Sealing components, manufacturing methods thereof, and sealing sheets

Abstract

The objective of this invention is to provide a sealing composition that can form a sealing layer that combines vapor permeation barrier properties and transparency, thereby exhibiting excellent dispersibility (storage stability) of calcium oxide. The solution of this invention is a sealing composition comprising the following components (A) to (D): (A) an olefinic polymer having an anhydride group and / or a carboxyl group with a number average molecular weight of less than 10,000; (B) a polymer with a number average molecular weight of 10,000 or more; (C) calcium oxide with a median particle size of 300 nm or less; and (D) a nonionic surfactant and / or anionic surfactant.

Description

Technical Field

[0001] This invention relates to a sealing composition useful for sealing electronic devices and the like. Prior Technology

[0002] To protect electronic devices such as organic EL (electroluminescence) devices and solar cells from moisture, an operation is performed to seal the electronic devices using a sealing layer formed from a sealing composition or a sealing sheet. For example, Patent Document 1 discloses a sealing resin composition comprising (A) a polyolefin resin and (B) a metal hydroxide selected from hydrotalcite and semi-fired hydrotalcite, and a sealing sheet formed therefrom that composition exhibits both good moisture resistance and transparency. However, hydrotalcite reversibly absorbs and releases moisture. Therefore, for sealing compositions using hydrotalcite, moisture absorbed by the hydrotalcite during its manufacturing process or distribution is released in the sealing layer of the electronic device formed using that composition, sometimes leading to deterioration of the electronic device. Previous technical documents Patent documents

[0003] Patent Document 1: International Publication No. 2017 / 057708. Summary of the Invention

[0004] The problem that the invention aims to solve

[0005] Calcium oxide is known as a hygroscopic filler. While sealing layers formed from sealing compositions using calcium oxide exhibit excellent water vapor permeation suppression properties (sometimes referred to as "water vapor permeation barrier" in this specification), the transparency of the sealing layer formed from such compositions is typically lost when calcium oxide is used as a hygroscopic filler in sealing compositions containing olefin polymers. To suppress this reduction in transparency, the use of finely ground calcium oxide has been considered; however, due to the poor dispersibility of finely ground calcium oxide, it is difficult to manufacture compositions with excellent transparency where finely ground calcium oxide is well dispersed in olefin polymers. Therefore, it is difficult to simultaneously achieve water vapor permeation barrier and transparency in sealing layers formed from sealing compositions containing olefin polymers.

[0006] Accordingly, the object of the present invention is to provide a sealing composition that can form a sealing layer that combines water vapor permeation barrier and transparency, thereby exhibiting excellent dispersibility (storage stability) of calcium oxide. Solution for solving the problem

[0007] In order to solve the above-mentioned problems, the inventors have conducted intensive research and found that by further including component (D): a nonionic surfactant and / or anionic surfactant, a sealing composition containing components (A) to (C) can be formed that can form a sealing layer that has both water vapor permeability barrier and transparency, and thus has excellent calcium oxide dispersibility (storage stability), thereby completing the present invention.

[0008] That is, the present invention has the following features; [1] A sealing composition comprising the following components (A) to (D): (A) Olefin polymers with an anhydride group and / or a carboxyl group whose number average molecular weight is less than 10,000; (B) Polymers with a number average molecular weight of 10,000 or higher (C) Calcium oxide with a median particle size of less than 300 nm, and (D) Nonionic surfactants and / or anionic surfactants; [2] As described in [1], the sealing composition, wherein component (D) is a nonionic surfactant; [3] The sealing composition as described in [2], wherein the nonionic surfactant is a polyoxyalkylene ether or a polyoxyalkylene aryl ether; [4] As described in [2], the sealing composition wherein the nonionic surfactant is a polyoxyalkylene aryl ether. [5] As described in [2], the sealing composition wherein the nonionic surfactant is a polyoxyalkylene aryl ether having the following structure. The structure is as follows:

[0009] [Chemical Formula 1]

[0010] (In the formula, n is an integer from 1 to 10, R1 and R2 are each independently a hydrogen atom or a methyl group, and Ar is an aromatic group with optional substituents). [6] The sealing composition described in any of [1] to [5], wherein (B) the polymer with a number average molecular weight of 10,000 or more is an olefin polymer with a number average molecular weight of 10,000 or more; [7] The sealing composition as described in [6], wherein (B) the polymer with a number average molecular weight of 10,000 or more is: at least one of an olefin polymer having an anhydride group and / or a carboxyl group with a number average molecular weight of 10,000 or more, and an olefin polymer having an epoxy group with a number average molecular weight of 10,000 or more; [8] A sealing composition as described in any of [1] to [7], wherein it further comprises (E) a liquid olefin polymer (other than (A) and (B) components); [9] A sealing composition as described in any of [1] to [8], wherein it further comprises (F) an adhesive agent;

[10] The sealing composition described in any of [1] to [9], wherein the content of component (C) is 10 to 70% by mass relative to 100% by mass of the non-volatile components of the sealing composition;

[11] The sealing composition described in any of [1] to

[10] , wherein the content of component (D) is 5 to 25% by mass relative to 100% by mass of the non-volatile component of the sealing composition;

[12] A sealing sheet having a laminated structure comprising a sealing layer formed of any of the sealing components described in [1] to

[11] . The effects of the invention

[0011] According to the present invention, a sealing composition can be provided that can form a sealing layer that combines water vapor permeation barrier and transparency, thereby providing excellent dispersibility (storage stability) of calcium oxide. Implementation

[0012] The present invention will now be described according to a preferred embodiment. [Sealing components] The sealing composition of the present invention comprises the following components (A) to (D) as essential components: (A) Olefin polymers with an anhydride group and / or a carboxyl group whose number average molecular weight is less than 10,000; (B) Polymers with a number average molecular weight of 10,000 or higher (C) Calcium oxide with a median particle size of less than 300 nm, and (D) Nonionic surfactants and / or anionic surfactants.

[0013] By using calcium oxide, which has a higher hygroscopicity than the hydrotalcite described in Patent Document 1, as a hygroscopic filler, a sealing layer with excellent water vapor permeability barrier properties can be formed.

[0014] When calcium oxide is used, the transparency of the resulting sealing layer decreases. To address this, in this invention, by using calcium oxide ((C) component) with a median particle size of 300 nm or less, the decrease in transparency can be suppressed.

[0015] Fine (C) components are difficult to disperse well in sealing compositions. However, in this invention, by using olefinic polymers ((A) components) with an anhydride and / or carboxyl groups having a number average molecular weight of less than 10,000, the dispersibility of fine (C) components in sealing compositions is improved. It is inferred that (A) components function as dispersants for the fine (C) components in this respect. However, the invention is not limited to this inference.

[0016] However, the dispersibility of component (C) may not be sufficient, and calcium oxide agglomeration and gelation of the composition coating may occur during the preparation (mixing) and storage of the coating used to make sealing sheets. Such agglomeration and gelation can be prevented by further including nonionic and / or anionic surfactants (component (D)) in the sealing composition.

[0017] In this specification, "olefin polymer" refers to a polymer in which structural units derived from olefins (hereinafter sometimes simply referred to as "olefin units") are the main structural units (i.e., the amount of olefin units is the largest among all structural units). Additionally, hereinafter, "structural units derived from butene" that serve as olefin units may sometimes be simply referred to as "butene units," etc.

[0018] Olefin polymers can be olefin resins (e.g., propylene-butene copolymers) or olefin rubbers (e.g., butyl rubber, i.e., isobutylene-isoprene copolymers). In this specification, "olefin resin" refers to an olefin polymer that cannot be cross-linked to form a rubber elastomer, and "olefin rubber" refers to an olefin polymer that can be cross-linked to form a rubber elastomer.

[0019] As an olefin, it is preferable to have a monoolefin having one olefinic carbon-carbon double bond and / or a diene having two olefinic carbon-carbon double bonds. Examples of monoolefins include α-olefins such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. Examples of dienes include 1,3-butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethylbutadiene.

[0020] Olefin polymers can be homopolymers or copolymers. Copolymers can be random copolymers or block copolymers. Furthermore, olefin polymers can be copolymers of olefins and monomers other than olefins. Examples of olefin copolymers include ethylene-nonconjugated diene copolymers, ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene copolymers, ethylene-propylene-butene copolymers, propylene-butene copolymers, propylene-butene-nonconjugated diene copolymers, isobutylene-isoprene copolymers, styrene-isobutylene copolymers, and styrene-isobutylene-styrene copolymers.

[0021] The following is a detailed description of each ingredient. Note that, unless otherwise specified in this instruction manual, each ingredient may be used in its entirety, either individually or in combination of two or more.

[0022] <(A)Component> Component (A) is an olefinic polymer with an anhydride group (i.e., carbonyloxycarbonyl group (-CO-O-CO-)) and / or a carboxyl group, having a number average molecular weight of less than 10,000. By incorporating component (A), calcium oxide (component (C)) can be well dispersed in the sealing composition. In addition, the reaction of the anhydride / carboxyl group with the epoxy group or with the calcium oxide ligand to form a cross-linked structure can exert water vapor permeation barrier properties. Component (A) is preferably an olefinic polymer with an anhydride group, having a number average molecular weight of less than 10,000.

[0023] When using an olefinic polymer with an anhydride group as component (A), the concentration of the 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 anhydride group is obtained from the acid value, which is defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the polymer, according to JIS K 2501.

[0024] When using an olefinic polymer with a number average molecular weight of less than 10,000 as component (A), the concentration of carboxyl groups in the polymer is preferably 0.05 to 20 mmol / g, more preferably 0.10 to 10 mmol / g. The concentration of carboxyl groups is obtained from the acid value, defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the polymer, according to JIS K 2501.

[0025] When using an olefinic polymer having an anhydride group and a carboxyl group as component (A), the total concentration of the anhydride group and the carboxyl group in the polymer is preferably 0.05 to 20 mmol / g, more preferably 0.10 to 10 mmol / g.

[0026] (A) The number average molecular weight of the components is less than 10,000. From the viewpoint of improving the coating properties of the sealing composition, the sealing performance of the formed sealing layer, and the mechanical strength, it is preferable to have a number average molecular weight of 100 to 10,000, more preferably 250 to 9,000, and even more preferably 500 to 8,000. The number average molecular weight of each component is determined by gel permeation chromatography (GPC) (polystyrene conversion). Specifically, the number average molecular weight determined by GPC can be measured using a Shimadzu Corporation "LC-9A / RID-6A" as the measuring apparatus, a Showa Denko Corporation "Shodex K-800P / K-804L / K-804L" as the column, toluene or the like as the mobile phase, at a column temperature of 40°C, and calculated using a calibration curve of standard polystyrene.

[0027] (A) The component may be manufactured, for example, by grafting an olefin polymer with an unsaturated compound having an anhydride group and / or a carboxyl group (e.g., maleic anhydride) under free radical reaction conditions, or by copolymerizing an unsaturated compound having an anhydride group and / or a carboxyl group with an α-olefin.

[0028] As component (A), a polymer that can be obtained, for example, from Toho Chemical Industry Co., Ltd., or Starlight PMC Co., Ltd. can be used. Examples of such polymers include "HV-300M" (maleic anhydride modified liquid polybutene) manufactured by Toho Chemical Industry Co., Ltd., "HV-100M" (maleic anhydride modified liquid polybutene) manufactured by Toho Chemical Industry Co., Ltd., "ER688" (maleic anhydride modified liquid polybutene) manufactured by Hoshino PMC Co., Ltd., "LUCANT A-5515" (acid-modified ethylene-α-olefin copolymer) manufactured by Mitsui Chemicals Co., Ltd., "LUCANT A-5260" (acid-modified ethylene-α-olefin copolymer) manufactured by Mitsui Chemicals Co., Ltd., "LUCANT A-5320H" (acid-modified ethylene-α-olefin copolymer) manufactured by Mitsui Chemicals Co., Ltd., "T-YP430" (maleic anhydride modified ethylene-methyl methacrylate copolymer) manufactured by Hoshino PMC Co., Ltd., "T-YP956" (maleic anhydride modified ethylene-propylene-butene random copolymer) manufactured by Hoshino PMC Co., Ltd., and "DIACARNA" manufactured by Mitsubishi Chemical Co., Ltd. 30M (copolymer of maleic anhydride and α-olefin), etc.

[0029] In one embodiment of the present invention, component (A) is a compound with a number average molecular weight of less than 10,000, namely: (i) Preferably, it is selected from at least one of the following: polybutene having an anhydride group and / or a carboxyl group; isobutylene-isoprene copolymer (i.e., butyl rubber) having an anhydride group and / or a carboxyl group; propylene-butene copolymer having an anhydride group and / or a carboxyl group; ethylene-methyl methacrylate copolymer having an anhydride group and / or a carboxyl group; and ethylene-propylene-butene copolymer having an anhydride group and / or a carboxyl group. (ii) Preferably, it is selected from at least one of polybutene having an anhydride group and / or a carboxyl group, isobutene-isoprene copolymer having an anhydride group and / or a carboxyl group, and propylene-butene copolymer having an anhydride group and / or a carboxyl group; (iii) More preferably, it is selected from at least one of polybutene having an anhydride group, isobutene-isoprene copolymer having an anhydride group, and propylene-butene copolymer having an anhydride group; (iv) Especially preferred are polybutenes with anhydride groups.

[0030] From the viewpoint of the dispersibility of fine calcium oxide ((C) component) in the sealing composition, the content of component (A) is preferably 3 to 50% by mass relative to 100% by mass of the non-volatile components of the sealing composition, more preferably 5 to 45% by mass, and even more preferably 10 to 40% by mass.

[0031] <(B) Ingredients> Component (B) is a polymer with a number average molecular weight of 10,000 or more. By incorporating component (B), a sealing layer that is difficult to deform and can maintain its shape can be obtained. If component (B) is not incorporated, film formation becomes difficult. There is no particular limitation on the polymer as component (B), as long as the number average molecular weight is 10,000 or more. From the viewpoint of compatibility, an olefin polymer is preferred. In addition, from the viewpoint of the dispersibility of calcium oxide (component (C)) in the sealing composition and the water vapor permeation barrier properties of the resulting sealing layer, it is preferred to select at least one of the following: an olefin polymer with a number average molecular weight of 10,000 or more that has an anhydride group and / or a carboxyl group (hereinafter also referred to as "component (B1)") that can form a cross-linked structure through the reaction of epoxy groups with anhydride groups / carboxyl groups, or through the coordination of anhydride groups / carboxyl groups to calcium oxide; and an olefin polymer with an epoxy group and a number average molecular weight of 10,000 or more (hereinafter also referred to as "component (B2)").

[0032] ((B1) component) The olefinic polymer having anhydride and / or carboxyl groups as component (B1) is as described in component (A) above, except that the number average molecular weight is 10,000 or more.

[0033] As component (B1), polymers available from companies such as Starlight PMC can be used. Examples of such polymers include "ER645" (maleic anhydride-butyl methacrylate random copolymer modified propylene-butene random copolymer) manufactured by Starlight PMC, "ER661" (maleic anhydride-butyl methacrylate random copolymer modified butyl rubber) manufactured by Starlight PMC, "ER641" (maleic anhydride modified butyl rubber) manufactured by Starlight PMC, "ER669" (maleic anhydride-2-ethylhexyl acrylate random copolymer modified butyl rubber) manufactured by Starlight PMC, "ER674" (maleic anhydride-lauryl methacrylate random copolymer modified butyl rubber) manufactured by Starlight PMC, "T-YP279" (maleic anhydride modified propylene-butene random copolymer) manufactured by Starlight PMC, and "T-YP212" (maleic anhydride modified propylene-butene random copolymer) manufactured by Starlight PMC.

[0034] ((B2) component) (B2) The concentration of epoxy groups in the component is preferably 0.05~10 mmol / g, more preferably 0.10~5 mmol / g. The epoxy group concentration is determined by the epoxy equivalent based on JIS K 7236-1995.

[0035] (B2) The component can be obtained, for example, by (i) grafting an olefin polymer with an epoxy-containing unsaturated compound (e.g., glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether) under free radical reaction conditions, or (ii) copolymerizing an epoxy-containing unsaturated compound with an α-olefin.

[0036] As component (B2), polymers available from companies such as Sumitomo Chemical Co., Ltd. and Starlight PMC Co., Ltd. can be used. Examples of such polymers include, for instance, "BONDFAST BF-7M" (ethylene-glycidyl methacrylate copolymer) manufactured by Sumitomo Chemical Co., Ltd., and "BONDFAST..." (also manufactured by Sumitomo Chemical Co., Ltd.). BF-2B (ethylene-glycidyl methacrylate-vinyl acetate copolymer), Sumitomo Chemical's BF-7L (ethylene-glycidyl methacrylate-methyl acrylate copolymer), Starlight PMC's ER829 (glycidyl methacrylate modified propylene-butene random copolymer), Starlight PMC's ER850 (glycidyl methacrylate modified butyl rubber), Starlight PMC's ER853 (glycidyl methacrylate modified propylene-butene random copolymer), Starlight PMC's ER866 (glycidyl methacrylate modified butyl rubber), Starlight PMC's T-YP276 (glycidyl methacrylate modified propylene-butene random copolymer), Starlight PMC's T-YP313 (glycidyl methacrylate modified propylene-butene random copolymer), etc.

[0037] (B2) Components are the following compounds with a number average molecular weight of 10,000 or more: (i) Preferably, it is selected from at least one of ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-glycidyl methacrylate-methyl acrylate copolymer, propylene-butene copolymer having epoxy groups, isobutylene-isoprene copolymer having epoxy groups (i.e., butyl rubber), and ethylene-methyl methacrylate copolymer having epoxy groups. (ii) More preferably, it is selected from at least one of propylene-butene copolymers having epoxy groups, isobutylene-isoprene copolymers having epoxy groups, and ethylene-methyl methacrylate copolymers having epoxy groups. (iii) Further preferably, it is a propylene-butene copolymer having epoxy groups, and / or an isobutylene-isoprene copolymer having epoxy groups. (iv) Particularly preferred are propylene-butene copolymers with epoxy groups, or isobutylene-isoprene copolymers with epoxy groups.

[0038] As component (B2), when using a propylene-butene copolymer with an epoxy group having an average molecular weight of 10,000 or more, the amount of butene units in the copolymer relative to the total number of propylene units and butene units is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and even more preferably 3 to 40% by mass. Furthermore, the aforementioned amount of butene units is based on the propylene units and butene units after removing the modified portion (e.g., the portion derived from (meth)acrylate for introducing epoxy groups).

[0039] When using an isobutylene-isoprene copolymer (i.e., butyl rubber) with an epoxy group having an average molecular weight of 10,000 or more as component (B2), from the viewpoint of resistance to yellowing of the sealing layer, the amount of isoprene units in the copolymer is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and even more preferably 0.5 to 10% by mass, relative to the total amount of isobutylene units and isoprene units. Furthermore, the aforementioned amount of isoprene units is based on the isobutylene units and isoprene units after removing the modified portion (e.g., the portion derived from (meth)acrylate for introducing epoxy groups).

[0040] When (B1) and (B2) are used together as component (B), the amounts of (B2) and (B1) are preferably determined based on the ratio of their functional groups. "Amount of epoxy groups (mol) in component (B2)": "The total amount of anhydride groups (mol) and carboxyl groups (mol) in component (B1)" varies depending on the crosslinking conditions (temperature, time), but is preferably 100:30 to 100:1500, more preferably 100:50 to 100:1250, further preferably 100:60 to 100:1000, and particularly preferably 100:70 to 100:900. Alternatively, for example, when component (B1) only has anhydride groups, the aforementioned "total amount of anhydride groups (mol) and carboxyl groups (mol)" refers to "the amount of anhydride groups (mol)".

[0041] As component (B), olefin polymers other than components (B1) and (B2) may also be used, namely non-liquid olefin polymers with a number average molecular weight of 10,000 or more that do not have any of the acid anhydride group, carboxyl group and epoxy group (hereinafter also referred to as "component (B3)").

[0042] In this invention, "non-liquid" in "non-liquid olefin polymer" refers to a viscosity exceeding 5000 Pa·s at 25°C.

[0043] As component (B3), polymers available from companies such as JSR Corporation can be used. Examples of such polymers include JSR Corporation's "BUTYL065", "BUTYL268", and "BUTYL365" (all butyl rubber), Sumitomo Chemical's "X1102" and "X1104" (both propylene-butene copolymers), DOW Corporation's "ENGAGE" (polyolefin elastomer), and REXtac Corporation's "RT2315" (propylene-ethylene copolymer).

[0044] (B3) Components are the following compounds with a number average molecular weight of 10,000 or more: (i) Preferably, it is a propylene-butene copolymer and / or an isobutylene-isoprene copolymer (i.e., butyl rubber). (ii) It is better to be an isobutylene-isoprene copolymer.

[0045] As component (B3), when a propylene-butene copolymer with a number average molecular weight of 10,000 or more is used, the amount of butene units in the copolymer relative to the total number of propylene units and butene units is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and even more preferably 3 to 40% by mass.

[0046] When using an isobutylene-isoprene copolymer (i.e., butyl rubber) with a number average molecular weight of 10,000 or more as component (B3), from the viewpoint of resistance to yellowing of the sealing layer, the amount of isoprene units in the copolymer is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and even more preferably 0.5 to 10% by mass, relative to the total amount of isobutylene units and isoprene units.

[0047] (B) The number of components has an average molecular weight of 10,000 or more. From the viewpoint of improving the coating properties of the sealing composition, the sealing performance of the formed sealing layer, and the mechanical strength, it is preferable to have a molecular weight of 10,000 to 500,000, and more preferably 15,000 to 400,000.

[0048] From the viewpoint of forming a sealing layer that is difficult to deform and can maintain its shape, the content of component (B) is preferably 0.1 to 25% by mass relative to 100% by mass of the non-volatile components of the sealing composition, more preferably 1 to 20% by mass, and even more preferably 3 to 15% by mass.

[0049] <(C) Ingredients> Component (C) is calcium oxide with a median particle size of 300 nm or less. By incorporating component (C) as a hygroscopic filler, the formed sealing layer can be endowed with water vapor permeation barrier properties. In addition, by setting the median particle size to 300 nm or less, a sealing layer with high transparency can be formed.

[0050] The median particle size of component (C) is 300 nm or less, and preferably 250 nm or less from the viewpoint of transparency of the formed sealing layer; from the viewpoint of dispersibility of component (C) in the sealing composition, preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more. In one embodiment of the present invention, the median particle size of component (C) is preferably 1 to 300 nm, more preferably 5 to 250 nm, and even more preferably 10 to 200 nm. The median particle size of component (C) is determined by dynamic light scattering (JIS Z 8828), and the median particle size in a volume-based particle size distribution (fine distribution) is prepared based on this determination. Dynamic light scattering is a method of calculating the particle size and particle size distribution by analyzing the fluctuations corresponding to the speed of Brownian motion using photon correlation based on the scattered light observed when particles in the dispersion medium are irradiated with a laser. Specifically, the median particle size can be measured and calculated as described in the examples.

[0051] As component (C), calcium oxide with a median particle size exceeding 300 nm can be pulverized and used, or commercially available calcium oxide with a median particle size of 300 nm or less can be used. Examples of commercially available calcium oxide with a median particle size exceeding 300 nm include "QC-X" manufactured by Inoue Lime Industry Co., Ltd., "WAC series" manufactured by Sankyo Flour Co., Ltd., and "HAL-G," "HAL-J," "HAL-F," "HAL-O," and "HAL-P" manufactured by Yoshizawa Lime Industry Co., Ltd. Examples of commercially available calcium oxide with a median particle size of 300 nm or less include "CaO Nano Powder" manufactured by Filgen Co., Ltd.

[0052] From the viewpoint of water vapor permeation barrier properties of the sealing layer, the content of component (C) relative to 100% by mass of the non-volatile components of the sealing composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. From the viewpoint of the adhesion properties of the sealing layer, it is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. In one embodiment of the present invention, the content of component (C) relative to 100% by mass of the non-volatile components of the sealing composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 15 to 60% by mass.

[0053] <(D) Components> Component (D) is a nonionic surfactant and / or anionic surfactant. By incorporating component (D), the dispersibility of component (C) in the sealing composition and the service life of the sealing composition coating can be improved. As for component (D), there are no particular limitations as long as it is a nonionic surfactant and / or anionic surfactant, and various types can be used. One type of nonionic surfactant and / or anionic surfactant can be used alone, or two or more can be mixed. Alternatively, nonionic surfactants and anionic surfactants can be mixed. Component (D) is preferably a nonionic surfactant.

[0054] Preferred nonionic surfactants in this invention include, for example, ether type, ester type, sorbitan ester type, sorbitan ester-ethylene oxide addition type, diester type, monoglyceride type, monoglyceride-ethylene oxide addition type, triglyceride-ethylene oxide addition type, sorbitan ester-ethylene oxide addition type, polyglycerol alkyl ester type, polyetheramine type, alkanolamide type, alkanolamide-ethylene oxide addition type, amine oxide type, polyethylene glycol-polypropylene glycol-block ether type (polyoxyethylene-polyoxypropylene-block copolymer type), ethylenediamine-based type, phenol type, etc., with ether type being preferred.

[0055] Typical examples of ether-type nonionic surfactants include General formula (1):

[0056] [Chemical Formula 2] The polyoxyalkylene ether shown,

[0057] General formula (2):

[0058] [Chemical Formula 3]

[0059] The polyoxyalkylene alkylphenyl ethers shown are examples of such ethers.

[0060] In formulas (1) and (2), R1 represents an alkyl or alkenyl group, preferably with 6 to 22 carbon atoms, more preferably 8 to 18, and particularly preferably 10 to 15. A represents an alkyl group, and X represents an phenyl group. n represents an integer from 1 to 70, preferably an integer from 10 to 30. Also, the alkyl group represented by AO can be a group formed from one alkyl group such as ethylene oxide or propylene oxide, or it can be a group composed of multiple alkyl groups such as ethylene oxide and propylene oxide.

[0061] Specific examples of polyoxyethylene alkyl ethers include, for instance, polyoxyethylene hexyl ether, polyoxyethylene heptayl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene dodecyl ether (also known as polyoxyethylene lauryl ether), polyoxyethylene tetradecyl ether, polyoxyethylene hexadecyl ether (also known as polyoxyethylene cetyl ether), polyoxyethylene octadecyl ether (also known as polyoxyethylene oil-based ether), polyoxyethylene eicosyl ether, polyoxyethylene oil-based ether, coconut oil reduced alcohol ethylene oxide adduct, tallow reduced alcohol ethylene oxide adduct, polyoxyethylene-polyoxypropylene-dodecyl ether (also known as polyoxyethylene-polyoxypropylene-lauryl ether), and polyoxypropylene dodecyl ether (also known as polyoxypropylene lauryl ether). Among these, polyoxyethylene dodecyl ether, polyoxypropylene dodecyl ether, and polyoxyethylene-polyoxypropylene-dodecyl ether are preferred.

[0062] Specific examples of polyoxyethylene alkyl phenyl ethers include, for example, polyoxyethylene hexyl phenyl ether, polyoxyethylene heptyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene decyl phenyl ether, polyoxyethylene dodecyl phenyl ether (also known as polyoxyethylene lauryl phenyl ether), polyoxyethylene tetradecyl phenyl ether, polyoxyethylene hexadecyl phenyl ether, polyoxyethylene octadecyl phenyl ether, and polyoxyethylene eicosyl phenyl ether.

[0063] The nonionic surfactants used in this invention can be commercially available products. Examples of ether-type ethers include: "NONION K-204" (polyoxyethylene lauryl ether), "NONION K-220" (polyoxyethylene lauryl ether), "NONION K-230", "PERSOFT NK-60", "PERSOFT NH-90C", "PERSOFT NK-100", "PERSOFT NK-100", "NONION EAD-13" (all polyoxyethylene alkyl ethers), "NONION P-208", "NONION P-210", "NONION P-213" (all polyoxyethylene cetyl ethers), "NONION E-202", "NONION E-202S", "NONION E-205", "NONION E-205S", "NONION E-212", and "NONION E-202S" manufactured by Nippon Oil Co., Ltd. E-215, NONION E-230 (all are polyoxyethylene oil-based ethers), NONION S-202, NONION S-207, NONION S-215, NONION S-220 (all are polyoxyethylene stearyl ethers), NONION ID-203, NONION ID-206, NONION ID-209 (all are polyoxyethylene isodecyl ethers), NONION EH-204 (polyoxyethylene 2-ethylhexyl ether), NONION EH-208 (polyoxyethylene 2-ethylhexyl ether), DISPANOL TOC, NONION ET-505, NONION ET-507, NONION ET-510, NONION ET-512, NONION ET-515, NONION ET-518 (the above are polyoxyethylene-polyoxypropylene-alkyl ethers), UNILUBE MS-70K (polyoxypropylene stearyl ether), DISPANOL 16, DISPANOL 16A, DISPANOL LS-100, NONION MN-811, DISPANOL WI-106, DISPANOL WI-115, DISPANOL W1-133, and PIONIN D-1004 (polyoxyethylene octyl ether) manufactured by Takemoto Oils Co., Ltd., etc.

[0064] Furthermore, examples include ADEKA Corporation's "LB-220", "LB-53B", "LB-720", "LB-820", "LB-54C", "LB-83", "LB-93", "LB-103", "LB-1220", "LB-1520" (all of which are polyoxyalkylene lauryl ether), "LA-675B", "LA-775", "LA-875", "LA-975", and "LA-1275" (all of which are polyoxyalkylene lauryl ether). These include polyoxyethylene lauryl ether, "OA-7" (polyoxyethylene oil-based ether), "TN-40", "TN-80", "TN-100", "TO-120", "UA-70N", "UA-90N", "LO-3", "LO-7" (the above are primary alcohol ethoxylates), "SO-80", "SO-105", "SO-120", "SO-135", "SO-145", "SO-160" (the above are secondary alcohol ethoxylates), etc.

[0065] Examples of ester-type esters include NONION L-2, NONION L-4 (all polyoxyethylene monolaurate), NONION S-2, NONION S-4, NONION S-6, NONION S-15, NONION S-15K, NONION S-15.4, NONION S-15.4V, NONION S-40 (all polyoxyethylene monostearate), NONION O-2, NONION O-3, NONION O-4, and NONION O-6 (all polyoxyethylene monooleate), and ADEKA Co., Ltd.'s OEG-102 (polyoxyethylene monooleate).

[0066] Examples of sorbitol esters include NONION CP-08R (sorbitol monocaprylate), NONION LP-20R (sorbitol monolaurate), NONION LP-20R (sorbitol monolaurate), NONION MP-30R (sorbitol monomyristate), NONION PP-40R PELLET (sorbitol monopalmitate), NONION SP-60R PELLET (sorbitol monostearate), NONION OP-80R (sorbitol monooleate), and NONION OP-83RAT (sorbitol sesquioleate). OP-85R (sorbitol trioleate), or S-20 (sorbitol laurate), S-60 (sorbitol stearate), and S-80 (sorbitol oleate) manufactured by ADEKA Co., Ltd.

[0067] Examples of polyoxyethylene sorbitol ester-ethylene oxide addition products include "NONION LT-221" (polyoxyethylene sorbitol monolaurate), "NONION ST-221" (polyoxyethylene sorbitol monostearate), "NONION OT-221" (polyoxyethylene sorbitol monooleate), "WILSURF TF-20" (polyoxyethylene sorbitol monolaurate), "WILSURF TF-60" (polyoxyethylene sorbitol monostearate), and "WILSURF TF-80" (polyoxyethylene sorbitol monooleate), manufactured by Nippon Oil Co., Ltd., and "T-81" (polyoxyethylene sorbitol monooleate) manufactured by ADEKA Co., Ltd.

[0068] Examples of diester-type products include "UNISTER E-275" (ethylene glycol distearate), "NONION DS-60HN" (polyethylene glycol distearate), "NONION DO-4" (polyethylene glycol dioleate), "NONION DO-6" (polyethylene glycol dioleate), "UNISAFE NKL-9520" (polypropylene glycol distearate), and "UNISAFE NUL-6589" (polypropylene glycol disuccinate), all manufactured by Nippon Oil Co., Ltd.

[0069] Examples of monoglyceride types include "MONOGLY D" (glyceryl monostearate), "MONOGLY MB" (glyceryl monostearate), and "MONOGLY M-14" (glyceryl monomyristate) manufactured by Nippon Oil Co., Ltd.

[0070] Examples of monoglyceride-ethylene oxide addition products include "UNIGLY MK-207" (polyoxyethylene coconut oil fatty acid glyceride), "UNIGLY MK-230" (polyoxyethylene coconut oil fatty acid glyceride), and "UNIGLY MK-278" (polyoxyethylene coconut oil fatty acid glyceride) manufactured by Nippon Oil Co., Ltd., and "NK-3", "NK-4", and "NK-7" manufactured by ADEKA Co., Ltd. (the above are glyceride ester ethylene oxide adducts).

[0071] Examples of triglyceride-ethylene oxide addition products include "UNIOX HC-8", "UNIOX HC-40", and "UNIOX HC-60" (all of which are polyoxyethylene hydrogenated castor oil) manufactured by Nippon Oil Co., Ltd.

[0072] Examples of sorbitan ester-ethylene oxide addition products include "UNIOX ST-30E", "UNIOX ST-40E", and "UNIOX ST-60E" (all of which are polyoxyethylene tetraoleic acid) manufactured by Nippon Oil Co., Ltd.

[0073] Examples of polyglycerol alkyl esters include "UNIGLY GO-102R" (polyglycerol oleate), "UNIGLY GO-106" (polyglycerol oleate), "UNIGLY GL-106" (polyglycerol laurate), and "UNIGLY GS-106" (polyglycerol stearate) manufactured by Nippon Oil Co., Ltd.

[0074] Examples of polyetheramines include "NYMEEN L-201" (N-hydroxyethyl laurylamine), "NYMEEN L-202", "NYMEEN L-207" (all polyoxyethylene laurylamine), "NYMEEN L-703" (polyoxyethylene-polyoxypropylene-laurylamine), "NYMEEN F-202", "NYMEEN F-215" (all polyoxyethylene alkyl (coconut)amine), "NYMEEN S-202", "NYMEEN S-204", "NYMEEN S-210", "NYMEEN S-215", "NYMEEN S-220" (all polyoxyethylene stearylamine), "NYMEEN O-205" (polyoxyethylene oil-based amine), "NYMEEN T2-202", "NYMEEN T2-210", and "NYMEEN..." manufactured by Nippon Oil Co., Ltd. "T2-230" (the above are polyoxyethylene tallow alkylamine), "NYMEEN T2-230", "NYMEEN DT-203", "NYMEEN DT-208" (polyoxyethylene-alkylpropylene diamine), etc.

[0075] Examples of alkanolamide-type products include: STAFOAM F (coconut oil fatty acid diethanolamide, 1:2 type), STAFOAM T (tallow fat fatty acid diethanolamide, 1:2 type), STAFOAM DL (laurate diethanolamide), STAFOAM DF-1, STAFOAM DF-2, STAFOAM DF-4, STAFOAM DFC (all coconut oil fatty acid diethanolamide), STAFOAM DO, STAFOAM DOS (all oleic acid diethanolamide), STAFOAM MF PELLET (coconut oil fatty acid monoethanolamide), and STAFOAM... LIPA (isopropanol laurate), etc., or CO (coconut oil fatty acid diethanolamine, 1:2 type) and COA (coconut oil fatty acid diethanolamine, 1:1 type) manufactured by ADEKA Co., Ltd.

[0076] Examples of alkanolamide-ethylene oxide addition products include "NYMID MF-203", "NYMID MF-210", and "NYMID MT-215" manufactured by Nippon Oil Co., Ltd. (these are polyoxyethylene fatty acid-monoethanolamides).

[0077] Examples of amine oxide-type products include "UNISAFE A-LM" (dimethyl lauryl-amine oxide aqueous solution), "UNISAFE A-SM" (dimethyl stearyl-amine oxide aqueous solution), "UNISAFE A-LE" (dihydroxyethyl lauryl-amine oxide aqueous solution), and "UNISAFE WHS-10" (dihydroxyethyl lauryl-amine oxide aqueous solution) manufactured by Nippon Oil Co., Ltd.

[0078] Examples of polyethylene glycol-polypropylene glycol-block ether type (polyoxyethylene-polyoxypropylene-block copolymer type) products include "PLONON#102", "PLONON#104", "PLONON#201", "PLONON#202B", "PLONON#204", "PLONON#208", "UNILUBE 70DP-600B", and "UNILUBE" manufactured by Nippon Oil Co., Ltd. 70DP-950B (the above are polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymers), etc., or "L-23", "L-31", "L-44", "L-61", "L-62", "L-64", "L-71", "L-72", "L-101", "L-121", "P-84", "P-85", "P-103", "F-68", "F-88", "F-108", etc. (the above are polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymers), "25R-1", "25R-2", "17R-2", "17R-3", "17R-4" (the above are polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymers), etc. manufactured by ADEKA Co., Ltd.

[0079] Examples of ethylenediamine-based products include "TR-701", "TR-702", and "TR-704" manufactured by ADEKA Inc. (these are adducts of ethylenediamine in polyoxyethylene and polyoxypropylene block copolymers).

[0080] Furthermore, polyethylene glycol, polypropylene glycol, and other substances with hydrophobic groups are also preferred nonionic surfactants in this invention (for example, ether-type nonionic surfactants with long-chain alkyl groups bonded to polyethylene glycol or aryl groups substituted with long-chain alkyl groups as hydrophobic groups). Commercially available polyethylene glycol (PEG) and polypropylene glycol (PPG) products with hydrophobic groups include, for example, "Pegnol 14-0", "Pegnol 24-0", "Pepol A-0638", "Pepol B-181", "Pepol B-182", "Pepol B-184", "Pepol B-188", and "Pepol BEP-0115" manufactured by Toho Chemical Industry Co., Ltd., or "NONION A-10R", "NONION A-13P", "NONION A-25B", "NONION C-2300", "NONION DIS-400", "NONION DIS-600", "NONION DL-4HN", "NONION DL-40HN", "NONION DO-4HN", and "NONION DO-40HN" manufactured by Nippon Oil Co., Ltd. DP-1.5HN", "NONION DS-4HN", "NONION DS-40HN", "NONION DS-110HN", "NONION IS-2", "NONION IS-4", "NONION IS-6", "NONION IS-15.4", etc.

[0081] In addition, polymeric compounds having side chains with oxidized alkenyl or polyoxyalkylene groups, such as compounds having the fragment shown in the following general formula (3), are also preferred nonionic surfactants in this invention.

[0082] [Chemical Formula 4] .

[0083] (In the formula, A1 represents an alkyl group, R2 represents hydrogen, alkyl or aryl, and n represents an integer from 1 to 100. Also, the alkyl group represented by A1-O can be a group formed from one alkyl group such as ethylene oxide or propylene oxide, or it can be a group composed of multiple alkyl groups such as ethylene oxide and propylene oxide).

[0084] Other nonionic surfactants besides those mentioned above include commercially available polyoxyethylene styrene phenyl ethers such as PIONIN D-6112, PIONIN D-6115, PIONIN D-6120, PIONIN D-6131, PIONIN D-6512, TAKESURF D-6413, DTD-51, and PIONIN D-6320 (all manufactured by Takemoto Oils & Fats Co., Ltd.); TS-1500, TS-2000, TS-2600, and SM-174N (all manufactured by Toho Chemical Co., Ltd.); and EMULGEN A-60, EMULGEN A-90, and EMULGEN A-500 (all manufactured by Kao Corporation). In addition, commercially available products of the aryl phenyl ether type include "PIONIN D-7240" (polyoxyethylene naphthyl ether) manufactured by Takemoto Oils & Fats Co., Ltd., YG-15, Y-PE polyoxyethylene monophenyl ether (manufactured by Yokkaichi Synthetic Co., Ltd.), diethylene glycol monophenyl ether (manufactured by TCI Co., Ltd.), dipropylene glycol phenyl ether (manufactured by DOW Co., Ltd.), and polyoxyethylene (10) octylphenyl ether (manufactured by Fujifilm and Koko Pure Chemical Co., Ltd.).

[0085] In this invention, the nonionic surfactant is preferably a nonionic surfactant with a polyoxyalkylene (polyoxyalkylene) backbone, and the polyoxyalkylene backbone of the nonionic surfactant with the polyoxyalkylene backbone is preferably a polyoxyethylene backbone and / or a polyoxypropylene backbone.

[0086] In one embodiment of the present invention, component (D) is preferably a polyoxyalkylene ether or a polyoxyalkylene aryl ether (preferably the polyoxyalkylene portion is polyethylene glycol or polypropylene glycol), more preferably a polyoxyalkylene aryl ether (e.g., polyoxyethylene alkylphenyl ether, polyoxyethylene styrene phenyl ether, etc.), and even more preferably a polyoxyalkylene aryl ether having the following structure.

[0087] [Chemical Formula 5] .

[0088] (In the formula, n is an integer from 1 to 10, R1 and R2 are independently hydrogen atoms or methyl groups, and Ar is an optional aromatic group with substituents). It is inferred that these nonionic surfactants exist near the surface of calcium oxide via hydrophilic alkyl groups and near hydrophobic olefin polymers via aromatic groups, thereby preventing the aggregation of calcium oxide / gelation of the coating composition. However, the present invention is not limited to this inference.

[0089] It is preferable that R1 and R2 are both hydrogen atoms.

[0090] Examples of aromatic groups, denoted by Ar as "optionally substituent aromatic groups", include phenyl and naphthyl groups. Examples of substituents include styryl, cumyl, and alkyl groups (e.g., methyl, ethyl, etc.). The number of substituents is, for example, 1 to 5. When multiple substituents are present, they may be the same or different. Phenyl, naphthyl, polystyrylphenyl, cumylphenyl, alkylphenyl, etc., are preferred as "optionally substituent aromatic groups".

[0091] Preferred anionic surfactants in this invention include, for example, saturated or unsaturated fatty acids, alkylbenzene sulfonic acids, dialkyl sulfosuccinic acids, α-olefin sulfonic acids, alkane sulfonic acids, N-acetylmethane taurine, alkyl sulfuric acid, alkenyl sulfuric acid, polyoxyalkylene alkyl ether sulfuric acid, polyoxyalkylene alkenyl ether sulfuric acid, polyoxyalkylene alkenyl aryl ether sulfuric acid, polyoxyalkylene alkenyl aryl ether sulfuric acid, polyoxyalkylene mono- or dialkyl ether phosphoric acid, polyoxyalkylene mono- or dialkyl ether phosphoric acid, polyoxyalkylene mono- or diphenyl ether phosphoric acid, and polyoxyalkylene alkyl Ether carboxylic acids, polyoxyalkyl alkenyl ether carboxylic acids, polyoxyalkyl alkenyl ether acetic acid, polyoxyalkyl alkenyl ether acetic acid, polyoxyalkyl alkenyl amide ether carboxylic acids, polyoxyalkyl alkenyl amide ether carboxylic acids, polyoxyalkyl arylphenyl ether sulfuric acid, polyoxyalkyl arylphenyl ether phosphoric acid, alkyl naphthalene sulfonic acid, and various salts thereof (fatty acid salts, carboxylates, sulfonates, succinates), polycarboxylic acid esters, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, phosphate esters, etc.

[0092] In this invention, the anionic surfactant is preferably anionic surfactant having a carboxylic acid group, a phosphate group, or a sulfonic acid group. Examples of commercially available products include, for instance, AJISPER PA111 (a higher fatty acid ester) manufactured by Ajinomoto Fine-Techno Co., Inc., and the MALIALIM (registered trademark) series manufactured by Nippon Oil Co., Ltd. ("MALIALIM AKM1511-60", "MALIALIM AKM0531", "MALIALIM AFB-1521", "MALIALIM A-60", "MALIALIM A-20", etc.).

[0093] From the viewpoint of preventing calcium oxide agglomeration / gelation of the composition coating, the content of component (D) is preferably 5 to 25% by mass relative to 100% by mass of the non-volatile components of the sealing composition, more preferably 7 to 23% by mass, and even more preferably 10 to 20% by mass.

[0094] <Other Ingredients> To the extent that it does not impair the effects of the present invention, the sealing composition of the present invention may also contain components other than components (A) to (D) (hereinafter sometimes referred to as "other components"). Examples of other components include, for example, liquid olefin polymers, adhesive agents, epoxy-modified olefin polymers with a number average molecular weight of less than 10,000, antioxidants, curing accelerators, plasticizers, etc. Only one of these components may be used, or two or more may be used in combination.

[0095] (Liquid olefin polymers (hereinafter also referred to as "(E) components)) Component (E) is a liquid olefin polymer that does not include components (A) and (B). By incorporating component (E), the formed sealing layer can be endowed with good adhesion and flexibility.

[0096] In this invention, "liquid" in "liquid olefin polymer" refers to a viscosity of 5000 Pa·s or less at 25°C. Furthermore, in this invention, "viscosity at 25°C" refers to the viscosity calculated by multiplying the dynamic viscosity at 25°C, measured using a dynamic viscoelasticity measuring device, by the density. Examples of dynamic viscoelasticity measuring devices include, for instance, a rheometer manufactured by TA Instruments (trade name: DISCOVERY HR-2).

[0097] In this invention, liquid olefin polymers having anhydride and / or carboxyl groups with a number average molecular weight of less than 10,000 are classified as component (A). Furthermore, in this invention, liquid olefin polymers with a number average molecular weight of 10,000 or more are classified as component (B). Therefore, component (E) in this invention refers to liquid olefin polymers other than components (A) and (B).

[0098] From the viewpoint of good sealing and flexibility of the formed sealing layer, the viscosity of component (E) at 25°C is preferably 5 to 5,000 Pa·s, more preferably 10 to 4,000 Pa·s, and even more preferably 20 to 3,000 Pa·s.

[0099] From the viewpoint of good coatability of the coating of the sealing composition, the number of components (E) with an average molecular weight is preferably 100 to 50,000, more preferably 200 to 30,000, and even more preferably 300 to 20,000.

[0100] (E) The ingredients may be commercially available products. Examples of such commercially available products include, for example, ENEOS's "HV-300" (liquid polybutene), ENEOS's "HV-1900" (liquid polybutene), ENEOS's "HV-50" (liquid polybutene), ENEOS's "HV-35" (liquid polybutene), Kothari's "950MW" (liquid polybutene), Kothari's "2400MW" (liquid olefin polymer), and INEOSCO's... H-1900 (liquid polybutene), INEOSCO's H-6000 (liquid polybutene), INEOSCO's H-18000 (liquid polybutene), Nippon Yukoshi's 200N (liquid polybutene), Nippon Soda's BI-2000 (hydrogenated polybutadiene), Nippon Soda's BI-3000 (hydrogenated polybutadiene), Nippon Soda's GI-3000 (hydrogenated polybutadiene), Mitsui Chemicals' LUCANT LX100 (liquid olefin polymer), Mitsui Chemicals' LUCANT LX400 (liquid olefin polymer), Idemitsu Showa Shell's Poly bd R-45HT (butadiene-based liquid rubber), Idemitsu Showa Shell's Poly bd R-15HT (butadiene-based liquid rubber), Idemitsu Showa Shell's Poly bd R-15HT (butadiene-based liquid rubber), Idemitsu Showa Shell's Poly bd R-45HT (butadiene-based liquid rubber). "ip" (liquid polyisoprene), "B-1000" (liquid polybutadiene) manufactured by Nippon Soda Co., Ltd., "B-3000" (liquid polybutadiene) manufactured by Nippon Soda Co., Ltd., "G-3000" (liquid polybutadiene) manufactured by Nippon Soda Co., Ltd., "LIR-30" (liquid polyisoprene) manufactured by Kuraray Co., Ltd., "LIR-390" (liquid polyisoprene) manufactured by Kuraray Co., Ltd., "LIR-290" (liquid polyisoprene) manufactured by Kuraray Co., Ltd., "LBR-302" (liquid polybutadiene) manufactured by Kuraray Co., Ltd., "LBR-305" (liquid polybutadiene) manufactured by Kuraray Co., Ltd., "LBR-361" (liquid polybutadiene) manufactured by Kuraray Co., Ltd., "L-SBR-820" (liquid styrene-butadiene random copolymer) manufactured by Kuraray Co., Ltd., CRAY VALLEY's "Ricon 154" (liquid butadiene) and CRAY VALLEY's "RICON 184" (liquid styrene-butadiene random copolymer), etc.

[0101] (E) The preferred component is liquid polybutene and / or hydrogenated polybutadiene, and more preferably liquid polybutene.

[0102] When using component (E), from the viewpoint of good sealing and flexibility of the formed sealing layer, its content relative to 100% by mass of the non-volatile components of the sealing composition is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less. In one embodiment of the present invention, the content of component (E) relative to 100% by mass of the non-volatile components of the sealing composition is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 30% by mass.

[0103] (Adhesion-enhancing agent (hereinafter also referred to as "(F) component)") Adhesion promoters are components that impart adhesiveness to sealing components. Examples of adhesion promoters include rosin-based resins, terpene resins, modified terpene resins (hydrogenated terpene resins, terpene phenol copolymer resins, aromatic modified terpene resins, etc.), petroleum resins (aliphatic petroleum resins, hydrogenated petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, copolymer petroleum resins), coumarone-indene resins, alkylphenol resins, xylene resins, etc.

[0104] Adhesion additives can be commercially available products. Examples of such commercially available products include, for example, the following rosin-based resins: PINECRYSTAL ME-H, PINECRYSTAL ME-D, PINECRYSTAL ME-G, PINECRYSTAL KR-85, PINECRYSTAL KE-311, PINECRYSTAL KE-359, PINECRYSTAL D-6011, PINECRYSTAL PE-590, PINECRYSTAL KE-604, and PINECRYSTAL PR-580 (all manufactured by Arakawa Chemical Industry Co., Ltd.).

[0105] 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 manufactured by Yasuhara Chemical Co., Ltd.).

[0106] Examples of hydrogenated terpene resins include the CLEARON P, CLEARON M, and CLEARON K series (all manufactured by Yasuhara Chemical Co., Ltd.).

[0107] Examples of terpene phenol copolymer resins include YS POLYSTER 2000, POLYSTER U, POLYSTER T, POLYSTER S, and Mighty Ace G (all manufactured by Yasuhara Chemical Co., Ltd.).

[0108] Examples of aromatic modified terpene resins include YS RESIN TO85, YS RESIN TO105, YS RESIN TO115, and YS RESIN TO125 (all manufactured by Anwha Chemical Co., Ltd.).

[0109] Examples of hydrogenated petroleum resins include Escorez 5300 and 5600 series (both manufactured by ExxonMobil); T-REZ OP501, T-REZ PR803, T-REZ HA085, T-REZ HA103, T-REZ HA105, and T-REZ HA125 (all hydrogenated dicyclopentadiene petroleum resins manufactured by ENEOS); Quintone 1325 and Quintone 1345 (both manufactured by Zeon Corporation of Japan); I-MARV S-100, I-MARV S-110, I-MARV P-100, I-MARV P-125, and I-MARV P-140 (all hydrogenated dicyclopentadiene petroleum resins manufactured by Idemitsu Kosan Corporation); and ARKON P-90, ARKON P-100, ARKON P-115, ARKON P-125, and ARKON P-125. P-140, ARKON M-90, ARKON M-100, ARKON M-115, ARKON M-135, TFS13-030 (all manufactured by Arakawa Chemical Industry Co., Ltd.), etc.

[0110] Examples of aromatic petroleum resins include ENDEX 155 (manufactured by Eastman Chemical Company), Neopolymer L-90, Neopolymer 120, Neopolymer 130, Neopolymer 140, Neopolymer 150, Neopolymer 170S, Neopolymer 160, Neopolymer E-100, Neopolymer E-130, Neopolymer M-1, Neopolymer S, Neopolymer S100, Neopolymer 120S, Neopolymer 130S, and Neopolymer EP-140 (all manufactured by ENEOS); Petcoal LX, Petcoal 120, Petcoal 130, and Petcoal 140 (all manufactured by Tosoh Corporation); and T-REZ RB093, T-REZ RC100, T-REZ RC115, T-REZ RC093, and T-REZ... RE100 (all manufactured by ENEOS Corporation), etc.

[0111] Examples of copolymerized petroleum resins include T-REZ HB103, T-REZ HB125, T-REZ PR801, T-REZ PR802, and T-REZ RD104 (all manufactured by ENEOS); Petrotack 60, Petrotack 70, Petrotack 90, Petrotack 90HS, Petrotack 90V, and Petrotack 100V (all manufactured by Tosoh Corporation); and Quintone D100 (manufactured by Zeon Corporation of Japan).

[0112] From the viewpoint of the heat resistance of the formed sealing layer, the softening point of the adhesive is preferably 50~200℃, more preferably 90~180℃, and even more preferably 100~170℃. Alternatively, the softening point can be determined according to JIS K2207 using the ring and ball method.

[0113] When using an adhesive agent, from the viewpoint of the adhesion and sealing properties of the formed sealing layer, the content of the non-volatile component relative to 100% by mass of the sealing composition is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and even more preferably 5 to 30% by mass.

[0114] (Epoxy-modified olefin polymers with a number average molecular weight of less than 10,000) "Epoxy-modified olefin polymer" is synonymous with "olefin polymer having epoxy groups". Epoxy-modified olefin polymers with a number average molecular weight of less than 10,000 are otherwise as described in component (B2) above, except that their number average molecular weight is less than 10,000. The epoxy groups of this epoxy-modified olefin polymer form a cross-linked structure through reaction with the anhydride / carboxyl groups in olefin polymers having anhydride and / or carboxyl groups (component (B1) and component (A) as appropriate), which can improve the dispersibility of calcium oxide (component (C)) in the sealing composition and the water vapor permeation barrier properties of the resulting sealing layer.

[0115] (Antioxidants) In this invention, the antioxidant is not particularly limited, and known substances can be used. Examples include "Irganox 1010" (hindered phenolic antioxidant) manufactured by BASF. When using an antioxidant, its content relative to 100% by mass of the non-volatile components of the sealing composition is preferably 0.01 to 5% by mass, more preferably 0.05 to 2.5% by mass, and even more preferably 0.10 to 2% by mass.

[0116] (hardening accelerator) In this invention, a curing accelerator may be used to promote the crosslinking reaction between the anhydride and / or carboxyl groups of components (B1) and (A) and the epoxy groups of component (B2) (and, depending on the case, epoxy-modified olefin polymers with a number average molecular weight of less than 10,000). Examples of curing accelerators include imidazole compounds, tertiary / quaternary amine compounds, dimethylurea compounds, organophosphorus compounds, etc.

[0117] Examples of imidazole compounds include 1H-imidazolium, 2-methylimidazolium, 2-phenyl-4-methylimidazolium, 2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 2-undecylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-phenyl-4,5-bis(hydroxymethyl)imidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 2-phenylimidazolium, 2-dodecylimidazolium, 2-heptadecanylimidazolium, 1,2-dimethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, etc. 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, and 2MA-OK (all manufactured by Shikoku Chemical Industry Co., Ltd.).

[0118] There are no particular limitations on the tertiary / quaternary amine compounds, and examples include quaternary ammonium salts such as tetramethylammonium bromide, tetrabutylammonium bromide, and triethylmethylammonium·2-ethylhexanoate; diazabicyclic compounds such as DBU (1,8-diazabicyclo[5.4.0]undecene-7), DBN (1,5-diazabicyclo[4.3.0]nonene-5), DBU-phenol salts, DBU-octanoate, DBU-p-toluenesulfonate, DBU-formate, and DBU-linear phenolic resin salts; tertiary amines or salts of benzyl dimethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol (TAP); dimethylurea compounds such as aromatic dimethylurea and aliphatic dimethylurea; etc.

[0119] Examples of dimethylurea compounds include aromatic dimethylureas such as DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) and U-CAT3512T (manufactured by San-Apro); and aliphatic dimethylureas such as U-CAT3503N (manufactured by San-Apro). From a curing perspective, aromatic dimethylureas are preferred.

[0120] Examples of organophosphorus compounds include: triphenylphosphine, tetraphenylphosphine tetratolylborate, tetraphenylphosphine tetraphenylborate, tri-tert-butylphosphine tetraphenylborate, (4-methylphenyl)triphenylphosphine thiocyanate, tetraphenylphosphine thiocyanate, butyltriphenylphosphine thiocyanate, and triphenylphosphine triphenylborane. Specific examples of organophosphorus compounds include TPP, TPP-MK, TPP-K, TTPub-K, TPP-SCN, and TPP-S (all manufactured by Beixing Chemical Industry Co., Ltd.).

[0121] When using a curing accelerator, in order to promote the crosslinking reaction of the anhydride and / or carboxyl groups of components (B1) and (A) with the epoxy groups of component (B2) (and, where applicable, epoxy-modified olefin polymers with a number average molecular weight of less than 10,000), its content is preferably 0.001 to 5% by mass, more preferably 0.001 to 2.5% by mass, and even more preferably 0.001 to 1% by mass, relative to 100% by mass of the non-volatile components of the sealing composition.

[0122] (Plasticizer) Examples of plasticizers include paraffin-based processed oils, naphthenic-based processed oils, fluid paraffin, mineral oils such as petrolatum, and vegetable oils such as castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, and olive oil.

[0123] When using plasticizers, from the viewpoint of the flexibility of the formed sealing layer, the content of the plasticizer is preferably 2 to 30% by mass relative to 100% by mass of the non-volatile components of the sealing composition, more preferably 4 to 25% by mass, and even more preferably 5 to 20% by mass.

[0124] [Manufacturing method of sealing components] Hereinafter, a preferred method for manufacturing the sealing composition of the present invention will be described. However, the sealing composition of the present invention may also be manufactured using methods other than those described below.

[0125] A preferred method for manufacturing the sealing composition of the present invention (hereinafter referred to as "the manufacturing method of the present invention") includes: a step of pulverizing a mixture comprising an olefinic polymer having an anhydride group and / or a carboxyl group with a number average molecular weight of less than 10,000 (i.e., component (A)), a polymer with a number average molecular weight of 10,000 or more (i.e., component (B)), calcium oxide with a median particle size of more than 300 nm, a nonionic surfactant and / or anionic surfactant (i.e., component (D)), and an organic solvent. Alternatively, the sealing composition of the present invention can be manufactured by mixing calcium oxide with a median particle size of less than 300 nm (i.e., component (C)) and components other than component (C). However, in this simple mixing, it is difficult to achieve good dispersion of fine calcium oxide in the sealing composition compared to the case described above. Furthermore, the large surface area of ​​fine calcium oxide results in increased hygroscopicity. To avoid such hygroscopicity, the processability of fine calcium oxide during the manufacturing of the sealing composition is also worse than that of calcium oxide of normal size. Therefore, the sealing composition of the present invention is preferably manufactured through the aforementioned steps. Hereinafter, the mixtures used in the manufacturing method of the present invention, such as those for pulverization, will be described sequentially.

[0126] A mixture for pulverization can be prepared by mixing calcium oxide with a median particle size exceeding 300 nm, component (A), component (D), and an organic solvent. Alternatively, an olefinic polymer having anhydride and / or carboxyl groups can be further mixed as component (B1) to prepare the mixture for pulverization. The content of the aforementioned calcium oxide is preferably 3-75% by mass, more preferably 5-70% by mass, relative to the overall mixture for pulverization. The content of component (A) is preferably 3-40% by mass, more preferably 5-35% by mass, relative to the overall mixture for pulverization. The content of component (D) is preferably 3-40% by mass, more preferably 5-35% by mass, relative to the overall mixture for pulverization. The content of the organic solvent is preferably 20-80% by mass, more preferably 30-70% by mass, relative to the overall mixture for pulverization. Other components (the "other components" mentioned above) may also be added to the mixture for pulverization. The order of addition of the components is not particularly limited; the components may be added sequentially or simultaneously.

[0127] Examples of organic solvents that can be used in the manufacturing method of this invention include: ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellolytic agents such as cellolytic agents; carbitols such as butyl carbitol; aromatics such as toluene and xylene; and aceamines such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Commercially available organic solvents can be used, such as "Swasol" manufactured by Maruzen Petrochemical Co., Ltd., and "Ipzole" manufactured by Idemitsu Kosan Co., Ltd. Only one organic solvent may be used, or two or more may be used in combination.

[0128] The grinding process can be carried out using a known grinder. Through grinding, calcium oxide is pulverized and dispersed in the mixture. Examples of known grinders include wet bead mills, planetary ball mills, attritors, air jet mills, ball mills, and vibratory ball mills. Examples of bead materials include zirconium oxide, alumina, glass, and steel. The bead diameter is, for example, approximately 0.03 to 5 mm. The rotational speed of the bead mill's shaft is, for example, approximately 10 to 10,000 rpm. The flow rate of the mixture for grinding into the grinding chamber of the bead mill is, for example, approximately 0.1 to 10,000 kg / hour. In wet grinding using a bead mill, to suppress the temperature rise of the mixture during grinding, it is preferable to perform cooling with cooling water simultaneously. The temperature of the cooling water is, for example, approximately 0 to 40°C.

[0129] Furthermore, the pulverized mixture can be mixed with any component. For example, a liquid olefin polymer, an adhesive additive, etc., can be added to and mixed with the pulverized mixture. When the sealing composition includes an epoxy-based olefin polymer as component (B2), it is preferable to mix the pulverized mixture with component (B2) to prevent cross-linking reactions due to heat during pulverization. That is, the manufacturing method of the present invention preferably further includes the step of mixing the pulverized mixture with an epoxy-based olefin polymer (i.e., component (B2)). Additionally, an olefin polymer with anhydride groups and / or carboxyl groups as component (B1) can also be mixed with the pulverized mixture. To avoid an increase in the viscosity of the mixture during pulverization, component (B1) is preferably mixed with the pulverized mixture. There is no particular limitation on the order of addition of the components; the components can be added sequentially or simultaneously.

[0130] The coating containing an organic solvent obtained as described above can have some or all of the organic solvent removed by drying or the like. The sealing composition of the present invention can be used in liquid form such as a coating or in solid form such as a film.

[0131] [Sealing sheet] The present invention also provides a sealing sheet having a laminated structure comprising a support body and a sealing layer formed from 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 can have a laminated structure comprising a support body, a sealing layer, and a protective sheet in sequence. Other layers may also exist between the support body and the sealing layer, and between the sealing layer and the protective sheet. Examples of other layers include, for example, an adhesive layer, a release layer, and a sealing layer formed from a sealing composition that does not contain calcium oxide.

[0132] The haze of the sealing layer is preferably below 60%, more preferably below 40%, and even more preferably below 30%. There is no particular limitation on the lower limit of the haze of the sealing layer; for example, the haze may be above 0%. This haze can be measured according to JIS K 7136. Specifically, the haze can be measured using the method described in the Examples section below, with glass as a reference and using D65 light.

[0133] Examples of plastic films that can serve as supports and protective sheets include: polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; cyclic olefin polymers; polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate; polycarbonate; and polyimide. Both the support and the protective sheet can be single-layer films or multilayer films.

[0134] As a support and protective sheet, a low-permeability membrane with a barrier layer, or a laminated membrane of a low-permeability membrane with a barrier layer and other membranes, can be used. Examples of barrier layers include inorganic membranes such as silicon dioxide vapor-deposited films, silicon nitride films, and silicon oxide films. The barrier layer can be composed of multiple layers of inorganic membranes (e.g., silicon dioxide vapor-deposited films). Alternatively, the barrier layer can be composed of organic and inorganic materials, or it can be a composite multilayer of organic and inorganic membranes.

[0135] In the protective sheet, it is preferable that the surface in contact with the sealing layer undergoes a demolding process. On the other hand, the support body may or may not undergo a demolding process. Examples of demolding processes include those using silicone resin-based mold release agents, alkyd resin-based mold release agents, and fluoropolymer-based mold release agents.

[0136] The thickness of the support and the protective sheet is not particularly limited, but from the viewpoint of the processability of the sealing sheet, it is preferably 10 to 150 μm, and more preferably 20 to 100 μm. Alternatively, if the support and the protective sheet are laminated films, the aforementioned thickness refers to the thickness of the laminated film. On the other hand, from the viewpoint of its transparency, sealing, and tightness, the thickness of the sealing layer is preferably 2 to 100 μm, more preferably 2 to 75 μm, and even more preferably 3 to 50 μm.

[0137] [Manufacturing method for sealing sheets] The sealing sheet of the present invention can be manufactured, for example, as follows: a coating of the sealing composition obtained as described above is applied to a support to form a coating film, and the resulting coating film is dried to form a sealing layer. Alternatively, a sealing sheet having a laminated structure comprising a support, a sealing layer, and a protective sheet in sequence can be manufactured, for example, as follows: a coating is applied to one of the support and the protective sheet and dried to form a sealing layer, and the other of the support and the protective sheet is laminated onto the formed sealing layer.

[0138] When using component (B2), in order to allow the reaction of the epoxy groups of component (B2) with the anhydride groups and / or carboxyl groups of component (B1) (and, in case (A)), the drying of the coating (i.e., removal of the organic solvent) is preferably carried out by heating the coating. The heating temperature of the coating is preferably 50–200°C, more preferably 80–150°C, and the heating time is preferably 1–60 minutes, more preferably 5–30 minutes. The heating of the coating can be carried out under normal pressure or under reduced pressure.

[0139] The coating obtained by removing the organic solvent can also be further subjected to heating (aging). The heating temperature is preferably 80~200℃, more preferably 100~150℃, and the heating time is preferably 10~240 minutes, more preferably 30~180 minutes. The heating can be carried out under normal pressure or under reduced pressure.

[0140] [Electronic Devices] The present invention also provides an electronic device comprising a sealing layer formed by the sealing composition of the present invention. Examples of electronic devices include, for instance, organic EL devices, organic light-emitting diodes (OLEDs), solar cells (especially organic solar cells (organic thin-film solar cells (OPV), perovskite solar cells (PSC), dye-sensitized solar cells (DSSC))), sensor devices, and touch panels having conductive substrates. Preferably, the electronic device is an organic EL device or a solar cell, which has relatively low resistance to moisture. Example

[0141] The present invention will be described in more detail below with examples, but the present invention is not limited to the following examples and may be implemented by appropriate modifications within the scope of the context, all of which are included within the technical scope of the present invention. Also, unless otherwise specified, "parts" and "%" in the amounts of components and copolymer units refer to "parts by mass" and "% by mass," respectively.

[0142] <ingredients> The ingredients used in the examples and comparative examples are shown below; (A)Ingredients: <Olefin polymers with anhydride / carboxyl groups and Mn < 10,000> • "HV-300M" (manufactured by Toho Chemical Industry Co., Ltd.): Maleic anhydride modified liquid polybutene, anhydride group concentration 0.77 mmol / g, number average molecular weight 2,100.

[0143] (B1) Ingredients: <Olefin polymers with anhydride / carboxyl groups and Mn ≥ 10,000> • "ER645" (manufactured by Starlight PMC, maleic anhydride-butyl methacrylate random copolymer modified propylene-butene random copolymer, butyl methacrylate unit concentration: 0.32 mmol / g, anhydride group concentration: 1.18 mmol / g, number average molecular weight: 59,000, propylene unit / butene unit: 71% / 29%) (non-volatile components: 20%) • "ER661" (manufactured by Starlight PMC Corporation, maleic anhydride-butyl methacrylate random copolymer modified butyl rubber, butyl methacrylate unit concentration: 0.32 mmol / g, anhydride group concentration: 0.46 mmol / g, number average molecular weight: 40,000, isobutylene unit / isoprene unit: 98.9% / 1.1%) (non-volatile components: 35%).

[0144] (B2) Ingredients: <Olefin polymers with epoxy groups and Mn ≥ 10000> • "ER829" (manufactured by Starlight PMC, glycidyl methacrylate modified propylene-butene random copolymer, propylene unit / butene unit: 71% / 29%, epoxy group concentration: 0.64 mmol / g, number average molecular weight: 168,000) (non-volatile components: 15%) • "ER866" (manufactured by Starlight PMC, glycidyl methacrylate modified butyl rubber, epoxy group concentration: 1.63 mmol / g, number average molecular weight: 113,000, isobutylene unit / isoprene unit: 98.9% / 1.1%) (non-volatile components: 27.5%).

[0145] (B3) Ingredient: <Non-liquid olefin polymers with Mn ≥ 10,000 that do not contain any of the following groups: anhydride, carboxyl, and epoxy groups> • "BUTYL065" (Made by JSR Corporation, butyl rubber, isobutylene unit / isoprene unit: 98.7% / 1.3%).

[0146] (C) Ingredients: • Calcium oxide (manufactured by Yoshizawa Lime Industry Co., Ltd., median particle size: 2.1 μm).

[0147] (D) Ingredients: <Nonionic surfactants> • "DISPARLON DA-550" (manufactured by Kusumoto Chemical Co., Ltd.): Nonionic surfactant • "PIONIN D-7240" (manufactured by Takemoto Oils & Fats Co., Ltd.): Polyoxyethylene Naphthyl Ether • "PIONIN D-1004" (manufactured by Takemoto Oils & Fats Co., Ltd.): Polyoxyethylene octyl ether <Anionic surfactants> • "AJISPER PA111" (manufactured by Ajinomoto Fine Chemicals Co., Ltd.): acidic dispersant (acid value 35mgKOH / g).

[0148] (E) Ingredients: <Liquid Olefin Polymers> • "HV-1900" (manufactured by ENEOS, liquid polybutene, number average molecular weight: 2900, viscosity at 25°C: 460 Pa·s).

[0149] (F)Ingredients: <Adhesion-enhancing agent> • "ARKON P-125" (manufactured by Arakawa Chemical Industry Co., Ltd., hydrogenated petroleum resin, softening point: 125℃).

[0150] Other ingredients: Antioxidants • "Irganox 1010" (manufactured by BASF): Hindered phenolic antioxidant Hardening accelerator ･2,4,6-Tris(dimethylaminomethyl)phenol (manufactured by KAYAKU NOURYON, hereinafter abbreviated as "TAP"). <Hygroscopic fillers> • Semi-fired hydrotalcite (DHT-4C manufactured by Kyowa Chemical Industry Co., Ltd., median particle size: 400nm, BET specific surface area: 15m² / g) <Catonic surfactants> • "AJISPER PB821" (manufactured by Ajinomoto Fine Chemicals Co., Ltd.): Alkaline dispersant (amine value 10mgKOH / g, acid value 17mgKOH / g).

[0151] <Example 1> Prepare the coating with the blending ratio shown in the table below according to the following steps, and use the resulting coating to make a sealing sheet. Note that the amounts (parts) of each component listed in the table below indicate the amount of non-volatile components in the coating. Additionally, in the table below, calcium oxide is listed as "CaO," and its median particle size is indicated in parentheses.

[0152] Specifically, maleic anhydride-modified liquid polybutene (Toho Chemical Co., Ltd. "HV-300M"), calcium oxide (Yoshizawa Lime Industry Co., Ltd.), nonionic surfactant (Kusumoto Chemical Co., Ltd. "DISPARLON DA-550"), and toluene are mixed to obtain a mixture for pulverization (relative to the total content of the mixture: toluene: 56.5%, maleic anhydride-modified liquid polybutene: 9%, calcium oxide: 30%, nonionic surfactant: 4.5%).

[0153] The mixture for pulverization is fed into a wet bead mill (LABSTAR Mini LMZ015 manufactured by Ashizawa Finetech Co., Ltd.), and the filling beads (bead diameter: 0.1 mm) are used to make up about 60% of the effective volume of the pulverization chamber. The pulverization process is carried out to obtain a pulverized mixture in which calcium oxide is pulverized and dispersed.

[0154] A small amount of the pulverized mixture was taken and diluted 100 times with toluene to prepare a test sample. The median particle size of calcium oxide was determined and calculated using a MICROTRAC nanoparticle size analyzer, the "NANOTRAC WAVE," via dynamic light scattering. The result showed that the median particle size of calcium oxide was 200 nm.

[0155] To the pulverized mixture, a Swasol solution (60% non-volatile component) of an adhesion promoter (ARKON P-125 manufactured by Arakawa Chemical Industry Co., Ltd.), liquid polybutene (HV-1900 manufactured by ENEOS Corporation), glycidyl methacrylate-modified propylene-butene random copolymer (ER829 manufactured by Starlight PMC Corporation), maleic anhydride-butyl methacrylate-modified propylene-butene random copolymer (ER645 manufactured by Starlight PMC Corporation), hindered phenolic antioxidant (Irganox 1010 manufactured by BASF Corporation), and curing accelerator (TAP manufactured by KAYAKU NOURYON Corporation) were added. The resulting mixture was then mixed using a high-speed rotary mixer to obtain a coating for sealing.

[0156] A polyethylene terephthalate (PET) film (SP3000, manufactured by Toyo Textile Co., Ltd., PET film thickness: 50 μm) treated with an organosilicone mold release agent on one side, and a low-permeability PET film (TECHBARRIER HX, manufactured by Mitsubishi Chemical Co., Ltd., PET film thickness: 12 μm) were laminated together with the untreated side of SP3000 in contact with TECHBARRIER HX to create a laminated film, which was used as a support and protective sheet for a sealing sheet. Hereinafter, the "side of the laminated film treated with an organosilicone mold release agent" will be referred to as the "molding-treated side".

[0157] The obtained coating is evenly applied to the release surface of the laminated film using a die-casting machine, and then heated at 150°C for 10 minutes to obtain a sealing sheet with a sealing layer of 10 μm thickness.

[0158] <Example 2> Except for changing the amount of toluene solution of glycidyl methacrylate modified propylene-butene random copolymer (Starlight PMC Co., Ltd. "ER829") from 10 parts to 0 parts, a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0159] <Example 3> Except for changing the amount of toluene solution used in the maleic anhydride-butyl methacrylate random copolymer modified propylene-butene random copolymer (Starlight PMC Co., Ltd. "ER645") from 10 parts to 0 parts, a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0160] <Example 4> Except for changing "DISPARLON DA-550" (manufactured by Kusumoto Chemical Co., Ltd.) to "PIONIN D-7240" (manufactured by Takemoto Oil Co., Ltd.), a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0161] <Example 5> Except for changing "DISPARLON DA-550" (manufactured by Kusumoto Chemical Co., Ltd.) to "PIONIN D-1004" (manufactured by Takemoto Oil Co., Ltd.), a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0162] <Example 6> Except for changing "DISPARLON DA-550" (manufactured by Kusumoto Chemical Co., Ltd.) to "AJISPER PA111" (manufactured by Ajinomoto Fine Chemicals Co., Ltd.), a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0163] <Example 7> Except for changing the amount of "DISPARLON DA-550" (manufactured by Kusumoto Chemical Co., Ltd.) from 45 parts to 90 parts, a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0164] <Example 8> Except for changing the amount of "DISPARLON DA-550" (manufactured by Kusumoto Chemical Co., Ltd.) from 45 parts to 20 parts, a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0165] <Example 9> The glycidyl methacrylate-modified propylene-butene random copolymer (manufactured by Starlight PMC Co., Ltd., "ER829") was replaced with glycidyl methacrylate-modified butyl rubber (manufactured by Starlight PMC Co., Ltd., "ER866"), and the maleic anhydride-butyl methacrylate random copolymer-modified propylene-butene random copolymer (manufactured by Starlight PMC Co., Ltd., "ER645") was replaced with maleic anhydride-butyl methacrylate random copolymer-modified butyl rubber (manufactured by Starlight PMC Co., Ltd., "ER661"). Otherwise, the coating for sealing composition and the sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0166] <Example 10> Except for changing the amount of calcium oxide used from 300 parts to 150 parts, a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0167] <Example 11> Except for changing the amount of calcium oxide used from 300 parts to 45 parts, a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0168] <Example 12> Except for changing the toluene solution of glycidyl methacrylate-modified propylene-butene random copolymer (Starlight PMC Corporation "ER829") and the maleic anhydride-butyl methacrylate random copolymer-modified propylene-butene random copolymer (Starlight PMC Corporation "ER645") to glycidyl methacrylate-modified butyl rubber (Starlight PMC Corporation "ER866"), a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0169] <Example 13> Except for replacing the glycidyl methacrylate-modified propylene-butene random copolymer (Starlight PMC Corporation "ER829") and the maleic anhydride-butyl methacrylate-modified propylene-butene random copolymer (Starlight PMC Corporation "ER645") with butyl rubber (JSR Corporation "BUTYL065"), a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0170] <Example 14> Except for changing the amount of toluene solution of glycidyl methacrylate modified propylene-butene random copolymer (Starlight PMC Co., Ltd. "ER829") from 10 parts to 20 parts, a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0171] <Example 15> Except for the Swasol solution (non-volatile component: 60%) which does not contain the adhesive additive (ARKON P-125 manufactured by Arakawa Chemical Industry Co., Ltd.) in the pulverized mixture, a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0172] <Comparative Example 1> Except that glycidyl methacrylate-modified propylene-butene random copolymer (manufactured by Starlight PMC Co., Ltd. "ER829") and maleic anhydride-butyl methacrylate-modified propylene-butene random copolymer (manufactured by Starlight PMC Co., Ltd. "ER645") are not incorporated into the mixture after pulverization, a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm are prepared using the same method as in Example 1.

[0173] <Comparative Example 2> Except that maleic anhydride-modified liquid polybutene ("HV-300M" manufactured by Toho Chemical Industry Co., Ltd.) is not incorporated into the mixture used for pulverization, a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm are prepared using the same method as in Example 1.

[0174] <Comparative Example 3> Except that "DISPARLON DA-550" (manufactured by Kusumoto Chemical Co., Ltd.) is not added to the mixture used for pulverization, a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm are prepared using the same method as in Example 1.

[0175] <Comparative Example 4> In a Swasol solution (non-volatile component: 60%) of an adhesive additive (ARKON P-125 manufactured by Arakawa Chemical Industry Co., Ltd.), maleic anhydride-modified liquid polybutene (HV-300M manufactured by Toho Chemical Industry Co., Ltd.), liquid polybutene (HV-1900 manufactured by ENEOS Corporation), semi-burnt hydrotalcite (DHT-4C manufactured by Kyowa Chemical Industry Co., Ltd.), and DISPARLON DA-550 (manufactured by Kusumoto Chemical Co., Ltd.) were mixed using a three-roll mill to obtain a mixture. In the resulting mixture, glycidyl methacrylate-modified propylene-butene random copolymer (ER829, manufactured by Starlight PMC), maleic anhydride-butyl methacrylate-modified propylene-butene random copolymer (ER645, manufactured by Starlight PMC), hindered phenolic antioxidant (Irganox 1010, manufactured by BASF), curing accelerator (TAP, manufactured by KAYAKU NOURYON), and toluene were incorporated and mixed using a high-speed rotary mixer to obtain a coating of sealing composition. A sealing sheet with a sealing layer of 10 μm thickness was prepared from the obtained coating using the same method as in Example 1.

[0176] <Comparative Example 5> In a Swasol solution (non-volatile component: 60%) containing an adhesive (ARKON P-125 manufactured by Arakawa Chemical Industry Co., Ltd.), maleic anhydride-modified liquid polybutene (HV-300M manufactured by Toho Chemical Industry Co., Ltd.), liquid polybutene (HV-1900 manufactured by ENEOS Corporation), DISPARLON DA-550 (manufactured by Kusumoto Chemical Co., Ltd.), glycidyl methacrylate-modified propylene-butene random copolymer (ER829 manufactured by Starlight PMC Corporation), maleic anhydride-butyl methacrylate-modified propylene-butene random copolymer (ER645 manufactured by Starlight PMC Corporation), hindered phenolic antioxidant (Irganox 1010 manufactured by BASF Corporation), curing accelerator (TAP, manufactured by KAYAKU NOURYON Corporation), and toluene, the mixture was mixed using a high-speed rotary mixer to obtain a coating with a sealing composition. A sealing sheet with a sealing layer of 10 μm thickness was made from the obtained coating using the same method as in Example 1.

[0177] <Comparative Example 6> Except for changing "DISPARLON DA-550" (manufactured by Kusumoto Chemical Co., Ltd.) to "AJISPER PB821" (manufactured by Ajinomoto Fine Chemicals Co., Ltd.), a coating for sealing composition and a sealing sheet having a sealing layer with a thickness of 10 μm were prepared using the same method as in Example 1.

[0178] The service life of the coatings for the sealing compositions obtained in the examples and comparative examples was evaluated using the following methods. Additionally, the optical properties (transparency) and water vapor permeation barrier properties of the sealing sheets obtained in the examples and comparative examples were evaluated using the following methods.

[0179] <Methods for assessing the service life of sealant coatings> The coatings of the sealing compositions prepared in the examples and comparative examples were refrigerated and evaluated over time (in succession) according to the following criteria. The results are recorded in the table below; ○: Even if more than 24 hours have passed since the coating was made, a film can still be formed. ×: Within 24 hours of coating preparation, gelation and precipitation occur, the coating deteriorates, and it becomes difficult to form a film.

[0180] <Methods for evaluating optical properties (transparency)> The sealing sheets prepared in the examples and comparative examples were cut into pieces 70 mm in length and 25 mm in width. A protective sheet was peeled off from the cut sealing sheets. The sealing sheets with the laminated structure of sealing layer / support were laminated onto a glass plate (Matsunami Glass Industry Co., Ltd. "White Glass Slide S1112 Edge Grinding No. 2", length: 76 mm, width: 26 mm, and thickness: 1.2 mm) using a batch vacuum laminator (Nichigo-Morton, V-160). This yielded an evaluation sample with a glass / sealing layer / support laminated structure. The lamination conditions were: temperature 80°C, decompression time 30 seconds, followed by a pressure of 0.3 MPa for 30 seconds.

[0181] The haze (%) was measured according to JIS K 7136. Specifically, after peeling off the support from the evaluation sample with a glass / sealing layer / support structure, the haze (%) of the evaluation sample with the support removed was measured using a Suga Testing Machine Co., Ltd. HZ-V3 haze meter (halogen lamp), with the glass as a reference, under D65 light. The transparency was evaluated according to the following criteria. The results are shown in the table below; (Benchmark for transparency) ○ (Good): Haze level less than 30% △ (Pass): Haze level is 30% or higher but less than 60%. × (Poor): Haze is above 60%.

[0182] <Methods for assessing water vapor permeability> As a support, a composite film consisting of aluminum foil and polyethylene terephthalate film (manufactured by Tokai Toyo Aluminum Sales Co., Ltd., "AL1N30 with PET" (aluminum foil thickness: 30μm, PET film thickness: 25μm)) is prepared.

[0183] In addition to using the aforementioned composite film as a support, a test sheet with a laminated structure of "support (composite film) / sealing layer / protective sheet (laminated film)" was obtained in the same manner as in the examples and comparative examples.

[0184] Prepare a 50 mm × 50 mm square glass plate made of alkali-free glass. Wash the glass plate with boiling isopropanol for 5 minutes and dry it at 150°C for at least 30 minutes.

[0185] On one side of the dried glass plate, calcium is vapor-deposited using a mask covering a peripheral area 0 mm to 2 mm from the end of the glass plate. As a result, a calcium film with a thickness of 200 nm (99.8% purity) is formed in the central part of one side of the glass plate, excluding the peripheral area 0 mm to 2 mm from the end of the glass plate.

[0186] In a nitrogen environment, the sealing layer of the aforementioned test sheet was bonded to the calcium film side of the aforementioned glass plate using a hot laminator (FUJIPLA "Lamipacker DAiSY A4 (LPD2325)") to obtain a laminate. This laminate was used as an evaluation sample.

[0187] Generally, calcium becomes transparent when it comes into contact with water to form calcium oxide. Furthermore, in the aforementioned evaluation samples, the glass plate and aluminum foil have sufficiently high water vapor permeability barrier properties, so moisture can typically move through the sealing layer end in the in-plane direction (perpendicular to the thickness direction) to reach the calcium film. If moisture permeates the evaluation sample, the calcium film gradually oxidizes from the end and becomes transparent, so shrinkage of the calcium film can be observed. Therefore, moisture permeation into the evaluation sample can be evaluated by measuring the sealing distance (mm) from the end of the evaluation sample to the calcium film. Therefore, evaluation samples containing calcium films can be used as models of electronic devices.

[0188] First, the sealing distance X2 (mm) from the end of the self-evaluation sample to the end of the calcium film was measured using a microscope (Mitutoyo Measuring Microscope MF-U).

[0189] Next, the evaluation sample was placed in a constant temperature and humidity bath set at 85°C and 85%RH. The evaluation sample was removed from the constant temperature and humidity bath when the sealing distance X1 (mm) between the end of the evaluation sample placed in the bath and the end of the calcium film increased by 0.1 mm compared to the initial sealing distance X2. The reduction start time t [hours] was calculated as the time from the moment the evaluation sample was placed in the constant temperature and humidity bath to the moment it was removed. This reduction start time t is equivalent to the time from the moment TP1 when the evaluation sample was placed in the constant temperature and humidity bath to the moment TP2 when the sealing distance X1 [mm] between the end of the evaluation sample placed in the bath and the end of the calcium film reaches "X2 + 0.1 mm".

[0190] Substituting the aforementioned sealing distance X1 and reduced start time t into the Fick diffusion formula in equation (1), the constant K, which serves as the water vapor permeability barrier parameter, is calculated.

[0191] [Mathematical Expression 1] .

[0192] Using the obtained constant K, the water vapor permeation barrier properties of the sealing layer were evaluated according to the following criteria. A smaller value of constant K indicates higher water vapor permeation barrier properties. Note that "hr" below refers to "hours". The results are recorded in the table below. Note that "(cm / hr^0.5)" in the table below means "(cm / hr 0.5)". (Benchmark for water vapor permeability barrier properties) ○ (Good): Constant K is below 0.025 cm / hr 0.5 ×(Defective): Constant K is 0.025 cm / hr or higher than 0.5.

[0193] .

[0194] .

[0195] As can be seen from the results in Table 1, for the sealing composition of the embodiments of the present invention, the evaluation of the coating service life is good, thus the dispersibility (storage stability) of calcium oxide is excellent, and a sealing layer with excellent water vapor permeation barrier and optical properties (transparency) can be formed.

[0196] Industrial availability The sealing composition of the present invention can form a sealing layer that combines water vapor permeation barrier and transparency, thereby exhibiting excellent calcium oxide dispersion (storage stability). Therefore, it is useful, for example, as a sealing material for electronic devices (e.g., organic EL devices, organic light-emitting diodes (OLEDs), solar cells (especially organic solar cells (organic thin-film solar cells (OPV), perovskite solar cells (PSC), dye-sensitized solar cells (DSSC))), sensor devices, touch panels with conductive substrates, etc.).

Claims

1. A sealing component, wherein, The product comprises the following components (A) to (D): (A) olefin polymers having an anhydride group and / or a carboxyl group with a number average molecular weight of less than 10,000, (B) polymers having a number average molecular weight of 10,000 or more, (C) calcium oxide with a median particle size of less than 300 nm, and (D) nonionic and / or anionic surfactants; (B) polymers having a number average molecular weight of 10,000 or more are: selected from at least one of olefin polymers having an anhydride group and / or a carboxyl group with a number average molecular weight of 10,000 or more, and olefin polymers having an epoxy group with a number average molecular weight of 10,000 or more.

2. As in the sealing components of claim 1, wherein, (D) is a nonionic surfactant.

3. As in claim 2, the sealing components, wherein, The nonionic surfactant is a polyoxyalkylene ether or a polyoxyalkylene aryl ether.

4. As in claim 2, the sealing components, wherein, The nonionic surfactant is a polyoxyalkylene aryl ether.

5. As in claim 2, the sealing components, wherein, The nonionic surfactant is a polyoxyalkylene aryl ether having the following structure: where n is an integer from 1 to 10, R1 and R2 are each independently a hydrogen atom or a methyl group, and Ar is an aromatic group with optional substituents.

6. As in claim 1 or 2, the sealing components, wherein, It further comprises (E) a liquid olefin polymer, wherein (E) liquid olefin polymer does not include components (A) and (B).

7. As in claim 1 or 2, the sealing components, wherein, It further includes (F) an adhesive agent.

8. As in claim 1 or 2, the sealing components, wherein, The content of component (C) is 10 to 70% by mass relative to 100% by mass of the non-volatile components of the sealing composition.

9. The sealing components as requested in item 1 or 2, wherein, The content of component (D) is 5 to 25% by mass relative to 100% by mass of the non-volatile components of the sealing composition.

10. A sealing sheet having a laminated structure comprising a sealing layer formed of any one of the sealing components of claims 1 to 9.