DE112020005939T5 - PEROVSKITE TYPE SEALANT, SEALING FOIL, ELECTRONIC COMPONENT AND SOLAR CELL - Google Patents

Abstract

A sealant for an electronic component containing a lead-containing portion, the sealant comprising a resin and an inorganic filler containing one or more types selected from the group consisting of semi-calcined hydrotalcite and calcined hydrotalcite.

Description

field of invention

The present invention relates to sealants for electronic devices with lead-containing parts, and sealing sheets, electronic components and perovskite-type solar cells using the same.

background

One of the electronic devices that has attracted much attention in recent years is a perovskite-type solar cell. A perovskite-type solar cell generally includes electrodes and a photoelectric conversion layer containing a perovskite compound. In order to protect the electrodes and the photoelectric conversion layer from water, the perovskite solar cell is usually provided with a sealing part. On such a sealing part, various investigations have hitherto been made (Patent Literature 1).

quote list

patent literature

[Patent Literature 1] International Publication No. 2018/056312

Summary of the Invention

Technical problem

The photoelectric conversion layer in the perovskite type solar cell may contain lead. If moisture gets into this photoelectric conversion layer, the lead could flow out of the photoelectric conversion layer and leak out of the solar cell. Such lead leakage may also occur in electronic devices other than the perovskite type solar cell having a lead-containing part like the photoelectric conversion layer described above. It is desirable from both an environmental and safety standpoint to reduce lead leakage.

The present invention was developed with the above problems in mind, and aims to provide a sealant for use in electronic parts/devices, which suppresses moisture infiltration and lead leakage from a lead-containing part outside the electronic part can; a sealing sheet containing the sealant; and a perovskite-type electronic component and solar cell using the sealant for sealing.

the solution of the problem

The present inventors have intensively studied in order to solve the above problems. As a result, the inventors found that the above problems can be solved when an inorganic filler and a resin are used in an appropriate combination, and thus completed the present invention.

Thus, the present invention includes the following.

• einen anorganischen Füllstoff; und
• ein Harz, wobei
• das Dichtmittel einen Bleiadsorptionsparameter von 10 µg/m² oder mehr aufweist,
• das Dichtmittel einen Feuchtigkeitseintritt-Barriereparameter von weniger als 0,025 cm/h⁰'⁵ aufweist,
• wobei der Bleiadsorptionsparameter die Masse des adsorbierten Bleis pro 1 m² einer Schicht der Dichtmittels darstellt, die bei der Durchführung eines Tests zur Bewertung der Bleiadsorptionsfähigkeit erhalten wird,
• wobei der Test zur Bewertung der Bleiadsorptionsfähigkeit beinhaltet: Herstellen einer ersten Testfolie (Sheet) mit einer Länge von 16 cm und einer Breite von 24 cm, die eine Polyethylenterephthalat-Folie und die auf der Polyethylenterephthalat-Folie gebildete Schicht des Dichtmittels mit einer Dicke von 20 µm enthält; Anhaften eines Nylonnetzgewebes (nylon mesh cloth) auf eine Schichtseite des Dichtmittels der ersten Testfolie; Schneiden der ersten Testfolie mit dem angebrachten Netzgewebe in 1 cm-Quadrate; und Eintauchen der geschnittenen ersten Testfolie in 50 ml einer bleiionenhaltigen wässrigen Lösung, die eine Bleiionenkonzentration von 20 µg/l aufweist und auf 20°C bis 25°C eingestellt ist, und Rühren für 15 Minuten,
• wobei der Feuchtigkeitseintritt-Barriereparameter eine aus der nachstehenden Formel (1) erhaltene Konstante K darstellt, wenn ein Test zur Bewertung der Feuchtigkeitsbarriere durchgeführt wird, und
• der Test zur Bewertung der Feuchtigkeitsbarriere beinhaltet: Trocknen einer zweiten Testfolie (Sheet), die eine Trägerfolie, welche eine 30 µm dicke Aluminiumfolie und eine 25 µm dicke Polyethylenterephthalatfolie umfasst, und eine auf der Aluminiumfolie der Trägerfolie gebildete Schicht des Dichtmittels enthält; Waschen einer aus einem alkalifreien Glas gebildeten Glasplatte von 50 mm im Quadrat mit gekochtem Isopropylalkohol für 5 Minuten und Trocknen; Dampfabscheidung von Calcium auf eine Seite der Glasplatte, mit Ausnahme eines Bereichs innerhalb eines Abstands von 0 mm bis 2 mm von einer Kante der Glasplatte, um einen 200 nm dicken Calciumfilm zu bilden; Anhaften der Dichtmittelschicht der zweiten Testfolie an die Calciumfilm-seitige Oberfläche der Glasplatte in einer Stickstoffatmosphäre, um eine Probe für die Bewertung zu erhalten; Messen eines Abstandes X2 [mm] zwischen einer Kante der Probe für die Bewertung und einer Kante des Calciumfilms; Lagern der Probe für die Bewertung in einem Thermo-Hygrostat bei einer Temperatur von 85°C und einer Feuchtigkeit von 85% RH (relative Luftfeuchtigkeit); Messen der verstrichenen Zeit t [Stunde] ab dem Zeitpunkt, an dem die Probe für die Bewertung in dem Thermo-Hygrostat gelagert wird, bis zu dem Zeitpunkt, an dem der Abstand X1 [mm] zwischen der Kante der in dem Thermo-Hygrostat gelagerten Probe für die Bewertung und der Kante/dem Rand des Calciumfilms „X2 + 0.1 mm“ erreicht; und Berechnen der Konstante K basierend auf der folgenden Formel (1): [Ausdruck 1] $$X1=K\surd t$$
  
• [2] Dichtmittel nach [1], wobei die zweite Testfolie in dem Test zur Bewertung der Feuchtigkeitsbarriere bei mindestens einer der Bedingungen 130°C für 60 Minuten und 100°C für 5 Minuten getrocknet wird.
• [3] Dichtmittel nach [1] oder [2], wobei der anorganische Füllstoff einen oder mehrere Typen enthält, ausgewählt aus der Gruppe bestehend aus semi-calciniertem Hydrotalcit, calciniertem Hydrotalcit, Calciumoxid und Zeolith.
• [4] Dichtmittel für ein elektronisches Bauelement, welches einen bleihaltigen Teil aufweist, wobei das Dichtmittel ein Harz und einen anorganischen Füllstoff, welcher einen oder mehrere Typen enthält, ausgewählt aus der Gruppe bestehend aus semi-calciniertem Hydrotalcit, calciniertem Hydrotalcit und Calciumoxid, umfasst.
• [5] Dichtmittel gemäß [3] oder [4], wobei der anorganische Füllstoff einen oder mehrere Typen enthält, ausgewählt aus der Gruppe bestehend aus semi-calciniertem Hydrotalcit, calciniertem Hydrotalcit und Calciumoxid, und das Harz ein Harz vom Polyolefintyp enthält.
• [6] Dichtmittel nach einem der Punkte [3] bis [5], wobei der anorganische Füllstoff einen oder mehrere Typen enthält, ausgewählt aus der Gruppe bestehend aus semi-calciniertem Hydrotalcit und Calciumoxid, und das Harz ein Epoxidharz enthält.
• [7] Dichtmittel nach einem der Punkte [1] bis [6], wobei die Menge des anorganischen Füllstoffs 5 Massen-% oder mehr und 80 Massen-% oder weniger ist, bezogen auf 100 Massen-% nichtflüchtigen Bestandteils des Dichtmittels.
• [8] Dichtungsfolie/Dichtungs-Sheet, mit:
  • einem Träger; und
  • einer auf dem Träger gebildeten Schicht des Dichtmittels gemäß einem der Punkte [1] bis [7].
• [9] Elektronisches Bauteil/elektronische Vorrichtung, mit:
  • einem bleihaltigen Teil; und
  • einem Dichtungsteil, das/der den bleihaltigen Teil abdichtet, wobei
  • das/der Dichtungsteil das Dichtmittel nach einem der Punkte [1] bis [7] enthält.
• [10] Solarzelle vom Perowskit-Typ, mit:
  • einer ersten Elektrode;
  • einer Perowskitschicht, die Bleiatome enthält;
  • einer zweiten Elektrode; und
  • einem Dichtungsteil, das/der die Perowskitschicht abdichtet, wobei
  • das/der Dichtungsteil das Dichtmittel nach einem der Punkte [1] bis [7] enthält.

[1] A sealant for an electronic component having a lead-containing portion, the sealant containing:

• an inorganic filler; and
• a resin, wherein
• the sealant has a lead adsorption parameter of 10 µg/m ² or more,
• the sealant has a moisture ingress barrier parameter of less than 0.025 cm/h ⁰ ' ⁵ ,
• wherein the lead adsorption parameter represents the mass of adsorbed lead per 1 m ² of a layer of the sealant obtained when conducting a lead adsorption ability evaluation test,
• wherein the test for evaluating the lead adsorption ability includes: preparing a first test sheet (sheet) with a length of 16 cm and a width of 24 cm, which contains a polyethylene terephthalate film and the layer of the sealant formed on the polyethylene terephthalate film with a thickness of 20 µm contains; adhering a nylon mesh cloth to a sealant layer side of the first test sheet; cutting the first test sheet with attached netting into 1 cm squares; and immersing the cut first test film in 50 ml of a lead ion-containing aqueous solution having a lead ion concentration of 20 µg/l and adjusted to 20°C to 25°C and stirring for 15 minutes,
• wherein the moisture ingress barrier parameter is a constant K obtained from the formula (1) below when a moisture barrier evaluation test is performed, and
• the moisture barrier evaluation test includes: drying a second test film (sheet) containing a carrier film comprising a 30 µm thick aluminum foil and a 25 µm thick polyethylene terephthalate film, and a sealant layer formed on the aluminum foil of the carrier film; washing a glass plate of 50 mm square formed of an alkali-free glass with boiled isopropyl alcohol for 5 minutes and drying; vapor-depositing calcium onto one side of the glass plate except for an area within a distance of 0 mm to 2 mm from an edge of the glass plate to form a 200 nm-thick calcium film; adhering the sealant layer of the second test sheet to the calcium film-side surface of the glass plate in a nitrogen atmosphere to obtain a sample for evaluation; measuring a distance X2 [mm] between an edge of the sample for evaluation and an edge of the calcium film; storing the sample for evaluation in a thermo-hygrostat at a temperature of 85°C and a humidity of 85% RH (relative humidity); Measuring the elapsed time t [hour] from when the sample for evaluation is stored in the thermo-hygrostat to when the distance X1 [mm] between the edge of the stored in the thermo-hygrostat sample for evaluation and the edge/margin of calcium film reached "X2 + 0.1mm"; and calculating the constant K based on the following formula (1): [expression 1] $$X1=K\surd t$$
  
• [2] The sealant according to [1], wherein the second test film in the moisture barrier evaluation test is dried under at least one of 130°C for 60 minutes and 100°C for 5 minutes.
• [3] The sealant according to [1] or [2], wherein the inorganic filler contains one or more types selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite, calcium oxide and zeolite.
• [4] A sealant for an electronic component having a lead-containing portion, the sealant comprising a resin and an inorganic filler containing one or more types selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide.
• [5] The sealant according to [3] or [4], wherein the inorganic filler contains one or more types selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide, and the resin contains a polyolefin type resin.
• [6] The sealant according to any one of [3] to [5], wherein the inorganic filler contains one or more types selected from the group consisting of semi-calcined hydrotalcite and calcium oxide, and the resin contains an epoxy resin.
• [7] The sealant 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 based on 100% by mass of the non-volatile component of the sealant.
• [8] Sealing foil/seal sheet, with:
  • a carrier; and
  • a layer formed on the substrate of the sealant according to any one of [1] to [7].
• [9] Electronic component/device, comprising:
  • a leaded part; and
  • a sealing part that seals the lead-containing part, wherein
  • the sealing part contains the sealant according to any one of items [1] to [7].
• [10] Perovskite-type solar cell, with:
  • a first electrode;
  • a perovskite layer containing lead atoms;
  • a second electrode; and
  • a sealing part that seals the perovskite layer, wherein
  • the sealing part contains the sealant according to any one of items [1] to [7].

Advantageous Effects of the Invention

According to the present invention, it is possible to provide a sealant for electronic components or electronic devices, with which the ingress of moisture and the leakage of lead from the lead-containing part outside the electronic component can be suppressed or prevented, a sealing sheet which containing the sealant, and a perovskite-type electronic component and solar cell using the sealant for sealing.

character list

• 1 Fig. 12 is a schematic cross-sectional view of an evaluation sample prepared in a moisture barrier evaluation test.
• 2 Fig. 12 is a schematic plan view of the evaluation sample seen from a glass plate side before storage in a thermo-hygrostat.
• 3 Fig. 12 is a schematic plan view of the evaluation sample viewed from the glass plate side after being stored in the thermo-hygrostat.
• 4 12 is a schematic cross-sectional view of an example of a perovskite-type solar cell according to an embodiment of the present invention.

Description of Embodiments

In the following, the present invention is explained in detail by means of embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and can be carried out with any modifications to the extent that does not depart from the scope of the claims and their equivalents.

[1. Overview of the sealant according to a first embodiment]

A sealant according to a first embodiment of the present invention includes an inorganic filler and a resin. The resin may suitably be generically referred to as a "binder resin" since it serves to bind and hold the inorganic filler. In addition to the inorganic filler and the binder resin, the sealant according to the present embodiment may contain another optional component. The sealant according to the present embodiment has a lead adsorption ability parameter within a certain range. Furthermore, the sealant according to the present embodiment has a moisture ingress barrier parameter within a specific range. When used for sealing an electronic component having a lead-containing part, this sealant can suppress intrusion of moisture into the lead-containing part and reduce lead leakage from the lead-containing part outside the electronic component.

[2. Lead adsorption parameters of the sealant according to the first embodiment]

The lead adsorption parameter of the sealant according to the first embodiment of the present invention is usually 10 μg/m ² or more, preferably 11 μg/m ² or more, more preferably 12 μg/m ² or more, and particularly preferably 13 μg/m ² or more more. An upper limit of the lead adsorption parameter is preferably larger. For example, the lead adsorption parameter can be 200 µg/m ² or less, 100 µg/m ² or less, or 50 µg/m ² or less.

The lead adsorption parameter represents the adsorbed mass of lead per 1 m ² of a layer of the sealant, which is determined by conducting the following lead adsorption ability evaluation test.

The lead adsorption ability evaluation test includes: preparing a first test sheet; adhering a nylon mesh cloth to a sealant layer side of the first test sheet; cutting the first test film with the netting attached into 1 cm squares; and immersing the cut first test sheet in 50 ml of a lead ion-containing aqueous solution having a lead ion concentration of 20 µg/l and adjusted to 20°C to 25°C and stirring for 15 minutes. The first test film is a film having a length of 16 cm and a width of 24 cm, comprising a polyethylene terephthalate film and a sealant layer having a thickness of 20 µm formed on the polyethylene terephthalate film. The reason for sticking the first test sheet to the netting in the lead adsorption ability evaluation test is to prevent the first test sheets from sticking to each other in the lead ion-containing aqueous solution. Typically, when the sealant is a thermosetting sealant, after adhering to the mesh, the sealant is thermally cured at 100°C for 60 minutes, after which the first test sheet is cut.

Therefore, for example, when the sealant is an adhesive sealant, the lead adsorption ability evaluation test is conducted as follows: preparing the first test sheet; adhering a nylon mesh fabric to the sealant layer side of the first test sheet; cutting the first test sheet having the attached nylon netting into 1 cm squares; and immersing the cut first test sheet in 50 ml of the lead ion-containing aqueous solution having a lead ion concentration of 20 µg/l and adjusted to 20 to 25°C and stirring for 15 minutes.

For example, when the sealant is a thermosetting sealant, the lead adsorption ability evaluation test is conducted as follows: preparing the first test sheet; adhering a nylon mesh fabric to the layer side of the sealant of the first test film and thermally curing the sealant at 100°C for 60 minutes; cutting the first test sheet with the netting attached to 1 square centimeter; and immersing the cut first test sheet in 50 ml of the lead ion-containing aqueous solution having a lead ion concentration of 20 g/l and adjusted to 20°C to 25°C; and stirring for 15 minutes.

In conducting the lead adsorption ability evaluation test, the mass of lead adsorbed on the sealant layer can be measured from the concentration of lead ions contained in the lead ion-containing aqueous solution. The lead ion concentration can be measured with a portable scanning lead analyzer (model name HSA-1000, manufactured by Hach Company). As the specific measurement methods, the methods described below in the examples can be used.

The lead adsorption parameter indicates the degree of lead adsorption ability of the sealant. In particular, a higher lead adsorption parameter means a greater lead adsorption capability of the sealant. The sealant having a lead adsorption parameter in the above range can effectively absorb/adsorb lead leaking from the lead-containing part when used for sealing the lead-containing part in an electronic component. Therefore, it is possible to suppress lead leakage to the outside of the electronic component. The above-mentioned lead leakage inhibiting effect is advantageous in a variety of situations when electronic components are stored, shipped, used, damaged and the like.

The lead adsorption parameter can e.g. B. can be adjusted depending on the type and amount of the inorganic filler.

[3. Moisture ingress barrier parameter of the sealant according to the first embodiment]

The moisture ingress barrier parameter of the sealant according to the first embodiment of the present invention is typically less than 0.025 cm/h ^0.5 , preferably less than 0.024 cm/h ^0.5 , more preferably less than 0.0230 cm/h ^{0. 5} , more preferably less than 0.022 cm/hr ^0.5 , and most preferably less than 0.021 cm/hr ^0.5 . A lower limit for the moisture barrier parameter is ideally 0.000 cm/hr ^0.5 or higher and may be 0.001 cm/hr ^0.5 or higher.

The moisture ingress barrier parameter is a constant K obtained from formula (1) when the following moisture barrier evaluation test is performed.

The moisture barrier evaluation test described above comprises: drying a second test sheet; washing a glass plate of 50 mm square formed of an alkali-free glass with boiled isopropyl alcohol for 5 minutes and drying it; vapor deposition of calcium to form a 200 nm thick calcium film on the central portion of one side of the glass plate; adhering the sealant layer of the second test sheet to the calcium film-side surface of the glass plate in a nitrogen atmosphere to obtain a sample for evaluation; measuring a sealing distance X2 [mm] of the sample for evaluation; storing the sample for evaluation in a thermo-hygrostat at a temperature of 85°C and a humidity of 85% RH (relative humidity); Measuring the elapsed time t [hour] from the point of time T _P1 at which the sample for evaluation is stored in the thermo-hygrostat to the point of time T _P2 at which the sealing distance X1 [mm] is measured in the thermo-hygrostat -Hygrostat stored sample for evaluation "X2 + 0.1mm"achieved; and calculating the constant K based on the following formula (1). In the following explanations, the aforesaid time t may be referred to as “delivery start time t”. When the sealant is curable, the evaluation sample is usually obtained by adhering the sealant layer of the second test sheet to the calcium film side surface of the glass plate and then curing the sealant layer. As conditions for hardening, e.g. B. the conditions described below in the examples can be used. The specific condition for hardening can e.g. B. 100°C for 60 minutes. It is preferable to sufficiently dry the second test film for the moisture barrier evaluation test. The specific condition for drying may be at least one of: 130°C for 60 minutes and 100°C for 5 minutes. When a moisture penetration barrier parameter in the moisture barrier evaluation test including drying at least one condition of 130°C for 60 minutes and 100°C for 5 minutes is obtained in the above range, the sealant can inhibit/prevent moisture penetration and suppress lead leakage from the lead-containing part of the electronic component. When the sealant is an adhesive sealant, drying is usually performed at 130°C for 60 minutes. When the sealant is a thermosetting sealant, drying is typically done at 100°C for 5 minutes.

For example, when the sealant is an adhesive sealant, the moisture barrier evaluation test can be performed as follows: drying the second test film at 130°C for 60 minutes; washing the 50 mm square alkali-free glass plate with boiled isopropyl alcohol for 5 minutes and drying it; vapor depositing calcium on the central portion of one side of the glass plate to form a 200 nm thick calcium film; adhering the sealant layer of the second test sheet to the calcium film-side surface of the glass plate in a nitrogen atmosphere to obtain the evaluation sample; measuring the sealing distance X2 [mm] of the evaluation sample; storing the evaluation sample in the thermo-hygrostat at a temperature of 85°C and a humidity of 85% RH; Measuring the elapsed decrease start time t [hour] from the time T _P1 when the evaluation sample is stored in the thermo-hygrostat to the time T _P2 when the sealing distance X1 [mm] of the evaluation sample stored in the thermo-hygrostat is " X2 + 0.1 mm"reached; and calculating the constant K according to the following formula (1).

For example, when the sealant is a thermosetting sealant, the moisture barrier evaluation test can be performed as follows: drying the second test film at 100°C for 5 minutes; washing the 50 mm square alkali-free glass plate with boiled isopropyl alcohol for 5 minutes and drying it; vapor depositing calcium on the central portion of one side of the glass plate to form a 200 nm thick calcium film; adhering the sealant layer of the second test sheet to the calcium film-side surface of the glass plate in a nitrogen atmosphere and then curing the sealant at 100°C to obtain the evaluation sample; measuring the sealing distance X2 [mm] of the evaluation sample; storing the evaluation sample in the thermo-hygrostat at a temperature of 85°C and a humidity of 85% RH; Measuring the elapsed pickup start time t [hour] from the time T _P1 when the evaluation sample is stored in the thermo-hygrostat to the time T _P2 when the sealing distance X1 [mm] of the evaluation sample stored in the thermo-hygrostat is "X2 + 0.1 mm "reached; and calculating the constant K according to the following formula (1).

The second test film (test sheet) refers to a film comprising: a base film including a 30 µm thick aluminum foil and a 25 µm thick polyethylene terephthalate film; and a layer of sealant formed on the aluminum foil of the base sheet. The thickness of the sealant layer can e.g. B. be 20 microns. The central portion of a side of the glass panel refers to a portion of a side of the glass panel excluding a peripheral portion thereof. The edge area of a side of the glass sheet refers to an area of a side of the glass sheet within a distance of 0 mm to 2 mm from the edge of the glass sheet. The evaluation sample dense distance refers to the distance between the edge of the evaluation sample and the edge of the calcium film.
The sealing distance is usually equal to the distance between the edge of the sealant layer and the edge of the calcium film.
[expression 2] $$X1=K\sqrt{t}$$

In formula (1),
X1 stands for the sealing distance [mm] from the edge of the evaluation sample to the edge of the calcium film obtained after placing in the thermo-hygrostat,
t is the decrease start time [hour] until X1 = X2 + 0.1 is reached, and
X2 is the sealing distance [mm] from the edge of the evaluation sample to the edge of the calcium film obtained before placing in the thermo-hygrostats.

The mechanism of the moisture barrier evaluation test described above and the meaning of the constant K as the moisture ingress barrier parameter determined by the test will now be explained with reference to the drawings.

1 Fig. 12 is a schematic cross-sectional view of an evaluation sample 10 prepared in the moisture barrier evaluation test. As in 1 As shown, the evaluation sample 10 prepared in the moisture barrier evaluation test has a square glass plate 100 washed with boiled isopropyl alcohol, a calcium film 200 formed on a surface 100U of the glass plate 100, and a second test film 300 attached to the surface 100U of the glass plate 100 is attached. The calcium film 200 is not formed in a peripheral portion 110U of the surface 100U of the glass sheet 100 where the distance L from the edge 100E of the glass sheet 100 is 0 mm to 2 mm. The calcium film 200 is formed on the central portion 120U of the surface 100U of the glass plate 100 except for the peripheral area 110U. The calcium film 200 is usually formed by evaporation using a mask (not shown) covering the peripheral area 110U, and has high purity (e.g., 99.8% or more). Furthermore, the second test film 300 has a layer 310 of the sealant and a carrier film 320 which comprises a polyethylene terephthalate film 321 and an aluminum foil 322 . The sealant layer 310 is adhered to the surface 100U of the glass panel 100 . Therefore, the calcium film 200 is sealed with the sealant layer 310 of the sealant.

The glass plate 100 and the base sheet 320 included in the above evaluation sample 10 are sufficiently capable of blocking moisture. Therefore, moisture around the evaluation sample 10 can pass the edge 310E of the sealant layer 310 and move through the inside of the sealant layer 310 in in-plane directions (directions perpendicular to the thickness direction) to penetrate into the calcium film 200, such as through the arrow A1 is indicated. Therefore, the calcium film 200 of the evaluation sample 10 stored in the thermo-hygrostat can be gradually oxidized from the edge 200E toward the center 200C.

2 12 is a schematic plan view of the evaluation sample 10 seen from the side of a glass plate 100 before being stored in a thermo-hygrostat. 3 12 is a schematic plan view of the evaluation sample 10 viewed from the glass plate 100 side after being stored in the thermo-hygrostat.

As in 2 As shown, the calcium film 200 is not oxidized by the ingress of moisture into the evaluation sample 10 before it is stored in the thermo-hygrostat. Therefore, the sealing distance X2 between the edge 10E of the evaluation sample 10 and the edge 200E of the calcium film 200 im Generally maintain the size immediately after the formation of the calcium film 200. However, when the evaluation sample 10 is stored in the thermo-hygrostat, moisture can penetrate through the sealant layer 310 (see 1 ) penetrate into the calcium film 200 and come into contact with calcium to cause calcium oxidation to form transparent calcium oxide. As in 3 Therefore, as shown in FIG. 1, the calcium film 200 can be gradually transformed into a transparent calcium oxide film 210 from the edge 200E toward the center 200C by the penetration of moisture. This transformation is observed as a shrinkage of the calcium film 200. Therefore, after storing the evaluation sample 10 in the thermo-hygrostat, the sealing distance X1 between the edge 10E of the evaluation sample 10 and the edge 200E of the calcium film 200 may gradually increase with time.

The movement of moisture through the sealant layer 310 generally follows Fick's diffusion equation. In the above moisture barrier evaluation test, the constant K is obtained as a moisture ingress barrier parameter according to Fick's diffusion equation expressed by the formula (1), where the sealing distance XI at which moisture moves through the sealant layer 310 , and the collection start time t required for the moisture movement at the sealing distance X1 (that is, the time from the time T _P1 at which the evaluation sample 10 is stored in the thermo-hygrostat to the time T _P2 at which the sealing Distance X1 [mm] of the evaluation sample stored in the thermo-hygrostat 10 "X2 + 0.1 mm" reached, elapsed time) used.

Therefore, the evaluation sample 10 described above can be a model for an electronic component, and the calcium film 200 can correspond to the lead-containing part to be sealed with the sealant. The moisture ingress barrier parameter represents the ability of the sealant provided on the electronic component to inhibit moisture ingress in the in-plane direction. A lower moisture ingress barrier parameter means a better ability of the sealant to inhibit moisture ingress. A sealant having a moisture ingress barrier parameter within the above range can inhibit moisture penetration into the lead-containing part when used to seal the lead-containing part in the electronic component. Therefore, it is possible to prevent components contained in the lead-containing part from being oxidized, and leakage of lead from the lead-containing part can be inhibited.

The moisture ingress barrier parameter can e.g. B. be adjusted depending on the type and amount of the inorganic filler and / or the type and amount of the binder resin.

[4. Inorganic filler contained in the sealant according to the first embodiment]

The sealant according to the first embodiment of the present invention contains an inorganic filler. A part or all of the inorganic filler may have hygroscopicity and lead adsorption ability in the sealant used as a resin composition containing the inorganic filler and the binder resin. One kind of inorganic filler can be used alone, or two or more kinds can be combined at any ratio. For example, an inorganic filler capable of showing hygroscopicity in the sealant can be used in combination with another inorganic filler capable of showing lead adsorption ability in the sealant. The inventors of the present invention first observed the phenomenon that the lead-adsorbing inorganic filler in the sealant, which is the resin composition containing the binder resin, can exhibit lead adsorption ability.

(4.1. Hydrotalcite)

An example of the inorganic filler is hydrotalcite. Hydrotalcite can be divided into uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite.

An example of the non-calcined hydrotalcite may be a metal hydroxide having a layered crystal structure represented by natural hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ ·4H ₂ O). The uncalcined hydrotalcite consists, for example, of a layer [Mg _1-Xa Al _Xa (OH) ₂ ] ^Xa+ , which serves as a backbone, and an intermediate layer [(CO ₃ ) _Xa/2 ·m _a H ₂ O] ^Xa- . where xa is a number satisfying 0<xa<1, and m _a is a positive number. Unless otherwise specified, the term "uncalcined hydrotalcite" refers to a concept encompassing hydrotalcite-like compounds such as synthetic hydrotalcite. Examples of hydrotalcite-like compounds may be compounds represented by the following formula (I) or (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⁺ stands for a divalent metal ion, such as e.g. B. Mg ²⁺ and Zn ²⁺ ,
Mi ³⁺ stands for a trivalent metal ion, such as e.g. B. Al ³⁺ and Fe ³⁺ ,
Ai ^{ni- stands} for an ni-valent anion, such as e.g. B. CO ₃ ^2- , Cl ^- and NO ₃ ^- ,
xi stands for a number that satisfies the condition 0 < xi < 1,
m _i is a number that satisfies the conditions 0 ≤ m _i < 1, and
ni stands for a positive number.)

In formula (I), Mi ²⁺ is preferably Mg ²⁺ . Furthermore, Mi ³⁺ is preferably Al ³⁺ . Furthermore, Ai ^{ni- is} preferably 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⁺ stands for a divalent metal ion such as e.g. B. Mg ²⁺ , Zn ²⁺ ,
Aii ^{nii- stands} for a nii-valent anion such as CO ₃ ^2- , Cl ^- and NO ^3- ,
xii represents a positive number of 2 or more,
zii represents a positive number of 2 or less,
m _ii is a positive number, and
nii stands for a positive number).

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

The uncalcined hydrotalcite can exhibit excellent adsorptivity of lead in the sealant. Therefore, for example, by appropriately combining the uncalcined hydrotalcite and an inorganic filler capable of showing hygroscopicity in the sealant, a sealant having the lead adsorption parameter and the moisture ingress barrier parameter in the ranges described above can be obtained.

The saturation water absorption rate of uncalcined hydrotalcite is usually below 1% by mass and can be less than 0.8% by mass or less than 0.6% by mass. The "saturated water absorption rate" of hydrotalcite, such as uncalcined hydrotalcite, is defined as the percentage increase in mass of the hydrotalcite allowed to stand at 60°C and 90% RH under atmospheric pressure for 200 hours, with respect to its starting mass . This saturation water absorbency can be measured by the following method.

1.5 g of hydrotalcite are weighed with a scale to determine the initial mass. The weighed hydrotalcite is allowed to stand for moisture absorption in a compact environmental test chamber SH-222, manufactured by ESPEC CORP.) adjusted to 60°C and 90% RH (relative humidity) under atmospheric pressure for 200 hours , and then the mass obtained after moisture absorption is measured. The saturation water absorbency is then calculated using the following formula (i): $$\begin{array}{l}\text{S}\ddot{\text{a}}\text{activities}-\text{water absorbency}\left[\text{crowds}-\%\right]=100\times \\ \left(\text{Mass after moisture absorption}-\text{initial mass}\right)/\\ \text{exit mass}\left(\text{i}\right).\end{array}$$

The thermal weight loss ratio of the uncalcined hydrotalcite at 280°C is usually 15% by mass or more, preferably 15.1% by mass or more, and more preferably 15.2% by mass or more.

The thermal weight loss fraction of hydrotalcite, such as uncalcined hydrotalcite, can be measured by thermogravimetric analysis. The thermogravimetric analysis can be performed with a thermal analyzer (thermal analyzer, TG/DTA EXSTAR 6300, manufactured by Hitachi High-Tech Science Corporation) by weighing 5 mg of hydrotalcite on an aluminum sample pan and then heating the weighed hydrotalcite at a temperature ramping from 30°C to 550°C at a rate of 10°C/min is allowed to stand under a nitrogen flow rate of 200 ml/min with the dish open and not covered with a lid. The thermal weight loss fraction can be calculated from the results of the above-described thermogravimetric analysis according to the following formula (ii). $$\begin{array}{l}\text{Thermal Weight Loss Fraction}\left(\text{crowds}-\%\right)=100\times \\ (\text{mass before heating}-\text{mass upon reaching a}\\ \text{specified temperature})/\text{mass before heating}\left(\text{ii}\right)\end{array}$$

In the measurement of the powder X-ray diffraction of the uncalcined hydrotalcite, only a peak at 2θ from about 8° to 18° is generally observed, or the relative intensity ratio (diffraction intensity on the small angle side/diffraction intensity on the high angle side) of the diffraction intensity on the smaller side Angle to high-angle side diffraction intensity is outside the range of 0.001 to 1000. Low-angle side diffraction intensity refers to the diffraction intensity of a peak or shoulder appearing on the low-angle (small 2θ) side . The diffraction intensity on the high angle side refers to the diffraction intensity of a peak or shoulder appearing on the high angle side (large 2θ side).

X-ray powder diffraction can be measured for hydrotalcite, such as uncalcined hydrotalcite, with a powder X-ray diffractometer (Empyrean from Panalytical Co.). The powder X-ray diffraction can be measured under the following conditions: counter cathode CuKα (1.5405 Å), voltage: 45 V, current: 40 mA, scan width: 0.0260°, scan speed: 0.0657°/s, and measurement diffraction angle range (2θ): 5 .0131° to 79.9711°. The peak search can be performed with the peak search function of the software connected to the diffractometer under the following conditions: minimum significance: 0.50, minimum peak top: 0.01°, maximum peak top: 1.00°, peak base width: 2, 00°, method: minimum value of the second derivative.

Examples of the uncalcined hydrotalcite may include "ALCAMIZER 1" (average particle diameter: 620 nm), "MAGCELER 1" (average particle diameter: 470 nm), and "DHT-4A" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle diameter: 400 nm), "STABIACE HT -1", "STABIACE HT-7" and "STABIACE HT-P" (Sakai Chemical Industry Co., Ltd.). One type of uncalcined hydrotalcite can be used alone, or two or more types can be combined at any ratio.

Semi-calcined hydrotalcite refers to a metal hydroxide which has a layered crystal structure with a reduced or removed amount of interlayer water and is obtained by calcining uncalcined hydrotalcite. The term “interfacial water” refers to “H ₂ O” described in the above-described compositional formulas of uncalcined natural hydrotalcite and hydrotalcite-like compounds when explained using the compositional formulas.

Semi-calcined hydrotalcite can exhibit excellent lead adsorption ability and hygroscopicity in the sealant. Therefore, by properly using semi-calcined hydrotalcite, it is possible to obtain sealants having the lead adsorption parameter and the moisture ingress barrier parameter in the ranges described above. The inventors of the present invention first found that the semicalcined hydrotalcite has lead adsorption ability.

Since semi-calcined hydrotalcite generally has a different saturation water absorptivity than uncalcined hydrotalcite, they can be distinguished from each other by their saturation water absorptivity. The saturation water absorption degree of semi-calcined hydrotalcite is usually 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more, and is generally below 20% by mass. The saturation water absorption rate of semi-calcined hydrotalcite can be measured by the same method as that of uncalcined hydrotalcite.

Since semi-calcined hydrotalcite generally has a different thermal weight loss ratio than uncalcined hydrotalcite, they can also be distinguished from each other by their thermal weight loss ratios. The thermal weight loss fraction of semi-calcined hydrotalcite at 280°C is typically below 15% by mass, preferably below 14% by mass and more preferably below 13% by mass. The thermal weight loss fraction of semi-calcined hydrotalcite at 380°C is usually 12% by mass or more, preferably 15% by mass or more, and more preferably 16% by mass or more. The thermal weight loss percentage of semi-calcined hydrotalcite can be measured by the same method as that of uncalcined hydrotalcite.

Semi-calcined hydrotalcite generally shows different peaks and relative intensity ratios than uncalcined hydrotalcite by powder X-ray diffraction, so these can be distinguished from each other by the peaks and relative intensity ratios measured by powder X-ray diffraction. In the measurement of powder X-ray diffraction, semi-calcined hydrotalcite generally shows two split peaks or a peak with a shoulder formed by combining the two peaks around 8° to 18° in 2θ, where the relative intensity ratio (diffraction intensity of the small angle side / diffraction intensity of large angle side) between the diffraction intensity of small angle side and the diffraction intensity of large angle side is 0.001 to 1000. The powder X-ray diffraction can be measured for semi-calcined hydrotalcite in the same way as the in-powder X-ray diffraction for uncalcined hydrotalcite.

Examples of semi-calcined hydrotalcite are "DHT-4C" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle diameter: 400 nm) and "DHT-4A-2" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle diameter: 400 nm). One kind of semi-calcined hydrotalcite can be used alone, or two or more kinds thereof can be combined at any ratio.

Calcined hydrotalcite is a metal hydroxide with an amorphous structure obtained by calcining uncalcined or semi-calcined hydrotalcite to remove not only the water in the interlayers but also the hydroxyl groups by condensation dehydration.

The calcined hydrotalcite in the sealant can exhibit excellent lead receptivity and hygroscopicity. Therefore, by appropriately using calcined hydrotalcite, it is possible to obtain sealants having the lead adsorption parameter and the moisture ingress barrier parameter in the ranges described above. The inventors of the present invention first found that calcined hydrotalcite has lead absorbing ability.

Calcined hydrotalcite generally has a different saturation water absorption level than uncalcined and semi-calcined hydrotalcite, so they can be distinguished from each other by their saturation water absorption levels. The saturation water absorption degree of calcined hydrotalcite is usually 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more. The saturation water absorption rate of calcined hydrotalcite can be measured in the same manner as that of uncalcined hydrotalcite.

Calcined hydrotalcite generally has a different thermal weight loss ratio than uncalcined hydrotalcite and semi-calcined hydrotalcite, so these can be distinguished from each other by their thermal weight loss ratios. The thermal weight loss fraction of calcined hydrotalcite at 380°C is typically below 12% by mass, preferably below 10% by mass and more preferably below 7% by mass. The thermal weight loss rate of calcined hydrotalcite can be measured in the same way as that of uncalcined hydrotalcite.

Calcined hydrotalcite generally differs from uncalcined and semi-calcined hydrotalcites in terms of peaks and relative intensity ratios measured by powder X-ray diffraction, so these can be distinguished by peaks and relative intensity ratios measured by powder X-ray diffraction . When measured by powder X-ray diffraction, calcined hydrotalcite generally has a characteristic peak at 43° in 2θ without a characteristic peak in a 2θ range from 8° to 18°. Measurement of powder X-ray diffraction of calcined hydrotalcite can be performed in the same manner as measurement of powder X-ray diffraction of uncalcined hydrotalcite.

An example of calcined hydrotalcite is "KW-2200" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle diameter: 400 nm). One kind of calcined hydrotalcite can be used alone, or two or more kinds thereof can be combined at any ratio.

(4.2. Calcium Oxide)

Another example of an inorganic filler is calcium oxide. Calcium oxide can provide excellent lead receptivity and hygroscopicity in the sealant. Therefore, by appropriately using calcium oxide, it is possible to obtain a sealant whose lead adsorption parameters and moisture ingress barrier parameters are in the ranges described above. The inventors of the present invention first found that calcium oxide has a lead receptivity. Calcium oxide can be contained in a mixture with another inorganic filler. Examples of such a mixture are calcined dolomite (a mixture of calcium oxide and magnesium oxide).

(4.3. Zeolite)

Another example of an inorganic filler is zeolite. Zeolite can have excellent lead receptivity in the sealant. In addition, zeolite in the sealant can exhibit excellent hygroscopicity, for example, if the composition is properly adjusted. Therefore, by properly using zeolite, it is possible to obtain a sealant whose lead adsorption parameters and moisture ingress barrier parameters are in the ranges described above.

From the viewpoint of increasing the hygroscopicity of the zeolite, the zeolite preferably has high hydrophilicity. The hydrophilicity of the zeolite can, for. B. be adjusted by the molar ratio of silica to alumina in the zeolite. The specific molar ratio (silica/alumina) of silica to alumina of the zeolite is preferably less than 100, more preferably less than 50 and even more preferably less than 25.

Zeolite generally has pores. The pore size of the zeolite is preferably adjusted in such a way that a high lead absorption capacity and hygroscopicity is achieved. The pore size of the zeolite is preferably 6 Å or less, more preferably 5 Å or less, and still more preferably 4 Å or less. "Å" stands for 1.0 × 10 ^-10 m. The pore size of the zeolite can be measured by a gas adsorption or mercury intrusion method.

(4.4. Examples of other inorganic fillers)

Another example of the inorganic filler is a hygroscopic metal oxide other than those mentioned above. Examples of such hygroscopic metal oxides can be magnesium oxide, strontium oxide, aluminum oxide and barium oxide. The hygroscopic metal oxide can exhibit excellent hygroscopicity in the sealant. For example, with an appropriate combination of the hygroscopic metal oxide and the inorganic filler capable of exhibiting lead adsorption ability in the sealant, it is possible to obtain sealant having a lead adsorption parameter and moisture ingress barrier parameter in the ranges described above.

(4.5. preferred inorganic filler)

Among the above examples, semi-calcined hydrotalcite, calcined hydrotalcite, calcium oxide and zeolite are preferred as the inorganic filler. These are excellent in lead receptivity and hygroscopicity in the sealant, enabling the lead adsorption parameter and moisture ingress barrier parameter of the sealant to be easily adjusted to the above ranges. Therefore, it is preferred that the sealant contains one or more inorganic fillers selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite, calcium oxide and zeolite.

(4.6. Surface treatment of inorganic filler)

The inorganic filler may be surface-treated with a suitable surface-treating agent. Unless otherwise specified, the term "inorganic filler" also includes those that have been subjected to a surface treatment. Examples of the surface-treating agent can be higher fatty acids, alkylsilane compounds, and silane coupling agents. Higher fatty acids and alkylsilane compounds are preferred. One kind of the surface-treating agent can be used alone, or two or more kinds thereof can be combined at any ratio.

Examples of higher fatty acids can be higher fatty acids having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid and palmitic acid. Among these, stearic acid is preferred.

Examples of the alkylsilane compounds are methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl(3-(trimethoxysilyl)propyl)ammonium chloride.

Examples of the silane coupling agents may be epoxy type silane coupling agents such as 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; mercapto-type silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane; Amino type silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl). )-3-aminopropyldimethoxymethylsilane; ureido-type silane coupling agents such as 3-ureidopropyltriethoxysilane; vinyl type silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; styryl type silane coupling agents such as p-styryltrimethoxysilane; acrylate type silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; isocyanate type silane coupling agents such as 3-isocyanatopropyltrimethoxysilane; sulfide-type silane coupling agents such as bis(triethoxysilylpropyl) disulfide and bis(triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane; methacryloxypropyltrimethoxysilane; imidazole silane; and triazinesilane.

The amount of the surface-treating agent may differ depending on the kinds of the inorganic filler and the surface-treating agent. The amount of the surface-treating agent to be used for the surface treatment with respect to 100 parts by mass of the surface-untreated inorganic filler is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and particularly preferably 1.0 part by mass or more, and is preferably 10 parts by mass or less, preferably 8 parts by mass or less, and particularly preferably 6 parts by mass or less. The surface treatment using the surface treatment agent in the above range of amount can prevent the inorganic filler from aggregating to increase the surface area of the inorganic filler, whereby the inorganic filler can easily exhibit the lead adsorption ability and hygroscopicity.

There are no restrictions on the methods of surface treatment of the inorganic filler. For example, the inorganic filler and the surface treatment agent can be mixed together for use in surface treatment. In particular, when hydrotalcite, such as. e.g. semi-calcined hydrotalcite, is used as the inorganic filler, the surface treatment is preferably carried out by spraying the surface treatment agent, while the untreated hydrotalcite is e.g. B. is stirred with a mixer. Normal temperature is preferably selected as the processing temperature. Stirring is preferably carried out for 5 minutes to 60 minutes. Examples of mixers are mixers such as V-blenders, ribbon blenders, bubble cone mixers, mixers such as Henschel mixers and concrete mixers, and mills such as ball mills and granulators. The surface treatment can e.g. B. be done by grinding the hydrotalcite and simultaneously mixing the hydrotalcite with the surface treatment agent.

(4.7 Inorganic filler particle diameter)

The average particle diameter of the inorganic filler is preferably 1 nm or more, more preferably 10 nm or more, still more preferably 100 nm or more, and particularly preferably 200 nm or more, and is preferably less than 10 μm, more preferably less than 5 μm, more preferably less than 1 µm, and more preferably less than 800 nm. In particular, when hydrotalcite such as semi-calcined hydrotalcite is used as the inorganic filler, the average particle diameter of hydrotalcite is preferably 1 nm or more, and more preferably 10 nm or more, and preferably 1000 nm or less, and more preferably 800 nm or less. Moreover, particularly when zeolite is used as the inorganic filler, the average particle diameter of zeolite is preferably 100 nm or more, more preferably 200 nm or more, and is preferably less than 10 µm, and particularly preferably less than 5 µm. By using the inorganic filler having such an average particle diameter range, better workability of the sealant is achieved, so that the sealing sheet can be easily manufactured.

The average particle diameter of the inorganic filler can be determined as a median diameter of particle diameter distribution measured volumetrically by laser diffraction scattering particle diameter 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, and preferably 250 m ² /g or less, and more preferably 200 m ² /g or less. In particular, when the inorganic filler hydrotalcite, such as. semi-calcined hydrotalcite, the hydrotalcite preferably has a BET specific surface area in the above range. By using the inorganic filler having a BET specific surface area in this range, better workability of the sealant is achieved, whereby the sealing sheet can be easily manufactured.

The BET specific surface area of the inorganic filler can be found by adsorbing nitrogen gas on a sample surface by the BET method using a specific surface area meter (Macsorb HM Model 1210, manufactured by Mountech Co., Ltd.) and calculating by a BET -Multipoint method to be determined.

(4.9. Amount of inorganic filler)

Based on 100% by mass of the nonvolatile component(s) of the sealant, 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, preferably 80% by mass or less, preferably 75% by mass or less, and more preferably 70% by mass or less, and may be, for example, 65% by mass or less, 60% by mass or less. When the amount of the inorganic filler is equal to or greater than the lower limit of the above range, the inorganic filler exhibits increased lead absorbency and hygroscopicity, thereby facilitating the adjustment of the lead adsorption parameter and the moisture ingress barrier parameter of the sealant to the ranges described above. When the amount of the inorganic filler is equal to or less than the upper limit of the above range, the sealant has excellent viscosity and wettability, whereby the adhesiveness between the sealant and the objects to be sealed such as the lead-containing part and the electrodes can be improved. Therefore, gap formation between the object to be sealed and the sealant can be effectively prevented, so that the sealing ability is improved, whereby in particular, the ingress of moisture and the leakage of lead can be effectively prevented.

[5. Overview of the components other than the inorganic filler that can be contained in the sealant according to the first embodiment]

The sealant according to the first aspect of the present invention contains a binder resin in combination with the inorganic filler described above. The binder resin can perform some or all of the following functions: preventing dust and other foreign matter from entering the electronic component, holding the inorganic filler to prevent it from coming off the sealing part, adhering the sealant to the objects to be sealed such as the lead adsorbing part, inhibiting moisture permeation and the like.

The sealant according to the first aspect of the present invention may contain an optional component in combination with the inorganic filler and the binder resin. Kinds and proportions of the binder resin and the optional component can be appropriately selected depending on the kind and amount of the inorganic filler and the required properties of the sealant.

Hereinafter, the binder resin and the optional component are described with reference to examples of components suitable for adhesive type sealants and thermosetting sealants. The adhesive sealant refers to a type of sealant that has adhesive properties and can seal the object to be sealed by pressing. The pressure-sensitive sealant can generally be adhered only by applying pressure for a relatively short time at normal temperature, and therefore can function as a pressure-sensitive adhesive. The thermosetting sealant refers to a sealant that can achieve sealing by thermally 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 used as examples of adhesive sealant specified, can also be used for other sealants (e.g. for thermosetting sealants). The components given as examples for thermosetting sealants can also be used for other sealants (e.g. adhesive sealants).

[6. Explanation of components suitable for adhesive sealants according to the first embodiment]

(6.1. Thermoplastic resin as binder resin)

An example of a component that can be contained in the sealant in combination with the inorganic filler is a thermoplastic resin. The thermoplastic resin is preferably used as the binder resin for the adhesive sealants. One type of the thermoplastic resin can be used alone, or two or more types can be combined at any ratio.

There are no restrictions on the thermoplastic resin. For example, the thermoplastic resins described below can be used as the binder resin for the thermosetting sealants. A preferred example of a thermoplastic resin is polyolefin resin. The polyolefin resin can be combined with the inorganic filler containing one or more types selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide to obtain the sealant having excellent transparency.

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

Examples of the copolymer are copolymers of two or more kinds of olefins and copolymers of an olefin and a monomer other than the olefin, e.g. B. a non-conjugated diene and styrene. Examples of preferred copolymers are ethylene-non-conjugated diene copolymer, ethylene-propylene copolymer, ethylene-propylene non-conjugated diene copolymer, ethylene-butene copolymer, propylene-butene copolymer, propylene-butene-non-conjugated diene copolymer, styrene-isobutylene copolymer and styrene-isobutylene-styrene copolymer.

The polyolefin resin may contain/be a polyolefin resin having an acid anhydride group (i.e., carbonyloxycarbonyl group (-CO-O-CO-)). The use of the polyolefin resin having an acid anhydride group can improve adhesiveness and moisture and heat resistance of the sealant.

Examples of the acid anhydride group may be a succinic anhydride-derived group, a maleic anhydride-derived group and a glutaric anhydride-derived group. One, two or more kinds of acid anhydride group can be used. The polyolefin resin having the acid anhydride group can be produced, for example, by graft-modifying the polyolefin resin with an unsaturated compound having an acid anhydride group under a radical reaction condition. The polyolefin resin having the acid anhydride group can be produced, for example, by radical copolymerization of the olefin with the unsaturated compound having the acid anhydride group.

The concentration of the acid anhydride group in the polyolefin type resin having the acid anhydride group is preferably 0.05 mmol/g or more, and more preferably 0.1 mmol/g or more, and is preferably 10 mmol/g or less, and more preferably 5 mmol/g or less. The concentration of the acid anhydride group is obtained from the acid value, which is defined as the number of mg of potassium hydroxide required to neutralize an acid present in 1 g of resin as specified in JIS K 2501.

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

The polyolefin resin may contain/be a polyolefin resin having an epoxy group. The use of the polyolefin resin having an epoxy group can improve the adhesiveness and the resistance of the sealant to moisture and heat.

The polyolefin resin having an epoxy group can be produced, for example, by graft-modifying the polyolefin resin with an unsaturated compound having an epoxy group such as glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether and allyl glycidyl ether under radical reaction conditions. As used herein, the term “glycidyl (meth)acrylate” means both glycidyl acrylate and glycidyl methacrylate. The polyolefin resin having an epoxy group can be produced, for example, by radical copolymerization of the olefin with the unsaturated compound having the epoxy group.

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

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

One type of the polyolefin resin can be used alone, or two or more types thereof can be used in combination at any ratio. In particular, it is preferable to use a combination of the polyolefin resin having the acid anhydride group and the polyolefin resin having the epoxy group. When the polyolefin resin having the acid anhydride group is used in combination with the polyolefin resin having the epoxy group, a crosslinked structure can be formed by a reaction between the acid anhydride group and the epoxy group, whereby the ability of the sealants to prevent moisture penetration can be effectively increased . In this case, the molar ratio (epoxide group:acid anhydride group) of the epoxide group to the 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.

Specific examples of the polyolefin type resin are described below.

Specific examples of polyisobutylene resins are “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 polybutene resins are "HV-1900" (manufactured by JX Energy Co., polybutene, number-average molecular weight: 2,900) and "HV-300M" (manufactured by Toho Chemical Industry Co., maleic anhydride-modified liquid polybutene (modified from "HV -300" (number-average molecular weight: 1,400)), number-average molecular weight: 2,100, number of carboxy groups constituting acid anhydride group: 3.2 per one molecule, acid value: 43.4 mgKOH/g, concentration of acid anhydride group: 0.77 mmol/ G).

Specific examples of styrene-isobutylene copolymers are "SIBSTAR T102" (manufactured by KANEKA CORPORATION, styrene-isobutylene-styrene block copolymer, number-average molecular weight: 100,000, styrene content: 30% by mass), "T-YP757B" (manufactured by SEIKO PMC CORPORATION, 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 SEIKO PMC CORPORATION, glycidyl methacrylate-modified styrene-isobutylene-styrene block copolymer, epoxy group concentration: 0.638 mmol/g, number-average molecular weight: 100,000), “T-YP8920” (manufactured by SEIKO PMC CORPORATION, maleic anhydride-modified styrene-isobutylene-styrene copolymer, acid anhydride group concentration: 0.464 mmol/g, number-average molecular weight: 35,800), and “T-YP8930” (manufactured by SEIKO PMC CORPORATION, glycidyl methacrylate-modified styrene-isobutylene-styrene copoly mer, concentration of epoxy group: 0.638 mmol/g, number average molecular weight: 48,700).

Specific examples of the polyethylene type resin or the polypropylene type resin may include "EPT X-3012P" (manufactured by Mitsui Chemicals, Inc., ethylene-propylene-5-ethylidene-2-norbornene copolymer), "EPT1070" (manufactured by Mitsui Chemicals, Inc., ethylene-propylene-dicyclopentadiene copolymer) and "TAFMER A4085" (manufactured by Mitsui Chemicals, Inc., ethylene-butene copolymer).

Specific examples of propylene-butene type copolymers may be: "T-YP341" (manufactured by SEIKO PMC CORPORATION, glycidyl methacrylate-modified propylene-butene random copolymer, amount of butene units per 100% by mass of total amount of propylene units and butene units: 29% by mass; concentration of epoxy groups: 0.638 mmol/g; number-average molecular weight: 155,000); "T-YP279" (manufactured by SEIKO PMC CORPORATION, maleic anhydride-modified propylene-butene random copolymer, amount of butene units per 100% by mass of the total amount of propylene units and butene units: 36% by mass, concentration of acid anhydride group: 0.464 mmol/g , number average molecular weight: 35,000); "T-YP276" (manufactured by SEIKO PMC CORPORATION, glycidyl methacrylate-modified propylene-butene random copolymer, amount of butene units per 100% by mass of the total amounts of propylene units and butene units: 36% by mass, concentration of epoxy groups: 0.638 mmol/g, number average molecular weight: 57,000); "T-YP312" (manufactured by SEIKO PMC CORPORATION, maleic anhydride-modified propylene-butene random copolymer, amount of butene units per 100% by mass of propylene units and total butene units: 29% by mass, concentration of acid anhydride group: 0.464 mmol/g, number average molecular weight: 60,900); "T-YP313" (manufactured by SEIKO PMC CORPORATION, glycidyl methacrylate-modified propylene-butene random copolymer, amount of butene units per 100% by mass of the total amount of propylene units and butene units: 29% by mass, concentration of epoxy groups: 0.638 mmol/g, number average molecular weight: 155,000); "T-YP429" (manufactured by SEIKO PMC CORPORATION, maleic anhydride-modified ethylene-methyl methacrylate copolymer, amount of methyl methacrylate units per 100% by mass of the total ethylene and methyl methacrylate units: 32% by mass, concentration of acid anhydride groups: 0 .46 mmol/g, number average molecular weight: 2,300); "T-YP430" (manufactured by SEIKO PMC CORPORATION, maleic anhydride-modified ethylene-methyl methacrylate copolymer, amount of methyl methacrylate units per 100% by mass of the total ethylene units and methyl methacrylate units: 32% by mass, concentration of acid anhydride groups: 1.18 mmol/g, number average molecular weight: 4,500); “T-YP431” (manufactured by SEIKO PMC CORPORATION, glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer, concentration of epoxy groups: 0.64 mmol/g, number-average molecular weight: 2,400); and “T-YP432” (manufactured by SEIKO PMC CORPORATION, glycidyl 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, still more preferably 5,000 or more, still more preferably 10,000 or more, still more preferably 30,000 or more, and particularly preferably 50,000 or more. By using the thermoplastic resin having a number-average molecular weight in such a range, repelling during application of the sealant paint can be prevented, thereby effectively increasing the sealing part's ability to prevent moisture penetration and the mechanical strength of the sealing part. The number-average molecular weight of the thermoplastic resin is preferably 1,000,000 or less, more preferably 800,000 or less, still more preferably 700,000 or less, still more preferably 600,000 or less, still more preferably 500,000 or less, still more preferably 450,000 or less, and particularly preferably 400,000 or less. By using the thermoplastic resin having the number-average molecular weight in such a range, the applicability of the sealing varnish can be improved as well as the compatibility of the thermoplastic resin with other components.

The number average molecular weight can be measured in polystyrene equivalent by gel permeation chromatography (GPC). Specifically, the number-average molecular weight by GPC method can be measured using LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko K.K. as a column and toluene or the like as the mobile phase. The column temperature can be set to 40°C for the measurement. Results can be calculated using a calibration curve of standard polystyrene.

The weight-average molecular weight of the thermoplastic resin is usually more 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, and is preferably 1,000,000 or less, more preferably 800,000 or less, still more preferably 600,000 or less and more preferably 500,000 or less.

The weight average molecular weight can be measured in polystyrene equivalent by gel permeation chromatography (GPC). Specifically, the weight-average molecular weight by GPC method can be measured using LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko KK as a column and chloroform or the like can be determined as the mobile phase. The column temperature can be set to 40°C for the measurement. Results can be calculated using a calibration curve of standard polystyrene.

The thermoplastic resin preferably has amorphous properties. The amorphous property refers to a property of a resin that does not have a definite melting point. Specifically, the amorphous property means that no clear peak is observed when the melting point is measured by DSC (Differential Scanning Calorimetry). The use of the amorphous thermoplastic resin prevents the sealant paint from thickening, thereby improving the fluidity of the paint.

With respect to 100% by mass of the non-volatile component(s) of the sealant, 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 preferably 7% by mass -% or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more. When the amount of the thermoplastic resin is in the above range, it is possible to increase the ability of the sealant to effectively prevent permeation of moisture and improve the transparency of the sealant. Based on 100% by mass of the non-volatile component of the sealant, 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 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 the above range, it is possible to improve the coatability and compatibility of the sealant paint, thereby effectively increasing the ability of the sealant paint to prevent moisture permeation and improving the handleability of the sealant paint (e.g. reduced stickiness).

With respect to 100 parts by mass of the inorganic filler, the amount of the thermoplastic resin is preferably 10 parts by mass or more, more preferably 20 parts by mass or more and particularly preferably 30 parts by mass or more, and is preferably 300 parts by mass or less, more preferably 200 parts by mass or less and particularly preferably 150 parts by mass or less. In particular, when the thermoplastic resin contains the polyolefin-type resin having the acid anhydride group, the amount of the polyolefin-type resin having the acid anhydride group, based on 100 parts by mass of the inorganic filler, is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more, and is 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 the polyolefin-type resin having the epoxy group, the amount of the polyolefin-type resin having the epoxy group based on 100 parts by mass of the inorganic filler is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and particularly preferably 3 parts by mass or more , and is 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-calcined hydrotalcite, it is desirable that the mass ratio of the semi-calcined hydrotalcite to the thermoplastic resin satisfies the above requirements. In particular, when the thermoplastic resin is used in such amounts, the sealant can effectively prevent permeation of moisture and leakage of lead.

(6.2. tackifier)

An example of a component that can be included in the sealant in combination with the inorganic filler is a tackifier. The tackifier is a compound that, in combination with the thermoplastic resin, can improve the adhesive properties of the sealant and is also known as a "tackifier". The tackifier is suitable for the adhesive type sealants and hence is preferably used in combination with the thermoplastic resin. One type of the tackifier can be used alone, or two or more types thereof can be combined at any ratio.

Examples of the tackifier may include terpene resins, modified terpene resins (hydrogenated terpene resins, terpene-phenol copolymer resins, aromatic modified terpene resins, etc.), coumarone resins, indene resins and petroleum resins (aliphatic petroleum resins, hydrogenated hydrocarbon petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, dicyclopentadiene type petroleum resins and their hydrides, etc.).

Among the above examples, petroleum resins are preferred from the viewpoints of adhesiveness, moisture penetration preventing ability, transparency and the like of the sealant. Examples of the petroleum resins may include aliphatic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins and hydrogenated hydrocarbon petroleum resins. The aromatic petroleum resins, the aliphatic aromatic copolymer petroleum resins, the hydrogenated hydrocarbon petroleum resins, the dicyclopentadiene petroleum resins and their hydrides are preferred from the viewpoints of adhesiveness, moisture permeation preventing ability and compatibility. From the viewpoint of transparency, the hydrogenated hydrocarbon petroleum rosins and the dicyclopentadiene petroleum rosin hydrides are particularly preferred.

As the hydrogenated hydrocarbon petroleum resin, a hydrogenated aromatic petroleum resin can be used. In this case, the degree of hydrogenation 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 degree of hydrogenation in the above range makes it possible to produce products with reduced coloring and excellent transparency at a low production cost. The degree of hydrogenation can be determined from the ratio of ¹ H-NMR peak intensities of hydrogen in the aromatic ring before and after hydrogenation.

As the hydrogenated hydrocarbon petroleum resin, cyclohexane ring-containing hydrogenated petroleum resins and dicyclopentadiene type hydrogenated petroleum resins are particularly preferred.

Specific examples of petroleum resins are described below.

Examples of terpene resins are 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 resins are 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 resins are Clearon P series, Clearon M series and Clearon K series (all manufactured by Yasuhara Chemical Co., Ltd.).

Examples of terpene-phenol copolymer resins are YS Polyster 2000, Polyster U, Polyster T, Polyster S and Mighty Ace G (all manufactured by Yasuhara Chemical Co., Ltd.).

Examples of liquid resins are YS Resin LP and YS Resin CP (both manufactured by Yasuhara Chemical Co., Ltd.).

Examples of the hydrocarbon resins may be: T-REZ RB093, T-REZ RC100, T-REZ RC115, T-REZ RC093 and T-REZ RE100 (all manufactured by JXTG Energy Co.); and Petrotac 60, Petrotac 70, Petrotac 90, Petrotac 90HS, Petrotac 90V and Petrotac 100V (all manufactured by Tosoh Corporation).

Examples of the hydrogenated hydrocarbon petroleum resins may be: Escorez 5300 series and 5600 series (both manufactured by Exxon Mobil Corporation); T-REZ OP501, T-REZ PR801, T-REZ PR803, T-REZ HA085, T-REZ HA103, T-REZ HA105, T-REZ HA125, T-REZ HB103 and T-REZ HB125 (all hydrogenated dicyclopentadiene petroleum resins , manufactured by JXTG Energy Co.); Quintone 1325 and Quintone 1345 (both manufactured by ZEON Corporation); and I-MARV S-100, I-MARV S-110, I-MARV P-100, I-MARV P-125 and I-MARV P-140 (all hydrogenated dicyclopentadiene petroleum resins manufactured by Idemitsu Kosan Co, Ltd. ).

Examples of the aromatic petroleum resins may be: ENDEX155 (manufactured by Eastman Chemical Company); 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, and Neopolymer EP-140 (all manufactured by JXTG Energy Co.); and Petcoal LX, Petcoal 120, Petcoal 130 and Petcoal 140 (all manufactured by Tosoh Corporation).

Examples of the aliphatic aromatic copolymers are Quintone D100 (manufactured by ZEON Corporation), T-REZ RD104 and T-REZ PR802 (manufactured by JXTG Energy Co.).

Examples of the cyclohexane ring-containing hydrogenated petroleum resins are ARKON P-90, ARKON P-100, ARKON P-115, ARKON P-125, ARKON P-140, ARKON M-90, ARKON M-100, ARKON M-115, and ARKON M- 135 (all manufactured by Arakawa Chemical Industries, Ltd.).

Examples of cyclohexane ring-containing saturated hydrocarbon resins can be TFS13-030 (manufactured by Arakawa Chemical Industries, Ltd.).

Examples of colorless rosins are PINECRYSTAL ME-H, PINECRYSTAL ME-D, PINECRYSTAL ME-G, PINECRYSTAL KR-85, PINECRYSTAL KE-311, PINECRYSTAL KE-359, PINECRYSTAL D-6011, PINECRYSTAL PE-590, PINECRYSTAL KE-604 and PINECRYSTAL PR-580 (all manufactured by Arakawa Chemical Industries, Ltd.).

The number-average molecular weight of the tackifier is preferably 100 to 2,000, more preferably 700 to 1,500, and still 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 still more preferably 100°C to 150°C. The softening point can be measured by a ring and ball method according to JIS K2207. The use of the tackifier having such a softening point facilitates sealing using the sealing sheet containing the sealant and increases the heat resistance of the sealant.

The amount of the tackifier is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more based on the 100% by mass of the non-volatile component of the sealant. When the amount of the tackifier is in the above range, it is possible to effectively improve the adhesiveness of the sealant. Based on 100% by mass of the non-volatile component of the sealant, the amount of the tackifier is preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. When the amount of the tackifier is in the above range, it is possible to effectively improve the ability of the sealants to prevent moisture permeation.

(6.3. Crosslinking agents and crosslinking accelerators)

Examples of a component which can be contained in the sealant in combination with the inorganic filler are crosslinking agents and crosslinking accelerators. The crosslinking agent and the crosslinking accelerator can react with a reactive group contained in another component to form a crosslinked structure. For example, when the thermoplastic resin has the reactive group such as the acid anhydride group and the epoxy group, the crosslinking agent and the crosslinking accelerator can react with the reactive group to form the crosslinked structure. The crosslinking agent and crosslinking accelerator do not include the thermoplastic resin and tackifier described above. One type of the crosslinking agent and the crosslinking accelerator can be used alone, or two or more types of them can be used in combination at any ratio.

Examples of the crosslinking agent and the crosslinking accelerator may be amine type compounds, guanidine type compounds, imidazole type compounds, phosphonium type compounds and phenol type compounds.

Examples of the amine type compound may be: quaternary ammonium salts such as tetramethyl ammonium bromide and tetrabutyl ammonium bromide; Diazabicyclo compounds such as DBU (1,8-diazabicyclo[5.4.0]undecene-7), DBN (1,5-diazabicyclo[4.3.0]nonene-5), DBU phenol salt, DBU octylate, DBU p-toluenesulfonate, DBU formate and DBU phenol novolac resin salt; tertiary amine such as benzyldimethylamine, 2-(dimethylaminomethyl)phenol and 2,4,6-tris(diaminomethyl)phenol and their salts; and dimethyl urea compounds such as aromatic dimethyl urea, aliphatic dimethyl urea and aromatic dimethyl urea.

Examples of guanidine type compounds are dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethyl guanidine, tetramethylguanidine, 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-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide and 1-(o-tolyl) biguanide.

Examples of imidazole-type compounds are 1H-imidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5- bis(hydroxymethyl)imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-dodecylimidazole, 2-heptadecylimidazole and 1,2 -dimethyl-imidazole.

Examples of the phosphonium type compounds are triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate and butyltriphenylphosphonium thiocyanate.

Examples of the kinds of phenol type compounds may include MEH-7700, MEH-7810 and MEH-7851 (manufactured by Meiwa Chemical Co. Ltd.), NHN, CBN and GPH (manufactured by Nippon Kayaku Co., Ltd.), SN170 , SN180, SN190, SN475, SN485, SN495, SN375 and SN395 (manufactured by Tohto Kasei Co., Ltd.) and TD2090 (manufactured by DIC Corporation). Specific examples of the phenol type triazine skeleton-containing compound may be LA3018 (manufactured by DIC Corporation) in particular. Specific examples of triazine skeleton-containing phenol novolac compounds include LA7052, LA7054 and LA1356 (manufactured by DIC Corporation).

Examples of the crosslinking agent can be resins having a functional group capable of reacting with an acid anhydride group. Examples of the functional group which can react with an acid anhydride group are hydroxyl group, primary or secondary amino group, thiol group, epoxy group and oxetane group. The epoxy group is preferred. As the resin having the functional group capable of reacting with an acid anhydride group, for example, the resin described in International Publication No. 2017/057708 can be used.

Examples of the crosslinking agent can be resins having a functional group capable of reacting with an epoxy group. Examples of functional groups that can react with an epoxy group are a hydroxyl group, phenolic hydroxyl group, amino group, carboxy group and acid anhydride group. The acid anhydride group is preferred. Examples of the acid anhydride group may be a succinic anhydride-derived group, a maleic anhydride-derived group and a glutaric anhydride-derived group. For example, the resin described in International Publication No. 2017/057708 can be used as the resin having a functional group capable of reacting with an epoxy group.

When one of the hardeners described below is capable of reacting with the reactive group of the component contained in the sealant, the hardener can be used as a crosslinking agent or a crosslinking accelerator.

The amount of the crosslinking agent and the crosslinking accelerator is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and particularly preferably 0.02% by mass or more based on 100% by mass of the nonvolatile component of the sealant. When the amount of the crosslinking agent and the crosslinking accelerator is in the above range, the handleability of the sealant can be improved (e.g. reduced stickiness). The amount of the crosslinking agent and the crosslinking accelerator is preferably 5% by mass or less, and more preferably 2.5% by mass or less, based on 100% by mass of the nonvolatile component of the sealant. When the amount of the crosslinking agent and the crosslinking accelerator is in the aforesaid range, it is possible to effectively improve the ability of the sealant to prevent permeation of moisture.

(6.4. Other components suitable for adhesive sealant)

Among the components that can be contained in the sealant, an example of the component suitable for the adhesive sealant is a plasticizer. The plasticizer can improve flexibility and moldability of the sealant. The plasticizer is preferably a material that is liquid at room temperature (25°C). Examples of the plasticizers are mineral oils such as paraffinic process oils, naphthenic Process oils, liquid paraffin, polyethylene wax, polypropylene wax and petroleum jelly, vegetable oils such as castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, coconut oil and olive oil, and liquid poly-α-olefin compounds such as 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, and more preferably 1,000 to 3,000 from the viewpoint of adhesiveness. One type of plasticizer can be used alone, or two or more types can be combined at any ratio. The amount of the plasticizer is preferably 50% by mass or less based on 100% by mass of the non-volatile component in the sealant.

Among the components that can be contained in the sealant, examples of components suitable for the adhesive type sealants can be: resins (e.g., epoxy resins, urethane resins, acrylic resins, polyamide resins, etc.) other than the above ; organic fillers such as rubber particles, silicone powder, nylon powder and fluororesin powder; thickeners such as Orben and Benton; silicone, fluoro and polymeric defoamers or leveling agents; adhesives such as triazole compounds, thiazole compounds, triazine compounds and porphyrin compounds; and antioxidants. Moreover, the adhesive type sealant may contain a component, which will be described below as a component that can be contained in the thermosetting sealant.

[7. Explanation of the component suitable for a thermosetting sealant according to the first embodiment].

(7.1. Thermosetting resin as binder resin)

An example of a component that can be contained in the sealant in combination with the inorganic filler is a thermosetting resin. The thermosetting resin is preferably used as the binder resin for the thermosetting sealant. One type of the thermosetting resin can be used alone, or two or more types can be combined at an arbitrary ratio.

Examples of thermosetting resins are epoxy resins, cyanate ester resins, phenolic resins, bismaleimide triazine resins, polyimide resins, acrylic resins and vinyl benzyl resins. The epoxy resins are preferred. When combined with the inorganic filler containing one or more types selected from the group consisting of semi-calcined hydrotalcite and calcium oxide, the epoxy resins make it possible to obtain a sealant with excellent transparency.

The epoxy resin preferably has an average of two or more epoxy groups per molecule. Examples of the epoxy resins are hydrogenated epoxy resins (bisphenol A type hydrogenated epoxy resins, bisphenol F type hydrogenated epoxy resins, etc.), fluorine-containing epoxy resins, aliphatic chain epoxy resins, cyclic aliphatic epoxy resins, fluorine-containing epoxy resins, aliphatic chain epoxy resins, epoxy resins bisphenol A type epoxy resins, biphenyl type epoxy resins, biphenylaralkyl type epoxy resins, fluorene type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, bisphenol F type epoxy resins, phosphorus epoxy resins, bisphenol S type epoxy resins, aromatic epoxy resins glycidylamine type (e.g. tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyltoluidine, diglycidylaniline etc.), alicyclic epoxy resins, phenol novolac type epoxy resins, alkylphenol type epoxy resins, cresol novolac type epoxy resins, bisphenol A epoxy resins -Novolac type, epoxy resins with butadiene structures, diglycidyl etherified products from Bi sphenols, diglycidyl etherified products of naphthalene diols, diglycidyl etherified products of phenols, diglycidyl etherified products of alcohols, and alkyl-substituted forms of these epoxy resins.

The epoxy resin can be a liquid epoxy resin, a solid epoxy resin, or a combination of liquid and solid epoxy resins. The term "liquid epoxy resin" refers to an epoxy resin that is liquid at normal temperature (25°C) and normal pressure (1 atm). The term "solid epoxy resin" refers to an epoxy resin that is solid at normal temperature (25°C) and normal pressure (1 atm). From the viewpoint of coatability, workability, and adhesiveness, the liquid epoxy resin is preferably 10% by mass or more with respect to the entire epoxy resin. In view of the kneadability with inorganic fillers and the paint viscosity, the liquid epoxy resin is particularly preferably used in combination with the solid epoxy resin. 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, particularly preferably 1:1.5 to 1:0.

As the epoxy resins, hydrogenated epoxy resins, fluorine-containing epoxy resins, aliphatic chain type epoxy resins, cyclic aliphatic epoxy resins and alkylphenol type epoxy resins are preferred. Among these, the hydrogenated epoxy resins, the fluorine-containing epoxy resins, the aliphatic chain type epoxy resins and the cyclic aliphatic epoxy resins are preferred. The use of these epoxy resins improves the transparency of the sealant.

The term "hydrogenated epoxy resin" refers to an epoxy resin obtained by hydrogenating an epoxy resin containing aromatic rings. The degree of hydrogenation of the hydrogenated epoxy resin is preferably 50% or more, and more preferably 70% or more. As the hydrogenated epoxy resins, bisphenol A type hydrogenated epoxy resins and bisphenol F type hydrogenated epoxy resins are preferably used. Examples of the bisphenol A type hydrogenated epoxy resins may include bisphenol A type liquid hydrogenated epoxy resins (e.g. "YX8000" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 205), "Denacol EX-252" (manufactured by Nagase ChemteX Corporation; epoxy equivalent: about 213) and bisphenol A type solid hydrogenated epoxy resins (e.g., “YX8040” (manufactured by Mitsubishi Chemical Corporation; epoxy equivalent: about 1000)).

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

The term "aliphatic chain-type epoxy resin" refers to an epoxy resin having linear or branched alkyl chains or alkyl ether chains. Examples of the aliphatic chain type epoxy resins may include polyglycerol polyglycidyl ether (e.g., "Denacol EX-512" and "Denacol EX-521" manufactured by Nagase ChemteX Corporation), pentaerythritol polyglycidyl ether (e.g., "Denacol EX-411") by Nagase ChemteX Corporation), diglycerol polyglycidyl ether (e.g., "Denacol EX-421" manufactured by Nagase ChemteX Corporation), glycerol polyglycidyl ether (e.g., "Denacol EX-313" and "Denacol EX-314" manufactured by Nagase ChemteX Corporation), trimethylolpropane polyglycidyl ether (e.g. "Denacol EX-321" manufactured by Nagase ChemteX Corporation), neopentyl glycol diglycidyl ether (e.g. "Denacol EX-211" manufactured by Nagase ChemteX Corporation), 1,6-hexanediol diglycidyl ether ( e.g., "Denacol EX-212" manufactured by Nagase ChemteX Corporation), ethylene glycol diglycidyl ether (e.g. "Denacol EX-810" and "Denacol EX-811" manufactured by Nagase ChemteX Corporation), diethylene glycol diglycidyl ether (e.g. B. “Denacol EX-850” and “Denacol EX-851" manufactured by Nagase ChemteX Corporation), polyethylene glycol diglycidyl ether (e.g. e.g., "Denacol EX-821", "Denacol EX-830", "Denacol EX-832", "Denacol EX-841" and "Denacol EX-861" manufactured by Nagase ChemteX Corporation), propyrol glycol diglycidyl ether (e.g ., "Denacol EX-911" manufactured by Nagase ChemteX Corporation), and polypropyrene glycol diglycidyl ether (e.g. "Denacol EX-941", "Denacol EX-920" and "Denacol EX-931" manufactured by Nagase ChemteX Corporation) .

The term "cyclic aliphatic epoxy resin" refers to an epoxy resin having a cyclic aliphatic backbone (e.g., cycloalkane backbone) in its molecule. Examples of cyclic aliphatic epoxy resins are "EHPE-3150" manufactured by Daicel Corporation and "TOPR-300" manufactured by Nippon Steel Chemical & Material Co.

The term "alkylphenol-type epoxy resin" refers to an epoxy resin having a benzene ring skeleton having one or more alkyl groups and one or more hydroxy groups as substituents, where the hydroxy group(s) is/are converted to a glycidyl ether group(s). Examples of the alkylphenol type epoxy resins may be: "HP-820" manufactured by DIC Corporation, "YDC-1312" manufactured by Nippon Steel Chemical & Material Co.Ltd. and "EX-146" manufactured by Nagase ChemteX Corporation.

In one aspect, the thermosetting resin preferably contains an aromatic ring-containing epoxy resin. The aromatic ring-containing epoxy resin refers to an epoxy resin containing an aromatic ring in its molecule. When using an aromatic ring-containing epoxy resin, the reactivity of the sealant, the glass transition temperature of the sealant after curing, and/or the adhesiveness tend to be improved. Examples of aromatic ring-containing epoxy resins are alkylphenol type epoxy resins and fluorine-containing aromatic epoxy resins.

Examples of the aromatic ring-containing epoxy resins are bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, biphenylaralkyl type epoxy resins, fluorene type epoxy resins and fluorine-containing aromatic epoxy resins. Among these, bisphenol type epoxy resins and fluorine-containing aromatic epoxy resins are preferred, bisphenol type epoxy resins are more preferred, and bisphenol A type and bisphenol F type epoxy resins are even more preferred.

Examples of bisphenol A type epoxy resins are: “828EL”, “1001” and “1004AF” manufactured by Mitsubishi Chemical Corporation; "840" and "850-S" manufactured by DIC Corporation; and "YD-128" manufactured by Nippon Steel Chemical & Material Co, Ltd. An example of a mixture of bisphenol A type liquid epoxy resin and bisphenol F type liquid epoxy resin is "ZX-1059" (epoxy equivalent weight: about 165) manufactured by Nippon Steel Chemical & Material Co, Ltd.

Examples of bisphenol F type epoxy resins are "807" manufactured by Mitsubishi Chemical Corporation, "830" manufactured by DIC Corporation, and "YDF-170" manufactured by Nippon Steel Chemical & Material Co, Ltd.

Examples of phenol novolac type epoxy resins may be: "N-730A", "N-740", "N-770" and "N-775" manufactured by DIC Corporation; and "152" and "154" manufactured by Mitsubishi Chemical Corporation.

The term "biphenylaralkyl-type epoxy resin" refers to an epoxy resin having a backbone that has a novolac structure and a divalent biphenyl structure bonded to the novolac structure. Examples of biphenylaralkyl type epoxy resins may be "NC-3000", "NC-3000L" and "NC-3100" manufactured by Nippon Kayaku Co.

The term "fluorene-type epoxy resin" refers to an epoxy resin having a fluorene backbone. Examples of fluorene type epoxy resins are "OGSOL PG-100", "CG-500EG-200" and "EG-280" manufactured by Osaka Gas Chemicals Co, Ltd.

The term "fluorine-containing aromatic epoxy resin" refers to a fluorine-containing epoxy resin having an aromatic ring. Examples of the fluorine-containing aromatic epoxy resins can be fluorine-containing aromatic epoxy resins described in International Publication No. 2011/089947.

The aromatic ring-containing epoxy resins generally have high refractive indices. Therefore, with a view to improving the transparency of the sealant, by making the refractive indexes of the resin and the inorganic filler approach each other, the refractive index of the entire epoxy resin can be adjusted by combining the aromatic ring-containing epoxy resin with the epoxy resin having no aromatic ring structure. Examples of epoxy resins which do not contain aromatic ring structures and are suitable for combination with the aromatic ring-containing epoxy resins are hydrogenated epoxy resins, fluorine-containing epoxy resins, chain aliphatic-type epoxy resins and cyclic aliphatic epoxy resins. Among these, the hydrogenated epoxy resins, the fluorine-containing epoxy resins and the cyclic aliphatic epoxy resins are preferred. In addition, the bisphenol A type hydrogenated epoxy resins, the bisphenol F type hydrogenated epoxy resins and the fluorine-containing epoxy resins are preferred. The bisphenol A type hydrogenated epoxy resins and the bisphenol F type hydrogenated epoxy resins are more preferred. The bisphenol A type hydrogenated epoxy resins are particularly preferred. In this case, the amount of the aromatic ring-containing epoxy resin is preferably 0.5% to 40% by mass, more preferably 1% to 35% by mass, and further preferably 2% to 30% by mass, based on 100% by mass of the total of the aromatic ring-containing epoxy resin and the epoxy resin containing no aromatic ring structure.

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 from the viewpoint of reactivity. The term "epoxide equivalent" refers to the number of grams of resin containing one gram of epoxy group equivalent (g/eq), which can be measured by 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 still more preferably 400 to 1,500. The weight-average molecular weight of the thermosetting resin can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC).

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 or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and more preferably 85% by mass or less, based on 100% by mass of the non-volatile component of the sealant.

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

(7.2. Thermoplastic resin as binder resin)

The thermosetting sealant may contain a thermoplastic resin in combination with the thermosetting resin as a binder resin. When the binder resin contains a combination of thermosetting and thermoplastic resins, the flexibility of the sealants as well as the applicability of the sealant paint can be improved (reduction in repellency). One type of the thermoplastic resin can be used alone, or two or more types can be combined at any ratio.

Examples of thermoplastic resins may be phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamide-imide resins, polyethersulfone resins, polysulfone resins, polyester resins, and (meth)acrylic resins. 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-described thermoplastic resin suitable as the binder resin for the adhesive sealant can be used.

As the thermoplastic resin to be combined with the thermosetting resin, phenoxy resin is preferably used. Phenoxy resins have good compatibility with the thermosetting resins (especially epoxy resins). When phenoxy resin is used, it can effectively improve the sealant's ability to prevent moisture penetration. The phenoxy resin is preferably a phenoxy resin having one or more skeletons selected from a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenolacetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton and a norbornene skeleton.

Examples of commercially available phenoxy resins are YX7200B35 (manufactured by Mitsubishi Chemical Corporation: biphenyl skeleton-containing phenoxy resin), 1256 (manufactured by Mitsubishi Chemical Corporation: bisphenol A skeleton-containing phenoxy resin) and YX6954BH35 (manufactured by Mitsubishi Chemical Corporation: bisphenol-acetophenone skeleton-containing phenoxy resin).

The weight-average molecular weight range of the thermoplastic resin to be combined with the thermosetting resin may be the same as the weight-average molecular weight range of the thermoplastic resin described above as the binder resin for the adhesive sealant. The thermoplastic resin having such a weight-average molecular weight range can improve the flexibility of the sealant, the applicability of the sealant varnish (reduction of repellency), and the compatibility between the thermosetting resin and the thermoplastic resin. The weight-average molecular weight of the phenoxy resins is preferably 10,000 to 500,000, and more preferably 20,000 to 300,000. The method of measuring the weight-average molecular weight is 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, and is preferably 60% by mass or less, more preferably 50 % by mass or less, more preferably 25% by mass or less, and particularly preferably 15% by mass or less based on 100% by mass of the non-volatile component of the sealant.

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

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, and is preferably 80 parts by mass or less, more preferably 60 parts by mass or less and particularly preferably 40 parts by mass or less based on 100 parts by mass of the thermosetting resin.

(7.3. Hardeners and hardening accelerators)

An example of a component that can be contained in the sealant in combination with the inorganic filler is a hardener or a hardening agent. When used in combination with the thermosetting resin, the hardener has a function of reacting with the thermosetting resin to harden the sealant. From the viewpoint of preventing thermal degradation of electronic components during curing of the sealant, 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 the hardener can be used alone, or two or more types can be combined in any proportion.

The type of hardener can be selected according to the type of thermosetting resin. The hardeners compatible with the epoxy resin as the preferred thermosetting resin are described below. Examples of the esters compatible with epoxy resins are ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine compounds, dimethylurea compounds, amine adduct compounds, organic acid dihydrazide compounds, organic phosphine compounds, dicyandiamide compounds, and primary and secondary amine compounds. Among these, ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine compounds, dimethylurea compounds and amine adduct compounds are preferred. More preferred are ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine type compounds and dimethylurea compounds.

The sealant may contain a curing accelerator in combination with the curing agent. Only one type of the curing accelerator can be used, or two or more types thereof can be used in combination. The type of curing accelerator can be selected according to the type of thermosetting resin. The curing accelerator compatible with the epoxy resin as the preferred thermosetting resin is described below. Examples of curing accelerators compatible with epoxy resins are imidazole compounds, tertiary amine compounds, dimethylurea compounds and amine adduct compounds. Among these, imidazole compounds, tertiary amine compounds and dimethylurea compounds are preferred.

The ionic liquid as a curing agent is preferably an ionic liquid capable of curing the thermosetting resin (epoxy resin in particular) at a temperature of 140°C or lower (preferably 120°C or lower). In other words, the ionic liquid is preferably a salt that can melt in a temperature range of 140°C or lower (preferably 120°C or lower) and exerts the curing function on the thermosetting resins (epoxy resins in particular). The ionic liquid is preferably used to be uniformly dissolved in the thermosetting resin (epoxy resin in particular). In general, the ionic liquids can effectively improve the sealant's ability to prevent moisture penetration.

Examples of cations as components of the ionic liquid used as a curing accelerator may be: ammonium type cations such as imidazolium ion, piperidinium ion, pyrrolidinium ion, pyrazonium ion, guanidinium ion and pyridinium ion; phosphonium type cations such as tetraalkylphosphonium cations (e.g., tetrabutylphosphonium ion, tributylhexylphosphonium ion, etc.); and sulfonium type cations such as triethylsulfonium ion.

Examples of anions as components of the ionic liquids used as hardeners can be: halide anions such as fluoride, chloride, bromide and iodide ions; alkylsulfonate type anions such as methanesulfonate ion; anions of fluorine-containing compounds such as trifluoromethanesulfonate ion, hexafluorophosphate ion, trifluorotris(pentafluoroethyl)phosphate ion, bis(trifluoromethanesulfonyl)imide ion, trifluoroacetate ion and tetrafluoroborate ion; phenol type anions such as phenol ion, 2-methoxyphenol ion and 2,6-di-tert-butylphenol ion; acidic amino acid ions such as aspartate and glutamate; neutral amino acid ions such as glycine ion, alanine ion and phenylalanine ion; N-acylamino acid ions represented by the following formula (A), such as N-benzoylalanine ion, N-acetylphenylalanine ion and N-acetylglycine ion; and carboxylic acid type anions such as formate ion, acetate ion, decano ion, 2-pyrrolidone-5-carbonate ion, α-lipoion, lactation, tartration, hippuration, N-methylhippuration ion and benzoate ion.
[Formula 1]

In the formula (A), R ^A 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 the amino acid. Examples of the amino acid in the formula (A) can be aspartic acid, glutamic acid , glycine, alanine and phenylalanine. Among these, glycine is preferred.

Among the above, the cation is preferably an ammonium type cation and a phosphonium type cation, and more preferably an imidazolium ion and a phosphonium ion. Examples of the imidazolium ion are 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion and 1-propyl-3-methylimidazolium ion.

The anion is preferably a phenol type anion, the N-acylamino acid ion represented by formula (A) or a carboxylic acid type anion, and more preferably an N-acylamino acid ion or a carboxylic acid type anion.

A specific example may be the phenol type anion 2,6-di-tert-butylphenol ion.

Specific examples of the carboxylic acid type anion include acetate ion, decano ion, 2-pyrrolidone-5-carboxyl ion, formate ion, α-lipo ion, lactate ion, tartrate ion, hippurate ion and N-methylhippurate ion. Among these, acetate ion, 2-pyrrolidone-5-carboxylation, formation, lactation, tartration, hippuration and N-methylhippuration are preferred. The acetate ion, decano ion, N-methylhippuration and formation ion are more preferred.

Specific examples of the N-acylamino acid ion of the formula (A) may be N-benzoylalanine ion, N-acetylphenylalanine ion, aspartate ion, glycine ion and N-acetylglycine ion. Among these, N-benzoylalanine ion, N-acetylphenylalanine ion and N-acetylglycine ion are preferred. N-acetylglycine ion is more preferred.

Preferred examples of the ionic liquids are 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium trifluoroacetate, tetrabutylphosphonium α-lipoate, tetrabutylphosphonium formate, tetrabutylphosphonium lactate, bis(tetrabutylphosphonium) tartrate, tetrabutylphosphonium hippurate, tetrabutylphosphonium -N-methylhippurate, benzoyl-DL-alanine tetrabutylphosphonium salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2,6-di-tert-butylphenol tetrabutylphosphonium salt, L-aspartate mono-tetrabutylphosphonium salt, glycine tetrabutylphosphonium salt, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl -3-methylimidazolium lactate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium hippurate, 1-ethyl-3-methylimidazolium N-methylhippurate , bis(1-ethyl-3-methylimidazolium) tartrate and N-acetylglycine-1-ethyl-3-methylimidazolium salt. More preferred examples of ionic liquids are tetrabutylphosphonium decanoate, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium hippurate and 1-ethyl-3-methylimidazolium-N-methylhippurate.

An example of a method for synthesizing the ionic liquids is an anion exchange method in which NaBF ₄ , NaPF ₆ , CF ₃ SO ₃ Na, LiN(SO ₂ CF ₃ ) ₂ or the like is reacted with a precursor consisting of a cation part, such as alkylimidazolium, alkylpyridinium, alkylammonium and alkylsulfonium ions, and an anionic portion containing a halogen. Another example of the synthesis method of the ionic liquid is the acid ester method in which an amine substance is reacted with an acid ester to introduce an alkyl group with an organic acid residue acting as a counter anion. Another example of the ionic liquid synthesis method is a neutralization method in which amines are neutralized with an organic acid to obtain a salt. at In the neutralization method using the anion, the cation and the solvent, equal amounts of the anion and the cation are used to obtain a reaction solution. After the solvent is evaporated from the solution, the resulting product can be used as is. Alternatively, the resulting reaction solution can be mixed with an organic solvent (methanol, toluene, ethyl acetate, acetone, etc.) and then concentrated for use.

Examples of the acid anhydride compound as the curing agent may be tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride and dodecenylsuccinic anhydride. Specific examples of acid anhydride compounds are RIKACID TH, TH-1A, HH, MH, MH-700 and MH-700G (all manufactured by New Japan Chemical Co., Ltd.).

Examples of the imidazole compound as a curing agent or curing accelerator may include 1H-imidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-undecylimidazole , 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6-(2'-undecylimidazolyl-(1'))-ethyl-s-triazine, 2-phenyl-4,5 -bis(hydroxymethyl)imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenylimidazole, 2-dodecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2'-methylimidazolyl-(1'))ethyl-s-triazine and 2,4-diamino-6-(2'-methylimidazolyl-(1') '))-ethyl-s-triazine-isocyanuric acid adducts. Specific examples of imidazole compounds are CUREZOL 2MZ, 2P4MZ, 2E4MZ, 2E4MZ-CN, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2PHZ, 1B2MZ, 1B2PZ, 2PZ, C17Z, 1.2DMZ, 2P4MHZ-PW, 2MZ-A and 2MA-OK (all manufactured by Shikoku Chemicals Corporation).

Specific examples of the tertiary amine compound type compound as a curing agent or curing accelerator may include DBN (1,5-diazabicyclo[4.3.0]non-5-ene), DBU (1,8-diazabicyclo[5.4.0]undec-7-ene ), organic acid salts of DBU such as 2-ethylhexanoate of DBU, phenolate salt of DBU, p-toluenesulfonate of DBU, U-CAT SA 102 (manufactured by San-Apro Ltd.: octanoate of DBU) and formate of DBU and tris(dimethylaminomethyl) phenol (TAP).

Specific examples of the dimethyl urea compound as a curing agent or curing accelerator may be: aromatic dimethyl urea such as DCMU (3-(3,4-dichlorophenyl)-1,1-dimethyl urea) and U-CAT3512T (manufactured by San-Apro Ltd.); and aliphatic dimethylurea such as U-CAT3503N (manufactured by San-Apro Ltd.). Among these, the aromatic dimethyl urea is preferred in terms of curability.

Examples of the amine adduct compound as a curing agent or curing accelerator may be epoxy adduct compounds obtained by stopping addition reaction of tertiary amine to epoxy resin. Specific examples of the amine adduct compound may 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 and Amicure PN-40J (all manufactured by Ajinomoto Fine-Techno Co., Inc.).

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

Examples of the organic phosphine compound as a curing agent or curing accelerator may be triphenylphosphine, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tritert-butylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and triphenylphosphine triphenylborane. Specific examples of the organic phosphine compound are TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN and TPP-S (manufactured by Hokko Chemical Industry Co., Ltd.).

An example of the dicyandiamide compound as a hardener is dicyandiamide. Specific examples of the dicyandiamide compound may be DICY7 and DICY15 (both manufactured by Mitsubishi Chemical Corporation), which are pulverized products of dicyandiamide.

Examples of the primary and secondary amine compounds as curing agents can be: aliphatic amines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, dipropyrenediamine, diethylaminopropylamine, bis(4-aminocyclohexyl)methane, norbornenediamine and 1,2 -diaminocyclohexane; alicyclic amines such as N-aminoethylpiverazine and 1,4-bis(3-aminopropyl)piperazine; and aromatic amines such as diaminodiphenylamine than, m-phenylenediamine, m-xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and diethyltoluenediamine. Specific examples of primary and secondary amine compounds may be Kayahard AA (Nippon Kayaku Co., Ltd.: 4,4'-diamino-3,3'-dimethyldiphenylmethane).

When any of the above crosslinking agent and crosslinking accelerator is capable of reacting with the thermosetting resin to cure the sealant, the crosslinking agent and crosslinking accelerator can be used as the curing agent.

The hardener and the hardening accelerator are preferably used in combination. Preferable combinations of the curing agent and the curing accelerator may include two or more types selected from ionic liquids, acid anhydride compounds, imidazole compounds, tertiary amine type compounds, dimethylurea compounds and amine adduct compounds.

The amount of the hardener is preferably 0.1% by mass to 40% by mass, more preferably 0.5% by mass to 38% by mass, and still more preferably 1% by mass to 35% by mass based on 100% by mass of the non-volatile component of the sealant. When the amount of the curing agent is equal to or more than the lower limit of the above range, there is a possibility that curing of the sealant proceeds sufficiently. When the amount of the curing agent is equal to or smaller than the upper limit of the above range, the storage stability of the sealant can be improved. Specifically, 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 the 100% by mass of the nonvolatile component of the sealant. When the amount of the ionic liquid is in the above range, the ability of the sealant to effectively prevent permeation of moisture can be increased.

The amount of the curing accelerator is preferably from 0.05% to 10% by mass, more preferably from 0.1% to 8% by mass, and still more preferably from 0.5% to 5% by mass, based on 100% by mass. % of the non-volatile component of the sealant. If the amount of the curing accelerator is equal to or more than the lower limit of the above range, the curing of the sealant may progress rapidly. When the amount of the curing accelerator is equal to or less than the upper limit of the above range, the storage stability of the sealant can be improved.

(7.4. Other components suitable for thermosetting sealant)

Among the components that can be included in the sealant, an example of a component suitable for the thermosetting sealant is a coupling agent. When the sealant is contained, the sealant prevents the aggregation of the inorganic filler and thus increases the surface area of the inorganic filler, so that the inorganic filler easily exhibits the lead adsorption ability and hygroscopicity. One type of the coupling agent can be used alone, or two or more types thereof can be combined at any ratio.

Examples of the coupling agent may be silane coupling agent, aluminate coupling agent and titanate coupling agent.

Examples of silane coupling agents may be: epoxy type silane coupling agents such as 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; mercapto-type silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane; Amino type silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl). )-3-aminopropyldimethoxymethylsilane; ureido-type silane coupling agents such as 3-ureidopropyltriethoxysilane; vinyl type silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; styryl type silane coupling agents such as p-styryltrimethoxysilane; acrylate type silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; isocyanate type silane coupling agents such as 3-isocyanatopropyltrimethoxysilane; sulfide-type silane coupling agents such as bis(triethoxysilylpropyl) disulfide and bis(triethoxysilylpropyl) tetrasulfide; and phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane and triazinesilane. Among these, the vinyl type silane coupling agents and the epoxy type silane coupling agents are preferred, and the epoxy type silane coupling agents are particularly preferred.

Examples of the aluminate coupling agent may be alkyl acetoacetate aluminum diisopropylate (e.g. "PLENACT AL-M" manufactured by Ajinomoto Fine Techno Co., Ltd.).

Specific examples of the titanate coupling agent may be 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 Co., Ltd.). .

The amount of the coupling agent is preferably 0% by mass to 15% by mass, and more preferably 0.5% by mass to 10% by mass, based on 100% by mass of the nonvolatile component of the sealant.

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

Among the components that can be contained in the sealant, examples of a component suitable for the thermosetting sealants are: organic fillers such as rubber particles, silicone powder, nylon powder and fluororesin powder, thickeners such as Orben and Benton, silicone, fluoro and polymeric defoaming or leveling agents and coupling agents such as triazole compounds, thiazole compounds, triazine compounds and porphyrin compounds. Furthermore, the thermosetting sealant may contain the components described above, which may also be contained in the adhesive-type sealant.

[8th. Transparency of the sealant according to the first embodiment]

The sealant according to the first embodiment of the present invention preferably has high transparency. The transparency of the sealant can be expressed in terms of parallel transmission with respect to D65 light. In particular, the parallel transmission of a 20 µm thick layer of the sealant is preferably 80% to 100%, and more preferably 85% to 100%. The parallel transmittance of the sealant can be calculated by forming a multilayer body containing the sealant on a glass plate and using air as a reference. Specifically, the parallel transmission can be measured by the following method.

A sealing foil or web is produced which has a 20 μm thick layer of the sealing agent. The sealing sheet is cut into a length of 70 mm and a width of 25 mm, and then using a batch vacuum laminator (V-160, manufactured by Nichigo-Morton Co., Ltd.) onto a glass plate (microslide glass with a length of 76 mm, a width of 26 mm and a thickness of 1.2 mm, white slide glass S1112 Edge Polishing No. 2 manufactured by Matsunami Glass Ind., Ltd.) to obtain the multi-layered body. The laminating conditions are as follows: decompression at a temperature of 80°C for 30 seconds and then pressurization at a pressure of 0.3 MPa for 30 seconds. In the case of the thermosetting sealant, the multi-layered body is heated in a thermal cycle oven at 100°C for 60 minutes to obtain a sample. The parallel transmittance (%) of the sample is measured with a turbidity meter HZ-V3 (halogen lamp) manufactured by Suga Test Instruments Co., Ltd. measured at D65 light with air as reference.

[9. sealant according to second embodiment]

The sealant according to the second aspect of the present invention contains the binder resin and the inorganic filler containing one or more types selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide. With the semi-calcined hydrotalcite, the calcined hydrotalcite and the calcium oxide capable of exhibiting excellent lead receptivity and hygroscopicity in the sealant, the sealant can prevent the penetration of moisture to the lead-containing part and can prevent lead leaks out of the lead-containing portion from the electronic component when used to seal the component having the lead-containing portion.

The sealant according to the second aspect of the present invention may or may not have the lead adsorption parameter and the moisture ingress barrier parameter in the ranges described above. Also, the sealant according to the second embodiment of the present invention contains one or more types of the inorganic fillers selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide. Except for the above points, the sealant according to the second embodiment of the present invention can have the same composition and properties as the sealant according to the first embodiment, thereby providing the same advantages as the sealant according to the first embodiment.

[10. Process for making the sealant]

There are no restrictions on the manufacturing process of the sealant. The sealant can be prepared by mixing the mixture ingredients with a mixing device such as a kneading roller and a rotary mixer. In this mixing process, a solvent can also be mixed with the mixture components.

[11. use of the sealant]

When used in sealing applications, the sealant can prevent moisture ingress and lead leakage. Therefore, it is preferably used for sealing electronic components that have a lead-containing part. The types of such electronic parts are not limited. Examples of electronic parts can be: solar cells such as perovskite type solar cells, secondary batteries such as lead-acid batteries, and electronic components containing lead solder.

[12. Sealing foil or web (sheet)]

(12.1. Composition of the sealing foil)

The sealing sheet according to an embodiment of the present invention comprises a support and a layer of the sealant formed on the support. The layer of sealant is a layer formed from the sealant, thus containing the sealant described above. Such a sealing sheet may be layered so that the layer of the sealant is in contact with the object to be sealed, thereby achieving the sealing of the object to be sealed with the sealant. In general, the layering is performed so that the object to be sealed comes in direct contact with the sealant layer. The "direct" contact between two elements means that there is no other element between the two elements.

The thickness of the sealant layer can be determined depending on the object to be sealed. The precise 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. If the thickness of the sealant layer is equal to or thicker than the lower limit of the aforesaid range, it is possible to reduce the damage caused by coating the sealing sheet on the object to be sealed and the uniformity of the thickness of the after coating the sealant than Layer to improve sealing part obtained. When the thickness of the sealant layer is equal to or thinner than the upper limit of the above range, it is possible to effectively prevent moisture from entering the electronic device. For example, in a perovskite-type solar cell comprising a first substrate and a second substrate with the thin sealing part as a layer of the sealant, it is possible to use the area at a side part where the sealing part is in contact with the outside air , which can effectively prevent the ingress of moisture (see 4 below).

A foil made of a suitable material is generally used as the carrier. Examples of the support may be: plastic films made of polyolefins such as polyethylene, polypropylene and polyvinyl chloride, cycloolefin polymers, polyesters such as polyethylene terephthalate (hereinafter referred to as "PET") and polyethylene naphthalate, polycarbonates or polyimides, and metal foils such as aluminum foil, stainless steel foil and copper foil. A composite film in which the metal foil and the plastic film are laminated can be used as the support.

The support may contain a barrier layer from the viewpoint of improving resistance to moisture permeation. Especially when the support contains the plastic film, it is preferred to use a support with a suitable barrier layer in combination with the plastic film. An example of a barrier layer material is an inorganic material. Examples of inorganic materials are: nitrides such as silicon nitride and SiCN, oxides such as silicon oxide and aluminum oxide, amorphous silicon and metals such as stainless steel and aluminum. The barrier layer can e.g. B. be formed by vapor deposition of the above material.

The support may be subjected to a surface treatment. Examples of the surface treatment may be frosting, corona treatment, and mold release treatment. Examples of the releasing treatment may be a releasing treatment with a releasing agent such as a silicone resin-based releasing agent, an alkyd resin-based releasing agent and a fluororesin-based releasing agent.

Specific examples of the support may include "AL1N30 with PET" manufactured by Toyo Tokai Aluminum Hanbai Co, "AL3025 with PET" manufactured by Fukuda Metal Foil & Powder Co, and "Alpet" manufactured by Panac Co as commercial polyethylene terephthalate film products be with aluminum foil. Other specific examples of the carrier may include TECHBARRIER HX, AX, LX and L series (manufactured by Mitsubishi Plastics, Inc.) and X-BARRIER (manufactured by Mitsubishi Plastics, Inc.) having a higher moisture-proof effect than those TECHBARRIER HX, AX, LX and L series.

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

The sealing film may include a protective film as needed. For example, in the sealing sheet including the support, the sealant layer, and the protective sheet in this order, the sealant layer can be protected with the protective sheet. Protection with the protective film can prevent dust from adhering to the surface of the sealant layer and reduce scratches thereon.

For example, the same plastic film can be used as the protective film as for the carrier. The protective film can be subjected to a surface treatment corresponding to that of the carrier. The thickness of the protective film is not particularly limited, but may be usually 1 µm or more, preferably 10 µm or more, and may be usually 150 µm or less, preferably 100 µm or less, more preferably 40 µm or less, and still more preferably be 30 µm or less.

(12.2. Manufacturing process for sealing film)

The sealing sheet can be manufactured by a manufacturing process involving the formation of the sealant layer on the substrate. The layer of sealant can be formed by a method known e.g. B. the preparation of the paint containing the sealant and solvent, the application of the paint to the substrate and the drying of the applied paint comprises.

As the solvent, an organic solvent is generally used. Examples of the organic solvent may be: ketone solvents such as acetone, methyl ethyl ketone (hereinafter referred to as “MEK”) and cyclohexanone; acetate ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; and aromatic mixed solvents such as solvent naphtha. Examples of aromatic mixed solvents are “Swasol” (manufactured by Maruzen Petrochemical Co., product name) and “IPSOL” (manufactured by Idemitsu Kosan Co., product name). One kind of the solvent may be used alone, or two or more kinds thereof may be used in combination at any ratio.

The paint can z. B. be dried by heating, hot air blowing, etc. The drying conditions are not particularly limited. The temperature can e.g. B. be set to 50 ° C to 100 ° C. The drying time is preferably 1 minute or more, more preferably 3 minutes or more, and is preferably 60 minutes or less, more preferably 15 minutes or less. The layer of sealant can be formed on the substrate by applying the paint to the substrate and then drying the applied paint to remove the solvent.

The method of manufacturing the sealing sheet may include heating the sealant layer as needed. The heating can support the reaction of reactive groups in the sealant, so that reactions such as crosslinking and polymerization reactions can proceed to the extent that the Hardness of the sealant layer is increased. Heating is preferred when the adhesive sealant is used. The above heating is particularly preferable in the use of adhesive sealants containing the polyolefin type resin having reactive groups such as acid anhydride group and epoxy group. By heating before sealing, thermal decomposition of the components contained in the object to be sealed can be avoided. There are no restrictions on the heating conditions. The heating temperature is preferably 50 to 200°C, more preferably 100 to 180°C, still more preferably 120 to 160°C. The heating time is preferably 15 minutes to 120 minutes, more preferably 30 minutes to 100 minutes.

The method of manufacturing the sealing sheet may include providing the protective sheet as needed. The protective film can B. be provided by adhering the protective film to the sealant layer. In the case of heating the sealant layer, the protective film may be provided before or after the sealant layer is heated.

(12.3. Use of the sealing foil)

The sealing sheet can be used for sealing objects such as the lead-containing part as well as the electrode to be sealed. The sealing method using the sealing sheet generally includes laminating the sealant layer of the sealing sheet onto the object to be sealed. When the sealing sheet includes the protective sheet, the layering described above is generally performed after removing the protective sheet. The layering process can be carried out batchwise or as a continuous process using a roller.

Usually, in the above coating, the sealant layer and the support are provided in this order on the object to be sealed. Therefore, after coating with the layer of the sealant and the carrier, the object to be sealed can be covered. The sealing method using the sealing sheet can be performed without removing the substrate, so that a state in which the object to be sealed is covered with the layer of the sealant and the substrate is obtained. In this state, the object to be sealed is sealed not only with the sealant layer but also with the substrate, whereby permeation of moisture can be effectively inhibited. For example, in the case of using the sealing sheet with a support having high resistance to moisture permeation, such as the support having the barrier layer and the support having a metal foil, it is preferable to seal with the layer of the sealant and the support as described above.

For example, in the sealing method with the sealing sheet, the support may be removed after the above coating to achieve a state where the object to be sealed is covered with the sealing sheet. In this state, the sealing layer that seals the object to be sealed can effectively prevent moisture intrusion. For example, if the sealing sheet contains a substrate with low resistance to moisture transmission, such as e.g. B. the carrier without a barrier layer and the carrier without metal foil, it is preferred to seal with the sealant layer described above.

The sealing method using the sealing film can, for. B. also include the provision of a sealing substrate. In particular, when the carrier is removed as described above, it is preferable to provide an appropriate sealing substrate on the surface of the layer of the sealant exposed by the removal of the carrier. The sealing substrate can be the same foil as the carrier described above or a rigid plate such as e.g. B. a glass plate, a metal plate or a steel plate can be used. The intended sealing substrate can effectively inhibit the intrusion of moisture.

The sealing method using the sealing sheet may include, for example, curing the sealant layer after lamination. In general, the sealant layer is heated to promote reactions such as crosslinking and polymerization reactions of reactive groups in the sealant and to thermally cure the sealant layer. Thereby, the adhesiveness between the sealant and the object to be sealed and the mechanical strength of the sealant layer can be improved, thereby increasing the sealing ability of the sealant. Therefore, the penetration of water and the leakage of lead can be suppressed particularly effectively. Such thermal curing after lamination is suitable when a thermosetting sealant is used.

During the thermal curing described above, the sealant layer is typically heated with a suitable heat treatment device. Examples of heat treatment devices are hot air ovens, infrared heaters, heat guns, and high frequency induction heaters. For example, a heating tool can be pressed onto the sealant layer to heat the sealant layer. From the viewpoint of improving the adhesiveness between the sealant layer and the object to be sealed, the curing temperature is preferably 50°C or higher, more preferably 55°C or higher, and particularly preferably 60°C or higher. Furthermore, the curing temperature is preferably 150° C. or lower, more preferably 100° C. or lower, and still more preferably 80° C. or lower, from the viewpoint of preventing thermal degradation of the components contained in the object to be sealed. The curing time is preferably 10 minutes or more, and more preferably 20 minutes or more.

In all of the sealing methods described above, sealing is achieved through the layer of sealant. Therefore, when the object to be sealed contains a lead-containing part, it is possible to inhibit not only the ingress of moisture into the lead-containing part but also the leakage of lead from the lead-containing part.

[13. electronic component]

An electronic component according to an embodiment of the present invention includes the lead-containing part and the sealing part that seals the lead-containing part. The sealing part contains the sealant described above. In this case, the sealing agent contained in the sealing part may be hardened. The gasket part containing this (fully)cured sealant is summarized by the term "sealant-containing gasket part". In such an electronic component, penetration of moisture into the lead-containing part can be prevented by the sealing part. Moreover, the leakage of lead from the lead-containing part outside the electronic component to the outside of the electronic equipment can be prevented by the sealing part.

The lead-containing part is the part containing lead atoms, which can include a wide range of parts depending on the type of electronic component. The electronic component is explained below using an example of a perovskite-type solar cell that includes a perovskite layer as a lead-containing part.

4 FIG. 4 is a schematic cross-sectional view of an example of the perovskite solar cell 400 according to an embodiment of the present invention. As in 4 For example, as shown, the perovskite-type solar cell 400 includes a first electrode 410, a perovskite layer 420 containing lead atoms, a second electrode 430, and a sealing portion 440 containing a sealant that can be hardened. In this solar cell 400, the perovskite layer 420 is provided between the first electrode 410 and the second electrode 430 so that the charges generated in the perovskite layer 420 functioning as a photoelectric conversion layer can be dissipated through the first electrode 410 and the second electrode 430 .

The first electrode 410 and the second electrode 430 are formed from electrically conductive materials. Although there is no limitation on the types of electrically conductive materials, one or both of the first electrode 410 and the second electrode 430 are preferably formed of transparent electrically conductive materials. Examples of such materials can be electrically conductive oxides such as ITO (indium tin oxide), SnO ₂ , AZO (aluminum zinc oxide), IZO (indium zinc oxide) and GZO (gallium zinc oxide) and a conductive polymer .

The perovskite layer 420 contains a perovskite compound and can generate charges when exposed to light. An example of the perovskite compound is a compound represented by the following formula (P): $${\text{A}}^{\text{P}}{}_{\text{k}}{\text{M}}^{\text{P}}{\text{X}}^{\text{P}}{}_{\left(\text{k+2}\right)}$$

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

In the formula (P), A ^p represents a monovalent organic molecule or an ion thereof. The monovalent organic molecules are not particularly limited. Examples of monovalent organic molecules are methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropyla min, tributylamine, tripentylamine, trihexylamine, ethylmethylamine, methylpropylamine, butylmethylamine, methylpentylamine, hexylmethylamine, ethylpropylamine, ethylbutylamine, imidazole, azole, pyrrole, aziridine, azirine, azetidine, aceto, azole, imidazoline and carbazole. Examples of ions of the monovalent organic molecules can be methyl ammonium (CH ₃ NH ₃ ) and phenethyl ammonium. Among these, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and ions thereof, and phenethylammonium are preferred. More preferred are methylamine, ethylamine, propylamine and their ions.

In the formula (P), M ^p represents a divalent metal atom. M ^p preferably contains lead as the divalent metal atom. M ^p may also contain a metal atom other than lead in combination with lead. Examples of metal atoms other than lead are tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum and europium. One kind of these metal atoms can be used alone, and two or more kinds of them can be used in combination.

In the formula (P), XP represents a halogen atom or a chalcogen atom. The halogen atom is not particularly limited and may be, for example, chlorine, bromine, iodine and sulfur. The chalcogen atom is not particularly limited and may be selenium. One of these species can be used alone, and two or more species can be used in combination.

Specific examples of the above perovskite compounds can be perovskite compounds disclosed in International Publication No. 2014/045021 , Japanese Patent Application Laid-Open No. 2014-49596 and Japanese Patent Application Laid-Open No. 2016-82003 are described.

Among the above, the perovskite compound is preferably a compound containing one or more lead atoms such as CH ₃ NH ₃ PbI ₃ . One type of the perovskite compound can be used alone, or two or more types thereof can be combined at any ratio. The perovskite layer 420 may include an optional component such as an oxide semiconductor in combination with the perovskite compound.

The sealing part 440 is provided to seal the perovskite layer 420 . Therefore, a part or the whole surface of the perovskite layer 420 is covered with the sealing part 440 .
The surface of the perovskite layer 420 is not exposed. For explanation, reference is made to an in 4 Illustrated example is referred to, in which the 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 member 440. Such a perovskite layer is sealed with the sealing part 440 between the outside air and the perovskite layer 420 . Therefore, moisture in the outside air can be prevented from entering the perovskite layer 420 . In addition, the lead contained in the perovskite layer 420 can be prevented from leaking outside the solar cell 400 . In general, not only the perovskite layer 420 but also the first electrode 410 and the second electrode 430 are sealed with the sealing part 440 in order to achieve protection from water.

Preferably, the solar cell 400 also includes a first substrate 450 and a second substrate 460. Generally, one of the first substrate 450 and the second substrate 460 is used as a support substrate to support the solar cell 400 or its intermediate manufacturing product during manufacture and use. The other of the first substrate 450 and the second substrate 460 is generally used as a sealing substrate to largely seal the main surface of the solar cell 400 . The first electrode 410 , the perovskite layer 420 and the second electrode 430 are generally provided in the space between the first substrate 450 and the second substrate 460 . Therefore, as in 4 As illustrated, the sealing part 440 may be provided so that the space between the first substrate 450 and the second substrate 460 is filled, thereby forming the first electrode 410, the perovskite layer 420, the second electrode 430 and other elements between the first substrate 450 and the second substrate 460 are provided with which the sealing part 440 can be sealed.

In general, the first substrate 450 and the second substrate 460 are formed of materials through which moisture does not easily permeate, or have a large thickness, which greatly hinders permeation of moisture. Therefore, in the solar cell 400 according to the above example, the penetration path of moisture leading to the perovskite layer 420 can be restricted to the in-plane penetration path A4 through a side part 440S of the sealing part 440 . The one described above Sealing agent has the effect, in particular, of inhibiting or preventing the penetration of moisture into such a penetration path A4. Therefore, when used to seal the perovskite layer 420 between the first substrate 450 and the second substrate 460, the above-described sealant can exhibit particularly remarkable effects such as prevention of moisture penetration and lead leakage.

The perovskite type solar cell 400 can be realized with further modifications. For example, the perovskite-type solar cell 400 can have an optional layer between the first electrode 410 and the perovskite layer 420 . For example, the perovskite-type solar cell 400 can have an optional layer between the perovskite layer 420 and the second electrode 430 . Examples of optional layers can be an electron transport layer and a hole transport layer.

There are no restrictions on the manufacturing methods for the electronic components. For example, they can be manufactured by a method involving formation of the lead-containing layer and formation of the sealing member that seals the lead-containing layer. The sealing part can be formed as a sealant layer covering the lead-containing part by laminating using the sealing sheet, for example. In a specific example, the perovskite-type solar cell 400 including the sealing portion 440 as a sealant layer can be manufactured by a method that includes the formation of the first electrode 410, the perovskite layer 420, and the second electrode 430 on the first substrate 450 and then laminating the sealant layer of the sealing foil (not shown) to partially or completely cover the first electrode 410, the perovskite layer 420 and the second electrode 430. In this case, the substrate of the sealing sheet can be used as the second substrate 460 . After the sealing film carrier is removed, another second substrate 460 may be provided on the sealing portion 440 .

[Examples]

The invention is explained in more detail below using examples. However, the present invention is not limited by the following examples. In the following examples, "part" and "%" represent "part by mass" and "% by mass" unless otherwise specified.

[Evaluation Methods]

[Evaluation Method for Lead Adsorption Ability of Sealants]

10 µl of a lead standard solution was added to 500 ml of water and purified to prepare a lead ion-containing aqueous solution having a lead concentration of 20 µg/l at a water temperature of 20°C to 25°C.

A sealing sheet prepared in Examples and Comparative Examples was cut into 16 cm in length and 24 cm in width to obtain a first test sheet. On a sealant layer side of the first test sheet, a bolting cloth (nylon) mesh 40 NB-40, manufactured by As One Corporation) was adhered. Then, the first test film was cut into small pieces of 1 cm square, placed in 50 ml of the lead ion-containing aqueous solution, and then stirred with a high-speed rotary mixer (Thinky mixier ARE-310, rotary speed 2000 rpm) for 15 minutes (test for evaluation of lead adsorption ability). In Examples 5 and 6 and Comparative Example 4 relating to a thermosetting sealant, the sealant was thermally cured at 100°C for 60 minutes after the mesh was adhered. Then the first test film was cut into small pieces. The lead ion concentration M1 of the lead ion-containing aqueous solution obtained after stirring was measured.

The lead ion concentration M1 of the lead ion-containing aqueous solution obtained after immersing the first test sheet was subtracted from the lead ion concentration of 20 µg/L of the lead ion-containing aqueous solution obtained before immersing the first test sheet by the amount of change in to obtain lead ion concentration. This amount of change is multiplied by the volume of 50 ml of the lead ion-containing aqueous solution to calculate the lead adsorption amount. The calculated lead adsorption amount was divided by the area of 384 cm ² of the sealant layer contained in the first test sheet to calculate a mass X (µg/m ² ) of lead adsorbed per 1 m ² of the sealant layer. This mass X of adsorbed lead corresponds to the lead adsorption parameter. on based on the mass X of the adsorbed lead, the lead adsorption ability of the sealant was evaluated according to the following criteria.

(Criteria for the adsorption capacity of lead)

"Good": The mass X of the adsorbed lead is 10 g/m ² or more.

"Poor": The mass X of the adsorbed lead is less than 10 g/m ² .

The concentration of lead ions in the lead-containing aqueous solutions was measured by the following method.

5 ml of the lead ion-containing aqueous solution was placed in a test tube in a lead sensor pack (lead sensor pack, manufactured by Hach Company), and a reagent tablet (a measuring reagent supplied with the above lead sensor pack) was dissolved in the solution . Then, a test electrode was immersed in the aqueous solution containing lead ions, and the lead ion concentration was measured with a portable scanning lead analyzer (model name HSA-1000, manufactured by Hach Company).

[Method of Evaluation of Moisture Ingress Barrier Property of a Sealant]

As the base film, a composite film "AL1N30 with PET" (thickness of aluminum foil: 30 µm, thickness of polyethylene terephthalate film: 25 µm, manufactured by Toyo Tokai Aluminum Hanbai K.K.) comprising an aluminum foil and a polyethylene terephthalate film was prepared. The sealant layer was formed on the aluminum foil side surface of the base sheet in the same manner as the method for producing the sealing sheet in each of Examples and Comparative Examples except that the above base sheet was used instead of the base. This allows the production of a second test film containing the carrier film and the layer of sealant. The second test sheet thus obtained was dried under a nitrogen atmosphere to remove adsorbed water contained in the sealant layer. In Examples 1 to 4 and Comparative Examples 1 to 3 using the adhesive sealant, drying was carried out at 130°C for 60 minutes. In Examples 5 and 6 and Comparative Example 4 using the thermosetting sealant, drying was carried out at 100°C for 5 minutes.

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

Calcium was evaporated on one side of this glass plate using a mask covering a peripheral area at a distance of 0 mm to 2 mm from an edge of the glass plate. This enables the formation of a 200 nm thick calcium film (99.8% purity) on a central portion of one side of the glass plate excluding the peripheral area within 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 was adhered to the calcium film side surface of the above glass plate using a thermal laminator (manufactured by FUJIPLA, Lamipacker DAiSY A4 (LPD2325)) to obtain a multilayer body. In Examples 1 to 4 and Comparative Examples 1 to 3 relating to adhesive sealants, the obtained multi-layered body was obtained as an evaluation sample. In Examples 5 and 6 and Comparative Example 4 concerning the thermosetting sealant, the obtained multi-layered body was heated at a temperature of 100°C for 60 minutes to cure the sealant layer to obtain the evaluation sample.

When calcium comes into contact with water, it generally forms transparent calcium oxide. Since the glass plate and aluminum foil in the evaluation samples described above have a sufficiently high barrier property against moisture penetration, moisture can generally move in the in-plane direction (direction perpendicular to the thickness direction) through the edge of the sealant layer to the calcium film to reach. Therefore, when moisture enters the evaluation sample, the calcium film is gradually oxidized from the edge and becomes transparent, so that the shrinkage of the calcium film can be observed. Moisture penetration into the evaluation sample can therefore be judged by measuring the sealing distance [mm] from the edge of the evaluation sample to the calcium film. Therefore, the evaluation sample containing the calcium film can be used as a model of a lead-containing electronic component.

First, the sealing distance X2 [mm] from the edge of the evaluation sample to the edge of the calcium film was measured with a microscope (Measuring Microscope MF-U, manufactured by Mitutoyo Corporation). In the following, this sealing distance X2 is referred to as the initial sealing distance X2.

Then, the sample was stored in a thermo-hygrostat at a temperature of 85°C and a humidity of 85% RH. The evaluation sample was taken out from the thermo-hygrostat when the sealing distance X1 (mm) between the edge of the evaluation sample stored in the thermo-hygrostat and the edge of the calcium film was increased by 0.1 mm from the initial sealing distance X2. The time elapsed from the time of storing the evaluation sample in the thermo-hygrostat to the time of taking out the evaluation sample from the thermo-hygrostat was determined as the collection start time t [hour]. The sampling start time t corresponds to the time elapsed from the time T _P1 when the evaluation sample is stored in the thermo-hygrostats to the time T _P2 when the sealing distance X1 [mm] between the edge of the thermo-hygrostats hygrostat stored evaluation sample and the edge of the calcium film "X2 + 0.1 mm" reached.

The above sealing distance X1 and the decrease start time t were substituted into Fick's diffusion equation in Formula (1) to calculate the constant K as a moisture ingress barrier parameter.
[expression 3] $$X1=K\sqrt{t}$$

The determined constant K was used to evaluate the moisture penetration barrier property as the ability of the sealant to prevent moisture penetration according to the following criteria. The smaller the value of the constant K, the higher the moisture ingress barrier property. The character "h" stands for "hour".

(Criteria for Moisture Ingress Barrier Property)

"Good": The constant K is less than 0.025 cm/h ⁰ ' ⁵ .

"Poor": The constant K is 0.025 cm/h ^0.5 or more.

[Synthesis Example 1: Synthesis of an Ionic Liquid Hardener]

The ionic liquid hardener, N-acetylglycine tetrabutylphosphonium salt, was synthesized by the following procedure.

To 20.0 g of an aqueous solution of 41.4% tetrabutylphosphonium hydroxide (Hokko Chemical Industry Co., Ltd.) at 0°C was added 3.54 g of N-acetylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.). The resulting solution was stirred for 10 minutes. After stirring, the reaction solution was concentrated with an evaporator under a pressure of 40 mmHg to 50 mmHg at 60°C to 80°C for 2 hours and then at 90°C for 5 hours. The concentrate obtained was dissolved in 14.2 ml of ethyl acetate (Junsei Chemical Co., Ltd.) at room temperature to prepare a solution. The obtained solution was concentrated using the evaporator at a pressure of 40 mmHg to 50 mmHg at 70°C to 90°C for 3 hours to obtain 11.7 g of an oily compound, N-acetylglycine tetrabutylphosphonium salt (purity: 96.9 %) to produce.

[I. Examples and Comparative Examples of Adhesive Type Sealants]

[Example 1]

(manufacture of varnish)

77.5 parts by mass of the nonvolatile component of Swazol solution (nonvolatile component 60%) of dicyclopentadiene petroleum resin (T-REZ HA105, manufactured by JXTG Energy, softening point 105°C) was prepared as a tackifier. The solution was then mixed with 2.3 parts of an antioxidant tels (Irganox 1010, manufactured by BASF Co.) was added and dissolved. To this solution were added 21 parts of maleic anhydride-modified liquid polybutene (HV-300M, manufactured by TOHO Chemical Industry Co., Ltd: 0.77 mmol/g, number-average molecular weight: 2,100), 94 parts of polybutene (HV-1900, manufactured by JX Energy Co., number-average molecular weight: 2,900) and 100 parts of a commercial product of semi-calcined hydrotalcite A (semi-calcined hydrotalcite, BET specific surface area: 13m ² /g, average particle diameter: 400 nm) as an inorganic filler dispersed with a three-roll mill to obtain a mixture.

To the resulting mixture was added 20 parts by mass of the non-volatile component of the Swazol solution (non-volatile component 20%) of glycidyl methacrylate-modified propylene-butene random copolymer (T-YP341, manufactured by SEIKO PMC CORPORATION, propylene unit/butene unit: 71%/29% , Epoxy group concentration: 0.638 mmol/g, Number-average molecular weight: 155,000), 0.1 part of amine compound (2,4,6-tris(diaminomethyl)phenol; hereinafter referred to as “TAP”; manufactured by Kayaku Akzo Co., Ltd.) and 210 parts of toluene added. The obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish containing the sealant.

(manufacture of sealing foil)

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 release agent (release-treated surface) was prepared. On the release-treated surface of the substrate, the above varnish was applied uniformly with a coater, and then heated at 140°C for 30 minutes to obtain a sealing sheet having a 20 µm-thick layer of the sealant.

[Example 2]

The type of the 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 diameter: 400 nm). The varnish containing the sealant and the sealing sheet containing the 20 μm thick sealant layer were prepared by the same method as in Example 1 except for the above points.

[Example 3]

The type of the inorganic filler was changed from semi-calcined hydrotalcite A to commercially available calcium oxide (BET specific surface area: 5 m ² /g, average particle diameter: 4000 nm). The varnish containing the sealant and the sealing sheet containing the 20 µm thick sealant layer were prepared by the same method as in Example 1 except for the above points.

[Example 4]

The type of the inorganic filler was changed from semi-calcined hydrotalcite A to nanozeolite (Zeoal 4A manufactured by Nakamura Choukou Co., Ltd., average particle diameter 300 nm, pore size 4 Å). The varnish containing the sealant and the sealing sheet containing the 20 µm thick sealant layer were prepared by the same method as in Example 1 except for the above points.

[Comparative Example 1]

Semi-calcined hydrotalcite A as an inorganic filler was not used. The varnish containing the sealant and the sealing sheet containing the 20 µm thick sealant layer were prepared by the same method as in Example 1 except for the above points.

[Comparative Example 2]

The type of the inorganic filler was changed from semi-calcined hydrotalcite A to commercially available uncalcined hydrotalcite D (BET specific surface area: 10 m ² /g, average particle diameter: 400 nm). Apart from the above, the sealant was included tende paint and the sealing film, which contains the 20 micron thick sealant layer, prepared by the same method as in Example 1.

[Comparative Example 3]

The type of the inorganic filler was changed from semi-calcined hydrotalcite A to synthetic mica (PDM-5B, manufactured by Topy Industries Co., average particle diameter: 6.0 µm). The varnish containing the sealant and the sealing sheet containing the 20 µm thick sealant layer were prepared by the same method as in Example 1 except for the above points.

[Valuation]

Using the varnishes and sealing sheets obtained in Examples and Comparative Examples, lead adsorption properties and moisture penetration barrier properties were evaluated according to the evaluation methods described above. The evaluation results are shown in Table 1 below. [Table 1] Table 1: Results of Examples 1 to 4 and Comparative Examples 1 to 3) Ex 1 Ex 2 Ex 3 Ex 4 See Ex. 1 See Ex. 2 See Ex. 3 inorganic filler Semi-calcined hydrotalcite A [parts] 100 - - - - - - calcined hydrotalcite C [parts] - 100 - - - - - CaO [parts] - - 100 - - - - Zeolite [parts] - - - 100 - - - uncalcined hydrotalcite D [parts] - - - - - 100 - synthetic mica PDM-5B [parts] - - - - - - 100 Polyolefin type resin Glycidyl methacrylate modified propylene-butene copolymer T-YP341 [parts] 20 20 20 20 20 20 20 Polybutene HV-1900 [parts] 94 94 94 94 94 94 94 Maleic Anhydride Modified Polybutene HV-300M [Parts] 21 21 21 21 21 21 21 tackifier T-REZ HA105 [Parts] 77.5 77.5 77.5 77.5 77.5 77.5 77.5 antioxidant Irganox1010 2.3 2.3 2.3 2.3 2.3 2.3 2.3 crosslinking agents or crosslinking accelerators TAP [parts] 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Lead adsorption capacity X [µg/m ² ] 13.0 14.3 13.0 24.7 0 14.3 0 valuation Well Well Well Well poor Well poor Moisture ingress barrier property K [cm/h ^0.5 ] 0.018 0.020 0.012 0.023 >0.04 0.025 >0.04 valuation Well Well Well Well poor poor poor

[II. Examples and Comparative Examples of Thermosetting Sealants]

[Example 5]

(manufacture of varnish)

162 parts of a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd.) was mixed with 150 parts of a commercially available semi-calcined hydrotalcite A (semi-calcined hydrotalcite, BET specific surface area: 13 m ² /g, average particle diameter: 400 nm) as an inorganic filler, and 7.5 parts of a silane coupling agent ("KMB403", manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidyloxypropyltriethoxysilane). The product obtained was dispersed with the three-roll mill to obtain the mixture.

In a solution obtained by dissolving 7.5 parts of a curing accelerator ("U-CAT3512T" manufactured by San-Apro Ltd.) in 163 parts of a phenoxy resin solution ("YX7200B35" manufactured by Mitsubishi Chemical Corporation, solvent: methyl ethyl ketone, non-volatile Component: 35%) (57 parts of resin), 108 parts of an alicyclic skeleton-containing epoxy resin ("TOPR-300" manufactured by Nippon Steel Chemical & Material Co, Ltd.), the mixture prepared above and 9 parts of the in Synthesis Example 1 synthesized ionic liquid curing agent (N-acetylglycine tetrabutylphosphonium salt). The obtained product was uniformly dispersed with a high-speed rotary mixer to obtain the sealant-containing varnish

(manufacture of sealing foils)

As a support, a polyethylene terephthalate film (38 µm thick; hereinafter referred to as “release-treated PET film”) having a surface (release-treated surface) treated with an alkyd release agent was prepared. On the release-treated surface of the support, the above varnish was applied uniformly with a die coater so that the thickness of the sealant layer after drying was 20 µm, and then dried at 80°C for 5 minutes to form the sealant layer. Thereafter, a PET release sheet as a protective sheet was placed on the surface of the sealant layer to obtain the sealing sheet comprising the support, the sealant layer and the PET peelable sheet in this order.

[Example 6]

The type of the inorganic filler was changed from semi-calcined hydrotalcite A to commercially available calcium oxide (BET specific surface area: 5 m ² /g, average particle diameter: 4000 nm). The varnish containing the sealant and the sealing sheet containing the 20 µm thick layer of the sealant were prepared by the same method as in Example 5 except for the above points.

[Comparative Example 4]

The type of the inorganic filler was changed from semi-calcined hydrotalcite A to commercially available uncalcined hydrotalcite D (BET specific surface area: 10 m ² /g, average particle diameter: 400 nm). The varnish containing the sealant and the sealing sheet containing the 20 µm thick layer of the sealant were prepared by the same method as in Example 5 except for the above points.

[Valuation]

Using the varnishes and sealing sheets obtained in Examples and Comparative Examples, the lead adsorption ability and moisture penetration barrier properties were evaluated according to the evaluation methods described above.

However, in the method of evaluating the lead adsorption ability, the first test sheet was prepared by cutting the sealing sheet and then removing the PET peel-off sheet as the protective sheet. Therefore, the lead adsorbability evaluation method was performed using the first test sheet containing the sealant layer with an exposed surface.

In the moisture penetration barrier property evaluation method, the peelable PET film as a protective film was removed from the second test film, and then the second test film was dried.

The evaluation results are shown in Table 2. [Table 2] Table 2: Results of Examples 5 to 6 and Comparative Example 4] Ex 5 item 6 See Ex. 4 inorganic filler Semi-calcined hydrotalcite A [parts] 150 - - CaO [parts] - 150 - uncalcined hydrotalcite D [parts] - - 150 epoxy resin ZX1059 [Parts] 162 162 162 TOPR-300 [Parts] 108 108 108 phenoxy resin YX7200B35 [Parts] 57 57 57 silane coupling agent KBM403 [Parts] 7.5 7.5 7.5 Harder Hardener from Synthesis Example 1 [parts] 9 9 9 curing accelerator U-CAT [Parts] 7.5 7.5 7.5 Lead adsorption capacity X [µg/m ² ] 14.3 14.3 15.6 valuation Well Well Well Moisture ingress barrier property K [cm/h ^0.5 ] 0.019 0.014 0.031 valuation Well positive bad

[III. Measurement of moisture transmission rate using moisture transmission rate test method (WVTR measurement method)]

[Reference Example 1: Evaluation for the Gasket Sheet of Example 1]

The sealant layer of the sealing sheet prepared in Example 1 and a reference sheet (polyethylene terephthalate sheet "Lumirror 38 R80", thickness 35 µm, manufactured by Toray Sales) having a known moisture permeability rate P2 were laminated with a batch vacuum laminator (V-160, manufactured by Nichigo- Morton Co., Ltd.). The laminating conditions are as follows: decompression at a temperature of 80°C for 30 seconds and then pressurization at a pressure of 0.3 MPa for 30 seconds. Then the support was removed to obtain a resin sheet containing the sealant layer and the reference sheet.

The moisture permeation rate P0 of the obtained resin sheet was determined by an infrared sensor method in accordance with JIS K7129B. The moisture permeability (g/m ² ·24 hours) was measured with a moisture permeation rate meter (manufactured by MOCON Inc., PERMATRAN-W 3/34) at a temperature of 40°C and a relative humidity of 90%.

The moisture transmission rate P0 of the resin film and the water vapor transmission rate P2 of the reference film were substituted into the following formula (2) to calculate the water vapor transmission rate P1 of the sealant layer. At this time, the moisture transmission rate P2 of the reference film was set at 15 g/m ² ·24 hours. $$1/\text{P0}=1/\text{P}1+1/\text{P}2$$

[Reference Example 2: Evaluation for the Gasket Sheet of Comparative Example 1]

The moisture permeability rate P1 of the sealant layer was measured in the same manner as in Reference example 1, except that the sealing sheet prepared in Comparative example 1 was used instead of the sealing sheet prepared in Example 1.

[Reference Example 3: Evaluation for the Gasket Sheet of Comparative Example 3]

The moisture permeability rate P1 of the sealant layer was measured in the same manner as in Reference example 1, except that the sealing sheet prepared in Comparative example 3 was used instead of the sealing sheet prepared in Example 1.

[Result]

The results of Reference Examples 1 to 3 are shown in Table 3 below. Also shown in Table 3 is the evaluation of the moisture penetration barrier properties of the moisture barrier in Example 1 and Comparative Examples 1 and 3, which correspond to Reference Examples 1 to 3. [Table 3] Table 3: Results of Reference Examples 1 to 3] Reference example 1 Reference example 2 Reference example 3 Moisture Transmission Rate Mocon, WVTR [g/m ² -day] 19 21 0.7 corresponding example or comparative example example 1 Comparative example 1 Comparative example 3 Moisture ingress barrier property K [cm/h ^0.5 ] 0.018 >0.04 >0.04 valuation Well bad bad

In the WVTR measurement method used in Reference Examples 1 to 3, the permeability of moisture passing through the sealant layer in the direction of its thickness is measured. As is clear from the results of Reference Examples 1 to 3, Reference Example 1 is superior to Reference Example 2 in the ability to prevent moisture penetration in the thickness direction, but Reference Example 3 is even better. However, as is apparent from the results of the moisture ingress barrier properties of Example 1 and Comparative Examples 1 and 3, Example 1, which corresponds to Reference Example 1, is Comparative Examples 1 and 3, which corresponds to Reference Examples 2 and 3, in terms of ability to prevent the penetration of moisture in the direction of the plane perpendicular to the thickness direction. It is therefore understood that the ability of the sealant to prevent moisture ingress may vary depending on the direction of moisture ingress. It goes without saying that the sealants mentioned in the examples have a particularly high moisture ingress barrier property in the inner-plane direction.

[IV. Evaluation of Physical Properties of Hydrotalcite]

[Reference Examples 4 to 6]

(measurement of water absorption of hydrotalcite)

1.5 g of each hydrotalcite used in the above-described Examples and Comparative Examples was weighed on a balance to determine the initial mass. Each weighed hydrotalcite was allowed to stand for moisture absorption in a compact environmental test chamber (SH-222, manufactured by ESPEC CORP.) adjusted to 60°C and 90% RH (relative humidity) under atmospheric pressure for 200 hours. The mass obtained after absorbing moisture was then measured. From the measured mass, the saturation water absorbency was calculated according to the following formula (i): $$\begin{array}{l}\text{S}\ddot{\text{a}}\text{activities}-\text{water absorbency}\left[\text{crowds}-\%\right]=100\times \\ (\text{Mass after moisture absorption}-\\ \text{exit mass})\text{/initial mass}\end{array}$$

(Measurement of thermal weight loss fraction of hydrotalcite)

The thermogravimetric analysis was carried out for each of the hydrotalcites used in Examples and Comparative Examples with a thermal analyzer (TG/DTA EXSTAR 6300 manufactured by Hitachi High-Tech Science Corporation). 10 mg of hydrotalcite was weighed and placed in an unlidded aluminum sample pan and heated under a nitrogen flow rate of 200 ml/min, increasing the temperature at 10°C/min from 30°C to 550°C. The thermal weight loss fraction was determined according to the following formula (ii) at 280°C and 380°C: $$\begin{array}{l}\text{Thermal Weight Loss Fraction}\left[\text{crowds}-\%\right]=100\times \\ (\text{mass before heating}-\text{mass upon reaching a}\\ \text{specified temperature})/\text{mass before heating}\end{array}$$

(Powder X-ray Diffraction Measurement of Hydrotalcite)

The powder X-ray diffraction was measured for each hydrotalcite used in the above-described Examples and Comparative Examples. The powder X-ray diffraction measurements were carried out with a powder X-ray diffractometer (Empyrean, manufactured by Malvern Panalytical Ltd.) under the following conditions: counter cathode CuKa (1.5405 Å), voltage: 45 V, current: 40 mA, scanning width: 0.0260 °, scan speed: 0.0657°/s, and measurement diffraction angle range (2θ): 5.0131° to 79.9711°. The peak search was performed with a peak search function of the software connected to the diffractometer under the following conditions: minimum significance: 0.50, minimum peak top: 0.01°, maximum peak top: 1.00°, peak base width: 2.00 °, method: minimum value of the second derivative. Two divided peaks or a peak with a shoulder formed by combining the two peaks were detected in a 2θ range from 8° to 18°. The diffraction intensities of the peaks or shoulder appearing on the small-angle side (= small-angle side diffraction intensity) and the diffraction intensities of the peaks or shoulder appearing on the large-angle side (= large-angle side diffraction intensity) were measured, and then a relative intensity ratio was calculated (= small-angle side diffraction intensity/large-angle side diffraction intensity) is calculated.

(Results)

The evaluation results for each hydrotalcite are shown in Table 4. [Table 4] Table 4: Evaluation results of hydrotalcites] reference example Type Saturated water absorption degree [%] thermal weight loss fraction [%] X-ray powder diffraction 280°C 380°C 4 Hydrotalcite A Semi-calcined hydrotalcite 11 6.7 18.7 relative intensity ratio = 1.3 5 Hydrotalcite C calcined hydrotalcite 58 4.5 5.1 No peak appears in the range 2θ=8°-18°, a peak appears at 20=43° 6 Hydrotalcite D uncalcined hydrotalcite 0 15.3 27.1 Only one peak without a shoulder appears

The results of saturation water absorption rate, thermal weight loss rate and powder X-ray diffraction show that hydrotalcite A is "semi-calcined hydrotalcite", hydrotalcite C is "calcined hydrotalcite" and hydrotalcite D is "uncalcined hydrotalcite".

reference list

10

evaluation sample

100

glass plate

200

calcium film

300

Second test slide

310

sealant layer

320

carrier 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 substrate

460

Second substrate

QUOTES INCLUDED IN DESCRIPTION

This list of documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent Literature Cited

• WO 2014/045021 [0243]
• JP 201449596 [0243]
• JP 201682003 [0243]

Claims (10)

A sealant for an electronic component having a lead-containing portion, the sealant containing: an inorganic filler; and a resin, wherein the sealant has a lead adsorption parameter of 10 µg/m ² or more, the sealant has a moisture ingress barrier parameter of less than 0.025 cm/h ^0.5 , the lead adsorption parameter being the mass of lead adsorbed per 1 m ² of a layer of the sealant obtained by conducting a lead adsorption ability evaluation test, the lead adsorption ability evaluation test comprising: preparing a first test film (sheet) having a length of 16 cm and a width of 24 cm, comprising a polyethylene terephthalate - film and the layer of sealant formed on the polyethylene terephthalate film with a thickness of 20 µm; adhering a nylon mesh cloth to a sealant layer side of the first test sheet; cutting the first test sheet with attached netting into 1 cm squares; and immersing the cut first test sheet in 50 ml of a lead ion-containing aqueous solution having a lead ion concentration of 20 µg/l and adjusted to 20°C to 25°C and stirring for 15 minutes, wherein the moisture ingress barrier parameter is one of the following Formula (1) represents the constant K obtained when a moisture barrier evaluation test is carried out, and the moisture barrier evaluation test involves: drying a second test film (sheet) comprising a carrier film comprising a 30 µm thick aluminum foil and a 25 µm thick polyethylene terephthalate film, and having a layer of the sealant formed on the aluminum foil of the base film; washing a glass plate of 50 mm square formed of an alkali-free glass with boiled isopropyl alcohol for 5 minutes and drying; vapor-depositing calcium onto one side of the glass plate except for an area within a distance of 0 mm to 2 mm from an edge of the glass plate to form a 200 nm-thick calcium film; adhering the sealant layer of the second test sheet to the calcium film-side surface of the glass plate in a nitrogen atmosphere to obtain a sample for evaluation; measuring a distance X2 [mm] between an edge of the sample for evaluation and an edge of the calcium film; storing the sample for evaluation in a thermo-hygrostat at a temperature of 85°C and a humidity of 85% RH (relative humidity); Measuring the elapsed time t [hour] from when the sample for evaluation is stored in the thermo-hygrostat to when the distance X1 [mm] between the edge of the stored in the thermo-hygrostat sample for the evaluation and the edge of the calcium film reached "X2 + 0.1mm"; and calculating the constant K based on the following formula (1): [expression 1] $$X1=K\surd t$$

A sealant according to claim wherein the second test film in the moisture barrier evaluation test is dried under at least one of 130°C for 60 minutes and 100°C for 5 minutes. sealant after claim 1 or 2 wherein the inorganic filler contains one or more types selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite, calcium oxide and zeolite. A sealant for an electronic component having a lead-containing portion, the sealant comprising a resin and an inorganic filler containing one or more types selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide. sealant after claim 3 or 4 wherein the inorganic filler contains one or more types selected from the group consisting of semi-calcined hydrotalcite, calcined hydrotalcite and calcium oxide, and the resin contains a polyolefin type resin. Sealant according to one of claims 3 until 5 , wherein the inorganic filler contains one or more types selected from the group consisting of of semi-calcined hydrotalcite and calcium oxide, and the resin contains an epoxy resin. Sealant according to one of Claims 1 until 6 , wherein the amount of the inorganic filler is 5% by mass or more and 80% by mass or less based on 100% by mass of the nonvolatile component of the sealant. Sealing sheet, comprising: a carrier; and a layer formed on the substrate of the sealant according to any one of Claims 1 until 7 . Electronic component, comprising: a lead-containing part; and a sealing part that seals the lead-containing part, wherein the sealing part uses the sealant according to any one of Claims 1 until 7 contains. A perovskite-type solar cell, comprising: a first electrode; a perovskite layer containing lead atoms; a second electrode; and a sealing part that seals the perovskite layer, the sealing part containing the sealant according to any one of Claims 1 until 7 contains.

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