WO2014091727A1 - 導電性高分子の積層体 - Google Patents

導電性高分子の積層体 Download PDF

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WO2014091727A1
WO2014091727A1 PCT/JP2013/007178 JP2013007178W WO2014091727A1 WO 2014091727 A1 WO2014091727 A1 WO 2014091727A1 JP 2013007178 W JP2013007178 W JP 2013007178W WO 2014091727 A1 WO2014091727 A1 WO 2014091727A1
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group
acid
layer
polymer
polyaniline
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PCT/JP2013/007178
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French (fr)
Japanese (ja)
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西村　剛
真吾 小野寺
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出光興産株式会社
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0216—Reduction of cross-talk, noise or electromagnetic interference
    • H05K1/0218—Reduction of cross-talk, noise or electromagnetic interference by printed shielding conductors, ground planes or power plane
    • H05K1/0224—Patterned shielding planes, ground planes or power planes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0326—Inorganic, non-metallic conductor, e.g. indium-tin oxide [ITO]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0329—Intrinsically conductive polymer [ICP]; Semiconductive polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/07—Electric details
    • H05K2201/0707—Shielding
    • H05K2201/0723—Shielding provided by an inner layer of PCB

Definitions

  • the present invention relates to a laminate having a conductive polymer layer and a method for producing the same.
  • Conductive polymers are used as electronic materials such as capacitors and antistatic films. When used as an electronic material, long-term stability in the air may be required. In a laminate including a base material layer and a general conductive polymer layer such as polyaniline, the conductive polymer layer has low atmospheric stability. Specifically, in the atmosphere, the conductivity decreases with time and the surface resistance increases. In contrast, Patent Document 1 discloses that atmospheric stability is imparted by adding naphthalenediol or the like. However, further atmospheric stability has been sought.
  • An object of the present invention is to provide a laminate of a conductive polymer having atmospheric stability.
  • the laminate according to 2, wherein the polyaniline of the polyaniline complex is an unsubstituted polyaniline. 4). 4. The laminate according to 2 or 3, wherein the polyaniline complex contains di-2-ethylhexylsulfosuccinate ion as a dopant. 5. 5. The laminate according to any one of 1 to 4, wherein the substrate has a thickness of 2 ⁇ m or more. 6). The laminate according to any one of 1 to 5, wherein the substrate is a polyethylene terephthalate (PET) film. 7). The laminate according to any one of 1 to 6, wherein the thickness of the second layer is 10 ⁇ m or less. 8).
  • PET polyethylene terephthalate
  • R is a hydrogen atom or a methyl group.
  • R ′ represents a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, a substituted or unsubstituted cyclic aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic Group hydrocarbon group.
  • n is the degree of polymerization.
  • a step of forming a first layer containing a conductive polymer by applying a coating solution obtained by dissolving a conductive polymer in a solvent to a substrate; and an acrylate polymer, a methacrylate polymer, or Apply a coating solution in which a polyester urethane resin having an ester bond and a urethane bond as a repeating unit in the main chain is dissolved in a solvent, and then an acrylate polymer, a methacrylate polymer, or an ester bond and urethane Forming a second layer containing a polyester urethane resin having a bond as a repeating unit.
  • ITO indium tin oxide
  • the laminate of the present invention has a base material, a layer containing a conductive polymer (first layer), an acrylate polymer, a methacrylate polymer, or an ester bond and a urethane bond in the main chain.
  • a layer (second layer) containing a polyester urethane resin as a unit is laminated in this order.
  • Base material is not particularly limited, and may be a metal, an inorganic material (ceramics, glass, or the like), or a resin. Moreover, the base material which covered the metal completely with resin, the composite material (For example, FRP, glass epoxy composite material) of an inorganic type material and resin, etc. may be sufficient.
  • the resin include polycarbonate, acrylic, nylon, polyimide, polyester, styrene, and phenol. Moreover, when heat resistance is required, syndiotactic polystyrene (SPS), polyimide (PI), polyethylene naphthalate (PEN), and the like can be given.
  • a polyethylene terephthalate (PET) film is preferred as the substrate.
  • the thickness of the base material is preferably 2 ⁇ m or more.
  • it is 10 ⁇ m or more, 20 ⁇ m or more, 50 ⁇ m or more.
  • an upper limit is not specifically limited, For example, it is 100 mm or less, 10 mm or less, and 1 mm or less.
  • the conductive polymer (polymer) included in the first layer is preferably a ⁇ -conjugated polymer composite in which a ⁇ -conjugated polymer is doped with a dopant.
  • a polyaniline composite in which a substituted or unsubstituted polyaniline is doped with a dopant a polypyrrole composite in which a substituted or unsubstituted polypyrrole is doped with a dopant, and a substituted or unsubstituted polythiophene with a dopant.
  • An example is a doped polythiophene complex.
  • a polyaniline composite in which substituted or unsubstituted polyaniline is doped with a dopant is preferable.
  • the weight average molecular weight (hereinafter referred to as molecular weight) of polyaniline is preferably 20,000 or more. If the molecular weight is less than 20,000, the strength and stretchability of the layer may be reduced.
  • the molecular weight is preferably 20,000 to 500,000, more preferably 20,000 to 300,000, and still more preferably 20,000 to 200,000.
  • the molecular weight is, for example, 50,000 to 200,000, 53,000 to 200,000.
  • the above weight average molecular weight is not the molecular weight of the polyaniline complex but the molecular weight of polyaniline.
  • the molecular weight distribution is preferably 1.5 or more and 10.0 or less. A smaller molecular weight distribution is preferable from the viewpoint of conductivity, but a wider molecular weight distribution may be preferable from the viewpoint of solubility in solvents and moldability.
  • the molecular weight and molecular weight distribution are measured in terms of polystyrene by gel permeation chromatography (GPC).
  • substituent of the substituted polyaniline examples include linear or branched hydrocarbon groups such as methyl group, ethyl group, hexyl group and octyl group; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; Halogenated hydrocarbons such as a fluoromethyl group (—CF 3 group) are exemplified.
  • the polyaniline is preferably unsubstituted polyaniline from the viewpoints of versatility and economy.
  • the substituted or unsubstituted polyaniline is preferably a polyaniline obtained by polymerization in the presence of an acid containing no chlorine atom.
  • the acid containing no chlorine atom is, for example, an acid composed of atoms belonging to Group 1 to Group 16 and Group 18. Specific examples include phosphoric acid.
  • Examples of the polyaniline obtained by polymerization in the presence of an acid not containing a chlorine atom include polyaniline obtained by polymerization in the presence of phosphoric acid.
  • the polyaniline obtained in the presence of an acid containing no chlorine atom can lower the chlorine content of the polyaniline complex.
  • the chlorine content of the polyaniline complex is preferably 0.6% by weight or less. More preferably, it is 0.1 weight% or less, More preferably, it is 0.04 weight% or less, Most preferably, it is 0.0001 weight% or less.
  • the chlorine content of the polyaniline complex is measured by combustion-ion chromatography.
  • Examples of the dopant of the polyaniline complex include Bronsted acid ions generated from Bronsted acid or Bronsted acid salts, preferably organic acid ions generated from organic acids or salts of organic acids, and more preferably the following formula: It is an organic acid ion generated from the compound (proton donor) represented by (I).
  • the dopant when expressed as a specific acid, and when the dopant is expressed as a specific salt, the specific acid ions generated from the specific acid or the specific salt are both described above.
  • the doped ⁇ -conjugated polymer shall be doped.
  • M in the formula (I) is a hydrogen atom, an organic radical or an inorganic radical.
  • the organic free radical include a pyridinium group, an imidazolium group, and an anilinium group.
  • examples of the inorganic free radical include lithium, sodium, potassium, cesium, ammonium, calcium, magnesium, and iron.
  • X in the formula (I) is an anion group, for example, —SO 3 — group, —PO 3 2- group, —PO 4 (OH) 2 — group, —OPO 3 2- group, —OPO 2 (OH) — Group, —COO 2 — group, and —SO 3 — group is preferable.
  • a in formula (I) is a substituted or unsubstituted hydrocarbon group.
  • the hydrocarbon group is a chain or cyclic saturated aliphatic hydrocarbon group, a chain or cyclic unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group.
  • Examples of the chain saturated aliphatic hydrocarbon group include a linear or branched alkyl group.
  • Examples of the cyclic saturated aliphatic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • the cyclic saturated aliphatic hydrocarbon group may be a condensation of a plurality of cyclic saturated aliphatic hydrocarbon groups. Examples thereof include a norbornyl group, an adamantyl group, and a condensed adamantyl group.
  • Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group.
  • Examples of the chain unsaturated aliphatic hydrocarbon include a linear or branched alkenyl group.
  • A is a substituted hydrocarbon group
  • the substituent is alkyl group, cycloalkyl group, vinyl group, allyl group, aryl group, alkoxy group, halogen group, hydroxy group, amino group, imino group, nitro group.
  • R in formula (I) is bonded to A, and each independently represents —H, —R 1 , —OR 1 , —COR 1 , —COOR 1 , — (C ⁇ O) — (COR 1 ).
  • hydrocarbon group for R 1 examples include a methyl group, an ethyl group, a linear or branched butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a pentadecyl group, and an eicosanyl group. Is mentioned.
  • the substituent of the hydrocarbon group is an alkyl group, a cycloalkyl group, a vinyl group, an allyl group, an aryl group, an alkoxy group, a halogen group, a hydroxy group, an amino group, an imino group, a nitro group, or an ester group.
  • the hydrocarbon group for R 3 is the same as R 1 .
  • Examples of the alkylene group for R 2 include a methylene group, an ethylene group, and a propylene group.
  • N in the formula (I) is an integer of 1 or more, and m in the formula (I) is a valence of M / a valence of X.
  • dialkylbenzenesulfonic acid dialkylnaphthalenesulfonic acid, or a compound containing two or more ester bonds is preferable.
  • the compound containing two or more ester bonds is more preferably a sulfophthalic acid ester or a compound represented by the following formula (II).
  • M and X are the same as those in formula (I).
  • X is preferably a —SO 3 — group.
  • R 4 , R 5 and R 6 in the formula (II) are each independently a hydrogen atom, a hydrocarbon group or an R 9 3 Si— group (where R 9 is a hydrocarbon group, and three R 9 are They may be the same or different).
  • Examples of the hydrocarbon group when R 4 , R 5 and R 6 are hydrocarbon groups include linear or branched alkyl groups having 1 to 24 carbon atoms, aryl groups containing aromatic rings, and alkylaryl groups. It is done.
  • the hydrocarbon group for R 9 is the same as in the case of R 4 , R 5 and R 6 .
  • R 7 and R 8 in the formula (II) are each independently a hydrocarbon group or — (R 10 O) q —R 11 group [wherein R 10 is a hydrocarbon group or a silylene group, and R 11 is A hydrogen atom, a hydrocarbon group or R 12 3 Si— (wherein R 12 is a hydrocarbon group, and three R 12 may be the same or different), and q is an integer of 1 or more] .
  • hydrocarbon group when R 7 and R 8 are hydrocarbon groups include linear or branched alkyl groups having 1 to 24 carbon atoms, preferably 4 or more carbon atoms, aryl groups containing aromatic rings, and alkylaryl
  • specific examples of the hydrocarbon group when R 7 and R 8 are hydrocarbon groups include, for example, a linear or branched butyl group, pentyl group, hexyl group, octyl group, decyl group Etc.
  • Examples of the hydrocarbon group when R 10 in R 7 and R 8 is a hydrocarbon group include a linear or branched alkylene group having 1 to 24 carbon atoms, an arylene group containing an aromatic ring, an alkylarylene group, An arylalkylene group.
  • R 7 and R 8 when R 11 and R 12 are hydrocarbon groups, the hydrocarbon group is the same as in R 4 , R 5 and R 6 , and q is 1 to 10 Preferably there is.
  • the compound represented by the above formula (II) is more preferably a sulfosuccinic acid derivative represented by the following formula (III).
  • M is the same as in formula (I).
  • M ′ is the valence of M.
  • R 13 and R 14 in the formula (III) are each independently a hydrocarbon group or — (R 15 O) r —R 16 group [wherein R 15 is independently a hydrocarbon group or a silylene group, R 16 is a hydrogen atom, a hydrocarbon group or an R 17 3 Si— group (wherein R 17 is independently a hydrocarbon group, and r is an integer of 1 or more).
  • the hydrocarbon group when R 13 and R 14 are hydrocarbon groups is the same as R 7 and R 8 .
  • the hydrocarbon group when R 15 is a hydrocarbon group is the same as R 10 described above.
  • the hydrocarbon group in the case where R 16 and R 17 are hydrocarbon groups is the same as R 4 , R 5 and R 6 described above.
  • r is preferably from 1 to 10.
  • R 13 and R 14 are a — (R 15 O) r —R 16 group are the same as those for — (R 10 O) q —R 11 in R 7 and R 8 .
  • the hydrocarbon group for R 13 and R 14 is the same as R 7 and R 8 and is preferably a butyl group, a hexyl group, a 2-ethylhexyl group, or a decyl group.
  • the conductivity of the polyaniline complex and the solubility in a solvent can be controlled by changing the structure of the dopant (Japanese Patent No. 338466).
  • an optimum dopant can be selected according to required characteristics for each application.
  • the compound represented by the formula (I) is preferably di-2-ethylhexylsulfosuccinic acid or sodium di-2-ethylhexylsulfosuccinate.
  • the dopant of the present invention is preferably di-2-ethylhexyl sulfosuccinate ion.
  • the dopant of the polyaniline complex is doped to the substituted or unsubstituted polyaniline by ultraviolet / visible / near-infrared spectroscopy or X-ray photoelectron spectroscopy. As long as it has sufficient acidity to generate odor, it can be used without any restriction on the chemical structure.
  • the dopant doping ratio with respect to polyaniline is preferably 0.35 or more and 0.65 or less, more preferably 0.42 or more and 0.60 or less, and further preferably 0.43 or more and 0.57 or less. Preferably they are 0.44 or more and 0.55 or less.
  • the doping rate is defined by (number of moles of dopant doped in polyaniline) / (number of moles of monomer unit of polyaniline).
  • a doping ratio of a polyaniline complex containing unsubstituted polyaniline and a dopant of 0.5 means that one dopant is doped with respect to two monomer unit molecules of polyaniline.
  • the doping rate can be calculated if the number of moles of the dopant and the polyaniline monomer unit in the polyaniline complex can be measured.
  • the dopant is an organic sulfonic acid
  • the number of moles of sulfur atoms derived from the dopant and the number of moles of nitrogen atoms derived from the monomer unit of polyaniline are quantified by organic elemental analysis, and the ratio of these values is calculated.
  • the doping rate can be calculated.
  • the calculation method of the dope rate is not limited to the means.
  • the polyaniline complex preferably contains unsubstituted polyaniline and a sulfonate ion as a dopant, and satisfies the following formula (5). 0.42 ⁇ S 5 / N 5 ⁇ 0.60 (5) (In the formula, S 5 is the total number of moles of sulfur atoms contained in the polyaniline complex, and N 5 is the total number of moles of nitrogen atoms contained in the polyaniline complex. The number of moles of nitrogen and sulfur atoms is a value measured by, for example, an organic elemental analysis method. )
  • the polyaniline complex may or may not further contain phosphorus.
  • the phosphorus content is, for example, not less than 10 ppm by weight and not more than 5000 ppm by weight.
  • phosphorus content is 2000 weight ppm or less, 500 weight ppm or less, and 250 weight ppm or less, for example.
  • the phosphorus content can be measured by ICP emission spectrometry.
  • it is preferable that a polyaniline composite does not contain a Group 12 element (for example, zinc) as an impurity.
  • the polyaniline complex can be produced by a known method (for example, polymerization of aniline in the presence of hydrochloric acid), but is preferably substituted or substituted in a solution containing a proton donor and phosphoric acid and having two liquid phases. It is produced by chemical oxidative polymerization of unsubstituted aniline.
  • the “solution having two liquid phases” means a state in which two liquid phases that are incompatible with each other exist in the solution. For example, it means a state in which a “high polarity solvent phase” and a “low polarity solvent phase” exist in the solution.
  • a solution having two liquid phases includes a state in which one liquid phase is a continuous phase and the other liquid phase is a dispersed phase. For example, a state where the “high polarity solvent phase” is a continuous phase and the “low polarity solvent phase” is a dispersed phase, and the “low polarity solvent phase” is a continuous phase and the “high polarity solvent phase” is a dispersed phase.
  • a highly polar solvent used for the manufacturing method of the said polyaniline complex water is preferable and aromatic hydrocarbons, such as toluene and xylene, are preferable as a low polarity solvent, for example.
  • the proton donor is preferably a compound represented by the above formula (I).
  • the amount of the proton donor used is preferably 0.1 to 0.5 mol, more preferably 0.3 to 0.45 mol, and still more preferably 0.35 to 0.005 mol per mol of aniline monomer. 4 mol.
  • the amount of the proton donor used is larger than the above range, for example, there is a possibility that the “high-polar solvent phase” and the “low-polar solvent phase” cannot be separated after completion of the polymerization.
  • the concentration of phosphoric acid used is 0.3 to 6 mol / L, more preferably 1 to 4 mol / L, still more preferably 1 to 2 mol / L with respect to the highly polar solvent.
  • Oxidizing agents used for chemical oxidative polymerization include peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide; ammonium dichromate, ammonium perchlorate, potassium iron (III) sulfate, trichloride Iron (III), manganese dioxide, iodic acid, potassium permanganate, iron paratoluenesulfonate, etc. can be used, and persulfates such as ammonium persulfate are preferred. These oxidizing agents may be used alone or in combination of two or more.
  • the amount of the oxidizing agent used is preferably 0.05 to 1.8 mol, more preferably 0.8 to 1.6 mol, and still more preferably 1.2 to 1.4 mol with respect to 1 mol of the aniline monomer. It is. A sufficient degree of polymerization can be obtained by setting the amount of the oxidizing agent used within the above range. Further, since aniline is sufficiently polymerized, it is easy to recover the liquid separation, and there is no possibility that the solubility of the polymer is lowered.
  • the polymerization temperature is usually ⁇ 5 to 60 ° C., preferably ⁇ 5 to 40 ° C. The polymerization temperature may be changed during the polymerization reaction. Side reactions can be avoided when the polymerization temperature is within this range.
  • the polyaniline complex can be produced by the following method.
  • a solution in which a proton donor and an emulsifier are dissolved in toluene is placed in a separable flask placed in a stream of inert atmosphere such as nitrogen, and a substituted or unsubstituted aniline is added to the solution. Thereafter, phosphoric acid containing no chlorine as an impurity is added to the solution, and the solution temperature is cooled.
  • a 1st layer can be manufactured using the coating liquid containing a polyaniline complex.
  • the coating liquid preferably contains a phenolic compound.
  • the phenolic compound is not particularly limited as long as it is a compound having a phenolic hydroxyl group.
  • the compound having a phenolic hydroxyl group is a polymer compound composed of a compound having one phenolic hydroxyl group, a compound having a plurality of phenolic hydroxyl groups, and a repeating unit having one or more phenolic hydroxyl groups.
  • the compound having one phenolic hydroxyl group is preferably a compound represented by the following formulas (A), (B) and (C). (Wherein n is an integer of 1 to 5, preferably 1 to 3, more preferably 1.
  • R is an alkyl group, alkenyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. )
  • the —OR substitution position is preferably a meta position or a para position with respect to the phenolic hydroxyl group.
  • phenolic compound represented by the formula (A) examples include methoxyphenol (for example, 4-methoxyphenol), ethoxyphenol, propoxyphenol, isopropoxyphenol, butyloxyphenol, isobutyloxyphenol, and tertiary butyloxyphenol. Can be mentioned.
  • n is an integer of 0 to 7, preferably 0 to 3, more preferably 1.
  • R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkylthio group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group.
  • Specific examples of the phenolic compound represented by the formula (B) include hydroxynaphthalene.
  • R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkylthio group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group.
  • Specific examples of the compound represented by the formula (C) include o-, m- or p-cresol, o-, m- or p-ethylphenol, o-, m- or p-propylphenol (eg, 4-isopropyl Phenol), o-, m- or p-butylphenol, o-, m- or p-pentylphenol (for example, 4-tert-pentylphenol).
  • examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tertiary butyl.
  • examples of the alkenyl group include groups having an unsaturated bond in the molecule of the alkyl group described above.
  • examples of the cycloalkyl group include cyclopentane and cyclohexane.
  • examples of the aryl group include phenyl and naphthyl.
  • examples of the alkylaryl group and the arylalkyl group include groups obtained by combining the above-described alkyl group and aryl group.
  • Examples of the compound having one phenolic hydroxyl group are shown.
  • Specific examples of the substituted phenols include phenol, o-, m- or p-chlorophenol, salicylic acid, and hydroxybenzoic acid.
  • Specific examples of the compound having a plurality of phenolic hydroxyl groups include catechol, resorcinol, and a compound represented by the following formula (D).
  • R is a hydrocarbon group, a hetero atom-containing hydrocarbon group, a halogen atom, a carboxylic acid group, an amino group, an SH group, a sulfonic acid group, or a hydroxyl group.
  • N may be an integer of 0 to 6)
  • the phenolic compound represented by the formula (D) preferably has two or more hydroxyl groups that are not adjacent to each other.
  • Specific examples of the phenolic compound represented by the formula (D) include 1,6 naphthalenediol, 2,6 naphthalenediol, and 2,7 naphthalenediol.
  • polymer compound composed of a repeating unit having one or more phenolic hydroxyl groups include phenol resin, polyphenol, and poly (hydroxystyrene).
  • the content of the phenolic compound in the coating solution containing the polyaniline complex and the phenolic compound is preferably such that the molar concentration of the phenolic compound is 0.01 [mmol / g] or more and 100 [g] relative to 1 g of the polyaniline complex.
  • mol / g] or less more preferably 0.05 [mmol / g] or more and 1 [mol / g] or less, further preferably 0.1 [mmol / g] or more and 500 [mmol / g] or less, particularly preferably 0. .2 [mmol / g] or more and 80 [mmol / g] or less.
  • the conductive polymer is polypyrrole
  • the molecular weight of polypyrrole, the molecular weight distribution, and the substituent of the substituted polypyrrole are the same as those of the polyaniline.
  • Typical examples include polystyrene sulfonic acid, paratoluene sulfonic acid, methane sulfonic acid, trifluoromethane sulfonic acid, anthraquinone sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid, sulfosalicylic acid, dodecyl benzene sulfonic acid, allyl sulfonic acid.
  • Sulfonic acids such as perchloric acid, halogens such as chlorine and bromine, Lewis acids, proton acids and the like. These may be in the acid form or in the salt form.
  • tetrabutylammonium perchlorate Preferred from the viewpoint of solubility in monomers, tetrabutylammonium perchlorate, tetraethylammonium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluorosulfonimide, dodecylbenzene Examples thereof include sulfonic acid and p-toluenesulfonic acid.
  • the amount of the dopant used is preferably an amount of 0.01 to 0.3 molecules of dopant per pyrrole polymer unit unit.
  • the amount is 0.01 molecule or less, the amount of dopant necessary to form a sufficient conductive path is insufficient, and it is difficult to obtain high conductivity.
  • addition of 0.3 molecule or more does not improve the doping rate, so the addition of 0.3 molecule or more dopant is not economically preferable.
  • the pyrrole polymer unit unit refers to a repeating portion corresponding to one molecule of a pyrrole polymer monomer obtained by polymerizing a pyrrole monomer.
  • the conductive polymer is polythiophene
  • the molecular weight of the polythiophene, the molecular weight distribution, and the substituent of the substituted polythiophene are the same as those of the polyaniline.
  • the substituted polythiophene polyethylenedioxythiophene (PEDOT) is preferable.
  • Examples of the dopant of the polythiophene complex include organic acid ions and inorganic acid ions of an anionic surfactant.
  • Examples of the organic acid ions of the anionic surfactant include sulfonic acid ions and esterified sulfate ions.
  • Examples of inorganic acid ions include sulfate ions, halogen ions, nitrate ions, perchlorate ions, hexacyanoferrate ions, phosphate ions, and phosphomolybdate ions.
  • the first layer is usually formed using a coating solution in which a conductive polymer is dissolved in a solvent.
  • the solvent used in preparing the coating solution may be an organic solvent or an inorganic solvent such as water, or may be a single type or a mixed solvent of two or more types.
  • An organic solvent is preferable.
  • the organic solvent may be a water-soluble organic solvent or an organic solvent that is substantially immiscible with water (water-immiscible organic solvent).
  • the water-soluble organic solvent may be a protic polar solvent or an aprotic polar solvent, for example, alcohols such as isopropanol, 1-butanol, 2-butanol, 2-pentanol and benzyl alcohol; ketones such as acetone; Ethers such as tetrahydrofuran and dioxane; and aprotic polar solvents such as N-methylpyrrolidone.
  • alcohols such as isopropanol, 1-butanol, 2-butanol, 2-pentanol and benzyl alcohol
  • ketones such as acetone
  • Ethers such as tetrahydrofuran and dioxane
  • aprotic polar solvents such as N-methylpyrrolidone.
  • water-immiscible organic solvent examples include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; halogen-containing solvents such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, and tetrachloroethane; ethyl acetate, Examples thereof include ester solvents such as isobutyl acetate and n-butyl acetate, ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone and cyclohexanone, and ether solvents such as cyclopentyl methyl ether.
  • hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin
  • halogen-containing solvents such as methylene chloride, chloroform
  • toluene, xylene, methyl isobutyl ketone (MIBK), chloroform, trichloroethane, and ethyl acetate are preferable in that the solubility of the doped polyaniline is excellent.
  • a mixed organic solvent in which a water-immiscible organic solvent and a water-soluble organic solvent are mixed at a ratio of 99 to 50: 1 to 50 (mass ratio) can generate gels during storage. This is preferable because it can be prevented and stored for a long time.
  • a low-polar organic solvent can be used, and the low-polar organic solvent is preferably toluene or chloroform.
  • a highly polar organic solvent can be used as the water-soluble organic solvent of the mixed organic solvent.
  • methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran or Diethyl ether is preferred.
  • the proportion of the composite of the conductive polymer in the solvent depends on the type of the solvent, but is usually 900 g / kg or less, preferably 0.01 g / kg or more and 300 g / kg or less, more preferably 10 g / kg.
  • the range is 300 g / kg or less, more preferably 30 g / kg or more and 300 g / kg or less. If the content of the composite is too high, the solution state cannot be maintained, handling during formation of the layer becomes difficult, the uniformity of the layer is impaired, and as a result, the electrical properties, mechanical strength, and transparency are reduced. May occur. On the other hand, if the content of the composite is too small, only a very thin film can be produced when the film is formed by the method described later, which may make it difficult to produce a uniform conductive film.
  • the coating liquid containing a polyaniline complex preferably contains a heat resistance stabilizer.
  • the heat resistance stabilizer is an acidic substance or a salt of an acidic substance, and the acidic substance may be either an organic acid (an acid of an organic compound) or an inorganic acid (an acid of an inorganic compound).
  • the conductive polymer layer may contain a plurality of heat stabilizers.
  • the acidic substance is preferably a compound different from the proton donor of the polyaniline complex
  • the conductive polymer layer contains only a salt of the acidic substance.
  • the salt of the acidic substance is a compound, unlike the proton donor of the polyaniline complex.
  • the conductive polymer layer contains both an acidic substance and an acidic substance salt as a heat-resistant stabilizer
  • at least one of the acidic substance and the acidic substance salt is preferably a compound different from the proton donor. It is.
  • the acidic substance is preferably different from the phenolic compound.
  • the salt of the acidic substance is preferably different from the phenolic compound.
  • the conductive polymer layer contains both an acidic substance and an acidic substance salt as a heat stabilizer, preferably at least one of the acidic substance and the acidic substance salt is different from the phenolic compound. .
  • the acidic substance that is a heat-resistant stabilizer is preferably an organic acid, more preferably an organic acid having one or more sulfonic acid groups, carboxy groups, phosphoric acid groups, or phosphonic acid groups, and more preferably sulfonic acid.
  • the organic acid having one or more sulfonic acid groups is preferably a cyclic, linear or branched alkylsulfonic acid, substituted or unsubstituted aromatic sulfonic acid, or polysulfonic acid having one or more sulfonic acid groups.
  • alkyl sulfonic acid include methane sulfonic acid, ethane sulfonic acid, and di-2-ethylhexyl sulfosuccinic acid.
  • the alkyl group here is preferably a linear or branched alkyl group having 1 to 18 carbon atoms.
  • aromatic sulfonic acid examples include a sulfonic acid having a benzene ring, a sulfonic acid having a naphthalene skeleton, a sulfonic acid having an anthracene skeleton, a substituted or unsubstituted benzenesulfonic acid, a substituted or unsubstituted naphthalenesulfonic acid, and a substituted
  • unsubstituted anthracene sulfonic acid may be mentioned, and naphthalene sulfonic acid is preferable.
  • naphthalene sulfonic acid dodecylbenzene sulfonic acid, and anthraquinone sulfonic acid.
  • the substituent is, for example, a substituent selected from the group consisting of an alkyl group, an alkoxy group, a hydroxy group, a nitro group, a carboxy group, and an acyl group, and one or more substituents may be substituted.
  • the polysulfonic acid is a sulfonic acid in which a plurality of sulfonic acid groups are substituted on the main chain or side chain of the polymer chain. For example, polystyrene sulfonic acid is mentioned.
  • the organic acid having one or more carboxy groups is preferably a cyclic, linear or branched alkyl carboxylic acid, substituted or unsubstituted aromatic carboxylic acid, or polycarboxylic acid having one or more carboxy groups.
  • alkyl carboxylic acid include undecylenic acid, cyclohexane carboxylic acid, and 2-ethylhexanoic acid.
  • the alkyl group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms.
  • the substituted or unsubstituted aromatic carboxylic acid include substituted or unsubstituted benzene carboxylic acid and naphthalene carboxylic acid.
  • the substituent is, for example, a substituent selected from the group consisting of a sulfonic acid group, an alkyl group, an alkoxy group, a hydroxy group, a nitro group, and an acyl group, and one or more substituents may be substituted.
  • substituents include salicylic acid, benzoic acid, naphthoic acid, and trimesic acid.
  • the organic acid having at least one phosphoric acid group or phosphonic acid group is preferably a cyclic, linear or branched alkylphosphoric acid or alkylphosphonic acid having at least one phosphoric acid group or phosphonic acid group; substituted or unsubstituted aromatic An aromatic phosphoric acid or an aromatic phosphonic acid; a polyphosphoric acid or a polyphosphonic acid.
  • Examples of the alkyl phosphoric acid or alkylphosphonic acid include dodecyl phosphoric acid and bis (2-ethylhexyl) hydrogen phosphate.
  • the alkyl group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms.
  • aromatic phosphoric acid and aromatic phosphonic acid examples include substituted or unsubstituted benzene sulfonic acid or phosphonic acid, and naphthalene sulfonic acid or phosphonic acid.
  • the substituent is, for example, a substituent selected from the group consisting of an alkyl group, an alkoxy group, a hydroxy group, a nitro group, a carboxy group, and an acyl group, and one or more substituents may be substituted.
  • An example is phenylphosphonic acid.
  • the salt of the acidic substance contained in the coating liquid examples include the salt of the acidic substance.
  • the coating solution may contain two or more acidic substances and / or salts of acidic substances that are heat-resistant stabilizers. Specifically, the coating liquid may contain a plurality of different acidic substances and / or salts of different acidic substances.
  • the acidic substance is preferably the same or different sulfonic acid as the proton donor.
  • the acidic substance salt is preferably the same or different sulfonic acid salt as the proton donor of the polyaniline complex.
  • the coating liquid contains an acidic substance and a salt of the acidic substance as a heat stabilizer, at least one of the acidic substance and the salt of the acidic substance is a sulfonic acid or a sulfonic acid salt that is the same as or different from the proton donor. Preferably there is.
  • the coating solution contains only sulfonic acid as the heat stabilizer, it is preferable to satisfy the formula (12), and preferably when the coating solution contains only a sulfonic acid salt as the heat stabilizer. Satisfies the formula (13).
  • the formula (14) is preferably satisfied.
  • S 2 is the total number of moles of sulfur atoms of all acidic substances contained in the coating solution
  • N 2 is the total number of nitrogen atoms of all polyaniline complexes contained in the coating solution. This means the total number of moles
  • S 3 is the total number of moles of sulfur atoms in the salts of all acidic substances contained in the coating solution
  • N 3 is all the polyaniline contained in the coating solution.
  • N 4 is coated (It means the total number of moles of nitrogen atoms of all polyaniline complexes contained in the liquid.)
  • the coating liquid of the present invention satisfies any of the above formulas (12), (13), or (14), the coating liquid preferably further satisfies the following formula (11). 0.36 ⁇ S 1 / N 1 ⁇ 1.15 (11) (Here, S 1 is the number of moles of sulfur atoms contained in the coating solution, and N 1 is the number of moles of nitrogen atoms contained in the coating solution.)
  • the acidity (pKa) of the said acidic substance is 5.0 or less.
  • the lower limit of the acidity is not particularly limited.
  • the acidity of the salt of the acidic substance is preferably 5.0 or less.
  • the minimum of acidity it is the same as that of the said acidic substance.
  • the acidic substance When the coating liquid contains both an acidic substance and an acidic substance salt, the acidic substance has an acidity of 5.0 or lower and an acidic substance salt of 5.0 or lower and satisfies at least one of the acidic substance salts Is preferred.
  • the lower limit of acidity is the same as described above.
  • Acidity is defined by computational chemistry methods. A. Journal of Physical Chemistry 1995, Vol. 99, p. 50, which calculates the charge density on the surface of a molecule by quantum chemical calculation developed by Klamt et al. The method described in 2224 is used. Specifically, using “TURBOMOLE Version 6.1” (manufactured by COSMO logic), the structure is optimized using TZVP as a basis function, and the COSMO-RS method calculation is performed using this structure using “COSMO therm version C2”. .1 Release 01.10 "(manufactured by COSMO logic).
  • the pKa is calculated by inputting the conditions of 25 ° C. in an aqueous solvent, the chemical formula of the molecule, and the chemical formula of the deprotonated molecule in “COSMO thermion C2.1 Release 01.10”. be able to.
  • the content of the heat resistance stabilizer is preferably 1 to 1000 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polyaniline complex.
  • the coating liquid may further contain additives such as other resins, inorganic materials, curing agents, plasticizers, and organic conductive materials.
  • additives such as other resins, inorganic materials, curing agents, plasticizers, and organic conductive materials.
  • Other resin is added as a binder base material, a plasticizer, and a matrix base material, for example.
  • resins include, for example, polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, polystyrene, polyester, polyamide, polyacetal, polyethylene terephthalate, polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid ester, Examples thereof include polymethacrylic acid ester and polyvinyl alcohol.
  • thermosetting resin such as an epoxy resin, a urethane resin, or a phenol resin, or a precursor capable of forming these thermosetting resins may be included.
  • the inorganic material is added, for example, for the purpose of improving strength, surface hardness, dimensional stability and other mechanical properties, or improving electrical properties such as conductivity.
  • Specific examples of the inorganic material include, for example, silica (silicon dioxide), titania (titanium dioxide), alumina (aluminum oxide), Sn-containing In 2 O 3 (ITO), Zn-containing In 2 O 3 , and In 2 O 3 .
  • Examples include co-substituted compounds (oxides in which tetravalent elements and divalent elements are substituted with trivalent In), Sb-containing SnO 2 (ATO), ZnO, Al-containing ZnO (AZO), and Ga-containing ZnO (GZO). .
  • the curing agent is added for the purpose of, for example, improving strength, surface hardness, dimensional stability, and other mechanical properties.
  • Specific examples of the curing agent include a thermosetting agent such as a phenol resin, and a photocuring agent using an acrylate monomer and a photopolymerization initiator.
  • the plasticizer is added for the purpose of improving mechanical properties such as tensile strength and bending strength.
  • specific examples of the plasticizer include phthalic acid esters and phosphoric acid esters.
  • examples of the organic conductive material include carbon materials such as carbon black and carbon nanotubes, and conductive polymers other than the polyaniline obtained in the present invention.
  • the coating liquid is, for example, 90% by weight or more, 95% by weight or more, 98% by weight or more, and 100% by weight of the conductive polymer, optionally phenolic compound, solvent, heat stabilizer, other resin, inorganic It may be an additive such as a material, a curing agent, a plasticizer, or an organic conductive material.
  • a 1st layer can be formed by apply
  • the coating can be performed by a known method such as spin coating or bar coater.
  • the first layer is usually formed by applying a coating solution and then drying.
  • the thickness of the first layer is preferably 0.3 to 5 ⁇ m.
  • the second layer includes an acrylic ester polymer, a methacrylic ester polymer, or a polyester urethane resin having an ester bond and a urethane bond as a repeating unit in the main chain.
  • acrylic ester polymer and the methacrylic ester polymer include polymers represented by the following formula (A1).
  • R is a hydrogen atom or a methyl group.
  • R ′ represents a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, a substituted or unsubstituted cyclic aliphatic hydrocarbon group, or a substituted or unsubstituted aromatic Group hydrocarbon group.
  • an alkyl group having 1 to 40 carbon atoms is preferable. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Octyl, decyl, dodecyl, stearyl, methoxyethyl, ethoxyethyl and phenoxyethyl groups are preferred.
  • the branched aliphatic hydrocarbon group preferably has 3 to 40 carbon atoms, and specifically, an isopropyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, or a 3,7-dimethyloctyl group is preferable.
  • the cycloaliphatic hydrocarbon group preferably has 3 to 40 carbon atoms, and specifically, a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group is preferable.
  • the aromatic hydrocarbon group preferably has 6 to 40 carbon atoms, and specifically, a phenyl group, a naphthyl group, a pyrenyl group, a phenanthryl group, or a biphenyl group is preferable.
  • each group is not particularly limited as long as the effect of the present invention can be obtained.
  • examples thereof include an alkyl group having 1 to 4 carbon atoms such as a methyl group, a cyclohexyl group, and an alkoxy group.
  • n is the degree of polymerization, for example, 100 to 100,000.
  • Specific examples of the acrylate polymer include methyl acrylate and methyl methacrylate.
  • M2000 manufactured by Soken Chemical Co., Ltd.
  • Almatex L1044 manufactured by Mitsui Chemicals
  • Aron S-1017 manufactured by Toa Gosei Chemical Co., Ltd.
  • polyester urethane resin having an ester bond and a urethane bond as a repeating unit in the main chain a resin having two or more hydroxyl groups in one molecule obtained by esterifying a polybasic acid and a polyhydric alcohol is used.
  • the polybasic acid that is a production starting material include polyvalent carboxylic acids having two or more carboxyl groups in one molecule.
  • polyvalent carboxylic acid examples include aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid, phthalic acid, isophthalic acid, Aromatic polybasic acids such as terephthalic acid, trimellitic acid and pyromellitic acid, and aliphatic polybasic acids such as butanetricarboxylic acid, tricarbaryl acid and citric acid can be mentioned.
  • aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid
  • phthalic acid isophthalic acid
  • Aromatic polybasic acids such as terephthalic acid, trimellitic acid and pyromellitic acid
  • aliphatic dibasic acid may be used as the polybasic acid, but the main component is an aliphatic dibasic acid, and a small percentage of the aromatic polybasic acid or aliphatic polybasic acid is added thereto. What was mix
  • blended may be used.
  • these dibasic acids or polybasic acids may be used individually by 1 type, and 2 or more types may be used together.
  • polyhydric alcohol a compound having two or more hydroxyl groups in one molecule such as a dihydric alcohol or a trihydric or higher polyhydric alcohol is used.
  • divalent alcohol include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 2,2-dimethyl-1,3-propane.
  • Diol 2,2-diethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, etc.
  • polyhydric alcohols include aliphatic glycol, glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol. Etc. The. In the present invention, only a dihydric alcohol may be used as the polyhydric alcohol, or a dihydric alcohol such as an aliphatic glycol is used as a main component, and a small proportion of the polyhydric alcohol is used. It is preferable that the main component is aliphatic glycol. These divalent alcohols or polyhydric alcohols may be used alone or in combination of two or more.
  • polyester polyol compound obtained by a ring-opening reaction of caprolactone may be used as the polyester polyol.
  • the polyisocyanate compound reacted with the polyester polyol is a compound having two or more free isocyanate groups in one molecule.
  • hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and trimethylene Aliphatic diisocyanates such as diisocyanates; alicyclic diisocyanates such as isophorone diisocyanate, methylenebis (cyclohexyl isocyanate) and cyclohexane diisocyanate; aromatic diisocyanates such as xylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate and biphenylene diisocyanate; . These may be used individually by 1 type and 2 or more types may be used together.
  • reaction conditions for usual urethanization reaction can be widely applied.
  • the polyester urethane resin having an ester bond and a urethane bond as a repeating unit in the main chain includes a copolymer having a structural unit represented by the following formulas (B1) and (B2).
  • R 1 to R 3 each represents a divalent group.
  • R 1 is a divalent group resulting from a dicarboxylic acid compound or the like that is a raw material for the polymer
  • R 2 is a divalent group resulting from a diol compound or the like that is a raw material for the polymer
  • Reference numeral 3 denotes a divalent group derived from an isocyanate compound or the like that is a raw material for the polymer.
  • Examples of the divalent group represented by R 1 to R 3 include substituted or unsubstituted alkylene having 1 to 40 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 40 carbon atoms, substituted or unsubstituted carbon atoms having 5 to 40 aromatic ring groups can be mentioned.
  • alkylene a methylene group, an ethylene group, a propylene group, a butylene group, a pentene group, a hexylene group, an octylene group, a decylene group, and a dodecylene group are preferable.
  • cycloalkylene a cyclopropylene group, a cyclopentene group, and a cyclohexylene group are preferable.
  • aromatic ring group a benzene ring, naphthalene ring, pyrene ring, and phenanthrene ring are preferable.
  • the substituent for the divalent group is not particularly limited as long as the effect of the present invention can be obtained.
  • Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a methyl group and an aromatic group such as a phenyl group.
  • polyester urethane resin examples include aromatic polyester urethane resins.
  • the aromatic polyester urethane resin means a copolymer in which at least one of R 1 and R 2 is a substituted or unsubstituted aromatic ring group having 5 to 40 carbon atoms.
  • the commercially available aromatic polyester urethane resin Byron UR1400, Byron UR1700, Byron UR4800, Byron UR8200 (all manufactured by Toyobo Co., Ltd.) are preferable.
  • the second layer can be formed by applying a coating solution in which the resin component is dissolved by a known method and drying it.
  • a coating solution for example, a toluene solution of M2000 (manufactured by Soken Chemical Co., Ltd.) is preferable.
  • the thickness of the second layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 2 ⁇ m or less. For example, it is 1 ⁇ m or less. Thereby, bending becomes easy. There is no particular lower limit, but it is, for example, 0.01 ⁇ m or more.
  • the laminate of the present invention comprises a step of coating a base material with a coating solution obtained by dissolving a conductive polymer in a solvent to form a first layer containing the conductive polymer, an acrylate polymer, Apply an acid ester polymer, or a coating solution in which a polyester urethane resin having an ester bond and a urethane bond as a repeating unit in the main chain is dissolved in a solvent, an acrylate polymer, a methacrylate polymer, or And a step of forming a second layer containing a polyester urethane resin having an ester bond and a urethane bond as repeating units in the main chain.
  • the laminated body of this invention may form layers, such as an adhesion layer, as needed on a 2nd layer.
  • Production Example 1 [Production of polyaniline complex] A solution of 37.8 g of aerosol OT (sodium di-2-ethylhexylsulfosuccinate) in 600 mL of toluene was placed in a 6 L separable flask under nitrogen flow, and 22.2 g of aniline was added to the solution. . Thereafter, 1800 mL of 1M phosphoric acid was added to the solution, and the temperature of the solution having two liquid phases of toluene and water was cooled to 5 ° C.
  • aerosol OT sodium di-2-ethylhexylsulfosuccinate
  • Toluene 1500 mL was added to the organic phase side, and washed once with 600 mL of 1M phosphoric acid and three times with 600 mL of ion-exchanged water to obtain a polyaniline complex (protonated polyaniline) toluene solution.
  • the molecular weight of polyaniline in the polyaniline complex was measured by the GPC method under the following conditions. 0.25 g of the obtained polyaniline complex was dissolved in 4.75 g of toluene and 0.25 g of isopropyl alcohol, and 10 mL of 1M sodium hydroxide aqueous solution was added to the solution and stirred for 15 minutes. Thereafter, the whole amount was No. The residue was washed with 10 mL of toluene three times, 10 mL of ion-exchanged water three times, and 10 mL of methanol three times. The obtained solid content was dried under reduced pressure to prepare polyaniline for molecular weight measurement.
  • a solution was prepared by dissolving 0.40 g of the polyaniline complex obtained in Production Example 1 in a mixed solvent of 6.57 g of toluene and 1.39 g of methyl isobutyl ketone (MIBK). To this, 1.60 g of 4-methoxyphenol and 0.04 g of naphthalenesulfonic acid were added, and mixed with stirring at 30 ° C. for 30 minutes.
  • MIBK methyl isobutyl ketone
  • Example 1 As shown in FIG. 1, spin coating (2000 rpm) using the coating liquid prepared in Production Example 1 on a glass substrate 1 having four ITO electrodes 2 patterned in parallel in a strip shape, followed by 80 ° C.
  • the conductive polymer layer as the first layer was formed by drying on a hot plate for 5 minutes.
  • an acrylic resin Soken Chemical Co., Ltd., M2000
  • a coating liquid having a resin solid content of 10 wt% was spin-coated (300 rpm) on the first layer, and then heated on an 80 ° C. hot plate.
  • a second layer was formed by drying for 5 minutes to prepare a laminate.
  • the layer thickness of the second layer was 1 ⁇ m.
  • the time-dependent change of resistance value was evaluated.
  • the evaluation method is as follows. In the laminated body, the first layer and the second layer were scraped off under a nitrogen atmosphere to form a strip shape (laminated body 3 of the first layer and the second layer) orthogonal to the ITO electrode 2 as shown in FIG. . Store the laminate in air at room temperature, and measure the resistance of the membrane by the 4-terminal method using Lorester GP (Mitsubishi Chemical Corp .; resistivity meter by the 4-terminal method) using the ITO electrode terminals exposed on the surface. Then, the temporal change of the resistance value from the initial stage was evaluated.
  • Lorester GP Mitsubishi Chemical Corp .
  • resistivity meter by the 4-terminal method the temporal change of the resistance value from the initial stage was evaluated.
  • the initial resistance value (R 0 ) was 1718 ⁇
  • the resistance value (R 7 ) after 7 days was 1574 ⁇
  • the resistance value (R 14 ) after 14 days was 1606 ⁇ .
  • Table 7 shows the 7-day change rate [(R 7 ) / (R 0 )] and 14-day change rate [(R 14 ) / (R 0 )] of the resin used in the second layer and the resistance value of the first layer. It is shown in 1.
  • Example 2-8 Comparative Example 1-7 A laminate was prepared and evaluated in the same manner as in Example 1 except that the resin of the second layer was used as described in Table 1. The results are shown in Table 1.
  • Resins used in the second layers of the examples and comparative examples are shown below.
  • the molecular weight is the catalog value of the vendor.
  • Example 9 The coating liquid prepared in Production Example 1 was applied onto a 100 ⁇ m thick polyethylene terephthalate (PET) film (Toyobo Co., Ltd., Cosmo Shine A4300) using a bar coater # 10, and on a hot plate at 80 ° C. By drying for 10 minutes, a conductive polymer layer as the first layer was formed (the film thickness was about 1 ⁇ m). Next, a coating solution in which an acrylic resin (manufactured by Soken Chemical Co., Ltd., M2000) was dissolved in toluene and the resin solid content was 10 wt% was applied onto the first layer using a bar coater # 10, and heated at 80 ° C. A second layer was formed by drying on a plate for 10 minutes to produce a laminate. The film thickness of the second layer was about 1 ⁇ m. The obtained laminate could be easily bent.
  • PET polyethylene terephthalate
  • Example 10 A laminate was prepared in the same manner as in Example 9, except that the second layer was replaced with the acrylic resin of Example 9 (M2000, manufactured by Soken Chemical Co., Ltd.). The film thickness of the second layer was about 1 ⁇ m. The obtained laminate could be easily bent.
  • Example 11 A laminate was produced in the same manner as in Example 9 except that the resin of Example 3 was used instead of the acrylic resin of Example 9 (M2000, manufactured by Soken Chemical Co., Ltd.) as the second layer resin.
  • the film thickness of the second layer was about 1 ⁇ m. The obtained laminate could be easily bent.
  • Example 12 A laminate was prepared in the same manner as in Example 9, except that the resin of Example 4 was replaced with the acrylic resin of Example 9 (M2000, manufactured by Soken Chemical Co., Ltd.). The film thickness of the second layer was about 1 ⁇ m. The obtained laminate could be easily bent.
  • Example 13 A laminate was prepared in the same manner as in Example 9, except that the resin of Example 5 was replaced with the acrylic resin of Example 9 (M2000, manufactured by Soken Chemical Co., Ltd.). The film thickness of the second layer was about 1 ⁇ m. The obtained laminate could be easily bent.
  • Example 14 A laminate was prepared in the same manner as in Example 9, except that the resin of Example 6 was used instead of the acrylic resin of Example 9 (M2000, manufactured by Soken Chemical Co., Ltd.) as the second layer resin.
  • the film thickness of the second layer was about 1 ⁇ m. The obtained laminate could be easily bent.
  • Example 15 A laminate was prepared in the same manner as in Example 9 except that the resin of Example 7 was used instead of the acrylic resin of Example 9 (M2000, manufactured by Soken Chemical Co., Ltd.) as the second layer resin.
  • the film thickness of the second layer was about 1 ⁇ m. The obtained laminate could be easily bent.
  • Example 16 A laminate was prepared in the same manner as in Example 9 except that the resin of Example 8 was replaced with the acrylic resin of Example 9 (M2000, manufactured by Soken Chemical Co., Ltd.). The film thickness of the second layer was about 1 ⁇ m. The obtained laminate could be easily bent.
  • the conductive polymer layer can maintain a long-term stable resistance value. Moreover, since it is a conductive polymer laminated body whose outside is an insulator, it can be incorporated into an electronic component.
  • the laminate of the present invention can be used, for example, for electromagnetic wave shielding films and electromagnetic wave absorption applications.

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JP2011126956A (ja) * 2009-12-16 2011-06-30 Toyobo Co Ltd 易接着性熱可塑性樹脂フィルム
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