TW201840910A - Pretreatment method for plating, plating method, article pretreated for plating, and plated article - Google Patents

Abstract

The purpose of the present invention is to improve adhesiveness between a member to be plated having a surface inert to plating and a plating film formed on the member to be plated. Provided is a method for chemically bonding a silane coupling agent to the surface of a member to be plated. The silane coupling agent is chemically bonded to at least one of the multiple functional groups of a polyfunctional compound capable of forming a chelate complex with metal ions that form a plating film.

Description

Processing method before electroplating, electroplating method, pre-plating treatment, and electroplating

The present invention relates to a method of processing prior to electroplating, a method of electroplating, a pretreatment of electroplating, and an electroplating.

Although it is expected that electroplating is performed on a member similar to a carbon material, it is presumed that since the carbon material has a chemically inactive surface, it has been difficult to form a plating film which is homogeneous and excellent in adhesion. In order to overcome this disadvantage, for example, Patent Document 1 describes a method of performing electroplating on black lead to perform a treatment before electroplating in which the surface of the member to be plated is oxidized and heated. The plated member such as metal has various types of contamination, and it is known that the surface activation system is electrolytic degreasing as described in Non-Patent Document 1, and it is estimated that it is one of the above oxidation steps, but when the plated member is a carbon material. Unable to confirm the effect, lack of close trust. [Prior Technical Literature] [Patent Literature]

[Patent Document 1]: JP-A-2015-503032 [Non-Patent Document]

[Non-Patent Document 1]: Sakamoto Yoshihiko, Cleaning Technology in Electroplating, Vacuum, Vol. 43, No. 6, 667~671, 200 years

[Problems to be solved by the invention]

Therefore, although it is expected to improve the adhesion of the plating film formed on the plated member having an inactive surface such as black lead to the member to be plated, the plating film formed by the previous treatment has a small adhesion force. Lack of trust.

An important object of the present invention is to improve the adhesion of a plating film formed on a member to be plated with respect to a surface which is inactive to plating, with respect to a member to be plated. [Method of solving the problem]

The pretreatment method of electroplating of the present invention is to chemically bond a decane coupling agent to the surface of the member to be plated. At least one of the plurality of functional groups of the polyfunctional compound capable of forming a chelate complex with the metal ion constituting the plating film is chemically bonded to the decane coupling agent. Therefore, the pre-plating treatment produced by the pre-plating treatment method of the present invention is such that the surface of the member to be plated is provided with a functional group capable of forming a chelate complex with the metal constituting the plating film. Therefore, by using the pre-plating treatment method of the present invention, even if the member to be plated has a member which is inactive with respect to the surface to be plated, the adhesion of the plated film to the member to be plated can be made higher, and it is homogeneous. Plating film.

In the pre-plating treatment method of the present invention, the polyfunctional compound preferably has a plurality of carboxyl groups.

In the pre-plating treatment method of the present invention, the polyfunctional compound preferably has three or more functional groups which are bondable to metal ions constituting the plating film.

In the pre-plating treatment method of the present invention, the polyfunctional compound is preferably derived from ethyldiaminetetraacetic acid, ethyldiamine-N,N'-diacetic acid, and ethyldiamine-N,N'-diacetic acid. -N,N'-dipropionic acid hydrate, hydroxyethyl-extended ethylenediaminetriacetic acid, di-extension ethyltriaminepentaacetic acid, tri-ethylidenetetraamine hexaacetic acid, di-extension ethyltriaminepentaacetic acid, cyanide Triacetic acid, hydroxyethyliminodiacetic acid, L-aspartic acid-NN-diacetic acid, hydroxyiminodisuccinic acid, trans-1,2-diaminocyclohexane-N,N, At least one selected from the group consisting of N', N'-tetraacetic acid-hydrate, O, O'-bis(2-aminoethyl)ethylene glycol-N,N,N'N'-tetraacetic acid .

In the pre-plating treatment method of the present invention, the decane coupling agent is preferably a decane coupling agent having at least one functional group selected from the group consisting of a primary amino group, an epoxy group and an isocyanate group in at least one of a chain and a terminal. .

In the pre-plating treatment method of the present invention, an inorganic member capable of introducing a hydroxyl group can be used as the member to be plated.

In the pre-plating treatment method of the present invention, a carbon material, an aluminum nitride material or a tantalum nitride material may be used for the member to be plated. Further, in the present invention, the "carbon material" includes "black lead material".

In the electroplating method of the present invention, the pretreatment method of the electroplating of the present invention is carried out by performing a pretreatment step. After the pre-treatment step, electroplating is performed on the surface of the member to be plated to form a plating step of the plating film.

In the plating method of the present invention, the pretreatment step is preferably a step of oxidizing the surface of the member to be plated.

The pre-plating treatment of the present invention is provided with a member to be plated, a decane coupling agent chemically bonded to the surface of the member to be plated, and at least one conjugated decane coupling agent in the plural functional group, which can constitute electricity The coated metal ions form a polyfunctional compound that sequesters the complex.

The electroplating material of the present invention is provided with a member to be plated, a decane coupling agent chemically bonded to the surface of the member to be plated, and at least one conjugated decane coupling agent in the plural functional group, which can form a plating film. The metal ion forms a polyfunctional compound of a chelate complex, and a plating film of a plurality of functional groups in which the decane coupling agent is not bonded to the bonded polyfunctional compound. [Effects of the Invention]

According to the present invention, the adhesion of the plating film formed on the member to be plated with respect to the surface in which the plating is inactive with respect to the member to be plated can be improved.

An example of a preferred embodiment for carrying out the invention will now be described. However, the following embodiments are merely exemplified. The present invention is not limited to the following embodiments.

(Electroplating method) The method of electroplating the member to be plated in the present embodiment is provided with a pretreatment step of bonding a chelating agent to the surface of the member to be plated, and a member to be plated by the bonding of the chelating agent The surface is plated to form a plating step of the plating film.

<Chelating Agent> The chelating agent is formed of a polyfunctional compound which can form a chelate complex with a metal constituting the plating film.

The polyfunctional compound is preferably a compound having a plurality of carboxyl groups.

The polyfunctional compound preferably has three or more functional groups capable of bonding to a metal constituting the plating film, and more preferably has four or more. However, when the number of functional groups bonded to the metal constituting the plating film is too large, the metal may not be properly disposed due to steric hindrance, and thus the plating film may not be formed properly. Therefore, a compound capable of forming a chelate complex is preferable. Six or less functional groups which may be bonded to a metal constituting the plating film.

Specific examples of preferred polyfunctional compounds used are, for example, ethyldiaminetetraacetic acid, ethyldiamine-N,N'-diacetic acid, and ethyldiamine-N,N'-diacetic acid-N. N'-dipropionic acid hydrate, hydroxyethyl-ethylidene diamine triacetic acid, di-ethyltriamine pentaacetic acid, tri-ethylidenetetraamine hexaacetic acid, di-ethyltriaminepentaacetic acid, cyanotriacetic acid , hydroxyethyliminodiacetic acid, L-aspartic acid-NN-diacetic acid, hydroxyiminodisuccinic acid, trans-1,2-diaminocyclohexane-N,N,N'N '-Tetraacetic acid-hydrate, O, O'-bis(2-aminoethyl)ethylene glycol-N, N, N'N'-tetraacetic acid, and the like. These compounds may be used alone or in plural.

<Electrically Plated Member> The member to be plated of the member to be plated in the present invention is not particularly limited. As the member to be plated, an inorganic member capable of introducing a hydroxyl group can be used. Specific examples of the member to be plated in the present invention include a carbon material, an aluminum nitride material, a tantalum nitride material, and the like.

The shape and size of the member to be plated are not particularly limited. The member to be plated may be, for example, a flake, a powder, a sphere, a straight solid, a cube, a column, or the like.

<Cerane coupling agent> The decane coupling agent can be appropriately selected depending on the member to be plated and the polyfunctional compound. The decane coupling agent used in the case where the plated member is, for example, black lead is preferably an epoxy decane coupling agent, an amine decane coupling agent, an isocyanate decane coupling agent or the like.

Among these, a decane coupling agent having at least one functional group selected from a primary amino group, an epoxy group and an isocyanate group in at least one of the chain and the terminal is preferably used, and more preferably an amine group at the terminal is used. The amine based decane coupling agent. Specific examples of the amino group-based decane coupling agent having an amino group at the terminal are, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl) 3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and the like.

The above decane coupling agent may be used alone or in plural.

<Condensation agent> In order to promote the reaction of a decane coupling agent with a polyfunctional compound, a condensing agent can be used. Specific examples of the preferred condensing agent to be used include a diazine-based condensing agent, a carbodiimide-based condensing agent, an imidazole-based condensing agent, an oxime-based condensing agent, a urea-based condensing agent, and a halogenated urea-based condensing agent.

It is more preferable to use a triazine-based condensing agent among these. Specific examples of the triazine-based condensing agent include DMT-MM (4-4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium Chloride n-Hydrate and the like.

<Electroplating Treatment> In the present embodiment, when plating is performed on the member to be plated, first, the pre-plating treatment is performed. Specifically, the surface of the member to be plated is chemically bonded to the decane coupling agent. At least one of the plurality of functional groups of the polyfunctional compound capable of forming a chelate complex with the metal ion constituting the plating film is chemically bonded to the decane coupling agent. Preferably, the surface of the member to be plated is bonded with three or more functional groups which are functional groups bonded to the metal constituting the plating film, and more preferably four or more surfaces are bonded to the surface of the member to be plated. A metal-bonded functional group-like polyfunctional compound.

When it is difficult to directly bond the decane coupling agent to the surface of the member to be plated, it is preferred to subject the surface of the member to be plated to oxidation treatment before the surface of the member to be plated is treated with a decane coupling agent. Thereby, the hydroxyl group can be disposed on the surface of the member to be plated, and the decane coupling agent can be easily bonded. The method of the oxidation treatment is not particularly limited. For example, nitric acid, hydrochloric acid, sulfuric acid or a mixed acid of two or more kinds may be used for wet oxidation treatment or oxygen plasma oxidation treatment.

Further, from the viewpoint of promoting the condensation reaction between the decane coupling agent and the polyfunctional compound, the above condensing agent can be used.

(Pre-plating treatment) The plating treatment precursor can be produced by the above steps. The pre-plating treatment material is provided with a plated member, a decane coupling agent bonded to the member to be plated, and a bonded decane coupling agent, and a polyfunctional compound capable of forming a chelate complex with a metal ion constituting the plating film. The details of the electroplated member, the decane coupling agent, and the polyfunctional compound constituting the plating film are as described above.

Finally, a plating film is formed by performing electroplating on the surface of the member to be plated by bonding the polyfunctional compound. That is, after the processing step before the pre-treatment method described above is performed, a plating step of forming a plating film is performed. The plating can be carried out, for example, by electrolytic plating or by electroless plating.

The type of the plating film is not particularly limited. The plating film may be, for example, a Cu plating film, a Ni plating film, an Fe plating film, a Cr plating film, an Ag plating film, an Au plating film, a Pd plating film, a Sn plating film, or containing Cu, Ni, Fe, Cr, Ag, Au. a plating film formed of an alloy of at least one element selected from the group consisting of Pd and Sn, and the like. Further, a laminate of a plurality of plating films can be formed.

Figure 1 shows the use of black lead as a member to be plated, 3-aminopropyltrimethoxydecane as a decane coupling agent, DMT-MM as a condensing agent, and EDTA as a polyfunctional compound. step.

(Electroplating) Fig. 2 is a schematic cross-sectional view showing the electroplated article produced. As shown in FIG. 2, the plating material 1 is provided with a plated member 10 and a plating film 11 provided on the surface of the member to be plated 10. On the surface 10a of the plated member 10 on which the plating film 11 is formed, the metal constituting the plating film 11 is bonded to the polyfunctional compound. The adhesion, uniformity, and homogeneity of the plated member 10 and the plating film 11 can be improved by the polyfunctional compound.

As described above, in the present embodiment, the surface of the pre-plated material is provided with a polyfunctional compound capable of forming a chelate complex with the metal constituting the plating film 11. Therefore, by using the pre-plating treatment method of the present embodiment, even when the member to be plated 10 is a member having a surface which is inactive with respect to the plating film, the formation of the plating film 11 with respect to the member to be plated 10 can be made high-density. A uniform, uniform and homogeneous plating film 11.

From the viewpoint of achieving higher adhesion of the plating film 11 with respect to the member to be plated 10, a polyfunctional compound capable of forming a chelate complex is preferable, and has three or more functional groups capable of bonding with a metal constituting the plating film 11. More preferably, it has four or more.

According to the plating method of the present embodiment, for example, when the surface of the member to be plated 10 is smooth, even if the arithmetic mean roughness (Ra) specified in JIS B0601-2001 is small, it is possible to form a battery having a high adhesion force. Coating 11. The arithmetic mean roughness (Ra) of the member to be plated 10 can be, for example, 5 μm or less, 3 or less, or 1 or less.

In the following, the present invention will be described in more detail based on the specific examples, but the present invention is not limited to the following examples, and modifications may be appropriately made without departing from the spirit and scope of the invention.

(Example 1) An isotropic black lead material (IG-43: CIP-A manufactured by Toyo Carbon Co., Ltd.) was immersed in a 0.5 M aqueous solution of nitric acid at room temperature, and after 1 hour, it was washed with water and dried. Next, it was immersed in a methanol solution containing 1% by mass of 3-aminopropyltrimethoxydecane (decane coupling agent: CP-A) for 1 hour to introduce an aminopropyl group. Thereafter, the isotropic black lead material into which the aminopropyl group is introduced is immersed in a 1 mM ethylenediaminetetraacetic acid (EDTA: chelating agent), and the condensing agent is 1.1 times the triazine condensing agent (DMT). The reaction was carried out for 1 hour in a methanol solution of -MM), washed with dilute hydrochloric acid, and dried to obtain a black lead material having a surface-introduced EDTA. The black lead material introduced into the surface of the EDTA was subjected to electrolytic copper plating to obtain a black lead material coated with a copper plating film having a thickness of 8 μm. The plating film has no spots, and the plating film has a homogeneous film quality. The cross-cut test described in JIS K5600-5-6-1999 was cut into a rectangular grid pattern to evaluate the adhesion of the obtained plating film, and as a result, the number of peeling was 0/25. Although the plating film was peeled off at the cutting edge and the intersection, the state was judged to be 2 according to the classification method described in JIS.

(Example 2) A black lead material having a surface-introduced EDTA was obtained in the same manner as in Example 1 except that the isotropic black lead material was changed to CIP-B (ISEM-8 manufactured by Toyo Carbon Co., Ltd.). The black lead material introduced into the EDTA on the surface was subjected to electrolytic copper plating to obtain a black lead material coated with a copper plating film. The plating film has no spots, and the plating film has a homogeneous film quality. The cross-cut test result of the obtained plating film was 0/25, and was classified into 2.

(Example 3) CIP-A was immersed in a 1.0 M aqueous solution of nitric acid at room temperature, and after 1 hour, it was washed with water and dried. Next, it was immersed in a methanol solution containing 1% by mass of CP-A for 1 hour to introduce an aminopropyl group. Thereafter, the isotropic black lead material into which the aminopropyl group was introduced was immersed in a solution containing 1 mmol of EDTA, and the condensing agent was reacted with a 1.1-fold molar solution of DMT-MM in methanol for 1 hour, washed with dilute hydrochloric acid, and dried. A black lead material of EDTA was introduced on the surface. The black lead material introduced into the surface of the EDTA was subjected to electrolytic copper plating to obtain a black lead material coated with a copper plating film having a thickness of 8 μm. The plating film has no spots, and the plating film has a homogeneous film quality. The cross-cut test result of the obtained plating film was 0/25, which was classified into 1.

(Example 4) CIP-A was immersed in a 1.0 M aqueous solution of nitric acid at room temperature, and after 1 hour, it was washed with water and dried. Next, it was immersed in a methanol solution containing 1% by mass of N-2 (aminoethyl) 3-aminopropylmethyldimethoxydecane (decane coupling agent: CP-B) for 1 hour, and an amine group was introduced. Propyl. Thereafter, the isotropic black lead material introduced into the aminopropyl group was immersed in 1 mmol of trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid-hydrate ( CyDTA: a chelating agent), which was reacted with a condensing agent in a methanol solution of 1.1 times a mole of a triazine-based condensing agent (DMT-MM) for 1 hour, washed with dilute hydrochloric acid, and dried to obtain a black lead material having a surface-introduced CyDTA. Electrodeposited copper plating was carried out on the black lead material into which CyDTA was introduced, and a black lead material coated with a copper plating film having a thickness of 8 μm was obtained. The plating film has no spots, and the plating film has a homogeneous film quality. The cross-cut test result of the obtained plating film was 0/25, and it was classified into 0.

(Example 5) A black lead material coated with a copper plating film was obtained in the same manner as in Example 3 except that the decane coupling agent was 3-glycidoxypropyltrimethoxydecane (CP-C). The cross-cut test result of the obtained plating film was 0/25, and it was classified into 0.

(Example 6) A black lead material coated with a copper plating film was obtained in the same manner as in Example 4 except that the plating method was electroless plating. Electroless plating, after washing CIP-A, immersed in the pretreatment liquid of PdCl ₂ with sensitizer added SnCl ₂ and activator, using copper sulfate as copper ion source, and reducing agent as EDTA formaldehyde. The surface of the substrate was coated with copper having a uniform film thickness of 2 μm. The cross-cut test result of the obtained plating film was 0/25, which was classified into 1. (Example 7) A copper-coated black lead material was obtained in the same manner as in Example 4 except that the chelating agent was di-ethyltriaminepentaacetic acid (DTPA). The cross-cut test result of the obtained plating film was 0/25, and it was classified into 0. (Example 8) The same procedure as in Example 4 except that the chelating agent was O,O'-bis(2-aminoethyl)ethylene glycol-N,N,N'N'-tetraacetic acid (EGTA). Copper black lead material. The cross-cut test result of the obtained plating film was 0/25, which was classified into 1. (Example 9) A copper-coated black lead material was obtained in the same manner as in Example 4 except that the chelating agent was trimethylethylamine hexaacetic acid (TTHA). The cross-cut test result of the obtained plating film was 0/25, and it was classified into 0.

(Comparative Example 1) CIP-A was immersed in a 1.0 M aqueous solution of nitric acid at room temperature, and after 1 hour, it was washed with water and dried. Next, it was immersed in a methanol solution containing 1% by mass of CP-A for 1 hour to introduce an aminopropyl group. Electrolytic copper plating was carried out on the black lead material into which CP-A was introduced on the surface, and a black lead material coated with a copper plating film having a thickness of 8 μm was obtained. The plating film has no spots, and the plating film has a homogeneous film quality. The cross-cut test result of the obtained plating film was 1/25, which was classified into 3.

(Comparative Example 2) CIP-A was immersed in a 1.0 M aqueous solution of nitric acid at room temperature, and after 1 hour, it was washed with water and dried. Next, it was immersed in a methanol solution containing 1% by mass of CP-B for 1 hour to introduce an aminopropyl group. Electrolytic copper plating is performed on the black lead material introduced into the surface of CP-B to obtain a black lead material coated with a copper plating film. The plating film has no spots, and the plating film has a homogeneous film quality. The cross-cut test result of the obtained plating film was 2/25, which was classified into 3.

(Comparative Example 3) Electrolytic copper plating was carried out on the black lead material on which CP-C was introduced on the surface, except that CP-A was changed to CP-C, to obtain a black lead material coated with a copper plating film. The plating film has no spots, and the plating film has a homogeneous film quality. The cross-cut test result of the obtained plating film was 2/25, which was classified into 3. (Comparative Example 4) CIP-A was immersed in a 0.5 M aqueous solution of nitric acid at room temperature, and after 1 hour, it was washed with water, dried, and subjected to electrolytic copper plating to obtain a black lead material coated with a copper plating film having a thickness of 8 μm. Part of the peeling was observed in the obtained plating film, and the plating film did not have a homogeneous film quality. The cross-cut test result of the plating film was 11/25, which was classified into 3. (Comparative Example 5) Electrolytic copper plating having a thickness of 8 μm was performed on the isotropic black lead material without performing surface treatment with respect to CIP-A. Part of the peeling was observed in the obtained plating film, and the plating film did not have a homogeneous film quality. The cross-cut test result of the plating film was 7/25, which was classified as 4. (Comparative Example 6) Electroless copper plating was carried out in the same manner as in Example 5 except that the surface treatment was not carried out with respect to CIP-A. The cross-cut test result of the plating film was 10/25, which was classified as 5.

(Comparative Example 7) Electroless copper plating was carried out in the same manner as in Comparative Example 2, except that CIP-B was not subjected to surface treatment. The cross-cut test result of the plating film was 12/25, which was classified as 5.

1‧‧‧Electroplating

10‧‧‧Elected parts

10a‧‧‧ Surface of the plated component

11‧‧‧ plating film

Fig. 1 is a view showing an example of a plating process step. Fig. 2 is a schematic cross-sectional view showing an electroplated article according to an embodiment of the present invention.

Claims (11)

A pre-plating treatment method comprising a step of chemically bonding a decane coupling agent to a surface of a member to be plated, and a complex functional group for a polyfunctional compound capable of forming a chelate complex with a metal ion constituting the plating film At least one of the steps of chemically bonding to the decane coupling agent. The pre-plating treatment method of claim 1, wherein the polyfunctional compound has a plurality of carboxyl groups. The pre-plating treatment method according to claim 1 or 2, wherein the polyfunctional compound has three or more functional groups bondable to metal ions constituting the plating film. The pre-plating treatment method according to any one of claims 1 to 3, wherein the polyfunctional compound is an ethylenediaminetetraacetic acid, an ethyldiamine-N,N'-diacetic acid, or an ethylenediamine -N,N'-diacetic acid-N,N'-dipropionic acid hydrate, hydroxyethyl-extended ethyldiaminetriacetic acid, di-extension ethyltriaminepentaacetic acid, tri-extension ethyltetraamine hexaacetic acid, di-extension Ethyltriaminepentaacetic acid, cyanotriacetic acid, hydroxyethyliminodiacetic acid, L-aspartic acid-NN-diacetic acid, hydroxyiminodisuccinic acid, trans-1,2-diamine Cyclohexane-N,N,N'N'-tetraacetic acid-hydrate, O,O'-bis(2-aminoethyl)ethylene glycol-N,N,N'N'-tetraacetic acid At least one of the selected groups. The pre-plating treatment method according to any one of claims 1 to 4, wherein the decane coupling agent has at least one of a chain and a terminal having at least one selected from the group consisting of a primary amino group, an epoxy group and an isocyanate group. A functional decane coupling agent. The pre-plating treatment method according to any one of claims 1 to 5, wherein the electroplated member is an inorganic member capable of introducing a hydroxyl group. The pre-plating treatment method of claim 6, wherein the electroplated member is a carbon material, an aluminum nitride material or a tantalum nitride material. An electroplating method which is provided with a pre-processing step of performing the pre-plating treatment method according to any one of claims 1 to 7, and electroforming the surface of the electroplated member after performing the foregoing pre-treatment step Electroplating step of coating. The electroplating method of claim 8, wherein the pre-treatment step is a step of oxidizing the surface of the electroplated member. A pre-plating treatment material, which is a decane coupling agent which is provided with a member to be plated and chemically bonded to a surface of a member to be plated, and at least one of a plurality of functional groups is bonded to the decane coupling agent to form a plating film. The metal ion forms a polyfunctional compound that chelate the complex. An electroplating material, which is provided with a member to be plated, and a decane coupling agent chemically bonded to a surface of a member to be plated, and at least one of a plurality of functional groups is bonded to the decane coupling agent, and the metal constituting the plating film The ion forms a polyfunctional compound of a chelate complex, and a plating film which is bonded to a plurality of functional groups of the aforementioned decane coupling agent to which the polyfunctional compound is not bonded.