JP6178659B2 - Composition for forming electroless plating base film - Google Patents

Description

  The present invention relates to a composition for forming an electroless plating base film, an electroless plating base film, and a 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, which is a kind of conductive polymer, can be synthesized relatively easily from inexpensive aniline in addition to its electrical characteristics, and exhibits excellent stability against oxygen and the like in a state of conductivity. Has advantages and characteristics. In addition, a highly conductive polyaniline can be easily obtained by the method described in Patent Document 1.
In addition, many conductive polymers have a reducing power, and by taking advantage of this property, they are attracting attention as base films for electroless plating of various substrates such as polycarbonate (PC) and polyethylene terephthalate (PET) (patents) Literature 2-8).

  However, the electroless plating base film made of the polyaniline composite alone has not been sufficiently adhered to a substrate such as polycarbonate, polyamide, or polyimide. In addition, when the electroless plating base film is incorporated in an electronic component, it is desired to withstand heat resistance and a thermal shock test.

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 an electroless plating base film having improved moldability, plating deposition and plating adhesion.

（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。）
８．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無電解めっき６記載の下地膜形成用組成物。
９．前記ウレタン樹脂が、２種のウレタン樹脂である１〜８のいずれか記載の無電解めっき下地膜形成用組成物。
１０．前記ウレタン樹脂が、ＭＡＵシリーズ、ＡＳＰＵシリーズ、ハイドランシリーズ、ユーコートシリーズ、アクリットシリーズ及びＰＴＧ−ＲＳＮからなる群から選ばれる少なくとも２種のウレタン樹脂である１〜８のいずれか記載の無電解めっき下地膜形成用組成物。
１１．さらに溶剤を含む１〜１０のいずれか記載の無電解めっき下地膜形成用組成物。
１２．１〜１１のいずれか記載の無電解めっき下地形成用組成物から得られる無電解めっき下地膜。
１３．金属を含む無電解めっき層と、
１２記載の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面と前記無電解めっき下地膜の面が接しているめっき積層体。
１４．前記金属が銅である１３記載のめっき積層体。
１５．前記基板が樹脂である１３又は１４記載のめっき積層体。
１６．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１５記載のめっき積層体。
１７．１〜１１のいずれか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。
１８．基板上に、１〜１１のいずれか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。
１９．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１８記載の無電解めっき積層体の製造方法。
２０．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１９記載の無電解めっき積層体の製造方法。
２１．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１８〜２０のいずれか記載の無電解めっき積層体の製造方法。 According to the present invention, the following electroless plating base film forming composition, electroless plating base film, and plating laminate are provided.
1. Including conductive polymer, urethane resin and isocyanate,
The composition for electroless plating base film formation whose compounding quantity of the said isocyanate is 0.5 to 5 weight% with respect to a conductive polymer, a urethane resin, and isocyanate.
2. The composition for forming an electroless plating base film according to 1, further comprising a polyvinyl acetal resin.
3. The composition for forming an electroless plating base film according to 2, wherein the polyvinyl acetal resin is polyvinyl butyral.
4). The composition for forming an electroless plating base film according to any one of 1 to 3, wherein the isocyanate has a curing temperature of 100 ° C or higher.
5. The composition for forming an electroless plating base film according to any one of 1 to 4, wherein the isocyanate is a blocked isocyanate.
6). The composition for forming an electroless plating base film according to any one of 1 to 5, wherein the conductive polymer is a polyaniline composite in which substituted or unsubstituted polyaniline is doped with a dopant.
7). The composition for forming an electroless plating base film according to 6, 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.)
8). The composition for base film formation of the electroless plating 6 whose said dopant is sodium di-2-ethylhexyl sulfosuccinate.
9. The composition for forming an electroless plating base film according to any one of 1 to 8, wherein the urethane resin is two types of urethane resins.
10. The electroless plating according to any one of 1 to 8, wherein the urethane resin is at least two types of urethane resins selected from the group consisting of MAU series, ASPU series, hydran series, U-coat series, Acryt series, and PTG-RSN. Composition for forming a base film.
11. Furthermore, the composition for electroless plating base film formation in any one of 1-10 containing a solvent.
12. An electroless plating base film obtained from the electroless plating base forming composition according to any one of 12.1 to 11.
13. An electroless plating layer containing metal;
Electroless plating base film according to 12,
A plating laminate comprising a substrate, wherein the surface of the electroless plating layer is in contact with the surface of the electroless plating base film.
14 The plating laminate according to 13, wherein the metal is copper.
15. The plating laminate according to 13 or 14, wherein the substrate is a resin.
16. 16. The plated laminate according to 15, 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 17.1-11.
18. The process of forming an electroless-plating base film using the composition for electroless-plating base film formation in any one of 1-11 on a board | substrate, and the electroless plating containing a metal on the said electroless-plating base film The manufacturing method of the electroless-plating laminated body including the process of forming a layer.
19. 19. The method for producing an electroless plating laminate according to 18, wherein palladium is supported on the electroless plating base film and then contacted with the electroless plating solution to form an electroless plating layer.
20. 20. The method for producing an electroless plating laminate according to 19, wherein palladium is supported by bringing a palladium chloride solution into contact with the electroless plating base film.
21. The method for producing an electroless plating laminate according to any one of 18 to 20, 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, the composition for electroless-plating base film formation which has the improved moldability, plating precipitation property, and plating adhesiveness can be provided.

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

[Composition for forming electroless plating base film]
The composition for forming an electroless plating base film of the present invention contains a conductive polymer, a urethane resin and an isocyanate, and the blending amount of the isocyanate is 0.2% by weight based on the total of the conductive polymer, the urethane resin and the isocyanate. -35% by weight.
Moreover, the composition for electroless plating base film formation of this invention can contain a solvent arbitrarily.
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 by using 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 deposit copper ions.
The composition of the present invention is used to form an underlayer for an electroless plating layer.

  When the composition of the present invention contains a urethane resin, the adhesion to the base material and the plating layer is increased, and further, by mixing a predetermined amount of isocyanate, the molding processability and the plating deposition property can be improved.

  The composition of the present invention, excluding the solvent, is, for example, 90% or more, 95% or more, 98% or more, or 100% by weight of conductive polymer, urethane resin, isocyanate, and optionally polyvinyl acetal resin, You may consist of a heat-resistant stabilizer.

[Method for producing composition for forming electroless plating base film]
By mixing each component of the composition for forming an electroless plating base film of the present invention, a composition for forming an electroless plating base film can be obtained.

[Conductive polymer]
Examples of conductive polymers include π-conjugated polymer composites in which a π-conjugated polymer is doped with a dopant, specifically, polyaniline composites in which substituted or unsubstituted polyaniline is doped with a dopant, substituted Or a polypyrrole complex in which an unsubstituted polypyrrole is doped with a dopant, and a polythiophene complex in which a substituted or unsubstituted polythiophene is doped with a dopant, and a substituted or unsubstituted polyaniline is doped with a dopant A polyaniline complex is preferred.

  The weight average molecular weight of polyaniline (hereinafter referred to as molecular weight) is preferably 20,000 or more. 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. 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 electrical conductivity, but a wider molecular weight distribution may be preferable from the viewpoint of solubility in a solvent.
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.
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.

  As the compound represented by the formula (I), di-2-ethylhexylsulfosuccinic acid and sodium di-2-ethylhexylsulfosuccinate (aerosol OT) are 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.
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 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.
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.

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 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 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.

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 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.

The content of the conductive polymer in the coating film, that is, the ratio of the conductive polymer to the total of the conductive polymer, urethane resin and epoxy resin in the composition is preferably 31% by weight to 85% by weight, more preferably 40%. % By weight to 70% by weight, more preferably 50% by weight to 60% by weight.
If the ratio of the conductive polymer is as low as 30% by weight or less, the deposition property of the plating may be deteriorated.

[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 ratio of the urethane resin to the total of the conductive polymer, urethane resin and epoxy resin in the composition is preferably 10% by weight to 68.5% by weight, more preferably 20% by weight to 65% by weight, and even more preferably 25%. % By weight to 60% by weight, most preferably 30% by weight to 50% by weight.
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 urethane resins include MAU series such as MAU1008, MAU4308HV, MAU5022, and MAU9022 (manufactured by Dainichi Seika Kogyo Co., Ltd.), ASPU series such as ASPU360, ASPU112, ASPU116, and ASPU121 (manufactured by DIC Corporation), Hydran AP. -20, AP-30F, AP-40F, WLS-213 and other hydran series (made by DIC), Ucourt UX-150, UX-200, UX-310, UWS-145 and other eucoat series (manufactured by Sanyo Kasei) ), Acrit series (manufactured by Taisei Fine Chemical Co., Ltd.), PTG-RSN (manufactured by DIC Graphics), and the like.

The MAU series can introduce polar groups such as amino groups and carboxyl groups, and can improve compatibility and adhesiveness with various binders. By having a reactive group, a flexible coating film can be formed even after curing.
The ASPU series is a solvent system, and it is possible to produce a flexible and tough film by having a reactive group as well as weather resistance, wear resistance and flexibility.
The hydran series is aqueous and can be dissolved in various solvents to have the same performance as the ASPU series.
The Acryt series is a urethane emulsion that has no reactive groups. Can be used for water-based paints.

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.

A urethane resin may be used individually by 1 type, or may use 2 or more types together. It is preferable to use two or more types of urethane resins.
By using two or more kinds of urethane resins, it is possible to produce a coating film rich in processability.

  Specifically, it is preferable to use two types of urethane resins selected from the group consisting of MAU series, ASPU series, hydran series, Ucourt series, Acryt series, and PTG-RSN.

[Isocyanate]
Isocyanate is a compound having an isocyanate group (-NCO group) and may be a raw material for polyurethane. The isocyanate is preferably a polyisocyanate having a plurality of isocyanate groups.
Polyisocyanates, for example, R '- is a (NCO) compound represented by _o. In the formula, R ′ is an aliphatic hydrocarbon such as methyl, ethyl, propyl, or butyl, or an aromatic hydrocarbon such as a benzene ring or a naphthalene ring, or a blocking group such as methyl ethyl ketone oxime. It is an integer.

Moreover, block isocyanate can be used as isocyanate.
Since the -NCO group is usually very reactive, in the blocked isocyanate, the -NCO group is blocked so that the reactivity can be suppressed and controlled. Blocked isocyanate blocks a reactive group such as -NCO group in the system, thereby suppressing the reaction, removing the blocking group by heating, and starting the reaction.

  The predetermined amount of isocyanate imparts excellent molding processability and plating depositability, coating film strength improving effect and coating film adhesion improving effect to the composition for forming an electroless plating base film.

Specific examples of the isocyanate include MF-K60B, MF-B60B, and 17B-60P manufactured by Asahi Kasei Chemicals Corporation.
Examples of the isocyanate include HDI (hexamethylene diisocyanate) -based ones such as TPA-100, TKA-100, P301-75E, and 24A-100.

  MF-K60B, MF-B60B, 17B-60P can also be used as a curing agent for non-yellowing urethane resin, and when blended in the composition, improves the mechanical and chemical properties, It can be used in a wide range of fields such as inks, adhesives, adhesives, and electronic materials.

The curing temperature of the isocyanate is preferably 100 ° C. or higher, more preferably 110 ° C. to 180 ° C., and further preferably 120 ° C. to 160 ° C.
In the case of blocked isocyanate, the curing temperature is the temperature at which the blocking group is eliminated.
When forming a base film using an electroless plating base film forming composition containing isocyanate, the curing temperature of the isocyanate is within the above range, thereby improving the heat resistance and thermal shock resistance of the base film. it can.

In other words, by applying a composition in which isocyanate is mixed with a conductive polymer such as a polyaniline complex to a base material to form a base film, the base film follows the substrate without losing molding processability, and electroless plating is performed. In the subsequent heat resistance test and thermal shock test, it exhibits excellent adhesion to the substrate film and the plating film.
This is because the addition of isocyanate to conductive polymers such as polyaniline composites increases flexibility and coating strength and adhesion strength, thus improving resistance to heat tests and thermal shock tests after printing, molding and plating. I think that.

The ratio of the isocyanate to the total of the conductive polymer and urethane resin and isocyanate in the composition is preferably 0.5% by weight to 5% by weight, more preferably 1% by weight to 3.7% by weight.
If the isocyanate content is within the above range, the moldability and plating precipitation can be improved. In addition, the base film follows the substrate without impairing moldability, and can exhibit excellent adhesion to the base film and the plating film in the heat test and thermal shock test after electroless plating.

[Polyvinyl acetal resin]
The composition of the present invention may further contain a polyvinyl acetal resin.
Examples of the polyvinyl acetal resin include polyvinyl butyral and polyvinyl formal. Of these, polyvinyl butyral is preferable.
By using the polyvinyl acetal resin, adhesion to various substrates can be expected.

  The content of the polyvinyl acetal resin is preferably 0.1 parts by weight to 10 parts by weight, more preferably 0.3 parts by weight to 100 parts by weight in total of the conductive polymer, urethane resin and epoxy resin in the composition. 3 parts by weight, more preferably 0.5 parts by weight to 1.5 parts by weight.

[Phenolic compounds]
When the composition of the present invention includes a polyaniline complex as a conductive polymer, the composition may further include a phenolic compound having an effect of improving electrical conductivity as a part of the polyaniline complex.
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 polyaniline complex 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 content of the phenolic compound is preferably such that the molar concentration of the phenolic compound is 0.01 [mol / g] or more with respect to 1 g of the polyaniline complex. 100 [mol / g] or less, more preferably 0.05 [mol / g] or more and 1 [mol / g] or less.

[Heat resistance stabilizer]
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 only the acidic substance is included as the heat stabilizer, the acidic substance is preferably a compound different from the proton donor of the polyaniline complex, and when only the salt of the acidic substance is included as the heat stabilizer, The salt of the acidic substance is preferably a compound different from the proton donor of the polyaniline complex.
When both the acidic substance and the salt of the acidic substance are included as the heat stabilizer, preferably at least one of the acidic substance and the salt of the acidic substance is a compound different from the proton donor.

When only the acidic substance is included as a heat stabilizer, the acidic substance is preferably different from the phenolic compound. When only the salt of the acidic substance is included as the heat stabilizer, the salt of the acidic substance is The phenolic compound is preferably different.
Further, when both the acidic substance and the salt of the acidic substance are included as the heat stabilizer, at least one of the acidic substance and the salt of the acidic substance is preferably different from the phenolic compound.

  The acidic substance that is a heat-resistant stabilizer is preferably an organic acid, more preferably an organic acid having one or more sulfonic acid groups, carboxy groups, phosphoric acid groups, or phosphonic acid groups, and more preferably sulfonic acid. 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 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 a sulfonic acid and contains only an acidic substance as a heat stabilizer, the acidic substance is preferably the same or different sulfonic acid as the proton donor. In addition, when only a salt of an acidic substance is included as a heat stabilizer, the salt of the acidic substance is preferably a sulfonic acid salt that is the same as or different from the proton donor of the polyaniline complex.
When an acid substance and a salt of the acid substance are included as a heat stabilizer, at least one of the acid substance and the salt of the acid substance is preferably a sulfonic acid or a sulfonic acid salt that is the same as or different from the proton donor. .

  The content of the heat-resistant stabilizer is preferably 1 to 1000 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the polyaniline complex.

[solvent]
The solvent of the composition for forming an electroless plating base film of the present invention is not particularly limited, but methanol, ethanol, isopropyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, diacetone alcohol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, ethyl carbitol, butyl carbitol, acetone, methyl ethyl ketone, methyl isobutyl ketone, solvent naphtha, tetrahydrofuran, diethyl ether, n-butyl acetate, n-butanol, propylene glycol monomethyl ether acetate And γ-butyrolactone are used.
The content of the solvent is preferably 25 parts by weight to 4900 parts by weight, more preferably 100 parts by weight to 900 parts by weight with respect to 100 parts by weight of the total of the conductive polymer, urethane resin and epoxy resin in the composition. Preferably they are 233 weight part-400 weight part.

[Other ingredients]
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 polyisocyanate, epoxy resin, urethane resin, 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.
There is no particular upper limit on the dry film thickness.

[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 (film) containing a conductive polymer, a urethane resin and an isocyanate, and a substrate layer, and one of the electroless plating layers The surface is in contact with one surface of the electroless plating base layer.

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 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.
After forming the base film, it is preferable to perform a molding step and a degreasing step before forming the electroless plating layer.

In the forming step, the substrate on which the electroless plating base layer is formed is heated and vacuum-formed using a mold, whereby the substrate can be formed into an arbitrary mold.
Although the heating temperature of a shaping | molding process is not specifically limited, Usually, it is 50 to 300 degreeC.
The mold used in the molding process is not particularly limited, and examples thereof include a circular shape and an elliptical shape.
The degree of vacuum in vacuum forming is preferably 0.1 MPa to 0.9 MPa.

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, but is, for example, about 20 to 50 ° C. for a low temperature bath and 50 to 90 ° C. for a high temperature.
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 while maintaining the internal temperature of the solution at 5 ° C. for 18 hours from the start of dropping. 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 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]
Mani g of polyaniline complex (powder) obtained in production 2, MAU1008 (manufactured by Dainichi Seika Kogyo Co., Ltd., solid content concentration 30%, solvent: γ-butyrolactone), urethane resin, ASPU360, urethane resin (DIC Corporation, solid content concentration 30%, solvent: 3-methoxy-3-methyl-1-butanol) 2.0 g, polyisocyanate MF-B60B (Asahi Kasei Chemicals Corporation, solid content concentration 60%, Solvent: n-butyl acetate and n-butanol, curing temperature: 120 ° C.) 0.3 g, 3-methoxy-3-methyl-1-butanol (MMB) 8.9 g, butyl carbitol 1.3 g, solvent naphtha 5 g was mixed and stirred to prepare a uniform plating base forming composition. The composition of the plating underlayer forming composition is shown in Table 1. In Table 1, the compounding quantity of each component is represented by (g). Moreover, () in Table 1 represents the blending amount with respect to the total of the polyaniline complex (powder), urethane resin and polyisocyanate, and is represented by weight% in the polyaniline complex (powder), urethane resin and polyisocyanate, In MMB, butyl carbitol, solvent naphtha, and KS-10 described later, it is expressed in parts by weight.
The obtained coating liquid was printed on a carbo glass C110C (manufactured by Asahi Glass Co., Ltd.), which is a polycarbonate film, using a screen printer, and dried at 120 ° C. for 60 minutes to form a plating base film. The thickness of the plating base film was 10 μm.

[Measurement of curing temperature]
In accordance with JIS K 6769, a glass film was formed on a glass with a bar coater (bar # 5), and then heated on a hot plate at 80 ° C., 90 ° C., 100 ° C., 110 ° C., 120 ° C., or 130 ° C. for 30 minutes. The heat-cured coating film was peeled off, and the initial weight of the coating film was measured. The coating film was immersed in acetone at 25 ° C. for 24 hours, and then the coating film was pulled up. The pulled up coating film was dried at 80 ° C. for 30 minutes, and the remaining weight was measured. At that time, the temperature at which the ratio of residual weight / initial weight was 80% or more was determined as the curing temperature.

[Molding process]
Using a drawdown type vacuum forming machine, the printed polycarbonate film was heated to about 160 ° C., and vacuum forming was performed at 0.5 MPa using a circular mold having a diameter of 5 cm.
Molding processability is confirmed by checking whether the printed coating on the curved surface portion is torn or not. When the film is stretched cleanly, “○”, when there is no tearing, but when confirming blackening of the coating, “△ "If there was a tear, it was determined as" x ".

[Degreasing process]
Degreasing treatment is performed by immersing the entire base material provided with the plating base film in an aqueous solution of 3% Dianol CDE (coconut oil fatty acid diethanolamide; nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) at room temperature for 5 minutes. Went.
Furthermore, 10 g of sodium hydrogen sulfite was dissolved in 90 g of ion-exchanged water to prepare a 10 wt% sodium hydrogen sulfite aqueous solution. The entire base material provided with the plating base film was immersed in this 10 wt% sodium hydrogen sulfite aqueous solution at 60 ° C. for 5 minutes for degreasing treatment.

[Pd metal loading process]
The entire base material provided with the plating base film after the degreasing treatment is immersed in a 20-fold diluted solution of a catalytic treatment agent activator (palladium aqueous solution, manufactured by Okuno Pharmaceutical Co., Ltd.) for 5 minutes at 30 ° C. to carry a metal Pd support Went.

[Plating layer forming process]
About the base material which provided the plating base film after Pd carrying | support process, the plating process was performed for 60 degreeC for 60 minute (s) using the electroless copper plating solution TSP810 (made by Okuno Pharmaceutical Co., Ltd.).
The plating deposition property is divided into a flat portion and a curved surface portion, and “◯” is obtained when the plating is deposited on the entire surface, and there is no undeposited portion, but “△” is obtained when a portion with a thin plating thickness is confirmed. When there was an undeposited portion, it was determined as “x”. The results are shown in Table 2. * In Table 2 indicates a blending amount (weight (wt)%) with respect to the total of the polyaniline composite (powder), urethane resin and polyisocyanate.

[Plating adhesion test]
About the plating film, according to JIS5600-5-6, a lattice-like damage | wound of 2 mm space | interval was attached with the cutter, the cellophane (made by Nichiban Co., Ltd.) was stuck, it peeled off at an angle of 90 degrees, and the crosscut test was done. Regarding adhesion, “◯” was determined when peeling was not observed, and “X” was determined when peeling was observed. The results are shown in Table 2. Note that “−” means that measurement was not possible because plating did not deposit on the entire surface in the flat portion.

[Heat resistance test]
After the plated laminate was put into a circulation oven at 80 ° C. for 240 hours, the cross cut test was performed.
Regarding adhesion, even in a plated laminate after 240 hours, when peeling was not observed in the crosscut test, “◯”, and in the plated laminate after 24 hours, peeling was observed in the crosscut test. In the case of “×”, the plated laminate after 120 hours did not peel off, but the plated laminate after 240 hours was judged as “Δ” when peeled off by the cross-cut test. The results are shown in Table 2.

[Thermal shock test]
The plated laminate was put into a thermal shock tester at -55 ° C to 110 ° C for 15 minutes and 256 cycles, and then the cross-cut test was performed.
For adhesion, “○” when no peeling was observed in the cross-cut test even in the plated laminate after 256 cycles, and when peeling was observed in the cross-cut test after 48 cycles In the case of “×”, the plating laminate after 144 cycles did not peel, but the plating laminate after 256 cycles was judged as “Δ” when peeled by the cross-cut test. The results are shown in Table 2.

Example 2
As shown in Table 1, a plating base forming composition was prepared and evaluated in the same manner as in Example 1 except that 0.6 g of MF-B60B was used. The results are shown in Table 2.

Example 3
As shown in Table 1, in place of MF-B60B, polyisocyanate 17B-60P (Asahi Kasei Chemicals Corporation, solid content concentration 60%, solvent: propylene glycol monomethyl ether acetate, curing temperature: 130 ° C.) is 0. A composition for forming a plating base was prepared and evaluated in the same manner as in Example 1 except that 3 g was used. The results are shown in Table 2.

Example 4
As shown in Table 1, a plating base forming composition was prepared and evaluated in the same manner as in Example 1 except that 0.6 g of 17B-60P was used instead of MF-B60B. The results are shown in Table 2.

Example 5
As shown in Table 1, instead of MF-B60B, 0.3 g of 17B-60P was used, and further, ESREC KS-10 (Sekisui Chemical Co., Ltd., polyvinyl butyral (PVB) resin), which is a polyvinyl acetal resin, was used. A plating underlayer forming composition was prepared and evaluated in the same manner as in Example 1 except that 0.1 g was used. The results are shown in Table 2.

Example 6
As shown in Table 1, in place of MF-B60B, 0.6 g of 17B-60P was used, and further, 0.1 g of ESREC KS-10, which is a polyvinyl acetal resin, was used. A composition for forming a plating base was prepared and evaluated. The results are shown in Table 2.

Comparative Example 1
As shown in Table 1, a plating underlayer forming composition was prepared and evaluated in the same manner as in Example 1 except that 0.9 g of MF-B60B was used. The results are shown in Table 2.

Comparative Example 2
As shown in Table 1, a plating base forming composition was prepared and evaluated in the same manner as in Example 1 except that 1.5 g of MF-B60B was used. The results are shown in Table 2.

Comparative Example 3
As shown in Table 1, a plating base forming composition was prepared and evaluated in the same manner as in Example 1 except that 0.9 g of 17B-60P was used instead of MF-B60B. The results are shown in Table 2.

Comparative Example 4
As shown in Table 1, a plating base forming composition was prepared and evaluated in the same manner as in Example 1 except that 1.5 g of 17B-60P was used instead of MF-B60B. The results are shown in Table 2.

Example 7
As shown in Table 1, instead of MF-B60B, polyisocyanate MF-K60B (Asahi Kasei Chemicals Corporation, solid content concentration 60%, solvent: n-butyl acetate and n-butanol, curing temperature: 90 ° C. ) Was used in the same manner as in Example 1 except that 0.3 g was used, and the composition for forming a plating base was prepared and evaluated. The results are shown in Table 2.

Example 8
As shown in Table 1, the plating base forming composition was prepared and evaluated in the same manner as in Example 1 except that 0.6 g of MF-K60B was used instead of MF-B60B. The results are shown in Table 2.

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

DESCRIPTION OF SYMBOLS 1 Plating laminated body 10 Substrate 20 Electroless plating base film 30 Electroless plating layer

Claims (19)

A polyaniline composite in which a substituted or unsubstituted polyaniline is doped with a dopant, comprising two or more urethane resins and a blocked isocyanate;
  The dopant is a compound represented by the following formula (I):
  The composition for electroless plating base film formation whose compounding quantity of the said block isocyanate is 0.5 to 5 weight% with respect to the said polyaniline complex, the said urethane resin, and the said block isocyanate.
      M (XARn) m (I)
(In formula, M is a hydrogen atom, an organic free radical, or an inorganic free radical.
  X is an anionic group.
  A is a substituted or unsubstituted hydrocarbon group.
  R is bonded to A and is —H, —R, respectively. ¹ , -OR ¹ , -COR ¹ , -COOR ¹ ,-(C = O)-(COR ¹ ), Or-(C = O)-(COOR ¹ And a substituent represented by R) ¹ Is a hydrocarbon group, silyl group, alkylsilyl group,-(R ² O) x-R ³ Group, or-(OSiR ³ ₂ ) X-OR ³ It is. R ² Are each an alkylene group, R ³ Is a hydrocarbon group, and x is an integer of 1 or more.
  n is an integer of 1 or more, and m is the valence of M / the valence of X. )   Furthermore, the composition for electroless-plating base film formation of Claim 1 containing polyvinyl acetal resin.   The composition for forming an electroless plating base film according to claim 2, wherein the polyvinyl acetal resin is polyvinyl butyral. The composition for forming an electroless plating base film according to any one of claims 1 to 3, wherein the curing temperature of the blocked isocyanate is 100 ° C or higher. The composition for forming an electroless plating base film according to any one of claims 1 to 4, 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 any one of claims 1 to 5, 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 6, wherein the two or more types of urethane resins are urethane resins each having a structure represented by the following formula and having different structures.

(In the formula, R and X are each a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, or one or more substituted or unsubstituted divalent hydrocarbon groups. (A divalent group in which an aromatic hydrocarbon group and one or more substituted or unsubstituted divalent aliphatic hydrocarbon groups are bonded in any order.) Furthermore, the composition for electroless-plating base film formation of any one of Claims 1-7 containing a solvent. The electroless-plating foundation | substrate film obtained from the composition for electroless-plating foundation | substrate formation in any one of Claims 1-8 . An electroless plating layer containing metal;
The electroless plating base film according to claim 9 ,
A plating laminate comprising a substrate, wherein the surface of the electroless plating layer is in contact with the surface of the electroless plating base film. The plated laminate according to claim 10 , wherein the metal is copper. The plating laminate according to claim 10 or 11 , wherein the substrate is a resin. The plated laminate according to claim 12 , 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 which apply | coats the composition for electroless-plating base film formation in any one of Claims 1-8 to a base material, and dries . The method for producing an electroless plating base film according to claim 14, wherein the base material is made of polycarbonate resin, acrylic resin, nylon resin, polyimide resin, polyester resin, styrene resin, phenol resin, or polyphenylene sulfide resin. The process of forming an electroless-plating base film using the composition for electroless-plating base film formation in any one of Claims 1-8 on a board | substrate, and the non-containing containing metal on the said electroless-plating base film The manufacturing method of the electroless-plating laminated body including the process of forming an electroplating 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 of manufacturing 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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