WO2022172551A1 - 積層体、層形成用組成物、層、積層体の製造方法及び電子素子 - Google Patents

積層体、層形成用組成物、層、積層体の製造方法及び電子素子 Download PDF

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WO2022172551A1
WO2022172551A1 PCT/JP2021/042784 JP2021042784W WO2022172551A1 WO 2022172551 A1 WO2022172551 A1 WO 2022172551A1 JP 2021042784 W JP2021042784 W JP 2021042784W WO 2022172551 A1 WO2022172551 A1 WO 2022172551A1
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layer
group
compound
formula
laminate
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PCT/JP2021/042784
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English (en)
French (fr)
Japanese (ja)
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直矢 野坂
和憲 高梨
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Jsr株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a laminate, a layer-forming composition, a layer, a method for producing a laminate, and an electronic device.
  • a laminate in which a conductive thin film is arranged on an insulating substrate is widely used for electronic elements, especially electronic elements provided in large-area electronic devices.
  • Patent Document 1 describes a method of obtaining a conductive transparent electrode by coating a dispersion liquid containing graphene on a glass substrate, drying and baking it.
  • Patent Document 2 a dispersion of carbon nanotubes is coated on a plastic substrate and dried to form a conductive transparent film, and furthermore, by patterning this conductive transparent film, a dye-sensitized type A method of obtaining a counter electrode for a solar cell is described.
  • the adhesion of the conductive material to the lower layer is poor. Therefore, it is not easy to perform processes such as patterning and cleaning of the layer containing the conductive material in the manufacturing process. Moreover, since the fixation rate of the conductive material is low, there is also a problem that most of the conductive material cannot be effectively used.
  • the present invention has been made based on the circumstances as described above. It is an object to provide a method as well as an electronic device comprising such a laminate.
  • One aspect of the invention that has been made to solve the above problems is a laminate having, in this order, a substrate, a first layer containing a compound having a condensed polycyclic hydrocarbon structure, and a second layer containing a conductive material is the body.
  • compositions for forming a layer disposed between a substrate and a layer containing a conductive material the composition containing a compound having a condensed polycyclic hydrocarbon structure. It is a composition for
  • Another aspect of the present invention is a layer formed from the layer-forming composition.
  • Another aspect of the present invention includes a step of applying the layer-forming composition to one side of a substrate, a step of heating the coating film obtained by the application, and a first and forming a second layer containing a conductive material on the surface of the layer of (1).
  • Another aspect of the present invention is an electronic device including the laminate.
  • a laminate having good adhesion of a layer containing a conductive material, a layer-forming composition capable of forming such a laminate, a layer, a manufacturing method, and an electronic device comprising such a laminate can be provided.
  • FIG. 1 is a schematic cross-sectional view showing a laminate according to one embodiment of the invention.
  • a laminate 10 of FIG. 1 has a substrate 11, a first layer 12 and a second layer 13 in that order.
  • the substrate 11 is generally a substrate whose surface (upper surface in FIG. 1) in contact with the first layer 12 is partly or wholly insulative.
  • the entire substrate 11 may be made of an insulating material.
  • the material of the substrate 11 is not particularly limited, but examples thereof include glass, quartz, quartz, silicon, and resin.
  • resins include polyimide, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, addition polymers of cyclic olefins, ring-opening polymers of cyclic olefins, and hydrogenated products thereof.
  • the substrate 11 may be subjected to pretreatment such as chemical treatment using a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vacuum deposition, or the like.
  • the first layer 12 contains a compound having a condensed polycyclic hydrocarbon structure (hereinafter also referred to as "[A] compound").
  • First layer 12 may be a patterned layer.
  • the first layer 12 is preferably formed from a layer-forming composition containing the [A] compound. The layer-forming composition will be described in detail below.
  • the layer-forming composition contains the [A] compound.
  • the layer-forming composition may further contain [B] a solvent, [C] an acid generator, [D] a crosslinkable compound, other optional components, and the like. Each component will be described below.
  • the [A] compound is a compound having a condensed polycyclic hydrocarbon structure.
  • the layer-forming composition can form a layer having good adhesion to a layer containing a conductive material. That is, in the laminate 10, the first layer 12 containing the [A] compound is provided between the substrate 11 and the second layer 13 containing the conductive material, so that the second layer 12 containing the conductive material The adhesion of the layer 13 is good.
  • the condensed polycyclic hydrocarbon structure is not particularly limited as long as it is a structure in which a plurality of hydrocarbon ring structures are condensed, and may be an alicyclic structure or an aromatic ring structure, but a structure containing an aromatic ring is preferably
  • the [A] compound is preferably a compound having a partial structure represented by the following formula (1).
  • the condensed polycyclic hydrocarbon structure of the [A] compound is preferably a structure represented by the following formula (1).
  • X is a divalent group represented by formula (i), (ii), (iii) or (iv) below.
  • Y and Y' are each independently a monovalent organic group having 1 to 20 carbon atoms. * and ** indicate a site that binds to a portion other than the partial structure represented by the above formula (1) in the above compound.
  • n1 and n2 are each independently an integer of 0-2.
  • n3 and n4 are each independently an integer of 0-8.
  • n5 and n6 are each independently an integer of 0-8.
  • n4 is 2 or more, multiple Y's are the same or different.
  • n3+n5 is 8 or less
  • n4+n6 is 8 or less
  • n5+n6 is 1 or more.
  • R 1 and R 2 are each independently a hydrogen atom, a hydroxy group, a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon It is an aralkyl group of 7 to 20 numbers, or represents part of a ring structure of 3 to 20 ring members composed of R 1 and R 2 taken together and together with the carbon atom to which they are attached.
  • R 3 and R 4 are each independently a hydrogen atom, a hydroxy group, or a monovalent organic group having 1 to 20 carbon atoms, or R 3 and R 4 are combined with each other It represents part of a 3- to 20-membered ring structure formed with the carbon atoms to which they are attached.
  • R 5 is a hydrogen atom, a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms.
  • R 6 is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms.
  • the monovalent organic group having 1 to 20 carbon atoms represented by Y and Y′ includes, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a divalent and a group obtained by substituting some or all of the hydrogen atoms of the above hydrocarbon groups and groups ( ⁇ ) with monovalent heteroatom-containing groups.
  • the monovalent hydrocarbon group having 1 to 20 carbon atoms includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
  • Aliphatic hydrocarbon groups include aliphatic chain hydrocarbon groups and alicyclic hydrocarbon groups. Examples of aliphatic chain hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group, alkenyl groups such as ethenyl group, propenyl group and butenyl group, ethynyl group, propynyl group and butynyl group.
  • the alicyclic hydrocarbon group includes cycloalkyl groups such as cyclopentyl group and cyclohexyl group; cycloalkenyl groups such as cyclopropenyl group, cyclopentenyl group and cyclohexenyl group; and bridged ring hydrocarbon groups such as norbornyl group and adamantyl group. etc.
  • aromatic hydrocarbon groups include aryl groups such as phenyl, tolyl, xylyl and naphthyl groups, and aralkyl groups such as benzyl, phenethyl and naphthylmethyl groups.
  • divalent heteroatom-containing groups examples include -CO-, -CS-, -NH-, -O-, -S-, and groups in which these are combined.
  • Examples of the group ( ⁇ ) containing a divalent heteroatom-containing group between the carbon-carbon atoms of the hydrocarbon group or at the end include a heteroatom-containing chain group, an aliphatic heterocyclic group, an aromatic heterocyclic group, and the like.
  • Examples of heteroatom-containing chain groups include oxoalkyl groups, thioalkyl groups, alkylaminoalkyl groups, alkoxyalkyl groups, and alkylthioalkyl groups.
  • Examples of aliphatic heterocyclic groups include oxocycloalkyl groups, thiocycloalkyl groups, azacycloalkyl groups, oxacycloalkyl groups, thiacycloalkyl groups, oxocycloalkenyl groups, and oxathiacycloalkyl groups.
  • Examples of aromatic heterocyclic groups include pyrrolyl, pyridyl, quinolyl, isoquinolyl, furyl, pyranyl, thienyl, and benzothiophenyl groups.
  • Examples of monovalent heteroatom-containing groups include a hydroxy group, a sulfanyl group, a cyano group, a nitro group, and a halogen atom.
  • Y and Y′ are each independently preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group, more preferably an aliphatic chain hydrocarbon group, even more preferably an alkyl group, and particularly preferably a methyl group. .
  • n1 and n2 are preferable as n1 and n2, and 0 is more preferable.
  • n3 and n4 are preferably 0 to 3, more preferably 0 to 2, still more preferably 0 and 1, and particularly preferably 0.
  • n5 and n6 are preferably 0 to 6, more preferably 0 to 4, and particularly preferably n5 is 1 and n6 is 0.
  • the unsubstituted monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R 1 , R 2 and R 6 include aliphatic chain hydrocarbon groups and alicyclic hydrocarbon groups.
  • aliphatic chain hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group, alkenyl groups such as ethenyl group, propenyl group and butenyl group, ethynyl group, propynyl group and butynyl group.
  • the alicyclic hydrocarbon group includes cycloalkyl groups such as cyclopentyl group and cyclohexyl group; cycloalkenyl groups such as cyclopropenyl group, cyclopentenyl group and cyclohexenyl group; and bridged ring hydrocarbon groups such as norbornyl group and adamantyl group. etc.
  • Substituents for the aliphatic hydrocarbon groups in R 1 , R 2 and R 6 include, for example, alkoxy groups such as methoxy and ethoxy groups, and cyano groups.
  • Examples of unsubstituted aralkyl groups having 7 to 20 carbon atoms represented by R 1 , R 2 and R 6 include benzyl group, o-methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group, naphthylmethyl group, ⁇ -phenethyl group, and the like.
  • Examples of substituents of the aralkyl groups in R 1 , R 2 and R 6 include halogen atoms such as fluorine atoms and chlorine atoms, and nitro groups.
  • Examples of monovalent organic groups having 1 to 20 carbon atoms represented by R 3 , R 4 and R 5 include groups similar to the organic groups exemplified as Y and Y′ in formula (1).
  • Examples of the 3- to 20-membered ring structure in which R 1 and R 2 or R 3 and R 4 are combined and formed together with the carbon atoms to which they are bonded include, for example, a cyclohexane structure, an alicyclic structure such as a cyclohexene structure, and azacyclohexane. structure, and an aliphatic heterocyclic structure such as an azacyclohexene structure.
  • R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms Alternatively, R 1 and R 2 are preferably part of a 3- to 20-membered ring structure formed together with the carbon atom to which they are attached.
  • R 1 is preferably a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms.
  • a hydrogen group and an unsubstituted aralkyl group are more preferred, an unsubstituted chain hydrocarbon group is even more preferred, and an alkynyl group and an alkenyl group are particularly preferred.
  • the number of carbon atoms in R 1 is preferably 1-8, more preferably 2-6, and even more preferably 3-5.
  • R 2 is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and an unsubstituted aralkyl group having 7 to 20 carbon atoms, more preferably an unsubstituted chain hydrocarbon group, alkynyl group and alkenyl groups are more preferred.
  • the number of carbon atoms in R 2 is preferably 1-8, more preferably 2-6, and even more preferably 3-5.
  • R 3 is preferably a monovalent organic group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and a substituted or unsubstituted 6 to 20 carbon atoms.
  • Naphthyl group, pyrenyl group, phenanthrenyl group, acetal group-substituted phenyl group, hydroxy group-substituted phenyl group, dialkylamino group-substituted phenyl group, alkynyl group-substituted phenyl group, and N-alkyl group-substituted carbazolyl group are more preferable. Especially preferred.
  • R 4 is preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom.
  • R 5 is preferably a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms, more preferably an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and still more preferably an alkyl group or an aryl group.
  • R 6 is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and an unsubstituted aralkyl group having 7 to 20 carbon atoms, more preferably an unsubstituted chain hydrocarbon group, and further an alkyl group. preferable.
  • the number of carbon atoms in R 6 is preferably 1-8, more preferably 1-4.
  • X is preferably a group represented by the above formula (i), (ii) or (iv).
  • Compounds include compounds represented by the following formula (2). By using the compound represented by Formula (2), the adhesion of the layer containing the conductive material can be improved.
  • Z is the partial structure represented by formula (1) when n5 is 1 and n6 is 0.
  • R A is an m-valent organic group having 1 to 30 carbon atoms.
  • m is an integer from 1 to 20; When m is 2 or more, multiple Zs are the same or different.
  • the m-valent organic group having 1 to 30 carbon atoms represented by RA is, for example, (m-1) hydrogen atoms from those exemplified as monovalent organic groups for Y and Y' in formula (1). and groups other than
  • R A in formula (2) is a substituted or unsubstituted 6-20 ring-membered arene or a substituted or unsubstituted 5-20 ring-membered heteroarene with m hydrogen atoms. Groups excluding are preferred.
  • Examples of unsubstituted arenes having 6 to 20 ring members that give RA include benzene, naphthalene, anthracene, phenanthrene, tetracene, pyrene, triphenylene and perylene. Among these, benzene and naphthalene are preferred, and benzene is more preferred.
  • Examples of unsubstituted heteroarene having 5 to 20 ring members that give RA include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole and the like.
  • triazines are preferred, and 1,3,5-triazines are more preferred.
  • Substituents of arenes and heteroarenes that give RA include, for example, alkyl groups, alkoxy groups, cyano groups, nitro groups, halogen atoms and the like.
  • R A is preferably an unsubstituted arene having 6 to 20 ring members or a group obtained by removing m hydrogen atoms from an unsubstituted heteroarene having 5 to 20 ring members.
  • the lower limit of m is preferably 2, more preferably 3.
  • the upper limit of m is preferably 12, more preferably 8, even more preferably 6, and particularly preferably 3.
  • R A is a benzene-1,3,5-triyl group obtained by removing the hydrogen atoms at the 1,3,5-positions from benzene or removing the hydrogen atoms at the 2,4,6-positions from 1,3,5-triazine
  • the symmetry of the [A] compound is higher, and as a result, the adhesion of the layer containing the conductive material is better.
  • the [A] compound for example, in the partial structure represented by formula (1), a compound represented by the following formula (3) when n1 is 0, n3 is 0, n5 is 4, and n6 is 0 mentioned.
  • the adhesion of the layer containing the conductive material can be improved.
  • X has the same definition as X in formula (1).
  • Y 1 , Y 2 and Y 3 are each independently synonymous with Y' in Formula (1).
  • p1, p2 and p3 are each independently synonymous with n2 in formula (1).
  • p4, p5 and p6 are each independently synonymous with n4 in formula (1).
  • the compound preferably has an aromatic carbocyclic ring or an aromatic heterocyclic ring in a portion other than the partial structure represented by formula (1), and an aromatic compound that binds to the partial structure represented by formula (1) Those having a monocyclic carbocyclic ring or an aromatic heterocyclic ring are more preferred.
  • the aromatic carbocyclic ring and the aromatic heterocyclic ring are preferably a benzene ring and a 1,3,5-triazine ring, and the 1,3,5-position of the benzene ring and the 2,3,5-triazine ring of the More preferably, a partial structure represented by formula (1) wherein n5 is 1 and n6 is 0 is bound to the 4,6-positions.
  • the [A] compound having such a structure can be easily synthesized from the corresponding acetyl group-containing fluorene compound, cyano group-containing fluorene compound, or the like.
  • such a compound has high symmetry and can improve adhesion of a layer containing a conductive material.
  • the compound preferably has a crosslinkable group.
  • crosslinkable groups include alkynyl groups, alkenyl groups, (meth)acryloyl groups, epoxy groups, hydroxymethyl groups, alkoxyalkyl groups, and alkoxyalkylated amino groups.
  • Examples of the [A] compound having a crosslinkable group include compounds having a partial structure represented by formula (1) where at least one of R 1 to R 6 , Y and Y′ is a crosslinkable group. mentioned.
  • [A] compounds include compounds represented by the following formula.
  • Y and Y' are synonymous with Y and Y' in formula (1).
  • p7, p8 and p9 are each independently an integer of 0-3.
  • p10, p11 and p12 are each independently an integer of 0-4.
  • p8 and p9 are 2 or more, multiple Y's are the same or different.
  • p10, p11, and p12 is 2 or more, multiple Y's are the same or different.
  • the lower limit of the molecular weight of the compound is preferably 350, more preferably 400, even more preferably 500, and particularly preferably 600.
  • the upper limit of the molecular weight is preferably 3,000, more preferably 2,000, and even more preferably 1,500.
  • the lower limit of the weight average molecular weight (Mw) of the [A] compound is preferably 500, more preferably 1,000.
  • the upper limit of Mw is preferably 50,000, more preferably 10,000, and even more preferably 8,000.
  • the lower limit of the content of the [A] compound is preferably 70% by mass, more preferably 80% by mass, and even more preferably 85% by mass, relative to the total solid content of the layer-forming composition.
  • the upper limit of the content may be, for example, 100% by mass, and 99% by mass is preferable in some cases.
  • Total solid content means the total sum of components other than the [B] solvent in the layer-forming composition.
  • the preferred content range of the [A] compound in the first layer 12 is the same as the preferred content range of the [A] compound relative to the total solid content of the layer-forming composition. The same applies to the content ranges of other components in the first layer 12 .
  • the lower limit of the content of the [A] compound in the layer-forming composition is preferably 1% by mass, more preferably 3% by mass, and even more preferably 5% by mass.
  • the upper limit of the content is preferably 50% by mass, more preferably 30% by mass, and even more preferably 15% by mass.
  • [A] compound can be used individually by 1 type or in combination of 2 or more types.
  • the solvent is not particularly limited as long as it is a component capable of dissolving or dispersing the [A] compound and optionally contained optional components.
  • Solvents include, for example, alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, and the like.
  • a solvent can be used individually by 1 type or in combination of 2 or more types.
  • alcoholic solvents examples include monoalcoholic solvents such as methanol, ethanol and n-propanol, and polyhydric alcoholic solvents such as ethylene glycol and 1,2-propylene glycol.
  • ketone solvents include chain ketone solvents such as methyl ethyl ketone and methyl-iso-butyl ketone, and cyclic ketone solvents such as cyclohexanone.
  • ether solvents include chain ether solvents such as diethyl ether, polyhydric alcohol ether solvents such as cyclic ether solvents such as tetrahydrofuran, and polyhydric alcohol partial ether solvents such as diethylene glycol monomethyl ether.
  • ester solvents include carbonate solvents such as diethyl carbonate, acetic acid monoester solvents such as methyl acetate and ethyl acetate, lactone solvents such as ⁇ -butyrolactone, diethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate.
  • carbonate solvents such as diethyl carbonate
  • acetic acid monoester solvents such as methyl acetate and ethyl acetate
  • lactone solvents such as ⁇ -butyrolactone
  • diethylene glycol monomethyl ether acetate diethylene glycol monomethyl ether acetate
  • propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate.
  • Valued alcohol partial ether carboxylate solvents such as methyl lactate and ethyl lactate, and the like are included.
  • nitrogen-containing solvents examples include linear nitrogen-containing solvents such as N,N-dimethylacetamide and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.
  • Preferred solvents are ketone solvents, ether solvents and ester solvents.
  • ether-based solvents having a glycol structure and ester-based solvents having a glycol structure are more preferable from the viewpoint of excellent film-forming properties.
  • ether solvents having a glycol structure and ester solvents having a glycol structure examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and acetic acid.
  • Propylene glycol monopropyl ether and the like can be mentioned. Among these, propylene glycol monomethyl ether acetate is particularly preferred.
  • the lower limit of the content of the ether solvent having a glycol structure and the ester solvent having a glycol structure in the solvent is preferably 20% by mass, more preferably 60% by mass, further preferably 90% by mass, and 100% by mass. % by weight is particularly preferred.
  • the [C] acid generator generates an acid by the action of heat or light, and crosslinks the [A] compound when the [A] compound has a crosslinkable group and the optional [D] crosslinkable compound. It is a stimulating ingredient.
  • the [C] acid generator in the layer-forming composition, the cross-linking reaction of the [A] compound and/or [D] cross-linkable compound having a cross-linkable group is promoted, and the hardness of the formed layer is increased. can be increased, etc.
  • the acid generator may be used alone or in combination of two or more.
  • Acid generators include, for example, onium salt compounds and N-sulfonyloxyimide compounds.
  • onium salt compounds include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, and ammonium salts.
  • Sulfonium salts include, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2 -tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate and the like.
  • Tetrahydrothiophenium salts include, for example, 1-(4-n-butoxynaphthalene-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalene-1-yl)tetrahydrothiophenium nona and fluoro-n-butanesulfonate.
  • iodonium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoro ethanesulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate and the like.
  • ammonium salts include triethylammonium trifluoromethanesulfonate, triethylammonium nonafluoro-n-butanesulfonate, and the like.
  • N-sulfonyloxyimide compounds include N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(nonafluoro-n-butanesulfonyloxy ) bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide and the like.
  • the acid generator is preferably an onium salt compound, more preferably an iodonium salt or an ammonium salt, still more preferably an iodonium salt, and particularly preferably bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate. .
  • the lower limit of the content of the acid generator [C] is preferably 0.1 parts by mass with respect to 100 parts by mass of the compound [A]. , more preferably 1 part by mass, and more preferably 3 parts by mass.
  • the upper limit of the content is preferably 20 parts by mass, more preferably 15 parts by mass, and even more preferably 10 parts by mass.
  • the [D] crosslinkable compound is a component that forms crosslinks between components such as the [A] compound in the layer-forming composition by the action of heat or acid, or that itself forms a crosslinked structure. (However, those corresponding to [A] compounds are excluded).
  • the [D] crosslinkable compound in the layer-forming composition By including the [D] crosslinkable compound in the layer-forming composition, the hardness of the layer to be formed can be increased.
  • a crosslinkable compound can be used individually by 1 type or in combination of 2 or more types.
  • crosslinkable compound for example, a polyfunctional (meth)acrylate compound, an epoxy compound, a hydroxymethyl group-substituted phenol compound, an alkoxyalkyl group-containing phenol compound, an alkoxyalkylated amino group-containing compound, the following formula (11 -P), a random copolymer of acenaphthylene and hydroxymethylacenaphthylene, and compounds represented by the following formulas (11-1) to (11-12).
  • a polyfunctional (meth)acrylate compound an epoxy compound, a hydroxymethyl group-substituted phenol compound, an alkoxyalkyl group-containing phenol compound, an alkoxyalkylated amino group-containing compound, the following formula (11 -P), a random copolymer of acenaphthylene and hydroxymethylacenaphthylene, and compounds represented by the following formulas (11-1) to (11-12).
  • Me represents a methyl group
  • Et represents an ethyl group
  • Ac represents an acetyl group
  • the compounds represented by formulas (11-1) to (11-12) can be synthesized with reference to the following documents.
  • Compound represented by formula (11-1) Guo, Qun-Sheng; Lu, Yong-Na; Liu, Bing; Xiao, Jian; Li, Jin-Shan Journal of Organometallic Chemistry, 2006, vol. 691, #6 p. 1282-1287
  • polyfunctional (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta( meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethylene glycol di(meth)acrylate, 1,3-butanediol di (Meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tri
  • Epoxy compounds include, for example, novolac epoxy resins, bisphenol epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.
  • hydroxymethyl group-substituted phenol compounds examples include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene [2,6-bis (hydroxymethyl)-p-cresol] and the like.
  • alkoxyalkyl group-containing phenol compounds examples include methoxymethyl group-containing phenol compounds and ethoxymethyl group-containing phenol compounds.
  • methoxymethyl group-containing phenol compounds examples include compounds represented by the following formula (11-Q).
  • Me represents a methyl group.
  • Examples of compounds having an alkoxyalkylated amino group include (poly)methylolated melamine, (poly)methylolated glycoluril, (poly)methylolated benzoguanamine, (poly)methylolated urea, and the like. wherein at least one hydrogen atom of the hydroxy group of the methylol group is substituted with an alkyl group such as a methyl group or a butyl group.
  • the compound having an alkoxyalkylated amino group may be a mixture of a plurality of substituted compounds, or may contain an oligomer component partially self-condensed.
  • Compounds having an alkoxyalkylated amino group include, for example, 1,3,4,6-tetrakis(methoxymethyl)glycoluril.
  • methoxymethyl group-containing phenol compounds compounds having an alkoxyalkylated amino group, and random copolymers of acenaphthylene and hydroxymethyl acenaphthylene are preferable, and methoxymethyl group-containing phenol compounds and More preferred are compounds having an alkoxyalkylated amino group, 4,4′-(1-(4-(1-(4-hydroxy-3,5-bis(methoxymethyl)phenyl)-1-methylethyl) Phenyl)ethylidene)bis(2,6-bis(methoxymethyl)phenol (compound represented by formula (11-Q) above) and 1,3,4,6-tetrakis(methoxymethyl)glycoluril are more preferred.
  • the lower limit of the content of the [D] crosslinkable compound is preferably 0.1 parts by mass with respect to 100 parts by mass of the [A] compound. , more preferably 1 part by mass, more preferably 3 parts by mass, and particularly preferably 5 parts by mass.
  • the upper limit of the content is preferably 100 parts by mass, more preferably 50 parts by mass, still more preferably 30 parts by mass, and particularly preferably 20 parts by mass.
  • Other optional ingredients include, for example, surfactants and adhesion aids.
  • the composition for forming a layer can improve coatability by containing a surfactant. can be suppressed.
  • Surfactant can be used individually by 1 type or in combination of 2 or more types.
  • surfactants include nonionic surfactants and anionic surfactants.
  • nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, and polyethylene glycol dilaurate. , polyethylene glycol distearate, and the like.
  • Anionic surfactants include potassium rosinate, sodium rosinate, potassium oleate, potassium laurate, sodium laurate, sodium stearate, potassium stearate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate and the like.
  • surfactants include KP341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, same No. 95 (Kyoeisha Chemical Co., Ltd.), F-TOP EF101, EF204, EF303, EF352 (Tochem Products), Megafac F171, F172, F173 (DIC Corporation), Florard FC430, the same FC431, FC135, FC93 (Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass).
  • the lower limit of the content of the surfactant is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, relative to 100 parts by mass of the [A] compound. is more preferable, and 0.1 parts by mass is even more preferable.
  • the upper limit of the content is preferably 10 parts by mass, more preferably 5 parts by mass, and even more preferably 1 part by mass.
  • the layer-forming composition is prepared by mixing [A] compound, [B] solvent, optionally [C] acid generator, [D] crosslinkable compound and other optional components in a predetermined ratio, preferably It can be prepared by filtering the obtained mixture through a membrane filter of about 0.1 ⁇ m or the like.
  • the lower limit of the solid content concentration of the layer-forming composition is preferably 0.1% by mass, more preferably 1% by mass, still more preferably 3% by mass, and particularly preferably 5% by mass.
  • the upper limit of the solid content concentration is preferably 50% by mass, more preferably 30% by mass, still more preferably 20% by mass, and particularly preferably 15% by mass.
  • the average thickness of the first layer 12 is preferably 1 nm or more and 500 nm or less, more preferably 5 nm or more and 100 nm or less, even more preferably 10 nm or more and 50 nm or less, and the upper limit is even more preferably 30 nm and particularly preferably 20 nm.
  • Adhesion with the second layer 13 can be enhanced by setting the average thickness of the first layer 12 to the above lower limit or more.
  • the average thickness of the first layer 12 equal to or less than the above upper limit, the transparency of the first layer 12 and the laminate 10 can be enhanced.
  • the second layer 13 is a layer laminated on the first layer 12 .
  • the second layer 13 may be a patterned layer.
  • the second layer 13 may be patterned together with the first layer 12 .
  • the first layer 12 may have a surface region where the second layer 13 is not laminated.
  • the second layer 13 contains a conductive material.
  • conductive materials include metals and carbon materials, with carbon materials being preferred.
  • a carbon material refers to a material containing carbon as a main constituent element.
  • the main constituent element means the element with the highest content on a mass basis.
  • the content of carbon elements in the carbon material is preferably 90% by mass or more, more preferably 99% by mass or more.
  • One or more conductive materials can be used.
  • the carbon material is preferably one or more selected from the group consisting of carbon nanotube (CNT), carbon nanofiber, carbon black, graphene, fullerene, and graphite, preferably contains CNT, and is preferably CNT. more preferred.
  • CNT carbon nanotube
  • the second layer 13 can have appropriate conductivity and the adhesion to the first layer 12 can be further enhanced.
  • CNTs may be single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), multi-walled carbon nanotubes (MWCNTs), etc., but SWCNTs are preferred.
  • CNTs can be produced by conventionally known methods such as the laser ablation method, CVD method, super-growth CVD method, HiPco method, arc method, and DIPS method, and commercially available products can be used.
  • the average particle size of the conductive material is preferably 0.5 nm or more and 100 ⁇ m or less.
  • the average particle size means a volume-based median size (D50) measured using a laser diffraction scattering method.
  • the average length is preferably 5 nm or more and 50 ⁇ m or less.
  • the average length means the average length of 50 arbitrary particles (conductive material) observed with an electron microscope or the like.
  • the content of the conductive material in the second layer 13 is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more, further preferably 70% by mass or more, and even more preferably 90% by mass or more. , 95% by mass or more is particularly preferred.
  • the second layer 13 may further contain a dispersant as a component other than the conductive material.
  • the second layer 13 can usually be formed by applying a dispersion containing a conductive material. At this time, when the dispersion liquid further contains a dispersant, the dispersibility of the conductive material is improved, and the adhesion of the formed second layer 13 to the first layer 12 is improved. . By washing the second layer 13 after forming the second layer 13 in the manufacturing process, the content of the dispersant remaining in the second layer 13 is reduced, and the second layer 13 is removed. Conductivity can also be increased. Examples of the dispersant include various surfactants exemplified as optional components of the layer-forming composition, and anionic surfactants are preferred.
  • the content of the dispersant in the second layer 13 is preferably more than 0% by mass and 70% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, and even more preferably 10% by mass or less, 5% by mass or less is particularly preferred.
  • the conductivity of the second layer 13 can be enhanced.
  • the second layer 13 may further contain components other than the conductive material and the dispersant, it is preferably substantially composed of the conductive material and the dispersant.
  • the total content of the conductive material and the dispersant in the second layer 13 is preferably 90% by mass or more, more preferably 99% by mass or more, and even more preferably 99.9% by mass or more.
  • the upper limit of the average thickness of the second layer 13 is not particularly limited. By making the average thickness of the second layer 13 equal to or less than the above upper limit, the transparency of the second layer 13 and the laminate 10 can be enhanced.
  • the lower limit of the average thickness of the second layer 13 is, for example, preferably 1 nm, more preferably 5 nm, and even more preferably 10 nm. By setting the average thickness of the second layer 13 to the lower limit or more, the conductivity of the second layer 13 can be enhanced. Further, by adjusting the average thickness of the second layer 13, the conductivity of the second layer 13 can be adjusted.
  • the layer containing the conductive material (second layer 13) has good adhesion. Therefore, the layered product 10 can be sufficiently subjected to patterning of the second layer 13 and the like, cleaning treatment, and the like. Therefore, the laminate 10 can be applied to transparent electrodes, display elements, photoelectric elements, touch screens, solar cells, fuel cells, secondary batteries, supercapacitors, electromagnetic wave shielding layers, noise shielding layers, and the like.
  • a layer-forming composition according to one embodiment of the present invention is used for forming a layer (first layer 12) disposed between a substrate 11 and a layer (second layer 13) containing a conductive material. containing a compound having a condensed polycyclic hydrocarbon structure.
  • the layer-forming composition preferably further contains a crosslinkable compound other than the compound having a condensed polycyclic hydrocarbon structure.
  • the specific form and preferred form of the layer-forming composition are as described above for the layer-forming composition for forming the first layer 12 provided in the laminate 10 according to one embodiment of the present invention.
  • a layer according to one embodiment of the present invention is a layer formed from a layer-forming composition according to one embodiment of the present invention.
  • the layer is an underlying layer for the layer containing the conductive material.
  • the layer can enhance the adhesion of the layer containing the conductive material laminated on the surface of this layer.
  • the specific form and preferred form of the layer are as described above for the first layer 12 provided in the laminate 10 according to one embodiment of the present invention.
  • a method for manufacturing a laminate according to an embodiment of the present invention includes: a step of applying a layer-forming composition according to one embodiment of the present invention to one side of a substrate (step 1); A step of heating the coating film obtained by the coating (step 2); and forming a second layer containing a conductive material on the surface of the first layer obtained by the heating (step 3).
  • Step 1 the layer-forming composition described above is used to form a coating film on one side of the substrate. Specifically, the layer-forming composition is applied to a substrate, preferably pre-baked to remove the solvent and form a coating film.
  • the coating method known methods such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, and an inkjet method can be employed.
  • the inkjet method is preferable.
  • the pre-baking conditions may vary depending on the type of each component, the ratio of use, etc., but can be, for example, 60° C. or higher and 130° C. or lower for about 30 seconds or more and 10 minutes or less.
  • the lower limit of the average thickness of the coating film to be formed is preferably 5 nm, more preferably 10 nm, and even more preferably 15 nm as a value after prebaking.
  • the upper limit of this average thickness is preferably 500 nm, more preferably 100 nm, and even more preferably 20 nm.
  • Step 2 the coating film obtained in step 1 is heated.
  • This heating can be performed using a known heating device such as a hot plate and an oven.
  • the heat treatment promotes the crosslinking reaction and cures the coating film.
  • the lower limit of the heating temperature in step 2 is preferably 150°C, more preferably 200°C, even more preferably 230°C, and even more preferably 250°C.
  • the upper limit of the heating temperature is preferably 500°C, more preferably 450°C, and even more preferably 400°C.
  • the heating time is, for example, preferably 15 seconds or more and 1,200 seconds or less, more preferably 30 seconds or more and 300 seconds or less.
  • the coating film is heated to form the first layer.
  • the coating film can be cured by a combination of heating and exposure to form the first layer.
  • the radiation used for this exposure may be, depending on the type of acid generator [C], visible light, ultraviolet rays, far ultraviolet rays, X-rays, electromagnetic waves such as gamma rays, particle beams such as electron beams, molecular beams, and ion beams. Selected as appropriate.
  • step 3 a second layer containing a conductive material is formed on the surface of the first layer obtained through step 2.
  • the second layer can be effectively formed by coating and drying a dispersion containing a conductive material.
  • the dispersion medium for the dispersion liquid water or an organic solvent can usually be suitably used.
  • the content of the conductive material in the dispersion can be, for example, 10 ppm or more and 10,000 ppm or less.
  • the dispersion preferably contains a dispersant along with the conductive material.
  • the mixing ratio (mass ratio) between the conductive material and the dispersing agent in the dispersion is, for example, preferably in the range of 1:0.1 to 1:500, more preferably in the range of 1:0.5 to 1:50.
  • a method for applying the dispersion liquid for example, known methods such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, a solution immersion method, and an inkjet method can be employed.
  • a slit die coating method or an inkjet method is preferred.
  • the method for manufacturing the laminate it is possible to manufacture a laminate in which the layer (second layer) containing the conductive material has good adhesion.
  • the method for manufacturing the laminate may further include, after step 3, a step of washing the second layer, a step of patterning the second layer, and the like. For example, by performing a washing step, the content of the dispersant contained in the second layer can be reduced, and the conductivity of the second layer can be increased. Water, an acidic aqueous solution, an alkaline aqueous solution, an organic solvent, or the like is used as the cleaning liquid used in the cleaning step.
  • the second layer is less likely to peel off even after the washing process and the patterning process, and various It is excellent in workability for parts of electronic devices.
  • An electronic device includes the laminate according to one embodiment of the present invention.
  • the electronic elements include display elements, photoelectric elements, touch screens, solar cells, fuel cells, secondary batteries, supercapacitors, electromagnetic wave shielding layers, noise shielding layers, and the like.
  • the display element may be an electronic paper display element or the like.
  • These display elements, photoelectric elements, touch screens, solar cells, fuel cells, secondary batteries, supercapacitors, electromagnetic wave shielding layers and noise shielding layers are conventionally provided with the laminate according to one embodiment of the present invention.
  • the same configuration as known display elements, photoelectric elements, touch screens, solar cells, fuel cells, secondary batteries, supercapacitors, electromagnetic wave shielding layers and noise shielding layers can be employed.
  • Average layer thickness The average thickness of the layer was measured using a spectroscopic ellipsometer ("M2000D" from JA WOOLLAM).
  • compound (A′-1) The collected precipitate was washed with methanol and then dried at 100° C. under reduced pressure to obtain an aromatic polyimide (hereinafter referred to as “compound (A′-1)”).
  • the imidization rate of the obtained compound (A'-1) was 50%.
  • the temperature of the solution was set to 40° C., and evaporation was carried out while maintaining this temperature to remove the ion-exchanged water and methanol and ethanol generated by hydrolytic condensation. Then 80 g of benzyl alcohol was added and evaporation was carried out again. After evaporation, benzyl alcohol was further added so that the solid content concentration was 40% by mass. Polysiloxane (hereinafter referred to as "compound (A'-2)”) was thus obtained.
  • the obtained compound (A'-2) had a number average molecular weight (Mn) of 2,285 and a molecular weight distribution (Mw/Mn) of 2.1.
  • A-1 to A-13 Synthesized compounds (A-1) to (A-13)
  • A'-1 The synthesized compound (A'-1) (aromatic polyimide resin)
  • A'-2 The synthesized compound (A'-2) (polysiloxane)
  • [[D] crosslinkable compound] D-1 a compound represented by the following formula (D-1) (in formula (D-1), Me is a methyl group);
  • Example 1-1 [A] 10 parts by mass of (A-1) as compound was dissolved in 63 parts by mass of (B-1) and 27 parts by mass of (B-2) as [B] solvent. The resulting solution was filtered through a membrane filter with a pore size of 0.1 ⁇ m to prepare a layer-forming composition (J-1).
  • Examples 1-2 to 1-13 and Comparative Examples 1-1 to 1-2 Layer-forming compositions (J-2) to (J-13) and (j-1) were prepared in the same manner as in Example 1-1, except that the types and contents of the components shown in Table 1 below were used. ) to (j-2) were prepared. "-" in Table 1 indicates that the corresponding component was not used.
  • SWCNT which is a conductive material
  • anionic dispersant sodium dodecylbenzenesulfonate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • Example 2-1 to 2-13 and Comparative Examples 2-1 to 2-3 A substrate in which a SiN x film was formed on a silicon wafer was prepared as a substrate. Each of the layer-forming compositions prepared above was applied onto the substrate by spin coating. Next, a first layer having an average thickness of 20 nm was formed by heating (firing) in an air atmosphere at a heating temperature (°C) and a heating time (sec) shown in Table 2 below. Then, the dispersion prepared above was applied onto the first layer and dried to form a second layer having an average thickness of 10 nm. As described above, laminates of Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-3 were obtained. In Comparative Example 2-3, the dispersion was applied directly on the substrate, ie without forming the first layer, to form the second layer.
  • the laminate of each example had good washability and chemical resistance, and had good adhesion to the second layer (layer containing a conductive material). did it.
  • the adhesion of the conductive material in the second layer is good, the washing effectively removes the dispersant while the conductive material remains sufficiently. , the conductivity was sufficiently increased.
  • the adhesion of the second layer was good, the deterioration of the conductivity of the second layer was suppressed even after being immersed in the acetone bath.
  • the laminate of the present invention can be suitably used as display elements, photoelectric elements, touch screens, solar cells, fuel cells, secondary batteries, supercapacitors, electromagnetic wave shielding layers, noise shielding layers, and the like.

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