JP2014132104A - Composition for forming electroless plating primer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a primer film that, in electroless plating, has sufficient adhesion to a substrate such as polycarbonate (PC), and has sufficient adhesion to a plating layer as well.SOLUTION: The present invention provides the composition for forming an electroless plating primer film that contains a conductive polymer and a urethane resin.

Description

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

  Conductive polymers are used for electrolytic capacitors, backup batteries for electronic devices, electrodes for lithium ion batteries used in mobile phones and notebook computers, and the like.

  For example, polyaniline, a kind of conductive polymer, can be synthesized relatively easily from inexpensive aniline in addition to its electrical properties, and exhibits excellent stability against oxygen and the like in a state of conductivity. Has advantages and characteristics. In addition, a highly conductive polyaniline can be easily obtained by the method described in Patent Document 1.

In addition, many conductive polymers have reducing power, and are attracting attention as base films for electroless plating taking advantage of this characteristic (Patent Documents 2 to 8).
An electroless plating base film made of a polyaniline complex alone has not been sufficiently adhered to various substrates such as polycarbonate (PC) and polyethylene terephthalate (PET). Moreover, the adhesiveness with a plating layer was not enough.

International Publication No. 2005/052058 Pamphlet JP 2007-270180 A JP 2008-163371 A JP 2011-208174 A JP 2011-168814 A JP 2011-168813 A JP 2011-74407 A JP 2010-95776 A

  An object of the present invention is to provide a composition for forming a base film that has sufficient adhesion to a substrate such as polycarbonate (PC) in electroless plating and also has sufficient adhesion to a plating layer. It is.

（式（III）中、Ｍは、水素原子、有機遊離基又は無機遊離基である。ｍ’は、Ｍの価数である。Ｒ^１３及びＲ^１４は、それぞれ炭化水素基又は−（Ｒ^１５Ｏ）_ｒ−Ｒ^１６基である。Ｒ^１５は、それぞれ炭化水素基又はシリレン基であり、Ｒ^１６は水素原子、炭化水素基又はＲ^１７ _３Ｓｉ−基であり、ｒは１以上の整数である。Ｒ^１７は、それぞれ炭化水素基である。）
４．前記ドーパントがジ−２−エチルヘキシルスルホコハク酸ナトリウムである２又は３に記載の無電解めっき下地膜形成用組成物。
５．前記導電性ポリマー及びウレタン樹脂の合計に対する前記ウレタン樹脂の割合が２０〜８０重量％である１〜４のいずれかに記載の無電解めっき下地膜形成用組成物。
６．１〜５のいずれかに記載の無電解めっき下地膜形成用組成物から得られる無電解めっき下地膜。
７．金属を含む無電解めっき層と、
導電性ポリマー及びウレタン樹脂を含む無電解めっき下地膜と、
基板とを含み、
前記無電解めっき層の一方の面と前記無電解めっき下地膜の一方の面が接しているめっき積層体。
８．前記導電性ポリマーが置換又は無置換のポリアニリンがドーパントによってドープされたポリアニリン複合体である７に記載のめっき積層体。
９．前記ドーパントが下記式（III）で表されるスルホコハク酸誘導体である８に記載のめっき積層体。

（式（III）中、Ｍは、水素原子、有機遊離基又は無機遊離基である。ｍ’は、Ｍの価数である。Ｒ^１３及びＲ^１４は、それぞれ炭化水素基又は−（Ｒ^１５Ｏ）_ｒ−Ｒ^１６基である。Ｒ^１５は、それぞれ炭化水素基又はシリレン基であり、Ｒ^１６は水素原子、炭化水素基又はＲ^１７ _３Ｓｉ−基であり、ｒは１以上の整数である。Ｒ^１７は、それぞれ炭化水素基である。）
１０．前記ドーパントがジ−２−エチルヘキシルスルホコハク酸ナトリウムである８又は９に記載のめっき積層体。
１１．前記導電性ポリマー及びウレタン樹脂の合計に対する前記ウレタン樹脂の割合が２０〜８０重量％である７〜１０のいずれかに記載のめっき積層体。
１２．前記金属が銅である７〜１１のいずれかに記載のめっき積層体。
１３．前記基板が樹脂である７〜１２のいずれかに記載のめっき積層体。
１４．前記基板がポリカーボネート樹脂、ポリエステル樹脂、ポリイミド樹脂、又はポリフェニレンサルファイド樹脂である１３に記載のめっき積層体。
１５．１〜５のいずれかに記載の無電解めっき下地膜形成用組成物を用いる無電解めっき下地膜の製造方法。
１６．基板上に、１〜５のいずれかに記載の無電解めっき下地膜形成用組成物を用いて無電解めっき下地膜を形成する工程、及び
前記無電解めっき下地膜上に、金属を含む無電解めっき層を形成する工程を含む
無電解めっき積層体の製造方法。
１７．前記無電解めっき下地膜にパラジウムを担持させ、その後前記無電解めっき液に接触させることにより無電解めっき層を形成する１６に記載の無電解めっき積層体の製造方法。
１８．前記無電解めっき下地膜に塩化パラジウム溶液を接触させることによりパラジウムを担持させる１７に記載の無電解めっき積層体の製造方法。
１９．前記無電解めっき液がＣｕ、Ｎｉ、Ａｕ、Ｐｄ、Ａｇ、Ｓｎ、Ｃｏ及びＰｔから選択される１以上の金属を含む１６〜１８のいずれかに記載の無電解めっき積層体の製造方法。 According to the present invention, the following composition for forming an electroless plating base film is provided.
1. A composition for forming an electroless plating base film comprising a conductive polymer and a urethane resin.
2. 2. The composition for forming an electroless plating base film according to 1, wherein the conductive polymer is a polyaniline composite in which substituted or unsubstituted polyaniline is doped with a dopant.
3. The composition for forming an electroless plating base film according to 2, wherein the dopant is a sulfosuccinic acid derivative represented by the following formula (III).

(In formula (III), M is a hydrogen atom, an organic free radical or an inorganic free radical. M ′ is a valence of M. R ¹³ and R ¹⁴ are a hydrocarbon group or — (R ¹⁵ , respectively). O) _r— R ¹⁶ group, wherein R ¹⁵ is a hydrocarbon group or a silylene group, R ¹⁶ is a hydrogen atom, a hydrocarbon group or an R ¹⁷ ₃ Si— group, and r is an integer of 1 or more. R ¹⁷ is each a hydrocarbon group.)
4). The composition for forming an electroless plating base film according to 2 or 3, wherein the dopant is sodium di-2-ethylhexyl sulfosuccinate.
5. The composition for forming an electroless plating base film according to any one of 1 to 4, wherein the ratio of the urethane resin to the total of the conductive polymer and the urethane resin is 20 to 80% by weight.
The electroless-plating base film obtained from the composition for electroless-plating base film formation in any one of 6.1-5.
7). An electroless plating layer containing metal;
An electroless plating base film containing a conductive polymer and a urethane resin;
Including a substrate,
A plating laminate in which one surface of the electroless plating layer is in contact with one surface of the electroless plating base film.
8). The plating laminate according to 7, wherein the conductive polymer is a polyaniline composite in which substituted or unsubstituted polyaniline is doped with a dopant.
9. 9. The plating laminate according to 8, wherein the dopant is a sulfosuccinic acid derivative represented by the following formula (III).

(In formula (III), M is a hydrogen atom, an organic free radical or an inorganic free radical. M ′ is a valence of M. R ¹³ and R ¹⁴ are a hydrocarbon group or — (R ¹⁵ , respectively). O) _r— R ¹⁶ group, wherein R ¹⁵ is a hydrocarbon group or a silylene group, R ¹⁶ is a hydrogen atom, a hydrocarbon group or an R ¹⁷ ₃ Si— group, and r is an integer of 1 or more. R ¹⁷ is each a hydrocarbon group.)
10. The plating laminate according to 8 or 9, wherein the dopant is sodium di-2-ethylhexyl sulfosuccinate.
11. The plating laminated body in any one of 7-10 whose ratio of the said urethane resin with respect to the sum total of the said conductive polymer and urethane resin is 20 to 80 weight%.
12 The plating laminated body in any one of 7-11 whose said metal is copper.
13. The plating laminated body in any one of 7-12 whose said board | substrate is resin.
14 14. The plated laminate according to 13, wherein the substrate is a polycarbonate resin, a polyester resin, a polyimide resin, or a polyphenylene sulfide resin.
15. A method for producing an electroless plating base film using the electroless plating base film forming composition according to any one of 15.1 to 5.
16. A step of forming an electroless plating base film using the composition for forming an electroless plating base film according to any one of 1 to 5 on a substrate, and electroless containing a metal on the electroless plating base film The manufacturing method of the electroless-plating laminated body including the process of forming a plating layer.
17. The manufacturing method of the electroless-plating laminated body of 16 which forms palladium on the said electroless-plating base film, and forms an electroless-plating layer by making it contact with the said electroless-plating liquid after that.
18. 18. The method for producing an electroless plating laminate according to 17, wherein palladium is supported by bringing a palladium chloride solution into contact with the electroless plating base film.
19. The method for producing an electroless plating laminate according to any one of 16 to 18, wherein the electroless plating solution contains one or more metals selected from Cu, Ni, Au, Pd, Ag, Sn, Co, and Pt.

  ADVANTAGE OF THE INVENTION According to this invention, in electroless plating, the composition for base film formation which has sufficient adhesiveness with base materials, such as PC, and sufficient adhesiveness with a plating layer can be provided.

It is the schematic which shows the layer structure of one Embodiment of the plating laminated body of this invention.

The composition for forming an electroless plating base film of the present invention includes a conductive polymer and a urethane resin.
Electroless plating is a metal plating method that does not perform electrolysis and has a self-catalytic action using a reducing agent. For example, in the case of electroless copper plating, a copper ion in a solution is used with a reducing agent such as formaldehyde This is a chemical process in which a metallic copper film is deposited by reduction, and the deposited metallic copper becomes an autocatalyst to further metallize and precipitate copper ions.
The composition of the present invention is used to form an underlayer for an electroless plating layer.

  Since the composition of the present invention is mixed with a urethane resin as a binder for improving the adhesion, the adhesion with various substrates such as PC and PET becomes sufficient, and the adhesion with the plating layer is also excellent. It can be set as the plating laminated body with favorable adhesiveness.

[Conductive polymer]
Examples of the conductive polymer include a π-conjugated polymer complex in which a π-conjugated polymer is doped with a dopant. Specifically, a polyaniline complex in which a substituted or unsubstituted polyaniline is doped with a dopant, a substituted or non-substituted polymer. Examples include polypyrrole composites in which substituted polypyrrole is doped with a dopant, and polythiophene composites in which substituted or unsubstituted polythiophene is doped with a dopant, and polyaniline composites in which substituted or unsubstituted polyaniline is doped with a dopant The body is preferred.

  The weight average molecular weight of polyaniline (hereinafter referred to as molecular weight) is preferably 20,000 or more. If the molecular weight is less than 20,000, the strength and stretchability of the conductive article obtained from the composition may be reduced. Molecular weight becomes like this. Preferably it is 20,000-500,000, More preferably, it is 20,000-300,000, More preferably, it is 20,000-200,000. The molecular weight is, for example, 50,000 to 200,000, 53,000 to 200,000. Here, the above weight average molecular weight is not the molecular weight of the polyaniline complex but the molecular weight of polyaniline.

The molecular weight distribution is preferably 1.5 or more and 10.0 or less. A smaller molecular weight distribution is preferable from the viewpoint of conductivity, but a wider molecular weight distribution may be preferable from the viewpoint of solubility in solvents and moldability.
The molecular weight and molecular weight distribution are measured in terms of polystyrene by gel permeation chromatography (GPC).

Examples of the substituent of the substituted polyaniline include linear or branched hydrocarbon groups such as methyl group, ethyl group, hexyl group and octyl group; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; Halogenated hydrocarbons such as a fluoromethyl group (—CF ₃ group) are exemplified.
The polyaniline is preferably unsubstituted polyaniline from the viewpoints of versatility and economy.

The substituted or unsubstituted polyaniline is preferably a polyaniline obtained by polymerization in the presence of an acid containing no chlorine atom. The acid containing no chlorine atom is, for example, an acid composed of atoms belonging to Group 1 to Group 16 and Group 18. Specific examples include phosphoric acid. Examples of the polyaniline obtained by polymerization in the presence of an acid not containing a chlorine atom include polyaniline obtained by polymerization in the presence of phosphoric acid.
The polyaniline obtained in the presence of an acid containing no chlorine atom can lower the chlorine content of the polyaniline complex.

The chlorine content of the polyaniline complex is preferably 0.6% by weight or less, more preferably 0.1% by weight or less, still more preferably 0.04% by weight or less, and most preferably 0.0001%. % By weight or less.
When the chlorine content of the polyaniline complex is more than 0.6% by weight, the metal part that comes into contact with the polyaniline complex may be corroded.
The chlorine content is measured by combustion-ion chromatography.

Examples of the dopant of the polyaniline complex include Bronsted acid ions generated from Bronsted acid or Bronsted acid salts, preferably organic acid ions generated from organic acids or salts of organic acids, and more preferably the following formula: It is an organic acid ion generated from the compound (proton donor) represented by (I).
In the present invention, when the dopant is expressed as a specific acid, and when the dopant is expressed as a specific salt, the specific acid ion generated from the specific acid or the specific salt may be used. The above-mentioned π-conjugated polymer is doped.

M (XARn) m (I)
M in the formula (I) is a hydrogen atom, an organic radical or an inorganic radical.
Examples of the organic free radical include a pyridinium group, an imidazolium group, and an anilinium group. Examples of the inorganic free radical include lithium, sodium, potassium, cesium, ammonium, calcium, magnesium, and iron.
X in the formula (I) is an anionic group, for example, —SO ₃ ^— group, —PO ₃ ^{2 —} group, —PO ₄ (OH) ^{2 —} , —OPO ₃ ^{2 —} group, —OPO ₂ (OH) ^—. group, -COO ^- group, and preferably -SO ₃ ^- is a group.

A in formula (I) (the definition of A in M (XARn) m) is a substituted or unsubstituted hydrocarbon group.
The hydrocarbon group is a chain or cyclic saturated aliphatic hydrocarbon group, a chain or cyclic unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group.

Examples of the chain saturated aliphatic hydrocarbon group include a linear or branched alkyl group.
Examples of the cyclic saturated aliphatic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The cyclic saturated aliphatic hydrocarbon group may be a condensation of a plurality of cyclic saturated aliphatic hydrocarbon groups. Examples thereof include a norbornyl group, an adamantyl group, and a condensed adamantyl group.

  Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the chain unsaturated aliphatic hydrocarbon include linear or branched alkenyl groups.

  Here, when A is a substituted hydrocarbon group, the substituent is alkyl group, cycloalkyl group, vinyl group, allyl group, aryl group, alkoxy group, halogen group, hydroxy group, amino group, imino group, nitro group. Group, silyl group or ester group.

R in formula (I) is bonded to A, and each represents —H, —R ¹ , —OR ¹ , —COR ¹ , —COOR ¹ , — (C═O) — (COR ¹ ), or — There is a substituent represented by (C═O) — (COOR ¹ ), and R ¹ is a hydrocarbon group that may contain a substituent, a silyl group, an alkylsilyl group, — (R ² O) x—R 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 a methyl group, an ethyl group, a linear or branched butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a pentadecyl group, and an eicosanyl group. Is mentioned. The substituent of the hydrocarbon group is an alkyl group, a cycloalkyl group, a vinyl group, an allyl group, an aryl group, an alkoxy group, a halogen group, a hydroxy group, an amino group, an imino group, a nitro group, or an ester group. The hydrocarbon group for R ³ is the same as R ¹ .

Examples of the alkylene group for R ² include a methylene group, an ethylene group, and a propylene group.
N in the formula (I) is an integer of 1 or more, and m in the formula (I) is a valence of M / a valence of X.

式（II）中、Ｍ及びＸは、式（Ｉ）と同様である。Ｘは、−ＳＯ_３ ⁻基が好ましい。
Ｒ^４、Ｒ^５及びＲ^６は、それぞれ水素原子、炭化水素基又はＲ^９ _３Ｓｉ−基である。ここで、３つのＲ^９はそれぞれ炭化水素基である。
Ｒ^４、Ｒ^５及びＲ^６が炭化水素基である場合の炭化水素基としては、炭素数１〜２４の直鎖もしくは分岐状のアルキル基、芳香環を含むアリール基、アルキルアリール基等が挙げられる。
Ｒ^９の炭化水素基としては、Ｒ^４、Ｒ^５及びＲ^６の場合と同様である。 As the compound represented by the formula (I), dialkylbenzenesulfonic acid, dialkylnaphthalenesulfonic acid, or a compound containing two or more ester bonds is preferable.
The compound containing two or more ester bonds is more preferably a sulfophthalic acid ester or a compound represented by the following formula (II).

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 each a hydrogen atom, a hydrocarbon group or an R ⁹ ₃ Si— group. Here, each of three R ⁹ is a hydrocarbon group.
Examples of the hydrocarbon group when R ⁴ , R ⁵ and R ⁶ are hydrocarbon groups include linear or branched alkyl groups having 1 to 24 carbon atoms, aryl groups containing aromatic rings, and alkylaryl groups. It is done.
The hydrocarbon group for R ⁹ is the same as in the case of R ⁴ , R ⁵ and R ⁶ .

R ⁷ and R ^{8 in} the formula (II) are each 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. Three R < ¹² > is a hydrocarbon group, respectively.

When R ⁷ and R ⁸ are hydrocarbon groups, the hydrocarbon group is a linear or branched alkyl group having 1 to 24 carbon atoms, preferably 4 or more carbon atoms, an aryl group containing an aromatic ring, or an alkylaryl. Specific examples of the hydrocarbon group when R ⁷ and R ⁸ are hydrocarbon groups include, for example, a linear or branched butyl group, pentyl group, hexyl group, octyl group, decyl group Etc.

Examples of the hydrocarbon group when R ¹⁰ in R ⁷ and R ⁸ is a hydrocarbon group include a linear or branched alkylene group having 1 to 24 carbon atoms, an arylene group containing an aromatic ring, an alkylarylene group, An arylalkylene group. In addition, the hydrocarbon group in the case where R ¹¹ and R ¹² in R ⁷ and R ⁸ are hydrocarbon groups is the same as in the case of R ⁴ , R ⁵ and R ⁶ , and q is 1 to 10 Preferably there is.

（式中、Ｘは式（Ｉ）と同様である。） Specific examples of the compound represented by the formula (II) when R ⁷ and R ⁸ are — (R ¹⁰ O) _q —R ¹¹ group include two compounds represented by the following formulas.

(Wherein X is the same as in formula (I).)

式（III）中、Ｍは、式（Ｉ）と同様である。ｍ’は、Ｍの価数である。
Ｒ^１３及びＲ^１４は、それぞれ、炭化水素基又は−（Ｒ^１５Ｏ）_ｒ−Ｒ^１６基である。Ｒ^１５はそれぞれ炭化水素基又はシリレン基であり、Ｒ^１６は水素原子、炭化水素基又はＲ^１７ _３Ｓｉ−基であり、ｒは１以上の整数である。３つのＲ^１７はそれぞれ炭化水素基である。 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 in formula (I). m ′ is the valence of M.
R ¹³ and R ¹⁴ are each a hydrocarbon group or a — (R ¹⁵ O) _r —R ¹⁶ group. R ¹⁵ is a hydrocarbon group or a silylene group, R ¹⁶ is a hydrogen atom, a hydrocarbon group or an R ¹⁷ ₃ Si— group, and r is an integer of 1 or more. Each of the three R ¹⁷ is a hydrocarbon group.

The hydrocarbon group when R ¹³ and R ¹⁴ are hydrocarbon groups is the same as R ⁷ and R ⁸ .
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 R ¹³ and R ¹⁴ , the hydrocarbon group in the case where R ¹⁶ and R ¹⁷ are hydrocarbon groups is the same as R ⁴ , R ⁵ and R ⁶ described above.
r is preferably from 1 to 10.

Specific examples in the case where R ¹³ and R ¹⁴ are — (R ¹⁵ O) _r —R ¹⁶ groups are the same as those for — (R ¹⁰ O) _q —R ¹¹ in R ⁷ and R ⁸ .
The hydrocarbon group for R ¹³ and R ¹⁴ is the same as R ⁷ and R ⁸ and is preferably a butyl group, a hexyl group, a 2-ethylhexyl group, or a decyl group.

  It is known that the conductivity of the polyaniline complex and the solubility in a solvent can be controlled by changing the structure of the above dopant (Japanese Patent No. 338466). In the present invention, an optimum dopant can be selected according to required characteristics for each application. In the present invention, the compound represented by the formula (I) is preferably di-2-ethylhexylsulfosuccinic acid or sodium di-2-ethylhexylsulfosuccinate (aerosol OT). As the dopant of the present invention, di-2-ethylhexyl sulfosuccinate ion is preferable.

  It can be confirmed that the dopant of the polyaniline complex is doped to the substituted or unsubstituted polyaniline by ultraviolet / visible / near-infrared spectroscopy or X-ray photoelectron spectroscopy. As long as it has sufficient acidity to generate odor, it can be used without any restriction on the chemical structure.

The dopant doping ratio with respect to polyaniline is preferably 0.35 or more and 0.65 or less, more preferably 0.42 or more and 0.60 or less, and further preferably 0.43 or more and 0.57 or less. Preferably they are 0.44 or more and 0.55 or less. When the dope rate is less than 0.35, the solubility of the polyaniline complex in the organic solvent may not be increased.
The doping rate is defined by (number of moles of dopant doped in polyaniline) / (number of moles of monomer unit of polyaniline). For example, a doping ratio of a polyaniline complex containing unsubstituted polyaniline and a dopant of 0.5 means that one dopant is doped with respect to two monomer unit molecules of polyaniline.

  The dope rate can be calculated if the number of moles of the dopant and the polyaniline monomer unit in the polyaniline complex can be measured. For example, when the dopant is an organic sulfonic acid, the number of moles of sulfur atoms derived from the dopant and the number of moles of nitrogen atoms derived from the monomer unit of polyaniline are quantified by organic elemental analysis, and the ratio of these values is calculated. The doping rate can be calculated. However, the calculation method of the dope rate is not limited to the means.

The polyaniline complex preferably contains unsubstituted polyaniline and a sulfonate ion as a dopant, and satisfies the following formula (5).
0.42 ≦ S ₅ / N ₅ ≦ 0.60 (5)
(In the formula, S ₅ is the total number of moles of sulfur atoms contained in the polyaniline complex, and N ₅ is the total number of moles of nitrogen atoms contained in the polyaniline complex.)
The number of moles of nitrogen and sulfur atoms is a value measured by, for example, an organic elemental analysis method.

The polyaniline complex may or may not further contain phosphorus.
When the polyaniline complex contains phosphorus, the phosphorus content is, for example, not less than 10 ppm by weight and not more than 5000 ppm by weight. Moreover, phosphorus content is 2000 weight ppm or less, 500 weight ppm or less, and 250 weight ppm or less, for example.
The phosphorus content can be measured by ICP emission spectrometry.
Moreover, it is preferable that a polyaniline composite does not contain a Group 12 element (for example, zinc) as an impurity.

The polyaniline complex can be produced by a known production method. For example, it can be produced by chemical oxidative polymerization of a substituted or unsubstituted aniline in a solution containing a proton donor, phosphoric acid, and an emulsifier different from the proton donor and having two liquid phases. Moreover, it can manufacture by adding an oxidation polymerization agent in the solution which contains the emulsifier different from a substituted or unsubstituted aniline, a proton donor, phosphoric acid, and a proton donor, and has two liquid phases.
In addition, it is thought that the emulsifier plays the role which prevents the phase inversion mentioned later. When a polyaniline complex is produced by chemically oxidatively polymerizing a substituted or unsubstituted aniline in a solution containing a proton donor and phosphoric acid and having two liquid phases, compared to the case where hydrochloric acid is used instead of phosphoric acid. , Low molecular weight components will increase. From the state during polymerization when phosphoric acid is used, it is considered that the two liquid phases cause phase inversion during the polymerization. And it is thought that this phase inversion increases the low molecular weight component. This phenomenon of phase inversion is a phenomenon in which the liquid phase that was a continuous phase changes to a dispersed phase, and the other liquid phase that was a dispersed phase changes to a continuous phase.

Here, the “solution having two liquid phases” means a state in which two liquid phases that are incompatible with each other exist in the solution. For example, it means a state in which a “high polarity solvent phase” and a “low polarity solvent phase” exist in the solution.
Further, “a solution having two liquid phases” includes a state in which one liquid phase is a continuous phase and the other liquid phase is a dispersed phase. For example, a state where the “high polarity solvent phase” is a continuous phase and the “low polarity solvent phase” is a dispersed phase, and the “low polarity solvent phase” is a continuous phase and the “high polarity solvent phase” is a dispersed phase. Is included.
As a highly polar solvent used for the manufacturing method of the said polyaniline composite_body | complex, water is preferable and aromatic hydrocarbons, such as toluene and xylene, are preferable as a low polarity solvent, for example.

The proton donor is preferably a compound represented by the above formula (I).
The amount of the proton donor used is preferably 0.1 to 0.5 mol, more preferably 0.3 to 0.45 mol, and still more preferably 0.35 to 0.005 mol per mol of the aniline monomer. 4 mol.
When the amount of the proton donor used is larger than the above range, for example, there is a possibility that the “high-polar solvent phase” and the “low-polar solvent phase” cannot be separated after completion of polymerization.

  The emulsifier can be either an ionic emulsifier whose hydrophilic part is ionic or a nonionic emulsifier whose non-ionic hydrophilic part is used, or a mixture of one or more emulsifiers. May be used.

Examples of the ionic emulsifier include a cationic emulsifier, an anionic emulsifier, and a zwitter emulsifier.
Specific examples of the anionic emulsifier (anionic emulsifier) include fatty acids, disproportionated rosin soaps, higher alcohol esters, polyoxyethylene alkyl ether phosphates, alkenyl succinic acids, sarcosinates, and salts thereof.
Specific examples of the cationic emulsifier (cationic emulsifier) include alkyl dimethyl benzyl ammonium salt and alkyl trimethyl ammonium salt.
Specific examples of the zwitterionic emulsifier (both ion 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.

Of the above emulsifiers, anionic emulsifiers and nonionic emulsifiers are preferred.
As the anionic emulsifier, an anionic emulsifier having a phosphate ester structure is more preferable. Further, 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 preferably 0.001 to 0.1 mol, more preferably 0.002 to 0.02 mol, and still more preferably 0.003 to 0.01 mol with respect to 1 mol of the aniline monomer. is there.
When the amount of the emulsifier used is larger than the above range, the “high polar solvent phase” and the “low polar solvent phase” may not be separated after the completion of the polymerization.

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

Oxidizing agents used for chemical oxidative polymerization include peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide; ammonium dichromate, ammonium perchlorate, potassium iron (III) sulfate, trichloride Iron (III), manganese dioxide, iodic acid, potassium permanganate, iron paratoluenesulfonate, etc. can be used, and persulfates such as ammonium persulfate are preferred.
These oxidizing agents may be used alone or in combination of two or more.

The amount of the oxidizing agent used is preferably 0.05 to 1.8 mol, more preferably 0.8 to 1.6 mol, still more preferably 1.2 to 1.4 mol, relative to 1 mol of the aniline monomer. It is. A sufficient degree of polymerization can be obtained by setting the amount of the oxidizing agent used within the above range. Further, since aniline is sufficiently polymerized, it is easy to recover the liquid separation, and there is no possibility that the solubility of the polymer is lowered.
The polymerization temperature is usually −5 to 60 ° C., preferably −5 to 40 ° C. The polymerization temperature may be changed during the polymerization reaction. Side reactions can be avoided when the polymerization temperature is within this range.

Specifically, the polyaniline complex can be produced by the following method.
A solution in which a proton donor and an emulsifier are dissolved in toluene is placed in a separable flask placed in a stream of inert atmosphere such as nitrogen, and a substituted or unsubstituted aniline is added to the solution. Thereafter, phosphoric acid containing no chlorine as an impurity is added to the solution, and the solution temperature is cooled.

After the solution internal temperature is cooled, stirring is performed. A solution in which ammonium persulfate is dissolved in phosphoric acid is dropped using a dropping funnel and reacted. Thereafter, the solution temperature is raised and the reaction is continued. After completion of the reaction, the aqueous phase 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 a polyaniline complex (protonated polyaniline) toluene solution.
Some insolubles contained in the obtained complex solution are removed, and a toluene solution of the polyaniline complex is recovered. The solution is transferred to an evaporator, heated and decompressed to evaporate and remove volatile components, whereby a polyaniline complex is obtained.

  The molecular weight of polypyrrole, the molecular weight distribution, and the substituent of the substituted polypyrrole are the same as those of the above polyaniline.

There is no restriction | limiting in particular as a dopant of a polypyrrole composite_body | complex, The acceptor type dopant used suitably for the conductive polymer which generally contains the polymer of a pyrrole and / or a pyrrole derivative can be used suitably.
Typical examples include polystyrene sulfonic acid, paratoluene sulfonic acid, methane sulfonic acid, trifluoromethane sulfonic acid, anthraquinone sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid, sulfosalicylic acid, dodecyl benzene sulfonic acid, allyl sulfonic acid. Sulfonic acids such as perchloric acid, halogens such as chlorine and bromine, Lewis acids, proton acids and the like. These may be in the acid form or in the salt form. Preferred from the viewpoint of solubility in monomers, tetrabutylammonium perchlorate, tetraethylammonium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluorosulfonimide, dodecylbenzene Examples thereof include sulfonic acid and p-toluenesulfonic acid.

  When the dopant is used, the dopant is preferably used in an amount of 0.01 to 0.3 molecule of dopant per pyrrole polymer unit unit. When the amount is 0.01 molecule or less, the amount of dopant necessary to form a sufficient conductive path is insufficient, and it is difficult to obtain high conductivity. On the other hand, addition of 0.3 molecule or more does not improve the doping rate, so the addition of 0.3 molecule or more dopant is not economically preferable. Here, the pyrrole polymer unit unit refers to a repeating portion corresponding to one molecule of a pyrrole polymer monomer obtained by polymerizing a pyrrole monomer.

  The molecular weight of polythiophene, the molecular weight distribution, and the substituent of the substituted polythiophene are the same as those of the polyaniline. As the substituted polythiophene, polyethylenedioxythiophene (PEDOT) is preferable.

  Examples of the dopant of the polythiophene complex include organic acid ions and inorganic acid ions of an anionic surfactant. Examples of the organic acid ions of the anionic surfactant include sulfonic acid ions and esterified sulfate ions. Examples of inorganic acid ions include sulfate ions, halogen ions, nitrate ions, perchlorate ions, hexacyanoferrate ions, phosphate ions, and phosphomolybdate ions.

[Urethane resin]
As the urethane resin, for example, those obtained by reacting polyisocyanate and polyol can be used.

The polyisocyanate is not particularly limited as long as it is a compound having at least two isocyanate groups, and known ones can be used.
Specifically, for example, TDI (tolylene diisocyanate), MDI (diphenylmethane diisocyanate), XDI (xylylene diisocyanate), NDI (naphthylene 1,5-diisocyanate), TMXDI (tetramethylene xylylene diisocyanate) Aromatic isocyanate such as IPDI (isophorone diisocyanate), H12MDI (hydrogenated MDI, dicyclohexylmethane diisocyanate), H6XDI (hydrogenated XDI), and the like, HDI (hexamethylene diisocyanate), DDI There are aliphatic isocyanates such as (dimer acid diisocyanate) and NBDI (norbornene diisocyanate). These may be used alone or in combination of two or more.

  Polyols include polyether polyols such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol, polyester polyols such as polyethylene adipate, polyethylene-butylene adipate, and polycaprolactone, acrylic polyols, and polycarbonates. Examples thereof include polyols, polydimethylsiloxane-ethylene oxide adducts, polydimethylsiloxane-propylene oxide adducts, and castor oil. These may be used alone or in combination of two or more.

Since the urethane resin is soft and stretchable, even if it is mixed with polyaniline, the stretch following property 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% to 90 wt%, more preferably 20 wt% to 80 wt%, Preferably it is 30 wt%-60 wt%, Most preferably, it is 40 wt%-60 wt%.
When there is too little content, there exists a possibility that the adhesiveness to a base material may not express but it may peel easily. Moreover, since the ratio of polyaniline will fall when there is too much, there exists a possibility that the precipitation of plating may deteriorate.

  Specific examples of the urethane resin include hydran series (manufactured by DIC) such as hydran AP-20, AP-30F, AP-40F, WLS-213, U-coat UX-150, UX-200, UX-310, UWS. U-coat series (manufactured by Sanyo Kasei Co., Ltd.) such as -145, Acryt series (manufactured by Taisei Fine Chemical Co., Ltd.) such as ACRITT WBR-2018, WBR-016U, WEM-3008, PTG-RSN (manufactured by DIC Graphics), etc. It is done.

式中、Ｒ及びＸは、それぞれウレタン樹脂を合成する際のモノマーに由来する、置換もしくは無置換の２価の芳香族炭化水素基、置換もしくは無置換の２価の脂肪族炭化水素基、又は１以上の置換もしくは無置換の２価の芳香族炭化水素基と１以上の置換もしくは無置換の２価の脂肪族炭化水素基とを任意の順で結合した２価の基である。
２価の芳香族炭化水素基としては、環形成炭素数６〜５０の芳香族炭化水素基等が挙げられる。具体的には、フェニレン基、ナフチレン基等が挙げられる。
２価の脂肪族炭化水素基としては、炭素数６〜５０の直鎖状脂肪族炭化水素基、炭素数６〜５０の分岐状脂肪族炭化水素基等が挙げられる。具体的には、メチレン基、エチレン基、プロピレン基等が挙げられる。
１以上の２価の芳香族炭化水素基と１以上の２価の脂肪族炭化水素基とを任意の順で結合した２価の基としては、フェニレン基とメチレン基が結合した基、ナフチレン基とエチレン基が結合した基等が挙げられる。
置換基を有する場合の置換基としては、ヒドロキシル基、カルボキシル基、ニトロ基、シアノ基、アミノ基等が挙げられる。 The urethane resin usually has a structure represented by the following formula.

In the formula, R and X are each a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic hydrocarbon group derived from a monomer for the synthesis of a urethane resin, or A divalent group in which one or more substituted or unsubstituted divalent aromatic hydrocarbon groups and one or more substituted or unsubstituted divalent aliphatic hydrocarbon groups are bonded in any order.
Examples of the divalent aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 50 ring carbon atoms. Specific examples include a phenylene group and a naphthylene group.
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 a methylene group, an ethylene group, and a propylene group.
As the divalent group in which one or more divalent aromatic hydrocarbon groups and one or more divalent aliphatic hydrocarbon groups are bonded in any order, a group in which a phenylene group and a methylene group are bonded, a naphthylene group And a group in which an ethylene group is bonded.
Examples of the substituent in the case of having a substituent include a hydroxyl group, a carboxyl group, a nitro group, a cyano group, and an amino group.

The composition of the present invention may contain other components other than the conductive polymer, the urethane resin and the solvent within the range not impairing the effects of the present invention, and substantially contains the conductive polymer, the urethane resin and the solvent. Or a conductive polymer, a urethane resin and a solvent alone.
Here, “substantially” means that 95% to 100% by weight (preferably 98% to 100% by weight) of the composition is a conductive polymer, a urethane resin, and a solvent.
Examples of other components include phenolic compounds and heat stabilizers described later.

When the composition of the present invention contains a polyaniline complex as a conductive polymer, it may further contain a phenolic compound.
The phenolic compound is not particularly limited as long as it is a compound having a phenolic hydroxyl group. The compound having a phenolic hydroxyl group is a polymer compound composed of a compound having one phenolic hydroxyl group, a compound having a plurality of phenolic hydroxyl groups, and a repeating unit having one or more phenolic hydroxyl groups.

（式中、ｎは１〜５の整数であり、好ましくは１〜３であり、より好ましくは１である。
Ｒは、炭素数１〜２０のアルキル基、アルケニル基、シクロアルキル基、アリール基、アルキルアリール基又はアリールアルキル基である。） The compound having one phenolic hydroxyl group is preferably a compound represented by the following formulas (A), (B) and (C).

(In formula, n is an integer of 1-5, Preferably it is 1-3, More preferably, it is 1.
R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group. )

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

  Specific examples of the phenolic compound represented by the formula (A) include methoxyphenol (for example, 4-methoxyphenol), ethoxyphenol, propoxyphenol, isopropoxyphenol, butyloxyphenol, isobutyloxyphenol, and tertiary butyloxyphenol. Can be mentioned.

（式中、ｎは０〜７の整数であり、好ましくは０〜３であり、より好ましくは１である。
Ｒは、それぞれ炭素数１〜２０のアルキル基、アルケニル基、アルキルチオ基、炭素数３〜１０のシクロアルキル基、炭素数６〜２０のアリール基、アルキルアリール基又はアリールアルキル基である。）
式（Ｂ）で表わされるフェノール性化合物の具体例としては、ヒドロキシナフタレンが挙げられる。

(In formula, n is an integer of 0-7, Preferably it is 0-3, More preferably, it is 1.
R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkylthio group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group. )
Specific examples of the phenolic compound represented by the formula (B) include hydroxynaphthalene.

（式中、ｎは１〜５の整数であり、好ましくは１〜３であり、より好ましくは１である。
Ｒは、それぞれ炭素数１〜２０のアルキル基、アルケニル基、アルキルチオ基、炭素数３〜１０のシクロアルキル基、炭素数６〜２０のアリール基、アルキルアリール基又はアリールアルキル基である。）
式（Ｃ）で表わされる化合物の具体例としては、ｏ−，ｍ−もしくはｐ−クレゾール、ｏ−，ｍ−もしくはｐ−エチルフェノール、ｏ−，ｍ−もしくはｐ−プロピルフェノール（例えば４−イソプロピルフェノール）、ｏ−，ｍ−もしくはｐ−ブチルフェノール、ｏ−，ｍ−もしくはｐ−ペンチルフェノール（例えば、４−ｔｅｒｔ−ペンチルフェノール）が挙げられる。

(In formula, n is an integer of 1-5, Preferably it is 1-3, More preferably, it is 1.
R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkylthio group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group. )
Specific examples of the compound represented by the formula (C) include o-, m- or p-cresol, o-, m- or p-ethylphenol, o-, m- or p-propylphenol (for example, 4-isopropyl Phenol), o-, m- or p-butylphenol, o-, m- or p-pentylphenol (for example, 4-tert-pentylphenol).

Regarding R in formulas (A), (B), and (C), examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tertiary butyl.
Examples of the alkenyl group include groups having an unsaturated bond in the molecule of the alkyl group described above.
Examples of the cycloalkyl group include cyclopentane and cyclohexane.
Examples of the aryl group include phenyl and naphthyl.
Examples of the alkylaryl group and the arylalkyl group include groups obtained by combining the above-described alkyl group and aryl group.

（式中、Ｒは炭化水素基、ヘテロ原子含有炭化水素基、ハロゲン原子、カルボン酸基、アミノ基、ＳＨ基、スルホン酸基、又は水酸基であり、複数のＲはそれぞれ互いに同一であっても異なっていてもよい。ｎは０〜６の整数である。） Although the example of the compound which has one said phenolic hydroxyl group was shown, a phenol, o-, m- or p-chlorophenol, a salicylic acid, hydroxybenzoic acid is mentioned as a specific example of substituted phenols. Specific examples of the compound having a plurality of phenolic hydroxyl groups include catechol, resorcinol, and a compound represented by the following formula (D).

(In the formula, R is a hydrocarbon group, a hetero atom-containing hydrocarbon group, a halogen atom, a carboxylic acid group, an amino group, an SH group, a sulfonic acid group, or a hydroxyl group. May be different, n is an integer from 0 to 6.)

The phenolic compound represented by the formula (D) preferably has two or more hydroxyl groups that are not adjacent to each other.
Specific examples of the phenolic compound represented by the formula (D) include 1,6-naphthalenediol, 2,6-naphthalenediol, and 2,7-naphthalenediol.

  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 phenolic compound content is preferably such that the molar concentration of the phenolic compound is 0.01 [mmol / g] or more per 1 g of the polyaniline complex. 100 [mol / g] or less, more preferably 0.05 [mmol / g] or more and 1 [mol / g] or less, further preferably 0.1 [mmol / g] or more and 500 [mmol / g] or less, particularly preferably Is in the range of 0.2 [mmol / g] to 80 [mmol / g].
When there is too little content of a phenolic compound, there exists a possibility that the electrical conductivity improvement effect may not be acquired. On the other hand, when there is too much content of a phenolic compound, there exists a possibility that film quality may worsen. In addition, a large amount of heat, time, and other labor are required to volatilize and remove, which increases costs.

When the composition of the present invention contains a polyaniline complex as a conductive polymer, it may further contain a heat resistance stabilizer.
The heat resistance stabilizer is an acidic substance or a salt of an acidic substance, and the acidic substance may be either an organic acid (an acid of an organic compound) or an inorganic acid (an acid of an inorganic compound). Further, the conductive polymer layer may contain a plurality of heat stabilizers.

When the composition of the present invention contains only an acidic substance as a heat stabilizer, the acidic substance is preferably a compound different from the proton donor of the polyaniline complex, and the composition of the present invention is used as a heat stabilizer. When only the salt of the acidic substance is contained, the salt of the acidic substance is preferably a compound different from the proton donor of the polyaniline complex.
In addition, when the composition of the present invention contains both an acidic substance and an acidic substance salt as a heat stabilizer, preferably at least one of the acidic substance and the acidic substance salt is a compound different from the proton donor. It is.

When the composition of the present invention contains only an acidic substance as a heat stabilizer, the acidic substance is preferably different from a phenolic compound, and the composition of the present invention is a salt of an acidic substance as a heat stabilizer. In the case where only the salt is contained, preferably the salt of the acidic substance is different from the phenolic compound.
Further, when the composition of the present invention contains both an acidic substance and an acidic substance salt as a heat stabilizer, preferably at least one of the acidic substance and the acidic substance salt is a phenolic compound and Different.

  The acidic substance that is a heat-resistant stabilizer is preferably an organic acid, more preferably an organic acid having one or more sulfonic acid groups, carboxy groups, phosphoric acid groups, or phosphonic acid groups, and more preferably sulfonic acid. An organic acid having one or more groups.

The organic acid having one or more sulfonic acid groups is preferably a cyclic, chain or branched alkyl sulfonic acid, substituted or unsubstituted aromatic sulfonic acid, or polysulfonic acid having one or more sulfonic acid groups.
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 a sulfonic acid having a benzene ring, a sulfonic acid having a naphthalene skeleton, a sulfonic acid having an anthracene skeleton, a substituted or unsubstituted benzenesulfonic acid, a substituted or unsubstituted naphthalenesulfonic acid, and a substituted Alternatively, unsubstituted anthracene sulfonic acid may be mentioned, and naphthalene sulfonic acid is preferable. Specific examples include naphthalene sulfonic acid, dodecylbenzene sulfonic acid, and anthraquinone sulfonic acid.
The substituent is, for example, a substituent selected from the group consisting of an alkyl group, an alkoxy group, a hydroxy group, a nitro group, a carboxy group, and an acyl group, and one or more substituents may be substituted.
The polysulfonic acid is a sulfonic acid in which a plurality of sulfonic acid groups are substituted on the main chain or side chain of the polymer chain. For example, polystyrene sulfonic acid is mentioned.

The organic acid having one or more carboxy groups is preferably a cyclic, linear or branched alkyl carboxylic acid, substituted or unsubstituted aromatic carboxylic acid, or polycarboxylic acid having one or more carboxy groups.
Examples of the alkyl carboxylic acid include undecylenic acid, cyclohexane carboxylic acid, and 2-ethylhexanoic 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 a sulfonic acid group, an alkyl group, an alkoxy group, a hydroxy group, a nitro group, and an acyl group, and one or more substituents may be substituted. Specific examples include salicylic acid, benzoic acid, naphthoic acid, and trimesic acid.

The organic acid having at least one phosphoric acid group or phosphonic acid group is preferably a cyclic, linear or branched alkylphosphoric acid or alkylphosphonic acid having at least one phosphoric acid group or phosphonic acid group; substituted or unsubstituted aromatic An aromatic phosphoric acid or an aromatic phosphonic acid; a polyphosphoric acid or a polyphosphonic acid.
Examples of the alkyl phosphoric acid or alkylphosphonic acid include dodecyl phosphoric acid and bis (2-ethylhexyl) hydrogen phosphate. 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 benzene sulfonic acid or phosphonic acid, and naphthalene sulfonic acid or phosphonic acid. The substituent is, for example, a substituent selected from the group consisting of an alkyl group, an alkoxy group, a hydroxy group, a nitro group, a carboxy group, and an acyl group, and one or more substituents may be substituted. An example is phenylphosphonic acid.

Examples of the salt of the acidic substance contained in the composition of the present invention include the salt of the acidic substance.
The composition of the present invention may contain two or more acidic substances and / or salts of acidic substances that are heat-resistant stabilizers. Specifically, the composition of the present invention may include different acidic substances and / or salts of different acidic substances.

When the proton donor of the polyaniline complex is sulfonic acid and the composition of the present invention contains only an acidic substance as a heat stabilizer, the acidic substance may be the same or different sulfonic acid as the proton donor. preferable. Further, when the composition of the present invention contains only the salt of the acidic substance as the heat stabilizer, the salt of the acidic substance may be the same or different sulfonic acid salt as the proton donor of the polyaniline complex. preferable.
When the composition of the present invention includes an acidic substance and a salt of the acidic substance as a heat stabilizer, at least one of the acidic substance and the salt of the acidic substance is a sulfonic acid or a sulfonic acid that is the same as or different from the proton donor. A salt is preferred.

When the composition of the present invention contains only sulfonic acid as the heat stabilizer, preferably satisfies the formula (12), and when the composition of the present invention contains only the salt of sulfonic acid as the heat stabilizer. Preferably, when the formula (13) is satisfied and the composition of the present invention contains a sulfonic acid and a sulfonic acid salt as a heat stabilizer, the formula (14) is preferably satisfied.
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 all polyaniline complexes contained in the composition of the present invention. Is the sum of the number of moles of nitrogen atoms, S ₃ is the sum of the number of moles of sulfur atoms of the salts of all acidic substances contained in the composition of the present invention, and N ₃ is the composition of the present invention. means the total number of moles of nitrogen atoms of all the polyaniline complex contained in, S ₄ are the number of moles of sulfur atoms in the salts of all the acidic substance and acidic substance contained in the composition of the present invention N ₄ means the total number of moles of nitrogen atoms of all polyaniline complexes contained in the composition of the present invention.)

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

When the composition of this invention contains only an acidic substance, it is preferable that the acidity (pKa) of the said acidic substance is 5.0 or less. The lower limit of the acidity is not particularly limited. For example, when an acid substance having an acidity of −4.0 or less is included, the polyaniline complex may be deteriorated.
When the composition of this invention contains only the salt of an acidic substance, it is preferable that the acidity of the salt of the said acidic substance is 5.0 or less. About the minimum of acidity, it is the same as that of the said acidic substance.
When the composition of the present invention includes both an acidic substance and an acidic substance salt, at least one of the acidic substance salts having an acidity of 5.0 or less and an acidity of 5.0 or less is included. It is preferable to satisfy. The lower limit of acidity is the same as described above.

Acidity (pKa) is defined by computational chemistry methods. A. Journal of Physical Chemistry 1995, Vol. 99, p. 50, which calculates the charge density on the surface of a molecule by quantum chemical calculation developed by Klamt et al. The method described in 2224 is used.
Specifically, using “TURBOMOLE Version 6.1” (manufactured by COSMO logic), the structure is optimized using TZVP as a basis function, and the COSMO-RS method calculation is performed using this structure using “COSMO therm version C2”. .1 Release 01.10 "(manufactured by COSMO logic).
Here, the pKa is calculated by inputting the conditions of 25 ° C. in an aqueous solvent, the chemical formula of the molecule, and the chemical formula of the deprotonated molecule in “COSMO thermion C2.1 Release 01.10”. be able to.

  In the composition of the present invention, the content of the heat resistance stabilizer is preferably 1 to 1000 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polyaniline complex.

The solvent may be an organic solvent or an inorganic solvent such as water, or may be a single type or a mixed solvent of two or more types. An organic solvent is preferable.
The organic solvent may be a water-soluble organic solvent or an organic solvent that is substantially immiscible with water (water-immiscible organic solvent).

  The water-soluble organic solvent may be a protic polar solvent or an aprotic polar solvent, for example, alcohols such as isopropanol, 1-butanol, 2-butanol, 2-pentanol and benzyl alcohol; ketones such as acetone; Ethers such as tetrahydrofuran and dioxane; and aprotic polar solvents such as N-methylpyrrolidone.

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

When an organic solvent is used as a solvent, the use of a mixed organic solvent in which a water-immiscible organic solvent and a water-soluble organic solvent are mixed at a ratio of 99 to 50: 1 to 50 (mass ratio) causes generation of gels and the like during storage. This is preferable because it can be prevented and stored for a long time.
As the water-immiscible organic solvent of the mixed organic solvent, a low-polar organic solvent can be used, and the low-polar organic solvent is preferably toluene or chloroform. Moreover, as a water-soluble organic solvent of a mixed organic solvent, a highly polar organic solvent can be used, for example, methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, diacetone alcohol, 3-methoxy-1- Butanol, 3-methyl-3-methoxy-1-butanol, ethyl carbitol, butyl carbitol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran or diethyl ether are preferred.

The proportion of the conductive polymer in the solvent is usually 900 g / kg or less, preferably 0.01 g / kg or more and 300 g / kg or less, more preferably 10 g / kg or more and 300 g / kg depending on the type of the solvent. Or less, more preferably in the range of 30 g / kg to 300 g / kg.
If the content of the conductive polymer is too large, the solution state cannot be maintained, and handling during molding becomes difficult, the uniformity of the molded body is impaired, and consequently the electrical properties and mechanical strength of the molded body. There is a risk of lowering transparency. On the other hand, if the content of the conductive polymer is too small, only a very thin film can be produced when the film is formed by the method described later, which may make it difficult to produce a uniform conductive film.

The composition of the present invention may further contain additives such as other resins, inorganic materials, curing agents, plasticizers, and organic conductive materials.
Examples of other resins include a binder substrate, a plasticizer, and a matrix substrate.

  Specific examples of other resins include, for example, polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, polystyrene, polyester, polyamide, polyacetal, polyethylene terephthalate, polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid ester, Examples thereof include polymethacrylic acid ester and polyvinyl alcohol.

  Further, instead of the above resin, together with the resin, a thermosetting resin such as an epoxy resin, a urethane resin, or a phenol resin, or a precursor capable of forming these thermosetting resins may be included.

The inorganic material is added, for example, for the purpose of improving strength, surface hardness, dimensional stability and other mechanical properties, or improving electrical properties such as conductivity.
Specific examples of the inorganic material include, for example, silica (silicon dioxide), titania (titanium dioxide), alumina (aluminum oxide), Sn-containing In ₂ O ₃ (ITO), Zn-containing In ₂ O ₃ , and In ₂ O ₃ . Examples include co-substituted compounds (oxides in which tetravalent elements and divalent elements are substituted with trivalent In), Sb-containing SnO ₂ (ATO), ZnO, Al-containing ZnO (AZO), and Ga-containing ZnO (GZO). .

  The curing agent is added for the purpose of, for example, improving strength, surface hardness, dimensional stability, and other mechanical properties. Specific examples of the curing agent include a thermosetting agent such as a phenol resin, and a photocuring agent using an acrylate monomer and a photopolymerization initiator.

For example, the plasticizer is added for the purpose of improving mechanical properties such as tensile strength and bending strength.
Specific examples of the plasticizer include phthalic acid esters and phosphoric acid esters. Examples of the organic conductive material include carbon materials such as carbon black and carbon nanotubes, and conductive polymers other than the polyaniline obtained in the present invention.

[Electroless plating base film]
The electroless plating base film (layer) of the present invention is obtained from the above composition. The method for forming the electroless plating base film of the present invention is as described later.
The dry film thickness of the electroless plating base film is preferably 0.1 μm or more, more preferably 0.2 μm or more. If the film thickness is less than 0.1 μm, the adhesion between the base material and the plating film cannot be maintained, so that the film is easily peeled off. Further, there is a possibility that the area where the Pd metal is not supported increases, and there is a possibility that the area where electroless plating is not performed increases.
The upper limit of the dry film thickness is not particularly limited, but is, for example, 100 μm or less, 10 μm or less, 5.0 μm or less.

[Method of manufacturing electroless plating base film]
The method for producing an electroless plating base film of the present invention uses the composition for forming an electroless plating base film of the present invention. This manufacturing method will not be specifically limited if the composition of this invention is used, For example, the coating method of apply | coating the composition of this invention on a base material by the bar-coat method, and drying is mentioned.

[Plating laminate]
The plating laminate of the present invention includes an electroless plating layer containing a metal, an electroless plating base layer containing a conductive polymer and a urethane resin, and a substrate layer, one surface of the electroless plating layer, and electroless One surface of the plating underlayer is in contact.

FIG. 1 is a schematic view showing a layer configuration of an embodiment of the plated laminate of the present invention.
The plating laminate 1 includes an electroless plating base layer 20 and an electroless plating layer 30 laminated on a substrate 10 in this order.
The plating laminated body of this invention can be manufactured with the manufacturing method of the plating laminated body of this invention mentioned later.

[substrate]
The substrate is not particularly limited, and may be a metal, an inorganic material (ceramics, glass, or the like), or a resin. Moreover, the base material which covered the metal completely with resin, the composite material (For example, FRP, glass epoxy composite material) of an inorganic type material and resin, etc. may be sufficient. Examples of the resin include polycarbonate resin, acrylic resin, nylon resin, polyimide resin, polyester resin, styrene resin, phenol resin, and PPS (polyphenylene sulfide) resin.
As a specific example of the substrate, for example, easy-adhesion-treated PET (A4300 manufactured by Toyobo) can be mentioned.

[Electroless plating underlayer]
The electroless plating underlayer includes a conductive polymer and a urethane resin. The conductive polymer and the urethane resin are as described above.
The electroless plating underlayer can be produced using the composition of the present invention. The formation method is as described above.

[Electroless plating layer]
Examples of the metal species of the electroless plating layer include copper, nickel, cobalt, palladium, silver, gold, platinum, and tin. In addition to these, elements such as phosphorus, boron, and iron may be contained. The forming method is as described later.

[Method for producing electroless plating laminate]
The method for producing an electroless plating laminate of the present invention comprises a step of forming an electroless plating base film on the substrate layer using the electroless plating base film forming composition of the present invention, and an electroless plating base film The process of forming the electroless-plating layer containing a metal is included.

The formation of the electroless plating base film can be performed by the above-described method for manufacturing an electroless plating base film.
It is preferable to perform a degreasing step after forming the base film and before forming the electroless plating layer. In the degreasing step, the surface of the polyaniline layer is degreased and washed with a solvent such as a surfactant or alcohol to improve wettability.
As the surfactant, an anionic, cationic or nonionic surfactant can be appropriately used, and a cationic surfactant is preferable. When a cationic surfactant is used, it is diluted to 1 to 3% with, for example, ion exchange water.

After the formation of the electroless plating base film, preferably after the degreasing step, a Pd compound solution is usually brought into contact with the base film in order to support Pd metal (catalyst metal) responsible for the electroless plating catalytic action.
When the Pd compound solution is brought into contact, a conductive polymer such as a polyaniline complex adsorbs Pd ions, and Pd ions are reduced to Pd metal by the reduction action. In addition, if it is not reduced Pd, that is, Pd in a metal state, it does not exhibit a catalytic action in electroless plating.
The Pd adhesion amount (including Pd ions and Pd metal) per unit area is preferably 1.7 μg / cm ² or more, and more preferably 2.5 μg / cm ² or more.

  As the Pd compound, palladium chloride is preferable. As the solvent, hydrochloric acid is generally used. However, Pd is only required to be present in an aqueous solution in an ionic state, and is not limited to a hydrochloric acid aqueous solution. 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 base layer, the film obtained above is brought into contact with an electroless plating solution. When the underlayer and the electroless plating solution are in contact, the supported Pd metal acts as a catalyst, and a plating layer is formed on the polyaniline layer.

  Examples of the metal species contained in the electroless plating solution include copper, nickel, cobalt, palladium, silver, gold, platinum, and tin. In addition to these, elements such as phosphorus, boron, and iron may be contained.

The contact temperature with the electroless plating solution varies depending on the type and thickness of the plating bath.
Moreover, although the contact time with an electroless-plating liquid also changes with plating bath types, thickness, etc., it is 1 to 30 minutes, for example, and 5 to 15 minutes. It is possible to use only electroless plating, or it is possible to provide a metal film of the same type or different by electrolytic plating after providing a metal thin film by electroless plating.

Production Example 1
[Production of polyaniline complex]
37.8 g of aerosol OT (sodium di-2-ethylhexylsulfosuccinate) (AOT) and 1.47 g of sorbon T-20 (manufactured by Toho Chemical Co., Ltd.), which is a nonionic emulsifier having a polyoxyethylene sorbitan fatty acid ester structure, were added to toluene. The solution dissolved in 600 mL was placed in a 6 L separable flask placed under a nitrogen stream, and 22.2 g of aniline was further added to this solution. Thereafter, 1800 mL of 1M phosphoric acid was added to the solution, and the temperature of the solution having two liquid phases of toluene and water was cooled to 5 ° C.

  When the internal temperature of the solution reached 5 ° C., stirring was performed at 390 rpm. A solution obtained by dissolving 65.7 g of ammonium persulfate in 600 mL of 1M phosphoric acid was dropped using a dropping funnel over 2 hours. The reaction was carried out for 18 hours while maintaining the internal temperature of the solution at 5 ° C. Thereafter, the reaction temperature was raised to 40 ° C., and the reaction was continued for 1 hour. Then, it left still and isolate | separated the toluene phase. 1500 ml of toluene is added to the obtained toluene phase, 500 mL of 1M phosphoric acid is washed once with 500 mL of ion-exchanged water, the toluene phase is left to stand, concentrated for concentration adjustment, and a polyaniline complex toluene solution 900 g was obtained. The polyaniline complex concentration of this polyaniline complex toluene solution was 5.7% by weight.

Production Example 2
The polyaniline / AOT complex toluene solution obtained in Production Example 1 was dried under reduced pressure in a 60 ° C. hot water bath and dried to obtain 51.3 g of a polyaniline complex (powder).

Example 1
[Plating foundation film forming process]
2.8 g of the polyaniline powder obtained in Production Example 2 was dissolved in 17 g of methyl isobutyl ketone (MIBK: manufactured by Wako Pure Chemical Industries) and 8.5 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, 5.7 g of ASPU112 (made by DIC Corporation, solid content concentration 30%), which is a urethane resin, was added and stirred to prepare a uniform coating solution for forming a plating base.
The obtained coating solution was applied onto a carbo glass film C110C (PC film, manufactured by Asahi Glass Co., Ltd.), which is a polycarbonate film, using a bar coater and dried at 120 ° C. for 30 minutes to form a plating base film. The thickness of the plating base film was 1 μm. The polyaniline concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.

[Degreasing process]
The obtained film (plating base film) is degreased by immersing it in an aqueous solution of 3% Dianol CDE (coconut oil fatty acid diethanolamide; nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) for 5 minutes at room temperature. Went. In addition, this degreasing process aims at the improvement of wettability.

[Step of contacting with Pd compound solution]
The film after the degreasing treatment was immersed in a 5-fold diluted solution of red summer (palladium aqueous solution, manufactured by Nippon Kanisen Co., Ltd.) at 30 ° C. for 5 minutes to carry out a metal Pd carrying treatment.

[Step of 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 Ad Copper IW” (Okuno Pharmaceutical Co., Ltd.).

[Cross cut test]
About the obtained plating part, according to JIS-5600, the grid | lattice-like damage | wound was made to the plating film with the cutter, the cellophane (made by Nichiban Co., Ltd.) was peeled off, and it peeled off vigorously, and the crosscut test was done. As a result, no peeling was observed and the adhesion was good.

Example 2
A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 6.8 g of Juliano U301 (made by Arakawa Chemical Co., Ltd., solid concentration 25%), which is a urethane resin, was added instead of ASPU112. Produced. The polyaniline concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.

Example 3
A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 6.8 g of TSP3301 (made by Arakawa Chemical Co., Ltd., solid concentration 25%), which is a urethane resin, was added instead of ASPU112. . The polyaniline concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.

Example 4
A coating solution for forming a plating base and a plating base film in the same manner as in Example 1 except for adding 5.7 g of diferamin MAU1008 (manufactured by Dainichi Seika Co., Ltd., solid content concentration: 30%) instead of adding ASPU112. Was made. The polyaniline concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.

Example 5
Instead of adding ASPU112, a coating solution for forming a plating base and a plating base film are the same as in Example 1 except for adding 5.7 g of urethane resin Diferamin MAU1005 (manufactured by Dainichi Seika Co., Ltd., solid content concentration 30%). Was made. The polyaniline concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.

Example 6
A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 4.8 g of diferamin MAU4308HV (made by Dainichi Seika Co., Ltd., solid content concentration 35%), which is a urethane resin, was added instead of ASPU112. did. The polyaniline concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.

Example 7
Instead of ASPU112, 2.8 g of urethane resin Daiferamin MAU1008 (manufactured by Dainichi Seika Co., Ltd., solid content concentration 30%) and 2.8 g of urethane resin ASPU112 (DIC Corporation, solid content concentration 30%) A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except for the addition. The polyaniline concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt% (MAU1008: ASPU = 1: 1).
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.

Example 8
Example except that 2.8 g of ASPU112 (made by DIC Corporation, solid content concentration 30%) and 0.85 g of KS-10 (made by Sekisui Chemical Co., Ltd.) which is polyvinyl butyral were added instead of ASPU112. In the same manner as in Example 1, a coating solution for forming a plating base and a plating base film were prepared. The polyaniline concentration in the plating base film was 62.5 wt%, the urethane resin concentration was 18.75 wt%, and the polyvinyl butyral concentration was 18.75 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, no peeling was observed and the adhesion was good.

Comparative Example 1
A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that the ASPU 112 was not added. The polyaniline concentration in the plating base film was 100 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the entire test part was peeled off at the interface between the plating base film and the Cu plating layer. Moreover, as a result of performing the crosscut test similarly in the part which the plating base film exposed, the test part also peeled the whole surface also in the PC film and plating base film interface.

Comparative Example 2
A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 5.7 g of Byron 20SS (manufactured by Toyobo Co., Ltd., solid content concentration 30%), which is a polyester resin, was added instead of ASPU112. The polyaniline concentration in the plating base film was 62.5 wt%, and the polyester resin concentration was 37.5 wt%. At this time, when the plating base film was observed, the compatibility between the polyaniline composite and Byron 20SS was poor, and the plating base film became non-uniform and fragile.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, since the plating base film was brittle, peeling from the middle of the plating base film was confirmed.

Comparative Example 3
A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 1.7 g of Byron 50DS (Toyobo Co., Ltd.), which is a polyester resin, was added instead of ASPU112. When the plating base film was observed, the compatibility between the polyaniline composite and Byron 50DS was poor, and the plating base film was uneven and brittle.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, since the plating base film was brittle, peeling from the middle of the plating base film was confirmed.

Comparative Example 4
In the same manner as in Example 1, except that 8.5 g of Super Clone 822 (Nippon Paper Chemical Co., Ltd., solid content concentration: 20%), which is a chlorinated polyolefin, was added instead of ASPU112, a plating base forming coating solution and a plating base film were used. Was made. The polyaniline concentration in the plating base film was 62.5 wt%, and the chlorinated polyolefin concentration was 37.5 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the adhesion between the plating base film and the Cu layer interface was good, but the entire test part was peeled off at the plating base film and PC film interface.

Comparative Example 5
A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 5.7 g of GDP 6140 (manufactured by Gunei Chemical Co., Ltd., solid content concentration 30%), which is a phenol resin, was added instead of ASPU112. . The polyaniline concentration in the plating base film was 62.5 wt%, and the phenol resin concentration was 37.5 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the adhesion between the plating base film and the Cu layer interface was good, but the entire test part was peeled off at the plating base film and PC film interface.

Comparative Example 6
A plating base forming coating solution and a plating base film were prepared in the same manner as in Example 1 except that 1.7 g of KS-10 (manufactured by Sekisui Chemical Co., Ltd.), which is a polyvinyl butyral resin, was added instead of ASPU112. The polyaniline concentration in the plating base film was 62.5 wt%, and the polyvinyl butyral resin concentration was 37.5 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the adhesion between the plating base film and the Cu layer interface was good, but part of the test portion was peeled off at the plating base film and PC film interface.

Comparative Example 7
A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 1.7 g of Toresin EF-30T (manufactured by Nagase ChemteX Corporation), which is a polyamideimide resin, was added instead of ASPU112. The polyaniline concentration in the plating base film was 62.5 wt%, and the polyamideimide resin concentration was 37.5 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the entire test part was peeled off at the interface between the plating base film and the Cu layer. Moreover, as a result of performing the same crosscut test in the portion where the plating base film was exposed, there was no peeling at the interface between the plating base film and the PC film, and the adhesion was good.

Comparative Example 8
A coating solution for forming a plating base and a plating base film were prepared in the same manner as in Example 1 except that 1.7 g of Toresin F-30K (manufactured by Nagase ChemteX Corporation), which is a polyamide-imide resin, was added instead of ASPU112. The polyaniline concentration in the plating base film was 62.5 wt%, and the polyamideimide resin concentration was 37.5 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the entire test part was peeled off at the interface between the plating base film and the Cu layer. Moreover, as a result of performing the same crosscut test in the portion where the plating base film was exposed, there was no peeling at the interface between the plating base film and the PC film, and the adhesion was good.

Comparative Example 9
A coating solution for forming a plating base and a plating base film in the same manner as in Example 1 except that 6.8 g of Bilomax HR-87TD (made by Toyobo Co., Ltd., solid content concentration 25%), which is a polyamide-imide resin, was added instead of ASPU112. Was made. The polyaniline concentration in the plating base film was 62.5 wt%, and the polyamideimide resin concentration was 37.5 wt%.
Thereafter, degreasing, carrying Pd and plating were performed in the same manner as in Example 1, and a cross-cut test was conducted. As a result, the adhesion between the plating base film and the Cu layer interface was good, but part of the test portion was peeled off at the plating base film and PC film interface.

Example 9
3.75 g of the polyaniline powder obtained in Production Example 2 was dissolved in 17 g of MIBK (manufactured by Wako Pure Chemical Industries, Ltd.) and 8.5 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, 2.5 g of ASPU112 (manufactured by DIC Corporation, solid content concentration 30%), which is a urethane resin, was added and stirred to prepare a uniform coating solution for forming a plating base. The obtained coating solution was applied to a Carboglass film C110C (PC film, manufactured by Asahi Glass Co., Ltd.), which is a polycarbonate film, with a bar coater and dried at 120 ° C. for 30 minutes to form a plating base film. The thickness of the plating base film was 1 μm. The polyaniline concentration in the plating base film was 83 wt%, and the urethane resin concentration was 17 wt%.
Thereafter, plating was performed in the same manner as in Example 1, and a cross-cut test was performed. As a result, no peeling was observed and the adhesion was good.

Example 10
1.5 g of the polyaniline powder obtained in Production Example 2 was dissolved in 17 g of MIBK (manufactured by Wako Pure Chemical Industries, Ltd.) and 8.5 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, 10 g of ASPU112 (made by DIC Corporation, solid content concentration 30%), which is a urethane resin, was added and stirred to prepare a uniform coating solution for forming a plating base. The obtained coating solution was applied to a Carboglass film C110C (PC film, manufactured by Asahi Glass Co., Ltd.), which is a polycarbonate film, with a bar coater and dried at 120 ° C. for 30 minutes to form a plating base film. The thickness of the plating base film was 1 μm. The polyaniline concentration in the plating base film was 33 wt%, and the urethane resin concentration was 67 wt%.
Thereafter, plating was performed in the same manner as in Example 1, and a cross-cut test was performed. As a result, no peeling was observed and the adhesion was good.

Example 11
Instead of ASPU112 (5.7 g), 2.8 g of urethane resin, diferamin MAU1008 (manufactured by Dainichi Seika Co., Ltd., solid content concentration 30%), and ASPU112 (made by DIC Corporation, solid content concentration 30%), urethane resin ) Was added in the same manner as in Example 1 except that 2.8 g was added. Moreover, the plating base film was produced similarly to Example 1 except having used the cosmo shine (PET film, Toyobo Co., Ltd.) which is a polyester resin instead of C110C. The polyaniline concentration in the plating base film was 62.5 wt%, and the urethane resin concentration was 37.5 wt% (MAU1008: ASPU = 1: 1).
Thereafter, degreasing, carrying Pd and plating 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 (made by Toray DuPont), which is a polyimide resin, was used instead of Cosmo Shine (PET film, produced by Toyobo Co., Ltd.).
Then, degreasing, carrying Pd and plating were performed in the same manner as in Example 11 to obtain a plated laminate.

Example 13
A plated laminate was obtained in the same manner as in Example 11 except that Torelina (PPS film, manufactured by Toray Industries, Inc.), which is a PPS resin, was used instead of Cosmo Shine (PET film, manufactured by Toyobo Co., Ltd.).
Then, degreasing, carrying Pd and plating were performed in the same manner as in Example 11 to obtain a plated laminate.

Table 1 below shows the results of evaluation of adhesion in Examples and Comparative Examples.

  The evaluation criteria for adhesion in Examples and Comparative Examples are as follows. That is, “◯” indicates that no peeling is observed at the interface and the adhesion is good, “△” indicates that peeling is observed at a part of the interface, The case where peeling occurred in the middle was taken as “x”.

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

1 Plated Laminate 10 Substrate 20 Electroless Plating Underlayer 30 Electroless Plating Layer

Claims (19)

  A composition for forming an electroless plating base film comprising a conductive polymer and a urethane resin.   The composition for forming an electroless plating base film according to claim 1, wherein the conductive polymer is a polyaniline composite in which substituted or unsubstituted polyaniline is doped with a dopant. The composition for forming an electroless plating base film according to claim 2, wherein the dopant is a sulfosuccinic acid derivative represented by the following formula (III).

(In formula (III), M is a hydrogen atom, an organic free radical or an inorganic free radical. M ′ is a valence of M. R ¹³ and R ¹⁴ are a hydrocarbon group or — (R ¹⁵ , respectively). O) _r— R ¹⁶ group, wherein R ¹⁵ is a hydrocarbon group or a silylene group, R ¹⁶ is a hydrogen atom, a hydrocarbon group or an R ¹⁷ ₃ Si— group, and r is an integer of 1 or more. R ¹⁷ is each a hydrocarbon group.)   The composition for forming an electroless plating base film according to claim 2 or 3, wherein the dopant is sodium di-2-ethylhexyl sulfosuccinate.   The composition for forming an electroless plating base film according to any one of claims 1 to 4, wherein a ratio of the urethane resin to a total of the conductive polymer and the urethane resin is 20 to 80% by weight.   An electroless plating base film obtained from the composition for forming an electroless plating base film according to claim 1. An electroless plating layer containing metal;
An electroless plating base film containing a conductive polymer and a urethane resin;
Including a substrate,
A plating laminate in which one surface of the electroless plating layer is in contact with one surface of the electroless plating base film.   The plated laminate according to claim 7, wherein the conductive polymer is a polyaniline composite in which substituted or unsubstituted polyaniline is doped with a dopant. The plating laminate according to claim 8, wherein the dopant is a sulfosuccinic acid derivative represented by the following formula (III).

(In formula (III), M is a hydrogen atom, an organic free radical or an inorganic free radical. M ′ is a valence of M. R ¹³ and R ¹⁴ are a hydrocarbon group or — (R ¹⁵ , respectively). O) _r— R ¹⁶ group, wherein R ¹⁵ is a hydrocarbon group or a silylene group, R ¹⁶ is a hydrogen atom, a hydrocarbon group or an R ¹⁷ ₃ Si— group, and r is an integer of 1 or more. R ¹⁷ is each a hydrocarbon group.)   The plated laminate according to claim 8 or 9, wherein the dopant is sodium di-2-ethylhexyl sulfosuccinate.   The ratio of the said urethane resin with respect to the sum total of the said conductive polymer and urethane resin is 20 to 80 weight%, The plating laminated body in any one of Claims 7-10.   The plated laminate according to claim 7, wherein the metal is copper.   The plated laminate according to claim 7, wherein the substrate is a resin.   The plating laminate according to claim 13, wherein the substrate is a polycarbonate resin, a polyester resin, a polyimide resin, or a polyphenylene sulfide resin.   The manufacturing method of the electroless-plating base film using the composition for electroless-plating base film formation in any one of Claims 1-5. A step of forming an electroless plating base film using the composition for forming an electroless plating base film according to any one of claims 1 to 5 on a substrate, and a metal on the electroless plating base film The manufacturing method of the electroless-plating laminated body including the process of forming an electroless-plating layer.   The manufacturing method of the electroless-plating laminated body of Claim 16 which forms an electroless-plating layer by carrying | supporting palladium on the said electroless-plating base film, and making it contact with the said electroless-plating liquid after that.   The method for producing an electroless plating laminate according to claim 17, wherein palladium is supported by bringing a palladium chloride solution into contact with the electroless plating base film.   The method for producing an electroless plating laminate according to any one of claims 16 to 18, wherein the electroless plating solution contains one or more metals selected from Cu, Ni, Au, Pd, Ag, Sn, Co, and Pt. .

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