JPWO2008081593A1 - LAMINATE FOR LIGHT EMITTING ELEMENT AND LIGHT EMITTING ELEMENT - Google Patents

Abstract

The subject of this invention is providing the light emitting element laminated body and light emitting element which can be used conveniently as a sealing layer for light emitting elements, such as an organic EL element, a sealing container, and a raw material for light emitting element formation. . The laminate for a light-emitting element includes a metal thin film layer formed of metal and having an oxygen permeability of 0.01 cc / cm 2 · day or less, and a resin layer containing an oxygen-absorbing resin. The light emitting element is formed by laminating the light emitting element laminate, the light emitting layer, and the transparent substrate in this order.

Description

  The present invention relates to a light-emitting element laminate and a light-emitting element, and more specifically, a light-emitting element used for a substrate for a light-emitting element such as an organic electroluminescence element (referred to as an organic EL element), a sealing container, a sealing plate, and the like. The present invention relates to a laminate for a light emitting device, and a light emitting element using the laminate for a light emitting element.

  An organic EL element useful as a light emitting element is a light emitting element having a laminated structure in which an organic light emitting layer is disposed between a cathode and an anode in principle. Specifically, the organic EL element has a light emitting element body which is a laminated structure in which an organic light emitting layer containing a light emitting organic compound having an electroluminescence function is disposed between a cathode layer and an anode layer. It consists of Usually, an organic light emitting layer is formed on a cathode layer side of a light emitting organic compound layer containing a light emitting organic compound, a hole injection layer and a transport layer formed on the anode layer side, and a light emitting organic compound layer. An electron injection layer and a transport layer. And the whole light emitting element main body is covered with the board | substrate and the sealing container for the purpose of protecting this light emitting element main body from the external environment. The substrate is made of glass or plastic, and the sealing container is often made of metal. In the organic EL panel, a plurality of light emitting element bodies are arranged on one substrate. In an organic EL panel, a plurality of light emitting element bodies are covered with a single sealing container, or a plurality of light emitting element bodies arranged on a substrate are covered with a plurality of sealing containers for each light emitting element body. .

  An organic EL element is a very effective light-emitting element, but since the organic light-emitting layer contains a relatively unstable light-emitting organic compound, it has a drawback that it is easily deteriorated by harmful substances such as oxygen and moisture. The organic light-emitting layer must be protected from harmful substances. Therefore, normally, a drug placement portion is provided in the sealed space formed by the sealed container, and a dehumidifying agent and an inorganic oxygen scavenger are placed in the drug placement portion, thereby providing the inside of the sealed space. The organic light emitting layer is protected by removing the existing oxygen and moisture.

  In addition, in Patent Document 1, a protective layer formed of a fluoropolymer or an oxide insulator is formed on the outer surface of the laminated structure, 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 inserted between a protective layer and a glass container and an inert medium is enclosed. Patent Document 2 describes an organic EL element device in which the side surface of an organic EL element is sealed with an epoxy resin adhesive containing a deoxidizing agent. Patent Document 3 describes the application of an ultraviolet curable resin as an adhesive between a plastic organic EL panel substrate and a laminated structure.

  In Patent Document 4, an organic EL element is sealed with a sealing film made of an oxygen absorbing film using a mixture of a hydrogenated styrene butadiene rubber containing an oxygen reactive thermoplastic resin and a transition metal catalyst and another thermoplastic resin. How to do is described.

  In addition, the organic EL element emits light, and the deterioration of the light-emitting element body including the light-emitting organic compound is promoted by the heat generation of the organic EL element itself, the heat generation of the driving elements and electrodes formed on the substrate, and the like. There is a problem in that the life of the light emitting element is reduced. Patent Document 5 proposes a method of conducting heat generated by a light emitting element to a metal foil heat dissipating member installed on a sealing substrate by a sealing material containing conductive particles and dissipating heat from the metal foil heat dissipating member. Has been. However, an organic EL element using a direct sealing material in which a protective substrate or a sealing container itself has a heat dissipation function and also has an oxygen absorption function has not yet been found.

JP-A-10-275682 JP 2002-175877 A JP 2004-47381 A JP 2004-319136 A JP 2004-186045 A

  As described above, various attempts have been made to extend the lifetime of the organic EL element. However, development of an excellent material and method for completely isolating the light emitting element body from the outside for a long period of time has been awaited. In particular, in an organic EL panel having flexibility, it is difficult to prevent oxygen and moisture from entering from a bonded portion of the substrate and the sealing container, a flexible plastic substrate, a sealing container, or the like. there were. Thus, as described above, an organic EL element that incorporates an oxygen scavenger and a moisture absorbent in a sealed container has been developed, but the light emitting element body can be isolated from the outside for a long period of time, and more flexible. Development of a possible organic EL panel has been desired.

  The present invention solves such a conventional problem, and can be suitably used as a sealing layer for a light emitting element such as an organic EL element, a sealing container, and a material for forming a light emitting element. Another object is to provide a light-emitting element.

As means for solving the above problems,
Claim 1 has a metal thin film layer formed of metal and having an oxygen permeability of 0.01 cc / cm ² · day or less, and a resin layer containing an oxygen-absorbing resin. A laminate,
Claim 2 is the laminate for a light emitting device according to claim 1, wherein the resin layer further contains an adhesive resin having adhesiveness to the metal thin film layer.
Claim 3 is for the light emitting element according to claim 1 or 2, wherein the metal thin film layer is laminated on the surface of the resin layer via a first adhesive layer containing an adhesive resin. A laminate,
According to a fourth aspect of the present invention, the second adhesive layer containing an adhesive resin is formed on one surface of the resin layer, and the metal thin film layer is laminated on the other surface. Is a laminate for a light-emitting element according to any one of
According to a fifth aspect of the present invention, the oxygen-absorbing resin is a conjugated diene polymer cyclized product obtained by cyclizing a conjugated diene polymer, wherein the conjugated diene polymer is bonded to an unsaturated bond in the conjugated diene polymer. The laminate for a light-emitting device according to any one of claims 1 to 4, which is a conjugated diene polymer cyclized product having a reduction rate of unsaturated bonds present in the compound cyclized product of 30% or more,
Claim 6 is the laminate for a light emitting device according to any one of claims 2 to 5, wherein the adhesive resin is a resin having a polar group.
In Claim 7, the polar group is at least one selected from the group consisting of an acid anhydride group, an acid amide group, a carboxyl group, an amino group, an epoxy group, a hydroxyl group, and an isocyanate group. It is a laminate for a light emitting element as described,
An eighth aspect of the present invention is the light emitting element laminate according to any one of the first to seventh aspects, wherein the resin layer further contains a moisture absorbing resin.
The moisture absorbing resin is selected from the group consisting of an ethylene-vinyl alcohol copolymer, an ethylene-vinyl acetate copolymer, an acrylic acid polymer, an acrylamide resin, an acetal resin, a urethane resin, and a cellulose resin. The light emitting device laminate according to claim 8, wherein the laminate is at least one of
A tenth aspect is a light-emitting element formed by laminating the laminate for a light-emitting element according to any one of the first to ninth aspects, a light-emitting layer, and a transparent substrate in this order.

  The laminate for a light-emitting element of the present invention has a function of blocking oxygen, so that it can be used as a protective material that can realize a light-emitting element with a long life and little deterioration. Furthermore, this light-emitting element resin laminate has a function of blocking oxygen and a function of absorbing moisture, thereby preventing deterioration of the light-emitting element due to oxygen and delamination of the laminate due to intrusion of moisture, etc. It can be used as a protective material that can prevent deterioration of the light emitting element.

  Since the light emitting device of the present invention uses the laminate for a light emitting device of the present invention, there is no deterioration due to oxygen, and there is no deterioration due to moisture when it has a water-absorbing resin, and it is thin, excellent in flexibility, super Lifespan can be maintained.

FIG. 1 is a cross-sectional explanatory view showing an example of a laminate for a light emitting device according to the present invention. FIG. 2 is a cross-sectional explanatory view showing another example of a laminate for a light emitting device according to the present invention. FIG. 3 is a cross-sectional explanatory view showing another example of the light emitting element laminate according to the present invention. FIG. 4 is a cross sectional view showing a light emitting device according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Laminate for light emitting elements 2 Metal thin film layer 3 Resin layer 4 Adhesive layer 5 Transparent substrate 6 Light emitting layer 7 Light emitting element

1. As shown in FIG. 1, the light-emitting element laminate 1 according to the present invention includes a metal thin film layer 2 and a resin layer 3 containing an oxygen-absorbing resin. In this invention, when the resin layer 3 in the laminate for a light emitting element has adhesiveness to the metal thin film layer 2, the resin layer 3 is directly adhered to one surface side of the metal thin film layer 2 for the light emitting element. The laminate 1 can be formed, and when the resin layer 3 has insufficient adhesion to the metal thin film layer 2, and further firmly adheres the resin layer 3 to one surface side of the metal thin film layer 2. When the necessity arises, as shown in FIG. 2, the light-emitting element laminate 1 includes a metal thin film layer 2, the resin layer 3, and the metal thin film layer 2 and the resin layer 3. You may have the laminated structure formed by laminating | stacking the 1st contact bonding layer 4 interposed. When the laminate for light emitting element is used as a covering member for covering the light emitting element layer formed on the surface of the substrate, the resin layer has insufficient adhesion to the light emitting element layer and the substrate, and When it becomes necessary to adhere the resin layer to the light-emitting element layer and the substrate more firmly, the laminate 1 for light-emitting element includes a metal thin film layer 2 and the resin layer 3 as shown in FIG. And the second adhesive layer 4 are laminated in this order.

1-1. Metal thin film layer This metal thin film layer is a metal layer that can prevent oxygen existing outside the light emitting element from reaching the light emitting element. In this invention, the oxygen transmission rate is 0.01 cc / cm ^2. Any metal film that is less than a day may be used. If the oxygen permeability of the metal thin film layer is 0.01 cc / cm ² · day or less, the lower limit is not particularly limited, but if it is mentioned, the lower limit is 0.000001 cc / cm ² · day. is there. This is because even if the oxygen permeability is not more than the above lower limit value, no significant difference can be found in the oxygen blocking function of the laminate for a light emitting element. In other words, the metal thin film layer has an oxygen permeability of 0.01 to 0. If it is adjusted to 000001 cc / cm ² · day, the object of the present invention can be sufficiently achieved.

  The oxygen permeability of the metal thin film layer can be calculated by measuring under the conditions of a temperature of 25 ° C. and a humidity of 75% RH with an oxygen transmission rate measuring device such as “OXYTRAN” manufactured by MOCON.

  Examples of the metal that can form the metal thin film layer include aluminum, copper, nickel, stainless steel, gold, silver, and an aluminum alloy. Aluminum and copper are preferable from the viewpoint of workability and production yield. . The metal thin film layer may be a metal foil or a vapor deposition film formed by vapor deposition.

  In the present invention, in order to make the oxygen permeability of the metal thin film layer within the above range, when the metal thin film layer is a metal foil, the film thickness is 0.01 mm or more, preferably 0.025 mm or more. Is done. On the other hand, when the metal thin film layer is a vapor deposition film formed by vapor deposition, vapor deposition is performed so that the film thickness of the vapor deposition layer is 100 nm or more on the plastic film, and the vapor deposition layer is composed of two or more layers. Thus, the oxygen transmission rate of the present invention is achieved.

  The thickness of the metal thin film layer is appropriately determined according to the use of the light emitting element laminate. For example, when the light emitting element is formed using the light emitting element laminate, it is usually determined to be 200 nm to 1 mm. The

  On the surface of the metal thin film layer, for example, a desired print pattern such as a character, a figure, a symbol, a pattern, and a pattern can be applied by surface printing or back printing by a normal printing method.

1-2. Resin layer The resin layer in this invention contains oxygen-absorbing resin. This oxygen-absorbing resin has an oxygen absorption amount measured by the method described later of 5 ml / g at the smallest, and further has an oxygen absorption rate measured by the method described later of 1 ml / m ² · day at the lowest.

  In order to set the oxygen absorption amount within the above range, for example, the content of the ethylenically unsaturated hydrocarbon resin is 30% by mass or more of the entire resin, or the unit containing tertiary carbon in the resin is 30% by mass or more. Or a conjugated diene polymer cyclized product obtained by cyclization reaction of a conjugated diene polymer with a (meth) acrylic resin unit having a cyclohexene group being 50% by mass or more, in the conjugated diene polymer This is achieved by setting the reduction rate of the unsaturated bonds present in the conjugated diene polymer cyclized product relative to the unsaturated bonds to 30% or more.

  Among them, a conjugated diene polymer cyclized product in which the reduction rate of the unsaturated bond present in the conjugated diene polymer cyclized product relative to the unsaturated bond in the conjugated diene polymer is 30% or more can be mentioned as a preferred example. .

  The thickness of the resin layer is appropriately determined according to the use of the laminate for light emitting element. For example, when forming a light emitting element using the laminate for light emitting element, it is usually determined to be 0.001 to 10 mm. Is done.

1-2-1. Oxygen-absorbing resin, conjugated diene polymer cyclized product The conjugated diene polymer cyclized product that can be used in the present invention is obtained by cyclizing a conjugated diene polymer in the presence of an acid catalyst. Examples of the conjugated diene polymer include a homopolymer of a conjugated diene monomer, a copolymer obtained by combining two or more monomers, or a copolymer of a conjugated diene monomer and a monomer copolymerizable therewith. Polymers can be used.

  The conjugated diene monomer is not particularly limited, and specific examples thereof include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1, Examples include 3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene.

  Examples of other monomers copolymerizable with the conjugated diene monomer include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, and pt. Aroma such as butyl styrene, α-methyl styrene, α-methyl-p-methyl styrene, o-chloro styrene, m-chloro styrene, p-chloro styrene, p-bromo styrene, 2,4-dibromo styrene, vinyl naphthalene Group vinyl monomers; chain olefin monomers such as ethylene, propylene and 1-butene; cyclic olefin monomers such as cyclopentene and 2-norbornene; 1,5-hexadiene, 1,6-heptadiene, 1,7 -Non-conjugated diene monomers such as octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene; (meth) acryl (Meth) acrylic acid esters such as methyl acid and ethyl (meth) acrylate; other (meth) acrylic acid derivatives such as (meth) acrylonitrile and (meth) acrylamide; In this specification, the expression “(meth) acryl ...” means a compound or a substituent of “acryl ...” and “methacryl ...”.

  These monomers may be used alone or in combination of two or more.

  Specific examples of the conjugated diene polymer include natural rubber; homopolymer of conjugated diene such as polyisoprene; butadiene-isoprene copolymer; styrene-butadiene copolymer, styrene-isoprene copolymer, isoprene-isobutylene copolymer Copolymer, copolymer of ethylene-propylene-diene copolymer rubber, aromatic vinyl-conjugated diene block copolymer such as styrene-isoprene block copolymer, and monomer copolymerizable therewith A polymer can be mentioned. Of these, natural rubber, polyisoprene, and styrene-isoprene block copolymers are preferable, and polyisoprene and styrene-isoprene block copolymers are more preferable.

  The content of the conjugated diene monomer unit in the copolymer of the conjugated diene and the monomer copolymerizable therewith is appropriately selected within a range not impairing the effects of the present invention, but usually 40 mol% or more , Preferably it is 60 mol% or more, More preferably, it is 80 mol% or more. Especially, what consists only of a conjugated diene monomer unit is preferable. If the content of the conjugated diene monomer unit is too small, it may be difficult to obtain a suitable range of unsaturated bond reduction rate.

  When the conjugated diene polymer cyclized product is a cyclized product of an aromatic vinyl-conjugated diene block copolymer, the aromatic vinyl monomer unit content in the cyclized product is not particularly limited, but is usually 1 to 90% by mass. The amount is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. If the content is too small, the initial mechanical strength of the oxygen-absorbing resin composition tends to decrease, and the mechanical strength after oxygen absorption tends to decrease. On the other hand, when the aromatic vinyl monomer unit content is too large, the ratio of the conjugated diene polymer cyclized product block is relatively decreased, and the oxygen absorption amount tends to decrease or the oxygen absorption rate tends to decrease.

  The polymerization method of the conjugated diene polymer may be in accordance with a conventional method, for example, solution polymerization or emulsification using an appropriate catalyst such as a Ziegler polymerization catalyst, an alkyl lithium polymerization catalyst or a radical polymerization catalyst containing titanium as a catalyst component. Performed by polymerization.

  The conjugated diene polymer cyclized product used in the present invention is obtained by subjecting the conjugated diene polymer to a cyclization reaction in the presence of an acid catalyst.

  Known acid catalysts can be used for the cyclization reaction. Specific examples thereof include sulfuric acid; fluoromethanesulfonic acid, difluoromethanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, alkylbenzenesulfonic acid having an alkyl group having 2 to 18 carbon atoms, anhydrides and alkyl esters thereof, and the like. Organic sulfonic acid compounds: boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, diethylaluminum monochloride, ethylammonium chloride, aluminum bromide, antimony pentachloride, tungsten hexachloride, iron chloride, etc. A Lewis acid; and the like. These acid catalysts may be used alone or in combination of two or more. Among these, organic sulfonic acid compounds are preferable, and p-toluenesulfonic acid and xylenesulfonic acid are more preferable.

  The usage-amount of an acid catalyst is 0.05-10 mass parts normally per 100 mass parts of conjugated diene polymers, Preferably it is 0.1-5 mass parts, More preferably, it is 0.3-2 mass parts.

  The cyclization reaction is usually performed by dissolving a conjugated diene polymer in a hydrocarbon solvent.

  The hydrocarbon solvent is not particularly limited as long as it does not inhibit the cyclization reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene; n-pentane, n-hexane, n-heptane, n -Aliphatic hydrocarbons such as octane; Alicyclic hydrocarbons such as cyclopentane and cyclohexane; and the like. The boiling point of these hydrocarbon solvents is preferably 70 ° C. or higher.

  The solvent used for the polymerization reaction of the conjugated diene polymer and the solvent used for the cyclization reaction may be of the same type. In this case, an acid catalyst for cyclization reaction can be added to the polymerization reaction solution after completion of the polymerization reaction, and the cyclization reaction can be carried out following the polymerization reaction.

  The amount of the hydrocarbon solvent used is such that the solid content concentration of the conjugated diene polymer is usually 5 to 60% by mass, preferably 20 to 40% by mass.

  The cyclization reaction can be carried out under any pressure of pressure, reduced pressure and atmospheric pressure, but it is desirable to carry out under atmospheric pressure from the viewpoint of easy operation. When the cyclization reaction is performed in a dry air flow, particularly in an atmosphere of dry nitrogen or dry argon, side reactions caused by moisture can be suppressed.

  The reaction temperature and reaction time in the cyclization reaction are not particularly limited. The reaction temperature is usually 50 to 150 ° C., preferably 70 to 110 ° C., and the reaction time is usually 0.5 to 10 hours, preferably 2 to 5 hours.

  After carrying out the cyclization reaction, the acid catalyst is deactivated and the acid catalyst residue is removed by a conventional method, and then the hydrocarbon solvent is removed to obtain a solid conjugated diene polymer cyclized product. .

  The conjugated diene polymer cyclized product used in the present invention is a modified conjugated diene polymer cyclized product (hereinafter sometimes abbreviated as a modified conjugated diene polymer cyclized product) as long as the object of the present invention is not impaired. Is more preferable than the unmodified conjugated diene polymer cyclized product. Of the modified conjugated diene polymer cyclized product, a polar group-containing conjugated diene polymer cyclized product modified to contain a polar group is preferred. The modified conjugated diene polymer cyclized product having a polar group introduced exhibits adhesion to the adherend of the resin layer containing the polymer, and when the resin layer contains fine particles, dispersion of the fine particles Has the effect of improving the performance. One kind of the modified conjugated diene polymer cyclized product containing a polar group may be contained in the resin layer, and a plurality of kinds having different polar groups may be contained in the resin layer. Further, a conjugated diene polymer cyclized product having two or more kinds of functional groups may be used.

  The polar group is not particularly limited, and examples thereof include an acid anhydride group, carboxyl group, hydroxyl group, thiol group, ester group, epoxy group, amino group, amide group, cyano group, silyl group, and halogen. Can be mentioned. Among these, an acid anhydride group, a carboxyl group, a hydroxyl group, an epoxy group, or an amide group is preferable.

  Examples of the acid anhydride group or carboxyl group include maleic anhydride, itaconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, vinyl carboxylic acid compounds such as acrylic acid, methacrylic acid, and maleic acid. Examples include a group having a structure added to a cyclized product of a polymer, and among them, a group having a structure in which maleic anhydride is added to a cyclized product of a conjugated diene polymer is preferable in terms of reactivity and economy.

  Amide group is introduced by grafting conjugated diene polymer cyclized product using unsaturated compound containing amide group; introducing functional group using unsaturated compound containing functional group Then, it can be introduced by a method of reacting the introduced functional group with a compound having an amide group. Examples of the unsaturated compound containing an amide group include acrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, and N-benzylacrylamide.

  Examples of the hydroxyl group include hydroxyalkyl esters of unsaturated acids such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, and N- (2 -Unsaturated acid amides having hydroxyl groups such as hydroxyethyl) (meth) acrylamide, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and poly (ethylene glycol-propylene glycol) mono (meth) acrylate Groups of structures in which polyalkylene glycol monoesters of unsaturated acids such as, and polyhydric alcohol monoesters of unsaturated acids such as glycerol mono (meth) acrylate are added to the conjugated diene polymer cyclized product, This Among al, hydroxyalkyl esters of unsaturated acids are preferred, particularly 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate is a group of the structure obtained by adding the conjugated diene polymer cyclized product preferred.

  Examples of vinyl compounds containing other polar groups include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl ( And (meth) acrylate, (meth) acrylamide, and (meth) acrylonitrile.

  The content of the polar group in the modified conjugated diene polymer cyclized product, particularly the polar group-containing conjugated diene polymer cyclized product is not particularly limited, but is usually 0.1 to 15 mol%, preferably 0.5 to 10 mol. %, More preferably in the range of 1 to 7 mol%. If the content is too small or too large, the oxygen absorption function tends to be inferior. In addition, content of a polar group makes 1 mol the molecular weight equivalent amount of the polar group couple | bonded with the molecule | numerator of a modified conjugated diene polymer cyclization thing.

  As a method for producing a modified conjugated diene polymer cyclized product, (1) a method in which a conjugated diene polymer cyclized product obtained by the above-described method is subjected to an addition reaction with a polar group-containing vinyl compound, and (2) a polar group is contained. A method of obtaining a conjugated diene polymer by cyclization reaction by the above-mentioned method, (3) An addition reaction of a vinyl compound containing a polar group to a conjugated diene polymer not containing a polar group, followed by a cyclization reaction. And (4) a method of further adding a polar group-containing vinyl compound to the product obtained by the method (2) or (3). Especially, the point of said (1) is preferable from the point which can adjust an unsaturated bond decreasing rate more easily.

  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 diene polymer cyclized product. For example, an acid anhydride group, a carboxyl group, a hydroxyl group, a thiol group, Preferred examples include vinyl compounds having polar groups such as ester groups, epoxy groups, amino groups, amide groups, cyano groups, silyl groups, epoxy 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 acid anhydride, acrylic acid, methacrylic acid, and maleic acid. Maleic anhydride can be preferably used in terms of reactivity and economy. As a vinyl compound containing a hydroxyl group, for example, hydroxyalkyl esters of unsaturated acids are preferable, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are particularly preferable vinyl compounds.

  The method for adding a polar group-containing vinyl compound to a conjugated diene polymer cyclized product and introducing a polar group derived from the polar group-containing vinyl compound is not particularly limited, but is generally an ene addition reaction or a graft polymerization reaction. What is necessary is just to follow the well-known reaction called. This addition reaction is carried out by contacting the conjugated diene polymer cyclized product with the polar group-containing vinyl compound in the presence of a radical generator, if necessary. Examples of the radical generator include peroxides such as di-tert-butyl peroxide, dicumyl peroxide, and benzoyl peroxide, and azonitriles such as azobisisobutyronitrile.

  The addition reaction may be performed in a solid phase state or a solution state, but is preferably performed in a solution state from the viewpoint of easy reaction control. Examples of 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 is within the above-described preferred range.

  The reaction for introducing a polar group can be carried out under pressure, reduced pressure or atmospheric pressure, but is preferably carried out under atmospheric pressure from the viewpoint of ease of operation. When carried out in an atmosphere of nitrogen or dry argon, side reactions caused by moisture can be suppressed. Moreover, reaction temperature, reaction time, etc. should just follow a conventional method, Reaction temperature is 30-250 degreeC normally, Preferably it is 60-200 degreeC, Reaction time is usually 0.1-5 hours, Preferably Is 0.5-3 hours.

  The conjugated diene polymer cyclized product has at least two kinds of unsaturated bonds, ie, a linear unsaturated bond inherent to the conjugated diene and a cyclic unsaturated bond of the cyclized portion, except for a 100% cyclized product. ing. In the conjugated diene polymer cyclized product, it is considered that the cyclic unsaturated bond portion greatly contributes to oxygen absorption, and the linear unsaturated bond portion hardly contributes to oxygen absorption. Therefore, the conjugated diene polymer cyclized product having a reduction rate of unsaturated bonds (unsaturated bond reduction rate) in the conjugated diene polymer cyclized product with respect to the unsaturated bond in the conjugated diene polymer is 30% or more. It is important as a material for the oxygen absorbing member in the light emitting device of the invention. The unsaturated bond reduction rate of the conjugated diene polymer cyclized product is preferably 40 to 80%, more preferably 55 to 75%. If the unsaturated bond reduction rate is too low, oxygen absorption tends to deteriorate. The conjugated diene polymer cyclized product prevents the conjugated diene polymer cyclized product from becoming brittle by making the unsaturated bond reduction rate not more than the upper limit of the above preferred range. Progression is suppressed, transparency is improved, and it can be used for many purposes. Further, if the unsaturated bond reduction rate exceeds 50%, adhesiveness is exhibited, and this property can be utilized.

Here, the unsaturated bond reduction rate is an index representing the degree to which the unsaturated bond is reduced by the cyclization reaction in the conjugated diene monomer unit site in the conjugated diene polymer, and is a numerical value obtained as follows. is there. That is, by proton NMR ( ¹ H-NMR) analysis, in the conjugated diene monomer unit portion in the conjugated diene polymer, the ratio of the peak area of protons directly bonded to double bonds to the peak area of all protons is Calculate the reduction rate before and after the chemical reaction.

Now, in the conjugated diene polymer unit site in the conjugated diene polymer, 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, and the total proton after the cyclization reaction When the peak area is SAT and the peak area of the proton peak directly bonded to the double bond is SAU, the peak area ratio (SB) of the proton directly bonded to the double bond before the cyclization reaction is SB = SBU / SBT, The peak area ratio (SA) of the proton directly bonded to the double bond after the cyclization reaction is expressed as SA = SAU / SAT. Therefore, the unsaturated bond reduction rate is
Unsaturated bond reduction rate (%) = 100 × (SB−SA) / SB
As required.

  The conjugated diene polymer cyclized product has a weight average molecular weight of 5,000 to 2,000,000, preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000. If the weight average molecular weight is too low, the oxygen absorption amount of the conjugated diene polymer cyclized product tends to decrease, and if it is too high, the fluidity and plasticity are reduced during the production and use of the conjugated diene polymer cyclized product. , Tend to be difficult to handle. The weight 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 can be appropriately selected depending on the application, but is usually 0 to 250 ° C, preferably 0 to 200 ° C, more preferably 30. It is -180 degreeC, Most preferably, it is the range of 40-150 degreeC. When the glass transition temperature of the conjugated diene polymer cyclized product is out of these ranges, there is a problem in the moldability of the conjugated diene polymer cyclized product, the strength of the member, the adhesion to other members, and the handleability. There is. The glass transition temperature of the conjugated diene polymer cyclized product can be adjusted by appropriately selecting the monomer used as the raw material, the molecular weight of the conjugated diene polymer cyclized product, the unsaturated bond reduction rate, and the like.

  The oxygen absorption amount of the conjugated diene polymer cyclized product suitably used in the present invention is 5 ml / g or more, preferably 10 ml / g or more, more preferably 50 ml / g or more. The oxygen absorption amount is the amount of oxygen absorbed by 1 g of the conjugated diene polymer cyclized product when the conjugated diene polymer cyclized product is sufficiently absorbed as a powder or thin film to reach a saturated state at 23 ° C. The amount of oxygen absorbed is mainly correlated with the unsaturated bond reduction rate in the conjugated diene polymer cyclized product.

In the present invention, the conjugated diene polymer cyclized product suitably used has an oxygen absorption rate from the surface of 1.0 ml / m ² · day or more, preferably 5.0 ml / m ² · day or more, more preferably 10 ml / day. m ² · day or more. When used as a sealing container for a light-emitting element, oxygen that has existed or entered in the sealed space for some reason must be quickly absorbed and removed by the conjugated diene polymer cyclized product layer. From this point of view, those having the above-described oxygen absorption rate are desirable.

  The measurement of the oxygen absorption amount and the oxygen absorption rate is performed as follows.

  A sample such as a conjugated diene polymer cyclized product is compression-molded at 100 ° C. in a nitrogen atmosphere and then stretched to obtain a film having a thickness of 100 μm. And this is cut | judged to the dimension of 100 mm x 100 mm, and it is set as the sample for oxygen absorption. This oxygen-absorbing sample is placed in an oxygen-impermeable bag made of a three-layer film of polyethylene terephthalate film (PET) / aluminum foil (Al) / polyethylene film (PE) having a size of 150 mm × 220 mm together with 200 ml of air. Seal. This is left at the temperature to be measured, and the oxygen concentration in the bag is measured with an oxygen concentration meter every 24 hours, and the oxygen absorption amount is calculated from the oxygen decrease amount when the oxygen concentration stops decreasing. The oxygen absorption rate is expressed as the amount of oxygen absorbed for 24 hours after the start of measurement. As the oxygen concentration meter, a commercially available oxygen concentration meter may be used. The oxygen absorption rate refers to a value measured at 23 ° C. when no measurement temperature is indicated.

  When only the oxygen-absorbing resin is contained in the resin, the content of the conjugated diene polymer cyclized product in the resin layer is usually 5 to 100% by mass, preferably 15 to 100% by mass. %. When the content of the conjugated diene polymer cyclized product is lower than the lower limit value, there may be a problem that the oxygen absorption ability and the adhesion strength at normal temperature (25 ° C.) are lowered.

1-2-2. Adhesive Resin In addition to the oxygen-absorbing resin, the resin layer in this invention can further contain an adhesive resin. By containing an adhesive resin in the resin layer, the adhesiveness of the resin layer to the metal thin film layer can be improved.

  The adhesive resin in the present invention refers to a resin having a width of 10 mm and a 90 degree peel strength of 170 g / 10 mm or more, preferably 400 g / 10 mm or more when bonded to a metal thin film layer.

  The peel strength is achieved by using a resin having a polar group, preferably a resin containing 0.1 to 15 mol%, more preferably 0.5 to 10 mol% of a polar group. Here, mol% indicates the ratio of the number of moles of repeating units into which a polar group is introduced out of the total number of moles of repeating units of the resin serving as the base of the adhesive resin.

  Specific examples of the adhesive resin include α-olefin as a main component, α-olefin and vinyl acetate, acrylic acid ester, methacrylic acid ester and the like; copolymer; α-olefin homopolymer or copolymer; Examples thereof include an acid-modified poly α-olefin resin modified with an unsaturated carboxylic acid; an ionomer resin; a modified conjugated diene polymer cyclized product; a modified alicyclic polyolefin resin; and a mixture thereof.

  Examples of the polar group include at least one group selected from the group consisting of an acid anhydride group, an acid amide group, a carboxyl group, an amino group, an epoxy group, a hydroxyl group, and an isocyanate group. Since these groups have dipoles, they contribute to improving the adhesive force in the adhesive resin. Among the polar groups, an acid anhydride group and an epoxy group are preferable. Examples of the resin having an acid anhydride and / or epoxy group include maleic anhydride-modified polyisoprene, styrene-maleic anhydride copolymer, maleic anhydride-modified alicyclic polyolefin resin, and maleic anhydride-modified conjugated diene polymer cyclized product. And epoxy-modified conjugated diene polymer cyclized product.

  Among the various adhesive resins, maleic anhydride-modified conjugated diene polymer cyclized product and epoxy-modified conjugated diene polymer cyclized product are preferable. These adhesive resins alone can have both an adhesion function with the metal layer and an oxygen absorption function.

  When only the oxygen-absorbing resin and the adhesive resin are contained in the resin layer, the content ratio of the adhesive resin in the resin layer is 100 parts by mass in total of the oxygen-absorbing resin and the adhesive resin. On the other hand, it is usually 100 parts by mass or less, preferably 10 to 95 parts by mass, particularly preferably 15 to 90 parts by mass. When the content ratio of the adhesive resin is within the above range, the adhesion with the metal thin film layer can be improved while maintaining the oxygen gas barrier property of the resin layer, and the metal thin film layer in the laminate for a light emitting element Peeling from the resin layer can be prevented for a long time.

1-2-3. Water-absorbing resin This resin layer preferably further contains a water-absorbing resin. When this moisture-absorbing resin is contained in the resin layer, moisture entering from the outside of the light-emitting element according to the present invention and a minute amount of moisture remaining on the element surface and inside the element in the manufacturing process are removed from the entire resin layer. The effect of extending the lifetime of the element is exhibited by diffusing and absorbing.

  The moisture-absorbing resin refers to a resin having a moisture absorption amount of 0.5% by weight or more based on the resin weight after being left in water at 25 ° C. for 24 hours.

  The moisture-absorbing resin can achieve the moisture absorption amount by having a functional group that forms a hydrogen bond with water molecules.

  Specific examples of the water-absorbing resin are selected from the group consisting of ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, acrylic acid polymer, acrylamide resin, acetal resin, urethane resin, and cellulose resin. At least one of them.

  When the oxygen-absorbing resin, the adhesive resin, and the moisture-absorbing resin are contained in the resin layer, the content of the moisture-absorbing resin in the resin layer is usually 20 to 80% by mass. Preferably, it is 30-70 mass%. If the content of the water-absorbing resin is less than the lower limit value, the water absorption ability may be reduced, resulting in a disadvantage that the life of the light emitting element is reduced. If the content exceeds the upper limit value, the oxygen absorption capacity is reduced. Or when the resin composition is molded into a sheet or film, the mechanical strength may decrease.

1-2-4. Other components As long as the resin layer in the laminate for a light emitting device according to the present invention does not hinder the object of the present invention, and in order to improve the degree of achievement of the object of the present invention, an inorganic desiccant, a heat dissipating fine powder, Various additives and the like can be contained.

1-2-4-1. Inorganic desiccant The inorganic desiccant that can be included in the resin layer preferably has a number average particle size of 100 μm or less. Since the inorganic desiccant having such a number average particle size is uniformly dispersed in the resin layer, when the inorganic desiccant is contained in the resin layer, the resin layer absorbs moisture and forms water into the light emitting layer. Adverse effects can be blocked.

  The inorganic desiccant is not particularly limited as long as it has a property of absorbing moisture. For example, alkaline earth metal oxides such as calcium oxide, barium oxide and magnesium oxide, sulfates such as sodium sulfate and calcium sulfate, hydrogen Moisture-absorbing desiccants such as alkaline earth metal hydride salts such as calcium hydroxide and strontium hydride, moisture-reactive inorganic compounds such as alkaline earth metals such as calcium and barium, silica gel, alumina and various zeolites can be used. Of these, calcium oxide, which is excellent in moisture reactivity and is a commercially available product and has a wide variety of particle sizes, is preferred. Although it is not particularly limited as a dispersion method, a kneading method such as a biaxial kneading method or a master batch kneading can be adopted, and a method of mixing a resin component and an inorganic desiccant in a solvent such as toluene. Can also be adopted.

  The content of the inorganic desiccant in the resin layer is usually 2 to 50% by mass, preferably 5 to 30% by mass. If the content of the inorganic desiccant is less than the lower limit, moisture absorption capacity may be reduced, resulting in inconveniences such as a decrease in device life. If the upper limit is exceeded, the mechanical strength of the resin layer is reduced. May cause inconvenience.

1-2-4-2. Heat-dissipating fine powder It is preferable to disperse a heat-dissipating fine powder having a number average particle diameter of 100 μm or less in the resin layer in the laminate for a light-emitting element according to the present invention. The heat dissipating fine powder is not particularly limited as long as it has heat dissipation characteristics. For example, metal powder having high thermal conductivity such as aluminum, iron, copper, silver, gold, etc .; glass powder, carbon black, carbon nanotube, etc. Can be mentioned. Among these various heat dissipating fine powders, metal powders of aluminum, copper and iron, and carbon nanotubes are preferable.

1-2-4-3. Various additives For the resin layer in the present invention, various additives such as an antioxidant, a catalyst having an action of enhancing oxygen absorption, a photoinitiator, a thermal stabilizer, and an adhesive are used unless the effects of the present invention are impaired. Additives such as materials, reinforcing agents, fillers, flame retardants, colorants, plasticizers, UV absorbers, lubricants, deodorants, antistatic agents, anti-tacking agents, antifogging agents, surface treatment agents, etc. it can. These additives can be appropriately selected according to the purpose from various conventionally known substances and commercially available products, and can be 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.

  Isoprene-derived double bonds that are contained in the conjugated diene polymer cyclized product existing in the resin layer and remain as they are without cyclization are prone to oxidative degradation due to chemical structure. Because of the tendency, it is effective to add an antioxidant to the conjugated diene polymer cyclized product having a low unsaturated bond rate. The antioxidant 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 antioxidants and phosphite antioxidants.

  Antioxidants may be used alone or in combination of two or more. The content of the antioxidant is preferably 500 ppm or less, more preferably 400 ppm or less, and particularly preferably 300 ppm or less. When this content is too large, a tendency to lower the oxygen absorbability appears. The lower limit of the content of the antioxidant is preferably 10 ppm, more preferably 20 ppm. Cyclic isoprene that does not contain an antioxidant may deteriorate at high temperatures or may have reduced mechanical strength after absorbing oxygen.

  A typical example of the catalyst having an action of increasing oxygen absorption is a transition metal salt. The resin composition for a light-emitting device in the present invention exhibits sufficient oxygen absorption even when such a transition metal salt is not contained, but the oxygen absorption is further improved by containing the transition metal salt. . However, when used in the present invention, it is necessary to consider that the addition of a metal component does not adversely affect transparency and other purposes of use. Examples of such transition metal salts include cobalt (II) oleate, cobalt (II) naphthenate, cobalt (II) 2-ethylhexanoate, cobalt (II) stearate, and cobalt (II) neodecanoate. Preferably, cobalt (II) 2-ethylhexanoate, cobalt (II) stearate, and cobalt (II) neodecanoate are more preferable. The blending amount of the transition metal salt is usually 10 to 10,000 ppm, preferably 20 to 5,000 ppm, more preferably 50 to 5,000 ppm of the total amount of the oxidizing absorbent.

  The photoinitiator has an action of promoting the start of the oxygen absorption reaction when the conjugated diene polymer cyclized product is irradiated with energy rays. Examples of the photoinitiator include those exemplified in JP-T-2003-504042. The amount of the photoinitiator to be blended is usually 0.001 to 10% by mass, preferably 0.01 to 1% by mass, based on the total amount of cyclized polyisoprene.

1-3. 1st adhesive layer and 2nd adhesive layer The laminated body for light emitting elements which concerns on this invention has the 1st adhesive layer containing adhesive resin between a metal thin film layer and the resin layer containing the said oxygen absorptive resin. It is good also as a structure which has a metal thin film layer, the resin layer containing the said oxygen absorptive resin, and the 2nd contact bonding layer containing adhesive resin in this order.

  The adhesive resin used for the first adhesive layer and the second adhesive layer can be formed of an adhesive resin similar to that described in the section “1-2-2. Adhesive resin”.

  The thickness of the first adhesive layer is usually 0.1 to 30 μm, particularly preferably 5 to 10 μm, and the thickness of the second adhesive layer is usually 0.1 to 30 μm, particularly preferably 5 to 10 μm.

1-4. Preparation of Laminate for Light-Emitting Element A laminate for a light-emitting element according to the present invention comprises, for example, a coating method, an extrusion coating method, a dry coating method, and the like. It can be formed by a lamination method, a coextrusion lamination method, a coextrusion film method, or the like.

  The laminate for a light emitting element according to the present invention is a laminate having a metal thin film layer, a first adhesive layer, and a resin layer, or a laminate having a metal thin film layer, a first adhesive layer, a resin layer, and a second adhesive layer. A laminated body having a first adhesive layer and a resin layer, or a laminated body having a first adhesive layer, a resin layer and a second adhesive layer, an extrusion coating method, a sandwich lamination method, a dry lamination method, etc. It is also possible to adopt a method of laminating the obtained laminate and the metal film or metal sheet for forming a metal thin film.

2. Light emitting element The light emitting element according to the present invention comprises a laminate for a light emitting element according to the present invention, a light emitting layer, and a transparent substrate, which are laminated in this order, and more specifically, on the surface of the transparent substrate and the transparent substrate. The disposed light emitting layer and the surface of the light emitting layer and the transparent substrate exposed without being covered with the light emitting layer are disposed on the opposite side of the light emitting element laminate from the metal thin film layer, such as a resin layer or a second layer. 2 The light emitting layer and the light emitting element laminate laminated on the surface of the transparent substrate exposed without being covered with the light emitting layer so as to cover the adhesive layer.

2-1. Transparent substrate As long as the transparent substrate can be mounted with a light emitting layer and a laminate for a light emitting element and is transparent, an appropriate material can be used depending on the situation around the light emitting element in the device in which the light emitting element is installed. It can be formed into a shape.

  Examples of the transparent substrate include a plate, a film, a sheet and the like formed of an inorganic material such as glass, an alicyclic olefin resin, a polycarbonate, and a transparent synthetic resin such as polymethyl (meth) acrylate.

  The transparent substrate may have a laminated structure composed of a plurality of layers formed of different materials or the same material.

2-2. Light-Emitting Layer The light-emitting layer is a layer that emits light by electric energy. In a normal case, a laminate including an anode, a hole transport layer, a light-emitting compound-containing layer, an electron transport layer, and a cathode can be exemplified.

  The anode has a function of injecting holes into the hole transport layer. The anode is usually a metal such as aluminum, gold, silver, nickel, palladium, or platinum, a metal oxide such as an oxide of indium and / or tin, a metal halide such as copper iodide, carbon black, or poly ( 3-methylthiophene), polypyrrole, polyaniline and other conductive polymers. The anode can usually be formed by sputtering, vacuum deposition, etc. Also, metal fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder In the case of forming the anode by, for example, it can be formed by dispersing in an appropriate binder resin solution and coating on the substrate. Further, when the anode is formed of a conductive polymer, a polymerized thin film can be formed directly on the substrate by electrolytic polymerization, or a conductive polymer can be applied on the substrate (Appl. Phys). Lett., 60, 2711, 1992).

  The anode usually has a single-layer structure, but it can also have a laminated structure composed of a plurality of materials if desired. The thickness of the anode varies depending on the required transparency. When transparency is required, the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness of the anode is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably about 500 nm or less. When opaqueness is acceptable, the thickness of the anode is arbitrary, and if desired, it may be formed of metal and serve as a substrate.

  The hole transport layer is a layer having high hole injection efficiency from the anode and efficiently transporting the injected holes. For this purpose, the ionization potential is small, the transparency to visible light is high, the hole mobility is large, the stability is high, and trapping impurities are unlikely to be generated during manufacturing or use. Required. In addition, it is desirable not to quench the light emitted from the light emitting compound-containing layer in contact with the light emitting compound-containing layer, or to form an exciplex with the light emitting compound-containing layer to reduce the efficiency. In addition to the above general requirements, when considering a light-emitting element for in-vehicle display, the light-emitting element is further required to have heat resistance. Therefore, a material having a glass transition point (Tg) of 85 ° C. or higher is desirable.

  Examples of such a hole transport material include two or more tertiary amines represented by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, and two or more Aromatics having a starburst structure such as aromatic diamines in which condensed aromatic rings are substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234681), 4,4 ', 4'-tris (1-naphthylphenylamino) triphenylamine Group amine compounds (J. Lumin., 72-74, 985, 1997), aromatic amine compounds consisting of tetramers of triphenylamine (Chem. Commun., 2175, 1996), 2, 2 Spiro compounds such as', 7,7'-tetrakis- (diphenylamino) -9,9'-spirobifluorene (Synth. Metals, 91, 209, 19 7 years), and the like. These compounds may be used alone or in combination as necessary.

  In addition to the above compounds, polyarylene ether sulfone (Polym. Adv. Tech.) Containing polyvinyl carbazole, polyvinyl triphenylamine (Japanese Patent Laid-Open No. 7-53953), and tetraphenylbenzidine as a material for the hole transport layer 4. 7, Vol. 33, 1996).

  The hole transport layer is formed by a normal coating method such as a spray method, a printing method, a spin coating method, a dip coating method, or a die coating method, a wet film forming method such as an ink-jet method or a screen printing method, or a vacuum deposition method. It can be formed by a dry film forming method such as a method.

  In the case of the coating method, one or more hole transport materials are added, and if necessary, additives such as binder resins and coating property improvers that do not trap holes are added and dissolved in a suitable solvent. A solution is prepared, applied onto the anode by a method such as spin coating, and dried to form a hole transport layer. Examples of the binder resin include polycarbonate, polyarylate, and polyester. When the amount of the binder resin added is large, the hole mobility is lowered.

In the case of the vacuum deposition method, the hole transport material is put in a crucible installed in a vacuum vessel, and after evacuating the inside of the vacuum vessel to about 10 ⁻⁴ Pa with a suitable vacuum pump, the crucible is heated, The hole transport material is evaporated and a hole transport layer is formed on the substrate on which the anode is formed, placed opposite to the crucible.

  The thickness of the hole transport layer is usually 5 nm or more, preferably 10 nm or more, and usually 300 nm or less, preferably 100 nm or less. In order to uniformly form such a thin film, a vacuum deposition method is generally used.

  The light-emitting compound-containing layer is excited by recombination between holes injected from the anode and moving through the hole transport layer and electrons injected from the cathode and transferred through the hole blocking layer between electrodes to which an electric field is applied. And formed from a compound that exhibits strong luminescence.

  The light emitting compound used in the light emitting compound-containing layer has a stable thin film shape, exhibits a high emission (fluorescence or phosphorescence) quantum yield in the solid state, and can efficiently transport holes and / or electrons. A compound can be mentioned. Furthermore, examples of suitable light-emitting compounds include compounds that are electrochemically and chemically stable and in which trapping impurities are less likely to occur during manufacture and use.

  For the purpose of improving the light emission efficiency of the light emitting element and changing the emission color, for example, doping a fluorescent dye for laser such as coumarin with an aluminum complex of 8-hydroxyquinoline as a host material (J. Appl. Phys., 65 Vol. 3610 (1989), etc., and it is preferable to dope a fluorescent dye into the light emitting compound-containing layer in the light emitting device of the present invention.

  As a doping material, various fluorescent dyes can be used in addition to coumarin. Examples of fluorescent dyes that emit blue light include perylene, pyrene, anthracene, coumarin, and derivatives thereof. Examples of the green fluorescent dye include quinacridone derivatives and coumarin derivatives. Examples of yellow fluorescent dyes include rubrene and perimidone derivatives. Examples of red fluorescent dyes include DCM compounds, benzopyran derivatives, rhodamine derivatives, benzothioxanthene derivatives, azabenzothioxanthene and the like.

  Other than the above-mentioned fluorescent dyes for doping, depending on the host material, listed in Laser Research, 8, 694, 803, 958 (1980); 9, 9, 85 (1981). Fluorescent dyes and the like that can be used as a doping material for the light emitting compound-containing layer.

The amount by which the fluorescent dye is doped with respect to the host material is preferably 10 ⁻³ mass% or more, and more preferably 0.1 mass%. Moreover, 10 mass% or less is preferable and 3 mass% or less is more preferable. If the lower limit is not reached, it may not be possible to contribute to improving the luminous efficiency of the device. If the upper limit is exceeded, concentration quenching may occur, leading to a reduction in luminous efficiency.

  On the other hand, the light emitting compound-containing layer that exhibits phosphorescence is usually formed by including a phosphorescent dopant and a host material. Examples of the phosphorescent dopant include an organometallic complex containing a metal selected from Groups 7 to 11 of the periodic table, and a charge transporting organic material having T1 higher than T1 (the lowest excited triplet level) of such a metal complex. It is preferred to use a compound as the host material.

  Preferred examples of the metal in the phosphorescent organometallic complex containing a metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold. As these organometallic complexes, compounds described in JP-A-2006-203227 are preferable.

  The amount of the organometallic complex contained as a dopant in the light emitting compound-containing layer is preferably 0.1% by mass or more, and more preferably 30% by mass or less. If the lower limit is not reached, it may not be possible to contribute to improving the luminous efficiency of the device. If the upper limit is exceeded, concentration quenching may occur due to the formation of a dimer between organometallic complexes, etc. There is.

  The amount of the phosphorescent dopant in the phosphorescent compound-containing layer that emits phosphorescence is slightly larger than the amount of the fluorescent dye (dopant) contained in the phosphorescent compound-containing layer in the conventional device using fluorescence (singlet). There is a tendency to be preferable. Moreover, when a fluorescent pigment | dye is contained in a light emitting compound content layer with a phosphorescent dopant, 0.05 mass% or more is preferable and 0.1 mass% or more is more preferable. Moreover, 10 mass% or less is preferable and 3 mass% or less is more preferable.

The film thickness of the light emitting compound-containing layer is usually 3 nm or more, preferably 5 nm or more, and is usually 200 nm or less, preferably 100 nm or less.
In addition, the light emitting compound content layer may contain components other than the above in the range which does not impair the performance of this invention.

  As a component other than the above components that may be contained in the light emitting compound-containing layer, for example, a metal complex such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), 10-hydroxybenzo [h] Metal complexes of quinoline (JP-A-6-322362), bisstyrylbenzene derivatives (JP-A-1-245087, JP-A-2-222484), bisstyrylarylene derivatives (JP-A-2-247278), ( 2-hydroxyphenyl) benzothiazole metal complexes (JP-A-8-315983), silole derivatives, and other fluorescent compounds, carbazole derivatives such as 4,4′-N, N′-dicarbazole biphenyl (WO00) / 70655 gazette), Tris (8-hydroxyquinoline) alumini (USP 6,303,238), 2,2 ′, 2 ′ '-( 1,3,5-benzenetolyl) tris [1-phenyl-1H-benzimidazole] (Appl. Phys. Lett., 78, 1622, 2001), a compound that generates phosphorescence, such as polyvinyl carbazole (Japanese Patent Laid-Open No. 2001-257076), and the like.

  The luminescent compound-containing layer can also be formed by the same method as the hole transport layer. A method of doping the above-described fluorescent dye and / or phosphorescent dye (phosphorescent dopant) into the host material of the luminescent compound-containing layer will be described below.

  In the case of coating, the light-emitting compound, the dye for doping, and, if necessary, an additive such as a binder resin that does not become an electron trap or a light-quenching quencher, and a coating property improving agent such as a leveling agent were added and dissolved. A coating solution is prepared, applied onto the hole transport layer by a method such as spin coating, and dried to form a luminescent compound-containing layer. Examples of the binder resin include polycarbonate, polyarylate, and polyester. When the amount of the binder resin added is large, the hole / electron mobility is lowered. Therefore, the smaller amount is desirable, and 50% by mass or less is preferable.

In the case of the vacuum vapor deposition method, the host material is put in a crucible installed in a vacuum vessel, a dye to be doped is put in another crucible, and the inside of the vacuum vessel is 1.0 × 10 ⁻⁴ Torr with an appropriate vacuum pump. After evacuating to a degree, each crucible is heated and evaporated simultaneously to form a layer on the substrate placed opposite the crucible. As another method, a mixture of the above materials in a predetermined ratio may be evaporated using the same crucible.

  When each of the above dopants is doped in the luminescent substance-containing layer, it is doped uniformly in the film thickness direction of the luminescent substance-containing layer, but there may be a concentration distribution in the film thickness direction. For example, it may be doped only in the vicinity of the interface with the hole transport layer, or conversely, it may be doped in the vicinity of the interface of the hole blocking layer. The luminescent substance-containing layer can also be formed by the same method as the hole transport layer, but usually a vacuum deposition method is used.

  The electron transport layer is formed using a compound capable of efficiently transporting electrons injected from the cathode between electrodes to which an electric field is applied to the light emitting compound-containing layer. Examples of such compounds include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline, oxadiazole derivatives, and distyrylbiphenyl derivatives. , Silole derivatives, 3- or 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Pat. No. 5,645,948), quinoxaline compounds (JP-A-6-207169) ), Phenanthroline derivatives (JP-A-5-331459), 2-t-butyl-9,10-N, N'-dicyanoanthraquinonediimine, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n Type zinc selenide.

  The film thickness of the electron transport layer is usually 5 nm or more, preferably 10 nm or more, and is usually 200 nm or less, preferably 100 nm or less. The electron transport layer is formed by laminating on the hole blocking layer 6 by a coating method or a vacuum deposition method in the same manner as the hole transport layer. Usually, a vacuum deposition method is used.

The cathode plays a role of injecting electrons into the luminescent compound-containing layer. The material used as the cathode can be the material used for the anode, but a metal having a low work function is preferable for efficient electron injection, such as tin, magnesium, indium, calcium, aluminum, A suitable metal such as silver or an alloy thereof is used. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy. Furthermore, inserting a very thin insulating film (0.1 to 5 nm) such as LiF, MgF ₂ , or Li ₂ O at the interface between the cathode and the light emitting compound-containing layer or the electron transport layer also improves the light emission efficiency of the light emitting element. This is an effective method (Japanese Patent Laid-Open No. 10-74586). The thickness of the cathode is usually the same as that of the anode. For the purpose of protecting the cathode made of a low work function metal, further laminating a metal layer having a high work function and stable to the atmosphere on the cathode increases the stability of the light emitting device. For this purpose, metals such as aluminum, silver, copper, nickel, chromium, gold, platinum are used.

2-3. Production of Light-Emitting Element A light-emitting element according to the present invention is covered with a transparent substrate 5, a light-emitting layer 6 disposed on the surface thereof, and the surface of the light-emitting layer 6 and the light-emitting layer 6, as shown in FIG. A light-emitting element 7 formed by laminating the light-emitting element laminate 1 that is in close contact with the exposed surface of the transparent substrate 5 and in which the light-emitting layer 6 is embedded can be exemplified. The transparent substrate 5 and the light emitting layer 6 are as already described. Since the transparent substrate 5 is transparent and the light emitting element laminate 1 has a metal thin film layer, the light emitted from the light emitting layer 6 and reflected by the metal thin film layer in the light emitting element laminate and the light emitting layer 6 Since the light emitted toward the transparent substrate 5 is transmitted through the transparent substrate 5 and emitted, the light emitting element 7 can function as a planar light emitter.

  The present invention will be described more specifically with reference to examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

  Measurement and evaluation of various physical properties and the like were performed as follows.

(1) Unsaturated bond reduction rate of conjugated diene polymer cyclized product The unsaturated bond reduction rate was determined by proton NMR measurement with reference to the methods described in the following documents (i) and (ii).
(I) M.M. a. Golub and J.M. Heller. Can. J. et al. Chem, 41, 937 (1963)
(Ii) Y. Tanaka and H.M. Sato, J .; Poyim. Sci: Poiy. Chem. Ed. , 17, 3027 (1979)
Now, in the conjugated diene polymer unit site in the conjugated diene polymer, 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, and the total proton after the cyclization reaction When the peak area is SAT and the peak area of the proton peak directly bonded to the double bond is SAU, the peak area ratio (SB) of the proton directly bonded to the double bond before the cyclization reaction is
SB = SBU / SBT
The peak area ratio (SA) of the proton directly bonded to the double bond after the cyclization reaction is
SA = SAU / SAT
Therefore, the unsaturated bond reduction rate is obtained by the following equation.
Unsaturated bond reduction rate (%) = 100 × (SB−SA) / SB

(2) Oxygen absorption amount The sample is stretched into a film having a thickness of 100 μm after compression molding at 100 ° C. in a nitrogen atmosphere. And this is cut | judged to the dimension of 100 mm x 100 mm, and it is set as the sample for oxygen absorption amount measurement. This oxygen absorption amount measurement sample was placed in an oxygen-impermeable bag made of a three-layer film of polyethylene terephthalate film (PET) / aluminum foil (Al) / polyethylene film (PE) having a size of 150 mm × 220 mm in 200 ml. Seal with air. This was left at 23 ° C., and the oxygen concentration in the bag was measured with an oximeter every 24 hours. When the oxygen concentration stopped decreasing, the absorption of oxygen reached saturation, and 1 g of sample absorbed. Calculate oxygen uptake. As an oxygen concentration meter, an oxygen analyzer HS-750 manufactured by Neutronics was used.

(3) Oxygen absorption rate The oxygen absorption rate was measured by measuring the oxygen absorption amount in the same manner as the measurement of the oxygen absorption amount in (2) above, and was expressed as the oxygen absorption amount 24 hours after the start of the measurement. The measurement temperature was 23 ° C.

(4) Moisture absorption (when 48 hours have passed)
A 100 μm-thick film produced by extrusion and stretching was cut into 100 mm × 100 mm, and the mass was measured accurately in a dry box. This film was allowed to stand in a desiccator whose humidity was controlled to 60% (filled with nitrogen gas), and the water absorption after 48 hours was measured from the change in mass. The laminate was cut into 100 mm × 100 mm, and the same operation was performed to measure the moisture absorption.

(5) Weight average molecular weight The weight average molecular weight was shown by the standard polystyrene conversion value by gel permeation chromatography analysis.

(6) Content of polar group The content of the acid anhydride group is determined by measuring the peak intensity (1760-1780 cm ⁻¹ ) of the acid anhydride group by Fourier transform infrared absorption spectrum analysis, and then measuring the acid anhydride group by a calibration curve method. Determine the content of the physical group. Similarly, the peak intensity (1700 cm ⁻¹ ) of the carboxyl group was measured, and the carboxyl group content was determined by a calibration curve method.

  The amount of epoxy group and amide group introduced was measured by NMR, and the content was determined from the ratio of protons derived from the functional group.

(Production Example 1)
Polyisoprene (73% cis-1,4 bond units, 22% trans-1,4 bond units, 3% 22% trans-1,4 bond units) cut into a 10 mm square in a pressure-resistant reactor equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas introduction pipe , 4-bond unit 5%, weight average molecular weight 174,000) 300 parts by mass together with 700 parts by mass of toluene. After purging the inside of the reactor with nitrogen, the mixture was heated to 85 ° C. and polyisoprene was completely dissolved in toluene with stirring. Thereafter, 2.4 parts by mass of p-toluenesulfonic acid obtained by reflux dehydration in toluene so that the water content was 150 ppm or less was added, and a cyclization reaction was performed at 85 ° C. After reacting for 4 hours, 25% sodium carbonate aqueous solution containing 0.83 parts by mass of sodium carbonate was added to stop the reaction. Washing with 300 parts by mass of ion-exchanged water was repeated 3 times at 85 ° C. to remove catalyst residues in the reaction system, and a polymer cyclized product solution was obtained.

  After adding a phenolic antioxidant (Irganox 1010: manufactured by Ciba Specialty Chemicals) in an amount corresponding to 100 ppm to the polymer cyclized product, A portion of the toluene was distilled off, followed by vacuum drying to remove the toluene, and a conjugated diene polymer cyclized product (B1) was obtained. The unsaturated bond reduction rate, oxygen absorption amount, oxygen absorption rate, weight average molecular weight and water absorption amount of the conjugated diene polymer cyclized product (B1) were measured. The evaluation results are shown in Table 1.

(Production Example 2)
The conjugated diene was prepared in the same manner as in Production Example 1 except that the amount of p-toluenesulfonic acid used was changed to 2.25 parts by mass and the amount of sodium carbonate added after the cyclization reaction was changed to 0.78 parts by mass. A polymer cyclized product (B2) was obtained. These were evaluated in the same manner as in Production Example 1. The evaluation results are shown in Table 1.

(Production Example 3)
Polyisoprene (cis-1,4 units 73%, trans-1,4 units 22%, 3,4) cut into 10 mm square in a pressure-resistant reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube -Unit 5%, weight average molecular weight 154,000) 300 parts by mass were charged together with 700 parts by mass of cyclohexane. After purging the inside of the reactor with nitrogen, the mixture was heated to 75 ° C. and polyisoprene was completely dissolved in cyclohexane with stirring. Thereafter, 2.19 parts by mass of p-toluenesulfonic acid dehydrated in toluene so as to have a water content of 150 ppm or less was added, and a cyclization reaction was performed at 80 ° C. or less. After reacting for 7 hours, 25% sodium carbonate aqueous solution containing 0.84 parts by mass of sodium carbonate was added to stop the reaction. After removing water by azeotropic reflux dehydration at 80 ° C., the catalyst residue in the reaction system was removed with a glass fiber filter having a pore size of 2 μm.

  After adding an antioxidant (Irganox 1076: manufactured by Ciba Specialty Chemicals) in an amount corresponding to 100 ppm to the polymer cyclized product, A part of cyclohexane was distilled off and further toluene was removed by vacuum drying to obtain a solid conjugated diene polymer cyclized product (B3). These were evaluated in the same manner as in Production Example 1. The evaluation results are shown in Table 1.

(Production Example 4)
10 parts by mass of xylene and 10 parts by mass of maleic anhydride were added to the polymer cyclized product obtained in Production Example 1, and an addition reaction was performed at 160 ° C. for 4 hours in a nitrogen atmosphere. The reaction was performed at a bath temperature of 180 ° C. for 1 hour while distilling off xylene in the reaction solution. After cooling to 120 ° C., a phenolic antioxidant (Irganox 1010: manufactured by Ciba Specialty Chemicals) in an amount corresponding to 300 ppm was added to the polymer cyclized product, followed by stirring for 30 minutes. Furthermore, vacuum drying was performed to remove xylene and unreacted maleic anhydride to obtain a maleic acid-modified conjugated diene polymer cyclized product (B4). These were evaluated in the same manner as in Production Example 1. The evaluation results are shown in Table 1. The polar group content of the maleic acid-modified conjugated diene polymer cyclized product (B4) was an introduction rate of 6.8 mol%. This is also shown in Table 1.

(Production Example 5)
To the polymer cyclized product obtained in Production Example 1, 10 parts by mass of xylene and 5.0 parts by mass of allyl glycidyl ether were added, and an addition reaction was performed at 160 ° C. for 3 hours in a nitrogen atmosphere. After reacting for 1 hour at a bath temperature of 180 ° C. while distilling off xylene in the reaction solution, the reaction solution was cooled to 120 ° C. and then an amount of phenolic antioxidant (Irganox 1010) corresponding to 300 ppm with respect to the polymer cyclized product. : Ciba Specialty Chemicals) was added, followed by stirring for 30 minutes. Furthermore, it vacuum-dried at 120 degreeC, xylene and the unreacted allyl glycidyl ether were removed, and the epoxy-modified conjugated diene polymer cyclization product (B5) was obtained. These were evaluated in the same manner as in Production Example 1. The evaluation results are shown in Table 1. The polar group content of the epoxy-modified conjugated diene polymer cyclized product (B5) was determined by NMR measurement from the proton ratio derived from the epoxy group. The results are also shown in Table 1.

(Production Example 6)
The maleic acid-modified conjugated diene polymer cyclized product (B4) obtained in Production Example 4 was dissolved in anhydrous toluene under a nitrogen atmosphere to obtain a uniform solution having a resin concentration of 20%. To this homogeneous solution was added 10 parts by mass of diethylamine and reacted at 40 ° C. for 6 hours, and then toluene was distilled off under reduced pressure. Further, the amide group-modified conjugated diene polymer cyclized product (B6) was obtained by drying under reduced pressure for 10 hours at 100 ° C. and 1.3332 × 10 ⁻⁴ (1 torr). The amide group introduction rate was determined from the result of measuring protons derived from the amide group by NMR. The results are shown in Table 1.

(Reference Production Example 1)
Compression molding of polyisoprene (73% cis-1,4 bond units, 22% trans-1,4 bond units, 5% 3,4-bond units, weight average molecular weight 174,000) at 100 ° C. in a nitrogen atmosphere Thus, a polyisoprene film having a thickness of 100 μm was prepared. This film was cut into 100 mm × 100 mm to obtain test pieces. The same evaluation as in Production Example 1 was performed. The evaluation results are shown in Table 1.

(Reference Production Example 2)
An autoclave equipped with a stirrer was charged with 8000 parts by mass of cyclohexane, 320 parts by mass of styrene, and 1.28 parts by mass of n-butyllithium (a hexane solution having a concentration of 1.56 mol / liter), and the internal temperature was raised to 60 ° C. to 30 Polymerized for minutes. The polymerization conversion of styrene was almost 100%. A part of the polymerization solution was collected, and the weight average molecular weight of the obtained polystyrene was measured and found to be 14,800. Subsequently, 1840 parts by mass of isoprene was continuously added over 60 minutes while controlling the internal temperature so as not to exceed 75 ° C. After completion of the addition, the reaction was further continued at 70 ° C. for 1 hour. The polymerization conversion rate at this point was almost 100%. A diblock composed of a polystyrene block and a polyisoprene block was added to the above polymerization solution by adding 0.362 parts by mass of a 1% aqueous solution of sodium salt of β-naphthalenesulfonic acid-formalin condensate to stop the polymerization reaction. A block copolymer a having a structure was obtained. A portion of this was sampled and the weight average molecular weight was measured to be 178,000.

  While stirring 1000 parts by mass (solid content concentration = 20.9%) of the obtained block copolymer a, the solvent was distilled off at 120 ° C. until the solid content concentration reached 80% by mass. To this, 4.41 parts by mass of maleic anhydride was added, and an addition reaction was performed at 160 ° C. for 3 hours. Thereafter, unreacted maleic anhydride and solvent were removed at 160 ° C. under reduced pressure, and after adding 0.062 parts by mass of a phenolic antioxidant (Irganox 1010: manufactured by Ciba Specialty Chemicals), Was cast in a container coated with tetrafluoroethylene resin. This was dried under reduced pressure at 75 ° C. to obtain a maleic anhydride-modified conjugated diene copolymer to which maleic anhydride was added. And evaluation similar to the manufacture example 1 was performed. The evaluation results are shown in Table 1.

<Production of oxygen and moisture absorption film>
(Production Example 7)
50 parts by mass of calcium oxide (F Lime-2000, Calfine Co., Ltd.) finely divided into 450 parts by mass of a pulverized product obtained by mechanically crushing the conjugated diene polymer cyclized product (B1) obtained in Production Example 1 Dry blended. By further blending 300 parts by mass of pellets of ethylene-vinyl alcohol copolymer (EVOH, ethylene content 44 mol%, manufactured by Kuraray Co., Ltd., trade name: E105B) with this mixture, an oxygen / water absorbing resin composition A product (M1) was obtained.

  This oxygen / water-absorbing resin composition (M1) was extruded with a lab plast mill twin screw extruder connected with a T-die and a biaxial stretching test device (both manufactured by Toyo Seiki Seisakusho Co., Ltd.), width 100 mm, thickness An oxygen / water absorption film (F1) having a thickness of 100 μm was obtained. Table 2 shows the oxygen absorption amount, oxygen absorption rate, and water absorption amount of this oxygen / water absorption film (F1).

(Production Example 8)
Instead of the conjugated diene polymer cyclized product (B1) used in Production Example 7, the conjugated diene polymer cyclized product (B2) obtained in Production Example 2 was used, and under the same conditions, an oxygen / water absorbing film (F2) Got. Table 2 shows the oxygen absorption amount, oxygen absorption rate, and water absorption amount of the oxygen / water absorption film (F2).

(Production Example 9)
The conjugated diene polymer cyclized product (B3) obtained in Production Example 3 was used in place of the conjugated diene polymer cyclized product (B1) used in Production Example 7, and the oxygen / water absorbing film (F3) was prepared under the same conditions. Obtained. Table 2 shows the oxygen absorption amount, oxygen absorption rate, and water absorption amount of this oxygen / water absorption film (F3).

(Production Example 10)
In place of the conjugated diene polymer cyclized product (B1) used in Production Example 7, the maleic acid-modified conjugated diene polymer cyclized product (B4) obtained in Production Example 4 was used, and an oxygen / water absorbing film ( F4) was obtained. Table 2 shows the oxygen absorption amount, oxygen absorption rate, and water absorption amount of this oxygen / water absorption film (F4).

(Production Example 11)
In place of the conjugated diene polymer cyclized product (B1) used in Production Example 7, the epoxy-modified conjugated diene polymer cyclized product (B5) obtained in Production Example 5 was used, and under the same conditions, an oxygen / water absorbing film (F5 ) Table 2 shows the oxygen absorption amount, oxygen absorption rate, and water absorption amount of this oxygen / water absorption film (F5).

(Production Example 12)
The amide group-modified conjugated diene polymer cyclized product (B6) obtained in Production Example 6 was used instead of the conjugated diene polymer cyclized product (B1) used in Production Example 7, and an oxygen / water absorbing film ( F6) was obtained. Table 2 shows the oxygen absorption amount, oxygen absorption rate, and water absorption amount of this oxygen / water absorption film (F6).

(Reference Production Example 3)
450 parts by mass of polyisoprene obtained in Reference Production Example 1 and 300 parts by mass of pellets of an ethylene-vinyl alcohol copolymer (EVOH, ethylene content 44 mol%, manufactured by Kuraray Co., Ltd., trade name: E105B) are dry blended. As a result, an oxygen / water-absorbing resin composition (RM1) was obtained.

  This oxygen / water-absorbing resin composition (RM1) was extruded with a lab plast mill twin screw extruder connected to a T die and a biaxial stretching test apparatus (both manufactured by Toyo Seiki Seisakusho Co., Ltd.), width 100 mm, thickness A film (RF3) having a thickness of 100 μm was obtained. Table 2 shows the oxygen absorption amount, oxygen absorption rate, and water absorption amount of this oxygen / water absorption film (RF3).

(Reference Production Example 4)
450 parts by mass of maleic anhydride-modified conjugated diene copolymer obtained in Reference Production Example 2 and pellets of ethylene-vinyl alcohol copolymer (EVOH, ethylene content 44 mol%, manufactured by Kuraray Co., Ltd., trade name: E105B) By dry blending 300 parts by mass, an oxygen / water absorbing resin composition (RM2) was obtained.

  This oxygen / water-absorbing resin composition (RM2) was extruded with a lab plast mill twin screw extruder connected with a T die and a biaxial stretching test device (both manufactured by Toyo Seiki Seisakusho Co., Ltd.), width 100 mm, thickness A film (RF4) having a thickness of 100 μm was obtained. Table 2 shows the oxygen absorption amount, oxygen absorption rate, and water absorption amount of this oxygen / water absorption film (RF4).

<Manufacture of laminates>
Example 1
The oxygen / water absorption film (F1) obtained in Production Example 7 is sandwiched between an aluminum foil (thickness: 100 μm, manufactured by Sumikari Aluminum Co., Ltd.) and a fluororesin (trade name: Teflon (registered trademark)) sheet, and then vacuumed Using a laminator, adhesion was performed so that air bubbles would not be trapped at the interface for 60 seconds under vacuum, adhesion temperature 100 ° C., adhesion pressure 0.9 Mpa, and adhesion time 300 seconds. After cooling to room temperature, the fluororesin sheet was peeled off to produce a laminate (R1) of an aluminum foil and an oxygen / water absorbing film (F1).

  The oxygen absorption amount, oxygen absorption rate, and water absorption amount of this laminate (R1) were measured. The results are shown in Table 3.

(Example 2)
A laminate (R2) was produced in the same manner as in Example 1 except that the oxygen / water absorption film (F2) was used instead of the oxygen / water absorption film (F1). The oxygen absorption amount, oxygen absorption rate, and water absorption amount of this laminate (R2) were measured. The results are shown in Table 3.

(Example 3)
A laminate (R3) was produced in the same manner as in Example 1 except that the oxygen / water absorption film (F3) was used instead of the oxygen / water absorption film (F1). The oxygen absorption amount, oxygen absorption rate, and water absorption amount of this laminate (R3) were measured. The results are shown in Table 3.

Example 4
A laminate (R4) was produced in the same manner as in Example 1, except that the oxygen / water absorption film (F4) was used instead of the oxygen / water absorption film (F1). The oxygen absorption amount, oxygen absorption rate, and water absorption amount of this laminate (R4) were measured. The results are shown in Table 3.

(Example 5)
A laminate (R5) was produced in the same manner as in Example 1 except that the oxygen / water absorption film (F5) was used instead of the oxygen / water absorption film (F1). The oxygen absorption amount, oxygen absorption rate, and water absorption amount of this laminate (R5) were measured. The results are shown in Table 3.

(Example 6)
A laminate (R6) was produced in the same manner as in Example 1 except that the oxygen / water absorption film (F6) was used instead of the oxygen / water absorption film (F1). The oxygen absorption amount, oxygen absorption rate, and water absorption amount of this laminate (R6) were measured. The results are shown in Table 3.

(Example 7)
In Example 4, a laminate (R7) was produced under the same conditions except that a copper foil (FO-WS 70 μm, Furukawa Circuit Foil) was used instead of the aluminum foil. The oxygen absorption amount, oxygen absorption rate, and water absorption amount of this laminate (R7) were measured. The results are shown in Table 3.

(Example 8)
The maleic acid-modified conjugated diene polymer cyclized product (B4) obtained in Production Example 4 was dissolved in toluene to obtain a varnish having a resin concentration of 20% by mass. This varnish was coated on a polyethylene naphthalate film (Teijin DuPont Films, Q51, film thickness 100 μm) so that the dry film thickness was 10 μm, and dried. The coating film (A1) of the resulting maleic acid-modified conjugated diene polymer cyclized product (B4) was peeled off from the polyethylene naphthalate film. Aluminum foil (thickness 100 μm, manufactured by Sumikara Aluminum Co., Ltd.) / Oil film (A1) / Oxygen / water absorption film (F1) obtained in Production Example 7 / Fluorine resin (Teflon (registered trademark)) sheet The layers were laminated using a vacuum laminator, and the layers were adhered to each other so as not to cause bubbles at the interface at 60 seconds for evacuation, 100 ° C. for adhesion, 0.9 MPa for adhesion, and 300 seconds for adhesion. After cooling to room temperature, the fluororesin sheet is peeled off to produce a laminate (R8) in which aluminum foil / the coating film (first adhesive layer) (A1) / oxygen / water absorption film (F1) are laminated in this order. did. The laminated body (R8) was measured for oxygen absorption, oxygen absorption rate, and moisture absorption. The results are listed in Table 3.

Example 9
In Example 8, the structure of the laminate to be bonded using a vacuum laminator is aluminum foil (thickness: 100 μm, manufactured by Sumi Aluminum Co., Ltd.) / The coating film (A1) / oxygen / water absorption obtained in Production Example 7. The aluminum foil / the coating film was bonded under the same conditions as in Example 8 except that the film (F1) / the coating film (A1) / the fluororesin (Teflon (registered trademark)) sheet was laminated in this order. A laminate (R9) of (first adhesive layer) (A1) / oxygen / water absorption film (F1) / coating film (second adhesive layer) (A1) was produced. The laminated body (R9) was measured for oxygen absorption, oxygen absorption rate, and moisture absorption. The results are listed in Table 3.

(Comparative Example 1)
In Example 8, instead of the oxygen / water absorption film (F1), the film (RF3) obtained in Reference Production Example 3 was used except that the aluminum foil / the coating film (adhesive resin) was bonded under the same conditions. A laminate (R10) of (layer) (A1) / film (RF3) was produced. The oxygen absorption amount, oxygen absorption rate, and water absorption amount of this laminate (R10) were measured. The results are listed in Table 3.

(Comparative Example 2)
In Example 8, instead of the oxygen / water absorption film (F1), the film (RF4) obtained in Reference Production Example 4 was used except that the aluminum foil / coating film (adhesive resin) was bonded under the same conditions. A laminate (R11) of (layer) (A1) / film (RF4) was produced. The oxygen absorption amount, oxygen absorption rate, and moisture absorption amount of this laminate (R11) were measured. The results are listed in Table 3.

<Organic EL light emitting device>
(Example 10)
ITO, which is a transparent electrode as an anode, is formed on a glass substrate (0.7 mm, manufactured by Dow Corning) so as to have a film thickness of 200 nm by DC sputtering, and N, N′-bis (3-methylphenyl) -N, N′-diphenyl- [1,1′-biphenyl] -4,4′-diamine (hereinafter abbreviated as TPD), 4,4′-bis (2 , 2′-diphenylvinyl) biphenyl (hereinafter abbreviated as DPVBi), tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ), and the thickness of the TPD layer is 60 nm and DPVBi by vacuum deposition. thickness of 40 nm, the film thickness of Alq ₃ is formed in this order so that 20 nm, the film thickness of a mixture of magnesium and silver as the cathode in Alq ₃ layer on the vacuum evaporation method 150 Formed to have a m, further an aluminum layer laminated to a film thickness of 100nm by vacuum evaporation to form a purpose deposited silica layer an element surface to prevent further short gas entry. Furthermore, an oxygen / water absorption film (F1) surface, which is a laminate (R1), is overlaid on the vapor-deposited silica layer, and bonded to the substrate surface so as not to bite the gas using a vacuum laminator. Formed. The bonding conditions were: vacuum drawing 60 seconds, bonding temperature 80 ° C., bonding time 300 seconds, and bonding pressure 0.9 MPa. Except for the vacuum laminator adhesion operation, the test was performed under conditions where oxygen and moisture were completely eliminated. An organic EL light emitting device was manufactured by fixing the outer peripheral portion of the organic EL light emitting device with a UV curable epoxy adhesive and sealing the light emitting device with a laminate (R1). When this organic EL light emitting element was turned on and it was confirmed whether or not a dark area was generated in the organic EL light emitting element, no dark area was generated even after 500 hours of continuous lighting.

(Example 11)
In Example 10, the laminate (R4) obtained in Example 4 was used instead of the laminate (R1), and the organic EL was sealed under the same conditions except that the UV curable epoxy adhesive was not used. A light emitting element was manufactured. The oxygen / water absorption film itself of the laminate (R4) had a strong adhesive force, and the outer peripheral portion did not need to be fixed with a UV curable epoxy adhesive. When this organic EL light emitting element was turned on and it was confirmed whether or not a dark area was generated in the organic EL light emitting element, no dark area was generated even after 500 hours of continuous lighting.

(Example 12)
In Example 10, the laminate (R9) obtained in Example 9 was used instead of the laminate (R1), and the organic EL was sealed under the same conditions except that the UV curable epoxy adhesive was not used. A light emitting element was manufactured. By using the maleic acid-modified conjugated diene polymer cyclized product of the second adhesive resin layer, the organic EL light-emitting device has strong sealing adhesive strength, so that the organic EL light emission can be achieved without fixing the outer periphery with a UV curable epoxy adhesive. The element was sealed. When this organic EL light emitting element was turned on and it was confirmed whether or not a dark area was generated in the organic EL light emitting element, no dark area was generated even after 500 hours of continuous lighting.
(Comparative Example 3)
In Example 10, except that the laminate (R10) was used instead of the laminate (R1), the production of the organic EL light emitting device, the sealing of the organic EL light emitting device, and the lighting of the organic EL light emitting device were performed under the same conditions. Went. During continuous lighting for 500 hours, many dark spots were visually confirmed.
(Comparative Example 4)
In Example 10, except that the laminate (R11) was used instead of the laminate (R1), the organic EL light emitting device was produced under the same conditions, the organic EL light emitting device was sealed, and the organic EL light emitting device was turned on. Went. During continuous lighting for 500 hours, many dark spots were visually confirmed.

Claims (10)

A metal thin film layer having an oxygen permeability of 0.01 cc / cm ² · day or less formed of metal;
A laminate for a light-emitting element, comprising: a resin layer containing an oxygen-absorbing resin.   The laminate for a light emitting device according to claim 1, wherein the resin layer further contains an adhesive resin having adhesiveness to the metal thin film layer.   The laminate for a light-emitting element according to claim 1, wherein the metal thin film layer is laminated on the surface of the resin layer via a first adhesive layer containing an adhesive resin.   The said resin layer has the 2nd contact bonding layer containing adhesive resin in the one surface, and the said metal thin film layer is laminated | stacked on the other surface. The laminated body for light emitting elements as described in any one of.   The oxygen-absorbing resin is a conjugated diene polymer cyclized product obtained by cyclizing a conjugated diene polymer, and the conjugated diene polymer cyclized product with respect to an unsaturated bond in the conjugated diene polymer The laminate for a light emitting device according to any one of claims 1 to 4, which is a conjugated diene polymer cyclized product having a reduction rate of an unsaturated bond present of 30% or more.   The laminate for a light-emitting element according to any one of claims 2 to 5, wherein the adhesive resin is a resin having a polar group.   The light-emitting element according to claim 6, wherein the polar group is at least one selected from the group consisting of an acid anhydride group, an acid amide group, a carboxyl group, an amino group, an epoxy group, a hydroxyl group, and an isocyanate group. Laminated body.   The laminate for a light emitting device according to any one of claims 1 to 7, wherein the resin layer further contains a moisture absorbing resin.   The moisture absorbing resin is at least one selected from the group consisting of ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, acrylic acid polymer, acrylamide resin, acetal resin, urethane resin, and cellulose resin. The laminate for a light emitting device according to claim 8.   The light emitting element formed by laminating | stacking the laminated body for light emitting elements as described in any one of the said Claims 1-9, a light emitting layer, and a transparent substrate in this order.

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