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WO2024204562A1 - Composition pour film protecteur destiné à une couche électroconductrice - Google Patents

Composition pour film protecteur destiné à une couche électroconductrice Download PDF

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Publication number
WO2024204562A1
WO2024204562A1 PCT/JP2024/012699 JP2024012699W WO2024204562A1 WO 2024204562 A1 WO2024204562 A1 WO 2024204562A1 JP 2024012699 W JP2024012699 W JP 2024012699W WO 2024204562 A1 WO2024204562 A1 WO 2024204562A1
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group
composition
mass
isobutene
metal
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PCT/JP2024/012699
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English (en)
Japanese (ja)
Inventor
賢 大橋
麻衣 細井
直輝 名取
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味の素株式会社
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Publication of WO2024204562A1 publication Critical patent/WO2024204562A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09D123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C09D123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines

Definitions

  • the present invention relates to a composition for protecting (sealing) a conductive layer that constitutes a conductive substrate.
  • Patent Document 1 describes a method in which a protective layer containing a chelating agent is used on a silver nanowire-containing conductive layer.
  • Patent Document 2 also describes an acrylic polymer resin composition as an adhesive layer for bonding a substrate on which metal mesh wiring and silver nanowires are formed.
  • Patent Document 1 an acrylic resin composition is selected for forming the protective layer, and UV irradiation is required to ensure that it functions properly.
  • the resin has a high water vapor permeability, so it cannot fully function as a protective layer in long-term high temperature and high humidity tests.
  • Patent Document 2 adhesion is achieved while suppressing migration of metal into the adhesive layer, but there is no mention of flexibility.
  • the present invention has been made in light of the above-mentioned circumstances, and its purpose is to provide a composition that can form a protective (sealing) film that can protect (seal) the conductive layer that constitutes a conductive substrate, while simultaneously achieving transparency, adhesion strength, and flex resistance, and suppressing changes in the surface resistivity of the conductive substrate and migration of conductors.
  • the inventors discovered that by using the composition for protecting (sealing) the conductive layer that constitutes the conductive substrate as described below, it is possible to form a protective (sealing) film that can suppress changes in the surface resistivity of the conductive substrate and migration of conductors while simultaneously achieving transparency, adhesion strength, and flex resistance, and thus completed the present invention.
  • a composition for a protective film of a conductive layer of a conductive substrate comprising: (A) a crosslinked polymer having an isobutene-isoprene copolymer chain; the conductive layer is composed of a conductive material including at least one selected from metal nanowires, metal meshes, metal nanoparticles, and conductive polymers; Composition.
  • composition according to [2] The composition according to [1], wherein the crosslinked polymer having an isobutene-isoprene copolymer chain (A) is at least one selected from the group consisting of a reaction product of an isobutene-isoprene copolymer having an epoxy group with 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 with an olefin-based polymer having an epoxy group.
  • A crosslinked polymer having an isobutene-isoprene copolymer chain (A) is at least one selected from the group consisting of a reaction product of an isobutene-isoprene copolymer having an epoxy group with an olefin-based polymer having a carboxy group and/or an acid anhydride group, and a reaction product of
  • composition according to [6] wherein the hygroscopic inorganic filler (C) is one or more selected from uncalcined hydrotalcite and semi-calcined hydrotalcite.
  • the content of the (C) component is 1 to 60 mass% based on 100 mass% of the nonvolatile content of the composition.
  • 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.
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • polypyrrole polypyrrole
  • polythiophene polythiophene
  • graphene polyacetylene
  • poly(p-phenylene) poly(p-phenylenevinylene)
  • polyaniline polyaniline
  • the present invention provides a composition that can form a protective (sealing) film that can protect (seal) the conductive layer that constitutes a conductive substrate, while simultaneously achieving transparency, adhesion strength, and flex resistance, and suppressing changes in the surface resistivity of the conductive substrate and migration of conductors.
  • the present invention will now be described with reference to preferred embodiments thereof.
  • the composition of the present invention is used for a protective film of a conductive layer of a conductive substrate, (A) a crosslinked polymer having an isobutene-isoprene copolymer chain;
  • the conductive layer is made of a conductive material including at least one selected from metal nanowires, metal meshes, metal nanoparticles, and conductive polymers.
  • Component (A) Crosslinked polymer having isobutene-isoprene copolymer chain>
  • the component (A) is a crosslinked polymer having an isobutene-isoprene copolymer (i.e., butyl rubber) chain. Only one type of the component (A) may be used, or two or more types may be used in combination.
  • a protective (sealing) film that suppresses an increase in the surface resistivity of the conductive substrate (which exhibits low moisture permeability and can prevent the intrusion of oxygen and ions that cause an increase in the surface resistivity) and has excellent bending resistance.
  • Component (A) can be formed by reacting an isobutene-isoprene copolymer (i.e., butyl rubber having a first reactive functional group) having a reactive functional group (hereinafter sometimes referred to as a "first reactive functional group”) with an olefin-based polymer having a reactive functional group (hereinafter sometimes referred to as a "second reactive functional group”) that can react with the first reactive functional group.
  • olefin-based polymer means a polymer in which structural units derived from olefins (hereinafter sometimes abbreviated as “olefin units”) are the main structural units (i.e., the amount of olefin units is the largest among all structural units).
  • structural units derived from butene which is an olefin unit, etc. may be abbreviated as “butene units”, etc.
  • olefin a monoolefin having one olefinic carbon-carbon double bond and/or a diolefin having two olefinic carbon-carbon double bonds are preferred.
  • monoolefins include ⁇ -olefins such as ethylene, propylene, 1-butene, isobutene (isobutylene), 1-pentene, 1-hexene, 1-heptene, and 1-octene.
  • diolefins include 1,3-butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethylbutadiene.
  • the olefin-based polymer may be a homopolymer or a copolymer.
  • the copolymer may be a random copolymer or a block copolymer.
  • the olefin-based polymer may also be a copolymer of an olefin and a monomer other than an olefin.
  • olefin-based copolymers examples 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.
  • the olefin polymer having a second reactive functional group is preferably a butene polymer having a second reactive functional group.
  • butene polymer means a polymer in which butene units are the main structural unit (i.e., the amount of butene units is the largest among all structural units). Examples of butene include 1-butene and isobutene. Examples of butene polymer 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).
  • a homopolymer e.g., 1-butene homopolymer, isobutene homopolymer
  • a copolymer e.g., a copolymer of 1-butene and isobutene
  • the isobutene-isoprene copolymer having a first reactive functional group and the olefin polymer having a second reactive functional group may each be used alone or in combination of two or more types.
  • Examples of combinations of a first reactive functional group and a second reactive functional group include a combination of an epoxy group and a carboxy group and/or an acid anhydride group (i.e., a carbonyloxycarbonyl group (-CO-O-CO-)), a combination of a carboxy group and/or an acid anhydride group and an epoxy group, a combination of an epoxy group and an amino group, a combination of an amino group and an epoxy group, a combination of a hydroxy group and an isocyanate group (i.e., an isocyanato group), a combination of an isocyanate group and a hydroxy group, and a combination of functional groups having double bonds (e.g., a vinyl group or a (meth)acryloyl group).
  • an epoxy group and a carboxy group and/or an acid anhydride group i.e., a carbonyloxycarbonyl group (-CO-O-CO-)
  • the combination of an epoxy group and a carboxy group and/or an acid anhydride group, and the combination of a carboxy group and/or an acid anhydride group and an epoxy group are preferred, and the combination of an epoxy group and an acid anhydride group and the combination of an acid anhydride group and an epoxy group are more preferred.
  • the former reactive functional group represents the first reactive functional group
  • the latter reactive functional group represents the second reactive functional group.
  • component (A) is preferably at least one selected from the group consisting of a reaction product of an isobutene-isoprene copolymer having an epoxy group with an olefin 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 with an olefin polymer having an epoxy group.
  • the olefin polymer is preferably a butene polymer, more preferably polybutene or an isobutene-isoprene copolymer.
  • the carboxy group and/or the acid anhydride group is preferably an acid anhydride group.
  • component (A) is preferably a reaction product of an isobutene-isoprene copolymer having an epoxy group and a polybutene having a carboxy group and/or an acid anhydride group.
  • the carboxy group and/or the acid anhydride group is preferably an acid anhydride group.
  • component (A) is preferably a reaction product of an isobutene-isoprene copolymer having an epoxy group and an isobutene-isoprene copolymer having a carboxy group and/or an acid anhydride group.
  • the carboxy group and/or the acid anhydride group is preferably an acid anhydride group.
  • the amount of isobutene-isoprene copolymer having a reactive functional group is preferably 15 to 100% by mass, more preferably 20 to 100% by mass, and even more preferably 30 to 100% by mass, based on the total amount of polymers used to form component (A) (e.g., the total amount of isobutene-isoprene copolymer having a first reactive functional group and olefin-based polymer having a second reactive functional group).
  • a reactive functional group e.g., epoxy group, carboxy group, and/or acid anhydride group
  • the "amount of isobutene-isoprene copolymer having a reactive functional group used" 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 used.”
  • the number average molecular weight of the isobutene-isoprene copolymer having reactive functional groups (e.g., epoxy groups, carboxy 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 the present invention is measured by gel permeation chromatography (GPC) method (polystyrene equivalent).
  • the number average molecular weight by the GPC method is measured using Shimadzu Corporation's "LC-9A/RID-6A” as a measuring device, Showa Denko Corporation's "Shodex K-800P/K-804L/K-804L” as a column, toluene or the like as a mobile phase, at a column temperature of 40°C, and can be calculated using a calibration curve of standard polystyrene.
  • the number average molecular weight of the olefin polymer (excluding isobutene-isoprene copolymer) having a second reactive functional group (e.g., epoxy group, carboxy group, and/or acid anhydride group) used to form component (A) is preferably 500 to 500,000, more preferably 1,000 to 300,000, and even more preferably 1,500 to 200,000.
  • the amount of isoprene units in the isobutene-isoprene copolymer having reactive functional groups (e.g., epoxy groups, carboxy 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 modified portions (e.g., portions derived from maleic anhydride for introducing acid anhydride groups).
  • the concentration of epoxy groups in the olefin polymer having epoxy groups (e.g., isobutene-isoprene copolymer having epoxy groups, polybutene having epoxy groups) used to form component (A) is preferably 0.01 to 10 mmol/g, more preferably 0.05 to 5 mmol/g.
  • the epoxy group concentration is determined from the epoxy equivalent obtained based on JIS K 7236-1995.
  • the concentration of carboxy groups in the olefin polymer having carboxy groups (e.g., isobutene-isoprene copolymer having carboxy groups, polybutene having carboxy groups) used to form component (A) is preferably 0.01 to 10 mmol/g, more preferably 0.05 to 5 mmol/g.
  • the concentration of carboxy groups is obtained from the acid value, which is defined as the number of milligrams of potassium hydroxide required to neutralize the acid present in 1 g of resin, according to the description in JIS K 2501.
  • 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) used to form component (A) is preferably 0.01 to 10 mmol/g, 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 milligrams of potassium hydroxide required to neutralize the acid present in 1 g of resin, according to the description in JIS K 2501.
  • the sum of the concentration of carboxy groups and the concentration of acid anhydride groups in the olefin polymer having carboxy groups and acid anhydride groups (for example, an isobutene-isoprene copolymer having carboxy groups and acid anhydride groups, or a polybutene having carboxy groups and acid anhydride groups) used to form component (A) is preferably 0.01 to 10 mmol/g, and more preferably 0.05 to 5 mmol/g.
  • the amounts of isobutene-isoprene copolymer having epoxy groups and olefin polymer having carboxy groups are not particularly limited as long as the crosslinked polymer (A) component can be formed, but the ratio of the amount (mol) of epoxy groups to the amount (mol) of carboxy groups (i.e., amount (mol) of epoxy groups: amount (mol) of carboxy groups) is preferably 100:10 to 100:500, more preferably 100:25 to 100:475, and even more preferably 100:40 to 100:450.
  • the amounts of the isobutene-isoprene copolymer having epoxy groups and the olefin polymer having acid anhydride groups are not particularly limited as long as the crosslinked polymer (A) component can be formed, but the ratio of the amount (mol) of epoxy groups to the amount (mol) of acid anhydride groups (i.e., amount (mol) of epoxy groups: amount (mol) of acid anhydride groups) is preferably 100:10 to 100:500, more preferably 100:25 to 100:475, and even more preferably 100:40 to 100:450.
  • the amounts of the isobutene-isoprene copolymer having epoxy groups and the olefin polymer having carboxy groups and acid anhydride groups are not particularly limited as long as the crosslinked polymer (A) component can be formed, but the ratio of the "amount (mol) of epoxy groups" to the "total amount (mol) of carboxy groups and amount (mol) of acid anhydride groups" (i.e., amount (mol) of epoxy groups): (amount (mol) of carboxy groups + amount (mol) of acid anhydride groups) is preferably 100:10 to 100:500, more preferably 100:25 to 100:475, and even more preferably 100:40 to 100:450.
  • Olefin polymers having epoxy groups e.g., isobutene-isoprene copolymers having epoxy groups, polybutenes having epoxy groups
  • Olefin polymers 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.
  • Olefin polymers having epoxy groups may be commercially available products.
  • Commercially available isobutene-isoprene copolymers having epoxy groups include, for example, Seiko PMC's "ER866” (glycidyl methacrylate modified butyl rubber, epoxy group concentration: 1.63 mmol/g, number average molecular weight: 113,000) and Seiko PMC's "ER850” (glycidyl methacrylate modified butyl rubber, epoxy group concentration: 0.65 mmol/g, number average molecular weight: 99,200).
  • olefin polymers having epoxy groups include, for example, Seiko PMC's "T-YP341" (glycidyl methacrylate modified propylene-butene random copolymer, epoxy group concentration: 0.64 mmol/g, number average molecular weight: 155,000), Seiko PMC's "T-YP276” (glycidyl methacrylate modified propylene-butene random copolymer, epoxy group concentration: 0.64 mmol/g, number average molecular weight: 57,000), and Seiko PMC's "T-YP313” (glycidyl methacrylate modified propylene-butene random copolymer, epoxy group concentration: 0.64 mmol/g, number average molecular weight: 155,000).
  • Olefin polymers having carboxy groups and/or acid anhydride groups e.g., isobutene-isoprene copolymers having carboxy groups and/or acid anhydride groups, polybutenes having carboxy groups and/or acid anhydride groups
  • Olefin polymers having carboxy groups and/or acid anhydride groups can be obtained by graft-modifying an olefin polymer with an unsaturated compound having a carboxy group and/or acid anhydride group (e.g., maleic anhydride) under radical reaction conditions.
  • olefin polymers having carboxyl groups and/or acid anhydride groups may be used.
  • commercially available isobutene-isoprene copolymers having carboxyl groups and/or acid anhydride groups include, for example, "ER661” manufactured by Seiko PMC (maleic anhydride modified butyl rubber, acid anhydride group concentration: 0.77 mmol/g, number average molecular weight: 40,000) and "ER641” manufactured by Seiko PMC (maleic anhydride modified butyl rubber, acid anhydride group concentration: 0.46 mmol/g, number average molecular weight: 57,000).
  • Examples of commercially available olefin polymers having a carboxyl group and/or an acid anhydride group include "HV-300M” manufactured by Toho Chemical Industry Co., Ltd. (maleic anhydride-modified polybutene, acid anhydride group concentration: 1.16 mmol/g, number average molecular weight: 2,100), "T-YP279” manufactured by Seiko PMC Co., Ltd. (maleic anhydride-modified propylene-butene random copolymer, acid anhydride group concentration: 0.46 mmol/g, number average molecular weight: 35,000), and "H-YP279” manufactured by Seiko PMC Co., Ltd.
  • 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, and from the viewpoint of moisture blocking properties, it is preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
  • 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.
  • composition of the present invention may contain a liquid polyolefin resin and/or a liquid rubber.
  • liquid means that the viscosity at 25°C is 5,000 Pa ⁇ s or less.
  • viscosity at 25°C means a viscosity calculated by multiplying the dynamic viscosity at 25°C measured by a dynamic viscoelasticity measuring device by the density.
  • a dynamic viscoelasticity measuring device is a rheometer manufactured by TA Instruments (product name: DISCOVERY HR-2), etc.
  • liquid polyolefin resin refers to an olefin polymer that has a viscosity of 5,000 Pa ⁇ s or less at 25°C and is incapable of forming a rubber elastomer by crosslinking
  • liquid rubber refers to a material that has a viscosity of 5,000 Pa ⁇ s or less at 25°C and is capable of forming a rubber elastomer by crosslinking.
  • liquid polyisoprene is classified as a liquid rubber because it can form a rubber elastomer by crosslinking.
  • the viscosity of the liquid polyolefin resin and 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.
  • the (B) component may be used alone or in combination of two or more types. By using the (B) component, good adhesion (particularly adhesion at high temperatures) can be achieved and the viscoelasticity of the composition can be controlled.
  • the composition of the present invention may also contain a hygroscopic inorganic filler, which will be described below. However, if a large amount of hygroscopic inorganic filler is used, the adhesion of the protective (sealing) film decreases. In this regard, by using the (B) component, good adhesion can be achieved even when a large amount of hygroscopic inorganic filler is used.
  • 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.
  • 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.
  • 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).
  • liquid polyolefin resins and/or liquid rubbers can be used.
  • Commercially available liquid polyolefin resins include, for example, ENEOS "HV-300” (liquid polybutene), ENEOS “HV-1900” (liquid polybutene), ENEOS “HV-50” (liquid polybutene), ENEOS “HV-35” (liquid polybutene), Kothari "950MW” (liquid polybutene), Kothari "2400MW”, INEOS "H-1900” (liquid polybutene), INEOS "H-6000” (liquid polybutene), and others.
  • liquid polybutene liquid polybutene
  • INEOS' "H-18000” liquid polybutene
  • NOF's "200N” liquid polybutene
  • Nippon Soda's "BI-2000” hydrogenated polybutadiene
  • Nippon Soda's "BI-3000” hydrogenated polybutadiene
  • Nippon Soda's "GI-3000” hydrogenated polybutadiene
  • Mitsui Chemicals' "Lucant LX100” liquid olefin polymer
  • Mitsui Chemicals' "Lucant LX400” liquid olefin polymer
  • liquid rubber products include, for example, Idemitsu Showa Shell's "Poly bd R-45HT” (butadiene liquid rubber), Idemitsu Showa Shell's “Poly bd R-15HT” (butadiene liquid rubber), Idemitsu Showa Shell's "Poly ip” (liquid polyisoprene), Nippon Soda's "B-1000" (liquid polybutadiene), Nippon Soda's “B-3000” (liquid polybutadiene), Nippon Soda's “G-3000” (liquid polybutadiene), Kuraray's "LIR-30” (liquid polyisoprene), and Kuraray's "LIR-390” ( liquid polyisoprene), Kuraray's "LIR-290” (liquid polyisoprene), Kuraray's "LBR-302” (liquid polybutadiene), Kuraray's "LBR-305" (liquid polybutadiene), Kuraray''s
  • the content of component (B) in the composition is, from the viewpoint of adhesion, preferably 5% by mass or more, more preferably 7.5% by mass or more, and even more preferably 10% by mass or more, based on 100% by mass of the nonvolatile content of the composition, and, from the viewpoint of adhesion at high temperatures, is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
  • the content of component (B) is preferably 5 to 50% by mass, and more preferably 7.5 to 40% by mass or less, based on 100% by mass of the nonvolatile content of the composition.
  • composition of the present invention may contain a hygroscopic inorganic filler. Only one type of (C) component may be used, or two or more types may be used in combination. By using the (C) component, good moisture blocking properties can be achieved, and by trapping ionic impurities, an increase in surface resistivity in a high-temperature, high-humidity environment can be suppressed, and electrical conductivity can be maintained.
  • component (C) examples include 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, etc.
  • Component (C) is preferably one or more selected from uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite, and more preferably one or more selected from uncalcined hydrotalcite and semi-calcined hydrotalcite.
  • Hydrotalcite can be classified into uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite.
  • Uncalcined hydrotalcite is a metal hydroxide having a layered crystal structure, such as that typified by natural hydrotalcite ( Mg6Al2 ( OH ) 16CO3.4H2O ), and is composed of, for example , a basic skeletal layer [ Mg1 - XAlX (OH) 2 ] X+ and an intermediate layer [( CO3 ) X/ 2.mH2O ] X- .
  • the concept of uncalcined hydrotalcite includes hydrotalcite-like compounds such as synthetic hydrotalcite. Examples of hydrotalcite-like compounds include those represented by the following formula (I) and formula (II):
  • M 2+ represents a divalent metal ion such as Mg 2+ or Zn 2+
  • M 3+ represents a trivalent metal ion such as Al 3+ or Fe 3+
  • a n- represents CO 3 2 represents an n-valent anion such as ⁇ , Cl ⁇ , or NO 3 ⁇ , where 0 ⁇ x ⁇ 1, 0 ⁇ m ⁇ 1, and n is a positive number.
  • M 2+ is preferably Mg 2+
  • M 3+ is preferably Al 3+
  • a n- is preferably CO 3 2- .
  • M 2+ represents a divalent metal ion such as Mg 2+ or Zn 2+
  • a n- represents an n-valent anion such as CO 3 2- , Cl - or NO 3 -
  • x represents
  • z is a positive number equal to or less than 2
  • m is a positive number
  • n is a positive number.
  • M 2+ is preferably Mg 2+
  • a n- is preferably CO 3 2- .
  • Semi-calcined hydrotalcite refers to a metal hydroxide obtained by calcining uncalcined hydrotalcite and having a layered crystal structure in which the amount of interlayer water is reduced or eliminated.
  • interlayer water refers to "H 2 O” described in the composition formula of the above-mentioned uncalcined natural hydrotalcite and hydrotalcite-like compound.
  • calcined hydrotalcite is obtained by calcining uncalcined or semi-calcined hydrotalcite, and is a metal oxide with an amorphous structure in which not only the interlayer water but also the hydroxyl groups have disappeared through condensation dehydration.
  • Uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by their saturated water absorption.
  • the saturated water absorption of semi-calcined hydrotalcite is 1% by mass or more and less than 20% by mass.
  • the saturated water absorption of uncalcined hydrotalcite is less than 1% by mass, and the saturated water absorption of calcined hydrotalcite is 20% by mass or more.
  • the saturated water absorption rate of the semi-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.
  • Uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by the rate of thermal weight loss measured by thermogravimetric analysis.
  • the rate of thermal weight loss of semi-calcined hydrotalcite at 280°C is less than 15% by mass, and its rate of thermal weight loss at 380°C is 12% by mass or more.
  • the rate of thermal weight loss of uncalcined hydrotalcite at 280°C is 15% by mass or more, and the rate of thermal weight loss of calcined hydrotalcite at 380°C is less than 12% by mass.
  • Thermogravimetric analysis can be performed using a Hitachi High-Tech Science TG/DTA EXSTAR6300 by weighing 5 mg of hydrotalcite into an aluminum sample pan, leaving the pan open without a lid, in an atmosphere with a nitrogen flow rate of 200 mL/min, and at a heating rate of 10° C./min from 30° C. to 550° C.
  • Uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by the peaks and relative intensity ratios measured by powder X-ray diffraction.
  • uncalcined hydrotalcite has only one peak near 8 to 18°, or the relative intensity ratio of the diffraction intensity of the peak or shoulder appearing on the low-angle side to the peak or shoulder appearing on the high-angle side is outside the aforementioned range.
  • Calcined hydrotalcite does not have a characteristic peak in the 8° to 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: anticathode CuK ⁇ (1.5405 ⁇ ), voltage: 45 V, current: 40 mA, sampling width: 0.0260°, scanning speed: 0.0657°/s, measurement diffraction angle range (2 ⁇ ): 5.0131 to 79.9711°. Peak searches were performed using the peak search function of the software provided with the diffractometer under the following conditions: "minimum significance: 0.50, minimum peak tip: 0.01°, maximum peak tip: 1.00°, peak base width: 2.00°, method: minimum value of second derivative.”
  • the BET specific surface area of the semi-calcined hydrotalcite is preferably 1 to 250 m 2 /g, and more preferably 5 to 200 m 2 /g. These BET specific surface areas can be calculated according to the BET method by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM Model 1210, manufactured by Mountech Co., Ltd.) and using the BET multipoint method.
  • a specific surface area measuring device Macsorb HM Model 1210, manufactured by Mountech Co., Ltd.
  • 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 sizes of the particle size distribution when the particle size distribution is created on a volume basis using laser diffraction scattering particle size distribution measurement (JIS Z8825).
  • Uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be used after surface treatment with a surface treatment agent.
  • the surface treatment agent that can be used for the surface treatment include higher fatty acids, alkyl silanes, and silane coupling agents, with higher fatty acids and alkyl silanes being particularly preferred.
  • One or more types of surface treatment agents can be used.
  • uncalcined hydrotalcite can be used.
  • examples of commercially available products include “DHT-4A” (particle size (median size): 370 nm), “Almakaiser” (particle size (median size): 620 nm), and “Magcera 1” (particle size (median size): 470 nm) manufactured by Kyowa Chemical Industry Co., Ltd., and "STABIACE HT-1,” “STABIACE HT-7,” and “STABIACE HT-P” manufactured by Sakai Chemical Industry Co., Ltd.
  • calcined hydrotalcite can be used.
  • examples of commercially available products include "KW-2200" (particle diameter (median diameter): 400 nm) and “KW-2200” (particle diameter (median diameter): 400 nm) manufactured by Kyowa Chemical Industry Co., Ltd.
  • calcium oxide products can be used. Examples of such products include “QC-X” manufactured by Inoue Seki Kogyo Co., Ltd.; “Moistop #10” manufactured by Sankyo Flour Milling Co., Ltd.; “HAL-G”, “HAL-J”, and “HAL-F” manufactured by Yoshizawa Seki Kogyo Co., Ltd.; and "CaO Nano Powder” manufactured by Filgen.
  • the particle size of calcium oxide and the particle size of the mixture containing calcium oxide are preferably 0.03 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, and even more preferably 0.1 to 3 ⁇ m. These particle sizes are the median sizes of the particle size distribution when the particle size distribution is created on a volume basis using laser diffraction scattering particle size distribution measurement (JIS Z 8825).
  • 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 is 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.
  • the composition may contain components other than components (A) to (C) (hereinafter sometimes referred to as "other components") to the extent that the effects of the present invention are not impaired.
  • 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 a central metal. These may be used alone or in combination of two or more types.
  • the tackifier is a component that imparts tackiness to the protective (sealing) film and improves adhesion.
  • the tackifier used in the present invention there are no particular limitations on the tackifier used in the present invention, and any known tackifier can be used.
  • 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 according to JIS K2207.
  • tackifiers can be used. Examples of commercially available tackifiers include Arakawa Chemical Industries' “Arcon P-90”, “Arcon P-100”, “Arcon P-115”, “Arcon P-125”, “Arcon P-140”, “Arcon M-90”, “Arcon M-100”, “Arcon M-115”, and “Arcon M-135" (all of which are hydrogenated petroleum resins containing cyclohexane rings).
  • the content of the tackifier is preferably 0 to 30 mass %, more preferably 0 to 25 mass %, and even more preferably 0 to 22.5 mass %, relative to 100 mass % of the non-volatile content of the composition, from the viewpoint of the adhesion and sealing properties of the protective (sealing) film.
  • Cure accelerators include, for example, imidazole compounds, tertiary and quaternary amine compounds, dimethylurea compounds, and organic phosphine compounds.
  • imidazole compounds include 1H-imidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 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.
  • imidazole compounds include Curesol 2MZ, 2P4MZ, 2E4MZ, 2E4MZ-CN, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2PHZ, 1B2MZ, 1B2PZ, 2PZ, C17Z, 1.2DMZ, 2P4MHZ-PW, 2MZ-A, and 2MA-OK (all manufactured by Shikoku Chemical Industry Co., Ltd.).
  • tertiary and quaternary amine compounds 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 salt, DBU-p-toluenesulfonate, DBU-formate salt, 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.
  • diazabicyclo compounds such as DBU (1,8-diaza
  • dimethylurea compounds examples include aromatic dimethylureas such as DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) and U-CAT3512T (manufactured by San-Apro Co., Ltd.); and aliphatic dimethylureas such as U-CAT3503N (manufactured by San-Apro Co., Ltd.).
  • aromatic dimethylureas are preferably used from the viewpoint of curability.
  • organic phosphine compounds include triphenylphosphine, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, triphenylphosphine triphenylborane, etc.
  • Specific examples of organic phosphine compounds include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, TPP-S (all manufactured by Hokko Chemical Industry Co., Ltd.), etc.
  • component (A) i.e., a crosslinked polymer having an isobutene-isoprene copolymer chain
  • component (A) i.e., a crosslinked polymer having an isobutene-isoprene copolymer chain
  • the antioxidant there is no particular limitation on the antioxidant, and any known antioxidant can be used.
  • its content is preferably 0.01 to 0.5 mass%, more preferably 0.05 to 0.4 mass%, and even more preferably 0.1 to 0.3 mass%, based on 100 mass% of the nonvolatile content of the composition.
  • Plasticizers include, for example, mineral oils such as paraffin-based process oil, naphthenic process oil, liquid paraffin, and Vaseline, and vegetable oils such as castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, and olive oil.
  • the metal complex is preferably a metal complex represented by the following formula (1) (hereinafter referred to as "metal complex (1)").
  • M is a central metal of the metal complex and represents a metal of the second to sixth periods of the periodic table
  • R1 and R3 each 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
  • M is preferably a metal from the third to fifth periods, more preferably Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, Zr, In, or Sn, and even more preferably Al, Ti, or Zr.
  • halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
  • the alkyl group may be either linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a 1-ethylpropyl group, a hexyl group, an isohexyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a 3,3-dimethylbutyl group, and a 2-ethylbutyl group.
  • the alkyl group may have a substituent. Examples of the substituent include a hal
  • the alkenyl group may be either linear or branched.
  • the number of carbon atoms in the alkenyl group is preferably 2 to 20.
  • the alkenyl group include an ethenyl group (i.e., a vinyl group), a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 3-methyl-2-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 4-methyl-3-pentenyl group, a 1-hexenyl group, a 3-hexenyl group, a 5-hexenyl group, and an octadecenyl group (e.g., a 9-octadecenyl group).
  • substituent that
  • the alkynyl group may be either linear or branched.
  • the number of carbon atoms in the alkynyl group is preferably 2 to 10, and 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 the substituent that the alkynyl group may have include a halogen atom, a hydroxy group, and an amino group that may have a substituent.
  • the number of carbon atoms in the aryl group is preferably 6 to 18, and more preferably 6 to 14.
  • the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group.
  • the aryl group may have a substituent.
  • the substituent include a halogen atom, a hydroxy group, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and an amino group which may have a substituent.
  • the number of carbon atoms in the aralkyl group is preferably 7 to 16.
  • the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a phenylpropyl group.
  • the aralkyl group may have a substituent.
  • the substituent include a halogen atom, a hydroxyl group, and an amino group which may have a substituent.
  • amino groups which may have a substituent 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), etc.
  • mono- or di-alkylamino groups e.g., methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group,
  • alkyl group in an alkoxy group i.e., an alkyloxy group
  • the alkoxy group may have a substituent.
  • substituents include a halogen atom, a hydroxyl group, and an amino group which may have a substituent.
  • alkenyl group in the alkenyloxy group is described in the same manner as the alkenyl group described above.
  • the alkenyloxy group may have a substituent.
  • substituents include a halogen atom, a hydroxyl group, and an amino group which may have a substituent.
  • the aryloxy group may have a substituent.
  • substituents include a halogen atom, a hydroxy group, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and an amino group which may have a substituent.
  • the aralkyloxy group may have a substituent.
  • substituents include a halogen atom, a hydroxyl group, and an amino group which may have a substituent.
  • alkyl group in the alkoxycarbonyl group (i.e., the alkyloxycarbonyl group) is the same as that of the alkyl group described above.
  • the alkoxycarbonyl group may have a substituent.
  • substituents include a halogen atom, a hydroxyl group, and an amino group which may have a substituent.
  • the alkenyloxycarbonyl group may have a substituent.
  • substituents include a halogen atom, a hydroxyl group, and an amino group which may have a substituent.
  • the oxygen-monodentate ligand represented by X in formula (1) is usually a conjugate base of a Bronsted acid, and examples thereof include RO ⁇ (R: organic group) and RCOO ⁇ (R: organic group).
  • the organic group R may be either an aliphatic group or an aromatic group.
  • 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.
  • Examples of RO- include methoxide anion, ethoxide anion, propoxide anion, isopropoxide anion, butoxide anion, isobutoxide anion, sec-butoxide anion, tert-butoxide anion, pentyloxide anion, and hexyloxide anion.
  • the organic group R may be either an aliphatic group or an aromatic group.
  • 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.
  • Examples of RCOO- include anions corresponding to carboxylic acids such as acetic acid, propionic acid, and benzoic acid.
  • the brackets in [ ] in formula (1) represent oxygen-bidentate ligands.
  • 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, eth
  • Examples of metal complexes (1) in which the central metal M is Al include (octadecenylacetoacetate)aluminum diisopropylate, (ethylacetoacetate)aluminum diisopropylate, (ethylacetoacetate)aluminum di-n-butylate, (propylacetoacetate)aluminum diisopropylate, and (n-butylacetoacetate)aluminum diisopropylate.
  • Examples of metal complexes (1) in which the central metal M is Ti include titanium allylacetoacetate triisopropoxide, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), titanium methylphenoxide, and titanium oxide bis(pentanedionate).
  • Examples of metal complexes (1) in which the central metal M is Zr include zirconium allylacetoacetate triisopropoxide, zirconium di-n-butoxide (bis-2,4-pentanedionate), zirconium diisopropoxide (bis-2,4-pentanedionate), zirconium diisopropoxide bis(tetramethylheptanedionate), zirconium diisopropoxide bis(ethylacetoacetate), zirconium butoxide (acetylacetate) (bisethylacetoacetate), zirconium tributoxymonoacetylacetonate, etc.
  • the content is preferably 0.05 to 5.0 mass%, more preferably 0.1 to 4.0 mass%, and even more preferably 0.15 to 3.0 mass%, based on 100 mass% of the nonvolatile content of the composition.
  • the conductive layer of the conductive substrate protected (sealed) by the composition of the present invention is composed of a conductive material containing one or more selected from metal nanowires, metal meshes, metal nanoparticles, and conductive polymers.
  • the metal constituting the metal nanowires, metal meshes, and/or metal nanoparticles is not particularly limited, and is, 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.
  • the conductive layer of the conductive substrate is composed of a conductive material containing silver nanowires.
  • the method for producing the composition of the present invention is not particularly limited, and examples thereof include a method in which the above-mentioned blended components are mixed, if necessary, with a solvent, etc., using a kneading roller or a rotary mixer.
  • the method for forming a protective (sealing) film on the conductive layer of the conductive substrate (protecting (sealing) the conductive layer) is not particularly limited, and may be, 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 in which a sealing sheet having a composition layer on a support is prepared, the composition layer of the sealing sheet is attached to a conductive layer, and the support is peeled off to form a protective (sealing) film; etc.
  • Method (1) can be carried out, for example, by mixing an organic solvent to form a varnish-like composition, applying the composition to a conductive layer using a die coater or the like, and then drying the resulting coating by heating or blowing hot air onto the conductive layer to form a protective (sealing) film on the conductive layer.
  • organic solvents examples include ketones such as acetone, methyl ethyl ketone (hereinafter also abbreviated as "MEK”), and cyclohexanone; acetate 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 of the organic solvents may be used alone, or two or more may be used in combination.
  • ketones such as acetone, methyl ethyl ketone (hereinafter also abbreviated as "MEK")
  • cyclohexanone examples include ketones such as acetone, methyl ethyl ketone (hereinafter also abbreviated as "ME
  • drying conditions typically a temperature of 50 to 100°C for 3 to 15 minutes is optimal.
  • the thickness of the protective (sealing) film after drying is usually in the range of 3 ⁇ m to 200 ⁇ m, preferably 5 ⁇ m to 100 ⁇ m, and more preferably 5 ⁇ m to 50 ⁇ m.
  • Method (2) can be carried out, for example, by applying a varnish-like composition prepared by mixing an organic solvent onto a support using a die coater or the like, drying the resulting coating by heating or blowing hot air onto the support, and producing a sealing sheet in which a composition layer is formed on the support.
  • a roll laminator, vacuum laminator, or the like the composition layer of the sealing sheet is laminated onto a conductive layer by a batch method, a continuous method with a roll, or the like, and the support is peeled off to form a protective (sealing) film on the conductive layer.
  • the support may be a plastic film such as a polyolefin such as polyethylene, polypropylene, or polyvinyl chloride, a cycloolefin polymer, a polyester such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") or polyethylene naphthalate, a polycarbonate, or a polyimide. PET is particularly preferable as a plastic film.
  • the support may also be a metal foil such as aluminum foil, stainless steel foil, or copper foil.
  • the surface of the support on which the composition layer is formed may be subjected to a release treatment using a silicone resin-based release agent, an alkyd resin-based release agent, a fluorine resin-based release agent, or the like, a matte treatment, a corona treatment, or the like.
  • a release treatment using a silicone resin-based release agent, an alkyd resin-based release agent, a fluorine resin-based release agent, or the like, a matte treatment, a corona treatment, or the like.
  • the release layer is also considered to be part of the support.
  • the thickness of the support is not particularly limited, but from the viewpoint of handleability, etc., it is preferably 20 to 200 ⁇ m, and more preferably 20 to 125 ⁇ m.
  • the organic solvent, drying conditions, and thickness of the protective (sealing) film after drying are the same as those in method (1) above.
  • composition of the present invention can be used for protecting (sealing) a conductive layer of a conductive substrate using metal nanowires, metal meshes, metal nanoparticles, conductive polymers, particularly metal nanowires and metal nanoparticles as conductors.
  • PET film Lumirror R80 manufactured by Toray Industries, Inc., 38 ⁇ m, water vapor transmission rate 20 g/m 2 /day (40° C.-90% RH, MOCON method)
  • Barrier film Reiko Co., Ltd. Beleal 38UD001, 38 ⁇ m, water vapor transmission rate 5 ⁇ 10 ⁇ 4 g/m 2 /day (40° C.-90% RH, MOCON method)
  • Example 1 A varnish having the blending ratio shown in Table 1 was prepared by the following procedure, and an encapsulating sheet was prepared using the obtained varnish.
  • the amount (parts) of each component used in the following table indicates the amount of non-volatile content of each component in the varnish.
  • a swasol solution (non-volatile content: 60%) of cyclohexane ring-containing hydrogenated petroleum resin (tackifier, Arakawa Chemical Industries Co., Ltd.'s "Arcon P-125”) was mixed with maleic anhydride modified liquid polybutene (Toho Chemical Industries Co., Ltd.'s "HV-300M”), polybutene (ENEOS Corporation's "HV-1900"), a toluene solution (non-volatile content: 25%) of glycidyl methacrylate modified butyl rubber (Seiko PMC Corporation's "ER866”), a toluene solution (non-volatile content: 35%) of maleic acid modified butyl rubber (Seiko PMC Corporation's "ER661”), a curing accelerator (TAP, Kayaku Nouryon Co., Ltd.) and toluene, and the resulting mixture was uniformly dispersed in a high-speed rotating mixer to obtain
  • the obtained varnish was uniformly applied with a die coater onto the release-treated surface of a polyethylene terephthalate (PET) film ("SP4020" manufactured by Toyo Cross Co., Ltd., PET film thickness: 50 ⁇ m) that had been treated with a silicone-based release agent, and heated at 130°C for 30 minutes to obtain a sealing sheet having a composition layer with a thickness of 20 ⁇ m.
  • PET polyethylene terephthalate
  • the mixture was mixed with glycidyl methacrylate-modified butyl rubber (Seiko PMC Co., Ltd. "ER866”), maleic acid-modified butyl rubber (Seiko PMC Co., Ltd. "ER661”), a curing accelerator (TAP, Kayaku Nouryon Co., Ltd.), and toluene, and the mixture was uniformly dispersed with a high-speed rotating mixer to obtain a varnish of the composition.
  • the obtained varnish was uniformly applied by a die coater onto a release-treated surface of a polyethylene terephthalate (PET) film ("SP4020" manufactured by Toyo Cross Co., Ltd., thickness of PET film: 50 ⁇ m) that had been treated with a silicone-based release agent, and heated at 130° C. for 30 minutes to obtain a sealing sheet having a composition layer with a thickness of 20 ⁇ m.
  • PET polyethylene terephthalate
  • the resulting varnish was uniformly applied with a die coater onto the release-treated surface of a PET film ("SS1A" manufactured by Nippa Corporation) that had been treated with a fluorine-based release agent, and heated at 150°C for 1 minute to obtain a sealing sheet having a composition layer with a thickness of 20 ⁇ m.
  • the obtained varnish was uniformly applied with a die coater onto the release-treated surface of a PET film ("NS80A” manufactured by Fujimori Kogyo Co., Ltd., PET film thickness: 38 ⁇ m) treated with an alkyd-based release agent, and heated at 130 ° C. for 30 minutes to obtain a sealing sheet having a composition layer with a thickness of 20 ⁇ m.
  • Haze (%) and total light transmittance (%) were measured in accordance with JIS 7136.
  • the sealing sheets of Production Examples 1 to 6 prepared by the above-mentioned method 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 ("OA-10G” manufactured by Nippon Electric Glass Co., Ltd., thickness: 700 ⁇ m) using a vacuum laminator ("V-160” manufactured by Nikko Materials Co., Ltd., temperature 80 ° C., 0.3 MPa, 30 seconds) to prepare a measurement sample.
  • OA-10G manufactured by Nippon Electric Glass Co., Ltd., thickness: 700 ⁇ m
  • V-160 vacuum laminator manufactured by Nikko Materials Co., Ltd., temperature 80 ° C., 0.3 MPa, 30 seconds
  • the sealing sheet of Production Example 6 was peeled off the PET film and heated at 100 ° C. for 60 minutes to perform a curing treatment.
  • the haze (%) and total light transmittance (%) of the prepared measurement sample were measured using a haze meter HZ-V3 (halogen lamp) manufactured by Suga Test Instruments Co., Ltd., with air as a reference, using D65 light. The results are shown in Table 1.
  • the sealing sheets prepared in Production Examples 1 to 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.), a composite film (“PET AL1N30" manufactured by Tokai Toyo Aluminum Sales Co., Ltd., thickness of aluminum foil: 30 ⁇ m, thickness of PET film: 25 ⁇ m) having an aluminum foil and a polyethylene terephthalate (PET) film was laminated onto the composition layer of the sealing sheet. The lamination was performed under conditions of a temperature of 80° C., a time of 30 seconds, and a pressure of 0.3 MPa.
  • PET AL1N30 manufactured by Tokai Toyo Aluminum Sales Co., Ltd.
  • the PET film was peeled off from the sealing sheet, and a polyimide film ("Upilex-S" manufactured by Ube Industries, Ltd., thickness: 50 ⁇ m) was laminated onto the exposed composition layer under the same conditions as above to obtain a laminate having a laminate structure of "composite film / composition layer / polyimide film".
  • the sealing sheet of Production Example 6 was peeled off the PET film, and the polyimide film was laminated under the same conditions as above, and then heated at 100 ° C for 60 minutes to perform a curing treatment.
  • the adhesive strength room temperature adhesive strength
  • the adhesive strength high temperature adhesive strength
  • 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 manufactured in Manufacturing Examples 1 to 6 were processed to A5 size, and the composition layer was laminated to the substrate described in Table 2 using a vacuum laminator (Nikko Materials Co., Ltd. "V-160", 80 ° C., 0.3 MPa, 30 seconds). Thereafter, the PET film was peeled off from 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 an evaluation sample.
  • the composition layer was laminated to the silver nanowire layer, and then heated at 100 ° C. for 60 minutes to perform a curing treatment.
  • the initial surface resistivity ( ⁇ /Sq.) of the encapsulated silver nanowire laminated conductive film was measured using an eddy current sheet resistance meter (EddyCusTF Protable 1010 manufactured by SURAGUS Corp.)
  • the encapsulated silver nanowire laminated conductive film was then stored in a constant temperature and humidity tester (85° C., 85% RH), and the surface resistivity ( ⁇ /Sq.) was measured again after 100 hours using the eddy current sheet resistance meter.
  • Change rate (%) [(surface resistivity after storage at 85°C and 85% RH for 100 hours) / (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 but less than 20%. ⁇ The rate of change in surface resistivity is 20% or
  • the PET film was peeled off from the sealing sheet produced in Production Examples 1 to 6, and a polyimide film (manufactured by Unitika Ltd., 25 ⁇ m) was attached to both sides of the composition layer by vacuum lamination (80° C., 0.3 MPa, 30 seconds) to produce an evaluation sample having a structure of “polyimide (PI) film/composition layer/polyimide (PI) film”.
  • the obtained evaluation sample was placed in a clamshell type bending tester "CL40R type-E02" (manufactured by Yuasa System Co., Ltd.) and bent 100,000 times under conditions of a temperature of 60°C, humidity of 90% RH, a radius of curvature (R) of 2.0 mm, and a speed of 60 rpm. After bending, the evaluation sample was observed using a Keyence Corporation digital microscope "VHX-5000" (magnification: 20 times), and the bending resistance was evaluated according to the following criteria. The results are shown in Table 2. (Evaluation Criteria for Bending Resistance) ⁇ (Acceptable): No peeling ⁇ (Not acceptable): Peeling and air bubbles
  • Tables 1 and 2 show that Examples 1 to 4 have good values for haze, total light transmittance, and adhesion strength, and also have good evaluations for surface resistivity and flex resistance.
  • the composition of the present invention can form a protective (sealing) film that can suppress changes in the surface resistivity of the conductive substrate and migration of conductors while simultaneously achieving transparency, adhesion strength, and flex resistance when protecting (sealing) the conductive layer that constitutes the conductive substrate, and therefore can be used to protect (seal) the conductive layer of a conductive substrate that uses metal nanowires, metal meshes, metal nanoparticles, conductive polymers, and especially metal nanowires and metal nanoparticles as conductors.

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Abstract

Le but de la présente invention est de fournir une composition pouvant former un film protecteur (d'étanchéité) qui, afin de protéger (étanchéifier) une couche électroconductrice qui constitue un substrat électroconducteur, peut supprimer un changement de la résistivité de surface du substrat électroconducteur et la migration d'un conducteur électrique tout en conservant simultanément sa transparence, sa force d'adhésion et sa résistance à la flexion. L'invention concerne une composition pour un film protecteur destiné à une couche électroconductrice d'un substrat électroconducteur, la composition comprenant (A) un polymère réticulé comportant une chaîne de copolymère d'isobutène-isoprène. La couche électroconductrice est constituée d'un matériau électroconducteur contenant au moins un élément choisi parmi des nanofils métalliques, des treillis métalliques, des nanoparticules métalliques et des polymères électroconducteurs.
PCT/JP2024/012699 2023-03-28 2024-03-28 Composition pour film protecteur destiné à une couche électroconductrice WO2024204562A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013035699A (ja) * 2011-08-04 2013-02-21 Sony Corp グラフェン構造体、グラフェン構造体の製造方法、光電変換素子、太陽電池及び撮像装置
JP2015502868A (ja) * 2012-01-06 2015-01-29 エルジー・ケム・リミテッド 封止用フィルム
JP2017513205A (ja) * 2014-03-27 2017-05-25 エルジー・ケム・リミテッド 封止フィルム及びこれを含む有機電子装置
JP2023007246A (ja) * 2021-07-01 2023-01-18 味の素株式会社 封止用シート

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013035699A (ja) * 2011-08-04 2013-02-21 Sony Corp グラフェン構造体、グラフェン構造体の製造方法、光電変換素子、太陽電池及び撮像装置
JP2015502868A (ja) * 2012-01-06 2015-01-29 エルジー・ケム・リミテッド 封止用フィルム
JP2017513205A (ja) * 2014-03-27 2017-05-25 エルジー・ケム・リミテッド 封止フィルム及びこれを含む有機電子装置
JP2023007246A (ja) * 2021-07-01 2023-01-18 味の素株式会社 封止用シート

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