WO2015178469A1

WO2015178469A1 - Manufacturing method for sealed body

Info

Publication number: WO2015178469A1
Application number: PCT/JP2015/064671
Authority: WO
Inventors: 有希山本
Original assignee: 味の素株式会社
Priority date: 2014-05-23
Filing date: 2015-05-22
Publication date: 2015-11-26
Also published as: CN106465505B; CN106465505A; JP6572887B2; JPWO2015178469A1; KR20170009974A; TW201608753A

Abstract

　Provided is a method for producing a sealed body obtained by sealing an organic EL element on a substrate with a sealing layer, said method comprising: a laminating step in which a roll laminator is used to laminate a sealing sheet having a thermosetting resin composition layer formed on a support, onto a substrate in such a manner that the thermosetting resin composition layer comes into contact with the organic EL element; a smoothing step in which the laminated sealing sheet surface is smoothed by thermal pressing; and a curing step in which the thermosetting resin composition layer is thermoset to form a sealing layer.

Description

Manufacturing method of sealing body

The present invention relates to a method for producing a sealed body (in particular, an organic EL device) in which an organic EL (electroluminescence) element on a substrate is sealed with a sealing layer. The present invention also relates to a method for sealing an organic EL element on a substrate.

An organic EL element is a light emitting element using an organic substance as a light emitting material, and has recently attracted attention because it can emit light with high luminance at a low voltage. However, organic EL elements are extremely vulnerable to moisture, and the light emitting material (light emitting layer) is altered by moisture, resulting in a decrease in luminance, no light emission, or peeling of the interface between the electrode and the light emitting layer due to moisture. There is a problem that the metal is oxidized to increase the resistance. For this reason, in order to block the inside of the device from moisture in the outside air, for example, a sealing layer made of a resin composition is formed so as to cover the entire surface of the light emitting layer formed on the substrate to seal the organic EL device. Is done.

Examples of the organic EL element sealing method include a method of laminating a sealing sheet in which a resin composition layer is formed on a moisture-proof support on an organic EL element substrate. For the resin composition layer, for example, a thermoplastic resin composition or a thermosetting resin composition is used. When a thermosetting resin composition is used, a sealing layer is formed by thermosetting after lamination. The As a means for laminating the sealing sheet on the organic EL element, for example, a method of laminating in a vacuum state using a vacuum laminator or a vacuum press machine is known (Patent Documents 1 to 3, etc.).

International Publication No. 2010/084938 International Publication No. 2010/084939 International Publication No. 2011/016408

The generation of voids can be prevented by laminating the sealing sheet and the organic EL element substrate in a vacuum state. However, this requires a vacuum facility such as a vacuum laminator, which is expensive. Then, if the sealing layer excellent in adhesiveness can be formed in the laminate under normal pressure without generating voids, the manufacturing cost of the organic EL device can be reduced. In addition, before sealing the organic EL element, it is desirable to use an inert gas atmosphere in order not to deteriorate the organic EL element. In this regard, when vacuum equipment such as a vacuum laminator is used, the state of the inert gas atmosphere is released, and depending on the type of the organic EL element, there may be a problem that it deteriorates due to the influence of moisture even in a vacuum state.

However, as described above, when the laminating method under normal pressure is adopted, problems such as generation of voids and deterioration of the adhesion of the sealing layer to the support may occur. Further, in the organic EL element substrate for display, the surface of the sealing layer is smoothed by unevenness on the surface of the substrate (that is, the difference in height between the convex portion where the organic EL element exists and the concave portion where the element does not exist). It tends to get worse. A sealing layer with poor smoothness may cause uneven brightness or uneven color.

The present invention has been made paying attention to the above situation, and even when a sealing sheet is laminated to an organic EL element substrate under normal pressure and a sealing layer is formed, voids are generated. It is another object of the present invention to provide a method for manufacturing a sealed body that can form a sealing layer excellent in smoothness and adhesion.

As a result of intensive studies by the present inventors, the above problem can be solved by laminating the sealing sheet on the surface of the organic EL element of the substrate with a roll laminator, and then hot pressing the laminated sealing sheet surface. As a result, the following present invention has been completed.

[1] A method for producing a sealed body in which an organic EL element on a substrate is sealed with a sealing layer,
A laminating step of laminating a sealing sheet having a thermosetting resin composition layer formed on a support on a substrate using a roll laminator so that the thermosetting resin composition layer is in contact with the organic EL element,
A production method comprising a smoothing step of smoothing a laminated sealing sheet surface by hot pressing, and a curing step of thermosetting a thermosetting resin composition layer to form a sealing layer.

[2] The production method according to [1], wherein the laminating is performed in an inert gas atmosphere.
[3] The production method according to [1] or [2], wherein the laminating is performed under normal pressure.

[4] The production method according to any one of [1] to [3], wherein the roll speed of the roll laminator is 0.01 to 1.5 m / min.
[5] The production method according to any one of [1] to [3], wherein a roll speed of the roll laminator is 0.1 to 0.5 m / min.

[6] The production method according to any one of [1] to [5], wherein the roll laminator has a roll pressure of 0 to 0.5 MPa.
[7] The production method according to any one of [1] to [5], wherein the roll pressure of the roll laminator is 0 to 0.3 MPa.

[8] The production method according to any one of [1] to [7], wherein the laminating temperature is 60 to 120 ° C.
[9] The production method according to any one of [1] to [7], wherein the laminating temperature is 80 to 100 ° C.

[10] The production method according to any one of [1] to [9], wherein the pressing pressure in the smoothing step is 0.01 to 0.5 MPa.
[11] The production method according to any one of [1] to [9], wherein the pressing pressure in the smoothing step is 0.01 to 0.3 MPa.

[12] The production method according to any one of [1] to [11], wherein a press temperature in the smoothing step is 60 to 120 ° C.
[13] The production method according to any one of [1] to [11], wherein a press temperature in the smoothing step is 80 to 100 ° C.

[14] The production method according to any one of [1] to [13], wherein the pressing time in the smoothing step is 20 to 450 seconds.
[15] The production method according to any one of [1] to [13], wherein the smoothing step has a pressing time of 60 to 300 seconds.

[16] The production method according to any one of [1] to [15], wherein the support is a plastic film which may have a barrier layer.
[17] The production method according to any one of [1] to [16], wherein the support has a thickness of 30 to 200 μm.
[18] The production according to any one of [1] to [17], wherein the substrate is at least one selected from the group consisting of glass, polyimide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and cycloolefin polymer. Method.
[19] The manufacturing method according to any one of [1] to [18], wherein the substrate has a thickness of 0.1 to 1.0 mm.
[20] The production method according to any one of [1] to [19], wherein the curing step is performed simultaneously with the smoothing step.
[21] The production method according to any one of [1] to [20], wherein the sealing body is an organic EL device.

[22] A method for sealing an organic EL element on a substrate,
Laminating a sealing sheet having a thermosetting resin composition layer formed on a support using a roll laminator on a substrate so that the thermosetting resin composition layer is in contact with the organic EL element,
A method comprising a smoothing step of smoothing a laminated sealing sheet surface by hot pressing, and a curing step of thermosetting the thermosetting resin composition layer to form a sealing layer.

[23] The method according to [22], wherein the laminating is performed in an inert gas atmosphere.
[24] The method according to [22] or [23], wherein the laminating is performed under normal pressure.

[25] The method according to any one of [22] to [24] above, wherein the roll speed of the roll laminator is 0.01 to 1.5 m / min.
[26] The method according to any one of [22] to [24] above, wherein the roll speed of the roll laminator is 0.1 to 0.5 m / min.

[27] The method according to any one of [22] to [26], wherein the roll pressure of the roll laminator is 0 to 0.5 MPa.
[28] The method according to any one of [22] to [26], wherein the roll pressure of the roll laminator is 0 to 0.3 MPa.

[29] The method according to any one of [22] to [28], wherein the laminating temperature is 60 to 120 ° C.
[30] The method according to any one of [22] to [28], wherein the laminating temperature is 80 to 100 ° C.

[31] The method according to any one of [22] to [30], wherein the pressing pressure in the smoothing step is 0.01 to 0.5 MPa.
[32] The method according to any one of [22] to [30], wherein the pressing pressure in the smoothing step is 0.01 to 0.3 MPa.

[33] The method according to any one of [22] to [32] above, wherein the pressing temperature in the smoothing step is 60 to 120 ° C.
[34] The method according to any one of [22] to [32] above, wherein the pressing temperature in the smoothing step is 80 to 100 ° C.

[35] The method according to any one of [22] to [34], wherein the pressing time of the smoothing step is 20 to 450 seconds.
[36] The method according to any one of [22] to [34] above, wherein the smoothing step has a pressing time of 60 to 300 seconds.

[37] The method according to any one of [22] to [36], wherein the support is a plastic film which may have a barrier layer.
[38] The method according to any one of [22] to [37], wherein the support has a thickness of 30 to 200 μm.
[39] The method according to any one of [22] to [38], wherein the substrate is at least one selected from the group consisting of glass, polyimide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and cycloolefin polymer. .
[40] The method according to any one of [22] to [39], wherein the substrate has a thickness of 0.1 to 1.0 mm.
[41] The method according to any one of [22] to [40], wherein the curing step is performed simultaneously with the smoothing step.

According to the method of the present invention, it is possible to produce a sealed body (particularly, an organic EL device) in which an organic EL element is sealed with a sealing layer having high smoothness and adhesion without generating voids. In addition, there is no need to use a vacuum laminator, which is advantageous in terms of cost. Moreover, according to the method of the present invention, laminating can be carried out under an inert gas with little damage to the organic EL element.

The production method of the present invention is characterized in that smoothing by hot pressing is performed after laminating by a roll laminator (hereinafter sometimes abbreviated as “roll laminating”).
First, the laminating process by roll lamination and the smoothing process by hot pressing in the production method of the present invention will be described in order.

[Roll laminate]
The production method of the present invention is excellent in smoothness and adhesion without generating voids by laminating a sealing sheet and an organic EL element substrate by roll lamination and then smoothing by hot pressing. An encapsulating layer can be formed. The ambient pressure at the time of laminating is not particularly limited, but it can be reduced to normal pressure from the viewpoint of cost-effective production without using a vacuum laminator. Here, the normal pressure means that it is not in a state in which a vacuum (decompression) state is artificially made using a vacuum device such as a vacuum laminator.

Further, it is preferable that the lamination is performed in an inert gas atmosphere. In the present invention, since it is not necessary to perform lamination under vacuum (reduced pressure) using a vacuum laminator, lamination can be performed in a nitrogen atmosphere with little damage to the organic EL during lamination. Examples of the inert gas include nitrogen, argon, helium, neon, and the like. Of these, nitrogen is preferred. Lamination under an inert gas atmosphere can be performed under normal pressure. The ambient pressure (inert gas pressure) when laminating in an inert gas atmosphere is preferably 911.925 to 1215.9 hPa, more preferably 101.25 to 1114.575 hPa.

The roll speed of the roll laminator is preferably 0.01 to 1.5 m / min, more preferably, in order to achieve good adhesion of the sealing layer (cured product of the thermosetting resin composition layer) to the support. Is 0.1 to 0.5 m / min.

The roll pressure of the roll laminator is preferably 0 to 0.5 MPa, more preferably 0 to 0.3 MPa in order to avoid damage to the organic EL element. Here, the roll pressure means an applied pressure by an air syringe and is displayed as a gauge pressure (original pressure). Moreover, the roll pressure being 0 means that the applied pressure is 0.

The laminating temperature by the roll laminator is preferably 60 to 120 ° C., more preferably 80 to 100 ° C. in order to soften the thermosetting resin and improve the followability to the substrate. Here, the lamination temperature means the temperature of the roll surface digitally controlled by incorporating a heater in the roll, and can be measured by a surface contact type K thermocouple.

A commercially available roll laminator can be used for roll lamination. Examples of commercially available roll laminators include “Roll Laminator VA770H”, “Roll Laminator VA700”, “Roll Laminator VAII-700” manufactured by Taisei Laminator, and “Mach630up” manufactured by Hakuto Co., Ltd. Examples of the material of the roll of the roll laminator include stainless steel and silicone rubber. Silicone rubber is preferable.

[Hot press]
In the production method of the present invention, the smoothing step by hot pressing is performed after the laminating step by roll lamination. The surface of the sealing sheet laminated in the laminating process has undulations following the unevenness of the organic EL element surface of the substrate. This is smoothed by hot pressing. The hot pressing is preferably performed using a flat plate such as a metal plate (for example, using a flat plate press).
The hot pressing may be performed in an air atmosphere or an inert gas atmosphere. When hot pressing is performed in an air atmosphere, the ambient pressure is preferably atmospheric pressure. Examples of the inert gas include nitrogen, argon, neon, helium and the like. Hot pressing under an inert gas atmosphere can be performed under normal pressure. When hot pressing is performed in an inert gas atmosphere, the ambient pressure (that is, the pressure of the inert gas) is preferably 911.925 to 1215.9 hPa, more preferably 101.25 to 1114.575 hPa, and still more preferably 1013.75 to 1017.75 hPa.

The press pressure is preferably 0.01 to 0.5 MPa, more preferably 0.01 to 0.3 MPa in order to prevent cracking of the EL element due to the pressure. Here, the press pressure means a pressure applied to the pressed body controlled by a vacuum hydraulic cylinder or a load (that is, a pressure applied to the surface of the sealing sheet) and can be adjusted by a hot press apparatus.

The press temperature is preferably 60 to 120 ° C., more preferably 80 to 100 ° C. in order to ensure smoothness. Here, the press temperature means the temperature of the press part surface that is digitally controlled by incorporating a cartridge heater on the surface of the press part (for example, a flat plate such as a metal plate) of the hot press device, and measured by a surface contact type K thermocouple. can do.

The pressing time is not particularly limited as long as smoothing is achieved, but when hot pressing is performed using a flat plate such as a metal plate, it is preferably 20 to 450 seconds, more preferably 60 to 300 seconds.

A commercially available hot press apparatus can be used for the hot press. Examples of commercially available heat press apparatuses include flat plate presses such as “Batch type vacuum pressure laminator CVP-300” manufactured by Morton, and Kitakawa Seiki Co., Ltd., vacuum pressure press “VHI-2051”. Examples of the material for the flat plate for pressing include alloys such as stainless steel and iron, and stainless steel is preferable.

[Formation of sealing layer]
Formation of the sealing layer (that is, thermosetting of the thermosetting resin composition layer) may be performed after the support of the sealing sheet is peeled off, or may be performed with the support attached. The thermosetting can be performed, for example, with a hot air circulation oven, an infrared heater, a heat gun, a high frequency induction heating device, or the like. Thermosetting may be performed after hot pressing, or may be performed simultaneously with hot pressing by heating by hot pressing. The curing temperature varies depending on the thermosetting resin composition layer to be used and the support, but is usually 80 to 120 ° C., preferably 80 to 110 ° C., and the curing time is usually 10 to 120 minutes, preferably 10 to 30. Minutes. The thickness of the sealing layer to be formed is preferably 3 to 100 μm, more preferably 5 to 50 μm, and still more preferably 5 to 20 μm.

[Sealing sheet]
Next, the sealing sheet used in the present invention will be described. In the present invention, the sealing sheet is not particularly limited, and for example, those described in Patent Documents 1 to 3 can be used. Hereinafter, a preferable sealing sheet will be described.

The thermosetting resin composition preferably contains an epoxy resin and a curing agent. There is no limitation in particular in an epoxy resin and a hardening | curing agent, A conventionally well-known thing can be used. The thermosetting resin composition may further contain a hygroscopic metal oxide, a thermoplastic resin, an inorganic filler (excluding the hygroscopic metal oxide), and the like.

[Epoxy resin]
The epoxy resin can be used without limitation as long as it has two or more epoxy groups per molecule on average. For example, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine Type epoxy resin (for example, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyltoluidine, diglycidylaniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac Type epoxy resin, bisphenol A novolac type epoxy resin, epoxy resin having butadiene structure, diglycidyl etherified product of bisphenol, naphthalenediol Diglycidyl ethers of Le, glycidyl ethers of phenols, and diglycidyl ethers of alcohols, and alkyl substituted derivatives of these epoxy resins, halides and hydrogenated products or the like. Any one of these epoxy resins can be used or a mixture of two or more can be used.

Among them, the epoxy resin preferably has a transmittance of 80% or more, more preferably has a transmittance of 85% or more, and particularly preferably has a transmittance of 90% or more. Examples of such suitable epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, biphenyl aralkyl type epoxy resins, alicyclic epoxy resins, and aliphatic chain epoxy resins. . Here, the transmittance refers to the total light transmittance, and is a light transmittance considering reflection and scattering measured for the purpose of examining how much brightness is transmitted through the material. The incident light is measured by using visible light or ultraviolet light and collecting the transmitted light with an integrating sphere.

The epoxy resin may be liquid or solid, and both liquid epoxy resin and solid epoxy resin may be used. Here, “liquid” and “solid” are states of the epoxy resin at normal temperature (25 ° C.). From the viewpoint of coatability, workability, and adhesiveness, it is preferable that at least 10% by mass or more of the entire epoxy resin to be used is liquid.

From the viewpoint of reactivity, the epoxy equivalent of the epoxy resin is preferably 100 to 1000 g / eq, more preferably 120 to 1000 g / eq, and further preferably 150 to 1000 g / eq. Here, the epoxy equivalent is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method defined in JIS K 7236. The weight average molecular weight of the epoxy resin is preferably 5,000 or less.

The content of the epoxy resin in the thermosetting resin composition is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the entire thermosetting resin composition (nonvolatile content). Even more preferably, it is 50 to 65% by weight.

[Hygroscopic metal compound]
The resin composition of the present invention can further contain a hygroscopic metal oxide in order to further improve the moisture permeability resistance. Here, the “hygroscopic metal oxide” means a metal oxide that has a capability of absorbing moisture and chemically reacts with moisture that has been absorbed to become a hydroxide. Specifically, it is one kind selected from calcium oxide, magnesium oxide, strontium oxide, aluminum oxide, barium oxide or the like, or a mixture or solid solution of two or more kinds. Specific examples of the mixture or solid solution of two or more types include calcined dolomite (a mixture containing calcium oxide and magnesium oxide), calcined hydrotalcite (a solid solution of calcium oxide and aluminum oxide), and the like. It is done. Among these, calcium oxide, magnesium oxide, and hydrotalcite are preferable, and hydrotalcite is more preferable from the viewpoint of high hygroscopicity, cost, and stability of raw materials. Hydrotalcite is not particularly limited as long as it has water absorption. Examples of hydrotalcite include natural hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O) and / or synthetic hydrotalcite (hydrotalcite-like compound), When used as a hygroscopic agent, in general, calcined hydrotalcite is preferably used in which hydrotalcite is calcined to reduce the amount of OH in the chemical structure or disappear in order to improve water absorption. Preferred hydrotalcites include, for example, a sintered body of a synthetic hydrotalcite (hydrotalcite-like compound) represented by the following general formula (I), and a synthetic hydrotalcite (hydrotalc) represented by the following general formula (II) Site-like compound) and the like.

[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] ^{x +} · [(A ⁿ⁻ ) _{x / n} · mH ₂ O] ^x− (I)
^{(Wherein, M 2+} is ^Mg 2+, a divalent metal ion such as ^{Zn ^2+,} ^{M 3+} represents a trivalent metal ion such as ^Al ^{^3+, Fe} 3+, ^{A n-} is _CO ³ 2-, Cl Represents an n-valent anion such as ⁻ and NO ₃ ^— , 0 <x <1, 0 ≦ m <1, and n is a positive number.)

M ²⁺ _x Al ₂ (OH) _{2x + 6-nz} (A ⁿ⁻ ) _z · mH ₂ O (II)
^{(Wherein, M 2+} is ^Mg 2+, a divalent metal ion such as ^{Zn ^2+,} ^{A n-} is _{^{^{CO 3 2-, Cl -, NO}}} 3 - shows a n-valent anion, such as, x is 2 or more Z is a positive number of 2 or less, m is a positive number, and n is a positive number.)

The calcined hydrotalcite is preferably obtained by calcining natural hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O) and / or synthetic hydrotalcite (hydrotalcite-like compound), A composite oxide obtained by vaporizing an anion and a water molecule, preferably at 400 to 900 ° C., more preferably at 500 to 700 ° C., for 30 minutes to 5 hours, more preferably for 30 minutes to 3 hours. More preferred is a composite oxide obtained by firing for 45 minutes to 2 hours.

A preferred calcined hydrotalcite is a Mg—Al based composite oxide obtained by firing a Mg—Al based hydrotalcite-like compound such as a double hydroxide of the above formula (II), and the Mg—Al based composite oxide. The oxide is more preferably a composite oxide having a composition ratio where x is 2 ≦ x ≦ 6 when the composition ratio of Mg and Al is Mg: Al = x: 2, where x is 3 ≦ x ≦ 6. A composite oxide having a certain composition ratio is more preferable, and a composite oxide having a composition ratio in which x is 4 ≦ x ≦ 6 is particularly preferable.

The hygroscopic metal oxide is known as a hygroscopic material in various technical fields, and a commercially available product can be used. Specifically, calcium oxide (“Moystop # 10” manufactured by Sankyo Flour Milling Co., Ltd.), magnesium oxide (“Kyowa Mag MF-150”, “Kyowa Mag MF-30” manufactured by Kyowa Chemical Industry Co., Ltd., “Pure Mag” manufactured by Tateho Chemical Industry Co., Ltd. FNMG ”, etc.), lightly burned magnesium oxide (“ Tatehomag # 500 ”,“ Tatehomag # 1000 ”,“ Tatehomag # 5000 ”, etc., manufactured by Tateho Chemical Industries, Ltd.), calcined dolomite (“ Ysawa ”,“ KT ”etc.), calcined hydro Examples include talcite (“KW2200”, “DHT-4A”, “DHT-4A-2”, “DHT-4C”, etc., manufactured by Kyowa Chemical Industry Co., Ltd.).

As the hygroscopic metal oxide, a surface treated with a surface treatment agent can be used. As the surface treatment agent used for the surface treatment, for example, higher fatty acids, alkylsilanes, silane coupling agents and the like can be used, and among these, higher fatty acids and alkylsilanes are preferable. One or more surface treatment agents can be used.

Examples of the higher fatty acid include higher fatty acids having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid, and palmitic acid, among which stearic acid is preferable. You may use these 1 type or in combination of 2 or more types. Alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl ( And 3- (trimethoxysilyl) propyl) ammonium chloride. You may use these 1 type or in combination of 2 or more types. Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Epoxy silane coupling agents such as silane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane ; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrime Amino silane cups such as xylsilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Ringing agents; Ureido silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; p-styryltrimethoxysilane Styryl-based silane coupling agents; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; 3-isocyanatopropyltrimethoxy Isocyanate-based silane coupling agents such as silane, sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole Examples thereof include silane and triazine silane. You may use these 1 type or in combination of 2 or more types.

The surface treatment of the hygroscopic metal oxide is performed, for example, by adding and spraying the surface treatment agent and stirring for 5 to 60 minutes while stirring and dispersing the untreated hygroscopic metal oxide at room temperature with a mixer. Can do. As a mixer, a well-known mixer can be used, For example, blenders, such as V blender, a ribbon blender, and a bubble cone blender, mixers, such as a Henschel mixer and a concrete mixer, a ball mill, a cutter mill, etc. are mentioned. In addition, when the hygroscopic metal oxide is pulverized with a ball mill or the like, a method of surface treatment by mixing the higher fatty acid, alkylsilanes or silane coupling agent is also possible. The treatment amount of the surface treatment agent varies depending on the type of the hygroscopic metal oxide or the type of the surface treatment agent, but is preferably 1 to 10% by mass relative to the hygroscopic metal oxide.

The content of the hygroscopic metal oxide in the thermosetting resin composition is preferably 3 to 38 parts by mass with respect to 80 parts by mass of the epoxy resin, and more preferably 5% from the viewpoint of moisture resistance and permeability. Is 35 parts by mass, more preferably 10-35 parts by mass. The content of the hygroscopic metal oxide is preferably 2 to 24% by mass, more preferably 5 to 23% by mass, based on the entire thermosetting resin composition (nonvolatile content).

[Inorganic filler]
The thermosetting resin composition of the present invention includes the moisture-absorbing metal described above from the viewpoint of the moisture barrier property of the resin composition, the coating property (prevention of repelling) of the resin composition varnish when preparing a sealing sheet, and the like. An inorganic filler other than the compound can be further contained. Examples of inorganic fillers include talc, silica, alumina, barium sulfate, clay, mica, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, and titanic acid. Examples include strontium, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium zirconate, calcium zirconate, and silicate. From the standpoint of maintaining a high transmittance, the primary particle size of the inorganic filler is preferably 5 μm or less, and more preferably 1 μm or less. For example, primary particles having a particle size of 1 to 100 nm, more preferably 1 to 50 nm, even more preferably 10 to 20 nm, and particularly preferably 10 to 15 nm can be used. Since measurement of the primary particle diameter of an inorganic filler that is 1 μm or less may be relatively difficult, a converted value from a specific surface area measurement value (based on JIS Z8830) may be used. For example, the nano inorganic filler has a BET specific surface area of 2720 to 27 m ² / g, preferably 2720 to 54 m ² / g, more preferably 272 to 136 m ² / g, more preferably 272. Those having a density of ˜181 m ² / g can be used.

The particle form of the inorganic filler is not particularly limited, and may be a substantially spherical shape, a rectangular parallelepiped shape, a plate shape, a linear shape such as a fiber, or a branched shape. The inorganic filler is preferably talc, silica, zeolite, titanium oxide, alumina, zirconium oxide, silicate, mica, mica, magnesium hydroxide, aluminum hydroxide, and more preferably silica. As the silica, wet silica, dry silica, colloidal silica (water dispersion type, organic solvent dispersion type, gas phase silica, etc.) is preferable, and it is difficult to precipitate and settle, and it is easy to form a composite with a resin. Dispersed colloidal silica (organosilica sol) is particularly preferred.

As the inorganic filler, commercially available products can be used. For example, “FG-15F” (talc powder) manufactured by Nippon Talc, “MEK-EC-2130Y” manufactured by Nissan Chemical Industries, Ltd. (amorphous silica particle size of 10 to 15 nm, nonvolatile content) 30% by mass, MEK solvent), “PGM-AC-2140Y” manufactured by Nissan Chemical Industries, Ltd. (silica particle size 10-15 nm, nonvolatile content 40% by mass, PGM (propylene glycol monomethyl ether) solvent), manufactured by Nissan Chemical Industries, Ltd. MIBK-ST ”(silica particle size 10 to 15 nm, nonvolatile content 30% by mass, MIBK (methyl isobutyl ketone) solvent), colloidal silica sol“ PL-2L-MEK ”manufactured by Fuso Chemical Industries (silica particle size 15 to 20 nm, Nonvolatile content 20% by mass, MEK (methyl ethyl ketone) solvent) and the like.

In the present invention, one or more inorganic fillers can be used. When the resin composition of the present invention contains an inorganic filler, the content of the inorganic filler is preferably 10% by mass or less, more preferably 9% by mass or less, based on the entire resin composition (nonvolatile content). .

[Thermoplastic resin]
In the thermosetting resin composition, the provision of flexibility to the sealing layer obtained by curing the thermosetting resin composition layer, the thermosetting resin composition varnish when preparing the sealing sheet From the viewpoint of coatability (prevention of repelling) and the like, a thermoplastic resin can be contained. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, and polysulfone resin. Any one of these thermoplastic resins may be used, or two or more thereof may be mixed and used. The content of the thermoplastic resin in the thermosetting resin composition is preferably 1 to 40% by mass and more preferably 5 to 30% by mass with respect to the entire thermosetting resin composition (nonvolatile content).

The thermoplastic resin has a weight average molecular weight of 15 from the viewpoint of imparting flexibility to the sealing layer and coating properties (preventing repelling) of the thermosetting resin composition varnish when preparing a sealing sheet. Is preferably 20,000 or more, and more preferably 20,000 or more. However, if the weight average molecular weight is too large, the compatibility with the epoxy resin tends to be reduced. Therefore, the weight average molecular weight is preferably 1,000,000 or less, more preferably 800,000 or less. . In addition, "the weight average molecular weight of a thermoplastic resin" here is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column, and mobile phase. It can be calculated by using a calibration curve of standard polystyrene by measuring at a column temperature of 40 ° C. using chloroform or the like.

The thermoplastic resin preferably has a transmittance of 80% or more, and more preferably has a transmittance of 90% or more. Of the above-described examples, the thermoplastic resin is particularly preferably a phenoxy resin. The phenoxy resin has good compatibility with the epoxy resin, and acts advantageously on the permeability and moisture resistance of the thermosetting resin composition.

The phenoxy resin has one or more skeletons selected from bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, etc. Is mentioned. One or more phenoxy resins can be used. As commercially available products of phenoxy resin, for example, YX7200B35, 1256, YX6954BH35 manufactured by Mitsubishi Chemical Corporation can be suitably used.

[Coupling agent]
The thermosetting resin composition can contain a coupling agent from the viewpoint of improving the adhesive strength of the thermosetting resin composition. Examples of such coupling agents include titanium coupling agents, aluminum coupling agents, silane coupling agents, and the like. Among these, a silane coupling agent is preferable. A coupling agent can be used 1 type or in combination of 2 or more types.

Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Epoxy silane coupling agents such as silane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropylto Amino silanes such as methoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Coupling agents; Ureido silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; p-styryltrimethoxysilane Styryl silane coupling agents such as; acrylate silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; Isocyanate-based silane coupling agents such as xysilane, sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole Examples thereof include silane and triazine silane. Among these, an epoxy-based silane coupling agent is particularly suitable.

When a coupling agent is used, the content of the coupling agent in the thermosetting resin composition is preferably 0.5 to 10% by mass with respect to the entire thermosetting resin composition (nonvolatile content). More preferable is 5% by mass. When the content of the coupling agent is outside this range, it is not possible to obtain an effect of improving the adhesion due to the addition of the coupling agent.

[Curing agent]
The thermosetting resin composition containing an epoxy resin usually contains an epoxy resin curing agent. Although it will not specifically limit if a hardening | curing agent has a function which hardens | cures an epoxy resin, From a viewpoint of suppressing the thermal deterioration of light emitting elements, such as an organic EL element at the time of the hardening process of a thermosetting resin composition, 140 degrees C or less Those capable of curing the epoxy resin at a temperature (preferably 120 ° C. or lower) are preferable.

Examples of the curing agent include primary amine, secondary amine, tertiary amine-based curing agent, polyaminoamide-based curing agent, dicyandiamide, and organic acid dihydrazide. Among these, amine adduct compounds (Amicure PN-23, Amicure MY-24, Amicure PN-D, Amicure MY-D, Amicure PN-H, Amicure MY-H, Amicure PN-31, Amicure from the viewpoint of fast curing properties. PN-40, Amicure PN-40J, etc. (all manufactured by Ajinomoto Fine Techno Co., Ltd.), organic acid dihydrazide (Amicure VDH-J, Amicure UDH, Amicure LDH, etc. (all manufactured by Ajinomoto Fine Techno Co., Ltd.)) and the like are particularly preferable.

An ionic liquid capable of curing the epoxy resin at a temperature of 140 ° C. or lower (preferably 120 ° C. or lower), that is, a salt that can be melted in a temperature range of 140 ° C. or lower (preferably 120 ° C. or lower), A salt having a curing action of the resin can also be used particularly suitably as a curing agent. The ionic liquid is desirably used in a state where it is uniformly dissolved in the epoxy resin. In addition, the ionic liquid has an advantageous effect on improving the moisture permeation resistance of the cured product of the thermoplastic resin composition.

Examples of the cation constituting the ionic liquid include imidazolium ions, piperidinium ions, pyrrolidinium ions, pyrazonium ions, guanidinium ions, pyridinium ions, and other ammonium-based cations; tetraalkylphosphonium cations (for example, tetrabutylphosphonium ions, Phosphonium cations such as tributylhexyl phosphonium ion; and sulfonium cations such as triethylsulfonium ion.

Examples of the anion constituting the ionic liquid include halide anions such as fluoride ion, chloride ion, bromide ion and iodide ion; alkyl sulfate anions such as methanesulfonate ion; trifluoromethanesulfonate ion, Fluorine-containing compound anions such as hexafluorophosphonate ion, trifluorotris (pentafluoroethyl) phosphonate ion, bis (trifluoromethanesulfonyl) imide ion, trifluoroacetate ion, tetrafluoroborate ion; phenol ion, 2-methoxy Phenolic anions such as phenol ion and 2,6-di-tert-butylphenol ion; acidic amino acid ions such as aspartate ion and glutamate ion; glycine ion, alanine ion, pheny Neutral amino acid ions such as alanine ion; N-acyl amino acid ions represented by the following formula (1) such as N-benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion; formate ion, acetate ion, decanoic acid Examples thereof include carboxylic acid anions such as ions, 2-pyrrolidone-5-carboxylate ions, α-lipoic acid ions, lactate ions, tartrate ions, hippurate ions, N-methylhippurate ions, and benzoate ions.

(In the formula, R is a linear or branched hydrocarbon group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group, and X represents a side chain of an amino acid. Examples of amino acids include asparagine. Acid, glutamic acid, glycine, alanine, phenylalanine, etc.)

Among the above, the cation is preferably an ammonium cation or a phosphonium cation, and more preferably an imidazolium ion or a phosphonium ion. More specifically, the imidazolium ion is 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-propyl-3-methylimidazolium ion or the like.

The anion is preferably a phenolic anion, an N-acyl amino acid ion or a carboxylic acid anion represented by the formula (1), and more preferably an N-acyl amino acid ion or a carboxylic acid anion.

Specific examples of the phenolic anion include 2,6-di-tert-butylphenol ion. Specific examples of the carboxylate anion include acetate ion, decanoate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, α-lipoic acid ion, lactate ion, tartrate ion, hippurate ion, N- Methyl hippurate ion and the like, among which acetate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, lactate ion, tartrate ion, hippurate ion and N-methylhippurate ion are preferable, acetate ion, N -Methyl hippurate ion and formate ion are particularly preferred. Specific examples of the N-acylamino acid ion represented by the formula (1) include N-benzoylalanine ion, N-acetylphenylalanine ion, aspartate ion, glycine ion, N-acetylglycine ion and the like. N-benzoylalanine ion, N-acetylphenylalanine ion and N-acetylglycine ion are preferable, and N-acetylglycine ion is particularly preferable.

Specific ionic liquids include, for example, 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium tri Fluoroacetate, tetrabutylphosphonium α-lipoate, tetrabutylphosphonium formate, tetrabutylphosphonium lactate, bis (tetrabutylphosphonium) tartrate, tetrabutylphosphonium hippurate, tetrabutylphosphonium N-methylhippurate, benzoyl-DL -Alanine tetrabutylphosphonium salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2,6-di-tert-butylphenoltetrabutylphospho Um salt, L-aspartate monotetrabutylphosphonium salt, glycine tetrabutylphosphonium salt, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium lactate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium hippurate, 1-ethyl-3-methylimidazolium N-methylhippurate, bis (1-ethyl-3-tartrate) Methyl imidazolium) salt, N-acetylglycine 1-ethyl-3-methylimidazolium salt, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-formate Methylimidazolium salt, 1-ethyl hippurate Particularly preferred are 3-methylimidazolium salt and 1-ethyl-3-methylimidazolium salt of N-methylhippuric acid.

As a method for synthesizing the ionic liquid, a precursor composed of a cation moiety such as an alkylimidazolium, alkylpyridinium, alkylammonium and alkylsulfonium ions and an anion moiety containing a halogen is added to NaBF ₄ , NaPF ₆ , CF ₃ SO ₃ Anion exchange method in which Na, LiN (SO ₂ CF ₃ ) ₂ or the like is reacted, an acid ester in which an organic acid residue becomes a counter anion while introducing an alkyl group by reacting an amine substance with an acid ester Methods, and neutralization methods in which amines are neutralized with an organic acid to obtain a salt, but are not limited thereto. In the neutralization method using an anion, a cation, and a solvent, it is possible to use an anion and a cation in equal amounts, distill off the solvent in the obtained reaction solution, and use it as it is. Furthermore, an organic solvent (methanol, (Toluene, ethyl acetate, acetone, etc.) may be added and concentrated.

The content of the curing agent in the thermosetting resin composition is preferably 0.1 to 50% by mass with respect to the total amount (nonvolatile content) of the epoxy resin contained in the thermosetting resin composition. If the content is less than 0.1% by mass, sufficient curability may not be obtained. If the content is more than 50% by mass, the storage stability of the thermosetting resin composition may be impaired. When an ionic liquid is used, the amount thereof is preferably 0.1 to 10% by mass with respect to the total amount (nonvolatile content) of the epoxy resin from the viewpoint of moisture resistance of the cured product of the thermosetting resin composition. .

When an ionic liquid is used as the curing agent, a polythiol compound having two or more thiol groups in the molecule together with the ionic liquid may be contained in the thermosetting resin composition. Inclusion of a polythiol compound having two or more thiol groups in the molecule can increase the curing speed. Specific examples of the polythiol compound having two or more thiol groups in the molecule include, for example, trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris ( Examples include thiol compounds obtained by esterification reaction of polyols such as β-thiopropionate), pentaerythritol tetrakis (β-thiopropionate), dipentaerythritol poly (β-thiopropionate) and mercapto organic acid. It is done. Such a thiol compound is a thiol compound having two or more thiol groups in the molecule, which does not require the use of a basic substance for production.

Examples of the polythiol compound having two or more thiol groups in the molecule include alkyl polythiol compounds such as 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol; terminal thiol group-containing polyether; Examples include a terminal thiol group-containing polythioether; a thiol compound obtained by a reaction between an epoxy compound and hydrogen sulfide; a thiol compound having a terminal thiol group obtained by a reaction between a polythiol compound and an epoxy compound. In addition, thiol compounds obtained by reaction of epoxy compounds and hydrogen sulfide, thiol compounds having terminal thiol groups obtained by reaction of polythiol compounds and epoxy compounds, etc., using basic substances as reaction catalysts in the production process It is preferable to use what has been subjected to dealkalization treatment and has an alkali metal ion concentration of 50 ppm or less. As a method for such dealkalization treatment, for example, the polythiol compound to be treated is dissolved in an organic solvent such as acetone or methanol, neutralized by adding an acid such as dilute hydrochloric acid or dilute sulfuric acid, and then desalted by extraction or washing. A method of adsorbing using an ion exchange resin, a method of purification by distillation, and the like, but are not limited thereto.

When such a polythiol compound is used, the ratio of the blend amount of the polythiol compound / SH equivalent to the blend amount of the epoxy resin / epoxy equivalent (ie, “(blend amount of polythiol compound / SH equivalent) / (blend amount of epoxy resin / epoxy) It is preferable to mix the epoxy resin and the polythiol compound so that the equivalent)) ”) is 0.2 to 1.2. If this ratio is less than 0.2, sufficient fast curability may not be obtained, while if it is more than 1.2, physical properties of the cured product such as heat resistance may be impaired. From the viewpoint of stabilizing the adhesiveness, this ratio is more preferably 0.5 to 1.0. Here, “SH equivalent” means “molecular weight of polythiol compound / number of SH groups”, and “epoxy equivalent” means “molecular weight of epoxy resin / number of epoxy groups”.

[Curing accelerator]
The thermosetting resin composition containing an epoxy resin may contain a curing accelerator for the purpose of adjusting the curing time. Examples of the curing accelerator include organic phosphine compounds, imidazole compounds, amine adduct compounds (for example, epoxy adduct compounds in which a tertiary amine is added to an epoxy resin to stop the reaction, etc.), tertiary amine compounds, and the like. Can be mentioned. Specific examples of the organic phosphine compound include TPP, TPP-K, TPP-S, and TPTP-S (trade name of Hokuko Chemical Co., Ltd.). Specific examples of the imidazole compound include Curazole 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2MZOK, 2MA-OK, and 2PHZ (trade names of Shikoku Kasei Kogyo Co., Ltd.). Specific examples of amine adduct compounds include Fuji Cure (trade name of Fuji Kasei Kogyo Co., Ltd.). Specific examples of the tertiary amine compounds include DBU (1,8-diazabicyelo [5.4.0] undec-7-ene), DBU 2-ethylhexanoate, octylate and other DBU-organic acid salts, U And aromatic dimethylurea such as U-3503T (manufactured by San Apro), and the like. Of these, urea compounds are preferable from the viewpoint of moisture resistance, and aromatic dimethylurea is particularly preferably used. The content of the curing accelerator in the thermosetting resin composition is usually 0.05 to 5% by mass when the total amount of the epoxy resin in the thermosetting resin composition is 100% by mass (nonvolatile content). . If it is less than 0.05% by mass, curing tends to be slow and a long thermosetting time is required, and if it exceeds 5% by mass, the storage stability of the thermosetting resin composition tends to decrease.

The thermosetting resin composition may optionally contain various additives other than the components described above. Examples of such additives include organic fillers such as silicone powder, nylon powder, and fluororesin powder, thickeners such as olben and benton, silicone-based, fluorine-based, and polymer-based antifoaming agents or leveling agents. , Adhesion imparting agents such as triazole compounds, thiazole compounds, triazine compounds, and porphyrin compounds.

The thermosetting resin composition is prepared by further adding components with an organic solvent, if necessary, and mixing them using a kneading roller or a rotating mixer.

The sealing sheet is prepared by a method known to those skilled in the art, for example, by preparing a varnish in which a thermosetting resin composition is dissolved in an organic solvent, applying the varnish on a support, and further heating or blowing hot air. It can manufacture by drying a solvent and forming a thermosetting resin composition layer. The thickness of the thermosetting resin composition layer after drying is preferably 3 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 20 μm.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate esters such as carbitol acetate, cellosolves such as cellosolve, Examples thereof include carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. One of these organic solvents may be used alone, or two or more thereof may be used in combination.

Examples of the support for the sealing sheet include polyolefins such as polyethylene and polypropylene (PP), polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), polyimide (PI), Examples thereof include plastic films such as cycloolefin polymer (COP) and polyvinyl chloride. As the plastic film, polyethylene terephthalate, polyethylene naphthalate, and cycloolefin polymer are preferable.

In order to improve the moisture resistance of the sealing sheet, a plastic film having a barrier layer may be used as a support. Examples of the barrier layer include nitrides such as silicon nitride, oxides such as aluminum oxide, metals such as stainless steel and aluminum, and the like. As a support for a plastic film having a barrier layer, the plastic film is preferably at least one selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polycarbonate and cycloolefin polymer, and the plastic film is polyethylene terephthalate, More preferred is at least one selected from the group consisting of polyethylene naphthalate and cycloolefin polymer, and more preferred is that the plastic film is polyethylene terephthalate. A commercial product may be used as the plastic film having the barrier layer. Examples of commercially available polyethylene terephthalate films with aluminum foil include “Alpet 1N30” manufactured by Tokai Toyo Aluminum Sales Co., “Alpet 3025” manufactured by Fukuda Metals Co., Ltd.

The support may be subjected to a release treatment using a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, a mat treatment, a corona treatment, or the like. The thickness of the support is not particularly limited, but is preferably 20 to 200 μm, more preferably 20 to 125 μm, from the viewpoint of the handleability of the sealing sheet.

The thermosetting resin composition layer may be protected with a cover film in order to prevent dust from adhering to the surface and scratches. The cover film is peeled off before laminating the sealing sheet and the organic EL element substrate. The cover film is preferably a plastic film similar to the support. The cover film may be subjected to a release treatment with a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, a mat treatment, a corona treatment, or the like. The thickness of the cover film is not particularly limited, but is, for example, 15 to 75 μm, preferably 15 to 50 μm.

[Organic EL element substrate]
The substrate of the organic EL element substrate (hereinafter sometimes abbreviated as “substrate”) is not particularly limited, and a known substrate can be used. The substrate is preferably at least one selected from the group consisting of glass, polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), and cycloolefin polymer (COP).

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

In order to extract light from the organic EL element, it is necessary that either the substrate of the organic EL element substrate or the support for the sealing sheet is transparent. For example, when an opaque support (for example, a plastic film having an opaque barrier layer) is used for the sealing sheet, it is necessary to use a transparent substrate in order to extract light from the substrate side.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.

<Production of ionic liquid curing agent>
To 20.0 g of tetrabutylphosphonium hydroxide aqueous solution (Hokuko Chemical Co., Ltd., concentration: 41.4% by mass), 3.54 g of N-acetylglycine (Tokyo Chemical Industry Co., Ltd.) was added at 0 ° C. and stirred for 10 minutes. did. The pressure was reduced to 40-50 mmHg using an evaporator, and the mixture was concentrated at 60-80 ° C. for 2 hours and at 90 ° C. for 5 hours. Redissolve in 14.2 mL of ethyl acetate (manufactured by Junsei Co., Ltd.) at room temperature, depressurize to 40-50 mmHg using an evaporator, concentrate at 70-90 ° C. under reduced pressure for 3 hours, and N-acetylglycinetetrabutyl 11.7 g (purity 96.9%) of the phosphonium salt was obtained as an oily compound.

<Preparation of sealing sheet 1>
56 parts by mass of liquid bisphenol A type epoxy resin (Mitsubishi Chemical "jER828EL", epoxy equivalent of about 185 g / eq), 1.2 parts by mass of silane coupling agent (Shin-Etsu Chemical "KBM403"), talc powder 2 parts by mass (“FG-15F” manufactured by Nippon Talc Co., Ltd.) and 15 parts by mass of calcined hydrotalcite (“KW2200” manufactured by Kyowa Chemical Industry Co., Ltd.) were kneaded and then dispersed in a three-roll mill to obtain a mixture. .

1.5 parts by mass of a curing accelerator (“U-3512T” manufactured by San Apro Co., Ltd.) and 81 parts by mass of a methyl ethyl ketone (MEK) solution of phenoxy resin (“YX7200B35” manufactured by Mitsubishi Chemical Co., Ltd., concentration 35% by mass) (phenoxy resin 28. MEK solution (solid bisphenol A type epoxy resin (“jER1001” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 475 g / eq)) prepared by dispersing the mixture in a mixture dissolved in 4 parts by mass with a three-roll mill. 30 parts by weight of an organic solvent-dispersed colloidal silica (silica particle size 10-15 nm, nonvolatile content 30% by weight, MEK solvent, “MEK-EC-2130Y” manufactured by Nissan Chemical Industries, Ltd.) And 3 parts by weight of an ionic liquid curing agent (N-acetylglycine tetrabutylphosphonium salt) Uniformly dispersed to obtain a resin composition varnish Sir.

Next, the obtained resin composition varnish is dried on a polyethylene terephthalate film (hereinafter abbreviated as “support PET film”) (thickness 38 μm) treated with an alkyd mold release agent. The film was uniformly coated with a die coater so as to have a thickness of 20 μm and dried at 80 to 100 ° C. (average 90 ° C.) for 5 minutes (the amount of residual solvent in the resin composition layer was about 2% by mass). Next, a 38 μm-thick polyethylene terephthalate film (hereinafter abbreviated as “cover PET film”) treated with an alkyd release agent as a cover film was wound into a roll while being bonded to the surface of the resin composition layer. The roll-shaped sealing sheet was slit to a width of 507 mm to obtain a sealing sheet 1 having a size of 507 × 336 mm.

<Preparation of sealing sheets 2 to 4>
Using the sealing sheet 1 and any of the following supports 2 to 4, sealing sheets 2 to 4 were produced.
-Plastic film having a barrier layer Support 2: “Alpet 1N30” manufactured by Tokai Toyo Aluminum Sales Co., Ltd. (plastic film: PET with a thickness of 25 μm, barrier layer: aluminum foil with a thickness of 30 μm)
Support 3: a plastic film (PET having a thickness of 125 μm) in which an adhesive layer and a barrier layer (inorganic vapor deposition layer) are sequentially provided. A plastic film without a barrier layer. Support 4: “Lumirror T60” manufactured by Toray Industries, Inc. (PET with a thickness of 100 μm)

A sealing sheet 1 (width 20 mm, length 50 mm) from which a cover PET film has been peeled off is applied to a support cut to a width of 25 mm and a length of 100 mm, and the thermosetting resin composition layer is one of the supports 2 to 4 Overlaid so that it touches. In addition, when using the support body 2 or 3 which has a barrier layer, the sheet | seat 1 for sealing and support body 2 or 3 which peeled the cover PET film so that a thermosetting resin composition layer might contact this barrier layer. And superimposed. The superposed ones are laminated using a roll laminator VA770H (manufactured by Taisei Laminator Co., Ltd., laminating temperature 80 ° C., roll speed 0.5 mL / min, roll pressure 0.1 MPa) to support each thermosetting resin composition layer. The sealing sheets 2 to 4 on the bodies 2 to 4 were obtained.

<Example 1>
(1) Preparation of samples for evaluation of smoothness and voids Polyimide tape with copper foil etched to form a striped pattern with a linear copper foil and a portion without copper foil (product name “AJ-”, manufactured by Mitsui Kinzoku Co., Ltd.) C0002-30 / 40 ”, copper foil thickness 5 μm, polyimide thickness 40 μm, (linear copper foil (line) width 15 μm, copper foil-free portion (space) width 15 μm) as a pattern substrate, Samples for smoothness and void evaluation were produced as follows.

The pattern substrate was temporarily fixed on a stainless steel (SUS) plate having a thickness of 0.8 mm. The cover PET film is peeled off from the sealing sheet 1, and the thermosetting resin composition layer is overlapped with the pattern substrate so as to be in contact with the pattern substrate, and roll laminator VA770H (manufactured by Taisei Laminator Co., Ltd., roll material: silicone rubber) is used. These were laminated using a lamination temperature of 80 ° C., a roll speed of 0.1 m / min, a roll pressure of 0 MPa, and atmospheric pressure in the atmosphere. Subsequently, a batch-type vacuum press laminator CVP-300 (manufactured by Morton, flat plate material: SUS 603H) as a hot press apparatus (flat plate press machine) was applied at a press temperature of 90 ° C., a press pressure of 0.15 MPa, and a press time of 300. The pattern substrate on which the sealing sheet was laminated was hot-pressed for 2 seconds under the condition of atmospheric pressure under atmospheric pressure. Next, the support PET film was peeled from the pressed sealing sheet. Thereafter, the thermosetting resin layer was cured at 110 ° C. for 30 minutes to form a sealing layer (cured product of the thermosetting resin composition layer), and samples for smoothness and void evaluation were produced.

(2) Preparation of sample for adhesion and void evaluation A glass plate (width 26 mm, length 76 mm, thickness 1 mm) was temporarily fixed on a SUS plate having a thickness of 0.8 mm. The support PET film is peeled from each of the sealing sheets 2 to 4, and the sealing sheet and the glass plate are overlapped so that the thermosetting resin composition layer is in contact with the glass plate, and a roll laminator VA770H (Taisei Laminator) is used. Were used under the conditions of a lamination temperature of 80 ° C., a roll speed of 0.1 m / min, a roll pressure of 0 MPa, and atmospheric pressure in the atmosphere. Subsequently, a batch type vacuum pressure laminator CVP-300 (manufactured by Morton) was used as a hot press apparatus (flat plate press machine) at a press temperature of 90 ° C., a press pressure of 0.15 MPa, a press time of 300 seconds, and a large amount in the atmosphere. The glass plate on which the sealing sheet was laminated was hot-pressed under the conditions under atmospheric pressure. Thereafter, the thermosetting resin layer was cured at 110 ° C. for 30 minutes to form a sealing layer (cured product of the thermosetting resin composition layer), and a sample for evaluation of adhesion and void was prepared.

<Example 2>
A sample for smoothness and void evaluation and a sample for adhesion and void evaluation were prepared in the same manner as in Example 1 except that the roll speed was changed from 0.1 m / min to 1.0 m / min.

<Example 3>
Samples for smoothness and void evaluation and adhesion and voids were the same as in Example 2 except that the roll laminating step was performed in an inert gas (nitrogen) atmosphere (pressure: 1013.25 hPa) in a glove box. An evaluation sample was produced.

<Comparative Example 1>
A sample for smoothness and void evaluation and a sample for adhesion and void evaluation were prepared in the same manner as in Example 1 except that heat pressing was not performed after lamination by a roll laminator.

<Comparative example 2>
A sample for smoothness and void evaluation and a sample for adhesion and void evaluation were produced in the same manner as in Comparative Example 1 except that the roll speed was changed from 0.1 m / min to 1.0 m / min.

<Comparative Example 3>
A sample for smoothness and void evaluation and a sample for adhesion and void evaluation were produced in the same manner as in Comparative Example 1 except that the roll pressure was changed from 0 MPa to 0.15 MPa.

<Comparative example 4>
A sample for smoothness and void evaluation and a sample for adhesion and void evaluation were prepared in the same manner as in Example 1 except that only the heat press was performed without performing the lamination with the roll laminator.

<Comparative Example 5>
A sample for smoothness and void evaluation and a sample for adhesion and void evaluation were prepared in the same manner as in Comparative Example 4 except that the press temperature was changed from 90 ° C. to 110 ° C. and the press time was changed from 300 seconds to 1800 seconds. Produced.

<Comparative Example 6>
(1) Preparation of sample for evaluation of smoothness and voids As in Example 1, a polyimide tape with copper foil was used as a pattern substrate, and samples for evaluation of smoothness and voids were prepared as follows.

The pattern substrate was temporarily fixed on a 0.8 mm thick SUS plate. The cover PET film is peeled off from the sealing sheet 1 and the sealing sheet and the pattern substrate are overlapped so that the thermosetting resin composition layer is in contact with the pattern substrate, and a diaphragm vacuum pressurizing laminator V-160 ( (Morton Co., Ltd.) was held for 20 seconds under the conditions of a set temperature of 80 ° C. and a vacuum degree of 1.2 hPa, then the vacuum state was returned to the atmospheric atmosphere, and the atmospheric pressure in the atmospheric atmosphere, laminating pressure 0.1 MPa, laminating time These were laminated under the condition of 20 seconds. Next, the support PET film was peeled from the pressed sealing sheet. Thereafter, the thermosetting resin layer was cured at 110 ° C. for 30 minutes to form a sealing layer (cured product of the thermosetting resin composition layer), and samples for smoothness and void evaluation were produced.

(2) Preparation of sample for adhesion and void evaluation A glass plate (width 26 mm, length 76 mm, thickness 1 mm) was temporarily fixed on a SUS plate having a thickness of 0.8 mm. The support PET film is peeled off from each of the sealing sheets 2 to 4, and the sealing sheet and the glass plate are overlapped so that the thermosetting resin composition layer is in contact with the glass plate. After holding for 20 seconds at V-160 (manufactured by Morton) under the conditions of a set temperature of 80 ° C. and a vacuum of 1.2 hPa, the vacuum state is returned to the atmosphere, and the laminate pressure is reduced to atmospheric pressure in the atmosphere. These were laminated under the conditions of 0.1 MPa and a lamination time of 20 seconds. Thereafter, the thermosetting resin layer was cured at 110 ° C. for 30 minutes to form a sealing layer (cured product of the thermosetting resin composition layer), and a sample for evaluation of adhesion and void was prepared.

Using the smoothness and void evaluation samples and the adhesion and void evaluation samples prepared in the above Examples and Comparative Examples, the voids, smoothness and adhesion were evaluated as follows.

<Evaluation of void>
Observe whether a void exists between the sealing layer and the pattern substrate or the glass plate in the sample for smoothness and void evaluation and the sample for adhesion and void evaluation by visual observation and optical microscope (magnification 150 times) did. The case where a void was not observed with an optical microscope was evaluated as good (◯), and the case where a void was observed visually or with an optical microscope was evaluated as poor (×).

<Smoothness evaluation (gap measurement)>
Using a non-contact type surface roughness meter (BYCO Instruments WYKO, GT-3) under the conditions of a VSI contact mode, a 50 × lens, and a measurement range of 126 μm × 94 μm, the surface of the sealing layer of the sample for smoothness and void evaluation Thus, the height difference (gap) between the portion with the linear copper foil (line) and the portion without the copper foil (space) in the pattern substrate was measured.

<Adhesion evaluation (peel strength measurement)>
In accordance with JIS C6481, using an Instron universal testing machine at room temperature and a speed of 50 mm / min, the load when the support was peeled 20 mm vertically from the sample for adhesion and void evaluation, It was measured as the peel strength between the support and the sealing layer.

Table 1 shows the sealing methods and conditions of Examples and Comparative Examples, and Table 2 shows the evaluation results.

As shown in Tables 1 and 2, in Examples 1 to 3, in which hot pressing was performed following roll lamination, a sealing layer having high smoothness and adhesiveness was obtained without generating voids.

On the other hand, in Comparative Examples 1 to 3 in which only roll lamination is performed, the smoothness of the obtained sealing layer is low. Moreover, in Comparative Examples 4 and 5 in which only hot pressing is performed, voids are generated in the obtained sealing layer, and the smoothness and adhesion are low. Further, in Comparative Example 6 in which high-cost vacuum lamination was performed, a sealing layer having high adhesion was obtained without generating voids, but the sealing layer was smoother than in Examples 1 and 2. The sex was inferior.

The manufacturing method of the sealing body (especially organic EL device) of this invention can seal an organic EL element with the sealing layer with smoothness and high adhesiveness, without generating a void, and is also a vacuum laminator. This is advantageous in terms of cost. Moreover, according to the manufacturing method of this invention, a lamination can be implemented under inert gas with little damage to an organic EL element.

This application is based on Japanese Patent Application No. 2014-107471 filed in Japan, the contents of which are incorporated in full herein.

Claims

A method for producing a sealed body in which an organic EL element on a substrate is sealed with a sealing layer,
A laminating step of laminating a sealing sheet having a thermosetting resin composition layer formed on a support on a substrate using a roll laminator so that the thermosetting resin composition layer is in contact with the organic EL element,
A production method comprising a smoothing step of smoothing a laminated sealing sheet surface by hot pressing, and a curing step of thermosetting a thermosetting resin composition layer to form a sealing layer.
The manufacturing method according to claim 1, wherein the laminating is performed in an inert gas atmosphere.
The production method according to claim 1 or 2, wherein the roll speed of the roll laminator is 0.01 to 1.5 m / min.
The production method according to claim 1 or 2, wherein the roll speed of the roll laminator is 0.1 to 0.5 m / min.
The production method according to any one of claims 1 to 4, wherein the roll pressure of the roll laminator is 0 to 0.5 MPa.
The production method according to any one of claims 1 to 5, wherein the laminating temperature is 60 to 120 ° C.
The production method according to any one of claims 1 to 6, wherein a pressing pressure in the smoothing step is 0.01 to 0.5 MPa.
The production method according to any one of claims 1 to 7, wherein a pressing temperature in the smoothing step is 60 to 120 ° C.
The production method according to any one of claims 1 to 8, wherein the support is a plastic film which may have a barrier layer.
The production method according to any one of claims 1 to 9, wherein the thickness of the support is 30 to 200 µm.
The production method according to any one of claims 1 to 10, wherein the substrate is at least one selected from the group consisting of glass, polyimide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and cycloolefin polymer.
The manufacturing method according to any one of claims 1 to 11, wherein the thickness of the substrate is 0.1 to 1.0 mm.
The production method according to any one of claims 1 to 12, wherein the curing step is performed simultaneously with the smoothing step.
The manufacturing method according to any one of claims 1 to 13, wherein the sealing body is an organic EL device.
A method of sealing an organic EL element on a substrate,
Laminating a sealing sheet having a thermosetting resin composition layer formed on a support using a roll laminator on a substrate so that the thermosetting resin composition layer is in contact with the organic EL element,
A method comprising a smoothing step of smoothing a laminated sealing sheet surface by hot pressing, and a curing step of thermosetting the thermosetting resin composition layer to form a sealing layer.