CN111868162A

CN111868162A - Sealing composition

Info

Publication number: CN111868162A
Application number: CN201980022235.1A
Authority: CN
Inventors: 名取直辉; 户村文弥; 山本有希; 增山学; 大桥贤
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2018-03-30
Filing date: 2019-03-29
Publication date: 2020-10-30
Also published as: JP7334731B2; KR102664520B1; JPWO2019189723A1; WO2019189723A1; KR20200138344A

Abstract

The present invention provides a sealing composition containing the following components (A) to (C). (A) A polyolefin resin and/or a polyolefin rubber, (B) an inorganic filler, and (C) a metal complex in which a bidentate ligand in which both coordinating atoms are oxygen atoms and a monodentate ligand in which the coordinating atom is an oxygen atom are bonded to a central metal.

Description

Sealing composition

Technical Field

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

Background

Organic EL devices are light-emitting devices using organic substances as light-emitting materials, and have recently attracted attention because they can emit light with high luminance at low voltage. However, the organic EL element has poor resistance to moisture, and it is necessary to block moisture in the inside of the element from the outside air. Thus, the following operations may be performed: the sealing layer is formed from the composition to cover the entire surface of the light-emitting layer formed on the substrate, thereby sealing the organic EL element. Since good adhesion to a substrate on which an element is formed is required, a tackifier resin is sometimes used in such a sealing composition. For example, patent document 1 discloses a composition containing a polyisobutylene resin, a polyisoprene resin and/or a polyisobutylene resin having a functional group reactive with an epoxy group, a tackifier resin, and an epoxy resin. Further, patent document 2 discloses a composition containing a styrene-isobutylene modified resin and a tackifier resin. Patent document 3 discloses a sealing composition containing a polyolefin resin, hydrotalcite, and a tackifier resin.

In recent years, development of flexible electronic devices that are flexible and bendable (hereinafter, also simply referred to as "flexible devices") has been actively promoted, and for example, sealing materials used for flexible organic EL devices are increasingly required to have excellent bendability. On the other hand, a composition using a polyolefin rubber or the like is generally excellent in flexibility, and is considered to be advantageous as a sealing material for flexible electronic devices. In addition, it is considered that the addition of an inorganic filler is useful for improving the properties of the sealing material such as moisture resistance.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2011/62167 pamphlet

Patent document 2: international publication No. 2013/108731 pamphlet

Patent document 3: international publication No. 2017/057708 pamphlet.

Disclosure of Invention

Problems to be solved by the invention

However, as a result of studies by the present inventors, it has been found that when an inorganic filler is added to a composition containing a polyolefin resin and/or a polyolefin rubber, the flexibility of a flexible device and the adhesiveness between a substrate provided with an electronic component (hereinafter, also simply referred to as an "element substrate") and the composition tend to be reduced. Accordingly, an object of the present invention is to provide a sealing composition having excellent adhesiveness and bendability.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that a composition obtained by blending a metal complex having a structure in which a bidentate ligand having 2 coordinating atoms as oxygen atoms and a monodentate ligand having a coordinating atom as oxygen atoms are coordinated to a central metal together with an inorganic filler in a polyolefin resin or a polyolefin rubber is excellent in adhesiveness and bendability, and have completed the present invention.

That is, the present invention has the following features,

[1] a sealing composition comprising the following components (A) to (C),

(A) a polyolefin resin and/or a polyolefin rubber,

(B) an inorganic filler, wherein the inorganic filler is an inorganic filler,

(C)2 bidentate ligands with oxygen atoms as coordination atoms and monodentate ligands with oxygen atoms as coordination atoms are combined with the central metal to form a metal complex;

[2] the sealing composition according to the above [1], wherein the central metal of the (C) metal complex is aluminum, titanium or zirconium;

[3] the sealing composition according to the above [1], wherein the metal complex (C) is a metal complex represented by the general formula (1).

[ chemical formula 1]

。

(in the formula, wherein,

m represents a metal in the 2 nd to 6 th periods of the periodic Table,

R₁And R₃Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent,

R₂represents a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, an alkoxycarbonyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent,

x represents a monodentate ligand whose coordinating atom is an oxygen atom,

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

[] The dotted line between the oxygen atom (O) in (A) and M represents a coordinate bond, and

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

[4] The sealing composition according to the above [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 the above [1] to [5], wherein the polyolefin resin and/or the polyolefin rubber is a polymer having a polyisobutylene skeleton;

[7] the sealing composition according to any one of the above [1] to [6], wherein the polyolefin resin contains a polyolefin resin having an acid anhydride group and/or a polyolefin resin having an epoxy group;

[8] The sealing composition according to any one of the above [1] to [6], wherein the polyolefin rubber contains a polyolefin rubber having an acid anhydride group and/or a polyolefin rubber having an epoxy group;

[9] the sealing composition according to any one of the above [1] to [6], which satisfies at least one of the following (a) to (d),

(a) the polyolefin resin comprises a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group,

(b) the polyolefin rubber comprises a polyolefin rubber having an acid anhydride group and a polyolefin rubber having an epoxy group,

(c) the polyolefin-based resin includes a polyolefin-based resin having an acid anhydride group, the polyolefin-based rubber includes a polyolefin-based rubber having an epoxy group,

(d) the polyolefin rubber includes a polyolefin rubber having an acid anhydride group, and the polyolefin resin includes a polyolefin 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 of (D) a tackifier resin per 100% by mass of nonvolatile components of the composition;

[11] the sealing composition according to any one of the above [1] to [10], which is used for sealing a flexible electronic device;

[12] The sealing composition 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 sealing sheet comprising a support and a layer of the composition according to [9] above formed on the support, the layer of the composition having a crosslinked structure formed by a reaction of an acid anhydride group and an epoxy group;

[15] the sealing sheet according to the above [13] or [14], wherein the support is composed of at least one member selected from a releasable support, a moisture-proof support and a circularly polarizing plate;

[16] the sealing sheet according to any one of the above [13] to [15], which is used for sealing a flexible electronic device;

[17] the sealing sheet according to the above [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 the above [1] to [8] and [10 ];

[19] a flexible electronic device wherein an electronic element formed on a plastic substrate is sealed with the sealing composition according to [9] above, the sealing composition having a crosslinked structure formed by a reaction between an acid anhydride group and an epoxy group;

[20] The flexible electronic device according to the above [18] or [19], wherein the electronic element is an organic EL element, and the flexible electronic device is a flexible organic EL device.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can realize a sealing composition having excellent adhesiveness and bendability. Therefore, the sealing composition of the present invention exhibits excellent effects particularly as a sealing material for flexible electronic devices in which an element substrate is formed of a plastic substrate.

Detailed Description

[ composition for sealing ]

The sealing composition of the present invention (hereinafter, also simply referred to as "composition") contains, as essential components, (a) a polyolefin resin and/or a polyolefin rubber, (B) an inorganic filler, and (C) a metal complex in which 2 bidentate ligands each having an oxygen atom as a coordinating atom and monodentate ligands each having an oxygen atom as a coordinating atom are bonded to a central metal.

< (A) polyolefin resin and/or polyolefin rubber

The sealing composition of the present invention contains a polyolefin resin and/or a polyolefin rubber (hereinafter, also referred to as "component (a)"). The polyolefin resin and the polyolefin rubber are not particularly limited as long as each has a skeleton derived from an olefin. The term "olefin" as used herein means a monoolefin and/or diolefin. The monoolefin is preferably an α -olefin such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc., and the diolefin is preferably 1, 3-butadiene, isoprene, 1, 3-pentadiene, 2, 3-dimethylbutadiene, etc. The monoolefin and the diolefin may be each 1 kind or 2 or more kinds.

In the present invention, the component (a) may be 1 kind of polymer or a mixture of 2 or more kinds of polymers, and may include various forms such as 1 kind of polyolefin resin, 1 kind of polyolefin rubber, a mixture of 2 or more kinds of polyolefin resins, a mixture of 2 or more kinds of polyolefin rubbers, and a mixture of 1 or more kinds of polyolefin resins and 1 or more kinds of polyolefin rubbers.

(polyolefin resin)

The polyolefin resin may be any of a homopolymer, a random copolymer, and a block copolymer. In addition, as the copolymer, there may be mentioned: (i) copolymers of 2 or more kinds of monoolefins, (ii) copolymers of monoolefins and diolefins, and (iii) copolymers of monoolefins and unsaturated compounds (excluding diene monomers) other than olefins, such as unsaturated carboxylic acid esters (e.g., methyl methacrylate) and aromatic vinyl compounds (e.g., styrene).

The polyolefin resin is preferably a polyisobutylene resin or a polypropylene resin. Here, the "polyisobutylene-based resin" refers to a resin in which the main units (maximum content units) of all the olefin monomer units constituting the polymer are isobutylene, and the "polypropylene-based resin" refers to a resin in which the main units (maximum content units) of all the olefin monomer units constituting the polymer are propylene.

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

The polyolefin resin may contain a polyolefin resin having an acid anhydride group (i.e., carbonyloxycarbonyl group (-CO-O-CO-)) and/or a polyolefin resin having an epoxy group, from the viewpoint of further improving the adhesiveness of the sealing composition to a sealing object, the adhesion moisture-heat resistance of the composition, and the like. Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, and a group derived from glutaric anhydride. 1 or 2 or more acid anhydride groups may be present. The polyolefin-based resin having an acid anhydride group can be obtained by, for example, graft-modifying a polyolefin-based resin with an unsaturated compound having an acid anhydride group under radical reaction conditions. In addition, the unsaturated compound having an acid anhydride group may be subjected to radical copolymerization together with an olefin. Similarly, the polyolefin resin having an epoxy group can be obtained by graft-modifying a polyolefin resin with an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, or allyl glycidyl ether under radical reaction conditions. In addition, the unsaturated compound having an epoxy group may be subjected to radical copolymerization together 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 10mmol/g, more preferably 0.1 to 5 mmol/g. The concentration of the acid anhydride group can be obtained from the value of the acid value defined as the mg number of potassium hydroxide required for neutralizing the acid present in 1g of the resin in accordance with JIS K2501.

In the polyolefin resin having epoxy groups, the concentration of epoxy groups in the resin is preferably 0.05 to 10mmol/g, more preferably 0.1 to 5 mmol/g. The epoxy group concentration can be determined from the epoxy equivalent obtained in accordance with JIS K7236-1995.

(polyolefin rubber)

Examples of the polyolefin-based rubber include butyl rubber (IIR) (a rubber-like copolymer of isobutylene and isoprene), Isoprene Rubber (IR), Butadiene Rubber (BR), a carboxylated rubber-like copolymer of styrene and butadiene (XSBR), a chlorinated rubber-like Copolymer of Isobutylene and Isoprene (CIIR), a brominated rubber-like copolymer of isobutylene and isoprene (BIIR), and the like. 1 or 2 or more of them may be used. Among them, butyl rubber, isoprene rubber and butadiene rubber are preferable, and butyl rubber is more preferable.

The polyolefin rubber may contain a polyolefin rubber having an acid anhydride group (i.e., carbonyloxycarbonyl group (-CO-O-CO-)) and/or a polyolefin rubber having an epoxy group, from the viewpoint of further improving the adhesiveness of the sealing composition to a sealing object, the adhesion moisture-heat resistance of the composition, and the like. Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, and a group derived from glutaric anhydride. The acid anhydride group may have 1 or 2 or more. The polyolefin rubber having an acid anhydride group can be obtained, for example, by graft-modifying a polyolefin rubber with an unsaturated compound having an acid anhydride group under radical reaction conditions. In addition, the unsaturated compound having an acid anhydride group may be subjected to radical copolymerization together with an olefin or the like. Similarly, the polyolefin rubber having an epoxy group can be obtained by graft-modifying a polyolefin rubber with an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, or allyl glycidyl ether under a radical reaction condition. In addition, an unsaturated compound having an epoxy group may be subjected to radical copolymerization together with an olefin or the like.

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, and particularly preferably a butyl rubber having an acid anhydride group. The polyolefin 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 10mmol/g, more preferably 0.1 to 5 mmol/g. The concentration of the acid anhydride group can be obtained from the value of the acid value defined as the mg number of potassium hydroxide required for neutralizing the acid present in 1g of the rubber in accordance with JIS K2501.

In the polyolefin rubber having epoxy groups, the concentration of epoxy groups in the rubber is preferably 0.05 to 10mmol/g, more preferably 0.1 to 5 mmol/g. The epoxy group concentration can be determined from the epoxy equivalent obtained in accordance with JIS K7236-1995.

A preferable embodiment of the present invention includes an embodiment in which 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 of the entire component (A).

In the case of the embodiment in which the component (a) contains the polyolefin resin having an acid anhydride group and/or the polyolefin rubber having an acid anhydride group, the amount of the polyolefin resin having an acid anhydride group and/or the polyolefin rubber having an acid anhydride group is preferably 1 to 70% by mass, and more preferably 10 to 50% by mass, based on the whole component (a). In the case of the embodiment in which the component (a) contains a polyolefin resin having epoxy groups and/or a polyolefin rubber having epoxy groups, the amount of the polyolefin resin having epoxy groups and/or the polyolefin rubber having epoxy groups is preferably 1 to 70% by mass, and more preferably 10 to 50% by mass, based on the entire component (a).

From the viewpoint of further improving the moisture resistance of the sealing composition, the component (a) is preferably a form that satisfies at least one of the following (a) to (d):

(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.

In the component (a), the acid anhydride group and the epoxy group react with each other by heating to form a crosslinked structure. Therefore, the composition of the present invention can form a sealing layer having further improved moisture permeation resistance and the like. The crosslinked structure may be formed after the sealing with the composition (i.e., after the formation of the sealing layer), but for example, in the case of including an element whose resistance to heat is weak in a device to be sealed such as an organic EL element, it is preferable to form the crosslinked structure in advance in the composition layer formed on the substrate at the time of producing the sealing sheet.

The ratio of the polyolefin-based resin having an acid anhydride group and/or the polyolefin-based rubber having an acid anhydride group to the polyolefin-based resin having an epoxy group and/or the polyolefin-based rubber having an epoxy group is not particularly limited as long as an appropriate crosslinked structure can be formed, and the molar ratio of the epoxy group to the acid anhydride group (epoxy group: acid anhydride group) is preferably 100: 10-100: 200, more preferably 100: 50-100: 150, particularly preferably 100: 90-100: 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) a mixture of butyl rubber, butyl rubber having an acid anhydride group and butyl rubber having an epoxy group.

(A) The number average molecular weight of the component is not particularly limited, but is preferably 1,000,000 or less, more preferably 750,000 or less, even more preferably 500,000 or less, and even more preferably 400,000 or less, from the viewpoint of providing a good coatability of the varnish of the sealing composition and good compatibility with other components in the composition. On the other hand, from the viewpoint of preventing the coating film from sagging (ハジキ) when the varnish of the sealing composition is applied, and of making the formed sealing composition layer exhibit moisture permeation resistance and improving mechanical strength, it is preferably 2,000 or more, more preferably 10,000 or more, still more preferably 30,000 or more, and particularly preferably 50,000 or more. The number average molecular weight can be measured by Gel Permeation Chromatography (GPC) (in terms of polystyrene). The number average molecular weight by GPC was measured at a column temperature of 40 ℃ using a measuring apparatus LC-9A/RID-6A manufactured by Shimadzu corporation, a mobile phase Shodex K-800P/K-804L/K-804L manufactured by Showa Denko K.K., toluene or the like, and a standard curve of standard polystyrene.

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

Specific examples of the component (A) are described below;

specific examples of the polypropylene resin include: "T-YP 341" (glycidyl methacrylate-modified propylene-butene random copolymer, available from Star light PMC., amount of butene units based on 100 mass% of the total of propylene units and butene units: 29 mass%, epoxy group concentration: 0.638mmol/g, number average molecular weight: 155,000), "T-YP 279" (maleic anhydride-modified propylene-butene random copolymer, available from Star light PMC., amount of butene units based on 100 mass% of the total of propylene units and butene units: 36 mass%, acid anhydride group concentration: 0.464mmol/g, number average molecular weight: 35,000), "T-YP 276" (glycidyl methacrylate-modified propylene-butene random copolymer, available from Star light PMC., amount of butene units based on 100 mass% of the total of propylene units and butene units: 36 mass%, epoxy group concentration: 0.638mmol/g, number average molecular weight: 57,000) and "T-YP 312" (maleic anhydride-modified propylene-butene random copolymer, available from starlight PMC corporation, the amount of butene units based on 100 mass% of the total of propylene units and butene units: 29 mass%, acid anhydride group concentration: 0.464mmol/g, number average molecular weight: 60,900), and "T-YP 313" (glycidyl methacrylate-modified propylene-butene random copolymer, available from star PMC corporation, the amount of butene units based on 100 mass% of the total of propylene units and butene units: 29 mass%, epoxy group concentration: 0.638mmol/g, number average molecular weight: 155,000), etc.

Specific examples of the polyisobutylene-based resin include "OPPANOL B100" (polyisobutylene, viscosity average molecular weight: 1,110,000) manufactured by BASF corporation and "N50 SF" (polyisobutylene, viscosity average molecular weight: 400,000) manufactured by BASF corporation.

Specific examples of the polyolefin-based rubber include "065" (butyl rubber) manufactured by JSR corporation, "ER 641" (maleic anhydride-modified butyl rubber having an acid anhydride group concentration of 0.46mmol/g and a number average molecular weight of 57,000) manufactured by starlight PMC corporation, "ER 850" (glycidyl methacrylate-modified butyl rubber having an epoxy group concentration of 0.64mmol/g and a number average molecular weight of 110,000) manufactured by Kraton Polymer corporation, "IR-307", "IR-310" (isoprene rubber having a number average molecular weight of 2,000,000)), and "BR 150B" (butadiene rubber having a number average molecular weight of 500,000) manufactured by yu kohsin corporation.

The content of the component (a) in the sealing composition of the present invention is not particularly limited, and is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 82% by mass or less, and further preferably 80% by mass or less, with respect to the entire nonvolatile components in the composition, from the viewpoint of providing good coatability and compatibility and ensuring good handling properties (suppressing stickiness). From the viewpoint of improving the moisture permeability resistance of the composition, the content is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more, based on the whole nonvolatile components in the composition.

(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 examples thereof include: 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; metal carbonates such as calcium carbonate and 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; metal zirconate such as barium zirconate and calcium zirconate; aluminum borate; mineral fillers such as natural or synthetic clays and organically modified clays. Among them, mineral fillers are preferable.

Among the mineral fillers, natural or synthetic clays may be exemplified by: mica (mica), fluoromica (fluoromica), pyrophyllite (pyrophyllite), glauconite (glauconite), vermiculite (vermiculite), sepiolite (sepiolite), allophane (allophonite), imogolite (imogolite), talc (talc), illite (illite), saponite (sobockite), smifordite (svinfordite), kaolinite (kaolinite), dickite (dickite), nacrite (nacrite), anauxite (anauxite), sericite (serite), triolite (ledikite), smectite (monotronite), halloysite (metahalloysite), serpentine clay (serpenterincalay), chrysotile (chrysolite), phyllite (atroonite), attapulgite (attapulgite), montmorillonite (attapulgite), montmorillonites (attapulgite), smectite (montmorillonite), smectite clay (montmorillonite), smectite (smectite), smectite (smectiteite), smectite (montmorillonite (smectiteite), smectiteite (smectite), smectite (montmorillonite), smectite (smectite), smectite (montmorillonite (smectite), smectite (montmorillonite), smectite (montmorillonite), smectite (montmorillonite), smectite, Bentonite (bentonite), beidellite (beidellite), hectorite (hectorite), sodium hectorite (sodium hectorite), saponite (saponite), sauconite (sauconite), fluorohectorite (fluorohectorite), stevensite (stevensite), volkonskoite (volkonskoite), magadite (magadiite), kenyaite (kenyaite), halloysite (halloyite), hydrotalcite (hydrotalcite), smectite (smitete), smectite-type (smithite-type) clays, and the like.

The organically modified clay refers to a smectite or smectite-type clay produced by allowing a non-functional clay to interact with one or more organizing agents (intercalant). In this case, the type of the organic compound to be used is usually a neutral or ionic organic compound. Examples of the neutral organic compound include monomeric, oligomeric, and polymeric compounds of polar compounds such as amide, ester, lactam, nitrile, urea, carbonate, phosphate, phosphonate, sulfate, sulfonate, and nitro compounds. Such neutral organic compounds incompletely replace the charge-balancing ions of the clay and intercalate into the interlayer of the clay through hydrogen bonds. Examples of the ionic organic compound include onium compounds such as ammonium (primary, secondary, tertiary or quaternary ammonium), phosphonium, sulfonium derivatives, aromatic or aliphatic amines, phosphines, and thioethers; and quaternary ammonium ions having at least 1 long-chain aliphatic group (e.g., octadecyl, myristyl, or oleyl) bonded to a quaternary nitrogen atom.

Among the mineral fillers, mica, hydrotalcite, and smectite are preferable from the viewpoint of moisture resistance, and smectite and hydrotalcite are more preferable, and hydrotalcite is particularly preferable from the viewpoint of facilitating transparency of the sealing layer formed from the composition of the present invention.

Hydrotalcite, which is particularly preferred as the inorganic filler, will be described below. The hydrotalcite may be classified into uncalcined hydrotalcite, semi-calcined hydrotalcite, and the semi-calcined hydrotalcite is particularly preferable from the viewpoint of transparency and moisture resistance of the composition. The uncalcined hydrotalcite is, for example, a natural hydrotalcite (Mg)₆Al₂(OH)₁₆CO₃・4H₂O) as typified by a metal hydroxide having a layered crystal structure, for example, a layer [ Mg ] as a basic skeleton_1-XAl_X(OH)₂]^X+And an intermediate layer [ (CO)₃)_X/2・mH₂O]^X-And (4) forming. The uncalcined hydrotalcite in the present invention is a concept including hydrotalcite-like compounds such as synthetic hydrotalcite. Examples of the hydrotalcite-like compound include compounds represented by the following formula (I) and the following formula (II).

(in the formula, M^2＋Represents Mg^2＋、Zn^2＋Metal ion of equivalent valence 2, M^3＋Represents Al^3＋、Fe^3＋Aliovalent 3 valent metal ion, A^n-Represents CO₃ ^2-、Cl^-、NO₃ ^-The anion with the valence of n is equal to the anion, x is more than 0 and less than 1, m is more than or equal to 0 and less than 1, and n is a positive number. )

In the formula (I), M^2＋Preferably Mg^2＋，M^3＋Preferably Al^3＋，A^n-Preferably CO₃ ^2-。

(in the formula, M^2＋Represents Mg^2＋、Zn^2＋Aliovalent 2-valent metal ion, A^n-Represents CO₃ ^2-、Cl^-、NO₃ ^-An n-valent anion, x is a positive number of 2 or more, z is a positive number of 2 or less, m is a positive number, and n is a positive number. )

In the formula (II), M^2＋Preferably Mg^2＋，A^n-Preferably CO₃ ^2-。

The semi-calcined hydrotalcite refers to a metal hydroxide having a layered crystal structure in which the amount of interlayer water is reduced or eliminated, which is obtained by calcining an uncalcined hydrotalcite. The term "interlayer water" as used herein means "H" described in the above-mentioned compositional formula of the uncalcined natural hydrotalcite and hydrotalcite-like compound ₂O”。

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

Uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by saturated water absorption. The half-calcined hydrotalcite has a saturated water absorption of 1 wt% or more and less than 20 wt%. On the other hand, the non-calcined hydrotalcite has a saturated water absorption of less than 1 wt%, and the calcined hydrotalcite has a saturated water absorption of 20 wt% or more.

The "saturated water absorption" mentioned above means: after measuring an initial mass of uncalcined hydrotalcite, semi-calcined hydrotalcite or calcined hydrotalcite taken out of a scale of 1.5g, the resultant was allowed to stand for 200 hours in a small environmental tester (SH-222 manufactured by ESPEC) set at 60 ℃ and 90% RH (relative humidity) under atmospheric pressure, and the rate of increase in mass of the initial mass after the standing for 200 hours was determined from the following formula (i):

saturated water absorption (mass%) =100 × (mass after moisture absorption-initial mass)/initial mass (i).

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

The uncalcined hydrotalcite, the half-calcined hydrotalcite and the calcined hydrotalcite can be distinguished from each other by the rate of thermal weight loss measured by thermogravimetric analysis. The thermal weight loss rate of the semi-calcined hydrotalcite at 280 ℃ is less than 15 mass%, and the thermal weight loss rate thereof at 380 ℃ is 12 mass% or more. On the other hand, the thermal weight loss rate at 280 ℃ of the uncalcined hydrotalcite was 15 mass% or more, and the thermal weight loss rate at 380 ℃ of the calcined hydrotalcite was less than 12 mass%.

For thermogravimetric analysis, 5mg of hydrotalcite was weighed into an aluminum sample tray using TG/DTA EXSTAR6300 manufactured by Hitach High-Tech Science, and the weighing was carried out under conditions of a temperature rise rate of 10 ℃ per minute from 30 ℃ to 550 ℃ in an atmosphere with a nitrogen flow rate of 200 mL/minute in an open state without a lid. The thermal weight loss ratio can be determined by the following formula (ii):

thermal weight loss ratio (mass%) =100 × (mass before heating-mass at the time of reaching a predetermined temperature)/mass before heating (ii).

The uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite may be distinguished by the peak and relative intensity ratio measured by powder X-ray diffraction. The semi-calcined hydrotalcite exhibits a peak that is split into two peaks or has a shoulder peak by synthesis of two peaks at around 8-18 DEG 2 [ theta ] by powder X-ray diffraction, and the relative intensity ratio (low-angle side diffraction intensity/high-angle side diffraction intensity) between the diffraction intensity (= low-angle side diffraction intensity) of a peak or shoulder peak appearing on the low-angle side and the diffraction intensity (= high-angle side diffraction intensity) of a peak or shoulder appearing on the high-angle side is 0.001-1,000. On the other hand, the uncalcined hydrotalcite has only one peak in the vicinity of 8 to 18 °, or the relative intensity ratio of the diffraction intensity of the peak or shoulder appearing on the low angle side to the peak or shoulder appearing on the high angle side falls outside the aforementioned range. The calcined hydrotalcite has no characteristic peak in the region of 8 ° to 18 ° and has a characteristic peak at 43 °. The powder X-ray diffraction measurement was performed using a powder X-ray diffraction apparatus (Empyrean, manufactured by PANalytical corporation) under the conditions of CuK α (1.5405 Å) for the cathode, a voltage of 45V, a current of 40mA, a sampling width of 0.0260 °, a scanning speed of 0.0657 °/s, and a measurement diffraction angle range (2 θ) of 5.0131 ° to 79.9711 °. The Peak search (Peak search) can be performed under the conditions of "the minimum degree of significance is 0.50, the minimum Peak Tip (Peak Tip) is 0.01 °, the maximum Peak Tip is 1.00 °, the Peak base width is 2.00 °, and the method is the minimum value of the second order differential" by using the Peak search function of software attached to the diffraction device.

Specific examples of the uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite include the following:

zizania DHT-4C (manufactured by synergetics chemical industries corporation): semi-calcined hydrotalcite (average particle diameter: 400nm, BET specific surface area: 15 m)²/g)

Zizania DHT-4A-2 (manufactured by Synhonia chemical industries Co., Ltd.): semi-calcined hydrotalcite (average particle diameter: 400nm, BET specific surface area: 13 m)²/g)

Ziziphi KW-2200 (manufactured by cooperative chemical industries Co., Ltd.): calciningHydrotalcite calcined (average particle diameter: 400nm, BET specific surface area: 146m²/g)

Zizania DHT-4A (manufactured by synergestic chemical industries, Ltd.): uncalcined hydrotalcite (average particle diameter: 400nm, 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, still more preferably 10 μm or less, particularly preferably 5 μm or less, and most preferably 1 μm or less, from the viewpoint of the influence on the object to be sealed and moisture resistance. On the other hand, from the viewpoint of dispersibility of the inorganic filler and viscosity of the composition, it is preferably 0.001 μm or more, more preferably 0.01 μm or more, and still more preferably 0.1 μm or more.

The average particle diameter of the inorganic filler can be determined by a laser diffraction-scattering method based on Mie scattering theory. Specifically, it can be determined by: the particle size distribution of the inorganic filler was prepared on a volume basis by using a laser diffraction particle size distribution measuring apparatus, and the median particle size was defined as an average particle size. The measurement sample may use a product obtained by dispersing an inorganic filler in water using ultrasonic waves. As the laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by horiba, Ltd.

In the inorganic filler, the hydrotalcite preferably has an average particle diameter of 1 to 1,000nm, more preferably 10 to 800 nm. The average particle diameter of hydrotalcite is a median particle diameter of a particle size distribution obtained by measuring the particle size distribution by laser diffraction scattering method (JIS Z8825) and preparing the particle size distribution on a volume basis.

In addition, in the inorganic filler, the BET specific surface area of the hydrotalcite is preferably 1 to 250m²A concentration of 5 to 200m²(ii) in terms of/g. The BET specific surface area of hydrotalcite can be calculated by the BET multipoint method by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring apparatus (manufactured by Macsorb HMModel 1210 MOUNTECH co.ltd.).

(B) The component (C) may be a surface-treated product of a surface-treating agent. 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 them, higher fatty acids and alkylsilanes are preferable. The surface treatment agent may be used in 1 kind or 2 kinds or more.

Examples of the higher fatty acid include higher fatty acids having a carbon number of 18 or more, such as stearic acid, montanic acid, myristic acid, palmitic acid, and the like, and stearic acid is preferable. 1 kind of them may be used or 2 or more kinds may be used in combination. Examples of the alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, and n-octadecyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride. 1 kind of them may be used or 2 or more kinds may be used in combination. Examples of the silane coupling agent include epoxy-based silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (dimethoxy) methylsilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane; amino 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-based silane coupling agents such as 3-ureidopropyltriethoxysilane; vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; styrene-based silane coupling agents such as p-styryltrimethoxysilane; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltrimethoxysilane; sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane and the like. 1 kind of them may be used or 2 or more kinds may be used in combination.

(B) The surface treatment of the composition can be carried out, for example, by: while stirring the untreated component (B) at room temperature using a mixer, the surface treatment agent is added by spraying and stirred for 5 to 60 minutes. As the mixer, a known mixer can be used, and examples thereof include a mixer such as a V-type mixer (blender), a ribbon mixer (ribbon blender), and a double cone mixer (バブルコーンブレンダー), a mixer such as a Henschel mixer (Henschel mixer) and a concrete mixer, a ball mill, a chopper mill (chopper mill), and the like. In addition, when the moisture absorbent material is pulverized by a ball mill or the like, a method of mixing the above-mentioned higher fatty acid, alkylsilane, or silane coupling agent and performing surface treatment may be used. The amount of the surface treatment agent to be treated differs depending on the type of the component (B), the type of the surface treatment agent, and the like, and is preferably 1 to 10 parts by mass per 100 parts by mass of the component (B).

In the present invention, 1 or 2 or more components (B) can be used. The content of the component (B) in the composition is not particularly limited, and is preferably 60% by mass or less, preferably 55% by mass or less, more preferably 50% by mass or less, and still more preferably 45% by mass or less, based on 100% by mass of the total nonvolatile components in the composition, from the viewpoints of adhesion of the sealing layer formed from the composition to electronic components and plastic substrates of flexible electronic devices and transparency of the sealing layer. 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, and still more preferably 10% by mass or more, based on 100% by mass of the total nonvolatile components in the composition.

< (C) Metal Complex

The composition of the present invention contains not only the component (a) and the component (B), but also a metal complex (hereinafter, also referred to as "component (C)") in which a bidentate ligand having 2 coordinating atoms all of which are oxygen atoms and a monodentate ligand having a coordinating atom of which is an oxygen atom are bonded to a central metal.

In the present invention, the metal complex is a chemical species in which a metal atom or ion is bonded with another atom, molecule or ion. The ligand means a molecule or ion bonded to a metal atom or ion. The atom directly involved in the binding is referred to as a coordinating atom, the ligand having 2 coordinating atoms is referred to as a bidentate ligand, and the ligand having 1 coordinating atom is referred to as a monodentate ligand.

(C) The component (b) is not particularly limited as long as it is a metal complex having a structure in which a bidentate ligand in which 2 coordinating atoms are all oxygen atoms (hereinafter, also simply referred to as "oxygen-bidentate ligand") and a monodentate ligand in which the coordinating atoms are oxygen atoms (hereinafter, also simply referred to as "oxygen-monodentate ligand") are bonded to a central metal, and a known metal complex satisfying the above structure can be used. Among them, preferred are metal complexes In which the central metal is a metal In the 2 nd to 6 th periods of the periodic table, more preferred are metal complexes In which the central metal is a metal In the 3 rd to 5 th periods, still more preferred are metal complexes In which the central metal is Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, Zr, In, or Sn, and particularly preferred are metal complexes In which the central metal is Al (aluminum), Ti (titanium), or Zr (zirconium).

Examples of the oxy-bidentate ligand include compounds represented by the following formula (a).

[ chemical formula 2]

。

In the formula (a), R₁、R₂、R₃These meanings are the same as those in the formula (1) described later.

The compound represented by formula (a) represents an oxygen-bidentate ligand before coordinating to the central metal. In the present invention, the oxygen-bidentate ligand in the state of being coordinated to the central metal and the oxygen-bidentate ligand before being coordinated to the central metal are sometimes referred to as "oxygen-bidentate ligand" without being particularly distinguished. Specific examples of the compound represented by the formula (a) are the same as those of the oxygen-bidentate ligand in the metal complex represented by the formula (1) described later.

Examples of the oxygen-monodentate ligand include alkoxide anion (RO)^-) Carboxylate anion (RCOO)^-) And the like. Specific examples of the oxygen-monodentate ligand are also the same as those of the oxygen-monodentate ligand in the metal complex represented by formula (1) described later. In the present invention, the oxygen-monodentate ligand in a state of being coordinated to the central metal and the oxygen-monodentate ligand (alcohol (ROH) or carboxylic acid (RCOOH)) before being coordinated to the central metal are sometimes referred to as "oxygen-monodentate ligands" and are not particularly distinguished.

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

(C) The component (b) 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)).

[ chemical formula 3]

。

In the formula (1), the reaction mixture is,

m is a central metal of the metal complex and represents a metal in the 2 nd to 6 th periods of the periodic table. Preferably a metal of periods 3 to 5, more preferably Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, Zr, In or Sn, and further preferably Al (aluminum), Ti (titanium) or Zr (zirconium);

R₁and R₃Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group;

R₂represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl groupOr aralkyl;

x represents an oxygen-monodentate ligand.

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

m is an integer of 3 or 4, n is an integer of 1-3, and m is greater than n.

R₁、R₂And R₃The alkyl group in ((4) may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a 1-ethylpropyl group, a hexyl group, an isohexyl group, a 1, 1-dimethylbutyl group, a 2, 2-dimethylbutyl group, a 3, 3-dimethylbutyl group, and a 2-ethylbutyl group. The alkyl group optionally has a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an optionally substituted amino group, and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the optionally substituted amino group include an amino group, a mono-or di-alkylamino group (e.g., methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dibutylamino), a mono-or di-cycloalkylamino group (e.g., cyclopropylamino, cyclohexylamino), a mono-or di-arylamino group (e.g., phenylamino), a mono-or di-aralkylamino group (e.g., benzylamino, dibenzylamino), a heterocyclic amino group (e.g., pyridylamino), and the like.

R₁、R₂And R₃The alkoxy group in (3) is preferably an alkoxy group having 1 to 6 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. The alkoxy group optionally has a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an optionally substituted amino group, and the like. Specific examples of the halogen atom and specific examples of the amino group which may have a substituent are the same as those described above.

R₁、R₂And R₃The number of carbon atoms of the aryl group in (1) is preferably 6 to 18, more preferably 6 to 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 optionally has a substituent. Examples of the substituent include a halogen atom, a hydroxyl 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, an amino group which may have a substituent, and the like.

The alkenyl group may be linear or branched. The number of carbon atoms of the alkenyl group is preferably 2 to 10, more preferably 2 to 6. Examples thereof include vinyl (i.e., vinyl), 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl and the like. Examples of the substituent which the alkenyl group may have include a halogen atom, a hydroxyl group, an optionally substituted amino group and the like. Specific examples of the halogen atom and specific examples of the amino group which may have a substituent are the same as those described above.

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

R₁、R₂And R₃The number of carbon atoms of the aralkyl group in (1) is preferably 7 to 16. Examples thereof include benzyl, phenethyl, naphthylmethyl, and phenylpropyl. The aralkyl group optionally has a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an optionally substituted amino group, and the like. Specific examples of the halogen atom, optionally substitutedSpecific examples of the amino group of the group are the same as those described above.

R₂The alkoxycarbonyl group in (1) is preferably an alkoxycarbonyl group having 1 to 6 carbon atoms of an alkoxy group, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, and a hexyloxycarbonyl group. The alkoxycarbonyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an optionally substituted amino group, and the like. Specific examples of the halogen atom are the same as those of the halogen atom as a substituent of the above-mentioned alkyl group, and specific examples of the amino group optionally having a substituent are the same as those of the amino group optionally having a substituent as a substituent of the above-mentioned alkyl group.

In the formula, the oxygen-monodentate ligand represented by X is usually a conjugate base of Bronsted acid (Bronsted acid), and examples thereof include alkoxide anion (RO) ^-) Carboxylate anion (RCOO)^-) And the like.

Alkoxide anion (RO)^-) In (3), the organic group R may be any of an aliphatic group or an aromatic group. In addition, the aliphatic group may be any of a saturated aliphatic group or an unsaturated aliphatic group. The number of carbon atoms of the organic group R is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. As alkoxide anion (RO)^-) Examples thereof include methoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide, sec-butoxide, tert-butoxide, pentoxide and hexanoxide.

Carboxylate anion (RCOO)^-) In (3), the organic group R may be any of an aliphatic group or an aromatic group. In addition, the aliphatic group may be any of a saturated aliphatic group or an unsaturated aliphatic group. The number of carbon atoms of the organic group R is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. As carboxylate anions (RCOO)^-) Examples thereof include carboxylate anions corresponding to carboxylic acids such as acetic acid, propionic acid, and benzoic acid.

Wherein [ ] represents an oxygen-bidentate ligand. Specific examples of the oxy-bidentate ligand include acetylacetone, 3-methyl-2, 4-pentanedione, acetoacetal, 2, 4-hexanedione, 2, 4-heptanedione, 5-methyl-2, 4-hexanedione, 5, 5-dimethyl-2, 4-hexanedione, benzoylacetone, benzoylacetophenone, salicylaldehyde, 1,1, 1-trifluoroacetylacetone, 1,1,5,5, 5-hexafluoroacetylacetone, 3-methoxy-2, 4-pentanedione, 3-cyano-2, 4-pentanedione, 3-nitro-2, 4-pentanedione, 3-chloro-2, 4-pentanedione, acetoacetic acid, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, isopropyl acetoacetate, methyl acetoacetate, isopropyl acetoacetate, and the like, Salicylic acid, methyl salicylate, malonic acid, dimethyl malonate, diethyl malonate, etc. In the state of being coordinated to the central metal, the oxygen-bidentate ligand has a structure in which one or more protons are removed from them.

Specific examples of the metal complex of formula (1) include the following. Examples of the metal complex in which the central metal M is Al (aluminum) include alkylaluminum diisopropyl acetoacetate (9-octadecylaluminum diisopropyl acetoacetate), ethylaluminum diisopropyl acetoacetate, ethylaluminum di-n-butyl acetoacetate, propylaluminum diisopropyl acetoacetate, and n-butylaluminum diisopropyl acetoacetate.

Examples of the metal complex in which the central metal M is Ti (titanium) include allyl titanium acetylacetonate triisopropyl ester, di-n-butoxytitanium (bis-2, 4-pentanedionate), diisopropoxybis (tetramethylheptanedionate), diisopropoxybis (ethoxyacetoacetato) titanium, cresyltitanium, bis (pentanedionato) titanium oxide, and the like.

Examples of the metal complex in which the central metal M is Zr (zirconium) include allyl zirconium acetylacetonate triisopropyl ester, di-n-butoxyzirconium (bis-2, 4-pentanedionate), diisopropoxybioxyzirconium (bis-2, 4-pentanedionate), diisopropoxybis (tetramethylheptanedionate), diisopropoxybis (ethoxyacetoacetato) zirconium, butoxyzirconium (acetoacetato) (diethoxyacetoacetate) (bisethoxyacetoacetato) zirconium (zirconium butoxide), and zirconium tributoxymonoacetylacetonate.

(C) The component (A) may be 1 or more than 2. The content of the component (C) in the composition is not particularly limited, but is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on 100% by mass of the total nonvolatile components in the composition, from the viewpoint of achieving the object of the present invention at a higher level. When the content of the component (C) in the composition is 0.1 mass% or more, sufficient surface modification of the inorganic filler tends to be easily achieved, and the desired effect tends to be easily obtained, and when the content of the component (C) in the composition is 5 mass% or less, the influence on the sealing object due to the external gas from the component (C) tends to be easily suppressed.

Even when 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 a central metal but no oxygen-monodentate ligand is bonded to the central metal; or a metal complex in which an oxygen-monodentate ligand is bonded to a central metal but no oxygen-bidentate ligand is bonded to the central metal) is combined with the component (A) and the component (B), a composition having both excellent adhesion and excellent bendability cannot be obtained. The reason for this is not necessarily clear, but is presumed as follows: the metal complex having a structure in which the oxygen-bidentate ligand and the oxygen-monodentate ligand as the component (C) of the present invention are bonded to the central metal has an oxygen-monodentate ligand that is easily hydrolyzed, and therefore, the surface of the inorganic filler as the component (B) can be easily modified, and the component (B) can be sufficiently dispersed in the polyolefin resin and/or polyolefin rubber as the component (a), and further, when the composition is bonded to a sealing object, the oxygen-bidentate ligand is chelate-exchanged with a functional group present on the surface of glass, plastic, inorganic film, or the like on the surface of the sealing object to be sealed, and thus, a strong bond is generated, and as a result, the composition has improved followability to deformation such as bending of the sealing object, and therefore, the composition is excellent in adhesiveness and bendability.

(D) tackifying resin

If necessary, a tackifier resin (hereinafter, also simply referred to as "component (D)") may be added to the sealing composition of the present invention in order to improve adhesiveness to a sealing object. However, the resin composition of the present invention can achieve sufficient adhesiveness without including a tackifier resin, and the blending of a tackifier resin tends to lower the stability of the resin composition in a high temperature region. Therefore, the amount of the tackifier resin to be added is preferably 20% by mass or less, preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, further preferably 7% by mass or less, further preferably 6% by mass or less, further preferably 5% by mass or less, further preferably 4% by mass or less, further preferably 3% by mass or less, further preferably 2% by mass or less, further preferably 1% by mass or less, and most preferably 0% by mass, based on 100% by mass of the total nonvolatile components in the composition.

The tackifier resin is not particularly limited, and examples thereof include terpene-based tackifier resins, terpene-phenol-based tackifier resins, rosin-based tackifier resins, hydrogenated terpene-based resins, aromatic modified terpene-based resins, etc., coumarone resins, indene resins, petroleum resins (aliphatic petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymerized petroleum resins, alicyclic petroleum resins, dicyclopentadiene (hereinafter, also simply referred to as "DCPD") -based petroleum resins, hydrogenated dicyclopentadiene-based petroleum resins, etc.), etc., and from the viewpoint of adhesiveness and transparency, dicyclopentadiene-based petroleum resins, hydrogenated dicyclopentadiene-based petroleum resins are more preferable, and hydrogenated dicyclopentadiene-based petroleum resins are particularly preferable.

Additive (E)

The composition of the present invention may contain a mineral oil softener, a vegetable oil softener, an ointment (サブファクチス), a fatty acid salt, a synthetic organic compound, a synthetic oil or other softener, as long as the effects of the present invention are not impaired; a curing agent; organic fillers such as rubber particles, silicone powder, nylon powder, and fluororesin powder; silicon-based, fluorine-based, polymer-based defoaming agents or leveling agents; adhesion imparting agents such as triazole compounds, thiazole compounds, triazine compounds, and porphyrin compounds; thickeners such as Orben, Benton, and the like; an antioxidant; a heat stabilizer; light stabilizers and the like.

(curing agent)

When the composition of the present invention contains a polyisobutylene-based resin having an epoxy group, an isobutylene-based 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-based curing agents, guanidine-based curing agents, imidazole-based curing agents, phosphonium-based curing agents, and phenol-based curing agents.

The amine-based curing agent is not particularly limited, and examples thereof include quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide; diazabicyclo compounds such as DBU (1, 8-diazabicyclo [5.4.0] undecene-7), DBN (1, 5-diazabicyclo [4.3.0] nonene-5), DBU-phenolate, DBU-octanoate, DBU-p-toluenesulfonate, DBU-formate, and DBU-phenolnovolak resin salts; tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, and 2,4, 6-tris (diaminomethyl) phenol (TAP), and salts thereof, and dimethylurea compounds such as aromatic dimethylurea and aliphatic dimethylurea; and so on. 1 kind of them may be used or 2 or more kinds may be used in combination.

The guanidine-based curing agent is not particularly limited, examples thereof include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecyl biguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1- (o-tolyl) biguanide. 1 kind of them may be used or 2 or more kinds may be used in combination.

The imidazole-based curing agent is not particularly limited, and examples thereof include 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl-imidazole, 2-phenyl-4, 5-bis (hydroxymethyl) -imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-imidazole, 2-dodecyl-imidazole, 2-heptadecylimidazole, and 1, 2-dimethyl-imidazole. 1 kind of them may be used or 2 or more kinds may be used in combination.

The phosphonium-based curing agent is not particularly limited, and examples thereof include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like. 1 kind of them may be used or 2 or more kinds may be used in combination.

The phenolic curing agent is not particularly limited, and examples thereof include MEH-7700, MEH-7810, MEH-7851 (manufactured by Minghu chemical Co., Ltd.), NHN, CBN, GPH (manufactured by Nippon chemical Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Tokyo chemical Co., Ltd.), TD2090 (manufactured by DIC Co., Ltd.), and the like. Specific examples of the phenol-based curing agent having a triazine skeleton include LA3018 (manufactured by DIC). Specific examples of the triazine skeleton-containing phenol novolac resin curing agent include LA7052, LA7054, and LA1356 (available from DIC corporation). 1 kind of them may be used or 2 or more kinds may be used in combination.

The content of the curing agent in the composition is not particularly limited, and is preferably 5% by mass or less, more preferably 1% by mass or less, based on 100% by mass of the total nonvolatile components in the composition, from the viewpoint of preventing the moisture resistance and the like of the sealing layer (composition layer) from being lowered. On the other hand, from the viewpoint of suppressing stickiness of the composition, the content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, based on 100% by mass of the total nonvolatile components in the composition.

(F) organic solvent

For example, an organic solvent may be added to the composition of the present invention from the viewpoint of coating properties of the composition when producing a sealing sheet in which a layer of the composition is formed on a support described later. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter, also simply referred to as "MEK"), cyclohexanone, and the like, 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, and N-methylpyrrolidone. The organic solvent may be used alone in 1 kind, or 2 or more kinds may be used in combination. The amount of the organic solvent is not particularly limited, and is preferably used in such an amount that the viscosity (25 ℃) of the composition becomes 300 to 2000mPa · s from the viewpoint of coatability.

< method for producing composition >

The composition of the present invention can be produced by mixing the above-mentioned components (including at least the components (a) to (C)) using a kneading roll, a rotary mixer, or the like. The component (B) and the component (C) may be mixed first, and then the other components (the other components including at least the component (a)) may be mixed in the mixture. Alternatively, after mixing component (C) with components other than component (B), component (B) may be mixed and then the remaining components may be mixed.

< use >)

The sealing composition of the present invention is particularly suitable for sealing a flexible electronic device in which electronic elements such as thin film transistors, LCD elements, LED elements, EL elements (organic EL elements, inorganic EL elements), and solar cells are formed on a thin plastic substrate (plastic film). As a plastic substrate (plastic film) having a small thickness of a flexible electronic device, for example, a plastic film such as a film of poly (ethylene terephthalate) (PET), poly (butylene terephthalate) (PBT), poly (ethylene naphthalate) (PEN), Polycarbonate (PC), Polyimide (PI), Liquid Crystal Polymer (LCP), cycloolefin polymer (COP), Polysulfone (PSO), poly (p-Phenylene Ether Sulfone) (PES) or the like can be used, and the composition of the present invention exhibits excellent adhesiveness to the various plastic films.

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

< sheet for sealing >

For example, a sealing sheet is obtained by applying the composition of the present invention in a varnish form with an organic solvent to a support and drying the obtained coating film by heating or blowing hot air, and a layer of the composition of the present invention is formed on the support. In the case of using a sealing sheet prepared by using a composition containing, as the component (a), a polyolefin-based resin having an acid anhydride group or a polyolefin-based rubber having an acid anhydride group and a polyolefin-based resin having an epoxy group or a polyolefin-based rubber having an acid anhydride group in the composition, the acid anhydride group and the epoxy group are reacted in advance to form a crosslinked structure during the preparation thereof, whereby the moisture permeation resistance of the layer of the composition is improved, and a sealing sheet having higher sealing performance (barrier performance against moisture and oxygen in the air, etc.) can be obtained.

Examples of the support used for the sealing sheet include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), and polyethylene naphthalate, and plastic films such as polycarbonate and polyimide. 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 matte treatment or a corona treatment, and may be subjected to a mold release treatment (hereinafter, the "support subjected to a mold release treatment" is also referred to as a "releasable support"). Examples of the mold release treatment include mold release treatment using a mold release agent such as a silicone resin mold release agent, an alkyd resin mold release agent, or a fluororesin mold 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 handling and the like.

The releasable support is a support obtained by subjecting one surface on which the layer of the composition of the present invention is formed to a mold release treatment, and is released before the sealing sheet is actually used for forming the sealing structure. Therefore, the moisture-proof property is not essential for the releasable support, but the moisture-proof property is preferable from the viewpoint of preventing the moisture from entering the layer of the composition during storage before the sealing sheet is sealed. 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-resistant support"). Examples of the barrier layer include nitrides such as silicon nitride, oxides such as aluminum oxide, stainless steel foils, and metal foils such as aluminum foils. Examples of the plastic film include the plastic films described above. The plastic film having a barrier layer may be a commercially available plastic film. The moisture-proof support may be a film obtained by laminating a metal foil and a plastic film in a composite manner. Examples of commercially available products of polyethylene terephthalate films with aluminum foil include "AL 1N30 with PET" manufactured by eastern ocean aluminum vending company of the east ocean, and "AL 3025 with PET" manufactured by fuda metal company. In addition, a support having a multilayer structure of 2 or more layers, for example, a support obtained by laminating the above plastic film and the above metal foil via an adhesive, may be used. It is inexpensive and advantageous from the viewpoint of handling properties.

In the sealing sheet, the layer of the composition may be protected with a protective film. The protective film prevents dust from adhering to the surface of the composition layer or from damaging the surface of the composition layer. The protective film is preferably a plastic film similar to the support. Similarly, the protective film may be subjected to a matte treatment, a corona treatment, and a mold release treatment. The thickness of the protective film is not particularly limited, but is usually 1 to 150 μm, preferably 10 to 100 μm.

When a support having moisture resistance and high transmittance is used as the support for the sealing sheet, the sealing sheet can be laminated to the object to be sealed, thereby forming a sealed structure having high moisture resistance. Examples of such a support having moisture resistance and high transmittance include plastic films having a surface deposited with an inorganic substance such as silicon oxide (silicon dioxide), silicon nitride, SiCN, or amorphous silicon. Examples of the plastic film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonates, and polyimides. As the plastic film, PET is particularly preferable. Examples of commercially available plastic films having moisture resistance include TECHNBARRIER HX, AX, LX, L series (manufactured by Mitsubishi resins corporation), and X-BARRIER (manufactured by Mitsubishi resins corporation) having further improved moisture resistance. As the support, a support having a multilayer structure of 2 or more layers can be used.

In the case of a sealing sheet having a releasable support, the support may be released after the sealing sheet is laminated to a sealing object, and a separately prepared sealing substrate (a moisture-proof plastic film, a metal foil such as a copper foil or an aluminum foil) may be laminated.

As the support for the sealing sheet of the present invention, a circularly polarizing plate can be used. Generally, a circularly polarizing plate is constituted by a polarizing plate and an 1/4 wave plate. When a circularly polarizing plate is used as the support, an 1/4 wave plate is usually disposed on the composition layer side. In the case of using a support containing both the circularly polarizing plate and the moisture-proof support, it is preferable that the moisture-proof support is disposed on the composition layer side and the 1/4 wave plate of the circularly polarizing plate is disposed on the moisture-proof support side. The moisture-proof support and the circularly polarizing plate may be bonded by an adhesive or the like, and the adhesive is not particularly limited as long as it is an adhesive having high transparency, and for example, an acrylic adhesive, a polyvinyl alcohol adhesive, or the like may be used.

In addition, a protective film for protecting the polarizer (polarizing plate) may be provided in the circularly polarizing plate, and a known protective film may be used as the protective film, and examples thereof include those described in japanese patent laid-open publication No. 2016-.

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

< Flexible electronic device >

When a flexible electronic device in which an electronic element is sealed is manufactured using the composition of the present invention, sealing is preferably performed using the sealing sheet. That is, by laminating the sealing sheet of the present invention to a plastic substrate (element substrate) provided with an electronic element of a flexible electronic device, a flexible electronic device in which the electronic element is sealed can be obtained.

The sealing composition of the present invention has excellent adhesion to a sealing object and excellent flexibility, and therefore, can realize high performance and long life of a flexible electronic device.

Examples

The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these examples. In the following description, "part" and "%" in the amounts of the components and the copolymerized units represent "part by mass" and "% by mass", respectively, unless otherwise specified.

The raw materials used in the examples and comparative examples were as follows,

(A) polyolefin resin or polyolefin rubber

Seeds 065 (manufactured by JSR corporation): butyl rubber (isobutylene-isoprene copolymer)

Seed N50SF (manufactured by BASF corporation): polyisobutylene (number average molecular weight: 400,000)

Seeding ER850 (manufactured by starlight PMC corporation): 20% toluene solution of Glycidyl Methacrylate (GMA) -modified butyl rubber (epoxy group concentration of 0.64mmol/g, number average molecular weight of 110,000)

Seed ER641 (manufactured by starlight PMC corporation): maleic Anhydride (MA) modified butyl rubber (anhydride group concentration of 0.46mmol/g, number average molecular weight of 57,000) in 35% toluene.

(B) Inorganic filler

Zizania DHT-4C (manufactured by synergetics chemical industries corporation): semi-calcined hydrotalcite (average particle size 400nm, BET specific surface area 15 m)²/g)

Seed MK300 (manufactured by Co-op Chemical Co., Ltd.): mica (average particle size 15 μm)

Seeds (manufactured by Co-op Chemical Co., Ltd.): smectite (average particle size 50 nm).

(C) Metal complexes

(titanium Complex)

Seed and seed orcatix TC710 (manufactured by Matsumoto Fine Chemical corporation): diisopropoxybis (ethoxyacetoacetyl) titanium, Ti content 7.1% by mass

Seed and seed orcatix TC750 (manufactured by Matsumoto Fine Chemical corporation): diisopropoxybis (ethoxyacetoacetyl) titanium, the Ti content being 11.0% by mass.

(aluminum complexes)

Seed (アルミキレート) M (manufactured by Kawaken Fine Chemicals Co., Ltd.): alkyl aluminum acetyl diisopropyl acetate.

(zirconium complex)

Seed OrGATIX ZC540 (manufactured by Matsumoto Fine Chemical Co., Ltd.): zirconium tributoxymonoacetylacetonate.

(C') Metal Complex

(titanium Complex)

Seeds and seeds Plenoct 38S (manufactured by the same-Techni Co., Ltd.): titanium isopropoxide tris (dioctylpyrophosphate).

(aluminum complexes)

Seed and seed AL-3200 (manufactured by Matsumoto Fine Chemical Co., Ltd.): aluminum monoacetylacetonate ethylated with bisethylacetate.

(zirconium complex)

Seed OrGATIX ZC320 (manufactured by Matsumoto Fine Chemical Co., Ltd.): zirconium stearate.

(E) Additive agent

(E-1) antioxidant

As a seed Irganox 1010 (manufactured by BASF corporation)

(E-2) curing agent

A seeding amine-based curing agent (2,4, 6-tris (diaminomethyl) phenol, hereinafter abbreviated as "TAP").

(F) Organic solvent

Seed or seed of toluene

Seed (Ipzole (イプゾール) #1000 (manufactured by mitsung corporation): an aromatic mixed solvent.

< example 1 >

To 3 parts of butyl rubber (065), 20 parts of Ipzole 100 was added, and the mixture was stirred for 3 hours, followed by dispersing 1 part of alkylaluminum diisopropyl acetoacetate (Aluminum Chemate M) and 20 parts of half-calcined hydrotalcite (DHT-4C) by a three-roll mill to obtain a mixture. To the obtained mixture was added 493 parts of toluene to 87 parts of butyl rubber (065) in the total amount and stirred for 3 hours, and further 1 part of antioxidant (Irganox 1010) and 9 parts of toluene were added, and the obtained mixture was uniformly dispersed by a high-speed rotary mixer to obtain varnish (varnish 1) of the composition.

< example 2 >

To 3 parts of butyl rubber (065), 20 parts of Ipzole 100 was added, and the mixture was stirred for 3 hours, followed by dispersing 1 part of alkylaluminum diisopropyl acetoacetate (Aluminum Chemate M) and 20 parts of half-calcined hydrotalcite (DHT-4C) by a three-roll mill to obtain a mixture. To the obtained mixture was added a total amount of a dissolved product obtained by adding 226.6 parts of toluene to 37 parts of butyl rubber (065) and stirring for 3 hours, and further 100 parts of glycidyl methacrylate-modified butyl rubber (ER850, 20% toluene solution), 86 parts of maleic anhydride-modified butyl rubber (ER641, 35% toluene solution), 1 part of antioxidant (Irganox 1010), 9 parts of toluene, and 0.2 part of amine-based curing agent (TAP) were blended, and the obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain varnish (varnish 2) of the composition.

< example 3 >

A varnish (varnish 3) of a composition was obtained in the same manner as in varnish 2 (example 2) except that 20 parts of half-calcined hydrotalcite (DHT-4C) was changed to 15 parts using polyisobutylene (Oppanol N50SF) in place of butyl rubber (065) and 1 part of diisopropoxybis (ethoxyacetoacetyl) titanium (TC710) was added in place of 1 part of alkylaluminum acetoacetate (Aluminum Chemate M).

< example 4 >

A varnish (varnish 4) of a composition was obtained in the same manner as in varnish 3 (example 3) except that 1 part of diisopropoxybis (ethoxyacetoacetyl) titanium (TC750) was added in place of 1 part of diisopropoxybis (ethoxyacetoacetyl) titanium (TC 710).

< example 5 >

A varnish (varnish 5) of a composition was obtained in the same manner as in varnish 3 (example 3) except that 2.2 parts of zirconium tributoxymmonoacetylacetonate (ZC540) was added in place of 1 part of titanium diisopropoxide bis (ethoxyacetoacetyl) oxide (TC 710).

< example 6 >

To 3 parts of butyl rubber (065), 20 parts of Ipzole 100 was added, and the mixture was stirred for 3 hours, and 1 part of alkylaluminum diisopropyl acetoacetate (Aluminum chemical M) and 20 parts of mica (MK300) were dispersed by a three-roll mill to obtain a mixture. To the obtained mixture was added 493 parts of toluene to 87 parts of butyl rubber (065) in the total amount and stirred for 3 hours to obtain a dissolved product, and the obtained mixture was uniformly dispersed by a high-speed rotary mixer to obtain a varnish (varnish 6) of the composition.

< example 7 >

A varnish (varnish 7) of the composition was obtained in the same manner as in the varnish 6 (example 6) except that 20 parts of Smectite (STN) was added instead of 20 parts of mica (MK 300).

< comparative example 1 >

A varnish (varnish 8) of the composition was obtained in the same manner as in varnish 1 (example 1) except that 1 part of alkylaluminum diisopropyl acetoacetate (Aluminum Chelate M) was not contained.

< comparative example 2 >

A varnish (varnish 9) of a composition was obtained in the same manner as in the varnish 5 (example 5) except that 1.2 parts of zirconium stearate (ZC320) was used instead of 2.2 parts of zirconium tributoxymonoacetylacetonate (ZC 540).

< comparative example 3 >

A varnish (varnish 10) of the composition was obtained in the same manner as in the varnish 6 (example 6) except that 1 part of alkylaluminum diisopropyl acetoacetate (Aluminum chemical M) was not contained.

< comparative example 4 >

A varnish (varnish 11) of a composition was obtained in the same manner as in varnish 3 (example 3) except that 1 part of aluminum monoethylacetacetate ethoxide (AL-3200) was added in place of 1 part of bis (ethoxyacetoacetyl) titanium diisopropoxide (TC 710).

< comparative example 5 >

A varnish (varnish 12) of a composition was obtained in the same manner as in varnish 3 (example 3) except that 1 part of tris (dioctylphosphato) titanium isopropoxide (Plenoct 38S) was added in place of 1 part of bis (ethoxyacetoacetyl) titanium diisopropoxide (TC 710).

< production of sheet for sealing >

Using the varnishes prepared in the examples and comparative examples, the varnish was applied to the release-treated surface of the PET film subjected to release treatment with the silicone-based release treatment agent, and dried at 120 ℃ for 15 minutes to prepare a sealing sheet (sealing sheet in each example and comparative example).

< evaluation >

The following evaluations were performed on the sealing sheets of the examples and comparative examples.

< evaluation of adhesion >

The sealing sheet was cut into a size of 50mm in length and 20mm in width, and the cut sealing sheet was laminated to a PET face of an aluminum foil/PET composite film "AL 1N30 with PET" (aluminum foil: 30 μm, PET: 25 μm, trade name manufactured by Toyo aluminum vending Co., Ltd.) having a length of 100mm and a width of 25mm using a batch vacuum laminator (manufactured by Nichigo-Morton Co., Ltd., V-160). The lamination was carried out at a temperature of 80 ℃ for 300 seconds and a pressure of 0.3 MPa. Then, the PET film of the sealing sheet subjected to the release treatment with the silicone-based release treatment agent was peeled off, and a glass plate (length 76mm, width 26mm, thickness 1.2mm, micro glass slide) was further laminated on the exposed composition layer under the same conditions as described above. The obtained laminate was measured for adhesion strength (peel strength) to a glass plate surface when peeled at a tensile rate of 300 mm/min in a direction 180 degrees with respect to the longitudinal direction of the aluminum foil/PET composite film, and the adhesion was evaluated according to the following criteria.

Good (∘): the adhesive strength is more than 0.3kgf/cm

Eligibility (Δ): the adhesive strength is more than 0.2 and less than 0.3kgf/cm

Poor (x): the adhesive strength is less than 0.2 kgf/cm.

< evaluation of bendability >

< sample >

(1) Sample A

An inorganic film (SiO 500nm thick) was formed on a cycloolefin polymer film (50 μm thick) by bonding a sealing sheet to the cycloolefin polymer film using a batch vacuum laminator (V-160 manufactured by Nichigo-Morton Co., Ltd.)₂Film) was formed on the inorganic film surface of the barrier film to prepare a film for evaluation of bendability (sample a).

(2) Sample B

An inorganic film (SiO 500nm thick) was formed on a cycloolefin polymer film (50 μm thick) by bonding a sealing sheet to the cycloolefin polymer film using a batch vacuum laminator (V-160 manufactured by Nichigo-Morton Co., Ltd.)₂Film) was laminated on the inorganic film surface of the barrier film by using a batch vacuum laminator (V-160, manufactured by Nichigo-Morton corporation) to form a film for evaluation of flexibility (sample B) by laminating a polyimide film (thickness 25 μm) on the sealing sheet side of the laminate film.

< bending test >

(1) Sample A

The film for evaluation of flexibility was set in a U-fold (reverse り to し) tester (manufactured by YUASA corporation) so that the sealing sheet was positioned inside, and was bent 1 ten thousand times at a radius of curvature of 5mm and a bending speed of 60rpm/min, and cracks of the inorganic film after bending were confirmed with a microscope. The flexural properties were evaluated up to 10 ten thousand times;

(2) Sample B

The film for evaluation of flexibility was set in a U-fold tester (manufactured by YUASA) so that the cycloolefin polymer film was positioned on the inner side, and was bent 1 thousand times at a curvature radius of 5mm and a bending speed of 60rpm/min, respectively, and cracks of the inorganic film after bending were confirmed by a microscope. The flexural properties were evaluated up to 1 ten thousand times.

(Standard of evaluation)

Sample A

Good (∘): after 10 ten thousand bends, no crack (100K <)

Eligibility (Δ): cracks (80K to 100K) are generated by 8 ten thousand to 10 ten thousand times of bending

Poor (x): cracks (80K >) were generated by less than 8 ten thousand bendings.

Sample B

Good (∘): after 1 ten thousand bends, no crack (10K <)

Eligibility (Δ): cracks (8K to 10K) are generated by 8 thousand to 1 ten thousand times of bending

Poor (x): cracks (8K >) are produced by less than 8 thousand bends.

Tables 1 and 2 below show the compositions of the examples and the compositions of the comparative examples and the results of the evaluation tests.

[ Table 1]

。

[ Table 2]

。

In the tables, all the numerical values other than the solvent represent nonvolatile values. From the results of the above tables, it was confirmed that the sealing films of examples 1 to 7 were excellent in adhesion to glass, and were also confirmed to be capable of suppressing the tendency of cracking at the interface after bending in the bending property evaluation.

Industrial applicability

The sealing composition of the present invention is suitably used for sealing electronic components and the like in flexible electronic devices.

The present application is based on japanese patent application No. 2018-066922 filed in japan, the entire contents of which are incorporated in the present specification.

Claims

1. A sealing composition comprising the following components (A) to (C),

(A) a polyolefin resin and/or a polyolefin rubber,

(B) an inorganic filler, wherein the inorganic filler is an inorganic filler,

(C) a bidentate ligand with two coordination atoms of oxygen atoms and a monodentate ligand with the coordination atoms of oxygen atoms are combined with the central metal to form the metal complex.

2. The sealing composition according to claim 1, wherein the central metal of the (C) metal complex is aluminum, titanium or zirconium.

3. The sealing composition according to claim 1, wherein the (C) metal complex is a metal complex represented by the general formula (1),

in the formula (I), the compound is shown in the specification,

m represents a metal in the 2 nd to 6 th periods of the periodic Table,

X represents a monodentate ligand whose coordinating atom is an oxygen atom,

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

4. The sealing composition according to claim 3, wherein M in formula (1) is aluminum, titanium or zirconium.

5. The sealing composition according to any one of claims 1 to 4, wherein (B) the inorganic filler is surface-treated with (C) the 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 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.

8. The sealing composition according to any one of claims 1 to 6, wherein the polyolefin rubber contains a polyolefin rubber having an acid anhydride group and/or a polyolefin rubber having an epoxy group.

9. The sealing composition according to any one of claims 1 to 6, which satisfies at least one of the following (a) to (d),

10. The sealing composition according to any one of claims 1 to 9, further comprising 10% by mass or less of (D) a tackifier resin with respect to 100% by mass of nonvolatile components of the composition.

11. The sealing composition according to any one of claims 1 to 10, which is used for sealing a flexible electronic device.

12. The sealing composition according to claim 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 claims 1 to 8 and 10 formed on the support.

14. A sealing sheet comprising a support and a layer of the composition according to claim 9 formed on the support,

The layer of the composition has a crosslinked structure formed by the reaction of an acid anhydride group and an epoxy group.

15. The sealing sheet according to claim 13 or 14, wherein the support is composed of at least one member selected from a releasable support, a moisture-proof support and a circularly polarizing plate.

16. The sealing sheet according to any one of claims 13 to 15, which is used for sealing a flexible electronic device.

17. The sealing sheet according to claim 16, wherein the flexible electronic device is a flexible organic EL device.

18. A flexible electronic device, wherein an electronic component formed on a plastic substrate is sealed with the sealing composition according to any one of claims 1 to 8 and 10.

19. A flexible electronic device wherein an electronic component formed on a plastic substrate is sealed with the sealing composition according to claim 9 or 10,

the sealing composition has a crosslinked structure formed by the reaction of an acid anhydride group and an epoxy group.

20. 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.