TW202313837A - Sealing composition - Google Patents

Abstract

Provided is a sealing composition with which it is possible to form a sealing layer having both excellent water vapor intrusion barrier properties and excellent transparency. A sealing composition containing (A) an olefin polymer and (B) calcium oxide, and optionally (C) semi-calcined hydrotalcite, the component (A) containing an olefin polymer having an acid anhydride group and/or a carboxyl group, and the component (B) having a median diameter of 300 nm or less.

Description

Composition for sealing

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

In order to protect electronic devices such as organic EL (Electroluminescence) devices and solar cells from moisture, electronic devices are sealed using a sealing layer formed of a sealing composition or a sealing sheet. As such a composition or sheet, for example, Patent Document 1 discloses a sealing resin comprising (A) a polyolefin resin and (B) a metal hydroxide selected from hydrotalcite and semi-baked hydrotalcite. The composition and the sealing sheet formed therefrom have both good moisture permeability resistance and transparency. However, hydrotalcite reversibly absorbs and releases water. Therefore, in the sealing composition using hydrotalcite, the moisture absorbed in the hydrotalcite during the production process or distribution process is released in the sealing layer of the electronic device formed using the composition, which may cause deterioration of the electronic device.

On the other hand, Patent Document 2 discloses a method of suppressing deterioration of an organic EL element due to moisture absorbed into the resin composition by blending calcium oxide into a sealing resin composition containing hydrotalcite. In addition, Patent Document 2 describes an acrylic resin and an epoxy resin as resins constituting the sealing resin composition.

[Prior Art Literature] [Patent Document] Patent Document 1: International Publication No. 2017/057708 Patent Document 2: International Publication No. 2019/167905.

The problem to be solved by the invention

Calcium oxide is known to act as a hygroscopic filler. Although the sealing layer formed of the sealing composition obtained by using calcium oxide is excellent in the property of suppressing water vapor intrusion (in this specification, it is described as "water vapor intrusion barrier property"), the olefin-based polymer When calcium oxide as a hygroscopic filler is contained in the composition for sealing, the sealing layer formed from this composition will lose transparency normally. In order to suppress the decrease in transparency, it is conceivable to use fine calcium oxide, but since fine calcium oxide has poor dispersibility, it is difficult to produce a composition with excellent transparency in which fine calcium oxide is well dispersed in the olefin-based polymer. Therefore, in a sealing layer formed of a sealing composition containing an olefin-based polymer, it is difficult to achieve both water vapor penetration barrier properties and transparency.

In addition, since the refractive index of the acrylic resin and epoxy resin described in Patent Document 2 differs greatly from the refractive index of semi-baked hydrotalcite, it is made of a sealing material containing acrylic resin, epoxy resin, and semi-baked hydrotalcite. The sealing layer formed from the composition had poor transparency. On the other hand, since the refractive index of the olefin-based polymer is close to that of semi-calcined hydrotalcite, the sealing layer formed of the sealing composition containing the olefin-based resin polymer and semi-calcined hydrotalcite has excellent transparency. However, when calcium oxide is added to a sealing composition containing an olefin-based polymer and semi-calcined hydrotalcite in order to further improve the water vapor penetration barrier properties, the transparency of the sealing layer formed from the composition usually decreases. In order to suppress this decrease in transparency, it is conceivable to use fine calcium oxide, but fine calcium oxide has poor dispersibility in olefin-based polymers. Therefore, it is difficult to form a sealing layer excellent in both water vapor intrusion barrier properties and transparency.

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

means to solve problems The present invention that can realize above-mentioned object is as follows; [1] A sealing composition comprising the following components (A) and (B) for sealing, (A) olefin-based polymers, and (B) calcium oxide, Among them, the (A) component contains an olefin-based polymer having an acid anhydride group and/or a carboxyl group, And, the median diameter of the component (B) is 300 nm or less; [2] The sealing composition as in [1], which further includes the following component (C): (C) half-baked hydrotalcite; [3] The sealing composition according to [1] or [2], wherein the median diameter of the component (B) is 1 nm or more; [4] The sealing composition according to [1], wherein the content of the component (B) is 20 to 80% by mass based on 100% by mass of the non-volatile components of the sealing composition; [5] The sealing composition 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 components of the sealing composition; [6] The sealing composition 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 components of the sealing composition; [7] The sealing composition according to any one of [1] to [6], wherein the olefin-based polymer having an acid anhydride group and/or carboxyl group is an olefin-based polymer having an acid anhydride group; [8] The sealing composition according to any one of [1] to [7], wherein the component (A) contains an olefin-based polymer having an epoxy group; [9] The sealing composition according to any one of [1] to [8], wherein the component (A) contains a liquid olefin polymer; [10] The sealing composition according to any one of [1] to [9], further comprising an adhesion imparting agent; [11] A sheet for sealing, which has 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 sealing sheet according to [11], wherein the sealing layer has a haze of 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] A method for producing a sealing composition according to any one of [1] to [10], including the step of pulverizing a mixture containing: an olefin-based compound having an acid anhydride group and/or a carboxyl group Polymers, calcium oxide with a median diameter exceeding 300 nm, and organic solvents; [15] The production method according to [14], further comprising a step of mixing the pulverized mixture with an olefin-based polymer having an epoxy group.

Invention effect According to the present invention, it is possible to obtain an adhesive composition capable of forming a sealant layer excellent in both water vapor intrusion barrier properties and transparency.

Composition for sealing

The sealing composition of the present invention contains the following (A) component and (B) component: (A) olefin-based polymer, and (B) calcium oxide And optionally further comprise the following (C) component: (C) Half-baked hydrotalcite The composition for sealing, is characterized in that, (A) The component contains an olefin-based polymer having an acid anhydride group and/or a carboxyl group, and (B) The median diameter of the component is 300 nm or less.

The olefin-based polymer (component (A)) and the semi-calcined hydrotalcite (component (C)) used in the present invention have similar refractive indices, so a sealing layer excellent in transparency can be formed from the sealing composition of the present invention . In addition, by using calcium oxide ((B) component) and semi-baked hydrotalcite ((C) component) together as a hygroscopic filler, it is possible to capture the semi-baked hydrotalcite (((C) component) with calcium oxide ((B) component). C) Component) can form a sealing layer with excellent water vapor intrusion barrier properties. Also, if calcium oxide is used, the transparency of the resulting sealing layer generally decreases. However, in this invention, the fall of this transparency can be suppressed by using the calcium oxide ((B) component) whose median diameter is 300 nm or less.

On the other hand, fine calcium oxide is difficult to disperse well in the sealing composition. However, in the present invention, by using an olefin-based polymer having an acid anhydride group and/or a carboxyl group, a composition for sealing in which fine (B) components are well dispersed can be produced. On this point, it is presumed that the olefin-based polymer having an acid anhydride group and/or a carboxyl group functions as a dispersant for fine calcium oxide ((B) component). However, the present invention is not limited to this speculation.

Hereinafter, (A) component - (C)component are demonstrated sequentially. In addition, in this specification, unless otherwise specified, each component may use only 1 type, and may use 2 or more types together.

＜(A)Ingredient＞ (A) component used in this invention is an olefin type polymer. In this specification, "olefin-based polymer" refers to a constituent unit derived from an olefin (hereinafter, abbreviated as "olefin unit") as the main constituent unit (that is, the amount of the olefin unit is the largest among all constituent units). polymer. In addition, hereinafter, the "constituent unit derived from butene" etc. which are olefin units may be abbreviated as "butene unit" or the like.

The olefin-based polymer may be an olefin-based resin (for example, a propylene-butene copolymer), or may be an olefin-based rubber (for example, butyl rubber, that is, an isobutylene-isoprene copolymer). In this specification, "olefin-based resin" refers to an olefin-based polymer that cannot form a rubber elastic body by crosslinking, and "olefin-based rubber" refers to an olefin-based polymer that can form a rubber elastic body by crosslinking.

The olefin is preferably a monoolefin having one olefinic carbon-carbon double bond and/or a diolefin having two olefinic carbon-carbon double bonds. Examples of monoolefins include α-olefins such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. Examples of dienes include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene and the like.

The olefin-based polymer may be a homopolymer or a copolymer. The copolymer may be a random copolymer or a block copolymer. In addition, the olefin-based polymer may be a copolymer of olefin and a monomer other than olefin. Examples of olefin-based copolymers include ethylene-non-conjugated diene copolymers, ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene copolymers, ethylene-butene copolymers, ethylene-propylene-butylene copolymers, and ethylene-propylene-butene copolymers. ethylene copolymer, propylene-butene copolymer, propylene-butene-non-conjugated diene copolymer, isobutylene-isoprene copolymer, styrene-isobutylene copolymer, styrene-isobutylene-styrene copolymer, etc. .

((A1) ingredient) One of the characteristics of the present invention is that the component (A) contains an olefin-based polymer (described as " (A1) Ingredient” case). (A1) The component is preferably an olefin-based polymer having an acid anhydride group. In addition, description and illustration of "olefin" and "olefin polymer" in (A1) component are the same as those of the above-mentioned (A) component.

When an olefin-based polymer having an acid anhydride group is used as the 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 the acid anhydride group is obtained from the value of the acid value defined as the mg of potassium hydroxide required to neutralize the acid present in 1 g of the polymer according to JIS K 2501.

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

When an olefin-based polymer having an acid anhydride group and a carboxyl group is used as the component (A1), the total of the concentration of the acid anhydride group and the concentration of the carboxyl group in the polymer is preferably 0.05 to 20 mmol/g, more preferably 0.10 to 20 mmol/g. 10 mmol/g.

The number average molecular weight of the component (A1) is preferably from 1,000 to 1,000,000, more preferably from 1,000 to 750000. In addition, the number average molecular weight of each component was measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight measured by the GPC method can use "LC-9A/RID-6A" manufactured by Shimadzu Corporation as a measuring device, and "Shodex K-800P/K-804L/K-804L" manufactured by Showa Denko Corporation as a tube. For the column, use toluene or the like as the mobile phase, measure at a column temperature of 40° C., and calculate using a calibration curve of standard polystyrene.

The component (A1) can be produced, for example, by (i) grafting an olefin-based polymer with an unsaturated compound having an acid anhydride group and/or carboxyl group (for example, maleic anhydride) under free radical reaction conditions denaturation, or (ii) copolymerize an unsaturated compound having an acid anhydride group and/or carboxyl group with an α-olefin.

As (A1) component, the polymer available from Toho Chemical Industry Co., Ltd., Hoshiko PMC Co., Ltd., etc. can be used, for example. Examples of such polymers include "HV-300M" (maleic anhydride-denatured liquid polybutene) manufactured by Toho Chemical Industry Co., Ltd., "ER688" (maleic anhydride-denatured liquid polybutene) manufactured by Hoshiko PMC Co., Ltd., "T-YP279" (maleic anhydride-modified propylene-butene random copolymer) manufactured by PMC Co., Ltd. "T-YP312" (maleic anhydride-modified propylene-butene random copolymer) manufactured by Starlight PMC Co., Ltd., Starlight "ER661" (maleic anhydride-modified isobutylene-isoprene random copolymer) manufactured by PMC Corporation, "T-YP430" (maleic anhydride-modified ethylene-methyl methacrylate copolymer) manufactured by Starlight PMC Corporation, Starlight PMC "T-YP956" (maleic anhydride-modified ethylene-propylene-butene random copolymer) manufactured by the company, "DIACARNA 30M" (copolymer of maleic anhydride and α-olefin) manufactured by Mitsubishi Chemical, etc.

In one aspect of the present invention, the component (A1) is as follows: (i) is preferably selected from polybutene having acid anhydride groups and/or carboxyl groups, isobutylene-isoprene copolymers having acid anhydride groups and/or carboxyl groups (ie, butyl rubber), having acid anhydride groups/or carboxyl groups At least one of propylene-butene copolymers, ethylene-methyl methacrylate copolymers with acid anhydride groups and/or carboxyl groups, and ethylene-propylene-butene copolymers with acid anhydride groups and/or carboxyl groups; (ii) is more preferably selected from polybutene having acid anhydride groups and/or carboxyl groups, isobutylene-isoprene copolymers having acid anhydride groups and/or carboxyl groups, and propylene-butene having acid anhydride groups and/or carboxyl groups at least one of copolymers; (iii) more preferably at least one selected from polybutene with anhydride groups, isobutylene-isoprene copolymers with anhydride groups, and propylene-butene copolymers with anhydride groups; (iv) Particularly preferred is polybutene having an acid anhydride group.

From the viewpoint of the dispersibility of fine calcium oxide ((B) component) in the sealing composition, etc., the content of (A1) component is preferably 1% by mass relative to 100% by mass of the non-volatile components of the sealing composition. % or more, more preferably at least 3% by mass, more preferably at least 5% by mass, more preferably at most 45% by mass, more preferably at most 40% by mass, and more preferably at most 35% by mass.

((A2) component) It is preferable that (A) component contains the olefin type polymer which has an epoxy group (it may describe as "(A2) component" in this specification). By using together the (A1) component which has an acid anhydride group and/or a carboxyl group, and the (A2) component which has an epoxy group, the strong sealing layer which has a crosslinked structure can be formed. In addition, description and illustration of "olefin" and "olefin polymer" in (A2) component are the same as those in the above-mentioned (A) component.

(A2) The density|concentration of the epoxy group in a component becomes like this. Preferably it is 0.05-10 mmol/g, More preferably, it is 0.10-5 mmol/g. The epoxy group concentration was determined based on the epoxy equivalent based on JIS K 7236-1995.

The number average molecular weight of the component (A2) is preferably from 1,000 to 1,000,000, more preferably from 2,000 to 750,000, more preferably 2,000 to 500,000.

The (A2) component can be produced, for example, by (i) using an unsaturated compound having an epoxy group (for example, glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, Allyl glycidyl ether) to graft and denature olefin polymers under free radical reaction conditions, or (ii) copolymerize unsaturated compounds with epoxy groups and α-olefins.

As (A2) component, the polymer available from Sumitomo Chemical Co., Ltd., Hoshiko PMC Corporation, etc. can be used, for example. Examples of such polymers include "BONDFAST BF-7M" (ethylene-glycidyl methacrylate copolymer) manufactured by Sumitomo Chemical Co., Ltd., "BONDFAST BF-2B" (ethylene-glycidyl methacrylate copolymer) manufactured by Sumitomo Chemical Co., Ltd. Glyceride-vinyl acetate copolymer), Sumitomo Chemical Co., Ltd. "BF-7L" (ethylene-glycidyl methacrylate-methyl acrylate copolymer), Starlight PMC Co., Ltd. "ER829" (glycidyl methacrylate Denatured propylene-butene random copolymer), "ER850" (glycidyl methacrylate-modified butyl rubber) manufactured by Starlight PMC Co., Ltd. "ER853" (glycidyl methacrylate-modified propylene-butylene rubber) manufactured by Starlight PMC Co., Ltd. random copolymer), Starlight PMC Co., Ltd. "ER866" (glycidyl methacrylate modified butyl rubber), Starlight PMC Co., Ltd. "T-YP276" (glycidyl methacrylate denatured propylene-butylene random copolymer product), Starlight PMC Co., Ltd. "T-YP313" (glycidyl methacrylate-modified propylene-butene random copolymer), Starlight PMC Co., Ltd. "T-YP431" (glycidyl methacrylate denatured ethylene-methacrylate methyl acrylate copolymer) and the like.

(A2) The ingredients are as follows: (i) is preferably selected from ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-glycidyl methacrylate-methyl acrylate copolymer, having At least A sort of; (ii) is more preferably selected from propylene-butene copolymers having epoxy groups, isobutylene-isoprene copolymers having epoxy groups, and ethylene-methyl methacrylate copolymers having epoxy groups at least one of (iii) is further more preferably selected from propylene-butene copolymers with epoxy groups and/or isobutylene-isoprene copolymers with epoxy groups; (iv) A propylene-butene copolymer having an epoxy group or an isobutylene-isoprene copolymer having an epoxy group is particularly preferable.

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

In the case of using an isobutylene-isoprene copolymer (that is, butyl rubber) having an epoxy group as the component (A2), from the viewpoint of the yellowing resistance of the sealing layer, etc., relative to the isobutylene unit and isoprene The amount of isoprene units in the copolymer is preferably from 0.1 to 20% by mass, more preferably from 0.3 to 15% by mass, and still more preferably from 0.5 to 10% by mass, based on the total amount of olefinic units. Here, the amount of the aforementioned isoprene unit is based on the isobutylene unit and the isoprene unit after removing the denatured part (for example, the part derived from glycidyl (meth)acrylate for introducing epoxy group).

When the component (A2) is used, in order to form a strong sealing layer, its content is preferably at least 0.1% by mass, more preferably at least 1% by mass, and still more preferably at least 100% by mass of the non-volatile components of the sealing composition. The best is at least 3% by mass, more preferably at most 25% by mass, more preferably at most 20% by mass, and more preferably at most 15% by mass.

In the case of using component (A2), the amount of component (A2) having an epoxy group and the amount of component (A1) having an acid anhydride group and/or carboxyl group are preferably based on the difference between the functional groups they have. ratio to decide. Also, from the viewpoint of the dispersibility of the (B) component, it is preferable to set the conditions that the (A1) component will not be completely consumed due to the formation of crosslinks with the (A2) component and a certain amount will remain. The proportion of functional groups. Although it also varies depending on the crosslinking conditions (temperature, time), etc., in one embodiment of the present invention, "the amount (mol) of epoxy groups contained in the component (A2)": "the amount of epoxy groups contained in the component (A1)" The total amount of acid anhydride groups (mol) and carboxyl groups (mol)" is preferably 100:50-100:1500, more preferably 100:60-100:1250, and more preferably 100:70-100: 1000, particularly preferably 100:80 to 100:900, in another embodiment of the present invention in which the sealing composition contains (C) component, preferably 100:10 to 100:1500, more preferably 100:15 to 100:1250, further preferably 100:20～100:1000. Furthermore, for example, when the component (A1) has only acid anhydride groups, the aforementioned "sum of the amount (mol) of acid anhydride groups and the amount (mol) of carboxyl groups" means "the amount (mol) of acid anhydride groups".

((A3) ingredient) The (A) component preferably contains a liquid olefin-based polymer (in this specification, it may be described as "(A3) component"). Favorable adhesiveness and flexibility can be provided to a sealant layer by using (A3)component. In addition, description and illustration of "olefin" and "olefin-type polymer" in (A3) component are the same as those in the above-mentioned (A) component.

In the present invention, "liquid" in "liquid olefin polymer" means that the viscosity at 25°C is 5000 Pa･s or less. Moreover, in this invention, "the viscosity at 25 degreeC" means the viscosity calculated by multiplying the dynamic viscosity at 25 degreeC measured using the dynamic viscoelasticity measuring apparatus by density. As a dynamic viscoelasticity measuring device, the rheometer (trade name: DISCOVERY HR-2) etc. made by TA Instrument company is mentioned, for example.

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

From the viewpoint of good adhesion and flexibility of the sealing layer, the viscosity of the component (A3) at 25°C is preferably 5 to 5000 Pa･s, more preferably 10 to 4000 Pa･s, still more preferably Department of 20 ~ 3000 Pa･s.

The number average molecular weight of the component (A3) is preferably from 100 to 50,000, more preferably from 200 to 30,000, and 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. Such commercially available items include, for example, "HV-300" (liquid polybutene) manufactured by ENEOS Corporation, "HV-1900" (liquid polybutene) manufactured by ENEOS Corporation, "HV-50" ( Liquid polybutene), ENEOS Corporation "HV-35" (liquid polybutene), Kothari Corporation "950MW" (liquid polybutene), Kothari Corporation "2400MW" (liquid olefin-based polymer), INEOS Corporation "H-1900" (liquid polybutene), INEOS "H-6000" (liquid polybutene), INEOS "H-18000" (liquid polybutene), NOF "200N" (liquid polybutene), Nippon Soda Co., Ltd. "BI-2000" (hydrogenated polybutadiene), Nippon Soda Co., Ltd. "BI-3000" (hydrogenated polybutadiene), Nippon Soda Co., Ltd. "GI-3000" (hydrogenated polybutadiene), "LUCANT LX100" (liquid olefin polymer) manufactured by Mitsui Chemicals, "LUCANT LX400" (liquid olefin polymer) manufactured by Mitsui Chemicals, "Poly bd R- 45HT” (butadiene-based liquid rubber), Idemitsu Showa Shell Co., Ltd. “Poly bd R-15HT” (butadiene-based liquid rubber), Idemitsu Showa Shell Co., Ltd. “Poly ip” (liquid polyisoprene), Nippon Soda Co., Ltd. "B-1000" (liquid polybutadiene), Nippon Soda Co., Ltd. "B-3000" (liquid polybutadiene), Nippon Soda Co., Ltd. "G-3000" (liquid polybutadiene) , "LIR-30" (liquid polyisoprene) manufactured by Kuraray Corporation, "LIR-390" (liquid polyisoprene) manufactured by Kuraray Corporation, "LIR-290" (liquid polyisoprene) manufactured by Kuraray Corporation pentadiene), Kuraray Co., Ltd. "LBR-302" (liquid polybutadiene), Kuraray Co., Ltd. "LBR-305" (liquid polybutadiene), Kuraray Co., Ltd. "LBR-361" (liquid Polybutadiene), "L-SBR-820" (liquid styrene-butadiene random copolymer) manufactured by Kuraray Corporation, "Ricon 154" (liquid butadiene ), "RICON 184" (liquid styrene-butadiene random copolymer) manufactured by Crayville Co., Ltd., etc.

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

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

((A4) ingredient) Component (A) may contain olefin-based polymers other than components (A1) to (A3), that is, non-liquid olefin-based polymers that do not have any of acid anhydride groups, carboxyl groups, and epoxy groups (see When described as "(A4) Components"). In addition, description and illustration of "olefin" and "olefin polymer" in (A4) component are the same as those in the above-mentioned (A) component.

In the present invention, "non-liquid" in "non-liquid olefin-based polymer" means that the viscosity at 25°C exceeds 5000 Pa･s.

(A4) The number average molecular weight of a component becomes like this. Preferably it is 10,000-1,000,000, More preferably, it is 20,000-750,000.

(A4) The ingredients are as follows: (i) preferably propylene-butene copolymer and/or isobutylene-isoprene copolymer (i.e. butyl rubber); (ii) More preferably, it is an isobutylene-isoprene copolymer.

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

When an isobutylene-isoprene copolymer (that is, butyl rubber) is used as the component (A4), from the viewpoint of the yellowing resistance of the sealant layer, etc., with respect to the total of the isobutylene unit and the isoprene unit, The amount of the isoprene unit in the copolymer 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.

The content of the component (A4) is preferably from 0 to 25 mass %, more preferably from 0 to 20 mass %, and still more preferably from 0 to 15 mass %, based on 100 mass % of the nonvolatile content of the sealing composition.

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

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

As the component (B), calcium oxide having a median diameter exceeding 300 nm may be pulverized and used, or a commercially available calcium oxide having a median diameter of 300 nm or less may be used. As commercial products of calcium oxide having a median diameter exceeding 300 nm, for example, "QC-X" manufactured by Inoue Lime Industry Co., Ltd., "WAC series" manufactured by Sankyo Flour Milling Co., Ltd., "HAL-G" manufactured by Yoshizawa Lime Industry Co., Ltd., " HAL-J", "HAL-F", "HAL-O", "HAL-P", etc. As a commercial item of calcium oxide whose median diameter is 300 nm or less, "CaO Nano Powder" by Filgen company etc. are mentioned, for example.

In one embodiment of the present invention, the content of the component (B) is preferably 20% by mass or more from the viewpoint of the water vapor intrusion barrier property of the sealing layer with respect to 100% by mass of the non-volatile components of the sealing composition, More preferably, it is at least 25% by mass, more preferably at least 30% by mass, from the viewpoint of the adhesion of the sealant layer, it is preferably at most 80% by mass, more preferably at most 75% by mass, and still more preferably at most 70% by mass. the following.

Moreover, in another embodiment of the present invention in which the composition for sealing contains (C) component, with respect to 100% by mass of non-volatile components of the resin composition for sealing, from the viewpoint of the water vapor intrusion barrier property of the sealing layer, The content of the component (B) is preferably at least 5% by mass, more preferably at least 10% by mass, still more preferably at least 15% by mass, from the viewpoint of adhesion of the sealant layer, preferably at most 30% by mass, and more preferably at least 30% by mass. Preferably it is 25% by mass or less, more preferably 20% by mass or less.

＜(C)Ingredient＞ The component (C) used in the present invention is semi-baked hydrotalcite. Hydrotalcite can be classified into unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite.

Unfired hydrotalcite is a metal hydroxide having a layered crystal structure represented by natural hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ ･4H ₂ O), for example, composed of layers [Mg _{1 -X} Al _X (OH) ₂ ] ^X+ and the middle layer [(CO ₃ ) _X/2 ･mH ₂ O] ^X- . Unbaked hydrotalcite is a concept including hydrotalcite-like compounds such as synthetic hydrotalcite. Examples of the hydrotalcite-like compound include compounds represented by the following formula (I) and the following formula (II).

[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] ^x+ ･[(A ^n- ) _x/n ･mH ₂ O] ^x- (I) (where M ²⁺ represents Mg ²⁺ , Zn ²⁺ and other divalent metal ions, M ³⁺ means Al ³⁺ , Fe ³⁺ and other trivalent metal ions, ^An- means CO ₃ ^2- , Cl ^- , NO ₃ ^- and other n-valent anions, 0<x<1 , 0≤m<1, n is a positive number.) In formula (I), M ²⁺ is preferably Mg ²⁺ , M ³⁺ is preferably Al ³⁺ , ^{and An-} is preferably CO ₃ ^2- .

M ²⁺ _x Al ₂ (OH) _2x+6-nz (A ^n- ) _z ･mH ₂ O (II) (wherein, M ²⁺ represents divalent metal ions such as Mg ²⁺ , Zn ²⁺ , and A ^{n -} represents n-valent anions such as CO ₃ ^2- , Cl ^- , NO ₃ ^- , x is a positive number greater than 2, z is a positive number less than 2, m is a positive number, and n is a positive number.) In formula (II), M ²⁺ It is preferably Mg ²⁺ , and ^An- is more preferably CO ₃ ^2- .

Semi-baked hydrotalcite refers to a metal hydroxide having a layered crystal structure in which the amount of interlayer water is reduced or disappeared, which is obtained by calcining unbaked hydrotalcite. When described using the composition formula, "interlayer water" refers to "H ₂ O" described in the composition formula of the above-mentioned unburned natural hydrotalcite and hydrotalcite-like compound.

On the other hand, fired hydrotalcite refers to a metal having an amorphous structure obtained by firing unfired hydrotalcite or semi-fired hydrotalcite, in which not only interlayer water but also hydroxyl groups disappear due to condensation dehydration oxide.

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

"Saturation water absorption" refers to weighing 1.5 g of a test sample (for example, semi-burnt hydrotalcite) with a balance, measuring the initial mass, and then measuring it in a small environment set at atmospheric pressure, 60°C, and 90%RH (relative humidity) The mass increase rate relative to the initial mass after standing in the tester (SH-222 manufactured by ESPEC Co., Ltd.) for 200 hours can be obtained by the following formula (i): Saturated water absorption (mass%) =100×(mass after moisture absorption-initial mass)/initial mass (i).

The saturated water absorption of the half-baked hydrotalcite is preferably at least 3% by mass and less than 20% by mass, more preferably at least 5% by mass and less than 20% by mass.

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

For thermogravimetric analysis, TG/DTA EXSTAR6300 manufactured by Hitachi High-Tech Science Co., Ltd. can be used. Weigh 5 mg of hydrotalcite into an aluminum sample pan, and open it without a cover in an atmosphere with a nitrogen flow rate of 200 mL/min. Under the condition that the temperature is raised from 30°C to 550°C at a heating rate of 10°C/min. The thermal weight loss rate can be obtained by the following formula (ii); Thermal weight reduction rate (mass%) =100×(mass before heating-mass when reaching the specified temperature)/mass before heating (ii).

Furthermore, unbaked hydrotalcite, semi-baked hydrotalcite, and baked hydrotalcite can be distinguished by peaks and relative intensity ratios measured by powder X-ray diffraction. For semi-burned hydrotalcite, powder X-ray diffraction shows two peaks that split into two near 2θ of 8 to 18°, or a peak with a shoulder due to the synthesis of two peaks. The relative intensity ratio of the diffraction intensity of peaks or shoulders appearing on the high-angle side (=low-angle side diffraction intensity) to the diffraction intensity of peaks or shoulders appearing on the high-angle side (=high-angle side diffraction intensity) (low-angle side diffraction intensity) Intensity/high angle side diffraction intensity) is 0.001-1000. On the other hand, for unburned hydrotalcite, there is only one peak around 8° to 18°, or the difference between the diffraction intensity of the peak or shoulder peak appearing on the low angle side and the peak or shoulder peak appearing on the high angle side The relative intensity ratio is outside the aforementioned range. The roasted hydrotalcite has no characteristic peak in the region of 8°-18°, but has a characteristic peak at 43°. For powder X-ray diffraction measurement, using a powder X-ray diffractometer (PANalytical, Empyrean), in the counter cathode CuKα (1.5405Å), voltage: 45V, current: 40mA, sampling width: 0.0260°, scanning speed: 0.0657 °/s, measuring diffraction angle range (2θ): 5.0131～79.9711°. Peak search (peak search) can use the peak search function of the software attached to the diffraction device, in the "minimum significant degree of 0.50, minimum peak tip (Peak Tip) of 0.01°, maximum peak tip of 1.00°, peak baseline width of 2.00° , The method is the minimum value of the second order differential".

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

The particle size of the semi-roasted hydrotalcite is preferably 1 to 1000 nm, more preferably 10 to 800 nm. These particle diameters are the median diameter of the particle size distribution when the particle size distribution is obtained on a volume basis by laser diffraction scattering particle size distribution measurement (JIS Z 8825).

As the half-baked hydrotalcite, what has been surface-treated with a surface-treating agent can be used. As a surface treatment agent for surface treatment, for example, higher fatty acids, alkylsilanes, silane coupling agents, etc. can be used, among which higher fatty acids and alkylsilanes are suitable. One type or two or more types of surface treatment agents can be used.

Commercially available items can be used as the half-baked hydrotalcite. As its commercially available item, "DHT-4C" and "DHT-4A-2" manufactured by Kyowa Chemical Industry Co., Ltd., etc. are mentioned, for example.

With respect to 100% by mass of the non-volatile components of the sealing composition, the content of the component (C) is preferably at least 20% by mass, more preferably at least 25% by mass, from the viewpoint of the water vapor intrusion barrier properties of the sealing layer, More preferably, it is at least 30% by mass, and from the viewpoint of the adhesiveness of the sealant layer, it is preferably at most 70% by mass, more preferably at most 65% by mass, and still more preferably at most 60% by mass.

＜Other ingredients＞ The sealing composition of the present invention may contain components other than components (A) to (C) within a range that does not inhibit the effects of the present invention (hereinafter sometimes described as "other components"). Examples of other components include tackifiers, metal complexes, antioxidants, hardening accelerators, plasticizers, and the like. These may use only 1 type, and may use 2 or more types together. Hereinafter, the tackifier and the like will be described sequentially.

(adhesion imparting agent) The tackifier is a component that imparts tackiness to the sealing composition. Examples of tackifiers include rosin-based resins, terpene resins, denatured terpene resins (hydrogenated terpene resins, terpene-phenol copolymer resins, aromatic denatured terpene resins, etc.), petroleum resins (aliphatic petroleum resins) , hydrogenated petroleum resin, alicyclic petroleum resin, aromatic petroleum resin, copolymerized petroleum resin), coumarone-indene resin, alkylphenol resin, xylene resin, etc.

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

Examples of terpene resins 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 of which are from Yasuhara Chemical Co., Ltd. system) etc.

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

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

As an aromatic denatured terpene resin, YS RESIN TO85, YS RESIN TO105, YS RESIN TO115, YS RESIN TO125 (all are made by Yasuhara Chemical Co., Ltd.) etc. are mentioned, for example.

Examples of hydrogenated petroleum resins include Escorez 5300 series and 5600 series (both manufactured by Exxon Mobil Corporation), T-REZ OP501, T-REZ PR803, T-REZ HA085, T-REZ HA103, T-REZ HA105, T-REZ HA125 (both are hydrogenated dicyclopentadiene-based petroleum resins, manufactured by ENEOS), Quintone 1325, Quintone 1345 (both are manufactured by Zeon Corporation), I-MARV S-100, I-MARV S -110, I-MARV P-100, I-MARV P-125, I-MARV P-140 (all are hydrogenated dicyclopentadiene-based petroleum resins, manufactured by Idemitsu Kosan Co., Ltd.), ARKON P-90, ARKON P -100, ARKON P-115, ARKON P-125, ARKON P-140, ARKON M-90, ARKON M-100, ARKON M-115, ARKON M-135, TFS13-030 (all made by Arakawa Chemical Industry Co., Ltd.) wait.

Examples of aromatic petroleum resins include ENDEX 155 (manufactured by Eastman Chemical Co.), 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 made by ENEOS), Petcoal LX, Petcoal 120, Petcoal 130, Petcoal 140 (all made by Tosoh company), T-REZ RB093, T-REZ RC100, T-REZ RC115, T-REZ RC093, T-REZ RE100 (all made by ENEOS company), etc.

Examples of copolymerized petroleum resins include T-REZ HB103, T-REZ HB125, T-REZ PR801, T-REZ PR802, T-REZ RD104 (all manufactured by ENEOS), Petrotack 60, Petrotack 70, Petrotack 90. Petrotack 90HS, Petrotack 90V, Petrotack 100V (both manufactured by Tosoh Corporation), Quintone D100 (made by Zeon Corporation, Japan), etc.

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

In the case of using an adhesion imparting agent, from the viewpoint of the adhesiveness and sealing performance of the sealing layer, the content thereof is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, more preferably 5 to 30% by mass.

(metal complex) In order to better disperse the component (C) in the sealing composition, it is possible to use a bidentate complex whose two coordinating atoms are both oxygen atoms (hereinafter referred to as "oxygen-bidente complex") ) and a monodentate ligand whose coordinating atom is an oxygen atom (hereinafter referred to as "oxygen-unidentate ligand") is a metal complex formed by combining with a central metal.

The aforementioned metal complex is preferably a metal complex represented by the following formula (1) (hereinafter may be simply referred to as "metal complex (1)").

。 [chemical formula 1]

.

[In the formula (1), M represents a metal with a valence of more than 2; R ₁ and R ₃ independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, an alkenyloxyl group, an aryl group, or an aralkyl group _R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, an alkenyloxyl group, an alkoxycarbonyl group, an aryl group, or an aralkyl group; X represents a monodentate ligand; Formula (1 The solid line between the oxygen atom (O) and M in [ ] in ) represents a covalent bond; the dotted line between the oxygen atom (O) and M in [ ] in formula (1) represents a coordination bond; And m represents 3 or 4, n represents an integer of 0 to 4, m≧n]. Metal complexes (1) may be used alone or in combination of two or more.

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 the present specification, the halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

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

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

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

In the present specification, the number of carbon atoms of the aryl group is preferably 6-18, more preferably 6-14. Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, and 9-anthracenyl. The aryl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, and an optionally substituted amino group.

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

In this specification, as the amino group that may have a substituent, for example, an amino group, a mono- or di-alkylamine group (for example, a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, amino group, propylamine group, dibutylamino group), mono- or di-cycloalkylamine group (for example, cyclopropylamine group, cyclohexylamine group), mono- or diarylamine group (for example , phenylamino group), mono- or di-aralkylamine group (for example, benzylamine group, dibenzylamine group), heterocyclic amine group (for example, pyridylamine group) and the like.

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

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

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

Examples of monodentate ligands represented by X in formula (1) include alkoxide (alkoxide) anion (RO ⁻ ) (in the aforementioned formula, R represents an organic group), carboxylate anion (RCOO ⁻ ) ( In the aforementioned formula, R represents an organic group), oxo (O) and the like.

The alkoxide anion is represented by RO ⁻ (in the aforementioned formula, R represents an organic group). The organic group R may be either an aliphatic group or an aromatic group. Also, the aliphatic group may be either a saturated aliphatic group or an unsaturated aliphatic group. The number of carbon atoms in the organic group R is preferably 1-20, more preferably 6-18, particularly preferably 8-14. Examples of the alkoxide anion (RO ⁻ ) include methoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide, sec-butoxide, tert-butoxide, pentanolate, Alkoxide, hexanolate, phenoxide, 4-methylphenoxide, etc.

The carboxylate anion is represented by RCOO ^- (in the aforementioned formula, R represents an organic group). The organic group R may be either an aliphatic group or an aromatic group. Also, the aliphatic group may be either a saturated aliphatic group or an unsaturated aliphatic group. The number of carbon atoms in the organic group R is preferably 1-20, more preferably 6-18, particularly preferably 8-14. Examples of the carboxylate anion (RCOO ⁻ ) include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, octalic acid, nonanoic acid, capric acid, deca Carboxylate anions, etc. .

[ ] in the formula (1) represents a multidentate ligand, and examples of the multidentate ligand 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, acetoacetate, acetoacetate Methyl ester, ethyl acetoacetate, propyl acetoacetate, salicylic acid, methyl salicylate, malonic acid, dimethyl malonate, diethyl malonate, etc. In a state coordinated to the central metal, the multidentate complex forms a structure obtained by removing one or more protons therefrom.

As specific examples of metal complexes (1) in which M is aluminum, aluminum diisopropylate mono-sec-butyrate (Aluminum diisopropylate mono-sec-butyrate), tri-secondary aluminum butylate (Aluminum tri-sec-butyrate), aluminum triisopropylate, aluminum triethylate, ginseng (acetylpyruvate) aluminum, bis(ethylacetylacetate) mono(acetylpyruvate) aluminum (Aluminum bis(ethyl acetoacetate) mono(acetylacetonate)), ginseng (ethyl acetylacetate) aluminum (Aluminum tris(ethylacetoacetate)), acetylacetate octadecyl aluminum diisopropylate (Aluminum octadecenyl acetoacetate diisopropylate), ethyl Ethylaluminum diisopropyl acetate, ethylaluminum di-n-butyl acetylacetate, propylaluminum diisopropyl acetylacetate, n-butylaluminum diisopropyl acetylacetate, ginseng (ethyl acetylacetate Aluminum mono(acetylacetonate) bis(ethyl acetoacetate), Aluminum mono(acetylacetonate) bis(ethyl acetoacetate), aluminum ginseng(acetylacetonate).

Specific examples of metal complexes (1) in which M is titanium include: tetraisopropyl titanate, tetra-n-butyl titanate, tetraoctyl titanate, tetratert-butyl titanate, titanic acid Tetrastearyl ester, Titanium tetra-acetylacetonate, Titanium octylenglycolate (alias: bis(2-ethylhexyloxy)bis(2-ethyl-3-oxy Hexyloxy) titanium (IV)), bis (ethyl acetate) diisopropyl titanate, allyl acetoacetate triisopropoxide titanium (Titanium allyl acetoacetate triisopropoxide), di-n-butoxybis (2,4-pentanedionate) titanium (Titanium di-n-butoxide bis(2,4-pentanedionate)), diisopropoxybis(tetramethylheptanedionate) titanium, bis(acetyl Ethyl acetate) diisopropyl titanate, titanium cresyl (Titanium (IV) tetra (methylphenoxide)), bis (2,4-pentanedionyl) titanium oxide, monoisopropyl titanate triisostearate ester, diisopropyl titanate diisostearate.

Specific examples of the metal complex (1) in which M is zirconium include: tetra-n-propoxy zirconium (Zirconium tetra-n-propoxide, zirconium n-propoxide), tetra-n-butoxy zirconium, tetraacetyl Zirconium acetonate, allyl acetoacetate triisopropoxyzirconium, zirconium di-n-butoxybis(2,4-pentanedionate), zirconium diisopropoxybis(2,4-pentanedionate) Zirconium, zirconium diisopropoxybis(tetramethylheptanedionate), zirconium diisopropoxybis(ethylacetoacetate), butoxy(acetoacetate) ) zirconium butoxide (acetylacetate) bis(ethylacetoacetate)), zirconium tributoxide monoacetylacetonate, zirconium octoate, zirconium stearate, zirconium monooctanoate Tri-n-butyl ester, tri-n-butyl zirconate monostearate.

In the case of using a metal complex, from the viewpoint of the dispersibility of the component (C), its content is preferably 0.01 to 3% by mass, more preferably 0.05 to 2.5% by mass, more preferably 0.10 to 2% by mass.

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

(hardening accelerator) In the present invention, a curing accelerator can be used in order to accelerate the crosslinking reaction of the acid anhydride group and/or carboxyl group of the component (A1) and the epoxy group of the component (A2). Examples of the curing accelerator include imidazole compounds, tertiary amine/quaternary amine compounds, dimethylurea compounds, organic phosphine compounds, and the like.

Examples of imidazole compounds include 1H-imidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl 4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitic acid salt, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenylimidazole, 2-deca Dialkylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and the like. Specific examples of imidazole compounds include Curezol 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 Chemical Industry Co., Ltd.), etc.

The tertiary amine/quaternary amine compound is not particularly limited, and examples include tetramethylammonium bromide, tetrabutylammonium bromide, triethylmethylammonium・2-ethylhexanoate quaternary ammonium salt; DBU (1,8-diazabicyclo[5.4.0]undecene-7), DBN(1,5-diazabicyclo[4.3.0]nonene-5) , DBU-phenolate, DBU-octanoate, DBU-p-toluenesulfonate, DBU-formate, DBU-novolak resin salt and other diazabicyclic compounds; benzyl dimethylamine, 2-(two Tertiary amines such as methylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol (TAP) or their salts, aromatic dimethylurea, aliphatic Dimethylurea compounds such as dimethylurea, etc.

Examples of dimethylurea compounds include aromatic compounds such as DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) and U-CAT3512T (manufactured by San-Apro Corporation). aliphatic dimethylurea; aliphatic dimethylurea such as U-CAT3503N (manufactured by San-Apro Co., Ltd.); Among them, aromatic dimethylurea is preferably used from the viewpoint of curability.

As an organic phosphine compound, for example: triphenylphosphine, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate, ( 4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, triphenylphosphinetriphenylborane and the like. Specific examples of the organic phosphine compound include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, and TPP-S (all are manufactured by Hokko Chemical Industry Co., Ltd.).

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

(plasticizer) The sealing composition of the present invention may further contain a plasticizer. Examples of plasticizers include mineral oils such as paraffin-based processing oils, naphthene-based processing oils, liquid paraffin, vaseline, castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, and coconut oil. , olive oil and other vegetable oils.

<Manufacturing method of sealing composition> Hereinafter, a suitable production method of the sealing composition of the present invention will be described. However, the sealing composition of the present invention can also be produced by methods other than the following methods.

A suitable production method of the composition for sealing of the present invention (hereinafter referred to as "the production method of the present invention") includes: an olefin-based polymer (that is, (A1) component) having an acid anhydride group and/or carboxyl group, a medium diameter A step in which the mixture of calcium oxide exceeding 300 nm and an organic solvent is pulverized. The sealing composition of the present invention can also be produced by mixing calcium oxide having a median diameter of 300 nm or less (that is, component (B)) with components other than component (B), but this simple mixing is not the same as going through the aforementioned steps. Compared with the case of this method, it is difficult to disperse fine calcium oxide well in the sealing composition. In addition, fine calcium oxide has a large surface area, and as a result, the hygroscopicity also increases. In order to avoid such moisture absorption, the workability of fine calcium oxide in the production of the sealing composition is worse than that of normal size calcium oxide. Therefore, the sealing composition of the present invention is preferably produced through the aforementioned steps. Hereinafter, the mixture for pulverization and the like used in the production method of the present invention will be sequentially described.

A mixture for pulverization can be produced by mixing calcium oxide having a median diameter exceeding 300 nm, component (A1), and an organic solvent. The content of the calcium oxide is preferably from 3 to 75% by weight, more preferably from 5 to 70% by weight, based on the entire mixture for pulverization. The content of the component (A1) is preferably from 3 to 40% by weight, more preferably from 5 to 35% by weight, based on the entire mixture for pulverization. In one embodiment of the present invention, the content of the organic solvent is preferably 20 to 70% by mass, more preferably 30 to 60% by mass based on the entire mixture for pulverization, or the composition for sealing contains (C) component In another embodiment of the present invention, it is preferably 20-60% by mass, more preferably 30-50% by mass. Components other than the above-mentioned components (for example, semi-calcined hydrotalcite (that is, (C) component), (A3) component, an adhesion imparting agent, etc.) may be added to the mixture for pulverization. The order of adding each component is not particularly limited, and each component may be added sequentially or simultaneously.

Examples of organic solvents that can be used in the production method of the present invention include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl Acetate esters such as base ether acetate and carbitol acetate; cellosolves such as cellosolves; carbitols such as butyl carbitol; aromatic hydrocarbons such as toluene and xylene; Amides such as methylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Commercially available organic solvents such as "Swasol" manufactured by Maruzen Petrochemical Co., Ltd. and "Ipzole" manufactured by Idemitsu Kosan Co., Ltd. can be used. An organic solvent may use only 1 type, and may use 2 or more types together.

The pulverization treatment can be performed using a known pulverizer. Calcium oxide is uniformly pulverized and dispersed in the mixture by pulverization. As a well-known pulverizer, a wet bead mill etc. are mentioned, for example. Examples of the material of the beads include zirconia, alumina, glass, steel, and the like. The bead diameter is, for example, about 0.03 to 5 mm. The rotational speed of the rotating shaft of the bead mill is, for example, about 10 to 10000 rpm. The flow rate at which the mixture for pulverization is supplied to the pulverization chamber of the bead mill is, for example, about 0.1 to 10000 kg/hour. In the wet pulverization using a bead mill, in order to suppress the temperature rise of the mixture being pulverized, it is preferably performed while cooling with cooling water. The temperature of the cooling water is, for example, about 0 to 40°C.

In addition, the pulverized mixture may be mixed with optional components. For example, (A2) component, (A3) component, an adhesion imparting agent, etc. can be added to the pulverization-processed mixture, and can be mixed. When the composition for sealing contains an olefin-based polymer having an epoxy group as the component (A2), in order to prevent a crosslinking reaction due to heat during the pulverization treatment, it is preferable to mix the pulverized mixture with (A2) Components are mixed. That is, the production method of the present invention preferably further includes a step of mixing the pulverized mixture with an epoxy group-containing olefin-based polymer (ie, component (A2)). The order of adding each component is not particularly limited, and each component may be added sequentially or simultaneously.

When the mixture for pulverization treatment contains semi-calcined hydrotalcite (ie, component (C)), a varnish of the sealing composition of the present invention containing an organic solvent can be produced by the above pulverization treatment. When the mixture for pulverization processing does not contain (C)component, the varnish of the composition for sealing of this invention containing an organic solvent can be manufactured by mixing the mixture after pulverization processing and (C)component.

The varnish of the sealing composition containing an organic solvent obtained as described above can remove part or all of the organic solvent by drying or the like. The sealing composition of the present invention can be used in a liquid state such as a varnish, or in a solid state such as a film.

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

The haze of the sealing layer is preferably less than 60%, more preferably at most 40%, and more preferably at most 20%. The lower limit of the haze of the sealing layer is not particularly limited, and the haze of the sealing layer is, for example, 0% or more. This haze can be measured based on JISK7136. Specifically, this haze can be measured by the method described in the Examples section described later 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, polyethylene terephthalate (hereinafter referred to as "PET"), Polyester such as polyethylene naphthalate, polycarbonate, plastic film such as polyimide, etc. Both the support body and the protective sheet can be a single-layer film or a laminated film.

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. Examples of the barrier layer include inorganic films such as silicon dioxide vapor-deposited films, silicon nitride films, and silicon oxide films. The barrier layer may be composed of multiple layers of inorganic films (for example, silicon dioxide deposited films). In addition, the barrier layer may be composed of an organic substance and an inorganic substance, or may be a composite multilayer of an organic layer and an inorganic film.

The surface of the protective sheet that is in contact with the sealing layer is preferably subjected to mold release treatment. On the other hand, the support body may or may not have been subjected to a release treatment. As the mold release treatment, for example, mold release treatment using a mold release agent such as a silicone resin-based mold release agent, an alkyd resin-based mold release agent, or a fluororesin-based mold release agent is mentioned.

The thicknesses of the support and the protective sheet are not particularly limited, but are preferably 10 to 150 μm, more preferably 20 to 100 μm, respectively, from the viewpoint of handling properties of the sealing sheet. In addition, when the support body and the protective sheet are laminated films, the aforementioned thickness is the thickness of the laminated film. On the other hand, from the point of view of both hermeticity and adhesion, in one embodiment of the present invention, the thickness of the sealing layer is preferably 2-100 μm, more preferably 2-75 μm, and even more preferably 3-75 μm. 50 μm, or in another embodiment of the present invention in which the composition for sealing contains (C) component, it is preferably 3 to 200 μm, more preferably 3 to 150 μm, and still more preferably 3 to 100 μm.

＜Manufacturing method of sealing sheet＞ The sealing sheet of the present invention can be produced, for example, by applying the varnish of the sealing composition obtained above to a support to form a coating film, and drying the obtained coating film to form a sealing layer. Also, a sealing sheet having a laminated structure including a support, a sealing layer, and a protective sheet in this order can be produced, for example, by applying a varnish to one of the supporting body and the protective sheet and drying it to form a sealing layer, and then The other of the support and the protective sheet is laminated on the sealing layer.

In the case of using the component (A2), in order to make the reaction between the epoxy group of the component (A2) and the acid anhydride group and/or carboxyl group of the component (A1) proceed, the drying of the coating film (that is, the removal of the organic solvent) can be performed by It is performed by heating the coating film. The heating temperature of the coating film is preferably from 50 to 200°C, more preferably from 80 to 150°C, and the heating time is preferably from 1 to 60 minutes, more preferably from 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 80-200°C, more preferably 100-150°C, and the heating time is preferably 10-240 minutes, more preferably 30-180 minutes. This heating may be performed under normal pressure or under reduced pressure.

Electronic Device The present invention also provides an electronic device including a sealing layer formed from the sealing composition of the present invention. Examples of the electronic device include an organic EL device, a solar cell, a sensor device, a touch panel having a conductive substrate, and the like. The electronic device is preferably an electronic device that has low resistance to moisture, such as an organic EL device or a solar cell. Example

Hereinafter, the present invention will be described in more detail by citing the examples, but the present invention is not limited by the following examples, and can also be appropriately modified and implemented within the scope of the gist of the context, which are all included in the scope of the present invention. within the technical range. In addition, unless otherwise specified, "parts" and "%" in the amount of components and the amount of copolymerized units mean "parts by mass" and "% by mass", respectively.

＜Ingredients＞ Components used in Examples and Comparative Examples are as follows.

(1) (A1) Ingredients "HV-300M" (manufactured by Toho Chemical Industry Co., Ltd., maleic anhydride-denatured liquid polybutene, acid anhydride group concentration: 0.77 mmol/g, number average molecular weight: 2100).

(2) (A2) Ingredients "ER829" (manufactured by Starlight PMC Co., Ltd., glycidyl methacrylate denatured propylene-butene random copolymer, propylene unit/butene unit: 71%/29%, epoxy group concentration: 0.64 mmol/g, number average Molecular weight: 168000) "ER866" (manufactured by Starlight PMC Co., Ltd., glycidyl methacrylate modified butyl rubber, epoxy group concentration: 1.63 mmol/g, number average molecular weight: 113000, isobutylene unit/isoprene unit: 98.9%/1.1% ).

(3) (A3) Ingredients "HV-1900" (manufactured by ENEOS, liquid polybutene, number average molecular weight: 2900, viscosity at 25°C: 460 Pa·s).

(4) (A4) Ingredients "BUTYL065" (manufactured by JSR Corporation, butyl rubber, isobutylene unit/isoprene unit: 98.7%/1.3%).

(5) Hygroscopic filler (5-1) Calcium oxide Calcium oxide (manufactured by Yoshizawa Lime Industry Co., Ltd., median diameter: 2.1 μm) (5-2) (C) Component "DHT-4C" (manufactured by Kyowa Chemical Industry Co., Ltd., Semi-baked hydrotalcite, median diameter: 400 nm, BET specific surface area: 15 m ² /g).

(6) Adhesion imparting agent "ARKON P-125" (manufactured by Arakawa Chemical Industry Co., Ltd., hydrogenated petroleum resin, softening point: 125° C.).

(7) Metal complexes "PLENACT Al-M" (manufactured by Ajinomoto Fine-Techno Co., Ltd., octadecenyl aluminum diisopropyl acetylacetate).

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

(9) hardening accelerator 2,4,6-tris(dimethylaminomethyl)phenol (manufactured by KAYAKU NOURYON, hereinafter abbreviated as "TAP").

<Example 1> A varnish having a compounding ratio shown in Table 1 below was prepared according to the following procedure, and a sealing sheet was produced using the obtained varnish. In addition, the usage-amount (part) of each component described in following Table 1 shows the amount of the non-volatile matter of each component in a varnish. In addition, in the following Table 1, calcium oxide is described as "CaO", and its diameter is described in parentheses. Furthermore, the following Table 1 shows the content of the hygroscopic filler with respect to 100% by mass of the nonvolatile content of the sealing composition.

Specifically, maleic anhydride-denatured liquid polybutene (manufactured by Toho Chemical Industry Co., Ltd. "HV-300M"), liquid polybutene (manufactured by ENEOS "HV-1900"), calcium oxide (manufactured by Yoshizawa Lime Industry Co., Ltd.), and toluene to obtain a mixture for pulverization (organic solvent relative to the entire mixture content (that is, the total content of Swasol and toluene): 24%, content of maleic anhydride denatured liquid polybutene: 10%, content of calcium oxide: 48%, content of adhesion imparting agent: 7%, liquid polybutene Alkene content: 11%).

Put the mixture for pulverization into a wet bead mill (LABSTAR Mini "LMZ015" manufactured by Ashizawa Finetech Co., Ltd.), fill the beads (bead diameter: 0.2 mm) to about 60% by volume of the effective volume of the pulverization chamber, and pulverize treatment to obtain a pulverized mixture in which calcium oxide is pulverized and dispersed.

A small amount of the pulverized mixture was taken out and diluted 100 times with toluene to prepare a measurement sample, and the median diameter of calcium oxide was measured and calculated by the dynamic light scattering method using a nanoparticle size measuring device "NANOTRAC WAVE" manufactured by MICROTRAC Co., Ltd. . As a result, the median diameter of calcium oxide was 246 nm.

To the pulverized mixture, a toluene solution (non-volatile content: 15%) of glycidyl methacrylate-modified propylene-butene random copolymer (manufactured by Starlight PMC Co., Ltd. "ER829"), hindered phenolic antibiotic An oxidizing agent ("Irganox 1010" manufactured by BASF Corporation) and a hardening accelerator (TAP, manufactured by KAYAKU NOURYON Co., Ltd.) were mixed with a high-speed rotary mixer to obtain a varnish of a sealing composition.

Polyethylene terephthalate film ("SP4020" manufactured by TOYO CLOTH CO., LTD.) treated with a silicone-based release agent on one side, PET film thickness: 50 μm ) and low moisture permeability polyethylene terephthalate film ("TECHBARRIER HX" manufactured by Mitsubishi Chemical Corporation, PET film thickness: 12 μm), and the surface of SP4020 that has not been treated with a silicone-based release agent and " TECHBARRIER HX" is bonded in contact, and a laminated film is produced, which is used as a support and a protective sheet for the sealing sheet. Hereinafter, "the surface of the laminated film treated with a silicone-based mold release agent" will be described as the "release-treated surface".

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

<Example 2> Except having changed the usage-amount of calcium oxide into 120 parts from 300 parts, the sheet|seat for sealing which has the sealing layer of thickness 10 micrometers was produced by the method similar to Example 1.

<Example 3> A sealing sheet having a sealing layer with a thickness of 10 μm was produced 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. Furthermore, the median diameter of calcium oxide in the pulverized mixture of Example 3 was measured in the same manner as in Example 1, and the median diameter was 185 nm.

<Example 4> A sheet for sealing 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 sheet for sealing was produced 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> Except that the toluene solution (non-volatile content: 15%) of glycidyl methacrylate-modified propylene-butylene random copolymer ("ER829" manufactured by Starlight PMC Co., Ltd.) was changed to glycidyl methacrylate-modified butyl rubber ( A sealing sheet having a sealing layer with a thickness of 10 μm was prepared in the same manner as in Example 3 except for a toluene solution (non-volatile content: 25%) of “ER866” manufactured by Starlight PMC Co., Ltd.

<Example 7> Except changing the toluene solution (non-volatile content: 15%) of glycidyl methacrylate-modified propylene-butylene random copolymer ("ER829" manufactured by Starlight PMC Co., Ltd.) to butyl rubber ("BUTYL065" manufactured by JSR Corporation) Except for the toluene solution (non-volatile content: 15%), a sealing sheet having a sealing layer with a thickness of 10 μm was produced by the same method as in Example 3.

＜Comparative example 1＞ Maleic anhydride-denatured liquid polybutene ("HV -300M"), liquid polybutene ("HV-1900" manufactured by ENEOS Co., Ltd.), semi-baked hydrotalcite ("DHT-4C" manufactured by Kyowa Chemical Industry Co., Ltd.), and a mixture was obtained. To the obtained mixture, a Swasol solution (non-volatile content: 15%) of a glycidyl methacrylate-modified propylene-butene random copolymer (manufactured by Starlight PMC Co., Ltd. "ER829"), hindered phenolic antioxidant ( "Irganox 1010" manufactured by BASF Corporation), a hardening accelerator (TAP, manufactured by KAYAKU NOURYON Co., Ltd.) and toluene were mixed with a high-speed rotary mixer to obtain a varnish of a sealing composition. From the obtained varnish, a sealing sheet having a sealing layer with a thickness of 10 μm was produced by the same method as in Example 1.

＜Comparative example 2＞ In the same manner as in Comparative Example 1, except that semi-burnt hydrotalcite ("DHT-4C" manufactured by Kyowa Chemical Industry Co., Ltd.) was replaced with calcium oxide (manufactured by Yoshizawa Lime Industry Co., Ltd., median diameter: 2.1 μm), A sealing sheet having a sealing layer having a thickness of 10 μm.

＜Comparative example 3＞ Except not using maleic anhydride-denatured liquid polybutene ("HV-300M" manufactured by Toho Chemical Industry Co., Ltd.), the same operation was carried out as in Example 1 to prepare a mixture for pulverization (with respect to the organic solvent of the entire mixture). content (that is, the sum of the contents of Swasol and toluene): 26%, the content of calcium oxide: 53%, the content of adhesion imparting agent: 8%, the content of liquid polybutene: 12%).

The mixture for pulverization was put into a wet bead mill (LABSTAR Mini "LMZ015" manufactured by Ashizawa Finetech Co., Ltd., bead diameter: 0.2 mm), and the pulverization and dispersion of calcium oxide were tried. The viscosity increased, and it was not possible to obtain a varnish for sealing a composition for sealing in which calcium oxide having a median diameter of 300 nm or less was dispersed.

<Example 8> A varnish having a compounding ratio shown in Table 2 below was prepared according to the following procedure, and a sealing sheet was produced using the obtained varnish. In addition, the usage-amount (part) of each component described in following Table 2 shows the amount of the non-volatile matter of each component in a varnish. In addition, in the following Table 2, calcium oxide is described as "CaO", "calcium oxide having a median diameter exceeding 300 nm" is described as "(B') component", and the median diameter of the calcium oxide used is also described. Furthermore, the following Table 2 shows the content of calcium oxide and the content of semi-baked hydrotalcite with respect to 100% by mass of non-volatile components of the sealing composition.

Specifically, maleic anhydride-denatured liquid polybutene (manufactured by Toho Chemical Industry Co., Ltd. "HV-300M"), liquid polybutene (manufactured by ENEOS "HV-1900"), calcium oxide (manufactured by Yoshizawa Lime Industry Co., Ltd.), and toluene to obtain a mixture for pulverization (organic solvent relative to the entire mixture content (that is, the total content of Swasol and toluene): 35%, content of maleic anhydride denatured liquid polybutene: 7%, content of calcium oxide: 23%, content of adhesion imparting agent: 16%, liquid polybutene Alkene content: 19%).

Put the mixture for pulverization into a wet bead mill (LABSTAR Mini "LMZ015" manufactured by Ashizawa Finetech Co., Ltd.), fill the beads (bead diameter: 0.1 mm) to about 60% by volume of the effective volume of the pulverization chamber, and pulverize treatment to obtain a pulverized mixture in which calcium oxide is pulverized and dispersed.

A small amount of the pulverized mixture was taken out and diluted 100 times with toluene to prepare a measurement sample, and the median diameter of calcium oxide was measured and calculated by the dynamic light scattering method using a nanoparticle size measuring device "NANOTRAC WAVE" manufactured by MICROTRAC Co., Ltd. . As a result, the median diameter of calcium oxide was 185 nm.

To the pulverized mixture, semi-calcined hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd. "DHT-4C"), glycidyl methacrylate denatured propylene-butene random copolymer (manufactured by Hoshiko PMC Co., Ltd. "ER829 ") toluene solution (non-volatile content: 15%), metal complex ("PLENACT Al-M" manufactured by Ajinomoto Fine Chemicals Co., Ltd.), hindered phenolic antioxidant ("Irganox 1010" manufactured by BASF), hardened Accelerator (TAP, manufactured by KAYAKU NOURYON Co., Ltd.), and the obtained mixture were mixed with a high-speed rotary mixer to obtain a varnish of a composition for sealing.

Polyethylene terephthalate film ("SP4020" manufactured by TOYO CLOTH CO., LTD., PET film thickness: 50 μm) treated with a silicone-based release agent on one side With a low moisture permeability polyethylene terephthalate film ("TECHBARRIER HX" manufactured by Mitsubishi Chemical Corporation, PET film thickness: 12μm), the surface of SP4020 that has not been treated with a silicone-based release agent and "TECHBARRIER HX" contact method to make a laminated film, which is used as a support for the sealing sheet and a protective sheet. Hereinafter, "the surface of the laminated film treated with a silicone-based mold release agent" will be described as the "release-treated surface".

The obtained varnish was uniformly coated on the release-treated surface of the first laminated film with a die coater, and heated at 140° C. for 30 minutes. Then, the second laminated film was laminated so that the release-treated surface was in contact with the composition layer, and then heated at 130° C. for 60 minutes to obtain a sealing sheet having a sealing layer with a thickness of 50 μm.

<Example 9> Except that the usage amount of (B) component is changed from 96 parts to 60 parts, and the usage amount of (C) component is changed from 144 parts to 180 parts, by the same method as in Example 8, a product with a thickness of 50 μm is made. The sealing sheet of the sealing layer.

<Example 10> A sheet for sealing 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 with a thickness of 20 μm was produced 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. Furthermore, when the median diameter of the calcium oxide in the pulverized mixture of Example 11 was measured in the same manner as in Example 8, the median diameter was 246 nm.

<Example 12> Except that the toluene solution (non-volatile content: 15%) of glycidyl methacrylate-modified propylene-butylene random copolymer ("ER829" manufactured by Starlight PMC Co., Ltd.) was changed to glycidyl methacrylate-modified butyl rubber ( Except for the toluene solution (non-volatile content: 25%) of "ER866" manufactured by Starlight PMC Co., Ltd., a sealing sheet having a sealing layer with a thickness of 50 μm was produced in the same manner as in Example 8.

<Example 13> Except changing the toluene solution (non-volatile content: 15%) of glycidyl methacrylate-modified propylene-butylene random copolymer ("ER829" manufactured by Starlight PMC Co., Ltd.) to butyl rubber ("BUTYL065" manufactured by JSR Corporation) Except for the toluene solution (non-volatile content: 15%), by the same method as in Example 8, a sealing sheet having a sealing layer with a thickness of 50 μm was produced.

＜Comparative example 4＞ Maleic anhydride-denatured liquid polybutene ("HV -300M"), liquid polybutene ("HV-1900" manufactured by ENEOS Co., Ltd.), semi-baked hydrotalcite ("DHT-4C" manufactured by Kyowa Chemical Industry Co., Ltd.), and a mixture was obtained. To the obtained mixture, a Swasol solution (non-volatile content: 15%) of a glycidyl methacrylate-modified propylene-butene random copolymer (manufactured by Starlight PMC Co., Ltd. "ER829"), hindered phenolic antioxidant ( "Irganox 1010" manufactured by BASF Corporation), a hardening accelerator (TAP, manufactured by KAYAKU NOURYON Co., Ltd.) and toluene were mixed with a high-speed rotary mixer to obtain a varnish of a sealing composition. From the obtained varnish, a sealing sheet having a sealing layer with a thickness of 50 μm was produced by the same method as in Example 8.

＜Comparative example 5＞ Except changing the amount of component (C) from 240 parts to 180 parts, and further using 60 parts of calcium oxide (median diameter: 2.1 μm), a seal with a thickness of 50 μm was produced by the same method as Comparative Example 4. Layers of sealing sheets.

＜Comparative example 6＞ Except not using maleic anhydride-denatured liquid polybutene ("HV-300M" manufactured by Toho Chemical Industry Co., Ltd.), the same operation was carried out as in Example 8 to prepare a mixture for pulverization (with respect to the organic solvent of the entire mixture). Content (that is, the sum of the contents of Swasol and toluene): 38%, the content of calcium oxide: 24%, the content of adhesion imparting agent: 17%, the content of liquid polybutene: 20%).

The mixture for pulverization was put into a wet bead mill (LABSTAR Mini "LMZ015" manufactured by Ashizawa Finetech Co., Ltd., bead diameter: 0.1 mm), and the pulverization and dispersion of calcium oxide were tried, but the mixture for pulverization was significantly Viscosity increased, and a varnish of a sealing composition in which calcium oxide having a median diameter of 300 nm or less was dispersed could not be obtained.

Regarding the sealing layers of the sealing sheets obtained in Examples and Comparative Examples, transparency and water vapor penetration barrier properties were evaluated by the following methods.

＜Evaluation method of transparency＞ The sealing sheets prepared in Examples and Comparative Examples were cut into lengths of 70 mm and widths of 25 mm, the protective sheets were peeled off from the cut sealing sheets, and the sealing sheets having the laminated structure of the sealing layer/support were divided into parts. Batch vacuum laminator (manufactured by Nichigo-Morton, V-160) was laminated on a glass plate (manufactured by Matsunami Glass Industry Co., Ltd. "white slide S1112 edged No. 2", length: 76 mm, width: 26 mm and Thickness: 1.2 mm), a sample for evaluation having a laminated structure of glass/sealing layer/support was obtained. The lamination conditions were a temperature of 80° C. and a pressure reduction time of 30 seconds, followed by pressurization at a pressure of 0.3 MPa for 30 seconds.

Haze (%) was measured in accordance with JIS K 7136. Specifically, after peeling off the support of the evaluation sample having a laminated structure of glass/sealing layer/support, using a haze meter HZ-V3 (halogen lamp) manufactured by Suga Testing Instrument Co. The haze (%) of the sample for evaluation from which the support body peeled off was measured, and transparency was evaluated based on the following criteria. The results are shown in the following table; (standard of transparency) ○ (good): Haze is less than 30% △(Pass): The haze is more than 30% and less than 60% × (poor): The haze is 60% or more.

＜Evaluation method of water vapor intrusion barrier property＞ As a support, a composite film ("AL1N30 with PET" manufactured by Tokai Toyo Aluminum Sales Co., Ltd. (thickness of aluminum foil: 30 μm, thickness of PET film: 25 μm)) including an aluminum foil and a polyethylene terephthalate film was prepared.

Except using the aforementioned composite film as a support, 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.

A 50 mm×50 mm square glass plate formed of non-alkali glass was prepared. This glass plate was washed with boiled isopropanol for 5 minutes, and dried at 150° C. for 30 minutes or more.

Calcium was vapor-deposited on one surface of the dried glass plate using a mask covering a peripheral region 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%) with a thickness of 200 nm was formed on one side of the glass plate except for the central portion 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 above-mentioned test sheet was bonded to the surface of the glass plate on the calcium film side with a thermal laminator ("Lamipacker DAiSY A4 (LPD2325)" manufactured by FUJIPLA Corporation) to obtain a laminate. This laminate was used as an evaluation sample.

Generally, when calcium contacts water and forms calcium oxide, it becomes transparent. Also, in the aforementioned evaluation samples, the glass plate and aluminum foil have sufficiently high water vapor intrusion barrier properties, so moisture can usually move through the end of the sealing layer in the in-plane direction (direction perpendicular to the thickness direction) and reach the calcium film. When moisture penetrates into the evaluation sample, the calcium film is gradually oxidized from the edge to become transparent, so shrinkage of the calcium film can be observed. Therefore, the intrusion of moisture into the evaluation sample can be evaluated by measuring the sealing distance (mm) from the edge of the evaluation sample to the calcium film. Therefore, the evaluation sample of the calcium-containing 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 at a temperature of 85° C. and a humidity of 85% RH. When the sealing distance X1 (mm) between the end of the evaluation sample housed in the constant temperature and humidity chamber and the end of the calcium film increased by 0.1 mm compared to the initial sealing distance X2, the evaluation sample was changed from the constant temperature and humidity chamber to the end of the calcium film. slot out. The time from when the evaluation sample was stored in the constant temperature and humidity chamber to when the evaluation sample was taken out from the constant temperature and humidity chamber was determined as the reduction start time t [hour]. This decrease start time t corresponds to 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 from the time T _P1 when the evaluation sample was stored in the constant temperature and humidity chamber. The time until the time T _P2 when "X2+0.1 mm" is reached.

Substituting the aforementioned sealing distance X1 and decrease start time t into the Fickian diffusion equation of Equation (1), the constant K, which is a water vapor intrusion barrier parameter, is calculated.

使用所得的常數K，依據下述的標準對密封層的水蒸氣侵入阻隔性進行了評價。常數K的值越小，則表示水蒸氣侵入阻隔性越高。尚且，下述「hr」表示「小時」。結果記載於下述表中。尚且，下述表中的「(cm/hr＾0.5)」意指「(cm/hr ^0.5)」； (水蒸氣侵入阻隔性的標準) ○(良好)：常數K未滿0.025 cm/hr ^0.5×(不良)：常數K為0.025 cm/hr ^0.5以上。

Using the obtained constant K, the water vapor intrusion barrier properties of the sealing layer were evaluated according to the following criteria. The smaller the value of the constant K, the higher the water vapor intrusion barrier property. Also, the following "hr" means "hour". The results are shown in the following tables. Also, "(cm/hr＾0.5)" in the following table means "(cm/hr ^0.5 )"; (standard of water vapor intrusion barrier property) ○ (good): constant K is less than 0.025 cm/hr ^0.5 × (poor): The constant K is 0.025 cm/hr ^0.5 or more.

Compared with the sealing layer formed of the sealing composition of Comparative Example 1 in which semi-burned hydrotalcite was used instead of calcium oxide, the sealing layer formed of the sealing compositions of Examples 1 to 7 satisfying the requirements of the present invention was more resistant to water vapor. Intrusion barrier is more excellent. Also, the sealing layer formed of the sealing compositions of Examples 1 to 7 had lower haze and was transparent than the sealing layer formed of the sealing composition of Comparative Example 2 using calcium oxide having a median diameter exceeding 300 nm. more excellent.

Compared with the sealing layer formed of the sealing composition of Comparative Example 4 in which component (B) was not used, the water vapor intrusion barrier properties of the sealing layer formed from the sealing compositions of Examples 8 to 13 satisfying the requirements of the present invention were significantly improved. more excellent. Also, the sealing layer formed from the sealing compositions of Examples 8 to 13 and the sealing composition of Comparative Example 5 in which the (B) component was replaced by calcium oxide ((B') component) having a median diameter exceeding 300 nm Compared with the formed sealing layer, the haze is lower and the transparency is more excellent.

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

Claims (15)

A sealing composition comprising the following (A) component and (B) component sealing composition, (A) olefin-based polymers, and (B) calcium oxide, Among them, the (A) component contains an olefin-based polymer having an acid anhydride group and/or a carboxyl group, Moreover, the median diameter of (B) component is 300 nm or less. The composition for sealing as claimed in claim 1, which further comprises the following component (C): (C) Half-baked hydrotalcite. The sealing composition according to claim 1 or 2, wherein the median diameter of the component (B) is 1 nm or more. The sealing composition according to claim 1, wherein the content of the component (B) is 20 to 80 mass % with respect to 100 mass % of non-volatile components of the sealing composition. The sealing composition according to claim 2, wherein the content of the component (B) is 5 to 30 mass % with respect to 100 mass % of non-volatile components of the sealing composition. The sealing composition according to claim 2, wherein the content of the component (C) is 20 to 70% by mass based on 100% by mass of non-volatile components of the sealing composition. The sealing composition according to claim 1 or 2, wherein the olefin-based polymer having an acid anhydride group and/or carboxyl group is an olefin-based polymer having an acid anhydride group. The sealing composition according to claim 1 or 2, wherein the component (A) contains an olefin-based polymer having an epoxy group. The sealing composition according to claim 1 or 2, wherein the component (A) contains a liquid olefin polymer. The sealing composition according to claim 1 or 2, further comprising an adhesion imparting agent. A sealing sheet having a laminated structure, The laminated structure includes a support and a sealing layer formed of the sealing composition according to claim 1 or 2. The sheet for sealing according to claim 11, wherein the haze of the sealing layer is less than 60%. An electronic device, comprising a sealing layer formed of the sealing composition according to claim 1 or 2. A method for manufacturing the sealing composition according to claim 1 or 2, including the step of pulverizing the mixture, The mixture includes: an olefinic polymer having an acid anhydride group and/or a carboxyl group, calcium oxide with a median diameter exceeding 300 nm, and an organic solvent. The production method according to claim 14, further comprising a step of mixing the pulverized mixture with an olefin-based polymer having an epoxy group.