Laminate, layer-forming composition, layer, method for producing laminate, and electronic device

Abstract

The present invention provides a laminate in which an electroconductive-material-containing layer has excellent adhesiveness, a layer-forming composition with which it is possible to form such a laminate, a layer, a manufacturing method, and an electronic element comprising such a laminate. One embodiment of the present invention is a laminate having a substrate, a first layer that includes a compound having a condensed polycyclic hydrocarbon structure, and a second layer that includes an electroconductive material, in the stated order.

Description

[Technical Field]

[0001] The present invention relates to a laminate, a layer-forming composition, a layer, a method for producing a laminate, and an electronic device. [Background technology]

[0002] BACKGROUND ART Electronic elements, particularly those provided in large-area electronic devices, widely use laminates in which a conductive thin film is disposed on an insulating substrate.

[0003] Patent Document 1 describes a method for obtaining a conductive transparent electrode by applying a dispersion liquid containing graphene onto a glass substrate, drying and baking the resulting material. Patent Document 2 describes a method for obtaining a counter electrode for a dye-sensitized solar cell by applying a dispersion liquid of carbon nanotubes onto a plastic substrate, drying the resulting material to form a conductive transparent film, and then patterning the conductive transparent film. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-109434 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-146338 Summary of the Invention [Problem to be solved by the invention]

[0005] In conventional laminates obtained by the above-described methods, the conductive material has poor adhesion to the underlying layer. Therefore, it is difficult to perform processes such as patterning and cleaning of the layer containing the conductive material during the manufacturing process. In addition, there is a problem that the adhesion rate of the conductive material is low, making it difficult to effectively utilize most of the conductive material.

[0006] The present invention has been made based on the above circumstances, and aims to provide a laminate having a layer containing a conductive material with good adhesion, a layer-forming composition and layer capable of forming such a laminate, and a manufacturing method thereof, as well as an electronic device including such a laminate. [Means for solving the problem]

[0007] One aspect of the invention 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.

[0008] Another aspect of the present invention is a composition for forming a layer to be disposed between a substrate and a layer containing a conductive material, the layer-forming composition containing a compound having a condensed polycyclic hydrocarbon structure.

[0009] Another aspect of the present invention is a layer formed from the layer-forming composition.

[0010] Another aspect of the present invention is a method for producing a laminate, comprising the steps of applying the layer-forming composition to one side of a substrate, heating the coating film obtained by the application, and forming a second layer containing a conductive material on the surface of the first layer obtained by the heating.

[0011] Another aspect of the present invention is an electronic device including the laminate. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a laminate having a layer containing a conductive material with good adhesion, a layer-forming composition and layer capable of forming such a laminate, and a manufacturing method thereof, as well as an electronic device including such a laminate. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic cross-sectional view showing a laminate according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0014] Preferred embodiments of the present invention will be described in detail below. It should be understood that the present invention is not limited to the embodiments described below, but also includes various modifications that are implemented within the scope of the present invention.

[0015] <Laminate> The laminate 10 of FIG. 1 according to one embodiment of the present invention comprises a substrate 11, a first layer 12 and a second layer 13 in that order.

[0016] <Substrate> The substrate 11 is usually a substrate in which part or all of the surface in contact with the first layer 12 (the upper surface in FIG. 1 ) is insulating. 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, silicon, and resin. Specific examples of 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 with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vacuum deposition, or the like.

[0017] <First Layer> The first layer 12 contains a compound having a condensed polycyclic hydrocarbon structure (hereinafter also referred to as "compound [A]"). The first layer 12 may be a patterned layer. The first layer 12 is preferably formed from a layer-forming composition containing compound [A]. The layer-forming composition will be described in detail below.

[0018] <Layer forming composition> The layer-forming composition contains a compound [A]. The layer-forming composition may further contain a solvent [B], an acid generator [C], a crosslinkable compound [D], and other optional components. Each component will be described below.

[0019] ([A] compound) The compound [A] is a compound having a condensed polycyclic hydrocarbon structure. By including the compound [A] in the layer-forming composition, a layer containing a conductive material can be formed with good adhesion. That is, in the laminate 10, the first layer 12 containing the compound [A] is provided between the substrate 11 and the second layer 13 containing a conductive material, so that the second layer 13 containing a conductive material has good adhesion.

[0020] 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 aliphatic ring structure or an aromatic ring structure, but is preferably a structure containing an aromatic ring.

[0021] The compound [A] is preferably a compound having a partial structure represented by the following formula (1): In other words, the fused polycyclic hydrocarbon structure of the compound [A] is preferably a structure represented by the following formula (1):

[0022] [ka]

[0023] In formula (1), X is a divalent group represented by formula (i), (ii), (iii), or (iv). Y and Y' are each independently a monovalent organic group having 1 to 20 carbon atoms. * and ** represent a bonding site to a portion of the compound other than the partial structure represented by formula (1). n1 and n2 are each independently an integer of 0 to 2. n3 and n4 are each independently an integer of 0 to 8. n5 and n6 are each independently an integer of 0 to 8. When n3 is 2 or greater, multiple Y's are the same or different. When n4 is 2 or greater, multiple Y's are the same or different. However, n3 + n5 is 8 or less, n4 + n6 is 8 or less, and n5 + n6 is 1 or greater.

[0024] [ka]

[0025] In formula (i), 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 aralkyl group having 7 to 20 carbon atoms, or R 1 and R 2 and represent a part of a ring structure having 3 to 20 ring members formed by combining with each other and the carbon atoms to which they are attached. In formula (ii), R 3 and R 4 are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 20 carbon atoms, or R 3 and R 4 and represent a part of a ring structure having 3 to 20 ring members formed by combining with each other and the carbon atoms to which they are attached. In formula (iii), R 5 is a hydrogen atom, a hydroxy group, or a monovalent organic group having 1 to 20 carbon atoms. In formula (iv), 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.

[0026] Examples of the monovalent organic group having 1 to 20 carbon atoms represented by Y and Y' include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group (α) containing a divalent heteroatom-containing group between carbon atoms or at the terminal of this hydrocarbon group, and groups in which some or all of the hydrogen atoms in the hydrocarbon group and group (α) have been substituted with a monovalent heteroatom-containing group.

[0027] Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Examples of aliphatic hydrocarbon groups include chain aliphatic hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain aliphatic hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, and pentyl; alkenyl groups such as ethenyl, propenyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl. Examples of alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl and cyclohexyl; cycloalkenyl groups such as cyclopropenyl, cyclopentenyl, and cyclohexenyl; and bridged ring hydrocarbon groups such as norbornyl and adamantyl. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, tolyl, xylyl, and naphthyl; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl.

[0028] Examples of the divalent heteroatom-containing group include -CO-, -CS-, -NH-, -O-, -S-, and combinations of these groups.

[0029] Examples of the group (α) containing a divalent heteroatom-containing group between carbon atoms of a hydrocarbon group or at the terminal include a heteroatom-containing chain group, an aliphatic heterocyclic group, and an aromatic heterocyclic group. Examples of the heteroatom-containing chain group include an oxoalkyl group, a thioalkyl group, an alkylaminoalkyl group, an alkoxyalkyl group, and an alkylthioalkyl group. Examples of the aliphatic heterocyclic group include an oxocycloalkyl group, a thiocycloalkyl group, an azacycloalkyl group, an oxacycloalkyl group, a thiacycloalkyl group, an oxocycloalkenyl group, and an oxathiacycloalkyl group. Examples of the aromatic heterocyclic group include a pyrrolyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a furyl group, a pyranyl group, a thienyl group, and a benzothiophenyl group.

[0030] Examples of the monovalent heteroatom-containing group include a hydroxy group, a sulfanyl group, a cyano group, a nitro group, and a halogen atom.

[0031] Y and Y' are each independently preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group, even more preferably an aliphatic chain hydrocarbon group, even more preferably an alkyl group, and particularly preferably a methyl group.

[0032] As n1 and n2, 0 and 1 are preferable, and 0 is more preferable.

[0033] n3 and n4 are preferably 0 to 3, more preferably 0 to 2, further preferably 0 and 1, and particularly preferably 0.

[0034] n5 and n6 are preferably 0 to 6, more preferably 0 to 4, and it is particularly preferable that n5 is 1 and n6 is 0.

[0035] R 1 , R 2 and R 6Examples of the unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms and represented by the formula (I) include aliphatic chain hydrocarbon groups and alicyclic hydrocarbon groups. Examples of the aliphatic chain hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, and pentyl groups; alkenyl groups such as ethenyl, propenyl, and butenyl groups; and alkynyl groups such as ethynyl, propynyl, and butynyl groups. Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl and cyclohexyl groups; cycloalkenyl groups such as cyclopropenyl, cyclopentenyl, and cyclohexenyl groups; and bridged ring hydrocarbon groups such as norbornyl and adamantyl groups. R 1 , R 2 and R 6 Examples of the substituent on the aliphatic hydrocarbon group in the formula (I) include alkoxy groups such as methoxy and ethoxy groups, and cyano groups.

[0036] R 1 , R 2 and R 6 Examples of the unsubstituted aralkyl group having 7 to 20 carbon atoms represented by the formula (R) include a benzyl group, an o-methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group, a naphthylmethyl group, and an α-phenethyl group. 1 , R 2 and R 6 Examples of the substituent of the aralkyl group in the formula (I) include a halogen atom such as a fluorine atom or a chlorine atom, and a nitro group.

[0037] R 3 , R 4 and R 5 Examples of the monovalent organic group having 1 to 20 carbon atoms represented by the formula (1) include the same organic groups as exemplified as Y and Y' in formula (1).

[0038] R 1 and R 2 or R 3 and R 4Examples of the ring structure having 3 to 20 ring members formed by combining these together with the carbon atoms to which they are bonded include alicyclic structures such as a cyclohexane structure and a cyclohexene structure, and aliphatic heterocyclic structures such as an azacyclohexane structure and an azacyclohexene structure.

[0039] 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, or R 1 and R 2 and are preferably combined with each other to form a part of a ring structure having 3 to 20 ring members, which is formed together with the carbon atoms to which they are bonded.

[0040] R 1 R is preferably 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, more preferably an unsubstituted aliphatic hydrocarbon group or an unsubstituted aralkyl group, still more preferably an unsubstituted chain hydrocarbon group, and particularly preferably an alkynyl group or an alkenyl group. 1 The number of carbon atoms is preferably 1 to 8, more preferably 2 to 6, and even more preferably 3 to 5.

[0041] R 2 R 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 preferably an alkynyl group or an alkenyl group. 2 The number of carbon atoms is preferably 1 to 8, more preferably 2 to 6, and even more preferably 3 to 5.

[0042] R 3is 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, still more preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and particularly preferably a naphthyl group, a pyrenyl group, a phenanthrenyl group, an acetal group-substituted phenyl group, a hydroxy group-substituted phenyl group, a dialkylamino group-substituted phenyl group, an alkynyl group-substituted phenyl group, or an N-alkyl group-substituted carbazolyl group.

[0043] R 4 is preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom.

[0044] R 5 As the alkyl group, a hydroxy group and a monovalent organic group having 1 to 20 carbon atoms are preferred, an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms is more preferred, and an alkyl group and an aryl group are even more preferred.

[0045] R 6 R is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an unsubstituted aralkyl group having 7 to 20 carbon atoms, more preferably an unsubstituted chain hydrocarbon group, and even more preferably an alkyl group. 6 The number of carbon atoms is preferably 1 to 8, and more preferably 1 to 4.

[0046] X is preferably a group represented by the above formula (i), (ii) or (iv).

[0047] The compound [A] may be a compound 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.

[0048] [ka]

[0049] In formula (2), Z is a partial structure represented by formula (1) when n5 is 1 and n6 is 0. Ais an m-valent organic group having 1 to 30 carbon atoms, where m is an integer of 1 to 20. When m is 2 or more, multiple Zs may be the same or different.

[0050] R A Examples of the m-valent organic group having 1 to 30 carbon atoms represented by the formula (1) include groups in which (m-1) hydrogen atoms have been removed from the monovalent organic groups exemplified as Y and Y' in formula (1).

[0051] R in Equation (2) A From the viewpoint of ease of synthesis, etc., the group is preferably a group in which m hydrogen atoms have been removed from a substituted or unsubstituted arene having 6 to 20 ring members or a substituted or unsubstituted heteroarene having 5 to 20 ring members.

[0052] R A Examples of unsubstituted arenes having 6 to 20 ring members that give the formula include benzene, naphthalene, anthracene, phenanthrene, tetracene, pyrene, triphenylene, and perylene. Among these, benzene and naphthalene are preferred, and benzene is more preferred. A Examples of unsubstituted heteroarenes having 5 to 20 ring members that give the formula (I) 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, etc. Among these, triazine is preferred, and 1,3,5-triazine is more preferred.

[0053] R A Examples of the substituents of the arenes and heteroarenes that give the above formula include alkyl groups, alkoxy groups, cyano groups, nitro groups, and halogen atoms.

[0054] R AAs the group, a group in which m hydrogen atoms have been removed from an unsubstituted arene having 6 to 20 ring members or an unsubstituted heteroarene having 5 to 20 ring members is preferred.

[0055] The lower limit of m is preferably 2, and more preferably 3. The upper limit of m is preferably 12, more preferably 8, still more preferably 6, and particularly preferably 3.

[0056] R A is a benzene-1,3,5-triyl group obtained by removing hydrogen atoms at the 1,3,5-positions from benzene, or a 1,3,5-triazine-2,4,6-triyl group obtained by removing hydrogen atoms at the 2,4,6-positions from 1,3,5-triazine, the symmetry of compound [A] becomes higher, resulting in better adhesion of the layer containing the conductive material.

[0057] Examples of the compound [A] include a compound represented by the following formula (3) in which, in the partial structure represented by formula (1), n1 is 0, n3 is 0, n5 is 4, and n6 is 0. Use of the compound represented by formula (3) can also improve the adhesion of the layer containing a conductive material.

[0058] [ka]

[0059] In formula (3), X has the same meaning as X in formula (1). 1 , Y 2 and Y 3 are each independently defined as Y' in formula (1). p1, p2, and p3 are each independently defined as n2 in formula (1). p4, p5, and p6 are each independently defined as n4 in formula (1).

[0060] Compound [A] preferably has an aromatic carbocycle or aromatic heterocycle in a portion other than the partial structure represented by formula (1), and more preferably has an aromatic carbocycle or aromatic heterocycle bonded to the partial structure represented by formula (1). As the aromatic carbocycle and aromatic heterocycle, a benzene ring and a 1,3,5-triazine ring are preferred, and more preferably, a partial structure represented by formula (1) where n5 is 1 and n6 is 0 is bonded to the 1,3,5-position of the benzene ring and the 2,4,6-position of the 1,3,5-triazine ring. Compound [A] having such a structure can be easily synthesized from the corresponding acetyl group-containing fluorene compound or cyano group-containing fluorene compound. Furthermore, such compounds have high symmetry and can improve the adhesion of layers containing conductive materials.

[0061] The compound [A] preferably has a crosslinkable group. When the compound [A] has a crosslinkable group, the hardness of the layer to be formed can be increased. Examples of the crosslinkable group include an alkynyl group, an alkenyl group, a (meth)acryloyl group, an epoxy group, a hydroxymethyl group, an alkoxyalkyl group, and an alkoxyalkylated amino group. The compound [A] having a crosslinkable group includes R 1 ~R 6 and compounds having a partial structure represented by formula (1) in which at least one of Y and Y' is a crosslinkable group.

[0062] Specific examples of the compound [A] include compounds represented by the following formulas.

[0063] [ka]

[0064] [ka]

[0065] In the above formula, Y and Y' have the same meanings as Y and Y' in formula (1). p7, p8, and p9 each independently represent an integer of 0 to 3. p10, p11, and p12 each independently represent an integer of 0 to 4. When the sum of p7, p8, and p9 is 2 or greater, multiple Y's are the same or different. When the sum of p10, p11, and p12 is 2 or greater, multiple Y's are the same or different.

[0066] The lower limit of the molecular weight of the compound [A] 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. By setting the molecular weight of the compound [A] within the above range, the adhesion of the layer containing the conductive material can be improved.

[0067] When the compound [A] is a mixture or a compound having a molecular weight distribution, the lower limit of the weight-average molecular weight (Mw) of the compound [A] is preferably 500, more preferably 1,000. The upper limit of the Mw is preferably 50,000, more preferably 10,000, and even more preferably 8,000.

[0068] The lower limit of the content of the compound [A] is preferably 70% by mass, more preferably 80% by mass, and even more preferably 85% by mass, based on the total solid content of the layer-forming composition. The upper limit of the content may be, for example, 100% by mass, and in some cases, 99% by mass is preferred. The "total solid content" refers to the sum of all components in the layer-forming composition other than the solvent [B]. The preferred range of the content of the compound [A] in the first layer 12 is the same as the preferred range of the content of the compound [A] based on the total solid content of the layer-forming composition. The same applies to the ranges of the contents of other components in the first layer 12.

[0069] The lower limit of the content of the compound [A] 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. The compound [A] may be used alone or in combination of two or more.

[0070] ([B] Solvent) The solvent (B) is not particularly limited as long as it is a component that can dissolve or disperse the compound (A) and any optional components that may be contained as needed.

[0071] Examples of the solvent [B] include alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, etc. The solvent [B] can be used alone or in combination of two or more.

[0072] Examples of alcohol solvents include monoalcohol solvents such as methanol, ethanol, and n-propanol, and polyalcohol solvents such as ethylene glycol and 1,2-propylene glycol.

[0073] Examples of the ketone solvent include chain ketone solvents such as methyl ethyl ketone and methyl-iso-butyl ketone, and cyclic ketone solvents such as cyclohexanone.

[0074] Examples of 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.

[0075] Examples of ester-based solvents include carbonate-based solvents such as diethyl carbonate, acetate monoester-based solvents such as methyl acetate and ethyl acetate, lactone-based solvents such as γ-butyrolactone, polyhydric alcohol partial ether carboxylate-based solvents such as diethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, and lactate-based solvents such as methyl lactate and ethyl lactate.

[0076] Examples of the nitrogen-containing solvent include chain nitrogen-containing solvents such as N,N-dimethylacetamide, and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.

[0077] The solvent [B] is preferably a ketone solvent, an ether solvent, or an ester solvent. Among these, from the viewpoint of excellent film-forming properties, an ether solvent having a glycol structure and an ester solvent having a glycol structure are more preferred.

[0078] Examples of ether solvents having a glycol structure and ester solvents having a glycol structure include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Among these, propylene glycol monomethyl ether acetate is particularly preferred.

[0079] 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 [B] is preferably 20% by mass, more preferably 60% by mass, even more preferably 90% by mass, and particularly preferably 100% by mass.

[0080] ([C] Acid generator) The acid generator [C] is a component that generates acid when exposed to heat or light, and promotes crosslinking of the compound [A] (when the compound [A] has a crosslinkable group) and the optional crosslinkable compound [D]. The layer-forming composition containing the acid generator [C] promotes the crosslinking reaction of the compound [A] and / or the crosslinkable compound [D] that have a crosslinkable group, thereby increasing the hardness of the layer that is formed. The acid generator [C] can be used alone or in combination of two or more.

[0081] Examples of the acid generator (C) include onium salt compounds and N-sulfonyloxyimide compounds.

[0082] Examples of the onium salt compound include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, and ammonium salts.

[0083] Examples of sulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, and 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate.

[0084] Examples of tetrahydrothiophenium salts include 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium nonafluoro-n-butanesulfonate, and the like.

[0085] Examples of iodonium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, and bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate.

[0086] Examples of the ammonium salt include triethylammonium trifluoromethanesulfonate and triethylammonium nonafluoro-n-butanesulfonate.

[0087] Examples of the N-sulfonyloxyimide compound 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.

[0088] The acid generator (C) 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.

[0089] When the layer-forming composition contains an acid generator [C], the lower limit of the content of the acid generator [C] is preferably 0.1 parts by mass, more preferably 1 part by mass, and even more preferably 3 parts by mass, relative to 100 parts by mass of the compound [A]. 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. By setting the content of the acid generator [C] within the above range, the crosslinking reaction of the compound [A] having a crosslinkable group and / or the crosslinkable compound [D] can be more effectively promoted.

[0090] ([D]Crosslinkable compound) The crosslinkable compound [D] is a component that forms crosslinks between components such as the compound [A] in the layer-forming composition or that itself forms a crosslinked structure by the action of heat or acid (excluding compounds that fall under the category of compound [A]). When the layer-forming composition contains the crosslinkable compound [D], it is possible to increase the hardness of the layer that is formed. The crosslinkable compound [D] can be used alone or in combination of two or more types.

[0091] [D] Examples of the crosslinkable compound include polyfunctional (meth)acrylate compounds, epoxy compounds, hydroxymethyl group-substituted phenol compounds, alkoxyalkyl group-containing phenol compounds, compounds having an alkoxyalkylated amino group, random copolymers of acenaphthylene and hydroxymethylacenaphthylene represented by the following formula (11-P), and compounds represented by the following formulas (11-1) to (11-12).

[0092] [ka]

[0093] [ka]

[0094] In the formulas (11-1) to (11-12), Me represents a methyl group, Et represents an ethyl group, and Ac represents an acetyl group.

[0095] The compounds represented by formulae (11-1) to (11-12) can be synthesized with reference to the following documents. Compounds 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 Compounds represented by formula (11-2): Badar, Y. et al. Journal of the Chemical Society,1965,p.1412-1418 Compounds represented by formula (11-3): Hsieh, Jen-Chieh; Cheng, Chien-Hong Chemical Communications (Cambridge, United Kingdom), 2008, #26 p.2992-2994 Compounds represented by formula (11-4): Japanese Patent Application Publication No. 5-238990 Compounds represented by formula (11-5): Bacon,RGR;Bankhead,R. Journal of the Chemical Society,1963,p.839-845 Compounds represented by formulae (11-6), (11-8), (11-11) and (11-12): Macromolecules 2010,vol.43,p2832-2839 Compounds represented by formulae (11-7), (11-9) and (11-10): Polymer Journal 2008,vol.40,No.7,p645-650, and Journal of Polymer Science:Part A,Polymer Chemistry,Vol.46,p4949-4958

[0096] Examples of 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, and 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, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, and the like.

[0097] Examples of the epoxy compound include novolac type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

[0098] Examples of hydroxymethyl group-substituted phenol compounds include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene [2,6-bis(hydroxymethyl)-p-cresol], and the like.

[0099] Examples of alkoxyalkyl group-containing phenolic compounds include methoxymethyl group-containing phenolic compounds, ethoxymethyl group-containing phenolic compounds, etc. Examples of methoxymethyl group-containing phenolic compounds include compounds represented by the following formula (11-Q):

[0100] [ka]

[0101] In formula (11-Q), Me represents a methyl group.

[0102] Examples of compounds having an alkoxyalkylated amino group include nitrogen-containing compounds having multiple active methylol groups in one molecule, such as (poly)methylolated melamine, (poly)methylolated glycoluril, (poly)methylolated benzoguanamine, and (poly)methylolated urea, in which at least one hydrogen atom of the hydroxyl group in 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 multiple substituted compounds, or may contain an oligomer component formed by partial self-condensation. Examples of compounds having an alkoxyalkylated amino group include 1,3,4,6-tetrakis(methoxymethyl)glycoluril.

[0103] Among the crosslinkable compounds [D], preferred are methoxymethyl group-containing phenolic compounds, compounds having an alkoxyalkylated amino group, and random copolymers of acenaphthylene and hydroxymethylacenaphthylene, more preferred are methoxymethyl group-containing phenolic compounds and compounds having an alkoxyalkylated amino group, and even more preferred are 4,4'-(1-(4-(1-(4-hydroxy-3,5-bis(methoxymethyl)phenyl)-1-methylethyl)phenyl)ethylidene)bis(2,6-bis(methoxymethyl)phenol (the compound represented by the above formula (11-Q)) and 1,3,4,6-tetrakis(methoxymethyl)glycoluril.

[0104] When the layer-forming composition contains a crosslinkable compound [D], the lower limit of the content of the crosslinkable compound [D] is preferably 0.1 parts by mass, more preferably 1 part by mass, even more preferably 3 parts by mass, and particularly preferably 5 parts by mass, relative to 100 parts by mass of the compound [A]. The upper limit of the content is preferably 100 parts by mass, more preferably 50 parts by mass, even more preferably 30 parts by mass, and particularly preferably 20 parts by mass. By setting the content of the crosslinkable compound [D] within the above range, the crosslinking reaction can be more effectively induced, thereby increasing the hardness of the formed layer.

[0105] (Other optional ingredients) Other optional components include, for example, surfactants and adhesion aids.

[0106] (surfactant) The layer-forming composition can improve its coatability by containing a surfactant, which results in improved coating surface uniformity of the layer (coating film) formed and suppresses the occurrence of coating spots. The surfactants can be used alone or in combination of two or more.

[0107] Examples of surfactants include nonionic surfactants and anionic surfactants. Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate. Examples of anionic surfactants include potassium rosinate, sodium rosinate, potassium oleate, potassium laurate, sodium laurate, sodium stearate, potassium stearate, sodium lauryl sulfate, and sodium dodecylbenzenesulfonate. Commercially available surfactants include KP341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, No. 95 (Kyoeisha Chemical Co., Ltd.), F-Top EF101, EF204, EF303, EF352 (Tochem Products Co., Ltd.), Megafac F171, F172, F173 (DIC Corporation), Fluorad FC430, FC431, FC135, FC93 (Sumitomo 3M Limited), Asahiguard AG710, Surflon S382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), and the like.

[0108] When the layer-forming composition contains a surfactant, the lower limit of the surfactant content is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, and even more preferably 0.1 parts by mass, relative to 100 parts by mass of the compound [A]. 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. By setting the surfactant content within the above range, the coatability of the layer-forming composition can be improved.

[0109] (Method for preparing layer-forming composition) The layer-forming composition can be prepared by mixing [A] compound, [B] solvent, if necessary [C] acid generator, [D] crosslinkable compound, and other optional components in a predetermined ratio, and then filtering the resulting mixture through a membrane filter or the like with a pore size of approximately 0.1 μm. The lower limit of the solids concentration of the layer-forming composition is preferably 0.1% by mass, more preferably 1% by mass, even more preferably 3% by mass, and particularly preferably 5% by mass. The upper limit of the solids concentration is preferably 50% by mass, more preferably 30% by mass, even more preferably 20% by mass, and particularly preferably 15% by mass.

[0110] 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, and even more preferably 10 nm or more and 50 nm or less, with the upper limit being even more preferably 30 nm, and particularly preferably 20 nm. By making the average thickness of the first layer 12 equal to or more than the above-mentioned lower limit, the adhesion to the second layer 13 can be improved. On the other hand, by making the average thickness of the first layer 12 equal to or less than the above-mentioned upper limit, the transparency of the first layer 12 and the laminate 10 can be improved.

[0111] <Second Layer> 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 also have a surface region on which the second layer 13 is not laminated.

[0112] The second layer 13 contains a conductive material. Examples of conductive materials include metals and carbon materials, with carbon materials being preferred. A carbon material refers to a material containing carbon as its main constituent element. A main constituent element refers to the element with the highest content by mass. The carbon element content in the carbon material is preferably 90 mass% or more, and more preferably 99 mass% or more. One or more conductive materials can be used.

[0113] The carbon material is preferably at least one selected from the group consisting of carbon nanotubes (CNTs), carbon nanofibers, carbon black, graphene, fullerenes, and graphite, and preferably includes CNTs, more preferably is CNTs. By using such a carbon material as the conductive material, the second layer 13 can have appropriate conductivity and can further improve adhesion to the first layer 12.

[0114] The CNTs may be any of 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 laser ablation, CVD, super-growth CVD, HiPco, arc, and DIPS, and commercially available products can be used.

[0115] The average particle diameter of the conductive material is preferably 0.5 nm or more and 100 μm or less. The average particle diameter refers to the volume-based median diameter (D50) measured using a laser diffraction scattering method. When the conductive material is in the form of fibers such as CNTs, the average length is preferably 5 nm or more and 50 μm or less. The average length refers to the average length of 50 random particles (conductive material) observed using an electron microscope or the like. Using a conductive material of such a size improves the dispersibility of the conductive material, adhesion to the first layer 12, and the like.

[0116] 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, even more preferably 70% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. By setting the content of the conductive material in the second layer 13 within the above range, good conductivity can be exhibited.

[0117] 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 the conductive material. If the dispersion 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. Note that, after forming the second layer 13 during the manufacturing process, the second layer 13 can be washed to reduce the content of dispersant remaining in the second layer 13 and thereby increase the conductivity of the second layer 13. Examples of dispersants include various surfactants exemplified as optional components of the layer-forming composition, and anionic surfactants are preferred.

[0118] The content of the dispersant in the second layer 13 is preferably more than 0 mass % and not more than 70 mass %, more preferably not more than 50 mass %, even more preferably not more than 30 mass %, even more preferably not more than 10 mass %, and particularly preferably not more than 5 mass %. By setting the content of the dispersant in the second layer 13 within the above range, the conductivity of the second layer 13 can be increased.

[0119] The second layer 13 may further contain components other than the conductive material and the dispersant, but is preferably composed essentially 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.

[0120] The upper limit of the average thickness of the second layer 13 is not particularly limited and may be, for example, 1 μm, preferably 100 nm, more preferably 50 nm, even more preferably 30 nm, and even more preferably 20 nm. By setting the average thickness of the second layer 13 to the above upper limit or less, it is possible to increase the transparency of the second layer 13 and the laminate 10. 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 above lower limit or more, it is possible to increase the conductivity of the second layer 13. Furthermore, by adjusting the average thickness of the second layer 13, it is possible to adjust the conductivity of the second layer 13.

[0121] The laminate 10 has good adhesion to the layer containing a conductive material (second layer 13). This allows the laminate 10 to be sufficiently subjected to patterning, cleaning, etc. of the second layer 13. This makes the laminate 10 applicable to transparent electrodes, display elements, photoelectric elements, touch screens, solar cells, fuel cells, secondary batteries, supercapacitors, electromagnetic wave shielding layers, noise shielding layers, etc.

[0122] <Layer forming composition> A layer-forming composition according to one embodiment of the present invention is a composition for forming a layer (first layer 12) disposed between a substrate 11 and a layer containing a conductive material (second layer 13), and contains 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. Specific and preferred forms of the layer-forming composition are as described above for the layer-forming composition for forming the first layer 12 included in the laminate 10 according to one embodiment of the present invention.

[0123] <layer> The 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. This layer is a base layer for a layer containing a conductive material. This layer can improve the adhesion of a layer containing a conductive material that is laminated on the surface of this layer. Specific and preferred forms of this layer are as described above for the first layer 12 provided in the laminate 10 according to one embodiment of the present invention.

[0124] <Method of manufacturing laminate> A method for producing a laminate according to one embodiment of the present invention includes the steps of: A step (step 1) of applying a layer-forming composition according to one embodiment of the present invention to one surface of a substrate; A step (step 2) of heating the coating film obtained by the above coating; a step (step 3) of forming a second layer containing a conductive material on the surface of the first layer obtained by the heating; Equipped with.

[0125] (Process 1) In step 1, the layer-forming composition described above is used to form a coating film on one side of a substrate. Specifically, the layer-forming composition is applied to a substrate, and the substrate is preferably pre-baked to remove the solvent, thereby forming a coating film.

[0126] Examples of the coating method include spraying, roll coating, rotary coating (spin coating), slit die coating, bar coating, and inkjet coating. Of these, inkjet coating is preferred.

[0127] The pre-baking conditions vary depending on the type and proportion of each component, but can be, for example, at 60° C. to 130° C. for 30 seconds to 10 minutes.

[0128] The lower limit of the average thickness of the coating film formed after prebaking is preferably 5 nm, more preferably 10 nm, and even more preferably 15 nm, and the upper limit of this average thickness is preferably 500 nm, more preferably 100 nm, and even more preferably 20 nm.

[0129] (Process 2) In 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 or an oven. When the layer-forming composition contains the compound [A] and / or the crosslinkable compound [D] having a crosslinkable group, the heat treatment promotes the crosslinking reaction and hardens the coating film.

[0130] 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. By setting the heating temperature at or above the lower limit, a first layer in a well-cured state can be obtained. 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, and more preferably 30 seconds or more and 300 seconds or less.

[0131] In the method for producing the laminate, the coating film is heated to form the first layer, but when the layer-forming composition contains an acid generator [C] and the acid generator [C] is a radiation-sensitive acid generator, the coating film can be cured by combining heating and exposure to light to form the first layer. The radiation used for this exposure is appropriately selected from electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, X-rays, and gamma rays, and particle beams such as electron beams, molecular beams, and ion beams, depending on the type of acid generator [C].

[0132] In step 3, a second layer containing a conductive material is formed on the surface of the first layer obtained through step 2. Usually, the second layer can be effectively formed by applying and drying a dispersion liquid containing the conductive material.

[0133] As the dispersion medium for the dispersion, 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. As described above, the dispersion preferably contains a dispersant together with the conductive material. The mixing ratio (mass ratio) of the conductive material to the dispersant in the dispersion is, for example, preferably in the range of 1:0.1 to 1:500, and more preferably in the range of 1:0.5 to 1:50.

[0134] Examples of a method for applying the dispersion include known methods such as spraying, roll coating, rotary coating (spin coating), slit die coating, bar coating, solution immersion, and inkjet coating. Of these, slit die coating and inkjet coating are preferred.

[0135] According to this method for producing a laminate, a laminate having a layer (second layer) containing a conductive material with good adhesion can be produced. The method for producing a laminate may further include, after step 3, a step of cleaning the second layer, a step of patterning the second layer, etc. For example, by performing the cleaning step, the content of the dispersant contained in the second layer can be reduced, and the conductivity of the second layer can be increased. Examples of cleaning solutions used in the cleaning step include water, an acidic aqueous solution, an alkaline aqueous solution, and an organic solvent. According to this method for producing a laminate, the layer (second layer) containing a conductive material with good adhesion is less likely to peel off even after the cleaning step and patterning step, and the laminate is excellent in processability for forming components of various electronic devices.

[0136] <Electronic elements> An electronic device according to an embodiment of the present invention includes a laminate according to an embodiment of the present invention. Examples of such electronic devices include display devices, photoelectric devices, touch screens, solar cells, fuel cells, secondary batteries, supercapacitors, electromagnetic wave shielding layers, and noise shielding layers. The display device may be an electronic paper display device or the like. These display devices, photoelectric devices, touch screens, solar cells, fuel cells, secondary batteries, supercapacitors, electromagnetic wave shielding layers, and noise shielding layers may have the same configurations as conventionally known display devices, photoelectric devices, touch screens, solar cells, fuel cells, secondary batteries, supercapacitors, electromagnetic wave shielding layers, and noise shielding layers, except that they include a laminate according to an embodiment of the present invention. [Example]

[0137] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Measurement methods for various physical properties are shown below.

[0138] Average layer thickness The average thickness of the layer was measured using a spectroscopic ellipsometer (JAWOOLLAM "M2000D").

[0139] <Synthesis of Compound [A]> The compounds represented by the following formulas (A-1) to (A-13) were synthesized according to the following procedure.

[0140] [ka]

[0141] [ka]

[0142] [Synthesis Example 1] (Synthesis of Compound (a-1)) In a reaction vessel, 20.0 g of 2-acetylfluorene and 20.0 g of m-xylene were charged under a nitrogen atmosphere and dissolved at 110°C. Next, 3.14 g of dodecylbenzenesulfonic acid was added, and the mixture was heated to 140°C and reacted for 16 hours. After the reaction was completed, the reaction solution was diluted with 80 g of xylene, cooled to 50°C, and poured into 500 g of methanol for reprecipitation. The obtained precipitate was washed with toluene, and the solid was collected on filter paper and dried to obtain a compound represented by the following formula (a-1).

[0143] [ka]

[0144] [Synthesis Example 2] (Synthesis of Compound (A-1)) In a reaction vessel, 10.0 g of the compound (a-1), 18.8 g of propargyl bromide, and 50 g of toluene were added under a nitrogen atmosphere, and after stirring, 25.2 g of a 50% by mass aqueous solution of sodium hydroxide and 1.7 g of tetrabutylammonium bromide were added, and the reaction was carried out at 92°C for 12 hours. The reaction solution was cooled to 50°C, and 25 g of tetrahydrofuran was added. After removing the aqueous phase, 50 g of a 1% by mass aqueous solution of oxalic acid was added to perform liquid separation and extraction, and then the mixture was poured into hexane and reprecipitated. The precipitate was collected with filter paper and dried to obtain the compound (A-1).

[0145] [Synthesis Example 3] (Synthesis of Compound (A-2)) The above compound (A-2) was obtained in the same manner as in Synthesis Example 2, except that 18.8 g of propargyl bromide was changed to 19.1 g of allyl bromide.

[0146] [Synthesis Example 4] (Synthesis of Compound (A-3)) The above compound (A-3) was obtained in the same manner as in Synthesis Example 2, except that 18.8 g of propargyl bromide was changed to 9.9 g of 1-naphthaldehyde.

[0147] [Synthesis Example 5] (Synthesis of Compound (A-4)) The above compound (A-4) was obtained in the same manner as in Synthesis Example 2, except that 18.8 g of propargyl bromide was changed to 14.6 g of 1-formylpyrene.

[0148] [Synthesis Example 6] (Synthesis of Compound (A-5)) The above compound (A-5) was obtained in the same manner as in Synthesis Example 2, except that 18.8 g of propargyl bromide was changed to 13.2 g of terephthalaldehyde mono(diethyl acetal).

[0149] [Synthesis Example 7] (Synthesis of Compound (a-2)) In a nitrogen atmosphere, 10.0 g of 2-cyanofluorene and 88.8 g of dichloromethane were added to a reaction vessel, and after cooling to 5° C., 7.9 g of trifluoromethanesulfonic acid was added dropwise and reacted for 24 hours at 20° C. to 25° C. The reaction solution was neutralized by adding a large amount of aqueous sodium hydrogen carbonate solution, and the precipitated solid was collected with filter paper, washed with dichloromethane, and dried to obtain a compound represented by the following formula (a-2).

[0150] [ka]

[0151] [Synthesis Example 8] (Synthesis of Compound (A-6)) In a reaction vessel, 5.0 g of the compound (a-2), 7.5 g of propargyl bromide, 12.6 g of a 50% by mass aqueous solution of sodium hydroxide, 0.8 g of tetrabutylammonium bromide, and 25.7 g of toluene were added under a nitrogen atmosphere and reacted at 92°C for 12 hours. The reaction solution was cooled to 50°C and then diluted with 25 g of tetrahydrofuran. After removing the aqueous phase, 50 g of a 1% by mass aqueous solution of oxalic acid was added to perform liquid separation and extraction, and then the mixture was poured into hexane and reprecipitated. The precipitate was collected using filter paper and dried to obtain the compound (A-6).

[0152] [Synthesis Example 9] (Synthesis of Compound (A-7)) In a reaction vessel, 15.0 g of 2-acetyl-9-ethylcarbazole, 14.9 g of thionyl chloride, and 2.8 g of ethanol were added under a nitrogen atmosphere, and the mixture was reacted for 8 hours at 80° C. 50 g of water and 50 g of dichloromethane were added to the resulting reaction solution, followed by separation and extraction. The resulting organic layer was concentrated using an evaporator and dried to obtain the above compound (A-7).

[0153] [Synthesis Example 10] (Synthesis of Compound (A-8)) In a nitrogen atmosphere, 10.0 g of truxene, 31.3 g of propargyl bromide, and 50 g of toluene were added to a reaction vessel and stirred. Then, 42.0 g of a 50% by mass aqueous solution of sodium hydroxide and 2.8 g of tetrabutylammonium bromide were added, and the mixture was reacted at 92°C for 12 hours. After the reaction solution was cooled to 50°C, the aqueous phase was removed, and 50 g of a 1% by mass aqueous solution of oxalic acid was added to perform liquid separation and extraction. The mixture was then poured into a methanol / water (70 / 30 (mass ratio)) mixed solvent and reprecipitated. The precipitate was collected with filter paper and dried to obtain the compound (A-8).

[0154] [Synthesis Example 11] (Synthesis of Compound (A-9)) In a nitrogen atmosphere, 10.0 g of the compound (a-1), 12.76 g of 4-(trimethylsilylethynyl)benzaldehyde, and 50 g of tetrahydrofuran were added to a reaction vessel and stirred. After stirring, 37.9 g of 20% by mass aqueous sodium hydroxide and 1.7 g of tetrabutylammonium bromide were added, and the reaction was carried out at 35°C for 3 hours. The reaction solution was cooled to room temperature, and 15 g of methyl isobutyl ketone was added. After removing the aqueous phase, the mixture was subjected to separation and extraction three times with 50 g of 1% by mass aqueous oxalic acid solution, and then poured into hexane to reprecipitate. The precipitate was collected using filter paper and dried to obtain the compound (A-9).

[0155] [Synthesis Example 12] (Synthesis of Compound (A-10)) In a reaction vessel, under a nitrogen atmosphere, 10.0 g of the compound (a-1), 11.4 g of 4-(2-tetrahydro-2H-pyranoxy)benzaldehyde, and 50 g of tetrahydrofuran were added and stirred. Then, 25.2 g of 50% by mass aqueous sodium hydroxide solution and 1.7 g of tetrabutylammonium bromide were added and reacted at 50°C for 12 hours. After removing the aqueous phase, 10 g of 35% hydrochloric acid was added and stirred for 2 hours to carry out a deprotection reaction. After the reaction, 15 g of methyl isobutyl ketone was added, and the aqueous phase was removed. Separation and extraction with 50 g of water was repeated three times, followed by pouring into hexane and reprecipitation. The precipitate was collected with filter paper and dried to obtain the compound (A-10).

[0156] [Synthesis Example 13] (Synthesis of Compound (A-11)) The above compound (A-11) was obtained in the same manner as in Synthesis Example 2, except that 18.8 g of propargyl bromide was changed to 6.5 g of 4-diethylaminobenzaldehyde.

[0157] [Synthesis Example 14] (Synthesis of Compound (A-12)) The above compound (A-12) was obtained in the same manner as in Synthesis Example 2, except that 18.8 g of propargyl bromide was changed to 12.3 g of N-ethylcarbazole-3-carboxaldehyde.

[0158] [Synthesis Example 15] (Synthesis of Compound (A-13)) The above compound (A-13) was obtained in the same manner as in Synthesis Example 2, except that 18.8 g of propargyl bromide was changed to 11.4 g of 9-phenanthrenecarbaldehyde.

[0159] Comparative Synthesis Example 1 (Synthesis of Compound (A'-1)) 95 mol parts of 2,3,5-tricarboxycyclopentylacetic dianhydride and 100 mol parts of 4,4'-diaminodiphenyl ether were dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a polyamic acid solution with a polymer concentration of 15% by mass. NMP was added to the obtained polyamic acid solution to dilute it to a polymer concentration of 10% by mass, after which a predetermined amount of pyridine and acetic anhydride were added and the mixture was reacted at 110°C for 4 hours. The resulting reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried under reduced pressure at 100°C to obtain an aromatic polyimide (hereinafter referred to as "compound (A'-1)"). The imidization rate of the obtained compound (A'-1) was 50%.

[0160] Comparative Synthesis Example 2 (Synthesis of Compound (A'-2)) A vessel equipped with a stirrer was charged with 28.3 g (0.14 mol) of phenyltrimethoxysilane, 95.6 g (0.70 mol) of methyltrimethoxysilane, 41.8 g (0.20 mol) of tetraethoxysilane, and 47.0 g of ion-exchanged water, and the mixture was heated to 60°C. After the solution temperature reached 60°C, a 4.4 mass% benzyl alcohol solution of oxalic acid was added, heated to 75°C, and maintained for 3 hours. The solution temperature was then raised to 40°C, and evaporation was performed while maintaining this temperature to remove the ion-exchanged water and the methanol and ethanol generated by the hydrolysis condensation. Next, 80 g of benzyl alcohol was added, and evaporation was performed again. After evaporation, further benzyl alcohol was added to adjust the solids concentration to 40 mass%. This resulted in the production of a polysiloxane (hereinafter referred to as "compound (A'-2)"). The resulting compound (A'-2) had a number average molecular weight (Mn) of 2,285 and a molecular weight distribution (Mw / Mn) of 2.1.

[0161] <Preparation of Layer-Forming Composition> The [A] compound, [B] solvent, [C] acid generator, and [D] crosslinkable compound used in the preparation of the layer-forming composition are shown below.

[0162] [[A] compound] A-1 to A-13: The above synthesized compounds (A-1) to (A-13) A'-1: The above synthesized compound (A'-1) (aromatic polyimide resin) A'-2: The above synthesized compound (A'-2) (polysiloxane)

[0163] [[B] Solvent] B-1: Propylene glycol monomethyl ether acetate B-2: Cyclohexanone

[0164] [[C] Acid generator] C-1: bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate (compound represented by the following formula (C-1))

[0165] [ka]

[0166] [[D]Crosslinkable compound] D-1: A compound represented by the following formula (D-1): (In formula (D-1), Me is a methyl group.)

[0167] [ka]

[0168] [Example 1-1] 10 parts by mass of (A-1) as the compound [A] was dissolved in 63 parts by mass of (B-1) and 27 parts by mass of (B-2) as the solvent [B]. The resulting solution was filtered through a membrane filter with a pore size of 0.1 μm to prepare a layer-forming composition (J-1).

[0169] [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) to (j-2) were prepared in the same manner as in Example 1-1, except that the types and amounts of each component were used as shown in Table 1. In Table 1, "-" indicates that the corresponding component was not used.

[0170] [Table 1]

[0171] <Preparation of Dispersion> The conductive material SWCNT and an anionic dispersant (sodium dodecylbenzenesulfonate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed in water at a mass ratio of 1:50 and dispersed using an ultrasonic homogenizer to prepare a dispersion with an SWCNT content of 500 ppm.

[0172] <Manufacturing of laminate> [Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-3] The substrate is a silicon wafer with SiN x A substrate on which a film was formed was prepared. 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 (baking) in an air atmosphere at the heating temperature (°C) and heating time (sec) shown in Table 2 below. Next, the dispersion prepared above was applied onto the first layer and dried to form a second layer having an average thickness of 10 nm. In this manner, each of the laminates of Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-3 was obtained. In Comparative Example 2-3, the dispersion was applied directly onto the substrate, i.e., without forming a first layer, to form a second layer.

[0173] <Evaluation> The resulting laminates were evaluated for the following items by the methods described below. The evaluation results are shown in Table 2.

[0174] <Sheet resistance> The surface resistance of the second layer of each laminate was measured using a four-terminal contact surface resistance meter ("Loresta GP" manufactured by Mitsubishi Chemical Analytech Co., Ltd.) Ten measurements were taken while slightly shifting the measurement position at the center of the laminate, and the average of the ten measurements was taken as the surface resistance. The surface resistance was measured at three stages: after the "manufacturing of laminate" described above, after treatment in the evaluation of "cleanability" described below, and after treatment in the evaluation of "chemical resistance" described below.

[0175] <Cleaning ability> To remove the dispersant from the second layer, the laminate was immersed in ion-exchanged water for 10 minutes, then in an alkaline solution for 10 minutes, and then washed with ion-exchanged water for 1 minute. The surface resistance of the second layer after this treatment was measured, and the state of the remaining second layer (cleanability) was evaluated. The laminate was rated as "cleanability: A" when the surface resistance after treatment decreased or increased by less than 50% compared to the surface resistance after production, "cleanability: B" when the surface resistance after treatment increased by 50% or more but less than 100%, and "cleanability: C" when the surface resistance after treatment increased by 100% or more or was unmeasurable.

[0176] <Chemical resistance> After the cleaning evaluation, the laminate was immersed in an acetone bath for 10 minutes and then washed with ion-exchanged water for 1 minute. The surface resistance of the second layer after this treatment was measured to determine the state of the remaining second layer (chemical resistance). When the surface resistance value after treatment was reduced or increased by less than 50% compared to the surface resistance value after production of the laminate, it was rated as "Chemical resistance: A." When the surface resistance value after treatment was increased by 50% or more but less than 100%, it was rated as "Chemical resistance: B." When the surface resistance value after treatment increased by 100% or more or was unmeasurable, it was rated as "Chemical resistance: C."

[0177] [Table 2]

[0178] As shown in Table 2, the laminates of each Example were confirmed to have good washability and chemical resistance, and good adhesion of the second layer (layer containing a conductive material). In the laminates of each Example, the adhesiveness of the conductive material in the second layer was good, so washing effectively removed the dispersant while leaving a sufficient amount of the conductive material remaining, resulting in a sufficiently high conductivity. In the laminates of each Example, the adhesiveness of the second layer was good, so a decrease in the conductivity of the second layer was suppressed even after immersion in an acetone bath. [Industrial Applicability]

[0179] The laminate of the present invention can be suitably used as a display element, a photoelectric element, a touch screen, a solar cell, a fuel cell, a secondary battery, a supercapacitor, an electromagnetic wave shielding layer, a noise shielding layer, and the like. [Explanation of symbols]

[0180] 10 Laminate 11 Circuit Board 12 First Layer 13 Second Layer

Claims

1. A substrate; a first layer containing a compound having a condensed polycyclic hydrocarbon structure; a second layer comprising a conductive material; in that order, The laminate, wherein the compound having a condensed polycyclic hydrocarbon structure is a compound represented by the following formula (2) or (3): 【Chemistry 1】 In the above formula (2), Z is a partial structure represented by the following formula (1): Ａ represents a group in which m hydrogen atoms have been removed from a substituted or unsubstituted arene having 6 to 20 ring members or a substituted or unsubstituted heteroarene having 5 to 20 ring members, where m is 3. Multiple Z's may be the same or different. 【Chemistry 2】 In the above formula (1), X is a divalent group represented by the following formula (i), (ii), (iii), or (iv). Y and Y' are each independently a monovalent organic group having 1 to 20 carbon atoms. * represents R in the above formula (2). Ａ The binding site is shown. n1 and n2 are each independently an integer of 0 to 2. n3 and n4 are each independently an integer of 0 to 8. n5 is 1. n6 is 0. When n3 is 2 or more, multiple Y's are the same or different. When n4 is 2 or more, multiple Y's are the same or different. However, n3+n5 is 8 or less, and n4+n6 is 8 or less. 【Transformation 3】 In the above formula (i), R １ and R ２ are each independently a hydroxy group, 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, or R １ and R ２ and represent a part of a ring structure having 3 to 20 ring members formed by combining with each other and the carbon atoms to which they are attached. In the above formula (ii), R ３ and R ４ are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 20 carbon atoms, or R ３ and R ４ and represent a part of a ring structure having 3 to 20 ring members formed by combining with each other and the carbon atoms to which they are attached. In the above formula (iii), R ５ is a hydrogen atom, a hydroxy group, or a monovalent organic group having 1 to 20 carbon atoms. In the above formula (iv), 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. 【Chemistry 4】 In the above formula (3), X has the same meaning as X in the above formula (1). １ , Y ２ and Y ３ are each independently defined as Y' in formula (1). p1, p2, and p3 are each independently defined as n2 in formula (1). p4, p5, and p6 are each independently defined as n4 in formula (1).

2. 2. The laminate according to claim 1, wherein the second layer has an average thickness of 100 nm or less.

3. 3. The laminate according to claim 1, wherein the conductive material is a carbon material.

4. 4. The laminate according to claim 3, wherein the carbon material is at least one selected from the group consisting of carbon nanotubes, carbon nanofibers, carbon black, graphene, fullerene, and graphite.

5. 5. The laminate according to claim 1, wherein R A in the formula (2) is a benzene-1,3,5-triyl group obtained by removing hydrogen atoms at the 1,3,5-positions from benzene, or a 1,3,5-triazine-2,4,6-triyl group obtained by removing hydrogen atoms at the 2,4,6-positions from 1,3,5-triazine.

6. In the formula (2), Y and Y′ in the formula (1) and R in the formulas (i) to (iv) １ ~R ６ The laminate according to any one of claims 1 to 5, wherein at least one of the groups is a crosslinkable group.

7. Y in the above formula (3) １ , Y ２ and Y ３ The laminate according to any one of claims 1 to 5, wherein at least one of the groups is a crosslinkable group.

8. 8. The laminate according to claim 1, wherein the compound having a condensed polycyclic hydrocarbon structure is represented by any one of the following formulas: 【Transformation 5】 【Transformation 6】 In the above formula, Y and Y' have the same meanings as Y and Y' in formula (1). p7, p8, and p9 each independently represent an integer of 0 to 3. p10, p11, and p12 each independently represent an integer of 0 to 4. When the sum of p7, p8, and p9 is 2 or greater, multiple Y's are the same or different. When the sum of p10, p11, and p12 is 2 or greater, multiple Y's are the same or different.

9. A composition for forming a first layer in the laminate according to any one of claims 1 to 8, comprising: A layer-forming composition containing the compound having the above condensed polycyclic hydrocarbon structure.

10. The layer-forming composition according to claim 9 , further comprising a crosslinkable compound other than the compound having the condensed polycyclic hydrocarbon structure.

11. A layer formed from the layer-forming composition according to claim 9 or 10.

12. a step of applying the layer-forming composition according to claim 9 or 10 to one surface of a substrate; a step of heating the coating film obtained by the coating; forming a second layer containing a conductive material on the surface of the first layer obtained by the heating; A method for manufacturing a laminate comprising:

13. An electronic device comprising the laminate according to any one of claims 1 to 8.

14. 14. The electronic device according to claim 13, which is a display device, a photoelectric device, a touch screen, a solar cell, a fuel cell, a secondary battery, a supercapacitor, an electromagnetic wave shielding layer, or a noise shielding layer.

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