KR20230005780A - Sealing composition - Google Patents

Abstract

The present invention is to provide a sealing composition capable of forming a sealing layer excellent in both water vapor penetration barrier properties and transparency. The sealing composition contains (A) an olefinic polymer and (B) calcium oxide, and optionally further contains (C) semi-calcined hydrotalcite, wherein the component (A) includes an olefinic polymer having an acid anhydride group and/or a carboxyl group, and a median diameter of the component (B) is 300 nm or less.

Description

Composition for sealing {SEALING COMPOSITION}

The present invention relates to a composition for sealing useful for sealing electronic devices and the like.

BACKGROUND ART In order to protect electronic devices such as organic EL (Electroluminescence) devices and solar cells from moisture, sealing of electronic devices is performed using a sealing layer formed of a sealing composition or a sheet for sealing. As such a composition or sheet, for example, in Patent Literature 1, (A) a polyolefin-based resin and (B) a resin composition for sealing containing a metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite, and It is disclosed that the sheet|seat for sealing formed from this has favorable moisture permeability resistance and transparency. However, hydrotalcite reversibly absorbs and releases moisture. Therefore, in the sealing composition using hydrotalcite, moisture absorbed by the hydrotalcite during the manufacturing process or distribution process is released from the sealing layer of the electronic device formed using the composition, causing deterioration of the electronic device. There are cases.

On the other hand, Patent Document 2 discloses a method of suppressing deterioration of an organic EL element due to moisture sucked into the resin composition by blending calcium oxide with a resin composition for sealing containing hydrotalcite. Moreover, in patent document 2, as resin which comprises the resin composition for sealing, an acrylic resin and an epoxy resin are described.

International Publication No. 2017/057708 International Publication No. 2019/167905

Calcium oxide is known as a hygroscopic filler. The sealing layer formed of the sealing composition obtained using calcium oxide is excellent in the property of suppressing the penetration of water vapor (sometimes described as "water vapor penetration barrier property" in this specification), but contains an olefinic polymer When the sealing composition contains calcium oxide as a hygroscopic filler, transparency of the sealing layer formed from the composition is usually lost. In order to suppress the decrease in transparency, it is considered to use fine calcium oxide, but since fine calcium oxide has poor dispersibility, it is difficult to prepare a composition having excellent transparency in which fine calcium oxide is well dispersed in an olefin polymer. did Therefore, in the sealing layer formed from the sealing composition containing an olefinic polymer, it has been difficult to achieve both water vapor permeation barrier properties and transparency.

Further, since the refractive indices of the acrylic resin and the epoxy resin described in Patent Document 2 are significantly different from those of the semi-fired hydrotalcite, the sealing layer formed from the sealing composition containing the acrylic resin, the epoxy resin and the semi-fired hydrotalcite is transparency is poor. On the other hand, since the refractive index of the olefin-based polymer is close to that of the semi-fired hydrotalcite, the sealing layer formed from the sealing composition containing the olefin-based resin polymer and the semi-fired hydrotalcite has excellent transparency. However, when calcium oxide is added to a sealing composition containing an olefinic polymer and semi-fired hydrotalcite to further improve the water vapor permeation barrier property, the sealing layer formed of the composition usually has lower transparency. It is conceivable to use fine calcium oxide to suppress such a decrease in transparency, but fine calcium oxide has poor dispersibility into the olefinic polymer. Therefore, it has been difficult to form a sealing layer excellent in both water vapor permeation barrier properties and transparency.

The present invention has been made in view of the above circumstances, and its object is to provide a sealing composition capable of forming a sealing layer excellent in both water vapor permeation barrier properties and transparency.

The present invention that can achieve the above object is as follows.

[1] The following (A) component and (B) component:

(A) an olefinic polymer and

(B) calcium oxide

As a sealing composition comprising a,

(A) component contains an olefinic polymer having an acid anhydride group and/or a carboxyl group;

(B) The composition for sealing whose median diameter of component is 300 nm or less.

[2] The following (C) component:

(C) semi-calcined hydrotalcite

The composition for sealing as described in [1] which further contains.

[3] The composition for sealing according to [1] or [2], wherein the component (B) has a median diameter of 1 nm or more.

[4] The composition for sealing according to [1], wherein the content of the component (B) is 20 to 80% by mass relative to 100% by mass of the non-volatile content of the composition for sealing.

[5] The composition for sealing according to [2], wherein the content of the component (B) is 5 to 30% by mass based on 100% by mass of the non-volatile content of the composition for sealing.

[6] The composition for sealing according to [2] or [5], wherein the content of the component (C) is 20 to 70% by mass based on 100% by mass of the non-volatile content of the composition for sealing.

[7] The composition for sealing according to any one of [1] to [6], wherein the olefin-based polymer having an acid anhydride group and/or a carboxy group is an olefin-based polymer having an acid anhydride group.

[8] The composition for sealing according to any one of [1] to [7], wherein the component (A) contains an olefinic polymer having an epoxy group.

[9] The composition for sealing according to any one of [1] to [8], wherein the component (A) contains a liquid olefin polymer.

[10] The composition for sealing according to any one of [1] to [9], further comprising a tackifier.

[11] A sealing sheet having a laminated structure including a support and a sealing layer formed of the sealing composition according to any one of [1] to [10].

[12] The sheet for sealing according to [11], wherein the haze of the sealing layer is less than 60%.

[13] An electronic device comprising a sealing layer formed of the sealing composition according to any one of [1] to [10].

[14] Any one of [1] to [10], which includes a step of pulverizing a mixture containing an olefinic polymer having an acid anhydride group and/or a carboxyl group, calcium oxide having a median diameter exceeding 300 nm, and an organic solvent. The manufacturing method of the composition for sealing of 1 term|claim.

[15] The production method described in [14], which further includes a step of mixing the mixture after grinding treatment with an olefinic polymer having an epoxy group.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition which can form the sealing layer excellent in both water vapor permeation barrier property and transparency can be obtained.

Composition for sealing

The composition for sealing of the present invention includes the following components (A) and (B):

(A) an olefinic polymer and

(B) calcium oxide

and optionally the following components (C):

(C) semi-calcined hydrotalcite

As a sealing composition further comprising,

(A) component contains an olefinic polymer having an acid anhydride group and/or a carboxyl group;

(B) It is characterized in that the median diameter of component is 300 nm or less.

Since the olefinic polymer (component (A)) and the semi-fired hydrotalcite (component (C)) used in the present invention have similar refractive indices, the sealing composition of the present invention can form a sealing layer having excellent transparency. can Further, as a hygroscopic filler, by using calcium oxide (component (B)) and semi-calcined hydrotalcite (component (C)) in combination, calcium oxide (component (B)) can be used in combination with semi-calcined hydrotalcite ((C) component) can capture moisture brought in and form a sealing layer with excellent water vapor penetration barrier properties. Moreover, when calcium oxide is used, the transparency of the sealing layer normally obtained will fall. However, in the present invention, such a decrease in transparency can be suppressed by using calcium oxide (component (B)) having a median diameter of 300 nm or less.

On the other hand, it is difficult to properly disperse fine calcium oxide in the sealing composition. However, in the present invention, by using an olefinic polymer having an acid anhydride group and/or a carboxy group, a sealing composition in which the fine component (B) is well dispersed can be prepared. From this, it is presumed that the olefinic polymer having an acid anhydride group and/or a carboxy group functions as a dispersing agent for fine calcium oxide (component (B)). However, the present invention is not limited to such estimation.

Hereinafter, components (A) to (C) will be sequentially described. In addition, as long as there is no special description in this specification, each component may use only 1 type in all, and may use 2 or more types together.

<Component (A)>

Component (A) used in the present invention is an olefin polymer. In this specification, "olefin-based polymer" is a structural unit derived from olefin (hereinafter sometimes abbreviated as "olefin unit") as the main structural unit (that is, the amount of olefin unit is the largest among all structural units). ) means a polymer. In addition, below, "structural unit derived from butene" which is an olefin unit may be abbreviated as "butene unit" or the like.

The olefin-based polymer may be an olefin-based resin (eg, a propylene-butene copolymer) or an olefin-based rubber (eg, butyl rubber, ie, an isobutene-isoprene copolymer). In the present specification, "olefin-based resin" means an olefin-based polymer that cannot form a rubber elastic body by crosslinking, and "olefin-based rubber" means an olefin-based polymer that can form a rubber elastic body through crosslinking do.

As the olefin, monoolefins having one olefinic carbon-carbon double bond and/or diolefins having two olefinic carbon-carbon double bonds are preferred. Examples of monoolefins include α-olefins such as ethylene, propylene, 1-butene, isobutene (isobutylene), 1-pentene, 1-hexene, 1-heptene, and 1-octene. Examples of the diolefin include 1,3-butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethylbutadiene.

The olefinic polymer may be a homopolymer or a copolymer. The copolymer may be a random copolymer or a block copolymer. Further, the olefin-based polymer may be a copolymer of an olefin and a monomer other than the olefin. Examples of the olefin copolymer include ethylene-non-conjugated diene copolymers, ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene copolymers, ethylene-butene copolymers, ethylene-propylene-butene copolymers, and propylene-propylene copolymers. butene copolymers, propylene-butene-non-conjugated diene copolymers, isobutene-isoprene copolymers, styrene-isobutene copolymers, and styrene-isobutene-styrene copolymers.

(Component (A1))

In the present invention, component (A) is an olefinic polymer having an acid anhydride group (ie, a carbonyloxycarbonyl group (-CO-O-CO-)) and/or a carboxyl group (referred to as "component (A1)" in the present specification) It is one of the features to include). Component (A1) is preferably an olefinic polymer having an acid anhydride group. In addition, the description and illustration of "olefin" and "olefin type polymer" in component (A1) are the same as those of the said component (A).

When using an olefinic polymer having an acid anhydride group as component (A1), the concentration of the acid anhydride group in the polymer is preferably 0.05 to 10 mmol/g, more preferably 0.10 to 5 mmol/g. The concentration of acid anhydride groups is obtained from the value of the acid value, which is defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the polymer according to JIS K 2501.

When using an olefinic polymer having a carboxy group as component (A1), the concentration of the carboxy group in the polymer is preferably 0.05 to 20 mmol/g, more preferably 0.10 to 10 mmol/g. The concentration of the carboxy group is obtained from the value of the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the polymer according to JIS K 2501.

(A1) When using an olefinic polymer having an acid anhydride group and a carboxy group as the component, the sum of the concentration of the acid anhydride group and the concentration of the carboxy group in the polymer is preferably 0.05 to 20 mmol/g, more preferably 0.10 to 10 mmol/g.

The number average molecular weight of the component (A1) is preferably 1,000 to 1,000,000, more preferably 1,000 to 750,000, from the viewpoint of improving the good coatability of the varnish of the sealing composition and the sealing performance and mechanical strength of the sealing layer formed. to be. In addition, the number average molecular weight of each component is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method is measured using "LC-9A/RID-6A" manufactured by Shimadzu Corporation as a measuring device and "Shodex K-800P/K-804L/K" manufactured by Showa Denko Corporation as a column. -804L” can be measured at a column temperature of 40° C. using toluene or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

Component (A1) is, for example, (i) an unsaturated compound having an acid anhydride group and/or a carboxyl group (e.g., maleic anhydride) by graft modification of an olefinic polymer under radical reaction conditions, or (ii) It can be manufactured by copolymerizing an unsaturated compound having an acid anhydride group and/or a carboxy group with an α-olefin.

As the component (A1), polymers available from Toho Chemical Co., Ltd., Seiko PMC Co., etc. can be used, for example. As such a polymer, for example, "HV-300M" (maleic anhydride-modified liquid polybutene) manufactured by Toho Chemical Co., Ltd., "ER688" (maleic anhydride-modified liquid polybutene) manufactured by Seiko PMC, and manufactured by Seiko PMC "T-YP279" (maleic anhydride-modified propylene-butene random copolymer), Seiko PMC "T-YP312" (maleic anhydride-modified propylene-butene random copolymer), Seiko PMC "ER661" (male anhydride) Acid-modified isobutene-isoprene random copolymer), Seiko PMC "T-YP430" (maleic anhydride-modified ethylene-methyl methacrylate copolymer), Seiko PMC "T-YP956" (maleic anhydride-modified ethylene -Propylene-butene random copolymer), Mitsubishi Chemical Corporation "Diacarna 30M" (copolymer of maleic anhydride and α-olefin), etc. are mentioned.

In one aspect of the present invention, component (A1) is,

(i) Preferably polybutene having acid anhydride groups and/or carboxy groups, isobutene-isoprene copolymers having acid anhydride groups and/or carboxy groups (i.e. butyl rubber), propylene having acid anhydride groups and/or carboxy groups -At least one selected from the group consisting of butene copolymers, ethylene-methylmethacrylate copolymers having acid anhydride groups and/or carboxyl groups, and ethylene-propylene-butene copolymers having acid anhydride groups and/or carboxy groups,

(ii) more preferably polybutene having an acid anhydride group and/or carboxy group, an isobutene-isoprene copolymer having an acid anhydride group and/or a carboxy group, and a propylene-butene copolymer having an acid anhydride group and/or a carboxy group At least one selected from the group consisting of

(iii) more preferably at least one selected from the group consisting of polybutene having an acid anhydride group, isobutene-isoprene copolymer having an acid anhydride group, and propylene-butene copolymer having an acid anhydride group,

(iv) Polybutene having an acid anhydride group is particularly preferred.

The content of component (A1) is preferably 1% by mass or more with respect to 100% by mass of the non-volatile content of the composition for sealing, from the viewpoint of the dispersibility of fine calcium oxide (component (B)) in the composition for sealing, etc. It is more preferably 3% by mass or more, still more preferably 5% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less.

(Component (A2))

The component (A) preferably contains an olefinic polymer having an epoxy group (sometimes referred to as "component (A2)" in this specification). By using together the component (A1) having an acid anhydride group and/or a carboxy group and the component (A2) having an epoxy group, a strong sealing layer having a crosslinked structure can be formed. In addition, the description and illustration of "olefin" and "olefin type polymer" in component (A2) are the same as those of the said component (A).

The concentration of the epoxy group in component (A2) is preferably 0.05 to 10 mmol/g, more preferably 0.10 to 5 mmol/g. The epoxy group concentration is obtained from the epoxy equivalent obtained based on JIS K 7236-1995.

The number average molecular weight of the component (A2) is preferably 1,000 to 1,000,000, more preferably 2,000 to 750,000, from the viewpoint of improving the good coatability of the varnish of the sealing composition and the sealing performance and mechanical strength of the sealing layer formed. , more preferably from 2,000 to 500,000.

(A2) component, for example, (i) an unsaturated compound having an epoxy group (for example, glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether) , which can be obtained by graft modification of an olefinic polymer under radical reaction conditions or (ii) copolymerization of an unsaturated compound having an epoxy group with an α-olefin.

As the component (A2), polymers available from Sumitomo Chemical Co., Ltd., Seiko PMC Co., etc. can be used, for example. Examples of such a polymer include "BONDFAST BF-7M" manufactured by Sumitomo Chemical Co., Ltd. (ethylene-glycidyl methacrylate copolymer) and "BONDFAST BF-2B" manufactured by Sumitomo Chemical Co., Ltd. (ethylene-glycidyl methacrylate copolymer). -Vinyl acetate copolymer), "BF-7L" (ethylene-glycidyl methacrylate-methyl acrylate copolymer) by Sumitomo Chemical Co., Ltd., "ER829" (glycidyl methacrylate-modified propylene- by Seiko PMC) Butene random copolymer), "ER850" (glycidyl methacrylate-modified butyl rubber) manufactured by Seiko PMC, "ER853" (glycidyl methacrylate-modified propylene-butene random copolymer) manufactured by Seiko PMC, Seiko PMC "ER866" (glycidyl methacrylate-modified butyl rubber) manufactured by Seiko PMC, "T-YP276" (glycidyl methacrylate-modified propylene-butene random copolymer) manufactured by Seiko PMC, "T-YP313" manufactured by Seiko PMC (Glycidyl methacrylate-modified propylene-butene random copolymer), and Seiko PMC's "T-YP431" (glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer).

(A2) component,

(i) preferably ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-glycidyl methacrylate-methyl acrylate copolymer, propylene having an epoxy group -At least one selected from the group consisting of a butene copolymer, an isobutene-isoprene copolymer (i.e., butyl rubber) having an epoxy group, and an ethylene-methyl methacrylate copolymer having an epoxy group,

(ii) more preferably at least one selected from the group consisting of a propylene-butene copolymer having an epoxy group, an isobutene-isoprene copolymer having an epoxy group, and an ethylene-methyl methacrylate copolymer having an epoxy group,

(iii) more preferably a propylene-butene copolymer having an epoxy group and/or an isobutene-isoprene copolymer having an epoxy group;

(iv) Particularly preferred is a propylene-butene copolymer having an epoxy group or an isobutene-isoprene copolymer having an epoxy group.

When a propylene-butene copolymer having an epoxy group is used as component (A2), the amount of butene units in the copolymer is preferably 1 to 50% by mass, more preferably 2% by mass, per the total of propylene units and butene units. to 45% by mass, more preferably 3 to 40% by mass. In addition, the amount of the butene unit is based on the propylene unit and the butene unit excluding the modified portion (for example, the portion derived from glycidyl (meth)acrylate for introducing an epoxy group).

(A2) When an isobutene-isoprene copolymer having an epoxy group (ie, butyl rubber) is used as the component, from the viewpoint of yellowing resistance of the sealing layer, the amount of isoprene units in the copolymer is the isobutene unit and the isoprene unit , is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, still more preferably 0.5 to 10% by mass, per total of . In addition, the amount of the isoprene units is based on isobutene units and isoprene units excluding modified portions (for example, portions derived from glycidyl (meth)acrylate for introducing an epoxy group).

When using the component (A2), the content thereof is preferably 0.1% by mass or more, more preferably 1% by mass or more, in order to form a strong sealing layer with respect to 100% by mass of the non-volatile matter of the sealing composition. More preferably, it is 3% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

When using the component (A2), the amount of the component (A2) having an epoxy group and the amount of the component (A1) having an acid anhydride group and/or a carboxy group are preferably determined by the ratio of the functional groups they have. In addition, from the viewpoint of the dispersibility of component (B), it is preferable to set the ratio of the functional groups that component (A1) has so that a certain amount remains without being completely consumed by crosslinking with component (A2). Depending on the crosslinking conditions (temperature, time), etc., "amount of epoxy groups (mol) of component (A2)": "amount of acid anhydride groups (mol) and carboxy groups (mol) of component (A1) In one embodiment of the present invention, "the sum of" is preferably 100:50 to 100:1,500, more preferably 100:60 to 100:1,250, still more preferably 100:70 to 100:1,000, It is particularly preferably 100:80 to 100:900, and in another embodiment of the present invention in which the composition for sealing includes component (C), it is preferably 100:10 to 100:1,500, more preferably 100: 15 to 100:1,250, more preferably 100:20 to 100:1,000. In addition, for example, when the component (A1) has only acid anhydride groups, the above "sum of the amount of acid anhydride groups (mol) and the amount of carboxy groups (mol)" is "the amount of acid anhydride groups (mol)" means

(Component (A3))

The component (A) preferably contains a liquid olefin polymer (sometimes referred to as "component (A3)" in this specification). By using the component (A3), good adhesion and flexibility can be imparted to the sealing layer. In addition, the description and illustration of "olefin" and "olefin type polymer" in component (A3) are the same as those of the said component (A).

In the present invention, "liquid" in "liquid olefin polymer" means that the viscosity at 25°C is 5,000 Pa·s or less. In the present invention, "viscosity at 25°C" means a viscosity calculated by multiplying the kinematic viscosity at 25°C measured with a dynamic viscoelasticity measuring device by the density. As a dynamic viscoelasticity measuring apparatus, the TA Instruments company make rheometer (brand name: DISCOVERY HR-2) etc. are mentioned, for example.

In the present invention, the liquid olefin polymer having an acid anhydride group and/or a carboxyl group is classified as component (A1). In addition, in this invention, the liquid olefin type polymer which has an epoxy group is classified as component (A2). Therefore, the component (A3) in the present invention is a liquid olefin polymer other than the component (A1) and the component (A2).

The viscosity of component (A3) at 25°C is preferably 5 to 5,000 Pa·s, more preferably 10 to 4,000 Pa·s, still more preferably 20 to 3,000 Pa·s, from the viewpoint of good adhesion and flexibility of the sealing layer. It is Pa·ss.

The number average molecular weight of component (A3) is preferably from 100 to 50,000, more preferably from 200 to 30,000, still more preferably from 300 to 20,000, from the viewpoint of good coatability of the varnish of the sealing composition.

(A3) A commercial item can be used for a component. As such a commercial item, "HV-300" (liquid polybutene) by ENEOS, "HV-1900" (liquid polybutene) by ENEOS, "HV-50" (liquid polybutene) by ENEOS, "HV-35" (liquid polybutene) manufactured by ENEOS, "950MW" (liquid polybutene) manufactured by Kothari, "2400MW" (liquid olefinic polymer) manufactured by Kothari, "H-1900" (liquid polybutene) manufactured by INEOS butene), "H-6000" (liquid polybutene) manufactured by INEOS, "H-18000" (liquid polybutene) manufactured by INEOS, "200N" (liquid polybutene) manufactured by Nichiyu, "BI- 2000" (hydrogenated polybutadiene), "BI-3000" (hydrogenated polybutadiene) manufactured by Nippon Soda Co., Ltd. "GI-3000" (hydrogenated polybutadiene) manufactured by Nippon Soda Co., Ltd., "Lucant LX100" manufactured by Mitsui Chemicals Co., Ltd. (liquid olefin polymer), "Lucant LX400" (liquid olefin polymer) manufactured by Mitsui Chemicals, "Poly bd R-45HT" (butadiene liquid rubber) manufactured by Idemitsu Showa Shell, "Poly bd R-15HT" manufactured by Showa Shell, Idemitsu (butadiene-based liquid rubber), "Poly ip" (liquid polyisoprene) manufactured by Idemitsu Showa Shell, "B-1000" (liquid polybutadiene) manufactured by Nippon Soda, "B-3000" (liquid poly butadiene), "G-3000" (liquid polybutadiene) manufactured by Nippon Soda, "LIR-30" (liquid polyisoprene) manufactured by Kuraray, "LIR-390" (liquid polyisoprene) manufactured by Kuraray, " "LIR-290" (liquid polyisoprene), "LBR-302" (liquid polybutadiene) manufactured by Kuraray, "LBR-305" (liquid polybutadiene) manufactured by Kuraray, "LBR-361" (liquid polybutadiene) manufactured by Kuraray ), Kuraray's "L-SBR-820" (liquid styrene-butadiene random copolymer), CRAY VALLEY's "Ricon 154" (liquid butadiene), CRAY VALLEY's "RICON 184" (liquid styrene-butadiene random copolymers) and the like.

Component (A3) is preferably liquid polybutene and/or hydrogenated polybutadiene, more preferably liquid polybutene.

When component (A3) is used, its content is preferably 3% by mass or more, more preferably 5% by mass, based on 100% by mass of the non-volatile content of the sealing composition, from the viewpoint of good adhesion and flexibility of the sealing layer. or more, more preferably 10% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less.

(Component (A4))

Component (A) is an olefin polymer other than the component (A1) to (A3), that is, a non-liquid olefin polymer having neither an acid anhydride group, a carboxy group, or an epoxy group (in this specification, "component (A4) ”) may be included. In addition, the description and illustration of "olefin" and "olefin type polymer" in component (A4) are the same as those of the said component (A).

In the present invention, "non-liquid phase" in "non-liquid olefin polymer" means that the viscosity at 25°C is more than 5,000 Pa·s.

(A4) The number average molecular weight of the component is preferably 10,000 to 1,000,000, more preferably 20,000 to 750,000.

(A4) component,

(i) preferably a propylene-butene copolymer and/or an isobutene-isoprene copolymer (i.e. butyl rubber);

(ii) more preferably an isobutene-isoprene copolymer.

(A4) When a propylene-butene copolymer is used as the component, the amount of butene units in the copolymer is preferably 1 to 50% by mass, more preferably 2 to 45 mass%, based on the total amount of propylene units and butene units. %, more preferably 3 to 40% by mass.

(A4) When an isobutene-isoprene copolymer (i.e., butyl rubber) is used as the component, from the viewpoint of yellowing resistance of the sealing layer, etc., the amount of isoprene units in the copolymer is per total of isobutene units and isoprene units , preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, still more preferably 0.5 to 10% by mass.

The content of component (A4) is preferably 0 to 25% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 15% by mass, based on 100% by mass of the non-volatile matter in the sealing composition.

<Component (B)>

Component (B) used in the present invention is calcium oxide having a median diameter of 300 nm or less.

From the viewpoint of transparency of the sealing layer, the median diameter of component (B) is 300 nm or less, preferably 250 nm or less, and from the viewpoint of dispersibility of component (B), it is preferably 1 nm or more, more preferably 5 nm or more, and even more. Preferably it is 10 nm or more. The median diameter of component (B) is determined by measuring the particle diameter of component (B) by a dynamic light scattering method (JIS Z 8828), and the median of the volume-based particle size distribution (particle size distribution) created based on this measurement. is the diameter The dynamic light scattering method is a method of calculating particle diameters and particle diameter distributions by analyzing fluctuations corresponding to the speed of Brownian motion by a photon correlation method from scattered light observed when particles in a dispersion medium are irradiated with a laser beam. Specifically, this median diameter can be measured and calculated as described in Examples.

As component (B), calcium oxide with a median diameter of more than 300 nm may be pulverized and used, or a commercial item of calcium oxide with a median diameter of 300 nm or less may be used. As commercially available products of calcium oxide having a median diameter of more than 300 nm, for example, "QC-X" manufactured by Inoue Sekkaiko Co., Ltd., "WAC Series" manufactured by Sankyo Seikan Co., Ltd., "HAL-G" manufactured by Yoshizawa Sekkaiko Co., Ltd., "HAL-J", "HAL-F", "HAL-O", "HAL-P", etc. are mentioned. As a commercial item of calcium oxide with a median diameter of 300 nm or less, "CaO Nano Powder" by Filgen, etc. is mentioned, for example.

In one embodiment of the present invention, the content of component (B) is preferably 20% by mass or more, more preferably 20% by mass or more, from the viewpoint of the water vapor penetration barrier property of the sealing layer with respect to 100% by mass of the non-volatile matter of the composition for sealing. is 25% by mass or more, more preferably 30% by mass or more, and from the viewpoint of the adhesiveness of the sealing layer, is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less. .

In another embodiment of the present invention in which the sealing composition includes component (C), the content of component (B) is based on 100% by mass of the non-volatile content of the sealing composition, from the viewpoint of the water vapor permeation barrier property of the sealing layer. , preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and from the viewpoint of the adhesiveness of the sealing layer, preferably 30% by mass or less, more preferably 25% by mass % or less, more preferably 20% by mass or less.

<Component (C)>

Component (C) used in the present invention is semi-calcined hydrotalcite. Hydrotalcite can be classified into uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite.

Uncalcined hydrotalcite is, for example, a metal hydroxide having a layered crystal structure represented by natural hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ 4H ₂ O), and, for example, has a basic skeleton. It consists of a layer [Mg _1-X Al _X (OH) ₂ ] ^X+ and an intermediate layer [(CO ₃ ) _X/2 mH ₂ O] ^X- . Uncalcined hydrotalcite is a concept including hydrotalcite-like compounds such as synthetic hydrotalcite. Examples of the hydrotalcite-like compound include those represented by the following formula (I) and the following formula (II).

[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] ^x+ [(A ^n- ) _x/n mH ₂ O] ^x- (I)

(In the formula, M ²⁺ represents a divalent metal ion such as Mg ²⁺ and Zn ²⁺ , M ³⁺ represents a trivalent metal ion such as Al ³⁺ and Fe ³⁺ , and A ^n- represents CO ₃ ^2- , Cl ^- , NO ₃ ^- represents an n-valent anion, such as 0<x<1, 0≤m<1, and n is a positive number)

In formula (I), M ²⁺ is preferably Mg ²⁺ , M ³⁺ is preferably Al ³⁺ , and A ^n- is preferably CO ₃ ^2- .

M ²⁺ _x Al ₂ (OH) _2x+6-nz (A ^n- ) _z mH ₂ O (II)

(In the formula, M ²⁺ represents a divalent metal ion such as Mg ²⁺ , Zn ²⁺ , A ^n- represents an n-valent anion such as CO ₃ ^2- , Cl ^- , NO ₃ ^- , and x is 2 is a positive number greater than or equal to, z is a positive number less than or equal to 2, m is a positive number, and n is a positive number)

In formula (II), M ²⁺ is preferably Mg ²⁺ , and A ^n- is preferably CO ₃ ^2- .

Semi-calcined hydrotalcite refers to a metal hydroxide obtained by calcining uncalcined hydrotalcite and having a layered crystal structure in which the amount of interlayer water is reduced or eliminated. "Interlayer water" refers to "H ₂ O" described in the composition formula of the above-mentioned uncalcined natural hydrotalcite and hydrotalcite-like compound when explained using the composition formula.

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

Uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by the saturation water absorption. The saturated water absorption of the semi-calcined hydrotalcite is 1% by mass or more and less than 20% by mass. On the other hand, the saturated water absorption of uncalcined hydrotalcite is less than 1% by mass, and the saturated water absorption of calcined hydrotalcite is 20% by mass or more.

"Saturation water absorption" is measured by weighing 1.5 g of a measurement sample (e.g., semi-calcined hydrotalcite) on a balance, measuring the initial mass, and then setting it at 60°C and 90% RH (relative humidity) under atmospheric pressure. The mass increase rate relative to the initial mass when left still in a small environmental tester (SH-222 manufactured by Espec Co., Ltd.) for 200 hours, and the following formula (i):

Saturated water absorption (% by mass)

= 100 × (mass after moisture absorption - initial mass) / initial mass (i)

can be obtained with

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

Further, uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by the thermogravimetric reduction ratio measured by thermogravimetric analysis. The semi-calcined hydrotalcite has a thermogravimetric loss rate at 280°C of less than 15 mass%, and its thermogravimetric reduction rate at 380°C is 12 mass% or more. On the other hand, the thermogravimetric loss rate at 280°C of uncalcined hydrotalcite is 15 mass% or more, and the thermogravimetric loss rate of calcined hydrotalcite at 380°C is less than 12 mass%.

For thermogravimetric analysis, 5 mg of hydrotalcite was weighed into an aluminum sample pan using a TG/DTA EXSTAR6300 manufactured by Hitachi High-Tech Science, Inc., in an open state without a lid, in an atmosphere with a nitrogen flow rate of 200 mL/min at 30 °C. It can be carried out under conditions of a temperature increase rate of 10 °C/min from °C to 550 °C. The thermogravimetric loss rate is expressed by the formula (ii):

Thermogravimetric loss (% by mass)

= 100 × (mass before heating - mass when reaching a predetermined temperature) / mass before heating (ii)

can be obtained with

Further, uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by a peak measured by powder X-ray diffraction and a relative intensity ratio. Semi-calcined hydrotalcite shows a peak split into two at 2θ around 8 to 18° by powder X-ray diffraction or a peak with a shoulder by synthesis of two peaks, and diffraction of a peak or shoulder appearing on the low angle side The relative intensity ratio (low angle side diffraction intensity/high angle side diffraction intensity) of the intensity (= low angle side diffraction intensity) and the diffraction intensity of a peak or shoulder appearing on the high angle side (= high angle side diffraction intensity) is 0.001 to 1,000. On the other hand, uncalcined hydrotalcite has only one peak at around 8 to 18°, or the relative intensity ratio of diffraction intensities of a peak or shoulder appearing on the low angle side and a peak or shoulder appearing on the high angle side is outside the above range. Calcined hydrotalcite does not have a characteristic peak in the range of 8° to 18° and has a characteristic peak in the region of 43°. Powder X-ray diffraction measurement was performed using a powder X-ray diffractometer (manufactured by PANalytical, Empyrean), large cathode CuKα (1.5405 Å), voltage: 45 V, current: 40 mA, sampling width: 0.0260 It was carried out under conditions of °, scanning speed: 0.0657 °/s, measurement diffraction angle range (2θ): 5.0131 to 79.9711 °. For peak search, use the peak search function of the software included with the diffraction device, “minimum significance: 0.50, minimum peak chip: 0.01°, maximum peak chip: 1.00°, peak base width: 2.00°, method: second derivative It can be done under the condition of “the minimum value of

The BET specific surface area of the semi-calcined hydrotalcite is preferably 1 to 250 m ² /g, and more preferably 5 to 200 m ² /g. These BET specific surface areas can be calculated using the BET multi-point method by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring device (Macsorb HM Model 1210 manufactured by Mountec Co., Ltd.) according to the BET method.

The particle size of the semi-calcined hydrotalcite is preferably 1 to 1,000 nm, and more preferably 10 to 800 nm. These particle diameters are the median diameter of the particle size distribution when the particle size distribution is created on a volume basis by laser diffraction scattering particle size distribution measurement (JIS Z 8825).

As the semi-calcined hydrotalcite, one subjected to surface treatment with a surface treatment agent can be used. As a surface treatment agent used for surface treatment, higher fatty acids, alkylsilanes, silane coupling agents, etc. can be used, for example, and among these, higher fatty acids and alkylsilanes are suitable. 1 type or 2 or more types can be used for a surface treatment agent.

Commercially available products can be used as the semi-calcined hydrotalcite. As said commercial item, "DHT-4C" by Kyowa Chemical Industry Co., Ltd., "DHT-4A-2", etc. are mentioned, for example.

The content of component (C) is preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably, from the viewpoint of the water vapor permeation barrier property of the sealing layer with respect to 100% by mass of the non-volatile matter of the sealing composition. It is 30% by mass or more, and from the viewpoint of the adhesiveness of the sealing layer, it is preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less.

<Other ingredients>

The composition for sealing of the present invention may contain components other than components (A) to (C) (hereinafter sometimes referred to as "other components") within a range that does not impair the effects of the present invention. As other components, a tackifier, a metal complex, an antioxidant, a hardening accelerator, a plasticizer etc. are mentioned, for example. All of these may use only 1 type, and may use 2 or more types together. Hereinafter, the tackifier and the like are described in order.

(tackifier)

A tackifier is a component which imparts tackiness to the sealing composition. Examples of the tackifier include rosin-based resins, terpene resins, modified terpene resins (hydrogenated terpene resins, terpene phenol copolymer resins, aromatic modified terpene resins, etc.), petroleum resins (aliphatic petroleum resins, hydrogenated petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, copolymerized petroleum resins), coumarone-indene resins, alkylphenol resins, and xylene resins.

A commercially available product can be used as the tackifier. As said commercial item, the following are mentioned, for example. Examples of the rosin-based resin include Fine Crystal ME-H, Fine Crystal ME-D, Fine Crystal ME-G, Fine Crystal KR-85, Fine Crystal KE-311, Fine Crystal KE-359, and Fine Crystal D-6011. , Fine Crystal PE-590, Fine Crystal KE-604, Fine Crystal PR-580 (all manufactured by Arakawa Chemical Industry Co., Ltd.), and the like.

Examples of the terpene resin include YS Resin PX1000, YS Resin PX1150, YS Resin PX1150N, YS Resin PX1250, YS Resin TH130, YS Resin TR105, YS Resin LP, and YS Resin CP (all manufactured by Yasuhara Chemical Co., Ltd.). there is.

As hydrogenated terpene resin, Clearon P, Clearon M, and Clearon K series (all are Yasuhara Chemical Co., Ltd. make) etc. are mentioned, for example.

As a terpene phenol copolymer resin, YS Polystar 2000, Polystar U, Polystar T, Polystar S, and Mighty Ace G (all are Yasuhara Chemical Co., Ltd. make) etc. are mentioned, for example.

As aromatic modified terpene resin, YS resin TO85, YS resin TO105, YS resin TO115, YS resin TO125 (all are Yasuhara Chemical company make) etc. are mentioned, for example.

Examples of hydrogenated petroleum resins include Escorez 5300 series and 5600 series (all manufactured by ExxonMobil); T-REZ OP501, T-REZ PR803, T-REZ HA085, T-REZ HA103, T-REZ HA105, T-REZ HA125 (all hydrogenated dicyclopentadiene-based petroleum resins, manufactured by ENEOS); Quintone 1325, Quintone 1345 (both manufactured by Nippon Zeon Co., Ltd.); Imav S-100, Imav S-110, Imav P-100, Imav P-125, Imav P-140 (all hydrogenated dicyclopentadiene-based petroleum resins, manufactured by Idemitsu Kosan Co., Ltd.); Alcon P-90, Alcon P-100, Alcon P-115, Alcon P-125, Alcon P-140, Alcon M-90, Alcon M-100, Alcon M-115, Alcon M-135, TFS13-030 (All Arakawa Kagakuko Co., Ltd.) etc. are mentioned.

As an aromatic petroleum resin, it is ENDEX155 (made by Eastman Corporation), for example; Neopolymer L-90, Neopolymer 120, Neopolymer 130, Neopolymer 140, Neopolymer 150, Neopolymer 170S, Neopolymer 160, Neopolymer E-100, Neopolymer E-130, Neopolymer M-1, Neopolymer S, Neopolymer S100, Neopolymer 120S, Neopolymer 130S, Neopolymer EP-140 (all manufactured by ENEOS); Petocol LX, Petocol 120, Petocol 130, Petocol 140 (all manufactured by Tosoh Corporation); T-REZ RB093, T-REZ RC100, T-REZ RC115, T-REZ RC093, T-REZ RE100 (all are made by ENEOS), etc. are mentioned.

Examples of copolymerized petroleum resins include T-REZ HB103, T-REZ HB125, T-REZ PR801, T-REZ PR802, and T-REZ RD104 (all are manufactured by ENEOS); Petrotak 60, Petrotak 70, Petrotak 90, Petrotak 90HS, Petrotak 90V, Petrotak 100V (all manufactured by Tosoh Corporation); Quintone D100 (manufactured by Nippon Zeon Co., Ltd.); and the like.

The softening point of the tackifier is preferably 50 to 200°C, more preferably 90 to 180°C, still more preferably 100 to 170°C, from the viewpoint of the heat resistance of the sealing composition and the like. In addition, the softening point is measured by the ring and ball method according to JIS K2207.

When a tackifier is used, its content is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of the non-volatile content of the sealing composition, from the viewpoint of the adhesiveness and sealability of the sealing layer. %, more preferably 5 to 30% by mass.

(metal complex)

(C) In order to better disperse the component in the sealing composition, a bidentate ligand in which two coordinating atoms are both oxygen atoms (hereinafter sometimes referred to as "oxygen-bidentate ligand") and a coordinating atom in which an oxygen atom is used. A metal complex in which a monodentate ligand (hereinafter sometimes referred to as an "oxygen-mondentate ligand") is bonded to a central metal may be used.

The metal complex is preferably the following formula (1):

[Formula (1)]

[in Formula (1),

M represents a divalent or higher metal,

R ₁ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkenyloxy group, an aryl group or an aralkyl group;

R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkenyloxy group, an alkoxycarbonyl group, an aryl group or an aralkyl group;

X represents a monodentate ligand,

The solid line between the oxygen atom (O) and M in [ ] in Formula (1) represents a covalent bond,

In Formula (1), the broken line between the oxygen atom (O) and M in [ ] represents a coordinate bond,

m represents 3 or 4, n represents an integer from 0 to 4, and m≥n]

It is a metal complex (hereinafter sometimes abbreviated as “metal complex (1)”) represented by . As for the metal complex 1, only 1 type may be used, and 2 or more types may be used together.

M in the above formula (1) is preferably a metal of Group 4 of the Periodic Table or a metal of Group 13 of the Periodic Table, more preferably aluminum, titanium or zirconium.

In this specification, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

In this specification, any of the linear or branched chain may be sufficient as an alkyl group. The number of carbon atoms in the alkyl group (except for the alkyl group in the long-chain alkyl (meth)acrylate) is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and 1-ethylpropyl. group, hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, etc. are mentioned. The alkyl group may have a substituent. As said substituent, a halogen atom, a hydroxyl group, the amino group which may have a substituent, etc. are mentioned, for example.

In this specification, either linear or branched alkenyl group may be sufficient as it. The number of carbon atoms in the alkenyl group is preferably 2 to 20. Examples of the alkenyl group include ethenyl group (namely, vinyl group), 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, and 3-butenyl group. , 3-methyl-2-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group , 5-hexenyl group, etc. are mentioned. The alkenyl group may have a substituent. As said substituent, a halogen atom, a hydroxyl group, the amino group which may have a substituent, etc. are mentioned, for example.

In this specification, an alkynyl group may be linear or branched. The number of carbon atoms in the alkynyl group is preferably 2 to 10, more preferably 2 to 6. As an alkynyl group, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group , 4-pentynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 4-methyl-2-pentynyl group and the like. The alkynyl group may have a substituent. As said substituent, a halogen atom, a hydroxyl group, the amino group which may have a substituent, etc. are mentioned, for example.

In this specification, the number of carbon atoms in the aryl group is preferably 6 to 18, more preferably 6 to 14. As an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-antryl group, 2-antryl group, 9-antryl group etc. are mentioned, for example. The aryl group may have 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.

In this specification, carbon number of an aralkyl group is preferably 7 to 16. As an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a phenylpropyl group etc. are mentioned, for example. The aralkyl group may have a substituent. As said substituent, a halogen atom, a hydroxyl group, the amino group which may have a substituent, etc. are mentioned, for example.

In this specification, as an amino group which may have a substituent, for example, an amino group, a mono- or di-alkylamino group (eg, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dibutylamino group), Mono- or di-cycloalkylamino group (eg cyclopropylamino group, cyclohexylamino group), mono- or di-arylamino group (eg phenylamino group), mono- or di-aralkylamino group (eg benzylamino group, dibenzyl group) amino group), heterocyclic amino group (eg, pyridylamino group), and the like.

In this specification, the description of the alkyl group in the alkoxy group (ie, alkyloxy group) is the same as that of the above alkyl group. The alkoxy group may have a substituent. As said substituent, a halogen atom, a hydroxyl group, the amino group which may have a substituent, etc. are mentioned, for example.

In this specification, the description of the alkenyl group in the alkenyloxy group is the same as that of the above alkenyl group. The alkenyloxy group may have a substituent. As said substituent, a halogen atom, a hydroxyl group, the amino group which may have a substituent, etc. are mentioned, for example.

In this specification, the description of the alkyl group in the alkoxycarbonyl group (ie, alkyloxycarbonyl group) is the same as that of the above alkyl group. The alkoxycarbonyl group may have a substituent. As said substituent, a halogen atom, a hydroxyl group, the amino group which may have a substituent, etc. are mentioned, for example.

As a monodentate ligand represented by X in Formula (1), for example, an alkoxide anion (RO ^- ) (in the formula, R represents an organic group), a carboxylate anion (RCOO ^- ) (in the formula, R is an organic group), oxo (O), and the like.

The alkoxide anion is represented by RO ^- (wherein R represents an organic group). The organic group R may be either an aliphatic group or an aromatic group. In addition, either a saturated aliphatic group or an unsaturated aliphatic group may be sufficient as an aliphatic group. The number of carbon atoms in the organic group R is preferably 1 to 20, more preferably 6 to 18, and particularly preferably 8 to 14. Examples of the alkoxide anion (RO ^- ) include methoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide, sec-butoxide, tert-butoxide, pentyloxide, hexyloxide, Phenoxide, 4-methylphenoxide, etc. are mentioned.

The carboxylate anion is represented by RCOO ^- (wherein R represents an organic group). The organic group R may be either an aliphatic group or an aromatic group. In addition, either a saturated aliphatic group or an unsaturated aliphatic group may be sufficient as an aliphatic group. The number of carbon atoms in the organic group R is preferably 1 to 20, more preferably 6 to 18, and particularly preferably 8 to 14. As the carboxylate anion (RCOO ^- ), for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, octylic acid, nonanoic acid, decanoic acid, dodecanoic acid, stearic acid, oleic acid, linoleic acid , carboxylate anions corresponding to carboxylic acids such as linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and benzoic acid.

Examples of the polydentate ligand represented by [ ] in formula (1) include acetylacetone, 3-methyl-2,4-pentanedione, acetylacetaldehyde, 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, 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, salicylic acid, methyl salicylate, malonic acid, dimethyl malonate, diethyl malonate and the like. In the state coordinated to the central metal, the polydentate ligand has a structure in which one or more protons are removed from it.

Specific examples of the metal complex (1) in which M is aluminum include aluminum diisopropylate monosec-butylate, aluminum trisec-butylate, aluminum triisopropylate, aluminum triethylate, aluminum tris(acetylacetonate), Aluminum bis(ethylacetoacetate) mono(acetylacetonate), aluminum tris(ethylacetoacetate), aluminum octadecenylacetoacetate diisopropylate, aluminum ethylacetoacetate diisopropylate, aluminum ethylacetoacetate din-butyl Rate, aluminum propylacetoacetate diisopropylate, aluminum n-butylacetoacetate diisopropylate, aluminum tris (ethylacetoacetate), aluminum mono (acetylacetonate) bis (ethylacetoacetate), aluminum tris (acetylacetonate) ) can be heard.

Specific examples of the metal complex (1) in which M is titanium include tetraisopropyl titanate, tetranormal butyl titanate, tetraoctyl titanate, tetratert-butyl titanate, tetrastearyl titanate, titanium tetraacetylacetonate, and titanium. Octylene glycolate (alias: bis(2-ethylhexyloxy)bis(2-ethyl-3-oxohexyloxy)titanium(IV)), titanium diisopropoxide bis(ethylacetoacetate), titanium allyl Acetoacetate triisopropoxide, titanium dinormal butoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate) ), titanium (IV) tetra(methylphenolate), titanium oxide bis(2,4-pentanedionate), monoisopropoxytitanium triisostearate, and diisopropoxytitanium diisostearate.

Specific examples of the metal complex (1) in which M is zirconium include zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetra(acetylacetonate), zirconium allylacetoacetate triisopropoxide, and zirconium dinormal butoxide bis. (2,4-pentanedionate), zirconium diisopropoxide bis (2,4-pentanedionate), zirconium diisopropoxide bis (tetramethylheptanedionate), zirconium diisopropoxide bis ( Ethyl acetoacetate), zirconium butoxide (acetyl acetate) bis (ethylacetoacetate), zirconium tributoxide monoacetylacetonate, zirconium octylate, zirconium stearate, tri-normal butoxy zirconium monooctylate, tri-normal butoxy zirconium Monostearate is mentioned.

When a metal complex is used, its content is preferably 0.01 to 3% by mass, more preferably 0.05 to 2.5% by mass, based on 100% by mass of the non-volatile content of the sealing composition, from the viewpoint of the dispersibility of component (C) and the like. % by mass, more preferably 0.10 to 2% by mass.

(Antioxidants)

In the present invention, the antioxidant is not particularly limited, and a known antioxidant can be used. When an antioxidant is used, its content is preferably 0.01 to 5% by mass, more preferably 0.05 to 2.5% by mass, still more preferably 0.10 to 2% by mass, based on 100% by mass of the non-volatile matter in the sealing composition. to be.

(curing accelerator)

In this invention, in order to accelerate the crosslinking reaction of the acid anhydride group and/or carboxy group of component (A1), and the epoxy group of component (A2), you may use a hardening accelerator. Examples of the curing accelerator include imidazole compounds, tertiary and quaternary amine compounds, dimethylurea compounds, and organic phosphine compounds.

Examples of the imidazole compound include 1H-imidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2. -Ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2 -Phenyl-4,5-bis(hydroxymethyl)imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenylimidazole, 2-dodecyl Midazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. are mentioned. Specific examples of the imidazole compound include Curazole 2MZ, 2P4MZ, 2E4MZ, 2E4MZ-CN, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2PHZ, 1B2MZ, 1B2PZ, 2PZ, C17Z, 1.2DMZ, 2P4MHZ-PW, 2MZ-A, 2MA-OK (all manufactured by Shikoku Kasei Kogyo), etc. are mentioned.

The tertiary/quaternary amine compound is not particularly limited, and examples thereof include quaternary ammonium salts such as tetramethylammonium bromide, tetrabutylammonium bromide, and triethylmethylammonium/2-ethylhexanoic acid salt; DBU (1,8-diazabicyclo[5.4.0]undecene-7), DBN (1,5-diazabicyclo[4.3.0]nonene-5), DBU-phenol salt, DBU-octylate, DBU Diazabicyclo compounds such as p-toluenesulfonic acid salt, DBU-formate, and DBU-phenol novolac resin salt; Tertiary amines such as benzyldimethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol (TAP) or salts thereof, dimethylurea such as aromatic dimethylurea and aliphatic dimethylurea A compound etc. are mentioned.

Examples of the dimethylurea compound include aromatic dimethylurea such as DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) and U-CAT3512T (manufactured by San Afro); Aliphatic dimethyl urea, such as U-CAT3503N (made by San Afro), etc. are mentioned. Among these, aromatic dimethylurea is preferably used from the viewpoint of curability.

Examples of organic phosphine compounds include triphenylphosphine, tetraphenylphosphonium tetra-p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tri-tert-butylphosphonium tetraphenyl borate, and (4-methylphenyl). Triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, triphenylphosphine triphenylborane, etc. are mentioned. Specific examples of the organic phosphine compound include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, and TPP-S (all manufactured by Hoko Chemical Co., Ltd.).

In the case of using a curing accelerator, its content is based on 100% by mass of the non-volatile content of the sealing composition in order to accelerate the crosslinking reaction between the acid anhydride group and/or carboxy group of component (A1) and the epoxy group of component (A2). It is preferably 0.001 to 5% by mass, more preferably 0.001 to 2.5% by mass, still more preferably 0.001 to 1% by mass.

(plasticizer)

The composition for sealing of this invention may further contain the plasticizer. Examples of the plasticizer include mineral oils such as paraffinic process oil, naphthenic process oil, liquid paraffin and petrolatum, and vegetable oils such as castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, and olive oil.

<Method for producing sealing composition>

Hereinafter, a suitable method for producing the sealing composition of the present invention will be described. However, you may manufacture the composition for sealing of this invention other than the following method.

A suitable method for producing the composition for sealing of the present invention (hereinafter referred to as "the production method of the present invention") is an olefinic polymer having an acid anhydride group and/or a carboxyl group (ie, component (A1))), median diameter A step of pulverizing the mixture containing the calcium oxide exceeding 300 nm and the organic solvent is included. The sealing composition of the present invention may be prepared by mixing calcium oxide having a median diameter of 300 nm or less (ie, component (B)) with components other than component (B), but in such a simple mixing, when the above steps are performed In contrast, it is difficult to properly disperse fine calcium oxide in the sealing composition. In addition, fine calcium oxide has a large surface area, and as a result, hygroscopicity also increases. In order to avoid such moisture absorption, the handleability of fine calcium oxide at the time of producing the sealing composition is inferior to that of calcium oxide of normal size. Therefore, it is preferable to manufacture the composition for sealing of this invention through the said process. Hereinafter, the mixture for pulverization used in the production method of the present invention and the like will be described in order.

A mixture for grinding treatment can be prepared by mixing calcium oxide having a median diameter of more than 300 nm, component (A1), and an organic solvent. The content of the calcium oxide is preferably 3 to 75% by mass, more preferably 5 to 70% by mass, based on the entire mixture for grinding treatment. The content of component (A1) is preferably 3 to 40% by mass, more preferably 5 to 35% by mass, based on the total amount of the mixture for grinding treatment. The content of the organic solvent is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, in one embodiment of the present invention, with respect to the entire mixture for pulverization treatment, and the sealing composition is (C ) component, preferably from 20 to 60% by mass, more preferably from 30 to 50% by mass. Components other than the above components (for example, semi-calcined hydrotalcite (ie, component (C)), component (A3), tackifier, etc.) may be added to the mixture for pulverization treatment. The order of addition of each component is not particularly limited, and each component may be added sequentially or simultaneously.

Examples of the organic solvent that can be used in the production method of the present invention include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; Acetate esters, such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellosolves such as cellosolve; carbitols such as butyl carbitol; Aromatic hydrocarbons, such as toluene and xylene; Amides of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are mentioned. You may use a commercially available organic solvent, for example, "Swazol" by Maruzen Sekiyu Chemical Co., Ltd., "Ipsol" by Idemitsu Kosan Co., Ltd., etc. The organic solvent may use only 1 type, and may use 2 or more types together.

The crushing treatment can be performed using a known crusher. The grinding treatment causes the calcium oxide to be ground and dispersed uniformly in the mixture. As a known grinder, a wet bead mill etc. are mentioned, for example. As a material of a bead, zirconia, alumina, glass, steel etc. are mentioned, for example. The bead diameter is, for example, about 0.03 to 5 mm. The number of revolutions of the rotating shaft of the bead mill is, for example, about 10 to 10000 rpm. The flow rate at which the mixture for grinding treatment is supplied to the grinding chamber of the bead mill is, for example, about 0.1 to 10000 kg/hour. In wet pulverization by a bead mill, it is preferable to perform while cooling with chiller water in order to suppress the temperature rise of the mixture during the pulverization process. The temperature of the filler water is, for example, about 0 to 40°C.

In addition, you may mix the mixture after grinding processing with arbitrary components. For example, you may add and mix component (A2), component (A3), a tackifier, etc. to the mixture after grinding process. When the sealing composition contains an olefinic polymer having an epoxy group as component (A2), in order to prevent the crosslinking reaction from proceeding due to heat or the like during pulverization treatment, mixing the mixture after pulverization treatment with component (A2) it is desirable That is, the production method of the present invention preferably further includes a step of mixing the mixture after grinding treatment with an olefinic polymer having an epoxy group (ie, component (A2)). The order of addition of each component is not particularly limited, and each component may be added sequentially or simultaneously.

When the mixture for grinding treatment contains semi-baked hydrotalcite (ie, component (C)), the varnish of the sealing composition of the present invention containing an organic solvent can be produced by the grinding treatment. When the mixture for pulverization does not contain component (C), the varnish of the composition for sealing of the present invention containing an organic solvent can be produced by mixing the mixture after pulverization with component (C).

The varnish of the composition for sealing containing the organic solvent obtained by the above may remove part or all of the organic solvent by drying etc. The composition for sealing of the present invention may be used in a liquid state such as varnish or in a solid state such as a film.

sheet for sealing

The present invention also provides a sheet for sealing having a laminated structure comprising a support and a sealing layer formed from the composition for sealing of the present invention. In the present invention, a protective sheet may be used. That is, the sheet for sealing of the present invention may have a laminated structure comprising a support, a sealing layer and a protective sheet in this order. Other layers may exist between the support and the sealing layer and between the sealing layer and the protective sheet. Examples of the other layer include an adhesive layer, a release layer, and a sealing layer formed of a sealing composition not containing calcium oxide and/or semi-baked hydrotalcite.

The haze of the sealing layer is preferably less than 60%, more preferably 40% or less, still more preferably 20% or less. The lower limit of the haze of the sealing layer is not particularly limited, but the haze of the sealing layer is, for example, 0% or more. This haze can be measured based on JIS K 7136. Specifically, this haze can be measured by the method described in the section of Examples below, using glass as a reference and using D65 light.

Examples of the support and protective sheet include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; cycloolefin polymers; polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate; polycarbonate; Plastic films, such as polyimide, etc. are mentioned. Both the support and the protective sheet may be single-layer films or laminated films.

As the support and the protective sheet, for example, a low moisture permeability film having a barrier layer or a laminated film of a low moisture permeability film having a barrier layer and another film can be used. As a barrier layer, inorganic membranes, such as a silica deposition film, a silicon nitride film, and a silicon oxide film, are mentioned, for example. The barrier layer may be composed of a plurality of layers of a plurality of inorganic films (for example, a silica deposition film). Further, the barrier layer may be composed of an organic material and an inorganic material, or may be a composite multilayer of an organic layer and an inorganic film.

It is preferable that the surface of the protective sheet in contact with the sealing layer is subjected to release treatment. On the other hand, the support body may be subjected to a release treatment or may not be subjected to a release treatment. As the release treatment, release treatment by a release agent such as a silicone resin type release agent, an alkyd resin type release agent, or a fluororesin type release agent is exemplified.

The thickness of the support and the protective sheet is not particularly limited, but from the viewpoint of handleability of the sealing sheet, etc., each is preferably 10 to 150 µm, more preferably 20 to 100 µm. In addition, when the support body and the protective sheet are laminated films, the above thickness is the thickness of the laminated film. On the other hand, the thickness of the sealing layer is preferably 2 to 100 μm, more preferably 2 to 75 μm, still more preferably 3 to 50 μm, or in another embodiment of the present invention in which the sealing composition includes component (C), preferably 3 to 200 μm, more preferably 3 to 150 μm, still more preferably 3 to 100 μm. μm.

<Method for Manufacturing Sheet for Sealing>

The sealing sheet of the present invention can be produced, for example, by applying the varnish of the sealing composition obtained as described above to a support to form a coating film, and drying the obtained coating film to form a sealing layer. Further, for a sealing sheet having a laminated structure comprising a support body, a sealing layer and a protective sheet in this order, for example, varnish is applied to one of the support body and the protective sheet and dried to form a sealing layer, thereby forming the sealing layer. It can be manufactured by laminating the other of the support and the protective sheet thereon.

When component (A2) is used, drying of the coating film (ie, removal of the organic solvent) is required to advance the reaction between the epoxy group of component (A2) and the acid anhydride group and/or carboxy group of component (A1). It is preferable to perform by heating. The heating temperature of the coating film is preferably 50 to 200°C, more preferably 80 to 150°C, and the time is preferably 1 to 60 minutes, more preferably 5 to 30 minutes. The heating of the coating film may be performed under normal pressure or under reduced pressure.

The coating film obtained by removing the organic solvent may be further heated (aged). The heating temperature is preferably 80 to 200°C, more preferably 100 to 150°C, and the time is preferably 10 to 240 minutes, more preferably 30 to 180 minutes. This heating may be performed under normal pressure or under reduced pressure.

electronic device

The present invention also provides an electronic device comprising a sealing layer formed from the composition for sealing of the present invention. As an electronic device, an organic EL device, a solar cell, a sensor device, a touch panel with a conductive substrate, etc. are mentioned, for example. The electronic device is preferably an electronic device sensitive to moisture such as an organic EL device or a solar cell.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and can be practiced with appropriate changes within the range suitable for the above and below purposes. and all of them are included in the technical scope of the present invention. In addition, "part" and "%" in the amount of components and the amount of copolymerization units mean "part by mass" and "% by mass", respectively, unless otherwise specified.

<Ingredients>

Components used in Examples and Comparative Examples are shown below.

(1) Component (A1)

"HV-300M" (manufactured by Toho Chemical Industry Co., Ltd., maleic anhydride-modified liquid polybutene, acid anhydride group concentration: 0.77 mmol/g, number average molecular weight: 2,100)

(2) Component (A2)

"ER829" (manufactured by Seiko PMC, glycidyl methacrylate-modified propylene-butene random copolymer, propylene unit/butene unit: 71%/29%, epoxy group concentration: 0.64 mmol/g, number average molecular weight: 168,000)

"ER866" (manufactured by Seiko PMC, glycidyl methacrylate-modified butyl rubber, epoxy group concentration: 1.63 mmol/g, number average molecular weight: 113,000, isobutene unit/isoprene unit: 98.9%/1.1%)

(3) Component (A3)

"HV-1900" (manufactured by ENEOS, liquid polybutene, number average molecular weight: 2,900, viscosity at 25°C: 460 Pa·s)

(4) Component (A4)

"BUTYL065" (manufactured by JSR, butyl rubber, isobutene unit/isoprene unit: 98.7%/1.3%)

(5) hygroscopic filler

(5-1) calcium oxide

Calcium oxide (manufactured by Yoshizawa Sekkaiko Co., Ltd., median diameter: 2.1 µm)

(5-2) (C) component

"DHT-4C" (manufactured by Kyowa Chemical Industry Co., Ltd., semi-calcined hydrotalcite, median diameter: 400 nm, BET specific surface area: 15 m ² /g)

(6) Tackifier

"Alcon P-125" (manufactured by Arakawa Kagakuko Co., Ltd., hydrogenated petroleum resin, softening point: 125°C)

(7) metal complex

"Frenact Al-M" (manufactured by Ajinomoto Fine Techno Co., Ltd., aluminum octadecenylacetoacetate diisopropylate)

(8) Antioxidants

"Irganox 1010" (manufactured by BASF, hindered phenolic antioxidant)

(9) Curing accelerator

2,4,6-tris(dimethylaminomethyl)phenol (manufactured by Kayaku Nurion Co., Ltd., hereinafter abbreviated as "TAP")

<Example 1>

A varnish having the compounding ratio shown in Table 1 below was produced in the following procedure, and a sheet for sealing was produced using the obtained varnish. In addition, the amount of use (parts) of each component described in Table 1 below indicates the amount of the non-volatile content of each component in the varnish. In Table 1 below, calcium oxide is described as "CaO", and its median diameter is described in parentheses. In addition, in following Table 1, content of the hygroscopic filler with respect to 100 mass % of the non-volatile matter of the composition for sealing is shown.

Specifically, maleic anhydride-modified liquid polybutene ("HV manufactured by Toho Chemical Industry Co., Ltd.) was added to a swarzol solution (non-volatile content: 60%) of a tackifier ("Alcon P-125" manufactured by Arakawa Chemical Industry Co., Ltd.) -300M”), liquid polybutene (“HV-1900” manufactured by ENEOS), calcium oxide (manufactured by Yoshizawa Sekkaiko Co., Ltd.) and toluene were blended to obtain a mixture for pulverization treatment (for the entire mixture, organic solvent Content (i.e., total content of swazole and toluene): 24%, content of maleic anhydride-modified liquid polybutene: 10%, content of calcium oxide: 48%, content of tackifier: 7%, liquid polybutene of: 11%).

The mixture for pulverization was put into a wet bead mill (Labosta Mini “LMZ015” manufactured by Ashizawa Finetech), and beads (bead diameter: 0.2 mm) were filled so that about 60% by volume of the effective volume of the pulverization chamber Then, pulverization was performed to obtain a mixture after pulverization in which calcium oxide was pulverized and dispersed.

A small amount was removed from the mixture after the grinding treatment, diluted 100 times with toluene, a measurement sample was prepared, and the median diameter of calcium oxide was measured by a dynamic light scattering method using a nanoparticle diameter measuring device "NANOTRAC WAVE" manufactured by Microtrak Co., Ltd. and calculated. As a result, the median diameter of calcium oxide was 246 nm.

To the mixture after the pulverization treatment, a toluene solution (non-volatile content: 15%) of a glycidyl methacrylate-modified propylene-butene random copolymer ("ER829" manufactured by Seiko PMC), a hindered phenolic antioxidant (manufactured by BASF " Irganox 1010”) and a curing accelerator (TAP, manufactured by Kayaku Nurion Co., Ltd.) were blended, and the obtained mixture was mixed with a high-speed rotary mixer to obtain a varnish of a composition for sealing.

A polyethylene terephthalate film (“SP4020” manufactured by Toyo Cross Co., Ltd., PET film thickness: 50 μm) treated with a silicone-based release agent on one side, and a polyethylene terephthalate film with low moisture permeability (“Tech Barrier HX” manufactured by Mitsubishi Chemical Corporation, PET film) thickness: 12 μm) was bonded so that the surface of SP4020 not treated with the silicone release agent and the Tech Barrier HX were in contact to prepare a laminated film, which was used as a support and a protective sheet for the sealing sheet. Hereinafter, "the surface treated with the silicone type release agent of the laminated film" is described as the "release treatment surface".

The obtained varnish was uniformly applied on the release-treated surface of the first laminated film with a die coater, and heated at 140°C for 30 minutes. Thereafter, the second laminated film was laminated so that the release treatment surface and the composition layer contacted, and then heated at 130° C. for 60 minutes to obtain a sealing sheet having a sealing layer having a thickness of 10 μm.

<Example 2>

A sealing sheet having a sealing layer having a thickness of 10 μm was prepared in the same manner as in Example 1 except that the amount of calcium oxide used was changed from 300 parts to 120 parts.

<Example 3>

A sealing sheet having a sealing layer having a thickness of 10 μm was prepared in the same manner as in Example 1 except that the bead diameter of the wet bead mill was changed from 0.2 mm to 0.1 mm. In addition, as a result of measuring the median diameter of calcium oxide in the mixture after the grinding treatment in Example 3 in the same manner as in Example 1, the median diameter was 185 nm.

<Example 4>

A sealing sheet was produced in the same manner as in Example 1 except that the thickness of the sealing layer was changed from 10 μm to 5 μm.

<Example 5>

A sealing sheet was prepared in the same manner as in Example 2, except that the thickness of the sealing layer was changed from 10 μm to 20 μm.

<Example 6>

A toluene solution (non-volatile content: 15%) of a glycidyl methacrylate-modified propylene-butene random copolymer (“ER829” manufactured by Seiko PMC) was mixed with glycidyl methacrylate-modified butyl rubber (“ER866” manufactured by Seiko PMC). ]), a sealing sheet having a sealing layer having a thickness of 10 μm was produced in the same manner as in Example 3 except for changing to a toluene solution (non-volatile content: 25%).

<Example 7>

A toluene solution (non-volatile content: 15%) of a glycidyl methacrylate-modified propylene-butene random copolymer ("ER829" manufactured by Seiko PMC), a toluene solution (non-volatile content) of butyl rubber ("BUTYL065" manufactured by JSR Corporation) : 15%), a sealing sheet having a sealing layer having a thickness of 10 μm was prepared in the same manner as in Example 3 except for changing to 15%).

<Comparative Example 1>

Maleic anhydride-modified liquid polybutene ("HV-300M" manufactured by Toho Chemical Industry Co., Ltd.) , liquid polybutene (“HV-1900” manufactured by ENEOS) and semi-fired hydrotalcite (“DHT-4C” manufactured by Kyowa Chemical Industry Co., Ltd.) were mixed with three rolls to obtain a mixture. To the obtained mixture, a swarzol solution (non-volatile content: 15%) of a glycidyl methacrylate-modified propylene-butene random copolymer ("ER829" manufactured by Seiko PMC), a hindered phenolic antioxidant ("Irganox manufactured by BASF") 1010”), a curing accelerator (TAP, manufactured by Kayaku Nurion Co.) and toluene were blended and mixed in a high-speed rotary mixer to obtain a varnish of a sealing composition. Using the obtained varnish, a sealing sheet having a sealing layer having a thickness of 10 μm was prepared in the same manner as in Example 1.

<Comparative Example 2>

The thickness A sheet for sealing having a sealing layer of 10 µm was produced.

<Comparative Example 3>

A mixture for grinding treatment was prepared in the same manner as in Example 1 except that maleic anhydride-modified liquid polybutene ("HV-300M" manufactured by Toho Kagaku Kogyo Co., Ltd.) was not used (organic solvent for the whole mixture content (i.e., the total content of swarzol and toluene): 26%, content of calcium oxide: 53%, content of tackifier: 8%, content of liquid polybutene: 12%).

The mixture for pulverization was put into a wet bead mill (Labosta Mini "LMZ015" manufactured by Ashizawa Finetech, bead diameter: 0.2 mm), and pulverization and dispersion of calcium oxide were attempted, but the mixture for pulverization was not significantly Due to the increase in viscosity, it was not possible to produce a varnish of a composition for sealing in which calcium oxide having a median diameter of 300 nm or less was dispersed.

<Example 8>

A varnish having the compounding ratio shown in Table 2 was produced in the following procedure, and a sheet for sealing was produced using the obtained varnish. In addition, the amount of use (parts) of each component described in Table 2 below indicates the amount of the non-volatile content of each component in the varnish. In Table 2 below, "calcium oxide" is described as "CaO", "calcium oxide having a median diameter exceeding 300 nm" is described as "component (B')", and the median diameter of the calcium oxide used is also described. do. In addition, in Table 2 below, the content of calcium oxide and the content of semi-fired hydrotalcite with respect to 100% by mass of the non-volatile matter of the composition for sealing are shown.

Specifically, maleic anhydride-modified liquid polybutene ("HV manufactured by Toho Chemical Industry Co., Ltd.) was added to a swarzol solution (non-volatile content: 60%) of a tackifier ("Alcon P-125" manufactured by Arakawa Chemical Industry Co., Ltd.) -300M”), liquid polybutene (“HV-1900” manufactured by ENEOS), calcium oxide (manufactured by Yoshizawa Sekkaiko Co., Ltd.) and toluene were blended to obtain a mixture for grinding treatment (organic solvent for the entire mixture) content (i.e., the total content of swazole and toluene): 35%, content of maleic anhydride-modified liquid polybutene: 7%, content of calcium oxide: 23%, content of tackifier: 16%, liquid poly Butene content: 19%).

The mixture for pulverization was put into a wet bead mill (Labosta Mini “LMZ015” manufactured by Ashizawa Finetech), and beads (bead diameter: 0.1 mm) were filled to about 60% by volume of the effective volume of the pulverizing chamber. Then, pulverization was performed to obtain a mixture after pulverization in which calcium oxide was pulverized and dispersed.

A small amount was taken out from the mixture after the grinding treatment, diluted 100 times with toluene to prepare a measurement sample, and using a nanoparticle diameter measuring device "NANOTRAC WAVE" manufactured by Microtrac, the median diameter of calcium oxide was measured by a dynamic light scattering method, and Calculated. As a result, the median diameter of calcium oxide was 185 nm.

To the mixture after the pulverization treatment, toluene of semi-calcined hydrotalcite ("DHT-4C" manufactured by Kyowa Chemical Industry Co., Ltd.) and glycidyl methacrylate-modified propylene-butene random copolymer ("ER829" manufactured by Seiko PMC) Solution (non-volatile content: 15%), metal complex ("Prenact Al-M" manufactured by Ajinomoto Fine Techno), hindered phenolic antioxidant ("Irganox 1010" manufactured by BASF), curing accelerator (TAP, Kayaku Nuri) manufactured by Onsa) was blended, and the resulting mixture was mixed with a high-speed rotary mixer to obtain a varnish of a sealing composition.

A polyethylene terephthalate film (“SP4020” manufactured by Toyo Cross Co., Ltd., PET film thickness: 50 μm) treated with a silicone-based release agent on one side, and a polyethylene terephthalate film with low moisture permeability (“Tech Barrier HX” manufactured by Mitsubishi Chemical Corporation, PET film) thickness: 12 μm) was bonded so that the surface of SP4020 not treated with the silicone release agent and the Tech Barrier HX were in contact to prepare a laminated film, which was used as a support and a protective sheet for the sealing sheet. Hereinafter, "the surface treated with the silicone type release agent of the laminated film" is described as the "release treatment surface".

The obtained varnish was uniformly applied on the release-treated surface of the first laminated film with a die coater, and heated at 140°C for 30 minutes. Then, after laminating|stacking the 2nd laminated|multilayer film so that the release treatment surface and the composition layer may contact, by heating at 130 degreeC for 60 minutes, the sealing sheet which has a sealing layer with a thickness of 50 micrometers was obtained.

<Example 9>

A sealing sheet having a sealing layer having a thickness of 50 μm in the same manner as in Example 8, except that the amount of component (B) was changed from 96 parts to 60 parts and the amount of component (C) was changed from 144 parts to 180 parts. was produced.

<Example 10>

A sealing sheet was produced in the same manner as in Example 8 except that the thickness of the sealing layer was changed from 50 μm to 20 μm.

<Example 11>

A sealing sheet having a sealing layer having a thickness of 20 μm was prepared in the same manner as in Example 8 except that the bead diameter of the wet bead mill was changed from 0.1 mm to 0.2 mm. In addition, as a result of measuring the median diameter of calcium oxide in the mixture after grinding in Example 11 in the same manner as in Example 8, the median diameter was 246 nm.

<Example 12>

A toluene solution (non-volatile content: 15%) of a glycidyl methacrylate-modified propylene-butene random copolymer (“ER829” manufactured by Seiko PMC) was mixed with glycidyl methacrylate-modified butyl rubber (“ER866” manufactured by Seiko PMC). A sealing sheet having a sealing layer having a thickness of 50 μm was prepared in the same manner as in Example 8 except for changing to a toluene solution (non-volatile content: 25%) of).

<Example 13>

A toluene solution (non-volatile content: 15%) of a glycidyl methacrylate-modified propylene-butene random copolymer ("ER829" manufactured by Seiko PMC), a toluene solution (non-volatile content) of butyl rubber ("BUTYL065" manufactured by JSR Corporation) : 15%), a sealing sheet having a sealing layer having a thickness of 50 μm was prepared in the same manner as in Example 8 except for changing to 15%).

<Comparative Example 4>

Maleic anhydride-modified liquid polybutene ("HV-300M" manufactured by Toho Chemical Industry Co., Ltd.) , liquid polybutene (“HV-1900” manufactured by ENEOS) and semi-fired hydrotalcite (“DHT-4C” manufactured by Kyowa Chemical Industry Co., Ltd.) were mixed with three rolls to obtain a mixture. To the obtained mixture, a swarzol solution (non-volatile content: 15%) of a glycidyl methacrylate-modified propylene-butene random copolymer ("ER829" manufactured by Seiko PMC), a hindered phenolic antioxidant ("Irganox manufactured by BASF") 1010”), a curing accelerator (TAP, manufactured by Kayaku Nurion Co.) and toluene were blended and mixed in a high-speed rotary mixer to obtain a varnish of a sealing composition. Using the obtained varnish, a sealing sheet having a sealing layer having a thickness of 50 μm was prepared in the same manner as in Example 8.

<Comparative Example 5>

A sealing sheet having a sealing layer having a thickness of 50 μm was prepared in the same manner as in Comparative Example 4 except that the amount of component (C) was changed from 240 parts to 180 parts and 60 parts of calcium oxide (median diameter: 2.1 μm) were used. produced.

<Comparative Example 6>

A mixture for grinding treatment was prepared in the same manner as in Example 8, except that maleic anhydride-modified liquid polybutene (“HV-300M” manufactured by Toho Kagaku Kogyo Co., Ltd.) was not used (organic solvent for the whole mixture (namely, the sum of the contents of swarzol and toluene): 38%, the content of calcium oxide: 24%, the content of the tackifier: 17%, the content of liquid polybutene: 20%).

The mixture for pulverization was put into a wet bead mill (Labosta Mini "LMZ015" manufactured by Ashizawa Finetech, bead diameter: 0.1 mm), and pulverization and dispersion of calcium oxide were attempted, but the mixture for pulverization was not significantly Due to the increase in viscosity, it was not possible to produce a varnish of a composition for sealing in which calcium oxide having a median diameter of 300 nm or less was dispersed.

About the sealing layer of the sheet|seat for sealing obtained by the Example and the comparative example, the transparency and water vapor permeation barrier property were evaluated by the following method.

<Evaluation method of transparency>

The sealing sheets prepared in Examples and Comparative Examples were cut to a length of 70 mm and a width of 25 mm, the protective sheet was peeled from the cut sealing sheet, and the sealing sheet having a laminated structure with the sealing layer/support was formed on a glass plate (Matsumoto). A batch-type vacuum laminator (V-160, manufactured by Nichigo Morton) was applied to "White Slide Glass S1112 Polishing No. 2" manufactured by Nami Karasco Gyoza, length: 76 mm, width: 26 mm, and thickness: 1.2 mm. and laminated using the same, and a sample for evaluation having a laminated structure of glass/sealing layer/support was obtained. The lamination conditions were pressurization at a pressure of 0.3 MPa for 30 seconds after a temperature of 80°C and a decompression time of 30 seconds.

Haze (%) was measured based on JIS K 7136. In detail, after peeling off the support of the sample for evaluation having a laminated structure of glass/sealing layer/support, using a haze meter HZ-V3 (halogen lamp) manufactured by Suga Shikenki Co., Ltd., using the glass as a reference, D65 light Then, the haze (%) of the sample for evaluation from which the support was peeled off was measured, and transparency was evaluated according to the following criteria. Results are shown in the table below.

(Criteria for transparency)

○ (good): haze is less than 30%

△ (a): Haze is 30% or more and less than 60%

× (defective): Haze is 60% or more

<Evaluation method of water vapor penetration barrier property>

As a support, a composite film (“PET Tsuki AL1N30” (thickness of aluminum foil: 30 μm, thickness of PET film: 25 μm), manufactured by Tokaido Aluminum Hanbai Co., Ltd.) comprising an aluminum foil and a polyethylene terephthalate film was prepared.

A test sheet having a laminated structure of "support (composite film)/sealing layer/protective sheet (laminated film)" was obtained in the same manner as in Examples and Comparative Examples except that the composite film was used as a support.

A 50 mm × 50 mm square glass plate formed of alkali-free glass was prepared. This glass plate was washed with boiled isopropyl alcohol for 5 minutes and dried at 150°C for 30 minutes or longer.

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

In a nitrogen atmosphere, the sealing layer of the test sheet and the surface of the glass plate on the calcium film side were bonded together using a thermal laminator ("Lamy Packer DAiSY A4 (LPD2325)" manufactured by Fujipla Co., Ltd.) to obtain a laminate. This laminate was used as an evaluation sample.

Generally, when calcium comes into contact with water to become calcium oxide, it becomes transparent. In addition, in the above evaluation sample, since the glass plate and the aluminum foil have sufficiently high water vapor permeation barrier properties, moisture usually moves in the in-plane direction (direction perpendicular to the thickness direction) through the end portion of the sealing layer and reaches the calcium film. do. When moisture penetrates the evaluation sample, the calcium film is gradually oxidized from the end and becomes transparent, so shrinkage of the calcium film is observed. Therefore, water penetration into the evaluation sample can be evaluated by measuring the sealing distance (mm) from the end of the evaluation sample to the calcium film. Therefore, an evaluation sample containing a calcium film can be used as a model of an electronic device.

First, the sealing distance X2 (mm) from the end of the evaluation sample to the end of the calcium film was measured with a microscope ("Measuring Microscope MF-U" manufactured by Mitutoyo Corporation).

Next, the evaluation sample was stored in a constant temperature and humidity chamber set to a temperature of 85°C and a humidity of 85% RH. When the sealing distance X1 (mm) from the end of the evaluation sample stored in the constant temperature and humidity chamber to the end of the calcium film increased by 0.1 mm from the original sealing distance X2, the evaluation sample was taken out of the constant temperature and humidity chamber. The time from when the evaluation sample was stored in the constant temperature and humidity chamber to the time when the evaluation sample was taken out of the constant temperature and humidity chamber was determined as the decrease start time t [time]. This decrease start time t is such that the sealing distance X1 (mm) between the end of the evaluation sample stored in the constant temperature and humidity chamber and the end of the calcium film becomes "X2 + 0.1 mm" from the time point T _P1 when the evaluation sample is stored in the constant temperature and humidity chamber. It corresponds to the time until the point T _P2 .

The sealing distance X1 and the reduction start time t were applied to the pick diffusion formula in Equation (1) to calculate a constant K as a water vapor intrusion barrier property parameter.

[Equation (1)]

Using the obtained constant K, the water vapor permeation barrier property of the sealing layer was evaluated according to the following criteria. The smaller the value of the constant K, the higher the water vapor permeation barrier property. In addition, "hr" below means "time". The results are reported in the table below. In addition, "(cm/hr^0.5)" in the table below means "(cm/hr ^0.5 )".

(Standard for water vapor penetration barrier property)

○ (amount): constant K less than 0.025 cm / h ^0.5

× (poor): constant K is 0.025 cm/hr ^0.5 or more

The sealing layer formed of the sealing composition of Examples 1 to 7 satisfying the requirements of the present invention has a water vapor permeation barrier, compared to the sealing layer formed of the sealing composition of Comparative Example 1 using semi-calcined hydrotalcite instead of calcium oxide. The castle was excellent. In addition, the sealing layer formed of the sealing composition of Examples 1 to 7 had a lower haze and excellent transparency than the sealing layer formed of the sealing composition of Comparative Example 2 using calcium oxide having a median diameter of more than 300 nm. .

The sealing layers formed of the sealing compositions of Examples 8 to 13 satisfying the requirements of the present invention are superior in moisture vapor permeation barrier properties compared to the sealing layers formed of the sealing composition of Comparative Example 4 in which the component (B) was not used. did Further, the sealing layer formed from the sealing composition of Examples 8 to 13 is the sealing composition of Comparative Example 5 using calcium oxide having a median diameter of more than 300 nm (component (B')) instead of component (B). Compared to the formed sealing layer, the haze was low and the transparency was excellent.

The composition for sealing and the sheet for sealing of the present invention are useful for, for example, sealing of electronic devices (for example, organic EL devices, solar cells, sensor devices, touch panels with conductive substrates, etc.).

Claims (15)

The following components (A) and (B):
(A) an olefinic polymer and
(B) calcium oxide
As a sealing composition comprising a,
(A) component contains an olefinic polymer having an acid anhydride group and/or a carboxyl group;
(B) The composition for sealing whose median diameter of component is 300 nm or less. The method according to claim 1, wherein the following (C) component:
(C) semi-calcined hydrotalcite
Further comprising a composition for sealing. The composition for sealing according to claim 1 or 2, wherein the median diameter of component (B) is 1 mm or more. The composition for sealing according to claim 1, wherein the content of the component (B) is 20 to 80% by mass with respect to 100% by mass of the non-volatile matter of the composition for sealing. The composition for sealing according to claim 2, wherein the content of component (B) is 5 to 30% by mass with respect to 100 mass% of the non-volatile matter of the composition for sealing. The composition for sealing according to claim 2, wherein the content of component (C) is 20 to 70% by mass with respect to 100 mass% of the non-volatile matter of the composition for sealing. The composition for sealing according to claim 1 or 2, wherein the olefinic polymer having an acid anhydride group and/or a carboxy group is an olefinic polymer having an acid anhydride group. The composition for sealing according to claim 1 or 2, wherein the component (A) contains an olefinic polymer having an epoxy group. The composition for sealing according to claim 1 or 2, wherein the component (A) contains a liquid olefin polymer. The composition for sealing according to claim 1 or 2, further comprising a tackifier. A sheet for sealing having a laminated structure comprising a support and a sealing layer formed of the composition for sealing according to claim 1 or 2. The sealing sheet according to claim 11, wherein the sealing layer has a haze of less than 60%. An electronic device comprising a sealing layer formed from the composition for sealing according to claim 1 or 2. The sealing composition according to claim 1 or 2, comprising a step of pulverizing a mixture containing an olefinic polymer having an acid anhydride group and/or a carboxy group, calcium oxide having a median diameter exceeding 300 nm, and an organic solvent. Manufacturing method of. The manufacturing method according to claim 14, further comprising a step of mixing the mixture after grinding treatment with an olefinic polymer having an epoxy group.