TWI622641B - Composition for forming electroless plating underlayer film - Google Patents

Abstract

The composition for forming an electroless plating underlayer film of the present invention contains a conductive polymer and a urethane resin.

Description

Composition for forming electroless plating underlayer film

The present invention relates to a method for producing a composition for forming an electroless plating underlayer film, a thin film obtained therefrom, a plated laminate, an electroless plating underlayer film, and a method for producing an electroless plating laminate.

Moreover, this invention relates to the manufacturing method of electroless plating.

The conductive polymer is an electrode of a lithium ion battery used in an electrolytic capacitor or a backup battery of an electronic device, a mobile phone, or a notebook computer.

For example, polyaniline, a type of conductive polymer, has the advantage of exhibiting excellent stability against oxygen and the like in the state of showing conductivity because it can be synthesized relatively easily from inexpensive aniline in addition to the electrical characteristics. And characteristics. In addition, by the method of Patent Document 1, polyaniline having high conductivity can be obtained simply and easily.

In addition, most of the conductive polymers have reducing power, and this feature is being used as a base film for electroless plating, which is attracting attention (Patent Documents 2 to 8).

The electroless plated base film made of polyaniline composite monomer has insufficient adhesion to various substrates such as polycarbonate (PC) or polyethylene terephthalate (PET). Also, the adhesion to the plating layer is insufficient.

[Prior Technical Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2005/052058 Specification

[Patent Document 2] Japanese Patent Laid-Open No. 2007-270180

[Patent Document 3] Japanese Patent Laid-Open No. 2008-163371

[Patent Document 4] Japanese Patent Laid-Open No. 2011-208174

[Patent Document 5] Japanese Patent Laid-Open No. 2011-168814

[Patent Document 6] Japanese Patent Laid-Open No. 2011-168813

[Patent Document 7] Japanese Patent Laid-Open No. 2011-74407

[Patent Document 8] Japanese Patent Application Publication No. 2010-95776

An object of the present invention is to provide a composition for forming an underlayer film with sufficient adhesion to a substrate such as polycarbonate (PC) and sufficient adhesion to a plating layer in electroless plating .

According to the present invention, the following composition for forming an electroless plating underlayer film and the like can be provided.

[1]. Composition for forming electroless plating base film containing conductive polymer and urethane resin.

[2]. The composition for forming an electroless plating underlayer film as described in [1] above, wherein the conductive polymer-based substituted or unsubstituted polyaniline is doped with a dopant Aniline complex.

[3]. The composition for electroless plating underlayer film formation described in [2] above, wherein the dopant is a sulfosuccinic acid derivative represented by the following formula (III).

(In formula (III), M is a hydrogen atom, an organic radical or an inorganic radical, m 'is a valence of M, R ¹³ and R ¹⁴ are respectively a hydrocarbon group or-(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 R ¹⁷ ₃ Si- group, r is an integer of 1 or more, and R ¹⁷ is a hydrocarbon group, respectively).

[4]. The composition for forming an electroless plating underlayer film as described in [2] or [3], wherein the dopant is sodium di-2-ethylhexylsulfosuccinate.

[5]. The composition for forming an electroless plating underlayer film according to any one of the above [1] to [4], wherein the total amount of the conductive polymer and the urethane resin is , The ratio of the aforementioned urethane resin is 20 ~ 80% by weight.

[6]. An electroless plating underlayer film obtained from the composition for forming an electroless plating underlayer film according to any one of the above [1] to [5].

[7]. A plating laminate comprising a metal-containing electroless plating layer, an electroless plating underlayer film containing a conductive polymer and a urethane resin, and a substrate, wherein the aforementioned electroless One side of the plating layer is in contact with one side of the aforementioned electroless plating underlayer film.

[8]. The plated laminate as described in [7] above, wherein the conductive polymer-based substituted or unsubstituted polyaniline is a polyaniline composite doped with a dopant.

[9]. The plated laminate as described in [8] above, wherein the dopant is a sulfosuccinic acid derivative represented by the following formula (III).

(In formula (III), M is a hydrogen atom, an organic radical or an inorganic radical, m 'is a valence of M, R ¹³ and R ¹⁴ are respectively a hydrocarbon group or-(R ¹⁵ O) _r -R ¹⁶ group, R ¹⁵ is a hydrocarbon group or a silyl group, R ¹⁶ is a hydrogen atom, a hydrocarbon group, or R ¹⁷ ₃ Si- group, r is an integer of 1 or more, and R ¹⁷ is a hydrocarbon group, respectively)

[10]. The plated laminate as described in [8] or [9], wherein the dopant is sodium di-2-ethylhexylsulfosuccinate.

[11]. The plated laminate according to any one of the above [7] to [10], wherein the amino acid is added to the total of the conductive polymer and the carbamate resin The proportion of ester resin is 20 to 80% by weight.

[12]. The plated laminate as described in any one of [7] to [11], wherein the metal is copper.

[13]. The plated laminate according to any one of [7] to [12], wherein the substrate is a resin.

[14]. The plated laminate as described in [13] above, wherein the substrate is a polycarbonate resin, polyester resin, polyimide resin, or polyphenylene sulfide resin.

[15]. A method for producing an electroless plating underlayer film, which uses the composition for forming an electroless plating underlayer film as described in any one of claims [1] to [5].

[16]. A manufacturing method of electroless plating laminate, which includes the following steps: A step of forming the electroless plating underlayer film using the composition for forming an electroless plating underlayer film described in any one of the above [1] to [5] on a substrate; and The step of forming a metal-containing electroless plating layer on the aforementioned electroless plating underlayer film.

[17]. Manufacture of electroless plated laminate as described in the aforementioned [16] A method in which palladium is carried on the electroless plating underlayer film, and then the electroless plating layer is formed by bringing it into contact with the electroless plating solution.

[18]. The method for producing an electroless plating laminate as described in [17] above, wherein the palladium chloride solution is brought into contact with the electroless plating underlayer film to support palladium.

[19]. The method for manufacturing an electroless plating laminate as described in any one of the aforementioned [16] to [18], wherein the electroless plating solution contains a material selected from the group consisting of Cu, Ni, Au, Pd, and Ag , Sn, Co and Pt more than one metal.

According to the present invention, in electroless plating, it is possible to provide a composition for forming an underlayer film having sufficient adhesion to a substrate such as PC and sufficient adhesion to a plating layer.

In addition, when polyaniline is used as the primer for electroless plating, a surfactant is conventionally used in the treatment step (degreasing step) before the primer. However, for the purpose of improving the adhesion, when the adhesive is added to the base film, or the film thickness of the base film is too thick, not only the effect of the degreasing step is not good, but the precipitation of the plating is reduced, and it may not form The problem of uniform coating film.

Another object of the present invention is to provide a method for manufacturing an electroless plated product, which can selectively and stably form a uniform plating film for an electroless plated base film portion using a conductive polymer.

According to the present invention, the following method for manufacturing electroless plated products can be provided.

[1]. A method of manufacturing an electroless plated article, comprising the steps of: forming an electroless plated base film containing a conductive polymer on a substrate, and making the aforementioned electroless plated base film and The standard electrode potential E ⁰ is the step of contacting an acidic reducing agent aqueous solution with E ⁰ = -1.00V ~ -0.10V, and forming an electroless plating layer on the electroless plating base film after contact with the aforementioned reducing agent aqueous solution step.

[2]. The method for producing an electroless plated article as described in [1] above, wherein the pH of the reducing agent aqueous solution is 6 or less.

[3]. The method for producing an electroless plated article as described in [1] or [2] above, wherein the pH of the reducing agent aqueous solution is 5 or less.

[4]. The method for producing an electroless plated article according to any one of the above [1] to [3], wherein the pH of the reducing agent aqueous solution is 3 or more.

[5]. The method of manufacturing an electroless plated article as described in any one of the above [1] to [4], wherein the standard electrode potential E ⁰ of the reducing agent aqueous solution is E ⁰ = -0.80V ~ -0.20 V.

[6]. The method for producing an electroless plated article according to any one of the above [1] to [5], wherein the aqueous solution of the reducing agent is an aqueous solution of sodium bisulfite.

[7]. A method of manufacturing an electroless plated article, comprising the steps of: forming an electroless plated base film containing a conductive polymer on a substrate, and making the aforementioned electroless plated base film and Above 2wt% and below 20wt% The step of contacting the sodium bisulfite aqueous solution of the reducing agent aqueous solution, and the step of forming the electroless plating layer on the electroless plating base film after contacting with the aforementioned reducing agent aqueous solution.

[8]. The method for producing an electroless plated article according to any one of the above [1] to [7], wherein the conductive polymer-based substituted or unsubstituted polyaniline is doped with a dopant Polyaniline complex.

[9]. The method for producing an electroless plated article as described in [8] above, wherein the dopant is represented by the following formula (III).

(In formula (III), M is a hydrogen atom, an organic radical or an inorganic radical, m 'is a valence of M, R ¹³ and R ¹⁴ are respectively a hydrocarbon group or-(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 R ¹⁷ ₃ Si- group, r is an integer of 1 or more, and R ¹⁷ is a hydrocarbon group, respectively).

[10]. The method for producing an electroless plated article as described in any one of the above [1] to [9], wherein the electroless plated underlayer film is formed on a part of the surface of the substrate, and The electroless plating layer is formed only on the formed electroless plating underlayer film.

[11]. The method for producing an electroless plated article as described in any one of the above [1] to [10], wherein after the contacting step with the reducing agent aqueous solution, Before the step of forming the electroless plating layer, there is a supporting step of supporting the electroless plating solution catalyst metal on the electroless plating underlayer film.

[12]. The method for producing an electroless plated article as described in [11] above, wherein the catalyst metal for the electroless plating solution is palladium.

[13]. The method for producing an electroless plated article as described in [11] or [12], wherein after the solution containing palladium ions is brought into contact with the electroless plated base film, the supporting step is performed.

[14]. The method for producing an electroless plated article as described in [13] above, wherein the solution containing palladium ions is a palladium chloride solution.

[15]. The method for producing an electroless plated article according to any one of the above [1] to [14], wherein the electroless plating solution is brought into contact with the electroless plating after contact with the aqueous solution of the reducing agent After the underlayer film, the aforementioned electroless plating layer is formed.

[16]. The method for producing an electroless plated article as described in [15] above, wherein the electroless plating solution comprises a material selected from the group consisting of copper, nickel, cobalt, palladium, silver, gold, platinum and tin More than one metal ion.

According to the present invention, it is possible to provide a method for manufacturing an electroless plated article, which can selectively and stably form a uniform plated film for an electroless plated base film portion using a conductive polymer.

1‧‧‧plated laminate

10‧‧‧ substrate

20‧‧‧ Electroless plating bottom layer

30‧‧‧electroless plating

Fig. 1 is a schematic view showing the layer configuration of one embodiment of the plated laminate of the present invention.

[The best form for carrying out the invention]

[1] Composition for forming an electroless plating underlayer film, thin film obtained therefrom, a plated laminate, a method for producing an electroless plating underlayer film, and a method for producing an electroless plating laminate

The composition for forming an electroless plating underlayer film of the present invention includes a conductive polymer and a urethane resin.

The so-called electroless plating refers to a method of plating a metal with an autocatalyst function that uses a reducing agent without electrical decomposition. For example, when electroless copper plating, a reducing agent such as formaldehyde is used to reduce the copper in the solution After ionization, the metal copper film is precipitated, and the precipitated metal copper becomes an autocatalyst, and then the copper ion is metallized and the chemical process of precipitation.

The composition of the present invention is used to form the bottom layer of an electroless plating layer.

The composition of the present invention is a mixture of a urethane resin as a tackifier to improve the adhesion, and the adhesion to various substrates such as PC or PET is sufficient, and the adhesion to the plating layer is also Excellent, so it can be used as a plated laminate with good adhesion.

[Conductive polymer]

As the conductive polymer, a π-conjugated polymer can be exemplified as a π-conjugated polymer composite doped with a dopant, specifically, a substituted or unsubstituted polyaniline can be exemplified as a dopant Doped polyaniline The composite, substituted or unsubstituted polypyrrole is a polypyrrole composite doped with a dopant, and the substituted or unsubstituted polythiophene is a polythiophene composite doped with a dopant, Preferably, the substituted or unsubstituted polyaniline is a polyaniline composite doped with a dopant.

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 or extensibility 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 and 53,000 to 200,000. Here, the above-mentioned weight average molecular weight is not the molecular weight of the polyaniline composite, 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 electrical conductivity, it is preferable that the polydispersity is small (that is, the molecular weight distribution is narrow), and from the viewpoint of the solubility or moldability of the solvent, the polydispersity is sometimes greater (That is, the molecular weight distribution is broad) is preferable.

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, ethyl, hexyl, and octyl; alkoxy groups such as methoxy and ethoxy; and aryloxy groups such as phenoxy Group; halogenated hydrocarbon groups such as trifluoromethyl (-CF ₃ group).

From the viewpoint of versatility and economy, the polyaniline is preferably an unsubstituted polyaniline.

The substituted or unsubstituted polyaniline is preferably a polyaniline obtained by polymerization in the presence of an acid containing no chlorine atom. The acid that does not contain a chlorine atom means an acid composed of atoms belonging to Groups 1 to 16 and 18, for example. Specifically, phosphoric acid can be exemplified. As the polyaniline obtained by polymerization in the presence of an acid not containing a chlorine atom, polyaniline obtained by polymerization in the presence of phosphoric acid can be exemplified.

The polyaniline obtained in the presence of an acid that does not contain a chlorine atom can further reduce the chlorine content of the polyaniline complex.

The chlorine content of the polyaniline composite is preferably 0.6% by weight or less, more preferably 0.1% by weight or less, more preferably 0.04% by weight or less, and most preferably 0.0001% by weight or less.

If the chlorine content of the polyaniline composite exceeds 0.6% by weight, the metal part in contact with the polyaniline composite may be corroded.

The chlorine content is measured by the combustion-ion chromatography method.

As the dopant of the polyaniline complex, for example, the Bronsted acid ion produced by Broensted acid or a salt of Brunsted acid, preferably an organic acid or a salt of an organic acid The generated organic acid ion is more preferably an organic acid ion generated from a compound (proton donor) represented by the following formula (I).

Still, in the present invention, when the dopant is represented by a specific acid, and the dopant is represented by a specific salt, whether it is a specific acid ion produced by a specific acid or a specific salt, It is assumed to be doped with the π-conjugated polymer.

M (XARn) m (I)

M in formula (I) is a hydrogen atom, an organic radical or an inorganic radical.

Examples of the above-mentioned organic radicals include pyridinium group, imidazolyl group, and anilium group. Examples of the inorganic radicals include ions of lithium, sodium, potassium, cesium, ammonium, calcium, magnesium, and iron.

X of formula (I) of the anionic group can be exemplified, for example, -SO ₃ ^- group, -PO ₃ ^2- group, -PO ₄ (OH) ^- group, -OPO ₃ ^2- group, -OPO ₂ (OH) ^- group , -COO ^- group, preferably -SO ₃ ^- group.

A of formula (I) is a substituted or unsubstituted hydrocarbon group.

The above-mentioned hydrocarbon group is a chain or cyclic saturated aliphatic hydrocarbon group, a chain or cyclic unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group.

As the chain-shaped saturated aliphatic hydrocarbon group, a linear or branched alkyl group can be exemplified.

Examples of cyclic saturated aliphatic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. The cyclic saturated aliphatic hydrocarbon group may be polymerized by plural cyclic saturated aliphatic hydrocarbon groups. Examples may include norbornyl, adamantyl, and polymerized adamantyl.

Examples of the aromatic hydrocarbon group include phenyl, naphthyl and anthracenyl. As the chain-shaped unsaturated aliphatic hydrocarbon group, a linear or branched alkenyl group can be exemplified.

Here, if A is a substituted hydrocarbon group, the substituents are alkyl, cycloalkyl, vinyl, allyl, aryl, alkoxy, halo, hydroxyl, amine, imino, nitro, Silyl (silyl) or ester group.

R of formula (I) is bonded to A, and -H, -R ¹ , -OR ¹ , -COR ¹ , -COOR ¹ ,-(C = O)-(COR ¹ ), or-(C = O)-(COOR ¹ ) substituent, R ¹ may also include a substituent hydrocarbon group, silane group, alkyl silane group,-(R ² O) xR ³ group, or-(OSiR ³ ₂ ) x -OR ³ . R ² is an alkylene group, R ³ is a hydrocarbon group, and x is an integer of 1 or more.

Examples of the hydrocarbon group for R ¹ include methyl, ethyl, linear or branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, di Decayl and so on. Moreover, the substituent of the said 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 hydroxyl group, an amine group, an imino group, a nitro group, or an ester group. The hydrocarbon group of R ³ is also the same as R ¹ .

Examples of the alkylene group of R ² include methylene group, ethyl group, and propyl group.

N in formula (I) is an integer of 1 or more, and m in formula (I) is the price of M / the price of X.

The compound represented by formula (I) is preferably a dialkylbenzenesulfonic acid, a dialkylnaphthalenesulfonic acid, or a compound containing 2 or more ester bonds.

The compound containing 2 or more ester bonds is more preferably a sulfophthalate or a compound represented by the following formula (II).

In 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 respectively hydrogen atom, hydrocarbon group or R ⁹ ₃ Si- group. Here, three R ⁹ are each a hydrocarbon group.

As the hydrocarbon group when R ⁴ , R ⁵ and R ⁶ are hydrocarbon groups, a straight-chain or branched alkyl group having 1 to 24 carbon atoms, an aryl group, an alkylaryl group, etc. may be mentioned.

The hydrocarbon group of R ⁹ is the same as the case of R ⁴ , R ⁵ and R ⁶ .

R ⁷ and R ^{8 in} 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-, and q is an integer of 1 or more. The three R ¹² are each a hydrocarbon group.

As the hydrocarbon group when R ⁷ and R ⁸ are hydrocarbon groups, the carbon number is 1 to 24, preferably linear or branched alkyl group, aryl group, alkyl aryl group having 4 or more carbon atoms, etc., as R ⁷ When R ⁸ is a hydrocarbon group, specific examples of the hydrocarbon group include linear or branched butyl, pentyl, hexyl, octyl, and decyl groups.

In R ⁷ and R ⁸ , as the hydrocarbon group when R ¹⁰ is a hydrocarbon group, for example, a straight-chain or branched alkylene group having 1 to 24 carbon atoms, an aryl group, an alkylene group, or an aryl alkylene group. In addition, in R ⁷ and R ⁸ , when R ¹¹ and R ¹² are hydrocarbon groups, the hydrocarbon groups are the same as in the case of R ⁴ , R ^5, and R ⁶ , and q is preferably 1-10.

As specific examples of the compound represented by formula (II) when R ⁷ and R ⁸ are-(R ¹⁰ O) _q -R ¹¹ groups, two kinds of compounds represented by the following formulas are used.

(In the formula, X is the same as the formula (I)).

The compound represented by the above formula (II) is more preferably a sulfosuccinic acid derivative represented by the following formula (III).

In formula (III), M is the same as formula (I). m 'is the price of M.

R ¹³ and R ¹⁴ are each a hydrocarbon group or-(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 R ¹⁷ ₃ Si- group, and r is an integer of 1 or more. The three R ¹⁷ are each a hydrocarbon group.

When R ¹³ and R ¹⁴ are hydrocarbon groups, they are the same as R ⁷ and R ⁸ .

In R ¹³ and R ¹⁴ , the hydrocarbon group when R ¹⁵ is a hydrocarbon group is the same as R ¹⁰ described above. In addition, R ¹³ and R ¹⁴ are the same as R ⁴ , R ⁵ and R ⁶ when R ¹⁶ and R ¹⁷ are hydrocarbon groups.

r is preferably 1-10.

Specific examples of when R ¹³ and R ¹⁴ are-(R ¹⁵ O) _r -R ¹⁶ groups are the same as-(R ¹⁰ O) _q -R ¹¹ in R ⁷ and R ⁸ .

The hydrocarbon groups of R ¹³ and R ^{14 are} the same as R ⁷ and R ⁸ , and preferably butyl, hexyl, 2-ethylhexyl, and decyl.

It is known that the above dopant can control the conductivity of the polyaniline composite or the solubility in the solvent by changing the structure (Japanese Patent No. 3384566). In the present invention, the most suitable dopant can be selected according to the required characteristics of individual applications. In the present invention, the compound represented by formula (I) is preferably di-2-ethylhexylsulfosuccinic acid and sodium di-2-ethylhexylsulfosuccinate (Aerosol OT). As the dopant of the present invention, di-2-ethylhexylsulfosuccinate ion is preferred.

The dopant of the polyaniline complex can be confirmed by ultraviolet, visible or near-infrared spectroscopy, or X-ray photoelectron spectroscopy to determine whether it is doped with substituted or unsubstituted polyaniline, as long as the dopant is capable of The polyaniline-generating carrier may be sufficiently acidic, and it can be used without any special restrictions on chemical structure.

The doping rate of the polyaniline dopant is preferably 0.35 or more and 0.65 or less, more preferably 0.42 or more and 0.60 or less, more preferably 0.43 or more and 0.57 or less, and particularly preferably 0.44 or more and 0.55 or less. If the doping rate is less than 0.35, the solubility of the polyaniline composite in organic solvents may not be improved.

Still, the doping rate is defined by (the number of moles of dopant doped in polyaniline) / (the number of moles of monomer unit of polyaniline). For example, when the doping rate of the polyaniline composite containing unsubstituted polyaniline and dopant is 0.5, it means that one dopant is doped with respect to two monomer unit molecules of polyaniline.

Still, as long as the molar number of the monomer unit of the dopant and polyaniline in the polyaniline composite can be measured, the doping rate can be calculated. For example, when the dopant is an organic sulfonic acid, the number of moles of sulfur atoms of the dopant and the number of nitrogen atoms of the monomer unit of polyaniline are determined by organic element analysis The ratio of these values can calculate the doping rate. However, the method of calculating the doping rate is not limited to this method.

The polyaniline composite system contains sulfonic acid ions of unsubstituted polyaniline and a dopant, and preferably 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).

In addition, the mole number of the above-mentioned nitrogen atom and sulfur atom is a value measured by, for example, an organic element analysis method.

The polyaniline composite may further contain phosphorus or not.

When the polyaniline composite contains phosphorus, the content of phosphorus is, for example, 10 wtppm or more and 5000 wtppm or less. Moreover, the phosphorus content is, for example, 2000 wtppm or less, 500 wtppm or less, 250 wtppm the following.

The phosphorus content can be measured by ICP emission spectrometry.

In addition, the polyaniline composite preferably contains no Group 12 element (for example, zinc) as an impurity.

The polyaniline composite system can be manufactured by a well-known manufacturing method, for example, by performing substitution 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 Manufactured by chemical oxidation polymerization. In addition, it can be produced by adding an oxidative polymerization agent to a solution having two liquid phases including a substituted or unsubstituted aniline, a proton donor, phosphoric acid, and an emulsifier different from the proton donor.

Still, the emulsifier is believed to serve the function of preventing the phase change mentioned later. When a polyaniline composite is produced by chemical oxidation polymerization of substituted or unsubstituted aniline in a solution containing a proton donor and phosphoric acid and having two liquid phases, it is lower than the case where hydrochloric acid is used instead of phosphoric acid The molecular weight component is increased. Here, from the aspect of polymerization when phosphoric acid is used, it is considered that the above two liquid phase systems undergo phase inversion during polymerization. In addition, it is considered that this phase change is a reason for increasing the low molecular weight component. The so-called phase change phenomenon refers to the phenomenon that the liquid phase of the continuous phase changes into a dispersed phase, and the liquid phase of the other side of the dispersed phase changes into a continuous phase.

Here, the so-called "solution with two liquid phases" refers to the existence of two liquid phases that are incompatible in the solution. For example, in the solution, there is a "high-polar solvent phase" and a "low-polar solvent phase". The meaning of status.

In addition, "a solution having two liquid phases" also includes a state where one liquid phase is a continuous phase and the other liquid phase is a dispersed phase. For example, it may include the state where the "high-polar solvent phase" is the continuous phase and the "low-polar solvent phase" is the dispersed phase, and the "low-polar solvent phase" is the continuous phase and the "high-polar solvent phase" is the dispersed phase. status.

The high-polarity solvent used in the method for producing the polyaniline composite is preferably water; and the low-polarity solvent is preferably aromatic hydrocarbons such as toluene and xylene.

The proton donor is preferably a compound represented by the above formula (I).

The use amount of the proton donor is 1 mol per aniline single body, preferably 0.1 to 0.5 mol, more preferably 0.3 to 0.45 mol, more preferably 0.35 to 0.4 mol.

If the usage amount of the proton donor is more than this range, after the completion of the polymerization, for example, there is a possibility that the "high polar solvent phase" and the "low polar solvent phase" may not be separated.

The above emulsifiers can use any of ionic emulsifiers whose hydrophilic part is ionic, and nonionic emulsifiers whose hydrophilic part is nonionic, and can also mix 1 or 2 types Use the above emulsifier.

Examples of the ionic emulsifiers include cationic emulsifiers, anionic emulsifiers and amphoteric emulsifiers.

As a specific example of the anionic emulsifier (anionic emulsifier), Examples are fatty acids, heterogeneous rosin soaps, higher alcohol esters, polyoxyethylene alkyl ether phosphates, alkenyl succinic acid, sarcosinate, and salts of these.

Specific examples of the cationic emulsifier (cationic emulsifier) include alkyl dimethyl benzyl ammonium salt and alkyl trimethyl ammonium salt.

Specific examples of the amphoteric emulsifier (zwitterionic emulsifier) include alkyl betaine type, alkyl amide betaine type, amino acid type, and amine oxide type.

Specific examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polypropylene glycol polyethylene glycol ether, polyoxyethylene glycerol borate fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.

Among the above emulsifiers, anionic emulsifiers and nonionic emulsifiers are preferred.

As the anionic emulsifier, an anionic emulsifier having a phosphate structure is more preferable. Moreover, as the nonionic emulsifier, a nonionic emulsifier having a polyoxyethylene sorbitan fatty acid ester structure is more preferable.

The amount of the emulsifier used is 1 mol per aniline unit, preferably 0.001 to 0.1 mol, more preferably 0.002 to 0.02 mol, more preferably 0.003 to 0.01 mol.

When the amount of the emulsifier used is more than this range, there is a possibility that the "high polar solvent phase" and the "low polar solvent phase" cannot be separated after the polymerization is completed.

The concentration of phosphoric acid is 0.3 to 6 mol / L, preferably 1 to 4 mol / L, more preferably 1 to 2 mol / L, relative to the highly polar solvent.

As an oxidant used in chemical oxidative polymerization, it can be used Sodium persulfate, potassium persulfate, persulfate such as ammonium persulfate, peroxide such as hydrogen peroxide, ammonium dichromate, ammonium perchlorate, potassium iron (III) sulfate, iron (III) chloride , Manganese dioxide, iodic acid, potassium permanganate, or iron p-toluenesulfonate, etc., preferably persulfates such as ammonium persulfate.

These oxidants can be used alone or in combination of two or more.

The amount of the oxidizing agent used is 1 mol per aniline unit, 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. By setting the use amount of the oxidizing agent within this range, a sufficient degree of polymerization can be obtained. In addition, since aniline is sufficiently polymerized, liquid separation and recovery are easy, and the solubility of the polymer does not decrease.

The polymerization temperature is usually -5 to 60 ° C, preferably -5 to 40 ° C. In addition, the polymerization temperature may be changed during the polymerization reaction. With the polymerization temperature within this range, side reactions can be avoided.

The polyaniline composite can be produced specifically using the following method.

Toluene is a solution in which a proton donor and an emulsifier are dissolved, and placed in a separator bottle under an inert atmosphere of nitrogen or the like, and then substituted or unsubstituted aniline is added to the solution. After that, phosphoric acid (which does not contain chlorine as an impurity) was added to this solution, and the solution temperature was cooled.

After the internal temperature of the solution was cooled, it was stirred. Using a dropping funnel, a solution in which ammonium persulfate was dissolved in phosphoric acid was dropped to allow the reaction to proceed. After that, the temperature of the solution was increased and the reaction was continued. After the reaction is completed, the liquid phase that is separated into two phases by standing is separated. Toluene is added to the organic phase side, and washed with phosphoric acid and ion-exchanged water to obtain polyaniline Toluene solution of the complex (protonated polyaniline).

The insoluble matter contained in the obtained composite solution was removed, and the toluene solution of the polyaniline composite was recovered. This solution was transferred to an evaporator, and volatiles were evaporated and distilled off by heating and depressurizing to obtain a polyaniline complex.

The molecular weight, molecular weight distribution, and substituents of the substituted polypyrrole of polypyrrole are the same as the above-mentioned polyaniline.

The dopant of the polypyrrole complex is not particularly limited, and an acceptor dopant suitable for use in a conductive polymer generally made of a polymer containing pyrrole and / or a pyrrole derivative can be suitably used.

Representative types include: polystyrene sulfonic acid, p-toluene sulfonic acid, methane sulfonic acid, trifluoromethane sulfonic acid, anthraquinone sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid, sulfosalic acid, dodecylbenzene Sulfonic acids such as sulfonic acid, allyl sulfonic acid, etc .; halogens such as perchloric acid, chlorine, bromine, Lewis acid, protonic acid, etc. These can be in acid form or salt form. From the viewpoint of the solubility of the monomer, tetrabutylammonium perchlorate, tetraethylammonium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium trifluoromethanesulfonate, Tetrabutylammonium fluorosulfonamide, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, etc.

When the dopant is used, the amount of the dopant used is preferably 0.01 to 0.3 molecules per unit of the pyrrole polymer unit. If it is 0.01 molecules or less, the doping amount necessary to form a sufficient conductive path becomes insufficient, making it difficult to obtain high conductivity. On the other hand, even if 0.3 molecules or more is added, since the doping rate cannot be improved, the addition of 0.3 molecules or more dopants is economically unsuitable. Here, all The so-called pyrrole polymer unit unit refers to a repeating portion corresponding to one molecule of the monomer of the pyrrole polymer obtained by polymerizing the pyrrole monomer.

The molecular weight, molecular weight distribution, and substituents of the substituted polythiophene of polythiophene are the same as those of the above polyaniline. The substituted polythiophene is preferably polyethylenedioxythiophene (PEDOT).

Examples of the dopant of the polythiophene complex include organic acid ions and inorganic acid ions of anionic surfactants. Examples of the organic acid ion of the anionic surfactant include sulfonic acid ions and esterified sulfate ions. Examples of inorganic acid ions include sulfate ion, halogen ion, nitric acid ion, perchloric acid ion, hexacyanoferrate ion, phosphoric acid ion, and phosphomolybdate ion.

[Urethane resin]

As the urethane resin, for example, a product obtained by reacting polyisocyanate and polyalcohol can be used.

The polyisocyanate is not particularly limited as long as it has at least two isocyanate groups, and known types can be used.

Specifically, there are, for example, TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate), XDI (xylene diisocyanate), NDI (naphthyl 1,5-diisocyanate), TMXDI ( Aromatic isocyanates such as tetramethylene xylene diisocyanate), IPDI (isophorone diisocyanate), H12MDI (hydrogenated MDI, dicyclohexylmethane diisocyanate), H6XDI (hydrogenated XDI), etc. Aliphatic isocyanate such as alicyclic isocyanate, HDI (hexamethylene diisocyanate), DDI (dimer acid diisocyanate), NBDI (norbornene diisocyanate), etc. These can be used alone or in combination of two or more.

In addition, examples of the polyalcohol include polyetherpolyols such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol, polyethylene adipate, and polyethylene adipate. Polyester-polyols such as polyethylene-butylene adipate, polycaprolactone, acrylic polyols, polycarbonate polyols, polydimethylsiloxane-epoxy Ethane adducts, polydimethylsiloxane-propylene oxide adducts, castor oil, etc. These can be used alone or in combination of two or more.

Because the urethane resin has soft extensibility, even if it is mixed with polyaniline, the extension followability of polyaniline is not impaired.

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% ~ 90wt%, preferably 20wt% ~ 80wt%, more preferably 30wt% ~ 60wt%, most preferably 40wt% ~ 60wt%.

If the content is too small, it will not exhibit adhesion to the substrate and may be easily peeled off. In addition, if the amount is too large, the ratio of polyaniline decreases, so that the precipitation property of plating may deteriorate.

As the urethane resin, specific examples include HYDRAN series of HYDRAN AP-20, AP-30F, AP-40F, WLS-213 (manufactured by DIC), UCOAT UX-150, UX- 200, UX-310, UWS-145 and other UCOAT series (manufactured by Sanyo Chemicals), Acrit WBR-2018, WBR-016U, WEM-3008 and other Acrit series (manufactured by Dacheng Fine Chemical), PTG-RSN (DIC Graphics Company system) etc.

The urethane resin system usually has a structure represented by the following formula.

In the formula, R and X are derived from monomers when synthesizing the urethane resin, respectively, are substituted or unsubstituted divalent aromatic hydrocarbon groups, substituted or unsubstituted divalent aliphatic hydrocarbon groups, or 1 or more A substituted or unsubstituted divalent aromatic hydrocarbon group is a divalent group to which at least one substituted or unsubstituted divalent aliphatic hydrocarbon group is bonded in any order.

Examples of the divalent aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 50 carbon atoms in the ring. Specifically, phenylene, naphthyl and the like can be mentioned.

Examples of the divalent aliphatic hydrocarbon group 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 methylene, ethylidene, and propylidene.

Examples of the divalent group in which the above 1 divalent aromatic hydrocarbon group and the above 1 divalent aliphatic hydrocarbon group are bonded in any order include a group bonded by phenylene and methylene, and naphthalene. The base to which the ethyl group and ethyl group are bonded, etc.

Examples of the substituent when having a substituent include a hydroxyl group, a carboxyl group, and a nitro group Group, cyano group, amine group, etc.

The composition of the present invention may contain other components in addition to the conductive polymer, the urethane resin and the solvent, as long as the effect of the present invention is not impaired, or may consist essentially of the conductive polymer, The urethane resin and the solvent, or consist only of the conductive polymer, the urethane resin and the solvent.

Here, "substantially" means that 95% by weight or more and 100% by weight or less (preferably 98% by weight or more and 100% by weight or less) of the composition is a conductive polymer, a urethane resin and a solvent .

Examples of other components include phenolic compounds and heat-resistant stabilizers described later.

When the composition of the present invention contains a polyaniline composite as a conductive polymer, it may further contain a phenolic compound.

The phenolic compound is not particularly limited as long as it has a phenolic hydroxyl group. The compound having a phenolic hydroxyl group means, for example, a compound having one phenolic hydroxyl group, a compound having a plurality of phenolic hydroxyl groups, and a polymer compound composed of 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).

(In the formula, n is an integer of 1 to 5, preferably 1 to 3, and more preferably 1.

R is alkyl having 1 to 20 carbons, alkenyl, cycloalkyl, aryl, alkylaryl or arylalkyl).

In the phenolic compound represented by formula (A), the substitution position of -OR is preferably meta or para to the phenolic hydroxyl group. By setting the substitution position of -OR to the meta or para position, the steric hindrance of the phenolic hydroxyl group can be reduced and the conductivity of the composition can be further improved.

Specific examples of the phenolic compound represented by formula (A) include methoxyphenol (eg 4-methoxyphenol), ethoxyphenol, propoxyphenol, isopropoxyphenol, butoxy Phenol, isobutoxyphenol, and third butoxyphenol.

(In the formula, n is an integer of 0 ~ 7, preferably 0 ~ 3, and more preferably 1.

R is respectively 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, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms).

As a specific example of the phenolic compound represented by the formula (B), there can be exemplified Hydroxynaphthalene.

(In the formula, n is an integer of 1 to 5, preferably 1 to 3, and more preferably 1.

R is respectively 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, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms).

As a specific example of the compound represented by the formula (C), o-, m- or p-cresol, o-, m- or p-ethylphenol, o-, m- or p-propylphenol can be exemplified (Eg 4-isopropylphenol), o-, m- or p-butylphenol, o-, m- or p-pentylphenol (eg 4-tert-pentylphenol).

Regarding R of the formulas (A), (B) and (C), as the alkyl group having 1 to 20 carbon atoms, there can be exemplified methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third Butyl and so on.

As the alkenyl group, a group having an unsaturated bond in the molecule of the above alkyl group can be exemplified.

Examples of cycloalkyl groups include cyclopentane and cyclohexane.

Examples of the aryl group include phenyl and naphthyl.

As the alkylaryl group and the arylalkyl group, the above-mentioned alkyl group and After the aryl group and so on.

An example of the above compound having one phenolic hydroxyl group is shown, but specific examples of 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 compounds represented by the following formula (D).

(In the formula, R is a hydrocarbon group, a hydrocarbon group containing a heteroatom, a halogen atom, a carboxylic acid group, an amine group, a SH group, a sulfonic acid group, or a hydroxyl group, and a plurality of R may be the same or different from each other. N is 0 ~ An integer of 6).

The phenolic compound represented by formula (D) preferably has two or more hydroxyl groups that are not adjacent to each other.

In addition, specific examples of the phenolic compound represented by the formula (D) include 1,6-naphthalenediol, 2,6-naphthalenediol, and 2,7-naphthalenediol.

Specific examples of the polymer compound composed of a repeating unit having one or more phenolic hydroxyl groups include phenol resin, polyphenol, and poly (hydroxystyrene).

When the composition of the present invention contains a polyaniline complex as a conductive polymer, the content of the phenolic compound is preferably 0.01 [mmol / g] relative to 1 g of the polyaniline complex. the above 100 [mol / g] or less, preferably 0.05 [mmol / g] or more and 1 [mol / g] or less, more preferably 0.1 [mmol / g] or more and 500 [mmol / g] or less, particularly preferably 0.2 [ mmol / g] to 80 [mmol / g "or less.

If the content of the phenolic compound is too small, there is a possibility that the effect of improving the electrical conductivity cannot be obtained. On the other hand, if the content of the phenolic compound is too large, the film quality may deteriorate. In addition, when removing the volatilization, a lot of labor such as heat or time is required to increase the cost.

When the composition of the present invention contains a polyaniline composite as a conductive polymer, it may further contain a heat-resistant stabilizer.

The heat-resistant stabilizer refers to an acidic substance or a salt of an acidic substance, and the acidic substance may be any of an organic acid (acid of an organic compound) and an inorganic acid (acid of an inorganic compound). In addition, the conductive polymer layer may contain a plurality of heat-resistant stabilizers.

If the composition of the present invention contains only an acidic substance as a heat-resistant stabilizer, the acidic substance is preferably a compound different from the proton donor of the polyaniline complex; and if the composition of the present invention contains only an acid-resistant substance When the salt of the acidic substance of the stabilizer is used, the salt of the acidic substance is preferably a compound different from the proton donor of the polyaniline complex.

Moreover, when the composition of the present invention contains both an acidic substance and a salt of an acidic substance as a heat-resistant stabilizer, it is preferable that at least one of the acidic substance and the salt of the acidic substance is different from the proton donor compound of.

If the composition of the present invention contains only an acidic substance as a heat-resistant stabilizer, it is preferable that the acidic substance and the phenolic compound are different; if the composition of the present invention contains only an acidic substance as a heat-resistant stabilizer, In the case of salts, it is preferable that the salt of the acidic substance is different from the phenolic compound.

Moreover, when the composition of the present invention contains both an acidic substance and a salt of an acidic substance as a heat-resistant stabilizer, it is preferable that at least one of the acidic substance and the salt of the acidic substance be in phase with the phenolic compound different.

The acidic substance of the heat-resistant stabilizer is preferably an organic acid, and more preferably an organic acid having one or more sulfonic acid groups, carboxyl groups, phosphoric acid groups, or phosphonic acid groups, more preferably one or more sulfonic acids Based organic acids.

The organic acid having at least one sulfonic acid group is preferably a cyclic, chain or branched alkyl sulfonic acid having one or more sulfonic acid groups, a substituted or unsubstituted aromatic sulfonic acid, or Polysulfonic acid.

Examples of the 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.

Examples of the aromatic sulfonic acid include sulfonic acid having a benzene ring, sulfonic acid having a naphthalene skeleton, sulfonic acid having an anthracene skeleton, substituted or unsubstituted benzenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, and substituted Or unsubstituted anthracene sulfonic acid, preferably naphthalene sulfonic acid. Specific examples include naphthalenesulfonic acid, dodecylbenzenesulfonic acid, and anthraquinonesulfonic acid.

As the substituent, for example, a substituent selected from the group consisting of alkyl, alkoxy, hydroxyl, nitro, carboxy, and acetyl may be substituted with one or more.

The above polysulfonic acid is a sulfonic acid substituted with a plurality of sulfonic acid groups on the main chain or side chain of the polymer chain. Examples are polystyrene sulfonic acid.

The organic acid having more than one carboxyl group is preferably a cyclic, chain or branched alkyl carboxylic acid having more than one carboxyl group, Substituted or unsubstituted aromatic carboxylic acid, or polycarboxylic acid.

Examples of the alkyl carboxylic acid include undecylenic acid, cyclohexanecarboxylic acid, and 2-ethylhexanecarboxylic acid. Here, the alkyl group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms.

Examples of the substituted or unsubstituted aromatic carboxylic acid include substituted or unsubstituted benzene carboxylic acid and naphthalene carboxylic acid. Here, the substituent is, for example, a substituent selected from the group consisting of: sulfonic acid group, alkyl group, alkoxy group, hydroxyl group, nitro group, and acetyl group, and may be substituted by one or more. As specific examples, salicylic acid, benzoic acid, naphthoic acid, trimesic acid can be mentioned.

Organic acids having more than one phosphoric acid group or phosphonic acid group, preferably cyclic, chain or branched alkyl phosphoric acid or alkylphosphonic acid having more than one phosphoric acid group or phosphonic acid group; substitution Or unsubstituted aromatic phosphoric acid or aromatic phosphonic acid; polyphosphoric acid or polyphosphonic acid.

Examples of the aforementioned alkyl phosphoric acid or alkyl phosphonic acid include dodecyl phosphoric acid and bis (2-ethylhexyl hydrogen phosphate). Here, the alkyl group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms.

Examples of the aromatic phosphoric acid and aromatic phosphonic acid include substituted or unsubstituted benzenesulfonic acid or phosphonic acid, naphthalenesulfonic acid or phosphonic acid, and the like. The substituent is, for example, a substituent selected from the group consisting of alkyl, alkoxy, hydroxy, nitro, carboxy, and acetyl, and may be substituted with one or more. Examples include phenylphosphonic acid.

Examples of the salt of the acidic substance containing the composition of the present invention include the salts of the above-mentioned acidic substances.

The composition of the present invention may also contain more than two heat-resistant stabilizers Acidic substances and / or salts of acidic substances. Specifically, the composition of the present invention may contain a plurality of different acidic substances and / or a salt of different plurality of acidic substances.

The proton donor of the polyaniline complex is sulfonic acid, and if the composition of the present invention contains only an acidic substance as a heat-resistant stabilizer, the acidic substance is preferably the same or different sulfonic acid as the proton donor. In addition, when the composition of the present invention contains only a salt of an acid substance as a heat-resistant stabilizer, the salt of the acid substance is preferably a salt of sulfonic acid which is the same as or different from the proton donor of the polyaniline complex.

When the composition of the present invention contains an acidic substance as a heat-resistant stabilizer and a salt of the aforementioned acidic substance, at least one of the acidic substance and the salt of the acidic substance is preferably the same or different sulfonate as the proton donor Salt of acid or sulfonic acid.

If the composition of the present invention contains only sulfonic acid as a heat-resistant stabilizer, it is preferably in accordance with formula (12); if the composition of the present invention contains only a salt of sulfonic acid as a heat-resistant stabilizer, it is preferably It meets formula (13); when the composition of the present invention contains sulfonic acid and a salt of sulfonic acid as a heat-resistant stabilizer, it preferably conforms to formula (14).

0.01 ≦ S ₂ / N ₂ ≦ 0.5 (12)

0.01 ≦ S ₃ / N ₃ ≦ 0.5 (13)

0.01 ≦ S ₄ / N ₄ ≦ 0.5 (14)

(Here, S ₂ is the total number of moles of sulfur atoms of all acidic substances contained in the composition of the present invention, and N ₂ is of all nitrogen atoms of the polyaniline complex contained in the composition of the present invention The total number of moles means; S ₃ is the total number of moles of sulfur atoms of the salts of all acidic substances contained in the composition of the invention, and N ₃ is the total polyaniline contained in the composition of the invention the molar sum of the number of nitrogen atoms composite meaning; the total number of S ₄ molar composition of the present invention, the salt of the sulfur atom contained in all of the acidic substance and the acidic substance, N ₄ of the present invention (The total number of moles of nitrogen atoms of all polyaniline complexes contained in the composition means).

When the 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 is the number of moles of nitrogen atoms contained in the composition of the present invention).

When the composition of the present invention contains only an acidic substance, the acidity (pKa) of the acidic substance is preferably 5.0 or less. Although the lower limit of the acidity is not particularly limited, when an acidic substance having an acidity of -4.0 or less is included, for example, the polyaniline composite may deteriorate.

When the composition of the present invention is a salt containing only an acidic substance, the acidity of the salt of the acidic substance is preferably 5.0 or less. The lower limit of the acidity is the same as the above-mentioned acidic substance.

If the composition of the present invention includes both the acidic substance and the salt of the acidic substance, it is preferable that at least one of the salts conforming to the acidity of the acidic substance has an acidity of 5.0 or less and an acidity of 5.0 or less. The lower limit for acidity is the same as described above.

Acidity (pKa) is defined by computational chemistry. That is, using the method described in the Journal of Physical Chemistry, 1995, Vol. 99, p. 2224: by the quantum chemistry calculation developed by A. Klamt et al., The charge density on the molecular surface is calculated to calculate The interaction between heterogeneous molecules serves as the activity coefficient.

Specifically, use "TURBOMOLE Version 6.1" (manufactured by COSMO logic company), and use TZVP as the basis function to optimize the structure. Using this structure, use "COSMO therm Version C2.1 Release 01.10" (manufactured by COSMO logic company) COSMO-RS method calculation.

Here, enter "COSMO therm Version C2.1 Release 01.10" in 25 ℃ water solvent conditions, molecular formula, and deprotonated molecule chemical formula to calculate pKa.

In the composition of the present invention, the content of the heat-resistant stabilizer is preferably 1 to 1000 parts by mass, and more preferably 10 to 100 parts by mass relative to 100 parts by mass of the polyaniline composite.

The solvent may be an organic solvent, an inorganic solvent such as water, or a single solvent or a mixed solvent of two or more. Organic solvents are preferred.

In addition, the organic solvent is a water-soluble organic solvent, or an organic solvent that is substantially immiscible in water (a water-immiscible organic solvent).

The water-soluble organic solvent is a protic polar solvent or an aprotic polar solvent, such as isopropyl alcohol, 1-butanol, 2-butanol, 2-pentanol, benzyl alcohol and other alcohols; acetone Ketones; tetrahydrofuran Ethers such as pyran and dioxane; aprotic polar solvents such as N-methylpyrrolidone.

Examples of the water-immiscible organic solvents include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene; methylene dichloride, chloroform, carbon tetrachloride, and dichloroethane Halogen-containing solvents such as alkane and tetrachloroethane; ester solvents such as ethyl acetate, isobutyl acetate, and n-butyl acetate; methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, Ketone solvents such as cyclohexanone; ether solvents such as cyclopentyl methyl ether. Among these, the solubility to the doped polyaniline is excellent, and toluene, xylene, methyl isobutyl ketone (MIBK), chloroform, trichloroethane, and ethyl acetate are preferable.

When the organic solvent is used as the solvent, the water-immiscible organic solvent and the water-soluble organic solvent are mixed organic solvents mixed in a range of 99-50: 1-50 (mass ratio) to prevent gels during storage, etc. Occurred because it can be stored for a long time, so it is appropriate.

As the water-immiscible organic solvent of the mixed organic solvent, a low-polarity organic solvent can be used, and the low-polarity organic solvent is preferably toluene or chloroform. In addition, as the water-soluble organic solvent of the mixed organic solvent, a highly polar organic solvent can be used, preferably, for example, methanol, ethanol, isopropanol, 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.

The proportion of the conductive polymer in the solvent is usually 900g / kg or less, preferably 0.01g / kg or more and 300g / kg according to the type of solvent It is further preferably in the range of 10 g / kg or more and 300 g / kg or less, and more preferably 30 g / kg or more and 300 g / kg or less.

If the content of the conductive polymer is too large, it will become impossible to maintain the state of the solution, and the operation when forming into a molded body becomes difficult, and the uniformity of the molded body is impaired, which further reduces the electrical characteristics or mechanical properties of the molded body The strength and transparency of the product. On the other hand, if the content of the conductive polymer is too small, when the film is formed by the method described later, only a very thin film can be produced, and the production of a uniform conductive film may become difficult.

The composition of the present invention may further contain additives such as other resins, inorganic materials, hardeners, plasticizers, organic conductive materials, and the like.

Examples of other resins include adhesive base materials, plasticizers, and matrix base materials.

As specific examples of other resins, polyolefins such as polyethylene or polypropylene, chlorinated polyolefins, polystyrene, polyester, polyamide, polyacetal, polyethylene terephthalate, Polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylate, polymethacrylate, polyvinyl alcohol.

In addition, instead of or in combination with the above-mentioned resin, it may contain a thermosetting resin capable of forming an epoxy resin, urethane resin, phenol resin, etc., or a precursor of such thermosetting resin .

The inorganic material is added for the purpose of improving electrical properties such as strength, surface hardness, dimensional stability of other mechanical properties, or electrical conductivity.

Specific examples of the inorganic material can be exemplified, for example, silicon dioxide (Silica), titania (Titania), aluminum oxide (Alumina), the Sn-containing In ₂ O ₃ (ITO), the Zn-containing In ₂ O _3, In ₂ O Co-substituted compounds of ₃ (4-valent elements and divalent elements are oxides substituted with trivalent In), SnO ₂ (ATO) containing Sb, ZnO, ZnO containing Al (AZO), ZnO containing Ga ( GZO) etc.

The hardener is added, for example, for the purpose of improving strength, surface hardness, dimensional stability and other mechanical properties. Specific examples of the curing agent include a thermal curing agent such as a phenol resin, and a photo curing agent obtained from an acrylate monomer and a photopolymerizable initiator.

The plasticizer is added for the purpose of improving mechanical properties such as tensile strength and bending strength.

As specific examples of the plasticizer, for example, phthalates or phosphates can be mentioned.

Examples of the organic conductive material include carbon black, carbon materials such as carbon nanotubes, and conductive polymers other than polyaniline obtained by the present invention.

[Electroless plating bottom film]

The electroless plating underlayer film (layer) of the present invention is obtained from the above composition. The method of forming the electroless plating underlayer film of the present invention is as described later.

The dry film thickness of the electroless plating underlayer film is preferably 0.1 μm or more, and more preferably 0.2 μm or more. When the film thickness is less than 0.1 μm, the adhesion between the base material and the plating film cannot be maintained, so it becomes easy to peel off. Also, unsupported The area of Pd metal may increase, and the area that cannot be electrolessly plated may increase.

The upper limit of the dry film thickness is not particularly limited, and is, for example, 100 μm or less, 10 μm or less, and 5.0 μm or less.

[Manufacturing method of electroless plating underlayer film]

The method for producing an electroless plating underlayer film of the present invention uses the composition for forming an electroless plating underlayer film of the present invention. The present production method is not particularly limited as long as the composition of the present invention is used. For example, a coating method in which the composition of the present invention is applied to a substrate by a bar coating method and dried.

[Plated laminate]

The plating lamination system of the present invention comprises an electroless plating layer containing metal, an electroless plating base film containing a conductive polymer and a urethane resin, and a substrate layer, one side of the electroless plating layer and One side of the bottom layer of electroless plating is in contact.

FIG. 1 is a schematic diagram showing the layer configuration of one embodiment of the plated laminate of the present invention.

The plated laminate 1 is attached to the substrate 10 and includes laminating the electroless plating base layer 20 and the electroless plating layer 30 in this order.

The plating laminate system of the present invention can be produced by the method for producing a plating laminate of the present invention described later.

[Substrate]

The substrate is not particularly limited, and may be metal, inorganic materials (ceramics, glass, etc.), or resin. In addition, a metal substrate completely covered with resin, or a composite material of an inorganic material and a resin (for example, FRP, glass epoxy composite material), or the like. Examples of the types of resins include polycarbonate resins, acrylic resins, nylon resins, polyimide resins, polyester resins, styrene resins, phenol resins, and PPS (polyphenylene sulfide) resins.

As a specific example of the substrate, for example, PET (A4300 manufactured by Toyobo Co., Ltd.) which is easy to adhere can be mentioned.

[Electroless plating bottom layer]

The bottom layer of electroless plating contains a conductive polymer and a urethane resin. The conductive polymer and the urethane resin are as described above.

The electroless plating base layer can be manufactured using the composition of the present invention. In addition, the forming method is as described above.

[Electroless plating]

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. In addition, the formation method will be described later.

[Manufacturing method of electroless plating laminate]

The manufacturing method of the electroless plating laminate of the present invention includes a step of forming an electroless plating underlayer film using the composition for forming an electroless plating underlayer film of the present invention on a substrate, and applying the electroless plating underlayer On the membrane, containing The step of forming electroless plating layer of metal.

The formation of the electroless plating underlayer film can be performed by the above-mentioned method of manufacturing the electroless plating underlayer film.

After forming the underlayer film, it is preferable to perform the degreasing step before forming the electroless plated layer. The degreasing step is to degrease and wash the surface of the polyaniline layer with a solvent such as surfactant or alcohol to improve the wettability.

As the surfactant system, anionic, cationic or nonionic types can be used as appropriate, and cationic surfactants are preferred. When a cationic surfactant is used, for example, it is diluted to 1 to 3% with ion exchanged water and used.

After the formation of the above-mentioned electroless plating underlayer film, preferably after the degreasing step, usually on the underlayer film in order to support the Pd metal (catalyst metal) responsible for the electroless plating catalyst action, so it is mixed with the Pd compound solution contact.

When contacted with a Pd compound solution, a conductive polymer such as a polyaniline complex not only adsorbs Pd ions, but can also reduce Pd ions to Pd metal by this reduction. Still, the Pd to be reduced must be Pd in a metallic state, otherwise the catalytic effect in electroless plating cannot be exhibited.

Pd adhesion amount per unit area of the above (containing Pd and Pd metal ion) is preferably 1.7μg / cm ² or more, and preferably 2.5μg / cm ² or more.

The Pd compound is preferably palladium chloride. Hydrochloric acid is generally used as a solvent. However, as long as Pd exists in the aqueous solution in an ionic state, it is not limited to the hydrochloric acid aqueous solution. Examples of the 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.

Next, in order to form a metal-containing layer (plating layer) on the underlayer, the thin film obtained above was brought into contact with the electroless plating solution. If the bottom layer is in contact with the electroless plating solution, the supported Pd metal acts as a catalyst, and a plating layer can be formed on the polyaniline layer.

Examples of the metal type contained in the electroless plating solution include copper, nickel, cobalt, palladium, silver, gold, platinum, and tin. The electroless plating solution system may include one or more metals selected from Cu, Ni, Au, Pd, Ag, Sn, Co, and Pt. 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 or thickness of the plating bath, but for example, it is about 20 to 50 ° C at low temperature bath and 50 to 90 ° C at high temperature.

In addition, the contact time with the electroless plating solution also varies depending on the type or thickness of the plating bath, for example, 1-30 minutes, 5-15 minutes. Even if it is only electroless plating, or after the metal thin film is formed by electroless plating, the same type or different metal film may be provided by electrolytic plating.

[2] Manufacturing method of electroless plating

The manufacturing method of the electroless plated article of the present invention includes the steps of forming an electroless plated base film containing a conductive polymer on a substrate, and making the electroless plated base film and the standard electrode potential E ⁰ to E ⁰ =- The step of contacting the acidic reducing agent aqueous solution of 1.00V ~ -0.10V, and the step of forming the electroless plating layer on the electroless plating base film after contact with the reducing agent aqueous solution.

Instead of surfactants, by contacting (impregnating) the above-mentioned reducing agent aqueous solution with the electroless plating underlayer film, even if the plating underlayer film contains a binder or if the film thickness is thick, the plating underlayer film The coating film can be uniformly formed on the top.

Moreover, according to the manufacturing method of the present invention, even when a plating base film is formed on a part of the surface of the substrate, a plating layer can be formed (precipitated) only on the plating base film. That is, on the surface of the base material without the plating base film (the portion where no plating is required), since the plating layer cannot be formed, plating can be selectively performed on the base material. This effect is particularly useful when forming a plated metal circuit on the substrate.

1. Electroless plating bottom film formation steps

In this step, an electroless plating underlayer film containing a conductive polymer is formed on the substrate.

As the conductive polymer, the π-conjugated polymer is preferably a π-conjugated polymer composite doped with a dopant. Specifically, a substituted or unsubstituted polyaniline is a polyaniline composite doped with a dopant, and a substituted or unsubstituted polypyrrole is a polypyrrole composite doped with a dopant The body and the substituted or unsubstituted polythiophene are polythiophene complexes doped with a dopant. In particular, it is preferred that the substituted or unsubstituted polyaniline is a polyaniline composite doped with a dopant.

The weight average molecular weight of polyaniline (hereinafter, referred to as molecular Amount) is preferably 20,000 or more. If the molecular weight is less than 20,000, the strength or extensibility 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, and 53,000 to 200,000. Here, the above-mentioned weight average molecular weight is not the molecular weight of the polyaniline composite, but the molecular weight of polyaniline.

The polydispersity (ie, "weight average molecular weight" / "number average molecular weight") is preferably 1.5 or more and 10.0 or less. From the viewpoint of conductivity, the one having a small polydispersity (that is, the molecular weight distribution is narrow) is preferable, but from the viewpoint of solubility or moldability of the solvent, the polydispersity is sometimes preferable. The larger (ie, the molecular weight distribution is broad).

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 straight-chain or branched hydrocarbon groups such as methyl, ethyl, hexyl, and octyl; alkoxy groups such as methoxy and ethoxy groups; Group; halogenated hydrocarbon groups such as trifluoromethyl (-CF ₃ group).

From the viewpoint of versatility and economy, the polyaniline is preferably an unsubstituted polyaniline.

The substituted or unsubstituted polyaniline is preferably a polyaniline obtained after polymerization in the presence of an acid containing no chlorine atom. The acid that does not contain a chlorine atom means an acid composed of atoms belonging to, for example, groups 1 to 16 and 18. Specifically, phosphoric acid can be exemplified. As the polyaniline obtained after polymerization in the presence of an acid not containing a chlorine atom, there can be exemplified in the presence of phosphoric acid Polyaniline obtained after polymerization.

The polyaniline obtained in the presence of an acid that does not contain a chlorine atom can reduce the chlorine content of the polyaniline complex.

The chlorine content of the polyaniline composite is preferably 0.6% by weight or less. It is preferably 0.1% by weight or less, more preferably 0.04% by weight or less, and most preferably 0.0001% by weight or less.

If the chlorine content of the polyaniline composite exceeds 0.6% by weight, the metal part in contact with the polyaniline composite may be corroded.

The chlorine content is measured by combustion-ion chromatography.

As the dopant of the polyaniline complex, there can be exemplified broensted acid ions generated from, for example, broensted acid or a salt of broensted acid, preferably from The organic acid ion generated by the organic acid or the salt of the organic acid is more preferably an organic acid ion generated by a compound (proton donor) represented by the following formula (I).

Still, in the present invention, the dopant is expressed as a specific acid, and the dopant is expressed as a specific salt, whether it is a specific acid ion generated by a specific acid or a specific salt Are all doped with the π-conjugated polymer.

M (XARn) m (I)

M in formula (I) is a hydrogen atom, an organic radical or an inorganic radical.

Examples of the above-mentioned organic radicals include pyridinium group, imidazolyl group, and anilium group. In addition, as the inorganic radical, for example, lithium, Ions of sodium, potassium, cesium, ammonium, calcium, magnesium, iron.

X of formula (I) of the anionic group can be exemplified, for example, -SO ₃ ^- group, -PO ₃ ^2- group, -PO ₄ (OH) ^- group, -OPO ₃ ^2- group, -OPO ₂ (OH) ^- group , -COO ^- group, preferably -SO ₃ ^- group.

A of formula (I) is a substituted or unsubstituted hydrocarbon group.

The above-mentioned hydrocarbon group is a chain or cyclic saturated aliphatic hydrocarbon group, a chain or cyclic unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group.

As the chain-shaped saturated aliphatic hydrocarbon group, a linear or branched alkyl group can be exemplified.

Examples of cyclic saturated aliphatic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. The cyclic saturated aliphatic hydrocarbon group may be a plurality of cyclic saturated aliphatic hydrocarbon groups condensed. Examples include norbornyl, adamantyl, and condensed adamantyl.

Examples of the aromatic hydrocarbon group include phenyl, naphthyl and anthracenyl. As the chain-shaped unsaturated aliphatic hydrocarbon group, a linear or branched alkenyl group can be exemplified.

Here, when A is a substituted hydrocarbon group, the substituents are alkyl, cycloalkyl, vinyl, allyl, aryl, alkoxy, halo, hydroxyl, amine, imino, nitro, silane Group (silyl) or ester group.

R of formula (I) is bonded to A, and independently -H, -R ¹ , -OR ¹ , -COR ¹ , -COOR ¹ ,-(C = O)-(COR ¹ ), or-( C = O)-(COOR ¹ ), R ¹ is a hydrocarbon group, silyl, alkyl silyl,-(R ² O) xR ³ group which may also contain a substituent , Or-(OSiR ³ ₂ ) x-OR ³ (R ² is independently an alkylene group, R ³ is independently a hydrocarbon group, and x is an integer of 1 or more).

Examples of the hydrocarbon group for R ¹ include methyl, ethyl, linear or branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, di Decayl and so on. Moreover, the substituent of the said 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 hydroxyl group, an amine group, an imino group, a nitro group, or an ester group. The hydrocarbon group of R ³ is also the same as R ¹ .

Examples of the alkylene group of R ² include methylene group, ethyl group, and propyl group.

N in formula (I) is an integer of 1 or more, and m in formula (I) is the price of M / the price of X.

The compound represented by formula (I) is preferably a compound containing 2 or more dialkylbenzenesulfonic acid, dialkylnaphthalenesulfonic acid, or ester bond.

The compound containing 2 or more ester bonds is more preferably a sulfophthalate or a compound represented by the following formula (II).

In the formula, M, m and X are the same as the formula (I). X is preferably a -SO ₃ ^- group.

R ⁴ , R ⁵ and R ^{6 of the} formula (II) are independently hydrogen atoms, hydrocarbon groups or R ⁹ ₃ Si- groups (here, R ⁹ is a hydrocarbon group, and three R ⁹ are the same or different).

Examples of the hydrocarbon group when R ⁴ , R ⁵ and R ⁶ are hydrocarbon groups include straight-chain or branched alkyl groups having 1 to 24 carbon atoms, aryl groups, and alkylaryl groups.

The hydrocarbon group of R ^{9 is} the same as the case of R ⁴ , R ⁵ and R ⁶ .

R ⁷ and R ^{8 of the} formula (II) are each independently a hydrocarbon group or-(R ¹⁰ O) _q -R ¹¹ group [here, 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- (R ¹² is a hydrocarbon group, three R ¹² are the same or different), and q is an integer of 1 or more].

When R ⁷ and R ⁸ are hydrocarbon groups, the hydrocarbon group has a carbon number of 1 to 24, preferably linear or branched alkyl groups, aryl groups, alkylaryl groups with a carbon number of 4 or more, as R ⁷ When R ⁸ is a hydrocarbon group, specific examples of the hydrocarbon group include linear or branched butyl, pentyl, hexyl, octyl, and decyl groups.

In R ⁷ and R ⁸ , when R ¹⁰ is a hydrocarbon group, for example, a straight-chain or branched alkylene group having 1 to 24 carbon atoms, an aryl group, an alkylene group, or an arylalkylene group. In addition, in R ⁷ and R ⁸ , the hydrocarbon group when R ¹¹ and R ¹² are hydrocarbon groups is the same as the case of R ⁴ , R ^5, and R ⁶ , and q is preferably 1-10.

When R ⁷ and R ⁸ are-(R ¹⁰ O) _q -R ¹¹ groups, specific examples of the compound represented by formula (II) are two compounds represented by the following formulas.

(In the formula, X is the same as the formula (I)).

The compound represented by the above formula (II) is more preferably a sulfosuccinic acid derivative represented by the following formula (III).

In formula (III), M is the same as formula (I). m 'is the price of M.

R ¹³ and R ^{14 of the} formula (III) are each independently a hydrocarbon group or-(R ¹⁵ O) _r -R ¹⁶ group [Here, R ^{15 is} independently a hydrocarbon group or a silylene group, and R ¹⁶ is a hydrogen atom, a hydrocarbon group, or R ¹⁷ ₃ Si- group (here, R ^{17 is} each independently a hydrocarbon group), and r is an integer of 1 or more].

When R ¹³ and R ¹⁴ are hydrocarbon groups, they are the same as R ⁷ and R ⁸ .

Among R ¹³ and R ¹⁴ , the hydrocarbon group when R ¹⁵ is a hydrocarbon group is the same as R ¹⁰ described above. In addition, R ¹³ and R ¹⁴ are the same as R ⁴ , R ⁵ and R ⁶ as the hydrocarbon groups when R ¹⁶ and R ¹⁷ are hydrocarbon groups.

r is preferably 1-10.

As specific examples when R ¹³ and R ¹⁴ are-(R ¹⁵ O) _r -R ¹⁶ groups, they are the same as-(R ¹⁰ O) _q -R ^{11 of} R ⁷ and R ⁸ .

The hydrocarbon groups for R ¹³ and R ^{14 are} the same as R ⁷ and R ⁸ , and butyl, hexyl, 2-ethylhexyl, and decyl are preferred.

It is known that the above dopant can control the conductivity of the polyaniline composite or the solubility in the solvent by changing its structure (Patent No. 3384566). In the present invention, the most suitable dopant can be selected according to the required characteristics of each application. In the present invention, the compound represented by formula (I) is preferably di-2-ethylhexylsulfosuccinic acid and sodium di-2-ethylhexylsulfosuccinate. As the dopant of the present invention, di-2-ethylhexylsulfosuccinate ion is preferred.

The dopant of the polyaniline complex can be confirmed by ultraviolet, visible or near-infrared spectroscopy, or X-ray photoelectron spectroscopy to determine whether it is doped with substituted or unsubstituted polyaniline, as long as the dopant is capable of The polyaniline-generating carrier may be sufficiently acidic, and it can be used without any special restrictions on chemical structure.

The doping rate of the polyaniline dopant is preferably 0.35 or more and 0.65 or less, more preferably 0.42 or more and 0.60 or less, more preferably 0.43 or more and 0.57 or less, and particularly preferably 0.44 or more and 0.55 or less. If the doping rate is less than 0.35, the solubility of the polyaniline composite in organic solvents There is a risk of not becoming higher.

Still, the doping rate is defined by (the number of moles of dopant doped in polyaniline) / (the number of moles of monomer unit of polyaniline). For example, when the doping rate of the polyaniline composite containing unsubstituted polyaniline and dopant is 0.5, it means that one dopant is doped relative to two monomer unit molecules of polyaniline.

Still, as long as the molar number of the monomer unit of the dopant and polyaniline in the polyaniline composite can be measured, the doping rate can be calculated. For example, when the dopant is an organic sulfonic acid, the number of moles of sulfur atoms from the dopant and the number of moles of nitrogen atoms from the monomer unit of polyaniline can be quantified by organic element analysis The ratio of these values can calculate the doping rate. However, the method of calculating the doping rate is not limited to this method.

The polyaniline composite preferably contains sulfonic acid ions of unsubstituted polyaniline and a dopant, and reaches 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. In addition, the nitrogen atoms and The molar number of sulfur atoms is a value determined by, for example, organic element analysis).

The polyaniline composite may further contain phosphorus or not.

When the polyaniline composite contains phosphorus, the content of phosphorus is, for example, 10 wtppm or more and 5000 wtppm or less. Moreover, the phosphorus content is, for example, 2000 wtppm or less, 500 wtppm or less, 250 wtppm the following.

The phosphorus content can be measured by ICP emission spectrometry.

In addition, the polyaniline composite preferably contains no Group 12 element (for example, zinc) as an impurity.

The polyaniline composite system can be manufactured by a well-known method (for example, the polymerization of aniline in the presence of hydrochloric acid), but it is preferable to replace the substituted or unsubstituted aniline in a solution containing a proton donor, phosphoric acid, and two liquid phases To be manufactured by chemical oxidative polymerization.

Here, the so-called "solution with two liquid phases" refers to the existence of two liquid phases that are incompatible in the solution. For example, it means the state of existence of "high-polarity solvent phase" and "low-polarity solvent phase" in the solution.

In addition, "a solution having two liquid phases" also includes a state where one liquid phase is a continuous phase and the other liquid phase is a dispersed phase. For example, it may include the state where the "high-polar solvent phase" is the continuous phase and the "low-polar solvent phase" is the dispersed phase, and the "low-polar solvent phase" is the continuous phase and the "high-polar solvent phase" is the dispersed phase. status.

The high-polarity solvent used in the method for producing the polyaniline composite is preferably water; and the low-polarity solvent is preferably aromatic hydrocarbons such as toluene and xylene.

The proton donor is preferably a compound represented by the above formula (I).

The amount of proton donor used relative to the aniline single body 1 mol, preferably 0.1 to 0.5 mol, and more preferably 0.3 to 0.45 mol, more preferably 0.35 to 0.4 mol.

If the usage amount of the proton donor is more than this range, after the completion of the polymerization, for example, there is a possibility that the "high polar solvent phase" and the "low polar solvent phase" may not be separated.

The use concentration of phosphoric acid is 0.3 to 6 mol / L, more preferably 1 to 4 mol / L, and more preferably 1 to 2 mol / L, relative to the highly polar solvent.

As the oxidant used in chemical oxidative polymerization, sodium persulfate, potassium persulfate, ammonium persulfate, peroxides such as hydrogen peroxide; ammonium dichromate, ammonium perchlorate, potassium iron (III), trisulfate Iron (III) chloride, manganese dioxide, iodic acid, potassium permanganate, or iron p-toluenesulfonate, etc., preferably persulfates such as ammonium persulfate.

These oxidants can be used alone or in combination of two or more.

The amount of the oxidizing agent used is 1 mol per aniline unit, 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. Since the amount of the oxidizing agent used is within this range, a sufficient degree of polymerization can be obtained. In addition, due to the sufficient polymerization of aniline, liquid separation and recovery are easy, and the solubility of the polymer is not likely to decrease.

The polymerization temperature is usually -5 to 60 ° C, preferably -5 to 40 ° C. In addition, the polymerization temperature may be changed during the polymerization reaction. With the polymerization temperature within this range, side reactions can be avoided.

The polyaniline composite can be produced specifically using the following method.

Toluene is a solution with proton donor and emulsifier dissolved in nitrogen Put it into a separator bottle under the flow of an inert atmosphere, and then add substituted or unsubstituted aniline to this solution. After that, phosphoric acid (which does not contain chlorine as an impurity) was added to this solution, and the solution temperature was cooled.

After the internal temperature of the solution was cooled, it was stirred. Using a dropping funnel, a solution in which ammonium persulfate was dissolved in phosphoric acid was dropped to allow the reaction to proceed. After that, the temperature of the solution was increased and the reaction was continued. After the reaction is completed, the liquid phase that is separated into two phases by standing is separated. Toluene was added on the organic phase side and washed with phosphoric acid and ion-exchanged water to obtain a toluene solution of a polyaniline complex (protonated polyaniline).

The insoluble matter contained in the obtained composite solution was removed, and the toluene solution of the polyaniline composite was recovered. This solution was transferred to an evaporator, and volatiles were evaporated and distilled off by heating and depressurizing to obtain a polyaniline complex.

As described later, the electroless plating underlayer film can be produced by using a solution (coating liquid) containing a conductive polymer such as a polyaniline composite. The coating liquid preferably contains phenolic compounds.

The phenolic compound is not particularly limited as long as it has a phenolic hydroxyl group. The compound having a phenolic hydroxyl group refers to 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).

(In the formula, n is an integer of 1 to 5, preferably 1 to 3, and more preferably 1.

R is alkyl having 1 to 20 carbons, alkenyl, cycloalkyl, aryl, alkylaryl or arylalkyl).

In the phenolic compound represented by formula (A), the substitution position of -OR is preferably meta or para to the phenolic hydroxyl group. By setting the substitution position of -OR to the meta or para position, the steric hindrance of the phenolic hydroxyl group can be reduced and the conductivity of the composition can be further improved.

Specific examples of the phenolic compound represented by formula (A) include methoxyphenol (eg 4-methoxyphenol), ethoxyphenol, propoxyphenol, isopropoxyphenol, butoxy Phenol, isobutoxyphenol, and third butoxyphenol.

(In the formula, n is an integer of 0 ~ 7, preferably 0 ~ 3, and more preferably 1.

R is respectively 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, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms).

As a specific example of the phenolic compound represented by the formula (B), hydroxynaphthalene can be exemplified.

(In the formula, n is an integer of 1 to 5, preferably 1 to 3, and more preferably 1.

R is respectively 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, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms).

As a specific example of the compound represented by the formula (C), o-, m- or p-cresol, o-, m- or p-ethylphenol, o-, m- or p-propylphenol can be exemplified (Eg 4-isopropylphenol), o-, m- or p-butylphenol, o-, m- or p-pentylphenol (eg 4-tert-pentylphenol).

Regarding R of the formulas (A), (B) and (C), as the alkyl group having 1 to 20 carbon atoms, there can be exemplified methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third Butyl and so on.

As the alkenyl group, there can be exemplified the unsaturated bond in the molecule of the above alkyl group Knot base.

Examples of cycloalkyl groups include cyclopentane and cyclohexane.

Examples of the aryl group include phenyl and naphthyl.

Examples of the alkylaryl group and the arylalkyl group include a group obtained by combining the above alkyl group and aryl group.

An example of the above-mentioned compound having one phenolic hydroxyl group is shown. Specific examples of 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 compounds represented by the following formula (D).

(In the formula, R is a hydrocarbon group, a hydrocarbon group containing a heteroatom, a halogen atom, a carboxylic acid group, an amine group, a SH group, a sulfonic acid group, or a hydroxyl group, and a plurality of R may be the same or different from each other. N is 0 ~ An integer of 6).

The phenolic compound represented by formula (D) preferably has two or more hydroxyl groups that are not adjacent to each other.

In addition, specific examples of the phenolic compound represented by the formula (D) include 1,6 naphthalenediol, 2,6 naphthalenediol, and 2,7 naphthalenediol.

As a specific example of a polymer compound composed of a repeating unit having one or more phenolic hydroxyl groups, phenol resin, polymer Phenol, poly (hydroxystyrene).

Contains polyaniline complex and phenolic compound. The content of the phenolic compound in the coating solution is preferably 0.01 [mmol / g] or more and 100 [mol] relative to 1 g of the polyaniline complex. / g] or less, preferably 0.05 [mmol / g] or more and 1 [mol / g] or less, still more preferably 0.1 [mmol / g] or more and 500 [mmol / g] or less, particularly preferably 0.2 [mmol / g] ] Above 80 [mmol / g] below the range.

If the content of the phenolic compound is too small, there is a possibility that the effect of improving the electrical conductivity cannot be obtained. On the other hand, if the content of the phenolic compound is too large, the film quality may deteriorate. In addition, when removing the volatilization, a lot of labor such as heat or time is required to increase the cost.

When the conductive polymer is polypyrrole, the molecular weight, molecular weight distribution, and substituent of the substituted polypyrrole of the polypyrrole are the same as the polyaniline described above.

The dopant of the polypyrrole complex is not particularly limited, and an acceptor dopant suitable for use in a conductive polymer generally made of a polymer containing pyrrole and / or a pyrrole derivative can be suitably used.

Representative types include, for example, polystyrenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, anthraquinonesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, sulfosalic acid, dodecylbenzenesulfonic acid Sulfonic acids such as acids and allyl sulfonic acids; halogens such as perchloric acid, chlorine and bromine, Lewis acids, protonic acids, etc. These can be in acid form or salt form. From the viewpoint of the solubility of the monomer, tetrabutylammonium perchlorate, tetraethylammonium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium trifluoromethanesulfonate, Fluorosulfonimide tetrabutyl Ammonium, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, etc.

When the dopant is used, the amount of the dopant used is preferably 0.01 to 0.3 molecules per unit of the pyrrole polymer unit. If it is 0.01 molecules or less, the doping amount necessary to form a sufficient conductive path becomes insufficient, making it difficult to obtain high conductivity.

On the other hand, even if 0.3 molecules or more is added, since the doping rate cannot be improved, the addition of 0.3 molecules or more dopants is economically unsuitable. Here, the unit of the pyrrole polymer unit refers to a repeating part corresponding to one molecule of the monomer of the pyrrole polymer obtained by polymerizing the pyrrole monomer.

When the conductive polymer is polythiophene, the molecular weight, molecular weight distribution of the polythiophene, and the substituent of the substituted polythiophene are the same as the polyaniline described above. The substituted polythiophene is preferably polyethylenedioxythiophene (PEDOT).

Examples of the dopant of the polythiophene complex include organic acid ions and inorganic acid ions of anionic surfactants. Examples of organic acid ions of anionic surfactants include sulfonic acid ions and esterified sulfate ions. Examples of inorganic acid ions include sulfate ion, halogen ion, nitric acid ion, perchloric acid ion, hexacyanoferrate ion, phosphoric acid ion, and phosphomolybdate ion.

The base material is not particularly limited, and may be metal, inorganic materials (ceramics, glass, etc.), or resin. In addition, the base material of the metal completely covered with resin, or the composite material (for example, FRP, glass epoxy composite material) of the inorganic material and the resin may be used. Examples of the type of resin include polycarbonate, acrylic, nylon, polyimide, polyester, and styrene. System, phenol system, etc. Moreover, when heat resistance is required, syndiotactic polystyrene (SPS), polyimide, polyethylene naphthalate (PEN), etc. are mentioned.

As the base material, a polyethylene terephthalate (PET) film is preferred.

From the viewpoints of flexibility of the substrate, dimensional stability during printing, and availability of the film, the thickness of the substrate is preferably 2 μm or more. For example, 10 μm or more, 20 μm or more, and 50 μm or more. The upper limit is not particularly limited, for example, 100 mm or less, 10 mm or less, and 1 mm or less.

The method of forming the electroless plating underlayer film is not particularly limited. For example, a coating method in which a solution (coating liquid) in which a conductive polymer is dissolved in a solvent is applied to a substrate by a bar coating method and dried.

As the above solvent, aromatic, ketone, aliphatic, alcohol, amide, ester, etc. can be suitably used, but specific examples include toluene, cresol, hexane, methyl isobutyl ketone, 2-butanone, 2-propanol, methanol, dimethylformamide, butyl acetate, ethyl acetate, etc. These can be used alone or in combination.

In order to improve the adhesion to the substrate, the coating liquid may also contain an adhesive. Examples of the binder include acrylic, urethane, epoxy, polyamide, vinyl, polyester, and polycarbonate.

Furthermore, monomers, oligomers, and polymers that have reactive functional groups such as acrylates and methacrylates at the ends and are hardened with UV (ultraviolet) or EB (electron rays), etc., are also used as binders. can. At this time, instead of the above solvent, it can also be adjusted as an added monomer or oligomer It is used in liquid solvent-free systems such as viscosity.

The dry film thickness of the electroless plating underlayer film is preferably 0.1 μm or more, and more preferably 0.2 μm or more. If the film thickness is less than 0.1 μm, the adhesion between the substrate and the plated film cannot be maintained, so it will be easily peeled off. In addition, there is a possibility that the area where the Pd metal is not supported may increase, and the area where the electroless plating is applied may increase. The upper limit of the dry film thickness is not particularly limited, for example, 100 μm or less, 10 μm or less, and 5.0 μm or less.

2. Contact procedure with acidic reducing agent aqueous solution

In this step, the electroless plated base film obtained as described above is brought into contact with an acidic reducing agent aqueous solution whose standard electrode potential E ⁰ is E ⁰ = -1.00V to -0.10V.

The reducing agent aqueous solution of the present invention is acidic, and the pH of the reducing agent aqueous solution is preferably 6 or less, and more preferably 5 or less. In addition, the pH of the reducing agent aqueous solution is preferably 3 or more. This means that the weakly acidic range is preferred. The pH is measured using a pH meter.

In addition, the standard electrode potential E ^{0 of the} reducing agent aqueous solution is preferably E ⁰ = -0.20V ~ -0.80V. The standard electrode potential is calculated based on the value measured with an oxidation-reduction potentiometer (ORP meter) under the condition of 25 ° C. Still, since the reducing agent aqueous solution of the present invention is acidic, the measurement of the redox potentiometer is also performed under an acidic environment.

As the reducing agent, sodium bisulfite is the best.

The concentration (weight ratio) of the reducing agent aqueous solution is preferably 2% to 20%, preferably 3 to 18%, more preferably 4% to 16%, and most preferably 8 to 16%. If the concentration is too low, there is a possibility that the conductive polymer such as polyaniline cannot be completely reduced.

Still, before the reducing agent treatment, in order to reform the state of the surface, it can be treated with a surfactant.

After the above contacting step, the step of supporting the catalytic metal on the electroless plating underlayer film is generally included.

The support of the catalyst metal can be carried out by contacting the solution of the monomer or compound of the catalyst metal (that is, the solution containing the catalyst metal ion) with the electroless plating underlayer film.

When contacting a solution containing catalytic metal ions, conductive polymers such as polyaniline composites not only adsorb catalytic metal ions, but also by catalytic polymer reduction, catalytic metal ions can be reduced to catalytic metals.

Still, the catalyst metal is in a reduced state, that is, it must be in a metallic state, otherwise the catalyst function in electroless plating cannot be exhibited.

Applied amount of the catalyst metal per unit area of (a catalyst comprising catalytic metal and metal ion) is preferably 1.7μg / cm ² or more, and preferably 2.5μg / cm ² or more.

The catalyst metal is preferably palladium (Pd). In addition, as the Pd compound, palladium chloride is preferred.

As a solvent, hydrochloric acid is generally used. However, as long as Pd exists in the aqueous solution in an ionic state, it is not limited to the aqueous hydrochloric acid solution. Examples of the Pd compound solution include 0.02% palladium chloride-0.01% hydrochloric acid aqueous solution (pH 3).

Contact temperature between Pd compound solution and electroless plating bottom film The degree 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.

3. Formation steps of electroless plating

In this step, an electroless plating layer is formed on the electroless plating underlayer film that has been subjected to the above-mentioned treatment.

The formation of the electroless plating layer can be performed after the electroless plating solution is brought into contact with the plating base film. If the plating underlayer film and the electroless plating solution are in contact, a plating layer can be formed on the plating underlayer film by the catalytic action of the supported catalyst metal.

The so-called electroless plating refers to the electroless plating of a metal with an autocatalytic effect using a reducing agent. For example, in electroless copper plating, a reducing agent such as formaldehyde is used to reduce the copper ions in the solution and the metal copper film is precipitated. After the precipitated metal copper becomes an autocatalyst, the copper ions are metalized and precipitated Chemical procedures.

As the electroless plating solution, a general electroless plating solution can be used. Examples of metal types for electroless plating include nickel, cobalt, palladium, silver, gold, platinum, and tin, in addition to copper. The electroless plating solution may contain 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 differs depending on the type and thickness of the plating bath, but, for example, as long as it is about 20 to 50 ° C at low temperature baths and about 50 to 90 ° C at high temperatures. In addition, the contact time with the electroless plating solution also varies according to the type or thickness of the plating bath, for example, 1 to 30 minutes, It is preferably 5 to 15 minutes.

Electroless plating may be used for plating, or after the metal thin film is provided by electroless plating, the same or different metal film may be provided by electrolytic plating.

[Example] Manufacturing Example 1 [Manufacture of polyaniline complex]

Aerosol OT (di-2-ethylhexyl sodium sulfosuccinate) (AOT) 37.8g and non-ionic emulsifier Sorbon T-20 (Toho Chemical Industry Co., Ltd.) with a polyoxyethylene sorbitan fatty acid ester structure (Produced by the company) 1.47 g of a solution dissolved in 600 mL of toluene was placed in a 6 L separator bottle under a nitrogen stream, and then 22.2 g of aniline was added to this solution. After that, 1800 mL of 1M phosphoric acid was added to the solution, and the temperature of the two liquid-phase solutions with toluene and water was cooled to 5 ° C.

When the internal temperature of the solution reached 5 ° C, stirring was performed at 390 revolutions per minute. 65.7 g of ammonium persulfate was dissolved in a solution of 600 mL of 1 M phosphoric acid, and the solution was dropped with a dropping funnel for 2 hours. 18 hours from the start of dripping, the reaction was carried out while maintaining the internal temperature of the solution to 5 ° C. Thereafter, the reaction temperature was raised to 40 ° C, and the reaction was continued for 1 hour. Thereafter, the toluene phase was left to stand and separated. To the obtained toluene phase, add 1500 ml of toluene, wash once with 500 mL of 1M phosphoric acid, and wash three times with 500 mL of ion-exchanged water, and stand still to separate the toluene phase due to concentration adjustment Concentration was performed to obtain 900 g of a polyaniline complex (polyaniline / AOT complex) toluene solution. The polyaniline complex toluene solution had a polyaniline complex concentration of 5.7% by weight.

Manufacturing Example 2

The polyaniline / AOT composite toluene solution obtained in Production Example 1 was dried in a water bath at 60 ° C. under reduced pressure to obtain 51.3 g of dry solid polyaniline composite (powder).

Example 1 [Procedure for forming the underlying film]

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 isopropyl alcohol (made by Wako Pure Chemical Industries). Thereafter, 5.7 g of the urethane resin ASPU112 (manufactured by DIC Co., Ltd., solid content concentration 30%) was added and stirred to prepare a uniform coating liquid for plating underlayer formation.

The obtained coating liquid was applied using a bar coater, applied to a carbon glass film C110C (PC film, manufactured by Asahi Glass Co., Ltd.) of a polycarbonate film, and dried at 120 ° C. for 30 minutes to form a plating base film. The thickness of the plating base film is 1 μm. The concentration of the polyaniline complex in the plating base film was 62.5wt%, and the concentration of the urethane resin was 37.5wt%.

[Degreasing step]

The obtained thin film (plating base film) at room temperature, in 3% DIANOL CDE (coconut oil fatty acid diethanolamine; nonionic surfactant, manufactured by Daiichi Pharmaceutical Co., Ltd.) was immersed in an aqueous solution for 5 minutes for degreasing treatment. Still, this degreasing treatment aims at improving the wettability.

[Step of contacting with Pd compound solution]

The film after degreasing treatment was immersed in a 5-fold dilution of red Schumer (a palladium aqueous solution, manufactured by KANIGEN Co., Ltd., Japan) at 30 ° C. for 5 minutes to perform a metal Pd support treatment.

[Procedure for contacting with electroless plating solution]

The film after the Pd metal supporting treatment was subjected to a plating treatment at 33 ° C for 15 minutes using an electroless copper plating solution "ATS add copper IW" (manufactured by Okuno Pharmaceutical Industry Co., Ltd.).

[Lattice test]

With respect to the obtained plated part, a grid-like mark was made with a blade on the plated film according to JIS-5600, and CELLOTAPE (registered trademark) (manufactured by Nichiban Co., Ltd.) was attached and peeled off to perform a grid test. As a result, not only the peeling was not observed, but also the adhesiveness was good.

Example 2

In addition to the addition of urethane resin UREARNO U301 (Arakawa Chemical Co., Ltd., solid content concentration 25%) 6.8 g was used instead of ASPU112, and the coating liquid for forming a plating underlayer and the plating underlayer film were produced in the same manner as in Example 1. The concentration of the polyaniline complex in the plating base film was 62.5wt%, and the concentration of the urethane resin was 37.5wt%.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, not only was no peeling observed, but the adhesion was good.

Example 3

Except for adding 6.8 g of TSP3301 (made by Arakawa Chemical Co., Ltd., with a solid concentration of 25%) of urethane resin in place of ASPU112, the coating liquid and the plating solution for plating underlayer formation were prepared in the same manner as Example Bottom film. The concentration of the polyaniline complex in the plating base film was 62.5wt%, and the concentration of the urethane resin was 37.5wt%.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, not only was no peeling observed, but the adhesion was good.

Example 4

Except for adding 5.7 g of DAIFERAMINE MAU1008 (manufactured by Dari Fine Chemicals Co., Ltd., solid content concentration of 30%) added with urethane resin instead of adding ASPU112, the same coating liquid and plating as in Example 1 were produced Apply the base film. The concentration of the polyaniline complex in the plating base film is 62.5wt%, and the concentration of the urethane resin is 37.5wt%.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, not only was no peeling observed, but the adhesion was good.

Example 5

Except for adding 5.7 g of DAIFERAMINE MAU1005 (manufactured by Dari Fine Chemicals Co., Ltd., solid content concentration of 30%) added with urethane resin instead of adding ASPU112, the same coating liquid and plating as used in Example 1 were prepared Apply the base film. The concentration of the polyaniline complex in the plating base film was 62.5wt%, and the concentration of the urethane resin was 37.5wt%.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, not only was no peeling observed, but the adhesion was good.

Example 6

Except for adding 4.8 g of DAIFERAMINE MAU4308HV (manufactured by Dari Fine Chemicals Co., Ltd., solid content concentration of 35%) added with urethane resin instead of ASPU112, the same coating liquid and plating as in Example 1 were prepared Bottom film. The concentration of the polyaniline complex in the plating base film was 62.5wt%, and the concentration of the urethane resin was 37.5wt%.

After that, degreasing, Pd loading, and Plating treatment, and lattice test. As a result, not only was no peeling observed, but the adhesion was good.

Example 7

In addition to 2.8 g of DAIFERAMINE MAU1008 (made by Dari Fine Chemicals Co., Ltd., solid content concentration 30%) added with urethane resin, ASPU112 (made by DIC Co., Ltd., solid content concentration 30%) of urethane resin Except for ASPU112 instead of 2.8g, a coating liquid for forming a plating underlayer and a plating underlayer film were produced in the same manner as in Example 1. The concentration of the polyaniline complex in the plating base film was 62.5wt%, and the concentration of the urethane resin was 37.5wt% (MAU1008: ASPU = 1: 1).

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, not only was no peeling observed, but the adhesion was good.

Example 8

In addition to the addition of 2.8 g of ASPU112 (manufactured by DIC Co., Ltd., solid content concentration) of 2.8 g of urethane resin, and 0.85 g of KS-10 (manufactured by Sekisui Chemical Co., Ltd.) of polyethylene butyraldehyde instead of ASPU112 In Example 1, a coating liquid for forming a plating underlayer and a plating underlayer film were produced. The concentration of the polyaniline complex in the plating base film is 62.5 wt%, the concentration of the urethane resin is 18.75 wt%, and the concentration of the polyvinyl butyraldehyde is 18.75 wt%.

After that, degreasing, Pd loading, and Plating treatment, and lattice test. As a result, not only was no peeling observed, but the adhesion was good.

Comparative example 1

The coating liquid for forming a plating underlayer and the plating underlayer film were produced in the same manner as in Example 1, except that ASPU112 was not added. The concentration of the polyaniline complex in the plating base film is 100 wt%.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, at the interface between the plating base film and the Cu plating layer, the test portion was completely peeled off. Furthermore, even if the same lattice test was performed on the exposed portion of the plating underlayer film, the test portion was completely peeled off at the interface between the PC film and the plating underlayer film.

Comparative example 2

A coating liquid for forming a plating underlayer and a plating underlayer film were produced in the same manner as in Example 1, except that 5.7 g of BYRON 20SS (manufactured by Toyobo Co., Ltd., solid content concentration of 30%) was added instead of ASPU112. The concentration of the polyaniline complex in the plating base film is 62.5% by weight, and the concentration of the polyester resin is 37.5% by weight. At this time, when the plating underlayer film is observed, the compatibility between the polyaniline composite and BYRON 20SS is poor, and the plating underlayer film is uneven and becomes fragile.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, since the plating base film becomes fragile, peeling from the middle of the plating base film can be confirmed.

Comparative Example 3

A coating liquid for forming a plating underlayer and a plating underlayer film were produced in the same manner as in Example 1, except that 1.7 g of BYRON 50DS (manufactured by Toyobo Co., Ltd.) of polyester resin was added instead of ASPU112. If the bottom coating film is observed, the compatibility between the polyaniline composite and BYRON 50DS is poor, and the bottom coating film is uneven and becomes fragile.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, since the plating base film becomes fragile, peeling from the middle of the plating base film can be confirmed.

Comparative Example 4

A coating liquid for forming a plating underlayer and a plating underlayer film were produced in the same manner as in Example 1, except that 8.5 g of Superchlon822 (manufactured by Nippon Paper Chemical Co., Ltd., solid content concentration of 20%) was added in place of ASPU112. The concentration of polyaniline complex in the plating base film is 62.5wt%, and the concentration of chlorinated polyolefin is 37.5wt%.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, the adhesion between the plating base film and the Cu layer was good, but the test portion was completely peeled off at the interface between the plating base film and the PC film.

Comparative Example 5

In addition to GDP6140 with phenol resin added (Qunrong Chemical Co., Ltd. In addition to ASPU112, in the same manner as in Example 1, a coating liquid for forming a plating underlayer and a plating underlayer film were produced in the same manner as in Example 1 except that 5.7 g of solid content and solid content concentration were changed to 5.7 g. The concentration of the polyaniline complex in the plating base film is 62.5wt%, and the concentration of the phenol resin is 37.5wt%.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, the adhesion between the underlayer film and the Cu layer was good, but the test portion was completely peeled off at the interface between the plated underlayer film and the PC film.

Comparative Example 6

Except for adding 1.7 g of KS-10 (manufactured by Sekisui Chemical Co., Ltd.) of polyethylene butyraldehyde resin in place of ASPU112, the coating liquid for forming a plating underlayer and the plating underlayer film were prepared in the same manner as in Example 1. The concentration of polyaniline complex in the plating base film is 62.5wt%, and the concentration of polyvinyl butyraldehyde resin is 37.5% wt.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, the adhesion between the plating base film and the Cu layer was good, but the test portion was partially peeled off at the interface between the plating base film and the PC film.

Comparative Example 7

Except for adding 1.7 g of TORESIN EF-30T (manufactured by Nagase ChemteX Co., Ltd.) of polyamide amide imide resin in place of ASPU112, the same coating as in Example 1 was made to form a coating for forming a plating base layer Liquid and plating the bottom film. The concentration of the polyaniline complex in the plating base film was 62.5wt%, and the concentration of the polyimide amide imine resin was 37.5wt%.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, the test part was completely peeled off at the interface between the plating base film and the Cu layer. In addition, as a result of performing the same lattice test with the plating base film as the exposed portion, not only was there no peeling at the interface between the plating base film and the PC film, but the adhesion was good.

Comparative Example 8

Except for adding 1.7 g of TORESINF-30K (manufactured by Nagase ChemteX Co., Ltd.) of polyamide amide imide resin instead of ASPU112, the coating liquid for forming a plating underlayer and the plating underlayer film were produced in the same manner as in Example 1. The concentration of the polyaniline complex in the plating base film was 62.5wt%, and the concentration of the polyimide amide imine resin was 37.5wt%.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, the test part was completely peeled off at the interface between the plating base film and the Cu layer. In addition, as a result of performing the same lattice test with the plating base film as the exposed portion, not only was there no peeling at the interface between the plating base film and the PC film, but the adhesion was good.

Comparative Example 9

Except for adding 6.8 g of VYLOMAX HR-87TD (manufactured by Toyobo Co., Ltd., with a solid concentration of 25%) of polyimide amide imide resin in place of ASPU112, the same coating as in Example 1 was made to form a coating for the formation of a plating base layer Liquid and plating the bottom film. The concentration of the polyaniline complex in the plating base film was 62.5wt%, and the concentration of the polyimide amide imine resin was 37.5wt%.

Thereafter, in the same manner as in Example 1, degreasing, Pd loading, and plating treatment were performed, and a lattice test was performed. As a result, the adhesion at the interface between the plating base film and the Cu layer was good, but the test portion was partially peeled off at the interface between the plating base film and the PC film.

Example 9

3.75 g of polyaniline powder obtained in Production Example 2 was dissolved in 17 g of MIBK (manufactured by Wako Pure Chemical Industries) and 8.5 g of isopropanol (manufactured by Wako Pure Chemical Industries). Thereafter, 2.5 g of ASPU112 (manufactured by DIC Corporation, solid content concentration) of urethane resin 2.5 g was added and stirred to prepare a uniform coating liquid for forming a plating underlayer. The obtained coating liquid was applied on the carbon glass film C110C of the polycarbonate film (PC film, manufactured by Asahi Glass Co., Ltd.) by bar coating, and dried at 120 ° C. for 30 minutes to form a plating base film. The thickness of the plating base film is 1 μm. The concentration of the polyaniline complex in the plating base film was 83% by weight, and the concentration of the urethane resin was 17% by weight.

Thereafter, plating was performed in the same manner as in Example 1, and a lattice test was performed. As a result, not only was no peeling observed, but the adhesion was good.

Example 10

1.5 g of polyaniline powder obtained in Production Example 2 was dissolved in 17 g of MIBK (manufactured by Wako Pure Chemical Industries) and 8.5 g of isopropanol (manufactured by Wako Pure Chemical Industries). After that, add the urethane resin ASPU112 (DIC Co., Ltd. Preparation, solid content concentration 30%) 10g, and stirring to prepare a uniform coating liquid for forming a plating base layer. The obtained coating liquid was applied on the carbon glass film C110C of the polycarbonate film (PC film, manufactured by Asahi Glass Co., Ltd.) by bar coating, and dried at 120 ° C. for 30 minutes to form a plating base film. The thickness of the plating base film is 1 μm. The concentration of the polyaniline complex in the plating base film was 33% by weight, and the concentration of the urethane resin was 67% by weight.

Thereafter, plating was performed in the same manner as in Example 1, and a lattice test was performed. As a result, not only was no peeling observed, but the adhesion was good.

Example 11

In addition to 2.8 g of DAIFERAMINE MAU1008 (made by Dari Fine Chemicals Co., Ltd., solid content concentration of 30%) added with urethane resin, and ASPU112 (made by DIC Co., Ltd., solid concentration of 30%) of urethane resin Except for ASPU112 (5.7g) instead of 2.8g, the coating liquid for forming a plating underlayer was prepared in the same manner as in Example 1. In addition, COMOSHINE (PET film, manufactured by Toyobo Co., Ltd.) of polyester resin was used instead of C110C, and a plating underlayer film was produced in the same manner as in Example 1. The concentration of the polyaniline complex in the plating base film was 62.5 wt%, and the concentration of the urethane resin was 37.5 wt% (MAU1008: ASPU = 1: 1).

Thereafter, degreasing, Pd loading, and plating treatment were performed in the same manner as in Example 1 to obtain a plated laminate.

Example 12

A plated laminate was obtained in the same manner as in Example 11 except that Kapton (manufactured by DU PONT-TORAY Co., Ltd.) of polyimide resin was used instead of COSMOSHINE (PET film, manufactured by Toyobo Co., Ltd.).

After that, degreasing, Pd support, and plating were performed in the same manner as in Example 11 to obtain a plated laminate.

Example 13

A plated laminate was obtained in the same manner as in Example 11 except that TORELINA (PPS film, manufactured by TORAY Co., Ltd.) of PPS resin was used instead of COSMOSHINE (PET film, manufactured by Toyobo Co., Ltd.).

After that, degreasing, Pd support, and plating were performed in the same manner as in Example 11 to obtain a plated laminate.

The evaluation results of the adhesiveness of Examples and Comparative Examples are shown in Table 1 below.

The evaluation criteria of the adhesiveness of the examples and comparative examples are as follows. That is, when peeling cannot be observed on the interface and the adhesion is good, "○" is used, and when it is observed on a part of the interface, "△" is used. When peeling occurs at all interfaces or when peeling occurs in the middle of the plating base film, "X" is marked.

Example 11 [Procedure for forming the underlying film]

2.8 g of polyaniline powder obtained in Production Example 2 was dissolved in 17 g of MIBK (manufactured by Wako Pure Chemical Industries) and 8.5 g of isopropanol (manufactured by Wako Pure Chemical Industries). Thereafter, 5.7 g of ASPU112 (manufactured by DIC Co., Ltd., solid content concentration: 30%) of the urethane resin was added and stirred to prepare a uniform coating liquid for forming an underlayer for plating. Apply the obtained coating liquid to a part of the surface of the carbon glass film C110C (PC film, PC film, manufactured by Asahi Glass Co., Ltd.) of polycarbonate film by bar coating, and dry at 120 ° C for 30 minutes After that, a plating base film is formed. At this time, the thickness of the plating base film was 1 μm. The concentration of polyaniline in the plating base film is 62.5wt%, and the concentration of the urethane resin is 37.5wt%.

[Pre-processing steps]

10 g of sodium bisulfite aqueous solution was prepared by dissolving 10 g of sodium bisulfite (Wako Pure Chemical Industries, Ltd.) in 90 g of ion-exchanged water.

The entire base material provided with the plating base film was immersed in the 10 wt% sodium bisulfite aqueous solution at 30 ° C. for 5 minutes to perform degreasing treatment.

[Pd metal loading step]

The degreased film was immersed in a 5-fold dilution of red Schumer (a palladium aqueous solution, manufactured by Japan KANIGEN Co., Ltd.) under conditions of 30 ° C and 5 minutes, and subjected to metal Pd support treatment.

[Procedure for forming plating layer]

The film after the Pd metal supporting treatment was subjected to a plating treatment at 33 ° C for 15 minutes using an electroless copper plating solution "ATS add copper IW" (manufactured by Okuno Pharmaceutical Industry Co., Ltd.).

As a result, it was confirmed that uniform copper plating was formed on the plating base film. In addition, copper plating cannot be formed in portions other than the plating underlayer film.

Example 12

In the pretreatment step, except that a 15 wt% aqueous solution of sodium bisulfite prepared by dissolving 15 g of sodium bisulfite in 85 g of ion-exchanged water was used instead of a 10 wt% aqueous solution of sodium bisulfite, it was carried out in the same manner as in Example 11. Electrolytic plating treatment.

As a result, it was confirmed that uniform copper plating was formed on the plating base film. In addition, copper plating cannot be formed in portions other than the plating underlayer film.

Example 13

In the pretreatment step, except that a 4 wt% sodium bisulfite aqueous solution prepared by dissolving 4 g of sodium bisulfite in 96 g of ion-exchanged water was used instead of a 10 wr% sodium bisulfite aqueous solution, the same procedure as in Example 11 was performed. Electrolytic plating treatment.

As a result, it was confirmed that uniform copper plating was formed on the plating base film. In addition, copper plating cannot be formed in portions other than the plating underlayer film.

Comparative Example 10

In the pretreatment step, in addition to using a 4wt% sodium thiosulfate aqueous solution prepared by dissolving 4g of sodium thiosulfate (made by Wako Pure Chemical Industries, Ltd.) in 96g of ion-exchanged water instead of a 10wt% sodium bisulfite aqueous solution, Electroless plating was performed in the same manner as in Example 11.

As a result, copper plating cannot be formed on the plating base film at all.

Comparative Example 11

In the pretreatment step, the same as Example 11 except that a 4 wt% sodium sulfite aqueous solution prepared by dissolving 4 g of sodium sulfite (Wako Pure Chemical Industries, Ltd.) in 96 g of ion-exchanged water was used instead of a 10 wt% aqueous sodium bisulfite solution. Electroless plating process.

As a result, it was confirmed that the copper plating part and the non-formed part were formed on the plating base film, and uniform copper plating could not be formed.

Comparative Example 12

In the pretreatment step, a 0.5 wt% aqueous solution of sodium borohydride prepared by dissolving 0.5 g of sodium borohydride (manufactured by Wako Pure Chemical Industries, Ltd.) in 99.5 g of ion-exchanged water was used instead of a 10 wt% aqueous solution of sodium bisulfite , Electroless plating was performed in the same manner as in Example 11.

As a result, copper plating was deposited even on the part without the plating base film, and there was no The method only selectively forms copper plating on the part of the plating underlying film.

The pH of the reducing agent aqueous solution used in Examples and Comparative Examples is shown below. Still, the PH system is measured using a pH meter.

10wt% sodium bisulfite: pH4.3

15wt% sodium bisulfite: pH4.1

4wt% sodium bisulfite: pH4.3

4wt% sodium thiosulfate: pH6.5

4wt% sodium sulfite: pH9.6

0.5wt% sodium borohydride: pH 13.2

In addition, the standard electrode potential E ⁰ of the reducing agent used in Examples and Comparative Examples is shown below. In addition, under the condition of 25 ° C, the standard electrode potential E ⁰ is calculated based on the value measured with an oxidation-reduction potentiometer (ORP meter).

Sodium bisulfite: E ⁰ = -0.45V

Sodium thiosulfate: E ⁰ = 0.08V

Sodium sulfite: E ⁰ = -0.93V

Sodium boron hydride: E ⁰ = -1.24V

The evaluation results of Examples and Comparative Examples are shown in Table 2.

In the evaluation of whether plating is formed in the area where the underlying film is plated (plating formation in the area), it can be confirmed that a uniform copper plating is formed on the plating underlying film. When copper plating is formed on the film and there is no formed part, and there is no uniform copper plating, "△" is used, and if no copper plating is formed on the underlying film, "×" is used.

Also, in areas other than the plating underlayer film, can excess In the evaluation of plating (out-of-area plating formation), it was not possible to confirm the formation of copper plating in areas other than the plating underlayer film with a "○" when confirming the formation of copper plating in areas other than the plating underlayer film When it is "×".

The comparative examples 10 to 12 are as follows.

The sodium thiosulfate used in Comparative Example 10 has a low reducing power and cannot make polyaniline completely reduced.

The sodium sulfite system used in Comparative Example 11 has reducing power under alkaline conditions, but as the reaction progresses, the solution gradually becomes acidic and does not have reducing energy, so that the plating performance is reduced.

The sodium boron hydride used in Comparative Example 12 has a very strong reducing power, so it will attack the substrate or the underlying film. Even if a small amount of sodium boron hydride remains on the surface of the base material, Pd will be supported in the portion other than the underlayer film, which may cause precipitation outside the range.

[Industrial Utilization]

The composition for forming an electroless plating underlayer film of the present invention can be used for electroless plating.

In addition, the method for producing the electroless plated article of the present invention can be used for electroless plating.

Although the above has described several implementation forms and / or embodiments of the present invention in detail, without substantial departure from the novel inspiration and effects of the present invention, those of ordinary skill in the art can easily understand Many changes have been made to the illustrated embodiments and / or examples. Therefore, these more changes are also included in the scope of the present invention.

The contents of the Japanese application specification that forms the basis of the priority of the present invention are all incorporated herein.

Claims (15)

A composition for forming an electroless plating underlayer film, comprising a polyaniline composite and a urethane resin doped with a substituted or unsubstituted polyaniline doped with a dopant, which is compounded with the polyaniline The total of the body and the urethane resin, the ratio of the urethane resin is 20 to 80% by weight. The composition for forming an electroless plating underlayer film according to claim 1, wherein the dopant is a sulfosuccinic acid derivative represented by the following formula (III),

(In formula (III), M is a hydrogen atom, an organic radical or an inorganic radical, m 'is a valence of M, R ¹³ and R ¹⁴ are respectively a hydrocarbon group or-(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 R ¹⁷ ₃ Si- group, r is an integer of 1 or more, and R ¹⁷ is a hydrocarbon group, respectively). The composition for electroless plating underlayer film formation according to claim 1 or 2, wherein the dopant is sodium di-2-ethylhexylsulfosuccinate. An electroless plating underlayer film obtained from the composition for forming an electroless plating underlayer film according to any one of claims 1 to 3. A plated laminate comprising a metal-containing electroless plating layer, a polyaniline composite containing substituted or unsubstituted polyaniline doped with a dopant, and a non-electrolyzed carbamate resin An underplating film and a substrate, wherein one surface of the electroless plating layer is in contact with one surface of the electroless plating underlayer film, and the electroless plating underlayer film is relative to the polyaniline composite and the amine group The total amount of formate resin, the proportion of the aforementioned urethane resin is 20 to 80% by weight. The plating laminate according to claim 5, wherein the dopant is a sulfosuccinic acid derivative represented by the following formula (III),

(In formula (III), M is a hydrogen atom, an organic radical or an inorganic radical, m 'is a valence of M, R ¹³ and R ¹⁴ are respectively a hydrocarbon group or-(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 R ¹⁷ ₃ Si- group, r is an integer of 1 or more, and R ¹⁷ is a hydrocarbon group, respectively). The plating laminate according to claim 5 or 6, wherein the aforementioned dopant is sodium di-2-ethylhexylsulfosuccinate. The plated laminate according to claim 5, wherein the aforementioned metal is copper. The plated laminate according to claim 5, wherein the substrate is a resin. The plated laminate according to claim 9, wherein the substrate is polycarbonate resin, polyester resin, polyimide resin, or polyphenylene sulfide resin. A method for manufacturing an electroless plating underlayer film, which uses the composition for forming an electroless plating underlayer film according to any one of claims 1 to 3. A method for manufacturing an electroless plating laminate, comprising the steps of: using the composition for forming an electroless plating underlayer film according to any one of claims 1 to 3 on a substrate to form an electroless plating underlayer A film step; and a step of forming a metal-containing electroless plating layer on the aforementioned electroless plating underlayer film. The method for manufacturing an electroless plating laminate according to claim 12, wherein palladium is supported on the electroless plating underlayer film, and then the electroless plating layer is formed by contacting the electroless plating solution . The method for manufacturing an electroless plating laminate according to claim 13, wherein the palladium chloride solution is brought into contact with the aforementioned electroless plating underlayer film to support palladium. The method for producing an electroless plating laminate according to claim 13 or 14, wherein the electroless plating solution contains one or more metals selected from Cu, Ni, Au, Pd, Ag, Sn, Co, and Pt.