Resin composition, method for producing same, and resin sheet

Abstract

Provided is a resin composition capable of forming a resin composition layer having both water vapor intrusion barrier properties and transparency. A resin composition comprising the following components (A) to (D): (A) a polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of 10000 or more; (B) a polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of less than 10000; (C) an isobutylene-containing polymer having a number average molecular weight of 10000 or more; and (D) calcium oxide having a median diameter of 300 nm or less.

Description

Technical Field

[0001] The present invention relates to a resin composition that can be used for sealing electronic devices and the like, a method for producing the same, and a resin sheet having a laminate structure including a resin composition layer formed from the resin composition. Background Art

[0002] In devices with weak moisture tolerance, such as OLEDs (Organic Light Emitting Diodes) and organic solar cells, high transparency is required for sealing materials to improve design and performance. For example, Patent Document 1 proposes a sealing resin composition using hydrotalcite as a hygroscopic material. However, the resin composition reversibly absorbs moisture during the manufacturing process and distribution process. If pre-drying is not performed, there is a problem of degradation of devices such as OLEDs.

[0003] Prior art literature Patent Literature Patent Document 1: International Publication No. 2017-057708. Summary of the Invention

[0004] Problems to be solved by the invention On the other hand, calcium oxide is known as a hygroscopic filler. A sealing layer formed from a sealing composition using calcium oxide exhibits excellent water vapor intrusion suppression properties (sometimes referred to herein as "water vapor intrusion barrier properties"). However, when calcium oxide is included as a hygroscopic filler in a sealing composition comprising an olefin polymer, the sealing layer formed from the composition generally loses transparency. To suppress this loss of transparency, the use of finely divided calcium oxide is considered, but it is necessary to suppress the loss of transparency or the yellowish odor caused by the calcium oxide.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition capable of forming a resin composition layer (sealing layer) having both water vapor intrusion barrier properties and transparency.

[0006] Means for solving problems The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that by blending the following components (A) to (D), a resin composition capable of forming a resin composition layer (sealing layer) having both water vapor intrusion barrier properties and transparency can be obtained, thereby completing the present invention.

[0007] That is, the present invention has the following features [1] A resin composition comprising the following components (A) to (D): (A) a polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of 10,000 or more, (B) a polymer having anhydride groups and / or carboxyl groups and having a number average molecular weight of less than 10,000, (C) an isobutylene-containing polymer having a number average molecular weight of 10,000 or more, and (D) calcium oxide with a median particle size of less than 300 nm; [2] The resin composition according to [1], wherein (A) the polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of 10,000 or more is an olefin-based polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of 10,000 or more; [3] The resin composition according to [1] or [2], wherein (B) the polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of less than 10,000 is an olefin-based polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of less than 10,000; [4] The resin composition according to any one of [1] to [3], wherein the number average molecular weight of component (B) is less than 3000; [5] The resin composition according to any one of [1] to [4], wherein (C) the isobutylene-containing polymer having a number average molecular weight of 10,000 or greater is an isobutylene-containing olefin polymer having a number average molecular weight of 10,000 or greater; [6] The resin composition according to [5], wherein (C) the isobutylene-containing polymer having a number average molecular weight of 10,000 or more is at least one member selected from the group consisting of polyisobutylene, isobutylene-isoprene copolymer, and styrene-isobutylene-styrene block copolymer having a number average molecular weight of 10,000 or more; [7] The resin composition according to any one of [1] to [6], further comprising (E) a liquid olefin polymer (excluding component (A), component (B), and component (C); [8] The resin composition according to any one of [1] to [7], further comprising (F) a tackifier; [9] The resin composition according to any one of [1] to [8], wherein the content of the component (A) is 0.1 to 25% by mass relative to 100% by mass of the non-volatile components of the resin composition;

[10] The resin composition according to any one of [1] to [9], wherein the content of component (B) is 3 to 50% by mass relative to 100% by mass of the non-volatile components of the resin composition;

[11] The resin composition according to any one of [1] to

[10] , wherein the content of the component (C) is 5 to 30% by mass relative to 100% by mass of the non-volatile components of the resin composition;

[12] The resin composition according to any one of [1] to

[11] , wherein the content of the component (D) is 10 to 70% by mass relative to 100% by mass of the non-volatile components of the resin composition;

[13] A resin sheet having a laminated structure including a resin composition layer formed from the resin composition according to any one of [1] to

[12] .

[0008] Effects of the Invention According to the present invention, a resin composition capable of forming a resin composition layer (sealing layer) having both water vapor intrusion barrier properties and transparency can be provided. DETAILED DESCRIPTION

[0009] Hereinafter, the present invention will be described according to its preferred embodiments; [Resin composition] The resin composition of the present invention contains the following components (A) to (D) as essential components: (A) a polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of 10,000 or more, (B) a polymer having anhydride groups and / or carboxyl groups and having a number average molecular weight of less than 10,000, (C) an isobutylene-containing polymer having a number average molecular weight of 10,000 or more, and (D) Calcium oxide with a median particle size of 300 nm or less.

[0010] By using calcium oxide having higher hygroscopicity than the hydrotalcite described in Patent Document 1 as a hygroscopic filler, a resin composition layer having excellent water vapor intrusion barrier properties can be formed.

[0011] When calcium oxide is used, the transparency of the resulting resin composition layer decreases. In this regard, in the present invention, by using calcium oxide (component (D)) having a median particle size of 300 nm or less, a decrease in transparency can be suppressed.

[0012] Finely divided component (D) is difficult to disperse well in a resin composition. However, in the present invention, by using a polymer (component (B)) having anhydride groups and / or carboxyl groups and having a number average molecular weight of less than 10,000, the dispersibility of finely divided component (D) in the resin composition is improved. In this regard, it is speculated that component (B) functions as a dispersant for finely divided component (D). However, the present invention is not limited to this speculation.

[0013] In this specification, an "olefin-based polymer" refers to a polymer containing olefin-derived structural units (hereinafter sometimes referred to simply as "olefin units") as the main structural units (i.e., the amount of olefin units is the largest among all structural units). Hereinafter, olefin units such as "butene-derived structural units" may be referred to simply as "butene units," etc.

[0014] The olefin polymer may be an olefin resin (e.g., propylene-butene copolymer) or an olefin rubber (e.g., butyl rubber, i.e., isobutylene-isoprene copolymer). In this specification, "olefin resin" refers to an olefin polymer that cannot form a rubber elastomer by crosslinking, and "olefin rubber" refers to an olefin polymer that can form a rubber elastomer by crosslinking.

[0015] The olefin is preferably a monoolefin having one olefinic carbon-carbon double bond and / or a diolefin having two olefinic carbon-carbon double bonds. Examples of the monoolefin include α-olefins such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. Examples of the diolefin include 1,3-butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethylbutadiene.

[0016] The olefin polymer may be a homopolymer or a copolymer. The copolymer may be a random copolymer or a block copolymer. In addition, the olefin polymer may be a copolymer of an olefin and a monomer other than the olefin. As the olefin copolymer, for example: ethylene-non-conjugated diene copolymer, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer, ethylene-butene copolymer, ethylene-propylene-butene copolymer, propylene-butene copolymer, propylene-butene-non-conjugated diene copolymer, isobutylene-isoprene copolymer, styrene-isobutylene copolymer, styrene-isobutylene-styrene copolymer etc. can be enumerated.

[0017] Hereinafter, each component will be described in detail. It should be noted that, unless otherwise specified in this specification, each component may be used alone or in combination of two or more.

[0018] <(A)Component> Component (A) is a polymer having an anhydride group (i.e., a carbonyloxycarbonyl group (-CO-O-CO-)) and / or a carboxyl group and a number average molecular weight of 10,000 or more. By combining component (A), a resin composition layer that is not easily deformed and can maintain its shape can be obtained. If component (A) is not combined, film formation becomes difficult. In addition, component (A) forms a cross-linked structure through the cross-linking reaction of anhydride groups / carboxyl groups, or forms a cross-linked structure through the coordination of anhydride groups / carboxyl groups to calcium oxide, thereby making it possible to disperse calcium oxide (component (D)) well in the resin composition, and furthermore, to exert water vapor intrusion barrier properties. As the polymer of component (A), there is no particular limitation as long as the number average molecular weight is 10,000 or more and it has anhydride groups and / or carboxyl groups, but from the viewpoint of compatibility, an olefin-based polymer having an anhydride group and / or carboxyl group and a number average molecular weight of 10,000 or more is preferred.

[0019] When an olefin polymer having an acid anhydride group and a number average molecular weight of 10,000 or more is used as component (A), the concentration of the acid anhydride group in the polymer is preferably 0.05 to 10 mmol / g, more preferably 0.10 to 5 mmol / g. The concentration of the acid anhydride group is obtained from the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the polymer in accordance with JIS K 2501.

[0020] When a carboxyl group-containing olefin polymer having a number average molecular weight of 10,000 or greater is used as component (A), the carboxyl group concentration in the polymer is preferably 0.05 to 20 mmol / g, more preferably 0.10 to 10 mmol / g. The carboxyl group concentration is determined by the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the polymer, as described in JIS K 2501.

[0021] When an olefin polymer having an acid anhydride group and a carboxyl group and having a number average molecular weight of 10,000 or more is used as component (A), the total concentration of the acid 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.

[0022] Component (A) can be produced, for example, by (i) grafting an olefin polymer with an unsaturated compound having anhydride and / or carboxyl groups (e.g., maleic anhydride) under free radical reaction conditions, or (ii) copolymerizing an unsaturated compound having anhydride and / or carboxyl groups with an α-olefin.

[0023] As the component (A), for example, a polymer available from Starlight PMC Co., Ltd. can be used. Examples of such polymers include "ER645" manufactured by Starlight PMC Co., Ltd. (maleic anhydride-butyl methacrylate random copolymer modified propylene-butene random copolymer), "ER661" manufactured by Starlight PMC Co., Ltd. (maleic anhydride-butyl methacrylate random copolymer modified butyl rubber), "ER641" manufactured by Starlight PMC Co., Ltd. (maleic anhydride modified butyl rubber), "ER669" manufactured by Starlight PMC Co., Ltd. (maleic anhydride-2-ethylhexyl acrylate random copolymer modified butyl rubber), "ER674" manufactured by Starlight PMC Co., Ltd. (maleic anhydride-lauryl methacrylate random copolymer modified butyl rubber), "T-YP279" manufactured by Starlight PMC Co., Ltd. (maleic anhydride modified propylene-butene random copolymer), and "T-YP212" manufactured by Starlight PMC Co., Ltd. (maleic anhydride modified propylene-butene random copolymer).

[0024] In one embodiment of the present invention, component (A) is the following polymer having a number average molecular weight of 10,000 or more: (i) preferably at least one selected from the group consisting of polybutene having anhydride groups and / or carboxyl groups, isobutylene-isoprene copolymers having anhydride groups and / or carboxyl groups (i.e., butyl rubber), propylene-butene copolymers having anhydride groups and / or carboxyl groups, ethylene-methyl methacrylate copolymers having anhydride groups and / or carboxyl groups, and ethylene-propylene-butene copolymers having anhydride groups and / or carboxyl groups, (ii) more preferably at least one selected from the group consisting of polybutene having anhydride groups and / or carboxyl groups, isobutylene-isoprene copolymers having anhydride groups and / or carboxyl groups, and propylene-butene copolymers having anhydride groups and / or carboxyl groups, (iii) more preferably at least one selected from polybutene having an acid anhydride group, an isobutylene-isoprene copolymer having an acid anhydride group, and a propylene-butene copolymer having an acid anhydride group, (iv) Polybutene having an acid anhydride group is particularly preferred.

[0025] The number average molecular weight of component (A) is 10,000 or more. From the viewpoint of improving the good coating property of the varnish of the resin composition, the sealing performance and mechanical strength of the formed resin composition layer, it is preferably 10,000 to 500,000, and more preferably 15,000 to 400,000. It should be noted that the number average molecular weight of each component is measured by gel permeation chromatography (GPC) method (polystyrene conversion). The number average molecular weight based on the GPC method can be determined by, specifically, using "LC-9A / RID-6A" manufactured by Shimadzu Corporation as a measuring device, "Shodex K-800P / K-804L / K-804L" manufactured by Showa Denko as a column, using toluene or the like as a mobile phase, measuring at a column temperature of 40°C, and calculating using a standard curve of standard polystyrene.

[0026] From the viewpoint of forming a resin composition layer that is less likely to deform and can maintain its shape, the content of component (A) is preferably 0.1 to 25 mass %, more preferably 1 to 20 mass %, and even more preferably 3 to 15 mass %, relative to 100 mass % of the nonvolatile components of the resin composition.

[0027] <(B) Ingredient> Component (B) is a polymer having anhydride and / or carboxyl groups and a number average molecular weight of less than 10,000. By adding component (B), calcium oxide (component (D)) can be well dispersed in the resin composition. Furthermore, the anhydride and carboxyl groups undergo a cross-linking reaction or coordinate with calcium oxide to form a cross-linked structure, thereby exhibiting water vapor intrusion barrier properties. Component (B) is preferably an olefin-based polymer having anhydride and / or carboxyl groups and a number average molecular weight of less than 10,000, and more preferably an olefin-based polymer having anhydride groups and a number average molecular weight of less than 10,000.

[0028] When an olefin polymer having an acid anhydride group and a number average molecular weight of less than 10,000 is used as component (B), the concentration of the acid anhydride group in the polymer is preferably 0.05 to 10 mmol / g, more preferably 0.10 to 5 mmol / g. The concentration of the acid anhydride group is obtained from the 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.

[0029] When a carboxyl group-containing olefin polymer having a number average molecular weight of less than 10,000 is used as component (B), the carboxyl group concentration in the polymer is preferably 0.05 to 20 mmol / g, more preferably 0.10 to 10 mmol / g. The carboxyl group concentration is determined by the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the polymer, as described in JIS K 2501.

[0030] When an olefin polymer having an acid anhydride group and a carboxyl group and having a number average molecular weight of less than 10,000 is used as component (B), the total concentration of the acid 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.

[0031] The number average molecular weight of component (B) is less than 10,000, and preferably less than 3,000 from the perspective of dispersibility of the hygroscopic filler (calcium oxide: component (D)). Furthermore, in one embodiment of the present invention, from the perspective of improving the coating properties of the resin composition varnish and the sealing properties and mechanical strength of the resulting resin composition layer, the number average molecular weight of component (B) is preferably 100 to 10,000 (but not including 10,000), more preferably 250 to 9,000, and even more preferably 500 to 8,000.

[0032] Component (B) can be produced, for example, by (i) grafting an olefin polymer with an unsaturated compound having anhydride and / or carboxyl groups (e.g., maleic anhydride) under free radical reaction conditions, or (ii) copolymerizing an unsaturated compound having anhydride and / or carboxyl groups with an α-olefin.

[0033] As the component (B), for example, a polymer available from Toho Chemical Industry Co., Ltd., Seiko PMC Co., Ltd., or the like 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 Seikyo PMC Co., Ltd., LUCANT A-5515 (acid-modified ethylene-α-olefin copolymer) manufactured by Mitsui Chemicals, Inc., LUCANT A-5260 (acid-modified ethylene-α-olefin copolymer) manufactured by Mitsui Chemicals, Inc., LUCANT A-5320H (acid-modified ethylene-α-olefin copolymer) manufactured by Mitsui Chemicals, Inc., T-YP430 (maleic anhydride-modified ethylene-methyl methacrylate copolymer) manufactured by Seikyo PMC Co., Ltd., T-YP956 (maleic anhydride-modified ethylene-propylene-butene random copolymer) manufactured by Seikyo PMC Co., Ltd., and DIACARNA® manufactured by Mitsubishi Chemical Corporation. 30M" (copolymer of maleic anhydride and α-olefin), etc.

[0034] In one embodiment of the present invention, component (B) is the following polymer having a number average molecular weight of less than 10,000: (i) preferably at least one selected from the group consisting of polybutene having anhydride groups and / or carboxyl groups, isobutylene-isoprene copolymers having anhydride groups and / or carboxyl groups (i.e., butyl rubber), propylene-butene copolymers having anhydride groups and / or carboxyl groups, ethylene-methyl methacrylate copolymers having anhydride groups and / or carboxyl groups, and ethylene-propylene-butene copolymers having anhydride groups and / or carboxyl groups, (ii) more preferably at least one selected from polybutene having an acid anhydride group and / or a carboxyl group, isobutylene-isoprene copolymer having an acid anhydride group and / or a carboxyl group, and propylene-butene copolymer having an acid anhydride group and / or a carboxyl group, (iii) more preferably at least one selected from polybutene having an acid anhydride group, isobutylene-isoprene copolymer having an acid anhydride group, and propylene-butene copolymer having an acid anhydride group, (iv) Polybutene having an acid anhydride group is particularly preferred.

[0035] From the viewpoint of dispersibility of fine calcium oxide (component (D)) in the resin composition, the content of component (B) is preferably 3 to 50% by mass, more preferably 5 to 45% by mass, and even more preferably 10 to 40% by mass relative to 100% by mass of the non-volatile components of the resin composition.

[0036] <(C) Ingredient> Component (C) is an isobutylene-containing polymer having a number average molecular weight of 10,000 or more, but does not include component (A). That is, component (C) is an isobutylene-containing polymer having a number average molecular weight of 10,000 or more and not having either an anhydride group or a carboxyl group. In this specification, "isobutylene-containing polymer" means a polymer containing a structural unit derived from isobutylene. By adding component (C), the yellow odor of the formed resin composition layer can be suppressed. Component (C) is preferably an isobutylene-containing olefin polymer having a number average molecular weight of 10,000 or more.

[0037] As the component (C), for example, a polymer available from JSR Corporation can be used. Examples of such polymers include "BUTYL 065," "BUTYL 268," and "BUTYL 365" manufactured by JSR Corporation (all butyl rubbers), "HIMOL" and "TETRAX" manufactured by JXTG Energy Corporation (all polyisobutylenes), "B10," "B15," "N50SF," and "N80SF" manufactured by BASF (all polyisobutylenes), and "SIBSTAR 103T-UL" manufactured by Kaneka Corporation (styrene-isobutylene-styrene block copolymer).

[0038] Component (C) is the following polymer having a number average molecular weight of 10,000 or more: (i) is preferably at least one selected from polyisobutylene, isobutylene-isoprene copolymer (i.e., butyl rubber) and styrene-isobutylene-styrene block copolymer, (ii) More preferably, it is an isobutylene-isoprene copolymer.

[0039] When an isobutylene-isoprene copolymer having a number average molecular weight of 10,000 or more (i.e., butyl rubber) is used as the component (C), the amount of the isobutylene units in the copolymer is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and even more preferably 3 to 40% by mass relative to the total of the isobutylene units and the isoprene units, from the viewpoint of yellowing resistance of the resulting resin composition layer.

[0040] When a styrene-isobutylene-styrene block copolymer having a number average molecular weight of 10,000 or more is used as the component (C), the amount of the isobutylene units in the copolymer is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and even more preferably 3 to 40% by mass relative to the total of the isobutylene units and the styrene units, from the viewpoint of yellowing resistance of the resulting resin composition layer.

[0041] The number average molecular weight of the component (C) is 10,000 or more, and is preferably 10,000 to 500,000, and more preferably 15,000 to 400,000, from the viewpoint of yellowing resistance of the resin composition layer to be formed.

[0042] From the viewpoint of yellowing resistance of the formed resin composition layer, the content of the component (C) is preferably 5 to 30 mass %, more preferably 7 to 25 mass %, and even more preferably 9 to 20 mass % relative to 100 mass % of the nonvolatile components of the resin composition.

[0043] <(D) Ingredient> Component (D) is calcium oxide having a median particle size of 300 nm or less. By adding component (D) as a hygroscopic filler, the resulting resin composition layer can be provided with water vapor intrusion barrier properties. Furthermore, by setting the median particle size to 300 nm or less, a highly transparent resin composition layer can be formed.

[0044] The median particle size of the (D) component is 300 nm or less, preferably 250 nm or less from the viewpoint of the transparency of the resin composition layer formed, and preferably 1 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more from the viewpoint of the dispersibility of the (D) component in the resin composition. In one embodiment of the present invention, the median particle size of the (D) component is preferably 1 to 300 nm, more preferably 5 to 250 nm, and further preferably 10 to 200 nm. The median particle size of the (D) component is the median particle size in the volume-based particle size distribution (particle size distribution) prepared by measuring the particle size of the (D) component by dynamic light scattering (JIS Z 8828). The dynamic light scattering method is a method for calculating the particle size and particle size distribution by analyzing the fluctuation corresponding to the speed of the Brownian motion using a photon correlation method based on the scattered light observed when the 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.

[0045] As component (D), calcium oxide having a median particle size exceeding 300 nm can be crushed and used, or commercially available calcium oxide having a median particle size of 300 nm or less can be used. Commercially available calcium oxide having a median particle size exceeding 300 nm includes, for example, “QC-X” manufactured by Inoue Lime Industry Co., Ltd., “WAC Series” manufactured by Sankyo Flour Milling Co., Ltd., and “HAL-G”, “HAL-J”, “HAL-F”, “HAL-O”, and “HAL-P” manufactured by Yoshizawa Lime Industry Co., Ltd. Commercially available calcium oxide having a median particle size of 300 nm or less includes, for example, “CaO Nano Powder” manufactured by Filgen Co., Ltd.

[0046] From the perspective of water vapor intrusion barrier properties of the resin composition layer, the content of component (D) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to 100% by mass of the non-volatile components of the resin composition. From the perspective of adhesiveness of the resin 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 (D) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 15 to 60% by mass, relative to 100% by mass of the non-volatile components of the resin composition.

[0047] <Other ingredients> The resin composition of the present invention may contain components other than components (A) to (D) (hereinafter sometimes referred to as "other components") within the scope that does not hinder the effects of the present invention. Examples of other components include liquid olefin polymers, tackifiers, antioxidants, curing accelerators, epoxy-modified olefin polymers having a number average molecular weight of less than 10,000, and plasticizers. These may be used alone or in combination of two or more.

[0048] (Liquid olefin polymer (hereinafter also referred to as "component (E)") The component (E) is a liquid olefin polymer other than the components (A), (B), and (C). By adding the component (E), good adhesion and flexibility can be imparted to the formed resin composition layer.

[0049] In the present invention, the "liquid" in "liquid olefin polymer" means a viscosity of 5000 Pa·s or less at 25°C. Furthermore, in the present invention, "viscosity at 25°C" refers to the viscosity calculated by multiplying the density by the kinetic viscosity at 25°C measured using a dynamic viscoelasticity measuring apparatus. Examples of dynamic viscoelasticity measuring apparatuses include a rheometer manufactured by TA Instruments (trade name: DISCOVERY HR-2).

[0050] In the present invention, a liquid olefin polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of 10,000 or greater is classified as component (A), a liquid olefin polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of less than 10,000 is classified as component (B), and a liquid isobutylene-containing olefin polymer having a number average molecular weight of 10,000 or greater is classified as component (C). Therefore, component (E) in the present invention is a liquid olefin polymer other than components (A) to (C).

[0051] From the viewpoint of good adhesion and flexibility of the formed resin composition layer, the viscosity of the component (E) 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.

[0052] From the viewpoint of good coating properties of the varnish of the resin composition, the number average molecular weight of the component (E) is preferably 100 to 50,000, more preferably 200 to 30,000, and even more preferably 300 to 20,000.

[0053] (E) component can use commercially available products. Examples of such commercial products include: "HV-100" (liquid polybutene) manufactured by ENEOS, "HV-300" (liquid polybutene) manufactured by ENEOS, "HV-1900" (liquid polybutene) manufactured by ENEOS, "HV-50" (liquid polybutene) manufactured by ENEOS, "HV-35" (liquid polybutene) manufactured by ENEOS, "950MW" (liquid polybutene) manufactured by Kothari, "2400" (liquid polybutene) manufactured by Kothari, and "HV-50" (liquid polybutene) manufactured by ENEOS. MW" (liquid olefin polymer), INEOS "H-1900" (liquid polybutene), INEOS "H-6000" (liquid polybutene), INEOS "H-18000" (liquid polybutene), NOF "200N" (liquid polybutene), Nippon Soda "BI-2000" (hydrogenated polybutadiene), Nippon Soda "BI-3000" (hydrogenated polybutadiene), Nippon Soda "GI-3000" (hydrogenated polybutadiene), Mitsui Chemicals "LUCANT LX100" (liquid olefin polymer), Mitsui Chemicals "LUCANT LX400" (liquid olefin polymer), Idemitsu Showa Shell "Poly bd R-45HT" (butadiene-based liquid rubber), Idemitsu Showa Shell "Poly bd R-15HT" (butadiene-based liquid rubber), Idemitsu Showa Shell Co., Ltd.'s "Poly 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., Ricon 154" (liquid butadiene), Ricon 184 (liquid styrene-butadiene random copolymer) manufactured by Cray Valley Company, etc.

[0054] The component (E) is preferably liquid polybutene and / or hydrogenated polybutadiene, and more preferably liquid polybutene.

[0055] When using (E) component, from the viewpoint of good adhesion and flexibility of the resin composition layer formed, its content 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, relative to 100% by mass of the non-volatile component of the resin composition. In one embodiment of the present invention, the content of (E) component is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 30% by mass, relative to 100% by mass of the non-volatile component of the resin composition.

[0056] (Thickener (hereinafter also referred to as "(F) component")) A tackifier is a component that imparts adhesiveness to a resin composition. Examples of tackifiers include rosin-based resins, terpene resins, modified terpene resins (hydrogenated terpene resins, terpene-phenol copolymer resins, aromatic modified terpene resins, etc.), petroleum resins (aliphatic petroleum resins, hydrogenated petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, copolymerized petroleum resins), coumarone-indene resins, alkylphenol resins, and xylene resins.

[0057] Commercially available tackifiers can be used. Examples of commercially available products include the following. Examples of rosin-based resins include Pine Crystal ME-H, Pine Crystal ME-D, Pine Crystal ME-G, Pine Crystal KR-85, Pine Crystal KE-311, Pine Crystal KE-359, Pine Crystal D-6011, Pine Crystal PE-590, Pine Crystal KE-604, and Pine Crystal PR-580 (all manufactured by Arakawa Chemical Industries, Ltd.).

[0058] Examples of the terpene resin include YS Resin PX1000, YS Resin PX1150, YS Resin PX1150N, YS Resin PX1250, YS Resin TH130, YS Resin TR105, YS Resin LP, and YS Resin CP (all manufactured by Yasuhara Chemical Co., Ltd.).

[0059] Examples of the hydrogenated terpene resin include CLEARON P, CLEARON M, and CLEARON K series (all manufactured by Yasuhara Chemical Industry Co., Ltd.).

[0060] Examples of the terpene-phenol copolymer resin include YS Polyster 2000, Polyster U, Polyster T, Polyster S, and Mighty Ace G (all manufactured by Yasuhara Chemical Industry Co., Ltd.).

[0061] Examples of the aromatic modified terpene resin include YS Resin TO85, YS Resin TO105, YSResin TO115, and YS Resin TO125 (all manufactured by Yasuhara Chemical Industry Co., Ltd.).

[0062] Examples of hydrogenated petroleum resins include Escorez 5300 series and 5600 series (all manufactured by ExxonMobil); T-REZ OP501, T-REZ PR803, T-REZ HA085, T-REZ HA103, T-REZ HA105, and T-REZ HA125 (all hydrogenated dicyclopentadiene petroleum resins manufactured by ENEOS); Quintone 1325 and Quintone 1345 (all manufactured by Zeon Corporation); I-MARV S-100, I-MARV S-110, I-MARV P-100, I-MARV P-125, and I-MARVP-140 (all hydrogenated dicyclopentadiene petroleum resins manufactured by Idemitsu Kosan Co., Ltd.); ARKON P-90, ARKON P-100, ARKON P-115, and ARKON P-125, ARKON P-140, ARKON M-90, ARKON M-100, ARKON M-115, ARKON M-135, TFS13-030 (all manufactured by Arakawa Chemical Industries, Ltd.), etc.

[0063] Examples of the aromatic petroleum resin 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); T-REZ RB093, T-REZ RC100, T-REZ RC115, T-REZ RC093, and T-REZ RE100 (both manufactured by ENEOS), etc.

[0064] Examples of the copolymer petroleum resin include T-REZ HB103, T-REZ HB125, TREZ 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).

[0065] From the viewpoint of heat resistance of the formed resin composition layer, the softening point of the tackifier is preferably 50 to 200° C., more preferably 90 to 180° C., and even more preferably 100 to 170° C. The softening point is measured by the ring and ball method according to JIS K 2207.

[0066] When a tackifier is used, the content thereof is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and even more preferably 5 to 30% by mass relative to 100% by mass of the non-volatile components of the resin composition, from the viewpoint of adhesion and sealing properties of the resulting resin composition layer.

[0067] (Antioxidant (hereinafter also referred to as "(G) component") In the present invention, the antioxidant is not particularly limited, and known antioxidants can be used. For example, "Irganox 1010" (hindered phenol antioxidant) manufactured by BASF Corporation can be mentioned. When an antioxidant is used, its content 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, relative to 100% by mass of the non-volatile component of the resin composition.

[0068] (Curing accelerator (hereinafter also referred to as "(H) component")) In the present invention, a curing accelerator may be used to accelerate the crosslinking reaction of the acid anhydride groups and / or carboxyl groups of components (A) and (B). Examples of the curing accelerator include imidazole compounds, tertiary amine / quaternary amine compounds, dimethyl urea compounds, and organic phosphine compounds.

[0069] Examples of the imidazole compound include 1H-imidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenylimidazole, 2-dodecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Specific examples of the 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 Chemicals Co., Ltd.).

[0070] The tertiary amine / quaternary amine compound is not particularly limited, and examples thereof 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-phenolate, DBU-octanoate, DBU-p-toluenesulfonate, DBU-formate, and DBU-novolac resin salt; tertiary amines such as benzyldimethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol (TAP), or salts thereof; and dimethylurea compounds such as aromatic dimethylurea and aliphatic dimethylurea.

[0071] Examples of dimethyl urea compounds include aromatic dimethyl ureas such as DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) and U-CAT3512T (manufactured by San-Apro Corporation); and aliphatic dimethyl ureas such as U-CAT3503N (manufactured by San-Apro Corporation). Among these, aromatic dimethyl ureas are preferably used from the viewpoint of curability.

[0072] Examples of the organic phosphine compound include triphenylphosphine, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and triphenylphosphine triphenylborane. Specific examples of the organic phosphine compound include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, and TPP-S (all manufactured by Hokko Chemical Industry Co., Ltd.).

[0073] When a curing accelerator is used, in order to promote the crosslinking reaction of the acid anhydride groups and / or carboxyl groups of the components (A) and (B), the content thereof 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 matter of the resin composition.

[0074] (Epoxy-modified olefin polymer with a number average molecular weight of less than 10,000) "Epoxy-modified olefin polymer" is synonymous with "olefin polymer having epoxy groups." The epoxy groups of this epoxy-modified olefin polymer react with the acid anhydride groups / carboxyl groups in the olefin polymer having acid anhydride groups and / or carboxyl groups (component (A) and, if necessary, component (B)) to form a crosslinked structure, thereby improving the dispersibility of calcium oxide (component (D)) in the resin composition and the water vapor intrusion barrier properties of the resulting resin composition layer.

[0075] The epoxy group concentration in the epoxy-modified olefin polymer having a number average molecular weight of less than 10000 is preferably 0.05 to 10 mmol / g, more preferably 0.10 to 5 mmol / g. The epoxy group concentration is determined from the epoxy equivalent obtained in accordance with JIS K 7236-1995.

[0076] The epoxy-modified olefin polymer having a number average molecular weight of less than 10,000 preferably has a number average molecular weight of 100 to 10,000, more preferably 250 to 9,000, and even more preferably 500 to 8,000, from the viewpoint of improving the good coating properties of the varnish of the resin composition, the sealing performance and mechanical strength of the formed resin composition layer, etc.

[0077] Epoxy-modified olefin polymers having a number average molecular weight of less than 10,000 can be obtained, for example, by the following methods: (i) grafting an olefin polymer with an unsaturated compound having an epoxy group (e.g., glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether) under free radical reaction conditions, or (ii) copolymerizing an unsaturated compound having an epoxy group with an α-olefin.

[0078] The epoxy-modified olefin polymer having a number average molecular weight of less than 10,000 is the following polymer having a number average molecular weight of less than 10,000: (i) preferably at least one selected from the group consisting of ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-glycidyl methacrylate-methyl acrylate copolymer, propylene-butene copolymer having an epoxy group, isobutylene-isoprene copolymer having an epoxy group (i.e., butyl rubber), and ethylene-methyl methacrylate copolymer having an epoxy group, (ii) more preferably at least one selected from a propylene-butene copolymer having an epoxy group, an isobutylene-isoprene copolymer having an epoxy group, and an ethylene-methyl methacrylate copolymer having an epoxy group, (iii) more preferably a propylene-butene copolymer having an epoxy group and / or an isobutylene-isoprene copolymer having an epoxy group, (iv) A propylene-butene copolymer having an epoxy group or an isobutylene-isoprene copolymer having an epoxy group is particularly preferred.

[0079] When a propylene-butene copolymer having an epoxy group and having a number average molecular weight of less than 10,000 is used as the epoxy-modified olefin polymer having a number average molecular weight of less than 10,000, the amount of butene units in the copolymer is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and even more preferably 3 to 40% by mass, relative to the total of the propylene and butene units. The above amount of butene units is based on the propylene and butene units excluding the modified portion (e.g., the portion derived from glycidyl (meth)acrylate for introducing the epoxy group).

[0080] When an isobutylene-isoprene copolymer having an epoxy group and having a number average molecular weight of less than 10,000 (i.e., butyl rubber) is used as the epoxy-modified olefin polymer having a number average molecular weight of less than 10,000, 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 of the isobutylene units and the isoprene units, from the viewpoint of yellowing resistance of the resin composition layer. The above amount of isoprene units is based on the isobutylene units and the isoprene units excluding the modified portion (e.g., the portion derived from glycidyl (meth)acrylate for introducing the epoxy group).

[0081] When an epoxy-modified olefin polymer having a number average molecular weight of less than 10,000 is used, its content is preferably 3 to 50% by mass, more preferably 5 to 45% by mass, and even more preferably 10 to 40% by mass relative to 100% by mass of the non-volatile components of the resin composition, from the viewpoint of improving the good coating properties of the varnish of the resin composition, the sealing performance and mechanical strength of the formed resin composition layer, etc.

[0082] (Plasticizer) Examples of the plasticizer include mineral oils such as paraffinic process oils, naphthenic process oils, liquid paraffin, and vaseline; and vegetable oils such as castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, and olive oil.

[0083] When a plasticizer is used, the content is preferably 2 to 30 mass %, more preferably 4 to 25 mass %, and even more preferably 5 to 20 mass % relative to 100 mass % of the nonvolatile components of the resin composition, from the viewpoint of flexibility of the formed resin composition layer.

[0084] [Method for producing resin composition] Hereinafter, a preferred method for producing the resin composition of the present invention will be described. However, the resin composition of the present invention may also be produced by methods other than the following method.

[0085] The preferred manufacturing method of the resin composition of the present invention (hereinafter referred to as "manufacturing method of the present invention") comprises the following steps: a mixture of a polymer having anhydride groups and / or carboxyl groups with a number average molecular weight of 10,000 or more (i.e., component (A)), a polymer having anhydride groups and / or carboxyl groups with a number average molecular weight of less than 10,000 (i.e., component (B)), an isobutylene-containing polymer with a number average molecular weight of 10,000 or more (i.e., component (C)), and / or calcium oxide with a median particle size exceeding 300 nm, and an organic solvent is pulverized. The resin composition of the present invention can also be manufactured by mixing calcium oxide with a median particle size of less than 300 nm (i.e., component (D)) with ingredients other than component (D). However, in such a simple mixing, it is difficult to disperse the fine calcium oxide well in the resin composition compared to the case of going through the above steps. In addition, the surface area of ​​the fine calcium oxide is large, and as a result, its hygroscopicity also becomes larger. In order to avoid such hygroscopicity, the handleability of the fine calcium oxide when manufacturing the resin composition is worse than that of calcium oxide of normal size. Therefore, the resin composition of the present invention is preferably produced through the above-mentioned steps. Hereinafter, the mixture for pulverization treatment used in the production method of the present invention will be described in order.

[0086] By mixing calcium oxide having a median particle size of more than 300 nm, component (B) and an organic solvent, a mixture for pulverization can be produced. In addition, an olefin polymer having an anhydride group and / or a carboxyl group and component (C) as component (A) can be further mixed to produce a mixture for pulverization. The content of the calcium oxide is preferably 3 to 75% by mass, more preferably 5 to 70% by mass, relative to the entire mixture for pulverization. The content of component (B) is preferably 3 to 40% by mass, more preferably 5 to 35% by mass, relative to the entire mixture for pulverization. The content of the organic solvent is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, relative to the entire mixture for pulverization. Components other than the above (the above-mentioned "other components") can be added to the mixture for pulverization. There is no particular limitation on the order of addition of the components, and the components can be added sequentially or simultaneously.

[0087] Examples of organic solvents that can be used in the production method of the present invention include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellosolves such as cellosolve; carbitols such as butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amides 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. A single organic solvent may be used alone, or two or more may be used in combination.

[0088] The pulverization process can be carried out using a known pulverizer. By pulverization, calcium oxide is pulverized and dispersed in the mixture. Examples of known pulverizers include wet bead mills, planetary ball mills, dry pulverizers (Atritor), air flow mills, ball mills, and vibrating ball mills. Examples of materials for beads include zirconium oxide, aluminum oxide, glass, and steel. The bead diameter is, for example, about 0.03 to 5 mm. The rotational speed of the rotating shaft of the bead mill is, for example, about 10 to 10,000 rpm. The flow rate of the mixture for pulverization supplied to the pulverization chamber of the bead mill is, for example, about 0.1 to 10,000 kg / hour. In the wet pulverization using a bead mill, in order to suppress the temperature rise of the mixture during pulverization, it is preferably carried out while cooling with cooling water. The temperature of the cooling water is, for example, about 0 to 40°C.

[0089] Furthermore, the mixture after the pulverization process can be mixed with any component. For example, a liquid olefin polymer, a tackifier, etc. can be added to the mixture after the pulverization process and mixed. In addition, an olefin polymer having anhydride groups and / or carboxyl groups as component (A) can also be mixed with the mixture after the pulverization process. In order to avoid an increase in the viscosity of the mixture during the pulverization process, component (A) is preferably mixed with the mixture after the pulverization process. There is no particular limitation on the order of adding the components, and the components can be added sequentially or simultaneously.

[0090] The varnish of the resin composition containing an organic solvent obtained as described above can be partially or entirely freed from the organic solvent by drying, etc. The resin composition of the present invention can be used in a liquid form such as a varnish or in a solid form such as a film.

[0091] [Resin sheet] The present invention also provides a resin sheet having a laminated structure comprising a support and a resin composition layer formed from the resin composition of the present invention. A protective sheet may also be used in the present invention. That is, the resin sheet of the present invention may have a laminated structure comprising a support, a resin composition layer, and a protective sheet in this order. Other layers may also be present between the support and the resin composition layer, and between the resin composition layer and the protective sheet. Examples of other layers include adhesive layers, release layers, and resin composition layers formed from a resin composition that does not contain calcium oxide.

[0092] The haze of the resin composition layer is preferably less than 60%, more preferably 40% or less, and further preferably 30% or less. There is no particular lower limit for the haze of the resin composition layer, and the haze of the resin composition layer is, for example, 0% or more. The haze can be measured according to JIS K 7136.

[0093] Examples of the support and protective sheet include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; cycloolefin polymers; polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate; polycarbonate; and plastic films such as polyimide. Both the support and protective sheet may be single-layer films or laminated films.

[0094] For example, a low-moisture-permeability film having a barrier layer, or a laminated film of a low-moisture-permeability film having a barrier layer and another film can be used as the support and protective sheet. Examples of barrier layers include inorganic films such as vapor-deposited silica films, silicon nitride films, and silicon oxide films. The barrier layer can also be composed of a multilayer of multiple inorganic films (e.g., vapor-deposited silica films). Furthermore, the barrier layer can be composed of both organic and inorganic materials, or a composite multilayer of organic and inorganic layers.

[0095] In the protective sheet, the surface in contact with the resin composition layer is preferably subjected to a release treatment. Meanwhile, the support may or may not be subjected to a release treatment. Examples of the release treatment include those using a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, and the like.

[0096] The thickness of the support and protective sheet is not particularly limited. From the perspective of resin sheet handling, each is preferably 10 to 150 μm, more preferably 20 to 100 μm. When the support and protective sheet are laminated films, the aforementioned thicknesses refer to the thickness of the laminated film. On the other hand, from the perspective of transparency, sealing, and adhesion, the thickness of the resin composition layer is preferably 2 to 100 μm, more preferably 2 to 75 μm, and even more preferably 3 to 50 μm.

[0097] [Method for producing resin sheet] The resin sheet of the present invention can be produced, for example, by applying a varnish of the resin composition obtained as described above onto a support to form a coating film, and then drying the resulting coating film to form a resin composition layer. Alternatively, a resin sheet having a laminated structure comprising a support, a resin composition layer, and a protective sheet in this order can be produced, for example, by applying a varnish onto one of a support and a protective sheet, followed by drying to form a resin composition layer, and then laminating the other of the support and protective sheet onto the formed resin composition layer.

[0098] The coating film obtained by removing the organic solvent may be further heated (aged). The heating temperature is preferably 80 to 200°C, more preferably 100 to 150°C, and the heating time is preferably 10 to 240 minutes, more preferably 30 to 180 minutes. The heating may be performed under normal pressure or under reduced pressure.

[0099] [Electronic devices] The present invention also provides an electronic device comprising a resin composition layer formed from the resin composition of the present invention. Examples of the electronic device include organic EL devices, organic light-emitting diodes (OLEDs), solar cells (particularly organic solar cells (organic thin-film solar cells (OPVs), perovskite solar cells (PSCs), dye-sensitized solar cells (DSSCs))), sensor devices, and touch panels having a conductive substrate. The electronic device is preferably an electronic device having a low tolerance to moisture, such as an organic EL device, an organic light-emitting diode, or a solar cell. Example

[0100] The present invention will be described in more detail below with reference to Examples. However, the present invention is not limited to the following Examples and can be practiced with appropriate modifications within the spirit of the context, all of which are encompassed by the technical scope of the present invention. It should be noted that, unless otherwise specified, "parts" and "%" in references to the amounts of components and copolymerized units refer to "parts by mass" and "% by mass," respectively.

[0101] <Ingredients> The components used in the Examples and Comparative Examples are as follows; (A)Ingredients: ER661 (produced by Seikyo PMC, maleic anhydride-modified butyl rubber (maleic anhydride-modified isobutylene-isoprene copolymer), anhydride group concentration: 0.77 mmol / g, number average molecular weight: 40,000, isobutylene unit / isoprene unit: 98.9% / 1.1%) "ER645" (produced 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 content: 20%).

[0102] (B) Ingredients: "HV-300M" (manufactured by Toho Chemical Industry Co., Ltd.): Maleic anhydride-modified liquid polybutene, semi-oxidized 33 KOH mg / g, number average molecular weight 2100 "HV-100M" (manufactured by Toho Chemical Industry Co., Ltd.): maleic anhydride-modified liquid polybutene, semi-oxidized 41 KOH mg / g, number average molecular weight 1220.

[0103] (C) Ingredients: "B10" (manufactured by BASF: polyisobutylene, number average molecular weight: 30,000) "N50SF" (manufactured by BASF: polyisobutylene, number average molecular weight: 300,000) "N80SF" (manufactured by BASF: polyisobutylene, number average molecular weight: 600,000) BUTYL065 (manufactured by JSR Corporation, butyl rubber, number average molecular weight: 200,000, isobutylene unit / isoprene unit: 98.7% / 1.3%) "SIBSTAR103T-UL" (manufactured by Kaneka Corporation, styrene-isobutylene-styrene block copolymer (SIBS), number average molecular weight: 100,000, styrene unit / isobutylene unit: 30% / 70%).

[0104] (D) Ingredients: Calcium oxide (manufactured by Yoshizawa Lime Industry Co., Ltd., median particle size: 2.1 μm).

[0105] (E) Ingredients: "HV-1900" (manufactured by ENEOS, liquid polybutene, number average molecular weight: 2900, viscosity at 25°C: 460 Pa·s).

[0106] (F)Ingredients: "ARKON P-125" (manufactured by Arakawa Chemical Industries, Ltd., hydrogenated petroleum resin, softening point: 125°C).

[0107] (G) Ingredients: "Irganox 1010" (manufactured by BASF): hindered phenol-based antioxidant.

[0108] (H) Ingredients: 2,4,6-Tris(dimethylaminomethyl)phenol (hereinafter referred to as "TAP") (manufactured by Kayaku Akzo Co., Ltd.): a tertiary amine curing accelerator.

[0109] <Example 1> Varnishes with the formulations shown in the table below were prepared according to the following procedures, and resin sheets were produced using the resulting varnishes. The amounts (parts) of the components listed in the table below represent the non-volatile content of each component in the varnish. In the table below, calcium oxide is indicated as "CaO," and its median particle size is indicated in parentheses.

[0110] Specifically, maleic anhydride-modified liquid polybutene ("HV-300M" manufactured by Toho Chemical Industry Co., Ltd.), calcium oxide (manufactured by Yoshizawa Lime Industry Co., Ltd.), and toluene were combined to obtain a mixture for pulverization treatment (relative to the entire mixture, toluene content: 38%, maleic anhydride-modified liquid polybutene content: 11%, calcium oxide content: 51%).

[0111] The mixture for pulverization was added to a wet bead mill (LABSTAR Mini "LMZ015" manufactured by Ashizawa Finetech Co., Ltd.), and beads (bead diameter: 0.1 mm) were filled to about 60% by volume of the effective volume of the pulverization chamber, and pulverization was performed to obtain a pulverized mixture in which calcium oxide was pulverized and dispersed.

[0112] A small amount of the pulverized mixture was diluted 100-fold with toluene to prepare a measurement sample. The median particle size of calcium oxide was measured and calculated using a dynamic light scattering method using a nanoparticle size measuring device "NANOTRAC WAVE" manufactured by Microtrac. The results showed that the median particle size of calcium oxide was 180 nm.

[0113] The pulverized mixture was mixed with a Swasol solution (non-volatile content: 60%) of a tackifier ("ARKON P-125" manufactured by Arakawa Chemical Industries, Ltd.), polyisobutylene ("B10" manufactured by BASF), butyl rubber modified with a maleic anhydride-butyl methacrylate random copolymer ("ER661" manufactured by Seiko PMC), a hindered phenol-based antioxidant ("Irganox 1010" manufactured by BASF), and a curing accelerator (TAP, manufactured by KAYAKU NOURYON Co., Ltd.). The resulting mixture was mixed using a high-speed rotary mixer to obtain a varnish of a resin composition.

[0114] A polyethylene terephthalate film ("SP4020" manufactured by Toyo Cloth, PET film thickness: 38 μm) treated on one side with a silicone release agent was laminated with a low-moisture-permeability polyethylene terephthalate film ("TECHBARRIER HX" manufactured by Mitsubishi Chemical Corporation, PET film thickness: 12 μm) so that the surface of the SP4020 film not treated with the silicone release agent came into contact with the TECHBARRIER HX. This laminated film was used as a support for a resin sheet. Hereinafter, the "surface of the laminated film treated with the silicone release agent" will be referred to as the "release-treated surface."

[0115] The obtained varnish was uniformly applied on the release-treated surface of the laminated film using a die coater, and heated at 150° C. for 10 minutes to obtain a resin sheet having a resin composition layer with a thickness of 10 μm.

[0116] <Example 2> A resin sheet having a 10 μm-thick resin composition layer was prepared in the same manner as in Example 1 except that polyisobutylene (“B10” manufactured by BASF) was replaced with polyisobutylene (“N50SF” manufactured by BASF).

[0117] <Example 3> A resin sheet having a 10 μm-thick resin composition layer was prepared in the same manner as in Example 1, except that polyisobutylene (“B10” manufactured by BASF) was replaced with polyisobutylene (“N80SF” manufactured by BASF).

[0118] <Example 4> A resin sheet having a 10 μm-thick resin composition layer was prepared in the same manner as in Example 1 except that polyisobutylene (“B10” manufactured by BASF) was replaced with butyl rubber (“BUTYL065” manufactured by JSR).

[0119] <Example 5> A resin sheet having a 10 μm thick resin composition layer was prepared in the same manner as in Example 1 except that polyisobutylene (“B10” manufactured by BASF) was replaced with a styrene-isobutylene-styrene block copolymer (“SIBSTAR103T-UL” manufactured by Kaneka Corporation).

[0120] <Example 6> A resin sheet having a 10 μm thick resin composition layer was prepared in the same manner as in Example 1, except that the maleic anhydride-modified liquid polybutene (“HV-300M” manufactured by Toho Chemical Industry Co., Ltd.) was replaced with maleic anhydride-modified liquid polybutene (“HV-100M” manufactured by Toho Chemical Industry Co., Ltd.).

[0121] <Example 7> A resin sheet having a resin composition layer with a thickness of 10 μm was prepared by the same method as in Example 6, except that the maleic anhydride-butyl methacrylate random copolymer-modified butyl rubber ("ER661" manufactured by Seikyo PMC Co., Ltd.) was replaced with a glycidyl methacrylate-modified propylene-butene random copolymer ("ER645" manufactured by Seikyo PMC Co., Ltd.).

[0122] <Example 8> A resin sheet having a 10 μm thick resin composition layer was prepared in the same manner as in Example 1 except that the amount of maleic anhydride-butyl methacrylate random copolymer-modified butyl rubber ("ER661" manufactured by Seikyo PMC) used was changed from 20 parts to 10 parts.

[0123] <Example 9> A resin sheet having a 10 μm thick resin composition layer was prepared in the same manner as in Example 1 except that the amount of maleic anhydride-butyl methacrylate random copolymer-modified butyl rubber ("ER661" manufactured by Seikyo PMC) used was changed from 20 parts to 30 parts.

[0124] <Example 10> A resin sheet having a 10 μm thick resin composition layer was prepared in the same manner as in Example 1, except that the amount of polyisobutylene (“B10” manufactured by BASF) used was changed from 45 parts to 22.5 parts, and the amount of liquid polybutene (“HV-1900” manufactured by ENEOS) used was changed from 45 parts to 22.5 parts.

[0125] <Example 11> A resin sheet having a 10 μm-thick resin composition layer was prepared in the same manner as in Example 1, except that the amount of polyisobutylene (“B10” manufactured by BASF) used was changed from 45 parts to 30 parts.

[0126] <Example 12> A resin sheet having a 10 μm-thick resin composition layer was prepared in the same manner as in Example 1, except that the amount of polyisobutylene (“B10” manufactured by BASF) used was changed from 45 parts to 60 parts.

[0127] <Comparative Example 1> A resin sheet having a 10 μm thick resin composition layer was prepared in the same manner as in Example 1 except that polyisobutylene (“B10” manufactured by BASF) was replaced with liquid polybutene (“HV-1900” manufactured by ENEOS).

[0128] <Comparative Example 2> A resin sheet having a resin composition layer having a thickness of 10 μm was prepared in the same manner as in Example 1 except that calcium oxide (manufactured by Yoshizawa Lime Industry Co., Ltd.) was not added.

[0129] <Comparative Example 3> A resin sheet having a 10 μm thick resin composition layer was prepared in the same manner as in Example 1 except that the maleic anhydride-modified liquid polybutene (“HV-300M” manufactured by Toho Chemical Industry Co., Ltd.) was not added.

[0130] <Comparative Example 4> A resin sheet having a 10 μm-thick resin composition layer was prepared in the same manner as in Example 1, except that the step of pulverizing calcium oxide (manufactured by Yoshizawa Lime Industry Co., Ltd.) was not performed.

[0131] <Comparative Example 5> A resin sheet having a 10 μm thick resin composition layer was prepared in the same manner as in Example 1 except that the maleic anhydride-butyl methacrylate random copolymer-modified butyl rubber ("ER661" manufactured by Seikyo PMC) was not added.

[0132] <Comparative Example 6> A resin sheet having a 10 μm-thick resin composition layer was prepared in the same manner as in Example 1 except that the polyisobutylene (“B10” manufactured by BASF) was not added.

[0133] <Comparative Example 7> A resin sheet having a resin composition layer with a thickness of 10 μm was prepared in the same manner as in Example 1, except that the maleic anhydride-butyl methacrylate random copolymer-modified butyl rubber ("ER661" manufactured by Seikyo PMC) was not added and the amount of polyisobutylene ("B10" manufactured by BASF) used was changed from 45 parts to 65 parts.

[0134] The resin composition layer of each resin sheet obtained in Examples and Comparative Examples was evaluated by the following method.

[0135] <Evaluation Method of Total Light Transmittance and b*> The resin sheets prepared in the Examples and Comparative Examples were cut into 50 mm long and 20 mm wide sheets. The resin composition layer of the cut resin sheets was then laminated onto a glass plate (microscope glass slide S1112, white, edge-grinded No. 2, manufactured by Matsunami Glass Industries, Ltd.) with a length of 76 mm, a width of 26 mm, and a thickness of 1.2 mm using a batch vacuum laminator (V-160 manufactured by Nichigo-Morton Co., Ltd.). The lamination conditions were a temperature of 80°C, a reduced pressure of 30 seconds, and then a pressurization of 0.3 MPa for 30 seconds. Then, the PET film of the resin sheet was peeled off, and the transmittance spectrum of the exposed cured resin composition layer was measured using a fiber optic spectrophotometer (MCPD-7700, Model 311C, manufactured by Otsuka Electronics Co., Ltd., with an external light source unit: halogen lamp MC-2564 (24V, 150W specification)) equipped with an 80 mm φ integrating sphere (Model SRS-99-010, reflectivity 99%). The total light transmittance (%) and b* at a wavelength of 450 nm were calculated and evaluated according to the following criteria. It should be noted that the distance between the integrating sphere and the sample (laminated body) was set to 0 mm, and air was used as a reference. The results are recorded in the following table; Total light transmittance Good (○): more than 90% Defective (×): less than 90% b* Good (○): less than 3% Defective (×): more than 3%.

[0136] <Evaluation Method of Water Vapor Intrusion Barrier Properties> As a support film, a composite film comprising aluminum foil and polyethylene terephthalate film, "AL1N30 with PET" (aluminum foil thickness 30 μm, polyethylene terephthalate film thickness 25 μm, manufactured by Tokai Toyo Aluminum Sales Co., Ltd.) was prepared. The resin sheet production method described in the Examples and Comparative Examples was repeated, except that this support film was used instead of the support. A resin composition layer was formed on the aluminum foil side of the support film. This yielded a test sheet comprising a support film and a resin composition layer.

[0137] A 50 mm x 50 mm square glass plate made of alkali-free glass was prepared, washed with boiled isopropyl alcohol for 5 minutes, and dried at 150° C. for 30 minutes or longer.

[0138] Calcium was vapor-deposited on one side of the glass plate using a mask covering the peripheral area 0 mm to 2 mm from the edge of the glass plate. This formed a 200 nm thick calcium film (99.8% purity) in the central portion of the glass plate, excluding the peripheral area 0 mm to 2 mm from the edge of the glass plate.

[0139] In a nitrogen atmosphere, the resin composition layer of the test sheet was bonded to the calcium film-side surface of the glass plate using a heat laminator ("Lamipacker DAiSY A4 (LPD2325)" manufactured by FUJIPLA) to obtain a laminate. This laminate was used as an evaluation sample.

[0140] In general, if calcium contacts with water and forms calcium oxide, it becomes transparent. In addition, in the evaluation sample, glass plate and aluminum foil have sufficiently high water vapor intrusion barrier properties, so moisture can usually move through the resin composition layer end along the in-plane direction (direction perpendicular to the thickness direction) to reach the calcium film. Therefore, if moisture invades the evaluation sample, the calcium film is gradually oxidized from the end and becomes transparent, so the reduction of the calcium film can be observed. Therefore, the moisture invasion to the evaluation sample can be evaluated by measuring the sealing distance (mm) from the end of the evaluation sample to the calcium film. Therefore, the evaluation sample containing calcium film can be used as a model of leaded electronic devices.

[0141] 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 Co., Ltd.) Hereinafter, this sealing distance X2 may be referred to as the initial sealing distance X2.

[0142] Next, the evaluation sample is placed in a constant temperature and humidity chamber set at a temperature of 85°C and a humidity of 85% RH. When the sealing distance X1 (mm) between the end of the evaluation sample placed in the constant temperature and humidity chamber and the end of the calcium film increases by 0.1 mm compared to the initial sealing distance X2, the evaluation sample is taken out of the constant temperature and humidity chamber. The time from the moment the evaluation sample is placed in the constant temperature and humidity chamber to the moment the evaluation sample is taken out of the constant temperature and humidity chamber is calculated as the reduction start time t [hours]. The reduction start time t is equivalent to the time T from the moment the evaluation sample is placed in the constant temperature and humidity chamber P1 From the time when the sealing distance X1 [mm] between the end of the evaluation sample stored in the constant temperature and humidity chamber and the end of the calcium film reaches "X2 + 0.1 mm" T P2 The time until now.

[0143] The sealing distance X1 and the reduction start time t are substituted into the Fick diffusion equation of formula (1) to calculate the constant K as a water vapor intrusion barrier parameter.

[0144] [Mathematical formula 1] .

[0145] The obtained constant K was used to evaluate the water vapor intrusion barrier properties, which are the ability of the resin composition layer to inhibit water intrusion, according to the following criteria. The smaller the value of the constant K, the higher the water vapor intrusion barrier properties. The results are recorded in the following table. It should be noted that "(cm / hr^0.5)" in the following table means "(cm / hr 0.5 )”; (Water vapor intrusion barrier performance standard) Good (○): Constant K is less than 0.025 cm / hr 0.5 Bad (×): Constant K is 0.025 cm / hr 0.5 above.

[0146] <Evaluation Method of Adhesion> A batch vacuum laminator (Morton-724, manufactured by Nichigo-Morton Co., Ltd.) was used to laminate a resin composition layer of a resin sheet (50 mm in length and 20 mm in width) using a PET film as a support onto the aluminum foil side of a composite film "AL1N30 with PET" (aluminum foil thickness 30 μm, polyethylene terephthalate film thickness 25 μm, manufactured by Tokai Toyo Aluminum Sales Co., Ltd.) comprising aluminum foil and polyethylene terephthalate film. Lamination was performed under the conditions of a temperature of 80°C, a time of 30 seconds, and a pressure of 0.3 MPa. The PET film was then peeled off, and a glass plate (76 mm in length, 26 mm in width, 1.2 mm in thickness, microscope slide) was further laminated on the exposed resin composition layer under the same conditions as above. The resulting laminate was subjected to a test of the adhesive strength (kgf / cm) when peeled at a tensile speed of 50 mm / min in a direction 90 degrees relative to the longitudinal direction of the aluminum foil. The laminate was placed in a constant temperature and humidity chamber set at 85°C and 85% RH for 100 hours, and the retention of adhesive strength was calculated. The results are reported in the following table. Good (○): Retention rate is above 70% Defective (×): Retention rate is less than 70%.

[0147] [Table 1-1] [Table 1-2] .

[0148] As shown in the results of Table 1, the resin compositions of Examples of the present invention can form resin composition layers having good total light transmittance and b* evaluations (ie, excellent transparency) and excellent water vapor intrusion barrier properties.

[0149] Industrial applicability The resin composition of the present invention can form a resin composition layer having both water vapor intrusion barrier properties and transparency, and is therefore useful as a sealing material for electronic devices (for example, organic EL devices, organic light-emitting diodes (OLEDs), solar cells (particularly organic solar cells (organic thin-film solar cells (OPVs), perovskite solar cells (PSCs), dye-sensitized solar cells (DSSCs))), sensor devices, touch panels having a conductive substrate, etc.).

[0150] This application is based on Japanese Patent Application No. 2023-033083 filed in Japan, the entire contents of which are incorporated herein by reference.

Claims

1. A resin composition comprising the following components (A) to (D): (A) a polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of 10,000 or more, (B) a polymer having anhydride groups and / or carboxyl groups and having a number average molecular weight of less than 10,000, (C) an isobutylene-containing polymer having a number average molecular weight of 10,000 or more, and (D) Calcium oxide with a median particle size of 300 nm or less.

2. The resin composition according to claim 1, wherein (A) The polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of 10,000 or more is an olefin-based polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of 10,000 or more.

3. The resin composition according to claim 1, wherein (B) The polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of less than 10,000 is an olefin-based polymer having an acid anhydride group and / or a carboxyl group and having a number average molecular weight of less than 10,000.

4. The resin composition according to claim 1, wherein The number average molecular weight of the component (B) is less than 3,000.

5. The resin composition according to claim 1, wherein (C) The isobutylene-containing polymer having a number average molecular weight of 10,000 or more is an isobutylene-containing olefin polymer having a number average molecular weight of 10,000 or more. The resin composition according to claim 5, wherein (C) The isobutylene-containing polymer having a number average molecular weight of 10,000 or more is at least one member selected from the group consisting of polyisobutylene, isobutylene-isoprene copolymer, and styrene-isobutylene-styrene block copolymer having a number average molecular weight of 10,000 or more.

7. The resin composition according to claim 1, wherein The composition further comprises (E) a liquid olefin polymer (excluding the components (A), (B), and (C).

8. The resin composition according to claim 1, wherein Further comprising (F) a tackifier.

9. The resin composition according to claim 1, wherein The content of the component (A) is 0.1 to 25% by mass relative to 100% by mass of the non-volatile matter in the resin composition.

10. The resin composition according to claim 1, wherein The content of the component (B) is 3 to 50% by mass relative to 100% by mass of the non-volatile matter in the resin composition.

11. The resin composition according to claim 1, wherein The content of the component (C) is 5 to 30% by mass relative to 100% by mass of the non-volatile matter in the resin composition.

12. The resin composition according to claim 1, wherein The content of the component (D) is 10 to 70% by mass relative to 100% by mass of the non-volatile matter in the resin composition. 13 . A resin sheet having a laminated structure comprising a resin composition layer formed from the resin composition according to claim 1 .

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