WO2021124802A1 - Composition d'encre servant à former une couche d'étanchéité de dispositif électronique, procédé de formation de couche d'étanchéité de dispositif électronique et couche d'étanchéité de dispositif électronique - Google Patents

Composition d'encre servant à former une couche d'étanchéité de dispositif électronique, procédé de formation de couche d'étanchéité de dispositif électronique et couche d'étanchéité de dispositif électronique Download PDF

Info

Publication number
WO2021124802A1
WO2021124802A1 PCT/JP2020/043482 JP2020043482W WO2021124802A1 WO 2021124802 A1 WO2021124802 A1 WO 2021124802A1 JP 2020043482 W JP2020043482 W JP 2020043482W WO 2021124802 A1 WO2021124802 A1 WO 2021124802A1
Authority
WO
WIPO (PCT)
Prior art keywords
electronic device
layer
sealing layer
forming
solvent
Prior art date
Application number
PCT/JP2020/043482
Other languages
English (en)
Japanese (ja)
Inventor
昇太 広沢
千代子 竹村
Original Assignee
コニカミノルタ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to KR1020227013023A priority Critical patent/KR20220066130A/ko
Priority to CN202080086721.2A priority patent/CN114830825A/zh
Priority to JP2021565400A priority patent/JP7439837B2/ja
Publication of WO2021124802A1 publication Critical patent/WO2021124802A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0082—Digital printing on bodies of particular shapes
    • B41M5/0088—Digital printing on bodies of particular shapes by ink-jet printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/291—Oxides or nitrides or carbides, e.g. ceramics, glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources

Definitions

  • the present invention relates to an ink composition for forming an electronic device encapsulating layer, an electronic device encapsulating layer forming method, and an electronic device encapsulating layer, and particularly excellent in encapsulation performance and bending resistance and suppresses deterioration of the electronic device.
  • the present invention relates to an ink composition for forming an electronic device encapsulating layer and the like.
  • organic electroluminescence devices are organic EL elements in order to prevent the organic materials and electrodes used from being deteriorated by moisture. It has been proposed to cover the surface of the OLED with a sealing layer.
  • polysilazane is used as the second protective film.
  • the interfacial adhesion between the first protective film and the second protective film deteriorates under high temperature and high humidity of 85 ° C. and 85% RH of 100 hours or more.
  • Patent Document 2 a composition for forming a silica film containing a silicon-containing polymer and a mixed solvent containing at least two kinds of solvents, and the mixed solvent has a surface tension of 5 to 35 nN / m at 25 ° C.
  • Patent Document 3 in a coating liquid containing polysilazane, oxygen atoms are introduced into the polysilazane and a part of the polysilazane, and the atomic composition ratio (O) of the oxygen (O) atom to the silicon (Si) atom is (O).
  • a coating liquid containing polysilazane oxide in which / Si) is in the range of 0.01 to 0.1 is disclosed.
  • the present invention has been made in view of the above problems and situations, and the problem to be solved is an ink for forming an electronic device sealing layer, which is excellent in sealing performance and bending resistance and can suppress deterioration of an electronic device.
  • the present invention provides a composition, a method for forming an electronic device sealing layer, and an electronic device sealing layer.
  • the present inventor contains polysilazane, a high-drying solvent A and a low-drying solvent B, and the mole fraction of each solvent in the process of examining the cause of the above problem.
  • an ink composition in which the sum of the products of the vapor pressures of each solvent is defined in a specific range for forming a sealing layer, it is possible to have excellent sealing performance and bending resistance and suppress deterioration of electronic devices. I found it and came up with the present invention. That is, the above-mentioned problem according to the present invention is solved by the following means.
  • An ink composition for forming an electronic device encapsulating layer Contains polysilazane, The ink composition contains at least one kind of a high drying solvent A having a vapor pressure of 8.0 ⁇ 10 2 Pa or more and a low drying solvent B having a vapor pressure of 4.0 ⁇ 10 2 Pa or less at 20 ° C. Contains more The mole fraction of the highly dry solvent A with respect to the total amount of the solvent is m a1 , m a2 , ..., And the mole fraction of the low dry solvent B is m b1 , m b2 , .... When the vapor pressures are P a1 , P a2 , ...
  • the process of forming the first sealing layer on the electronic device by the vapor phase method A method for forming an electronic device encapsulation layer, comprising a step of forming a second encapsulation layer by applying an ink composition for forming the electronic device encapsulation layer on the first encapsulation layer.
  • An electronic device sealing layer that seals an electronic device.
  • a first sealing layer containing silicon nitride, silicon oxide or silicon oxynitride, Defect areas mixed in the first sealing layer and A second sealing layer provided adjacent to the first sealing layer and containing polysilazane,
  • An electronic device sealing layer having a polysilazane region provided in a gap between the defect region and the first sealing layer and filled with polysilazane.
  • Item 2 The electronic device encapsulating layer according to Item 7, wherein the gap between the gaps is 15 nm or less when the cross section is observed using an electron microscope.
  • an ink composition for forming an electronic device sealing layer, an electronic device sealing layer forming method, and an electronic device sealing which are excellent in sealing performance and bending resistance and can suppress deterioration of an electronic device.
  • Layers can be provided.
  • the mechanism of expression or mechanism of action of the effect of the present invention has not been clarified, it is inferred as follows.
  • An ink composition containing polysilazane, a high-drying solvent A and a low-drying solvent B, and in which the sum of the mole fraction of each solvent and the product of the vapor pressure of each solvent is defined in a specific range is applied to the sealing layer.
  • the high-drying solvent A When used for formation, there is a difference in the drying rate between the high-drying solvent A and the low-drying solvent B in the process of drying the solvent. Due to the difference in drying rate between the high-drying solvent A and the low-drying solvent B, the high-drying solvent A is pinned by being dried first, and the lower layer (first sealing layer) formed by the vapor phase method is formed. It is presumed that it contributes to the stable adhesion of the solvent. Further, it is presumed that the interface becomes stronger due to the adhesion to the lower layer, so that the moisture diffusion at the interface is suppressed and the deterioration of the electronic device due to the moisture passing through the interface is prevented. Further, by containing the low-drying solvent B, the ink ejection property and the patterning accuracy are excellent even when the inkjet method is used.
  • the ink composition for forming an electronic device sealing layer of the present invention is an ink composition for forming an electronic device sealing layer, which contains polysilazane, and the ink composition has a vapor pressure of 8 at 20 ° C.
  • the highly dry solvent A containing at least one of the highly dry solvent A of 0.0 ⁇ 10 2 Pa or more and the low dry solvent B of 4.0 ⁇ 10 2 Pa or less each contain the above-mentioned highly dry solvent A with respect to the total amount of the solvent.
  • the mole fraction is ma1 , ma2 , ...
  • the mole fraction of the low-drying solvent B is m b1 , m b2 , ...
  • the vapor pressure of the high-drying solvent A is P a1 , P a2 , ...
  • the P total represented by the following formula (i) is 0.5 ⁇ 10 2 to 3.6 ⁇ 10 2 Pa. Is within the range of.
  • the highly dry solvent A is dibutyl ether from the viewpoint of solubility of polysilazane, and it is appropriate that the low dry solvent B is decalin. It is preferable in that dischargeability and patterning property can be obtained.
  • the method for forming an electronic device sealing layer of the present invention is a method for forming a sealing layer using the ink composition for forming the electronic device sealing layer, and the first sealing is performed on the electronic device by the vapor phase method. It includes a step of forming a stop layer and a step of forming a second sealing layer by applying the electronic device sealing layer forming ink on the first sealing layer.
  • the high-drying solvent A is pinned by being dried first due to the difference in drying speed between the high-drying solvent A and the low-drying solvent B contained in the ink composition, and is formed by the vapor phase method.
  • the adhesiveness between the first sealing layer and the second sealing layer is excellent, and the sealing performance and bending resistance are excellent. Further, since the interface is strengthened by the adhesion between the first sealing layer and the second sealing layer, the diffusion of water at the interface can be suppressed, and the deterioration of the electronic device due to the water passing through the interface can be suppressed.
  • a step of forming the third sealing layer on the second sealing layer by the vapor phase method from the viewpoint of excellent sealing performance. It is preferable to use an inkjet method for the step of forming the second sealing layer because the layer can be formed with high accuracy.
  • the electronic device encapsulation layer of the present invention has a first encapsulation layer containing silicon nitride, silicon oxide or silicon oxynitride, a defect region mixed in the first encapsulation layer, and adjacent to the first encapsulation layer. It has a second sealing layer containing polysilazane and a polysilazane region filled in a gap between the defect region and the first sealing layer.
  • the polysilazane region filled in the gap between the defect region and the first sealing layer provides excellent adhesion between the first sealing layer and the second sealing layer, and is excellent in sealing performance and bending resistance. ..
  • the interface is strengthened by the adhesion between the first sealing layer and the second sealing layer, the diffusion of water at the interface can be suppressed, and the deterioration of the electronic device due to the water passing through the interface can be suppressed.
  • the gap between the gaps is 15 nm or less when the cross section is observed using an electron microscope, because a superior effect can be obtained as compared with the conventional ink.
  • the ink composition for forming an electronic device encapsulating layer of the present invention (hereinafter, also simply referred to as an ink composition) is an ink composition for forming an electronic device encapsulating layer, which contains polysilazane and has the ink composition.
  • the product contains at least one or more of a high-drying solvent A having a vapor pressure of 8.0 ⁇ 10 2 Pa or more and a low-drying solvent B having a vapor pressure of 4.0 ⁇ 10 2 Pa or less at 20 ° C.
  • the molar proportions of the highly dry solvent A with respect to the total amount of the solvent are m a1 , ma2 , ..., And the molar proportions of the low dry solvent B are m b1 , m b2 , ...
  • the "electronic device” in the present invention refers to an element that generates, amplifies, converts, or controls an electric signal by utilizing the kinetic energy, potential energy, etc. of an electron.
  • active elements such as light emitting diode elements, organic electroluminescence elements, photoelectric conversion elements and transistors can be mentioned.
  • a passive element that performs passive work such as "resisting” and "storing” in response to an action from others, such as a resistor and a capacitor, is also included in the electronic device. Therefore, the ink composition of the present invention is used to form a sealing layer for sealing the electronic device described above.
  • the highly dry solvent A according to the present invention has a vapor pressure of 8.0 ⁇ 10 2 Pa or more at 20 ° C. and an upper limit of 2.0 ⁇ 10 4 Pa or less.
  • the vapor pressure (Pa) of the highly dry solvent A according to the present invention at 20 ° C. can be determined according to the following method. For example, a lead method based on JIS K2258-1: 2009, a triple expansion method based on JIS K2258-2: 2009, and the like can be mentioned. Further, a static method, a boiling point method, an isoteniscope, a gas flow method, and a DSC method, which are known as general methods for measuring vapor pressure, can also be applied. Furthermore, it is also possible to utilize the vapor pressure data described in publicly known documents, for example, "New Edition Solvent Pocket Book" (edited by the Church of Synthetic Organic Chemistry, Ohmsha).
  • the highly dry solvent A having a vapor pressure of 8.0 ⁇ 10 2 Pa or more is not particularly limited as long as it does not react with polysilazane, and known ones can be used as appropriate. Specific examples thereof include aromatic solvents, alcan solvents, ester solvents, ether solvents, ketone solvents, amide solvents, and other solvents.
  • xylene ethylene glycol monomethyl ether (also known as methyl cellosolve), isopentyl acetate (also known as isoamyl acetate), dibutyl ether (DBE), chlorobenzene, normal-butyl acetate, methyl-normal-butyl ketone, tetrachloroethylene (also known as:: Parkrolethylene), isobutyl acetate, methylisobutylketone, normal-propyl acetate, toluene, 1,4-dioxane, isopropyl alcohol, trimethylpentane (TMP), isopropyl acetate, trichloroethylene, 1,2-dichloroethane (also known as dichloride) Ethyl acetate), ethyl acetate, methyl ethyl ketone, carbon tetrachloride, 1,1,1-trichloroethane, normal hexane, t
  • the low-drying solvent B according to the present invention has a vapor pressure of 4.0 ⁇ 10 2 Pa or less at 20 ° C., and has a lower limit of 1.0 ⁇ 10 -1 Pa or more. In order to solve the problem of the present invention, it is necessary to be 4.0 ⁇ 10 2 Pa or less in order to obtain an appropriate drying rate, and in order to obtain a drying property for removing a solvent after coating film, 1.0 ⁇ It must be 10 -1 Pa or more.
  • a method for measuring the vapor pressure (Pa) of the low-drying solvent B at 20 ° C. the same method as the above-mentioned method for measuring the vapor pressure of the high-drying solvent A can be adopted.
  • the low-drying solvent B having a vapor pressure of 4.0 ⁇ 10 2 Pa or less is not particularly limited as long as it is a solvent that does not react with polysilazane, and a known solvent can be used as appropriate. Examples thereof include aromatic solvents, alcan solvents, ester solvents, ether solvents, ketone solvents, amide solvents, and other solvents.
  • hexadecane diethylene glycol dibutyl ether (DEGDBE), diphenyl ether, ethylene glycol, 1-methylnaphthylene, cyclohexylbenzene, 3,3,5-trimethylcyclohexanol, 4'-methylacetophenone, decamethylcyclopentasiloxane (D5), N.
  • DEGDBE diethylene glycol dibutyl ether
  • D5 decamethylcyclopentasiloxane
  • NMP -Methylpyrrolidone
  • 4-ethylanisole, tetralin, cresol butyl benzoate, diethylene glycol diacrylate, diethylene glycol diethyl ether, ethylene glycol mono-normal-butyl ether (also known as butyl cellosolve), n-butylbenzene, cyclohexyl acetate, 1 , 2-Dichlorobenzene, ethylene glycol monoethyl ether acetate (also known as cellosolve acetate), methylcyclohexanol, phenetol, sec-butylbenzene, tert-butylbenzene, decalin (also known as decahydronaphthalene), 1,3,5- Examples thereof include trimethylbenzene (mesitylene), diethylene glycol dimethyl ether, N, N-dimethylformamide, methylcyclohexanone, ethylene glycol monophenyl ether (EGMPE) and
  • the mole fraction of the high-drying solvent A is set to m a1 , m a2 , ...
  • the mole fraction of the low-drying solvent B is set to m b1 , m b2 , ... the vapor pressure of the drying solvent a and P a1, P a2, ... an, when the vapor pressure of the low drying solvent B was P b1, P b2, ... and, P total represented by the following formula (i) is, It is in the range of 0.5 ⁇ 10 2 to 3.6 ⁇ 10 2 Pa, and more preferably in the range of 1.4 ⁇ 10 2 to 3.4 ⁇ 10 2 Pa.
  • P total P a1 ⁇ ma1 + P a2 ⁇ ma2 +..., P b1 ⁇ m b1 + P b2 ⁇ m b2 +...
  • the mole fractions of the high-drying solvent A and the low-drying solvent B are not particularly limited as long as the formula (i) is satisfied, but for example, the molar fraction of the high-drying solvent A is 5.
  • the mole fraction of the low-drying solvent B is preferably in the range of 95 to 60 within the range of ⁇ 40.
  • the "polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond in its structure and is a precursor of silicon nitride, and a polymer having the structure of the following general formula (1) is preferably used. ..
  • R 1 , R 2 , and R 3 represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group, respectively.
  • perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms is particularly preferable from the viewpoint of the denseness of the obtained sealing layer.
  • the polysilazane used in the present invention preferably has a weight average molecular weight Mw of 1000 or more, more preferably 3000 or more, and particularly preferably 7000 or more. Further, it is preferable that such a high molecular weight polysilazane is contained in an amount of 50% by mass or more based on the total polysilazane. By containing the high molecular weight polysilazane, the viscosity of the ink composition can be adjusted.
  • polysilazane having an Mw of 3000 or more for example, a polysilazane having only a high molecular weight component having a weight average molecular weight Mw of 3000 or more can be obtained by referring to the method described in Japanese Patent No. 5172867.
  • the polysilazane used in the present invention those commercially available in the state of a solution dissolved in an organic solvent can be used.
  • the organic solvent is not particularly limited as long as it can dissolve polysilazane, but does not contain water and a reactive group (for example, a hydroxy group or an amine group) that easily reacts with polysilazane, and is resistant to polysilazane.
  • An inert organic solvent is preferred, and an aprotic organic solvent is more preferred.
  • an aproton solvent for example, carbonization of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, sorbesso, turpen and the like.
  • Hydrogen solvent Halogen hydrocarbon solvent such as methylene chloride and trichloroethane
  • Esters such as ethyl acetate and butyl acetate
  • Ketones such as acetone and methyl ethyl ketone
  • Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran, alicyclic ether and the like Ethers: Examples thereof include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglimes).
  • the solvent is selected according to the purpose such as the solubility of polysilazane and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more kinds. Further, the polysilazane raw solution in which polysilazane is dissolved in an organic solvent may be catalyst-free or may contain a catalyst.
  • a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N', N'- Amine catalysts such as tetramethyl-1,3-diaminopropane, N, N, N', N'-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, and Pd compounds such as propionic acid Pd. , Metal catalysts such as Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds.
  • the concentration of the catalyst to be added at this time is preferably in the range of 0.1 to 5% by mass, more preferably in the range of 0.5 to 2% by mass, based on the silicon compound.
  • concentration of the catalyst to be added at this time is preferably in the range of 0.1 to 5% by mass, more preferably in the range of 0.5 to 2% by mass, based on the silicon compound.
  • the viscosity of the ink composition of the present invention is preferably in the range of 1 to 20 mPa ⁇ s at 20 ° C. because it has an appropriate viscosity and the ejection stability by the inkjet method is good.
  • the viscosity can be measured by a commercially available rotary or vibration viscometer.
  • the ink composition of the present invention contains a volatile thickener because the viscosity of the ink composition can be adjusted.
  • a volatile thickener a liquid compound having volatileness that does not inhibit the film formation of the ink composition and having a viscosity at 20 ° C. of about 1 mPa ⁇ s or more, or a liquid compound having a viscosity of about 1 mPa ⁇ s or more when mixed, or 1 mPa ⁇ s or more by mixing.
  • Water-insoluble volatile oils and glycol ethers which are highly soluble and have low water solubility, are preferred.
  • the volatile oils include, for example, terepine, petrol, mineral spirit, ⁇ -pinene, isoparaffin, and volatile silicone oils
  • the glycol ethers include, for example, diethylene glycol dibutyl ether (DEGDBE) and tripropylene glycol dimethyl ether.
  • compounds having appropriate viscosity, volatility and water insolubility such as diethylene glycol dibutyl ether and volatile silicone oil can also be used as a diluting solvent. It is preferable in that it can be done.
  • the ink composition of the present invention can be obtained by adding a high-drying solvent A and a low-drying solvent B to a polysilazane raw solution dissolved in the above organic solvent so as to have a predetermined mole fraction.
  • the volatile thickener to the polysilazane original solution in addition to the highly dry solvent A and the low dry solvent B. It is preferable to stir during and after the addition of the high-drying solvent A, the low-drying solvent B and the volatile thickener, and further, it is preferable to heat and stir.
  • the heating temperature is preferably equal to or lower than the boiling point of the high-drying solvent A and the low-drying solvent B, and more preferably in the range of 50 to 120 ° C.
  • the heating means and the stirring means are not particularly limited, and a general method for heating and stirring the solution can be applied, but when heating, the container or the kettle containing the solution is indirectly heated. The method of heating the liquid with is preferable.
  • a method of rotating a shaft to which a stirring blade is attached by a motor a method of stirring using a stirrer and a stirrer if the amount of liquid is small, and the like can be applied.
  • a method of stirring using a stirrer and a stirrer if the amount of liquid is small, and the like can be applied.
  • the ink composition of the present invention can be a stable ink composition without bubbles when the amount of increase ( ⁇ V) of the dissolved gas amount after the elapsed time is ⁇ V ⁇ 100 ppm / day. It is preferable in that it can be done. Further, ⁇ V ⁇ 10 ppm / day is more preferable, and ⁇ V ⁇ 1 ppm / day is particularly preferable.
  • the method for measuring the amount of dissolved gas is, for example, to identify the gas by collecting the gas generated after heating, stirring or ultrasonically dispersing the ink composition, and combining GC / MS and a detector suitable for the gas to be detected. And quantification is possible.
  • ammonia gas and silane gas are the gases that are generated in the oxidation reaction of polysilazane and may be dissolved in the coating liquid, gas detector tubes and gas detectors according to the target gas are used. It is also possible to quantify the amount generated using this and estimate the total amount as the amount of dissolved gas.
  • the method for forming an electronic device encapsulating layer of the present invention is a method for forming an encapsulating layer using the above-mentioned ink composition of the present invention, and a first encapsulating layer is formed on an electronic device by a vapor phase method.
  • a step of forming a second sealing layer by applying the ink composition onto the first sealing layer is provided.
  • the first sealing layer forming step the first sealing layer is formed on the electronic device by the vapor phase method.
  • the vapor phase method includes a sputtering method (including a reactive sputtering method such as magnetron cathode sputtering, flat plate magnetron sputtering, bipolar AC flat plate magnetron sputtering, and bipolar AC rotating magnetron sputtering), and a vapor deposition method (for example, resistance heating).
  • the first sealing layer contains silicon nitride (SiN), silicon oxide (silicon monoxide, silicon dioxide, etc.) or silicon oxynitride.
  • the thickness of the first sealing layer is preferably in the range of, for example, 10 to 1000 nm, and more preferably in the range of 100 to 500 nm.
  • the second sealing layer is formed by applying the above-mentioned ink composition of the present invention on the first sealing layer. Specifically, it is preferable to further perform a drying step of applying the ink composition on the first sealing layer (coating step) and drying the obtained coating film, and after the drying step, obtain the ink composition. It may have a step of irradiating the coated film with vacuum ultraviolet rays in a nitrogen atmosphere to modify it.
  • any suitable method can be adopted as the coating method of the ink composition, for example, spin coating method, roll coating method, flow coating method, inkjet method, spray coating method, printing method, dip coating method, flow.
  • Examples include a spread film forming method, a bar coating method, and a gravure printing method.
  • the inkjet method As the inkjet method, a known method can be used.
  • the inkjet method is roughly divided into a drop-on-demand method and a continuous method, both of which can be used.
  • the drop-on-demand method includes an electric-mechanical conversion method (for example, single cavity type, double cavity type, bender type, piston type, shared mode type, shared wall type, etc.) and an electric-heat conversion method (for example, thermal).
  • an inkjet type a bubble jet (registered trademark) type, etc.)
  • an electrostatic attraction method for example, an electric field control type, a slit jet type, etc.
  • a discharge method for example, a spark jet type, etc.
  • an electric-mechanical conversion method or an electric-heat conversion method head A method of dropping droplets (for example, a coating liquid) by an inkjet method may be called an "inkjet method".
  • the ink composition When applying the ink composition, it is preferable to apply it in a nitrogen atmosphere.
  • the solvent contained in the coating film (solvent containing high drying solvent A, low drying solvent B, etc.) is dried by drying the coating film obtained by coating with the ink composition. Remove.
  • the drying step is also preferably performed in a nitrogen atmosphere.
  • the drying method shall be adopted with reference to the conventionally known paragraphs "0058" to "0064" of JP-A-2014-151571, paragraphs "0052” to "0056” of JP-A-2011-183773, and the like. Can be done.
  • the modification treatment step may include a step of irradiating the obtained coating film with vacuum ultraviolet rays in a nitrogen atmosphere after the drying step to perform the modification treatment.
  • the reforming treatment refers to a conversion reaction of polysilazane to silicon oxide or silicon nitride. Similarly, the reforming treatment is performed under a nitrogen atmosphere such as in a glove box or under reduced pressure.
  • a known method based on the conversion reaction of polysilazane can be selected.
  • a conversion reaction using plasma, ozone, or ultraviolet rays, which can be converted at a low temperature is preferable. Conventionally known methods can be used for plasma and ozone.
  • VUV vacuum ultraviolet light
  • the thickness of the second sealing layer is preferably in the range of 10 to 1000 nm, more preferably in the range of 100 to 500 nm.
  • the entire layer may be modified, but the thickness of the modified layer after modification is preferably in the range of 1 to 50 nm, and is preferably 1 to 30 nm. Within the range is more preferred.
  • the illuminance of the vacuum ultraviolet rays on the coating film surface received by the coating film is preferably in the range of 30 to 200 mW / cm 2 , and is preferably 50 to 160 mW / cm 2. It is more preferable that it is within the range of.
  • the reforming efficiency can be sufficiently improved, and when it is 200 mW / cm 2 or less, the damage occurrence rate to the coating film is extremely suppressed, and the substrate can be used. It is preferable because it can also reduce the damage of the illuminance.
  • the amount of vacuum ultraviolet irradiation energy on the coating film surface is preferably in the range of 1 to 10 J / cm 2 , and from the viewpoint of barrier properties and moist heat resistance for maintaining the desiccant function, 3 More preferably, it is in the range of about 7 J / cm 2.
  • a rare gas excimer lamp is preferably used as a light source for vacuum ultraviolet rays. Since vacuum ultraviolet light is absorbed by oxygen, the efficiency in the vacuum ultraviolet irradiation step tends to decrease. Therefore, it is preferable to irradiate vacuum ultraviolet light in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration during vacuum ultraviolet light irradiation is preferably in the range of 10 to 10000 ppm, more preferably in the range of 50 to 5000 ppm, further preferably in the range of 80 to 4500 ppm, and most preferably in the range of 100 to 1000 ppm. Is within the range of.
  • the reforming treatment can also be performed in combination with the heat treatment.
  • the heating conditions are preferably in the range of 50 to 300 ° C., more preferably in the range of 60 to 150 ° C., preferably in combination with heat treatment for 1 second to 60 minutes, more preferably 10 seconds to 10 minutes. By doing so, the dehydration condensation reaction at the time of modification can be promoted, and the modified product can be formed more efficiently.
  • Examples of the heat treatment include a method of contacting a base material with a heating element such as a heat block to heat the coating film by heat conduction, a method of heating the atmosphere with an external heater using a resistance wire or the like, and an infrared region such as an IR heater.
  • a method using the light of the above can be mentioned, but the method is not particularly limited. Further, a method capable of maintaining the smoothness of the coating film containing the silicon compound may be appropriately selected.
  • the third sealing layer is formed on the second sealing layer by the vapor phase method.
  • the vapor phase method is the same as the vapor phase method used in the first sealing layer forming step, such as a sputtering method (for example, magnetron cathode sputtering, flat plate magnetron sputtering, bipolar AC flat plate magnetron sputtering, bipolar AC rotary magnetron sputtering, etc.).
  • a sputtering method for example, magnetron cathode sputtering, flat plate magnetron sputtering, bipolar AC flat plate magnetron sputtering, bipolar AC rotary magnetron sputtering, etc.
  • vapor deposition method for example, resistance heating vapor deposition, electron beam deposition, ion beam vapor deposition, plasma-assisted vapor deposition, etc.
  • thermal CVD method catalytic chemical vapor deposition method (Cat-CVD), capacity.
  • Cat-CVD catalytic chemical vapor deposition method
  • Examples thereof include a combined plasma CVD method (CCP-CVD), an optical CVD method, a plasma CVD method (PE-CVD), an epitaxial growth method, a chemical vapor deposition method such as an atomic layer growth method, and the like. Above all, it is preferably formed by the CVD method.
  • the third sealing layer contains silicon nitride (SiN), silicon oxide (silicon monoxide, silicon dioxide, etc.) or silicon oxynitride.
  • the thickness of the third sealing layer is preferably in the range of, for example, 10 to 1000 nm, and more preferably in the range of 100 to 500 nm.
  • the second sealing layer is derived from polysilazane>
  • polysilazane as a precursor, particularly preferably perhydropolysilazane, but the final finished second sealing layer is made of polysilazane.
  • the formed layer can be demonstrated by analysis by the following method.
  • Equation (C) y 0.8-x / 3, x ⁇ 0, y ⁇ 0,
  • the original composition SiN 0.8 H w
  • all the compositions at each measurement point in the thickness direction are as described above. That would be the case (there is a few percent error).
  • the composition distribution of the Si-containing layer in the thickness direction is analyzed and indicated by SiO x N y , it is 80% or more of the thickness of the formed second sealing layer. If the composition of the measurement point is in the range of ⁇ 2% of the value of y (0.8-x / 3), it is estimated that the membrane is a sealing layer formed from perhydropolysilazane. Is possible.
  • the electronic device encapsulation layer of the present invention has a first encapsulation layer containing silicon nitride, silicon oxide or silicon oxynitride, a defect region mixed in the first encapsulation layer, and adjacent to the first encapsulation layer. It has a second sealing layer containing polysilazane and a polysilazane region provided in a gap between the defect region and the first sealing layer and filled with polysilazane.
  • the electronic device sealing layer of the present invention is formed by the method for forming an electronic device sealing layer. That is, the second sealing layer and the polysilazane region are formed by using the ink composition of the present invention described above. Further, in the electronic device encapsulation layer of the present invention, a third encapsulation layer formed by a vapor phase method may be further provided on the second encapsulation layer.
  • the first sealing layer is a layer formed on the electronic device by the vapor phase method described above. Specifically, it contains silicon nitride (SiN), silicon oxide (silicon monoxide, silicon dioxide, etc.) or silicon oxynitride.
  • Defect regions are mixed in the first sealing layer.
  • the "defect region” referred to in the present invention means a foreign substance mixed in the first sealing layer by the gas phase method when forming the first sealing layer, and a foreign substance formed by the gas phase method by the foreign substance.
  • the part where the membrane has grown abnormally Specifically, as shown in FIG. 1, the region including the foreign matter 4 and the abnormally grown portion 5 around the foreign matter 4 is referred to as a defect region 6. Further, a gap 7 is formed between the defect region 6 and the first sealing layer 2.
  • the interval P of the gap 7 is preferably 15 nm or less, preferably 10 nm or less, when the cross section is observed at a 200 k magnification (acceleration voltage 200 kV) using an electron microscope (for example, JEM-2010F manufactured by JEOL). Is more preferable.
  • the interval P of the gap 7 was measured as follows. First, a horizontal line A 1 at a position of 1/3 and a horizontal line A 2 at a position of 2/3 are drawn from the lower side of the thickness of the first sealing layer 2. Next, in the first sealing layer 2, a tangent line B 1 connecting the intersecting points of the horizontal line A 1 at the 1/3 position and the horizontal line A 2 at the 2/3 position is drawn.
  • reference numeral 1 indicates an electronic device
  • reference numeral 3 indicates a second sealing layer.
  • the gap is provided with a polysilazane region filled with polysilazane.
  • the polysilazane region is formed by applying the ink composition of the present invention containing polysilazane, a high-drying solvent A, and a low-drying solvent B on the first sealing layer (second sealing layer forming step). , The ink composition is applied to the gap to form the gap. Therefore, by drying the coating film to which the ink composition is applied, the solvent contained in the coating film (solvent containing high-drying solvent A, low-drying solvent B, etc.) is removed, and polysilazane is contained. A polysilazane region will be formed in the gap. Since the gap between the first sealing layer and the defective region is sealed by such a polysilazane region, the sealing performance is improved.
  • the second sealing layer is a layer provided adjacent to the first sealing layer and containing polysilazane.
  • the second sealing layer is formed by applying the ink composition on the first sealing layer. Therefore, the second sealing layer is a solvent contained in the coating film (high-drying solvent A and low-drying solvent) by drying the coating film coated with the ink composition, similarly to the polysilazane region. The solvent (solvent containing B and the like) is removed to form a layer containing polysilazane.
  • the third sealing layer is a layer provided adjacent to the second sealing layer and formed by the vapor phase method described above. Specifically, it contains silicon nitride (SiN), silicon oxide (silicon monoxide, silicon dioxide, etc.) or silicon oxynitride as in the first sealing layer.
  • examples of the electronic device to be sealed include an organic EL element, a liquid crystal display element (LCD), a thin film, a touch panel, an electronic paper, and a solar cell. (PV) and the like can be mentioned. From the viewpoint that the effects of the present invention can be obtained more efficiently, an organic EL element or a solar cell is preferable, and an organic EL element is particularly preferable.
  • LCD liquid crystal display element
  • PV solar cell.
  • the organic EL element adopted as the electronic device according to the present invention may be a bottom emission type, that is, one in which light is extracted from the transparent substrate side.
  • the bottom emission type is configured by laminating a transparent electrode serving as a cathode, a light emitting functional layer, and a counter electrode serving as an anode on a transparent base material in this order.
  • the organic EL element according to the present invention may be a top emission type, that is, one in which light is taken out from the transparent electrode side which is the cathode opposite to the base material.
  • the top emission type has a configuration in which a counter electrode serving as an anode is provided on the base material side, and a light emitting functional layer and a transparent electrode serving as a cathode are laminated in this order on the surface thereof.
  • the intermediate layer may be a charge generation layer or may have a multi-photon unit configuration.
  • Japanese Patent Application Laid-Open No. 2013-157634 Japanese Patent Application Laid-Open No. 2013-168552, Japanese Patent Application Laid-Open No. 2013-177361, Japanese Patent Application Laid-Open No. 2013-187211, JP-A-2013 2013-191644, 2013-191804, 2013-225678, 2013-235994, 2013-243234, 2013-243236, 2013-2013 242366, 2013-243371, 2013-245179, 2014-003249, 2014-003299, 2014-013910, 2014-017493
  • Examples thereof include the configurations described in Japanese Patent Application Laid-Open No. 2014-017494.
  • a base material (hereinafter, also referred to as a support substrate, a base, a substrate, a support, etc.) that can be used for the organic EL element, it is preferable to apply a glass or a resin film, and flexibility is required. If so, it is preferably a resin film. Further, it may be transparent or opaque. In the case of the so-called bottom emission type in which light is extracted from the base material side, the base material is preferably transparent.
  • Preferred resins include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, and cellulose acylate resin.
  • the base material is preferably made of a material having heat resistance. Specifically, a substrate having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) of 100 ° C. or more and 300 ° C. or less is used.
  • the base material meets the requirements for electronic component applications and laminated films for displays. That is, when the sealing film of the present invention is used for these applications, the base material may be exposed to a step of 150 ° C. or higher. In this case, if the coefficient of linear expansion of the base material exceeds 100 ppm / K, the substrate dimensions will not be stable when the substrate is passed through the process at the above temperature, and the blocking performance will deteriorate due to thermal expansion and contraction. Or, the problem of not being able to withstand the thermal process is likely to occur. If it is less than 15 ppm / K, the film may break like glass and the flexibility may deteriorate.
  • the Tg and the coefficient of linear expansion of the base material can be adjusted with an additive or the like. More preferable specific examples of the thermoplastic resin that can be used as a base material include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic type.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • alicyclic type alicyclic type.
  • Polyethylene for example, manufactured by Nippon Zeon Co., Ltd., Zeonoa (registered trademark) 1600: 160 ° C.), polyarylate (PAr: 210 ° C.), polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: Compound described in JP-A-2001-150584: 162 ° C.), Polyethylene (for example, manufactured by Mitsubishi Gas Chemicals Co., Ltd., Neoprim (registered trademark): 260 ° C.), Fluorene ring-modified polycarbonate (BCF-PC: JP-A.) Compound described in JP-A-2000-227603: 225 ° C.), alicyclic-modified polycarbonate (IP-PC: compound described in JP-A-2000-227603: 205 ° C.), acryloyl compound (Japanese Patent Laid-Open No. 2002-8
  • the base material is transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
  • the light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, an integrating sphere type light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.
  • the base material listed above may be an unstretched film or a stretched film.
  • the base material can be produced by a conventionally known general method. As for the method for producing these base materials, the matters described in paragraphs "0051" to "0055" of International Publication No. 2013/002026 can be appropriately adopted.
  • the surface of the base material may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, etc., and the above treatments may be combined as necessary. May be. Further, the base material may be subjected to an easy-adhesion treatment.
  • the base material may have a single layer or a laminated structure of two or more layers.
  • each base material may be of the same type or of a different type.
  • the thickness of the base material according to the present invention is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m.
  • the film base material has a gas barrier layer.
  • the gas barrier layer for the film base material may have a film of an inorganic substance, an organic substance, or a hybrid film of both of them formed on the surface of the film base material, and is measured by a method according to JIS K 7129-1992. and water vapor transmission rate is preferably (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is barrier film follows 0.01g / m 2 ⁇ 24h, more, JIS K 7126- oxygen permeability was measured in compliance with the method 1987 is, 1 ⁇ 10 -3 mL / m 2 ⁇ 24h ⁇ atm or less, the water vapor permeability is, 1 ⁇ 10 -3 g / m 2 ⁇ 24h or less high gas barrier It is preferably a sex film.
  • the material for forming the gas barrier layer may be any material having a function of suppressing infiltration of substances such as moisture and oxygen that cause deterioration of the element, and for example, silicon monoxide, silicon dioxide, silicon nitride, silicon nitride, and the like. Silicon carbide, silicon acid acid carbide and the like can be used.
  • the gas barrier layer is not particularly limited, but in the case of an inorganic gas barrier layer such as silicon monoxide, silicon dioxide, silicon nitride, silicon oxynitride, silicon carbide, silicon acid carbide, for example, the inorganic material is subjected to a sputtering method (for example).
  • Magneton cathode sputtering magneton cathode sputtering, flat plate magnetron sputtering, bipolar AC flat plate magnetron sputtering, bipolar AC rotary magnetron sputtering, etc.
  • vapor deposition method for example, resistance heating vapor deposition, electron beam deposition, ion beam deposition, plasma assisted vapor deposition, etc.
  • thermal CVD Method for example, resistance heating vapor deposition, electron beam deposition, ion beam deposition, plasma assisted vapor deposition, etc.
  • thermal CVD Method for example, resistance heating vapor deposition, electron beam deposition, ion beam deposition, plasma assisted vapor deposition, etc.
  • thermal CVD Method for example, resistance heating vapor deposition, electron beam deposition, ion beam deposition, plasma assisted vapor deposition, etc.
  • thermal CVD Method for example, resistance heating vapor deposition, electron beam deposition, ion beam deposition, plasma assisted vapor deposition, etc.
  • an inorganic gas barrier layer by applying a coating liquid containing an inorganic precursor such as polysilazane or tetraethyl orthosilicate (TEOS) on the support and then performing a modification treatment by irradiation with vacuum ultraviolet light or the like.
  • the inorganic gas barrier layer is also formed by metal plating on a resin base material, film metallization technology such as bonding a metal foil and a resin base material, and the like.
  • the inorganic gas barrier layer may include an organic layer containing an organic polymer. That is, the inorganic gas barrier layer may be a laminate of an inorganic layer containing an inorganic material and an organic layer.
  • the organic layer is, for example, coated with an organic monomer or an organic oligomer on a resin substrate to form a layer, which is subsequently polymerized using, for example, an electron beam device, a UV light source, a discharge device, or other suitable device. And, if necessary, it can be formed by cross-linking. It can also be formed, for example, by depositing an organic monomer or an organic oligomer capable of flash evaporation and radiation cross-linking, and then forming a polymer from the organic monomer or the organic oligomer. Coating efficiency can be improved by cooling the resin substrate.
  • Examples of the method for applying the organic monomer or organic oligomer include roll coating (for example, gravure roll coating) and spray coating (for example, electrostatic spray coating).
  • examples of the laminate of the inorganic layer and the organic layer include the laminate described in International Publication No. 2012/003198 and International Publication No. 2011/013341.
  • the thickness of each layer may be the same or different.
  • the thickness of the inorganic layer is preferably in the range of 3 to 1000 nm, more preferably in the range of 10 to 300 nm.
  • the thickness of the organic layer is preferably in the range of 100 nm to 100 ⁇ m, more preferably in the range of 1 to 50 ⁇ m.
  • DBE dibutyl ether
  • PHPS perhydropolysilazane
  • the weight average molecular weight (Mw) of polysilazane determined from GPC (Gel Permeation Chromatography) polystyrene conversion was 7,000.
  • the molecular weight of polysilazane was adjusted during the synthesis of polysilazane.
  • the mole fraction, vapor pressure, P total, etc. of each solvent in the obtained ink composition 1 are shown in the table below.
  • ⁇ Manufacturing of organic EL element 1-1> (1) Preparation of substrate A non-alkali glass substrate was prepared as a substrate. (2) Formation of First Electrode An Al film was formed on one surface of the glass substrate as the first electrode (metal layer) under the following conditions. The thickness of the formed first electrode was 150 nm. The thickness of the first electrode is a value measured by a contact type surface shape measuring instrument (DECTAK). The Al film was formed by using a vacuum deposition apparatus to reduce the pressure to a vacuum degree of 1 ⁇ 10 -4 Pa, and then using a tungsten resistance heating crucible.
  • DECTAK contact type surface shape measuring instrument
  • each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the following materials constituting each layer of the organic functional layer in the optimum amount for manufacturing the device.
  • a crucible for vapor deposition a crucible made of molybdenum or tungsten made of a resistance heating material was used.
  • Electron Injection Layer (Metal Affinity Layer)
  • a heating boat containing the following compound I-1 as an electron injection material is energized and heated, and the electron injection layer made of Liq is electron-transported. Formed on the layer.
  • the vapor deposition rate was set in the range of 0.01 to 0.02 nm / sec, and the thickness was set to 2 nm.
  • the electron injection layer functions as a metal affinity layer. From the above, an organic EL layer that emits white light was formed.
  • silicon nitride SiN, Vickers hardness HV900 having a thickness of 500 nm was used by a plasma CVD method. Formed.
  • Second Sealing Layer Formation of Second Sealing Layer
  • the cartridge-integrated head of the inkjet device was filled with the ink composition 1 prepared above.
  • the ink composition 1 is applied to the organic EL element formed up to the first sealing layer by an inkjet method in a nitrogen environment, and then the element is moved to a hot plate and dried at 100 ° C. for 5 minutes.
  • a second sealing layer having a thickness of 300 nm was formed.
  • silicon nitride SiN, Vickers hardness HV900 having a thickness of 500 nm was formed as a third sealing layer on the second sealing layer by a plasma CVD method, and the first -The organic EL element 1-1 for evaluation in which the third sealing layer was formed was obtained.
  • Each organic EL element 2-1 to 2-39 for evaluation is wrapped around a metal roller having a diameter of 10 mm and left in a constant temperature and humidity chamber under high temperature and high humidity (temperature 60 ° C., relative humidity 90%). Then, an accelerated deterioration test was conducted. At this time, the polyimide film is wound so as to be in contact with the metal roller. After 1500 hours, each organic EL element was taken out from the constant temperature and humidity chamber, and the state of light emission (dark spot area ratio) was confirmed by microscopic confirmation at room temperature. Ranks 3 to 5 of the following evaluation criteria were passed.
  • the organic EL device on which the sealing layer using the ink composition of the present invention is formed has higher sealing performance than the organic EL device of the comparative example, and at the time of bending. It can be seen that the adhesion between the sealing layer and the electronic device is good, and the light emitting performance is excellent.
  • the foreign matter portion is identified by SEM observation (Hitachi High-Tech S4800) on the surface, and the foreign matter portion is identified by the FIB apparatus (JEOL JIB-4000PLUS).
  • SEM observation Hagachi High-Tech S4800
  • FIB apparatus JEOL JIB-4000PLUS.
  • the polysilazane region and the second sealing layer can provide an organic EL device having excellent sealing performance and bending resistance.
  • the gaps were all 15 nm or less.
  • a void region was confirmed instead of the polysilazane region.
  • the present invention is used for an ink composition for forming an electronic device sealing layer, a method for forming an electronic device sealing layer, and an electronic device sealing layer, which are excellent in sealing performance and bending resistance and can suppress deterioration of an electronic device. can do.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Electroluminescent Light Sources (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente composition d'encre servant à former une couche d'étanchéité de dispositif électronique contient un polysilazane, et la composition d'encre contient au moins un type de chacun d'un solvant A à séchage élevé ayant une pression de vapeur à 20 °C de 8,0 × 102 Pa ou plus et d'un solvant B à faible séchage ayant une pression de vapeur à 20 °C égale ou inférieure à 4,0 × 102 Pa, Ptotale représentée par la formule (i) étant comprise dans la plage de 0,5 × 102 à 3,6 × 102 Pa, où ma1, ma2, . . . est la fraction molaire du solvant A à séchage élevé par rapport à la quantité totale de solvant, mb1, mb2, . . . est la fraction molaire du solvant B à faible séchage, Pa1, Pa2, . . . est la pression de vapeur du solvant A à séchage élevé et Pb1, Pb2, . . . est la pression de vapeur du solvant B à faible séchage. (Équation 1) Ptotale = Pa1 × ma1 + Pa2 × ma2 + . . ., Pb1 × m b1 + P b2 × mb2+ . . .
PCT/JP2020/043482 2019-12-17 2020-11-20 Composition d'encre servant à former une couche d'étanchéité de dispositif électronique, procédé de formation de couche d'étanchéité de dispositif électronique et couche d'étanchéité de dispositif électronique WO2021124802A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020227013023A KR20220066130A (ko) 2019-12-17 2020-11-20 전자 디바이스 밀봉층 형성용의 잉크 조성물, 전자 디바이스 밀봉층 형성 방법 및 전자 디바이스 밀봉층
CN202080086721.2A CN114830825A (zh) 2019-12-17 2020-11-20 电子器件密封层形成用的墨组合物、电子器件密封层形成方法及电子器件密封层
JP2021565400A JP7439837B2 (ja) 2019-12-17 2020-11-20 電子デバイス封止層形成用のインク組成物及び電子デバイス封止層形成方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-226917 2019-12-17
JP2019226917 2019-12-17

Publications (1)

Publication Number Publication Date
WO2021124802A1 true WO2021124802A1 (fr) 2021-06-24

Family

ID=76477226

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/043482 WO2021124802A1 (fr) 2019-12-17 2020-11-20 Composition d'encre servant à former une couche d'étanchéité de dispositif électronique, procédé de formation de couche d'étanchéité de dispositif électronique et couche d'étanchéité de dispositif électronique

Country Status (4)

Country Link
JP (1) JP7439837B2 (fr)
KR (1) KR20220066130A (fr)
CN (1) CN114830825A (fr)
WO (1) WO2021124802A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005056587A (ja) * 2003-08-01 2005-03-03 Toyota Industries Corp Ｅｌ装置及びその製造方法
JP2009111029A (ja) * 2007-10-26 2009-05-21 Az Electronic Materials Kk 緻密なシリカ質膜を得ることができるポリシラザン化合物含有組成物
JP2011238560A (ja) * 2010-05-13 2011-11-24 Toshiba Mobile Display Co Ltd 有機ｅｌ装置の製造方法、及び、有機ｅｌ装置の製造装置
JP2014051637A (ja) * 2012-09-10 2014-03-20 Tokyo Institute Of Technology シリカ複合材料、コーティング組成物、及びシリカ複合膜の製造方法
WO2016047362A1 (fr) * 2014-09-26 2016-03-31 富士フイルム株式会社 Materiau de revetement, procede de formation de motif, dispositif electronique et procede de fabrication associe
JP2017031040A (ja) * 2015-07-31 2017-02-09 三星エスディアイ株式会社Samsung SDI Co., Ltd. シリカ膜形成用組成物、シリカ膜の製造方法およびシリカ膜
JP2019036517A (ja) * 2017-08-18 2019-03-07 コニカミノルタ株式会社 塗布液、当該塗布液を用いたインクジェット用インク、封止膜及び封止膜の形成方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005056587A (ja) * 2003-08-01 2005-03-03 Toyota Industries Corp Ｅｌ装置及びその製造方法
JP2009111029A (ja) * 2007-10-26 2009-05-21 Az Electronic Materials Kk 緻密なシリカ質膜を得ることができるポリシラザン化合物含有組成物
JP2011238560A (ja) * 2010-05-13 2011-11-24 Toshiba Mobile Display Co Ltd 有機ｅｌ装置の製造方法、及び、有機ｅｌ装置の製造装置
JP2014051637A (ja) * 2012-09-10 2014-03-20 Tokyo Institute Of Technology シリカ複合材料、コーティング組成物、及びシリカ複合膜の製造方法
WO2016047362A1 (fr) * 2014-09-26 2016-03-31 富士フイルム株式会社 Materiau de revetement, procede de formation de motif, dispositif electronique et procede de fabrication associe
JP2017031040A (ja) * 2015-07-31 2017-02-09 三星エスディアイ株式会社Samsung SDI Co., Ltd. シリカ膜形成用組成物、シリカ膜の製造方法およびシリカ膜
JP2019036517A (ja) * 2017-08-18 2019-03-07 コニカミノルタ株式会社 塗布液、当該塗布液を用いたインクジェット用インク、封止膜及び封止膜の形成方法

Also Published As

Publication number Publication date
JP7439837B2 (ja) 2024-02-28
KR20220066130A (ko) 2022-05-23
JPWO2021124802A1 (fr) 2021-06-24
CN114830825A (zh) 2022-07-29

Similar Documents

Publication Publication Date Title
JP6056854B2 (ja) ガスバリア性フィルム、ガスバリア性フィルムの製造方法及び電子デバイス
US9646940B2 (en) Gas barrier film and electronic device
JP5803937B2 (ja) ガスバリア性フィルム、ガスバリア性フィルムの製造方法及び電子デバイス
US9362524B2 (en) Method for producing gas barrier film, gas barrier film, and electronic device
JP6504284B2 (ja) ガスバリア性フィルム、その製造方法、およびこれを用いた電子デバイス
JP5929775B2 (ja) ガスバリア性フィルムおよびその製造方法、ならびに前記ガスバリア性フィルムを含む電子デバイス
US7074501B2 (en) Coatings with low permeation of gases and vapors
JP5888329B2 (ja) ガスバリア性フィルム、ガスバリア性フィルムの製造方法、および電子デバイス
JP5862565B2 (ja) ガスバリア性フィルム、ガスバリア性フィルムの製造方法及び電子デバイス
EP2919557A1 (fr) Dispositif électronique et procédé de fabrication d'un film perméable au gaz
WO2015053405A1 (fr) Procédé pour fabriquer un film barrière contre les gaz
US20160072096A1 (en) Sealing film, method for producing same and functional element sealed by sealing film
WO2015119260A1 (fr) Polysilazane modifié, solution de revêtement contenant ledit polysilazane modifié, et film barrière contre les gaz obtenu à l'aide de ladite solution de revêtement
WO2021124802A1 (fr) Composition d'encre servant à former une couche d'étanchéité de dispositif électronique, procédé de formation de couche d'étanchéité de dispositif électronique et couche d'étanchéité de dispositif électronique
WO2016084791A1 (fr) Film d'étanchéité, élément fonctionnel et procédé de production film d'étanchéité
JP7013832B2 (ja) 塗布液、当該塗布液を用いたインクジェット用インク、封止膜及び封止膜の形成方法
WO2015133286A1 (fr) Procédé de scellement pour des éléments fonctionnels, et élément fonctionnel scellé par ledit procédé de scellement
JP2016089083A (ja) ガスバリアーフィルムの製造方法、ガスバリアーフィルム及び電子デバイス

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20902235

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20227013023

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2021565400

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20902235

Country of ref document: EP

Kind code of ref document: A1