CN107715842A - Water-capturing agent and preparation method thereof, desiccant composition, sealing structure, organic EL element - Google Patents
Water-capturing agent and preparation method thereof, desiccant composition, sealing structure, organic EL element Download PDFInfo
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- CN107715842A CN107715842A CN201710610167.3A CN201710610167A CN107715842A CN 107715842 A CN107715842 A CN 107715842A CN 201710610167 A CN201710610167 A CN 201710610167A CN 107715842 A CN107715842 A CN 107715842A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- H10K50/84—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
- H10K50/842—Containers
- H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
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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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract
The present invention relates to a kind of water-capturing agent, and it contains the oxide particle of alkaline including earth metal oxide.Oxide particle is surface-treated by the carboxy-modified silicone with silicon atom and the carboxyl group being bonded on the silicon atom.
Description
Technical field
The present invention relates to water-capturing agent and preparation method thereof, desiccant composition, sealing structure and organic EL element.
Background technology
In organic EL element, inorganic oxide particle is scattered in silicone resin (silicone resin) and is used as doing
Drying prescription.But due to inorganic oxide particle is hydrophily and silicone resin is hydrophobicity, therefore inorganic oxide particle be present
The trend reduced to the dispersion stabilization of silicone resin.
Therefore, the surface treatment to inorganic oxide particle is studied.For example, patent document 1 discloses include suction
The desiccant composition of moist inorganic oxide particle and polymer adhesive.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application Publication 2015-526270 publications
The content of the invention
But the dispersion stabilization aspect for inorganic oxide particle to adhesive, still have room for improvement.
Therefore, it is a primary object of the present invention to provide the water-capturing agent to adhesive with excellent dispersion stabilization and its
Preparation method.
On the one hand, the present invention provides a kind of water-capturing agent, and it contains the oxide particle of alkaline including earth metal oxide, the oxidation
Thing particle is surface-treated by carboxy-modified silicone (carboxyl modified silicone), the carboxy-modified silicone
With silicon atom and the carboxyl group being bonded on the silicon atom.Because the surface of oxide particle is hydrophobicity, therefore this
Kind water-capturing agent is excellent to the dispersion stabilization of adhesive.
The present invention may also provide above-mentioned oxide particle as the purposes (application) of water-capturing agent or for preparing water-capturing agent
Purposes (application).
On the other hand, the present invention provides the drier containing adhesive and the above-mentioned water-capturing agent being scattered in adhesive
Composition.Above-mentioned water-capturing agent is excellent to the dispersion stabilization of adhesive, therefore the water constituent of catching of drier can be uniformly distributed.
Adhesive can contain curable resin.If oxide particle is blended in curable resin, due to oxidation
The surface of thing particle is alkalescence, therefore can hinder the curing reaction of curable resin.But by above-mentioned desiccant composition institute
The alkalescence reduction on the oxide particle surface of the water-capturing agent contained, therefore the group for being not easy the solidification for hindering curable resin can be formed
Compound (i.e. curable resin easily solidifies).
The present invention may also provide above-mentioned composition as the purposes (application) of drier or the use for preparing drier
(apply) on the way.
On the other hand, the present invention provides a kind of sealing structure, and it includes：A pair of substrates of relative configuration, by a pair of substrates
Peripheral part sealing sealant and configuration in the inner side of sealant and be configured between a pair of substrates and comprising above-mentioned dry
The desiccant layer of drying prescription composition or its solidfied material.
On the other hand, the present invention provides a kind of organic EL element, and it includes：Device substrate and device substrate are oppositely disposed
Hermetic sealing substrate, by the peripheral part of device substrate and hermetic sealing substrate sealing sealant, be arranged on sealant inner side and setting
In on device substrate and with organic layer and clamp the organic layer a pair of electrodes layered product (laminated body), with
And configuration the inner side of sealant and be configured between device substrate and hermetic sealing substrate and comprising above-mentioned desiccant composition or
The desiccant layer of its solidfied material.
Moreover, on the other hand, the present invention provides a kind of preparation method of water-capturing agent, and it includes following process：Comprising containing
The oxide particle of alkaline earth oxide and the carboxyl of carboxyl group that there is silicon atom and be bonded on the silicon atom
In the mixture of modified silicone, oxide particle is crushed.According to this preparation method, it can further reduce the flat of oxide particle
Equal particle diameter, oxide particle can be surface-treated with carboxy-modified silicone.
In above-mentioned preparation method, mixture can also include alcohol.If carrying out the pulverization process of oxide particle in alcohol,
Then the surface of oxide particle can be handled by alcohol.If this oxide particle is used as into water-capturing agent, alcohol can be discharged when catching water.Institute
The alcohol of release sometimes dissolves the organic layer for forming organic EL element.
The acidity (pKa5 or so) of carboxy-modified silicone is more than the acidity (pKa16 or so) of alcohol.Therefore, above-mentioned preparation is passed through
Even if the water-capturing agent obtained by method carries out pulverization process in alcohol, carboxy-modified silicone can also be utilized optionally to oxide
Particle is surface-treated.In addition, the alcohol on oxide particle surface is reduced, therefore its result can also reduce alcohol when catching water
Release.
According to the present invention, there is provided water-capturing agent excellent to the dispersion stabilization of adhesive and preparation method thereof.Additionally, it is provided
It is not easy to hinder the desiccant composition of the solidification of curable resin.Moreover, also provide can reduce when catching water alcohol release catch water
Agent and preparation method thereof.
Brief description of the drawings
Fig. 1 is the diagrammatic cross-section for showing the organic EL element that an embodiment is related to.
Fig. 2 is infrared absorption (FT-IR) spectrum of the water-capturing agent of embodiment 1.
Fig. 3 is the calorimetric curve of means of differential scanning calorimetry (DSC) measure of the desiccant composition of embodiment 1 and comparative example 2.
Embodiment
Hereinafter, embodiments of the present invention are described in detail.But the present invention is not limited to implementation below.
Water-capturing agent
Water-capturing agent involved by one embodiment contains the oxide particle of alkaline including earth metal oxide, the oxide particle
It is surface-treated by carboxy-modified silicone, the carboxy-modified silicone, which has silicon atom and is bonded on the silicon atom, contains carboxylic
Base group.
[oxide particle]
Oxide particle includes can assign the alkaline earth oxide for catching water-based energy to oxide particle.With oxide particle
Quality on the basis of, oxide particle generally comprises more than 80 mass % or more than 90 mass % alkaline earth oxide.
Oxide particle can include a kind of alkaline earth oxide, or the two or more alkaline earth oxides that composition is different.
As alkaline earth oxide, such as can include：Magnesia (MgO), calcium oxide (CaO), strontium oxide strontia (SrO),
Barium monoxide (BaO) etc..Alkaline earth oxide is preferably calcium oxide and/or strontium oxide strontia.
The average grain diameter of oxide particle is not particularly limited, for example, can be 50nm~500 μm, 50nm~300 μm or
50nm~100 μm.If the average grain diameter of oxide particle is within this range, there is the trend for obtaining and more fully catching water-based energy.
In this specification, the average grain diameter of oxide particle refers to, the body determined with dynamic light scattering formula Particle Size Analyzer
Integrate the median of cloth.The average grain diameter is the dispersion liquid institute prepared using oxide particle is scattered in regulation decentralized medium
The value of measure.
Oxide particle comprising calcium oxide can for example be obtained by including the method for following process successively：To quick lime
(CaO) hydroxide is carried out to handle to obtain calcium hydroxide (Ca (OH)2) process, calcium hydroxide is calcined to obtain the work of quick lime
Sequence, the process for crushing quick lime.The calcining heat of calcium hydroxide can be 300~600 DEG C.Calcination time can be 1~20 hour.
[carboxy-modified silicone]
Carboxy-modified silicone has silicon atom and the carboxyl group being bonded on the silicon atom.More specifically, carboxyl
Modified silicone has siloxanes and carboxyl group, and siloxanes includes the silicon atom and oxygen atom of alternately bonding, carboxyl group
It is bonded on the silicon atom in siloxanes.Carboxy-modified silicone is for example represented by below general formula (1).
In formula (1), R represents the alkyl that carbon number is 1~4 or the alkane for being 1~4 with carboxyl and carbon number
Base, multiple R in a molecule can be the same or different, at least one in multiple R in a molecule be with carboxyl and
Carbon number is 1~4 alkyl.N represents more than 0 integer.
Alkyl as R for example can be：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl or
Person's tert-butyl group.
The alkyl that carboxyl and carbon number are 1~4 that has as R can be that 1~3 is removed from the alkyl of above-mentioned example
Individual any hydrogen atom and derivative group.
The functional equivalent of the carboxyl of carboxy-modified silicone is not particularly limited, and can be 1000~5000g/mol.
Carboxyl in carboxy-modified silicone can may be alternatively located at side chain positioned at end (single end or double ends), from being easy to adjust
From the aspect of the viscosity of gained desiccant composition, end is preferably placed at.
Carboxy-modified silicone can be synthesized with conventional method, also can purchase commercially available product.As suitable commercially available product, such as can arrange
Enumerate X-22-3710 (trade name, Shin-Etsu Chemial Co., Ltd, single carboxy-modified silicone of tip type).These are carboxy-modified
Silicone can be used alone or can be used in combination of two or more.
In water-capturing agent involved by one embodiment, oxide particle is surface-treated by carboxy-modified silicone.Cause
This, because its surface is hydrophobicity, so to adhesive, especially comprising organic siliconresin adhesive dispersion stabilization it is excellent
It is different.Surface treatment can by make oxide particle with carboxy-modified silicone in the presence of solvent or it is solvent-free in the presence of mix or connect
Touch to carry out.As solvent, such as the alcohol that carbon number is 1~12 can be included.The tool of oxide particle after surface treatment
Though body surface texture does not determine, it is considered that：Because the carboxyl that alkaline earth oxide is alkaline, carboxy-modified silicone is acid
Property, so producing chemical interaction therebetween.Surface treatment of the carboxy-modified silicone to oxide particle can be for example, by
Infrared absorption (FT-IR) spectrum confirms.
In water-capturing agent involved by one embodiment, the alkalescence that can make oxide particle surface by surface treatment reduces.
Therefore, water-capturing agent can turn into the case where being mixed with curable resin and be not easy to hinder the water-capturing agent of the solidification of curable resin.
During using oxide particle as 100 mass parts, the content of carboxy-modified silicone in the oxide particle after surface treatment
Can be 0.01~80 mass parts.The content of carboxy-modified silicone can be more than 0.01 mass parts, more than 0.5 mass parts or 0.1
More than mass parts, or below 80 mass parts, below 60 mass parts or below 40 mass parts.
The preparation method of water-capturing agent
The preparation method of water-capturing agent involved by present embodiment includes：Including oxide particle and carboxy-modified silicone
Mixture in the process (pulverizing process) that crushes oxide particle, the oxide particle contains alkaline earth oxide, should
Carboxy-modified silicone has silicon atom and the carboxyl group being bonded on the silicon atom.According to this preparation method, one can be entered
Step reduces the average grain diameter of oxide particle, and oxide particle is surface-treated with carboxy-modified silicone.In addition, institute
Water-capturing agent be surface-treated by carboxy-modified silicone due to oxide particle, therefore result can reduce alcohol when catching water
Generation.
The average grain diameter of the oxide particle used in pulverizing process is not particularly limited, such as can be 50nm~500 μm.
The average grain diameter of oxide particle can be below more than 50nm, more than 100nm or more than 500nm, or 500 μm, 300 μm
Below or less than 100 μm.
The addition of carboxy-modified silicone is not particularly limited, can be 0.01 during using oxide particle as 100 mass parts~
80 mass parts.The addition of carboxy-modified silicone can be 0.01 mass parts more than, it is more than 0.05 mass parts or 0.1 mass parts with
On, or below 80 mass parts, below 60 mass parts or below 40 mass parts.
It is not particularly limited, such as can be included using ball mill, ball milling as the breaking method used in pulverizing process
The method that the pulverizers such as machine, jet microniser are crushed.Pulverization conditions can suitably be adjusted according to the performance of pulverizer.
The breaking method used in pulverizing process can be that dry method is alternatively wet method, but the crush efficiency of wet method is excellent, because
This preferred wet method.
In the case that breaking method used is wet method in pulverizing process, mixture can also include alcohol.By making mixing
Thing includes alcohol, can improve crush efficiency, is easily obtained the smaller oxide particle of average grain diameter.As alcohol, such as can include
Carbon number is 1~12 alcohol.Because the acidity (pKa5 or so) of carboxy-modified silicone is more than the acidity (pKa16 or so) of alcohol,
Even if therefore crushing oxide particle in alcohol, can be also surface-treated optionally through carboxy-modified silicone.
In the case that mixture includes alcohol, during using oxide particle as 100 mass parts, the addition of alcohol is preferably more than 60 mass parts.
Average grain diameter through oxide particle in the water-capturing agent obtained by pulverizing process is not particularly limited, such as can be 50nm
~5 μm.The average grain diameter of oxide particle can be below more than 50nm, more than 60nm or more than 70nm, or 5 μm, 3 μm
Below or less than 1 μm.
Desiccant composition
Desiccant composition involved by present embodiment contains adhesive and the above-mentioned implementation being scattered in adhesive
Water-capturing agent involved by mode.
[adhesive]
As long as the resin that water-capturing agent disperses can be used for adhesive, it is not particularly restricted.As adhesive,
Such as it can include：Silicone resin, polyurethane resin, epoxy resin, polyamide, polyimide resin, polyamide-acyl are sub-
The moldable resins such as polyimide resin, polyester resin, phenolic resin, melmac, curable resin etc..These adhesives can be with
It is used alone a kind of or is used in combination of two or more.
Adhesive can include silicone resin.By making adhesive include silicone resin, can obtain to above-mentioned embodiment institute
The water-capturing agent being related to has the desiccant composition of more excellent dispersion stabilization.
Adhesive can contain curable resin.Water-capturing agent involved by above-mentioned embodiment is not easy to hinder curable resin
Solidification, therefore in the case where adhesive contains curable resin, desiccant composition can be made to be not easy to hinder curable resin
Solidify (i.e. curable resin easily solidifies).
Curable resin can be curing type silicone resin.As curing type silicone resin, such as addition reaction can be included
Type silicone resin, condensed type silicone resin.Curing type silicone resin does not generate accessory substance after curing reaction, therefore is preferably
Addition reaction-type silicone resin.In addition reaction-type silicone resin, such as platinum compounds can be used as curing catalysts.
The content of adhesive is not particularly limited in desiccant composition, according to desiccant composition total amount benchmark, can be
10~75 mass %.The content of adhesive can be more than 10 mass %, more than 20 mass % or more than 30 mass %, or
Below 75 mass %, below 60 mass % or below 50 mass %.
Desiccant composition is also filled out in addition to containing water-capturing agent, adhesive containing inorganic for example without functions/drying
Material.
Desiccant composition can be pasty state at 25 DEG C.If desiccant composition is pasty state, can be easy in organic EL members
Coating or desiccant-filled composition in the small airtight space of part.Viscosity of the desiccant composition at 25 DEG C can be 10~
250Pa·s.If viscosity of the desiccant composition at 25 DEG C is within this range, may be readily coated or desiccant-filled combination
Thing.From the same viewpoint, the viscosity of desiccant composition can be more than 10Pas or more than 50Pas, can also be
Below 250Pas or below 200Pas.
Coating can be carried out by distributor etc..The viscosity of desiccant composition can be according to the content of water-capturing agent or adhesive
Viscosity is adjusted.Viscosity herein is the value using rotary viscosity design determinings such as Brookfield viscometer, rheometers.
In the case where desiccant composition contains curable resin, by solidifying desiccant composition, can obtain dry
The solidfied material of drying prescription composition.Solidification can use the common method for solidifying curable resin.The bonding of desiccant composition
Agent composition is likely to become the reason for organic layer dissolving of organic EL element.If using desiccant composition solidfied material as organic
The desiccant layer of EL element, then it can suppress oozing out for adhesive ingredients, its result can suppress the dissolving of organic EL element organic layer.
Sealing structure
Sealing structure involved by present embodiment includes a pair of substrates, peripheral part of a pair of substrates is close of relative configuration
The sealant and desiccant layer of envelope, the desiccant layer are configured on the inside of sealant between a pair of substrates, include above-mentioned reality
Apply the desiccant composition or its solidfied material involved by mode.In addition, in this manual, desiccant layer can be by will be upper
The desiccant composition filling sealing space involved by embodiment is stated (between a pair of substrates and on the inside of sealant
Space) and the desiccant layer that is formed or it is made only in a part for sealing space, assigned position on such as substrate
Desiccant layer.
Sealing structure involved by present embodiment is particularly suitable for making when the equipment on easily being influenceed by moisture seals
With.As such equipment, such as the organic electronics such as organic EL element, organic semiconductor, organic photovoltaic cell can be included and set
It is standby.
Organic EL element
Fig. 1 is the diagrammatic cross-section for the embodiment for showing organic EL element.Organic EL element 1 shown in Fig. 1 is institute
The organic EL element of meaning filling sealing structure, including：Device substrate 2, the hermetic sealing substrate 3 being oppositely disposed with device substrate 2, set
On device substrate 2 and with organic layer 4 and clamp the anode 5 of organic layer 4 and the layered product of negative electrode 6, by the and of device substrate 2
The sealant 8 of the peripheral part sealing of hermetic sealing substrate 3 and setting (filling) are in the inner side of sealant 8 and device substrate 2 and sealing
Between substrate 3, and the desiccant layer 7 comprising the desiccant composition involved by above-mentioned embodiment or its solidfied material.
In organic EL element 1, in addition to desiccant layer 7, existing known thing can be used, letter is carried out to one example below
Unitary declaration.
Device substrate 2 is made up of the rectangle glass with insulating properties and translucency, on the device substrate 2, is utilized
Transparent conductive material ITO (Indium Tin Oxide) is formed with anode 5 (electrode).The anode 5 for example may be formed：Pass through
The PVD such as vacuum vapour deposition, sputtering method (Physical Vapor Deposition) method forms ito film on device substrate 2, and
And using photoresist method etching by the patterned predetermined pattern shape of the ito film.A part as the anode 5 of electrode is drawn
It is connected to the end of device substrate 2 with drive 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
The film of material is organic layer 4.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 the side of anode 5 has been sequentially laminated hole injection layer 4a, hole transmission layer 4b, luminescent layer 4c and electronics pass
Defeated layer 4d 4 Rotating fields.Hole injection layer 4a is formed by the tens of nm of such as thickness CuPc (CuPc).Hole transmission layer 4b by
Such as the tens of nm of thickness double [N- (1- naphthyls)-N- phenyl] benzidine (bis [N- (1-naphthyl)-N-phenyl]
Benzidine) (α-NPD) formation.Luminescent layer 4c by the tens of nm of such as thickness three (8-hydroxyquinoline) aluminium (Alq3) formed.Electricity
Sub- transport layer 4d is formed by such as thickness number nm lithium fluoride (LiF).Also, by anode 5, organic layer 4 and aftermentioned negative electrode 6 successively
It is laminated the layered product formed and forms illuminating part.
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
Negative electrode 6 (electrode).As the material of metallic film, for example, can include the small metallic monomer of the work functions such as Al, Li, Mg, In or
Small alloy of the work functions such as person Al-Li, Mg-Ag etc..Negative electrode 6 for example formed as tens of nm~hundreds of nm (be preferably 50nm~
Thickness 200nm).The end that a part for negative electrode 6 leads to device substrate 2 is connected with drive 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
All portions are sealed by sealant 8.As sealant, such as uv curing resin can be used.Moreover, desiccant layer 7 is arranged on
The inner side of sealant 8 and it is arranged between device substrate 2 and hermetic sealing substrate 3.Desiccant layer 7 is included involved by above-mentioned embodiment
Desiccant composition or its solidfied material.Desiccant layer 7 is by the way that the desiccant composition involved by above-mentioned embodiment is filled
Formed in sealing space (space between substrate and on the inside of sealant).In addition, organic EL element 1 or so-called hollow
The organic EL element of sealing structure, i.e., by the inner side for being arranged on sealant 8 and be arranged on hermetic sealing substrate 3 part or all
Desiccant layer 7 form.In the case, desiccant layer 7 is formed as 1~300 μm of thickness by being coated with desiccant composition.
The manufacture method of organic EL element
First, the layered product for preparing to be laminated with the grade of machine layer 4 (electrode is not shown) on device substrate 2 and being formed.
Then, the drier involved by above-mentioned embodiment is coated with the hermetic sealing substrate 3 separately prepared using distributor
Composition, form desiccant layer 7.Moreover, using distributor to surround the side for the desiccant composition being coated on hermetic sealing substrate 3
Formula is coated with sealant 8.Carried out in the glove box that nitrogen of these operations preferably below with -76 DEG C of dew point is replaced.
Then, the device substrate 2 for being laminated with the grade of organic layer 4 is bonded with hermetic sealing substrate 3.Pass through UV irradiations and 80 DEG C or so
Heating by the base plate seals of fitting, so as to manufacture the organic EL element 1 involved by present embodiment.
Embodiment
Hereinafter, more specific description is carried out to the present invention according to embodiment.But the present invention is not limited to these implementations
Example.
(embodiment 1)
1. the preparation of water-capturing agent
By calcium oxide particle (Ube Material Industries, Ltd. system) 500g of average grain diameter 50nm~20 μm,
Carboxy-modified silicone (single carboxy-modified silicone of tip type, trade name：X-22-3710, functional equivalent：1450g/mol, SHIN-ETSU HANTOTAI
Chemical industry Co. Ltd. system) 100g, 2- propyl alcohol 1000g mixing.Using bead mill apparatus by the oxidation in gained mixed solution
Calcium particle crushes 1 hour.Solvent is distilled off from the solution after crushing, obtains the water-capturing agent 500g of embodiment 1.Embodiment 1
Water-capturing agent in calcium oxide particle average grain diameter be 1 μm.
Fig. 2 is infrared absorption (FT-IR) spectrum of the water-capturing agent of embodiment 1.The water-capturing agent of embodiment 1 is in 2950cm-1Under
Observe strong absorption.It was found from the contrast with calcium oxide particle or the FT-IR spectrum of the water-capturing agent of aftermentioned comparative example 1, the absorption
From carboxy-modified silicone.This it is meant that calcium oxide particle is surface-treated by carboxy-modified silicone.It also means that
Because the acidity of carboxy-modified silicone is more than 2- propyl alcohol, therefore selectively it is surface-treated by carboxy-modified silicone, catches water
When alcohol release reduce.
2. the preparation of desiccant composition
Addition reaction-type silicone resin (trade name is added into the water-capturing agent 500g of gained embodiment 1：KER-2500A/B,
Shin-Etsu Chemial Co., Ltd's system) 500g is as adhesive.By the way that the two is kneaded, the drying of the embodiment 1 of pasty state is obtained
Agent composition.Viscosity at 25 DEG C is 150Pas.
(comparative example 1)
In addition to without using carboxy-modified silicone, with method similarly to Example 1 obtain comparative example 1 water-capturing agent and
Desiccant composition.Speculate that calcium oxide particle is surface-treated by 2- propyl alcohol in water-capturing agent.
(comparative example 2)
In addition to replacing carboxy-modified silicone using stearic acid, comparative example 2 is obtained in method similarly to Example 1
Water-capturing agent and desiccant composition.Speculate that calcium oxide particle is surface-treated by stearic acid in water-capturing agent.
3. evaluate [dispersion stabilization experiment]
The water-capturing agent 0.1g of embodiment 1 or comparative example 2 is scattered in silicone oil (trade name：Element PDMS 10-JC、
Momentive Performance Materials.Japan LLC. systems) in 20g, place 24 hours.Visually confirm scattered steady
It is qualitative, after the water-capturing agent of acetonideexample 1 is scattered in silicone oil, compared with using the water-capturing agent of comparative example 2, have no separation property.By
This can confirm that the water-capturing agent after being surface-treated by carboxy-modified silicone is to adhesive especially to the scattered steady of silicone resin
It is qualitative excellent.
[curability experiment]
Using embodiment 1, comparative example 1, comparative example 2 desiccant composition, its curing reaction is discussed respectively.Examination
Test and carry out in the following way：1g desiccant compositions (paste) are added into 10mL sample bottles, with baking oven at 100 DEG C/1 hour
Under the conditions of heated.The desiccant composition of embodiment 1 and comparative example 2 respectively obtains solidfied material.In contrast, comparative example 1
Desiccant composition do not carry out curing reaction, do not obtain solidfied material.
[means of differential scanning calorimetry measure]
Using embodiment 1 or the desiccant composition 10mg of comparative example 2, means of differential scanning calorimetry (DSC) survey has been carried out respectively
It is fixed.Fig. 3 shows the calorimetric curve of means of differential scanning calorimetry (DSC) measure of the desiccant composition of embodiment 1 and comparative example 2.Root
According to Fig. 3, show that the desiccant composition of embodiment 1 compared with the desiccant composition of comparative example 2, generates a large amount of reaction heat.
It is meant that when addition reaction-type silicone resin solidifies, curing reaction is unimpeded for the generation of a large amount of reaction heat.Thus, confirm
The water-capturing agent for the embodiment 1 being surface-treated by carboxy-modified silicone when being mixed in curable resin is not easy to hinder
The solidification of curable resin.
- symbol description-
1- organic EL elements；2- device substrates；3- hermetic sealing substrates；4- organic layers；4a- hole injection layers；4b- hole transports
Layer；4c- luminescent layers；4d- electron transfer layers；5- anodes；6- negative electrodes；7- desiccant layers；8- sealants.
Claims (7)
1. a kind of water-capturing agent, wherein,
The water-capturing agent contains the oxide particle of alkaline including earth metal oxide,
The oxide particle is surface-treated by carboxy-modified silicone, and the carboxy-modified silicone has silicon atom and key
Close the carboxyl group on the silicon atom.
2. a kind of desiccant composition, wherein,
The desiccant composition contains adhesive and the water-capturing agent described in the claim 1 being scattered in described adhesive.
3. desiccant composition according to claim 2, wherein,
Described adhesive includes curable resin.
4. a kind of sealing structure, wherein,
The sealing structure includes：
A pair of substrates of relative configuration；
Sealant, the peripheral part of the pair of substrate is sealed；And
Desiccant layer, it is arranged on the inner side of the sealant and is arranged between the pair of substrate, and includes claim 2
Or desiccant composition or its solidfied material described in 3.
5. a kind of organic EL element, wherein,
The organic EL element includes：
Device substrate；
Hermetic sealing substrate, it is oppositely disposed with the device substrate；
Sealant, the peripheral part of the device substrate and the hermetic sealing substrate is sealed；
Layered product, it is arranged on the inner side of the sealant and is arranged on the device substrate, and there is organic layer and clamping
A pair of electrodes of the organic layer；And
Desiccant layer, it is arranged on the inner side of the sealant and is arranged between the device substrate and the hermetic sealing substrate, and
And include the desiccant composition described in Claims 2 or 3 or its solidfied material.
6. a kind of preparation method of water-capturing agent, wherein,
The preparation method of the water-capturing agent includes：In the oxide particle comprising alkaline including earth metal oxide and with silicon original
In the mixture of the carboxy-modified silicone of son and the carboxyl group being bonded on the silicon atom, the oxide particle is crushed
Process.
7. preparation method according to claim 6, wherein,
The mixture also includes alcohol.
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| JP2016-157582 | 2016-08-10 | ||
| JP2016157582A JP6806490B2 (en) | 2016-08-10 | 2016-08-10 | Water catching agent and its manufacturing method, desiccant composition, sealing structure, and organic EL element |
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| CN111048687A (en) * | 2019-11-20 | 2020-04-21 | Tcl华星光电技术有限公司 | Packaging structure and display device |
| CN115193231A (en) * | 2021-04-06 | 2022-10-18 | 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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| KR102073457B1 (en) | 2020-02-04 |
| JP6806490B2 (en) | 2021-01-06 |
| JP2018023934A (en) | 2018-02-15 |
| CN107715842B (en) | 2020-12-01 |
| TWI651126B (en) | 2019-02-21 |
| KR20180018320A (en) | 2018-02-21 |
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