WO2021111855A1

WO2021111855A1 - Sealing agent, sealing sheet, electronic device, and perovskite type solar cell

Info

Publication number: WO2021111855A1
Application number: PCT/JP2020/042668
Authority: WO
Inventors: 賢大橋; 麻衣細井
Original assignee: 味の素株式会社
Priority date: 2019-12-03
Filing date: 2020-11-16
Publication date: 2021-06-10
Also published as: TW202134387A; JP2021089946A; CN114762144A; KR20220107195A; DE112020005939T5

Abstract

This sealing agent is for electronic devices provided with lead-containing parts, and contains a resin and an inorganic filler containing at least one selected from the group consisting of half-calcined hydrotalcite and calcined hydrotalcite.

Description

Encapsulants, encapsulants, electronic devices and perovskite solar cells

The present invention relates to a sealant for an electronic device having a lead-containing portion, and a sealing sheet using the lead-containing part, an electronic device, and a perovskite type solar cell.

One of the electronic devices that has been attracting attention in recent years is the perovskite type solar cell. A perovskite-type solar cell generally includes an electrode and a photoelectric conversion layer containing a perovskite compound. Further, in order to protect the electrodes and the photoelectric conversion layer from water, the perovskite type solar cell is usually provided with a sealing portion. Various studies have been conducted on such a sealing portion (Patent Document 1).

International Publication No. 2018/056312

Lead may be contained in the photoelectric conversion layer of the perovskite type solar cell. If water penetrates into the photoelectric conversion layer, lead may flow out from the photoelectric conversion layer and leak to the outside of the solar cell. Further, such lead leakage can also occur in an electronic device other than a perovskite type solar cell provided with a lead-containing portion such as the photoelectric conversion layer. Lead leakage is desired to be suppressed from both environmental and safety perspectives.

The present invention has been devised in view of the above problems, and is a sealing agent for electronic devices capable of suppressing the infiltration of water and suppressing the leakage of lead from the lead-containing portion to the outside of the electronic device; It is an object of the present invention to provide a sealing sheet containing the sealing agent; and an electronic device and a perovskite type solar cell using the sealing agent for sealing.

The present inventor has diligently studied to solve the above-mentioned problems. As a result, the present inventor has found that the above-mentioned problems can be solved when the inorganic filler and the resin are used in an appropriate combination, and completed the present invention.
That is, the present invention includes the following.

[1] A sealant for an electronic device including a lead-containing portion.
The encapsulant contains an inorganic filler and a resin.
The lead adsorption parameter of the sealant is 10 μg / m ² or more.
The water vapor penetration barrier parameter of the sealant is less than ^{0.025 cm / h 0.5.}
The lead adsorption parameter represents the mass of lead adsorbed per ^{1 m 2 of} the sealant layer when the lead adsorption capacity evaluation test is performed.
In the lead adsorption capacity evaluation test, a first test sheet having a length of 16 cm and a width of 24 cm, comprising a polyethylene terephthalate film and a layer of the sealant having a thickness of 20 μm formed on the polyethylene terephthalate film is provided. To prepare; a nylon mesh cloth is attached to the layer side of the sealant of the first test sheet; the first test sheet to which the mesh cloth is attached is cut into 1 cm squares. The cut first test sheet is immersed in 50 ml of a lead ion-containing aqueous solution having a lead ion concentration of 20 μg / L adjusted to 20 ° C to 25 ° C, and stirred for 15 minutes.
The water vapor infiltration barrier property parameter represents a constant K obtained from the following formula (1) when the water vapor barrier property evaluation test is performed.
In the water vapor barrier property evaluation test, a second support film including an aluminum foil having a thickness of 30 μm and a polyethylene terephthalate film having a thickness of 25 μm, and a layer of the sealant formed on the aluminum foil of the support film are provided. Drying the test sheet; washing a 50 mm square glass plate made of non-alkali glass with boiling isopropyl alcohol for 5 minutes and drying; one side of the glass plate, the end of the glass plate. Calcium is vapor-deposited on a portion excluding an area having a distance of 0 mm to 2 mm to form a calcium film having a thickness of 200 nm; in a nitrogen atmosphere, the sealant layer of the second test sheet and the sealant layer. The surface of the glass plate on the calcium film side is bonded to obtain an evaluation sample; the distance X2 [mm] between the end of the evaluation sample and the end of the calcium film is measured; The evaluation sample is stored in a constant temperature and humidity chamber having a temperature of 85 ° C. and a humidity of 85% RH; from the time when the evaluation sample is stored in the constant temperature and humidity chamber, the evaluation sample stored in the constant temperature and humidity chamber is used. To measure the time t [time] until the distance X1 [mm] between the end and the end of the calcium film becomes "X2 + 0.1 mm"; and based on the following formula (1). Calculating the constant K, the encapsulant.

[2] The sealant according to [1], wherein the drying of the second test sheet in the water vapor barrier property evaluation test is performed under the conditions of 130 ° C. for 60 minutes and 100 ° C. for 5 minutes at least one of them. ..
[3] The sealant according to [1] or [2], wherein the inorganic filler contains at least one selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite, calcium oxide, and zeolite. ..
[4] A sealant for an electronic device provided with a lead-containing portion.
A sealant containing a resin and an inorganic filler containing at least one selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide.
[5] The inorganic filler contains one or more selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide.
The encapsulant according to [3] or [4], wherein the resin contains a polyolefin-based resin.
[6] The inorganic filler contains one or more selected from the group consisting of semi-calcined hydrotalcite and calcium oxide.
The sealant according to any one of [3] to [5], wherein the resin contains an epoxy resin.
[7] The sealing according to any one of [1] to [6], wherein the amount of the inorganic filler is 5% by mass or more and 80% by mass or less with respect to 100% by mass of the non-volatile component of the sealing agent. Agent.
[8] A sealing sheet comprising a support and a layer of a sealing agent according to any one of [1] to [7] formed on the support.
[9] A lead-containing portion and a sealing portion for sealing the lead-containing portion are provided.
An electronic device in which the sealing portion contains the sealing agent according to any one of [1] to [7].
[10] A first electrode, a perovskite layer containing a lead atom, a second electrode, and a sealing portion for sealing the perovskite layer are provided.
A perovskite-type solar cell in which the sealing portion contains the sealing agent according to any one of [1] to [7].

According to the present invention, a sealing agent for an electronic device capable of suppressing the infiltration of water and suppressing the leakage of lead from the lead-containing portion to the outside of the electronic device; a sealing sheet containing the sealing agent; In addition, an electronic device and a perovskite type solar cell using the sealing agent for sealing can be provided.

FIG. 1 is a cross-sectional view schematically showing an evaluation sample produced in the water vapor barrier property evaluation test. FIG. 2 is a plan view schematically showing a state in which the evaluation sample before being stored in the constant temperature and humidity chamber is viewed from the glass plate side. FIG. 3 is a plan view schematically showing a state in which the evaluation sample after being stored in the constant temperature and humidity chamber is viewed from the glass plate side. FIG. 4 is a cross-sectional view schematically showing an example of a perovskite type solar cell according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be arbitrarily modified and implemented without departing from the claims and the equivalent scope thereof.

[1. Outline of the encapsulant according to the first embodiment]
The encapsulant according to the first embodiment of the present invention contains an inorganic filler and a resin. Since the resin usually plays a role of binding and holding an inorganic filler, it may be appropriately referred to as a "binder resin". The encapsulant according to the present embodiment may further contain an arbitrary component in addition to the inorganic filler and the binder resin. In addition, the encapsulant according to this embodiment has a specific range of lead adsorption parameters. Further, the encapsulant according to this embodiment has a specific range of water vapor infiltration barrier parameters. When this sealant is used for sealing an electronic device having a lead-containing portion, it can suppress the infiltration of water into the lead-containing portion and lead leakage from the lead-containing portion to the outside of the electronic device. Can be suppressed.

[2. Lead Adsorption Parameter of Encapsulant According to First Embodiment]
Lead adsorption parameter encapsulant according to a first embodiment of the present invention is usually 10 [mu] g / ^{m 2} or more, preferably 11μg / ^{m 2} or more, more preferably 12 [mu] g / ^{m 2} or more, particularly preferably 13 ug / ^{m 2} That is all. The larger the upper limit of the lead adsorption parameter is, the more preferable it is. For example, it may be 200 μg / m ² or less, 100 μg / m ² or less, 50 μg / m ² or less, and the like.

The lead adsorption parameter represents the mass of lead adsorbed per ^{1 m 2 of} the sealant layer when the following lead adsorption capacity evaluation test is performed.

In the lead adsorption capacity evaluation test, a first test sheet is prepared; a nylon mesh cloth is attached to the layer side of the sealant of the first test sheet; the mesh cloth is attached. The first test sheet was cut into 1 cm squares; the cut first test sheet was immersed in 50 ml of a lead ion-containing aqueous solution having a lead ion concentration of 20 μg / L adjusted to 20 ° C to 25 ° C. Stir for 15 minutes. The first test sheet represents a sheet having a length of 16 cm and a width of 24 cm, comprising a polyethylene terephthalate film and a layer of a sealant having a thickness of 20 μm formed on the polyethylene terephthalate film. The reason why the first test sheet and the mesh cloth are bonded in the lead adsorption capacity evaluation test is to prevent the first test sheets from adhering to each other in the lead ion-containing aqueous solution. When the encapsulant is a thermosetting encapsulant, the encapsulant is usually thermoset at 100 ° C. for 60 minutes after the mesh cloth is attached, and then the first test sheet is cut. ..

Therefore, for example, when the encapsulant is an adhesive type encapsulant, a first test sheet should be prepared in the lead adsorption capacity evaluation test; the layer side of the encapsulant of the first test sheet is made of nylon. The first test sheet to which the mesh cloth is attached is cut into 1 cm squares; the cut first test sheet is adjusted to 20 ° C to 25 ° C for lead ions. It can be immersed in 50 ml of a lead ion-containing aqueous solution having a concentration of 20 μg / L and stirred for 15 minutes.

Further, for example, when the encapsulant is a thermosetting encapsulant, a first test sheet should be prepared in the lead adsorption capacity evaluation test; nylon is placed on the layer side of the encapsulant of the first test sheet. The sealant is heat-cured at 100 ° C. for 60 minutes by laminating a mesh cloth made of the same material; the first test sheet to which the mesh cloth is bonded is cut into 1 cm squares; (1) The test sheet can be immersed in 50 ml of a lead ion-containing aqueous solution having a lead ion concentration of 20 μg / L adjusted to 20 ° C. to 25 ° C. and stirred for 15 minutes.

The mass of lead adsorbed on the sealant layer when the lead adsorption capacity evaluation test is performed can be measured by using the concentration of lead ions contained in the lead ion-containing aqueous solution. The lead ion concentration can be measured using a portable scanning lead measuring device (model name HSA-1000, manufactured by HACH). As a specific measurement method, the method described later in the examples can be adopted.

The lead adsorption parameter represents the magnitude of the ability of the encapsulant to adsorb lead. Specifically, the larger the lead adsorption parameter, the greater the ability of the encapsulant to adsorb lead. A sealant having a lead adsorption parameter in the above range can effectively adsorb lead flowing out from the lead-containing portion when used for sealing the lead-containing portion in an electronic device. Therefore, it is possible to suppress the leakage of lead from the electronic device to the outside. The effect of suppressing lead leakage as described above is beneficial in various situations such as storage, transportation, use, and damage of electronic devices.

The lead adsorption parameter can be adjusted, for example, by the type and amount of the inorganic filler.

[3. Water vapor infiltration barrier parameter of the sealant according to the first embodiment]
The water vapor infiltration barrier parameter of the encapsulant according to the first embodiment of the present invention is usually ^{less than 0.025 cm / h 0.5} , preferably less than 0.024 cm / h ^0.5 , more preferably 0.0230 cm / h. h less than ^0.5, more preferably less than 0.022Cm ^{/ h 0.5,} particularly preferably less than 0.021cm ^{/ h 0.5.} The lower limit of the water vapor penetration barrier parameter is ideally is 0.000cm ^{/ h 0.5} or more, it may be 0.001 cm ^{/ h 0.5} or more.

The water vapor infiltration barrier property parameter represents the constant K obtained from the equation (1) when the following water vapor barrier property evaluation test is performed.

In the water vapor barrier evaluation test, the second test sheet is dried; a 50 mm square glass plate made of non-alkali glass is washed with boiling isopropyl alcohol for 5 minutes and dried; the glass plate. To form a 200 nm-thick calcium film on the central portion of one side of the glass; in a nitrogen atmosphere, the sealant layer of the second test sheet and the calcium film side of the glass plate. The surface and the surface are bonded together to obtain an evaluation sample; the sealing distance X2 [mm] of the evaluation sample is measured; the evaluation sample is stored in a constant temperature and humidity chamber having a temperature of 85 ° C. and a humidity of 85% RH; Time t [hours] from T _P1 _{when the evaluation sample is stored in the constant temperature and humidity chamber to T P2} when the sealing distance X1 [mm] of the evaluation sample stored in the constant temperature and humidity chamber becomes "X2 + 0.1 mm". ], And the constant K is calculated based on the following equation (1). In the following description, the time t may be referred to as a “decrease start time t”. When the sealant is curable, usually, the sealant layer of the second test sheet and the surface of the glass plate on the calcium film side are bonded together, and then the sealant layer is cured. , Get an evaluation sample. As the curing conditions, for example, the conditions described later in the examples can be adopted. Specific curing conditions can be, for example, 100 ° C. for 60 minutes. Further, it is preferable that the second test sheet performed in the water vapor barrier property evaluation test is sufficiently dried. Specific drying conditions may be at least one of a condition of 130 ° C. for 60 minutes and a condition of 100 ° C. for 5 minutes. When the water vapor infiltration barrier property parameter in the above range can be obtained in the water vapor barrier property evaluation test including drying under at least one of the conditions of 130 ° C. for 60 minutes and the condition of 100 ° C. for 5 minutes, the sealant Can suppress the infiltration of water and also suppress the leakage of lead from the lead-containing portion to the outside of the electronic device. Normally, when the encapsulant is an adhesive encapsulant, it is dried under the condition of 130 ° C. for 60 minutes. In addition, when the sealant is a thermosetting type sealant, it is usually dried under the condition of 100 ° C. for 5 minutes.

So, for example, when the encapsulant is an adhesive encapsulant, in the steam barrier property evaluation test, the second test sheet is dried under the condition of 130 ° C. for 60 minutes; 50 mm formed of non-alkali glass. The corner glass plate is washed with boiling isopropyl alcohol for 5 minutes and dried; calcium is deposited on the central part of one side of the glass plate to form a calcium film with a thickness of 200 nm; in a nitrogen atmosphere. , The sealant layer of the second test sheet and the surface of the glass plate on the calcium film side are bonded to obtain an evaluation sample; the sealing distance X2 [mm] of the evaluation sample is measured; the evaluation sample, temperature 85 ° C., it is housed in a thermo-hygrostat RH 85% humidity; the evaluation sample from the time T _P1 housed in a thermo-hygrostat, the evaluation sample accommodated in the thermostat-humidistat chamber sealing _{Measure the decrease start time t [time] up to the time point T P2} when the distance X1 [mm] becomes "X2 + 0.1 mm"; and calculate the constant K based on the following equation (1). sell.

Further, for example, when the encapsulant is a heat-curable encapsulant, in the steam barrier property evaluation test, the second test sheet is dried under the condition of 100 ° C. for 5 minutes; it is formed of non-alkali glass. A 50 mm square glass plate is washed with boiling isopropyl alcohol for 5 minutes and dried; calcium is deposited on the central part of one side of the glass plate to form a calcium film with a thickness of 200 nm; in a nitrogen atmosphere. Then, the sealant layer of the second test sheet and the surface of the glass plate on the calcium film side are laminated and cured under the condition of 100 ° C. for 60 minutes to obtain an evaluation sample; the evaluation sample, temperature 85 ° C., it is housed in a thermo-hygrostat RH 85% humidity; measuring the sealing distance X2 [mm] evaluation samples from the time T _P1 housed in a thermo-hygrostat, a thermostat To measure the reduction start time t [time] up to the time _{point T P2} when the sealing distance X1 [mm] of the evaluation sample stored in the constant humidity bath becomes "X2 + 0.1 mm"; and to the following formula (1) Based on this, the constant K can be calculated.

The second test sheet represents a sheet including a support film including an aluminum foil having a thickness of 30 μm and a polyethylene terephthalate film having a thickness of 25 μm, and a sealant layer formed on the aluminum foil of the support film. The thickness of the sealant layer can be, for example, 20 μm. Further, the central portion of one side of the glass plate represents a portion of one side of the glass plate excluding the peripheral area. Further, the peripheral area on one side of the glass plate represents an area on one side of the glass plate having a distance of 0 mm to 2 mm from the end portion of the glass plate. The sealing distance of the evaluation sample represents the distance between the end of the evaluation sample and the end of the calcium film. The sealing distance usually corresponds to the distance between the edge of the sealant layer and the edge of the calcium membrane.

(In equation (1)
X1 is the sealing distance [mm] from the end of the evaluation sample to the end of the calcium film after being put into the constant temperature and humidity chamber.
t is the decrease start time [time] at which X1 = X2 + 0.1.
X2 is the sealing distance [mm] from the end of the evaluation sample to the end of the calcium film before being put into the constant temperature and humidity chamber. )

Hereinafter, the drawings will be shown to explain the mechanism of the water vapor barrier property evaluation test and the significance of the constant K as the water vapor infiltration barrier property parameter required by the test.

FIG. 1 is a cross-sectional view schematically showing an evaluation sample 10 manufactured in a water vapor barrier property evaluation test. As shown in FIG. 1, the evaluation sample 10 produced in the water vapor barrier property evaluation test includes a square glass plate 100 washed with boiling isopropyl alcohol and calcium formed on one side 100U of the glass plate 100. A film 200 and a second test sheet 300 attached to the surface 100U of the glass plate 100 are provided. The calcium film 200 is not formed on the peripheral area 110U of the surface 100U of the glass plate 100 at a distance L from the end 100E of the glass plate 100 of 0 mm to 2 mm. On the other hand, a calcium film 200 is formed on the central portion 120U of the surface 100U of the glass plate 100 excluding the peripheral area 110U. The calcium film 200 is usually formed by thin film deposition using a mask (not shown) covering the peripheral area 110U, and has a high purity (for example, a purity of 99.8% or more). Further, the second test sheet 300 includes a sealant layer 310 and a support film 320 including a polyethylene terephthalate film 321 and an aluminum foil 322, and the sealant layer 310 is a glass plate 100. It is attached to the surface 100U of. Therefore, the calcium film 200 is sealed by the sealant layer 310.

The glass plate 100 and the support film 320 included in the evaluation sample 10 have a sufficiently high ability to block water. Therefore, as shown by the arrow A1, the moisture around the evaluation sample 10 passes through the end portion 310E of the sealant layer 310 and passes through the sealant layer 310 in the in-plane direction (direction perpendicular to the thickness direction). ) And can infiltrate the calcium membrane 200. Therefore, the calcium film 200 of the evaluation sample 10 housed in the constant temperature and humidity chamber can be gradually oxidized from the end portion 200E toward the central portion 200C.

FIG. 2 is a plan view schematically showing a state in which the evaluation sample 10 before being stored in the constant temperature and humidity chamber is viewed from the glass plate 100 side. Further, FIG. 3 is a plan view schematically showing a state in which the evaluation sample 10 after being stored in the constant temperature and humidity chamber is viewed from the glass plate 100 side.
As shown in FIG. 2, in the evaluation sample 10 before being stored in the constant temperature and humidity chamber, the calcium film 200 was not oxidized due to the infiltration of water. Therefore, the sealing distance X2 between the end portion 10E of the evaluation sample 10 and the end portion 200E of the calcium film 200 can usually maintain the dimension immediately after the formation of the calcium film 200. However, when the evaluation sample 10 is stored in the constant temperature and humidity chamber, water penetrates into the calcium film 200 through the sealant layer 310 (see FIG. 1), and the calcium in contact with the water is oxidized. , Can be transparent calcium oxide. Therefore, as shown in FIG. 3, the calcium film 200 can gradually change from the end portion 200E to the central portion 200C to the transparent calcium oxide film 210 due to the infiltration of water. This change is observed as a shrinkage of the calcium membrane 200. Therefore, after the evaluation sample 10 is stored in the constant temperature and humidity chamber, the sealing distance X1 between the end portion 10E of the evaluation sample 10 and the end portion 200E of the calcium film 200 may gradually increase with the passage of time. ..

The movement of water through the sealant layer 310 generally follows Fick's diffusion formula. Therefore, in the above-mentioned water vapor barrier property evaluation test, the reduction start time t (that is, the evaluation sample 10 is stored in a constant temperature and humidity chamber) as the time required for the moisture to move within the sealing agent layer 310 by the sealing distance X1. from the time _{T P1} that, with time) to the time _{T P2} the sealing distance X1 [mm] of the evaluation sample 10 stored in a thermo-hygrostat is "X2 + 0.1 mm", a sealing distance X1 which is the movement Is applied to the diffusion equation of Fick represented by the equation (1) to derive the constant K as the water vapor infiltration barrier property parameter.

Therefore, the evaluation sample 10 can correspond to a model of an electronic device, and the calcium film 200 can correspond to a lead-containing portion to be sealed by a sealant. The water vapor infiltration barrier property parameter represents the magnitude of the ability of the sealant provided in the electronic device to suppress the infiltration of water in the in-plane direction. Specifically, the smaller the water vapor infiltration barrier parameter, the better the ability of the sealant to suppress the infiltration of water. A sealant having a water vapor infiltration barrier parameter in the above range can suppress the infiltration of water into the lead-containing portion when used for sealing the lead-containing portion in an electronic device. Therefore, it is possible to suppress the oxidation of the components contained in the lead-containing portion and suppress the outflow of lead from the lead-containing portion.

The water vapor infiltration barrier property parameter can be adjusted by, for example, the type and amount of the inorganic filler; the type and amount of the binder resin;

[4. Inorganic filler that can be contained in the sealant according to the first embodiment]
The encapsulant according to the first embodiment of the present invention contains an inorganic filler. Part or all of the inorganic filler can exhibit hygroscopicity and lead adsorption in the sealing agent as a resin composition containing the inorganic filler and the binder resin. One type of inorganic filler may be used alone, or two or more types may be used in combination at any ratio. For example, an inorganic filler capable of exhibiting hygroscopicity in the encapsulant and another inorganic filler capable of exhibiting lead adsorption in the encapsulant may be used in combination. It is a phenomenon that the present inventor has found for the first time that a lead-adsorbing inorganic filler can exhibit lead-adsorbing property in a sealing agent as a resin composition containing a binder resin as described above.

(4.1. Hydrotalcite)
Examples of inorganic fillers include hydrotalcite. Hydrotalcite can be classified into uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite.

Unfired hydrotalcites, e.g., as typified by natural hydrotalcite _{_{_{(Mg 6 Al 2 (OH)}}} 16 CO 3 · 4H 2 O), a metal hydroxide having a layered crystal structure. Unfired hydrotalcite, for example, consists of a composed layer _{_{[Mg 1-Xa Al Xa (}} OH) 2] Xa + basic skeleton intermediate layer _{_{_{[(CO 3) Xa / 2}}} · m a H 2 O] Xa- and .. Here, xa represents a number satisfying 0 <xa <1, and ma represents _a positive number. Unless otherwise noted, uncalcined hydrotalcite is a concept that includes hydrotalcite-like compounds such as synthetic hydrotalcite. Examples of the hydrotalcite-like compound include compounds represented by the following formula (I) or the following formula (II).

^{_{^{_{_{[Mi 2+ 1-xi Mi 3+}}}}} xi (OH) 2] xi + · [(Ai ni-) xi / ni · m i H 2 O] xi- (I)
(In formula (I)
Mi ²⁺ represents divalent metal ions such as Mg ²⁺ and Zn ^2+.
Mi ³⁺ represents trivalent metal ions such as Al ³⁺ and Fe ^3+.
Ai ^Ni- _{^{^{is, CO 3 2-, Cl -,}}} NO 3 - , such as, represent ni-valent anion,
xi represents a number satisfying 0 <xi <1.
m _i represents a number satisfying 0 ≦ _m i <1,
ni represents a positive number. )

In formula (I), Mi ²⁺ preferably represents ^{Mg 2+.} Further, Mi ³⁺ preferably represents ^{Al 3+.} Furthermore, Ai ^ni- preferably represents _{CO 3} ^2-.

^{_{_{_{Mii 2+ xii Al 2 (OH)}}}} 2xii + 6-niizii (Aii nii-) zii · m ii H 2 O (II)
(In formula (II)
Mii ²⁺ represents divalent metal ions such as Mg ²⁺ and Zn ^2+.
Aii ^Nii- _is, ^CO 3 _^2-, Cl _-, such as ^{NO 3-,} represent nii-valent anion,
xii represents a positive number greater than or equal to 2
zii represents a positive number less than or equal to 2.
m _ii represents a positive number
nii represents a positive number. )

In formula (II), Mii ²⁺ preferably represents ^{Mg 2+.} In addition, Aii ^nii- preferably represents _{CO 3} ^2-.

Unfired hydrotalcite can exhibit excellent lead adsorption in the encapsulant. Therefore, for example, when unfired hydrotalcite and an inorganic filler capable of exhibiting hygroscopicity in the sealing agent are used in an appropriate combination, the sealing having the lead adsorption parameter and the water vapor infiltration barrier property parameter in the above range is used. The agent can be obtained.

The saturated water absorption rate of uncalcined hydrotalcite is usually less than 1% by mass, and may be less than 0.8% by mass or less than 0.6% by mass. The "saturated water absorption rate" of hydrotalcite such as unfired hydrotalcite is based on the initial mass when hydrotalcite is allowed to stand in an environment of 60 ° C. and 90% RH (relative humidity) under atmospheric pressure for 200 hours. The rate of mass increase. This saturated water absorption rate can be measured by the following method.

Weigh 1.5 g of hydrotalcite with a balance and measure the initial mass. The weighed hydrotalcite is allowed to stand for 200 hours in a small environmental tester (SH-222 manufactured by ESPEC) set at 60 ° C. and 90% RH (relative humidity) under atmospheric pressure to absorb moisture, and after absorbing moisture. Measure the mass. Then, the saturated water absorption rate is calculated by the following formula (i).
Saturated water absorption rate (mass%) = 100 × (mass after moisture absorption-initial mass) / initial mass (i)

The thermogravimetric reduction rate of uncalcined hydrotalcite at 280 ° C. is usually 15% by mass or more, preferably 15.1% by mass or more, and particularly preferably 15.2% by mass or more.

The rate of decrease in thermal weight of hydrotalcite such as uncalcined hydrotalcite can be measured by thermogravimetric analysis. For thermogravimetric analysis, 5 mg of hydrotalcite was weighed in an aluminum sample pan using a thermal analyzer (TG / DTA EXSTAR6300, manufactured by Hitachi High-Tech Science Co., Ltd.), and the nitrogen flow rate was 200 mL in an open state without a lid. It can be carried out under the condition of a heating rate of 10 ° C./min from 30 ° C. to 550 ° C. in an atmosphere of / min. The thermogravimetric reduction rate can be calculated by the following formula (ii) using the result of the above thermogravimetric analysis.
Thermogravimetric reduction rate (mass%) = 100 × (mass before heating-mass when a predetermined temperature is reached) / mass before heating (ii)

When powder X-ray diffraction of unfired hydrotalcite is measured, 2θ usually has only one peak near 8 ° to 18 °, or the relative intensity between the low-angle side diffraction intensity and the high-angle side diffraction intensity. The ratio (low-angle side diffraction intensity / high-angle side diffraction intensity) is out of the range of 0.001 to 1,000. The low-angle side diffraction intensity represents the diffraction intensity of the peak or shoulder that appears on the low-angle side (the side where 2θ is small). The high-angle side diffraction intensity represents the diffraction intensity of the peak or shoulder that appears on the high-angle side (the side where 2θ is large).

Measurement of powder X-ray diffraction of hydrotalcite such as uncalcined hydrotalcite can be performed using a powder X-ray diffractometer (Empylean, manufactured by PANalytical). For powder X-ray diffraction measurement, anti-cathode CuKα (1.5405 Å), voltage: 45 V, current: 40 mA, sampling width: 0.0260 °, scanning speed: 0.0657 ° / s, measurement diffraction angle range (2θ). : Can be performed under the conditions of 5.0131 ° to 79.9711 °. The peak search uses the peak search function of the software attached to the diffractometer, and "minimum significance: 0.50, minimum peak tip: 0.01 °, maximum peak tip: 1.00 °, peak base width: 2". It can be performed under the condition of "0.00 °, method: minimum value of second derivative".

Examples of unfired hydrotalcites are "Almakaiser 1" (average particle size: 620 nm), "Magceller 1" (average particle size: 470 nm), and "DHT-4A" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size). : 400 nm), "STABIACE HT-1", "STABIACE HT-7", "STABIACE HT-P" (Sakai Chemical Industry Co., Ltd.) and the like. One type of uncalcined hydrotalcite may be used alone, or two or more types may be used in combination at any ratio.

Semi-calcined hydrotalcite refers to a metal hydroxide having a layered crystal structure in which the amount of interlayer water is reduced or eliminated, which is obtained by calcining uncalcined hydrotalcite. The term "interlayer water" refers to _{"H 2} O" described in the above-mentioned composition formulas of uncalcined natural hydrotalcite and hydrotalcite-like compounds, if it is described using a composition formula.

Semi-fired hydrotalcite can exhibit excellent lead adsorption and hygroscopicity in the encapsulant. Therefore, when semi-baked hydrotalcite is appropriately used, a sealant having the lead adsorption parameter and the water vapor infiltration barrier parameter in the above range can be obtained. It was first discovered by the present inventor that semi-calcined hydrotalcite exhibits lead adsorption.

Since semi-fired hydrotalcite usually has a saturated water absorption rate different from that of unfired hydrotalcite, they can be distinguished by the saturated water absorption rate. The saturated water absorption of the semi-baked hydrotalcite is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually less than 20% by mass. The saturated water absorption rate of semi-fired hydrotalcite can be measured by the same method as the saturated water absorption rate of unfired hydrotalcite.

Since semi-calcined hydrotalcite usually has a different thermogravimetric reduction rate from uncalcined hydrotalcite, they can be distinguished by the thermogravimetric reduction rate. The thermogravimetric reduction rate of the semi-calcined hydrotalcite at 280 ° C. is usually less than 15% by mass, preferably less than 14% by mass, and particularly preferably less than 13% by mass. The thermogravimetric reduction rate of the semi-baked hydrotalcite at 380 ° C. is usually 12% by mass or more, preferably 15% by mass or more, and particularly preferably 16% by mass or more. The thermogravimetric reduction rate of semi-baked hydrotalcite can be measured by the same method as the thermogravimetric loss rate of uncalcined hydrotalcite.

Semi-calcined hydrotalcites usually differ in peak and relative intensity ratios measured by powder X-ray diffraction from uncalcined hydrotalcites, so they are distinguished by peaks and relative intensity ratios measured by powder X-ray diffraction. it can. When the powder X-ray diffraction of semi-baked hydrotalcite is measured, it usually shows a peak in which 2θ is split into two in the vicinity of 8 ° to 18 °, or a peak having a shoulder due to the combination of the two peaks, and the low angle side. The relative intensity ratio (low-angle side diffraction intensity / high-angle side diffraction intensity) between the diffraction intensity and the high-angle side diffraction intensity is 0.001 to 1,000. The measurement of the powder X-ray diffraction of the semi-fired hydrotalcite can be performed by the same method as the measurement of the powder X-ray diffraction of the unfired hydrotalcite.

Examples of semi-baked hydrotalcite are "DHT-4C" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm); "DHT-4A-2" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm); And so on. One type of semi-baked hydrotalcite may be used alone, or two or more types may be used in combination at any ratio.

Calcined hydrotalcite refers to a metal oxide having an amorphous structure obtained by calcining uncalcined hydrotalcite or semi-calcined hydrotalcite, in which not only interlayer water but also hydroxyl groups are eliminated by condensation dehydration.

The calcined hydrotalcite can exhibit excellent lead adsorption and hygroscopicity in the encapsulant. Therefore, when the calcined hydrotalcite is appropriately used, a sealing agent having the lead adsorption parameter and the water vapor infiltration barrier parameter in the above range can be obtained. The fact that calcined hydrotalcite exhibits lead adsorption is the first discovery by the present inventor.

Since calcined hydrotalcite usually has a saturated water absorption rate different from that of uncalcined hydrotalcite and semi-fired hydrotalcite, they can be distinguished by the saturated water absorption rate. The saturated water absorption of the calcined hydrotalcite is usually 20% by mass or more, preferably 30% by mass or more, and particularly preferably 40% by mass or more. The saturated water absorption rate of calcined hydrotalcite can be measured by the same method as the saturated water absorption rate of uncalcined hydrotalcite.

Since calcined hydrotalcite usually has a different thermogravimetric reduction rate from uncalcined hydrotalcite and semi-calcined hydrotalcite, they can be distinguished by the thermogravimetric reduction rate. The thermogravimetric reduction rate of calcined hydrotalcite at 380 ° C. is usually less than 12% by mass, preferably less than 10% by mass, and particularly preferably less than 7% by mass. The thermogravimetric reduction rate of calcined hydrotalcite can be measured by the same method as the thermogravimetric loss rate of uncalcined hydrotalcite.

Since calcined hydrotalcites usually differ in peaks and relative intensity ratios measured by powder X-ray diffraction from uncalcined hydrotalcites and semi-calcined hydrotalcites, they are the peaks and peaks measured by powder X-ray diffraction. It can be distinguished by the relative strength ratio. When the powder X-ray diffraction of calcined hydrotalcite is measured, 2θ usually has no characteristic peak in the region of 8 ° to 18 °, and 2θ has a characteristic peak in 43 °. The measurement of the powder X-ray diffraction of the calcined hydrotalcite can be performed by the same method as the measurement of the powder X-ray diffraction of the uncalcined hydrotalcite.

Examples of calcined hydrotalcite include "KW-2200" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm) and the like. One type of calcined hydrotalcite may be used alone, or two or more types may be used in combination at an arbitrary ratio.

(4.2. Calcium oxide)
Another example of an inorganic filler is calcium oxide. Calcium oxide can exhibit excellent lead adsorption and hygroscopicity in the encapsulant. Therefore, when calcium oxide is appropriately used, a sealing agent having the lead adsorption parameter and the water vapor infiltration barrier parameter in the above range can be obtained. It was first discovered by the present inventor that calcium oxide exhibits lead adsorption. Calcium oxide may be used in a state of being contained in a mixture with other inorganic fillers. Examples of such a mixture include calcined dolomite (a mixture containing calcium oxide and magnesium oxide).

(4.3. Zeolite)
Yet another example of an inorganic filler is zeolite. Zeolites can exhibit excellent lead adsorption in the encapsulant. In addition, zeolite can exhibit excellent hygroscopicity in a sealing agent, for example, by appropriately adjusting the composition. Therefore, when zeolite is used appropriately, a sealing agent having the lead adsorption parameter and the water vapor infiltration barrier parameter in the above range can be obtained.

From the viewpoint of enhancing the hygroscopicity of zeolite, it is preferable that zeolite has high hydrophilicity. The hydrophilicity of zeolite can be adjusted, for example, by the molar ratio of silica and alumina contained in zeolite. The specific molar ratio of silica to alumina (silica / alumina) of the zeolite is preferably less than 100, more preferably less than 50, still more preferably less than 25.

Zeolites usually have pores. The pore size of the zeolite is preferably adjusted so that high lead adsorption and hygroscopicity can be obtained. The pore size of the zeolite is preferably 6 Å or less, more preferably 5 Å or less, still more preferably 4 Å or less. “Å” ^{represents 1.0 × 10-10} m. The pore size of zeolite can be measured by a gas adsorption method or a mercury intrusion method.

(4.4. Examples of other inorganic fillers)
Yet another example of the inorganic filler is a hygroscopic metal oxide other than those described above. Examples of such a hygroscopic metal oxide include magnesium oxide, strontium oxide, aluminum oxide, barium oxide and the like. The hygroscopic metal oxide can exhibit excellent hygroscopicity in the sealant. Therefore, for example, when a hygroscopic metal oxide and an inorganic filler capable of exhibiting lead adsorption in a sealing agent are used in an appropriate combination, a seal having the lead adsorption parameter and the water vapor infiltration barrier property parameter in the above range is used. A stop can be obtained.

(4.5. Preferred inorganic filler)
Among the above-mentioned examples, as the inorganic filler, semi-calcined hydrotalcite, calcined hydrotalcite, calcium oxide, and zeolite are preferable. Since these can exhibit excellent lead adsorption and hygroscopicity in the sealant, the lead adsorption parameter and the water vapor infiltration barrier parameter of the sealant can be easily adjusted within the above-mentioned ranges. Therefore, the encapsulant preferably contains one or more kinds of inorganic fillers selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite, calcium oxide, and zeolite.

(4.6. Surface treatment of inorganic filler)
As the inorganic filler, one that has been surface-treated with an appropriate surface treatment agent may be used. Unless otherwise specified, surface-treated ones are also included in the term "inorganic filler". Examples of the surface treatment agent include higher fatty acids, alkylsilane compounds and silane coupling agents, and higher fatty acids and alkylsilane compounds are suitable. One type of surface treatment agent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Examples of higher fatty acids include higher fatty acids having 18 or more carbon atoms, such as stearic acid, montanic acid, myristic acid, and palmitic acid. Of these, stearic acid is preferable.

Examples of the alkylsilane compound include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltrimethoxysilane, and n-octadecyl. Examples thereof include dimethyl (3- (trimethoxysilyl) propyl) ammonium chloride.

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 cups such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane Ring agent; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N- Amino-based silane coupling agents such as (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane; such as 3-ureidopropyltriethoxysilane. , Ureido-based silane coupling agent; vinyl-based silane coupling agent such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; styryl-based silane coupling agent such as p-styryltrimethoxysilane; 3 -Acrylate-based silane coupling agents such as acrylicoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanoxidetrimethoxysilane; bis (triethoxysilylpropyl) Examples thereof include sulfide-based silane coupling agents such as disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane; metharoxypropyltrimethoxysilane; imidazolesilane; triazinesilane; and the like.

The amount of surface treatment agent may vary depending on the type of inorganic filler and surface treatment agent. The amount of the surface treatment agent used for the surface treatment with respect to 100 parts by mass of the inorganic filler not subjected to the surface treatment is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and particularly preferably 1.0. It is 5 parts by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and particularly preferably 6 parts by mass or less. When the surface treatment is performed with an amount of the surface treatment agent in the above range, aggregation can be suppressed and the surface area of the inorganic filler can be increased, so that the lead adsorption property and hygroscopic property of the inorganic filler can be easily exhibited.

There is no limitation on the surface treatment method of the inorganic filler, and for example, the surface treatment may be performed by mixing the inorganic filler and the surface treatment agent. In particular, when hydrotalcite such as semi-baked hydrotalcite is used as the inorganic filler, the surface treatment is preferably performed by spraying a surface treatment agent while stirring the untreated hydrotalcite with a mixer, for example. .. The treatment temperature is preferably room temperature. Further, the stirring is preferably performed for 5 to 60 minutes. Examples of the mixer include blenders such as V blenders, ribbon blenders and bubble cone blenders; mixers such as Henshell mixers and concrete mixers; mills such as ball mills and cutter mills; Further, for example, the surface treatment may be performed by crushing the hydrotalcite and at the same time mixing the hydrotalcite with the surface treatment agent.

(4.7. Particle size of inorganic filler)
The average particle size of the inorganic filler is preferably 1 nm or more, more preferably 10 nm or more, further preferably 100 nm or more, particularly preferably 200 nm or more, preferably less than 10 μm, more preferably less than 5 μm, still more preferably 1 μm or less. Especially preferably, it is 800 nm or less. In particular, when hydrotalcite such as semi-baked hydrotalcite is used as the inorganic filler, the average particle size of hydrotalcite is preferably 1 nm or more, particularly preferably 10 nm or more, and preferably 1,000 nm or less, preferably 800 nm or less. Is particularly preferable. Further, particularly when zeolite is used as the inorganic filler, the average particle size of the zeolite is preferably 100 nm or more, more preferably 200 nm or more, preferably less than 10 μm, and particularly preferably less than 5 μm. When an inorganic filler having an average particle size in such a range is used, the processability of the encapsulant becomes good, and the encapsulating sheet can be easily produced.

The average particle size of the inorganic filler can be obtained as the median size of the particle size distribution by measuring the particle size distribution on a volume basis by laser diffraction scattering type particle size distribution measurement (JIS Z 8825).

(4.8. Specific surface area of inorganic filler)
The BET specific surface area of the inorganic filler is preferably 1 m ² / g or more, more preferably 5 m ² / g or more, preferably 250 m ² / g or less, and more preferably 200 m ² / g or less. In particular, when the inorganic filler contains hydrotalcite such as semi-baked hydrotalcite, it is preferable that the hydrotalcite has a BET specific surface area in the above range. When an inorganic filler having a BET specific surface area in such a range is used, the processability of the encapsulant becomes good, and the encapsulating sheet can be easily manufactured.

The BET specific surface area of the inorganic filler can be calculated by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM Model 1210, manufactured by Mountech) according to the BET method, and using the BET multipoint method.

(4.9. Amount of inorganic filler)
The amount of the inorganic filler is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more, based on 100% by mass of the non-volatile component of the sealant. It is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, and may be, for example, 65% by mass or less and 60% by mass or less. When the amount of the inorganic filler is equal to or higher than the lower limit of the above range, the lead adsorption property and hygroscopic property of the inorganic filler are largely exhibited. Therefore, the lead adsorption property parameter and the water vapor penetration barrier property parameter of the sealant are set in the above range. It becomes easy to adjust to. Further, when the amount of the inorganic filler is not more than the upper limit value in the above range, the viscosity and wettability of the sealant can be improved, so that the adhesion between the sealant and the object to be sealed such as the lead-containing part and the electrode Can be improved. Therefore, the formation of a gap between the sealing target and the sealing agent can be effectively suppressed, and thus the sealing property can be improved, so that the infiltration of water and the leakage of lead can be particularly effectively suppressed.

[5. Outline of components other than the inorganic filler that can be contained in the encapsulant according to the first embodiment]
The encapsulant according to the first embodiment of the present invention contains a binder resin in combination with the above-mentioned inorganic filler. The binder resin has a function of suppressing foreign substances such as dust from entering the electronic device, a function of holding the inorganic filler so as not to separate from the sealing portion, and a function of adhering the sealing agent to the sealing target such as the lead adsorption portion. , A function of suppressing the infiltration of water, and some or all of the functions can be exerted.

Further, the encapsulant according to the first embodiment of the present invention may contain an arbitrary component in combination with an inorganic filler and a binder resin. The type and ratio of the binder resin and any component can be appropriately selected depending on the type and amount of the inorganic filler and the properties required for the encapsulant.

Hereinafter, the binder resin and arbitrary components will be described by taking as an example the components suitable for the adhesive type encapsulant and the thermosetting type encapsulant. The adhesive type sealant represents a type of sealant that exhibits adhesiveness and can seal the object to be sealed by crimping. Since the adhesive type adhesive can usually be adhered only by applying pressure at room temperature for a relatively short time, it can function as a pressure-sensitive adhesive. Further, the thermosetting type sealant represents a type of sealant that can achieve sealing by heat-curing in contact with the object to be sealed. However, the components contained in the sealant are not limited to the examples described below. Therefore, the components shown as examples suitable for the adhesive type encapsulant may be used for other encapsulants (for example, thermosetting type encapsulant). Moreover, the component shown as an example suitable for a thermosetting type sealant may be used for other sealants (for example, an adhesive type sealant).

[6. Description of components suitable for the adhesive type encapsulant according to the first embodiment]
(6.1. Thermoplastic resin as binder resin)
An example of a component that the sealant can contain in combination with an inorganic filler is a thermoplastic resin. The thermoplastic resin is preferable as the binder resin for the adhesive type encapsulant. As the thermoplastic resin, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

The thermoplastic resin is not particularly limited, and for example, a thermoplastic resin described later may be used as a binder resin suitable for a thermosetting encapsulant. Among them, a polyolefin-based resin is mentioned as a preferable example of the thermoplastic resin. When the polyolefin resin is combined with an inorganic filler containing at least one selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide, a sealing agent having excellent transparency can be obtained.

As the polyolefin-based resin, a resin having a skeleton derived from an olefin monomer can be used. Examples of the polyolefin-based resin include the polyolefin-based resins described in International Publication No. 2011/62167 and International Publication No. 2013/108731. Of these, the isobutylene-modified resin described in International Publication No. 2011/62167 and the styrene-isobutylene-modified resin described in International Publication No. 2013/108731 are preferable. Further, preferred polyolefin-based resins include, for example, polyethylene-based resins, polypropylene-based resins, polybutene-based resins, and polyisobutylene-based resins. The polyolefin-based resin may be a homopolymer or a copolymer. Further, the copolymer may be a random copolymer or a block copolymer.

Examples of the copolymer include copolymers of two or more types of olefins; copolymers of olefins and monomers other than olefins such as non-conjugated diene and styrene; Examples of preferred copolymers include ethylene-non-conjugated diene copolymers, ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene copolymers, ethylene-butene copolymers, propylene-butene copolymers, Examples thereof include a propylene-butene-non-conjugated diene copolymer, a styrene-isobutylene copolymer, and a styrene-isobutylene-styrene copolymer.

The polyolefin-based resin may contain a polyolefin-based resin having an acid anhydride group (that is, a carbonyloxycarbonyl group (-CO-O-CO-)). When a polyolefin resin having an acid anhydride group is used, the adhesiveness and moisture heat resistance of the sealant can be improved.

Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride, and the like. The type of the acid anhydride group may be one type or two or more types. The polyolefin-based resin having an acid anhydride group can be produced, for example, by graft-modifying the polyolefin-based resin with an unsaturated compound having an acid anhydride group under radical reaction conditions. Further, the polyolefin-based resin having an acid anhydride group can be produced, for example, by radically copolymerizing an unsaturated compound having an acid anhydride group with an olefin.

The concentration of the acid anhydride group in the polyolefin resin having an acid anhydride group is preferably 0.05 mmol / g or more, more preferably 0.1 mmol / g or more, preferably 10 mmol / g or less, more preferably. It is 5 mmol / g or less. The concentration of the acid anhydride group is obtained from the value of the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the resin according to the description of JIS K2501.

The amount of the polyolefin-based resin having an acid anhydride group is preferably 0% by mass or more, more preferably 10% by mass or more, and particularly preferably 11% by mass or more, based on 100% by mass of the total amount of the polyolefin-based resin. It is preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

The polyolefin-based resin may contain a polyolefin-based resin having an epoxy group. When a polyolefin resin having an epoxy group is used, the adhesiveness and moisture heat resistance of the sealant can be improved.

The polyolefin-based resin having an epoxy group is an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether, and the polyolefin-based resin is subjected to radical reaction conditions. It can be manufactured by graft modification. Here, the term "glycidyl (meth) acrylate" includes both glycidyl acrylate and glycidyl methacrylate. Further, the polyolefin-based resin having an epoxy group can be produced, for example, by radically copolymerizing an unsaturated compound having an epoxy group with an olefin.

The concentration of the epoxy group in the polyolefin resin having an epoxy group is preferably 0.05 mmol / g or more, more preferably 0.1 mmol / g or more, preferably 10 mmol / g or less, more preferably 5 mmol / g or less. Is. The epoxy group concentration is determined from the epoxy equivalent obtained based on JIS K 7236-1995.

The amount of the polyolefin resin having an epoxy group is preferably 0% by mass or more, more preferably 10% by mass or more, particularly preferably 11% by mass or more, and preferably 11% by mass or more, based on 100% by mass of the total amount of the polyolefin resin. It is 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less.

One type of polyolefin resin may be used alone, or two or more types may be used in combination at any ratio. In particular, it is preferable to use a polyolefin-based resin having an acid anhydride group and a polyolefin-based resin having an epoxy group in combination. When a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group are used in combination, a crosslinked structure can be formed by the reaction of the acid anhydride group and the epoxy group, so that a sealing that suppresses the infiltration of water can be formed. The ability of the agent can be effectively enhanced. In this case, the molar ratio of the epoxy group to the acid anhydride group (epoxide group: acid anhydride group) is preferably 100:10 to 100: 400, more preferably 100: 50 to 100: 200, and particularly preferably 100. : 90 to 100: 150.

Hereinafter, specific examples of the polyolefin resin will be described.
Specific examples of the polyisobutylene resin include "Opanol B100" manufactured by BASF (viscosity average molecular weight: 1,110,000) and "B50SF" manufactured by BASF (viscosity average molecular weight: 400,000).

Specific examples of the polybutene resin include "HV-1900" (polybutene, number average molecular weight: 2,900) manufactured by JX Energy Co., Ltd. and "HV-300M" (male anhydride-modified liquid polybutene) manufactured by Toho Chemical Industry Co., Ltd. ("HV"). -300 "(modified product with number average molecular weight: 1,400), number average molecular weight: 2,100, number of carboxy groups constituting the acid anhydride group: 3.2 / 1 molecule, acid value: 43. 4 mgKOH / g, acid anhydride group concentration: 0.77 mmol / g).

Specific examples of the styrene-isobutylene copolymer include "SIBSTAR T102" manufactured by Kaneka (styrene-isobutylene-styrene block copolymer, number average molecular weight: 100,000, styrene content: 30% by mass), manufactured by Seikou PMC. "T-YP757B" (maleic anhydride-modified styrene-isobutylene-styrene block copolymer, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 100,000), "T-YP766" manufactured by Seikou PMC. (Glysidyl methacrylate-modified styrene-isobutylene-styrene block copolymer, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 100,000), "T-YP8920" manufactured by Seikou PMC (maleic anhydride-modified styrene-isobutylene anhydride) -Styrene copolymer, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 35,800), "T-YP8930" manufactured by Seikou PMC (glycidyl methacrylate-modified styrene-isobutylene-styrene copolymer, epoxy Group concentration: 0.638 mmol / g, number average molecular weight: 48,700).

Specific examples of the polyethylene-based resin or polypropylene-based resin include "EPT X-3012P" manufactured by Mitsui Chemicals, Inc. (ethylene-propylene-5-ethylidene-2-norbornene copolymer, "EPT1070" manufactured by Mitsui Chemicals, Ltd. (ethylene-propylene). -Dicyclopentadiene copolymer), "Toughmer A4085" (ethylene-butene copolymer) manufactured by Mitsui Chemicals, Inc. can be mentioned.

As a specific example of the propylene-butene copolymer, "T-YP341" manufactured by Seikou PMC (glycidyl methacrylate-modified propylene-butene random copolymer, amount of butene unit per 100% by mass of propylene unit and butene unit in total). : 29% by mass, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 155,000), "T-YP279" manufactured by Seikou PMC (maleic anhydride-modified propylene-butene random copolymer, propylene unit and butene) Amount of butene unit per 100% by mass of total units: 36% by mass, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 35,000), "T-YP276" (glycidyl methacrylate) manufactured by Seikou PMC. Modified propylene-butene random copolymer, amount of butene unit per 100% by mass of propylene unit and butene unit: 36% by mass, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 57,000), starlight PMC "T-YP312" (maleic anhydride-modified propylene-butene random copolymer, amount of butene units per 100% by mass of propylene units and butene units in total: 29% by mass, acid anhydride group concentration: 0 .464 mmol / g, number average molecular weight: 60,900), "T-YP313" manufactured by Seikou PMC (glycidyl methacrylate-modified propylene-butene random copolymer, butene units per 100% by mass of propylene units and butene units in total Amount: 29% by mass, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 155,000), "T-YP429" manufactured by Seikou PMC (maleic anhydride-modified ethylene-methyl methacrylate copolymer, ethylene unit) Amount of methyl methacrylate unit per 100% by mass of total methyl methacrylate unit: 32% by mass, acid anhydride group concentration: 0.46 mmol / g, number average molecular weight: 2,300), "T-YP430" manufactured by Seikou PMC. (Maleic anhydride-modified ethylene-methylmethacrylate copolymer, amount of methylmethacrylate units per 100% by mass of ethylene units and methylmethacrylate units: 32% by mass, acid anhydride group concentration: 1.18 mmol / g, number average Molecular weight: 4,500), "T-YP431" manufactured by Starlight PMC (glycidyl methacrylate-modified ethylene-methylmethacrylate copolymer, epoxy group concentration: 0.64 mmol / g, number average molecular weight: 2,400), Starlight PMC Made by "T-YP432" (Glysidyl methacrylate-modified ethylene-methyl methacrylate copolymer, epoxy group concentration: 1.63 mmol / g, number average molecular weight: 3,100).

The number average molecular weight of the thermoplastic resin is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, further preferably 10,000 or more, further preferably 30,000 or more, 50, 000 or more is particularly preferable. When a thermoplastic resin having a number average molecular weight in such a range is used, repelling during application of the varnish of the sealing agent can be suppressed, so that the ability of the sealing portion for suppressing the infiltration of water can be effectively enhanced. The mechanical strength of the sealing part can be increased. The number average molecular weight of the thermoplastic resin is preferably 1,000,000 or less, more preferably 800,000 or less, further preferably 700,000 or less, further preferably 600,000 or less, further preferably 500,000 or less. It is preferable, more preferably 450,000 or less, and particularly preferably 400,000 or less. When a thermoplastic resin having a number average molecular weight in such a range is used, the applicability of the varnish as a sealing agent can be improved, and the compatibility between the thermoplastic resin and other components can be improved.

The number average molecular weight can be measured in polystyrene conversion by the gel permeation chromatography (GPC) method. Specifically, the number average molecular weight by the GPC method is determined by using Shimadzu LC-9A / RID-6A as a measuring device and Showa Denko Shodex K-800P / K-804L / K-804L as a column. It can be measured at a column temperature of 40 ° C. using toluene or the like, and calculated using a standard polystyrene calibration curve.

The weight average molecular weight of the thermoplastic resin is usually larger than 5,000, preferably 8,000 or more, more preferably 10,000 or more, still more preferably 15,000 or more, and particularly preferably 20,000 or more. It is preferably 1,000,000 or less, more preferably 800,000 or less, still more preferably 600,000 or less, and particularly preferably 500,000 or less.

The weight average molecular weight can be measured in polystyrene conversion by the gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight by the GPC method is determined by using Shimadzu LC-9A / RID-6A as a measuring device and Showa Denko Shodex K-800P / K-804L / K-804L as a column. It can be measured at a column temperature of 40 ° C. using chloroform or the like, and calculated using a standard polystyrene calibration curve.

The thermoplastic resin preferably has amorphous properties. Amorphous means that the resin does not have a definite melting point. Specifically, amorphous means that no clear peak is observed when the melting point is measured by DSC (differential scanning calorimetry). When an amorphous thermoplastic resin is used, the thickening of the varnish of the sealing agent can be suppressed, so that the fluidity of the varnish can be improved.

The amount of the thermoplastic resin is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 7% by mass or more, based on 100% by mass of the non-volatile component of the encapsulant. , More preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more. When the amount of the thermoplastic resin is in such a range, the ability of the sealant to suppress the infiltration of water can be effectively enhanced, and the transparency of the sealant can be improved. Further, the amount of the thermoplastic resin is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass, based on 100% by mass of the non-volatile component of the encapsulant. % Or less, more preferably 55% by mass or less, and particularly preferably 50% by mass or less. When the amount of the thermoplastic resin is in such a range, the applicability and compatibility of the varnish of the sealant are improved, so that the ability of the sealant to suppress the infiltration of water is effectively enhanced or the sealant is sealed. It is possible to improve the handleability of the agent (for example, suppress the tack).

The amount of the thermoplastic resin is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and preferably 300 parts by mass or less, more preferably, with respect to 100 parts by mass of the inorganic filler. Is 200 parts by mass or less, particularly preferably 150 parts by mass or less. In particular, when the thermoplastic resin contains a polyolefin resin having an acid anhydride group, the amount of the polyolefin resin having an acid anhydride group is preferably 1 part by mass or more, preferably 1 part by mass or more, based on 100 parts by mass of the inorganic filler. Is 3 parts by mass or more, particularly preferably 5 parts by mass or more, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and particularly preferably 23 parts by mass or less. When the thermoplastic resin contains a polyolefin resin having an epoxy group, the amount of the polyolefin resin having an epoxy group is preferably 1 part by mass or more, preferably 2 parts by mass with respect to 100 parts by mass of the inorganic filler. As mentioned above, it is particularly preferably 3 parts by mass or more, preferably 30 parts by mass or less, more preferably 28 parts by mass or less, and particularly preferably 26 parts by mass or less. In particular, when the inorganic filler is semi-firing hydrotalcite, it is desirable that the mass ratio of the semi-firing hydrotalcite to the thermoplastic resin satisfies the above requirements. When the thermoplastic resin is used in such an amount, the encapsulant can particularly effectively suppress the infiltration of water and the leakage of lead.

(6.2. Adhesive imparting agent)
An example of a component that the sealant can contain in combination with the inorganic filler is a tackifier. The tackifier is a compound that can improve the tackiness of the sealant when used in combination with a plastic resin, and is also called "tack fire". The tackifier is suitable for a tacky sealant, and is therefore preferably used in combination with a thermoplastic resin. As the tackifier, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Examples of the tackifying resin include terpene resin, modified terpene resin (hydrocarboned terpene resin, terpene phenol copolymer resin, aromatic modified terpene resin, etc.), kumaron resin, inden resin, petroleum resin (aliphatic petroleum resin, water). Hydrocarbon petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, dicyclopentadiene petroleum resins and their hydrides, etc.) can be mentioned.

Among the above examples, petroleum resin is preferable from the viewpoints of adhesiveness of the sealant, ability to suppress the infiltration of water, transparency and the like. Examples of petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, and hydrogenated hydrocarbon petroleum resins. Aromatic petroleum resin, aliphatic aromatic copolymer petroleum resin, hydrogenated hydrocarbon petroleum resin, dicyclopentadiene petroleum resin and its hydrogen from the viewpoint of adhesiveness, ability to suppress water infiltration, and compatibility. The compound is more preferable. Further, from the viewpoint of transparency, hydrogenated hydrocarbon petroleum resins and hydrides of dicyclopentadiene petroleum resins are particularly preferable.

As the hydrogenated hydrocarbon petroleum resin, one obtained by hydrogenating an aromatic petroleum resin may be used. In this case, the hydrogenation rate of the hydrogenated hydrocarbon petroleum resin is preferably 30% to 99%, more preferably 40% to 97%, still more preferably 50% to 90%. The hydrogenated hydrocarbon petroleum resin having a hydrogenation rate in the above range is less colored, has excellent transparency, and can be produced at a low production cost. The hydrogenation rate can be determined from the ratio of the peak intensities of ¹ H-NMR of hydrogen in the aromatic ring before hydrogenation and after hydrogenation.

As the hydrogenated hydrocarbon petroleum resin, a cyclohexane ring-containing hydrogenated petroleum resin and a dicyclopentadiene-based hydrogenated petroleum resin are particularly preferable.

Hereinafter, specific examples of petroleum resins will be described.
Examples of the terpene resin include YS resin PX1000, YS resin PX1150, YS resin PX1150N, YS resin PX1250, YS resin TH130, and YS resin TR105 (all manufactured by Yasuhara Chemical Co., Ltd.).
Examples of the aromatic-modified terpene resin include YS resin TO85, YS resin TO105, YS resin TO115, and YS resin TO125 (all manufactured by Yasuhara Chemical Co., Ltd.).
Examples of the hydrogenated terpene resin include Clearon P, Clearon M, and Clearon K series (all manufactured by Yasuhara Chemical Co., Ltd.).
Examples of the terpene phenol copolymer resin include YS Polystar 2000, Polystar U, Polystar T, Polystar S, and Mighty Ace G (all manufactured by Yasuhara Chemical Co., Ltd.).
Examples of the liquid resin include YS resin LP and YS resin CP (both manufactured by Yasuhara Chemical Co., Ltd.).
Examples of the hydrocarbon resin include T-REZ RB093, T-REZ RC100, T-REZ RC115, T-REZ RC093, and T-REZ RE100 (all manufactured by JXTG Energy Co., Ltd.); Examples thereof include tack 90, petrotac 90HS, petrotac 90V, petrotac 100V (all manufactured by Tosoh Corporation).
Examples of hydrogenated hydrocarbon petroleum resins include Escorez 5300 series and 5600 series (all manufactured by Exxon Mobile Co., Ltd.); T-REZ OP501, T-REZ PR801, T-REZ PR803, T-REZ HA085, T-REZ HA103, T-REZ HA105, T-REZ HA125, T-REZ HB103, T-REZ HB125, (hydrocarbonated dicyclopentadiene petroleum resin, manufactured by JXTG Energy Co., Ltd.); Quintone1325, Quintone1345 (all manufactured by Nippon Zeon Co., Ltd.); Examples thereof include Imarb S-100, Imarb S-110, Imarb P-100, Imarb P-125, and Imarb P-140 (hydrocarbonated dicyclopentadiene petroleum resin, manufactured by Idemitsu Kosan Co., Ltd.).
Examples of the aromatic petroleum resin include ENDEX155 (manufactured by Eastman); neopolymer L-90, neopolymer 120, neopolymer 130, neopolymer 140, neopolymer 150, neopolymer 170S, neopolymer 160, neopolymer. E-100, Neopolymer E-130, Neopolymer M-1, Neopolymer S, Neopolymer S100, Neopolymer 120S, Neopolymer 130S, Neopolymer EP-140 (all manufactured by JXTG Energy Co., Ltd.), Petcol LX, Petcol Examples include 120, polymer 130, and polymer 140 (all manufactured by Toso Co., Ltd.).
Examples of the aliphatic aromatic copolymer petroleum resin include Quintone D100 (manufactured by Zeon Corporation), T-REZ RD104, and T-REZ PR802 (manufactured by JXTG Energy Co., Ltd.).
Examples of the cyclohexane ring-containing hydrogenated petroleum resin include Alcon P-90, Alcon P-100, Alcon P-115, Alcon P-125, Alcon P-140, Alcon M-90, Alcon M-100, and Alcon M-. 115, Alcon M-135 (both manufactured by Arakawa Chemical Co., Ltd.) and the like can be mentioned.
Examples of the cyclohexane ring-containing saturated hydrocarbon resin include TFS13-030 (manufactured by Arakawa Chemical Industries, Ltd.).
Examples of the ultra-light rosin resin include pine crystal ME-H, pine crystal ME-D, pine crystal ME-G, pine crystal KR-85, pine crystal KE-311, pine crystal KE-359, and pine crystal D-6011. , Pine Crystal PE-590, Pine Crystal KE-604, Pine Crystal PR-580 (all manufactured by Arakawa Chemical Co., Ltd.) and the like.

The number average molecular weight of the tackifier is preferably 100 to 2,000, more preferably 700 to 1,500, and even more preferably 500 to 1,000.

The softening point of the tackifier is preferably 50 ° C. to 200 ° C., more preferably 90 ° C. to 180 ° C., and even more preferably 100 ° C. to 150 ° C. The softening point can be measured by the ring-and-ball method according to JIS K2207. When a tackifier having such a softening point is used, sealing using a sealing sheet with a sealing agent can be easily performed, and the heat resistance of the sealing agent can be improved.

The amount of the tackifier is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, based on 100% by mass of the non-volatile component of the encapsulant. When the amount of the tackifier is in such a range, the adhesiveness of the sealant can be effectively enhanced. Further, the amount of the tackifier is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and 40% by mass or less with respect to 100% by mass of the non-volatile component of the encapsulant. Especially preferable. When the amount of the tackifier is in such a range, the ability of the sealant to suppress the infiltration of water can be effectively increased.

(6.3. Crosslinking agent and crosslinking accelerator)
Examples of components that the encapsulant can contain in combination with the inorganic filler include cross-linking agents and cross-linking accelerators. The cross-linking agent and the cross-linking accelerator can react with the reactive groups of other components to form a cross-linked structure. For example, when the thermoplastic resin has a reactive group such as an acid anhydride group and an epoxy group, the cross-linking agent and the cross-linking accelerator can react with the reactive group to form a cross-linked structure. However, the above-mentioned thermoplastic resin and tackifier are not included in the cross-linking agent and the cross-linking accelerator. As the cross-linking agent and the cross-linking accelerator, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Examples of the cross-linking agent and the cross-linking accelerator include amine compounds, guanidine compounds, imidazole compounds, phosphonium compounds, and phenol compounds.

Examples of the amine compound include quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide; DBU (1,8-diazabicyclo [5.4.0] undecene-7), DBN (1,5-diazabicyclo). [4.3.0] Nonen-5), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-gerate, DBU-phenolnovolac resin salt and other diazabicyclo compounds; benzyldimethyl Tertiary amines such as amines, 2- (dimethylaminomethyl) phenols, 2,4,6-tris (diaminomethyl) phenols and salts thereof; dimethyls such as aromatic dimethylurea, aliphatic dimethylurea and aromatic dimethylurea. Urea compounds; etc.

Examples of the guanidine compound include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine and tetramethyl. Guanidin, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca- 5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allyl Biguanides, 1-phenylbiguanides, 1- (o-tolyl) biguanides and the like can be mentioned.

Examples of the imidazole compound include 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl-imidazole, 2-phenyl-4,5-bis ( Hydroxymethyl) -imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-imidazole, 2-dodecyl-imidazole, 2-heptadecylimidazole , 1,2-dimethyl-imidazole and the like.

Examples of the phosphonium compound include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, and tetra. Examples thereof include phenylphosphonium thiocyanate and butyltriphenylphosphonium thiocyanate.

Types of phenolic compounds include, for example, MEH-7700, MEH-7810, MEH-7851 (manufactured by Meiwa Kasei Co., Ltd.), NHN, CBN, GPH (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, Examples thereof include SN495, SN375, SN395 (manufactured by Toto Kasei Co., Ltd.) and TD2090 (manufactured by DIC Corporation). In particular, specific examples of the triazine skeleton-containing phenolic compound include LA3018 (manufactured by DIC Corporation) and the like. Specific examples of the triazine skeleton-containing phenol novolac compound include LA7052, LA7054, LA1356 (manufactured by DIC Corporation) and the like.

Examples of the cross-linking agent include a resin having a functional group capable of reacting with an acid anhydride group. Examples of the functional group capable of reacting with the acid anhydride group include a hydroxyl group, a primary or secondary amino group, a thiol group, an epoxy group, an oxetane group and the like, and an epoxy group is preferable. As the resin having a functional group capable of reacting with the acid anhydride group, for example, the resin described in International Publication No. 2017/057708 can be used.

Examples of the cross-linking agent include a resin having a functional group capable of reacting with an epoxy group. Examples of the functional group capable of reacting with the epoxy group include a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group, an acid anhydride group and the like, and an acid anhydride group is preferable. Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride and the like. As the resin having a functional group capable of reacting with the epoxy group, for example, the resin described in International Publication No. 2017/057708 can be used.

Further, if some of the curing agents described later can react with the reactive group of the component contained in the sealing agent, the curing agent may be used as a cross-linking agent or a cross-linking accelerator.

The amount of the cross-linking agent and the cross-linking accelerator is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and particularly 0.02% by mass or more, based on 100% by mass of the non-volatile component of the sealing agent. preferable. When the amounts of the cross-linking agent and the cross-linking accelerator are in such a range, the handleability of the sealing agent can be improved (for example, tack suppression). The amount of the cross-linking agent and the cross-linking accelerator is preferably 5% by mass or less, more preferably 2.5% by mass or less, based on 100% by mass of the non-volatile component of the sealant. When the amount of the cross-linking agent and the cross-linking accelerator is in such a range, the ability of the sealing agent to suppress the infiltration of water can be effectively enhanced.

(6.4. Other ingredients suitable for adhesive type sealants)
Among the components that can be contained in the encapsulant, an example of a component suitable for the adhesive type encapsulant is a plasticizer. The plasticizer can improve the flexibility and moldability of the sealant. As the plasticizer, a material that is liquid at room temperature (25 ° C.) is preferable. Examples of plasticizers include paraffinic process oils, naphthenic process oils, liquid paraffins, polyethylene waxes, polypropylene waxes, mineral oils such as vaseline, castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, palm oil, olive oil, etc. Examples thereof include liquid polyα-olefin compounds such as vegetable oils, liquid polybutene, hydrogenated liquid polybutene, liquid polybutadiene, and hydrogenated liquid polybutadiene. The weight average molecular weight of the plasticizer is preferably 500 to 5,000, more preferably 1,000 to 3,000, from the viewpoint of adhesiveness. One type of plasticizer may be used alone, or two or more types may be used in combination at any ratio. The amount of the plasticizer is preferably 50% by mass or less with respect to 100% by mass of the non-volatile component in the encapsulant.

Among the components that can be contained in the sealant, examples of the components suitable for the adhesive type sealant include resins other than those described above (for example, epoxy resin, urethane resin, acrylic resin, polyamide resin, etc.); rubber particles, silicone. Organic fillers such as powders, nylon powders and fluororesin powders; thickeners such as olben and benton; silicone-based, fluorine-based and polymer-based defoaming agents or leveling agents; triazole compounds, thiazole compounds, triazine compounds, porphyrin Adhesion-imparting agents such as compounds; antioxidants; etc. can be mentioned. Further, the adhesive type sealant may contain a component described later as a component that can be contained in the thermosetting type sealant.

[7. Description of components suitable for thermosetting sealants according to the first embodiment]
(7.1. Thermosetting resin as a binder resin)
Examples of components that the sealant can contain in combination with the inorganic filler include thermosetting resins. The thermosetting resin is preferable as a binder resin for a thermosetting type sealing agent. One type of thermosetting resin may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Examples of the thermosetting resin include epoxy resin, cyanate ester resin, phenol resin, bismaleimide-triazine resin, polyimide resin, acrylic resin, vinylbenzyl resin and the like, and epoxy resin is preferable. When the epoxy resin is combined with an inorganic filler containing at least one selected from the group consisting of semi-baked hydrotalcite and calcium oxide, a sealing agent having excellent transparency can be obtained.

The epoxy resin preferably has two or more epoxy groups per molecule on average. Examples of epoxy resins include hydrogenated epoxy resins (hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, etc.), fluorine-containing epoxy resins, chain aliphatic epoxy resins, cyclic aliphatic epoxy resins, etc. Bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene 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, fragrance Group glycidylamine type epoxy resin (for example, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyltoluidine, diglycidylaniline, etc.), alicyclic epoxy resin, phenol novolac type epoxy resin, alkylphenol type epoxy resin, cresol Novolak type epoxy resin, bisphenol A Novolak type epoxy resin, epoxy resin having a butadiene structure, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, diglycidyl etherified product of phenols, and diglycidyl etherified product of alcohols , And alkyl substituents of these epoxy resins.

As the epoxy resin, a liquid epoxy resin may be used, a solid epoxy resin may be used, or a liquid epoxy resin and a solid epoxy resin may be used in combination. The "liquid epoxy resin" represents an epoxy resin that is liquid at normal temperature (25 ° C.) and atmospheric pressure (1 atm). Further, the "solid epoxy resin" represents a solid epoxy resin at normal temperature (25 ° C.) and atmospheric pressure (1 atm). From the viewpoint of coatability, processability and adhesiveness, it is preferable that 10% by mass or more of the total epoxy resin is a liquid epoxy resin. Further, from the viewpoint of kneadability with the inorganic filler and viscosity of the varnish, it is particularly preferable to use the liquid epoxy resin and the solid epoxy resin in combination. The mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1: 2 to 1: 0, more preferably 1: 1.5 to 1: 0.

As the epoxy resin, hydrogenated epoxy resin, fluorine-containing epoxy resin, chain aliphatic type epoxy resin, cyclic aliphatic type epoxy resin, and alkylphenol type epoxy resin are preferable. Of these, hydrogenated epoxy resins, fluorine-containing epoxy resins, chain aliphatic epoxy resins, and cyclic aliphatic epoxy resins are more preferable. When these epoxy resins are used, the transparency of the encapsulant can be enhanced.

"Hydrogenated epoxy resin" means an epoxy resin obtained by hydrogenating an aromatic ring-containing epoxy resin. The hydrogenation rate of the hydrogenated epoxy resin is preferably 50% or more, more preferably 70% or more. As the hydrogenated epoxy resin, hydrogenated bisphenol A type epoxy resin and hydrogenated bisphenol F type epoxy resin are preferable. Examples of the hydrogenated bisphenol A type epoxy resin include liquid hydrogenated bisphenol A type epoxy resin (for example, "YX8000" (manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: about 205)) and "Denacol EX-252" (Nagase Chemtex Co., Ltd.). , Epoxy equivalent: about 213)), solid hydrogenated bisphenol A type epoxy resin (for example, "YX8040" (manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: about 1000)).

Examples of the fluorine-containing epoxy resin include the fluorine-containing epoxy resin described in International Publication No. 2011/089947.

"Chain-aliphatic epoxy resin" means an epoxy resin having a linear or branched alkyl chain or an alkyl ether chain. Examples of the chain aliphatic epoxy resin include polyglycerol polyglycidyl ether (for example, "Denacol EX-512", "Denacol EX-521", manufactured by Nagase ChemteX Corporation), pentaerythritol polyglycidyl ether (for example, "Denacol EX-521"). Denacol EX-411 ", manufactured by Nagase ChemteX), diglycerol polyglycidyl ether (for example," Denacol EX-421 ", manufactured by Nagase Chemtex), glycerol polyglycidyl ether (for example," Denacol EX-313 "," Denacol EX-314 ", Nagase ChemteX, Trimethylol Propanepolyglycidyl Ether (for example," Denacol EX-321 ", Nagase Chemtex), Neopentyl glycol diglycidyl ether (for example," Denacol EX-211 " , Nagasechemtex, 1,6-hexanediol diglycidyl ether (eg, "Denacol EX-212", Nagasechemtex), ethylene glycol diglycidyl ether (eg, "Denacol EX-810", "Denacol EX-811", manufactured by Nagase ChemteX, diethylene glycol diglycidyl ether (for example, "Denacol EX-850", "Denacol EX-851", manufactured by Nagase Chemtex), polyethylene glycol diglycidyl ether (for example, manufactured by Nagase ChemteX). "Denacol EX-821", "Denacol EX-830", "Denacol EX-832", "Denacol EX-841", "Denacol EX-861", manufactured by Nagase ChemteX Corporation), propylene glycol diglycidyl ether (for example, "Denacol EX-911", manufactured by Nagase ChemteX), polypropylene glycol diglycidyl ether (for example, "Denacol EX-941", "Denacol EX-920", "Denacol EX-931", manufactured by Nagase ChemteX), etc. Can be mentioned.

The "cyclic aliphatic epoxy resin" means an epoxy resin having a cyclic aliphatic skeleton (for example, a cycloalkane skeleton) in the molecule. Examples of the cyclic aliphatic epoxy resin include "EHPE-3150" manufactured by Daicel Chemical Industries, Ltd., "TOPR-300" manufactured by Nittetsu Chemical & Materials Co., Ltd., and the like.

The "alkylphenol type epoxy resin" means an epoxy resin having a benzene ring skeleton having one or more alkyl groups and one or more hydroxy groups as a substituent, and the hydroxy groups are converted into glycidyl ether groups. Examples of the alkylphenol type epoxy resin include "HP-820" manufactured by DIC; "YDC-1312" manufactured by Nippon Steel & Sumitomo Metal Chemical Industries, Ltd .; "EX-146" manufactured by Nagase ChemteX Corporation.

In one embodiment, the thermosetting resin preferably contains an aromatic ring-containing epoxy resin. The aromatic ring-containing epoxy resin represents an epoxy resin containing an aromatic ring in the molecule. The use of aromatic ring-containing epoxy resins tends to improve the reactivity of the encapsulant, the glass transition temperature of the encapsulant after curing, or any or all of the adhesions. Examples of the aromatic ring-containing epoxy resin include an alkylphenol type epoxy resin and a fluorine-containing aromatic epoxy resin.

Examples of the aromatic ring-containing epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, and fluorine-containing aromatic epoxy resin. Among them, bisphenol type epoxy resin and fluorine-containing aromatic epoxy resin are preferable, bisphenol type epoxy resin is more preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are further preferable.

Examples of the bisphenol A type epoxy resin include "828EL", "1001" and "1004AF" manufactured by Mitsubishi Chemical Corporation; "840" and "850-S" manufactured by DIC Corporation; "YD-128" manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation. And so on. Examples of the mixture of the liquid bisphenol A type epoxy resin and the liquid bisphenol F type epoxy resin include "ZX-1059" (epoxy equivalent: about 165) manufactured by Nippon Steel Chemical Industries, Ltd.

Examples of the bisphenol F type epoxy resin include "807" manufactured by Mitsubishi Chemical Corporation; "830" manufactured by DIC Corporation; and "YDF-170" manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation.

Examples of the phenol novolac type epoxy resin include "N-730A", "N-740", "N-770" and "N-775" manufactured by DIC; "152" and "154" manufactured by Mitsubishi Chemical Corporation. Can be mentioned.

"Biphenyl aralkyl type epoxy resin" means an epoxy resin having a main chain in which a novolak structure and a divalent biphenyl structure are bonded. Examples of the biphenyl aralkyl type epoxy resin include "NC-3000", "NC-3000L" and "NC-3100" manufactured by Nippon Kayaku Co., Ltd.

"Fluorene type epoxy resin" means an epoxy resin having a fluorene skeleton. Examples of the fluorene type epoxy tree include "OGSOL PG-100", "CG-500EG-200" and "EG-280" manufactured by Osaka Gas Chemical Co., Ltd.

"Fluorine-containing aromatic epoxy resin" means a fluorine-containing epoxy resin having an aromatic ring. Examples of the fluorine-containing aromatic epoxy resin include the fluorine-containing aromatic epoxy resin described in International Publication No. 2011/089947.

Aromatic ring-containing epoxy resins generally have a high refractive index. Therefore, from the viewpoint of increasing the transparency of the encapsulant by bringing the refractive indexes of the resin and the inorganic filler closer to each other, the refractive index of the entire epoxy resin can be adjusted by combining the epoxy resin containing an aromatic ring and the epoxy resin not containing an aromatic ring structure. You may adjust. Among the epoxy resins that do not contain an aromatic ring structure, examples suitable for combination with an aromatic ring-containing epoxy resin include a hydrogenated epoxy resin, a fluorine-containing epoxy resin, a chain aliphatic type epoxy resin, and a cyclic aliphatic type. Epoxy resin can be mentioned. Of these, hydrogenated epoxy resins, fluorine-containing epoxy resins, and cyclic aliphatic epoxy resins are preferable. Further, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, and fluorine-containing epoxy resin are preferable, and hydrogenated bisphenol A type epoxy resin and hydrogenated bisphenol F type epoxy resin are more preferable. A type epoxy resin is particularly preferable. At this time, the amount of the aromatic ring-containing epoxy resin is preferably 0.5% by mass to 40% by mass, and 1% by mass, based on 100% by mass of the total of the aromatic ring-containing epoxy resin and the epoxy resin not containing the aromatic ring structure. % To 35% by mass is more preferable, and 2% by mass to 30% by mass is particularly preferable.

From the viewpoint of reactivity, the epoxy equivalent of the epoxy resin is preferably 50 to 5,000, more preferably 50 to 3,000, still more preferably 80 to 2,000, and particularly preferably 100 to 1,500. The "epoxy equivalent" is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and can be measured according to the method specified in JIS K 7236.

The weight average molecular weight of the thermosetting resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight average molecular weight of the thermosetting resin can be measured as a polystyrene-equivalent value by the gel permeation chromatography (GPC) method.

The amount of the thermosetting resin is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and particularly preferably 45% by mass, based on 100% by mass of the non-volatile component of the encapsulant. The above is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

The amount of the thermosetting resin is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, particularly preferably 160 parts by mass or more, and preferably 300 parts by mass or less, based on 100 parts by mass of the inorganic filler. It is preferably 250 parts by mass or less, and particularly preferably 200 parts by mass or less.

(7.2. Thermoplastic resin as binder resin)
The thermosetting sealant may contain a thermoplastic resin as a binder resin in combination with the thermosetting resin. When the binder resin contains a thermosetting resin and a thermoplastic resin in combination, it is possible to improve the flexibility of the sealing agent and the varnish coating property (repelling suppression) of the sealing agent. As the thermoplastic resin, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, polysulfone resin, polyester resin, (meth) acrylic resin and the like. Here, the term "(meth) acrylic resin" includes both acrylic resin and methacrylic resin. As the thermoplastic resin to be combined with the thermosetting resin, the above-mentioned thermoplastic resin may be used as the binder resin suitable for the adhesive type encapsulant.

Phenoxy resin is preferable as the thermoplastic resin to be combined with the thermosetting resin. The phenoxy resin has good compatibility with a thermosetting resin (particularly an epoxy resin). Further, when the phenoxy resin is used, the ability of the sealing agent for suppressing the infiltration of water can be effectively enhanced. The phenoxy resin has one or more skeletons selected from bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, and norbornene skeleton. Resin is preferred.

Commercially available phenoxy resins include, for example, YX7200B35 (Mitsubishi Chemical: biphenyl skeleton-containing phenoxy resin), 1256 (Mitsubishi Chemical: bisphenol A skeleton-containing phenoxy resin), YX6954BH35 (Mitsubishi Chemical: bisphenol acetophenone skeleton included). Phenoxy resin) and the like.

The range of the weight average molecular weight of the thermoplastic resin to be combined with the thermosetting resin may be the same range as the weight average molecular weight of the thermoplastic resin described above as a binder resin suitable for the adhesive type encapsulant. A thermoplastic resin having a weight average molecular weight in such a range has flexibility of the sealant, applicability of the varnish of the sealant (suppression of repelling), and compatibility between the thermosetting resin and the thermoplastic resin. Can be improved. Among them, the weight average molecular weight of the phenoxy resin is preferably 10,000 to 500,000, more preferably 20,000 to 300,000. The method for measuring the weight average molecular weight is as described above.

The amount of the thermoplastic resin to be combined with the thermosetting resin is preferably 0.1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more, based on 100% by mass of the non-volatile component of the encapsulant. It is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 25% by mass or less, and particularly preferably 15% by mass or less.

The amount of the thermoplastic resin to be combined with the thermosetting resin is preferably 1 part by mass or more, more preferably 5 parts by mass or more, particularly preferably 10 parts by mass or more, and preferably 90 parts by mass with respect to 100 parts by mass of the inorganic filler. It is less than or equal to parts by mass, more preferably 70 parts by mass or less, and particularly preferably 50 parts by mass or less.

The amount of the thermoplastic resin to be combined with the thermosetting resin is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more, based on 100 parts by mass of the thermosetting resin. Is 80 parts by mass or less, more preferably 60 parts by mass or less, and particularly preferably 40 parts by mass or less.

(7.3. Curing agent and curing accelerator)
Examples of components that the sealant can contain in combination with the inorganic filler include a curing agent. When used in combination with a thermosetting resin, the curing agent has a function of reacting with the thermosetting resin to cure the encapsulant. From the viewpoint of suppressing thermal deterioration of the electronic device during curing of the encapsulant, the curing agent is preferably one that can react with the thermosetting resin at a temperature of 140 ° C. or lower (preferably 120 ° C. or lower). One type of curing agent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

The type of curing agent can be selected according to the type of thermosetting resin. Hereinafter, a curing agent corresponding to an epoxy resin as a preferable thermosetting resin will be described. Examples of the curing agent corresponding to the epoxy resin include ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine compounds, dimethylurea compounds, amine adduct compounds, organic acid dihydrazide compounds, organic phosphine compounds, dicyandiamide compounds, 1 Examples thereof include secondary and secondary amine compounds. Of these, ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine compounds, dimethylurea compounds and amine adduct compounds are preferable. Further, ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine compounds, and dimethylurea compounds are more preferable.

The encapsulant may contain a curing accelerator in combination with the curing agent. Only one type of curing accelerator may be used, or two or more types may be used in combination. The type of curing accelerator can be selected according to the type of thermosetting resin. Hereinafter, a curing accelerator corresponding to an epoxy resin as a preferable thermosetting resin will be described. Examples of the curing accelerator compatible with the epoxy resin include imidazole compounds, tertiary amine compounds, dimethylurea compounds, and amine adduct compounds. Of these, imidazole compounds, tertiary amine compounds, and dimethylurea compounds are preferable.

The ionic liquid as a curing agent is preferably an ionic liquid capable of curing a thermosetting resin (particularly an epoxy resin) at a temperature of 140 ° C. or lower (preferably 120 ° C. or lower). That is, the ionic liquid is a salt that can be melted in a temperature range of 140 ° C. or lower (preferably 120 ° C. or lower), and a salt having a curing action of a thermosetting resin (particularly an epoxy resin) is preferable. The ionic liquid is preferably used in a state of being uniformly dissolved in a thermosetting resin (particularly an epoxy resin). Ionic liquids can usually effectively enhance the ability of the sealant to suppress the ingress of water.

Examples of the cation constituting the ionic liquid as a curing agent include ammonium cations such as imidazolium ion, piperidinium ion, pyrrolidinium ion, pyrazonium ion, guanidinium ion and pyridinium ion; and tetraalkylphosphonium cation (for example, tetraalkylphosphonium cation). Phosphonium-based cations such as tetrabutylphosphonium ion, tributylhexylphosphonium ion, etc .; sulfonium-based cations such as triethylsulfonium ion and the like can be mentioned.

Examples of the anion constituting the ionic liquid as a curing agent include halide-based anions such as fluoride ion, chloride ion, bromide ion and iodide ion; alkylsulfate-based anion such as methanesulfonate ion; trifluoromethanesulfone. Fluorine-containing compound anions such as acid ion, hexafluorophosphonate ion, trifluorotris (pentafluoroethyl) phosphonate ion, bis (trifluoromethanesulfonyl) imide ion, trifluoroacetate ion, tetrafluoroborate ion; phenol ion, Phenolic anions such as 2-methoxyphenol ion, 2,6-di-tert-butylphenol ion; acidic amino acid ions such as aspartate ion and glutamate ion; neutral amino acid ions such as glycine ion, alanine ion and phenylalanine ion; N N-acylamino acid ion represented by the following formula (A) such as -benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion; formate ion, acetate ion, decanoate ion, 2-pyrrolidone-5-carboxylic acid Examples thereof include carboxylic acid-based anions such as ions, α-lipoate ions, lactate ions, tartrate ions, horse urate ions, N-methyl horse urate ions and benzoate ions.

In the formula (A), ^RA represents a linear or branched alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group, and X ^A represents a side chain of an amino acid. Examples of the amino acid in the formula (A) include aspartic acid, glutamic acid, glycine, alanine, phenylalanine and the like, and glycine is preferable.

Among the above-mentioned cations, ammonium-based cations and phosphonium-based cations are preferable, and imidazolium ions and phosphonium ions are more preferable. Examples of the imidazolium ion include 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-propyl-3-methylimidazolium ion and the like.

Further, as the anion, a phenol-based anion, an N-acylamino acid ion represented by the formula (A), and a carboxylic acid-based anion are preferable, and an N-acylamino acid ion and a carboxylic acid-based anion are more preferable.

Specific examples of the phenolic anion include 2,6-di-tert-butylphenol ion.
Specific examples of carboxylic acid-based anions include acetate ion, decanoate ion, 2-pyrrolidone-5-carboxylic acid ion, formate ion, α-lipoate ion, lactate ion, tartrate ion, horse urate ion, and N-methyl horse. Examples thereof include acetate ion, 2-pyrrolidone-5-carboxylic acid ion, formate ion, lactate ion, tartrate ion, horse urate ion, N-methyl horse urate ion, and acetate ion and decanoate ion. , N-methylhorseurate ion, formate ion is more preferable.
Specific examples of the N-acylamino acid ion represented by the formula (A) include N-benzoylalanine ion, N-acetylphenylalanine ion, aspartate ion, glycine ion, N-acetylglycine ion and the like. -Benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion are preferable, and N-acetylglycine ion is more preferable.

Examples of the ionic liquid include 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium trifluoroacetate, and the like. Tetrabutylphosphonium α-lipoate, tetrabutylphosphonium formate salt, tetrabutylphosphonium lactate, bis (tetrabutylphosphonium) tartrate, tetrabutylphosphonium horseurate, tetrabutylphosphonium salt N-methylumaurate, benzoyl-DL-alaninetetra Butylphosphonium salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2,6-di-tert-butylphenol tetrabutylphosphonium salt, L-aspartate monotetrabutylphosphonium salt, glycinetetrabutylphosphonium salt, N-acetylglycinetetrabutylphosphonium Salt, 1-ethyl-3-methylimidazolium lactate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate salt, 1-ethyl-3-methylimidazolium salt horseurate, N -Methyl horseurate 1-ethyl-3-methylimidazolium salt, bis tartrate (1-ethyl-3-methylimidazolium) salt, N-acetylglycine 1-ethyl-3-methylimidazolium salt are preferable, and tetrabutylphosphonium. Decanoate, N-Acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium salt horseuriate, N -Methylhorseurate 1-ethyl-3-methylimidazolium salt is more preferred.

_{As a method for synthesizing an ionic liquid, for example, NaBF 4} , NaPF ₆ , and CF are used as a precursor composed of a cation moiety such as alkylimidazolium, alkylpyridinium, alkylammonium, and alkylsulfonium ion and an anion moiety containing halogen. ₃ An anion exchange method in which SO ₃ Na, LiN (SO ₂ CF ₃ ) _2, etc. are reacted can be mentioned. Further, as another method for synthesizing an ionic liquid, for example, there is an acid ester method in which an amine-based substance is reacted with an acid ester to introduce an alkyl group and an organic acid residue becomes a counter anion. Further, as another method for synthesizing an ionic liquid, for example, a neutralization method in which amines are neutralized with an organic acid to obtain a salt can be mentioned. In the neutralization method using an anion, cation and solvent, the anion and cation may be used in equal amounts, the solvent in the obtained reaction solution may be distilled off, and the solvent may be used as it is. Alternatively, the obtained reaction solution may be mixed with an organic solvent (methanol, toluene, ethyl acetate, acetone, etc.) and then concentrated for use.

Examples of the acid anhydride compound as a curing agent include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and dodecenyl succinic anhydride. Things etc. can be mentioned. Specific examples of the acid anhydride compound include Ricacid TH, TH-1A, HH, MH, MH-700, MH-700G (all manufactured by New Japan Chemical Co., Ltd.) and the like.

Examples of the imidazole compound as a curing agent or curing accelerator include 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-ethyl. -4-Methyl-imidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 2,4-diamino-6- (2'-un) Decylimidazolyl- (1'))-ethyl-s-triazine, 2-phenyl-4,5-bis (hydroxymethyl) -imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2 -Phenyl-imidazole, 2-dodecyl-imidazole, 2-heptadecylimidazole, 1,2-dimethyl-imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2') -Methylimidazolyl- (1') -ethyl-s-triazine, 2,4-diamino-6- (2'-methylimidazolyl- (1'))-ethyl-s-triazine isocyanuric acid adduct and the like can be mentioned. Specific examples of the imidazole compound include curesol 2MZ, 2P4MZ, 2E4MZ, 2E4MZ-CN, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2PHZ, 1B2MZ, 1B2PZ, 2PZ, C17Z, 1.2DMZ, 2P4MHZ-PW. , 2MZ-A, 2MA-OK (both manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like.

Specific examples of the tertiary amine-based compound as a curing agent or curing accelerator include DBN (1,5-diazabicyclo [4.3.0] non-5-ene) and DBU (1,8-diazabiclo [5. 4.0] undec-7-ene), DBU 2-ethylhexanate, DBU phenol salt, DBU p-toluenesulfonate, U-CAT SA 102 (manufactured by San-Apro: DBU octylate) , DBU-organic acid salt such as DBU formate, tris (dimethylaminomethyl) phenol (TAP) and the like.

Specific examples of the dimethylurea compound as a curing agent or curing accelerator include aromatic dimethyls such as DCMU (3- (3,4-dichlorophenyl) -1,1-dimethylurea) and U-CAT3512T (manufactured by San-Apro). Urea; Examples thereof include aliphatic dimethyl urea such as U-CAT3503N (manufactured by San-Apro). Of these, aromatic dimethylurea is preferable from the viewpoint of curability.

Examples of the amine adduct compound as a curing agent or curing accelerator include an epoxy adduct compound obtained by stopping the addition reaction of a tertiary amine to an epoxy resin in the middle. Specific examples of amine adduct compounds include Amicure PN-23, Amicure MY-24, Amicure PN-D, Amicure MY-D, Amicure PN-H, Amicure MY-H, Amicure PN-31, Amicure PN-40, Examples thereof include Amicure PN-40J (both manufactured by Ajinomoto Fine Techno Co., Ltd.).

Specific examples of the organic acid dihydrazide compound as a curing agent include Amicure VDH-J, Amicure UDH, Amicure LDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) and the like.

Examples of the organic phosphine compound as a curing agent or curing accelerator include triphenylphosphine, tetraphenylphosphonium tetra-p-tolylbolate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, triphenylphosphine triphenylborane and the like can be mentioned. Specific examples of the organic phosphine compound include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, TPP-S (manufactured by Hokuko Chemical Industry Co., Ltd.) and the like.

Examples of the dicyandiamide compound as a curing agent include dicyandiamide. Specific examples of the dicyandiamide compound include DICY7 and DICY15 (both manufactured by Mitsubishi Chemical Corporation), which are dicyandiamide finely pulverized products.

Examples of the primary and secondary amine compounds as the curing agent include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, and the like. Aliper amines such as diproprenedamines, diethylaminopropylamines, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane; N-aminoethylpyverazine, 1,4-bis (3-aminopropyl) ) Alicyclic amines such as piperazine; aromatic amines such as diaminodiphenylmethane, m-phenylenediamine, m-xylene diamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoluenediamine; Specific examples of the primary and secondary amine compounds include Kayahard AA (manufactured by Nippon Kayaku Co., Ltd .: 4,4'-diamino-3,3'-dimethyldiphenylmethane).

Further, if any of the above-mentioned cross-linking agents and cross-linking accelerators can react with the thermosetting resin to cure the sealing agent, the cross-linking agent and the cross-linking accelerator may be used as the curing agent.

It is preferable to use the curing agent and the curing accelerator in combination. Preferred combinations of the curing agent and the curing accelerator include two or more selected from ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine compounds, dimethyl urea compounds, and amine adduct compounds.

The amount of the curing agent is preferably 0.1% by mass to 40% by mass, more preferably 0.5% by mass to 38 parts by mass, and 1% by mass to 35% by mass with respect to 100% by mass of the non-volatile component of the encapsulant. The portion is more preferable. When the amount of the curing agent is not more than the lower limit of the above range, the curing of the encapsulant can be sufficiently advanced. Further, when the amount of the curing agent is not more than the upper limit value in the above range, the storage stability of the sealing agent can be enhanced. In particular, the amount of the ionic liquid as the curing agent is preferably 20% by mass or less, more preferably 18% by mass or less, and particularly preferably 15% by mass or less, based on 100% by mass of the non-volatile component of the encapsulant. When the amount of ionic liquid is in the above range, the ability of the sealant to suppress the infiltration of water can be effectively enhanced.

The amount of the curing accelerator is preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 8% by mass, and 0.5% by mass with respect to 100% by mass of the non-volatile component of the encapsulant. It is more preferably to 5% by mass. When the amount of the curing accelerator is not more than the lower limit of the above range, the curing of the encapsulant can be rapidly advanced. Further, when the amount of the curing accelerator is not more than the upper limit of the above range, the storage stability of the encapsulant can be enhanced.

(7.4. Other components suitable for thermosetting encapsulants)
Among the components that can be contained in the encapsulant, an example of a component suitable for the thermosetting encapsulant is a coupling agent. When the sealing agent contains a coupling agent, the aggregation of the inorganic filler is suppressed and the surface area of the inorganic filler can be increased, so that the lead adsorption property and the hygroscopic property of the inorganic filler can be easily exhibited. One type of coupling agent may be used alone, or two or more types may be used in combination at any ratio.

Examples of the coupling agent include a silane coupling agent, an aluminate coupling agent, and a titanate 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-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2) Amino-based silane coupling agents such as -aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane; ureido-based silanes such as 3-ureidopropyltriethoxysilane Coupling agent; Vinyl-based silane coupling agent such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; Styryl-based silane coupling agent such as p-styryltrimethoxysilane; 3-acrylicoxypropyltrimethoxy Acrylate-based silane coupling agents such as silane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanoxidetrimethoxysilane; bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) ) A sulfide-based silane coupling agent such as tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole silane, triazinesilane and the like can be mentioned. Among these, vinyl-based silane coupling agents and epoxy-based silane coupling agents are preferable, and epoxy-based silane coupling agents are particularly preferable.

Examples of the aluminate coupling agent include alkylacetoacetate aluminum diisopropylate (for example, "Plenact AL-M" manufactured by Ajinomoto Fine-Techno Co., Ltd.).

Specific examples of titanate-based coupling agents include Plenact TTS, Plenact 46B, Plenact 55, Plenact 41B, Plenact 38S, Plenact 138S, Plenact 238S, Plenact 338X, Plenact 44, and Plenact 9SA (all manufactured by Ajinomoto Fine-Techno). Can be mentioned.

The amount of the coupling agent is preferably 0% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass, based on 100% by mass of the non-volatile component of the encapsulant.

The amount of the coupling agent is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, particularly preferably 1 part by mass or more, and preferably 20 parts by mass with respect to 100 parts by mass of the inorganic filler. Hereinafter, it is more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less.

Among the components that can be contained in the encapsulant, examples of the components suitable for the thermosetting encapsulant are organic fillers such as rubber particles, silicone powder, nylon powder, and fluororesin powder; and thickening such as Orben and Benton. Agents: Silicone-based, fluoro-based, polymer-based defoaming agents or leveling agents; adhesion-imparting agents such as triazole compounds, thiazole compounds, triazine compounds, and porphyrin compounds; and the like. Further, the thermosetting type encapsulant may contain the above-mentioned components as the components that the adhesive type encapsulant can contain.

[8. Transparency of Encapsulant According to First Embodiment]
The encapsulant according to the first embodiment of the present invention preferably has high transparency. The transparency of the sealant can be expressed by the parallel line transmittance with respect to D65 light. Specifically, the parallel line transmittance of the 20 μm-thick sealant layer is preferably 80% to 100%, more preferably 85% to 100%. The parallel line transmittance of the sealant is calculated by forming a laminate in which the sealant is laminated on a glass plate and using air as a reference. Specifically, the parallel line transmittance can be measured by the following method.

Prepare a sealing sheet with a layer of sealing agent with a thickness of 20 μm. This sealing sheet is cut into a length of 70 mm and a width of 25 mm, and the sealing sheet is a glass plate (microslide glass having a length of 76 mm, a width of 26 mm and a thickness of 1.2 mm, a white slide glass manufactured by Matsunami Glass Industry Co., Ltd.). A laminated body is obtained by laminating S1112 edge polishing No. 2) with a batch type vacuum laminator (manufactured by Nichigo Morton, V-160). Laminating conditions are a temperature of 80 ° C., a depressurization time of 30 seconds, and then a pressure of 0.3 MPa for 30 seconds. In the case of a thermosetting sealant, this laminate is heated in a thermodynamic oven at 100 ° C. for 60 minutes to obtain a sample. Using a haze meter HZ-V3 (halogen lamp) manufactured by Suga Test Instruments Co., Ltd., measure the parallel line transmittance (%) of the sample with D65 light using air as a reference.

[9. Encapsulant according to the second embodiment]
The encapsulant according to the second embodiment of the present invention contains an inorganic filler containing at least one selected from the group consisting of semi-baked hydrotalcite, calcined hydrotalcite and calcium oxide, and a binder resin. Since semi-fired hydrotalcite, fired hydrotalcite and calcium oxide can exhibit excellent lead adsorption and hygroscopicity in the sealant, the sealant can be used to seal an electronic device having a lead-containing portion. When used in an application, it is possible to suppress the infiltration of water into the lead-containing portion and to suppress the leakage of lead from the lead-containing portion to the outside of the electronic device.

The encapsulant according to the second embodiment of the present invention may or may not have the lead adsorption parameter and the water vapor infiltration barrier parameter in the above range. In addition, the encapsulant according to the second embodiment of the present invention contains one or more kinds of inorganic fillers selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide. Except for the above items, the encapsulant according to the second embodiment of the present invention may have the same composition and physical properties as the encapsulant according to the first embodiment. You can get the same benefits.

[10. Manufacturing method of sealant]
The method for producing the sealant is not particularly limited. The sealant can be produced by a method of mixing the compounding components using a mixing device such as a kneading roller and a rotary mixer. Further, at the time of the above mixing, the solvent may be mixed in combination with the compounding ingredients.

[11. Use of sealant]
When used for sealing purposes, the sealing agent can suppress the infiltration of water and the leakage of lead. Therefore, it is preferable to use it for sealing an electronic device including a lead-containing portion. There are no restrictions on the types of such electronic devices. Examples of the electronic device include a solar cell such as a perovskite type solar cell; a secondary battery such as a lead storage battery; and an electronic component containing lead solder.

[12. Sealing sheet]
(12.1. Composition of sealing sheet)
A sealing sheet according to an embodiment of the present invention includes a support and a layer of the sealing agent formed on the support. Since the sealant layer is a layer formed of the sealant, it contains the above-mentioned sealant. By laminating such a sealing sheet so that the layer of the sealing agent is in contact with the sealing target, the sealing of the sealing target by the sealing agent can be achieved. Laminating is usually performed so that the object to be sealed and the layer of the sealant are in direct contact with each other. When two members are in "direct" contact, it means that there is no other member between them.

The thickness of the sealant layer can be set according to the object to be sealed. The specific thickness of the sealant layer is usually in the range of 3 μm to 200 μm, preferably 5 μm to 175 μm, and more preferably 5 μm to 150 μm. When the thickness of the sealant layer is equal to or greater than the lower limit of the above range, damage to the sealing target due to lamination with the sealing sheet can be suppressed, or sealing obtained as a sealant layer after lamination can be suppressed. The uniformity of the thickness of the part can be increased. Further, when the thickness of the sealant layer is not more than the upper limit of the above range, the infiltration of water into the electronic device can be effectively suppressed. For example, in a perovskite type solar cell provided with a first base material and a second base material, the thinner the sealing portion as the sealing agent layer, the smaller the area of the side portion where the outside air and the sealing portion are in contact with each other. The infiltration of water can be effectively suppressed (see FIG. 4 described later).

As the support, a film formed of an appropriate material is usually used. Examples of the support include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, cycloolefin polymers, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate and polyimide. Plastic film; metal foil such as aluminum foil, stainless foil, copper foil; and the like. Further, a composite film obtained by laminating a metal foil and a plastic film may be used as a support.

The support may be provided with a barrier layer from the viewpoint of enhancing moisture permeability. In particular, when the support includes a plastic film, it is preferable to use a support having an appropriate barrier layer in combination with the plastic film. Examples of the material of the barrier layer include inorganic substances. Examples of such an inorganic substance include nitrides such as silicon nitride and SiCN; oxides such as silicon oxide and aluminum oxide; amorphous silicon; stainless steel and metal of aluminum; and the like. The barrier layer can be formed, for example, by depositing the above-mentioned material.

The support may be surface-treated. Examples of the surface treatment include a matte treatment, a corona treatment, and a mold release treatment. Examples of the mold release treatment include a mold release treatment using a mold release agent such as a silicone resin-based mold release agent, an alkyd resin-based mold release agent, and a fluororesin-based mold release agent.

Specific examples of the support include "PET Tsuki AL1N30" manufactured by Tokai Toyo Aluminum Sales Co., Ltd., "PET Tsuki AL3025" manufactured by Fukuda Metal Co., Ltd., and "Alpet" manufactured by Panac Co., Ltd. as commercially available polyethylene terephthalate films with aluminum foil. Can be mentioned. As another specific example of the support, Tech Barrier HX, AX, LX, L series (manufactured by Mitsubishi Plastics); X-BARRIER (manufactured by Mitsubishi Plastics), which has a higher moisture-proof effect than the Tech Barrier HX, AX, LX, L series. Mitsubishi Plastics); etc.

The thickness of the support is not particularly limited, but from the viewpoint of handleability and the like, it is preferably 10 μm or more, more preferably 20 μm or more, preferably 200 μm or less, more preferably 150 μm or less, still more preferably 125 μm or less, in particular. It is preferably 100 μm or less.

The sealing sheet may be provided with a protective film, if necessary. For example, the sealing sheet may be provided with a support, a layer of a sealing agent, and a protective film in this order, so that the layer of the sealing agent may be protected by the protective film. By protecting with a protective film, it is possible to prevent dust from adhering to and scratching the surface of the sealant layer.

As the protective film, for example, a plastic film similar to the support can be used. The protective film may be surface-treated like the support. The thickness of the protective film is not particularly limited and may be usually 1 μm or more, preferably 10 μm or more, usually 150 μm or less, preferably 100 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less.

(12.2. Manufacturing method of sealing sheet)
The sealing sheet can be manufactured by a manufacturing method comprising forming a layer of a sealing agent on a support. The sealant layer is formed by, for example, preparing a varnish containing a sealant and a solvent, applying the varnish onto a support, and drying the applied varnish. Can be done.

As the solvent, an organic solvent is usually used. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone (hereinafter, also abbreviated as “MEK”) and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate. Carbitol solvents such as cellosolve and butylcarbitol; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; aromatic mixed solvents such as solventnaphtha; Be done. Examples of the aromatic mixed solvent include "Swazole" (manufactured by Maruzen Petroleum Co., Ltd., trade name) and "Ipsol" (manufactured by Idemitsu Kosan Co., Ltd., trade name). As the solvent, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

For drying the varnish, for example, a heating method, a hot air blowing method, or the like can be used. The drying conditions are not particularly limited, and the temperature can be, for example, 50 ° C. to 100 ° C. The drying time is preferably 1 minute or more, more preferably 3 minutes or more, preferably 60 minutes or less, and more preferably 15 minutes or less. After applying the varnish on the support, the applied varnish is dried to remove the solvent and obtain a layer of the sealant on the support.

The method for producing the sealing sheet may include heating the layer of the sealing agent, if necessary. Since the reaction of the reactive groups contained in the encapsulant can be allowed to proceed by heating, the hardness of the encapsulant layer can be increased by advancing the reaction such as the crosslinking reaction and the polymerization reaction to an appropriate degree. it can. This heating is suitable when an adhesive type sealant is used. In particular, when a pressure-sensitive adhesive containing a polyolefin resin having a reactive group such as an acid anhydride group and an epoxy group is used, it is preferable to carry out the above heating. By such heating before sealing, it is possible to avoid thermal deterioration of the components contained in the sealing target. The heating conditions are not particularly limited. The heating temperature is preferably 50 ° C. to 200 ° C., more preferably 100 ° C. to 180 ° C., and even more preferably 120 ° C. to 160 ° C. The heating time is preferably 15 minutes to 120 minutes, more preferably 30 minutes to 100 minutes.

The method for manufacturing the sealing sheet may include providing a protective film, if necessary. The protective film can be provided, for example, by laminating the protective film and the layer of the sealant. When heating the encapsulant layer, the protective film may be provided before heating the encapsulant layer or after heating the encapsulant layer.

(12.3. How to use the sealing sheet)
The sealing sheet can be used for sealing a lead-containing part, an electrode, or the like to be sealed. The sealing method using a sealing sheet usually involves laminating a layer of a sealing agent on the sealing sheet on the sealing target. When the sealing sheet includes a protective film, the above-mentioned lamination is usually performed after the protective film is peeled off. The laminating method may be a batch method or a continuous method using a roll.

Normally, according to the above-mentioned laminate, a layer of a sealant and a support are provided in this order on the object to be sealed. Therefore, the object to be sealed after lamination can be covered with a layer of a sealing agent and a support. In the sealing method using a sealing sheet, a state in which the sealing target is covered with a layer of a sealing agent and a support may be obtained without peeling the support. In this state, the object to be sealed is sealed not only by the layer of the sealing agent but also by the support, so that the infiltration of water can be effectively suppressed. For example, when a sealing sheet having a highly moisture-permeable support such as a support having a barrier layer or a support having a metal foil is used, sealing with a layer of a sealing agent and the support as described above is used. It is preferable to stop.

In the sealing method using a sealing sheet, for example, the support may be peeled off after the above-mentioned lamination to obtain a state in which the sealing target is covered with a layer of a sealing agent. Even in this state, the infiltration of water can be effectively suppressed by the layer of the sealing agent that seals the object to be sealed. For example, when a sealing sheet having a support that does not have high moisture permeability, such as a support that does not have a barrier layer and a support that does not have a metal foil, is used, the sealant layer is used as described above. It is preferable to perform sealing with.

The sealing method using the sealing sheet may include, for example, further providing a sealing base material. In particular, when the support is peeled off as described above, it is preferable to provide an appropriate sealing base material on the surface of the sealant layer exposed by the peeling of the support. As such a sealing base material, for example, the same film as the above-mentioned support may be used, or a rigid plate material such as a glass plate, a metal plate, or a steel plate may be used. By providing the sealing base material, the infiltration of water can be suppressed more effectively.

The sealing method using the sealing sheet may include, for example, curing the sealing agent layer after laminating. Usually, by applying heat to the sealant layer, reactions such as a cross-linking reaction and a polymerization reaction of reactive groups contained in the sealant are allowed to proceed, and the sealant layer is thermoset. As a result, the adhesion between the sealing target and the sealing agent can be improved, and the mechanical strength of the sealing agent layer can be improved, so that the sealing ability of the sealing agent can be enhanced. Therefore, the infiltration of water and the leakage of lead can be suppressed particularly effectively. Such thermosetting after lamination is suitable when a thermosetting type sealant is used.

During the above-mentioned thermosetting, the sealant layer is usually heated by an appropriate heat treatment device. Examples of the heat treatment apparatus include a hot air circulation type oven, an infrared heater, a heat gun, and a high frequency induction heating apparatus. Alternatively, the sealant layer may be heated, for example, by pressure-bonding the heat tool to the sealant layer. From the viewpoint of enhancing the adhesion between the object to be sealed and the layer of the sealant, the curing temperature is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and particularly preferably 60 ° C. or higher. Further, from the viewpoint of suppressing thermal deterioration of the components contained in the sealing target, the curing temperature is preferably 150 ° C. or lower, more preferably 100 ° C. or lower, and even more preferably 80 ° C. or lower. The curing time is preferably 10 minutes or more, more preferably 20 minutes or more.

With any of the above-mentioned sealing methods, sealing with a layer of a sealing agent is achieved. Therefore, when the target to be sealed contains a lead-containing portion, not only the infiltration of water into the lead-containing portion but also the leakage of lead from the lead-containing portion can be suppressed.

[13. Electronic device]
An electronic device according to an embodiment of the present invention includes a lead-containing portion and a sealing portion for sealing the lead-containing portion. The sealing portion contains the above-mentioned sealing agent. At this time, the sealing agent contained in the sealing portion may be cured. The sealing portion containing the sealing agent cured in this way is included in the "sealing portion containing the sealing agent". In such an electronic device, the infiltration of water into the lead-containing portion can be suppressed by the sealing portion. Further, the leakage of lead from the lead-containing portion to the outside of the electronic device can be suppressed by the sealing portion.

The lead-containing part is a part containing a lead atom, and can include a wide range of parts depending on the type of electronic device. Hereinafter, the electronic device will be specifically described by taking as an example a perovskite type solar cell including a perovskite layer as the lead-containing portion.

FIG. 4 is a cross-sectional view schematically showing an example of a perovskite type solar cell 400 according to an embodiment of the present invention. As shown in FIG. 4, the perovskite type solar cell 400 as an example includes a first electrode 410, a perovskite layer 420 containing a lead atom, a second electrode 430, and a seal containing a sealant which may be cured. A stop portion 440 is provided. In this solar cell 400, a perovskite layer 420 is provided between the first electrode 410 and the second electrode 430 so that the electric charge generated in the perovskite layer 420 as the photoelectric conversion layer can be taken out through the first electrode 410 and the second electrode 430. It is provided.

The first electrode 410 and the second electrode 430 are made of a conductive material. The type of the conductive material is not limited, but it is preferable that one or both of the first electrode 410 and the second electrode 430 are formed of a transparent conductive material. Examples of such materials include conductive oxides such as ITO (indium tin oxide), SnO ₂ , AZO (aluminum zinc oxide), IZO (indium zinc oxide), and GZO (gallium zinc oxide). Conductive polymer; and the like.

The perovskite layer 420 contains a perovskite compound, and the perovskite layer 420 can be irradiated with light to generate an electric charge. Examples of the perovskite compound include a compound represented by the following formula (P).
A ^P _k M ^P ^XP _{(k + 2)} (P)

In formula (P), k represents an integer of 1 or 2.

In formula (P), ^Ap represents a monovalent organic molecule or an ion thereof. The monovalent organic molecule is not particularly limited, but for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, dimethylamine, dipropylamine dibutylamine, dipentylamine, dihexylamine, etc. Trimethylamine, triethylamine, tripropylamine, tributylamine, trypentylamine, trihexylamine, ethylmethylamine, methylpropylamine, butylmethylamine, methylpentylamine, hexylmethylamine, ethylpropylamine, ethylbutylamine, imidazole, azole, Examples thereof include pyrrole, aziridine, azirin, azetidine, azeto, azole, imidazoline, carbazole and the like. Examples of monovalent organic molecule ions include methylammonium (CH ₃ NH ₃ ), phenethylammonium and the like. Of these, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and their ions, and phenethylammine are preferable, and methylamine, ethylamine, propylamine and these ions are more preferable.

In formula (P), M ^p represents a divalent metal atom. M ^p preferably includes lead as divalent metal atom. Further, M ^p may comprise a metal atom other than lead in combination with lead. Examples of metal atoms other than lead include tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, and europium. Can be mentioned. One type of these metal atoms may be used alone, or two or more types may be used in combination.

In formula (P), X ^p represents a halogen atom or a chalcogen atom. The halogen atom is not particularly limited, and examples thereof include chlorine, bromine, iodine, and sulfur. The chalcogen atom is not particularly limited, but selenium can be mentioned. One of these may be used alone, or two or more of them may be used in combination.

Specific examples of the perovskite compound include the perovskite compounds described in International Publication No. 2014/045021, Japanese Patent Application Laid-Open No. 2014-49596, Japanese Patent Application Laid-Open No. 2016-82003, and the like.

Among the above-mentioned compounds, as the perovskite compound, a compound containing a lead atom such as _{CH 3} NH ₃ PbI _{3 is preferable.} One type of perovskite compound may be used alone, or two or more types may be used in combination at any ratio. Further, the perovskite layer 420 may contain an arbitrary component such as an oxide semiconductor in combination with the perovskite compound.

The sealing portion 440 is provided so as to seal the perovskite layer 420. Therefore, part or all of the surface of the perovskite layer 420 is covered with the sealing portion 440, and the surface of the perovskite layer 420 is not exposed. In the example shown in FIG. 4, a portion of the surface of the perovskite layer 420 that is not in contact with the first electrode 410 or the second electrode 430 is covered with the sealing portion 440. In such a perovskite layer, the space between the outside air and the perovskite layer 420 is sealed by a sealing portion 440. Therefore, it is possible to suppress the infiltration of moisture in the outside air into the perovskite layer 420. Further, it is possible to prevent lead contained in the perovskite layer 420 from leaking to the outside of the solar cell 400. Normally, not only the perovskite layer 420 but also the first electrode 410 and the second electrode 430 are sealed by the sealing portion 440 to achieve protection from water.

It is preferable that the solar cell 400 further includes a first base material 450 and a second base material 460. Usually, one of the first base material 450 and the second base material 460 is used as a supporting base material for supporting the solar cell 400 or its manufacturing intermediate during manufacturing and use. The other of the first base material 450 and the second base material 460 is usually used as a sealing base material for sealing the main surface of the solar cell 400 in a wide range. The first electrode 410, the perovskite layer 420 and the second electrode 430 are generally provided in the space between the first base material 450 and the second base material 460. Therefore, as shown in FIG. 4, since the sealing portion 440 can be provided so as to fill the space between the first base material 450 and the second base material 460, the first base material 450 and the second base material 450 and the second base material Members such as the first electrode 410, the perovskite layer 420, and the second electrode 430 provided between the 460s can all be sealed by the sealing portion 440.

In general, the first base material 450 and the second base material 460 are made of a material that does not easily allow water to permeate or have a large thickness, so that the infiltration of water can be highly suppressed. Therefore, in the solar cell 400 according to the above example, the infiltration route of water into the perovskite layer 420 can be limited to the in-plane infiltration route A4 passing through the side portion 440S of the sealing portion 440. The above-mentioned sealant can particularly effectively suppress the infiltration of water in such an infiltration route A4. Therefore, when used for sealing the perovskite layer 420 provided between the first base material 450 and the second base material 460, the above-mentioned sealing agent is said to suppress the infiltration of water and the leakage of lead. It is possible to exert the effect particularly remarkably.

The perovskite type solar cell 400 may be further modified and implemented. For example, the perovskite type solar cell 400 may include an arbitrary layer between the first electrode 410 and the perovskite layer 420. Further, for example, the perovskite type solar cell 400 may include an arbitrary layer between the perovskite layer 420 and the second electrode 430. Examples of the optional layer include an electron transport layer and a hole transport layer.

There are no restrictions on the manufacturing method of electronic devices. For example, it can be produced by a method including forming a lead-containing layer and forming a sealing portion for sealing the lead-containing layer. The sealing portion can be formed as a layer of a sealing agent that covers the lead-containing portion, for example, by laminating a layer of a sealing agent using a sealing sheet. To give a specific example, after forming the first electrode 410, the perovskite layer 420 and the second electrode 430 on the first base material 450, a part of the first electrode 410, the perovskite layer 420 and the second electrode 430, or A perovskite-type solar cell 400 having a sealing portion 440 as a sealing agent layer can be manufactured by a method including laminating a sealing agent layer of a sealing sheet (not shown) so as to cover the whole. .. At this time, the support of the sealing sheet may be used as the second base material 460. Further, after the support of the sealing sheet is peeled off, another second base material 460 may be provided on the sealing portion 440.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples. In the following description, "parts" and "%" indicating quantities represent "parts by mass" and "% by mass" unless otherwise specified.

[Evaluation method]
[Evaluation method of lead adsorption capacity of sealant]
To 500 mL of water, 10 μL of a lead standard solution was added and purified to prepare a lead ion-containing aqueous solution having a lead ion concentration of 20 μg / L at a water temperature of 20 ° C. to 25 ° C.

The sealing sheets produced in Examples and Comparative Examples were cut into a length of 16 cm and a width of 24 cm to obtain a first test sheet. A mesh cloth (bolting cloth (nylon) mesh 40 NB-40, manufactured by AS ONE Corporation) is attached to the layer side of the sealant of this first test sheet, and then finely chopped into 1 cm squares to form a lead ion-containing aqueous solution. The mixture was placed in 50 ml and stirred with a high-speed rotary mixer (Kentaro ARE-310, rotation speed 2000 rpm) for 15 minutes (lead adsorption capacity evaluation test). At this time, in Examples 5 to 6 and Comparative Example 4 relating to the thermosetting type sealant, after the sealant was heat-cured under the condition of 100 ° C. for 60 minutes after the mesh cloth was attached, it was used for the first test. I chopped the sheet into small pieces. The lead ion concentration M1 of the lead ion-containing aqueous solution after stirring was measured.

The lead ion concentration of the lead ion-containing aqueous solution before immersing the first test sheet is 20 μg / L, minus the lead ion concentration M1 of the lead ion-containing aqueous solution after immersing the first test sheet. The amount of change was obtained. The amount of lead adsorption was calculated by multiplying this amount of change by the volume of the lead ion-containing aqueous solution of 50 mL. The calculated lead adsorption amount is divided by the area of the sealant layer of the first test sheet used, which is 384 cm ² ^{, and the mass of lead adsorbed per 1 m 2 of} the sealant layer X (μg / m). ² ) was calculated. The mass X of the adsorbed lead corresponds to the lead adsorbability parameter. Based on the mass X of adsorbed lead, the lead adsorption capacity of the encapsulant was evaluated according to the following criteria.

(Standard of lead adsorption capacity)
"Good": The mass X of adsorbed lead is 10 μg / m ² or more.
"Defective": The mass X of adsorbed lead is less than ^{10 μg / m 2.}

The lead ion concentration of the lead ion-containing aqueous solution was measured by the following method.
5 ml of a lead ion-containing aqueous solution was placed in a test tube in a lead sensor pack (manufactured by HACH), and a reagent tablet (a reagent for measurement attached to the lead sensor pack) was dissolved. Then, the test electrode was immersed in a lead ion-containing aqueous solution, and the lead ion concentration was measured using a portable scanning lead measuring device (model name HSA-1000, manufactured by HACH).

[Evaluation method of water vapor infiltration barrier property of sealant]
As a support film, a composite film "PET Tsuki AL1N30" (aluminum foil thickness 30 μm, polyethylene terephthalate film thickness 25 μm, manufactured by Tokai Toyo Aluminum Sales Co., Ltd.) including an aluminum foil and a polyethylene terephthalate film was prepared. A layer of a sealant was formed on the aluminum foil side surface of the support film in the same manner as in the manufacturing method of the sealing sheet in each Example and Comparative Example except that this support film was used instead of the support. did. As a result, a second test sheet provided with a support film and a layer of a sealant was obtained. The obtained second test sheet was dried in a nitrogen atmosphere in order to remove the adsorbed water contained in the sealant layer. Drying was carried out at 130 ° C. for 60 minutes in Examples 1 to 4 and Comparative Examples 1 to 3 using the adhesive type sealant. Further, the drying was carried out at 100 ° C. for 5 minutes in Examples 5 to 6 and Comparative Example 4 using the thermosetting type sealant.

A 50 mm x 50 mm square glass plate made of non-alkali glass was prepared. The glass plate was washed with boiling isopropyl alcohol for 5 minutes and dried at 150 ° C. for 30 minutes or more.

Calcium was vapor-deposited on one side of this glass plate using a mask covering the peripheral area at a distance of 0 mm to 2 mm from the end of the glass plate. As a result, a calcium film (purity 99.8%) having a thickness of 200 nm was formed on one side of the glass plate in the central portion excluding the peripheral area having a distance of 0 mm to 2 mm from the edge of the glass plate.

In a nitrogen atmosphere, the sealant layer of the second test sheet described above and the surface of the glass plate on the calcium film side are bonded together using a thermal laminator (Lamipacker DAiSY A4 (LPD2325) manufactured by Fujipla Co., Ltd.). To obtain a laminate. In Examples 1 to 4 and Comparative Examples 1 to 3 relating to the pressure-sensitive adhesive, the obtained laminate was obtained as an evaluation sample. Further, in Examples 5 to 6 and Comparative Example 4 relating to the thermosetting type sealant, the obtained laminate was heated at a temperature of 100 ° C. for 60 minutes to cure the sealant layer, and an evaluation sample was prepared. Obtained.

Generally, when calcium comes into contact with water and becomes calcium oxide, it becomes transparent. Further, in the above evaluation sample, since the glass plate and the aluminum foil have a sufficiently high water vapor infiltration barrier property, the moisture usually passes through the end portion of the sealant layer and is perpendicular to the in-plane direction (vertical to the thickness direction). Can move in the direction) to reach the calcium membrane. Therefore, when water penetrates into the evaluation sample, the calcium film is gradually oxidized from the end and becomes transparent, so that shrinkage of the calcium film is observed. Therefore, the intrusion of water into the evaluation sample can be evaluated by measuring the sealing distance [mm] from the end of the evaluation sample to the calcium film. Therefore, the evaluation sample containing the calcium film can be used as a model of the electronic device containing lead.

First, the sealing distance X2 [mm] from the end of the evaluation sample to the end of the calcium film was measured with a microscope (Measuring Microscope MF-U, manufactured by Mitutoyo). Hereinafter, this sealing distance X2 may be referred to as an initial sealing distance X2.

Next, the evaluation sample was stored in a constant temperature and humidity chamber set to a temperature of 85 ° C. and a humidity of 85% RH. When the sealing distance X1 (mm) from the end of the evaluation sample stored in the constant temperature and humidity chamber to the end of the calcium film increases by 0.1 mm from the initial sealing distance X2, the evaluation sample is prepared. It was taken out from a constant temperature and humidity chamber. The time from the time when the evaluation sample was stored in the constant temperature and humidity chamber to the time when the evaluation sample was taken out from the constant temperature and humidity chamber was determined as the decrease start time t [hour]. This decrease start time t is _{the sealing distance X1 [from the time point T P1} when the evaluation sample is stored in the constant temperature and humidity chamber to the end of the evaluation sample stored in the constant temperature and humidity chamber and the end of the calcium film. mm] corresponds to the time until the time _{point T P2} when it becomes “X2 + 0.1 mm”.

The sealing distance X1 and the reduction start time t were applied to the diffusion equation of Fick in the equation (1) to calculate the constant K as the water vapor infiltration barrier parameter.

Using the obtained constant K, the water vapor infiltration barrier property as the ability of the encapsulant to suppress the infiltration of water was evaluated according to the following criteria. The smaller the value of the constant K, the higher the water vapor infiltration barrier property. "H" means "time".

(Standard for water vapor infiltration barrier)
"Good": The constant K is less than ^{0.025 cm / h 0.5.}
"Defective": The constant K is 0.025 cm / h ^0.5 or more.

[Synthesis Example 1: Synthesis of ionic liquid curing agent]
The N-acetylglycine tetrabutylphosphonium salt, which is an ionic liquid curing agent, was synthesized by the following procedure.
To 20.0 g of a 41.4% tetrabutylphosphonium hydroxide aqueous solution (manufactured by Hokuko Chemical Industry Co., Ltd.), 3.54 g of N-acetylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at 0 ° C. and stirred for 10 minutes. did. After stirring, the reaction solution was concentrated using an evaporator at a pressure of 40 mmHg to 50 mmHg at 60 ° C. to 80 ° C. for 2 hours and 90 ° C. for 5 hours. The obtained concentrate was dissolved in 14.2 ml of ethyl acetate (manufactured by Junsei Chemical Co., Ltd.) at room temperature to prepare a solution. The obtained solution was concentrated using an evaporator at a pressure of 40 mmHg to 50 mmHg at 70 ° C. to 90 ° C. for 3 hours to obtain 11.7 g (purity: 96.9%) of N-acetylglycine tetrabutylphosphonium salt. Obtained as an oily compound.

[I. Examples and Comparative Examples of Adhesive Sealants]
[Example 1]
(Manufacturing of varnish)
After preparing 77.5 parts of a swazole solution (60% non-volatile component) of a dicyclopentadiene petroleum resin (T-REZ HA105, manufactured by JXTG Energy Co., Ltd., softening point 105 ° C.) as a tackifier. , 2.3 parts of an antioxidant (manufactured by Irganox 1010 BASF) was added and dissolved. In this solution, 21 parts of maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Toho Chemical Industry Co., Ltd., acid anhydride group concentration: 0.77 mmol / g, number average molecular weight: 2,100), polybutene (HV-1900, JX Energy Co., Ltd., number average molecular weight: 2,900) 94 parts, and commercially available semi-firing hydrotalcite A (semi-firing hydrotalcite, BET specific surface area: 13 m ² / g, average particle size: as an inorganic filler: 100 parts (400 nm) were dispersed with a three-roll mill to obtain a mixture.

In the obtained mixture, a glycidyl methacrylate-modified propylene-butene random copolymer (T-YP341, manufactured by Starlight PMC), propylene unit / butene unit: 71% / 29%, epoxy group concentration: 0.638 mmol / g, number average. 20 parts of a swazole solution (20% non-volatile component) having a molecular weight of 155,000), an amine compound (2,4,6-tris (diaminomethyl) phenol, hereinafter abbreviated as "TAP". 0.1 part and 210 parts of toluene were blended and uniformly dispersed with a high-speed rotary mixer to obtain a varnish containing a sealant.

(Manufacturing of sealing sheet)
As a support, a polyethylene terephthalate film (PET thickness 50 μm; SP3000, manufactured by Toyo Cloth Co., Ltd.) having a surface treated with a silicone-based mold release agent (release treated surface) was prepared. The varnish is uniformly applied on the mold release surface of the support with a die coater and heated at 140 ° C. for 30 minutes to obtain a sealing sheet having a layer of a sealing agent having a thickness of 20 μm. It was.

[Example 2]
The type of inorganic filler was changed from semi-calcined hydrotalcite A to commercially available calcined hydrotalcite C (calcined hydrotalcite, BET specific surface area: 190 m ² / g, average particle size: 400 nm). Except for the above items, a varnish containing a sealant and a sealing sheet provided with a layer of the sealant having a thickness of 20 μm were produced by the same method as in Example 1.

[Example 3]
The type of inorganic filler was changed from semi-calcined hydrotalcite A to commercially available calcium oxide (BET specific surface area: 5 m ² / g, average particle size: 4000 nm). Except for the above items, a varnish containing a sealant and a sealing sheet provided with a layer of the sealant having a thickness of 20 μm were produced by the same method as in Example 1.

[Example 4]
The type of inorganic filler was changed from semi-calcined hydrotalcite A to nanozeolite (Zeoal 4A, manufactured by Nakamura Choukousha, average particle size 300 nm, pore diameter 4 Å). Except for the above items, a varnish containing a sealant and a sealing sheet provided with a layer of the sealant having a thickness of 20 μm were produced by the same method as in Example 1.

[Comparative Example 1]
Semi-baked hydrotalcite A as an inorganic filler was not used. Except for the above items, a varnish containing a sealant and a sealing sheet provided with a layer of the sealant having a thickness of 20 μm were produced by the same method as in Example 1.

[Comparative Example 2]
The type of inorganic filler was changed from semi-fired hydrotalcite A to commercially available unfired hydrotalcite D (BET specific surface area: 10 m ² / g, average particle size: 400 nm). Except for the above items, a varnish containing a sealant and a sealing sheet provided with a layer of the sealant having a thickness of 20 μm were produced by the same method as in Example 1.

[Comparative Example 3]
The type of inorganic filler was changed from semi-baked hydrotalcite A to synthetic mica (PDM-5B, manufactured by Topy Industries, Ltd., average particle size: 6.0 μm). Except for the above items, a varnish containing a sealant and a sealing sheet provided with a layer of the sealant having a thickness of 20 μm were produced by the same method as in Example 1.

[Evaluation]
Using the varnish and the sealing sheet obtained in each Example and Comparative Example, the lead adsorption capacity and the water vapor infiltration barrier property of the sealing agent were evaluated by the above-mentioned evaluation method. The evaluation results are shown in Table 1 below.

[II. Examples and Comparative Examples of Thermosetting Encapsulants]
[Example 5]
(Manufacturing of varnish)
162 parts of a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin ("ZX1059" manufactured by Nittetsu Chemical & Materials Co., Ltd.) and commercially available semi-fired hydrotalcite A (semi-fired hydrotalcite," as an inorganic filler. After kneading 150 parts of BET specific surface area: 13 m ² / g, average particle size: 400 nm) and 7.5 parts of a silane coupling agent (“KMB403” manufactured by Shin-Etsu Chemical Industry Co., Ltd., 3-glycidyloxypropyltriethoxysilane). The mixture was dispersed with a 3-roll mill to obtain a mixture.

Dissolve 7.5 parts of the curing accelerator ("U-CAT3512T" manufactured by San-Apro) in 163 parts (57 parts of resin) of a phenoxy resin solution ("YX7200B35" manufactured by Mitsubishi Chemical Co., Ltd., solvent: methyl ethyl ketone, non-volatile component: 35%). 108 parts of an alicyclic skeleton-containing epoxy resin (“TOPR-300” manufactured by Nittetsu Chemical & Materials Co., Ltd.), the mixture prepared above, and the ionic liquid curing agent (N-) synthesized in Synthesis Example 1 were added to the prepared solution. A varnish containing 9 parts of acetylglycine tetrabutylphosphonium salt) was mixed and uniformly dispersed with a high-speed rotary mixer to obtain a varnish containing a sealant.

(Manufacturing of sealing sheet)
As a support, a polyethylene terephthalate film (thickness 38 μm, hereinafter sometimes referred to as “release PET film”) having a surface (release treated surface) treated with an alkyd-based mold release agent was prepared. The above varnish is uniformly applied on the release-treated surface of the support with a die coater so that the thickness of the sealing agent layer after drying is 20 μm, and dried at 80 ° C. for 5 minutes. , Formed a layer of sealant. Then, a release PET film was placed on the surface of the sealant layer as a protective film, and a seal sheet having a support, a sealant layer and a release PET film in this order was obtained.

[Example 6]
The type of inorganic filler was changed from semi-calcined hydrotalcite A to commercially available calcium oxide (BET specific surface area: 5 m ² / g, average particle size: 4000 nm). Except for the above items, a varnish containing a sealant and a sealing sheet provided with a layer of the sealant having a thickness of 20 μm were produced by the same method as in Example 5.

[Comparative Example 4]
The type of inorganic filler was changed from semi-fired hydrotalcite A to commercially available unfired hydrotalcite D (BET specific surface area: 10 m ² / g, average particle size: 400 nm). Except for the above items, a varnish containing a sealant and a sealing sheet provided with a layer of the sealant having a thickness of 20 μm were produced by the same method as in Example 5.

[Evaluation]
Using the varnish and the sealing sheet obtained in each Example and Comparative Example, the lead adsorption capacity and the water vapor infiltration barrier property of the sealing agent were evaluated by the above-mentioned evaluation method.
However, in the method for evaluating the lead adsorption capacity, after cutting the sealing film, the release PET film as a protective film was peeled off to obtain a first test sheet. Therefore, the method for evaluating the lead adsorption capacity was carried out using a first test sheet provided with a layer of a sealant having one surface exposed.
Further, in the method for evaluating the water vapor infiltration barrier property, the release PET film as a protective film was peeled off from the second test sheet, and then the second test sheet was dried.
The evaluation results are shown in Table 2 below.

[III. Measurement of water vapor permeability by water vapor permeability test method (WVTR measurement method)]
[Reference Example 1: Evaluation of the sealing sheet of Example 1]
A batch of the sealant layer of the sealing sheet produced in Example 1 and a reference film (polyethylene terephthalate film "Lumirror 38 R80", thickness 35 μm, manufactured by Toray Industries, Inc.) whose water vapor transmittance P2 is known. Laminated using a type vacuum laminator (V-160, manufactured by Nichigo Morton). The laminating conditions were a temperature of 80 ° C., a depressurization time of 30 seconds, and then a pressure of 0.3 MPa for 30 seconds. Then, the support was peeled off to obtain a resin sheet provided with a layer of a sealing agent and a reference film.

The water vapor transmittance P0 of the obtained resin sheet was determined by an infrared sensor method according to JIS K7129B. Water vapor permeability (g ^{/ m} 2 · 24 hours), the water vapor transmission rate measurement device (MOCON (MOCON) Co., PERMATRAN-W 3/34) using a temperature of 40 ° C., a relative humidity of 90% Measured in.

The water vapor transmittance P0 of the resin sheet and the water vapor transmittance P2 of the reference film were applied to the following formula (2) to calculate the water vapor transmittance P1 of the sealant layer. Here, the water vapor transmission rate P2 of the reference film was set to 15g ^{/ m} 2 · 24 hours.
1 / P0 = 1 / P1 + 1 / P2 (2)

[Reference Example 2: Evaluation of the Sealing Sheet of Comparative Example 1]
The water vapor transmittance P1 of the sealant layer was measured in the same manner as in Reference Example 1 except that the sealing sheet produced in Comparative Example 1 was used instead of the sealing sheet produced in Example 1. ..

[Reference Example 3: Evaluation of the Sealing Sheet of Comparative Example 3]
The water vapor transmittance P1 of the sealant layer was measured in the same manner as in Reference Example 1 except that the sealing sheet produced in Comparative Example 3 was used instead of the sealing sheet produced in Example 1. ..

[result]
The results of Reference Examples 1 to 3 are shown in Table 3 below. Table 3 also shows the evaluation of the water vapor infiltration barrier property in Examples 1 and Comparative Examples 1 and 3 corresponding to Reference Examples 1 to 3.

In the WVTR measurement method adopted in Reference Examples 1 to 3, the transmittance of water vapor that permeates the sealant layer in the thickness direction is measured. As can be seen from the results of Reference Examples 1 to 3, Reference Example 1 is superior to Reference Example 2 in the ability to suppress the infiltration of water in the thickness direction, but Reference Example 3 is further superior. However, as can be seen from the results of the water vapor infiltration barrier properties of Example 1 and Comparative Examples 1 and 3, the ability to suppress the infiltration of water in the in-plane direction perpendicular to the thickness direction is the example corresponding to Reference Example 1. 1 is superior to Comparative Examples 1 and 3 corresponding to Reference Examples 2 and 3. Therefore, it can be seen that the ability of the sealant to suppress the infiltration of water may differ depending on the infiltration direction of the water vapor. Further, it can be seen that the encapsulant according to the examples exhibits a specifically high water vapor infiltration barrier property in the in-plane direction.

[IV. Evaluation of physical properties of hydrotalcite]
[Reference Examples 4 to 6]
(Measurement of water absorption rate of hydrotalcite)
1.5 g of each hydrotalcite used in the above-mentioned Examples and Comparative Examples was weighed with a balance, and the initial mass was measured. Each of the weighed hydrotalcites was allowed to stand in a small environmental tester (SH-222 manufactured by ESPEC) set at 60 ° C. and 90% RH (relative humidity) under atmospheric pressure for 200 hours to absorb moisture. The mass after moisture absorption was measured. From the measured mass, the saturated water absorption rate was calculated by the following formula (i).
Saturated water absorption rate [mass%] = 100 × (mass after moisture absorption-initial mass) / initial mass (i)

(Measurement of thermogravimetric reduction rate of hydrotalcite)
Using a thermal analyzer (TG / DTA EXSTAR6300, manufactured by Hitachi High-Tech Science Corporation), thermogravimetric analysis of each hydrotalcite used in the above-mentioned Examples and Comparative Examples was performed. 10 mg of hydrotalcite was weighed in an aluminum sample pan, and the temperature was raised from 30 ° C. to 550 ° C. at 10 ° C./min under an atmosphere of a nitrogen flow rate of 200 mL / min in an open state without a lid. The thermogravimetric reduction rate at 280 ° C and 380 ° C was determined using the following formula (ii).
Thermogravimetric reduction rate [mass%] = 100 × (mass before heating-mass when a predetermined temperature is reached) / mass before heating (ii)

(Measurement of powder X-ray diffraction of hydrotalcite)
The powder X-ray diffraction of each hydrotalcite used in the above-mentioned Examples and Comparative Examples was measured. Powder X-ray diffraction is measured by a powder X-ray diffractometer (Empylean, manufactured by PANalytical), anti-cathode CuKα (1.5405 Å), voltage: 45 V, current: 40 mA, sampling width: 0.0260 °, scanning speed: The measurement was performed under the conditions of 0.0657 ° / s and the measurement diffraction angle range (2θ): 5.0131 to 79.9711 °. The peak search uses the peak search function of the software attached to the diffractometer, and "minimum significance: 0.50, minimum peak tip: 0.01 °, maximum peak tip: 1.00 °, peak base width: 2". It was carried out under the condition of "0.00 °, method: minimum value of second derivative". Two split peaks in which 2θ appears in the range of 8 ° to 18 °, or a peak with a shoulder is detected by combining the two peaks, and the peak appearing on the low angle side or the diffraction intensity of the shoulder (= low angle) The side diffraction intensity) and the diffraction intensity of the peak or shoulder appearing on the high angle side (= high angle side diffraction intensity) were measured, and the relative intensity ratio (= low angle side diffraction intensity / high angle side diffraction intensity) was calculated.

(result)
The evaluation results of each hydrotalcite are shown in Table 4 below.

From the results of the saturated water absorption rate, the thermal weight reduction rate and the powder X-ray diffraction, hydrotalcite A is "semi-calcined hydrotalcite" and hydrotalcite C is "calcined hydrotalcite". Site D is "unfired hydrotalcite".

10 Evaluation sample 100 Glass plate 200 Calcium film 300 Second test sheet 310 Encapsulant layer 320 Support film 321 Aluminum foil 322 Polyethylene terephthalate film 400 Perovskite type solar cell 410 First electrode 420 Perovskite layer 430 Second electrode 440 Sealing Part 450 First base material 460 Second base material

Claims

A sealant for electronic devices that has a lead-containing part.
The encapsulant contains an inorganic filler and a resin.
The lead adsorption parameter of the sealant is 10 μg / m 2 or more.
The water vapor penetration barrier parameter of the sealant is less than 0.025 cm / h 0.5.
The lead adsorption parameter represents the mass of lead adsorbed per 1 m 2 of the sealant layer when the lead adsorption capacity evaluation test is performed.
In the lead adsorption capacity evaluation test, a first test sheet having a length of 16 cm and a width of 24 cm, comprising a polyethylene terephthalate film and a layer of the sealant having a thickness of 20 μm formed on the polyethylene terephthalate film is provided. To prepare; a nylon mesh cloth is attached to the layer side of the sealant of the first test sheet; the first test sheet to which the mesh cloth is attached is cut into 1 cm squares. The cut first test sheet is immersed in 50 ml of a lead ion-containing aqueous solution having a lead ion concentration of 20 μg / L adjusted to 20 ° C to 25 ° C, and stirred for 15 minutes.
The water vapor infiltration barrier property parameter represents a constant K obtained from the following formula (1) when the water vapor barrier property evaluation test is performed.
In the water vapor barrier property evaluation test, a second support film including an aluminum foil having a thickness of 30 μm and a polyethylene terephthalate film having a thickness of 25 μm, and a layer of the sealant formed on the aluminum foil of the support film are provided. Drying the test sheet; washing a 50 mm square glass plate made of non-alkali glass with boiling isopropyl alcohol for 5 minutes and drying; one side of the glass plate, the end of the glass plate. Calcium is vapor-deposited on a portion excluding an area having a distance of 0 mm to 2 mm to form a calcium film having a thickness of 200 nm; in a nitrogen atmosphere, the sealant layer of the second test sheet and the sealant layer. The surface of the glass plate on the calcium film side is bonded to obtain an evaluation sample; the distance X2 [mm] between the end of the evaluation sample and the end of the calcium film is measured; The evaluation sample is stored in a constant temperature and humidity chamber having a temperature of 85 ° C. and a humidity of 85% RH; from the time when the evaluation sample is stored in the constant temperature and humidity chamber, the evaluation sample stored in the constant temperature and humidity chamber is used. To measure the time t [time] until the distance X1 [mm] between the end and the end of the calcium film becomes "X2 + 0.1 mm"; and based on the following formula (1). Calculating the constant K, the encapsulant.
The sealant according to claim 1, wherein the second test sheet in the water vapor barrier evaluation test is dried under the conditions of 130 ° C. for 60 minutes and 100 ° C. for 5 minutes at least one of them.
The encapsulant according to claim 1 or 2, wherein the inorganic filler contains at least one selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite, calcium oxide, and zeolite.
A sealant for electronic devices that has a lead-containing part.
A sealant containing a resin and an inorganic filler containing at least one selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide.
The inorganic filler contains one or more selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide.
The sealant according to claim 3 or 4, wherein the resin contains a polyolefin-based resin.
The inorganic filler contains one or more selected from the group consisting of semi-calcined hydrotalcite and calcium oxide.
The sealant according to any one of claims 3 to 5, wherein the resin contains an epoxy resin.
The sealing agent according to any one of claims 1 to 6, wherein the amount of the inorganic filler is 5% by mass or more and 80% by mass or less with respect to 100% by mass of the non-volatile component of the sealing agent.
With the support
A sealing sheet comprising the layer of the sealing agent according to any one of claims 1 to 7, which is formed on the support.
A lead-containing portion and a sealing portion for sealing the lead-containing portion are provided.
An electronic device in which the sealing portion contains the sealing agent according to any one of claims 1 to 7.
A first electrode, a perovskite layer containing a lead atom, a second electrode, and a sealing portion for sealing the perovskite layer are provided.
A perovskite-type solar cell in which the sealing portion contains the sealing agent according to any one of claims 1 to 7.