Composition for protective film of conductive layer

Abstract

The purpose of the present invention is to provide a composition capable of forming a protective (sealing) film that, in order to protect (seal) an electroconductive layer that constitutes an electroconductive substrate, is capable of suppressing a change in surface resistivity of the electroconductive substrate and migration of an electrical conductor while simultaneously maintaining transparency, adhesion strength, and bending resistance. Provided is a composition for a protective film for an electroconductive layer of an electroconductive substrate, the composition including (A) a crosslinked polymer having an isobutene-isoprene copolymer chain. The electroconductive layer is constituted of an electroconductive material containing at least one type selected from among metal nanowires, metal meshes, metal nanoparticles, and electroconductive polymers.

Description

[Technical Field]

[0001] The present invention relates to a composition for protecting (sealing) a conductive layer constituting a conductive substrate. [Background technology]

[0002] The development of conductive substrates using metal nanowires, metal meshes, metal nanoparticles, and conductive polymers as conductors is progressing, and their application to electrode materials for displays, electrode materials for touch panels, electromagnetic wave shielding materials, etc., is expected. However, these conductors have the problem that corrosion due to moisture occurs in high temperature and high humidity environments, causing their surface resistance to increase. To obtain substrates that exhibit stable conductivity even in high temperature and high humidity environments, it is necessary to seal them with a sealing sheet. For example, Patent Document 1 describes a method of using a protective layer containing a chelating agent on top of a conductive layer containing silver nanowires. Patent Document 2 also describes an acrylic polymer resin composition as an adhesive layer for bonding substrates forming metal mesh wiring and silver nanowires.

[0003] However, Patent Document 1 selects an acrylic resin composition for forming a protective layer, and UV irradiation is required for it to function. Furthermore, because the resin has a high water vapor permeability, it cannot adequately function as a protective layer in long-term high-temperature and high-humidity tests. In addition, Patent Document 2 achieves adhesion while suppressing migration of metal to the adhesive layer, but does not mention flexibility. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 7030277 [Patent Document 2] Japanese Patent Publication No. 2021-195449 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention has been made paying attention to the above circumstances, and its object is to form a protective (sealing) film that can suppress changes in the surface resistivity of a conductive substrate and migration of a conductor while achieving both transparency, adhesion strength, and bending resistance when protecting (sealing) the conductive layer constituting the conductive substrate. An object of the present invention is to provide a composition capable of forming a protective (sealing) film.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that, in a composition for protecting (sealing) a conductive layer constituting a conductive substrate, by adopting the following configuration, it is possible to achieve both transparency, adhesion strength, and bending resistance, while suppressing changes in the surface resistivity of the conductive substrate and migration of the conductor. Thus, the present invention has been completed.

[0007] That is, the present invention has the following features. [1] A composition for a protective film of a conductive layer of a conductive substrate, (A) containing a crosslinked polymer having an isobutene-isoprene copolymer chain, where the conductive layer is composed of a conductive material containing at least one selected from metal nanowires, metal meshes, metal nanoparticles, and conductive polymers, Composition. [2] The composition according to [1], wherein the crosslinked polymer having an isobutene-isoprene copolymer chain is at least one selected from the group consisting of a reaction product of an isobutene-isoprene copolymer having an epoxy group and an olefin-based polymer having a carboxy group and / or an acid anhydride group, and a reaction product of an isobutene-isoprene copolymer having a carboxy group and / or an acid anhydride group and an olefin-based polymer having an epoxy group. [3] The composition according to [1] or [2], wherein the content of component (A) is 10 to 75% by mass based on 100% by mass of the nonvolatile content of the composition. [4](B) The resin composition according to any one of [1] to [3], further comprising a liquid polyolefin resin and / or liquid rubber. [5] The composition according to [4], wherein the content of component (B) is 5 to 50% by mass relative to 100% by mass of the nonvolatile content of the composition. [6](C)The composition according to any one of [1] to [5], further comprising a hygroscopic inorganic filler. [7](C)The composition according to [6], wherein the hygroscopic inorganic filler is one or more selected from uncalcined hydrotalcite and semi-calcined hydrotalcite. [8] The composition according to [6] or [7], wherein the content of component (C) is 1 to 60% by mass based on 100% by mass of the nonvolatile content of the composition. [9] The composition according to any one of [1] to [8], wherein the metal constituting the metal nanowires, metal mesh and / or metal nanoparticles is one or more selected from silver, copper, gold, nickel, platinum, palladium, iron, cobalt and tin.

[10] The composition according to any one of [1] to [9], wherein the conductive polymer is one or more selected from poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole, polythiophene, graphene, polyacetylene, poly(p-phenylene), poly(p-phenylenevinylene), and polyaniline. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a composition that can form a protective (sealing) film that can suppress changes in the surface resistivity of the conductive substrate and migration of the conductor while achieving transparency, adhesion strength, and flexibility in protecting (sealing) the conductive layer constituting the conductive substrate. [Modes for carrying out the invention]

[0009] The present invention will be described below in reference to its preferred embodiments. [Composition for protective films on conductive layers of conductive substrates] The composition of the present invention is for a protective film of the conductive layer of a conductive substrate, (A) Containing a crosslinked polymer having an isobutene-isoprene copolymer chain, The conductive layer is composed of a conductive material containing one or more selected from metal nanowires, metal meshes, metal nanoparticles, and conductive polymers.

[0010] <(A) Component: Crosslinked polymer having isobutene-isoprene copolymer chains> Component (A) is a crosslinked polymer having isobutene-isoprene copolymer (i.e., butyl rubber) chains. Component (A) may be used alone or in combination of two or more types. By using component (A), it is possible to suppress the increase in surface resistivity of the conductive substrate (by exhibiting low moisture permeability and preventing the intrusion of oxygen and ions that cause an increase in surface resistivity), and to form a protective (sealing) film with excellent flexibility.

[0011] Component (A) can be formed by reacting an isobutene-isoprene copolymer having a reactive functional group (hereinafter sometimes referred to as the "first reactive functional group") (i.e., butyl rubber having the first reactive functional group) with an olefin polymer having a reactive functional group that can react with the first reactive functional group (hereinafter sometimes referred to as the "second reactive functional group"). Here, "olefin polymer" means a polymer in which the main constituent units are olefin-derived constituent units (hereinafter sometimes abbreviated as "olefin units") (i.e., the amount of olefin units is the largest among all constituent units). In the following, "butene-derived constituent units," etc., which are olefin units, may be abbreviated as "butene units," etc.

[0012] Preferred olefins are monoolefins having one olefinic carbon-carbon double bond and / or diolefins having two olefinic carbon-carbon double bonds. Examples of monoolefins include α-olefins such as ethylene, propylene, 1-butene, isobutene (isobutylene), 1-pentene, 1-hexene, 1-heptene, and 1-octene. Examples of diolefins include 1,3-butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethylbutadiene.

[0013] Olefin polymers may be homopolymers or copolymers. Copolymers may be random copolymers or block copolymers. Furthermore, olefin polymers may be copolymers of olefins and monomers other than olefins. Examples of olefin copolymers include ethylene-non-conjugated diene copolymers, ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene copolymers, ethylene-butene copolymers, propylene-butene copolymers, propylene-butene-non-conjugated diene copolymers, styrene-isobutene copolymers, styrene-isobutene-styrene copolymers, isobutylene-isoprene copolymers (i.e., butyl rubber), and the like.

[0014] The olefin polymer having the second reactive functional group is preferably a butene polymer having the second reactive functional group. Here, "butene polymer" means a polymer in which butene units are the main constituent units (i.e., the amount of butene units is the largest among all constituent units). Examples of butene include 1-butene and isobutene. Examples of butene polymers include polybutene and isobutene-isoprene copolymer. Polybutene may be a homopolymer (e.g., 1-butene homopolymer, isobutene homopolymer) or a copolymer (e.g., a copolymer of 1-butene and isobutene).

[0015] To form component (A), the isobutene-isoprene copolymer having a first reactive functional group and the olefin polymer having a second reactive functional group may be used individually or in combination of two or more.

[0016] Examples of combinations between the first reactive functional group and the second reactive functional group include combinations of epoxy group and carboxyl group and / or acid anhydride group (i.e., carbonyloxycarbonyl group (-CO-O-CO-)), combinations of carboxyl group and / or acid anhydride group and epoxy group, combinations of epoxy group and amino group, combinations of amino group and epoxy group, combinations of hydroxyl group and isocyanate group (i.e., isocyanate group), combinations of isocyanate group and hydroxyl group, and combinations of functional groups having double bonds (e.g., vinyl group and (meth)acryloyl group). Among these, from the viewpoint of moisture barrier properties, combinations of epoxy group and carboxyl group and / or acid anhydride group, and combinations of carboxyl group and / or acid anhydride group and epoxy group are preferred, and combinations of epoxy group and acid anhydride group and combinations of acid anhydride group and epoxy group are more preferred. In the above combinations, the former reactive functional group represents the first reactive functional group, and the latter reactive functional group represents the second reactive functional group.

[0017] In one embodiment of the present invention, component (A) is at least one selected from the group consisting of reaction products of an isobutene-isoprene copolymer having an epoxy group and an olefin polymer having a carboxyl group and / or an acid anhydride group, and reaction products of an isobutene-isoprene copolymer having a carboxyl group and / or an acid anhydride group and an olefin polymer having an epoxy group. In the above embodiment, the olefin polymer is preferably a butene polymer, and more preferably polybutene or isobutene-isoprene copolymer. In the above embodiment, the carboxyl group and / or acid anhydride group is preferably an acid anhydride group.

[0018] In one embodiment of the present invention, component (A) is preferably a reaction product of an isobutene-isoprene copolymer having an epoxy group and polybutene having a carboxyl group and / or an acid anhydride group. In the above embodiment, the carboxyl group and / or acid anhydride group is preferably an acid anhydride group.

[0019] In one embodiment of the present invention, component (A) is a reaction product of an isobutene-isoprene copolymer having an epoxy group and an isobutene-isoprene copolymer having a carboxyl group and / or an acid anhydride group. In the above embodiment, the carboxyl group and / or acid anhydride group is preferably an acid anhydride group.

[0020] The amount of isobutene-isoprene copolymer having a reactive functional group (e.g., epoxy group, carboxyl group, and / or acid anhydride group) used is preferably 15 to 100% by mass, more preferably 20 to 100% by mass, and even more preferably 30 to 100% by mass, relative to the total amount of polymer used to form component (A) (e.g., the total amount of isobutene-isoprene copolymer having a first reactive functional group and isobutene-isoprene copolymer having a second reactive functional group). When using isobutene-isoprene copolymer having a first reactive functional group and isobutene-isoprene copolymer having a second reactive functional group to form component (A), "amount of isobutene-isoprene copolymer having a reactive functional group" refers to "the total amount of isobutene-isoprene copolymer having a first reactive functional group and isobutene-isoprene copolymer having a second reactive functional group."

[0021] The number-average molecular weight of the isobutene-isoprene copolymer having reactive functional groups (e.g., epoxy groups, carboxyl groups, and / or acid anhydride groups) for forming component (A) is preferably 5,000 to 500,000, more preferably 10,000 to 400,000, and even more preferably 20,000 to 300,000. The number-average molecular weight in this invention is measured by gel permeation chromatography (GPC) (in polystyrene terms). Specifically, the number-average molecular weight by GPC can be measured using Shimadzu Corporation's "LC-9A / RID-6A" as the measuring instrument, Showa Denko Corporation's "Shodex K-800P / K-804L / K-804L" as the column, and toluene or the like as the mobile phase, at a column temperature of 40°C, and can be calculated using a calibration curve for standard polystyrene.

[0022] The number-average molecular weight of the olefin polymer (excluding isobutene-isoprene copolymer) having a second reactive functional group (e.g., epoxy group, carboxyl group, and / or acid anhydride group) for forming component (A) is preferably 500 to 500,000, more preferably 1,000 to 300,000, and even more preferably 1,500 to 200,000.

[0023] From the viewpoint of flexibility, the amount of isoprene units in the isobutene-isoprene copolymer having reactive functional groups (e.g., epoxy groups, carboxyl groups, and / or acid anhydride groups) for forming component (A) is preferably 0.1 to 20% by mass, more preferably 0.3 to 10% by mass, and even more preferably 0.5 to 15% by mass, based on the total of isobutene units and isoprene units. The amount of isoprene units is based on the isobutene units and isoprene units excluding the modified portion (e.g., the portion derived from maleic anhydride for introducing acid anhydride groups).

[0024] The concentration of epoxy groups in the epoxy-containing olefin polymer (e.g., epoxy-containing isobutene-isoprene copolymer, epoxy-containing polybutene) for forming component (A) is preferably 0.01 to 10 mmol / g, and more preferably 0.05 to 5 mmol / g. The epoxy group concentration is determined from the epoxy equivalent obtained according to JIS K 7236-1995.

[0025] The concentration of carboxyl groups in the olefin polymer having carboxyl groups (e.g., isobutene-isoprene copolymer having carboxyl groups, polybutene having carboxyl groups) for forming component (A) is preferably 0.01 to 10 mmol / g, and more preferably 0.05 to 5 mmol / g. The concentration of carboxyl groups is obtained from the acid value, which is defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of resin, in accordance with JIS K 2501.

[0026] (A) The concentration of acid anhydride groups in the olefin polymer having acid anhydride groups (e.g., isobutene-isoprene copolymer having acid anhydride groups, polybutene having acid anhydride groups) for forming component (A) is preferably 0.01 to 10 mmol / g, and more preferably 0.05 to 5 mmol / g. The concentration of acid anhydride groups is obtained from the acid value, which is defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of resin, in accordance with JIS K 2501.

[0027] (A) The sum of the concentrations of carboxyl groups and acid anhydride groups in the olefin polymer having carboxyl groups and acid anhydride groups (for example, isobutene-isoprene copolymer having carboxyl groups and acid anhydride groups, polybutene having carboxyl groups and acid anhydride groups) for forming component (A) is preferably 0.01 to 10 mmol / g, and more preferably 0.05 to 5 mmol / g.

[0028] The amount of epoxy group-containing isobutene-isoprene copolymer and carboxyl group-containing olefin polymer (e.g., carboxyl group-containing isobutene-isoprene copolymer, carboxyl group-containing polybutene) used is not particularly limited as long as component (A), which is a crosslinked polymer, can be formed. However, the ratio of the amount of epoxy groups (mol) to the amount of carboxyl groups (mol) (i.e., amount of epoxy groups (mol): amount of carboxyl groups (mol)) is preferably 100:10 to 100:500, more preferably 100:25 to 100:475, and even more preferably 100:40 to 100:450.

[0029] The amount of epoxy group-containing isobutene-isoprene copolymer and acid anhydride group-containing olefin polymer (e.g., acid anhydride group-containing isobutene-isoprene copolymer, acid anhydride group-containing polybutene) used is not particularly limited as long as component (A), which is a crosslinked polymer, can be formed. However, the ratio of the amount of epoxy group (mol) to the amount of acid anhydride group (mol) (i.e., amount of epoxy group (mol): amount of acid anhydride group (mol)) is preferably 100:10 to 100:500, more preferably 100:25 to 100:475, and even more preferably 100:40 to 100:450.

[0030] The amount of isobutene-isoprene copolymer having epoxy groups and olefin polymer having carboxyl groups and acid anhydride groups (e.g., isobutene-isoprene copolymer having carboxyl groups and acid anhydride groups, polybutene having carboxyl groups and acid anhydride groups) used is not particularly limited as long as component (A), which is a crosslinked polymer, can be formed. However, the ratio of "amount of epoxy groups (mol)" to "total amount of carboxyl groups (mol) and acid anhydride groups (mol)" (i.e., amount of epoxy groups (mol):(amount of carboxyl groups (mol) + amount of acid anhydride groups (mol)) is preferably 100:10 to 100:500, more preferably 100:25 to 100:475, and even more preferably 100:40 to 100:450.

[0031] Olefin polymers having epoxy groups (e.g., isobutene-isoprene copolymers having epoxy groups, polybutenes having epoxy groups) can be obtained by graft-modifying olefin polymers with unsaturated compounds having epoxy groups (e.g., glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether) under radical reaction conditions.

[0032] Commercially available olefin polymers containing epoxy groups may be used. Examples of commercially available isobutene-isoprene copolymers containing epoxy groups include "ER866" (glycidyl methacrylate-modified butyl rubber, epoxy group concentration: 1.63 mmol / g, number average molecular weight: 113,000) and "ER850" (glycidyl methacrylate-modified butyl rubber, epoxy group concentration: 0.65 mmol / g, number average molecular weight: 99,200) manufactured by Seikoh PMC. Examples of commercially available olefin polymers containing epoxy groups (excluding isobutene-isoprene copolymers) include "T-YP341" (glycidyl methacrylate-modified propylene-butene random copolymer, epoxy group concentration: 0.64 mmol / g, number average molecular weight: 155,000) manufactured by Seikoh PMC, "T-YP276" (glycidyl methacrylate-modified propylene-butene random copolymer, epoxy group concentration: 0.64 mmol / g, number average molecular weight: 57,000) and "T-YP313" (glycidyl methacrylate-modified propylene-butene random copolymer, epoxy group concentration: 0.64 mmol / g, number average molecular weight: 155,000) manufactured by Seikoh PMC.

[0033] Olefin polymers having carboxyl groups and / or acid anhydride groups (e.g., isobutene-isoprene copolymers having carboxyl groups and / or acid anhydride groups, polybutenes having carboxyl groups and / or acid anhydride groups) can be obtained by graft-modifying olefin polymers with unsaturated compounds having carboxyl groups and / or acid anhydride groups (e.g., maleic anhydride) under radical reaction conditions.

[0034] Commercially available olefin polymers having carboxyl groups and / or acid anhydride groups may be used. Examples of commercially available isobutene-isoprene copolymers having carboxyl groups and / or acid anhydride groups include "ER661" (maleic anhydride-modified butyl rubber, acid anhydride group concentration: 0.77 mmol / g, number average molecular weight: 40,000) and "ER641" (maleic anhydride-modified butyl rubber, acid anhydride group concentration: 0.46 mmol / g, number average molecular weight: 57,000) from Seikoh PMC. Examples of commercially available olefin polymers having carboxyl groups and / or acid anhydride groups (excluding isobutene-isoprene copolymers) include, for example, "HV-300M" from Toho Chemical Industry Co., Ltd. (maleic anhydride-modified polybutene, acid anhydride group concentration: 1.16 mmol / g, number average molecular weight: 2,100), and "T-YP279" from Seikoh PMC Co., Ltd. (maleic anhydride-modified propylene-butene random copolymer, acid anhydride group concentration: 0.46 mmol / g, number average molecular weight: 35,000). Examples include "T-YP312" (maleic anhydride-modified propylene-butene random copolymer, acid anhydride group concentration: 0.46 mmol / g, number average molecular weight: 60,900) from Hikari PMC, and "Lucant A-5260" (maleic anhydride-modified ethylene-α-olefin random copolymer, acid anhydride group concentration: 0.44 mmol / g, number average molecular weight: 5,400) and "Lucant A-5320" (maleic anhydride-modified ethylene-α-olefin random copolymer) from Mitsui Chemicals, Inc.

[0035] The content of component (A) in the composition layer is preferably 10% by mass or more, more preferably 12.5% ​​by mass or more, and even more preferably 15% by mass or more, based on 100% by mass of the nonvolatile content of the composition, from the viewpoint of flexibility, and preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less, from the viewpoint of moisture barrier properties. In one embodiment of the present invention, the content of component (A) is preferably 10 to 75% by mass, and more preferably 12.5 to 70% by mass or less, based on 100% by mass of the nonvolatile content of the composition.

[0036] <(B) Component: Liquid polyolefin resin and / or liquid rubber> The composition of the present invention may contain a liquid polyolefin resin and / or liquid rubber. In the present invention, "liquid" means that the viscosity at 25°C is 5,000 Pa·s or less. In the present invention, "viscosity at 25°C" means the viscosity calculated by multiplying the kinematic viscosity at 25°C, measured by a dynamic viscoelasticity measuring device, by the density. Examples of dynamic viscoelasticity measuring devices include the rheometer manufactured by TA Instruments Corporation (product name: DISCOVERY HR-2).

[0037] With respect to component (B) of the present invention, "liquid polyolefin resin" means an olefin polymer having a viscosity of 5,000 Pa·s or less at 25°C and that cannot form a rubber elastic body by crosslinking, and "liquid rubber" means a material having a viscosity of 5,000 Pa·s or less at 25°C and that can form a rubber elastic body by crosslinking. For example, liquid polyisoprene is classified as liquid rubber because it can form a rubber elastic body by crosslinking.

[0038] The viscosity of the liquid polyolefin resin and the liquid rubber at 40°C is preferably 5 to 5,000 Pa·s, more preferably 10 to 4,000 Pa·s, and even more preferably 20 to 3,000 Pa·s, respectively.

[0039] (B) Component may be used alone or in combination of two or more. By using component (B), good adhesion (especially at high temperatures) can be achieved, and the viscoelasticity of the composition can be controlled. Furthermore, the composition of the present invention may contain the hygroscopic inorganic filler described below, but if a large amount of hygroscopic inorganic filler is used, the adhesion of the protective (sealing) film will decrease. In this respect, by using component (B), good adhesion can be achieved even if a large amount of hygroscopic inorganic filler is used.

[0040] The number-average molecular weight of the liquid polyolefin resin is preferably 500 to 15,000, more preferably 750 to 12,500, and even more preferably 1,000 to 10,000. Similarly, the number-average molecular weight of the liquid rubber is 500 to 15,000, more preferably 750 to 12,500, and even more preferably 1,000 to 10,000.

[0041] The liquid polyolefin resin and / or liquid rubber is preferably one or more selected from liquid polybutene, hydrogenated polybutadiene, butadiene-based liquid rubber, and liquid polyisoprene, more preferably one or more selected from liquid polybutene and hydrogenated polybutadiene, and even more preferably liquid polybutene. The liquid polybutene may be a homopolymer (e.g., 1-butene homopolymer, isobutene homopolymer) or a copolymer (e.g., a copolymer of 1-butene and isobutene).

[0042] Liquid polyolefin resins and / or liquid rubbers can be commercially available. Examples of commercially available liquid polyolefin resins include ENEOS's "HV-300" (liquid polybutene), ENEOS's "HV-1900" (liquid polybutene), ENEOS's "HV-50" (liquid polybutene), ENEOS's "HV-35" (liquid polybutene), Kothari's "950MW" (liquid polybutene), Kothari's "2400MW", INEOS's "H-1900" (liquid polybutene), and INEOS's "H-6000" ( Examples include liquid polybutene, INEOS's "H-18000" (liquid polybutene), NOF Corporation's "200N" (liquid polybutene), Nippon Soda Co., Ltd.'s "BI-2000" (hydrogenated polybutadiene), Nippon Soda Co., Ltd.'s "BI-3000" (hydrogenated polybutadiene), Nippon Soda Co., Ltd.'s "GI-3000" (hydrogenated polybutadiene), Mitsui Chemicals Inc.'s "Lucant LX100" (liquid olefin polymer), and Mitsui Chemicals Inc.'s "Lucant LX400" (liquid olefin polymer).

[0043] Examples of commercially available liquid rubber include Idemitsu Showa Shell's "Poly bd R-45HT" (butadiene-based liquid rubber), Idemitsu Showa Shell's "Poly bd R-15HT" (butadiene-based liquid rubber), and Idemitsu Showa Shell's "Poly "ip" (liquid polyisoprene), Nippon Soda Co., Ltd. "B-1000" (liquid polybutadiene), Nippon Soda Co., Ltd. "B-3000" (liquid polybutadiene), Nippon Soda Co., Ltd. "G-3000" (liquid polybutadiene), Kuraray Co., Ltd. "LIR-30" (liquid polyisoprene), Kuraray Co., Ltd. "LIR-390" (liquid polyisoprene), Kuraray Co., Ltd. "LIR-290" (liquid polyisoprene), Kuraray Co., Ltd. "LBR-302" (liquid polybutadiene), Kuraray Co., Ltd. "LBR-305" (liquid polybutadiene), Kuraray Co., Ltd. "LBR-361" (liquid polybutadiene), Kuraray Co., Ltd. "L-SBR-820" (liquid styrene-butadiene random copolymer), Cray Valley Co., Ltd. "Ricon 154" (liquid butadiene), Cray Examples include "Ricon 184" (liquid styrene-butadiene random copolymer) manufactured by VALLEY.

[0044] The content of component (B) in the composition (or the total content of both liquid polyolefin resin and liquid rubber when both are used) is preferably 5% by mass or more, more preferably 7.5% by mass or more, and even more preferably 10% by mass or more, relative to 100% by mass of the nonvolatile content of the composition, from the viewpoint of adhesion, and preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of adhesion at high temperatures. In one embodiment of the present invention, the content of component (B) is preferably 5 to 50% by mass, and more preferably 7.5 to 40% by mass or less, relative to 100% by mass of the nonvolatile content of the composition.

[0045] <(C) Component: Hygroscopic inorganic filler> The composition of the present invention may contain a hygroscopic inorganic filler. Only one kind of component (C) may be used, or two or more kinds may be used in combination. By using the component (C), good moisture barrier properties can be achieved, and by trapping ionic impurities, an increase in surface resistivity in a high-temperature and high-humidity environment can be suppressed, and conductivity can be maintained.

[0046] Examples of the component (C) include, for example, uncalcined hydrotalcite, semi-calcined hydrotalcite, calcined hydrotalcite, calcium oxide, magnesium oxide, calcined dolomite (a mixture containing calcium oxide and magnesium oxide), calcium hydride, strontium oxide, aluminum oxide, barium oxide, molecular sieve, zeolite, silica, and the like. The component (C) is preferably at least one selected from uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite, and more preferably at least one selected from uncalcined hydrotalcite and semi-calcined hydrotalcite.

[0047] Hydrotalcite can be classified into uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite.

[0048] Uncalcined hydrotalcite is a metal hydroxide having a layered crystal structure represented by, for example, natural hydrotalcite (Mg6Al2(OH) 16 CO3·4H2O), and for example, a layer [Mg 1-X Al X [[ID=1}}\(OH)_2] X+ and an intermediate layer [(CO3) [[ID=2)}\(CO_3\) X / 2 ·mH2O] X- It consists of. Uncalcined hydrotalcite is a concept including hydrotalcite-like compounds such as synthetic hydrotalcite. Examples of the hydrotalcite-like compound include those represented by the following formula (I) and the following formula (II).

[0049] [M 2+ 1-x M 3+x (OH)2] x+ ·[(A n- ) x / n ·mH2O] x- (I) (where M 2+ represents divalent metal ions such as Mg 2+ , Zn 2+ etc., M 3+ represents trivalent metal ions such as Al 3+ , Fe 3+ etc., A n- represents an n-valent anion such as CO3 2- , Cl - , NO3 - etc., 0 < x < 1, 0 ≤ m < 1, and n is a positive number.) In formula (I), M 2+ is preferably Mg 2+ , and M 3+ is preferably Al 3+ , and A n- is preferably CO3 2- .

[0050] M 2+ x Al2(OH) 2x+6-nz (A n- ) z ·mH2O (II) (where M 2+ represents divalent metal ions such as Mg 2+ , Zn 2+ etc., A n- represents an n-valent anion such as CO3 2- , Cl - , NO3 - etc., x is a positive number of 2 or more, z is a positive number of 2 or less, m is a positive number, and n is a positive number.) In formula (II), M 2+ is preferably Mg 2+ ​​​​​​​​Partially calcined hydrotalcite refers to a metal hydroxide with a layered crystalline structure obtained by calcining uncalcined hydrotalcite, in which the amount of interlayer water is reduced or eliminated. "Interlayer water," when explained using the chemical formula, refers to "H2O" as shown in the chemical formula of the uncalcined natural hydrotalcite and hydrotalcite-like compounds mentioned above.

[0052] On the other hand, calcined hydrotalcite refers to a metal oxide having an amorphous structure obtained by calcining uncalcined or semi-calcined hydrotalcite, in which not only intercalated water but also hydroxyl groups have disappeared through condensation dehydration.

[0053] Uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by their saturation water absorption rates. The saturation water absorption rate of semi-calcined hydrotalcite is 1% by mass or more and less than 20% by mass. On the other hand, the saturation water absorption rate of uncalcined hydrotalcite is less than 1% by mass, and the saturation water absorption rate of calcined hydrotalcite is 20% by mass or more.

[0054] "Saturation water absorption rate" refers to the rate of mass increase relative to the initial mass when a 1.5g sample (e.g., semi-calcined hydrotalcite) is weighed using a balance, its initial mass is measured, and then it is left standing for 200 hours in a small environmental test chamber (SH-222, manufactured by ESPEC Corporation) set to atmospheric pressure, 60°C, and 90% RH (relative humidity). The formula is as follows (i): Saturated water absorption rate (mass%) = 100 × (mass after moisture absorption - initial mass) / initial mass (i) It can be calculated using this method.

[0055] The saturation water absorption rate of the partially calcined hydrotalcite is preferably 3% by mass or more and less than 20% by mass, and more preferably 5% by mass or more and less than 20% by mass.

[0056] Furthermore, uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by their thermogravimetric analysis rates. The thermogravimetric analysis rate for semi-calcined hydrotalcite is less than 15% by mass at 280°C, and its thermogravimetric analysis rate for semi-calcined hydrotalcite is 12% by mass or more at 380°C. On the other hand, the thermogravimetric analysis rate for uncalcined hydrotalcite is 15% by mass or more at 280°C, and the thermogravimetric analysis rate for calcined hydrotalcite is less than 12% by mass at 380°C.

[0057] Thermogravimetric analysis can be performed using a Hitachi High-Tech Science TG / DTA EXSTAR6300. 5 mg of hydrotalcite is weighed into an aluminum sample pan, and the pan is left open without a lid. The analysis is performed under a nitrogen flow rate of 200 mL / min, and the temperature is increased from 30°C to 550°C at a heating rate of 10°C / min. The thermogravimetric loss rate is calculated using the following formula (ii): Thermogravimetric reduction rate (mass%) It can be calculated as (ii) = 100 × (mass before heating - mass when the predetermined temperature is reached) / mass before heating.

[0058] Furthermore, uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by the peaks and relative intensity ratios measured by powder X-ray diffraction. Semi-calcined hydrotalcite shows a peak split into two around 8-18° 2θ by powder X-ray diffraction, or a peak with a shoulder formed by the combination of two peaks. The relative intensity ratio (low-angle diffraction intensity / high-angle diffraction intensity) between the diffraction intensity of the peak or shoulder appearing at the low angle (=low-angle diffraction intensity) and the diffraction intensity of the peak or shoulder appearing at the high angle (=high-angle diffraction intensity) is 0.001-1,000. On the other hand, uncalcined hydrotalcite has only one peak around 8-18°, or the relative intensity ratio of the diffraction intensity of the peak or shoulder appearing at the low angle and the peak or shoulder appearing at the high angle is outside the aforementioned range. Calcined hydrotalcite does not have a characteristic peak in the 8°-18° region, but has a characteristic peak at 43°. Powder X-ray diffraction measurements were performed using a powder X-ray diffractometer (PANalytical, Empyrean) under the following conditions: counter cathode CuKα (1.5405 Å), voltage: 45 V, current: 40 mA, sampling width: 0.0260°, scanning speed: 0.0657° / s, and measurement diffraction angle range (2θ): 5.0131~79.9711°. Peak search was performed using the peak search function of the software attached to the diffractometer, under the conditions of "minimum significance: 0.50, minimum peak tip: 0.01°, maximum peak tip: 1.00°, peak base width: 2.00°, method: minimum value of the second derivative".

[0059] The BET specific surface area of ​​partially calcined hydrotalcite is 1 to 250 m². 2 / g is preferred, 5-200m 2 / g is more preferable. These BET specific surface areas can be calculated using the BET method by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM Model 1210, manufactured by Mountec) and then using the BET multipoint method.

[0060] The particle size of uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite is preferably 1 to 1,000 nm, and more preferably 10 to 800 nm, from the viewpoint of transparency. These particle sizes are the median diameter of the particle size distribution when the particle size distribution is prepared on a volume basis by laser diffraction scattering particle size distribution measurement (JIS Z8825).

[0061] Uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be used after surface treatment with a surface treatment agent. Examples of surface treatment agents that can be used include higher fatty acids, alkylsilanes, and silane coupling agents, with higher fatty acids and alkylsilanes being particularly preferred. One or more surface treatment agents can be used.

[0062] Uncalcined hydrotalcite can be commercially available. Examples of commercially available products include Kyowa Chemical Industry's "DHT-4A" (particle size (median diameter): 370 nm), "Alma Kaiser" (particle size (median diameter): 620 nm), and "Magcellar 1" (particle size (median diameter): 470 nm), and Sakai Chemical Industry's "STABIACE HT-1", "STABIACE HT-7", and "STABIACE HT-P".

[0063] Semi-calcined hydrotalcite can be commercially available. Examples of such commercially available products include "DHT-4C" (particle size (median diameter): 400 nm) and "DHT-4A-2" (particle size (median diameter): 400 nm) manufactured by Kyowa Chemical Industry Co., Ltd.

[0064] Calcined hydrotalcite can be a commercially available product. Examples of such commercially available products include Kyowa Chemical Industry Co., Ltd.'s "KW-2200" (particle size (median diameter): 400 nm) and "KW-2200" (particle size (median diameter): 400 nm).

[0065] Commercially available calcium oxide can be used. Examples of such commercially available products include "QC-X" from Inoue Lime Industry Co., Ltd., "Moistop #10" from Sankyo Flour Milling Co., Ltd., "HAL-G", "HAL-J", and "HAL-F" from Yoshizawa Lime Industry Co., Ltd., and "CaO Nano Powder" from Filgen Inc.

[0066] The particle size of calcium oxide and the particle size of the mixture containing calcium oxide are preferably 0.03 to 10 μm, more preferably 0.05 to 5 μm, and even more preferably 0.1 to 3 μm, respectively. These particle sizes are the median diameters of the particle size distribution when the particle size distribution is prepared on a volume basis by laser diffraction scattering particle size distribution measurement (JIS Z 8825).

[0067] The content of component (C) in the composition is preferably 1% by mass or more, more preferably 2.5% by mass or more, and even more preferably 5.0% by mass or more, based on 100% by mass of the nonvolatile content of the composition, from the viewpoint of moisture barrier properties, and preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less, from the viewpoint of adhesion and flexibility.

[0068] The composition may contain components other than components (A) to (C) (hereinafter sometimes referred to as "other components"), to the extent that they do not impair the effects of the present invention. Examples of other components include tackifiers, curing accelerators, antioxidants, plasticizers, and metal complexes in which a bidentate ligand, in which both coordinating atoms are oxygen atoms, and a monodentate ligand, in which the coordinating atom is an oxygen atom, are bonded to the central metal. These may be used individually or in combination of two or more.

[0069] A tackifier is a component that imparts tackiness to a protective (sealing) film, thereby improving adhesion. In this invention, there are no particular limitations on the tackifier, and known tackifiers can be used.

[0070] The softening point of the tackifier is preferably 50 to 200°C, more preferably 90 to 180°C, and even more preferably 100 to 150°C, from the viewpoint of the heat resistance of the protective (sealing) film. The softening point is measured by the ring-and-ball method in accordance with JIS K2207.

[0071] Commercially available tackifiers can be used. Examples of such commercially available products include Arakawa Chemical Industries' "Alcon P-90," "Alcon P-100," "Alcon P-115," "Alcon P-125," "Alcon P-140," "Alcon M-90," "Alcon M-100," "Alcon M-115," and "Alcon M-135" (all cyclohexane ring-containing hydrogenated petroleum resins).

[0072] From the viewpoint of the adhesiveness and sealing properties of the protective (sealing) film, the content of the tackifier is preferably 0 to 30% by mass, more preferably 0 to 25% by mass, and even more preferably 0 to 22.5% by mass, based on 100% by mass of the nonvolatile content of the composition.

[0073] Examples of curing accelerators include imidazole compounds, tertiary and quaternary amine compounds, dimethylurea compounds, and organophosphine compounds.

[0074] Examples of imidazole compounds include 1H-imidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-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 imidazole compounds include Cureazole 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.).

[0075] There are no particular restrictions on tertiary and quaternary amine compounds, but examples include quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide; diazabicyclo compounds such as DBU (1,8-diazabicyclo[5.4.0]undecene-7), DBN (1,5-diazabicyclo[4.3.0]nonene-5), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, and DBU-phenol novolac resin salt; tertiary amines such as benzyldimethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol (TAP) or their salts, and dimethylurea compounds such as aromatic dimethylurea and aliphatic dimethylurea.

[0076] Examples of dimethylurea compounds include aromatic dimethylureas such as DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) and U-CAT3512T (manufactured by Sunapro Co., Ltd.), and aliphatic dimethylureas such as U-CAT3503N (manufactured by Sunapro Co., Ltd.). Among these, aromatic dimethylureas are preferred due to their curability.

[0077] Examples of organic phosphine compounds include triphenylphosphine, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and triphenylphosphinetriphenylborane. Specific examples of organic phosphine compounds include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, and TPP-S (all manufactured by Hokko Chemical Industry Co., Ltd.).

[0078] When a curing accelerator is used, its content is preferably 0.0001 to 0.1% by mass, more preferably 0.0002 to 0.075% by mass, and even more preferably 0.0002 to 0.05% by mass, based on 100% by mass of the nonvolatile content of the composition, in order to promote the formation of component (A) (i.e., a crosslinked polymer having an isobutene-isoprene copolymer chain).

[0079] In the present invention, there are no particular limitations on the antioxidant, and known antioxidants can be used. When an antioxidant is used, its content is preferably 0.01 to 0.5% by mass, more preferably 0.05 to 0.4% by mass, and even more preferably 0.1 to 0.3% by mass, based on 100% by mass of the nonvolatile content of the composition.

[0080] Examples of plasticizers include mineral oils such as paraffinic process oils, naphthenic process oils, liquid paraffin, and petrolatum, as well as vegetable oils such as castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, and olive oil.

[0081] To improve the adhesion and flexural resistance of the protective (sealing) film, metal complexes may be used in which a bidentate ligand (hereinafter sometimes referred to as "oxygen-bidentate ligand"), in which both coordinating atoms are oxygen atoms, and a monodentate ligand (hereinafter sometimes referred to as "oxygen-monodentate ligand"), in which one coordinating atom is an oxygen atom, are bonded to the central metal.

[0082] The aforementioned metal complex is preferably a metal complex represented by the following formula (1) (hereinafter referred to as "metal complex (1)").

[0083] [ka]

[0084] In formula (1), M is the central metal of a metal complex, representing a metal from the 2nd to the 6th period of the periodic table. R1 and R3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, or an aralkyloxy group. R2 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an alkoxycarbonyl group, or an alkenyloxycarbonyl group. X represents an oxygen-monodentate ligand, The solid line between the oxygen atom (O) and M in [ ] represents a covalent bond, the dashed line between the oxygen atom (O) and M in [ ] represents a coordinate bond, and m represents an integer between 3 and 4, and n represents an integer between 1 and 3, where m > n.

[0085] In formula (1), M is preferably a metal from the third to fifth period, more preferably Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, Zr, In, or Sn, and even more preferably Al, Ti, or Zr.

[0086] Examples of halogen atoms in this specification include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0087] In this specification, alkyl groups may be linear or branched. The number of carbon atoms in an alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, and 2-ethylbutyl. Alkyl groups may have substituents. Examples of substituents include halogen atoms, hydroxyl groups, and optionally substituted amino groups.

[0088] In this specification, the alkenyl group may be linear or branched. The number of carbon atoms in the alkenyl group is preferably 2 to 20. Examples of alkenyl groups include ethenyl group (i.e., vinyl group), 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 3-methyl-2-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, octadecenyl group (e.g., 9-octadecenyl group), etc. Examples of substituents that the alkenyl group may have include halogen atoms, hydroxyl groups, and amino groups which may have substituents.

[0089] In this specification, the alkynyl group may be linear or branched. The number of carbon atoms in the alkynyl group is preferably 2 to 10, more preferably 2 to 6. Examples include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, and 4-methyl-2-pentynyl group. Examples of substituents that the alkynyl group may have include halogen atoms, hydroxyl groups, and amino groups which may have substituents.

[0090] In this specification, the number of carbon atoms in the aryl group is preferably 6 to 18, and more preferably 6 to 14. Examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, and 9-anthryl groups. The aryl group may have substituents. Examples of substituents include halogen atoms, hydroxyl groups, optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, and optionally substituted amino groups.

[0091] In this specification, the number of carbon atoms in the aralkyl group is preferably 7 to 16. Examples of aralkyl groups include benzyl groups, phenethyl groups, naphthylmethyl groups, and phenylpropyl groups. The aralkyl group may have substituents. Examples of substituents include halogen atoms, hydroxyl groups, and optionally substituted amino groups.

[0092] In this specification, examples of amino groups that may have substituents include amino groups, mono- or di-alkylamino groups (e.g., methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dibutylamino group), mono- or di-cycloalkylamino groups (e.g., cyclopropylamino group, cyclohexylamino group), mono- or di-arylamino groups (e.g., phenylamino group), mono- or di-aralkylamino groups (e.g., benzylamino group, dibenzylamino group), heterocyclic amino groups (e.g., pyridylamino group), and the like.

[0093] In this specification, the description of alkyl groups in alkoxy groups (i.e., alkyloxy groups) is the same as the description of alkyl groups above. The alkoxy group may have substituents. Examples of substituents include halogen atoms, hydroxyl groups, and optionally substituted amino groups.

[0094] In this specification, the description of the alkenyl group in the alkenyloxy group is the same as the description of the alkenyl group above. The alkenyloxy group may have substituents. Examples of substituents include halogen atoms, hydroxyl groups, and optionally substituted amino groups.

[0095] In this specification, the description of the aryl group in the aryloxy group is the same as the description of the aryl group above. The aryloxy group may have substituents. Examples of substituents include halogen atoms, hydroxyl groups, optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, and optionally substituted amino groups.

[0096] In this specification, the description of the aralkyl group in the aralkyloxy group is the same as the description of the aralkyl group described above. The aralkyloxy group may have substituents. Examples of substituents include halogen atoms, hydroxyl groups, and optionally substituted amino groups.

[0097] In this specification, the description of the alkyl group in an alkoxycarbonyl group (i.e., an alkyloxycarbonyl group) is the same as the description of the alkyl group above. The alkoxycarbonyl group may have substituents. Examples of substituents include halogen atoms, hydroxyl groups, and optionally substituted amino groups.

[0098] In this specification, the description of alkenyl in an alkenyloxycarbonyl group is the same as the description of alkenyl above. The alkenyloxycarbonyl group may have substituents. Examples of substituents include halogen atoms, hydroxyl groups, and optionally substituted amino groups.

[0099] The oxygen-monodentate ligand represented by X in equation (1) is usually a conjugate base of a Brønsted acid, for example, RO - (R: organic group), RCOO - Examples include (R: organic group).

[0100] RO - In this, the organic group R may be either an aliphatic group or an aromatic group. Furthermore, the aliphatic group may be either a saturated aliphatic group or an unsaturated aliphatic group. The number of carbon atoms in the organic group R is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. RO - Examples include methoxy anions, ethoxide anions, propoxide anions, isopropoxide anions, butoxide anions, isobutoxide anions, sec-butoxide anions, tert-butoxide anions, pentyl oxide anions, and hexyl oxide anions.

[0101] RCOO - In this, the organic group R may be either an aliphatic group or an aromatic group. Furthermore, the aliphatic group may be either a saturated aliphatic group or an unsaturated aliphatic group. The number of carbon atoms in the organic group R is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. RCOO -Examples include anions corresponding to carboxylic acids such as acetic acid, propionic acid, and benzoic acid.

[0102] In formula (1), the terms in brackets [ ] represent oxygen-bidentate ligands. Specific examples of oxygen-bidentate ligands include acetylacetone, 3-methyl-2,4-pentanedione, acetylacetaldehyde, 2,4-hexanedione, 2,4-heptanedione, 5-methyl-2,4-hexanedione, 5,5-dimethyl-2,4-hexanedione, benzoylacetone, benzoylacetophenone, salicylaldehyde, 1,1,1-trifluoroacetylacetone, 1,1,1,5,5,5-hexafluoroacetylacetone, 3-methoxy-2,4-pentanedione, 3-cyano-2,4-pentanedione, 3-nitro-2,4-pentanedione, 3-chloro-2,4-pentanedione, acetoacetic acid, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, salicylic acid, methyl salicylate, malonic acid, dimethyl malonate, and diethyl malonate. When coordinated to a central metal, the oxygen-bidentate ligand takes on a structure from which one or more protons have been removed.

[0103] Examples of metal complexes (1) in which the central metal M is Al include (octadecenylacetate)aluminum diisopropylate, (ethylacetate)aluminum diisopropylate, (ethylacetate)aluminum di-n-butyrate, (propylacetate)aluminum diisopropylate, and (n-butylacetate)aluminum diisopropylate.

[0104] Examples of metal complexes (1) in which the central metal M is Ti include titanium allyl acetacetate triisopropoxide, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethyl acetate), titanium methylphenoxide, and titanium oxide bis(pentanedionate).

[0105] Examples of metal complexes (1) in which the central metal M is Zr include zirconium allyl acetate triisopropoxide, zirconium di-n-butoxide (bis-2,4-pentanedione), zirconium diisopropoxide (bis-2,4-pentanedione), zirconium diisopropoxide bis(tetramethylheptanedione), zirconium diisopropoxide bis(ethylacetate), zirconium butoxide (acetylacetate) (bisethylacetate), and zirconium triputoxymonoacetylacetonate.

[0106] When using metal complexes in which an oxygen-bidentate ligand and an oxygen-monodentate ligand are bonded to the central metal (particularly metal complex (1)), the content thereof is preferably 0.05 to 5.0% by mass, more preferably 0.1 to 4.0% by mass, and even more preferably 0.15 to 3.0% by mass, based on 100% by mass of the nonvolatile content of the composition.

[0107] <Conductive layer of conductive substrate> The conductive layer of a conductive substrate protected (sealed) by the composition of the present invention is composed of a conductive material comprising one or more selected from metal nanowires, metal meshes, metal nanoparticles, and conductive polymers. The metals constituting the metal nanowires, metal meshes, and / or metal nanoparticles are not particularly limited and are, for example, one or more selected from silver, copper, gold, nickel, platinum, palladium, iron, cobalt, and tin, with silver, copper, gold, and nickel being preferred. The conductive polymer is not particularly limited and is, for example, one or more selected from poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole, polythiophene, graphene, polyacetylene, poly(p-phenylene), poly(p-phenylenevinylene), and polyaniline, with PEDOT being preferred. In a preferred embodiment of the present invention, the conductive layer of the conductive substrate is composed of a conductive material comprising silver nanowires.

[0108] [Method for producing the composition] The method for producing the composition of the present invention is not particularly limited, and examples include mixing the above-mentioned components with a solvent or the like, if necessary, using a kneading roller or a rotary mixer.

[0109] [Method for forming a protective (sealing) film] The method for forming a protective (sealing) film on the conductive layer of a conductive substrate (protecting (sealing) the conductive layer) is not particularly limited, and for example, (1) A method of applying a varnish of the composition onto a conductive layer and drying it to form a protective (sealing) film; (2) A method of forming a protective (sealing) film by preparing a sealing sheet having a composition layer on a support, laminating the composition layer of the sealing sheet onto a conductive layer, and peeling off the support; These are some examples.

[0110] Method (1) can be carried out, for example, by coating a composition made into a varnish by incorporating an organic solvent onto a conductive layer using a die coater or the like, and then drying the resulting coating film by heating or blowing hot air to form a protective (sealing) film on the conductive layer.

[0111] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (hereinafter also abbreviated as "MEK"), and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Any one of these organic solvents may be used alone, or two or more may be used in combination.

[0112] There are no particular restrictions on drying conditions, but typically, drying at around 50-100°C for 3-15 minutes is preferable.

[0113] The thickness of the protective (sealing) film after drying is typically in the range of 3 μm to 200 μm, preferably 5 μm to 100 μm, and more preferably 5 μm to 50 μm.

[0114] Method (2) can be carried out by, for example, applying a composition made into a varnish by incorporating an organic solvent onto a support using a die coater or the like, drying the resulting coating film by heating or blowing hot air to create a sealing sheet in which a composition layer is formed on the support, and then laminating the composition layer of the sealing sheet onto a conductive layer using a roll laminator, vacuum laminator or the like in a batch or continuous roll method, peeling off the support, and forming a protective (sealing) film on the conductive layer.

[0115] Examples of support materials include plastic films such as polyethylene, polypropylene, polyvinyl chloride and other polyolefins, cycloolefin polymers, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate and other polyesters, polycarbonate, and polyimide. PET is particularly preferred as the plastic film. The support material may also be a metal foil such as aluminum foil, stainless steel foil, or copper foil. The surface on which the composition layer is formed of the support material may be subjected to a release treatment, matting treatment, corona treatment, etc., using a silicone resin-based release agent, alkyd resin-based release agent, fluororesin-based release agent, etc. In the present invention, if the support material has a release layer, the release layer is also considered to be part of the support material. The thickness of the support material is not particularly limited, but from the viewpoint of handling and other factors, it is preferably 20 to 200 μm, and more preferably 20 to 125 μm.

[0116] The organic solvent, drying conditions, and thickness of the protective (sealing) film after drying are the same as in method (1) above.

[0117] [Application] The compositions of the present invention can be used for protecting (sealing) the conductive layer of a conductive substrate using metal nanowires, metal meshes, metal nanoparticles, conductive polymers, and especially metal nanowires and metal nanoparticles as conductors. [Examples]

[0118] The present invention will be described in more detail below with reference to examples, but the present invention is not limited by the following examples, and it is possible to implement it with appropriate modifications within the scope that is consistent with the spirit of the above and below, and all such modifications are included in the technical scope of the present invention. In addition, unless otherwise specified, "parts" and "%" in relation to the amount of components mean "parts by mass" and "mass%", respectively.

[0119] <Ingredients> The ingredients used in the manufacturing example are shown below. (A) Ingredients: "ER866" (manufactured by Seikoh PMC, glycidyl methacrylate-modified butyl rubber (glycidyl methacrylate-modified isobutene-isoprene copolymer), epoxy group concentration: 1.63 mmol / g, number average molecular weight: 113,000, isobutene units / isoprene units: 98.9% / 1.1%) "ER661" (manufactured by Seikoh PMC, maleic anhydride-modified butyl rubber (maleic anhydride-modified isobutene-isoprene copolymer), acid anhydride group concentration: 0.77 mmol / g, number average molecular weight: 40,000, isobutene units / isoprene units: 98.9% / 1.1%) (B) Ingredients: "HV-300M" (manufactured by Toho Chemical Industry Co., Ltd., maleic anhydride-modified liquid polybutene, acid anhydride group concentration: 0.77 mmol / g, number average molecular weight: 2,100) "HV-1900" (manufactured by ENEOS Corporation, liquid polybutene, number average molecular weight: 2,900, viscosity at 25°C: 460 Pa·s) (C) Ingredients: Semi-calcined hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., "DHT-4C", particle size (median diameter): 400 nm, BET specific surface area: 15 m²) 2 / g) Uncalcined hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., "DHT-4A", particle size (median diameter): 370 nm, BET specific surface area: 11 m²) 2 / g) Other ingredients: "Alcon P-125" (Tackifier: Manufactured by Arakawa Chemical Industries, Ltd., Hydrogenated petroleum resin containing cyclohexane rings, Softening point: 125℃) "PlenAct Al-M" (metal complex: manufactured by Ajinomoto Fine Techno Co., Ltd., (octadecenylacetoacetate)aluminum diisopropylate) 2,4,6-Tris(dimethylaminomethyl)phenol (curing accelerator: hereinafter abbreviated as "TAP") (manufactured by Kayaku Akzo) Comparative ingredients: "KR-3700" (Shin-Etsu Chemical Co., Ltd., solvent-added silicone adhesive) "CAT-PL-50T" (manufactured by Shin-Etsu Chemical Co., Ltd., a toluene solution of divinyltetramethyldirosixane complex of chloroplatinic acid) "PARACRON S-2012" (manufactured by Negami Kogyo Co., Ltd., thermoplastic acrylic resin, weight-average molecular weight: 900,000, hydroxyl value: 6.5KOH mg / g, toluene solvent, solids content: 34.5% by weight) "Stabio D-376" (manufactured by Mitsui Chemicals, isocyanate curing agent, NCO%: 24%) "ZX-1059" (manufactured by Nippon Steel Chemical & Material Co., Ltd., liquid hydrogenated bisphenol A and F type epoxy resin, epoxy equivalent: 165 g / eq) "TOPR-300" (manufactured by Nippon Steel Chemical & Material Co., Ltd., solid epoxy resin) "YX7200B35" (manufactured by Mitsubishi Chemical Corporation, phenoxy resin solution, solvent: MEK, non-volatile content: 35%) "TBPDA" (manufactured by Hokko Chemical Industry Co., Ltd., ionic liquid curing agent)

[0120] <Base material> Polyethylene terephthalate (PET) film: Toray Industries Lumirror R80, 38 μm, water vapor transmission rate 20 g / m² 2 / day(40℃-90%RH, MOCON method) Barrier film: Belearl 38UD001, manufactured by Reikosha, 38μm, water vapor transmission rate 5×10 -4 g / m 2 / day(40℃-90%RH, MOCON method)

[0121] <Method for manufacturing sealing sheets> <Manufacturing Example 1> Varnishes with the mixing ratios shown in Table 1 were prepared using the following procedure, and sealing sheets were made using the obtained varnishes. The amounts (parts) of each component listed in the table below indicate the amount of non-volatile content of each component in the varnish.

[0122] Specifically, a swazol solution (non-volatile content: 60%) of cyclohexane ring-containing hydrogenated petroleum resin (tackifier, "Alcon P-125" manufactured by Arakawa Chemical Industries, Ltd.) was mixed with a toluene solution (non-volatile content: 25%) of maleic anhydride-modified liquid polybutene ("HV-300M" manufactured by Toho Chemical Industries, Ltd.), polybutene ("HV-1900" manufactured by ENEOS Corporation), glycidyl methacrylate-modified butyl rubber ("ER866" manufactured by Seikoh PMC Co., Ltd.), a toluene solution (non-volatile content: 35%) of maleic acid-modified butyl rubber ("ER661" manufactured by Seikoh PMC Co., Ltd.), a curing accelerator (TAP, manufactured by Kayaku Nurion Co., Ltd.), and toluene. The resulting mixture was uniformly dispersed in a high-speed rotary mixer to obtain the varnish composition. The obtained varnish was uniformly applied using a die coater to the release-treated surface of a polyethylene terephthalate (PET) film (Toyo Cloth Co., Ltd. "SP4020", PET film thickness: 50 μm) that had been treated with a silicone-based release agent. The film was then heated at 130°C for 30 minutes to obtain a sealing sheet having a composition layer with a thickness of 20 μm.

[0123] <Manufacturing Example 2> A mixture was obtained by dispersing maleic anhydride-modified liquid polybutene (HV-300M, Toho Chemical Industries, Ltd.), polybutene (HV-1900, ENEOS Corporation), uncalcined hydrotalcite (DHT-4A, Kyowa Chemical Industries, Ltd.), and a metal complex (Plenact Al-M, Ajinomoto Fine Techno Co., Ltd.) in a swazol solution (non-volatile content: 60%) of cyclohexane ring-containing hydrogenated petroleum resin (tackifier, "Alcon P-125", manufactured by Arakawa Chemical Industries, Ltd.) using a three-roll mixer. To the obtained mixture, glycidyl methacrylate-modified butyl rubber (ER866, Seikoh PMC, Ltd.), maleic acid-modified butyl rubber (ER661, Seikoh PMC, Ltd.), a curing accelerator (TAP, manufactured by Kayaku Nurion Co., Ltd.), and toluene were added, and the resulting mixture was uniformly dispersed in a high-speed rotary mixer to obtain a varnish composition. The obtained varnish was uniformly applied using a die coater to the release-treated surface of a polyethylene terephthalate (PET) film (Toyo Cloth Co., Ltd. "SP4020", PET film thickness: 50 μm) that had been treated with a silicone-based release agent. The film was then heated at 130°C for 30 minutes to obtain a sealing sheet having a composition layer with a thickness of 20 μm.

[0124] <Manufacturing Example 3> Except for changing the uncalcined hydrotalcite to semi-calcined hydrotalcite (DHT-4C manufactured by Kyowa Chemical Industry Co., Ltd.), a varnish of the composition and a sealing sheet having a composition layer with a thickness of 20 μm were obtained using the same method as in Production Example 2.

[0125] <Manufacturing Example 4> A solvent-added silicone adhesive (Shin-Etsu Chemical Co., Ltd. "KR-3700", a toluene solution with a solid content of 60% by weight) was mixed with a divinyltetramethyldirosixane complex of chloroplatinic acid (Shin-Etsu Chemical Co., Ltd. "CAT-PL-50T"). The resulting mixture was stirred in a high-speed rotary mixer to obtain a varnish of the composition. The obtained varnish was uniformly applied to the release-treated surface of a PET film (Nippa Co., Ltd. "SS1A") treated with a fluorine-based release agent using a die coater, and heated at 150°C for 1 minute to obtain a sealing sheet having a composition layer with a thickness of 20 μm.

[0126] <Manufacturing Example 5> A thermoplastic acrylic resin (PARACRON S-2012, manufactured by Negami Kogyo Co., Ltd., solids content: 34.5% by weight, toluene solvent) was mixed with an isocyanate curing agent (Stabio D-376, manufactured by Mitsui Chemicals, Inc.), and the resulting mixture was stirred with a high-speed rotary mixer to obtain a composition varnish. The obtained varnish was uniformly applied to the release-treated surface of a PET film (SP4020, manufactured by Toyo Cloth Co., Ltd., PET film thickness: 50 μm) treated with a silicone-based release agent using a die coater, and heated at 130°C for 30 minutes to obtain a sealing sheet having a composition layer with a thickness of 20 μm.

[0127] <Manufacturing Example 6> A mixture of liquid hydrogenated bisphenol A and F type epoxy resins ("ZX-1059" manufactured by Mitsubishi Chemical Corporation) and solid epoxy resin ("TOPR-300" manufactured by Nippon Steel Chemical & Material Co., Ltd.) was prepared. Then, a phenoxy resin solution ("YX7200B35" manufactured by Mitsubishi Chemical Corporation, solvent: MEK, non-volatile content: 35%) and an ionic liquid curing agent ("TBPDA" manufactured by Hokko Chemical Industry Co., Ltd.) were added and the mixture was uniformly dispersed in a high-speed rotary mixer to obtain a varnish of the composition. The obtained varnish was uniformly applied to the release-treated surface of a PET film ("NS80A" manufactured by Fujimori Kogyo Co., Ltd., PET film thickness: 38 μm) treated with an alkyd-type release agent using a die coater, and heated at 130°C for 30 minutes to obtain a sealing sheet having a composition layer with a thickness of 20 μm.

[0128] <Method for measuring the haze and total light transmittance of a composition layer> Haze (%) and total light transmittance (%) were measured in accordance with JIS 7136. Specifically, the sealing sheets of Production Examples 1 to 6, prepared by the method described above, were processed into 40 mm x 40 mm squares, and the composition layer was laminated to a 50 mm x 50 mm square alkali-free glass (Nippon Electric Glass Co., Ltd. "OA-10G", thickness: 700 μm) using a vacuum laminator (Nikko Materials Co., Ltd. "V-160", temperature 80°C, 0.3 MPa, 30 seconds) to prepare the measurement samples. For Production Example 6, after lamination, the PET film was peeled off and cured by heating at 100°C for 60 minutes. Next, the prepared measurement samples were measured using a Suga Test Instruments HZ-V3 haze meter (halogen lamp) with air as a reference and D65 light to determine Haze (%) and total light transmittance (%). The results are shown in Table 1.

[0129] <Method for measuring the adhesion strength of the composition layer> The sealing sheets produced in Manufacturing Examples 1-6 were cut to a length of 50 mm and a width of 20 mm. Next, using a batch-type vacuum laminator ("Morton-724" manufactured by Nichigo Morton Co., Ltd.), the aluminum foil of a composite film ("PET-Tsuki AL1N30" manufactured by Tokai Toyo Aluminum Sales Co., Ltd., aluminum foil thickness: 30 μm, PET film thickness: 25 μm) comprising aluminum foil and polyethylene terephthalate (PET) film was laminated onto the composition layer of the sealing sheet. Lamination was carried out under the conditions of a temperature of 80°C, a time of 30 seconds, and a pressure of 0.3 MPa. Next, the PET film was peeled off from the sealing sheet, and a polyimide film ("UPIREX-S" manufactured by Ube Industries, Ltd., thickness: 50 μm) was laminated onto the exposed composition layer under the same conditions as above to obtain a laminate having a laminated structure of "composite film / composition layer / polyimide film". In addition, for the sealing sheet in manufacturing example 6, after lamination, the PET film was peeled off, the polyimide film was laminated under the same conditions as above, and then cured by heating at 100°C for 60 minutes. For the resulting laminate, the adhesive strength (room temperature adhesive strength) was measured when the "composite film / composition layer" was peeled off from the polyimide film at room temperature in a direction 180 degrees to the length direction of the aluminum foil at a tensile speed of 300 mm / min. Furthermore, the adhesive strength (high temperature adhesive strength) was measured when the laminate prepared in the same manner as above was peeled off in the same manner under a 60°C environment. The results are shown in Table 1.

[0130] <Evaluation of surface resistivity of sealed silver nanowire laminated conductive film> A silver nanowire laminated conductive film (NovaFilm-AgNW; silver nanowire coated transparent conductive film (PET substrate)) manufactured by Novarials was prepared in A5 size. The sealing sheets prepared in Manufacturing Examples 1 to 6 were processed to A5 size, and the composition layer was laminated to the substrates listed in Table 2 using a vacuum laminator (Nikko Materials "V-160", 80°C, 0.3 MPa, 30 seconds). Subsequently, the PET film was peeled off the sealing sheet, and the exposed composition layer was laminated to the silver nanowire layer of the silver nanowire laminated conductive film under the same conditions as above to prepare evaluation samples. In Comparative Example 3, which used Manufacturing Example 6, the composition layer was cured by heating at 100°C for 60 minutes after lamination to the silver nanowire layer.

[0131] The initial surface resistivity (Ω / Sq.) of a sealed silver nanowire laminated conductive film was measured using an eddy current sheet resistance meter (SURAGUS "EddyCusTF Protable1010"). The sealed silver nanowire laminated conductive film was then stored in a constant temperature and humidity test chamber (85°C, 85%RH), and its surface resistivity (Ω / Sq.) was measured again after 100 hours using the same eddy current sheet resistance meter. Rate of change (%) = [(Surface resistivity after 100 hours of storage at 85℃ 85%RH) / (Initial surface resistivity)] × 100 - 100 The rate of change in surface resistivity was calculated and evaluated according to the following criteria. The results are shown in Table 2. (Evaluation criteria for surface resistivity) ◎ The rate of change in surface resistivity is less than 0%. ○ The rate of change in surface resistivity is 0% or more and less than 20%. × The rate of change in surface resistivity is 20% or more.

[0132] <Evaluation of flexural resistance> The PET film was peeled off from the sealing sheets prepared in manufacturing examples 1 to 6, and polyimide film (manufactured by Unitika, 25 μm) was laminated to both sides of the composition layer using vacuum lamination (80°C, 0.3 MPa, 30 seconds) to prepare evaluation samples with a structure of "polyimide (PI) film / composition layer / polyimide (PI) film".

[0133] The obtained evaluation samples were placed in a clamshell-type bending test apparatus "CL40R type-E02" (manufactured by Yuasa System Equipment Co., Ltd.), and the evaluation samples were bent 100,000 times under the conditions of a temperature of 60°C, humidity of 90%RH, radius of curvature (R) of 2.0 mm, and speed of 60 rpm. After bending, the evaluation samples were observed using a Keyence digital microscope "VHX-5000" (magnification: 20x), and the bending resistance was evaluated according to the following criteria. The results are shown in Table 2. (Evaluation criteria for flexibility) ○(acceptable): No peeling × (Not allowed): Peeling and bubble formation

[0134] [Table 1]

[0135] [Table 2]

[0136] From the results in Tables 1 and 2, it can be seen that Examples 1 to 4 showed good values ​​for haze, total light transmittance, and adhesion strength, and also showed good evaluations of surface resistivity and flexural resistance. [Industrial applicability]

[0137] The composition of the present invention can form a protective (sealing) film that suppresses changes in the surface resistivity of the conductive substrate and migration of the conductor while achieving transparency, adhesion strength, and flexibility in protecting (sealing) the conductive layer constituting a conductive substrate. Therefore, it can be used for protecting (sealing) the conductive layer of a conductive substrate using metal nanowires, metal meshes, metal nanoparticles, conductive polymers, and especially metal nanowires and metal nanoparticles as conductors.

[0138] This application is based on Japanese Patent Application No. 2023-052198, the same application

Claims

1. A composition for a protective film of the conductive layer of a conductive substrate, (A) A crosslinked polymer having an isobutene-isoprene copolymer chain, and (C) Hygroscopic inorganic filler Includes, (A) The content of component is 15% by mass or more relative to 100% by mass of the nonvolatile content of the composition. (C) Component is one or more selected from uncalcined hydrotalcite and semi-calcined hydrotalcite. (C) The content of component is 5 to 60% by mass relative to 100% by mass of the non-volatile content of the composition. The conductive layer is composed of a conductive material comprising one or more selected from metal nanowires, metal meshes, and metal nanoparticles. composition.

2. (A) The composition according to claim 1, wherein the crosslinked polymer having an isobutene-isoprene copolymer chain is at least one selected from the group consisting of reaction products of an isobutene-isoprene copolymer having an epoxy group and an olefin polymer having a carboxyl group and / or an acid anhydride group, and reaction products of an isobutene-isoprene copolymer having a carboxyl group and / or an acid anhydride group and an olefin polymer having an epoxy group.

3. (B) The resin composition according to claim 1, further comprising a liquid polyolefin resin and / or liquid rubber.

4. The composition according to claim 3, wherein the content of component (B) is 5 to 50% by mass based on 100% by mass of the nonvolatile content of the composition.

5. The composition according to claim 1, wherein the metal constituting the metal nanowires, metal meshes and / or metal nanoparticles is one or more selected from silver, copper, gold, nickel, platinum, palladium, iron, cobalt and tin.

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