WO2014106949A1 - 無電解めっき下地膜形成用組成物 - Google Patents

無電解めっき下地膜形成用組成物 Download PDF

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WO2014106949A1
WO2014106949A1 PCT/JP2014/000007 JP2014000007W WO2014106949A1 WO 2014106949 A1 WO2014106949 A1 WO 2014106949A1 JP 2014000007 W JP2014000007 W JP 2014000007W WO 2014106949 A1 WO2014106949 A1 WO 2014106949A1
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group
electroless plating
base film
plating base
plating
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PCT/JP2014/000007
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English (en)
French (fr)
Japanese (ja)
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師健 中村
文起 深津
真吾 小野寺
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出光興産株式会社
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Priority claimed from JP2013000573A external-priority patent/JP2014132104A/ja
Priority claimed from JP2013001249A external-priority patent/JP6050687B2/ja
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Publication of WO2014106949A1 publication Critical patent/WO2014106949A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers

Definitions

  • the present invention relates to a composition for forming an electroless plating base film, a thin film obtained therefrom, a plating laminate, a method for producing an electroless plating base film, and a method for producing an electroless plating laminate.
  • the present invention also relates to a method for producing an electroless plated product.
  • Conductive polymers are used for electrolytic capacitors, backup batteries for electronic devices, electrodes for lithium ion batteries used in mobile phones and notebook computers, and the like.
  • polyaniline which is a kind of conductive polymer
  • polyaniline can be synthesized relatively easily from inexpensive aniline in addition to its electrical characteristics, and exhibits excellent stability against oxygen and the like in a state of conductivity. Has advantages and characteristics.
  • a highly conductive polyaniline can be easily obtained by the method described in Patent Document 1.
  • Patent Documents 2 to 8 An electroless plating base film made of a polyaniline complex alone has not been sufficiently adhered to various substrates such as polycarbonate (PC) and polyethylene terephthalate (PET). Moreover, the adhesiveness with a plating layer was not enough.
  • PC polycarbonate
  • PET polyethylene terephthalate
  • An object of the present invention is to provide a composition for forming a base film that has sufficient adhesion to a substrate such as polycarbonate (PC) in electroless plating and also has sufficient adhesion to a plating layer. It is.
  • a substrate such as polycarbonate (PC) in electroless plating and also has sufficient adhesion to a plating layer. It is.
  • the following composition for forming an electroless plating base film is provided.
  • a composition for forming an electroless plating base film comprising a conductive polymer and a urethane resin.
  • the conductive polymer is a polyaniline composite in which substituted or unsubstituted polyaniline is doped with a dopant.
  • the dopant is a sulfosuccinic acid derivative represented by the following formula (III).
  • M is a hydrogen atom, an organic free radical or an inorganic free radical.
  • M ′ is a valence of M.
  • R 13 and R 14 are each a hydrocarbon group or — (R 15 O) r —R 16 group, wherein R 15 is a hydrocarbon group or a silylene group, R 16 is a hydrogen atom, a hydrocarbon group or an R 17 3 Si— group, and r is an integer of 1 or more. R 17 is each a hydrocarbon group.) 4).
  • the dopant is a sulfosuccinic acid derivative represented by the following formula (III).
  • M is a hydrogen atom, an organic free radical or an inorganic free radical.
  • M ′ is a valence of M.
  • R 13 and R 14 are each a hydrocarbon group or — (R 15 O) r —R 16 group, wherein R 15 is a hydrocarbon group or a silylene group, R 16 is a hydrogen atom, a hydrocarbon group or an R 17 3 Si— group, and r is an integer of 1 or more. R 17 is each a hydrocarbon group.) 10. 10. The plated laminate according to 8 or 9, wherein the dopant is sodium di-2-ethylhexyl sulfosuccinate. 11. The plating laminate according to any one of 7 to 10, wherein the ratio of the urethane resin to the total of the conductive polymer and the urethane resin is 20 to 80% by weight.
  • a step of forming an electroless plating base film using the composition for forming an electroless plating base film according to any one of 1 to 5 on a substrate; and electroless containing a metal on the electroless plating base film The manufacturing method of the electroless-plating laminated body including the process of forming a plating layer. 17. 17. The method for producing an electroless plating laminate according to 16, wherein the electroless plating base film is supported with palladium and then contacted with an electroless plating solution to form the electroless plating layer. 18. 18. The method for producing an electroless plating laminate according to 17, wherein palladium is supported by bringing a palladium chloride solution into contact with the electroless plating base film. 19. The method for producing an electroless plating laminate according to any one of 16 to 18, wherein the electroless plating solution contains one or more metals selected from Cu, Ni, Au, Pd, Ag, Sn, Co, and Pt.
  • composition for forming a base film that has sufficient adhesion to a substrate such as PC and has sufficient adhesion to a plating layer in electroless plating.
  • Another object of the present invention is to provide a method for producing an electroless plating product capable of selectively and stably forming a uniform plating film on an electroless plating base film portion using a conductive polymer.
  • the manufacturing method of the electroless-plated product of 1 or 2 whose pH of the said reducing agent aqueous solution is 5 or less. 4). 4. The method for producing an electroless plated product according to any one of 1 to 3, wherein the pH of the reducing agent aqueous solution is 3 or more. 5. 5. The method for producing an electroless plated product according to any one of 1 to 4, wherein a standard electrode potential E 0 of the reducing agent aqueous solution is E 0 ⁇ 0.80 V to ⁇ 0.20 V. 6). 6. The method for producing an electroless plated product according to any one of 1 to 5, wherein the reducing agent aqueous solution is a sodium hydrogen sulfite aqueous solution. 7).
  • M is a hydrogen atom, an organic free radical or an inorganic free radical.
  • M ′ is a valence of M.
  • R 13 and R 14 are each a hydrocarbon group or — (R 15 O) r —R 16 group, wherein R 15 is a hydrocarbon group or a silylene group, R 16 is a hydrogen atom, a hydrocarbon group or an R 17 3 Si— group, and r is an integer of 1 or more.
  • R 17 is each a hydrocarbon group.
  • Production method. 11 The method according to any one of 1 to 10, further comprising a supporting step of supporting a catalyst metal for an electroless plating solution on the electroless plating base film after the contact step with the reducing agent aqueous solution and before the electroless plating layer forming step. Method for producing electroless plating. 12
  • 14 The method for producing an electroless plated product according to 13, wherein the solution containing palladium ions is a palladium chloride solution.
  • 15. The method for producing an electroless plating product according to any one of 1 to 14, wherein the electroless plating layer is formed by bringing an electroless plating solution into contact with the electroless plating base film after contact with the reducing agent aqueous solution. 16. 16.
  • an electroless plating product capable of selectively and stably forming a uniform plating film on an electroless plating base film portion using a conductive polymer.
  • composition for forming electroless plating base film, thin film obtained therefrom, plating laminate, method for producing electroless plating base film, and method for producing electroless plating laminate The composition for forming electroless plating base film of the present invention
  • the object includes a conductive polymer and a urethane resin.
  • Electroless plating is a method of plating a metal having an autocatalytic action that does not perform electrolysis and uses a reducing agent. For example, in the case of electroless copper plating, a copper ion in a solution is replaced with a reducing agent such as formaldehyde.
  • composition of the present invention is used to form an underlayer for an electroless plating layer.
  • composition of the present invention is mixed with a urethane resin as a binder for improving the adhesion, the adhesion with various substrates such as PC and PET becomes sufficient, and the adhesion with the plating layer is also excellent. It can be set as the plating laminated body with favorable adhesiveness.
  • Examples of the conductive polymer include a ⁇ -conjugated polymer complex in which a ⁇ -conjugated polymer is doped with a dopant.
  • a polyaniline complex in which a substituted or unsubstituted polyaniline is doped with a dopant, a substituted or non-substituted polyaniline.
  • Polypyrrole composites in which substituted polypyrrole is doped with a dopant as well as polythiophene composites in which substituted or unsubstituted polythiophene is doped with a dopant, and polyaniline composites in which substituted or unsubstituted polyaniline is doped with a dopant
  • the body is preferred.
  • the weight average molecular weight of polyaniline (hereinafter referred to as molecular weight) is preferably 20,000 or more. If the molecular weight is less than 20,000, the strength and stretchability of the conductive article obtained from the composition 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 polydispersity (that is, “weight average molecular weight” / “number average molecular weight”) is preferably 1.5 or more and 10.0 or less. From the viewpoint of conductivity, it is preferable that the polydispersity is small (that is, the molecular weight distribution is narrow), but from the viewpoint of solubility in solvents and moldability, the polydispersity is large (that is, the molecular weight distribution is wide). May be preferred.
  • the weight average molecular weight, number average molecular weight, and polydispersity are measured in terms of polystyrene by gel permeation chromatography (GPC).
  • Examples of the substituent of the substituted polyaniline 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; And halogenated hydrocarbon groups such as a fluoromethyl group (—CF 3 group).
  • 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 0.1% by weight or less, still more preferably 0.04% by weight or less, and most preferably 0.0001%. % By 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 the dopant is expressed as a specific acid, and when the dopant is expressed as a specific salt, the specific acid ion generated from the specific acid or the specific salt may be used.
  • the above-mentioned ⁇ -conjugated polymer is 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.
  • the inorganic free radical include lithium, sodium, potassium, cesium, ammonium, calcium, magnesium, and iron ions.
  • 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 group 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 represents —H, —R 1 , —OR 1 , —COR 1 , —COOR 1 , — (C ⁇ O) — (COR 1 ), or — A substituent represented by (C ⁇ O) — (COOR 1 ), wherein R 1 is a hydrocarbon group, silyl group, alkylsilyl group, or — (R 2 O) x—R 3 group which may contain a substituent. Or-(OSiR 3 2 ) x-OR 3 .
  • R 2 is an alkylene group
  • R 3 is a hydrocarbon group
  • x is an integer of 1 or more.
  • 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 in formula (I).
  • X is preferably a —SO 3 — group.
  • R 4 , R 5 and R 6 are each a hydrogen atom, a hydrocarbon group or an R 9 3 Si— group.
  • each of three R 9 is a hydrocarbon group.
  • 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, and alkylaryl groups.
  • 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 a hydrocarbon group or a — (R 10 O) q —R 11 group.
  • R 10 is a hydrocarbon group or a silylene group
  • R 11 is a hydrogen atom, a hydrocarbon group or R 12 3 Si—
  • q is an integer of 1 or more.
  • Three R ⁇ 12 > is a hydrocarbon group, respectively.
  • 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, and alkylaryl groups.
  • 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, and the like. .
  • Examples of the hydrocarbon group in the case where 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, an alkylarylene group, and an arylalkylene group. is there.
  • 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 are each a hydrocarbon group or a — (R 15 O) r —R 16 group.
  • R 15 is a hydrocarbon group or a silylene group
  • R 16 is a hydrogen atom, a hydrocarbon group or an R 17 3 Si— group
  • r is an integer of 1 or more.
  • Each of the three R 17 is a hydrocarbon group.
  • 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 (aerosol OT).
  • 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 production method. For example, it can be produced by chemical oxidative polymerization of a substituted or unsubstituted aniline in a solution containing a proton donor, phosphoric acid, and an emulsifier different from the proton donor and having two liquid phases. Moreover, it can manufacture by adding an oxidation polymerization agent in the solution which contains the emulsifier different from a substituted or unsubstituted aniline, a proton donor, phosphoric acid, and a proton donor, and has two liquid phases. In addition, it is thought that the emulsifier plays the role which prevents the phase inversion mentioned later.
  • phase inversion is a phenomenon in which the liquid phase that was a continuous phase changes to a dispersed phase, and the other liquid phase that was a dispersed phase changes to a continuous phase.
  • 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 emulsifier can be either an ionic emulsifier whose hydrophilic part is ionic or a nonionic emulsifier whose non-ionic hydrophilic part is used, or a mixture of one or more emulsifiers. May be used.
  • the ionic emulsifier examples include a cationic emulsifier, an anionic emulsifier, and a zwitter emulsifier.
  • Specific examples of the anionic emulsifier include fatty acids, disproportionated rosin soaps, higher alcohol esters, polyoxyethylene alkyl ether phosphates, alkenyl succinic acids, sarcosinates, and salts thereof.
  • Specific examples of the cationic emulsifier (cationic emulsifier) include alkyl dimethyl benzyl ammonium salt and alkyl trimethyl ammonium salt.
  • zwitterionic emulsifier both ion emulsifier
  • alkyl betaine type alkyl betaine type
  • alkyl amide betaine type amino acid type
  • amine oxide type alkyl betaine type
  • nonionic emulsifier include polyoxyethylene alkyl ether, polypropylene glycol polyethylene glycol ether, polyoxyethylene glycerol borate fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.
  • anionic emulsifiers and nonionic emulsifiers are preferred.
  • anionic emulsifier an anionic emulsifier having a phosphate ester structure is more preferable.
  • nonionic emulsifier a nonionic emulsifier having a polyoxyethylene sorbitan fatty acid ester structure is more preferable.
  • the amount of the emulsifier used is preferably 0.001 to 0.1 mol, more preferably 0.002 to 0.02 mol, and still more preferably 0.003 to 0.01 mol with respect to 1 mol of the aniline monomer. is there.
  • the “high polar solvent phase” and the “low polar solvent phase” may not be separated after the 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 sodium persulfate, potassium persulfate, persulfates such as ammonium persulfate, peroxides such as hydrogen peroxide, ammonium dichromate, ammonium perchlorate, iron iron sulfate (III), iron trichloride (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.
  • 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 molecular weight of polythiophene, the molecular weight distribution, and the substituent of the substituted polythiophene are the same as those of the above 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.
  • urethane resin for example, those obtained by reacting polyisocyanate and polyol can be used.
  • the polyisocyanate is not particularly limited as long as it is a compound having at least two isocyanate groups, and known ones can be used. Specifically, for example, TDI (tolylene diisocyanate), MDI (diphenylmethane diisocyanate), XDI (xylylene diisocyanate), NDI (naphthylene 1,5-diisocyanate), TMXDI (tetramethylene xylylene diisocyanate) Aromatic isocyanates such as IPDI (isophorone diisocyanate), H12MDI (hydrogenated MDI, dicyclohexylmethane diisocyanate), H6XDI (hydrogenated XDI), etc., HDI (hexamethylene diisocyanate), DDI There are aliphatic isocyanates such as (dimer acid diisocyanate) and NBDI (norbornene diisocyanate). These may be used alone or
  • Polyols include polyether polyols such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol, polyester polyols such as polyethylene adipate, polyethylene-butylene adipate, and polycaprolactone, acrylic polyols, and polycarbonate series. Examples thereof include polyols, polydimethylsiloxane-ethylene oxide adducts, polydimethylsiloxane-propylene oxide adducts, and castor oil. These may be used alone or in combination of two or more.
  • the content of the urethane resin in the coating film that is, the ratio of the urethane resin to the total of the conductive polymer and the urethane resin in the composition is preferably 10 wt% to 90 wt%, more preferably 20 wt% to 80 wt%. Preferably, it is 30 wt% to 60 wt%, and most preferably 40 wt% to 60 wt%.
  • the ratio of polyaniline will fall when there is too much, there exists a possibility that the precipitation of plating may deteriorate.
  • urethane resins include hydran series (manufactured by DIC) such as hydran AP-20, AP-30F, AP-40F, WLS-213, UCOAT UX-150, UX-200, UX-310, UWS.
  • U-Coat series manufactured by Sanyo Chemical Co., Ltd.
  • ACRITT series manufactured by Taisei Fine Chemical Co., Ltd.
  • PTG-RSN manufactured by DIC Graphics
  • the urethane resin usually has a structure represented by the following formula.
  • R and X are each a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic hydrocarbon group derived from a monomer for the synthesis of a urethane resin, or A divalent group in which one or more substituted or unsubstituted divalent aromatic hydrocarbon groups and one or more substituted or unsubstituted divalent aliphatic hydrocarbon groups are bonded in any order.
  • the divalent aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 50 ring carbon atoms. Specific examples include a phenylene group and a naphthylene group.
  • divalent aliphatic hydrocarbon group examples include a linear aliphatic hydrocarbon group having 6 to 50 carbon atoms and a branched aliphatic hydrocarbon group having 6 to 50 carbon atoms. Specific examples include a methylene group, an ethylene group, and a propylene group.
  • divalent group in which one or more divalent aromatic hydrocarbon groups and one or more divalent aliphatic hydrocarbon groups are bonded in any order a group in which a phenylene group and a methylene group are bonded, a naphthylene group And a group in which an ethylene group is bonded.
  • substituent in the case of having a substituent include a hydroxyl group, a carboxyl group, a nitro group, a cyano group, and an amino group.
  • the composition of the present invention may contain other components other than the conductive polymer, the urethane resin and the solvent within the range not impairing the effects of the present invention, and substantially contains the conductive polymer, the urethane resin and the solvent. Or a conductive polymer, a urethane resin and a solvent alone.
  • substantially means that 95% to 100% by weight (preferably 98% to 100% by weight) of the composition is a conductive polymer, a urethane resin, and a solvent.
  • examples of other components include phenolic compounds and heat stabilizers described later.
  • the composition of the present invention may further contain 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 (for example, 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 phenolic compound content is preferably such that the molar concentration of the phenolic compound is 0.01 [mmol / g] or more per 1 g of the polyaniline complex. 100 [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 Is in the range of 0.2 [mmol / g] to 80 [mmol / g].
  • the composition of the present invention may further contain 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, and the composition of the present invention is used as a heat stabilizer.
  • the salt of the acidic substance is preferably a compound different from the proton donor of the polyaniline complex.
  • the composition of the present invention 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 a compound different from the proton donor. It is.
  • the acidic substance is preferably different from a phenolic compound
  • the composition of the present invention is a salt of an acidic substance as a heat stabilizer.
  • the salt of the acidic substance is different from the phenolic compound.
  • the composition of the present invention 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 a phenolic compound and Different.
  • 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, chain or branched alkyl sulfonic acid, substituted or unsubstituted aromatic sulfonic acid, or polysulfonic acid having one or more sulfonic acid groups.
  • alkylsulfonic acid include methanesulfonic acid, ethanesulfonic acid, and di-2-ethylhexylsulfosuccinic 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.
  • 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 A phosphoric acid or aromatic phosphonic acid; polyphosphoric acid or 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.
  • Examples of the salt of the acidic substance contained in the composition of the present invention include the salt of the acidic substance.
  • the composition of the present invention may contain two or more acidic substances and / or salts of acidic substances that are heat-resistant stabilizers.
  • the composition of the present invention may include different acidic substances and / or salts of different acidic substances.
  • the acidic substance may be the same or different sulfonic acid as the proton donor.
  • the salt of the acidic substance may be the same or different sulfonic acid salt as the proton donor of the polyaniline complex. preferable.
  • composition of the present invention includes 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 that is the same as or different from the proton donor.
  • a salt is preferred.
  • composition of the present invention contains only sulfonic acid as the heat stabilizer, preferably satisfies the formula (12), and when the composition of the present invention contains only the salt of sulfonic acid as the heat stabilizer.
  • formula (13) is satisfied and the composition of the present invention contains a sulfonic acid and a sulfonic acid salt as a heat stabilizer, the formula (14) is preferably satisfied.
  • S 2 is the total number of moles of sulfur atoms of all acidic substances contained in the composition of the present invention
  • N 2 is all polyaniline complexes contained in the composition of the present invention. Is the sum of the number of moles of nitrogen atoms
  • S 3 is the sum of the number of moles of sulfur atoms of the salts of all acidic substances contained in the composition of the present invention
  • N 3 is the composition of the present invention.
  • N 4 means the total number of moles of nitrogen atoms of all polyaniline complexes contained in the composition of the present invention.
  • composition of the present invention satisfies any of the above formulas (12), (13), or (14), the composition 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 composition of the present invention, and N 1 represents the number of moles of nitrogen atoms contained in the composition of the present invention.)
  • the acidity (pKa) of the said acidic substance is 5.0 or less.
  • the lower limit of the acidity is not particularly limited. For example, when an acidic substance having an acidity of ⁇ 4.0 or less is contained, the polyaniline complex may be deteriorated.
  • the acidity of the salt of the said acidic substance is 5.0 or less. About the minimum of acidity, it is the same as that of the said acidic substance.
  • composition of the present invention includes both an acidic substance and an acidic substance salt
  • at least one of the acidic substance salts having an acidity of 5.0 or less and an acidity of 5.0 or less is included. It is preferable to satisfy.
  • 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 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 solvent 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; 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, for example, methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, diacetone alcohol, 3-methoxy-1- Butanol, 3-methyl-3-methoxy-1-butanol, ethyl carbitol, butyl carbitol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran or diethyl ether are preferred.
  • the proportion of the conductive polymer in the solvent 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 or more and 300 g / kg depending on the type of the solvent. It is below, More preferably, it is the range of 30 g / kg or more and 300 g / kg or less. If the content of the conductive polymer is too large, the solution state cannot be maintained, and handling during molding becomes difficult, the uniformity of the molded body is impaired, and consequently the electrical properties and mechanical strength of the molded body. There is a risk of lowering transparency. On the other hand, if the content of the conductive polymer 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.
  • composition of the present invention 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 resins include a binder substrate, a plasticizer, and a matrix substrate.
  • 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 electroless plating base film (layer) of the present invention is obtained from the above composition.
  • the method for forming the electroless plating base film of the present invention is as described later.
  • the dry film thickness of the electroless plating base film is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more. If the film thickness is less than 0.1 ⁇ m, the adhesion between the base material and the plating film cannot be maintained, so that the film is easily peeled off. Further, there is a possibility that the area where the Pd metal is not supported increases, and there is a possibility that the area where electroless plating is not performed increases.
  • the upper limit of the dry film thickness is not particularly limited, but is, for example, 100 ⁇ m or less, 10 ⁇ m or less, 5.0 ⁇ m or less.
  • the method for producing an electroless plating base film of the present invention uses the composition for forming an electroless plating base film of the present invention.
  • This manufacturing method will not be specifically limited if the composition of this invention is used, For example, the coating method of apply
  • the plating laminate of the present invention includes an electroless plating layer containing a metal, an electroless plating base layer containing a conductive polymer and a urethane resin, and a substrate layer, one surface of the electroless plating layer, and electroless One surface of the plating underlayer is in contact.
  • FIG. 1 is a schematic view showing a layer configuration of an embodiment of the plated laminate of the present invention.
  • the plating laminate 1 includes an electroless plating base layer 20 and an electroless plating layer 30 laminated on a substrate 10 in this order.
  • the plating laminated body of this invention can be manufactured with the manufacturing method of the plating laminated body of this invention mentioned later.
  • the substrate is not particularly limited, and may be a metal, an inorganic material (ceramics, glass, or the like), or a resin.
  • substrate 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 resin, acrylic resin, nylon resin, polyimide resin, polyester resin, styrene resin, phenol resin, and PPS (polyphenylene sulfide) resin.
  • Specific examples of the substrate include easy-adhesion-treated PET (A4300 manufactured by Toyobo).
  • the electroless plating underlayer includes a conductive polymer and a urethane resin.
  • the conductive polymer and the urethane resin are as described above.
  • the electroless plating underlayer can be produced using the composition of the present invention. The formation method is as described above.
  • Electroless plating layer examples of the metal species of the electroless plating layer include copper, nickel, cobalt, palladium, silver, gold, platinum, and tin. In addition to these, elements such as phosphorus, boron, and iron may be contained. The forming method is as described later.
  • the method for producing an electroless plating laminate of the present invention includes a step of forming an electroless plating base film on a substrate using the electroless plating base film forming composition of the present invention, and an electroless plating base film And a step of forming an electroless plating layer containing a metal.
  • the formation of the electroless plating base film can be performed by the above-described method for manufacturing an electroless plating base film. It is preferable to perform a degreasing step after forming the base film and before forming the electroless plating layer.
  • the surface of the polyaniline layer is degreased and washed with a solvent such as a surfactant or alcohol to improve wettability.
  • a surfactant an anionic, cationic or nonionic surfactant can be appropriately used, and a cationic surfactant is preferable.
  • a cationic surfactant is used, it is diluted to 1 to 3% with, for example, ion exchange water.
  • a Pd compound solution is usually brought into contact with the base film in order to support Pd metal (catalyst metal) responsible for the electroless plating catalytic action.
  • Pd metal catalyst metal
  • a conductive polymer such as a polyaniline complex adsorbs Pd ions, and Pd ions are reduced to Pd metal by the reduction action.
  • Pd adhesion amount (including Pd ions and Pd metal) per unit area is preferably 1.7 ⁇ g / cm 2 or more, and more preferably 2.5 ⁇ g / cm 2 or more.
  • Pd compound palladium chloride is preferable.
  • solvent hydrochloric acid is generally used.
  • Pd is only required to be present in an aqueous solution in an ionic state, and is not limited to a hydrochloric acid aqueous solution.
  • Pd compound solution include 0.02% palladium chloride-0.01% hydrochloric acid aqueous solution (pH 3).
  • the contact temperature with the Pd compound solution is usually 20 to 50 ° C., preferably 30 to 40 ° C., and the contact time is usually 0.1 to 10 minutes, preferably 1 to 5 minutes.
  • the film obtained above is brought into contact with an electroless plating solution.
  • the supported Pd metal acts as a catalyst, and a plating layer is formed on the polyaniline layer.
  • the metal species contained in the electroless plating solution include copper, nickel, cobalt, palladium, silver, gold, platinum, and tin.
  • the electroless plating solution may include one or more metals selected from Cu, Ni, Au, Pd, Ag, Sn, Co, and Pt.
  • elements such as phosphorus, boron, and iron may be contained.
  • the contact temperature with the electroless plating solution varies depending on the type and thickness of the plating bath, but is, for example, about 20 to 50 ° C. for a low temperature bath and 50 to 90 ° C. for a high temperature.
  • the contact time with the electroless plating solution varies depending on the type and thickness of the plating bath, but is, for example, 1 to 30 minutes and 5 to 15 minutes. It is possible to use only electroless plating, or it is possible to provide a metal film of the same type or different by electrolytic plating after providing a metal thin film by electroless plating.
  • the method for producing an electroless plating product according to the present invention comprises a step of forming an electroless plating base film containing a conductive polymer on a substrate, the electroless plating base film being a standard electrode.
  • the plating base film By contacting (impregnating) the above reducing agent aqueous solution in place of the surfactant with the electroless plating base film, even if the plating base film contains a binder or is thick, the plating base film A uniform plating film can be formed thereon.
  • a plating layer can be formed (deposited) only on the plating base film. That is, the plating layer is not formed on the surface of the base material (the plating unnecessary portion) on which the plating base film is not provided, so that the plating can be selectively performed on the base material. This effect is particularly useful when a plated metal circuit is formed on a substrate.
  • Electroless plating base film forming step In this step, an electroless plating base film containing a conductive polymer is formed on a substrate.
  • the conductive polymer 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 polydispersity (that is, “weight average molecular weight” / “number average molecular weight”) is preferably 1.5 or more and 10.0 or less. From the viewpoint of conductivity, it is preferable that the polydispersity is small (that is, the molecular weight distribution is narrow), but from the viewpoint of solubility in solvents and moldability, the polydispersity is large (that is, the molecular weight distribution is wide). May be preferred.
  • the weight average molecular weight, number average molecular weight, and polydispersity are measured in terms of polystyrene by gel permeation chromatography (GPC).
  • Examples of the substituent of the substituted polyaniline 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; And halogenated hydrocarbon groups such as a fluoromethyl group (—CF 3 group).
  • 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.
  • the inorganic free radical include lithium, sodium, potassium, cesium, ammonium, calcium, magnesium, and iron ions.
  • 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 group 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 ).
  • a substituent represented by-(C O)-(COOR 1 ), wherein R 1 is a hydrocarbon group, silyl group, alkylsilyl group,-(R 2 O) x- R 3 group, or — (OSiR 3 2 ) x—OR 3
  • R 2 is independently an alkylene group
  • R 3 is each independently a hydrocarbon group
  • x is an integer of 1 or more).
  • 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, m and X are the same as 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, and alkylaryl groups.
  • 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 examples include linear or branched alkyl groups, aryl groups, alkylaryl groups having 1 to 24 carbon atoms, preferably 4 or more carbon atoms.
  • 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, and the like. .
  • Examples of the hydrocarbon group in the case where 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, an alkylarylene group, and an arylalkylene group. is there.
  • 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.
  • the electroless plating base film can be manufactured using a solution (coating liquid) containing a conductive polymer such as a polyaniline composite.
  • 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 substrate is not particularly limited, and may be a metal, an inorganic material (ceramics, glass, or the like), or a resin.
  • 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.
  • SPS syndiotactic polystyrene
  • PEN polyethylene naphthalate
  • PET polyethylene terephthalate
  • 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 formation method of the electroless plating base film is not particularly limited.
  • a coating method in which a solution (coating solution) obtained by dissolving a conductive polymer in a solvent is coated on a substrate by a bar coating method and dried.
  • aromatic, ketone, aliphatic, alcohol, amide, ester and the like can be used as appropriate. Specific examples include toluene, cresol, hexane, methyl isobutyl ketone, 2-butanone. 2-propanol, methanol, dimethylformamide, butyl acetate, ethyl acetate and the like. These may be used alone or in combination.
  • the coating liquid may contain a binder for improving the adhesion with the substrate.
  • a binder for improving the adhesion with the substrate.
  • the binder include acrylic, urethane, epoxy, polyamide, vinyl, polyester, and polycarbonate.
  • UV ultraviolet
  • EB electron beam
  • the dry film thickness of the electroless plating base film is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more. If the film thickness is less than 0.1 ⁇ m, the adhesion between the base material and the plating film cannot be maintained, so that the film is easily peeled off. Further, there is a possibility that the area where the Pd metal is not supported increases, and there is a possibility that the area where electroless plating is not performed increases. There is no particular upper limit on the dry film thickness.
  • the reducing agent aqueous solution in the present invention is acidic, and the pH of the reducing agent aqueous solution is preferably 6 or less, more preferably 5 or less.
  • the pH of the reducing agent aqueous solution is preferably 3 or more. Such a so-called weakly acidic range is preferable.
  • the pH is measured using a pH meter.
  • the standard electrode potential is calculated based on the value measured with an oxidation-reduction potentiometer (ORP meter) under the condition of 25 ° C.
  • ORP meter oxidation-reduction potentiometer
  • sodium bisulfite is most preferable.
  • the concentration (weight ratio) of the reducing agent aqueous solution is preferably 2% to 20%, more preferably 3 to 18%, more preferably 4% to 16%, and most preferably 8 to 16%. If the concentration is too low, the conductive polymer such as polyaniline may not be completely reduced. In addition, you may process with surfactant in order to arrange the surface state before a reducing agent process.
  • the catalyst metal can be supported by bringing a catalyst metal simple substance or compound solution, that is, a solution containing catalyst metal ions into contact with the electroless plating base film.
  • a catalyst metal simple substance or compound solution that is, a solution containing catalyst metal ions
  • the conductive polymer such as the polyaniline complex adsorbs the catalytic metal ion, and the catalytic metal ion is reduced to the catalytic metal by the reducing action of the conductive polymer.
  • the catalytic metal does not exhibit a catalytic action in electroless plating unless it is in a reduced state, that is, a metallic state.
  • the catalyst metal adhesion amount (including catalyst metal ions and catalyst metal) per unit area is preferably 1.7 ⁇ g / cm 2 or more, and more preferably 2.5 ⁇ g / cm 2 or more.
  • palladium (Pd) is preferable.
  • Pd compound palladium chloride is preferable.
  • hydrochloric acid is generally used as the solvent, it is not limited to hydrochloric acid because Pd only needs to be present in an aqueous solution in an ionic state. Examples of the Pd compound solution include 0.02% palladium chloride-0.01% hydrochloric acid aqueous solution (pH 3).
  • the contact temperature between the Pd compound solution and the electroless plating base film is usually 20 to 50 ° C., preferably 30 to 40 ° C., and the contact time is usually 0.1 to 10 minutes, preferably 1 to 5 minutes. .
  • Step of forming electroless plating layer an electroless plating layer is formed on the electroless plating base film subjected to the above treatment.
  • the electroless plating layer can be formed by bringing an electroless plating solution into contact with the plating base film. When the plating base film comes into contact with the electroless plating solution, a plating layer is formed on the plating base film by the catalytic action of the supported catalytic metal.
  • Electroless plating is electroless plating of a metal having a self-catalytic action performed using a reducing agent.
  • a metal having a self-catalytic action performed using a reducing agent.
  • the copper ion in the solution is reduced using a reducing agent such as formaldehyde to deposit a metallic copper film, and the deposited metallic copper becomes an autocatalyst to further metallize the copper ion, It is a chemical process for precipitation.
  • the electroless plating solution a normal electroless plating solution can be used.
  • the electroless plating metal species include nickel, cobalt, palladium, silver, gold, platinum, and tin in addition to copper.
  • the electroless plating solution can include one or more metal ions selected from copper, nickel, cobalt, palladium, silver, gold, platinum, and tin. In addition to these, elements such as phosphorus, boron, and iron may be contained.
  • the contact temperature with the electroless plating solution varies depending on the type and thickness of the plating bath, but is, for example, about 20 to 50 ° C. for a low temperature bath and about 50 to 90 ° C. for a high temperature.
  • the contact time with the electroless plating solution varies depending on the type and thickness of the plating bath, but is, for example, 1 to 30 minutes, preferably 5 to 15 minutes.
  • Plating may be performed by electroless plating, or it is possible to further provide the same or different metal film by electrolytic plating after providing a metal thin film by electroless plating.
  • Production Example 1 [Production of polyaniline complex] 37.8 g of aerosol OT (sodium di-2-ethylhexylsulfosuccinate) (AOT) and 1.47 g of sorbon T-20 (manufactured by Toho Chemical Co., Ltd.) which is a nonionic emulsifier having a polyoxyethylene sorbitan fatty acid ester structure are added to toluene. The solution dissolved in 600 mL was placed in a 6 L separable flask placed under a nitrogen stream, and 22.2 g of aniline was further added to this 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
  • sorbon T-20 manufactured by Toho Chemical Co., Ltd.
  • toluene phase 1500 ml of toluene was added, washed once with 500 mL of 1M phosphoric acid and three times with 500 mL of ion-exchanged water, the toluene phase was allowed to stand and concentrated to adjust the concentration, and the polyaniline complex (Polyaniline / AOT complex) 900 g of a toluene solution was obtained.
  • the polyaniline complex concentration of this polyaniline complex toluene solution was 5.7% by weight.
  • Production Example 2 The polyaniline / AOT complex toluene solution obtained in Production Example 1 was dried under reduced pressure in a 60 ° C. hot water bath and dried to obtain 51.3 g of a polyaniline complex (powder).
  • Example 1 [Plating foundation film forming process] 2.8 g of the polyaniline composite powder obtained in Production Example 2 was dissolved in 17 g of methyl isobutyl ketone (MIBK: manufactured by Wako Pure Chemical Industries) and 8.5 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, 5.7 g of ASPU112 (made by DIC Corporation, solid content concentration 30%), which is a urethane resin, was added and stirred to prepare a uniform coating solution for forming a plating base.
  • MIBK methyl isobutyl ketone
  • ASPU112 made by DIC Corporation, solid content concentration 30%
  • the obtained coating solution was applied onto a carbo glass film C110C (PC film, manufactured by Asahi Glass Co., Ltd.), which is a polycarbonate film, using a bar coater and dried at 120 ° C. for 30 minutes to form a plating base film.
  • the thickness of the plating base film was 1 ⁇ m.
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
  • the obtained film (plating base film) is degreased by immersing it in an aqueous solution of 3% Dianol CDE (coconut oil fatty acid diethanolamide; nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) for 5 minutes at room temperature. Went.
  • this degreasing process aims at the improvement of wettability.
  • Example 2 A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 6.8 g of Juliano U301 (made by Arakawa Chemical Co., Ltd., solid concentration 25%), which is a urethane resin, was added instead of ASPU112. Produced.
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
  • degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.
  • Example 3 A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 6.8 g of TSP3301 (made by Arakawa Chemical Co., Ltd., solid concentration 25%), which is a urethane resin, was added instead of ASPU112. .
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
  • degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.
  • Example 4 A coating solution for forming a plating base and a plating base film in the same manner as in Example 1 except for adding 5.7 g of diferamin MAU1008 (manufactured by Dainichi Seika Co., Ltd., solid content concentration: 30%) instead of adding ASPU112.
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
  • degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.
  • Example 5 a coating solution for forming a plating base and a plating base film are the same as in Example 1 except for adding 5.7 g of urethane resin Diferamin MAU1005 (manufactured by Dainichi Seika Co., Ltd., solid content concentration 30%).
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
  • degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.
  • Example 6 A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 4.8 g of diferamin MAU4308HV (made by Dainichi Seika Co., Ltd., solid content concentration 35%), which is a urethane resin, was added instead of ASPU112. did.
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
  • degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.
  • Example 7 Instead of ASPU112, 2.8 g of urethane resin Daiferamin MAU1008 (manufactured by Dainichi Seika Co., Ltd., solid content concentration 30%) and 2.8 g of urethane resin ASPU112 (DIC Corporation, solid content concentration 30%)
  • a coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except for the addition.
  • Example 8 Example except that 2.8 g of urethane resin ASPU112 (manufactured by DIC Corporation, solid content concentration 30%) and 0.85 g of polyvinyl butyral KS-10 (manufactured by Sekisui Chemical Co., Ltd.) were added instead of ASPU112.
  • a coating solution for forming a plating base and a plating base film were prepared.
  • the polyaniline complex concentration in the plating base film was 62.5 wt%
  • the urethane resin concentration was 18.75 wt%
  • the polyvinyl butyral concentration was 18.75 wt%.
  • degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.
  • Comparative Example 1 A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that the ASPU 112 was not added. The concentration of the polyaniline complex in the plating base film was 100 wt%. Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the entire test part was peeled off at the interface between the plating base film and the Cu plating layer. Moreover, as a result of performing the crosscut test similarly in the part which the plating base film exposed, the test part peeled whole surface also in the PC film and the plating base film interface.
  • Comparative Example 2 A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 5.7 g of Byron 20SS (manufactured by Toyobo Co., Ltd., solid content concentration 30%), which is a polyester resin, was added instead of ASPU112.
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the polyester resin concentration was 37.5 wt%.
  • the compatibility between the polyaniline composite and Byron 20SS was poor, and the plating base film became non-uniform and fragile.
  • Comparative Example 3 A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 1.7 g of Byron 50DS (Toyobo Co., Ltd.), which is a polyester resin, was added instead of ASPU112. When the plating base film was observed, the compatibility between the polyaniline composite and Byron 50DS was poor, and the plating base film was uneven and brittle. Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, since the plating base film was brittle, peeling from the middle of the plating base film was confirmed.
  • Byron 50DS Toyobo Co., Ltd.
  • Comparative Example 4 In the same manner as in Example 1, except that 8.5 g of Super Clone 822 (Nippon Paper Chemical Co., Ltd., solid content concentration: 20%), which is a chlorinated polyolefin, was added instead of ASPU112, a plating base forming coating solution and a plating base film were used. Was made. The polyaniline complex concentration in the plating underlayer was 62.5 wt%, and the chlorinated polyolefin concentration was 37.5 wt%. Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the adhesion between the plating base film and the Cu layer interface was good, but the entire test part was peeled off at the plating base film and PC film interface.
  • Super Clone 822 Nippon Paper Chemical Co., Ltd., solid content concentration: 20%
  • Comparative Example 5 A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 5.7 g of GDP 6140 (manufactured by Gunei Chemical Co., Ltd., solid content concentration 30%), which is a phenol resin, was added instead of ASPU112. .
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the phenol resin concentration was 37.5 wt%.
  • degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the adhesion between the plating base film and the Cu layer interface was good, but the entire test part was peeled off at the plating base film and PC film interface.
  • Comparative Example 6 A plating base forming coating solution and a plating base film were prepared in the same manner as in Example 1 except that 1.7 g of KS-10 (Sekisui Chemical Co., Ltd.), which is a polyvinyl butyral resin, was added instead of ASPU112.
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the polyvinyl butyral resin concentration was 37.5 wt%.
  • degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the adhesion between the plating base film and the Cu layer interface was good, but part of the test portion was peeled off at the plating base film and PC film interface.
  • Comparative Example 7 A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 1.7 g of Toresin EF-30T (manufactured by Nagase ChemteX Corporation), which is a polyamideimide resin, was added instead of ASPU112.
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the polyamideimide resin concentration was 37.5 wt%.
  • degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the entire test part was peeled off at the interface between the plating base film and the Cu layer.
  • Comparative Example 8 A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 1.7 g of Toresin F-30K (manufactured by Nagase ChemteX Corporation), which is a polyamideimide resin, was added instead of ASPU112.
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the polyamideimide resin concentration was 37.5 wt%.
  • degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the entire test part was peeled off at the interface between the plating base film and the Cu layer.
  • Comparative Example 9 A coating solution for forming a plating base and a plating base film in the same manner as in Example 1 except that 6.8 g of Bilomax HR-87TD (manufactured by Toyobo Co., Ltd., solid content concentration 25%), which is a polyamide-imide resin, is added instead of ASPU112. Was made.
  • the polyaniline complex concentration in the plating base film was 62.5 wt%, and the polyamideimide resin concentration was 37.5 wt%.
  • degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the adhesion between the plating base film and the Cu layer interface was good, but part of the test portion was peeled off at the plating base film and PC film interface.
  • Example 9 3.75 g of the polyaniline powder obtained in Production Example 2 was dissolved in 17 g of MIBK (manufactured by Wako Pure Chemical Industries, Ltd.) and 8.5 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, 2.5 g of ASPU112 (manufactured by DIC Corporation, solid content concentration 30%), which is a urethane resin, was added and stirred to prepare a uniform coating solution for forming a plating base. The obtained coating solution was applied to a Carboglass film C110C (PC film, manufactured by Asahi Glass Co., Ltd.), which is a polycarbonate film, with a bar coater and dried at 120 ° C.
  • MIBK manufactured by Wako Pure Chemical Industries, Ltd.
  • ASPU112 manufactured by DIC Corporation, solid content concentration 30%
  • plating base film The thickness of the plating base film was 1 ⁇ m.
  • the polyaniline complex concentration in the plating base film was 83 wt%, and the urethane resin concentration was 17 wt%.
  • plating was performed in the same manner as in Example 1, and a cross-cut test was performed. As a result, no peeling was observed and the adhesion was good.
  • Example 10 1.5 g of the polyaniline powder obtained in Production Example 2 was dissolved in 17 g of MIBK (manufactured by Wako Pure Chemical Industries, Ltd.) and 8.5 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, 10 g of ASPU112 (made by DIC Corporation, solid content concentration 30%), which is a urethane resin, was added and stirred to prepare a uniform coating solution for forming a plating base. The obtained coating solution was applied to a Carboglass film C110C (PC film, manufactured by Asahi Glass Co., Ltd.), which is a polycarbonate film, with a bar coater and dried at 120 ° C.
  • MIBK manufactured by Wako Pure Chemical Industries, Ltd.
  • ASPU112 made by DIC Corporation, solid content concentration 30%
  • the obtained coating solution was applied to a Carboglass film C110C (PC film, manufactured by Asahi Glass Co., Ltd.), which is a
  • plating base film The thickness of the plating base film was 1 ⁇ m.
  • the polyaniline complex concentration in the plating base film was 33 wt%, and the urethane resin concentration was 67 wt%.
  • plating was performed in the same manner as in Example 1, and a cross-cut test was performed. As a result, no peeling was observed and the adhesion was good.
  • Example 11 Instead of ASPU112 (5.7 g), 2.8 g of urethane resin, diferamin MAU1008 (manufactured by Dainichi Seika Co., Ltd., solid content concentration 30%), and ASPU112 (made by DIC Corporation, solid content concentration 30%), urethane resin ) was added in the same manner as in Example 1 except that 2.8 g was added. Moreover, the plating base film was produced similarly to Example 1 except having used the cosmo shine (PET film, Toyobo Co., Ltd.) which is a polyester resin instead of C110C.
  • the cosmo shine PET film, Toyobo Co., Ltd.
  • Example 12 A plated laminate was obtained in the same manner as in Example 11 except that Kapton (made by Toray DuPont), which is a polyimide resin, was used instead of Cosmo Shine (PET film, produced by Toyobo Co., Ltd.). Then, degreasing, carrying Pd and plating were performed in the same manner as in Example 11 to obtain a plated laminate.
  • Kapton made by Toray DuPont
  • Visco Shine PET film, produced by Toyobo Co., Ltd.
  • Example 13 A plated laminate was obtained in the same manner as in Example 11 except that Torelina (PPS film, manufactured by Toray Industries, Inc.), which is a PPS resin, was used instead of Cosmo Shine (PET film, manufactured by Toyobo Co., Ltd.). Then, degreasing, carrying Pd and plating were performed in the same manner as in Example 11 to obtain a plated laminate.
  • Torelina PPS film, manufactured by Toray Industries, Inc.
  • Cosmo Shine PET film, manufactured by Toyobo Co., Ltd.
  • Table 1 below shows the results of evaluation of adhesion in Examples and Comparative Examples.
  • Example 11 [Plating foundation film forming process] 2.8 g of the polyaniline powder obtained in Production Example 2 was dissolved in 17 g of MIBK (manufactured by Wako Pure Chemical Industries, Ltd.) and 8.5 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, 5.7 g of ASPU112 (made by DIC Corporation, solid content concentration of 30%), which is a urethane resin, was added and stirred to prepare a uniform coating solution for forming a plating base.
  • MIBK manufactured by Wako Pure Chemical Industries, Ltd.
  • ASPU112 made by DIC Corporation, solid content concentration of 30%
  • the obtained coating solution is applied to a part of the surface of a carbo glass film C110C (PC film, PC film, manufactured by Asahi Glass Co., Ltd.), which is a polycarbonate film, with a bar coater, and dried at 120 ° C. for 30 minutes to form a plating base film Formed.
  • the thickness of the plating base film was 1 ⁇ m.
  • the polyaniline concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
  • Pretreatment process 10 g of sodium hydrogen sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 90 g of ion-exchanged water to prepare a 10 wt% sodium hydrogen sulfite aqueous solution. The entire base material provided with the plating base film was immersed in this 10 wt% sodium hydrogen sulfite aqueous solution at 30 ° C. for 5 minutes for degreasing treatment.
  • Example 12 The same procedure as in Example 11 was used except that in the pretreatment step, a 15 wt% sodium hydrogen sulfite aqueous solution prepared by dissolving 15 g of sodium bisulfite in 85 g of ion exchange water was used instead of the 10 wt% sodium hydrogen sulfite aqueous solution. Electrolytic plating treatment was performed. As a result, it was confirmed that uniform copper plating was formed on the plating base film. Moreover, copper plating was not formed in parts other than a plating base film.
  • Example 13 In the pretreatment step, electroless electrolysis was carried out in the same manner as in Example 11 except that 4 wt% sodium hydrogen sulfite aqueous solution prepared by dissolving 4 g of sodium hydrogen sulfite in 96 g of ion-exchanged water instead of 10 wt% sodium hydrogen sulfite aqueous solution was used. Plating treatment was performed. As a result, it was confirmed that uniform copper plating was formed on the plating base film. Moreover, copper plating was not formed in parts other than a plating base film.
  • Comparative Example 10 In the pretreatment step, except that a 4 wt% sodium thiosulfate aqueous solution prepared by dissolving 4 g of sodium thiosulfate (manufactured by Wako Pure Chemical Industries, Ltd.) in 96 g of ion-exchanged water was used instead of the 10 wt% sodium hydrogen sulfite aqueous solution.
  • the electroless plating treatment was performed in the same manner as in Example 11. As a result, no copper plating was formed on the plating base film.
  • Comparative Example 11 Example 11 except that in the pretreatment step, a 4 wt% sodium sulfite aqueous solution prepared by dissolving 4 g of sodium sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) in 96 g of ion-exchanged water instead of the 10 wt% sodium hydrogen sulfite aqueous solution was used.
  • the electroless plating treatment was performed in the same manner as described above. As a result, a portion where copper plating was not formed and a portion where copper plating was not formed were confirmed on the plating base film, and uniform copper plating was not formed.
  • Comparative Example 12 In the pretreatment step, 0.5 wt% sodium borohydride prepared by dissolving 0.5 g of sodium borohydride (Wako Pure Chemical Industries, Ltd.) in 99.5 g of ion-exchanged water instead of 10 wt% sodium hydrogen sulfite aqueous solution The electroless plating treatment was performed in the same manner as in Example 11 except that the aqueous solution was used. As a result, the copper plating was deposited even to the portion without the plating base film, and the copper plating could not be selectively formed only on the plating base film portion.
  • the pH of the reducing agent aqueous solution used in Examples and Comparative Examples is shown below.
  • the pH was measured using a pH meter. 10 wt% sodium bisulfite: pH 4.3 15 wt% sodium bisulfite: pH 4.1 4 wt% sodium bisulfite: pH 4.3 4 wt% sodium thiosulfate: pH 6.5 4 wt% sodium sulfite: pH 9.6 0.5 wt% sodium borohydride: pH 13.2
  • the standard electrode potential E 0 of the reducing agent used in the examples and comparative examples is shown below.
  • the standard electrode potential E 0 was calculated based on the value measured with an oxidation-reduction potentiometer (ORP meter) at 25 ° C.
  • Sodium bisulfite: E 0 ⁇ 0.45V
  • Sodium thiosulfate: E 0 0.08V
  • Sodium sulfite: E 0 ⁇ 0.93 V
  • Sodium borohydride: E 0 ⁇ 1.24V
  • Table 2 shows the evaluation results in Examples and Comparative Examples.
  • “ ⁇ ” indicates that uniform copper plating has been formed on the plating base film, and copper on the plating base film.
  • the case where the plating is formed and the portion where the plating is not formed is confirmed and the uniform copper plating is not formed is indicated as “ ⁇ ”, and the case where no copper plating is formed on the plating base film is indicated as “ ⁇ ”. did.
  • Comparative examples 10 to 12 are considered as follows.
  • Sodium thiosulfate used in Comparative Example 10 has a low reducing power, and polyaniline could not be completely reduced.
  • the sodium sulfite used in Comparative Example 11 had a reducing power under basic conditions, but the solution gradually became acidic as the reaction proceeded, so that it did not have a reducing ability and the plating ability was lowered.
  • the sodium borohydride used in Comparative Example 12 has a very strong reducing power, it eroded the substrate and the base film. Even if a small amount of sodium borohydride remained on the surface of the base material, Pd was supported on the portion other than the base film, thereby causing out-of-range precipitation.
  • composition for forming an electroless plating base film of the present invention can be used for electroless plating.
  • manufacturing method of the electroless-plated product of this invention can be used for electroless plating.

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US10151035B2 (en) 2016-05-26 2018-12-11 Rohm And Haas Electronic Materials Llc Electroless metallization of through-holes and vias of substrates with tin-free ionic silver containing catalysts
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WO2020195905A1 (ja) * 2019-03-27 2020-10-01 出光興産株式会社 導電性高分子を含む溶液組成物
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JPWO2014192287A1 (ja) * 2013-05-28 2017-02-23 出光興産株式会社 無電解めっき下地膜形成用組成物
US10151035B2 (en) 2016-05-26 2018-12-11 Rohm And Haas Electronic Materials Llc Electroless metallization of through-holes and vias of substrates with tin-free ionic silver containing catalysts
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