WO2019189723A1

WO2019189723A1 - Sealing composition

Info

Publication number: WO2019189723A1
Application number: PCT/JP2019/013924
Authority: WO
Inventors: 直輝名取; 文弥戸村; 有希山本; 学増山; 賢大橋
Original assignee: 味の素株式会社
Priority date: 2018-03-30
Filing date: 2019-03-29
Publication date: 2019-10-03
Also published as: KR20200138344A; JP7334731B2; JPWO2019189723A1; CN111868162A

Abstract

Provided is a sealing composition that comprises components (A) to (C): (A) a polyolefin resin and/or a polyolefin rubber; (B) an inorganic filler; and (C) a metal complex wherein a bidentate ligand in which both of the two ligand atoms are oxygen atoms and a monodentate ligand in which the ligand atom is an oxygen atom are bonded to a center metal.

Description

Sealing composition

The present invention relates to a sealing composition, and specifically relates to a sealing composition suitable for sealing an electronic element or the like in a flexible electronic device.

An organic EL element is a light emitting element using an organic substance as a light emitting material, and has recently attracted attention because it can emit light with high luminance at a low voltage. However, the organic EL element is extremely weak against moisture, and it is necessary to block the inside of the element from moisture in the outside air. For this reason, an organic EL element is sealed by forming a sealing layer with a composition so as to cover the entire surface of the light emitting layer formed on the substrate. In such a sealing composition, a tackifying resin may be used because it requires good adhesion to the substrate on which the element is formed. For example, Patent Document 1 discloses a composition containing a polyisobutylene resin, a polyisoprene resin having a functional group capable of reacting with an epoxy group and / or a polyisobutylene resin, a tackifier resin, and an epoxy resin. ing. Patent Document 2 discloses a composition containing a styrene-isobutylene-modified resin and a tackifying resin. Patent Document 3 discloses a sealing composition containing a polyolefin-based resin, hydrotalcites and a tackifying resin.

In recent years, flexible and bendable flexible electronic devices (hereinafter simply referred to as “flexible devices”) have been actively developed. For example, in sealing materials used for flexible organic EL devices. Has been demanded to have excellent flexibility. On the other hand, a composition using a polyolefin-based rubber or the like is generally excellent in flexibility, and is considered advantageous as a sealing material for a flexible electronic device. In addition, it is considered useful to add an inorganic filler in order to improve the performance of the sealing material such as moisture resistance.

International publication 2011/62167 pamphlet International Publication No. 2013/108731 Pamphlet International Publication No. 2017/057708 Pamphlet

However, in the study by the present inventors, when an inorganic filler is added to a composition containing a polyolefin resin or polyolefin rubber, the flexibility of the flexible device and the substrate having an electronic element (hereinafter also referred to as “element substrate”). )) And the composition tend to cause a decrease in adhesion. Accordingly, an object of the present invention is to provide a sealing composition having excellent adhesiveness and flexibility.

As a result of intensive studies to solve the above problems, the present inventors have found that a bidentate ligand in which two coordinating atoms are oxygen atoms and a monodentate ligand in which the coordinating atoms are oxygen atoms are central metals. To find out that a composition obtained by blending a metal complex having a coordinated structure with a polyolefin resin or polyolefin rubber together with an inorganic filler can be a composition having excellent adhesion and flexibility, and to complete the present invention. It came.

That is, the present invention has the following features.
[1] A sealing composition comprising the following components (A) to (C).
(A) Polyolefin resin and / or polyolefin rubber (B) Inorganic filler (C) A bidentate ligand in which two coordination atoms are both oxygen atoms and a monodentate ligand in which the coordination atoms are oxygen atoms Metal complex bound to central metal [2] (C) The sealing composition according to the above [1], wherein the central metal of the metal complex is aluminum, titanium, or zirconium.
[3] (C) The metal complex has the general formula (1):

(Where
M represents the metal of the second period to the sixth period of the periodic table,
R ₁ and R ₃ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryl group that may have a substituent, or Represents an aralkyl group which may have a substituent,
R ₂ has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a substituent. An aryl group that may be substituted or an aralkyl group that may have a substituent,
X represents a monodentate ligand in which the coordination atom is an oxygen atom,
The solid line between the oxygen atom (O) and M in [] represents a covalent bond,
The broken line between the oxygen atom (O) and M in [] represents a coordination bond, and m is an integer of 3 or 4, n is an integer of 1 to 3, and m> n . )
The composition for sealing according to the above [1], which is a metal complex represented by the formula:
[4] The sealing composition according to [3], wherein M in the formula (1) is aluminum, titanium, or zirconium.
[5] The sealing composition according to any one of the above [1] to [4], wherein (B) the inorganic filler is surface-treated with (C) a metal complex.
[6] The sealing composition according to any one of claims 1 to 5, wherein the polyolefin resin and / or the polyolefin rubber is a polymer having a polyisobutylene skeleton.
[7] The sealing according to any one of the above [1] to [6], wherein the polyolefin resin includes a polyolefin resin having an acid anhydride group and / or a polyolefin resin having an epoxy group Composition.
[8] The sealing according to any one of [1] to [6], wherein the polyolefin rubber includes a polyolefin rubber having an acid anhydride group and / or a polyolefin rubber having an epoxy group. Composition.
[9] The sealing composition according to any one of [1] to [6], which satisfies at least one of the following (a) to (d):
(A) The polyolefin resin includes a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group.
(B) The polyolefin rubber includes a polyolefin rubber having an acid anhydride group and a polyolefin rubber having an epoxy group.
(C) The polyolefin resin includes a polyolefin resin having an acid anhydride group, and the polyolefin rubber includes a polyolefin rubber having an epoxy group.
(D) The polyolefin-based rubber includes a polyolefin-based rubber having an acid anhydride group, and the polyolefin-based resin includes a polyolefin-based resin having an epoxy group.
[10] The sealing composition according to any one of the above [1] to [9], further comprising 10% by mass or less (D) a tackifying resin with respect to 100% by mass of the nonvolatile component of the composition object.
[11] The sealing composition according to any one of [1] to [10], which is used for sealing a flexible electronic device.
[12] The composition for sealing according to the above [11], wherein the flexible electronic device is a flexible organic EL device.
[13] A sealing sheet comprising a support and a layer of the composition according to any one of the above [1] to [8] and [10] formed on the support.
[14] A support and a layer of the composition according to [9] formed on the support, wherein the composition layer is formed by a reaction between an acid anhydride group and an epoxy group. A sealing sheet having a crosslinked structure.
[15] The sealing sheet according to [13] or [14], wherein the support is composed of at least one selected from a peelable support, a moisture-proof support, and a circularly polarizing plate.
[16] The sealing sheet according to any one of [13] to [15], which is used for sealing a flexible electronic device.
[17] The sealing sheet according to [16], wherein the flexible electronic device is a flexible organic EL device.
[18] A flexible electronic device in which an electronic element formed on a plastic substrate is sealed with the sealing composition according to any one of [1] to [8] and [10].
[19] An electronic device formed on a plastic substrate is sealed with the sealing composition described in [9] above, and the sealing composition is reacted with an acid anhydride group and an epoxy group. A flexible electronic device having a formed cross-linked structure.
[20] The flexible electronic device according to [18] or [19], wherein the electronic element is an organic EL element, and the flexible electronic device is a flexible organic EL device.

According to the present invention, a sealing composition having excellent adhesion and flexibility can be realized. Therefore, the sealing composition of the present invention has an excellent effect as a sealing material for flexible electronic devices in which the element substrate is a plastic substrate.

[Sealing composition]
The sealing composition of the present invention (hereinafter also simply referred to as “composition”) includes, as essential components, (A) a polyolefin-based resin and / or polyolefin-based rubber, (B) an inorganic filler, and (C). It contains a metal complex in which a bidentate ligand in which two coordination atoms are oxygen atoms and a monodentate ligand in which the coordination atoms are oxygen atoms are bonded to a central metal.

<(A) Polyolefin resin and / or polyolefin rubber>
The composition for sealing of this invention contains polyolefin resin and / or polyolefin rubber (henceforth "(A) component"). The polyolefin-based resin and the polyolefin-based rubber can be used without particular limitation as long as each has an olefin-derived skeleton. In addition, "olefin" here means a monoolefin and / or a diolefin. Preferred monoolefins include α-olefins such as ethylene, propylene, 1-butene, isobutylene (isobutene), 1-pentene, 1-hexene, 1-heptene, 1-octene, and the like. Preferably, 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene and the like are mentioned. Each monoolefin and diolefin may be one kind or two or more kinds.

In the present invention, the component (A) may be one kind of polymer or a mixture of two or more kinds of polymers, for example, one kind of polyolefin resin, one kind of polyolefin rubber, two or more kinds of polyolefin resin. And a mixture of two or more polyolefin rubbers, a mixture of one or more polyolefin resins and one or more polyolefin rubbers, and the like.

(Polyolefin resin)
The polyolefin resin may be a homopolymer, a random copolymer, or a block copolymer. The copolymer may be (i) a copolymer of two or more monoolefins, (ii) a copolymer of monoolefins and diolefins, or (iii) a monoolefin and an unsaturated carboxylic acid ester (for example, And copolymers with ethylenically unsaturated compounds (excluding diene monomers) other than olefins such as methyl methacrylate and aromatic vinyl (for example, styrene).

The polyolefin resin is preferably a polyisobutylene resin or a polypropylene resin. Here, “polyisobutylene resin” refers to a resin whose main unit (maximum content unit) among all olefin monomer units constituting the polymer is isobutylene, and “polypropylene resin” refers to a polymer. This refers to a resin in which the main unit (maximum content unit) of all the olefin monomer units is propylene.

When the polyisobutylene resin is a copolymer, examples of monomer units other than isobutylene include 1-butene and styrene. When the polypropylene resin is a copolymer, examples of monomer units other than propylene include ethylene, 1-butene, and isoprene.

The polyolefin-based resin is an acid anhydride group (that is, a carbonyloxycarbonyl group (—CO—O—) from the viewpoint of further improving the adhesiveness of the sealing composition to an object to be sealed, the adhesive wet heat resistance of the composition, and the like. It may include a polyolefin resin having CO-)) and / or a polyolefin resin having an epoxy group. Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride, and the like. The acid anhydride group can have one type or two or more types. The polyolefin resin having an acid anhydride group can be obtained, for example, by an unsaturated compound having an acid anhydride group and graft-modifying the polyolefin resin under radical reaction conditions. Moreover, you may make it carry out radical copolymerization of the unsaturated compound which has an acid anhydride group with an olefin. Similarly, the polyolefin resin having an epoxy group is an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether, etc. It can be obtained by graft modification with Moreover, you may make it carry out radical copolymerization of the unsaturated compound which has an epoxy group with an olefin.

The polyolefin resin having an acid anhydride group is preferably a polyisobutylene resin having an acid anhydride group or a polypropylene resin having an acid anhydride group. The polyolefin resin having an epoxy group is preferably a polyisobutylene resin having an epoxy group or a polypropylene resin having an epoxy group.

In the polyolefin resin having an acid anhydride group, the concentration of the acid anhydride group in the resin is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g. The concentration of the acid anhydride group is obtained from the value of the acid value defined as the number of mg of potassium hydroxide necessary to neutralize the acid present in 1 g of resin according to the description of JIS K 2501.

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

(Polyolefin rubber)
Examples of polyolefin rubbers include butyl rubber (IIR) (rubber-like copolymer of isobutylene and isoprene), isoprene rubber (IR), butadiene rubber (BR), and rubbery copolymer of carboxylated styrene and butadiene. Examples thereof include a combination (XSBR), a chlorinated isobutylene and isoprene rubbery copolymer (CIIR), a brominated isobutylene and isoprene rubbery copolymer (BIIR), and the like. These can use 1 type (s) or 2 or more types. Of these, butyl rubber, isoprene rubber and butadiene rubber are preferable, and butyl rubber is more preferable.

Polyolefin rubber is an acid anhydride group (that is, a carbonyloxycarbonyl group (—CO—O—) from the viewpoint of further improving the adhesiveness of the sealing composition to a sealing target, the adhesive heat and heat resistance of the composition, and the like. A polyolefin rubber having CO-)) and / or a polyolefin rubber having an epoxy group may be included. Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride, and the like. The acid anhydride group can have one type or two or more types. The polyolefin rubber having an acid anhydride group can be obtained, for example, by an unsaturated compound having an acid anhydride group and graft-modifying the polyolefin rubber under radical reaction conditions. Moreover, you may make it carry out radical copolymerization of the unsaturated compound which has an acid anhydride group with an olefin. Similarly, an epoxy group-containing polyolefin rubber is an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether, etc. It can be obtained by graft modification with Moreover, you may make it carry out radical copolymerization of the unsaturated compound which has an epoxy group with an olefin.

The polyolefin rubber having an acid anhydride group is preferably a butyl rubber having an acid anhydride group, an isoprene rubber having an acid anhydride group, or a butadiene rubber having an acid anhydride group, particularly preferably having an acid anhydride group. Butyl rubber. The polyolefin-based rubber having an epoxy group is preferably a butyl rubber having an epoxy group, an isoprene rubber having an epoxy group, or a butadiene rubber having an epoxy group, and particularly preferably a butyl rubber having an epoxy group.

In the polyolefin rubber having an acid anhydride group, the concentration of the acid anhydride group in the rubber is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g. The concentration of the acid anhydride group is obtained from the value of the acid value defined as the number of mg of potassium hydroxide necessary to neutralize the acid present in 1 g of rubber according to the description of JIS K 2501.

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

A preferred embodiment of the present invention is that the component (A) is a polymer (resin and / or rubber) having a polyisobutylene skeleton. In this case, the proportion of the polyisobutylene skeleton is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on the total component (A).

In the case where the component (A) includes a polyolefin resin having an acid anhydride group and / or a polyolefin rubber having an acid anhydride group, the polyolefin type having an acid anhydride group per the entire component (A) The amount of the polyolefin rubber having a resin and / or an acid anhydride group is preferably 1 to 70% by mass, more preferably 10 to 50% by mass. In the case where the component (A) includes a polyolefin resin having an epoxy group and / or a polyolefin rubber having an epoxy group, the polyolefin resin and / or epoxy group having an epoxy group per the entire component (A) The amount of the polyolefin-based rubber having is preferably 1 to 70% by mass, more preferably 10 to 50% by mass.

The component (A) is preferably an embodiment satisfying at least one of the following (a) to (d) from the viewpoint of further improving the moisture resistance and the like of the sealing composition.
(A) The polyolefin resin includes a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group.
(B) The polyolefin rubber includes a polyolefin rubber having an acid anhydride group and a polyolefin rubber having an epoxy group.
(C) The polyolefin resin includes a polyolefin resin having an acid anhydride group, and the polyolefin rubber includes a polyolefin rubber having an epoxy group.
(D) The polyolefin-based rubber includes a polyolefin-based rubber having an acid anhydride group, and the polyolefin-based resin includes a polyolefin-based resin having an epoxy group.

Such component (A) can form a crosslinked structure by reacting an acid anhydride group and an epoxy group by heating. For this reason, the composition of this invention can form the sealing layer which moisture-proof resistance etc. improved further. In addition, although formation of a crosslinked structure can also be performed after sealing with a composition (that is, after formation of a sealing layer), for example, a device to be sealed includes an element that is vulnerable to heat, such as an organic EL element. It is desirable to form a crosslinked structure in the composition layer formed on the substrate at the time of producing the sealing sheet.

In addition, the ratio of the polyolefin resin having an acid anhydride group and / or the polyolefin rubber having an acid anhydride group and the polyolefin resin having an epoxy group and / or the polyolefin rubber having an epoxy group has an appropriate crosslinked structure. Although it is not particularly limited as long as it can be formed, the molar ratio of epoxy group to acid anhydride group (epoxy group: acid anhydride group) is preferably 100: 10 to 100: 200, more preferably 100: 50 to 100: 150, Particularly preferred is 100: 90 to 100: 110.

In the present invention, a particularly preferred embodiment of the component (A) is (i) butyl rubber, (ii) a mixture of butyl rubber having an acid anhydride group and butyl rubber having an epoxy group, or (iii) butyl rubber, acid anhydride. A mixture of butyl rubber having groups and butyl rubber having epoxy groups.

The number average molecular weight of the component (A) is not particularly limited, but from the viewpoint of providing good coatability of the varnish of the sealing composition and good compatibility with other components in the composition, It is preferably at most 000,000, more preferably at most 750,000, even more preferably at most 500,000, further preferably at most 400,000. On the other hand, from the viewpoint of preventing repelling at the time of coating the varnish of the sealing composition, expressing moisture resistance of the sealing composition layer to be formed, and improving mechanical strength, 2,000 or more Preferably, 10,000 or more is more preferable, 30,000 or more is even more preferable, and 50,000 or more is particularly preferable. The number average molecular weight is measured by gel permeation chromatography (GPC) method (polystyrene conversion). The number average molecular weight according to the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column, and toluene as a mobile phase. And measured at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

In the present invention, when the polyolefin resin and the polyolefin rubber are used in combination as the component (A), the blending ratio of both (polyolefin resin / polyolefin rubber) is preferably 1/99 to 50/50 by mass ratio. 10/90 to 45/55 are more preferable.

Hereinafter, specific examples of the component (A) will be described.
Specific examples of the polypropylene-based resin include, for example, “T-YP341” (glycidyl methacrylate-modified propylene-butene random copolymer manufactured by Seiko PMC Co., Ltd., butene unit amount per 100% by mass of propylene unit and butene unit: 29 mass. %, Epoxy group concentration: 0.638 mmol / g, number average molecular weight: 155,000), “T-YP279” (maleic anhydride-modified propylene-butene random copolymer, total of propylene units and butene units) manufactured by Seiko PMC Amount of butene unit per 100% by mass: 36% by mass, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 35,000), “T-YP276” (glycidyl methacrylate modified propylene- Butene random copolymer, a total of 10 propylene units and butene units Amount of butene units per mass%: 36 mass%, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 57,000, “T-YP312” (maleic anhydride modified propylene-butene random) manufactured by Seiko PMC Copolymer, amount of butene units per 100% by mass of propylene units and butene units: 29% by mass, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 60,900), Seiko PMC “T-YP313” (glycidyl methacrylate-modified propylene-butene random copolymer, amount of butene units per 100% by mass of propylene units and butene units: 29% by mass, epoxy group concentration: 0.638 mmol / g, number Average molecular weight: 155,000).

Specific examples of the polyisobutylene resin include, for example, “OPanol B100” manufactured by BASF (polyisobutylene, viscosity average molecular weight: 11,110,000), “N50SF” manufactured by BASF (polyisobutylene, viscosity average molecular weight: 400,000 ) And the like.

Specific examples of the polyolefin rubber include, for example, “065” (butyl rubber) manufactured by JSR, “ER641” manufactured by Starlight PMC (maleic anhydride-modified butyl rubber, acid anhydride group concentration 0.46 mmol / g, number average molecular weight 57, "ER850" (glycidyl methacrylate-modified butyl rubber, epoxy group concentration 0.64 mmol / g, number average molecular weight 110,000) manufactured by Seiko PMC, "IR-307", "IR-310" (isoprene manufactured by Kraton Polymer Co., Ltd.) Rubber, number average molecular weight 2,000,000)), “BR150B” (butadiene rubber, number average molecular weight 500,000) manufactured by Ube Industries, Ltd., and the like.

The content of the component (A) in the sealing composition of the present invention is not particularly limited, but brings about good coating properties and compatibility, and from the viewpoint of ensuring good handleability (tack suppression), The content is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 82% by mass or less, and further preferably 80% by mass or less, based on the entire nonvolatile content in the composition. Further, from the viewpoint of improving the moisture permeation resistance and the like of the composition, the content is preferably 20% by mass or more, more preferably 25% by mass or more, and more preferably 30% by mass or more per non-volatile content in the composition. Further preferred.

<(B) Inorganic filler>
The sealing composition of the present invention contains an inorganic filler (hereinafter also referred to as “component (B)”) from the viewpoint of moisture permeation resistance and the like.

The inorganic filler is not particularly limited, and silica such as nano silica; metal oxides such as magnesium oxide, strontium oxide, aluminum oxide and barium oxide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; calcium carbonate, Metal carbonates such as magnesium carbonate; metal nitrides such as aluminum nitride and titanium nitride; metal titanates such as barium titanate, strontium titanate, calcium titanate, magnesium titanate and bismuth titanate; barium zirconate and zircon Zirconic acid metal salts such as calcium acid; aluminum borate; mineral fillers such as natural or synthetic clay and organically modified clay. Among these, mineral fillers are preferable.

In the mineral filler, as natural or synthetic clay, for example, mica, fluoromica, pyrophyllite, glauconite, vermiculite, sepiolite, Allophone, imogolite, talc, illite, sobokite, svinfordite, kaolinite, dickite, nacrite, nacrite Site (anauxite), sericite (sericite), ladykite (ledikite), montronite (montronite), metahalloy site ( etahalloysite, serpentine clay, chrysotile, antigolite, attapulgite, palgorskite, kibashiro clay, Kibashiro clay Hisingerite, chlorite, montmorillonite, sodium montmorillonite, magnesium montmorillonite, calcium montmoronite, calcium montmorillonite nitrite, bentonite, beidellite, hectorite, sodium hectorite, saponite, saconite, fluorhectite site, fluorhectite site , Volkonskoite, magadiite, kenyaite, halloysite, hydrotalcite, smectite, smectite type, etc. Can do.

Organically modified clay means smectite or smectite type clay produced by interacting non-functional clay with one or more organic agents. At this time, the type of the organic agent used is generally a neutral or ionic organic compound. Examples of neutral organic compounds include monomeric, oligomeric or polymeric compounds of polar compounds such as amides, esters, lactams, nitriles, ureas, carbonates, phosphates, phosphonates, sulfates, sulfonates or nitro compounds. Such a neutral organic compound is inserted between the clay layers through hydrogen bonding without completely replacing the charge-balance ions of the clay. Examples of ionic organic compounds include ammonium (primary, secondary, tertiary or quaternary), onium compounds such as phosphonium, sulfonium derivatives, aromatic or aliphatic amines, phosphines and sulfides; and quaternary nitrogen. Cationic surfactants such as onium ions such as quaternary ammonium ions having at least one long chain aliphatic group attached to the atom (eg, octadecyl, myristyl or oleyl).

Among mineral fillers, mica, hydrotalcite, and smectite are preferable from the viewpoint of moisture resistance and the like, and smectite and hydrotalcite are more preferable from the viewpoint of easily making the sealing layer formed by the composition of the present invention transparent. Hydrotalcite is particularly preferable.

Hereinafter, hydrotalcite that is particularly preferable as the inorganic filler will be described. Hydrotalcite can be classified into unfired hydrotalcite, semi-fired hydrotalcite, and fired hydrotalcite, and semi-fired hydrotalcite is particularly preferable from the viewpoint of transparency and moisture resistance of the composition. Uncalcined hydrotalcite is a metal hydroxide having a layered crystal structure typified by natural hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O), for example, It consists of a layer [Mg _1-X Al _X (OH) ₂ ] ^{X +} and a middle layer [(CO ₃ ) _{X / 2} · mH ₂ O] ^{X— which are the} basic skeleton. The uncalcined hydrotalcite in the present invention is a concept including a hydrotalcite-like compound such as synthetic hydrotalcite. Examples of the hydrotalcite-like compound include those represented by the following formula (I) and the following formula (II).

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

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

Semi-fired hydrotalcite refers to a metal hydroxide having a layered crystal structure in which the amount of interlayer water is reduced or eliminated, obtained by firing unfired hydrotalcite. The “interlayer water” refers to “H ₂ O” described in the composition formula of the unfired natural hydrotalcite and hydrotalcite-like compound described above using a composition formula.

On the other hand, calcined hydrotalcite refers to a metal oxide having an amorphous structure obtained by calcining uncalcined hydrotalcite or semi-calcined hydrotalcite, and not only interlayer water but also hydroxyl groups disappeared by condensation dehydration.

Unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite can be distinguished by saturated water absorption. The saturated water absorption of the semi-fired hydrotalcite is 1% by weight or more and less than 20% by weight. On the other hand, the saturated water absorption of unfired hydrotalcite is less than 1% by weight, and the saturated water absorption of fired hydrotalcite is 20% by weight or more.

The above “saturated water absorption” is determined by measuring 1.5 g of uncalcined hydrotalcite, semi-calcined hydrotalcite or calcined hydrotalcite using a balance and measuring the initial mass, and then at 60 ° C. and 90 ° C. under atmospheric pressure. The mass increase rate with respect to the initial mass when left in a small environmental tester (Espec SH-222) set to% RH (relative humidity) for 200 hours is expressed by the following formula (i):
Saturated water absorption (mass%) = 100 × (mass after moisture absorption−initial mass) / initial mass (i)
Can be obtained.

The saturated water absorption rate of the semi-fired hydrotalcite is preferably 3% by mass or more and less than 20% by mass, more preferably 5% by mass or more and less than 20% by mass.

Further, unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite can be distinguished by the thermogravimetric reduction rate measured by thermogravimetric analysis. The thermal weight loss rate at 280 ° C. of the semi-calcined hydrotalcite is less than 15% by mass, and the thermal weight reduction rate at 380 ° C. is 12% by mass or more. On the other hand, the thermal weight reduction rate at 280 ° C. of the unfired hydrotalcite is 15% by mass or more, and the thermal weight reduction rate at 380 ° C. of the sintered hydrotalcite is less than 12% by mass.

Thermogravimetric analysis was performed using Hitachi High-Tech Science TG / DTA EXSTAR6300, weighing 5 mg of hydrotalcite into an aluminum sample pan, and without opening the lid, in an atmosphere with a nitrogen flow rate of 200 mL / min. The temperature can be increased from 30 ° C. to 550 ° C. at a temperature increase rate of 10 ° C./min. The thermal weight loss rate is expressed by the following formula (ii):
Thermal weight loss rate (mass%)
= 100 × (mass before heating−mass when reaching a predetermined temperature) / mass before heating (ii)
Can be obtained.

Further, unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite can be distinguished by the peak and relative intensity ratio measured by powder X-ray diffraction. Semi-calcined hydrotalcite shows a peak that is split into two around 8 to 18 ° by powder X-ray diffraction, or a peak having a shoulder due to the synthesis of two peaks. The relative intensity ratio (low angle side diffraction intensity / high angle side diffraction intensity) of the diffraction intensity (= low angle side diffraction intensity) and the peak or shoulder diffraction intensity appearing on the high angle side (= high angle side diffraction intensity) is 0.001. ~ 1,000. On the other hand, the uncalcined hydrotalcite has only one peak at around 8 to 18 °, or the relative intensity ratio of the diffraction intensity of the peak or shoulder appearing on the low angle side and the peak or shoulder appearing on the high angle side is in the above range. Get out. The calcined hydrotalcite does not have a characteristic peak in the region of 8 ° to 18 °, but has a characteristic peak at 43 °. Powder X-ray diffraction measurement was performed using a powder X-ray diffractometer (Empyrean, manufactured by PANalytical), counter-cathode CuKα (1.5405 mm), voltage: 45 V, current: 40 mA, sampling width: 0.0260 °, scanning speed: 0 0.0657 ° / s, diffraction angle range (2θ): 5.0131 to 79.9711 °. The peak search uses the peak search function of the software attached to the diffractometer. “Minimum significance: 0.50, minimum peak tip: 0.01 °, maximum peak tip: 1.00 °, peak base width: 2 0.000, method: minimum value of second derivative ”.

Specific examples of unfired hydrotalcite, semi-fired hydrotalcite, and fired hydrotalcite include the following.
DHT-4C (manufactured by Kyowa Chemical Industry Co., Ltd.): Semi-calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 15 m ² / g)
DHT-4A-2 (manufactured by Kyowa Chemical Industry Co., Ltd.): Semi-calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 13 m ² / g)
KW-2200 (manufactured by Kyowa Chemical Industry Co., Ltd.): calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 146 m ² / g)
DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.): uncalcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 10 m ² / g)

The average particle size of the inorganic filler is not particularly limited, but is preferably 25 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less, and even more preferably 5 μm or less, from the viewpoints of influence on the sealing target and moisture resistance. Is particularly preferable and 1 μm or less is most preferable. On the other hand, from the viewpoint of the dispersibility of the inorganic filler and the viscosity of the composition, it is preferably 0.001 μm or more, more preferably 0.01 μm or more, and further preferably 0.1 μm or more.

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis with a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. can be used.

Of the inorganic fillers, the average particle size of hydrotalcite is preferably 1 to 1,000 nm, and more preferably 10 to 800 nm. The average particle size of hydrotalcite is the median diameter of the particle size distribution when the particle size distribution is created on a volume basis by laser diffraction scattering type particle size distribution measurement (JIS Z 8825).

Also among the inorganic filler, BET specific surface area of the hydrotalcite is preferably 1 ~ 250m ² / g, more preferably 5 ~ 200m ² / g. The BET specific surface area of hydrotalcite can be calculated according to the BET method using a BET multipoint method by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device (Macsorb HM Model 1210 Mountec). .

(B) The component surface-treated with the surface treatment agent can be used. As the surface treatment agent used for the surface treatment, for example, higher fatty acids, alkylsilanes, silane coupling agents and the like can be used, and among these, higher fatty acids and alkylsilanes are preferable. One or more surface treatment agents can be used.

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

The surface treatment of the component (B) can be performed, for example, by adding and spraying the surface treatment agent while stirring the untreated component (B) at room temperature with a mixer and stirring for 5 to 60 minutes. As a mixer, a well-known mixer can be used, For example, blenders, such as V blender, a ribbon blender, and a bubble cone blender, mixers, such as a Henschel mixer and a concrete mixer, a ball mill, a cutter mill, etc. are mentioned. Further, when the hygroscopic material is pulverized with a ball mill or the like, a method of surface treatment by mixing the above-mentioned higher fatty acid, alkylsilanes or silane coupling agent is also possible. The treatment amount of the surface treatment agent varies depending on the type of component (B) or the type of surface treatment agent, but is preferably 1 to 10 parts by mass with respect to 100 parts by mass of component (B).

In the present invention, the component (B) can be used alone or in combination of two or more. Although content of (B) component in a composition is not specifically limited, From the viewpoint of the adhesiveness of the sealing layer formed with a composition, the electronic element of a flexible electronic device, and a plastic substrate, and transparency of a sealing layer Therefore, the content is preferably 60% by mass or less, preferably 55% by mass or less, more preferably 50% by mass or less, and further preferably 45% by mass or less, per 100% by mass of the total nonvolatile content in the composition. In addition, from the viewpoint of obtaining sufficient effects such as moisture resistance, the content is preferably 3% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass per 100% by mass of the total nonvolatile content in the composition. The above is more preferable.

<(C) Metal Complex>
The composition of the present invention comprises (A) component and (B) component, a bidentate ligand in which two coordinating atoms are both oxygen atoms, and a monodentate ligand in which the coordinating atoms are oxygen atoms are central metals. And a metal complex (hereinafter also referred to as “component (C)”).

In the present invention, a metal complex is a chemical species in which another atom, molecule, or ion is bonded to a metal atom or ion. A ligand refers to a molecule or ion bonded to a metal atom or ion. An atom directly involved in the bond is called a coordination atom, a ligand having two coordination atoms is called a bidentate ligand, and a ligand having one coordination atom is called a monodentate ligand.

Component (C) is a bidentate ligand in which two coordinating atoms are both oxygen atoms (hereinafter also abbreviated as “oxygen / bidentate ligand”) and a monodentate coordination in which the coordinating atoms are oxygen atoms. Any metal complex having a structure in which a child (hereinafter also abbreviated as “oxygen / monodentate ligand”) is bonded to the central metal is not particularly limited, and a known metal complex satisfying the structure can be used. . Among them, a metal complex in which the central metal is a metal in the second period to the sixth period of the periodic table is preferable, more preferably a metal complex in which the central metal is a metal in the third period to the fifth period, and more preferably, the center A metal complex in which the metal is Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, Zr, In, or Sn, and particularly preferably the central metal is Al (aluminum), Ti (titanium), or It is a metal complex which is Zr (zirconium).

Examples of the oxygen / bidentate ligand include compounds represented by the following formula (a).

In formula (a), R ₁ , R ₂ and R ₃ have the same meanings as those in formula (1) described later.

The compound represented by the formula (a) represents an oxygen / bidentate ligand before coordination with the central metal. In the present invention, the oxygen / bidentate ligand coordinated to the central metal and the oxygen / bidentate ligand before coordinated to the central metal are not particularly distinguished from each other by “oxygen / bidentate”. Sometimes referred to as “bidentate ligand”. Specific examples of the compound represented by the formula (a) are synonymous with specific examples of the oxygen / bidentate ligand in the metal complex represented by the following formula (1).

Examples of the oxygen / monodentate ligand include alkoxide anion (RO ⁻ ) and carboxylate anion (RCOO ⁻ ). Specific examples of the oxygen / monodentate ligand are also synonymous with specific examples of the oxygen / monodentate ligand in the metal complex represented by the following formula (1). In the present invention, oxygen / monodentate ligands coordinated to the central metal and oxygen / monodentate ligands (alcohol (ROH), carboxylic acid (RCOOH)) before coordination to the central metal are particularly selected. Without distinction, it may be referred to as “oxygen / monodentate ligand”.

In the metal complex of component (C), the number of oxygen / bidentate ligands is 1 or more, preferably 1 or more and 3 or less, more preferably 2. When there are a plurality of oxygen / bidentate ligands, they may be the same ligand or different ligands, but the same ligand is preferred. The number of oxygen / monodentate ligands is 1 or more, preferably 1 or more and 3 or less, more preferably 2 or 3. When there are a plurality of oxygen / monodentate ligands, they may be the same ligand or different ligands, but the same ligand is preferred.

The component (C) is more preferably a metal complex represented by the following general formula (1) (hereinafter also referred to as a metal complex of the formula (1)).

In equation (1),
M is a central metal of the metal complex and represents a metal in the second to sixth periods of the periodic table. Preferably, it is a metal of the third period to the fifth period, more preferably Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, Zr, In, or Sn, and more preferably Al (aluminum). ), Ti (titanium), or Zr (zirconium).
R ₁ and R ₃ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, or an aralkyl group.
X represents an oxygen / monodentate ligand.

The solid line between the oxygen atom (O) and M in [] represents a covalent bond, and the broken line between the oxygen atom (O) and M in [] represents a coordination bond.

M is an integer of 3 or 4, n is an integer of 1 to 3, and m> n.

The alkyl group in R ₁ , R ₂ , and R ₃ may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-10, particularly preferably 1-6. Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1-ethylpropyl group, Examples include hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group and the like. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, and an amino group which may have a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the amino group which may have the above substituent include an amino group, a mono- or di-alkylamino group (eg, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group). , Dibutylamino group), mono- or di-cycloalkylamino group (eg, cyclopropylamino group, cyclohexylamino group), mono- or di-arylamino group (eg, phenylamino group), mono- or di-aralkyl Examples include amino groups (eg, benzylamino group, dibenzylamino group), heterocyclic amino groups (eg, pyridylamino group) and the like.

The alkoxy group in R ₁ , R ₂ and R ₃ is preferably an alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy , Pentyloxy, hexyloxy and the like. The alkoxy group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, and an amino group which may have a substituent. Specific examples of the halogen atom and specific examples of the amino group which may have a substituent are the same as described above.

The number of carbon atoms of the aryl group in R ₁ , R ₂ , and R ₃ is preferably 6-18, more preferably 6-14. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group. The aryl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, The amino group etc. which may have a substituent are mentioned.

The above alkenyl group may be either linear or branched. The carbon number of the alkenyl group is preferably 2 to 10, more preferably 2 to 6. For example, ethenyl group (ie vinyl group), 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 3-methyl-2 -Butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, etc. It is done. Examples of the substituent that the alkenyl group may have include a halogen atom, a hydroxy group, and an amino group that may have a substituent. Specific examples of the halogen atom and specific examples of the amino group which may have a substituent are the same as described above.

The above alkynyl group may be either linear or branched. The carbon number of the alkynyl group is preferably 2 to 10, more preferably 2 to 6. For example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, Examples include 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 4-methyl-2-pentynyl group and the like. Examples of the substituent that the alkynyl group may have include a halogen atom, a hydroxy group, and an amino group that may have a substituent. Specific examples of the halogen atom and specific examples of the amino group which may have a substituent are the same as described above.

The number of carbon atoms of the aralkyl group in R ₁ , R ₂ , and R ₃ is preferably 7-16. For example, benzyl group, phenethyl group, naphthylmethyl group, phenylpropyl group and the like can be mentioned. The aralkyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, and an amino group which may have a substituent. Specific examples of the halogen atom and specific examples of the amino group which may have a substituent are the same as described above.

The alkoxycarbonyl group in R ₂ is preferably an alkoxycarbonyl group having 1 to 6 carbon atoms of alkoxy, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxy Examples include carbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl and the like. The alkoxycarbonyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, and an amino group which may have a substituent. Specific examples of the halogen atom are the same as those of the halogen atom that is a substituent of the alkyl group described above, and specific examples of the amino group that may have a substituent include a substituent that is a substituent of the alkyl group described above. It is the same as that of the amino group which may have a group.

In the formula, the oxygen / monodentate ligand represented by X is usually a conjugate base of Bronsted acid, and examples thereof include an alkoxide anion (RO ⁻ ) and a carboxylate anion (RCOO ⁻ ).

In the alkoxide anion (RO ⁻ ), the organic group R may be either an aliphatic group or an aromatic group. The aliphatic group may be either a saturated aliphatic group or an unsaturated aliphatic group. The carbon number of the organic group R is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. Examples of the alkoxide anion (RO ⁻ ) include methoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide, sec-butoxide, tert-butoxide, pentyl oxide, hexyl oxide and the like.

In the carboxylate anion (RCOO ⁻ ), the organic group R may be either an aliphatic group or an aromatic group. The aliphatic group may be either a saturated aliphatic group or an unsaturated aliphatic group. The carbon number of the organic group R is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. Examples of the carboxylate anion (RCOO ⁻ ) include carboxylate anions corresponding to carboxylic acids such as acetic acid, propionic acid and benzoic acid.

[] In the formula represents an oxygen / bidentate ligand. Specific examples of the oxygen / bidentate ligand include acetylacetone, 3-methyl-2,4-pentanedione, acetylacetaldehyde, 2,4-hexanedione, 2,4-heptanedione, and 5-methyl-2,4. -Hexanedione, 5,5-dimethyl-2,4-hexanedione, benzoylacetone, benzoylacetophenone, salicylaldehyde, 1,1,1-trifluoroacetylacetone, 1,1,1,5,5,5-hexafluoro Acetylacetone, 3-methoxy-2,4-pentanedione, 3-cyano-2,4-pentanedione, 3-nitro-2,4-pentanedione, 3-chloro-2,4-pentanedione, acetoacetic acid, aceto Methyl acetate, ethyl acetoacetate, propyl acetoacetate, salicylic acid, methyl salicylate, malonic acid, malonic acid Methyl, diethyl, etc. malonate. In the state coordinated to the central metal, the oxygen / bidentate ligand has a structure in which one or more protons are removed therefrom.

Specific examples of the metal complex of the formula (1) include the following. Examples of metal complexes in which the central metal M is Al (aluminum) include, for example, aluminum alkyl acetoacetate diisopropylate (aluminum 9-octadecynyl aceto-acetate diisopropoxide), aluminum ethyl acetoacetate diisopropylate, aluminum ethyl acetoacetate Examples thereof include di n-butyrate, aluminum propyl acetoacetate diisopropylate, aluminum n-butyl acetoacetate diisopropylate and the like.

Examples of metal complexes in which the central metal M is Ti (titanium) include titanium allyl acetoacetate triisopropoxide, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium diisopropoxide bis ( Tetramethylheptanedionate), titanium diisopropoxide bis (ethyl acetoacetate), titanium methylphenoxide, titanium oxide bis (pentanedionate) and the like.

Examples of metal complexes in which the central metal M is Zr (zirconium) include, for example, zirconium allyl acetoacetate triisopropoxide, zirconium di-n-butoxide (bis-2,4-pentanedionate), zirconium diisopropoxide ( Bis-2,4-pentanedionate), zirconium diisopropoxide bis (tetramethylheptanedionate), zirconium diisopropoxide bis (ethylacetoacetate), zirconium butoxide (acetylacetate) (bisethylacetoacetate), Examples include zirconium tributoxy monoacetylacetonate.

(C) A component can use 1 type (s) or 2 or more types. The content of the component (C) in the composition is not particularly limited, but from the viewpoint of achieving the object of the present invention at a higher level, 0.1 to 5 per 100% by mass of the total nonvolatile content in the composition. % By mass is preferable, and 0.3 to 3% by mass is more preferable. By setting it as 0.1 mass% or more, sufficient surface modification of the inorganic filler is easily achieved, and the intended effect tends to be easily obtained. By setting it as 5 mass% or less, it is derived from the component (C). It tends to be easy to suppress the influence of the outgas on the object to be sealed.

Even if it is a metal complex different from the component (C) of the present invention, for example, a metal complex in which an oxygen / bidentate ligand is bonded to the central metal, the oxygen / monodentate ligand is not bonded to the central metal. Even if it is a metal complex or a metal complex in which an oxygen / monodentate ligand is bonded to the central metal, the metal complex in which the oxygen / bidentate ligand is not bonded to the central metal, the component (A) and (B ) Even if it is blended with the component, a composition having both excellent adhesive properties and excellent flexibility cannot be realized. The reason is not necessarily clear, but the metal complex having a structure in which the oxygen / bidentate ligand and the oxygen / monodentate ligand, which are the component (C) of the present invention, are bonded to the central metal is easily hydrolyzed.・ Because it has a monodentate ligand, it is easy to modify the surface of the inorganic filler that is the component (B), and the component (B) is sufficiently dispersed in the polyolefin resin and / or polyolefin rubber of the component (A). Furthermore, when the composition is bonded to the object to be sealed, the oxygen / bidentate ligand chelate exchanges with functional groups on the surface of the object to be sealed, such as glass, plastic, and inorganic film. It is presumed that a strong bond is generated, and as a result, the followability of the composition with respect to deformation such as bending of the object to be sealed is improved, thereby resulting in a composition having excellent adhesiveness and flexibility.

<(D) Tackifying resin>
To the sealing composition of the present invention, a tackifier resin (hereinafter also abbreviated as “component (D)”) ”can be blended in order to enhance the adhesiveness to the sealing target if necessary. However, the resin composition of the present invention can achieve sufficient adhesion without containing a tackifying resin, while the addition of the tackifying resin tends to lower the stability of the resin composition in the high temperature region. is there. Accordingly, the blending amount when blending the tackifier resin is preferably 20% by mass or less, preferably 10% by mass or less, more preferably 9% by mass or less, per 100% by mass of the total nonvolatile content in the composition. % By mass or less is more preferable, 7% by mass or less is further preferable, 6% by mass or less is more preferable, 5% by mass or less is further preferable, 4% by mass or less is further preferable, and 3% by mass or less is further preferable. The following is more preferable, 1% by mass or less is further preferable, and 0% by mass is most preferable.

The tackifying resin is not particularly limited, and is a terpene tackifying resin, terpene phenol tackifying resin, rosin tackifying resin, hydrogenated terpene resin, aromatic modified terpene resin, etc., coumarone resin, indene resin, petroleum Resin (aliphatic petroleum resin, hydrogenated alicyclic petroleum resin, aromatic petroleum resin, aliphatic aromatic copolymer petroleum resin, alicyclic petroleum resin, dicyclopentadiene (hereinafter also abbreviated as “DCPD”) Etc.) from the viewpoint of adhesiveness and transparency, dicyclopentadiene petroleum resin, hydrogenated dicyclopentadiene petroleum resin are more preferable, Hydrogenated dicyclopentadiene petroleum resin is particularly preferred.

<(E) Additive>
Within the scope of not impairing the effects of the present invention, the composition of the present invention includes a mineral oil softener, a vegetable oil softener, a sub factice, a fatty acid, a fatty acid salt, a synthetic organic compound, a synthetic oil and the like; Organic fillers such as rubber particles, silicone powder, nylon powder and fluororesin powder; defoamers or leveling agents such as silicon, fluorine and polymer; triazole compounds, thiazole compounds, triazine compounds, porphyrin compounds, etc. Adhesion imparting agents; thickeners such as olben and benton; antioxidants; heat stabilizers; additives such as light stabilizers can be blended.

(Curing agent)
When the composition of the present invention contains a polyisobutylene resin having an epoxy group, an isobutylene rubber having an epoxy group, or the like, the composition of the present invention may contain a curing agent. The curing agent is not particularly limited, and examples thereof include amine curing agents, guanidine curing agents, imidazole curing agents, phosphonium curing agents, and phenol curing agents.

The amine curing agent is not particularly limited, but includes quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide; DBU (1,8-diazabicyclo [5.4.0] undecene-7), DBN ( 1,5-diazabicyclo [4.3.0] nonene-5), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, DBU-phenol novolac resin salt, etc. Diazabicyclo compounds; tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol (TAP) and their salts, aromatic dimethylurea, aliphatic dimethylurea And the like. These may be used alone or in combination of two or more.

The guanidine curing agent is not particularly limited, but dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, Trimethyl guanidine, tetramethyl guanidine, pentamethyl guanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4 .0] dec-5-ene, 1-methyl biguanide, 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 1-(o-tolyl) biguanide, and the like. These may be used alone or in combination of two or more.

The imidazole curing agent is not particularly limited, but 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl-imidazole, 2-phenyl-4 , 5-bis (hydroxymethyl) -imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-imidazole, 2-dodecyl-imidazole, Examples include 2-heptadecylimidazole and 1,2-dimethyl-imidazole. These may be used alone or in combination of two or more.

The phosphonium curing agent is not particularly limited, but is triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triate. Examples thereof include phenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. These may be used alone or in combination of two or more.

The phenolic curing agent is not particularly limited, but is MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei), NHN, CBN, GPH (Nippon Kayaku), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei Co., Ltd.), TD2090 (manufactured by DIC), and the like can be mentioned. Specific examples of the triazine skeleton-containing phenolic curing agent include LA3018 (manufactured by DIC). Specific examples of the triazine skeleton-containing phenol novolak curing agent include LA7052, LA7054, LA1356 (manufactured by DIC) and the like. These may be used alone or in combination of two or more.

Although there is no restriction | limiting in particular in content of the hardening | curing agent in a composition, From a viewpoint of preventing the fall of the moisture resistance etc. of a sealing layer (composition layer), per 100 mass% of total non volatile matter in a composition, 5 mass% or less is preferable and 1 mass% or less is more preferable. On the other hand, from the viewpoint of suppressing tackiness of the composition, 0.01 mass% or more is preferable and 0.05 mass% or more is more preferable per 100 mass% of the total nonvolatile content in the composition.

<(F) Organic solvent>
In the composition of the present invention, for example, an organic solvent is blended from the viewpoint of the coating property of the composition when producing a sealing sheet in which a layer of the composition is formed on a support described later. Can do. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter abbreviated as “MEK”), cyclohexanone, and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Only 1 type may be used for this organic solvent and it may use 2 or more types together. The amount of the organic solvent is not particularly limited, but it is preferable to use an amount that gives a viscosity (25 ° C.) of the composition of 300 to 2000 mPa · s from the viewpoint of coating properties.

<Method for producing composition>
The composition of the present invention can be produced by mixing the above-described components (including at least the components (A) to (C)) using a kneading roller, a rotary mixer, or the like. After mixing (B) component and (C) component first, you may mix the other component (Other component containing at least (A) component) with the mixture. Moreover, after mixing (C) component and any other than (B) component, (B) component may be mixed and the remaining component may be mixed after that.

<Application>
In particular, the sealing composition of the present invention is formed on a thin plastic substrate (plastic film) such as thin film transistors, LCD elements, LED elements, EL elements (organic EL elements, inorganic EL elements), and solar cells. It is suitable for sealing a flexible electronic device. Thin plastic substrates (plastic films) for flexible electronic devices include, for example, poly (ethylene terephthalate) (PET), poly (butylene terephthalate) (PBT), poly (ethylene naphthalate) (PEN), polycarbonate (PC), Plastic films such as films of polyimide (PI), liquid crystal polymer (LCP), cycloolefin polymer (COP), polysulfone (PSO) and poly (p-phenylene ether sulfone) (PES) are used. The composition exhibits excellent adhesion to these various plastic films.

The composition of the present invention is disposed so as to be in contact with the object to be sealed. Preferably, sealing is performed by laminating a sealing sheet having a composition layer formed on a support so that the composition layer is in contact with an element to be sealed (for example, an element substrate of a flexible electronic device). .

<Sealing sheet>
For example, the composition of the present invention, which is formed into a varnish by blending an organic solvent, is applied onto a support, and the resulting coating film is dried by heating or hot air blowing, etc. A sealing sheet which is a sheet on which a layer of the composition is formed is obtained. In the composition, as the component (A), a polyolefin resin having an acid anhydride group or a polyolefin rubber having an acid anhydride group, and a polyolefin resin having an epoxy group or a polyolefin rubber having an acid anhydride group In the case of a sealing sheet prepared by using a composition containing an acid anhydride group and an epoxy group at the time of preparation, a cross-linked structure is formed to prevent permeation resistance of the composition layer. A sheet for sealing with higher wettability and higher sealing performance (such as the ability to block moisture and oxygen in the air) can be obtained.

Examples of the support used for the sealing sheet include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes referred to as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and the like. The plastic film is mentioned. As the plastic film, PET is particularly preferable. The support may be a metal foil such as an aluminum foil, a stainless steel foil, or a copper foil. The support may be subjected to a release treatment in addition to the mat treatment and the corona treatment (hereinafter, the “support subjected to the release treatment” is also referred to as “releasable support”). Examples of the release treatment include a release treatment with a release agent such as a silicone resin release agent, an alkyd resin release agent, and a fluororesin release agent. In the present invention, when the support has a release layer, the release layer is also regarded as a part of the support. The thickness of the support is not particularly limited, but is preferably 20 to 200 μm, more preferably 20 to 125 μm, from the viewpoint of handleability and the like.

The peelable support is a support that has been subjected to a release treatment on one side on which the layer of the composition of the present invention is formed, and before the sealing sheet is actually used to form a sealing structure. A support to be peeled off. For this reason, the peelable support is not necessarily moisture-proof, but from the viewpoint of preventing moisture from entering the composition layer during the storage period until the sealing sheet is subjected to sealing, It is preferable to have moisture resistance. In order to improve the moisture resistance of the sealing sheet, a plastic film having a barrier layer may be used as a support (hereinafter, the plastic film having a barrier layer is also referred to as a “moisture-proof support”). Examples of the barrier layer include nitrides such as silicon nitride, oxides such as aluminum oxide, stainless steel foil, and metal foil of aluminum foil. Examples of the plastic film include the above-described plastic film. A commercial product may be used as the plastic film having the barrier layer. The moisture-proof support may be a film obtained by laminating a metal foil and a plastic film. For example, commercially available products of polyethylene terephthalate film with aluminum foil include “PET Tsuki AL1N30” manufactured by Tokai Toyo Aluminum Sales Co., “PET Tsuki AL3025” manufactured by Fukuda Metals. Moreover, what has the multilayer structure of 2 or more layers, for example, what bonded together said plastic film and said metal foil through the adhesive agent can also be used. This is inexpensive and advantageous from the viewpoint of handling properties.

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

The sealing sheet has high moisture resistance by laminating the sealing sheet on the object to be sealed if the supporting body has moisture resistance and a support having high transmittance. A sealing structure can be formed. Examples of such a support having moisture resistance and high transmittance include a plastic film in which an inorganic substance such as silicon oxide (silica), silicon nitride, SiCN, and amorphous silicon is deposited on the surface. Examples of the plastic film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, and polyimide. As the plastic film, PET is particularly preferable. Examples of commercially available moisture-proof plastic films include Tech Barrier HX, AX, LX, L series (Mitsubishi Plastics) and X-BARRIER (Mitsubishi Plastics) with improved moisture resistance. It is done. A support having a multilayer structure of two or more layers may be used.

In the case of a sealing sheet having a peelable support, after the sealing sheet is laminated to a sealing target, the support is peeled off, and a separately prepared sealing substrate (a moisture-proof plastic film, Metal foil such as copper foil and aluminum foil) can be laminated.

A circularly polarizing plate can be used as the support for the sealing sheet of the present invention. Generally, a circularly polarizing plate is composed of a polarizing plate and a quarter wavelength plate. When using a circularly-polarizing plate as a support body, a quarter wavelength plate is generally arrange | positioned at the composition layer side. Moreover, when using the support body which contains both a circularly-polarizing plate and a moisture-proof support body, Preferably a moisture-proof support body is arrange | positioned at the composition layer side, and the quarter wavelength plate of a circularly-polarizing plate is on the moisture-proof support side. Be placed. The moisture-proof support and the circularly polarizing plate can be bonded with an adhesive or the like, and the adhesive is not particularly limited as long as it is a highly transparent adhesive. For example, an acrylic adhesive, a polyvinyl alcohol adhesive Etc. are used.

The circularly polarizing plate can be provided with a protective film for protecting the polarizer (polarizing plate), and a known protective film can also be used. For example, JP-A-2016-105166 and International Mention may be made of the protective film described in the published 2014/003189 pamphlet and the like.

In the sealing sheet of the present invention, the support is preferably composed of at least one selected from a peelable support, a moisture-proof support and a circularly polarizing plate.

<Flexible electronic devices>
When a flexible electronic device in which an electronic element is sealed with the composition of the present invention is manufactured, it is preferable to perform sealing using the sealing sheet. That is, the flexible electronic device in which the electronic element is sealed is obtained by laminating the sealing sheet of the present invention on a plastic substrate (element substrate) including the electronic element of the flexible electronic device.

Since the sealing composition of the present invention has excellent adhesion to a sealing object and excellent flexibility, it is possible to improve the performance and life of flexible electronic devices.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the following description, “parts” and “%” in the amounts of components and copolymerized units mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

The raw materials used in Examples and Comparative Examples are as follows.
(A) Polyolefin resin or polyolefin rubber 065 (manufactured by JSR): Butyl rubber (isobutylene / isoprene copolymer)
N50SF (manufactured by BASF): polyisobutylene (number average molecular weight: 400,000)
ER850 (manufactured by Seiko PMC): 20% toluene solution of glycidyl methacrylate (GMA) modified butyl rubber (epoxy group concentration 0.64 mmol / g, number average molecular weight 110,000) ER641 (manufactured by Seiko PMC): maleic anhydride (MA) 35% toluene solution of modified butyl rubber (acid anhydride group concentration 0.46 mmol / g, number average molecular weight 57,000)

(B) Inorganic filler DHT-4C (manufactured by Kyowa Chemical Industry Co., Ltd.): Semi-calcined hydrotalcite (average particle diameter 400 nm, BET specific surface area 15 m ² / g)
MK300 (manufactured by Coop Chemical Co.): mica (average particle size 15 μm)
STN (manufactured by Corp Chemical): Smectite (average particle size 50 nm)

(C) Metal complex (titanium complex)
ORGATICS TC710 (manufactured by Matsumoto Fine Chemical Co.): titanium diisopropoxybis (ethyl acetoacetate) Ti content 7.1% by mass
ORGATICS TC750 (manufactured by Matsumoto Fine Chemical Co.): titanium diisopropoxybis (ethyl acetoacetate) Ti content 11.0% by mass

(Aluminum complex)
・ Aluminum chelate M (manufactured by Kawaken Fine Chemical Co.): Aluminum alkyl acetoacetate diisopropylate

(Zirconium complex)
・ Orgachix ZC540 (Matsumoto Fine Chemical Co., Ltd.): zirconium tributoxy monoacetylacetonate

(C ') Metal complex (titanium complex)
・ Plenact 38S (manufactured by Ajinomoto Fine Techno Co.): Titanium isopropoxy tris (dioctyl pyrophosphate)

(Aluminum complex)
AL-3200 (Matsumoto Fine Chemical Co., Ltd.): Aluminum bisethyl acetoacetate monoacetylacetonate

(Zirconium complex)
・ Orgachix ZC320 (Matsumoto Fine Chemical Co., Ltd.): Zirconium stearate

(E) Additive (E-1) Antioxidant Irganox 1010 (manufactured by BASF)
(E-2) Curing agent / Amine curing agent (2,4,6-tris (diaminomethyl) phenol, hereinafter abbreviated as “TAP”)

(F) Organic solvent / toluene / Ipsol # 1000 (made by Idemitsu): Aromatic mixed solvent

<Example 1>
Add 20 parts of ipsol 100 to 3 parts of butyl rubber (065) and stir for 3 hours. Roll 3 parts of 1 part of aluminum alkyl acetoacetate diisopropylate (aluminum chelate M) and 20 parts of semi-calcined hydrotalcite (DHT-4C). To obtain a mixture. To the obtained mixture, 493 parts of toluene was added to 87 parts of butyl rubber (065), and the total amount of the dissolved product obtained by stirring for 3 hours was added. Further, 1 part of an antioxidant (Irganox 1010) and 9 parts of toluene were blended. The obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish (varnish 1) of the composition.

<Example 2>
Add 20 parts of ipsol 100 to 3 parts of butyl rubber (065) and stir for 3 hours. Roll 3 parts of 1 part of aluminum alkyl acetoacetate diisopropylate (aluminum chelate M) and 20 parts of semi-calcined hydrotalcite (DHT-4C). To obtain a mixture. To the obtained mixture, 226.6 parts of toluene was added to 37 parts of butyl rubber (065) and stirred for 3 hours. 100 parts of glycidyl methacrylate-modified butyl rubber (ER850, 20% toluene solution) and maleic anhydride-modified butyl rubber (ER641, 35 parts toluene solution) 86 parts, antioxidant (Irganox 1010) 1 part, toluene 9 parts, amine curing agent (TAP) 0.2 part, and the resulting mixture is uniformly dispersed with a high-speed rotary mixer Thus, a varnish (varnish 2) of the composition was obtained.

<Example 3>
Instead of butyl rubber (065), polyisobutylene (Oppanol N50SF) is used, 20 parts of semi-calcined hydrotalcite (DHT-4C) is made 15 parts, and 1 part of aluminum alkyl acetoacetate diisopropylate (aluminum chelate M) is added. Instead, a varnish (varnish 3) of the composition was obtained in the same manner as varnish 2 (Example 2) except that 1 part of titanium diisopropoxybis (ethylacetoacetate) (TC710) was added.

<Example 4>
Instead of 1 part of titanium diisopropoxybis (ethylacetoacetate) (TC710), 1 part of titanium diisopropoxybis (ethylacetoacetate) (TC750) was added and the same procedure as in Varnish 3 (Example 3) A varnish (varnish 4) of the composition was obtained.

<Example 5>
Instead of 1 part of titanium diisopropoxybis (ethyl acetoacetate) (TC710), the same procedure as in varnish 3 (Example 3) except that 2.2 parts of zirconium tributoxy monoacetylacetonate (ZC540) was added, A varnish (varnish 5) of the composition was obtained.

<Example 6>
Add 20 parts of ipsol 100 to 3 parts of butyl rubber (065) and stir for 3 hours. Disperse 1 part of aluminum alkyl acetoacetate diisopropylate (aluminum chelate M) and 20 parts of mica (MK300) with 3 rolls. Got. To the obtained mixture, 493 parts of toluene was added to 87 parts of butyl rubber (065) and all the dissolved product obtained by stirring for 3 hours was added, and the resulting mixture was uniformly dispersed with a high-speed rotary mixer. A varnish (varnish 6) was obtained.

<Example 7>
A varnish (varnish 7) of the composition was obtained in the same manner as varnish 6 (Example 6) except that 20 parts of smectite (STN) was added instead of 20 parts of mica (MK300).

<Comparative Example 1>
A varnish (varnish 8) of the composition was obtained in the same manner as varnish 1 (Example 1) except that 1 part of aluminum alkyl acetoacetate diisopropylate (aluminum chelate M) was not included.

<Comparative example 2>
In the same manner as Varnish 5 (Example 5) except that 1.2 parts of zirconium stearate (ZC320) was used instead of 2.2 parts of zirconium tributoxy monoacetylacetonate (ZC540), the varnish ( Varnish 9) was obtained.

<Comparative Example 3>
A varnish (varnish 10) of the composition was obtained in the same manner as varnish 6 (Example 6) except that 1 part of aluminum alkyl acetoacetate diisopropylate (aluminum chelate M) was not included.

<Comparative example 4>
Similar to Varnish 3 (Example 3), except that 1 part of aluminum bisethylacetoacetate monoacetylacetonate (AL-3200) was added instead of 1 part of titanium diisopropoxybis (ethylacetoacetate) (TC710). Thus, a composition varnish (varnish 11) was obtained.

<Comparative Example 5>
Instead of 1 part of titanium diisopropoxybis (ethylacetoacetate) (TC710), 1 part of titanium isopropoxytris (dioctylpyrophosphate) (preneact 38S) was added and the same as in varnish 3 (Example 3). A varnish (varnish 12) of the composition was obtained.

<Preparation of sealing sheet>
Using each varnish prepared in each example and each comparative example, the varnish was coated on the release-treated surface of the PET film which was release-treated with the silicone-based release treatment agent, and dried at 120 ° C. for 15 minutes. Thus, a sealing sheet (sealing sheet of each example and each comparative example) was produced.

<Evaluation>
The following evaluation was performed about the sheet | seat for sealing of each Example and each comparative example.

<Adhesion evaluation>
The sealing sheet was cut to a length of 50 mm and a width of 20 mm, and the cut sealing sheet was made of aluminum having a length of 100 mm and a width of 25 mm using a batch-type vacuum laminator (Nichigo Morton, V-160). The film was laminated on the PET surface of a foil / PET composite film “PET Tsuki AL1N30” (aluminum foil: 30 μm, PET: 25 μm, trade name: Toyo Aluminum Sales Co., Ltd.). Lamination was performed under conditions of a temperature of 80 ° C., a time of 300 seconds, and a pressure of 0.3 MPa. Then, the PET film release-treated with the silicone-type release treatment agent of the sealing sheet is peeled off, and a glass plate (length 76 mm, width 26 mm, thickness 1.2 mm, micrometer) is further formed on the exposed composition layer. A glass slide was laminated under the same conditions as above. With respect to the obtained laminate, the adhesive strength (peel strength) to the glass plate surface when peeled at a tensile rate of 300 mm / min in the direction of 180 degrees with respect to the length direction of the aluminum foil / PET composite film is measured. Then, the adhesiveness was evaluated according to the following criteria.

Good (◯): Adhesive strength of 0.3 kgf / cm or higher Possible (Δ): Adhesive strength of 0.2 or higher to less than 0.3 kgf / cm Poor (x): Adhesive strength of less than 0.2 kgf / cm

<Flexibility evaluation>
<Sample>
(1) Sample A
A batch type vacuum laminator (manufactured by Nichigo Morton Co., Ltd.) is used on the inorganic film surface of the barrier film in which the inorganic film (SiO ₂ film having a thickness of 500 nm) is formed on the cycloolefin polymer film (thickness: 50 μm). , V-160) to obtain a film for evaluating flexibility (sample A).

(2) Sample B
A batch type vacuum laminator (manufactured by Nichigo Morton Co., Ltd.) is used on the inorganic film surface of the barrier film in which the inorganic film (SiO ₂ film having a thickness of 500 nm) is formed on the cycloolefin polymer film (thickness: 50 μm). , V-160) to obtain a laminated film, and a batch-type vacuum laminator (V-160, manufactured by Nichigo Morton Co., Ltd.) is used for the sealing film side of the laminated film and the polyimide film (thickness 25 μm). Was used as a film for evaluation of flexibility (sample B).

<Flexibility test>
(1) Sample A
The film for flexibility evaluation was installed with a U-shaped folding tester (manufactured by Yuasa Co., Ltd.) so that the sealing sheet was inside, and it was bent 10,000 times at a radius of curvature of 5 mm and a bending speed of 60 rpm / min. Then, cracks in the inorganic film after bending were confirmed with a microscope. Flexibility evaluation was performed up to 100,000 times.
(2) Sample B
A flexible evaluation film was installed with a U-shaped folding tester (manufactured by Yuasa Co., Ltd.) so that the cycloolefin polymer film was inside, and bent at a curvature radius of 5 mm and a bending speed of 60 rpm / min. The crack of the inorganic film after bending was confirmed with a microscope. Flexibility evaluation was performed up to 10,000 times.

(Evaluation criteria)
Sample A
Good (O): No crack after 100000 bendings (100K <)
Possible (△): Crack generated by 80,000 to 100,000 bends (80K to 100K)
Defect (x): Crack generated by bending less than 80,000 times (80K>)

Sample B
Good (○): No crack after 10,000 bending (10K <)
Possible (△): Crack generated by bending 8,000 to 10,000 times (8K to 10K)
Defect (x): Crack generated by bending less than 8,000 times (8K>)

Tables 1 and 2 below show the composition of Examples and Comparative Examples and the results of evaluation tests.

In the above table, all values other than the solvent are non-volatile values. From the results in the above table, the sealing films of Examples 1 to 7 were excellent in adhesion to glass, and in the evaluation of flexibility, it was recognized that cracks at the interface after bending were suppressed.

The sealing composition of the present invention is suitable for sealing electronic elements and the like in flexible electronic devices.

This application is based on Japanese Patent Application No. 2018-066992 filed in Japan, the contents of which are incorporated in full herein.

Claims

A sealing composition comprising the following components (A) to (C):
(A) Polyolefin resin and / or polyolefin rubber (B) Inorganic filler (C) A bidentate ligand in which two coordination atoms are both oxygen atoms and a monodentate ligand in which the coordination atoms are oxygen atoms Metal complex bound to the central metal
(C) The sealing composition according to claim 1, wherein the central metal of the metal complex is aluminum, titanium, or zirconium.
(C) The metal complex has the general formula (1):

(Where
M represents the metal of the second period to the sixth period of the periodic table,
R 1 and R 3 are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryl group that may have a substituent, or Represents an aralkyl group which may have a substituent,
R 2 has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a substituent. An aryl group that may be substituted or an aralkyl group that may have a substituent,
X represents a monodentate ligand in which the coordination atom is an oxygen atom,
The solid line between the oxygen atom (O) and M in [] represents a covalent bond,
The broken line between the oxygen atom (O) and M in [] represents a coordination bond, and m is an integer of 3 or 4, n is an integer of 1 to 3, and m> n . )
The composition for sealing of Claim 1 which is a metal complex represented by these.
The composition for sealing according to claim 3, wherein M in the formula (1) is aluminum, titanium, or zirconium.
The sealing composition according to any one of claims 1 to 4, wherein (B) the inorganic filler is surface-treated with (C) a metal complex.
The sealing composition according to any one of claims 1 to 5, wherein the polyolefin resin and / or the polyolefin rubber is a polymer having a polyisobutylene skeleton.
The sealing composition according to any one of claims 1 to 6, wherein the polyolefin resin comprises a polyolefin resin having an acid anhydride group and / or a polyolefin resin having an epoxy group.
The sealing composition according to any one of claims 1 to 6, wherein the polyolefin rubber comprises a polyolefin rubber having an acid anhydride group and / or a polyolefin rubber having an epoxy group.
The sealing composition according to any one of claims 1 to 6, which satisfies at least one of the following (a) to (d):
(A) The polyolefin resin includes a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group.
(B) The polyolefin rubber includes a polyolefin rubber having an acid anhydride group and a polyolefin rubber having an epoxy group.
(C) The polyolefin resin includes a polyolefin resin having an acid anhydride group, and the polyolefin rubber includes a polyolefin rubber having an epoxy group.
(D) The polyolefin-based rubber includes a polyolefin-based rubber having an acid anhydride group, and the polyolefin-based resin includes a polyolefin-based resin having an epoxy group.
The sealing composition according to any one of claims 1 to 9, further comprising 10% by mass or less of (D) a tackifying resin with respect to 100% by mass of the nonvolatile component of the composition.
The sealing composition according to any one of claims 1 to 10, which is used for sealing a flexible electronic device.
The sealing composition according to claim 11, wherein the flexible electronic device is a flexible organic EL device.
A sealing sheet comprising a support and a layer of the composition according to any one of claims 1 to 8 and 10 formed on the support.
A support and a layer of the composition according to claim 9 formed on the support, wherein the composition layer has a cross-linked structure formed by reaction of an acid anhydride group and an epoxy group. , Sheet for sealing.
The sealing sheet according to claim 13 or 14, wherein the support is composed of at least one selected from a peelable support, a moisture-proof support and a circularly polarizing plate.
The sealing sheet according to any one of claims 13 to 15, which is used for sealing a flexible electronic device.
The sealing sheet according to claim 16, wherein the flexible electronic device is a flexible organic EL device.
A flexible electronic device, wherein an electronic element formed on a plastic substrate is sealed with the sealing composition according to any one of claims 1 to 8 and 10.
An electronic device formed on a plastic substrate is sealed with the sealing composition according to claim 9 or 10, and the sealing composition is formed by a reaction between an acid anhydride group and an epoxy group. A flexible electronic device having a crosslinked structure.
The flexible electronic device according to claim 18 or 19, wherein the electronic element is an organic EL element, and the flexible electronic device is a flexible organic EL device.