CN106465505B

CN106465505B - The manufacturing method of seal

Info

Publication number: CN106465505B
Application number: CN201580026778.2A
Authority: CN
Inventors: 山本有希
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2014-05-23
Filing date: 2015-05-22
Publication date: 2019-09-20
Anticipated expiration: 2035-05-22
Also published as: KR20170009974A; CN106465505A; WO2015178469A1; JP6572887B2; TW201608753A; JPWO2015178469A1

Abstract

The manufacturing method of present invention offer seal, it is with sealant come the manufacturing method of the seal of the organic EL element on hermetic sealing substrate, the manufacturing method includes: laminating process, in the process, use layer of rolls press, the sealing sheet that compositions of thermosetting resin layer is formed on supporter is laminated on substrate, so that compositions of thermosetting resin layer is contacted with organic EL element；Process is smoothed, in the process, hot pressing is carried out to the sealing sheet surface of lamination to smooth；And curing process, in the process, makes the heat cure of compositions of thermosetting resin layer and form sealant.

Description

The manufacturing method of seal

Technical field

The present invention relates to the use of organic EL that sealant comes on hermetic sealing substrate (electroluminescent, Electroluminescence) the manufacturing method of the seal (especially organic EL device) of element.In addition, the present invention also relates to And the method for sealing the organic EL element on substrate.

Background technique

Organic EL element is the light-emitting component that organic substance is used in luminescent material, due to that can obtain at low voltage High brightness shines, therefore attracts attention in recent years.But organic EL element is extremely weak to the patience of moisture, luminescent material (shines Layer) go bad because of moisture, to generate following problems: shadow of the interface of brightness reduction, not luminous, electrode and luminescent layer by moisture Ring and remove or metal occur oxidation and improve resistance.Therefore, in order to by inside element with the moisture in extraneous gas every Absolutely, it such as has carried out following operation: having been formed in a manner of covering the whole surface of the luminescent layer formed on substrate and utilize resin group The sealant for closing object, is sealed organic EL element.

It as the encapsulating method of organic EL element, such as can enumerate, will be formed on the supporter with moisture resistance The sealing sheet of resin composition layer is laminated to the method on organic EL element substrate.Resin composition layer uses such as thermoplastic Property resin combination, compositions of thermosetting resin pass through heat cure after lamination using compositions of thermosetting resin And form sealant.As the method being laminated to sealing sheet in organic EL element, it is known that for example using vacuum laminator, The method (patent document 1 ~ 3 etc.) that vacuum pressed machine is laminated under vacuum conditions.

Existing technical literature

Patent document

Patent document 1: International Publication WO2010/084938

Patent document 2: International Publication WO2010/084939

Patent document 3: International Publication WO2011/016408.

Summary of the invention

Problems to be solved by the invention

By being under vacuum conditions laminated sealing sheet and organic EL element substrate, the generation in gap can be prevented. But the vacuum equipments such as vacuum laminator are needed thus, spend cost.If it is possible to pass through the lamination shape under normal pressure At the sealant for not generating gap, excellent adhesion, then the manufacturing cost of organic EL device can be reduced.In addition, will be organic Before EL element sealing, in order not to allow organic EL element to deteriorate, preferably inert gas atmosphere.In this regard, if using vacuum The vacuum equipments such as laminating machine, then be likely to occur following problems: the status releasing of inert gas atmosphere, according to the kind of organic EL element Class will receive under vacuum conditions the influence of moisture and be deteriorated.

But as described above, using laminating method under normal pressure, it sometimes appear that following problems: generating Gap, sealant reduce the adaptation of supporter.In addition, the organic EL element substrate for display is due to the substrate surface Bumps (that is, there are the convex portion of organic EL element with there is no the element recess portion difference in height), seal layer surface Flatness has the tendency that variation.The main reason for sealant of flatness difference is likely to become brightness disproportionation, uneven color.

The present invention is to be conceived to the invention completed such as above-mentioned situation, to solve the problems, such as to be to provide a kind of seal Manufacturing method, even if sealing sheet is laminated on organic EL element substrate under normal pressure and forms sealant by this method In the case of, also it is capable of forming the sealant for not generating gap, flatness and excellent adhesion.

The means used to solve the problem

Present inventor has performed further investigations, as a result, it has been found that by being used sealing with layer of rolls press (roll laminator) Sheet material is laminated on the organic EL element face of substrate, is then carried out hot pressing to the sealing sheet surface of lamination, is able to solve Problem is stated, so as to complete the present invention below.

[1] manufacturing method of seal is with sealant come the system of the seal of the organic EL element on hermetic sealing substrate Method is made, which includes:

Laminating process in the process, using layer of rolls press, will be formed with compositions of thermosetting resin layer on supporter Sealing sheet is laminated on substrate, so that compositions of thermosetting resin layer is contacted with organic EL element；

Process is smoothed, in the process, hot pressing is carried out to the sealing sheet surface of lamination to smooth；And

Curing process in the process, makes the heat cure of compositions of thermosetting resin layer and forms sealant.

[2] manufacturing method according to above-mentioned [1], wherein lamination carries out under inert gas atmosphere；

[3] manufacturing method according to above-mentioned [1] or [2], wherein lamination carries out under normal pressure.

[4] manufacturing method according to any one of above-mentioned [1] ~ [3], wherein mill speed (the ロー of layer of rolls press Le speed) it is 0.01 ~ 1.5m/ minutes；

[5] manufacturing method according to any one of above-mentioned [1] ~ [3], wherein the mill speed of layer of rolls press is 0.1 ~ 0.5m/ minutes.

[6] manufacturing method according to any one of above-mentioned [1] ~ [5], wherein draught pressure (the ロー of layer of rolls press Le pressure) it is 0 ~ 0.5MPa；

[7] manufacturing method according to any one of above-mentioned [1] ~ [5], wherein the draught pressure of layer of rolls press be 0 ~ 0.3MPa。

[8] manufacturing method according to any one of above-mentioned [1] ~ [7], wherein laminating temperature is 60 ~ 120 DEG C；

[9] manufacturing method according to any one of above-mentioned [1] ~ [7], wherein laminating temperature is 80 ~ 100 DEG C.

[10] manufacturing method according to any one of above-mentioned [1] ~ [9], wherein the pressing pressure for smoothing process is 0.01~0.5MPa；

[11] manufacturing method according to any one of above-mentioned [1] ~ [9], wherein the pressing pressure for smoothing process is 0.01~0.3MPa。

[12] manufacturing method according to any one of above-mentioned [1] ~ [11], wherein smooth the press temperature of process It is 60 ~ 120 DEG C；

[13] manufacturing method according to any one of above-mentioned [1] ~ [11], wherein smooth the press temperature of process It is 80 ~ 100 DEG C.

[14] manufacturing method according to any one of above-mentioned [1] ~ [13], wherein smooth the pressing time of process It is 20 ~ 450 seconds；

[15] manufacturing method according to any one of above-mentioned [1] ~ [13], wherein smooth the pressing time of process It is 60 ~ 300 seconds.

[16] manufacturing method according to any one of above-mentioned [1] ~ [15], wherein supporter is that can have barrier layer Plastic foil；

[17] manufacturing method according to any one of above-mentioned [1] ~ [16], wherein supporter with a thickness of 30 ~ 200 μ m；

[18] manufacturing method according to any one of above-mentioned [1] ~ [17], wherein substrate is sub- selected from glass, polyamides At least one in amine, polyethylene terephthalate, polyethylene naphthalate, polycarbonate and cyclic olefin polymer Kind；

[19] manufacturing method according to any one of above-mentioned [1] ~ [18], wherein substrate with a thickness of 0.1 ~ 1.0mm；

[20] manufacturing method according to any one of above-mentioned [1] ~ [19], wherein curing process and smoothing process It carries out simultaneously；

[21] manufacturing method according to any one of above-mentioned [1] ~ [20], wherein seal is organic EL device.

[22] by the method for the organic EL element sealing on substrate, this method comprises:

[23] method according to above-mentioned [22], wherein lamination carries out under inert gas atmosphere；

[24] method according to above-mentioned [22] or [23], wherein lamination carries out under normal pressure.

[25] method according to any one of above-mentioned [22] ~ [24], wherein the mill speed of layer of rolls press is 0.01 ~ 1.5m/ minutes；

[26] method according to any one of above-mentioned [22] ~ [24], wherein the mill speed of layer of rolls press be 0.1 ~ 0.5m/ minutes.

[27] method according to any one of above-mentioned [22] ~ [26], wherein the draught pressure of layer of rolls press be 0 ~ 0.5MPa；

[28] method according to any one of above-mentioned [22] ~ [26], wherein the draught pressure of layer of rolls press be 0 ~ 0.3MPa。

[29] method according to any one of above-mentioned [22] ~ [28], wherein laminating temperature is 60 ~ 120 DEG C；

[30] method according to any one of above-mentioned [22] ~ [28], wherein laminating temperature is 80 ~ 100 DEG C.

[31] method according to any one of above-mentioned [22] ~ [30], wherein the pressing pressure for smoothing process is 0.01~0.5MPa；

[32] method according to any one of above-mentioned [22] ~ [30], wherein the pressing pressure for smoothing process is 0.01~0.3MPa。

[33] method according to any one of above-mentioned [22] ~ [32], wherein the press temperature for smoothing process is 60 ~120℃；

[34] method according to any one of above-mentioned [22] ~ [32], wherein the press temperature for smoothing process is 80 ~100℃。

[35] method according to any one of above-mentioned [22] ~ [34], wherein the pressing time for smoothing process is 20 ~ 450 seconds；

[36] method according to any one of above-mentioned [22] ~ [34], wherein the pressing time for smoothing process is 60 ~ 300 seconds.

[37] method according to any one of above-mentioned [22] ~ [36], wherein supporter is the modeling that can have barrier layer Expect film；

[38] method according to any one of above-mentioned [22] ~ [37], wherein supporter with a thickness of 30 ~ 200 μm；

[39] method according to any one of above-mentioned [22] ~ [38], wherein substrate be selected from glass, polyimides, At least one of polyethylene terephthalate, polyethylene naphthalate, polycarbonate and cyclic olefin polymer；

[40] method according to any one of above-mentioned [22] ~ [39], wherein substrate with a thickness of 0.1 ~ 1.0mm；

[41] method according to any one of above-mentioned [22] ~ [40], wherein curing process and smoothing process are simultaneously It carries out.

The effect of invention

According to the method for the present invention, it can manufacture with gap, flatness and the high sealant of adaptation is not generated and seal The seal (especially organic EL device) of organic EL element, and due to without using vacuum laminator, cost aspect Also advantageous.In addition, according to the method for the present invention, can implement to be laminated under the few inert gas of the damage to organic EL element.

Specific embodiment

The manufacturing method of the present invention is characterized in that, the lamination (below sometimes referred to as " roll laminating ") using layer of rolls press it Afterwards, the smoothing using hot pressing is carried out.

Firstly, successively to the laminating process using roll laminating in the manufacturing method of the present invention, the smoothing using hot pressing Process is illustrated.

[roll laminating]

The manufacturing method of the present invention, by being sealed the layer with sheet material and organic EL element substrate using roll laminating Pressure, is then smoothed using hot pressing, is capable of forming and does not generate gap and the sealant of flatness and excellent adhesion. Environmental pressure when lamination is not particularly limited, from the sight advantageously manufactured in terms of cost without using vacuum laminator Point etc. sets out, and can be set under normal pressure.Herein, normal pressure refers to, is not artificially caused very using vacuum plants such as vacuum laminators The state of empty (decompression) state.

In addition, lamination preferably carries out under inert gas atmosphere.In the present invention, without using vacuum laminator in vacuum It can be laminated under the few nitrogen atmosphere of the damage to organic EL when being laminated, therefore be laminated under (decompression).As inertia Gas, such as nitrogen, argon gas, helium, neon can be enumerated etc..It is wherein preferably nitrogen.Lamination under inert gas atmosphere can It carries out under normal pressure.Environmental pressure (pressure of inert gas) when being laminated under inert gas atmosphere is preferably 911.925 ~ 1215.9hPa, more preferably 1013.25 ~ 1114.575hPa.

In order to realize good adaptation of the sealant (solidfied material of compositions of thermosetting resin layer) to supporter, roll laminating The mill speed of machine is preferably 0.01 ~ 1.5m/ minutes, more preferably 0.1 ~ 0.5m/ minutes.

In order to avoid the damage to organic EL element, the draught pressure of layer of rolls press is preferably 0 ~ 0.5MPa, more preferably 0 ~0.3MPa.Herein, draught pressure refers to the plus-pressure generated by air gun (エアシリ Application ジ), is expressed as gauge pressure (gauge Pressure) (first pressing).In addition, draught pressure is 0 to refer to that plus-pressure is 0.

In order to which thermosetting resin to be softened to, improved the tracing ability to substrate, the laminating temperature using layer of rolls press is preferably 60 ~ 120 DEG C, more preferably 80 ~ 100 DEG C.Herein, laminating temperature refers to, internal heater in roller, numerically controlled roller surface Temperature can be measured by surface contact-type K thermocouple.

Commercially available layer of rolls press can be used in roll laminating.As commercially available layer of rolls press, such as great achievement ラミネータ can be enumerated ー corporation " layer of rolls press (ロー Le ラミネーター) VA770H ", " layer of rolls press VA700 ", " layer of rolls press VAII- 700 ", eastern corporation " Mach630up " of uncle etc..The material of roller as layer of rolls press, such as stainless steel, silicon rubber can be enumerated Deng preferably silicon rubber.

[hot pressing]

In the manufacturing method of the present invention, the smooth chemical industry using hot pressing is carried out after the laminating process using roll laminating Sequence.It follows the bumps in the organic EL element face of substrate and generates fluctuating in the sealing sheet surface being laminated in laminating process.It will It is smoothed using hot pressing.It is preferable to use the plates such as metal plate (such as to use Flat pressure machine (plate プレス for hot pressing Machine) etc.) carry out.

Hot pressing can carry out in air atmosphere, can also carry out in an inert gas atmosphere.It is carried out in air atmosphere In the case where hot pressing, environmental pressure is preferably atmospheric pressure.As inert gas, for example, can enumerate nitrogen, argon gas, neon, Helium etc..Hot pressing under inert gas atmosphere can carry out under normal pressure.In the case where carrying out hot pressing in an inert gas atmosphere, Its environmental pressure (i.e. the pressure of inert gas) be preferably 911.925 ~ 1215.9hPa, more preferably 1013.25 ~ 1114.575hPa, further preferably 1013.75 ~ 1017.75hPa.

The crack caused by EL element as pressure in order to prevent, pressing pressure are preferably 0.01 ~ 0.5MPa, are more preferably 0.01~0.3MPa.Herein, pressing pressure refer to by vacuum liquid cylinder pressure or load control by pressure applied in laminate (being applied to the pressure on sealing sheet surface), can be adjusted by hot-press arrangement.

In order to ensure flatness, press temperature is preferably 60 ~ 120 DEG C, more preferably 80 ~ 100 DEG C.Herein, press temperature Refer to pressurized part (such as the plates such as metal plate) cartridge heater built in surface in hot-press arrangement, numerically controlled pressurization part The temperature for dividing surface, can be measured by surface contact-type K thermocouple.

As long as the pressing time realizes that smoothing is not particularly limited, hot pressing is being carried out using the plate such as metal plate In the case of, preferably 20 ~ 450 seconds, more preferably 60 ~ 300 seconds.

Commercially available hot-press arrangement can be used in hot pressing.As commercially available hot-press arrangement, such as モート Application corporation can be enumerated The flat-plate compresseds such as " intermittent vacuum pressurization laminating machine CVP-300 ", Beichuan essence machine corporation vacuum pressed press machine " VHI-2051 " Power machine.As the material of the plate for pressurization, such as alloy that stainless steel, iron can be enumerated etc. etc., preferably stainless steel.

[formation of sealant]

The formation (i.e. the heat cure of compositions of thermosetting resin layer) of sealant can be by the supporter of sealing sheet It carries out, can also directly be carried out with supporter after removing.Heat cure is for example using heated air circulation type baking oven, infrared heating Device, fan heater, high-frequency induction heating apparatus etc. carry out.Heat cure can carry out after hot-pressing, can also adding by hot pressing Heat carries out simultaneously with hot pressing.Solidification temperature difference according to used compositions of thermosetting resin layer and supporter, usually 80 ~ 120 DEG C, preferably 80 ~ 110 DEG C, curing time is usually 10 ~ 120 minutes, preferably 10 ~ 30 minutes.It is formed by sealing The thickness of layer is preferably 3 ~ 100 μm, more preferably 5 ~ 50 μm, further preferably 5 ~ 20 μm.

[sealing sheet]

Then, sealing sheet used in the present invention is illustrated.It is not special to sealing sheet in the present invention Limitation, it is, for example, possible to use the sealing sheets that patent document 1 ~ 3 is recorded.Hereinafter, being said to preferred sealing sheet It is bright.

Compositions of thermosetting resin preferably comprises epoxy resin and curing agent.Epoxy resin and curing agent do not limit especially It is fixed, known epoxy resin and curing agent can be used.Compositions of thermosetting resin can also contain hygroscopicity metal oxygen Compound, thermoplastic resin, inorganic filling material (except hygroscopicity metal oxide) etc..

[epoxy resin]

As long as epoxy resin average per molecule has the epoxy resin of more than two epoxy groups, then can unlimitedly make With.Such as it can enumerate: bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthols type ring Oxygen resin, naphthalene type epoxy resin, bisphenol f type epoxy resin, phosphorous epoxy resin, bisphenol-s epoxy resin, aromatic series shrink sweet Oleyl amine type epoxy resin is (for example, four glycidyl group diaminodiphenyl-methane, triglycidyl group para-aminophenol, two contractings Water glyceryl toluidines, diglycidylaniline etc.), cycloaliphatic epoxy resin, aliphatic chain epoxy resin, line style phenolic aldehyde Type epoxy resin, bisphenol-A phenolic type (novolac type) epoxy resin, has butadiene knot at Cresol formaldehyde type epoxy resin The epoxy resin of structure, the 2-glycidyl etherate of bis-phenol, the 2-glycidyl etherate of naphthalene glycol, phenols glycidol ether Alkyl substituents, halide and hydride of 2-glycidyl etherate and these epoxy resin of compound and alcohols etc..This A little epoxy resin can be used any or be use mixing two or more.

Wherein, the epoxy resin that the preferred transmitance of epoxy resin is 80% or more, the ring that more preferable transmitance is 85% or more Oxygen resin, the epoxy resin that particularly preferred transmitance is 90% or more.As this suitable epoxy resin, can enumerate: bis-phenol A type epoxy resin, bisphenol f type epoxy resin, novolac type epoxy resin, biphenyl aralkyl-type epoxy resin, aliphatic ring Oxygen resin, aliphatic chain epoxy resin etc..Herein, transmitance refers to total light transmittance, is when passing through material to investigate light The conduction degree of brightness and the considerations of measure reflection, scattering light transmittance.Incident light uses visible light, ultraviolet light, passes through use The method that integrating sphere collects penetrated light is measured.

Epoxy resin can be liquid, be also possible to solid-state, can be used liquid-state epoxy resin and solid epoxy resin this The two.Herein, " liquid " and " solid-state " refers to the state of the epoxy resin under room temperature (25 DEG C).From coating, processability, bonding From the perspective of property, it is preferable to use at least 10 mass % of whole epoxy resin the above are liquid.

In addition, the epoxide equivalent of epoxy resin is preferably 100 ~ 1000g/eq, more preferably from the viewpoint of reactivity 120 ~ 1000g/eq, further preferably 150 ~ 1000g/eq.Herein, epoxide equivalent refers to, the tree containing 1 gram equivalent of epoxy group The grams (g/eq) of rouge, is measured according to method specified in Japanese Industrial Standards JIS K7236.In addition, epoxy resin Weight average molecular weight is preferably 5000 or less.

In compositions of thermosetting resin the content of epoxy resin relative to whole compositions of thermosetting resin (it is non-volatile at Point), preferably 20 ~ 80 mass %, more preferably 30 ~ 70 mass % are even more preferably 50 ~ 65 mass %.

[hygroscopicity metallic compound]

In order to further increase resistance to penetrability, resin combination of the invention can also contain hygroscopicity metal oxide. Herein, " hygroscopicity metal oxide " refers to the ability for absorbing moisture, is chemically reacted and is given birth to the moisture of institute moisture absorption The metal oxide of hydrate.Specifically, can enumerate selected from calcium oxide, magnesia, strontium oxide strontia, aluminium oxide, oxidation One of barium etc. or two or more mixture or soluble solids.As the example of two or more mixture or soluble solids, tool For body, dolime (mixture containing calcium oxide and magnesia), calcined hydrotalcite (calcium oxide and aluminium oxide can be enumerated Soluble solids) etc..Wherein, from the high aspect of hygroscopicity, the stability aspect of cost, raw material, preferably calcium oxide, aoxidize Magnesium, hydrotalcite, more preferably hydrotalcite.As long as hydrotalcite is not particularly limited with water imbibition.As hydrotalcite, such as can Enumerate natural hydrotalcite (Mg₆Al₂(OH)₁₆CO₃·4H₂O) and/or synthetic hydrotalcite (houghite compound), it is being used as In the case where hygroscopic agent, it is usually preferred to use carrying out calcination processing to hydrotalcite to improve water imbibition makes OH in chemical structure The calcined hydrotalcite that amount is reduced or disappeared.Preferred hydrotalcite can for example enumerate the synthetic hydrotalcite of general formula (I) representative The calcined body for the synthetic hydrotalcite (houghite compound) that calcined body, the general formula (II) of (houghite compound) represent Deng,

[M²⁺ _1-xM³⁺ _x(OH)₂]^x+·[(A^n-)_x/n·mH₂O]^x- (I)

(in formula, M²⁺Indicate Mg²⁺、Zn²⁺Equal divalents metal ion, M³⁺Indicate Al³⁺、Fe³⁺Etc. trivalents metal ion, A^n-It indicates CO₃ ^2-、Cl^-、NO₃ ^-Equal n valence anion, 0 < x < 1,0≤m < 1, n is positive number.)

M²⁺ _xAl₂(OH)_2x+6-nz(A^n-)_z·mH₂O (II)

(in formula, M²⁺Indicate Mg²⁺、Zn²⁺Equal divalents metal ion, A^n-Indicate CO₃ ^2-、Cl^-、NO₃ ^-Equal n valence anion, x 2 Above positive number, z are 2 positive numbers below, and m is positive number, and n is positive number.).

Calcined hydrotalcite is preferably by natural hydrotalcite (Mg₆Al₂(OH)₁₆CO₃·4H₂) and/or synthetic hydrotalcite (class water O Talc compound) calcining, so that the anion of interlayer and hydrone is gasified resulting composite oxides, can suitably be enumerated as 400 ~ It is calcined at 900 DEG C, more preferably 500 ~ 700 DEG C 30 minutes ~ 5 hours, more preferably 30 minutes ~ 3 hours, further preferably 45 Minute ~ 2 hours resulting composite oxides.

Preferred calcined hydrotalcite is to forge the Mg-Al system such as complex hydroxide of above-mentioned formula (II) houghite compound Resulting Mg-Al system complex oxide is burnt, which is more preferably set as Mg for the ratio of components of Mg and Al: X is the composite oxides of the ratio of components of 2≤x≤6 when Al=x:2, and the further preferably x is answering for the ratio of components of 3≤x≤6 Oxide is closed, the particularly preferably x is the composite oxides of the ratio of components of 4≤x≤6.

In various technical fields, as well known to hygroscopic material, commercially available product can be used in hygroscopicity metal oxide.Tool Can enumerate for body: (consonance chemical industry is public for calcium oxide (three altogether powder corporation " モイストップ #10 " processed etc.), magnesia Department system " キョーワマグ MF-150 ", " キョーワマグ MF-30 ", タテホ chemical industrial company system " ピュアマグ FNMG " etc.), light calcined magnesia (タテホ chemical industrial company's system " TATEHOMAG#500 ", " TATEHOMAG#1000 ", TATEHOMAG#5000 " etc.), dolime (lucky pool lime corporation " KT " etc.), calcined hydrotalcite (consonance chemical industry Corporation " KW2200 ", " DHT-4A ", " DHT-4A-2 ", " DHT-4C " etc.) etc..

The hygroscopicity metal oxide that surface treated agent is surface-treated can be used in hygroscopicity metal oxide. As the surface treating agent for surface treatment, higher fatty acids, alkyl silicon alkanes, silane coupling agent etc. can be used for example, It is wherein suitably higher fatty acids, alkyl silicon alkanes.One or more can be used in surface treating agent.

As higher fatty acids, such as the carbon atom numbers such as stearic acid, montanic acid, myristic acid, palmitinic acid can be enumerated and be 18 or more higher fatty acids, wherein preferably stearic acid.These higher fatty acids can be used one kind or by two or more group It closes and uses.It as alkyl silicon alkanes, can enumerate: methyltrimethoxysilane, ethyl trimethoxy silane, hexyl trimethoxy Silane, octyl trimethoxy silane, ruthenium trimethoxysilane, octadecyl trimethoxysilane, dimethylformamide dimethyl oxygroup silicon Alkane, octyltri-ethoxysilane, n-octadecane base dimethyl (3- (trimethoxy silicon substrate) propyl) ammonium chloride etc..These alkyl silicons Alkanes can be used one kind or be used in combination of two or more.It as silane coupling agent, such as can enumerate: 3- glycidol oxygen Base propyl trimethoxy silicane, 3- glycidoxypropyl triethoxysilane, 3- glycidoxypropyl (dimethoxy Base) the epoxies silane coupling agent such as methyl-monosilane and 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane；3- sulfydryl third Base trimethoxy silane, 3- Mercaptopropyltriethoxysilane, 3- mercapto propyl methyl dimethoxy silane and 11- sulfydryl The sulfydryls such as undecyltrimethoxysilane system silane coupling agent；3- TSL 8330, three second of 3- aminopropyl Oxysilane, 3- aminopropyldimethoxy methyl-monosilane, N- phenyl -3- TSL 8330, N- methylamino Propyl trimethoxy silicane, N- (2- amino-ethyl) -3- TSL 8330 and N- (2- amino-ethyl) -3- The amino such as aminopropyldimethoxy methyl-monosilane system silane coupling agent；The urea groups such as 3- ureidopropyltriethoxysilane system silane Coupling agent；The ethylene such as vinyltrimethoxysilane, vinyltriethoxysilane and vinyl methyl diethoxy silane Base system silane coupling agent；To the styrene base system silane coupling agent such as styryltrimethoxysilane；3- acryloxypropyl The acrylic esters silane coupling agent such as trimethoxy silane and 3- methacryloxypropyl trimethoxy silane；3- isocyanic acid The isocyanates such as ester group propyl trimethoxy silicane system silane coupling agent；Bis- (triethoxy silicon substrate propyl) disulphide, bis- (three Ethyl-silicone propyl) tetrasulfide sulfides system silane coupling agent；Phenyltrimethoxysila,e, methacryloxy third Base trimethoxy silane, imidazoles base silane, triazine base silane etc..These silane coupling agents can be used one kind or will be two or more It is applied in combination.

The surface treatment of hygroscopicity metal oxide can for example carry out in the following manner: use mixing machine side at normal temperature Untreated hygroscopicity metal oxide is dispersed with stirring, surface treating agent is added on side by spraying, stirs 5 ~ 60 minutes.As mixing Machine can be used well known mixing machine, such as can enumerate: V-type blender, ribbon blender, bicone blender (バ Block Le コー Application Block レンダー) etc. blenders；The mixing machines such as Henschel mixer and concrete mixer；Ball mill, shredding machine (cutter mill) etc..In addition, can also use will when being crushed using ball mill etc. to hygroscopicity metal oxide Above-mentioned higher fatty acids, alkyl silicon alkanes or silane coupling agent mixing, the method being surface-treated.The processing of surface treating agent Amount is different according to the type of hygroscopicity metal oxide or the type of surface treating agent etc., preferably with respect to hygroscopicity metal oxygen Compound is 1 ~ 10 mass %.

The content of hygroscopicity metal oxide is preferably 3 relative to 80 mass parts of epoxy resin in compositions of thermosetting resin ~ 38 mass parts, from the viewpoint of resistance to penetrability, permeability, more preferably 5 ~ 35 mass parts, further preferably 10 ~ 35 matter Measure part.It should be noted that the content of hygroscopicity metal oxide is excellent relative to whole compositions of thermosetting resin (nonvolatile component) It is selected as 2 ~ 24 mass %, more preferably 5 ~ 23 mass %.

[inorganic filling material]

From resin combination resistance it is moist, prepare diaphragm seal when resin composition Chinese varnish coating (film is prevented to be recessed (はじ I prevents)) etc. viewpoints set out, in compositions of thermosetting resin of the invention can also containing above-mentioned hygroscopicity metallize Close the inorganic filling material other than object.It as inorganic filling material, such as can enumerate: talcum, silica, aluminium oxide, sulphur Sour barium, clay, mica (mica), mica, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminium borate, metatitanic acid Barium, strontium titanates, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, zirconium oxide, barium zirconate, calcium zirconate, silicate etc..It should be noted that It is preferably 5 μm hereinafter, more preferably 1 μ from viewpoints, the partial sizes of the primary particle of inorganic filling material such as high transmittance is maintained M or less.It is, for example, possible to use the partial size of primary particle be 1 ~ 100nm, more preferably 1 ~ 50nm, further preferably 10 ~ The inorganic filling material of 20nm, particularly preferably 10 ~ 15nm.Reach the primary particle size of 1 μm of inorganic filling material below Measurement it is sometimes relatively difficult, therefore sometimes using be based on specific area measuring value (according to Japanese Industrial Standards JIS Z8830) Scaled value.For example, it is 2720 ~ 27m that BET specific surface area, which can be used, in nano inorganic filling material²/ g, preferably 2720 ~ 54m²/ g, more preferably 272 ~ 136m²/ g, further preferably 272 ~ 181m²The nano inorganic filling material of/g.

The particle shape of inorganic filling material is not particularly limited, and can use approximate sphericity, rectangular-shape, plate, class Like the rectilinear form of fiber, the form of bifurcation of branch.Inorganic filling material be preferably talcum, silica, zeolite, titanium oxide, Aluminium oxide, zirconium oxide, silicate, mica, mica (mica), magnesium hydroxide, aluminium hydroxide etc., more preferably silica.Make For silica, preferably wet silicon dioxide, dry type silica, colloidal silicon dioxide (water-dispersion type, organic solvent dispersion Type, fumed silica etc.), it is particularly preferably organic molten easily and from the perspective of resin compounded from being difficult to heavy hall, sedimentation Agent dispersing type colloidal silicon dioxide (organic silicon sol).

Commercially available product can be used in inorganic filling material, such as can enumerate: Japanese タ Le Network corporation " FG-15F " (talcum Powder), Nissan Chemical Industries Company system " MEK-EC-2130Y " (10 ~ 15nm of amorphous silica partial size, 30 matter of nonvolatile component Measure %, MEK solvent), Nissan Chemical Industries Company system " PGM-AC-2140Y " (10 ~ 15nm of silica partial size, nonvolatile component 40 mass %, PGM (propylene glycol monomethyl ether) solvent), Nissan Chemical Industries Company system " MIBK-ST " (silica partial size 10 ~ 15nm, 30 mass %, MIBK of nonvolatile component (methyl iso-butyl ketone (MIBK)) solvent), chemical industrial company, Japan colloidal silica solution " PL-2L-MEK " (15 ~ 20nm of silica partial size, 20 mass %, MEK of nonvolatile component (methyl ethyl ketone) solvent) etc..

In the present invention, one or more are can be used in inorganic filling material.Contain in resin combination of the invention In the case where inorganic filling material, the content of inorganic filling material is preferably relative to all resins composition (nonvolatile component) 10 mass % are hereinafter, more preferably 9 mass % or less.

[thermoplastic resin]

Flexible, thermosetting property when preparing sealing sheet is assigned from resulting sealant is solidified to compositions of thermosetting resin layer The viewpoints such as the coating (film is prevented to be recessed) of resin composition Chinese varnish are set out, and thermoplasticity can be contained in compositions of thermosetting resin Resin.It as thermoplastic resin, such as can enumerate: phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamides Amine-imide resin, polyethersulfone resin, polysulfone resin etc..These thermoplastic resins can be used any or will be two or more It is used in mixed way.The content of thermoplastic resin is (non-volatile relative to whole compositions of thermosetting resin in compositions of thermosetting resin Ingredient) it is preferably 1 ~ 40 mass %, more preferably 5 ~ 30 mass %.

It (is prevented from the coating of compositions of thermosetting resin varnish when assigning flexibility to sealant, prepare sealing sheet Film recess) etc. viewpoints set out, the weight average molecular weight of thermoplastic resin is preferably 15000 or more, more preferably 20000 or more. But if weight average molecular weight is excessive, have with the trend such as the compatibility of epoxy resin decline, therefore weight average molecular weight is preferably 1000000 hereinafter, more preferably 800000 or less.It should be noted that so-called herein " weight average molecular weight of thermoplastic resin " uses Gel permeation chromatography (GPC) method (polystyrene conversion) is measured.Specifically, using the weight average molecular weight of GPC method can be with Use Shimadzu Seisakusho Ltd. LC-9A/RID-6A as measurement device, use Showa electrician corporation Shodex K-800P/K- 804L/K-804L as chromatographic column, use chloroform etc. as mobile phase, be measured at 40 DEG C of column temperature, utilize standard polyphenyl The standard curve of ethylene is calculated.

The thermoplastic resin that the preferred transmitance of thermoplastic resin is 80% or more, the thermoplastic that more preferable transmitance is 90% or more Property resin.In above-mentioned example object, thermoplastic resin is particularly preferably phenoxy resin.The compatibility of phenoxy resin and epoxy resin Well, play the role of for the permeability of compositions of thermosetting resin, resistance to penetrability advantageous.

As phenoxy resin, can enumerate has selected from bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-phenol acetophenone One of skeleton, phenolic aldehyde (novolac) skeleton, biphenyl backbone, fluorene skeleton, bicyclopentadiene skeleton, enb skeleton etc. The phenoxy resin of above skeleton.One or more can be used in phenoxy resin.As the commercially available product of phenoxy resin, such as It can be suitable for using Mitsubishi Chemical Ind YX7200B35,1256, YX6954BH35 etc..

[coupling agent]

It, can be containing even in compositions of thermosetting resin from the viewpoint of the adhesive strength for improving compositions of thermosetting resin Join agent.As such coupling agent, such as titanium system coupling agent, aluminium system coupling agent, silane coupling agent can be enumerated etc..Wherein preferably For silane coupling agent.Coupling agent can be used one kind or be used in combination of two or more.

It as silane coupling agent, such as can enumerate: 3- glycidoxypropyltrimewasxysilane, 3- glycidol Oxygroup propyl-triethoxysilicane, 3- glycidoxypropyl (dimethoxy) methyl-monosilane and 2- (3,4- epoxy hexamethylene Base) the epoxies silane coupling agent such as ethyl trimethoxy silane；3-mercaptopropyi trimethoxy silane, three ethoxy of 3- mercaptopropyi The sulfydryls system silane such as base silane, 3- mercapto propyl methyl dimethoxy silane and 11- mercapto-undecanoic base trimethoxy silane Coupling agent；3- TSL 8330,3-aminopropyltriethoxysilane, 3- aminopropyldimethoxy methyl silicon Alkane, N- phenyl -3- TSL 8330, N- dimethylaminopropyl trimethoxy silane, N- (2- amino-ethyl) -3- The amino system silicon such as TSL 8330 and N- (2- amino-ethyl) -3- aminopropyldimethoxy methyl-monosilane Alkane coupling agent；The urea groups such as 3- ureidopropyltriethoxysilane system silane coupling agent；Vinyltrimethoxysilane, vinyl three The ethylene base system silane coupling agent such as Ethoxysilane and vinyl methyl diethoxy silane；To styryl trimethoxy The styrene base system silane coupling agent such as silane；3- acryloyloxypropyltrimethoxysilane and 3- methacryloxy The acrylic esters silane coupling agent such as propyl trimethoxy silicane；The isocyanates such as 3- isocyanate group propyl trimethoxy silicane It is silane coupling agent；The vulcanization such as bis- (triethoxy silicon substrate propyl) disulphide, bis- (triethoxy silicon substrate propyl) tetrasulfides Object system silane coupling agent；Phenyltrimethoxysila,e, methacryloxypropyl trimethoxy silane, imidazoles base silane, three Piperazine base silane etc..Wherein, particularly preferred epoxy silane coupling agent.

Using coupling agent, the content of coupling agent is relative to whole thermosetting property trees in compositions of thermosetting resin Oil/fat composition (nonvolatile component) is preferably 0.5 ~ 10 mass %, more preferably 0.5 ~ 5 mass %.The content of coupling agent is in this range When outer, the adaptation improvement generated by coupling agent addition can not be obtained.

[curing agent]

Compositions of thermosetting resin containing epoxy resin usually contains the curing agent of epoxy resin.As long as curing agent has The function of epoxy resin cure is not particularly limited then, from organic EL element when inhibiting compositions of thermosetting resin curing process From the perspective of the heat deterioration of equal light-emitting components, preferably can 140 DEG C or less (preferably 120 DEG C or less) at a temperature of by epoxy The curing agent of resin solidification.

As curing agent, such as primary amine, secondary amine, tertiary amine system curing agent, polyamino amide system curing agent, double cyanogen can be enumerated Amine, organic acid dihydrazide etc..Wherein, from rapidly-curable aspect, particularly preferably amine additives based compound (アミキュアPN-23、アミキュアMY-24、アミキュアPN-D、アミキュアMY-D、アミキュアPN-H、アミキュア MY-H, アミキュア PN-31, アミキュア PN-40, アミキュア PN-40J etc. (are monosodium glutamate Off ァイ Application テ Network ノ Corporation)), (アミキュア VDH-J, アミキュア UDH, アミキュア LDH etc. (are monosodium glutamate Off to organic acid dihydrazide ァイ Application テ Network ノ corporation)) etc..

In addition, as curing agent can also the particularly suitable salt using the solidification with epoxy resin, which is can be At a temperature of 140 DEG C or less (preferably 120 DEG C or less) by the ionic liquid of epoxy resin cure, can be (excellent at 140 DEG C or less Be selected as 120 DEG C or less) temperature region fusing salt.The ionic liquid is preferably in the state that uniform dissolution is in epoxy resin It uses.In addition, ionic liquid play the role of for the raising of the resistance to penetrability of the solidfied material of thermoplastic resin composition it is advantageous.

As the cation for constituting such ionic liquid, can enumerate: imidazol ion, piperidines ion, pyrrolidines The ammoniums cations such as ion, pyrazolium ion, guanidinium ion (guanidinium ion), pyridinium ion；Si Wan Ji Phosphonium sun Ion (such as the) Deng Phosphonium cation such as 4-butyl-phosphonium ion, tributyl Ji Ji phosphonium ion；The sulfoniums such as triethyl group sulfonium cation system's sun from Son etc..

In addition, can be enumerated: fluorine ion, chloride ion, bromide ion, iodine as the anion for constituting such ionic liquid The halide series anion such as ion；The alkylsurfuric acids series anion such as tosylate ion；Trifluoromethanesulfonic acid radical ion, hexafluoro phosphonic acids Radical ion, trifluoro three (pentafluoroethyl group) phosphonium acid ion, bis- (trifyl) imide ionics, trifluoroacetic acid radical ion, The fluorochemicals series anion such as tetrafluoroborate ion；Phenol radical ion, 2- metoxyphenol radical ion, 2,6- di-t-butyl The phenol systems anion such as phenol radical ion；The acidic amino acids radical ions such as aspartic acid radical ion, glutamate ion；Glycine root The neutral amino acids radical ions such as ion, alanine radical ion, phenylalanine radical ion；N- benzoyl alanine N radical ion, N- second The N- acyl amino acid ion that acylphenylalanines radical ion, N- acetyl-glycine radical ion etc. are represented by following formula (1)；First Acid ion, acetate ion, capric acid radical ion, 2-Pyrrolidone -5- carboxylic acid ion, alpha-lipoic acid radical ion, lactate The carboxylic acids series anions such as ion, tartrate ion, hippuric acid radical ion, N- methylhippuric acid ion, benzoate anion ion.

[changing 1]

(in formula, R is the linear chain or branched chain alkyl or substituted or unsubstituted phenyl of carbon atom number 1 ~ 5, and X indicates amino The side chain of acid.As amino acid, such as aspartic acid, glutamic acid, glycine, alanine, phenylalanine can be enumerated etc..).

Wherein, cation is preferably ammonium cation, Phosphonium cation, more preferably imidazol ion, phosphonium ion.More in detail For thin, imidazol ion is 1- ethyl-3-methylimidazole ion, 1- butyl -3- methylimidazole ion, 1- propyl -3- Methylimidazole ion etc..

In addition, anion be preferably phenol system anion, formula (1) represent N- acyl amino acid ion or carboxylic serials yin from Son, more preferably N- acyl amino acid ion or carboxylic acid series anion.

As the concrete example of phenol system anion, 2,6- DI-tert-butylphenol compounds radical ion can be enumerated.In addition, as carboxylic serials The concrete example of anion can enumerate: acetate ion, capric acid radical ion, 2-Pyrrolidone -5- carboxylic acid ion, formate Ion, alpha-lipoic acid radical ion, lactate ion, tartrate ion, hippuric acid radical ion, N- methylhippuric acid ion Deng wherein preferably acetate ion, 2-Pyrrolidone -5- carboxylic acid ion, formate ion, lactate ion, tartaric acid Radical ion, hippuric acid radical ion, N- methylhippuric acid ion, more preferably acetate ion, N- methylhippuric acid ion, Formate ion.In addition, the concrete example of the N- acyl amino acid ion represented as formula (1), can enumerate: N- benzoyl third Propylhomoserin radical ion, N- acetyl phenyl alanine radical ion, aspartic acid radical ion, glycine radical ion, N- acetyl-glycine Radical ion etc., wherein preferably N- benzoyl alanine N radical ion, N- acetyl phenyl alanine radical ion, N- acetyl-glycine Radical ion, more preferably N- acetyl-glycine radical ion.

As specific ionic liquid, preferably such as 1- butyl -3- methylimidazole lactate, 4-butyl-phosphonium -2- pyrrole Pyrrolidone -5- carboxylate, 4-butyl-phosphonium acetate, 4-butyl-phosphonium caprate, 4-butyl-phosphonium trifluoroacetate, 4-butyl-phosphonium α-sulphur Caprylate, 4-butyl-phosphonium formates, 4-butyl-phosphonium lactate, two (4-butyl-phosphonium) tartrates, 4-butyl-phosphonium hippurate, four Fourth base Phosphonium N- methylhippuric hydrochlorate, 4-butyl-phosphonium benzoyl-DL-Alanine salt, 4-butyl-phosphonium N- acetyl phenyl alanine salt, four Ding Ji Phosphonium 2,6 di t butyl phenol salt, single 4-butyl-phosphonium L-Aspartic acid salt, 4-butyl-phosphonium glycinate, 4-butyl-phosphonium N- second Acylglycine salt, 1- ethyl-3-methylimidazole lactate, 1- ethyl-3-methylimidazole acetate, 1- ethyl -3- first Base imidazole formic acid salt, 1- ethyl-3-methylimidazole hippurate, 1- ethyl-3-methylimidazole N- methylhippuric hydrochlorate, Two (1- ethyl-3-methylimidazole) tartrates, 1- ethyl-3-methylimidazole N- acetyl-glycine salt, it is especially more excellent It is selected as 4-butyl-phosphonium N- acetyl-glycine salt, 1- ethyl-3-methylimidazole acetate, 1- ethyl-3-methylimidazole first Hydrochlorate, 1- ethyl-3-methylimidazole hippurate, 1- ethyl-3-methylimidazole N- methylhippuric hydrochlorate.

Synthetic method as above-mentioned ionic liquid, comprising: make by alkyl imidazole, alkyl pyridine, alkylammonium and alkane The precursor and NaBF that the cationic portions such as base sulfonium cation and halogen-containing anion part are constituted₄、NaPF₆、CF₃SO₃Na、LiN (SO₂CF₃)₂The anion exchange method of equal reactions；So that amine system substance is reacted with acid esters and is introduced alkyl, and make organic acid residue at For the acid esters method of counter anion (counter anion)；And the neutralisation etc. of salt is obtained with amine in organic acid, but simultaneously It is not limited to these methods.In the neutralisation carried out by anion, cation and solvent, can with equivalent using anion and sun from Direct use is distilled off in solvent in gained reaction solution by son, and organic solvent (methanol, toluene, acetic acid can also be added in turn Ethyl ester, acetone etc.) carry out liquid concentration.

The content of curing agent is relative to epoxy resin contained in compositions of thermosetting resin in compositions of thermosetting resin Total amount (nonvolatile component), preferably 0.1 ~ 50 mass %.The content is if it is less than 0.1 mass %, it is likely that can not obtain Sufficient curability then damages the storage stability of compositions of thermosetting resin if it is greater than 50 mass % sometimes.It should say It is bright, using ionic liquid, from the viewpoints such as the resistance to penetrability of the solidfied material of compositions of thermosetting resin, ion The amount of liquid is preferably 0.1 ~ 10 mass % relative to the total amount (nonvolatile component) of epoxy resin.

In the case where using ionic liquid as curing agent, in compositions of thermosetting resin can containing ionic liquid with And intramolecular has the multi-thioalcohol compound of 2 or more mercaptos.By having more sulphur of 2 or more mercaptos containing intramolecular Alcoholic compound can accelerate curing rate.There is the concrete example of the multi-thioalcohol compound of 2 or more mercaptos as intramolecular, Such as it can enumerate: trimethylolpropane tris (mercaptoacetate), pentaerythrite four (mercaptoacetate), ethylene glycol dimercapto second Acid esters, trimethylolpropane tris (β-mercaptopropionic acid ester), pentaerythrite four (β-mercaptopropionic acid ester), the more (β-mercapto of dipentaerythritol Base propionic ester) etc. by polyalcohol and sulfydryl organic acid the resulting mercaptan compound of esterification.Such mercaptan compound is Without using alkaline matter, mercaptan compound of the intramolecular with 2 or more mercaptos in manufacture.

In addition, having the multi-thioalcohol compound of 2 or more mercaptos as intramolecular, can enumerate: Isosorbide-5-Nitrae-succinimide mercaptans, The alkyl multi-thioalcohol compounds such as 1,6- ethanthiol, two mercaptan of the 1,10- last of the ten Heavenly stems；The polyethers of the base containing terminal mercaptan；Base containing terminal mercaptan Polythiaether；Resulting mercaptan compound is reacted with hydrogen sulfide by epoxide；By multi-thioalcohol compound and epoxide React the resulting mercaptan compound etc. with terminal mercaptan base.It should be noted that reacting institute with hydrogen sulfide by epoxide Mercaptan compound, the resulting mercaptan compound with terminal mercaptan base is reacted with epoxide by multi-thioalcohol compound Use in, in manufacturing process alkaline matter as in the case where catalysts, it is preferable to use carrying out dealkalize processing makes alkali Concentration of metal ions is 50ppm substance below.As the method for such dealkalize processing, it can enumerate: will for example locate The multi-thioalcohol compound of reason is dissolved in the organic solvents such as acetone, methanol, after the acid such as addition dilute hydrochloric acid, dilute sulfuric acid are neutralized, By the method for carrying out desalination such as extracting, washing；Or it is carried out using the method that ion exchange resin is adsorbed, by distillation The method etc. of purifying, but it is not limited to these methods.

Using such multi-thioalcohol compound, epoxy resin is mixed with multi-thioalcohol compound preferably, is made The ratio between use level/epoxide equivalent of the use level of multi-thioalcohol compound/SH equivalent and epoxy resin be (i.e. " (multi-thioalcohol compound Use level/SH equivalent)/(use level/epoxide equivalent of epoxy resin) ") it is 0.2 ~ 1.2.This is than if it is less than 0.2, then sometimes Sufficient rapidly-curable can not be obtained, on the other hand, if it is greater than 1.2, then damages the object of the solidfied materials such as heat resistance sometimes Property.From the viewpoint of being stablized adhesiveness, this is than being more preferably 0.5 ~ 1.0.Herein, " SH equivalent " refers to " multi-thioalcohol compound Molecular weight/SH base number ", " epoxide equivalent " refers to " molecular weight/epoxy group number of epoxy resin ".

[curing accelerator]

In order to adjust the purpose of curing time etc., the compositions of thermosetting resin containing epoxy resin can also promote containing solidification Into agent.As curing accelerator, such as can enumerate: organic phosphine compound, imidazolium compounds, amine additives compound (such as Make to react in epoxy resin and the midway of tertiary amine addition reaction and stop resulting epoxy addition compound etc.), tertiary amine compound etc.. It as the concrete example of organic phosphine compound, can enumerate: TPP, TPP-K, TPP-S, TPTP-S (quotient of Bei Xing chemical industrial company The name of an article) etc..As the concrete example of imidazolium compounds, can enumerate: キュアゾー Le 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2MZOK, 2MA-OK, 2PHZ (trade name of chemical conversion industry company, four countries) etc..As amine additives The concrete example for closing object, can enumerate: Off ジキュア (trade name of chemical conversion industry company, Fuji) etc..As tertiary amine compound Concrete example can enumerate: 2 ethyl hexanoic acid salt, the octanoic acid of DBU (1,8- diazabicyclo [5.4.0], 11 carbon -7- alkene), DBU The aromatic series dimethyl ureas, U-3503N (サ Application アプロ such as the DBU- such as salt acylate, U-3512T (サ Application アプロ corporation) Corporation) etc. aliphatic dimethyl urea etc..Wherein, from moisture resistance aspect, it is preferable to use carbamide compound, particularly preferably uses Aromatic series dimethyl urea.When the total amount of epoxy resin in compositions of thermosetting resin is set as 100 mass % (nonvolatile component), The content of curing accelerator is usually 0.05 ~ 5 mass % in compositions of thermosetting resin.If it is less than 0.05 mass %, then have solid Change the trend that delay needs to extend thermal curing time, if it is greater than 5 mass %, then there is the preservation of compositions of thermosetting resin to stablize Property downward trend.

Compositions of thermosetting resin can be arbitrarily containing the various additives other than mentioned component.As such additives, Such as it can enumerate: the organic fillers such as silicone powder, nylon powder, fluororesin powder；Orben(オルベン),Benton(ベント Application) etc. thickeners, organic silicon-type, fluorine system, macromolecular defoaming agent or levelling agent；Triazole compounds, thiazolium compounds, triazine Close adaptations imparting agents such as object, porphyrin compound etc..

Compositions of thermosetting resin can by using nip roll, rotary mixing machine etc. by ingredient and as needed into It is prepared by the mixing such as the organic solvent of one step addition.

Sealing sheet can be manufactured using method known in those skilled in the art, such as be made by the following method It makes: compositions of thermosetting resin being dissolved in organic solvent, varnish is made, varnish is coated on supporter, and then by adding Heat or heated-air drying etc. make organic solvent drying form compositions of thermosetting resin layer.Compositions of thermosetting resin layer after drying Thickness be preferably 3 ~ 100 μm, more preferably 5 ~ 50 μm, further preferably 5 ~ 20 μm.

As organic solvent, such as can enumerate: the ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, ethyl acetate, The acetate esters such as butyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate；The cellosolves such as cellosolve Class；The carbitols class such as butyl carbitol；The arenes such as toluene, dimethylbenzene；Dimethylformamide, dimethyl acetamide, N- first Base pyrrolidones etc..Such organic solvent can be used alone any, can also be used in combination of two or more.

It as the supporter for sealing sheet, such as can enumerate: the polyolefin such as polyethylene, polypropylene (PP)；It is poly- The polyester such as ethylene glycol terephthalate (PET), polyethylene naphthalate (PEN)；Polycarbonate (PC), polyimides (PI), the plastic foils such as cyclic olefin polymer (COP), polyvinyl chloride.As plastic foil, preferably polyethylene terephthalate Ester, polyethylene naphthalate, cyclic olefin polymer.

In order to improve the moisture resistance of sealing sheet, the plastic foil with barrier layer can be used as supporter.As Barrier layer, such as the metals such as the oxides such as the nitride such as silicon nitride, aluminium oxide, stainless steel, aluminium can be enumerated etc..It is hindered using having In the case that the plastic foil of barrier is as supporter, preferably plastic foil is selected from polyethylene terephthalate, poly- naphthalene diformazan At least one of sour glycol ester, polycarbonate and cyclic olefin polymer, more preferable plastic foil are selected from poly- terephthaldehyde At least one of sour glycol ester, polyethylene naphthalate and cyclic olefin polymer, further preferred plastic foil are poly- Ethylene glycol terephthalate.Commercially available product can be used in plastic foil with barrier layer.As the poly terephthalic acid with aluminium foil The commercially available product of glycol ester film, such as aluminium vendor company, East Sea Japan (East Sea Japan ア Le ミ buys to resell Sales society) system " ア Le can be enumerated ペット 1N30 ", FUKUDA METAL's corporation " ア Le ペット 3025 " etc..

Supporter can be implemented by organic siliconresin system release agent, alkyd resin system release agent, fluororesin system release agent Wait the demoulding processing, delustring processing, sided corona treatment etc. of progress.The thickness of supporter is not particularly limited, from sealing sheet The viewpoints such as operability are set out, and preferably 20 ~ 200 μm, more preferably 20 ~ 125 μm.

Its surface adhesive dust etc. or the scuffing in order to prevent of compositions of thermosetting resin layer, preferably uses protective film (カバー Off ィ Le system) it is protected.It should be noted that the protective film is removed before sealing sheet and the lamination of organic EL element substrate. It is preferable to use plastic foils identical with supporter for protective film.Furthermore it is possible to protective film implement by organic siliconresin system release agent, The demoulding processing of the progress such as alkyd resin system release agent, fluororesin system release agent, delustring processing, sided corona treatment etc..Protective film Thickness is not particularly limited, and for example, 15 ~ 75 μm, preferably 15 ~ 50 μm.

[organic EL element substrate]

The substrate (hereinafter sometimes referred to simply as " substrate ") of organic EL element substrate is not particularly limited, and can be used well known Substrate.Substrate is preferably selected from glass, polyimides (PI), polyethylene terephthalate (PET), poly- naphthalenedicarboxylic acid second two At least one of alcohol ester (PEN), polycarbonate (PC) and cyclic olefin polymer (COP).

The thickness of substrate is preferably 0.1 ~ 1.0mm, more preferably 0.1 ~ 0.7mm.The thickness of organic EL element is usually 0.01 ~ 1 μm, preferably 0.05 ~ 0.5 μm.

In order to extract the light from organic EL element, the supporter of the substrate and sealing sheet of organic EL element substrate Either one need to be transparent.For example, using opaque supporter (such as with opaque barrier layer on sealing sheet Plastic foil) when, in order to extract light from substrate-side, need using transparent substrate.

Embodiment

Hereinafter, carrying out more specific description to the present invention using embodiment, however, the present invention is not limited to these examples.

To Si butyl phosphonium hydroxides (tetrabutylphosphonium hydroxide) aqueous solution (northern Xinghua at 0 DEG C Learn industrial group's system, 41.4 mass % of concentration) N- acetyl-glycine (Tokyo chemical conversion industry corporation) is added in 20.0g 3.54g is stirred 10 minutes.Concentration 5 is small at being decompressed to 40 ~ 50mmHg using evaporator, being concentrated 2 hours, 90 DEG C at 60 ~ 80 DEG C When.It is dissolved in again in ethyl acetate (pure chemical company's system) 14.2mL at room temperature, 40 are decompressed to using evaporator ~ 50mmHg is concentrated 3 hours in 70 ~ 90 DEG C under decompression, obtains 4-butyl-phosphonium N- acetyl-glycine salt as oily compound 11.7g (purity 96.9%).

By liquid bisphenol A type epoxy resin (Mitsubishi Chemical Ind's system " jER828EL ", epoxide equivalent about 185g/eq) 56 matter Measure part, silane coupling agent (chemical industrial company, SHIN-ETSU HANTOTAI system " KBM403 ") 1.2 mass parts, talcum powder (Japanese タ Le Network corporation " FG-15F ") after 2 mass parts and calcined hydrotalcite (consonance chemical industrial company's system " KW2200 ") 15 mass parts mediate, use Three-high mill is dispersed, and mixture is obtained.

Curing accelerator (サ Application アプロ corporation " U-3512T ") 1.5 mass parts are dissolved in the methyl of phenoxy resin Ethyl ketone (MEK) solution (Mitsubishi Chemical Ind's system " YX7200B35 ", 35 mass % of concentration) 81 mass parts (28.4 matter of phenoxy resin Measure part) in formed mixture, into the mixture with share three-high mill dispersion and manufactured said mixture, solid-state bisphenol-A The MEK solution (80 mass % of concentration) 30 of type epoxy resin (Mitsubishi Chemical Ind's system " jER1001 ", epoxide equivalent about 475g/eq) (silica 10 ~ 15nm of partial size, 30 mass %, MEK of nonvolatile component are molten for mass parts, organic solvent dispersion type colloidal silicon dioxide Agent, Nissan Chemical Industries Company system " MEK-EC-2130Y ") 20 mass parts and ionic liquid curing agent (4-butyl-phosphonium N- second Acylglycine salt) 3 mass parts, resin composition Chinese varnish is obtained with high-speed rotary mixing machine is evenly dispersed.

Then, resulting resin composition Chinese varnish is uniformly coated on through alcohol with metal mold coating machine (ダイコーター) Acid system release agent treated polyethylene terephthalate film (hereinafter referred to as " supporter PET film ") (38 μm of thickness) On, make it is dry after resin composition layer with a thickness of 20 μm, dry 5 minutes (resin combinations under 80 ~ 100 DEG C (90 DEG C average) Residual solvent amount is about 2 mass % in nitride layer).It then, will be through alkyd system release agent treated 38 μm of thickness of poly- terephthaldehyde Sour glycol ester film (hereinafter referred to as " protection PET film ") is fitted in the surface top volume of resin composition layer as protection membrane edge It is coiled into web-like.The sealing sheet of web-like is cut into width 507mm, obtains the sealing sheet 1 of 507mm × 336mm size.

Using sealing sheet 1 and with any one of lower support 2 ~ 4, sealing sheet 2 ~ 4 is made.

Plastic foil with barrier layer

Supporter 2: (plastic foil: the PET that 25 μm of thickness stops aluminium vendor company, East Sea Japan system " ア Le ペット 1N30 " Layer: the aluminium foil that 30 μm of thickness)

Supporter 3: adhesive layer, barrier layer (inorganic matter vapor deposition are disposed on plastic foil (PET that 125 μm of thickness) Layer) film

There is no the plastic foil on barrier layer

Supporter 4: Toray system " Le ミラー T60 " (PET that 100 μm of thickness).

The sealing sheet 1 (width 20mm, length 50mm) for having removed protection PET film is overlapped and is cut into width 25mm On the supporter of length 100mm, contact any one of compositions of thermosetting resin layer and supporter 2 ~ 4.It should be noted that Using the supporter 2 with barrier layer or 3, the sealing sheet 1 and supporter 2 of protection PET film will have been removed Or 3 overlapping, contact compositions of thermosetting resin layer with the barrier layer.Use layer of rolls press VA770H (great achievement ラミネーター Corporation, 80 DEG C of laminating temperature, mill speed 0.5mL/ minutes, draught pressure 0.1MPa) overlapping body is laminated, it obtains each With each sealing sheet 2 ~ 4 of compositions of thermosetting resin layer on supporter 2 ~ 4.

(1) production of flatness and gap sample for evaluation

Using being etched into polyamide tape (three wells with copper foil for constituting fringe pattern by linear copper foil and without foil section Metal company system, the name of an article " AJ-C0002-30/40 ", 5 μm of copper thickness, 40 μm of polyimide thickness, linear copper foil (line (line)) 15 μm of width, 15 μm of the width of no foil section (space (space))) it is used as pattern substrate, it is as follows to make Flatness and gap sample for evaluation.

Pattern substrate is temporarily fixed on stainless steel (SUS) plate of thickness 0.8mm.PET film will be protected from sheet for sealing Material 1 is removed, and compositions of thermosetting resin layer contact patterns substrate is made, Chong Die with pattern substrate, (big using layer of rolls press VA770H At ラミネーター corporation, roller material: silicon rubber), in 80 DEG C of laminating temperature, mill speed 0.1m/ minutes, draught pressure In 0MPa, air atmosphere under atmospheric pressure under conditions of, they are laminated.Then, using intermittent vacuum pressurization laminating machine CVP-300 (モート Application corporation, plate material: SUS 603H) is used as hot-press arrangement (platen-press), in press temperature 90 DEG C, pressing pressure 0.15MPa, 300 seconds pressing times, in air atmosphere under atmospheric pressure under conditions of, to being laminated with sheet for sealing The pattern substrate of material carries out hot pressing.Then, supporter PET film is removed from pressed sealing sheet.Then, at 110 DEG C Under make thermoset resin layer solidify 30 minutes, formed sealant (solidfied material of compositions of thermosetting resin layer), flatness is made With gap sample for evaluation.

(2) production of adaptation and gap sample for evaluation

Glass plate (width 26mm, length 76mm, thickness 1mm) is temporarily fixed on the SUS plate of thickness 0.8mm.It will branch Support body PET film is removed from each sealing sheet 2 ~ 4, make compositions of thermosetting resin layer contact glass plate, by sealing sheet with Glass plate overlapping, using layer of rolls press VA770H (great achievement ラミネーター corporation), in 80 DEG C of laminating temperature, mill speed 0.1m/ minutes, draught pressure 0MPa, in air atmosphere under atmospheric pressure under conditions of, they are laminated.Then, between use Formula of having a rest vacuum pressed laminating machine CVP-300 (モート Application corporation) it is used as hot-press arrangement (platen-press), in press temperature 90 DEG C, pressing pressure 0.15MPa, 300 seconds pressing times, in air atmosphere under atmospheric pressure under conditions of, to being laminated with sheet for sealing The glass plate of material carries out hot pressing.Then, solidify thermoset resin layer 30 minutes, form sealant (thermosetting property tree The solidfied material of oil/fat composition layer), adaptation and gap sample for evaluation is made.

Other than mill speed was become 1.0m/ minutes from 0.1m/ minutes, similarly to Example 1, production flatness and Gap sample for evaluation and adaptation and gap sample for evaluation.

In addition to (pressure: 1013.25hPa), the interior process for implementing roll laminating of glove box under inert gas (nitrogen) atmosphere In addition, similarly to Example 2, flatness and gap sample for evaluation and adaptation and gap sample for evaluation are made.

Other than after the lamination using layer of rolls press without hot pressing, similarly to Example 1, flatness and sky are made Gap sample for evaluation and adaptation and gap sample for evaluation.

It is same as comparative example 1 other than mill speed was become 1.0m/ minutes from 0.1m/ minutes, production flatness and Gap sample for evaluation and adaptation and gap sample for evaluation.

It is same as comparative example 1 other than draught pressure is become 0.15MPa from 0MPa, it makes flatness and gap is commented Valence sample and adaptation and gap sample for evaluation.

In addition to only carrying out other than hot pressing without the lamination using layer of rolls press, similarly to Example 1, flatness is made With gap sample for evaluation and adaptation and gap sample for evaluation.

Other than press temperature being become 110 DEG C from 90 DEG C, the pressing time became 1800 seconds from 300 seconds, with comparative example 4 Equally, flatness and gap sample for evaluation and adaptation and gap sample for evaluation are made.

(1) production of flatness and gap sample for evaluation

Similarly to Example 1, use the polyamide tape with copper foil as pattern substrate, it is as follows make flatness and Gap sample for evaluation.

Pattern substrate is temporarily fixed on the SUS plate of thickness 0.8mm.Protection PET film is removed from sealing sheet 1, Make compositions of thermosetting resin layer contact patterns substrate, sealing sheet is Chong Die with pattern substrate, added using diaphragm type vacuum Pressurized layer press V-160 (モート Application corporation), it, will after being kept for 20 seconds under conditions of 80 DEG C of set temperature, vacuum degree 1.2hPa Vacuum state reverts to air atmosphere, in air atmosphere under atmospheric pressure, 20 seconds lamination pressure 0.1MPa, lamination times conditions Under, they are laminated.Then, supporter PET film is removed from pressed sealing sheet.Then, make at 110 DEG C Thermoset resin layer solidifies 30 minutes, is formed sealant (solidfied material of compositions of thermosetting resin layer), flatness and sky is made Gap sample for evaluation.

(2) production of adaptation and gap sample for evaluation

Glass plate (width 26mm, length 76mm, thickness 1mm) is temporarily fixed on the SUS plate of thickness 0.8mm.It will branch Support body PET film is removed from each sealing sheet 2 ~ 4, make compositions of thermosetting resin layer contact glass plate, by sealing sheet with Glass plate overlapping, uses diaphragm type vacuum pressed laminating machine V-160 (モート Application corporation), in 80 DEG C of set temperature, vacuum degree After being kept for 20 seconds under conditions of 1.2hPa, vacuum state is reverted into air atmosphere, in air atmosphere under atmospheric pressure, lamination pressure Power 0.1MPa, under conditions of lamination times 20 seconds, they are laminated.Then, solidify thermoset resin layer at 110 DEG C It 30 minutes, is formed sealant (solidfied material of compositions of thermosetting resin layer), adaptation and gap sample for evaluation is made.

Use manufactured flatness in above-described embodiment and comparative example and gap sample for evaluation and adaptation and gap Sample for evaluation as follows evaluates gap, flatness and adaptation.

By visual observation with optical microscopy (150 times of multiplying power), flatness and gap sample for evaluation and adaptation are observed And it whether there is gap in the sample for evaluation of gap between sealant and pattern substrate or glass plate.It is not observed with optical microscopy It is evaluated as good (zero) when to gap, is evaluated as bad (×) when by visual observation or optical microscopy observes gap.

Use non-contact type surface roughness meter (ビー U イ Application ス Star Le メ Application Star WYKO, GT-3), it is contacted in VSI Under conditions of mode, 50 times of lens, 94 μm of 126 μ m of measurement range, in the sealant table of flatness and gap sample for evaluation Face measures the difference in height (gap) for having the part of linear copper foil (line) with part (space) part of no copper foil in pattern substrate.

According to Japanese Industrial Standards JIS C6481, using INSTRON universal testing machine, in room temperature, 50mm/ minutes speed Under conditions of, load when supporter is vertically removed 20mm from adaptation and gap sample for evaluation by measurement is as branch Peel strength between support body and sealant.

The sealing means and condition of embodiment and comparative example are shown in table 1, evaluation result is shown in table 2.

[table 1]

¹⁾The roll laminating of embodiment 3 carries out in a nitrogen atmosphere.

[table 2]

¹⁾It is concave-convex excessive in the sealant of comparative example 1 and 2, gap can not be measured.

As shown in Tables 1 and 2, roll laminating followed by carries out not generated gap, flatness in the embodiment 1 ~ 3 of hot pressing The high sealant with adaptation.

On the other hand, in the comparative example 1 ~ 3 for only carrying out roll laminating, the flatness of resulting sealant is low.In addition, only carrying out In the comparative example 4 and 5 of hot pressing, resulting sealant generates gap, and flatness and adaptation are also low.In addition, having carried out Gao Chengben Vacuum lamination comparative example 6 in, do not generated the high sealant of gap, adaptation, but compared with Examples 1 and 2, sealing The flatness of layer is poor.

Industrial applicability-

The manufacturing method of seal (especially organic EL device) of the invention can be with not generating gap, flatness and close The high sealant of conjunction property carrys out sealing organic el element, and since without using vacuum laminator, cost aspect is also advantageous. In addition, manufacturing method according to the invention, can implement to be laminated in the few inert gas of the damage to organic EL element.

The application is by based on the Patent 2014-107471 in Japanese publication, content is integrally incorporated in this specification In.

Claims

1. the manufacturing method of seal is with sealant come the manufacturer of the seal of the organic EL element on hermetic sealing substrate Method,

The manufacturing method includes:

Laminating process in the process, using layer of rolls press, will be formed with the sealing of compositions of thermosetting resin layer on supporter It is laminated on substrate with sheet material, so that compositions of thermosetting resin layer is contacted with organic EL element；

Curing process in the process, makes the heat cure of compositions of thermosetting resin layer and forms sealant,

Lamination carries out under inert gas atmosphere.

2. manufacturing method described in claim 1, wherein the mill speed of layer of rolls press is 0.01 ~ 1.5m/ minutes.

3. manufacturing method described in claim 1, wherein the mill speed of layer of rolls press is 0.1 ~ 0.5m/ minutes.

4. manufacturing method described in claim 1, wherein the draught pressure of layer of rolls press is 0 ~ 0.5MPa.

5. manufacturing method described in claim 1, wherein laminating temperature is 60 ~ 120 DEG C.

6. manufacturing method described in claim 1, wherein the pressing pressure for smoothing process is 0.01 ~ 0.5MPa.

7. manufacturing method described in claim 1, wherein the press temperature for smoothing process is 60 ~ 120 DEG C.

8. manufacturing method described in claim 1, wherein supporter is the plastic foil that can have barrier layer.

9. manufacturing method described in claim 1, wherein supporter with a thickness of 30 ~ 200 μm.

10. manufacturing method described in claim 1, wherein substrate is selected from glass, polyimides, poly terephthalic acid second two At least one of alcohol ester, polyethylene naphthalate, polycarbonate and cyclic olefin polymer.

11. manufacturing method described in claim 1, wherein substrate with a thickness of 0.1 ~ 1.0mm.

12. manufacturing method described in claim 1, wherein curing process carries out simultaneously with smoothing process.

13. manufacturing method described in claim 1, wherein seal is organic EL device.

14. by the method for the organic EL element sealing on substrate, this method comprises:

Lamination carries out under inert gas atmosphere.