CN108310932A - desiccant composition, sealing structure and organic EL element - Google Patents
desiccant composition, sealing structure and organic EL element Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/28—Selection of materials for use as drying agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/02—Sealings between relatively-stationary surfaces
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/846—Passivation; Containers; Encapsulations comprising getter material or desiccants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/80—Water
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/012—Additives improving oxygen scavenging properties
Abstract
The invention discloses a kind of desiccant compositions, contain：With high molecular weight (methyl) acyclic compound at (methyl) acrylic, 25 DEG C being liquid；And the oxide particle of the oxide comprising alkaline-earth metal.
Description
Technical field
The present invention relates to desiccant composition, sealing structure and organic EL elements.
Background technology
Organic EL element usually has the organic layer comprising luminous organic material, it is expected that preventing from being referred to as stain
(darksport) generation and its expansion of the non-light emitting portion of organic layer.The main reason for being known as stain, moisture and oxygen
Influence is very big, especially moisture, can make a big impact to the generation of stain denier.
Therefore, the various methods for preventing moisture and oxygen from immersing organic EL element are studied.Such as, it is proposed that will have
Machine layer and electrode are sealed in the gas-tight container of dry inert gas atmosphere, and drier is sealed in gas-tight container
Hollow sealing structure.For example, patent document 1 discloses：The oxide particles such as phosphorus pentoxide as drier are mixed point
It dissipates in resin and constitutes desiccant layer, and the inner surface of sealing cover (sealing cap) is provided with the desiccant layer
Organic EL element.Herein, as resin, organic silicon-type resin, epoxy system resin etc. are used.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-035659 bulletins
Invention content
But have the existing organic EL element of the desiccant layer comprising organic silicon-type resin etc. in long-term preservation,
Organic layer in organic EL element can dissolve.Consider the reason is that, organic silicon-type resin etc. from desiccant layer ooze out and will be organic
Layer dissolving.
By using curable resin as the resin for disperseing the oxide particle of drier, and cured, it can
Expect to inhibit exudation of the resin component from desiccant layer.However, being used to form the drying of the desiccant layer containing curable resin
Agent composition causes to viscosify because of the progress of undesirable curing reaction sometimes in preservation or in.Using containing solid
When the desiccant composition of the property changed resin, usually by the coating of desiccant composition and it is formed by curing desiccant layer, but in order to
Stablize coating, it is expected that the viscosity of desiccant composition is steady in a long-term in manufacturing process.
Therefore, the main purpose of one aspect of the present invention is to provide a kind of desiccant composition, drier combination
Object can form the desiccant layer for the exudation for inhibiting resin component, and viscosity has excellent long-time stability.
One aspect of the present invention provides a kind of desiccant composition, which contains：With (methyl) third
Alkenyl ((meta) acryl group), be at 25 DEG C liquid high molecular weight (methyl) acyclic compound ((meta)
acrylic compound)；And the oxide particle of the oxide comprising alkaline-earth metal.In other words, a side of the invention
Face is related to a kind of application or composition application for manufacture drier of the composition as drier, and the composition contains：
With high molecular weight (methyl) acyclic compound at (methyl) acrylic, 25 DEG C being liquid；And include alkaline-earth metal
The oxide particle of oxide.
The desiccant composition can form the desiccant layer for inhibiting resin component exudation, and can have excellent viscosity
Stability.(methyl) acyclic compound has the trend easily polymerizeing when stored if being coexisted with oxide particle, but passes through
Using high molecular weight (methyl) acyclic compound, thickening caused by this polymerization is suppressed.By using room temperature (25 DEG C)
It is high molecular weight (methyl) acyclic compound of liquid down, can makes desiccant composition that there is the mobility suitable for coating.
Viscosity of the desiccant composition at 25 DEG C is relative to putting after being placed 24 hours or 48 hours in the environment of 25 DEG C
The variation of viscosity of the desiccant composition at 25 DEG C can be within+10% before setting.By adjusting high molecular weight (methyl) third
Content, molecular weight of olefin(e) acid compound etc. can easily make desiccant composition become the less drying of this viscosity change
Agent composition.
High molecular weight (methyl) acyclic compound can be the liquid modified polybutadiene with (methyl) acryloxy
Alkene, liquid modified silicone (modified silicone) or their compositions with (methyl) acryloxy.
On the other hand, the present invention provides a kind of sealing structure, which has：A pair of of substrate for configuring in opposite directions,
Sealant, the peripheral part sealing by a pair of of substrate and desiccant layer, are the solidfied material of above-mentioned desiccant composition, and
It is arranged in the inside of sealant and between being set to a pair of of substrate.
On the other hand, the present invention also provides a kind of organic EL element, which has：Device substrate；Sealing
Substrate configures in opposite directions with device substrate；Sealant seals the peripheral part of device substrate and hermetic sealing substrate；Laminated body, setting exist
It the inside of sealant and is set on device substrate, and with organic layer and is clamped a pair of electrodes of the organic layer；And it is dry
Drying prescription layer, is the solidfied material of above-mentioned desiccant composition, and is arranged in the inside of sealant and is set on hermetic sealing substrate.
Description of the drawings
Fig. 1 is a kind of diagrammatic cross-section for the embodiment for indicating organic EL element.
Fig. 2 is the chart for indicating the relationship between the viscosity of desiccant composition and standing time.
Specific implementation mode
Hereinafter, some embodiments of the present invention are described in detail.But the present invention is not limited to following embodiment party
Formula.In this specification, " (methyl) acrylic " refers to acrylic, methylpropenyl or both acrylic and methylpropenyl.
It is also the same in other similar expression such as (methyl) acryloxy.
<Desiccant composition>
Desiccant composition involved by one embodiment of the present invention is a kind of solidification compound, the curability group
Object is closed to contain：High molecular weight (methyl) acyclic compound with (methyl) acrylic and the oxidation comprising alkaline-earth metal
The oxide particle of object.
High molecular weight (methyl) acyclic compound, which is intramolecular, has 1 or 2 or more (methyl) acrylic (typical
For (methyl) acryloxy) high molecular weight free-radical polymerised compound.From curability and the viewpoint for inhibiting ingredient to ooze out
It sets out, high molecular weight (methyl) acyclic compound can have 2 or more (methyl) acrylic, it is possible to have 2 (first
Base) acrylic.
High molecular weight (methyl) acyclic compound is liquid at 25 DEG C.In other words, high molecular weight (methyl) acrylic acid
Compound has the high molecular weight for not curing at 25 DEG C and be liquid degree.As a result, by introducing liquid and high molecular weight
(methyl) acyclic compound, can obtain viscosity has the desiccant composition of excellent long-time stability.In addition, macromolecule
Amount (methyl) acyclic compound is for inhibiting the damage of the organic EL element caused by the volatile matter from dry wood layer also to have
Profit.More specifically, the molecular weight of high molecular weight (methyl) acyclic compound may be, for example, 900 or more, 3000 or more, 4000
Above, 5000 or more, 6000 or more, 7000 or more or 8000 or more or 30000 or less, 20000 or less or
15000 or less.These molecular weight can be number-average molecular weight.
Functional equivalent's (molecular weight of each (methyl) acrylic) of high molecular weight (methyl) acyclic compound can
It is 450~15000.Thereby, it is possible to the stability for keeping liquid and being largely responsible for viscosity to improve.Go out from same viewpoint
The functional equivalent of hair, high molecular weight (methyl) acyclic compound can be 1000 or more, 1400 or more, 2000 or more, 2500
Above, 3000 or more, 3500 or more or 4000 or more or 10000 or less or 7500 or less.
High molecular weight (methyl) acyclic compound can be liquid modified polybutadiene with (methyl) acryloxy,
Liquid modified silicone with (methyl) acryloxy or combination.
Liquid modified polybutadiene is for example indicated by lower formula (I).In formula (I), R1And R2Separately indicate hydrogen atom or
Methyl, l, m and n separately indicate 1 or more integer.The sequence of each recurring unit's connection is arbitrary.
Liquid modified silicone is for example indicated by lower formula (II).In formula (II), R3And R4Separately indicate the organic of divalent
Group, R5And R6Separately indicate hydrogen atom or methyl, the integer that x is 1 or more.R3And R4It can be alkylidene.
Desiccant composition can further contain other that can be copolymerized with high molecular weight (methyl) acyclic compound
Polymerizable compound.Other polymerizable compounds can contain with 1 or 2 or more (methyl) acryloyl group, with being less than
(methyl) acyclic compound of 900 molecular weight.From the viewpoint of the effect for improving viscosity stability, relative to macromolecule
Measure the total amount of (methyl) acyclic compound and other polymerizable compounds, the content of high molecular weight (methyl) acyclic compound
Can be 80~100 mass % or 90~100 mass %.
As (methyl) acyclic compound with 1 (methyl) acryloyl group, such as can enumerate：(methyl) propylene
Acid；(methyl) acrylamide；(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl)
The just own ester of acrylic acid, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (first
Base) isodecyl acrylate, (methyl) lauryl ester ((methyl) acrylic acid n-dodecane ester), (methyl) acrylic acid 18
(methyl) alkyl acrylate that the carbon atom number of the alkyl such as alkyl ester is 1~24；(methyl) benzyl acrylate, (methyl) acrylic acid
Benzene oxygen ethyl ester etc. has (methyl) acrylate of aryl radical；(methyl) cyclohexyl acrylate, the different ice of (methyl) acrylic acid
Piece ester, (methyl) acrylic acid bicyclopentyl ester etc. have (methyl) acrylate of alicyclic group；Poly glycol monomethyl ether (first
Base) the alkylene glycol containings chain such as acrylate, poly glycol monomethyl ether (methyl) acrylate (methyl) acrylate.
As (methyl) acyclic compound with 2 or more (methyl) acryloyl groups, such as can enumerate：Two (first
Base) acrylic acid alkylidene diol ester, two (methyl) acrylic acid glycol esters, two (methyl) propylene acid propylene glycol esters, polyethylene glycol
Two (methyl) acrylate and polypropylene glycol two (methyl) acrylate.
These (methyl) acyclic compounds can be used alone or be applied in combination two or more.
Relative to the gross mass of desiccant composition, in desiccant composition high molecular weight (methyl) acyclic compound and
The total amount of other polymerizable compounds can be 30~90 mass %.If the content of polymerizable compound is within this range, have
Have the tendency that being easy to ensure superior coating and catches aqueous energy.From the same viewpoint, high molecular weight (methyl) propylene
The total amount of acid compound and other polymerizable compounds can be 30 mass % or more or 50 mass % or more or 90 mass %
Below or 70 mass % or less.
Oxide particle in desiccant composition includes the alkaline-earth metal that can be assigned oxide particle and catch aqueous energy
Oxide.On the basis of the quality of oxide particle, oxide particle generally comprise 80 mass % or more or 90 mass % with
On alkaline-earth metal oxide.Oxide particle can contain the oxygen of a kind of or different ingredient two or more alkaline-earth metal
Compound.
As the oxide of alkaline-earth metal, for example, can enumerate magnesia (MgO), calcium oxide (CaO), strontium oxide strontia (SrO),
And barium monoxide (BaO).The oxide of alkaline-earth metal can be magnesia, calcium oxide or combination thereof.
The average grain diameter of oxide particle is not particularly limited, and may be, for example, 0.01~30 μm.If oxide particle
Average grain diameter within this range, then tends to obtain and higher catches aqueous energy.From the same viewpoint, oxide particle is averaged
Grain size can be 0.1 μm or more, 0.5 μm or more or 1 μm or more or 20 μm or less, 10 μm or less or 5 μm or less.
In this specification, the average grain diameter of oxide particle refers to the volume measured with dynamic light scattering formula Particle Size Analyzer
The median of distribution.The average grain diameter is to use the dispersion being scattered in oxide particle in defined decentralized medium after adjustment
The value that liquid is measured.
The specific surface area of oxide particle can be 5~60m2/g.If specific surface area is 5~60m2/ g, then drier can have
Have and more excellent catches aqueous energy.From the same viewpoint, the specific surface area of oxide particle can be 10m2/ g or more or
15m2/ g or more or 50m2/ g or less, 40m2/ g or less or 35m2/ g or less.Specific surface area herein refer to according to
The value that BET method measures.
Oxide particle containing calcium oxide can for example obtain by the following method.That is, this method includes successively：To raw stone
Grey (CaO) carries out hydroxide and handles to obtain calcium hydroxide (Ca (OH)2) process, calcium hydroxide is sintered to obtain quick lime process,
And the process for crushing quick lime.
Oxide particle can carry out surface modification by organic acid, acid anhydrides or both of which.By to oxide grain
Son carries out surface modification, and the alkalinity on oxide particle surface reduces, and as a result, it is possible to further suppress containing high molecular weight (first
Base) acyclic compound polymerizable compound undesirable polymerisation.
By including the method for mixing oxide particle with organic acid, acid anhydrides or both of which, can utilize organic
Acid, acid anhydrides or both of which carry out surface modification to oxide particle.The surface of oxide particle is modified, such as can be from general
Fever is generated when oxide particle is mixed with organic acid, acid anhydrides or both of which to confirm.
Relative to the gross mass of desiccant composition, the content of oxide particle can be 5~70 matter in desiccant composition
Measure %.If the content of oxide particle is within this range, tends to obtain and higher catch aqueous energy.Go out from same viewpoint
Hair, the content of oxide particle can be 10 mass % or more or 30 mass % or more or 60 mass % or less or 50 matter
Measure % or less.
Desiccant composition can also further contain Photoepolymerizationinitiater initiater to effectively carry out photocuring.As photopolymerization
Initiator, such as can enumerate：1- hydroxy-cyclohexyl-phenyls ketone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls) -
1- butanone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, 2- methyl-1s [4- (first sulfydryl) phenyl] -2- morpholinoes propane -
1- ketone, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone.
In the case where desiccant composition contains Photoepolymerizationinitiater initiater, relative to polymerism chemical combination in desiccant composition
The quality (total amount of high molecular weight (methyl) acyclic compound and other polymerizable compounds) of object, Photoepolymerizationinitiater initiater contains
Amount can be such as 0.01~10 mass %.
By making composition layer solidification (especially photocuring), the dry of the solidfied material as desiccant composition can be formed
Drying prescription layer.As long as curing reaction can carry out, then the type for being used for cured light is not particularly limited, such as can be UV (purple
Outside line) light.As light source, such as the mercury lamps such as low pressure mercury lamp can be enumerated.Exposure needed for solidification is, for example, 1~10J/cm2。
Time needed for solidification is, for example, 0.5~5 minute.
Desiccant composition can be paste at 25 DEG C.If desiccant composition is paste, organic by being coated on
In the small airtight space of EL element, composition layer can be more easily formed.Viscosity of the desiccant composition at 25 DEG C can
For 5~500Pas.It, can be by being coated with more easily if viscosity of the desiccant composition at 25 DEG C is within this range
Form composition layer.From the same viewpoint, the viscosity of desiccant composition can be 10Pas or more or 50Pas or more,
It is alternatively 400Pas or less or 300Pas or less.Viscosity herein is using rotational viscometers such as Brookfield viscometer, rheometers
The value of measurement.
When desiccant composition is placed under room temperature (25 DEG C), there can be stable viscosity.Specifically, 25 DEG C of environment
Desiccant composition is viscous before viscosity of the desiccant composition at 25 DEG C is relative to placement after lower placement 24 hours or 48 hours
The variation of degree can be within+10%.The desiccant composition with high viscosity stability can be stably formed drier as a result,
Layer.By the combination of oxide particle and high molecular weight (methyl) acyclic compound, can be readily derived with this height
The desiccant composition of viscosity stability.
<Sealing structure>
The sealing structure that one embodiment of the present invention is related to has：A pair of of substrate of relative configuration, by a pair of of substrate
The sealant of peripheral part sealing, the desiccant layer that is set on the inside of sealant between a pair of of substrate.Desiccant layer can be with
Contain the drier involved by the above embodiment.Sealing space (between a pair of of substrate and can be located at by desiccant layer
Space on the inside of sealant) filling.
The sealing structure of present embodiment can be particularly suitable for using when on being easily sealed by the equipment that moisture is influenced.Make
For such equipment, such as the organic electronic devices such as organic EL element, organic semiconductor, organic photovoltaic cell can be enumerated.
<Organic EL element>
Fig. 1 is a kind of diagrammatic cross-section for the embodiment for showing organic EL element.Organic EL element 1 shown in FIG. 1 is
The organic EL element of hollow sealing structure, including：Device substrate 2；The hermetic sealing substrate 3 configured in opposite directions with device substrate 2；Setting exists
On device substrate 2 and there is organic layer 4 and the laminated body of the anode 5 and cathode 6 of the organic layer 4 is clamped；By 2 He of device substrate
The sealant 8 of the peripheral part sealing of hermetic sealing substrate 3；And it is set to the desiccant layer on hermetic sealing substrate 3 in the inside of sealant 8
7.Desiccant layer 7 can be the solidfied material of the desiccant composition of the above embodiment.Since desiccant layer 7 is above-mentioned embodiment party
The solidfied material of the composition of formula, therefore the exudation of the desiccant layer ingredient can be inhibited.It should be noted that organic EL element is simultaneously
Be not limited to hollow sealing structure shown in FIG. 1, can also be the organic EL element of such as interstitital texture, with device substrate,
Hermetic sealing substrate and the desiccant layer being filled in the airtight space surrounded by sealant.
In organic EL element 1, about the element other than desiccant layer 7, conventional structure can be used, below to one
Example is briefly described.
Device substrate 2 is made of the rectangle glass with insulating properties and translucency, on the device substrate 2, utilizes
Transparent conductive material ITO (Indium Tin Oxide) is formed with anode 5 (electrode).The anode 5 such as shape in the following manner
At：It is formed on device substrate 2 by the PVD such as vacuum vapour deposition, sputtering method (Physical Vapor Deposition) method
Ito film, and using the etching of photoresist method by the patterned predetermined pattern shape of the ito film.One of anode 5 as electrode
The end that part leads to device substrate 2 is connect with driving circuit (not shown).
For example, by PVD methods such as vacuum vapour deposition, electrical resistance heatings, contain organic light emission in the upper surface layer briquetting of anode 5
Film, that is, organic layer 4 of material.Organic layer 4 can be formed by simple layer, can also be formed by the different multilayer of function.Present embodiment
In organic layer 4 be from 5 side of anode has been sequentially laminated hole injection layer 4a, hole transmission layer 4b, luminescent layer 4c and electronics pass
The four-layer structure of defeated layer 4d.Hole injection layer 4a is formed by the CuPc (CuPc) of for example tens of nm film thickness.Hole transmission layer 4b
By bis- [N- (1- naphthalenes)-N- phenyl] benzidine (bis [N- (1-naphthyl)-N-phenyl] of for example tens of nm film thickness
Benzidine) (α-NPD) is formed.Luminescent layer 4c by for example tens of nm film thickness three (8-hydroxyquinoline) aluminium (Alq3) formed.Electricity
Sub- transport layer 4d is formed by the lithium fluoride (LiF) for for example counting nm film thickness.Moreover, successively by anode 5, organic layer 4 and aftermentioned cathode 6
Laminated body made of lamination forms illumination region.
In the upper surface of organic layer 4 (electron transfer layer 4d), metallic film is laminated with i.e. by PVD methods such as vacuum vapour depositions
Cathode 6 (electrode).As the material of metallic film, for example, can enumerate the small metallic monomer of the work functions such as Al, Li, Mg, In or
The small alloy etc. of the work functions such as person Al-Li, Mg-Ag.Cathode 6 for example formed as tens of nm~hundreds of nm (preferably 50nm~
Film thickness 200nm).The end that a part for cathode 6 leads to device substrate 2 is connect with driving circuit (not shown).
Hermetic sealing substrate 3 is configured to clip organic layer 4 and opposed with device substrate 2, device substrate 2 and hermetic sealing substrate 3 it is outer
Circumference is sealed by sealant 8.As sealant, such as uv curing resin can be used.Moreover, the setting of desiccant layer 7 exists
The inside of sealant 8 and part or all being set on hermetic sealing substrate 3.Desiccant layer 7 is by being coated with the above embodiment
Drier and formed.Desiccant layer 7 is formed as 1~300 μm of film thickness.
Organic EL element can for example manufacture by the following method.That is, this method includes：It is coated on hermetic sealing substrate 3 dry
Drying prescription composition and form desiccant composition layer；Sealant 8 is coated in a manner of surrounding desiccant composition layer；By drier
Composition layer is solidified to form desiccant layer 7；The device substrate 2 for being laminated with organic layer 4 etc. is bonded with hermetic sealing substrate 3；According to
It needs to cure sealant 8.Desiccant composition and sealant can be coated using such as distributor, coating preferably with
It is carried out in glove box after the nitrogen displacement below of -76 DEG C of dew point.The desiccant composition being coated with can contain solvent, but typical
Desiccant composition be essentially solvent-free desiccant composition.Sealant usually can by UV irradiate, heating or
Combination thereof and be cured.
[embodiment]
Hereinafter, carrying out more specific description to the present invention according to embodiment.But the present invention is not limited to these implementations
Example.
1. the preparation of desiccant composition
(embodiment 1)
By calcium oxide particle (2 μm of average grain diameter, specific surface area 18m2/ g) 100 mass parts, by the liquid representated by formula (I)
Modified polybutadiene (polybutadiene diacrylate, ProductName：BAC-45, molecular weight：About 10000, Osaka Organic Chemical Industry
Co. Ltd. system) 100 mass parts and 2,2- dimethoxy -1,2- diphenylethane -1- ketone (radical polymerization initiator, product
Name：IRGACURE651, BASF AG's system) 1 mass parts with 1000 revs/min of centrifugal mixers 5 minutes, obtain the drying of white paste
Agent composition.
(embodiment 2)
In addition to the amount of calcium oxide particle is changed to 120 mass parts, the amount of liquid modified polybutadiene is changed to 80 mass parts
In addition, white paste desiccant composition is obtained in method similarly to Example 1.
(embodiment 3)
By calcium oxide particle (2 μm of average grain diameter, specific surface area 18m2/ g) 120 mass parts, by the liquid representated by formula (II)
State modified silicone (ProductName：X-22-2445, viscosity：55mPas (25 DEG C), functional equivalent：1600g/mol, SHIN-ETSU HANTOTAI's chemistry
Industrial Co., Ltd's system) 80 mass parts and 2,2- dimethoxy -1,2- diphenylethane -1- ketone (radical polymerization initiator,
ProductName：IRGACURE651, BASF society system) 1 mass parts with 1000 revs/min of centrifugal mixers 5 minutes, obtain white paste drying
Agent composition.
(comparative example 1)
By calcium oxide particle (2 μm of average grain diameter, specific surface area 18m2/ g) 100 mass parts, polypropyleneglycol diacrylate
(ProductName：The village APG-700, Xin Zhong chemical industry Co. Ltd. system, molecular weight：808) 100 mass parts, dimethoxy -1 2,2-,
2- diphenylethane -1- ketone (radical polymerization initiator, ProductName：IRGACURE651, BASF society system) 1 mass parts with 1000 turns/
Divide centrifugal mixer 5 minutes, obtains desiccant composition.The desiccant composition of gained cures at once under room temperature environment.
(comparative example 2)
By calcium oxide particle (2 μm of average grain diameter, specific surface area 18m2/ g) 100 mass parts, polypropyleneglycol diacrylate
(ProductName：The village APG-700, Xin Zhong chemical industry Co. Ltd. system, molecular weight：808) 100 mass parts, 5 mass parts of benzoic acid,
And 2,2- dimethoxy -1,2- diphenylethane -1- ketone (radical polymerization initiator, ProductName：IRGACURE651, BASF society
System) 1 mass parts with 1000 revs/min of centrifugal mixers 5 minutes, obtain white paste desiccant composition.
2. evaluation
[viscosity stability of desiccant composition]
In the environment of each desiccant composition is statically placed in room temperature (25 DEG C), viscosity under this state at 25 DEG C is measured at any time
Between variation.In table 1, the measurement result of viscosity is shown with the relative value (%) relative to the viscosity of (0 hour) before placement.Than
Desiccant composition compared with example 1 cures after preparation in the short time, therefore can not measure viscosity.Embodiment 1 after placing 24 hours
The viscosity of~3 desiccant composition relative to the viscosity of the desiccant composition at (0 hour) moment before placement variation+
In the range of 10%.Fig. 2 is the opposite of the viscosity in the longer standing time for indicating comparative example 2, embodiment 1 and embodiment 2
The chart of relationship between value and time.In Fig. 2, the percentage on the basis of initial viscosity indicates viscosity.As shown in Fig. 2, real
The desiccant composition for applying example 1,2 maintains the few state of viscosity change in more than the long-time after 48 hours.
[table 1]
[making of organic EL element]
By sputtering method by with the transparency conductive material ITO on device substrate with the film thickness of 140nm form a film.Profit
The etching of method with photoresist is by the patterned predetermined pattern shape of ito film, to form anode.
By electrical resistance heating the upper surface of established anode by CuPc (CuPc) with the film thickness of 70nm film forming from
And form hole injection layer, by the upper surface in hole injection layer will be bis- [N- (1- naphthalenes)-N- phenyl] benzidine (α-NPD)
It is formed a film with the film thickness of 30nm to form hole transmission layer, in the upper surface of hole transmission layer by three (8-hydroxyquinoline) aluminium
(Alq3) form a film to form luminescent layer with the film thickness of 50nm.Moreover, in the upper surface of luminescent layer by lithium fluoride (LiF) with the film of 7nm
Thickness film forming forms electron transfer layer, on the surface of electron transfer layer by aluminium using the film thickness physical vapor deposition of 150nm as cathode.As above
It is described, it is formed on device substrate and has been sequentially laminated anode, organic layer (hole injection layer/hole transmission layer/luminescent layer/electronics
Transport layer) and cathode laminated body.
Then, in dew point being the glove box of -76 DEG C of nitrogen below displacements, using distributor by the drying of embodiment 1
Agent composition is coated on the central portion of hermetic sealing substrate.It is irradiated in 3 minutes after the desiccant composition of coating Examples 1 total
6J/cm2UV (ultraviolet light) cured, to form desiccant layer.
Then, device substrate is bonded with hermetic sealing substrate in such a way that laminated body, desiccant layer and sealant become inside.
In this case, the peripheral part of device substrate and hermetic sealing substrate is sealed by ultraviolet light irradiation and 80 DEG C of heating, is obtained
The organic EL element of the hollow sealing structure of desiccant layer is provided in the airtight space of sealant encirclement.
[relative to the exudation distance by the time]
Under conditions of the organic EL element of gained is placed on 25 DEG C, the exudation distance of desiccant layer ingredient is determined at any time
Between variation.Exudation distance refers to distance of the desiccant layer ingredient until the front end for the part that desiccant layer oozes out, numerical value
Mean that the exudation of desiccant layer ingredient is more more greatly.Until the exudation of drier ingredient is not observed after 500 hours yet.
According to the present invention it is possible to the desiccant layer that can be formed and inhibit the wherein exudation of ingredient is provided, and viscosity has
There is the desiccant composition of excellent long-time stability.
Symbol description-
1：Organic EL element, 2：Device substrate, 3：Hermetic sealing substrate, 4：Organic layer, 4a：Hole injection layer, 4b：Hole transport
Layer, 4c：Luminescent layer, 4d：Electron transfer layer, 5：Anode, 6：Cathode, 7：Desiccant layer, 8：Sealant.
Claims (6)
1. a kind of desiccant composition, which is characterized in that contain：
With high molecular weight (methyl) acyclic compound at acrylic or methylpropenyl, 25 DEG C being liquid；And
Include the oxide particle of the oxide of alkaline-earth metal.
2. desiccant composition according to claim 1, which is characterized in that
Viscosity of the desiccant composition at 25 DEG C is relative to the drier before placing after being placed 24 hours in the environment of 25 DEG C
The variation of viscosity of the composition at 25 DEG C is within+10%.
3. desiccant composition according to claim 1 or 2, which is characterized in that
Viscosity of the desiccant composition at 25 DEG C is relative to the drier before placing after being placed 48 hours in the environment of 25 DEG C
The variation of viscosity of the composition at 25 DEG C is within+10%.
4. desiccant composition according to any one of claim 1 to 3, which is characterized in that
High molecular weight (methyl) acyclic compound is：Liquid modified polybutadiene with (methyl) acryloxy,
Liquid modified silicone with (methyl) acryloxy or their compositions.
5. a kind of sealing structure, which is characterized in that have：
A pair of of the substrate configured in opposite directions；
Sealant seals the peripheral part of the pair of substrate；And
Desiccant layer is the solidfied material of desiccant composition according to any one of claims 1 to 4, and is arranged in institute
It states the inside of sealant and is set between the pair of substrate.
6. a kind of organic EL element, which is characterized in that have：
Device substrate；
Hermetic sealing substrate configures in opposite directions with the device substrate；
Sealant seals the peripheral part of the device substrate and the hermetic sealing substrate；
Laminated body is arranged in the inside of the sealant and is set on the device substrate, and has organic layer and clamping
A pair of electrodes of the organic layer；And
Desiccant layer is the solidfied material of desiccant composition according to any one of claims 1 to 4, and is arranged in institute
It states the inside of sealant and is set on the hermetic sealing substrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016253049A JP6649243B2 (en) | 2016-12-27 | 2016-12-27 | Desiccant composition, sealing structure, and organic EL device |
| JP2016-253049 | 2016-12-27 |
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| CN108310932A true CN108310932A (en) | 2018-07-24 |
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| Country | Link |
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| JP (1) | JP6649243B2 (en) |
| KR (1) | KR102017389B1 (en) |
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Cited By (4)
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|---|---|---|---|---|
| CN110784950A (en) * | 2018-07-30 | 2020-02-11 | 双叶电子工业株式会社 | Organic EL element and method for manufacturing the same |
| CN110783477A (en) * | 2018-07-30 | 2020-02-11 | 双叶电子工业株式会社 | Organic EL element and method for manufacturing the same |
| CN113522223A (en) * | 2020-04-15 | 2021-10-22 | 双叶电子工业株式会社 | Desiccant, sealing structure, and organic EL element |
| CN114307565A (en) * | 2020-10-09 | 2022-04-12 | 双叶电子工业株式会社 | Desiccant composition, sealing structure, organic EL device, and method for manufacturing organic EL device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7262038B2 (en) * | 2018-08-03 | 2023-04-21 | パナソニックＩｐマネジメント株式会社 | Ultraviolet curable resin composition for encapsulating organic EL element, method for manufacturing organic EL light emitting device, and organic EL light emitting device |
| JP7312153B2 (en) * | 2020-10-09 | 2023-07-20 | 双葉電子工業株式会社 | Desiccant composition, sealing structure, and organic EL element |
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Also Published As
| Publication number | Publication date |
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| JP2018106961A (en) | 2018-07-05 |
| TW201827537A (en) | 2018-08-01 |
| KR20180076292A (en) | 2018-07-05 |
| KR102017389B1 (en) | 2019-09-02 |
| JP6649243B2 (en) | 2020-02-19 |
| TWI649382B (en) | 2019-02-01 |
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