JPWO2016175271A1 - Sealing resin composition and sealing sheet - Google Patents

Abstract

The present invention provides a thermosetting resin composition for sealing containing a thermosetting resin and two or more hydrotalcites having different water absorption rates.

Description

  The present invention relates to a sealing resin composition and a sealing sheet, and particularly, a sealing resin suitable for sealing light-emitting elements such as organic EL (Electroluminescence) elements and photoelectric conversion elements such as light-receiving elements such as solar cells. The present invention relates to a composition and a sealing sheet.

  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. In addition, the resin composition used for sealing the organic EL element is required to have a high moisture barrier property.

  Conventionally, as a resin composition of this type, hygroscopic metal oxide particles such as calcium oxide, magnesium oxide, strontium oxide, and barium oxide are included in the resin composition in order to achieve high barrier properties and high adhesive strength. Has been proposed (for example, Patent Document 1).

JP 2011-84667 A

  An object of this invention is to provide the resin composition for sealing which can maintain a moisture barrier property for a long time.

  As a result of diligent research to achieve the above object, the inventors of the present invention blend two or more hydrotalcites having different water absorption rates in a thermosetting resin composition for sealing containing a thermosetting resin. Thus, the water absorption of the encapsulating resin composition is maintained for a long time, and it is found that the degradation of the encapsulated device due to moisture can be suppressed and the device life can be greatly extended, thereby completing the present invention. It came to.

That is, the present invention has the following features.
[1] A thermosetting resin composition for sealing containing a thermosetting resin and two or more hydrotalcites having different water absorption rates.

[2] The thermosetting resin composition for sealing according to the above [1], wherein the water absorption is a saturated water absorption.
[3] The thermosetting resin composition for sealing according to the above [2], wherein the saturated water absorption is a water absorption measured by hydrotalcite under conditions of a temperature of 60 ° C., a relative humidity of 90%, and 200 hours.
[4] The above [2] or [3], wherein a difference in saturated water absorption between the hydrotalcite having the highest water absorption and the hydrotalcite having the lowest water absorption contained in the thermosetting resin composition is 5% by mass or more. ] The thermosetting resin composition for sealing as described in.

[5] The thermosetting resin composition for sealing according to any one of the above [2] to [4], comprising at least one hydrotalcite having a saturated water absorption rate of 25% by mass or more and 100% by mass or less.

[6] At least one hydrotalcite having a saturated water absorption rate of 25% by mass or more and 100% by mass or less (hereinafter sometimes referred to as “first superabsorbent hydrotalcite”) and a saturated water absorption rate. Any of the above [2] to [4], comprising at least one hydrotalcite (hereinafter sometimes referred to as “first low water-absorbing hydrotalcite”) of 1% by mass or more and less than 25% by mass. The thermosetting resin composition for sealing according to claim 1.

[7] The thermosetting for sealing according to the above [6], wherein all hydrotalcites are composed of at least one first superabsorbent hydrotalcite and at least one first low water absorbable hydrotalcite. Resin composition.

[8] The thermosetting resin composition for sealing according to the above [6] or [7], wherein the saturated water absorption rate of the first superabsorbent hydrotalcite is 30% by mass or more and 100% by mass or less.
[9] The thermosetting resin composition for sealing according to the above [6] or [7], wherein the saturated water absorption rate of the first superabsorbent hydrotalcite is 35% by mass or more and 100% by mass or less.
[10] The thermosetting resin composition for sealing according to the above [6] or [7], wherein the saturated water absorption rate of the first superabsorbent hydrotalcite is 40% by mass or more and 100% by mass or less.

[11] The thermosetting resin composition for sealing according to any one of the above [6] to [10], wherein the saturated water absorption rate of the first low water absorption hydrotalcite is 4% by mass or more and less than 25% by mass. object.
[12] The thermosetting resin composition for sealing according to any one of the above [6] to [10], wherein the saturated water absorption rate of the first low water-absorbing hydrotalcite is 5% by mass or more and less than 25% by mass. object.
[13] The thermosetting resin composition for sealing according to any one of the above [6] to [10], wherein the saturated water absorption rate of the first low water-absorbing hydrotalcite is 10% by mass or more and less than 25% by mass. object.
[14] The thermosetting resin composition for sealing according to any one of [6] to [10], wherein the saturated water absorption rate of the first low water-absorbing hydrotalcite is 15% by mass or more and less than 25% by mass. object.

[15] The thermosetting for sealing according to any of the above [6] to [14], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 25 to 85% by mass. Resin composition.
[16] The thermosetting for sealing according to any of the above [6] to [14], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 30 to 80% by mass. Resin composition.
[17] The thermosetting for sealing according to any one of the above [6] to [14], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 40 to 75% by mass. Resin composition.
[18] The thermosetting for sealing according to any of the above [6] to [14], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 50 to 70% by mass. Resin composition.

[19] At least one hydrotalcite having a saturated water absorption rate of 50% by mass or more and 100% by mass or less (hereinafter sometimes referred to as “second superabsorbent hydrotalcite”) and a saturated water absorption rate. Any one of the above [2] to [4], comprising at least one hydrotalcite (hereinafter sometimes referred to as “second low water-absorbing hydrotalcite”) of 1% by mass or more and less than 45% by mass. The thermosetting resin composition for sealing according to claim 1.

[20] The thermosetting for sealing according to the above [19], wherein all the hydrotalcites are composed of at least one second superabsorbent hydrotalcite and at least one second superabsorbent hydrotalcite. Resin composition.

[21] The thermosetting resin composition for sealing according to the above [19] or [20], wherein the second superabsorbent hydrotalcite has a saturated water absorption rate of 55% by mass or more and 100% by mass or less.
[22] The thermosetting resin composition for sealing according to the above [19] or [20], wherein the second superabsorbent hydrotalcite has a saturated water absorption rate of 60% by mass or more and 100% by mass or less.

[23] The thermosetting resin composition for sealing according to any one of the above [19] to [22], wherein the saturated water absorption rate of the second low water-absorbing hydrotalcite is 5% by mass or more and less than 45% by mass. object.
[24] The thermosetting resin composition for sealing according to any one of the above [19] to [22], wherein the saturated water absorption rate of the second low water-absorbing hydrotalcite is 10% by mass or more and less than 45% by mass. object.
[25] The thermosetting resin composition for sealing according to any one of the above [19] to [22], wherein the saturated water absorption rate of the second low water absorption hydrotalcite is 15% by mass or more and less than 45% by mass. object.

[26] The thermosetting for sealing according to any of the above [19] to [25], wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 25 to 85% by mass. Resin composition.
[27] The thermosetting for sealing according to any one of the above [19] to [25], wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 30 to 85% by mass. Resin composition.
[28] The thermosetting for sealing according to any one of the above [19] to [25], wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 40 to 85% by mass. Resin composition.
[29] The thermosetting for sealing according to any of the above [[19] to [25], wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 50 to 85% by mass. Resin composition.

[30] For sealing according to any one of the above [1] to [29], including 1 to 50% by mass of hydrotalcite with respect to 100% by mass of the nonvolatile content of the thermosetting resin composition for sealing. Thermosetting resin composition.
[31] For sealing according to any of the above [1] to [29], comprising 2 to 40% by mass of hydrotalcite with respect to 100% by mass of the nonvolatile content of the thermosetting resin composition for sealing. Thermosetting resin composition.
[32] For sealing according to any one of the above [1] to [29], including 5 to 40% by mass of hydrotalcite with respect to 100% by mass of the nonvolatile content of the thermosetting resin composition for sealing. Thermosetting resin composition.
[33] For sealing according to any one of the above [1] to [29], comprising 10 to 40% by mass of hydrotalcite with respect to 100% by mass of the nonvolatile content of the thermosetting resin composition for sealing. Thermosetting resin composition.
[34] For sealing according to any one of the above [1] to [29], comprising 15 to 40% by mass of hydrotalcite with respect to 100% by mass of the nonvolatile content of the thermosetting resin composition for sealing. Thermosetting resin composition.
[35] For sealing according to any one of the above [1] to [29], comprising 15 to 35% by mass of hydrotalcite with respect to 100% by mass of the nonvolatile content of the thermosetting resin composition for sealing. Thermosetting resin composition.

[36] The thermosetting resin composition for sealing according to any one of the above [1] to [35], which contains an epoxy resin as a thermosetting resin.
[37] The thermosetting resin composition for sealing according to any one of [1] to [36], further including a curing agent.
[38] The sealing thermosetting resin composition according to any one of [1] to [37], further including a thermoplastic resin.
[39] The thermosetting resin composition for sealing according to any one of [1] to [38], further including an inorganic filler (excluding hydrotalcite).
[40] The thermosetting resin composition for sealing according to any one of the above [1] to [39], which is used for sealing an organic EL element.

[41] A sealing sheet in which the sealing thermosetting resin composition according to any one of [1] to [40] is layered on a support.
[42] The sealing sheet according to [41], which is used for sealing the organic EL element.

[43] An organic EL device in which an organic EL element is sealed with the sealing thermosetting resin composition according to any one of [1] to [40].

[44] A method for producing a sealing thermosetting resin composition containing a thermosetting resin and hydrotalcite, wherein the composition containing the thermosetting resin has two or more hydrotalcites having different water absorption rates. The manufacturing method including the process of adding.
[45] A method for producing a sealing sheet in which a thermosetting resin composition is layered on a support, comprising a thermosetting resin composition varnish containing two or more hydrotalcites having different water absorption rates. The manufacturing method including the process of preparing, and the process of apply | coating and drying this varnish on a support body, and forming a thermosetting resin composition layer.

[46] The above [44], wherein the two or more hydrotalcites having different water absorption rates are at least one first high water-absorbing hydrotalcite and at least one first low water-absorbing hydrotalcite. Or the manufacturing method as described in [45].

[47] The production method of the above-mentioned [46], wherein all the hydrotalcites are composed of at least one first superabsorbent hydrotalcite and at least one first superabsorbent hydrotalcite.

[48] The production method according to the above [46] or [47], wherein the saturated water absorption rate of the first superabsorbent hydrotalcite is 30% by mass or more and 100% by mass or less.
[49] The production method according to the above [46] or [47], wherein the saturated water absorption rate of the first superabsorbent hydrotalcite is 35% by mass or more and 100% by mass or less.
[50] The production method according to the above [46] or [47], wherein the saturated water absorption rate of the first superabsorbent hydrotalcite is 40% by mass or more and 100% by mass or less.

[51] The production method according to any one of [46] to [50], wherein the first low water-absorbing hydrotalcite has a saturated water absorption rate of 4% by mass or more and less than 25% by mass.
[52] The production method according to any one of [46] to [50], wherein the first low water-absorbing hydrotalcite has a saturated water absorption rate of 5% by mass or more and less than 25% by mass.
[53] The production method according to any one of [46] to [50], wherein the saturated water absorption rate of the first low water-absorbing hydrotalcite is 10% by mass or more and less than 25% by mass.
[54] The production method according to any one of [46] to [50], wherein the saturated water absorption rate of the first low water-absorbing hydrotalcite is 15% by mass or more and less than 25% by mass.

[55] The production method according to any one of [46] to [54], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 25 to 85 mass%.
[56] The production method according to any one of [46] to [54], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 30 to 80% by mass.
[57] The production method according to any one of [46] to [54], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 40 to 75 mass%.
[58] The production method according to any one of [46] to [54], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 50 to 70% by mass.

[59] The above [44], wherein the two or more hydrotalcites having different water absorption rates are at least one second superabsorbent hydrotalcite and at least one second superabsorbent hydrotalcite. Or the manufacturing method as described in [45].

[60] The production method according to the above [59], wherein all the hydrotalcites are composed of at least one second superabsorbent hydrotalcite and at least one second superabsorbent hydrotalcite.

[61] The production method according to the above [59] or [60], wherein the second superabsorbent hydrotalcite has a saturated water absorption rate of 55% by mass or more and 100% by mass or less.
[62] The production method according to the above [59] or [60], wherein the second superabsorbent hydrotalcite has a saturated water absorption rate of 60% by mass or more and 100% by mass or less.

[63] The production method according to any one of [59] to [62], wherein the saturated water absorption rate of the second low water-absorbing hydrotalcite is 5% by mass or more and less than 45% by mass.
[64] The production method according to any one of [59] to [62], wherein the saturated water absorption rate of the second low water-absorbing hydrotalcite is 10% by mass or more and less than 45% by mass.
[65] The production method according to any one of [59] to [62], wherein the saturated water absorption rate of the second low water-absorbing hydrotalcite is 15% by mass or more and less than 45% by mass.

[66] The production method according to any one of [59] to [65], wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 25 to 85% by mass.
[67] The production method according to any one of [59] to [65], wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 30 to 85% by mass.
[68] The production method according to any one of [59] to [65], wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 40 to 85% by mass.
[69] The production method according to any one of [59] to [65], wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 50 to 85% by mass.

[70] A method for improving the moisture barrier property of a sealing thermosetting resin composition containing hydrotalcite, wherein two or more hydrotalcites having different water absorption rates are used in combination.
[71] A method for improving the moisture barrier property of a sealing sheet in which a thermosetting resin composition containing hydrotalcite is layered on a support, the hydrotalcite having two or more different water absorption rates The method characterized by using together.

[72] The above [70], wherein the two or more hydrotalcites having different water absorption rates are at least one first superabsorbent hydrotalcite and at least one first low water-absorbent hydrotalcite. Or the method as described in [71].

[73] The method of the above-mentioned [72], wherein all the hydrotalcites are composed of at least one first superabsorbent hydrotalcite and at least one first superabsorbent hydrotalcite.

[74] The method according to [72] or [73] above, wherein the saturated water absorption rate of the first superabsorbent hydrotalcite is 30% by mass or more and 100% by mass or less.
[75] The method according to [72] or [73] above, wherein the saturated water absorption rate of the first superabsorbent hydrotalcite is 35% by mass or more and 100% by mass or less.
[76] The method according to [72] or [73] above, wherein the saturated water absorption rate of the first superabsorbent hydrotalcite is 40% by mass or more and 100% by mass or less.

[77] The method according to any of [72] to [76] above, wherein the saturated water absorption rate of the first low water-absorbing hydrotalcite is 4% by mass or more and less than 25% by mass.
[78] The method according to any one of [72] to [76], wherein the saturated water absorption rate of the first low water absorption hydrotalcite is 5% by mass or more and less than 25% by mass.
[79] The method according to any of [72] to [76] above, wherein the saturated water absorption rate of the first low water-absorbing hydrotalcite is 10% by mass or more and less than 25% by mass.
[80] The method according to any of [72] to [76] above, wherein the saturated water absorption rate of the first low water-absorbing hydrotalcite is 15% by mass or more and less than 25% by mass.

[81] The method according to any one of [72] to [80], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 25 to 85 mass%.
[82] The method according to any one of [72] to [80], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 30 to 80% by mass.
[83] The method according to any one of [72] to [80], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 40 to 75% by mass.
[84] The method according to any one of [72] to [80], wherein the ratio of the first superabsorbent hydrotalcite in all hydrotalcites is 50 to 70% by mass.

[85] The above [70], wherein the two or more hydrotalcites having different water absorption rates are at least one second superabsorbent hydrotalcite and at least one second superabsorbent hydrotalcite. Or the method as described in [71].

[86] The method according to [85] above, wherein all the hydrotalcites comprise at least one second superabsorbent hydrotalcite and at least one second superabsorbent hydrotalcite.

[87] The method according to [85] or [86] above, wherein the second superabsorbent hydrotalcite has a saturated water absorption rate of 55% by mass or more and 100% by mass or less.
[88] The method according to [85] or [86] above, wherein the second superabsorbent hydrotalcite has a saturated water absorption rate of 60% by mass or more and 100% by mass or less.

[89] The method according to any one of [85] to [88], wherein the second water-absorbing hydrotalcite has a saturated water absorption rate of 5% by mass or more and less than 45% by mass.
[90] The method according to any one of [85] to [88], wherein the second low-water-absorbing hydrotalcite has a saturated water absorption rate of 10% by mass or more and less than 45% by mass.
[91] The method according to any one of [85] to [88], wherein the second low water-absorbing hydrotalcite has a saturated water absorption rate of 15% by mass or more and less than 45% by mass.

[92] The method according to any one of [85] to [91] above, wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 25 to 85% by mass.
[93] The method according to any one of [85] to [91], wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 30 to 85% by mass.
[94] The method according to any one of [85] to [91], wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 40 to 85% by mass.
[95] The method according to any one of [85] to [91] above, wherein the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is 50 to 85% by mass.

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition for sealing and the film for sealing which can maintain a moisture barrier property for a long time can be obtained. Therefore, if the thermosetting resin composition for sealing according to the present invention is used for sealing a moisture-sensitive element such as an organic EL element, the moisture barrier property is maintained for a longer time, which depends on the moisture of the element. Deterioration can be suppressed for a longer time, and the device life can be greatly extended.

The present invention provides the following:
(1) a thermosetting resin composition for sealing containing two or more hydrotalcites having different water absorption rates;
(2) A sealing sheet in which the sealing thermosetting resin composition is layered on a support;
(3) An organic EL device in which an organic EL element is sealed with the sealing thermosetting resin composition;
(4) A method for producing a thermosetting resin composition for sealing, including a step of adding two or more hydrotalcites having different water absorption rates to a composition containing a thermosetting resin;
(5) A step of preparing a thermosetting resin composition varnish containing two or more hydrotalcites having different water absorption rates, and applying and drying the varnish on a support to form a thermosetting resin composition layer The manufacturing method of the sheet | seat for sealing including the process to do;
(6) A method for improving the moisture barrier property of a thermosetting resin composition for sealing, using two or more types of hydrotalcite having different water absorption rates; and (7) Two or more types of hydrotalc having different water absorption rates. A method for improving the moisture barrier property of a sealing sheet using a site together.
Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Hydrotalcite]
The “hydrotalcite” in the present invention 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. The “hydrotalcite” in the present invention includes these calcined hydrotalcites. Preferable hydrotalcites include, for example, a fired product of synthetic hydrotalcite represented by the following general formula (I), a fired product of synthetic hydrotalcite represented by the following general formula (II), and the like.

Formula ^{_{(I): [M 2+ 1}} -x M 3+ x (OH) 2] x + · [(A n-) x / n · mH 2 O] x-
^{(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 ^-, NO ₃ ^- represents a n-valent anion, such as a 0 <x <1, a 0 ≦ m <1, n is a positive number).

Formula ^{_{(II): M 2+ x Al}} 2 (OH) 2x + 6-nz (A n-) z · mH 2 O
^{(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.)

  Examples of commercially available hydrotalcites include KW series (KW-2000, KW-2100, KW-2200) and DHT series (DHT-4, DHT-4A2, DHT-4C) manufactured by Kyowa Chemical Industry Co., Ltd. Can be mentioned.

  The average particle size of the hydrotalcite in the present invention is preferably 5 μm or less from the viewpoint of improving the transparency of the resin composition. The average particle diameter is a median diameter of the particle size distribution when the particle size distribution is created on a volume basis by laser diffraction scattering type particle size distribution measurement (JIS Z 8825). In addition, as the hydrotalcite in the present invention, a hydrotalcite having an average particle size of 1 μm or less by pulverization can be used. From the viewpoint of dispersibility during kneading and varnish viscosity, the average particle size of hydrotalcite is preferably 10 nm or more. Since it may be difficult to measure the average particle size of the hydrotalcite that has been finely divided, a more preferable hydrotalcite can be selected from the viewpoint of transparency by measuring the BET specific surface area.

As the hydrotalcite in the present invention, for example, hydrotalcite having a BET specific surface area of 5 to 200 m ² / g is preferably used from the viewpoints of transparency and water absorption. The BET specific surface area is more preferably 20 m ² / g or more, still more preferably 40 m ² / g or more, still more preferably 60 m ² / g or more, and particularly preferably 80 m ² / g or more. The BET specific surface area is more preferably 180 m ² / g or less, still more preferably 160 m ² / g or less, and still more preferably 140 m ² / g or less. This BET specific surface area is obtained by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device (Macsorb HM Model-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method. can get. Hydrotalcite can be prepared into a granular material having a large specific surface area by, for example, atomization by pulverization. Since hydrotalcite becomes porous by vaporization of water molecules during firing, a large specific surface area is easily obtained. The specific surface area of hydrotalcite can be adjusted by firing conditions (temperature, time), atomization by pulverization, and the like.

  1-50 mass% is preferable with respect to 100 mass% of non volatile matters of a thermosetting resin composition, and the content total of all the hydrotalcite in the thermosetting resin composition of this invention is 2-40 mass%. Is more preferable, and 5-35 mass% is further more preferable. If the total content is too small, the time for the sealing layer of the resin composition to maintain the moisture barrier property tends to decrease, and if it is too large, the transmittance of the sealing layer tends to decrease.

  The hydrotalcite in the present invention may be treated with a surface treatment agent. As the surface treatment agent, known ones can be used. For example, fatty acids having 8 to 22 carbon atoms such as stearic acid, palmitic acid, myristic acid, oleic acid and linolenic acid, triglycerides and diglycerides which are derivatives of these fatty acids, Fatty acid ester such as monoglyceride, fatty acid amide such as lauric acid amide, palmitic acid amide, stearic acid amide, coupling agent such as titanium coupling agent, aluminum coupling agent, silane coupling agent, methyltrimethoxysilane, ethyl Examples thereof include alkylsilanes such as trimethoxysilane and hexyltrimethoxysilane.

  For example, the surface treatment is performed by adding and spraying a surface treatment agent (higher fatty acid, alkylsilanes or silane coupling agent) while stirring and dispersing untreated hydrotalcite at room temperature using a mixer and stirring for 5 to 60 minutes. It can be done by doing. 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. Further, when the moisture absorbing material is pulverized with a ball mill or the like, a method of mixing the surface treatment agent and performing a surface treatment is also possible. The treatment amount of the surface treatment agent varies depending on the type of the calcined hydrotalcite or the type of the surface treatment agent, but is preferably 1 to 10 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the hydrotalcite. preferable.

The sealing thermosetting resin composition of the present invention contains two or more hydrotalcites having different water absorption rates. The water absorption rate of hydrotalcite in the present invention is expressed by the following formula:
Water absorption (mass%) = ((mass after moisture absorption−initial mass) / initial mass) × 100
Defined by Here, “mass after moisture absorption” means the mass of hydrotalcite after holding the hydrotalcite for a certain period of time at 60 ° C. and 90% RH (relative humidity) under atmospheric pressure. “Mass” means the mass of hydrotalcite before moisture absorption.

The difference in the water absorption rate of hydrotalcite is preferably judged by the saturated water absorption rate. According to the knowledge of the present inventors, when 1.5 g of hydrotalcite is left under atmospheric pressure at a temperature of 60 ° C. and a relative humidity of 90% for 200 hours, the water absorption rate of most hydrotalcites is almost saturated. It became a state. That is, 1.5 g of hydrotalcite was measured for water absorption after 50 hours, 110 hours, 200 hours, and 400 hours under conditions of atmospheric pressure, temperature 60 ° C., and relative humidity 90%. The change in water absorption over time was within 5% for all measured hydrotalcites. Therefore, the saturated water absorption rate of hydrotalcite in the present invention can be obtained as a mass increase rate with respect to the initial mass of hydrotalcite after being maintained for 200 hours under conditions of atmospheric pressure, temperature 60 ° C. and relative humidity 90%. it can. In other words, the saturated water absorption rate of hydrotalcite in the present invention is expressed by the following formula:
Saturated water absorption (mass%) = ((mass after saturated moisture absorption−initial mass) / initial mass) × 100
Defined by Here, “mass after saturated moisture absorption” means the mass of hydrotalcite after being held for 200 hours under conditions of atmospheric pressure, temperature 60 ° C., and relative humidity 90%.

  The thermosetting resin composition of the present invention preferably contains at least two hydrotalcites having a difference in saturated water absorption of hydrotalcite of 5% by mass or more. In this case, the difference in saturated water absorption between the hydrotalcite having the highest water absorption and the hydrotalcite having the lowest water absorption contained in the thermosetting resin composition may be 5% by mass or more. When a site is included, the value of the water absorption rate is not particularly limited. The difference in the saturated water absorption is preferably 10% by mass or more, more preferably 15% by mass or more. The upper limit is not particularly limited, but the difference in saturated water absorption is preferably 80% by mass or less, more preferably 70% by mass or less, more preferably 65% by mass or less, more preferably 60% by mass or less, and more preferably 50% or less. It is not more than mass%, more preferably not more than 40 mass%, still more preferably not more than 30 mass%.

  The saturated water absorption of the hydrotalcite having the highest saturated water absorption contained in the thermosetting resin composition of the present invention is preferably 25% by mass or more, more preferably 30% by mass or more, and 35% by mass. % Or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, particularly preferably 55% by weight or more, and 60% by weight or more. Is most preferred. The upper limit is not particularly set, but the saturated water absorption is generally 100% by mass or less.

  The saturated water absorption rate of the hydrotalcite having the lowest saturated water absorption rate contained in the thermosetting resin composition of the present invention is preferably 1% by mass or more, more preferably 4% by mass or more. More preferably, it is more preferably 10% by mass or more, and particularly preferably 15% by mass or more. The saturated water absorption is preferably less than 45% by mass, and more preferably less than 25% by mass.

  The saturated water absorption rate of hydrotalcite can be adjusted as appropriate depending on the degree of the hydrotalcite baking treatment. For example, hydrotalcite having a high saturated water absorption rate can be prepared by baking for a long time at a high temperature. Can do.

  The total content of all hydrotalcites contained in the thermosetting resin composition of the present invention is preferably in the range of 1 to 50% by mass with respect to 100% by mass of the nonvolatile content in the thermosetting resin composition, The range of 2-40 mass% is more preferable, the range of 5-40 mass% is still more preferable, the range of 10-40 mass% is still more preferable, the range of 15-40 mass% is still more preferable, 15-35 mass % Range is particularly preferred. If the total content is too small, the effect of blending hydrotalcite cannot be sufficiently obtained. If the total content is too large, the viscosity of the composition tends to increase, or the thermosetting resin composition. The strength of the cured product obtained from the above tends to decrease and become brittle.

  The ratio of hydrotalcite having the highest saturated water absorption in all hydrotalcites contained in the thermosetting resin composition of the present invention is preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably. It is 40% by mass or more, particularly preferably 50% by mass or more, preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and particularly preferably 70% by mass or less.

  In one embodiment (hereinafter referred to as “first embodiment”), the thermosetting resin composition of the present invention has a hydrotalcite having a saturated water absorption rate of 25% by mass or more and 100% by mass or less (that is, first And at least one hydrotalcite having a saturated water absorption rate of 1% by mass or more and less than 25% by mass (ie, the first low water absorptive hydrotalcite). preferable.

  In the aspect of the first aspect, all the hydrotalcites contained in the thermosetting resin composition of the present invention are at least one first superabsorbent hydrotalcite and at least one first low water absorption. It is preferable that it consists of a functional hydrotalcite.

  The saturated water absorption rate of the first superabsorbent hydrotalcite is preferably 30% by mass or more and 100% by mass or less, more preferably 35% by mass or more and 100% by mass or less.

  The saturated water absorption rate of the first low water absorption hydrotalcite is preferably 4% by mass or more and less than 25% by mass, more preferably 5% by mass or more and less than 25% by mass, and still more preferably 10% by mass or more and less than 25% by mass. Especially preferably, it is 15 mass% or more and less than 25 mass%.

  1st aspect WHEREIN: The ratio of the 1st superabsorbent hydrotalcite in all the hydrotalcites becomes like this. Preferably it is 25-85 mass%, More preferably, it is 30-80 mass%, More preferably, it is 40-75 mass. %, Particularly preferably 50 to 70% by mass.

  In one embodiment (hereinafter referred to as “second embodiment”), the thermosetting resin composition of the present invention has a hydrotalcite having a saturated water absorption rate of 50% by mass or more and 100% by mass or less (that is, first 2) and at least one hydrotalcite having a saturated water absorption rate of 1% by mass or more and less than 45% by mass (ie, the second low water absorptive hydrotalcite). Is preferred.

  The first and second aspects described above include overlapping ranges and non-overlapping ranges. For example, the thermosetting resin composition containing a hydrotalcite having a saturated water absorption rate of 60% by mass and a hydrotalcite having a saturated water absorption rate of 20% by mass is either in the first aspect or the second aspect. Are also included. On the other hand, for example, a thermosetting resin composition containing hydrotalcite having a saturated water absorption rate of 60% by mass and hydrotalcite having a saturated water absorption rate of 40% by mass is not included in the first aspect. Included in two aspects. These are all aspects of the present invention in that two or more hydrotalcites having different water absorption rates are used.

  2nd aspect WHEREIN: All the hydrotalcites contained in the thermosetting resin composition of this invention are at least 1 type of 2nd high water absorptive hydrotalcite, and at least 1 type of 2nd low water absorptive hydrous. It preferably consists of talcite.

  The saturated water absorption rate of the second superabsorbent hydrotalcite is preferably 55% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less.

  The saturated water absorption rate of the second low water absorption hydrotalcite is preferably 5% by mass or more and less than 45% by mass, more preferably 10% by mass or more and less than 45% by mass, and further preferably 15% by mass or more and less than 45% by mass. is there.

  In the second embodiment, the ratio of the second superabsorbent hydrotalcite in all hydrotalcites is preferably 25 to 85% by mass, more preferably 30 to 85% by mass, and further preferably 40 to 85% by mass. %, Particularly preferably 50 to 85% by mass.

[Thermosetting resin composition]
The thermosetting resin composition in the present invention preferably contains an epoxy resin as the thermosetting resin. Further, it preferably contains a curing agent. There are no particular limitations on the epoxy resin and the curing agent, and conventionally known ones such as those described in WO 2010/084938 can be used. The thermosetting resin composition may further contain a thermoplastic resin.

  The epoxy resin can be used without limitation as long as it has an average of two or more epoxy groups per molecule and has a high transmittance. For example, bisphenol A type epoxy resin, hydrogenated 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 epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, epoxy resin having butadiene structure, bisphenol jig Glycidyl etherified product, diglycidyl ethers of naphthalene diol, diglycidyl 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.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5,000, more preferably 50 to 3,000, more preferably 80 to 2,000, more preferably 100 to 1,000, from the viewpoint of reactivity and the like. Preferably it is 120-1,000, More preferably, it is 140-300. 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.

  Among them, the epoxy resin preferably has a transmittance of 80% or more, more preferably has a transmittance of 85% or more, and still more preferably has a transmittance of 90% or more. 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, naphthalene type epoxy resins, alicyclic epoxy resins, aliphatic chain epoxy resins, and the like. Can be mentioned.

  The transmittance in the present invention 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. Specifically, a fiber spectrophotometer (for example, MCPD-7700, manufactured by Otsuka Electronics Co., Ltd.) is used to irradiate the sample (insulating layer thickness 20 μm) with the incident light of a halogen lamp, and to a φ60 mm integrating sphere with 8 ° projection. The value obtained by measuring the 450 nm value of the total light transmittance spectrum collected in this manner using air as a reference can be used as the transmittance in the present invention.

  The epoxy resin may be liquid, solid, or both liquid and solid. 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. A particularly preferred embodiment from the viewpoint of kneadability with the main component hydrotalcite and varnish viscosity is a combination of liquid and solid, and the ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is The mass ratio is preferably 1: 2 to 1: 0, more preferably 1: 1 to 1: 0.1.

  As for content of the epoxy resin in the thermosetting resin composition in this invention, 20-80 mass% is preferable per whole resin composition (nonvolatile content), and it is more preferable that it is the range of 30-70 mass%, 50 Even more preferably, it is in the range of ˜65 mass%.

  The thermosetting resin composition in the present invention preferably contains an epoxy resin curing agent. That is, the sealing layer is obtained as a cured product layer obtained by curing the resin composition layer. The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, but is 140 ° C. or less (preferably from the viewpoint of suppressing thermal deterioration of a light emitting element such as an organic EL element during the curing treatment of the resin composition. What can harden | cure an epoxy resin under the temperature of 120 degrees C or less is preferable.

  Examples of the curing agent include primary amines, secondary amines, tertiary amine-based curing agents, polyaminoamide-based curing agents, dicyandiamide, and organic acid dihydrazides. Among them, from the viewpoint of fast curing, amine adducts are used. Compound (Amicure PN-23, Amicure MY-24, Amicure PN-D, Amicure MY-D, Amicure PN-H, Amicure MY-H, Amicure PN-31, Amicure PN-40, Amicure PN-40J, etc. (all Ajinomoto Fine Techno Co., Ltd.)), organic acid dihydrazide (Amicure VDH-J, Amicure UDH, Amicure LDH, etc. (all manufactured by Ajinomoto Fine Techno Co.)) and the like are particularly preferred.

  An ionic liquid that can cure 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 particularly preferably used. In the thermosetting resin composition in the present invention, it is desirable to use the ionic liquid in a state where the ionic liquid is uniformly dissolved in the epoxy resin, and the ionic liquid is advantageous for improving the moisture barrier property of the cured resin. Works.

  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 and phenyl Neutral amino acid ion such as lanine ion; N-acyl amino acid ion represented by the following general formula (1) such as N-benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion; formate ion, acetate ion, decanoic acid Carboxylic acid anions such as ions, 2-pyrrolidone-5-carboxylic acid ions, α-lipoic acid ions, lactic acid ions, tartrate ions, hippuric acid ions, N-methyl hippuric acid ions, benzoic acid ions, and the like.

(However, R is a linear or branched alkyl 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 the amino acid in the formula (1) include aspartic acid, glutamic acid, glycine, alanine, and phenylalanine. Among them, glycine is preferable.

  Among the above-mentioned, 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-acylamino acid ion or a carboxylic acid anion represented by the general formula (1), and more preferably an N-acylamino acid ion or a carboxylic acid anion.

  Specific examples of the phenolic anion include 2,6-di-tert-butylphenol ion. Specific examples of the carboxylic acid 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 them, 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 general formula (1) include N-benzoylalanine ion, N-acetylphenylalanine ion, aspartate ion, glycine ion, N-acetylglycine ion, and the like. Among these, 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-butylphenoltetrabutylphosphonium Salt, L-aspartic acid 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 and N-acetylglycine 1-ethyl-3-methylimidazolium salt are preferred, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-formate Methylimidazolium salt, 1-ethyl-3 hippurate -Methylimidazolium salt, N-methylhippuric acid 1-ethyl-3-methylimidazolium salt is particularly preferred.

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.

  In the thermosetting resin composition of the present invention, the content of the curing agent is used in the range of 0.1 to 50% by mass with respect to the total amount (nonvolatile content) of the epoxy resin contained in the resin composition. Is preferred. If the amount is less than this range, sufficient curability may not be obtained. If the amount is more than 50% by mass, the storage stability of the resin composition may be impaired. In addition, when using an ionic liquid, 0.1-10 mass% is preferable with respect to the total amount (nonvolatile content) of an epoxy resin from points, such as the water-blocking property of the hardened | cured material of a resin composition.

  The thermosetting resin composition in the present invention 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 (manufactured by Hokuko Chemical Co., Ltd.). Specific examples of the imidazole compound include Curazole 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2MZOK, 2MA-OK, 2PHZ (manufactured by Shikoku Chemical Industries). Specific examples of amine adduct compounds include Fuji Cure (Fuji Kasei Kogyo Co., Ltd.). Specific examples of the tertiary amine compound include DBU (1,8-diazabicyelo [5.4.0] undec-7-ene), DBU-organic acid salt such as 2-ethylhexanoate and octylate of DBU, U Aromatic dimethylurea such as -3512T (manufactured by San Apro), and aliphatic dimethylurea such as U-3503N (manufactured by San Apro). Of these, urea compounds are preferable from the viewpoint of moisture resistance, and aromatic dimethylurea is particularly preferably used. In the resin composition of the present invention, the content of the curing accelerator is usually used in a range of 0.05 to 5% by mass with respect to the total amount (nonvolatile content) of the epoxy resin contained in the resin composition. 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 resin composition tends to decrease.

  The heat-constituting resin composition of the present invention may contain a silane coupling agent. 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-aminopropyltri; Amino silane cups such as toxisilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Ringing agent; Ureido silane coupling agent such as 3-ureidopropyltriethoxysilane; Vinyl silane coupling agent 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-isocyanatopropyltrimeth 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. Among these, vinyl silane coupling agents and epoxy silane coupling agents are preferable, and epoxy silane coupling agents are particularly preferable. A silane coupling agent can use 1 type (s) or 2 or more types.

  The content of the silane coupling agent in the thermosetting resin composition of the present invention is preferably 0.5 to 10% by mass and more preferably 0.5 to 5% by mass with respect to the entire resin composition (nonvolatile content).

  The thermosetting resin composition of the present invention is provided with flexibility to the sealing layer obtained by curing the thermosetting resin composition, and the resin composition varnish is applied when preparing the sealing sheet. From the viewpoint of property (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. From the viewpoints of imparting flexibility to the sealing layer obtained by curing the resin composition, coating properties (preventing repelling) of the resin composition varnish when preparing the sealing sheet, and the like, The weight average molecular weight is preferably 15,000 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. .

  The weight average molecular weight in the present invention is measured by a 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, and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column. Using chloroform or the like as a phase, the measurement can be performed at a column temperature of 40 ° C., and a standard polystyrene calibration curve can be used.

  When the thermosetting resin composition of the present invention includes a thermoplastic resin, the thermoplastic resin is particularly preferably a phenoxy resin among the above-described examples. The phenoxy resin has good compatibility with the epoxy resin, and acts advantageously on the transparency and moisture barrier property of the resin composition. The phenoxy resin can have an epoxy group. The epoxy equivalent of the phenoxy resin is preferably more than 5,000 and not more than 16,000, more preferably not less than 10,000 and not more than 16,000.

  The phenoxy resin preferably has a transmittance of 80% or more, and more preferably has a transmittance of 90% or more. Examples of such a suitable phenoxy resin include one or more skeletons selected from a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, and the like. The thing which has is mentioned. One or more phenoxy resins can be used.

  As commercially available products of phenoxy resin, for example, YL7213B35 (biphenyl skeleton-containing phenoxy resin), 1256 (bisphenol A skeleton-containing phenoxy resin), YX6954BH35 (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation can be preferably used. it can.

  In the resin composition of the present invention, the content of the thermoplastic resin is preferably 1 to 40% by mass and more preferably 5 to 30% by mass with respect to the entire resin composition (nonvolatile content).

In the thermosetting resin composition of the present invention, other than hydrotalcite, 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 can be further contained. Examples of the inorganic filler include silica, alumina, barium sulfate, clay, mica, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, strontium titanate, Examples thereof include calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium zirconate, calcium zirconate, and silicate. In view of maintaining high transmittance, the inorganic filler is preferably 5 μm or less, and more preferably 1 μm or less. For example, a primary particle having a particle size of 1 to 100 nm, more preferably 1 to 50 nm, further 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 2720-27 m ² / g, preferably 2720-54 m ² / g, more preferably 272-136 m ² / g, more preferably What is 272-181 m < ² > / g can be used.

  The particle form of the inorganic filler is not particularly limited, and a substantially spherical shape, a rectangular parallelepiped shape, a plate shape, a linear shape such as a fiber, or a branched shape can be used. The inorganic filler is preferably silica, zeolite, titanium oxide, alumina, zirconium oxide, silicate, mica, mica, magnesium hydroxide, aluminum hydroxide or the like, more preferably silica, and the silica is wet silica, Dry silica and colloidal silica (water-dispersed, organic solvent-dispersed, gas-phase silica, etc.) are preferable. From the viewpoint that they are difficult to precipitate and settle and are easily combined with resin, organic solvent-dispersed colloidal silica (organosilica sol Is particularly preferred.

  Commercially available products can be used as the inorganic filler. For example, “MEK-EC-2130Y” (amorphous silica particle size 10 to 15 nm, nonvolatile content 30% by mass, MEK solvent) manufactured by Nissan Chemical Industries, Ltd., “ “PGM-AC-2140Y” (silica particle size 10 to 15 nm, nonvolatile content 40 mass%, PGM (propylene glycol monomethyl ether) solvent), “MIBK-ST” (silica particle size 10 to 15 nm, nonvolatile content) manufactured by Nissan Chemical Industries, Ltd. 30% by mass, MIBK (methyl isobutyl ketone) solvent), colloidal silica sol “PL-2L-MEK” (silica particle size 15-20 nm, nonvolatile content 20% by mass, MEK (methyl ethyl ketone) solvent) manufactured by Fuso Chemical Industries, Ltd. Can be mentioned.

  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). .

  The thermosetting resin composition in the present invention may further contain other additives. Examples of such additives include organic fillers such as rubber particles, silicone powder, nylon powder, and fluororesin powder; thickeners such as olben and benton; silicone-based, fluorine-based, and polymer-based antifoaming agents. Or a leveling agent; Adhesion imparting agents, such as a triazole compound, a thiazole compound, a triazine compound, and a porphyrin compound;

  The resin composition of the present invention is prepared by further adding a solvent or the like, if necessary, and mixing them using a kneading roller or a rotary mixer.

  The resin composition of the present invention can have a high transmittance. The formed sealing layer (that is, a cured product of the resin composition) may have a high transparency of preferably 70% or more, more preferably 84% or more, and still more preferably 86% or more.

  The resin composition of the present invention can be applied directly to the object to be sealed, and the coating layer can be cured to form a sealing layer. However, the resin composition layer of the present invention was formed on a support. A sealing sheet is prepared, and the sealing sheet is laminated on a necessary portion of the sealing object, the resin composition layer is transferred to the covering object, and cured to form the sealing layer. Good.

  The sealing sheet in which the thermosetting resin composition of the present invention is layered on a support is a method known to those skilled in the art, for example, a thermosetting resin composition in which the thermosetting resin composition is dissolved in an organic solvent. It can be produced by preparing a product varnish, applying the varnish on a support, and further drying the varnish applied by heating or blowing hot air to form a thermosetting resin composition layer. it can.

  Examples of the support used for the sealing sheet include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes referred to as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and the like. The plastic film is mentioned. As the plastic film, PET is particularly preferable. The support may be a metal foil such as an aluminum foil, a stainless steel foil, or a copper foil. The support may be subjected to a release treatment in addition to a mat treatment and a corona treatment. Examples of the release treatment include a release treatment with a release agent such as a silicone resin release agent, an alkyd resin release agent, and a fluororesin release agent.

  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, stainless steel foil, and metal foil of aluminum foil. Examples of the plastic film include the above-described plastic film. A commercial product may be used as the plastic film having the barrier layer. For example, commercially available products of polyethylene terephthalate film with aluminum foil include “PET Tsuki AL1N30” manufactured by Tokai Toyo Aluminum Sales Co., “PET Tsuki AL3025” manufactured by Fukuda Metals.

  The support 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. In the present invention, when the support has a release layer, the release layer is also regarded as a part of the support. Although the thickness of a support body is not specifically limited, From viewpoints, such as handleability, Preferably it is 20-200 micrometers, More preferably, it is 20-125 micrometers.

  Although the thickness of a support body is not specifically limited, From viewpoints, such as the handleability of a resin composition sheet, it is 10-150 micrometers normally, Preferably it is used in the range of 20-100 micrometers.

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

  The drying conditions are not particularly limited, but usually about 50 to 100 ° C. and about 3 to 15 minutes are preferable.

  The thickness of the resin composition layer formed after drying is usually 3 μm to 200 μm, preferably 5 μm to 100 μm, and more preferably 5 μm to 50 μm.

  The resin composition layer may be protected with a protective film. By protecting the resin composition layer with the protective film, it is possible to prevent adhesion or scratches of dust or the like to the surface of the resin composition layer. The protective film is preferably a plastic film similar to the support. Further, the protective film may be subjected to a release treatment in addition to the mat treatment and the corona treatment. The thickness of the protective film is not particularly limited, but is usually 1 to 150 μm, preferably 10 to 100 μm.

  If the sealing sheet has a moisture-proof and high-permeability support for the support, the sealing sheet is laminated on the necessary portion of the object to be sealed, and the resin composition is left as it is. By curing the layer to form a sealing layer, a sealing structure having high moisture resistance and high transparency can be formed. Examples of such a support having moisture resistance and high transmittance include a plastic film in which an inorganic substance such as silicon oxide (silica), silicon nitride, SiCN, and amorphous silicon is deposited on the surface. Examples of the plastic film include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, and plastic films such as polyester such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, and polyimide. As the plastic film, PET is particularly preferable. Examples of commercially available plastic films having moisture resistance include Tech Barrier HX, AX, LX, L series (Mitsubishi Resin Co., Ltd.) and X-BARRIER (Mitsubishi Resin Co., Ltd.) with enhanced moisture proofing effect. It is done. A sealing substrate having a multilayer structure of two or more layers may be used.

  When manufacturing the organic EL device etc. with which the organic EL element was sealed with the thermosetting resin composition for sealing of this invention, it is suitable to seal with the form of the said sheet | seat for sealing. That is, when the resin composition layer is protected by a protective film, the sealing sheet is peeled off, and then the sealing composition is sealed with the resin composition layer (for example, an organic EL element forming substrate). Laminate so as to be in direct contact with the above organic EL element or the like). The laminating method may be a batch method or a continuous method using a roll. After the lamination, the support is peeled off, and a thermosetting operation of the resin composition layer described later is performed. The support of the sealing sheet is a moisture-proof support, and after laminating the sealing sheet, the support is not peeled off and the thermosetting operation of the resin composition layer described below is performed as it is.

  The resin composition layer is usually cured by thermosetting. For example, a hot air circulation oven, an infrared heater, a heat gun, a high frequency induction heating device, heating by pressure bonding of a heat tool, and the like can be mentioned. Each lower limit value of the curing temperature and the curing time is 50 ° C. or more at the curing temperature from the viewpoint of bonding the cured resin composition layer (sealing layer) to the object to be sealed with sufficiently satisfying adhesive strength. The temperature is preferably 55 ° C. or higher, more preferably 20 minutes or longer, and more preferably 30 minutes or longer in the curing time.

  When the organic EL element forming substrate is an organic EL element formed on a transparent substrate, the support of the resin composition sheet is not necessarily provided if the transparent substrate side is a display surface of a display or a light emitting surface of a lighting fixture. It is not necessary to use a transparent material, and a metal plate, a metal foil, an opaque plastic film, or a plate may be used. Conversely, when the organic EL element formation substrate is formed on a substrate made of an opaque or low-transparency material, the sealing substrate side is used as the display surface of the display or the light emitting surface of the lighting fixture. As necessary, a transparent plastic film, a glass plate, a transparent plastic plate, or the like is used as the sealing substrate.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “%” means “% by mass” unless otherwise specified. As the hydrotalcite, commercially available hydrotalcite was used.

<Synthesis Example 1> Synthesis of ionic liquid curing agent N-acetylglycine tetrabutylphosphonium salt, which is an ionic liquid curing agent, was synthesized by the following procedure. 3.50 g of N-acetylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at 0 ° C. to 20.0 g of a 41.4% tetrabutylphosphonium hydroxide aqueous solution (manufactured by Hokuko Chemical Co., Ltd.), and stirred for 10 minutes. After stirring, the reaction solution was concentrated at a pressure of 40 to 50 mmHg at 60 to 80 ° C. for 2 hours and then at 90 ° C. for 5 hours. The resulting concentrate was dissolved in 14.2 ml of ethyl acetate (manufactured by Junsei Co., Ltd.) at room temperature to prepare a solution. Concentration gave 11.7 g (purity: 96.9%) of N-acetylglycine tetrabutylphosphonium salt as an oily compound.

<Example 1>
42 parts by mass of liquid bisphenol A type epoxy resin (Mitsubishi Chemical "jER828EL", epoxy equivalent of about 185), 1.2 parts by mass of silane coupling agent (Shin-Etsu Chemical "KBM403"), talc powder (Japan) talc Ltd. "FG15F") 2 parts by mass, and a commercially available hydrotalcite a (BET specific surface area 110m ² / g) 21 parts by mass, and a hydrotalcite B (BET specific surface area of 118m ² / g) 5 parts by weight After kneading, the mixture was dispersed with a three-roll mill to obtain a mixture. 1.5 parts by mass of a curing accelerator ("U-3512T" manufactured by San Apro) 81 parts by mass of a 35% MEK solution ("YX7200B35") of phenoxy resin ("YX7200" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 12,000) 24 mass of 80% MEK solution (“jER1001B80”) of the mixture previously prepared by the three roll mill and the solid bisphenol A type epoxy resin (“jER1001” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 475) Parts, organic solvent-dispersed colloidal silica (amorphous silica particle size 10 to 15 nm, nonvolatile content 30%, MEK solvent, “MEK-EC-2130Y” manufactured by Nissan Chemical Industries, Ltd.), and ionic liquid curing agent (N -Acetylglycine tetrabutylphosphonium salt) 3 parts by weight Dispersed in, to obtain a resin composition varnish.

  Next, the resin composition varnish is placed on a polyethylene terephthalate (PET) film (thickness 38 μm, support) treated with an alkyd mold release agent so that the thickness of the resin composition layer after drying is 20 μm. It apply | coated uniformly with the die coater, and it dried for 5 minutes at 80-100 degreeC (average 90 degreeC) (residual solvent amount in a resin composition layer: about 2%). Subsequently, it wound up in roll shape, bonding a 38-micrometer-thick polypropylene film on the surface of a resin composition layer. The roll-shaped sealing sheet was slit to a width of 507 mm to obtain a sealing sheet having a size of 507 × 336 mm.

<Example 2>
Instead of 21 parts by mass of hydrotalcite A and 5 parts by mass of hydrotalcite B in Example 1, 18 parts by mass of hydrotalcite A and 9 parts by mass of hydrotalcite D (BET specific surface area 15 m ² / g) were used. Except that, a sealing sheet was obtained in the same manner as in Example 1.

<Example 3>
42 parts by mass of a liquid mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 165) and a silane coupling agent (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) After kneading 1.2 parts by mass, 22 parts by mass of commercially available hydrotalcite B (BET specific surface area 118 m ² / g) and 22 parts by mass of hydrotalcite C (BET specific surface area 68 m ² / g), three Dispersion was performed with a roll mill to obtain a mixture. 1.5 parts by mass of a curing accelerator ("U-3512T" manufactured by San Apro) 81 parts by mass of a 35% MEK solution ("YX7200B35") of phenoxy resin ("YX7200" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 12,000) 24 mass of 80% MEK solution (“jER1001B80”) of the mixture previously prepared by the three roll mill and the solid bisphenol A type epoxy resin (“jER1001” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 475) Parts, organic solvent-dispersed colloidal silica (amorphous silica particle size 10 to 15 nm, nonvolatile content 30%, MEK solvent, “MEK-EC-2130Y” manufactured by Nissan Chemical Industries, Ltd.), and ionic liquid curing agent (N -Acetylglycine tetrabutylphosphonium salt) 3 parts by weight Dispersed in a resin composition was obtained varnish.
A sealing sheet was obtained in the same manner as in Example 1 except that the resin composition varnish produced as described above was used.

<Comparative Example 1>
A sealing sheet was obtained in the same manner as in Example 1 except that 26 parts by mass of hydrotalcite A was used instead of 21 parts by mass of hydrotalcite A and 5 parts by mass of hydrotalcite B in Example 1. It was.

<Comparative example 2>
A sealing sheet was obtained in the same manner as in Example 3 except that instead of 22 parts by mass of hydrotalcite B and 22 parts by mass of hydrotalcite C of Example 3, 26 parts by mass of hydrotalcite B was used. It was.

<Measurement of water absorption rate of hydrotalcite>
The initial mass (about 1.5 g) of hydrotalcite was measured with a balance. The hydrotalcite whose initial mass was measured was allowed to stand for a certain period of time in a small environmental tester (SH-222 manufactured by Espec Corp.) set at 60 ° C. and 90% RH (relative humidity) at atmospheric pressure for 50 hours and 110 hours. The mass after moisture absorption was measured every time, 200 hours, and 400 hours. The mass increase rate with respect to the initial mass of hydrotalcite was taken as the water absorption rate, and the water absorption rate was calculated by the following formula.
Water absorption rate (%) = ((mass after moisture absorption−initial mass) / initial mass) × 100
Since the change in water absorption between 200 hours and 400 hours was within 5% for all measured hydrotalcites, the water absorption for 200 hours was taken as the saturated water absorption. The water absorption rate for each hour is shown in Table 1.

<Measurement of water absorption of cured product>
Other than using PET film treated with silicone release agent ("E0007" manufactured by Toyobo Co., Ltd.) instead of PET film (support) treated with alkyd release agent of each Example and Comparative Example Obtained a sealing sheet in the same manner as in each Example and Comparative Example. The obtained sealing sheet was thermally cured at 110 ° C. for 30 minutes, and the support was peeled off to obtain a sheet-like cured product. The cured product was cut into 50 mm × 50 mm (N = 2), and these initial masses were measured with a precision balance. The cured product was sandwiched between waste cloths, and these were fixed with a vinyl tie so that they did not collapse. Boiling hot water at 100 ° C. was prepared in a size pan, fixed with the previous vinyl tie, submerged so that the entire cured product sandwiched between the waste water was covered with hot water, covered and left for 1 hour. After 1 hour, the cured product was taken out from the hot water and immersed in cold water for 15 minutes to cool the cured product. After cooling, the cured product was taken out from the cold water, and after the waste cloth was removed by overlapping the waste, the mass after moisture absorption was measured with a precision balance. The water absorption was calculated by the following formula, and the average value of N = 2 was taken as the water absorption of the cured product.
Water absorption rate (%) = ((mass after moisture absorption−initial mass) / initial mass) × 100

<Measurement of moisture permeability>
Other than using PET film treated with silicone release agent ("E0007" manufactured by Toyobo Co., Ltd.) instead of PET film (support) treated with alkyd release agent of each Example and Comparative Example Obtained a sealing sheet in the same manner as in each Example and Comparative Example. The obtained sealing sheet was thermally cured at 110 ° C. for 30 minutes, and the support was peeled off to obtain a sheet-like cured product. 7.5 g of calcium chloride was weighed into a petri dish, and a cured product cut into a circle with a diameter of 60 mm was attached to a moisture permeable cup (permeation area 2.826 × 10 ⁻³ m ² (60 mmφ). The initial mass of the moisture permeable cup was measured with a precision balance, and then the moisture permeable cup was left in a constant temperature test chamber at 60 ° C. and 90% RH for 24 hours, and then the moisture permeable mass of the moisture permeable cup was measured. Using a precision balance, the increase in the mass of the cup (= mass after moisture permeation−initial mass) is the water vapor transmission amount, and the ratio between the water vapor transmission amount and the transmission area is the water vapor transmission value. The value at was calculated (g / m ² ).

<Measurement of emission area reduction start time of organic EL element>
Instead of PET film (support) treated with the alkyd mold release agent of each Example and Comparative Example, aluminum foil / PET composite film “PET TSUKI AL1N30” (aluminum foil: 30 μm, PET: 25 μm, Tokai Toyo Aluminum Co., Ltd.) A sealing sheet was obtained in the same manner as in each Example and Comparative Example except that the trade name of the sales company was used.

  An alkali-free glass 50 mm × 50 mm square was washed with boiling isopropyl alcohol for 5 minutes and dried at 150 ° C. for 30 minutes or more. Calcium (purity 99.8%) was vapor-deposited (thickness 300 nm) using the mask which used the said glass and the distance from the edge part was 3 mm. In the glove box, the alkali-free glass on which calcium is vapor-deposited and the sealing sheet having the same resin composition layer as that of each of the examples and the comparative examples are pasted together with a thermal laminator (Lamipacker DAiSY A4 (LPD2325) manufactured by Fuji Plastics). A laminate was prepared, and the resulting laminate was heated at a temperature of 110 ° C. for 30 minutes to thermally cure the resin composition layer to obtain a sample for evaluation.

  When calcium comes into contact with water and becomes calcium oxide, it becomes transparent. Therefore, moisture penetration into the evaluation sample can be evaluated by measuring the distance (mm) from the end of the evaluation sample to calcium. Therefore, the sample for evaluation containing calcium was used as a model of an organic EL device.

  First, the distance of calcium deposited from the end of the sample for evaluation was measured with a Measuring Microscope MF-U manufactured by Mitutoyo Corporation, and this value was used as an initial value.

  Next, the sample for evaluation is allowed to stand for a certain period of time in a small environmental tester (SH-222 manufactured by Espec Corp.) set at a temperature of 60 ° C. and 90% RH, and from the end of the sample for evaluation to calcium every certain period of time. The distance of was measured. Fick's diffusion formula:

(In the formula, X represents the distance (mm) from the end of the sample for evaluation to calcium, t represents the time (hr) during which the sample for evaluation was left in a small environmental tester, and K represents a proportional constant. Show.)
Based on the above, the proportionality constant K is calculated by drawing the theoretical curve using the least squares method from the "distance from the end of the sample for evaluation to calcium" and the "time during which the sample for evaluation is left in a small environmental tester" did.

  Using the calculated K, the time when X becomes a value of (initial value + 0.1 mm) was calculated as the emission area decrease start time. The higher the moisture barrier property, the slower the moisture penetration rate and the longer the emission area reduction start time.

  The blending amount of each component for preparing the resin composition varnishes of Examples 1 to 3 and Comparative Examples 1 and 2, the hydrotalcite content with respect to 100% by mass of the nonvolatile content in the thermosetting resin composition, and the above-mentioned The measurement results are shown in Table 2.

  From the results shown in Table 2, compared to the sealing sheet of Comparative Example 1 containing only hydrotalcite A, the sealing sheets of Examples 1 and 2 have hydrotalcite A and a saturated water absorption rate higher than this. It can be seen that when the low hydrotalcite B or D is used in combination and the amount of hydrotalcite A is small, the emission area reduction start time is long (that is, the moisture blocking property can be maintained for a long time). Moreover, from the result shown in Table 2, compared with the sealing sheet of Comparative Example 2 containing only hydrotalcite B, the sealing sheet of Example 3 has hydrotalcite B and a saturated water absorption rate than this. It can be seen that although the low hydrotalcite C is used in combination and the amount of hydrotalcite B is small, the emission area reduction start time is long (that is, the moisture barrier property can be maintained for a long time).

  Since the thermosetting resin composition for sealing and the sealing sheet of the present invention maintain good moisture barrier properties for a long time, they can be suitably used for sealing elements that are sensitive to moisture such as organic EL elements. . Therefore, if the thermosetting resin composition for sealing and the sheet for sealing of the present invention are used, a device such as an organic EL device having a greatly extended element life can be provided.

  This application is based on patent application No. 2015-091052 filed in Japan, the contents of which are incorporated in full herein.

Claims (20)

  A thermosetting resin composition for sealing containing a thermosetting resin and two or more hydrotalcites having different water absorption rates.   The thermosetting resin composition for sealing according to claim 1, wherein the water absorption is a saturated water absorption.   The thermosetting resin composition for sealing according to claim 2, wherein the saturated water absorption is a water absorption measured by hydrotalcite under conditions of a temperature of 60 ° C., a relative humidity of 90%, and 200 hours.   The sealing according to claim 2 or 3, wherein a difference in saturated water absorption between the hydrotalcite having the highest water absorption and the hydrotalcite having the lowest water absorption contained in the thermosetting resin composition is 5% by mass or more. Thermosetting resin composition.   The thermosetting resin composition for sealing according to any one of claims 2 to 4, comprising at least one hydrotalcite having a saturated water absorption rate of 25% by mass or more and 100% by mass or less.   The hydrotalcite having a saturated water absorption rate of 25% by mass or more and 100% by mass or less and at least one hydrotalcite having a saturated water absorption rate of 1% by mass or more and less than 25% by mass is contained. The thermosetting resin composition for sealing according to any one of the above.   The hydrotalcite having a saturated water absorption rate of 50% by mass or more and 100% by mass or less and at least one hydrotalcite having a saturated water absorption rate of 1% by mass or more and less than 45% by mass is contained. The thermosetting resin composition for sealing according to any one of the above.   The thermosetting resin for sealing according to any one of claims 1 to 7, comprising 1 to 50% by mass of hydrotalcite with respect to 100% by mass of the nonvolatile content of the thermosetting resin composition for sealing. Composition.   The thermosetting resin composition for sealing according to any one of claims 1 to 8, comprising an epoxy resin as the thermosetting resin.   The thermosetting resin composition for sealing according to any one of claims 1 to 9, further comprising a curing agent.   Furthermore, the thermosetting resin composition for sealing of any one of Claims 1-10 containing a thermoplastic resin.   The thermosetting resin composition for sealing according to any one of claims 1 to 11, further comprising an inorganic filler (excluding hydrotalcite).   The thermosetting resin composition for sealing according to any one of claims 1 to 12, which is used for sealing an organic EL element.   The sheet | seat for sealing by which the thermosetting resin composition for sealing of any one of Claims 1-13 was layer-formed on the support body.   The sheet | seat for sealing of Claim 14 used in order to seal an organic EL element.   The organic EL device by which the organic EL element was sealed with the thermosetting resin composition for sealing of any one of Claims 1-13.   A method for producing a thermosetting resin composition for sealing containing a thermosetting resin and hydrotalcite, wherein two or more hydrotalcites having different water absorption rates are added to the composition containing a thermosetting resin. A manufacturing method including a process.   A method for producing a sealing sheet in which a thermosetting resin composition is layered on a support, and a step of preparing a thermosetting resin composition varnish containing two or more hydrotalcites having different water absorption rates And a step of applying the varnish on a support and drying to form a thermosetting resin composition layer.   A method for improving the water barrier property of a thermosetting resin composition for sealing containing hydrotalcite, wherein two or more hydrotalcites having different water absorption rates are used in combination.   A thermosetting resin composition containing hydrotalcite is a method for improving the moisture barrier property of a sealing sheet layered on a support, and uses two or more hydrotalcites having different water absorption rates in combination. A method characterized by that.