Polymer composition and polymer sheet

Abstract

Provided is a polymer composition capable of forming a polymer composition layer (as a sealing material) that exhibits high water vapor intrusion barrier properties. A polymer composition containing the following components (A) to (D): (A) an olefin polymer having an acid anhydride group and / or a carboxyl group; (B) a liquid olefin polymer; (C) calcium oxide; and (D) a plate-shaped filler having a BET specific surface area of 10 m2 / g or more.

Description

Technical Field

[0001] The present invention relates to polymer compositions for sealing electronic devices and the like, and polymer sheets having a laminated structure comprising a polymer composition layer formed from the polymer composition. Background Technology

[0002] To protect electronic devices with low moisture tolerance, such as OLEDs (Organic Light Emitting Diodes) or organic solar cells, from moisture, sealing materials containing hygroscopic materials in resin compositions are required. Examples of sealing materials include liquids or sheets, but sheets are preferred because they can be adhered to the electronic device for sealing. To achieve high sealing performance in sheet form, the content of hygroscopic material can be increased. For example, Patent Document 1 discloses a resin composition using a high content of hydrotalcite as the hygroscopic material. However, with the use of hydrotalcite, there is a problem: moisture is reversibly absorbed into the resin composition during the manufacturing process or distribution, and the device deteriorates if pre-drying is not performed. Patent Document 2 discloses a resin composition combining hygroscopic fillers and plate-shaped fillers, but as long as hydrotalcite is used in the same way as in Patent Document 1, the problem of device deterioration without pre-drying remains. Patent Document 3 proposes a sealing resin composition using calcium oxide as the hygroscopic material. However, if the content is increased to improve sealing performance, it becomes difficult to form a sheet shape, and the sealing performance deteriorates under high temperature and high humidity conditions, thus reducing the sealing performance. Patent document 4 proposes a resin composition that combines calcium oxide, layered clay minerals, and olefin polymers.

[0003] Prior art literature Patent documents Patent Document 1: International Publication No. 2021 / 065974 Patent Document 2: Japanese Patent Application Publication No. 2020-158739 Patent Document 3: Japanese Patent Application Publication No. 2022-21714 Patent document 4: Japanese Patent Publication No. 2022-535439. Summary of the Invention

[0004] The problem the invention aims to solve In Patent Document 1, a resin composition containing 45% or more of semi-calcined hydrotalcite is used as a constituent element to achieve high water vapor intrusion barrier properties. However, since semi-calcined hydrotalcite reversibly absorbs moisture, the sealing performance cannot be fully realized without pre-drying treatment. In Patent Document 2, although calcium oxide can be used as a hygroscopic filler, the BET specific surface area of ​​the plate-like filler is not specified. Furthermore, the content of the plate-like filler in the resin composition of Patent Document 2 is a relatively high value, ranging from 10% to 80% by mass. Patent Document 3 uses an olefin-based resin composition containing calcium oxide as a constituent element, but there is no mention of plate-like fillers. Patent Document 3 specifies a preferred calcium oxide content range of 40% to 80% by mass, but the calcium oxide content in the examples is 60% by mass or less. Additionally, Patent Document 3 does not address the problems encountered during sheet formation when calcium oxide is added at high concentrations. Patent Document 4 does not mention the BET specific surface area of ​​layered clay minerals, nor does it mention that layered clay minerals contribute to improving sheet forming ability.

[0005] The present invention was made in view of the above-mentioned situation, and its object is to provide a polymer composition capable of forming a polymer composition layer (as a sealing material) that exhibits high water vapor intrusion barrier properties.

[0006] means for solving problems In order to solve the above-mentioned problems (issues), the inventors conducted in-depth research and found that by combining the following components (A) to (D), a polymer composition capable of forming a polymer composition layer (as a sealing material) exhibiting high water vapor intrusion barrier properties can be obtained, thereby completing the present invention.

[0007] That is, the present invention has the following features: [1] A polymer composition comprising the following components (A) to (D): (A) Olefin polymers having anhydride and / or carboxyl groups, (B) Liquid olefin polymers (liquid olefin polymers other than component (A), i.e., liquid olefin polymers without anhydride and carboxyl groups), (C) Calcium oxide, and (D)BET has a specific surface area of ​​10m² 2 Plate-shaped packings with a density of / g or higher; [2] According to the polymer composition of [1], wherein (A) the number average molecular weight of the olefin polymer having an anhydride group and / or a carboxyl group is 950 or more; [3] According to the polymer composition of [1] or [2], wherein, relative to 100% by mass of the non-volatile components of the polymer composition, the content of (A) an olefin polymer having an anhydride group and / or a carboxyl group is 5 to 25% by mass; [4] The polymer composition according to any one of [1] to [3], wherein, relative to 100% by mass of the non-volatile components of the polymer composition, the content of (B) liquid olefin polymer is 5 to 25% by mass; [5] The polymer composition according to any one of [1] to [4], wherein the median particle size of (C) calcium oxide is less than 20 μm; [6] The polymer composition according to any one of [1] to [5], wherein the content of (C) calcium oxide is 15 to 70% by mass relative to 100% by mass of the non-volatile components of the polymer composition; [7] The polymer composition according to any one of [1] to [6], wherein the (D)BET specific surface area is 10 m². 2 The median particle size of plate-shaped packings with a particle size of / g or more is less than 2μm; [8] The polymer composition according to any one of [1] to [7], wherein the (D)BET specific surface area is 10 m² relative to 100% by mass of the non-volatile components of the polymer composition. 2 The content of plate-shaped packings of / g or above is 0.5% to 15% by mass; [9] A polymer sheet having a laminated structure comprising a polymer composition layer formed from any one of the polymer compositions described in [1] to [8];

[10] The polymer sheet according to [9] is used for sealing electronic devices;

[11] An electronic device wherein the polymer sheet described in [9] or

[10] is sealed.

[0008] The effects of the invention According to the present invention, a polymer composition capable of forming a polymer composition layer exhibiting high water vapor intrusion barrier properties (as a sealing material) and a polymer sheet having a laminated structure comprising the polymer composition layer formed from the polymer composition can be provided. Detailed Implementation

[0009] The present invention will now be described according to its preferred embodiments; [Polymer Composition] The polymer composition of the present invention comprises the following components (A) to (D) as essential components: (A) Olefin polymers having anhydride and / or carboxyl groups, (B) Liquid olefin polymers (C) Calcium oxide, and (D)BET has a specific surface area of ​​10m² 2 Plate-shaped packing materials with a density of / g or higher.

[0010] In this specification, "olefin-based polymer" refers to a polymer whose main structural unit is a structural unit derived from olefins (hereinafter sometimes simply referred to as "olefin unit") (i.e., the amount of olefin unit is the largest among all structural units). It should be noted that "structural units derived from butene" and the like, which are olefin units, are sometimes simply referred to as "butene units" or the like.

[0011] 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 olefin polymers that cannot be cross-linked to form rubber elastomers, and "olefin rubber" refers to olefin polymers that can be cross-linked to form rubber elastomers.

[0012] As olefins, monoolefins having one olefinic carbon-carbon double bond and / or dienes having two olefinic carbon-carbon double bonds are preferred. 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.

[0013] Olefin polymers can be homopolymers or copolymers. Copolymers can be random copolymers or block copolymers. Furthermore, olefin polymers can also 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-styrene copolymers, styrene-butene-butadiene copolymers, and styrene-ethylene-butene copolymers.

[0014] The following details each ingredient. It should be noted that, unless otherwise specified in this specification, each ingredient may be used in isolation or in combination with two or more ingredients.

[0015] <(A)Component> Component (A) is an olefinic polymer having an anhydride group (i.e., a carbonyl oxycarbonyl group (-CO-O-CO-)) and / or a carboxyl group. Examples of anhydride groups include those derived from succinic anhydride, maleic anhydride, and glutaric anhydride. One or more anhydride groups may be present. By incorporating component (A), a polymer composition layer that is not easily deformed and can maintain its shape can be obtained. Without component (A), film formation becomes difficult. Furthermore, component (A) forms a cross-linked structure through a cross-linking reaction of the anhydride / carboxyl group, or through coordination of the anhydride / carboxyl group with calcium oxide, thereby allowing calcium oxide (component (C)) to be well dispersed in the polymer composition and providing water vapor intrusion barrier properties.

[0016] When an olefinic polymer having an anhydride group is used 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 according to JIS K 2501, by the value of the acid value, defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the polymer.

[0017] When an olefinic polymer having carboxyl groups is used 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 according to JIS K 2501, by the value of the acid value, defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the polymer.

[0018] When an olefinic polymer having an anhydride group and a carboxyl group is used 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.

[0019] (A) The component can 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.

[0020] In one embodiment of the present invention, component (A) is: (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; ethylene-propylene copolymer 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; styrene-butene-butadiene copolymer having an anhydride group and / or a carboxyl group; styrene-ethylene-butene 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) More 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, ethylene-propylene copolymer having an anhydride group and / or a carboxyl group, styrene-ethylene-butene 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, isobutylene-isoprene copolymer having an anhydride group, ethylene-propylene copolymer having an anhydride group, propylene-butene copolymer having an anhydride group, and styrene-ethylene-butene copolymer having an anhydride group. (iv) Particularly preferred is at least one selected from polybutene having an anhydride group, isobutene-isoprene copolymer having an anhydride group, and ethylene-propylene copolymer having an anhydride group.

[0021] The number-average molecular weight of olefin polymers having anhydride and / or carboxyl groups is not particularly limited, but from the viewpoint of preventing defects (collapse) during the application of the varnish of the polymer composition, enabling the formed polymer composition layer to exhibit moisture permeability resistance, and improving mechanical strength, the number-average molecular weight is preferably 800 or more, more preferably 850 or more, further preferably 900 or more, and particularly preferably 950 or more. On the other hand, from the viewpoint of providing good coatability of the varnish of the polymer composition and good compatibility with other components in the polymer composition, it is preferably 1,000,000 or less, more preferably 750,000 or less, more preferably 500,000 or less, further preferably 400,000 or less, further more preferably 300,000 or less, particularly preferably 200,000 or less, and most preferably 150,000 or less. It should be noted that the number-average molecular weight in this invention is determined by gel permeation chromatography (GPC) (polystyrene conversion). The number-average molecular weight was determined using the GPC method. Specifically, the Shimadzu Corporation LC-9A / RID-6A was used as the measuring device, the Showa Denko Corporation Shodex K-800P / K-804L / K-804L was used as the column, toluene or the like was used as the mobile phase, the measurement was performed at a column temperature of 40°C, and the standard curve of standard polystyrene was used for calculation.

[0022] From the viewpoint of suppressing the decrease in fluidity caused by the thickening of the varnish, the olefin polymers having anhydride groups and / or carboxyl groups in this invention are preferably amorphous. Here, amorphous means that the olefin polymer does not have a definite melting point; for example, those in which no definite peak is observed when the melting point is determined by DSC (differential scanning calorimetry) of the olefin polymer can be used.

[0023] Next, specific examples of olefin polymers having anhydride groups and / or carboxyl groups will be described. Specific examples of polyisobutylene resins or polybutene-based resins include "HV-300M" (acid value: 65 mg KOH / g, anhydride concentration: 1.16 mmol / g, number-average molecular weight: 2100) manufactured by Toho Chemical Industry Co., Ltd., "HV-100M" (acid value: 82 mg KOH / g, anhydride concentration: 1.46 mmol / g, number-average molecular weight: 1218) manufactured by Toho Chemical Industry Co., Ltd., and "DOVERMULSEH1000" (acid value: 54 mg KOH, anhydride concentration: 0.96 mmol / g, number-average molecular weight: 1204) manufactured by DOVER Corporation.

[0024] Specific examples of styrene-isobutylene copolymers include "T-YP757B" (maleic anhydride-modified styrene-isobutylene-styrene block copolymer, anhydride concentration: 0.46 mmol / g, number average molecular weight: 100,000) manufactured by Xingguang PMC, "T-YP766" (glycidyl methacrylate-modified styrene-isobutylene-styrene block copolymer, epoxy group concentration: 0.64 mmol / g, number average molecular weight: 100,000) manufactured by Xingguang PMC, and "T-YP8920" (maleic anhydride-modified styrene-isobutylene-styrene copolymer, anhydride concentration: 0.46 mmol / g, number average molecular weight: 35,800) manufactured by Xingguang PMC.

[0025] Specific examples of polyethylene-based or polypropylene-based resins include Sanyo Chemical Industries' "UMEX1010" (anhydride concentration: 0.98 mmol / g, number average molecular weight: 30,000) and Riken Vitamins' "MG-441P" (anhydride concentration: 0.73 mmol / g).

[0026] Specific examples of propylene-butene copolymers include "T-YP279" (maleic anhydride-modified propylene-butene random copolymer, anhydride concentration: 0.46 mmol / g, number-average molecular weight: 35000) and "T-YP312" (maleic anhydride-modified propylene-butene random copolymer, anhydride concentration: 0.46 mmol / g, number-average molecular weight: 60900) manufactured by Starlight PMC. Specific examples of ethylene-propylene copolymers include "LUCANT A-5260" (anhydride concentration: 0.44 mmol / g, number-average molecular weight: 5400) manufactured by Mitsui Chemicals.

[0027] As a specific example of isobutylene-isoprene copolymer (butyl rubber), one can cite "ER661" (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: 40000) manufactured by Starlight PMC.

[0028] The content of component (A) in the polymer composition of the present invention is not particularly limited. However, from the viewpoint of providing good coatability and formability, and ensuring processability (tackiness suppression), this content is preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less, relative to 100% by mass of the non-volatile components in the polymer composition. On the other hand, from the viewpoint of ensuring good resistance to damp heat and dispersibility of the calcium oxide (C) component, this content is preferably 2% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more, relative to 100% by mass of the non-volatile components in the polymer composition. In one embodiment of the present invention, the content of component (A) is preferably 2 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, relative to 100% by mass of the non-volatile components in the polymer composition. In another embodiment of the present invention, the content of component (A) is preferably 5 to 25% by mass, relative to 100% by mass of the non-volatile components in the polymer composition.

[0029] <(B) Component> Component (B) is a liquid olefin polymer. By incorporating component (B), the dispersibility of calcium oxide (component (C)) in the polymer composition and the adhesion of the resulting polymer composition layer can be improved.

[0030] 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, as measured by 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).

[0031] In this invention, liquid olefin polymers having anhydride groups and / or carboxyl groups are classified as component (A). Therefore, component (B) in this invention is a liquid olefin polymer other than component (A). That is, component (B) in this invention is a liquid olefin polymer without anhydride groups and carboxyl groups.

[0032] From the viewpoint of good adhesion and flexibility of the formed polymer composition layer, the viscosity of component (B) at 25°C is preferably 5 to 5000 Pa·s, more preferably 10 to 4000 Pa·s, and even more preferably 20 to 3000 Pa·s.

[0033] From the viewpoint of good coatability of the polymer composition varnish, the number average molecular weight of component (B) is preferably 100 to 50,000, more preferably 200 to 30,000, and even more preferably 300 to 20,000.

[0034] (B) The ingredients may be commercially available products. Examples of such commercially available products include, for example, ENEOS's "HV-100" (liquid polybutene), 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), and Kothari's "2400" (liquid polybutene). MW (liquid olefin polymer), INEOS' "H-1900" (liquid polybutene), INEOS' "H-6000" (liquid polybutene), INEOS' "H-18000" (liquid polybutene), Nippon Oil's "200N" (liquid polybutene), Nippon Soda's "BI-2000" (liquid hydrogenated polybutadiene), Nippon Soda's "BI-3000" (liquid hydrogenated polybutadiene), Nippon Soda's "GI-3000" (liquid hydrogenated polybutadiene), Mitsui Chemicals' "LUCANT LX100" (liquid olefin polymer), Mitsui Chemicals' "LUCANTLX400" (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), "Poly" manufactured by Idemitsu Showa Shell Company Liquid polyisoprene (IP), Nippon Soda's "B-1000" (liquid polybutadiene), Nippon Soda's "B-3000" (liquid polybutadiene), Nippon Soda's "G-3000" (liquid polybutadiene), Kuraray's "LIR-30" (liquid polyisoprene), Kuraray's "LIR-390" (liquid polyisoprene), Kuraray's "LIR-290" (liquid polyisoprene), Kuraray's "LBR-302" (liquid polybutadiene), Kuraray's "LBR-305" (liquid polybutadiene), Kuraray's "LBR-361" (liquid polybutadiene), Kuraray's "L-SBR-820" (liquid styrene-butadiene random copolymer), and Krevelli's "Ricon" (liquid styrene-butadiene random copolymer). 154 (liquid butadiene), Ricon 184 (liquid styrene-butadiene random copolymer) manufactured by Clayville, etc.

[0035] (B) The preferred components are liquid polybutene and / or liquid hydrogenated polybutadiene, more preferably liquid polybutene.

[0036] The content of component (B) in the polymer composition of the present invention is not particularly limited. However, from the viewpoint of good adhesion and flexibility of the formed polymer composition layer, this content is preferably 2% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. On the other hand, from the viewpoint of good adhesion and flexibility of the formed polymer composition layer, and from the viewpoint of ensuring processability (adhesion suppression), this content is preferably 35% by mass or less, more preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less, relative to 100% by mass of the non-volatile components in the polymer composition. In one embodiment of the present invention, the content of component (B) relative to 100% by mass of the non-volatile components in the polymer composition is preferably 2 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass. In another embodiment of the present invention, the content of component (B) relative to 100% by mass of the non-volatile components in the polymer composition is preferably 5 to 25% by mass.

[0037] <(C) Ingredients> Component (C) is calcium oxide. By incorporating component (C) as a hygroscopic filler, the resulting polymer composition layer can be endowed with water vapor intrusion barrier properties.

[0038] To prevent damage to electronic devices from calcium oxide and other contaminants during the sealing process, the median particle size (D50) of component (C) is preferably 20 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and even more preferably 3 μm or less. From the viewpoint of the dispersibility of component (C) in the polymer composition, it is preferably 0.03 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more. In one embodiment of the present invention, the median particle size of component (C) is preferably 0.03 to 10 μm, more preferably 0.05 to 5 μm, and even more preferably 0.1 to 3 μm. The median particle size of component (C) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of component (C) can be determined by using a laser diffraction particle size distribution measuring device to prepare the particle size distribution of component (C) on a volume basis. The sample to be measured can preferably be a sample in which component (C) is dispersed in ethanol by ultrasonication. As a laser diffraction scattering particle size distribution measuring device, the LA-500 manufactured by Horiba Corporation can be used.

[0039] From the viewpoint of water vapor intrusion barrier properties of the polymer composition layer, the content of component (C) relative to 100% by mass of the non-volatile components of the polymer 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 adhesive properties of the polymer composition 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 polymer composition is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, and even more preferably 15 to 70% by mass.

[0040] The polymer composition of the present invention may also contain hygroscopic fillers other than calcium oxide (hereinafter sometimes referred to as "other hygroscopic fillers"). Examples of other hygroscopic fillers include, for example, semi-calcined hydrotalcite, calcined hydrotalcite, magnesium oxide, and molecular sieves. Only one type of other hygroscopic filler may be used, or two or more types may be used in combination. The content of hygroscopic fillers other than calcium oxide is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, and even more preferably 0 to 20% by mass, relative to 100% by mass of the non-volatile components of the polymer composition.

[0041] <(D) component> (D) The component is BET with a specific surface area of ​​10m². 2 / g or more of plate-shaped filler. Component (D) can contribute to the high water vapor intrusion barrier properties of the resulting polymer composition layer by combining with component (C). Specifically, by utilizing the high BET specific surface area, the cohesiveness of the polymer composition can be improved, which helps to accelerate the resistance to damp heat during testing.

[0042] (D) The plate-shaped packing material with a BET specific surface area of ​​10 m² is required. 2 There are no particular limitations for fillers of g or above, and examples include sheet-like glass (A glass, C glass, E glass, etc.), uncalcined hydrotalcite, and layered silicate minerals. Examples of layered silicate minerals include kaolinite, halloysite, talc, smectite, and mica. Among mica, synthetic fluorophlogopite is preferred from the viewpoint of excellent transparency. For sheet-like fillers, talc, mica, sheet-like glass, uncalcined hydrotalcite, smectite, and synthetic fluorophlogopite are preferred from the perspective of high aspect ratio and good water barrier properties. These sheet-like fillers can be used individually or in combination of two or more.

[0043] (D) The plate-shaped packing material has a BET specific surface area of ​​10 m². 2 From the viewpoint of suppressing shrinkage during sheet formation, a density of 12.5 μm or higher is preferred. 2 / g or more, preferably 15m 2 / g or more. On the other hand, from the viewpoint of the dispersibility of the (D) component in the polymer composition, 45m is preferred. 2 / g or less, preferably 40m 2 / g or less, more preferably 35m 2 / g or less, especially preferably 30m 2 / g or less. In one embodiment of the present invention, the BET specific surface area of ​​the plate-shaped packing of component (D) is preferably 10 to 40 m². 2 / g, more preferably 12.5–35m 2 / g, more preferably 15-30m 2 / g. The BET specific surface area of ​​the plate-shaped packing material of component (D) can be calculated using the BET method, by using a specific surface area measuring device (Macsorb HM Model 1210, manufactured by Mounttech) to adsorb nitrogen on the sample surface and then using the BET multi-point method.

[0044] The content of component (D) is not particularly limited as long as the effects of the present invention are achieved. It is preferably 0.10% by mass or more, more preferably 0.25% by mass or more, further preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 17.5% by mass or less, and further preferably 15% by mass or less, relative to 100% by mass of the non-volatile components of the polymer composition. In one embodiment of the present invention, the content of component (D) is preferably 0.10 to 20% by mass, more preferably 0.25 to 17.5% by mass, and further preferably 0.5 to 15% by mass, relative to 100% by mass of the non-volatile components of the polymer composition.

[0045] For the plate-shaped packing material of component (D), its average aspect ratio (average major diameter / average minor diameter) is preferably 2 or more, and more preferably 5 or more. By making the average aspect ratio 2 or more, the low moisture permeability performance can be more effectively achieved. Here, the aspect ratio in this specification is the average aspect ratio defined by the average major diameter / average minor diameter of the plate-shaped packing material.

[0046] The average major diameter, average minor diameter, and average aspect ratio of the plate-shaped packing can be obtained through image processing methods such as scanning electron microscopy (SEM) images. Here, the "average" of the average major diameter and average minor diameter refers to the average value obtained by measuring a reliable number (N) of plate-shaped packings. This number (N) is at least 10, preferably 100 or more. It should be noted that the average major diameter of the plate-shaped packing is the average value of the length along the longitudinal direction (length of the long side) when the plate-shaped packing is considered as a cuboid. Similarly, the average minor diameter of the plate-shaped packing is the average value of the length along the short side (length of the short side) when the plate-shaped packing is considered as a cuboid.

[0047] The average thickness of the plate-shaped filler of component (D) is preferably 0.01 to 20 μm, more preferably 0.05 to 10 μm.

[0048] (D) The average thickness of the plate-shaped filler of component (D) can be determined using the following method. Using a scanning electron microscope (SEM), the thickness of each of 100 particles is measured, and the average value is calculated. In this case, individual particles can be observed and measured using a scanning electron microscope. The filler (particle group) is filled into the resin, molded, and the molded body is broken; the fracture surface can be observed and measured. In any measurement method, the sample stage of the scanning electron microscope is adjusted using a sample stage fine-motion device so that the cross-section (thickness plane) of the particle is perpendicular to the electron beam axis of the scanning electron microscope.

[0049] To prevent damage to electronic devices by the plate-shaped filler during the sealing process, the median particle size (D50) of the plate-shaped filler of component (D) is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 2 μm or less. From the viewpoint of dispersibility, it is preferably 0.03 μm or more, more preferably 0.05 μm or more, and even more preferably 1 μm or more. In one embodiment of the present invention, the median particle size of the plate-shaped filler of component (D) is preferably 0.03 to 10 μm, more preferably 0.05 to 5 μm, and even more preferably 0.1 to 2 μm.

[0050] The median particle size of the plate-shaped packing material of component (D) can be measured by laser diffraction / scattering based on the Mie scattering theory. Specifically, the particle size distribution of component (D) can be determined by preparing a volume-based sample using a laser diffraction particle size distribution measuring device. The sample used for measurement is preferably a sample in which component (D) is dispersed in water by ultrasonication. As a laser diffraction particle size distribution measuring device, the LA-500 manufactured by Horiba Corporation can be used.

[0051] The polymer composition of the present invention may also contain a BET specific surface area of ​​less than 10 m². 2 / g of plate-shaped packing. BET specific surface area less than 10m² 2 Plate-shaped fillers of / g can be used alone or in combination with two or more types. The BET specific surface area is less than 10m² relative to 100% by mass of the non-volatile components of the polymer composition. 2 The content of plate-shaped packing per g is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and even more preferably 0 to 10% by mass.

[0052] <Other Ingredients> To the extent that it does not impair the effects of the present invention, the polymer 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, tackifiers, antioxidants, curing accelerators, epoxy-modified olefin polymers, plasticizers, etc. Only one of them may be used, or two or more may be used in combination.

[0053] (Thickening agent) Tackifiers, also known as tackifiers, are resins that impart adhesive properties when incorporated into plastic polymers. There are no particular limitations on tackifiers, but terpene resins, modified terpene resins (hydrogenated terpene resins, terpene phenol copolymer resins, aromatic modified terpene resins, etc.), coumarone resins, indene resins, and petroleum resins (aliphatic petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene petroleum resins and their hydrogenates, etc.) are preferred.

[0054] Regarding commercially available products that can be used as tackifiers, the following products can be cited as examples. For terpene resins, YS Resin PX and YS Resin PXN (both manufactured by Yasun Chemical Co., Ltd.) can be cited; for aromatic modified terpene resins, YS Resin TO and TR series (all manufactured by Yasun Chemical Co., Ltd.) can be cited; for hydrogenated terpene resins, CLEARON P, CLEARON M, and CLEARON K series (all manufactured by Yasun Chemical Co., Ltd.) can be cited; for terpene phenol copolymer resins, YSPOLYSTER 2000, POLYSTER U, POLYSTER T, POLYSTER S, and Mighty Ace G (all manufactured by Yasun Chemical Co., Ltd.) can be cited; and for hydrogenated alicyclic petroleum resins, Escorez can be cited. Examples of aromatic petroleum resins include the 5300 series and 5600 series (both manufactured by ExxonMobil). Examples of aliphatic aromatic copolymer petroleum resins include Quintone D100 (manufactured by Zeon Corporation of Japan). Examples of alicyclic petroleum resins include Quintone 1325 and Quintone 1345 (both manufactured by Zeon Corporation of Japan). Examples of saturated hydrocarbon resins include ARKONP 100, ARKON P125, ARKON P140, and TFS13-030 (all manufactured by Arakawa Chemical Industry Co., Ltd.).

[0055] Regarding the softening point of the tackifier, from the viewpoint that the sheet softens during the lamination process of the polymer composition sheet and has the desired heat resistance, it is preferably 50–200°C, more preferably 90–180°C, and even more preferably 100–150°C. It should be noted that the softening point is determined according to JIS K 2207 by the ring and ball method.

[0056] One type of tackifier or a combination of two or more can be used. There is no particular limitation on the content of the tackifier in the polymer composition. However, from the viewpoint of maintaining good moisture permeability of the polymer composition, when using a tackifier, its content relative to 100% by mass of the non-volatile components of the polymer composition is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less. On the other hand, from the viewpoint of having sufficient adhesiveness, when using a tackifier, its content relative to 100% by mass of the non-volatile components of the polymer composition is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more.

[0057] From the viewpoints of adhesiveness, moisture permeability resistance, and transparency of the polymer composition, petroleum resin is preferred. Examples of petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, and alicyclic petroleum resins. From the viewpoints of adhesiveness, moisture permeability resistance, and compatibility of the polymer composition, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, and alicyclic petroleum resins are more preferred. Furthermore, from the viewpoint of achieving good transparency, alicyclic petroleum resins are particularly preferred. The alicyclic petroleum resin can also be a resin obtained by hydrogenating an aromatic petroleum resin. In this case, the hydrogenation rate of the alicyclic petroleum resin is preferably 30–99%, more preferably 40–97%, and even more preferably 50–90%. If the hydrogenation rate is too low, there is a tendency for the transparency to decrease due to coloring; if the hydrogenation rate is too high, there is a tendency for production costs to increase. The hydrogenation rate can be determined by the ratio of hydrogen atoms in the aromatic rings before and after hydrogenation. 1 The ratio of peak intensities in H-NMR is used to determine the composition. Alicyclic petroleum resins are particularly preferred, especially hydrogenated petroleum resins containing a cyclohexane ring and dicyclopentadiene-based hydrogenated petroleum resins. One type of petroleum resin or a combination of two or more types can be used. The number-average molecular weight Mn of the petroleum resin is preferably 100–2500, more preferably 200–2000, and even more preferably 300–1500.

[0058] (Antioxidants) In this invention, there is no particular limitation on the antioxidant, and known antioxidants can be used. By incorporating an antioxidant, the lightfastness of the formed polymer composition layer can be improved. 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 polymer 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.

[0059] (Curing accelerator) In this invention, a curing accelerator can be used to open the ring of the anhydride group of component (A) and promote the crosslinking reaction and coordination with calcium oxide. Examples of curing accelerators include imidazole compounds, tertiary amine / quaternary amine compounds, dimethylurea compounds, organophosphorus compounds, etc.

[0060] 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.).

[0061] 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 salt of 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 their salts such as benzyl dimethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol (TAP); and dimethylurea compounds such as aromatic dimethylurea and aliphatic dimethylurea.

[0062] 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 the viewpoint of curability, aromatic dimethylureas are preferred.

[0063] 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, TTPuP-K, TPP-SCN, and TPP-S (all manufactured by Beixing Chemical Industry Co., Ltd.).

[0064] When using a curing accelerator, in order to promote the crosslinking reaction of the anhydride groups and / or carboxyl groups of component (A), its content is preferably 0.001 to 5% by mass relative to 100% by mass of the non-volatile components of the polymer composition, more preferably 0.001 to 2.5% by mass, and even more preferably 0.001 to 1% by mass.

[0065] (Epoxy-modified olefin polymers) "Epoxy-modified olefin polymer" has the same meaning as "olefin polymer with epoxy groups". The epoxy groups of the epoxy-modified olefin polymer form a cross-linked structure by reacting with the anhydride / carboxyl groups in the olefin polymer ((A) component) having anhydride and / or carboxyl groups, which can improve the dispersibility of calcium oxide ((C) component) in the polymer composition and the water vapor intrusion barrier properties of the resulting polymer composition layer.

[0066] The concentration of epoxy groups in the epoxy-modified olefin polymer is preferably 0.05–10 mmol / g, more preferably 0.10–5 mmol / g. The epoxy group concentration is determined based on the epoxy equivalent obtained in JIS K 7236-1995.

[0067] For epoxy-modified olefin polymers, from the viewpoint of improving the coatability of the varnish of the polymer composition, the sealing performance of the formed polymer composition layer and the mechanical strength, the number average molecular weight is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and even more preferably 2,000 to 200,000.

[0068] Epoxy-modified olefin polymers can be obtained, for example, by grafting an olefin polymer with an epoxy-containing unsaturated compound (e.g., glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether) under free radical reaction conditions, or by copolymerizing an epoxy-containing unsaturated compound with an α-olefin.

[0069] Commercially available products can be used for epoxy-modified olefin polymers. Examples of such commercially available products include: "ER829" (glycidyl methacrylate-modified propylene-butene random copolymer, epoxy group concentration: 0.64 mmol / g, number average molecular weight: 400,000) manufactured by Starlight PMC Co., Ltd.; "T-YP276" (glycidyl methacrylate-modified propylene-butene random copolymer, epoxy group concentration: 0.64 mmol / g, number average molecular weight: 57,000) manufactured by Starlight PMC Co., Ltd.; and "ER850" (glycidyl methacrylate-modified isobutylene-isoprene random copolymer, epoxy group concentration: 0.654 mmol / g, number average molecular weight: 99,200) manufactured by Starlight PMC Co., Ltd.

[0070] Epoxy-modified olefin polymers are: (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 with epoxy groups, isobutylene-isoprene copolymer with epoxy groups (i.e., butyl rubber), and ethylene-methyl methacrylate copolymer with 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 preferred are propylene-butene copolymers having epoxy groups and / or isobutylene-isoprene copolymers having epoxy groups. (iv) Particularly preferred are propylene-butene copolymers having epoxy groups or isobutylene-isoprene copolymers having epoxy groups.

[0071] When using an epoxy-modified olefin polymer, a propylene-butene copolymer having epoxy groups is employed. The amount of butene units in this copolymer, relative to the total amount of propylene 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. It should be noted that the above-mentioned amount of butene units is based on the propylene and butene units after removing the modified portion (e.g., the portion from glycidyl (meth)acrylate used to introduce the epoxy groups).

[0072] When using an isobutylene-isoprene copolymer (i.e., butyl rubber) with epoxy groups as an epoxy-modified olefin polymer, from the viewpoint of resistance to yellowing of the polymer composition 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. It should be noted that the above-mentioned amount of isoprene units is based on isobutylene units and isoprene units after removing the modified portion (e.g., the portion from glycidyl (meth)acrylate used to introduce epoxy groups).

[0073] When using epoxy-modified olefin polymers, from the viewpoint of improving the good coatability of the varnish of the polymer composition, the sealing performance of the formed polymer composition layer and the mechanical strength, the content of the non-volatile component is preferably 0 to 20% by mass relative to 100% by mass of the polymer composition, more preferably 0 to 15% by mass, and even more preferably 0 to 10% by mass.

[0074] (Plasticizer) By using plasticizers, the flexibility and formability of polymer compositions can be improved. There are no particular limitations on the plasticizer, but materials that are liquid at room temperature are preferred. Specific examples of plasticizers include: alkane-based processing oils, cycloalkane-based processing oils, liquid paraffin, polyethylene wax, polypropylene wax, mineral oils such as petrolatum, castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, vegetable oils such as olive oil, liquid polybutene, hydrogenated liquid polybutene, liquid polybutadiene, and other liquid polyalphaolefins. Liquid polyalphaolefins are preferred as the plasticizer used in this invention, and liquid polybutadiene is particularly preferred. Furthermore, from the viewpoint of adhesion, liquid polyalphaolefins with low molecular weight are preferred, and those with a weight-average molecular weight in the range of 500 to 5,000, and further, 1,000 to 3,000. These plasticizers can be used alone or in combination of two or more. It should be noted that "liquid state" here refers to the state of the plasticizer at room temperature (25°C). When using a plasticizer, from the viewpoint of not adversely affecting electronic devices, its content is preferably 50% by mass or less relative to 100% by mass of the non-volatile components of the polymer composition.

[0075] <Method for manufacturing polymer compositions> The method for manufacturing the polymer composition of the present invention is not particularly limited, and examples include: adding compounding components, adding solvents as needed, mixing using a mixing roller or rotary mixer, and drying the resulting mixture.

[0076] Drying mixtures by heating is simple. Heating can be carried out at atmospheric pressure or under reduced pressure. The heating temperature and time can vary depending on the components used. The heating temperature and time can be appropriately set by those skilled in the art based on the components used.

[0077] <Polymer Sheets and Their Manufacturing Methods> The present invention also provides polymer sheets having a laminated structure comprising a polymer composition layer formed from the polymer composition of the present invention.

[0078] The polymer composition layer of the polymer sheet can be formed using methods known to those skilled in the art. For example, it can be formed by preparing a varnish in which the above-mentioned components are dissolved in an organic solvent, applying the varnish to a support, and drying it. The non-volatile content of the varnish is preferably 20-80% by mass, more preferably 30-70% by mass.

[0079] Examples of organic solvents include: ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellolytic agents such as methyl carbitol; carbitols such as butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. One organic solvent can be used, or two or more can be used in combination.

[0080] Drying varnish by heating is simple. Heating can be carried out under normal pressure or under reduced pressure. The heating temperature and time can vary depending on the ingredients and organic solvents used. The heating temperature and time can be appropriately set by those skilled in the art based on the ingredients and organic solvents used.

[0081] When polymer sheets are prepared using a polymer composition containing an olefin polymer with an anhydride group and an epoxy-modified olefin polymer, a polymer sheet with improved moisture permeability and higher sealing performance (barrier performance against moisture and oxygen in the air) can be obtained by reacting the anhydride group with the epoxy group to form a cross-linked structure.

[0082] The thickness of the polymer composition layer in the polymer sheet is preferably 1 to 200 μm, more preferably 2 to 180 μm.

[0083] Examples of supports used in polymer sheets include: polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; cyclic olefin polymers; polyesters such as polyethylene terephthalate (hereinafter sometimes simply referred to as "PET") and polyethylene naphthalate; polycarbonate; and plastic films such as polyimide. A demolding treatment can be performed on the surface of the support that is bonded to the polymer composition layer. Examples of demolding treatments include those using silicone resin-based release agents, alkyd resin-based release agents, and fluoropolymer-based release agents.

[0084] The thickness of the support is not particularly limited, but from the viewpoint of the processability of the polymer sheet, it is preferably 10 to 150 μm, and more preferably 20 to 100 μm.

[0085] As a support used in polymer sheets, a support having a barrier layer (e.g., a plastic film with a barrier layer) is preferred. By using a support with low moisture permeability, moisture absorption of the polymer composition layer can be prevented during storage of the polymer sheet. Examples of barrier layers include inorganic films such as silicon dioxide vapor-deposited films, silicon nitride films, and silicon oxide films. The barrier layer may also be composed of multiple layers of inorganic films (e.g., silicon dioxide vapor-deposited films). Furthermore, the barrier layer may be composed of organic and inorganic materials, and may be a composite multilayer of organic and inorganic films.

[0086] As a support with a barrier layer, for example, a water vapor transmission rate (WVTR) of 0.0005 (g / m²) can be used. 2 High-barrier plastic film with a water vapor permeability of less than 24hr. Here, the film's water vapor permeability (g / m³) is used. 2 " / 24hr)" refers to the condition of temperature and humidity specified later, where the transmission area is 1m² for 24 hours. 2 The amount of water vapor (g) in the membrane. Examples of high-barrier plastic films include those manufactured by laminating inorganic films such as silicon dioxide, aluminum oxide, magnesium oxide, silicon nitride, silicon oxynitride, SiCN, and amorphous silicon onto the surface of a plastic film using chemical vapor deposition (e.g., chemical vapor deposition using heat, plasma, ultraviolet light, vacuum heat, vacuum plasma, or vacuum ultraviolet light) or physical vapor deposition (e.g., vacuum evaporation, sputtering, ion plating, laser deposition, molecular beam epitaxy). (See, for example, Japanese Patent Application Publication No. 2016-185705, Japanese Patent No. 5719106, Japanese Patent No. 5712509, and Japanese Patent No. 5292358). To prevent cracking of the inorganic film, it is preferable to alternately laminate inorganic films and transparent planarization layers (e.g., transparent plastic layers).

[0087] Additionally, as a support with a barrier layer, a WVTR of 0.01 (g / m³) can be used, for example.2 ( / 24hr) or more and 1 (g / m 2 Medium-barrier plastic films (with a lifespan of 24 hours or less) can be exemplified by, for example, inorganic films containing inorganic materials such as silicon dioxide, aluminum oxide, magnesium oxide, silicon nitride, silicon oxynitride, SiCN, and amorphous silicon, which are deposited on the surface of a substrate as a barrier layer, or plastic films manufactured by coating a coating liquid formed of a metal oxide and a barrier-resistant organic resin onto a substrate and then drying it (see, for example, Japanese Patent Application Publication No. 2013-108103, Japanese Patent No. 4028353, etc.).

[0088] Water vapor transmission rate can be measured using the PERMATRAN series water vapor transmission rate measuring apparatus manufactured by MOCON (according to ISO 15106-2, JIS K7129B). Specifically, the membrane is cut into 50cm sections. 2 After applying silicone grease to the fixture, ultrapure water was used and the temperature was adjusted to 40°C and the humidity to 90%RH for measurement until the water vapor transmission rate became constant.

[0089] Commercially available products can be used as supports with barrier layers. Examples of commercially available medium-barrier plastic films include "KURARISTER CI" manufactured by Kuraray Co., Ltd., "TECHBARRIER HX", "TECHBARRIER LX" and "TECHBARRIER L" manufactured by Mitsubishi Resin Co., Ltd., "IB-PET-PXB" manufactured by Dai Nippon Printing Co., Ltd., and "GL, GX series" manufactured by Toppan Printing Co., Ltd. Examples of commercially available high-barrier plastic films include "X-BARRIER" manufactured by Mitsubishi Resin Co., Ltd.

[0090] A protective film is preferably used to protect the polymer composition layer disposed on the support. The lamination of the protective film on the polymer composition layer can be performed using known equipment. Examples of equipment used for laminating the protective film include, for example, a roller laminator, a press, and a vacuum pressure laminator.

[0091] Examples of protective films include the aforementioned plastic films. It is preferable to perform a demolding treatment on the surface of the protective film that is bonded to the polymer composition layer. Examples of demolding treatments include those using silicone resin-based mold release agents, alkyd resin-based mold release agents, fluoropolymer-based mold release agents, etc.

[0092] The thickness of the protective film is not particularly limited, but from the viewpoint of the processability of polymer sheets, it is preferably 10 to 150 μm, and more preferably 20 to 100 μm.

[0093] To prevent the polymer composition layer from absorbing moisture after drying, the protective film is preferably a protective film with a barrier layer. Examples of protective films with a barrier layer include the aforementioned plastic films with barrier layers. From a cost perspective, the aforementioned medium-barrier plastic film is preferably used in the protective film.

[0094] <Uses> The polymer compositions and polymer sheets of the present invention are suitable for sealing electronic devices with poor moisture resistance, such as 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))), and organic transistors (OTFTs). Example

[0095] 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. It should be noted that unless otherwise specified, "parts" and "%" in the amount of components and copolymer units refer to "parts by mass" and "% by mass," respectively.

[0096] <Ingredients> The components used in the examples and comparative examples are shown below: (A) Composition: Olefin polymers with anhydride and / or carboxyl groups • "HV-300M" (manufactured by Toho Chemical Industry Co., Ltd.): Maleic anhydride modified liquid polybutene, anhydride group concentration: 1.16 mmol / g, number average molecular weight: 2100 • "LUCANT A-5260" (manufactured by Mitsui Chemicals): Maleic anhydride modified liquid polyolefin, number average molecular weight: 5400 • "ER661" (manufactured by Starlight PMC): 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: 40000, isobutylene unit / isoprene unit: 98.9% / 1.1% (non-volatile components: 35%).

[0097] (B) Composition: Liquid olefin polymer • "HV-1900" (manufactured by ENEOS): Liquid polybutene, number average molecular weight: 2900, viscosity at 25°C: 460 Pa·s • "BI-2000" (manufactured by Nippon Soda Corporation): Liquid hydrogenated polybutadiene, number average molecular weight: 2200, viscosity at 25°C: 43 Pa·s.

[0098] (C) Ingredient: Calcium oxide • "QC2-F1" (manufactured by Inoue Lime Industry Co., Ltd.): Calcium oxide, D50: 2.6μm • "F-lime-1300K" (made by Calfine): calcium oxide, D50: 5.0μm.

[0099] (D) Composition: BET specific surface area is 10m² 2 / g or more of plate packing • "D-600" (manufactured by Nippon Talc): Talc, BET specific surface area: 24m³ 2 / g, D50: 0.6μm • "FG-15" (manufactured by Japan Talc Company): Talc, BET specific surface area: 18m³ 2 / g, D50: 1.5μm.

[0100] (Other ingredients): <Tackifier> • "ARKON P-125" (manufactured by Arakawa Chemical Industry Co., Ltd., hydrogenated petroleum resin, softening point: 125℃) <Antioxidants> • "Irganox 1010" (manufactured by BASF): Hindered phenolic antioxidant <Curing Accelerator> ·2,4,6-Tris(dimethylaminomethyl)phenol (manufactured by KAYAKU NOURYON, hereinafter referred to as "TAP"). <Epoxy-Modified Olefin Polymers> • "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 component: 15%) <Hygroscopic fillers> • "DHT-4C" (manufactured by Kyowa Chemical Industry Co., Ltd.): Semi-calcined hydrotalcite, D50: 400nm, BET specific surface area: 15m² 2 / g <BET specific surface area less than 10m² 2 / g of plate-shaped packing > • "MK-300" (Made by Katakura & Co-op Agri): Mica, BET specific surface area: 2m³ 2 / g, D50: 12μm • "K-1" (manufactured by Japan Talc Company): Talc, BET specific surface area: 7m³ 2 / g, D50: 8μm.

[0101] <Example 1> Prepare the varnish according to the following steps, using the proportions shown in the table below. Use the resulting varnish to produce polymer sheets. It should be noted that the amounts (parts) of each component listed in the table below represent the amount of non-volatile components in the varnish.

[0102] Specifically, in an Ipsol solution (60% non-volatile component) of hydrogenated petroleum resin (tackifier: ARKON P-125, manufactured by Arakawa Chemical Industry Co., Ltd.), maleic anhydride-modified liquid polyolefin (LUCANT A-5260, manufactured by Mitsui Chemicals Co., Ltd.), liquid hydrogenated polybutadiene (BI-2000, manufactured by Nippon Soda Co., Ltd.), calcium oxide (QC2-F1, manufactured by Inoue Lime Industry Co., Ltd.), and talc (D-600, manufactured by Nippon Talc Co., Ltd.) were dispersed using a three-roll mill to obtain a mixture.

[0103] The mixture was mixed with hindered phenolic antioxidant (Irganox 1010, manufactured by BASF), curing accelerator (TAP, manufactured by KAYAKU NOURYON) and toluene, and the mixture was uniformly dispersed using a high-speed rotary mixer to obtain a varnish of polymer composition.

[0104] A laminated film is made by laminating a low-moisture-permeable polyethylene terephthalate (PET) film “SP3000” (trade name: PET: 50μm: manufactured by Toyo Cloth) with one side treated with a silicone-based mold release agent onto the other side, and using it as a support. Another laminated film is made by laminating a low-moisture-permeable polyethylene terephthalate (PET) film “SP8002K2” (trade name: PET: 25μm: manufactured by Toyo Cloth) with one side treated with a silicone-based mold release agent onto the other side, and using it as a protective film. The obtained varnish is uniformly applied to the mold-treated surface of the support using a die-casting machine, and heated at 150°C for 10 minutes to form a polymer composition layer. Then, a polymer composition layer is laminated on the release surface of the protective film to obtain a polymer sheet with a polymer composition layer of 50 μm thickness.

[0105] <Example 2> Except for changing component (A) from maleic anhydride modified liquid polyolefin (LUCANT A-5260, manufactured by Mitsui Chemicals) to maleic anhydride-butyl methacrylate random copolymer modified butyl rubber (ER661, manufactured by Hoshikatsu PMC) and maleic anhydride modified liquid polybutene (HV-300M, manufactured by Toho Chemical Industry Co., Ltd.), a polymer sheet having a polymer composition layer with a thickness of 50 μm was obtained by the same method as in Example 1.

[0106] <Example 3> Except for changing component (B) from liquid hydrogenated polybutadiene (BI-2000, manufactured by Nippon Soda Co., Ltd.) to liquid polybutene (HV-1900, manufactured by ENEOS Co., Ltd.), the same method as in Example 1 was used to obtain a polymer sheet having a polymer composition layer with a thickness of 50 μm.

[0107] <Example 4> Except for changing component (D) from talc (D-600, manufactured by Japan Talc Company) to talc (FG-15, manufactured by Japan Talc Company), polymer sheets with a polymer composition layer of thickness of 50 μm were obtained by using the same method as in Example 1.

[0108] <Example 5> Except for changing the amount of talc (D-600, manufactured by Japan Talc Company) from 3 parts to 1 part, a polymer sheet with a polymer composition layer of 50 μm thickness was obtained by using the same method as in Example 1.

[0109] <Example 6> Except for changing the amount of talc (D-600, manufactured by Japan Talc Company) from 3 parts to 8 parts and removing the tackifier (ARKON P125, manufactured by Arakawa Chemical Industry Co., Ltd.), a polymer sheet with a polymer composition layer of thickness of 50 μm was obtained by using the same method as in Example 1.

[0110] <Example 7> Except for changing the amount of calcium oxide (QC2-F1, manufactured by Inoue Lime Industry Co., Ltd.) from 60 parts to 30 parts and the amount of talc (D-600, manufactured by Japan Talc Co., Ltd.) from 3 parts to 5 parts, a polymer sheet with a polymer composition layer of 50 μm thickness was obtained by using the same method as in Example 1.

[0111] <Example 8> Except for changing the amount of calcium oxide (QC2-F1, manufactured by Inoue Lime Industry Co., Ltd.) from 60 parts to 90 parts and the amount of tackifier (ARKON P125, manufactured by Arakawa Chemical Industry Co., Ltd.) from 15 parts to 10 parts, a polymer sheet with a polymer composition layer of 50 μm thickness was obtained by using the same method as in Example 1.

[0112] <Example 9> Except for changing component (C) from calcium oxide (QC2-F1, manufactured by Inoue Lime Industries Co., Ltd.) to calcium oxide (F-lime-1300K, manufactured by Calfine Co., Ltd.), the same method as in Example 1 was used to obtain a polymer sheet having a polymer composition layer with a thickness of 50 μm.

[0113] <Example 10> Except for the addition of 5 parts of glycidyl methacrylate-modified propylene-butene random copolymer (ER829, manufactured by Starlight PMC) to the formulation in Example 1, a polymer sheet with a polymer composition layer of 50 μm thickness was obtained by the same method as in Example 1.

[0114] <Comparative Example 1> Except for removing liquid polybutene (HV-1900, manufactured by ENEOS) from the formulation of Example 3, a polymer sheet with a polymer composition layer of 50 μm thickness was obtained by the same method as in Example 3.

[0115] <Comparative Example 2> Except for removing maleic anhydride-modified liquid polyolefin (LUCANT A-5260, manufactured by Mitsui Chemicals) from the formulation of Example 3, a polymer sheet with a polymer composition layer of 50 μm thickness was obtained by the same method as in Example 3.

[0116] <Comparative Example 3> Except for removing talc (D-600, manufactured by Japanese Talc Company) from the formulation of Example 3, a polymer sheet with a polymer composition layer having a thickness of 50 μm was obtained by the same method as in Example 3.

[0117] <Comparative Example 4> Except for removing calcium oxide (QC2-F1, manufactured by Inoue Lime Industry Co., Ltd.) from the formulation of Example 3, and changing the amount of talc (D-600, manufactured by Japan Talc Co., Ltd.) from 3 parts to 10 parts, a polymer sheet with a polymer composition layer of thickness of 50 μm was obtained by the same method as in Example 3.

[0118] <Comparative Example 5> From the formulation of Example 3, talc (D-600, manufactured by Japan Talc Co., Ltd.) was removed, maleic anhydride modified liquid polyolefin (LUCANT A-5260, manufactured by Mitsui Chemicals Co., Ltd.) was replaced with maleic anhydride modified liquid polybutene (HV-300M, manufactured by Toho Chemical Co., Ltd.), the amount of liquid polybutene (HV-1900, manufactured by ENEOS Co., Ltd.) was changed from 10 parts to 19 parts, calcium oxide (QC2-F1, manufactured by Inoue Lime Industry Co., Ltd.) was replaced with semi-calcined hydrotalcite (DHT-4C, manufactured by Kyowa Chemical Co., Ltd.), and 4 parts of glycidyl methacrylate modified propylene-butene random copolymer (ER829, manufactured by Hoshikatsu PMC Co., Ltd.) were added. Otherwise, the same method as in Example 3 was used to obtain a polymer sheet with a polymer composition layer having a thickness of 50 μm.

[0119] <Comparative Example 6> Except that, in the combination of Example 3, talc (D-600, manufactured by Japanese Talc Company) was replaced with mica (MK-300, manufactured by Katakura & Co-op Agri Company), the same method as in Example 3 was used to obtain a polymer sheet with a polymer composition layer having a thickness of 50 μm.

[0120] <Comparative Example 7> Except that in Example 3, talc (D-600, manufactured by Japan Talc Company) was replaced with talc (K-1, manufactured by Japan Talc Company), the same method as in Example 3 was used to obtain a polymer sheet with a polymer composition layer having a thickness of 50 μm.

[0121] <Evaluation Methods for Film-Forming Properties> The condition of the polymer sheets produced in the following benchmark evaluation examples and comparative examples is as follows: 〇 (Good): The film forms well and can be used as a pressure-sensitive adhesive sheet. × (Defect): When heated at 150°C for 10 minutes, the film shrinks, resulting in poor dimensional stability or failure to form a film.

[0122] <Methods for evaluating bond strength> The protective film of the polymer sheet (50 mm in length and 20 mm in width) prepared in the examples and comparative examples was peeled off. Using a batch vacuum laminator (Morton-724, Nichigo-Morton), the exposed polymer composition layer was laminated onto the aluminum foil side of a composite film “AL1N30 with PET” (30 μm thick aluminum foil, 25 μm thick polyethylene terephthalate film, manufactured by Tokai Toyo Aluminum Sales Co., Ltd.) having aluminum foil and a polyethylene terephthalate film. Lamination was performed at a temperature of 80°C, a time of 30 seconds, and a pressure of 0.3 MPa. Then, the support of the polymer sheet was peeled off, and a glass plate (76 mm in length, 26 mm in width, 1.2 mm thick, micro-supported glass slide) was further laminated onto the exposed polymer composition layer under the same conditions as described above. For the resulting laminate, the adhesive strength (gf / cm) was measured when peeled at a tensile speed of 50 mm / min in a direction 90 degrees relative to the length direction of the aluminum foil (initial 90-degree adhesive strength).

[0123] <Evaluation Methods for Water Vapor Intrusion Barrier Properties> As a support film, a composite film "AL1N30 with PET" (30 μm thick aluminum foil, 25 μm thick polyethylene terephthalate film, manufactured by Tokai Toyo Aluminum Sales Co., Ltd.) comprising an aluminum foil and a polyethylene terephthalate film was prepared. Except that this support film was used instead of a support body, the polymer sheet was manufactured in the same manner as in the embodiments and comparative examples, forming a polymer composition layer on the aluminum foil side of the support film. Thus, a test sheet comprising a support film and a polymer composition layer was obtained.

[0124] A 50mm x 50mm square glass plate made of alkali-free glass was prepared. The glass plate was washed with boiling isopropanol for 5 minutes and dried at 150°C for at least 30 minutes.

[0125] On one side of the glass plate, calcium is deposited by vapor deposition using a mask covering the peripheral area 0 mm to 1 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 1 mm from the end of the glass plate.

[0126] In a nitrogen atmosphere, a hot laminator (Fujipla Lamipacker DAiSY A4 (LPD2325)) was used to bond the polymer composition layer of the above-mentioned test sheet to the calcium film side of the above-mentioned glass plate to obtain a laminate.

[0127] Normally, when calcium comes into contact with water, it forms calcium oxide and becomes transparent. Furthermore, in the evaluation samples described above, because the glass plate and aluminum foil have sufficiently high water vapor intrusion barrier properties, moisture typically moves through the ends of the polymer composition layer in an in-plane direction (perpendicular to the thickness direction) to reach the calcium film. Therefore, if moisture intrudes into the evaluation sample, the calcium film is gradually oxidized from the ends and becomes transparent, thus a shrinkage of the calcium film is observed. Therefore, the intrusion of moisture into the evaluation sample can be evaluated by measuring the sealing distance [mm] from the ends of the evaluation sample to the calcium film. Therefore, the evaluation sample containing the calcium film can be used as a model for lead-containing electronic devices.

[0128] First, the sealing distance X2 [mm] from the end of the evaluation sample to the end of the calcium film was measured using a microscope (Measuring Microscope MF-U, manufactured by Mitutoyo). Hereinafter, this sealing distance X2 is sometimes referred to as the initial sealing distance X2.

[0129] Next, the evaluation sample was placed in a constant temperature and humidity bath set to 85°C and 85%RH. The evaluation sample was removed from the bath when the sealing distance X1 (mm) between the end of the evaluation sample and the end of the calcium film increased by 0.1 mm compared to the initial sealing distance X2. The time from the moment the evaluation sample was placed in the bath to the moment it was removed was calculated as the reduction start time t [hours]. This reduction start time t corresponds to the time T from the moment the evaluation sample was placed in the bath. P1 The time T from the start of the sealing distance X1 [mm] between the end of the evaluation sample placed in the constant temperature and humidity bath and the end of the calcium film becomes "X2 + 0.1 mm". P2 The time up to that point.

[0130] Substituting the sealing distance X1 and the reduced start time t into the Fick diffusion equation (1), the constant K, which serves as the barrier parameter for water vapor intrusion, is calculated.

[0131] [Mathematical Expression 1] .

[0132] Using the obtained constant K, the water vapor intrusion barrier properties, which enable the polymer composition layer to inhibit moisture intrusion, are evaluated according to the following criteria. A smaller value for the constant K indicates higher water vapor intrusion barrier properties. "h" represents "hours".

[0133] (Benchmark for water vapor intrusion barrier) "Good": Constant K is less than 0.01 cm / h 0.5 "Poor": The constant K is 0.01 cm / h0.5 above.

[0134] [Table 1-1] [Table 1-2] .

[0135] Industrial availability The polymer composition of the present invention can form a polymer composition layer (as a sealing material) exhibiting high water vapor intrusion barrier properties, and is suitable for sealing electronic devices with weak moisture resistance, such as organic EL devices, organic light-emitting diodes (OLEDs), solar cells (especially organic solar cells (organic thin-film solar cells (OPVs), perovskite solar cells (PSCs), dye-sensitized solar cells (DSSCs))), and organic transistors (OTFTs).

[0136] This application is based on Japanese Patent Application No. 2023-047175, the contents of which are fully contained in this specification.

Claims

1. A polymer composition comprising the following components (A) to (D): (A) Olefin polymers having anhydride and / or carboxyl groups, (B) Liquid olefin polymers (C) Calcium oxide, and (D)BET has a specific surface area of ​​10m² 2 Plate-shaped packing materials with a density of / g or higher.

2. The polymer composition according to claim 1, wherein, (A) The number average molecular weight of olefin polymers having anhydride groups and / or carboxyl groups is 950 or more.

3. The polymer composition according to claim 1, wherein, The content of olefin polymers having anhydride and / or carboxyl groups is 5 to 25% by mass relative to 100% by mass of the non-volatile components of the polymer composition.

4. The polymer composition according to claim 1, wherein, (B) The content of liquid olefin polymer is 5 to 25% by mass relative to 100% by mass of the non-volatile components of the polymer composition.

5. The polymer composition according to claim 1, wherein, (C) The median particle size of calcium oxide is less than 20 μm.

6. The polymer composition according to claim 1, wherein, The content of (C) calcium oxide is 15 to 70% by mass relative to 100% by mass of the non-volatile components of the polymer composition.

7. The polymer composition according to claim 1, wherein, (D)BET has a specific surface area of ​​10m² 2 The median particle size of plate-shaped packings with a particle size of / g or more is less than 2μm.

8. The polymer composition according to claim 1, wherein, The specific surface area of ​​(D)BET is 100 m² relative to 100% by mass of the non-volatile components of the polymer composition. 2 The content of plate-shaped packings with a density of 0.5% to 15% by mass is above 0.5%.

9. A polymer sheet having a laminated structure comprising a polymer composition layer formed from the polymer composition of claim 1.

10. The polymer sheet according to claim 9, used for sealing electronic devices.

11. An electronic device, wherein, The polymer sheet of claim 9 was used for sealing.

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