhesive layer may have a thickness of about 1-100 ⁇ m, more preferably about 10-50 ⁇ m. Within this range, the organic EL device and the sealing film can be adhered well.
  • the first substrate may be made of a material such as a transparent glass, a film, a plastic sheet, a silicon or metal substrate, and may have a flexible or non-flexible characteristic and a transparent or non-transparent characteristic.
  • One or more organic EL elements are formed on one surface of the first substrate.
  • the organic EL element is composed of a transparent electrode, a hole transport layer, an organic EL layer and a back electrode.
  • the second substrate may be disposed on the organic EL element, spaced apart from the first substrate, and adhered to the first substrate by the adhesive layer.
  • the second substrate not only a glass material substrate but also a substrate having excellent barrier properties such as a plastic sheet on which metal is laminated may be used.
  • a getter 6 may be formed between the first substrate and the second substrate and on the side of the organic EL element to adhere the first substrate and the second substrate.
  • the apparatus includes a first substrate having an organic EL element formed on one surface thereof;
  • the substrate may be disposed between the first substrate and the second substrate to bond the first substrate to the second substrate, and may include an adhesive layer having a thermal expansion rate of about 100 ppm / ° C. or less from 0 ° C. to 100 ° C.
  • an organic EL display device 1 may include a first substrate 2, an organic EL element 3, a second substrate 4, and an adhesive layer 5. Can be.
  • the adhesive layer may have a thermal expansion rate of about 100 ppm / ° C. or less in a temperature range of 0 ° C. to 100 ° C. Within this range, the adhesive layer does not bend even under high temperature curing conditions accompanying the sealing process of the organic EL element, and the first substrate and the organic EL element are not misaligned.
  • the coefficient of thermal expansion may be greater than about 0 up to 100 ppm / ° C., more preferably greater than about 0 up to 51 ppm / ° C.
  • the coefficient of thermal expansion may be measured with an adhesive layer having a length of 8.0 ⁇ 0.5 mm ⁇ width 4.8 ⁇ 0.2 mm ⁇ thickness 0.2 ⁇ 0.1 mm.
  • the composition constituting the adhesive layer is filmed and laminated, and cured at 90 ° C. for 2 hours, and then cut into a length of 8.0 ⁇ 0.5mm ⁇ width 4.8 ⁇ 0.2mm ⁇ thickness 0.2 ⁇ 0.1mm and a thermomechanical analyzer (TMA, Thermal expansion coefficient was measured using Thermal Mechanical Apparatus).
  • TMA Thermal expansion coefficient was measured using Thermal Mechanical Apparatus.
  • the sample was hooked to a quartz hook and subjected to a force of 0.05 N and then heated to 10 ° C./min from ⁇ 30 ° C. to 250 ° C. under a nitrogen atmosphere.
  • required the value of the temperature range from 0 degreeC to 100 degreeC.
  • the adhesive layer is cured at 90 °C for 2 hours
  • the water transmittance in the adhesive layer thickness direction may be about 100g / m 2 ⁇ day or less at 50 °C and 100% relative humidity.
  • the water barrier effect is high and the peeling of the first substrate and the organic EL element can be prevented.
  • Moisture permeability may preferably be greater than about 0 up to 100 g / m 2 ⁇ day at 50 ° C. and 100% relative humidity, more preferably greater than about 50 g / m 2 ⁇ day up to 50 ° C. and 100% relative humidity. have.
  • Moisture permeability can be measured with an adhesive layer having a thickness of about 20-30 ⁇ m.
  • the composition constituting the adhesive layer is filmed to the thickness, and cured at 90 ° C. for 2 hours, and then measured by MOCON test using carrier gas as nitrogen gas under 50 ° C., 100% relative humidity, and 760 mmHg pressure. It is not limited.
  • the adhesive layer may have a thickness of about 10-50 ⁇ m, preferably about 20-30 ⁇ m.
  • the adhesive layer may include a plate-shaped filler.
  • the plate-shaped filler does not impart hygroscopicity by physical adsorption or chemical bonding or hygroscopicity by chemical bonding.
  • the plate-shaped filler may not only prevent the adhesive layer having a form such as a film from expanding under heat as a plate-like form, but also block moisture's movement path or increase its length to impart hygroscopicity. have.
  • the plate-shaped filler may comprise a plate-like structure having a size of about 50 nm-10 ⁇ m in length, about 50 nm-10 ⁇ m in width, and about 50 nm-10 ⁇ m in thickness. Within this range, the coefficient of thermal expansion may be low, the moisture permeability may be low, and film forming may be good.
  • the plate-shaped filler is not particularly limited as long as it is a plate-shaped structure, but may include, for example, one or more selected from the group consisting of talc, mica, plate silicate, graphite and clay.
  • the plate-shaped filler may be included at about 0.5-40% by weight based on solids in the adhesive layer. Within this range, the moisture permeability may be low to have a moisture proof effect, and the film formability does not deteriorate. Preferably about 4-20% by weight.
  • the plate-shaped filler may be included in an amount of about 10-80 parts by weight based on 100 parts by weight of the epoxy resin having a weight average molecular weight of about 50-10,000 g / mol. Within this range, the hygroscopic effect may be good and the film formability does not deteriorate and the adhesive force may have a high effect. Preferably about 15-50 parts by weight.
  • the adhesive layer may further include an epoxy resin having a weight average molecular weight of about 50-10,000 g / mol, a film former resin, and a curing agent, in addition to the plate-shaped filler.
  • the epoxy resin having the weight average molecular weight of about 50-10,000 g / mol are as described above.
  • the epoxy resin may be included in about 20-80% by weight based on the solids of the adhesive layer. Within this range, coating film properties and film formability may be good. Preferably about 20-65% by weight, more preferably about 27-63% by weight.
  • the film former resin may be included in about 10-70% by weight based on the solids of the adhesive layer. Within this range, the film formability may be good and the reliability may be good. Preferably about 20-70% by weight, more preferably about 25-67% by weight.
  • the film former resin is about 40-240 parts by weight, preferably about 100-200 parts by weight, more preferably about 100- parts by weight, based on 100 parts by weight of the epoxy resin having the weight average molecular weight of about 50-10,000 g / mol. It may be included in 150 parts by weight.
  • the curing agent may be included in about 0.1-10% by weight based on solids of the adhesive layer. Within this range, the film formability may be good and the reliability may be good. Preferably 1-10% by weight, more preferably about 1-5% by weight.
  • the curing agent may be included in about 1-20 parts by weight, preferably about 1-10 parts by weight, more preferably about 1-5 parts by weight based on 100 parts by weight of the film-forming resin.
  • the adhesive layer may further include a silane coupling agent.
  • the silane coupling agent may increase the properties and reliability of the film coating film. Details of the silane coupling agent are as described above.
  • the silane coupling agent may be included in an amount of about 0.1-20 parts by weight based on 100 parts by weight of the epoxy resin having a weight average molecular weight of about 50-10,000 g / mol.
  • the adhesive layer may further include one or more additives. Details of the additives are as described above.
  • the adhesive layer can be produced by drying and laminating an adhesive composition for sealing an organic EL device described below. Drying and laminating methods are not particularly limited but may include a method of drying at about 20-80 ° C. to about 0.2 m / s-1.5 m / s.
  • the adhesive layer may have a thickness of about 1-100 ⁇ m, more preferably about 10-50 ⁇ m. Within this range, the organic EL device and the sealing film can be adhered well.
  • a getter 6 may be formed between the first substrate and the second substrate and on the side of the organic EL element to adhere the first substrate and the second substrate.
  • Another aspect of the present invention relates to an adhesive composition for sealing an organic EL device.
  • the composition may be present on a film exhibiting non-flowability at 25 ° C. and heated at 50-100 ° C. to express fluidity and adhesiveness to encapsulate between the organic EL element formed on the first substrate and the second substrate. .
  • An organic EL element composed of a transparent electrode, a hole transport layer, an organic EL layer, and a back electrode can be formed on the first substrate, and the composition of the present invention can be thermally transferred, bonded to the second substrate, and joined to be sealed.
  • the composition of the present invention can be thermally transferred to a second substrate, and bonded to and sealed with a first substrate on which an organic EL element is formed.
  • a transparent electrode is formed to a thickness of about 0.1 mu m on the first substrate.
  • a transparent electrode there is a method by vacuum deposition and sputtering.
  • a hole transport layer and an organic EL layer are sequentially formed on the transparent electrode at a thickness of about 0.05 ⁇ m, respectively, and a back electrode is formed on the organic EL layer at a thickness of about 0.1-0.3 ⁇ m.
  • the composition of the present invention is transferred to a laminate or the like on top of the glass or film substrate which has finished film formation of the device. At this time, when the composition of the present invention is transferred to a release film to form a sheet can be easily transferred. Then, the second substrate is superimposed on top of the transferred composition.
  • thermosetting resin is completely cured at a curing temperature, for example, about 90 ° C. or less. It is also possible to transfer the composition to the second substrate first and polymerize the first substrate on which the organic EL layer is formed.
  • the composition may have a shelf life of 7 days or more at 25 °C.
  • the film or cured product layer prepared from the composition may have a thickness of about 1-100 ⁇ m, more preferably about 10-50 ⁇ m. It is possible to easily bond between two sheets of glass or film within the above range.
  • the composition may include (A) a plate-shaped filler, (B) an epoxy resin having a weight average molecular weight of about 50-10,000 g / mol, (C) film former resin, and (D) hardener. Details of the above components (A) to (D) are as described above.
  • the plate-shaped filler may be included in about 0.5-40% by weight based on solids of the composition. Within this range, room temperature stability may be good and film formability may be good. Preferably about 4-20% by weight.
  • the epoxy resin having a weight average molecular weight of about 50-10,000 g / mol may be included in an amount of about 20-80 wt% based on the solids content of the composition. Within this range, coating film properties and film formability may be good. Preferably about 20-65% by weight, more preferably about 27-63% by weight.
  • the film former resin may be included in about 10-70% by weight based on solids of the composition. Within this range, the film formability may be good and the reliability may be good. Preferably about 20-70% by weight, more preferably about 25-67% by weight.
  • the curing agent may be included in about 0.1-10% by weight based on solids of the composition. Within this range, the film formability may be good and the reliability may be good. Preferably about 1-10% by weight, more preferably about 1-5% by weight.
  • composition may further comprise the silane coupling agent described above, and may further comprise one or more of the additives described above.
  • YDF-8170 epoxy equivalent 159 g / g-eq., Mw. 318 g / mol
  • epoxy resin having a weight average molecular weight of 50-10,000 g / mol.
  • 2P4MZ (Shikoku) (2-phenyl-4-methylimidazole), which is a curing agent 1
  • 2P4MHZ (Shikoku) (2-phenyl-4-methyl-5-hydoxymethylimidazole), which was a curing agent 2
  • the film-forming resin was dispersed in methyl ethyl ketone and the solid content was mixed in the amount shown in Table 1 below. Then, an epoxy resin, an adsorbent, and a curing agent having a weight average molecular weight of 50-10,000 g / mol were added in the amounts shown in Table 1 below. Dispersion was carried out using a planetary mixer and a 3-roll mill. A coating film was formed with an applicator, dried and laminated to prepare an adhesive film having a thickness of 20 ⁇ m.
  • the film-forming resin and the plate-shaped filler were dispersed in methyl ethyl ketone, respectively, and the solids were mixed in the amounts shown in Table 2 below. Then, the obtained solution was mixed and an epoxy resin and a curing agent were added in the amounts shown in Table 2 below. Dispersion was carried out using a planetary mixer and a 3-roll mill. A coating film was formed with an applicator, dried and laminated to prepare an adhesive layer having a thickness of 20 ⁇ m.
  • Example 1-4 except that the weight average molecular weight of 50-10,000 g / mol epoxy resin, film former resin, adsorbent, curing agent was changed to the content shown in Table 1 below, the same method was carried out to a thickness of 20 A micrometer adhesive film was prepared.
  • An adhesive layer having a thickness of 20 ⁇ m was prepared in the same manner as in Example 5-8, except that the epoxy resin, the film former resin, and the curing agent were changed to the contents shown in Table 2 below.
  • Moisture permeability After heat curing at 90 °C for 2 hours, the film was 20 ⁇ m thickness MOCON test using nitrogen gas as a carrier gas under 50 °C, 100% relative humidity, 760mmHg pressure.
  • Tensile strength The film was cured at 100 ° C. for 2 hours, and then measured by UTM tensile strength measuring method for a film having a width of 8 mm and a thickness of 20 ⁇ m.
  • Example 1 Example 2
  • Example 3 Example 4 Comparative Example 1 Epoxy resin with a weight average molecular weight of 50-10,000 g / mol (parts by weight) 100 100 100 100 100 Film former resin (weight part) 100 100 50 240 100 Adsorbent (part by weight) 15 50 15 15 - Curing agent (part by weight) Curing agent 1 One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One One Hardener 2 4 4 4 4 4 Moisture permeability (g / m 2 ⁇ day) 37 29 36 43 378 Coating state ⁇ ⁇ ⁇ ⁇ ⁇ DSS after hardening (kgf) 76 72 80 64 73 DSS (kgf) after reliability evaluation 63 69 68 48 52
  • Tensile Strength (N / mm 2 ) 24.1 23.6 23.9 19.8 21.3 Availability ⁇ ⁇
  • the film containing the adsorbent of the present invention compared to the film not containing the adsorbent has a low moisture permeability, a good coating state, good adhesion and high usability as a film (Comparative Example 1 Reference).
  • Thermal expansion rate First, the composition constituting the adhesive layer is filmed, laminated, and cured at 90 ° C. for 2 hours, and then cut into 8.0 ⁇ 0.5 mm in length x 4.8 ⁇ 0.2 mm in width x 0.2 ⁇ 0.1 mm in thickness, followed by a thermal system Thermal expansion coefficient was measured using an analytical measuring device (TMA, Thermal Mechanical Apparatus). The sample was hooked to a quartz hook and subjected to a force of 0.05 N and then heated to 10 ° C./min from ⁇ 30 ° C. to 250 ° C. under a nitrogen atmosphere. The thermal expansion coefficient calculated
  • DSS die shear strength after hardening: The 20 ⁇ m thick film was laminated on a 5 mm x 5 mm glass substrate (adhesive conditions 120 °C 5kgf, 5 seconds) and cured for 2 hours at 100 °C DAGE 4000 (DAGE ⁇ ) was measured die shear strength.
  • Film usability When it can be used for organic electroluminescent element sealing use, it evaluated as (circle), (triangle
  • Example 5 Example 6
  • Example 7 Example 8 Comparative Example 2 Epoxy resin with a weight average molecular weight of 50-10,000 g / mol (parts by weight) 100 100 100 100 100 Film former resin (weight part) 100 100 50 240 100 Plate-shaped filler (parts by weight) 15 50 15 15 - Curing agent (part by weight) Curing agent 1 One One One One One One One One One One One One One One One One One One One One One One One Hardener 2 4 4 4 4 4 4 Power Thermal expansion rate (ppm / °C) 47 42 46 51 102 Moisture permeability (g / m 2 ⁇ day) 38 31 36 47 378 Coating state ⁇ ⁇ ⁇ ⁇ ⁇ Tensile Strength (N / mm 2 ) 25.7 30.2 24.5 21.0 21.3 DSS after hardening (kgf) 75 83 82 69 73 DSS (kgf) after reliability evaluation 66 71 68 51 52 Availability ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • the adhesive layer containing the plate-shaped filler of the present invention compared to the adhesive layer not containing the plate-shaped filler has a low thermal expansion and water permeability, a good coating state, good adhesion, and high usability as a film. (See Examples 5-8 and Comparative Example 2.)
  • the present invention provides an adhesive film for an organic EL device, a composition contained therein, and an organic EL display device including the same.

Landscapes

  • Electroluminescent Light Sources (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention porte sur un film adhésif pour dispositif électroluminescent (EL) organique, sur une composition comprise dans celui-ci, et sur un dispositif d'affichage EL organique le comprenant.
PCT/KR2012/000305 2011-04-26 2012-01-12 Film adhésif pour dispositif el organique, composition comprise dans celui-ci et dispositif d'affichage el organique le comprenant Ceased WO2012148071A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020110039178A KR101374370B1 (ko) 2011-04-26 2011-04-26 유기 ｅｌ 소자용 접착 필름, 이에 포함되는 조성물, 및 이를 포함하는 유기 ｅｌ 디스플레이 장치
KR10-2011-0039178 2011-04-26
KR1020110039180A KR101397692B1 (ko) 2011-04-26 2011-04-26 유기 ｅｌ 디스플레이 장치 및 이에 포함되는 유기 ｅｌ 소자 봉지용 접착제 조성물
KR10-2011-0039180 2011-04-26

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WO2012148071A2 true WO2012148071A2 (fr) 2012-11-01
WO2012148071A3 WO2012148071A3 (fr) 2012-12-20

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PCT/KR2012/000305 Ceased WO2012148071A2 (fr) 2011-04-26 2012-01-12 Film adhésif pour dispositif el organique, composition comprise dans celui-ci et dispositif d'affichage el organique le comprenant

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104293264A (zh) * 2014-09-17 2015-01-21 明光市锐创电气有限公司 一种高强度金属胶水

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003282243A (ja) * 2002-03-25 2003-10-03 Fuji Photo Film Co Ltd 発光素子
EP1804310B1 (fr) * 2005-12-30 2016-10-19 Samsung Display Co., Ltd. Dispositif d'affichage électroluminescent organique et son procédé de fabrication
JP5232528B2 (ja) * 2007-08-31 2013-07-10 富士フイルム株式会社 環境感受性デバイスの封止方法および画像表示素子
KR101330879B1 (ko) * 2008-04-03 2013-11-18 엘지전자 주식회사 유기전계발광표시장치

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104293264A (zh) * 2014-09-17 2015-01-21 明光市锐创电气有限公司 一种高强度金属胶水

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