WO2006080526A1 - Réservoir d’étanchéité pour élément luminescent et corps lumineux - Google Patents

Réservoir d’étanchéité pour élément luminescent et corps lumineux Download PDF

Info

Publication number
WO2006080526A1
WO2006080526A1 PCT/JP2006/301558 JP2006301558W WO2006080526A1 WO 2006080526 A1 WO2006080526 A1 WO 2006080526A1 JP 2006301558 W JP2006301558 W JP 2006301558W WO 2006080526 A1 WO2006080526 A1 WO 2006080526A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxygen
polymer
light emitting
conjugated
emitting element
Prior art date
Application number
PCT/JP2006/301558
Other languages
English (en)
Japanese (ja)
Inventor
Akira Tanaka
Original Assignee
Zeon Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeon Corporation filed Critical Zeon Corporation
Priority to JP2007500649A priority Critical patent/JP4877606B2/ja
Publication of WO2006080526A1 publication Critical patent/WO2006080526A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • 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
    • C09J115/00—Adhesives based on rubber derivatives
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/842—Containers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/846—Passivation; Containers; Encapsulations comprising getter material or desiccants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/08—Depolymerisation

Definitions

  • the present invention relates to a sealing container for a light-emitting element and a light-emitting body, and more specifically, for a light-emitting element that contains and seals an organic electoluminescence element (sometimes referred to as an organic EL element).
  • the present invention relates to a sealing container and a light emitter using the sealing container for a light emitting element.
  • An organic EL element useful as a light emitting element is a self-luminous element having a laminated structure in which an organic light emitting layer is disposed between a cathode layer and an anode layer.
  • the organic EL element has a light emitting layer 4 that is the organic light emitting layer disposed between a cathode layer 3 and an anode layer 5 and is laminated.
  • a laminated structure can be taken.
  • a light-emitting layer containing an organic light-emitting compound having an electrification effect is a hole injection layer and a transport layer on the anode layer side of the light-emitting layer present in the laminate, and an electron injection layer on the cathode layer side.
  • a laminated body of the light emitting elements is formed on the substrate 6, and the laminated body is sealed with an external force by the sealing container 1.
  • the substrate 6 is made of glass or plastic, and the sealed container 1 is often made of metal.
  • a drug placement unit 8 is provided, and the drug placement unit 8 stores an inorganic oxygen scavenger together with a dehumidifying agent.
  • a large number of such organic EL elements are arranged on the same substrate 6 to form an organic EL panel.
  • Such an organic EL device is a very effective light-emitting device, but the organic light-emitting compound contained in the light-emitting layer is unstable with respect to oxygen or moisture. There is a defect that easily deteriorates due to moisture. Furthermore, conventionally, it has been assumed that the organic EL device has a light emission characteristic such as light emission luminance, light emission efficiency, and uniformity of light emission luminance that is remarkably lowered after driving for a certain period of time compared to the initial state. The cause of such deterioration of the light emission characteristics is considered to be oxidation of the electrode due to oxygen and Z or moisture entering the organic EL element, and deterioration of acidity of various organic materials.
  • Patent Document 1 a protective layer made of an electrically insulating inorganic compound such as MgO is provided on the outer surface of the laminate, and a shield layer such as a glass plate is further provided outside the protective layer.
  • An organic EL device is described.
  • Patent Document 2 a protective layer of fluoropolymer or oxide insulator is formed on the outer surface of the laminate, and the outer side of the protective layer is covered with a glass container or the like. It is described that a dehydrating agent and an oxygen absorbent are put in between and an inert medium is enclosed.
  • Patent Document 3 describes an organic EL element device in which the side surface of an organic EL element is sealed with an epoxy resin-based adhesive containing an oxygen scavenger.
  • Patent Document 4 describes an oxygen absorber for an organic EL element in which a metal-based oxygen absorption accelerator is added to an unsaturated fatty acid compound and a chain hydrocarbon polymer.
  • Patent Document 5 describes the application of ultraviolet curable resin as an adhesive for bonding a plastic organic EL panel substrate and a sealing container.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-89959
  • Patent Document 2 Japanese Patent Laid-Open No. 10-275682 & US Patent US5990615A (1999-11-23)
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-175877 & US Patent US6686063B2 (2004 -02-03)
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2003-133061
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-47381 & International Publication No. 04/008812 Pamphlet Disclosure of Invention
  • Sarakuko aims to provide a transparent sealed container for a light-emitting element that can also extract light from the sealed container side.
  • Another object of the present invention is to provide a light emitter using the sealing container for a light emitting element.
  • a conjugated diene polymer cyclized product obtained by cyclization reaction of a conjugated diene polymer in a sealing container for a light emitting element comprising a cover part for covering a light emitting element mounted on a substrate, Conjugated polymer cyclized product having an unsaturated bond reduction rate of 10% or more indicating the number of unsaturated bonds present in the conjugated polymer cyclized product with respect to the number of unsaturated bonds in the conjugated polymer.
  • a sealed container for a light emitting device characterized by having an oxygen absorbing member containing
  • the oxygen absorbing member is a sealed container for a light emitting device according to (1), wherein the oxygen absorption rate is 10 mLZm 2 Z days or more.
  • the oxygen absorbing member has a wavelength of 400 ⁇ !
  • the oxygen-absorbing member is the sealing container for a light-emitting element according to (1), wherein the oxygen absorption amount is 0.5 mLZg or more.
  • the surface of the cover portion facing the light emitting element is formed of a transparent resin member having an oxygen transmission coefficient of 10 mLZm 2 Z or less, and the oxygen absorbing member is disposed on the surface facing the light emitting element.
  • the surface of the cover portion facing the light emitting element has a wavelength of 400 ⁇ !
  • a transparent resin substrate formed of a transparent resin having a light transmittance of 85% or more at 650 nm, and the oxygen absorbing member and an oxygen transmission coefficient of 10 mLZm 2 Z day or less on the surface of the transparent resin substrate
  • the conjugation polymer is a sealing container for a light emitting device according to (1), which is a copolymer of a conjugation monomer and another monomer,
  • a substrate a light emitting element body disposed on the substrate, and a sealing container disposed to cover the light emitting element, wherein the sealing container is for the light emitting element according to (1).
  • a light emitter characterized by being a sealed container.
  • the organic EL device including the sealing container for a light emitting device of the present invention can be used stably for a long period of time without deterioration due to oxygen.
  • the sealed container for a light emitting device of the present invention can be made of only plastic, is easy to manufacture, and is suitable for manufacturing a flexible organic EL panel.
  • the sealing container for a light-emitting element of the present invention can be a sealing container having excellent translucency, and is suitable for manufacturing an organic EL element having a light-emitting surface on the sealing container side.
  • FIG. 1 is an explanatory view of an example of a luminous body provided with a sealed container of the present invention.
  • FIG. 2 is an explanatory view of an example of a luminous body provided with the sealed container of the present invention.
  • FIG. 3 is an explanatory view of a light emitting body provided with a conventional sealed container.
  • FIG. 4 is an explanatory view of an example of a luminous body provided with the sealed container of the present invention.
  • a sealing container 1 for a light-emitting element that is an example of the present invention used for a light-emitting body 12 (hereinafter, a sealing container for a light-emitting element is abbreviated as “sealing container”).
  • a sealing container for a light-emitting element is abbreviated as “sealing container”.
  • the covering lid portion 10 includes a side wall portion 10a formed in a cylindrical shape and a canopy portion 10b that closes an upper portion of the side wall portion 10a.
  • the sealing container 1 has a phosphor 12 using a conventional organic EL element shown in FIG. 3, for example, in a region surrounded by the substrate 6 and the cover 10 coupled to the substrate 6.
  • the sealed container 1 of the present invention may have a drug placement portion 8 (not shown in FIG. 1; see FIG. 3) for storing a dehumidifying agent and the like together with the oxygen absorbing member 2.
  • the oxygen-absorbing member 2 contains a conjugated cyclized polymer having an unsaturated bond reduction rate of 10% or more.
  • the conjugated conjugated polymer cyclized product used in the present invention is a polymer which has excellent oxygen absorption performance and does not deteriorate even after oxygen absorption.
  • the shape of the sealed container according to the present invention is not limited to a covered cylindrical body having a side wall portion 10a and a canopy portion 10b that closes the upper portion thereof as shown in FIG.
  • the light-emitting element 9 can take various forms as long as the organic light-emitting compound contained has a structure or configuration that emits light when a voltage is applied.
  • the light-emitting layer 4 is provided between the cathode layer 3 and the anode layer 5. And a laminated structure in which these are laminated, and a laminated structure in which an electron transport layer and a hole transport layer are laminated.
  • the oxygen absorbing member 2 may be disposed at any position as long as it is within the sealed container 1. May be. For example, as shown in FIG. 1, it may be disposed so as to be in close contact with the ceiling surface of the sealing container 1 that covers the light emitting element 9 mounted on the substrate 6. Or you may arrange
  • the space formed by the sealing container 1 coupled to the substrate 6 and the substrate 6 is substantially filled so as to surround the light emitting element 9 mounted on the substrate 6.
  • the oxygen absorbing member 2 may be arranged so as to be filled. As shown in FIG. 1 or FIG.
  • the oxygen absorbing member 2 is arranged so that the upper surface of the light emitting element 9 in the sealing container 1 and the ceiling surface of the covering container 1 are in close contact with each other as shown in FIG. It becomes a state. Further, as shown in FIG. 4, a structure having an oxygen absorbing member 2 as a part of the member forming the sealed container 1 may be used.
  • the oxygen absorbing member 2 is a member that forms the sealed container 1 in direct contact with the outside air, that is, exposed to the outside air, the oxygen absorbing member absorbs a large amount of oxygen from the outside air. As a result, the oxygen absorption capacity is saturated, which is not preferable. As shown in FIG. 4, it is preferable that the outermost surface is entirely covered with a protective film 7 having an oxygen permeability coefficient of 10 mL / m 2 or less.
  • the conjugated diene polymer cyclized product used in the present invention can be obtained by cyclization reaction of a conjugated diene polymer in the presence of an acid catalyst, and has a ring structure derived from a conjugated diene monomer unit in the molecule.
  • the conjugation polymer a homopolymer of a conjugation monomer, a copolymer of plural conjugation monomers of different types, or a conjugation monomer and other monomers copolymerizable therewith Examples of such a copolymer may be mentioned.
  • Conjugation monomers that can be used are not particularly limited.
  • Other monomers copolymerizable with the conjugation monomer are not particularly limited. Specific examples include styrene, 0-methyl styrene, p-methyl styrene, m-methyl styrene, 2, 4-dimethyl styrene, ethyl styrene, pt-butynole styrene, ⁇ -methino styrene, ⁇ -methyl ⁇ .
  • -Aromatic butyl monomers such as methyl styrene, 0-chloro styrene, m-chloro styrene, p-chloro styrene, p- bromo styrene, 2, 4-dibu-mouthed styrene, and urnaphthalene, ethylene, propylene, and 1 -Chain olefin monomers such as butene, cyclopentene, and cyclic olefin monomers such as 2-norbornene, 1, 5-hexagen, 1, 6-heptagen, 1, 7-octadiene, dicyclopentagen , And non-conjugated diene monomers such as 5-ethylidene-2-norbornene, methyl (meth) acrylate, and (meth) acrylates such as (meth) acrylate ethyl Le, and (meth) acrylonitrile, and
  • styrene is preferred, which is preferably an aromatic butyl monomer, and styrene is more preferred, which is more preferably a-methylstyrene.
  • These polymerizable monomers may be used alone or in combination of two or more.
  • the content of the conjugation monomer unit in the conjugation polymer is appropriately selected within a range not impairing the effects of the present invention, but is usually 40 mol% or more, preferably 60 mol% or more, more preferably 80. More than mol%. If the content of the conjugation monomer unit is too small, it becomes difficult to increase the unsaturated bond reduction rate, and oxygen absorption tends to be inferior.
  • conjugation polymers include natural rubber (NR), styrene-butadiene rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), isoprene-isobutylene copolymer rubber (IIR). And ethylene-propylene-gen copolymer rubber and butadiene-isoprene copolymer rubber (BIR).
  • NR natural rubber
  • SBR styrene-butadiene rubber
  • IR polyisoprene rubber
  • BR polybutadiene rubber
  • IIR isoprene-isobutylene copolymer rubber
  • BIR ethylene-propylene-gen copolymer rubber and butadiene-isoprene copolymer rubber
  • polyisoprene rubber and polyisoprene rubber which are preferred, are more preferably used.
  • the conjugation polymer may be polymerized by a conventional method.
  • an appropriate catalyst such as a Ziegler polymerization catalyst, an alkyllithium polymerization catalyst, or a radical polymerization catalyst containing titanium or the like as a catalyst component is used. It is used by solution polymerization or emulsion polymerization.
  • the conjugated diene polymer cyclized product used in the present invention can be obtained by, for example, subjecting the above conjugated diene polymer to a cyclization reaction in the presence of an acid catalyst.
  • an acid catalyst used in the cyclization reaction a conventionally known compound can be used.
  • inorganic brominated acids such as sulfuric acid, fluoromethanesulfonic acid, difluoromethanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, and alkyl groups having 2 to 18 carbon atoms
  • Organic sulfonic acid compounds such as alkylbenzene sulfonic acid, their anhydrides, or alkyl esters, as well as boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, jetyl aluminum monochloride, ethylammodichloride, Examples thereof include metal halides such as aluminum bromide, antimony pentachloride, tungsten hexachloride, and salt iron salt.
  • These acid catalysts may be used alone or in combination of two or more.
  • P-toluenesulfonic acid and its anhydride which are preferably organic sulfonic acid compounds, can be used more preferably.
  • the amount of the acid catalyst to be used is usually 0.05 to: L0 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 0.3 to 2 parts by mass per 100 parts by mass of the conjugate polymer.
  • the cyclization reaction is usually carried out by dissolving a conjugated polymer in a hydrocarbon solvent and reacting in the presence of an acid catalyst.
  • the hydrocarbon solvent is not particularly limited as long as it does not inhibit the cyclization reaction. Specific examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and ethenylbenzene, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane, cyclopentane, and cyclohexane. And alicyclic hydrocarbons such as hexane.
  • the polymerization solvent can be used as it is as a solvent for the cyclization reaction, and in this case, the polymerization reaction solution after completion of the polymerization reaction is used.
  • a cyclization reaction can be carried out by adding an acid catalyst.
  • the amount of the hydrocarbon solvent used is such that the solid content concentration of the conjugated polymer is usually 5 to 60% by mass, preferably 20 to 40% by mass.
  • the cyclization reaction can be performed under pressure, reduced pressure, or atmospheric pressure. However, it is desirable to perform the reaction under atmospheric pressure from the viewpoint of ease of operation. When performed in an argon atmosphere, side reactions caused by moisture can be suppressed.
  • the reaction temperature and reaction time may be according to conventional methods.
  • the reaction temperature is usually 50 to 150 ° C, preferably 70 to 110 ° C, and the reaction time is usually 0.5. -10 hours, preferably 2-7 hours.
  • the acid catalyst is deactivated by a conventional method and the acid catalyst residue is removed. Then, if desired, an antioxidant is added to remove the hydrocarbon solvent and unreacted monomers. Hard Conjugated cyclized polymer having a shape can be obtained.
  • the conjugated conjugated polymer cyclized product used in the present invention is a modified conjugated conjugated polymer cyclized product (hereinafter referred to as a conjugated conjugated polymer cyclized product as long as the object of the present invention is not impaired). ) May be abbreviated as a compound cyclized product, and is more preferable than an unmodified conjugate conjugated polymer cyclized product.
  • a conjugated conjugated polymer cyclized product May be abbreviated as a compound cyclized product, and is more preferable than an unmodified conjugate conjugated polymer cyclized product.
  • polar group-containing conjugated conjugated polymer cyclized products modified to contain polar groups are preferred.
  • the polar group is not particularly limited, for example, an acid anhydride group, a carboxyl group, a hydroxyl group, a thiol group, an ester group, an epoxy group, an amino group, an amide group, a cyan group, a silyl group, and a noble group.
  • Examples include polar groups such as rogen.
  • Examples of the acid anhydride group or carboxyl group include maleic anhydride, itaconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, acrylic acid, methacrylic acid, and male carboxylic acid compounds such as maleic acid conjugates.
  • Examples include groups having a structure added to a cyclized product of a polymer. Among them, a group having a structure in which maleic anhydride is added to a cyclized polyisoprene is preferable in terms of reactivity and economy.
  • hydroxyl group examples include hydroxyalkyl esters of unsaturated acids such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and N-methylol (meth) acrylamide.
  • unsaturated acid amides having a hydroxyl group such as N- (2-hydroxyethyl) (meth) acrylamide, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and poly ( Polyalkylene glycol monoesters of unsaturated acids such as ethylene glycol-propylene glycol) mono (meth) talylate and polyhydric alcohol monoesters of unsaturated acids such as glycerol mono (meth) talylate Group of the structure added to the polymer cyclized product.
  • N- (2-hydroxyethyl) (meth) acrylamide polyethylene glycol mono (meth) acrylate
  • polypropylene glycol mono (meth) acrylate poly
  • Polyalkylene glycol monoesters of unsaturated acids such as ethylene glycol-propylene glycol) mono (meth) talylate
  • polyhydric alcohol monoesters of unsaturated acids such as glycerol
  • hydroxyalkyl esters are preferred instrument especially an acrylic acid 2-hydroxy-E chill unsaturated acid, or a group of 2-hydroxyethyl methacrylate, 2-hydroxypropyl E chill is added to the conjugated diene polymer cyclized product structure favored.
  • vinyl compounds containing other polar groups include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) ) Atarylate, dimethylaminopropyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, etc. Is mentioned.
  • the expression “(meth) atari ...” means a compound or substituent of “atari ...” and / or “metaatari ...”.
  • the content of the polar group in the conjugated conjugated polymer cyclized product, in particular the polar group-containing conjugated cyclized polymer cyclized product is not particularly limited, but is usually 0. 1 ⁇ 200 ⁇ Jimole, girls or 1 ⁇ : Monore, J girls or 5 ⁇ 50 ⁇ . If this content is too low or too high, the oxygen absorption function tends to be poor.
  • the content of the polar group is determined based on 1 mol of the molecular weight corresponding to the molecular weight of the polar group bonded to the molecule of the modified conjugate cyclized polymer.
  • the method for producing the modified conjugated gen polymer cyclized product includes (1) a method in which a conjugated gen polymer cyclized product obtained by the above method is subjected to an addition reaction with a polar group-containing vinyl compound, and (2) a polar group.
  • the method (1) is preferable from the viewpoint of easy adjustment of the unsaturated bond reduction rate.
  • the polar group-containing vinyl compound is not particularly limited as long as it is a compound that can introduce a polar group into a conjugated cyclized polymer, for example, an acid anhydride group, a force oxyl group, a hydroxyl group, Preferred examples include vinyl compounds having polar groups such as thiol groups, ester groups, epoxy groups, amino groups, amide groups, cyano groups, silyl groups, and halogens.
  • Examples of the vinyl compound having an acid anhydride group or a carboxyl group include maleic anhydride, itaconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, attalic acid, methacrylic acid, and maleic acid.
  • maleic anhydride can be preferably used from the viewpoint of reactivity and economy.
  • Examples of the vinyl compound containing a hydroxyl group include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, particularly preferred are hydroxyalkyl esters of unsaturated acids! /, Listed as vinyl compounds It is done.
  • a polar group-containing vinyl compound is subjected to an addition reaction with the conjugated conjugated polymer cyclized product.
  • the method for introducing the polar group derived from the functional group-containing vinyl compound is not particularly limited, and may be a known reaction generally called an addition reaction or a graft polymerization reaction.
  • This addition reaction is carried out by subjecting a conjugated cyclized polymer and a polar group-containing vinyl compound to a catalytic reaction in the presence of a radical generator, if necessary.
  • radical generators include peroxides such as di-tert-butyl peroxide, dicumyl peroxide, and benzoyl peroxide, and azo-tolyl such as azobisisobutyoxy-tolyl.
  • the addition reaction may be performed in a solid phase state or in a solution state, but it is preferably performed in a solution state because the reaction can be easily controlled.
  • the reaction solvent to be used include the same types of solvents as the inert solvent in the cyclization reaction as described above.
  • the amount of the polar group-containing vinyl compound used varies depending on the reaction conditions, but is appropriately selected so that the content of the introduced polar group falls within the above-mentioned preferred range.
  • the reaction for introducing a polar group can be carried out under pressure, reduced pressure, or atmospheric pressure. However, it is desirable to carry out the reaction under atmospheric pressure from the viewpoint of ease of operation. Water-induced side reactions can be suppressed when carried out under flow, especially in an atmosphere of dry nitrogen or argon.
  • the reaction temperature, reaction time, etc. are usually from 30 to 250. C, preferably 60-200. C, and the reaction time is usually 0.5 to 5 hours, preferably 1 to 3 hours.
  • conjugated-gen polymer cyclized product it is considered that the cyclic unsaturated bond part greatly contributes to oxygen absorption, and the linear unsaturated bond part hardly contributes to oxygen absorption. Therefore, a conjugated diene polymer cyclized product having an unsaturated bond reduction rate of 10% or more of the conjugated diene polymer cyclized product is essential as a material for the oxygen absorbing member in the light emitting device of the present invention.
  • the unsaturation rate of the conjugated cyclized polymer is preferably 40 to 75%, more preferably 55 to 70%. If the unsaturated bond reduction rate is too low, oxygen absorption tends to deteriorate.
  • the conjugated diene polymer cyclized product is produced by preventing the conjugated diene polymer cyclized product from becoming brittle by making the unsaturated bond reduction rate below the upper limit of the above preferred range. In addition, the progress of gelling during production can be suppressed, and the transparency can be improved so that it can be used in many applications. In addition, when the unsaturated bond reduction rate exceeds 50%, adhesiveness develops, so this property can also be utilized.
  • the unsaturated bond reduction rate is an index that represents the degree to which the unsaturated bond has been reduced by the cyclization reaction at the conjugation monomer unit site in the conjugation polymer, and is determined as follows. It is a numerical value. That is, by proton NMR analysis, the ratio of the peak area of the proton directly bonded to the double bond to the peak area of all the protons in the conjugation monomer unit portion in the conjugation polymer was measured before and after the cyclization reaction. Each is calculated and the reduction rate is calculated.
  • the total proton peak area before the cyclization reaction is SBT
  • the degree of cyclization of the conjugate polymer can also be evaluated by the cyclization rate.
  • the cyclization rate is determined by proton NMR measurement according to the method described in the following documents (i) and (ii).
  • the mass average molecular weight of the conjugated diene polymer cyclized product is 5,000 to 2,000, 000, preferably ⁇ or 10, 000 to 1,000,000, more preferably ⁇ or 20, 000 to 500, 000 force. ⁇ Desired! / ⁇ . If the mass average molecular weight is too low, the oxygen absorption amount of the conjugated diene polymer cyclized product tends to decrease. There is a tendency that the plasticity becomes small and the handling becomes difficult.
  • the mass average molecular weight is a standard polystyrene equivalent value measured using gel-permeation chromatography.
  • the glass transition temperature (Tg) of the conjugated diene polymer cyclized product is not particularly limited, and is a force that can be appropriately selected depending on the application. Usually, 0 to 250 ° C, preferably 0 to 200 ° C, More preferably, it is in the range of 30 to 180 ° C, particularly preferably 40 to 150 ° C. Conjugated polymer polymer Glass transition temperature force of cyclized product If these ranges are exceeded, problems may arise in the formability of the conjugated polymer polymer cyclized product, the strength of the member, the adhesion to other members, and the handleability. There is a case.
  • the glass transition temperature of the conjugated cyclized polymer can be adjusted by appropriately selecting the molecular weight of the monomer and conjugated cyclized polymer used as a raw material, the unsaturated bond reduction rate, and the like.
  • the conjugated conjugated polymer cyclized product used in the present invention has various additives such as an antioxidant, a catalyst having an action of enhancing oxygen absorption, light, and the like, unless the effects of the present invention are essentially impaired.
  • Initiators, heat stabilizers, adhesive materials, reinforcing agents, fillers, flame retardants, colorants, plasticizers, UV absorbers, lubricants, desiccants, deodorizers, antistatic agents, anti-sticking agents, anti-fogging agents, And additives such as surface treatment agents can be blended.
  • additives can be appropriately selected from conventionally known additives according to the purpose and blended in appropriate amounts.
  • the blending of the additive is not particularly limited, and can be performed by melt-kneading or mixing in a solution state.
  • a double bond derived from a conjugation monomer that remains as it is without cyclization is prone to oxidative degradation due to its chemical structure, and has a low unsaturated bond reduction rate. It is effective to add an antioxidant to the cyclized product.
  • the anti-oxidation agent is not particularly limited as long as it is usually used in the field of adhesives, resin materials or rubber materials. Specific examples include phenolic acid antioxidants and phosphite acid antioxidants. Antioxidants may be used alone or in combination of two or more.
  • the content of the antioxidant is preferably not more than 500 ppm, more preferably not more than 400 ppm, particularly preferably not more than 300 ppm in the layer that also has a conjugated cyclized polymer force.
  • the lower limit of the antioxidant content is Preferably it is 10 ppm, more preferably 20 ppm.
  • the conjugated polymer cyclized product containing no antioxidant may deteriorate at a high temperature or may have a reduced mechanical strength after absorbing oxygen.
  • Typical examples of the catalyst having an action of enhancing oxygen absorption include transition metal salts. Even if the conjugated gen polymer cyclized product of the present invention does not contain such a transition metal salt, it exhibits sufficient oxygen absorptivity, but the oxygen absorptivity is further improved by containing a transition metal salt. Can be made. However, when used in the present invention, it is necessary to consider the addition of metal components so as not to adversely affect the transparency and other purposes of use.
  • transition metal salts examples include cobalt oleate ( ⁇ ), naphthenic acid conol ( ⁇ ), 2-ethylhexanoic acid cobalt ( ⁇ ), cobalt stearate ( ⁇ ), and neodecanoate cobalt ( Preferred are cobalt 2-ethylhexanoate ( ⁇ ), cobalt stearate ( ⁇ ), and cobalt neodecanoate ( ⁇ ).
  • the amount of the transition metal salt is usually 10 to: LO, OOOppm, preferably 20 to 5, OOOppm, more preferably 50 to 5, OOOppm in the layer that also has a cyclized conjugate force.
  • the photoinitiator has an action of accelerating the initiation of an oxygen absorption reaction when the conjugated cyclized polymer is irradiated with energy rays.
  • Examples of the photoinitiator include the compounds exemplified in JP-T-2003-504042.
  • the amount in the case of blending a photoinitiator is usually conjugated diene polymer cyclized product the total amount of 0.001 to 10 mass 0/0, preferably from 0.01 to 1 mass 0/0.
  • the form of the oxygen-absorbing member containing the conjugated diene polymer cyclized product used in the present invention is not particularly limited, and may be used in various forms such as a film form, a sheet form, a pellet form, and a powder form. Can do. There are no restrictions on the shape of the pellet and the shape of the powder.
  • the method for making the oxygen absorbing member used in the present invention into a desired shape is not particularly limited, and conventionally known methods such as a compression molding method, an injection molding method, a solvent casting method, and a melt extrusion method can be employed. .
  • the oxygen-absorbing member having a conjugated diene polymer cyclized product force used in the present invention is used by mixing two or more types of conjugated diene polymer cyclized products, and also used by mixing with other resins.
  • Other resin include acrylic resin, alicyclic structure polymer, linear polyolefin, polyester, and polyamide. Above all, as other rosin, acid Those that are transparent are preferred. This is because the oxygen-absorbing ability of the conjugated conjugated polymer cyclized product is easily exhibited.
  • the oxygen absorption amount of the oxygen-absorbing member containing the conjugated diene polymer cyclized product used in the present invention is 0.5 mLZg or more, preferably 5 mLZg or more, more preferably 10 mLZg or more, and particularly preferably 30 mLZg or more.
  • the oxygen absorption amount is the amount of oxygen absorbed by the conjugated-gen polymer cyclized product lg when the conjugated-gen polymer cyclized product is sufficiently saturated with powdered or thin film to sufficiently absorb oxygen.
  • the measurement is the value carried out at 23 ° C. If the amount of oxygen absorbed is small, a large amount of conjugated diamine polymer cyclized product is required to stably absorb oxygen for a long period of time.
  • the amount of oxygen absorbed is mainly correlated with the rate of unsaturated bond reduction of the conjugated cyclized polymer.
  • oxygen absorbing member containing a conjugated diene polymer cyclized product used in the present invention is also of the oxygen absorption rate 10mLZm 2 Z day or more, preferably 30mLZm 2 Z day than on, more preferably 50 mLZm 2 Z days or more is desirable. Even if the cyclized product has a large oxygen absorption capacity, if the oxygen absorption rate is too slow, the sealed container covering the light emitting element may not be kept in a deoxygenated state. Oxygen present in or entering the sealed container for any reason must be quickly absorbed and removed by the oxygen absorbing member.
  • the oxygen absorbing member is preferably a member having the above-described oxygen absorption rate from such a viewpoint. The oxygen absorption rate is expressed as the amount of oxygen absorbed per unit area when 24 hours have passed since the measurement of the oxygen absorption was started.
  • the oxygen-absorbing member having a conjugated cyclized product force used in the present invention has a light transmittance of 85% or more at a wavelength of 400 nm to 650 nm. It is desirable that the organic EL element covered with the sealing container of the present invention can extract light also from the sealing container side as described later. Therefore, it is necessary that the light transmittance of the oxygen absorbing member that transmits light is high.
  • the light transmittance in the light emitting region of the organic EL element is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more.
  • the light emitting region of the organic EL element has a wavelength of 400 nm to 650 nm, it is desired that the light transmittance is high at all wavelengths in this region.
  • the light transmittance in the emission wavelength region satisfies the above requirements. Just do it.
  • the light transmittance can be measured using a commercially available turbidimeter in accordance with JIS K7361-1.
  • the transparent resin member having an oxygen permeability coefficient of 10 mLZm 2 Z days or less any material satisfying the above requirements may be used.
  • an alicyclic structure polymer, particularly a norbornene polymer has optical characteristics, Point strength with excellent mechanical strength and heat resistance is preferred.
  • the oxygen permeation coefficient can be calculated by measuring in an atmosphere at a temperature of 25 ° C. and a humidity of 75% RH with an oxygen permeation rate measuring device (for example, “OXYTRAN” manufactured by MOC ON).
  • a norbornene polymer and a bull alicyclic hydrocarbon polymer are preferable from the viewpoints of optical properties, heat resistance, and mechanical strength.
  • an alicyclic structure polymer having a polar group is used as the alicyclic structure polymer, the affinity with an inorganic substance can be improved without impairing the light transmittance.
  • the norbornene polymer used in the present invention includes a ring-opening polymer of a norbornene monomer, a ring-opening copolymer of a norbornene monomer and another monomer capable of ring-opening copolymerization thereof, a hydride thereof, and an addition weight of the norbornene monomer. And addition copolymers of norbornene monomers and other monomers copolymerizable therewith.
  • hydrides of ring-opening (co) polymers of norbornene monomers are most preferred from the viewpoints of optical properties, heat resistance, mechanical strength, and the like.
  • Examples of the substituent present in the ring include an alkyl group, an alkylene group, a vinyl group, and an alkoxy carboxylic group, and the norbornene monomer may have two or more of these. Each of these norbornene monomers is used alone or in combination of two or more. Examples of other monomers capable of ring-opening copolymerization with norbornene monomer include monocyclic cyclic olefin-based monomers such as cyclohexene, cycloheptene, and cyclootaten. Other monomers copolymerizable with these norbornene monomers can be used alone or in combination of two or more.
  • the ratio of the structural unit derived from norbornene monomer and the structural unit derived from other monomer copolymerizable in the addition copolymer is appropriately selected so as to be in the range of 30:70 to 99: 1, preferably 50:50 to 97: 3, more preferably 70:30 to 95: 5.
  • the monocyclic cycloolefin polymer for example, an addition polymer of a monocyclic cycloolefin monomer such as cyclohexene, cycloheptene, and cyclootaten can be used.
  • cyclic conjugated diene polymer for example, a polymer obtained by subjecting a cyclic conjugated diene monomer such as cyclopentadiene and cyclohexadiene to 1, 2 or 1, 4 addition polymerization and a hydride thereof, etc. are used. Can do.
  • bur cycloaliphatic hydrocarbon polymer examples include polymers of vinyl alicyclic hydrocarbon monomers such as bulcyclohexene and burcyclohexane, and hydrides thereof, styrene, And hydrides of aromatic ring portions of polymers obtained by polymerizing butyl aromatic monomers such as ⁇ -methylstyrene, and vinyl alicyclic carbonization. Examples thereof include a hydrogenated product of a copolymer of a hydrogen monomer, a vinyl aromatic monomer, and the like and another monomer copolymerizable with these monomers.
  • Examples of the polar group in the alicyclic structure polymer having a polar group include a polar group containing an oxygen atom, a nitrogen atom, a sulfur atom, and a key atom, and a halogen atom. From the viewpoints of dispersibility with inorganic compounds and compatibility with other resins, polar groups containing oxygen atoms and nitrogen atoms are preferred. Specific examples of the polar group include a carboxyl group, a carboxy-carboxy group, an epoxy group, a hydroxyl group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group. I can get lost.
  • a portion facing the light emitting element is formed of a transparent resin member, and an oxygen absorbing member having a conjugated cyclized polymer force on the outer side of the sealed container has an oxygen transmission coefficient.
  • a sealed container in which protective films of 10mLZm 2 Z days or less are sequentially laminated.
  • this is the structure of the oxygen absorbing member 2 having a structure as shown in FIG. 4 and containing a cyclized conjugate polymer on the outside of the transparent resin member 11 that maintains the mechanical strength of the sealed container.
  • a layer is formed, and a gas barrier protective film 7 for protecting the layer of the oxygen absorbing member 2 is provided on the outside thereof.
  • the gas barrier protective film 7 prevents oxygen from entering from the outside, and a small amount of oxygen that has permeated through the protective film 7 Since the oxygen absorbing member 2 serving as a combined cyclized product absorbs oxygen, it is possible to efficiently prevent oxygen from entering the sealed container.
  • a protective film made of a material that is transparent and has low oxygen permeability is preferable. Examples thereof include inorganic films such as a resin film such as polyvinyl alcohol, polyvinylidene chloride, polyacrylonitrile, nylon, polyester, and ethylene butyl alcohol copolymer, a silica thin film, and a titer thin film.
  • the reason why the transparency is required is to ensure the function of extracting light from the light emitting element from the sealed container side.
  • the oxygen permeability coefficient of the protective film is more preferably 1 mL / m day or less, more preferably 0.1 mL / m day or less.
  • the oxygen permeation coefficient is calculated by measuring in an atmosphere at a temperature of 25 ° C. and a humidity of 75% RH with an oxygen permeation rate measuring device (eg, “OXYTRAN” manufactured by MOCON).
  • the oxygen-absorbing member containing the conjugated-gen polymer cyclized product used in the present invention is an oxygen-absorbing member.
  • the amount of intrusion oxygen that can be absorbed during the lifetime calculated from the expected lifetime of the light emitting element and the oxygen transmission rate of the sealing container in the sealed container of the light emitting element that is to be kept oxygen-free because of its function. The above functions effectively. If the oxygen absorption amount of the conjugated cyclized polymer is 5 mLZg or more, it will function effectively with a sufficiently small practical amount.
  • the oxygen-absorbing member in the sealed container efficiently absorbs a small amount of oxygen that penetrates the organic EL element and the like, and the atmosphere of the organic EL element and the like that is always sealed with the base material and the sealed container is realized.
  • the oxygen absorption rate force of the surface force of the oxygen-absorbing member which is the conjugated-gen polymer cyclized product force, is 10 mLZm 2 Z days or more, and functions effectively in a sufficiently small practical area.
  • the oxygen-absorbing member of the present invention can be suitably applied to electronic components such as light-emitting elements that are used for a long period of time because it maintains its original function with little deterioration even when oxygen is absorbed.
  • the oxygen absorbing member has excellent adhesion to an alicyclic structure polymer as well as a normal organic material.
  • the oxygen absorbing member used in the present invention does not require a transition metal or the like for oxygen absorption, unlike the conventional oil-absorbing oxygen-absorbing material, and thus has excellent electrical insulation and dielectric characteristics. Material.
  • the oxygen-absorbing member in the present invention can provide a light-transmitting sealing container that is excellent in light transmission and less deteriorated by light.
  • the sealed container of the present invention can be produced only with a resin, and is suitable for manufacturing a sealed container excellent in flexibility and further an organic EL panel.
  • the sealed container is usually formed by processing a thin plate of aluminum or the like to form a container body, which is used as the sealed container 1, and a thin film made of conjugated cyclized polymer inside. Can be attached as the oxygen absorbing member 2.
  • the thin film of the oxygen absorbing member 2 may be the whole inside or a part of the inside of the sealing container 1, but usually faces the light emitting element 9 in the cover 10 in the sealing container 1 as shown in FIG. Affix to the entire surface.
  • the sealed container 1 is a transparent resin.
  • the cover 10 in the sealed container 1 It is preferable to attach a thin film of the oxygen absorbing member 2 to the entire surface facing the light emitting element 9 in FIG.
  • oxygen that has permeated from the transparent resin can be absorbed without entering the inside of the sealed container.
  • the area of the oxygen absorbing member 2 is determined so that the oxygen absorption rate is greater than the rate of oxygen entering from the main body of the sealed container 1, and then the oxygen absorbing member 2 enters during the expected lifetime of the light emitting element. What is necessary is just to manufacture the oxygen absorbing member 2 with a conjugated diamine polymer cyclized product in an amount capable of absorbing the amount of oxygen calculated.
  • the light emitter according to the present invention is a substrate 6 on which an organic EL element in which a sealed container 1 in which such an oxygen absorbing member 2 is arranged, an anode 5, a light emitting layer 4, and a cathode 3 are laminated in this order is mounted.
  • the organic EL element can be formed by covering it.
  • a commonly used adhesive such as an epoxy adhesive may be used.
  • an adhesive having low oxygen permeability is more preferable.
  • the unsaturated bond reduction rate was determined by the Proton NMR method according to the methods described in the following documents (i) and (ii).
  • the total proton peak area before the cyclization reaction is SBT
  • the peak area of the proton directly bonded to the double bond is SBU
  • SA peak area ratio of protons directly bonded to the double bond after the cyclization reaction
  • a sample is formed into a film with a thickness of 120 / zm by compression molding at 100 ° C under a nitrogen atmosphere. This is cut into a size of 100 mm x 100 mm to obtain a sample for measuring oxygen absorption.
  • This oxygen absorption measurement sample is sealed with 200 ml of air in a three-layer film bag of polyethylene terephthalate film (PET) Z aluminum foil (Al) Z polyethylene film (PE) with dimensions of 150 mm x 220 mm. did. This is left at 23 ° C, and the oxygen concentration in the bag is measured with an oximeter every 24 hours. When the oxygen concentration stops decreasing, the sample lg is absorbed. Calculate the amount of oxygen absorbed.
  • an oxygen analyzer HS-750 manufactured by Neutronics, Inc. was used as the oxygen concentration meter.
  • the mass average molecular weight was determined as a standard polystyrene conversion value using gel permeation chromatography.
  • the oxygen absorption rate is expressed as the amount of oxygen absorbed for 24 hours after the start of measurement after measuring the amount of oxygen absorbed in the same manner as the measurement of oxygen absorption in (2) above.
  • the light transmittance at a wavelength of 400 to 650 nm is obtained by pasting a sample film with a thickness of 100 / zm on a glass plate with a side of 40 mm to obtain a glass plate with a film.
  • the light transmittance of only a film computed the light transmittance of the glass plate before sticking a light transmittance of the glass plate with a film, and a film.
  • the light transmittance was measured using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., haze meter NDH2000) in accordance with JIS K7361-1.
  • the polar group content was calculated by a calibration curve method by measuring the characteristic peak intensity of the polar group by Fourier transform infrared absorption spectrum analysis. For example, in the case of an acid anhydride group, the peak intensity of the acid anhydride group (measured from 1760 to 1780 cm and Find the abundance. In the case of a carboxyl group, the peak intensity (1700 cm _1 ) of the carboxyl group was measured and determined by a calibration curve method.
  • the styrene unit content (mol%) was determined by NMR analysis.
  • the oxygen transmission coefficient was measured in an atmosphere at a temperature of 25 ° C and a humidity of 75% RH using an oxygen transmission rate meter (MOCON, Inc., “OXYTRAN”).
  • a box-shaped container having a length of 40 mm, a width of 40 mm, a height of 5 mm, and a wall thickness of 1 mm was produced by injection molding using Beketsuko and norbornene polymer ('ZEONOR1600 manufactured by Nippon Zeon Co., Ltd.) as a raw material.
  • the oxygen permeability coefficient of this container was 3 mLZm 2 'day or less.
  • the conjugated diene polymer cyclized product 1 prepared above was attached as a 100-m film to the entire inner bottom surface of the container, and this was used as a sealed container. Open this sealed container in a nitrogen atmosphere.
  • Example 2 Except that the amount of P-toluenesulfonic acid used was changed to 2.25 parts and the amount of sodium carbonate added after the cyclization reaction was changed to 0.78 parts, the same procedure as in Example 1 was carried out. Combined cyclized product 2 was obtained. The same evaluation as in Example 1 was performed using this conjugated gen polymer cyclized product. The evaluation results are shown in Tables 1 and 2.
  • the polyisoprene used in Example 1 was changed to high cis polyisoprene having a cis-1,4 bond unit of 99% or more and a mass average molecular weight of 302,000, and the amount of p-toluenesulfonic acid used was 2.16.
  • the conjugated diene polymer cyclized product 3 was obtained in the same manner as in Example 1 except that the amount of sodium carbonate added after the cyclization reaction was changed to 0.75 part.
  • the same evaluation as in Example 1 was performed using this conjugated-gene polymer cyclized product 3. The evaluation results are shown in Tables 1 and 2.
  • Polyisoprene was changed to polyisoprene with a weight average molecular weight of 141,000 consisting of 68% cis-1,4 bond units, 25% trans-1,4 bond units and 7% 3,4 bond units. Except that the amount of sulfonic acid used was changed to 2.69 parts, and the amount of sodium carbonate added after the cyclization reaction was changed to 1.03 parts, in the same manner as in Example 1, the conjugated diene polymer cyclized product Got 4. The same evaluation as in Example 1 was performed using this conjugated gen polymer cyclized product 4. The evaluation results are shown in Tables 1 and 2.
  • conjugate conjugate polymer cyclized product 5 To the conjugated cyclized polymer solution obtained in Example 1, 2.5 parts of maleic anhydride was added, and an addition reaction was performed at 160 ° C. for 4 hours. Part of the toluene in the solution is distilled off and After adding an amount of phenolic acid anti-oxidation agent (IRGANOX 1010: manufactured by Chinoku 'Specialty' Chemicals) equivalent to 20 ppm to the cyclized product of the role polymer, further vacuum drying is performed. Then, toluene and unreacted maleic anhydride were removed to obtain a modified conjugate conjugated polymer cyclized product (hereinafter referred to as conjugate conjugate polymer cyclized product 5).
  • IRGANOX 1010 manufactured by Chinoku 'Specialty' Chemicals
  • the amount of P-toluenesulfonic acid was changed to 2.25 parts, and the amount of sodium carbonate added after the cyclization reaction was changed to 0.78 parts. Except for the change, the conjugated gen polymer cyclized product obtained in the same manner as in Example 1 was used, and the modified conjugated gen polymer cyclized product (this was referred to as conjugated gen polymer cyclized product 6 and the same as in Example 5). Got). The same evaluation as in Example 5 was performed using this conjugated-gen polymer cyclized product 6. The evaluation results are shown in Tables 1 and 2.
  • Polyisoprene was changed to high cis polyisoprene with 99% or more of cis-1,4 bond units and a mass average molecular weight of 302,000, and the amount of P-toluenesulfonic acid was changed to 2.16 parts.
  • a modified conjugated gen polymer cyclized product (referred to as conjugated gen polymer cyclized product 7) was obtained in the same manner as in Example 5 except that the amount of sodium carbonate added after the reaction was changed to 0.75 part. It was.
  • the same evaluation as in Example 5 was performed using this conjugated-gen polymer cyclized product 7. The evaluation results are shown in Tables 1 and 2.
  • polyisoprene consists of 68% cis-1,4 bond units, 25% trans-1,4 bond units and 7% 3,4 bond units. Except for changing to polyisoprene with a mass average molecular weight of 141,000, changing the amount of p-toluenesulfonic acid used to 2.69 parts, and changing the amount of sodium carbonate added after the cyclization reaction to 1.03 parts.
  • Is a modified conjugated gen polymer cyclized product (referred to as conjugated gen polymer cyclized product 8) in the same manner as in Example 5. )
  • conjugated gen polymer cyclized product 8 The same evaluation as in Example 5 was performed using this conjugated gen polymer cyclized product 8. The evaluation results are shown in Tables 1 and 2.
  • conjugated conjugated polymer cyclized product 10 modified conjugate conjugated polymer cyclized product to which maleic anhydride was added.
  • conjugated conjugated polymer cyclized product 10 modified conjugate conjugated polymer cyclized product to which maleic anhydride was added.
  • conjugated conjugated polymer cyclized product 10 The same evaluation as in Example 9 was performed using this conjugated-gen polymer cyclized product 10. The evaluation results are shown in Tables 1 and 2. In addition, the polar group content was measured. Table 1 shows the measurement results. Note that none of the conjugated diamine polymer cyclized products obtained in Examples 9 and 10 substantially contained a gel insoluble in toluene.
  • Example 1 The polyisoprene in Example 1 was replaced with polyisoprene (cis 1,4 bond units 73%, trans 1,4 bond units 22%, 3,4 bond units 5%, mass average molecular weight 154,000), reaction temperature to 85 0 C power et 80 o C, p-cash example was the addition to preparative Honoré Enns Honoré acid amount 2.4 ⁇ et 2.19 ⁇ , in the same manner as in example 1, a conjugated diene polymer cyclized Compound 11 was obtained. A sealed container was produced in the same manner as in Example 1 except that conjugated polymer 11 was used instead of conjugated polymer cyclized product 1. This was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
  • a silica film having a thickness of 12 nm was formed by vapor deposition on one side of a 188 m-thick norbornene polymer film (glass transition temperature 160 ° C.) to prepare a silica film-forming film.
  • the oxygen permeability coefficient of this silica film-forming film was 0.8 mLZm 2 Z days.
  • a 100 m film of the conjugated-gen polymer cyclized product 1 produced in Example 1 was attached to the surface of the silica film-forming film opposite to the silica film by hot pressing in a nitrogen atmosphere to produce a laminated film. did.
  • This laminated film consists of a 120 nm thick SiO film and a 188 ⁇ m thick norbornene polymerized film.
  • the film is laminated in the order of a body film and a conjugated cyclized polymer film having a thickness of 100 ⁇ m.
  • a body film and a conjugated cyclized polymer film having a thickness of 100 ⁇ m.
  • an aluminum box-type container with a length of 40 mm, a width of 40 mm, a height of 5 mm, and a wall thickness of 0.7 mm was prepared.
  • the laminated film is placed in the opening of this box-type container, and the SiO film is on the outside of the container.
  • a 20% toluene solution of ⁇ -vinene polymer (YS resin ⁇ -1150 ⁇ ; manufactured by Yasuhara Chemical Co., Ltd.) was prepared, and then purified by precipitation with methanol to obtain a ⁇ -pinene polymer from which the antioxidant was removed.
  • a laminated film was obtained in the same manner as in Comparative Example 1 except that a ⁇ -vinene polymer from which the antioxidant was removed was used instead of polyisoprene, and a test piece was prepared from this to evaluate.
  • the evaluation results are shown in Tables 1 and 2. This comparative example relates to the case of using a polymer which is not a conjugated conjugated polymer cyclized product.
  • a 30% toluene solution of the ethylene-cyclopentene copolymer was prepared and applied onto a polyethylene terephthalate film having a thickness of 50 ⁇ m and dried to form a film of the ethylene-cyclopentene copolymer having a thickness of 120 ⁇ m.
  • the laminated film was obtained.
  • the formed copolymer film was peeled from the obtained laminated film, and cut into 100 mm ⁇ 100 mm to obtain test pieces. Evaluation was performed in the same manner as in Comparative Example 1 using the test piece.
  • the evaluation results are shown in Tables 1 and 2.
  • This comparative example relates to the case of using a polymer that is not a conjugated cyclized polymer.
  • the inside of the light emitting device sealing container of the present invention can be kept substantially oxygen-free.
  • the present invention it is possible to provide a sealed container for a light-emitting element typified by an organic EL element using an oxygen-absorbing member having a transparent polymer power. This makes it possible to provide a new U-light emitter that makes the entire sealed container light transmissive.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un réservoir d’étanchéité pour élément luminescent convenant également à un panneau EL organique souple. Ce réservoir d’étanchéité pour élément luminescent utilise un élément de réservoir d’étanchéité susceptible de loger, par exemple, un élément EL organique et emploie un élément de réservoir d’étanchéité que l’on peut former à partir d’un composé polymère ayant une capacité de désoxygénation. Ce réservoir d’étanchéité pour élément luminescent comprend une partie capot permettant de recouvrir un élément luminescent monté sur un substrat. Le réservoir d’étanchéité comprend un élément absorbant l’oxygène contenant un produit en cycle de polymère diène conjugué obtenu par mise en cycle d’un polymère diène conjugué. Pour le produit en cycle de polymère diène conjugué, la réduction en pourcentage de liaisons insaturées définie par une réduction du nombre de liaisons insaturées présentes dans le produit en cycle de polymère diène conjugué à partir du nombre de liaisons insaturées dans le polymère diène conjugué est supérieure ou égale à 10%.
PCT/JP2006/301558 2005-01-31 2006-01-31 Réservoir d’étanchéité pour élément luminescent et corps lumineux WO2006080526A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007500649A JP4877606B2 (ja) 2005-01-31 2006-01-31 発光素子用封止容器及び発光体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-022975 2005-01-31
JP2005022975 2005-01-31

Publications (1)

Publication Number Publication Date
WO2006080526A1 true WO2006080526A1 (fr) 2006-08-03

Family

ID=36740542

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/301558 WO2006080526A1 (fr) 2005-01-31 2006-01-31 Réservoir d’étanchéité pour élément luminescent et corps lumineux

Country Status (3)

Country Link
JP (1) JP4877606B2 (fr)
TW (1) TW200735693A (fr)
WO (1) WO2006080526A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008115383A (ja) * 2006-10-13 2008-05-22 Nippon Zeon Co Ltd 発光素子用樹脂組成物、発光素子用積層体、発光素子
WO2008081593A1 (fr) * 2006-12-28 2008-07-10 Zeon Corporation Corps laminé pour élément émetteur de lumière et cet élément
JP2013048115A (ja) * 2012-12-03 2013-03-07 Sony Corp 表示装置、表示装置の製造方法、および電子機器

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60223804A (ja) * 1984-04-20 1985-11-08 Japan Synthetic Rubber Co Ltd 共役ジエン重合体環化物の製法
JP2003012944A (ja) * 2001-04-26 2003-01-15 Toyo Seikan Kaisha Ltd 成形性及びガス遮断性に優れた樹脂組成物及び包装材料
JP2003317933A (ja) * 2002-04-22 2003-11-07 Asahi Glass Co Ltd 有機ｅｌ素子
JP2004319136A (ja) * 2003-04-11 2004-11-11 Mitsubishi Gas Chem Co Inc 有機ｅｌ素子
JP2005015055A (ja) * 2003-06-06 2005-01-20 Toyo Seikan Kaisha Ltd 多層容器

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003133061A (ja) * 2001-10-29 2003-05-09 Mitsubishi Gas Chem Co Inc 酸素吸収剤組成物
US6770502B2 (en) * 2002-04-04 2004-08-03 Eastman Kodak Company Method of manufacturing a top-emitting OLED display device with desiccant structures
JP2004231938A (ja) * 2002-09-13 2004-08-19 Sekisui Chem Co Ltd 有機ｅｌ素子封止用光硬化性接着剤組成物、有機ｅｌ素子の封止方法および有機ｅｌ素子
JP2005270959A (ja) * 2003-12-26 2005-10-06 Mitsubishi Gas Chem Co Inc 酸素吸収剤成形体及び有機ｅｌ素子
JP2006059620A (ja) * 2004-08-19 2006-03-02 Mitsui Chemicals Inc 電子デバイス用封止フィルムおよびそれを用いた表示素子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60223804A (ja) * 1984-04-20 1985-11-08 Japan Synthetic Rubber Co Ltd 共役ジエン重合体環化物の製法
JP2003012944A (ja) * 2001-04-26 2003-01-15 Toyo Seikan Kaisha Ltd 成形性及びガス遮断性に優れた樹脂組成物及び包装材料
JP2003317933A (ja) * 2002-04-22 2003-11-07 Asahi Glass Co Ltd 有機ｅｌ素子
JP2004319136A (ja) * 2003-04-11 2004-11-11 Mitsubishi Gas Chem Co Inc 有機ｅｌ素子
JP2005015055A (ja) * 2003-06-06 2005-01-20 Toyo Seikan Kaisha Ltd 多層容器

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008115383A (ja) * 2006-10-13 2008-05-22 Nippon Zeon Co Ltd 発光素子用樹脂組成物、発光素子用積層体、発光素子
WO2008081593A1 (fr) * 2006-12-28 2008-07-10 Zeon Corporation Corps laminé pour élément émetteur de lumière et cet élément
JPWO2008081593A1 (ja) * 2006-12-28 2010-04-30 日本ゼオン株式会社 発光素子用積層体、及び発光素子
JP2013048115A (ja) * 2012-12-03 2013-03-07 Sony Corp 表示装置、表示装置の製造方法、および電子機器

Also Published As

Publication number Publication date
JP4877606B2 (ja) 2012-02-15
JPWO2006080526A1 (ja) 2008-06-19
TW200735693A (en) 2007-09-16

Similar Documents

Publication Publication Date Title
JP4877605B2 (ja) 発光素子用積層体および発光素子
JP5365891B2 (ja) 発光素子用樹脂組成物、発光素子用積層体、発光素子
US20200109320A1 (en) Laminating film adhesives with ultra-low moisture permeability
KR101919294B1 (ko) 경화성 캡슐화제 및 그의 용도
TWI605085B (zh) Resin composition for sealing an organic electronic device, a resin sheet for sealing an element for an organic electronic device, an organic electroluminescent device, and an image display device
KR101847327B1 (ko) 전자 디바이스 밀봉용 수지 조성물 및 전자 디바이스
KR101851483B1 (ko) 전자 디바이스 밀봉용 수지 조성물 및 전자 디바이스
JPWO2008081593A1 (ja) 発光素子用積層体、及び発光素子
JP2007197517A (ja) 接着性封止組成物、封止フィルム及び有機ｅｌ素子
CN104737623B (zh) 密封剂组合物及由该组合物获得的密封用片
CN1320074A (zh) 区域规整官能化聚合物包装材料
JP5029959B2 (ja) 接着剤および発光素子
KR20130141588A (ko) 전자 장치를 캡슐화하기 위한 접착제 및 방법
WO2006080526A1 (fr) Réservoir d’étanchéité pour élément luminescent et corps lumineux
WO2015166657A1 (fr) Matériau d'étanchéité et produit durci correspondant
TW200806071A (en) Scavenger sheet for organic electron device and organic electron device
KR102159502B1 (ko) 점착제 조성물
JP2006335801A (ja) 酸素の捕捉方法および酸素吸収性包装容器の製造方法
KR102146529B1 (ko) 점착제 조성물
KR102166465B1 (ko) 점착제 조성물
JPWO2019044108A1 (ja) 積層体およびその製造方法
JP2023138466A (ja) 封止用組成物および封止用シート
KR20170112558A (ko) 점착제 조성물

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2007500649

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06712701

Country of ref document: EP

Kind code of ref document: A1

WWW Wipo information: withdrawn in national office

Ref document number: 6712701

Country of ref document: EP