WO2018147205A1 - Pretreatment method for plating, plating method, article pretreated for plating, and plated article - Google Patents

Pretreatment method for plating, plating method, article pretreated for plating, and plated article Download PDF

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WO2018147205A1
WO2018147205A1 PCT/JP2018/003725 JP2018003725W WO2018147205A1 WO 2018147205 A1 WO2018147205 A1 WO 2018147205A1 JP 2018003725 W JP2018003725 W JP 2018003725W WO 2018147205 A1 WO2018147205 A1 WO 2018147205A1
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plating
plated
acid
silane coupling
coupling agent
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PCT/JP2018/003725
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French (fr)
Japanese (ja)
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竹林　仁
太田　直人
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東洋炭素株式会社
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Priority to JP2018553162A priority Critical patent/JP6513308B2/en
Publication of WO2018147205A1 publication Critical patent/WO2018147205A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated

Definitions

  • the present invention relates to a pretreatment method for plating, a plating method, a pretreatment product for plating, and a plated product.
  • Patent Document 1 As a method for plating graphite, a pretreatment for plating that oxidizes or heats the surface of a member to be plated is performed. A method is described. There are a wide variety of stains on the member to be plated such as metal, and electrolytic degreasing as described in Non-Patent Document 1 used for removal and surface activation is well known. Although one may be considered, when the member to be plated is a carbon material, the effect is not recognized so much and the adhesion reliability is poor.
  • the plating film is formed by the conventional pretreatment. Even so, the adhesion was small and the reliability was poor.
  • the main object of the present invention is to improve the adhesion of a plating film formed on a member to be plated having a surface inert to plating to the member to be plated.
  • the silane coupling agent is chemically bonded to the surface of the member to be plated.
  • At least one of a plurality of functional groups of a polyfunctional compound capable of forming a chelate complex with a metal ion constituting the plating film is chemically bonded to the silane coupling agent.
  • a functional group capable of chelating complex with the metal constituting the plating film is arranged on the surface of the member to be plated.
  • the plating pretreatment method according to the present invention even if the member to be plated is a member having a surface that is inactive to plating, high adhesion to the member to be plated and uniform plating Formation of the film can be realized.
  • the polyfunctional compound preferably has a plurality of carboxyl groups.
  • the polyfunctional compound has three or more functional groups capable of binding to metal ions constituting the plating film.
  • the polyfunctional compound is ethylenediaminetetraacetic acid, ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N′-diacetic acid-N, N′-dipropionic acid hydrate.
  • Hydroxyethylethylenediaminetriacetic acid diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, L-aspartic acid-NNN-diacetic acid, hydroxyiminodisuccinic acid, trans -1,2-diaminocyclohexane-N, N, N ', N'-tetraacetic acid monohydrate, O, O'-bis (2-aminoethyl) ethylene glycol-N, N, N', N'- It is preferably at least one selected from the group consisting of tetraacetic acid.
  • a silane coupling agent a silane 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 the chain and the terminal It is preferable to use a coupling agent.
  • an inorganic member capable of introducing a hydroxyl group may be used as a member to be plated.
  • a carbon material in the plating pretreatment method according to the present invention, a carbon material, an aluminum nitride material, or a silicon nitride material may be used as a member to be plated.
  • carbon material includes “graphite material”.
  • a pretreatment process for performing the plating pretreatment method according to the present invention is performed.
  • a plating process for forming a plating film is performed by plating the surface of the member to be plated that has undergone the pretreatment process.
  • the plating method according to the present invention it is preferable to perform a step of oxidizing the surface of the member to be plated in the pretreatment step.
  • the pre-plating product according to the present invention includes a member to be plated, a silane coupling agent chemically bonded to the surface of the member to be plated, and a plating film in which at least one of a plurality of functional groups is bonded to the silane coupling agent. And a polyfunctional compound capable of forming a chelate complex.
  • the plated product according to the present invention constitutes a plated film in which a member to be plated, a silane coupling agent chemically bonded to the surface of the member to be plated, and at least one of a plurality of functional groups are bonded to the silane coupling agent.
  • the adhesion of a plating film formed on a member to be plated having a surface inactive to plating to the member to be plated can be improved.
  • a plating method for plating a member to be plated includes a pretreatment step of bonding a chelating agent to the surface of the member to be plated, and plating the surface of the member to be plated to which the chelating agent is bonded. And a plating step for forming a plating film.
  • the chelating agent is composed of a polyfunctional compound capable of forming a chelate complex with the metal constituting the plating film.
  • the polyfunctional compound preferably has a plurality of carboxyl groups.
  • the polyfunctional compound preferably has three or more functional groups that can bind to the metal constituting the plating film, and more preferably has four or more functional groups. However, if the number of functional groups that can be bonded to the metal constituting the plating film is too large, the metal cannot be properly provided due to steric hindrance, and thus the plating film may not be formed properly. Accordingly, the compound capable of forming a chelate complex preferably has 6 or less functional groups capable of binding to the metal constituting the plating film.
  • polyfunctional compounds preferably used include ethylenediaminetetraacetic acid, ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N′-diacetic acid-N, N′-dipropionic acid hydrate, hydroxyethyl Ethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, L-aspartic acid-NNN-diacetic acid, hydroxyiminodisuccinic acid, trans-1, 2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid monohydrate, O, O′-bis (2-aminoethyl) ethylene glycol-N, N, N ′, N′-tetraacetic acid, etc. Is mentioned
  • the member to be plated which is a member to be plated is not particularly limited.
  • an inorganic member into which a hydroxyl group can be introduced may be used.
  • specific examples of the member to be plated include a carbon material, an aluminum nitride material, a silicon nitride material, and the like.
  • the shape dimension of the member to be plated is not particularly limited.
  • the member to be plated may be, for example, a sheet shape, a powder shape, a spherical shape, a rectangular parallelepiped shape, a cubic shape, a column shape, or the like.
  • the silane coupling agent can be appropriately selected according to the member to be plated and the polyfunctional compound.
  • Examples of the silane coupling agent preferably used when the member to be plated is graphite include, for example, an epoxy silane coupling agent, an amino silane coupling agent, and an isocyanate silane coupling agent.
  • a silane 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 the chain and at least one of the ends is more preferably used.
  • An amino-based silane coupling agent having an amino group is more preferably used.
  • Specific examples of amino-based silane coupling agents having an amino group at the end include, for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Examples include trimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
  • silane coupling agent Only one kind of the silane coupling agent may be used, or a plurality of kinds may be used.
  • a condensing agent In order to promote the reaction between the silane coupling agent and the polyfunctional compound, a condensing agent may be used.
  • the condensing agent preferably used include, for example, a triazine condensing agent, a carbodiimide condensing agent, an imidazole condensing agent, a phosphonium condensing agent, a uronium condensing agent, a hauronium condensing agent, and the like.
  • triazine-based condensing agents are more preferably used.
  • Specific examples of the triazine-based condensing agent include, for example, DMT-MM (4- (4,6-Dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholine Chloride n-Hydrate) and the like. .
  • ⁇ Plating treatment> when plating is performed on a member to be plated, first, pre-plating treatment is performed. Specifically, the silane coupling agent is chemically bonded to the surface of the member to be plated. At least one of a plurality of functional groups of a polyfunctional compound capable of forming a chelate complex with a metal ion constituting the plating film is chemically bonded to the silane coupling agent.
  • the polyfunctional compound is preferably bonded to the surface of the member to be plated so that three or more functional groups capable of binding to the metal constituting the plating film are formed, and the functional group capable of binding to the metal constituting the plating film More preferably, the polyfunctional compound is bonded to the surface of the member to be plated so that four or more are formed.
  • the silane coupling agent When it is difficult to directly bond the silane coupling agent to the surface of the member to be plated, it is preferable to subject the surface of the member to be plated to oxidation prior to the treatment of the surface of the member to be plated with the silane coupling agent. . By doing so, since a hydroxyl group can be arranged on the surface of the member to be plated, the silane coupling agent is easily bonded.
  • the method of oxidation treatment is not particularly limited. For example, wet oxidation treatment may be performed using nitric acid, hydrochloric acid, sulfuric acid, or a mixed acid of two or more thereof, or oxygen plasma oxidation treatment may be performed.
  • the above-mentioned condensing agent may be used.
  • the pre-plating treatment includes a member to be plated, a silane coupling agent bonded to the member to be plated, and a polyfunctional compound capable of forming a chelate complex with the metal ions constituting the plating film bonded to the silane coupling agent.
  • a member to be plated a silane coupling agent bonded to the member to be plated
  • a polyfunctional compound capable of forming a chelate complex with the metal ions constituting the plating film bonded to the silane coupling agent a polyfunctional compound capable of forming a chelate complex with the metal ions constituting the plating film bonded to the silane coupling agent.
  • a plated film is formed by plating the surface of the member to be plated to which the polyfunctional compound is bonded. That is, after performing the pretreatment process which performs the pretreatment method mentioned above, the plating process which forms a plating film is performed.
  • the plating can be performed, for example, by an electrolytic plating method or an electroless plating method.
  • the type of plating film is not particularly limited.
  • the plating film is, for example, Cu plating film, Ni plating film, Fe plating film, Cr plating film, Ag plating film, Au plating film, Pd plating film, Sn plating film, Cu, Ni, Fe, Cr, Ag, Au, It may be a plating film made of an alloy containing at least one element selected from the group consisting of Pd and Sn. Moreover, you may form the laminated body of a some plating film.
  • FIG. 1 shows a plating process in the case of using graphite as a member to be plated, 3-aminopropyltrimethoxysilane as a silane coupling agent, DMT-MM as a condensing agent, and EDTA as a polyfunctional compound.
  • FIG. 2 is a schematic cross-sectional view of the manufactured plated product.
  • the plated article 1 includes a member to be plated 10 and a plating film 11 provided on the surface of the member to be plated 10.
  • the metal constituting the plating film 11 and the polyfunctional compound are bonded to the surface 10a of the member to be plated 10 on which the plating film 11 is formed.
  • this polyfunctional compound the adhesion, uniformity and homogeneity between the member to be plated 10 and the plating film 11 are improved.
  • the polyfunctional compound capable of forming a chelate complex with the metal constituting the plating film 11 is arranged on the surface of the plating pretreatment object. Therefore, by using the plating pretreatment method of this embodiment, even if the member to be plated 10 is a member having a surface that is inactive with respect to the plating film, the high adhesion of the plating film 11 to the member to be plated 10. A uniform and uniform plating film 11 can be formed.
  • the polyfunctional compound capable of forming a chelate complex has three or more functional groups capable of binding to the metal constituting the plating film 11. It is preferable to have four or more.
  • the plating method of the present embodiment for example, when the surface of the member to be plated 10 is smooth, that is, when the arithmetic average roughness (Ra) defined in JIS B0601-2001 is small, The plating film 11 having high adhesion can be formed.
  • the arithmetic average roughness (Ra) of the member to be plated 10 may be, for example, 5 ⁇ m or less, 3 or less, or 1 or less.
  • Example 1 An isotropic graphite material (IG-43: CIP-A manufactured by Toyo Tanso Co., Ltd.) was immersed in a 0.5 M nitric acid aqueous solution at room temperature for 1 hour, washed with water and dried. Next, it was immersed in a methanol solution containing 1% by mass of 3-aminopropyltrimethoxysilane (silane coupling agent: CP-A) for 1 hour to introduce aminopropyl groups.
  • silane coupling agent: CP-A 3-aminopropyltrimethoxysilane
  • methanol containing 1 mmol of ethylenediaminetetraacetic acid (EDTA: chelating agent) and 1.1-fold mol of triazine-based condensing agent (DMT-MM) as a condensing agent is an isotropic graphite material having aminopropyl groups introduced. It was immersed in the solution and allowed to react for another hour, washed with diluted hydrochloric acid and dried to obtain a graphite material having EDTA introduced on the surface. Electrolytic copper plating was performed on the graphite material having the EDTA introduced on the surface thereof to obtain a graphite material coated with a copper plating film having a thickness of 8 ⁇ m.
  • the plating film had a homogeneous film quality.
  • the adhesion of the obtained plated film was evaluated by cutting a right-angled lattice pattern in accordance with the crosscut test described in JIS K5600-5-6-1999, the number of peeling was 0/25 cells.
  • the plated film was peeled off at the cut edges and intersections, but the state was judged as 2 according to the classification method described in JIS.
  • Example 2 A graphite material having EDTA introduced on the surface was obtained in the same manner as in Example 1 except that the isotropic graphite material was changed to CIP-B (ISEM-8 manufactured by Toyo Tanso Co., Ltd.). Electrolytic copper plating was performed on the graphite material in which EDTA was introduced on the surface to obtain a graphite material coated with a copper plating film. There was no unevenness in the plating film, and the plating film had a homogeneous film quality. The resulting plated film had a crosscut test result of 0/25 and a classification of 2.
  • Example 3 CIP-A was immersed in a 1.0 M nitric acid aqueous solution at room temperature for 1 hour, 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 aminopropyl groups. Thereafter, the isotropic graphite material into which the aminopropyl group was introduced was immersed in a methanol solution containing 1 mmol of EDTA and 1.1-fold mol of DMT-MM as a condensing agent, and further reacted for 1 hour. After washing and drying, a graphite material having EDTA introduced on the surface was obtained.
  • Electrolytic copper plating was performed on the graphite material having the EDTA introduced on the surface thereof to obtain a graphite material coated with a copper plating film having a thickness of 8 ⁇ m. There was no unevenness in the plating film, and the plating film had a homogeneous film quality. The resulting plated film had a crosscut test result of 0/25 and a classification of 1.
  • Example 4 CIP-A was immersed in a 1.0 M nitric acid aqueous solution at room temperature for 1 hour, washed with water and dried. Next, it was immersed in a methanol solution containing 1% by mass of N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane (silane coupling agent: CP-B) for 1 hour to introduce aminopropyl groups.
  • silane coupling agent: CP-B silane coupling agent
  • the isotropic graphite material into which the aminopropyl group was introduced was converted to 1 mmol of trans-1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid monohydrate (CyDTA: chelating agent), Graphite in which CyDTA is introduced on the surface by immersing in a methanol solution containing 1.1-fold moles of triazine-based condensing agent (DMT-MM) as a condensing agent, reacting for 1 hour, washing and drying with dilute hydrochloric acid Obtained material.
  • CyDTA chelating agent
  • Electrolytic copper plating was performed on the graphite material having CyDTA introduced on the surface thereof to obtain a graphite material coated with a copper plating film having a thickness of 8 ⁇ m. There was no unevenness in the plating film, and the plating film had a homogeneous film quality. The resulting plated film had a crosscut test result of 0/25 and a classification of 0.
  • Example 5 A graphite material coated with a copper plating film was obtained in the same manner as in Example 3 except that 3-glycidoxypropyltrimethoxysilane (CP-C) was used as the silane coupling agent.
  • CP-C 3-glycidoxypropyltrimethoxysilane
  • Example 6 A graphite 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 was washed with water CIP-A, was immersed in the pretreatment solution PdCl 2 as the SnCl 2 and activator as a sensitizer is added, copper sulfate as the source of copper ions, EDTA as a complexing agent Used and reduced with formaldehyde. The substrate surface was coated with copper having a uniform thickness of 2 ⁇ m. The resulting plated film had a crosscut test result of 0/25 and a classification of 1.
  • Example 7 A graphite material coated with copper was obtained in the same manner as in Example 4 except that the chelating agent was diethylenetriaminepentaacetic acid (DTPA). The resulting plated film had a crosscut test result of 0/25 and a classification of 0. (Example 8) Coated with copper in the same manner as in Example 4 except that the chelating agent was O, O′-bis (2-aminoethyl) ethylene glycol-N, N, N ′, N′-tetraacetic acid (EGTA). A graphite material was obtained. The resulting plated film had a crosscut test result of 0/25 and a classification of 1.
  • DTPA diethylenetriaminepentaacetic acid
  • Example 9 A graphite material coated with copper was obtained in the same manner as in Example 4 except that the chelating agent was triethylenetetramine hexaacetic acid (TTHA). The resulting plated film had a crosscut test result of 0/25 and a classification of 0.
  • TTHA triethylenetetramine hexaacetic acid
  • Comparative Example 7 The surface treatment was not performed on CIP-B, and electroless copper plating was performed in the same manner as in Comparative Example 2.
  • the crosscut test result of the plating film was 12/25, and the classification was 5.
  • Plated object 10 Plated member 10a: Surface of the member to be plated 11: Plated film

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

めっきの前処理方法、めっき方法、めっき前処理物及びめっき物Plating pretreatment method, plating method, pre-plated product and plated product
　本発明は、めっきの前処理方法、めっき方法、めっき前処理物及びめっき物に関する。 The present invention relates to a pretreatment method for plating, a plating method, a pretreatment product for plating, and a plated product.
　炭素材料のような部材に対してめっきを行いたいという要望がある一方、炭素材料は化学的に不活性な表面を有するため、均質で密着性に優れためっき膜を形成することは従来から難しいと考えられている。そのような難点を克服することを目的として、例えば、特許文献１には、黒鉛に対してめっきを行う方法として、被めっき部材の表面を酸化したり、加熱したりするめっきの前処理を行う方法が記載されている。金属などの被めっき部材には多種多様な汚れが存在しており、その除去や表面活性化のために用いられる非特許文献１に記載のような電解脱脂は周知であり、上記の酸化工程の一つとも考えられるが、被めっき部材が炭素材料の場合に効果はあまり認められず、密着信頼性に乏しいものであった。 While there is a demand for plating on a member such as a carbon material, since a carbon material has a chemically inert surface, it is conventionally difficult to form a plating film having a uniform and excellent adhesion. It is believed that. For the purpose of overcoming such difficulties, for example, in Patent Document 1, as a method for plating graphite, a pretreatment for plating that oxidizes or heats the surface of a member to be plated is performed. A method is described. There are a wide variety of stains on the member to be plated such as metal, and electrolytic degreasing as described in Non-Patent Document 1 used for removal and surface activation is well known. Although one may be considered, when the member to be plated is a carbon material, the effect is not recognized so much and the adhesion reliability is poor.
特開２０１５－５０３０３２号公報Japanese Patent Laid-Open No. 2015-503032
　このように、黒鉛等の不活性な表面を有する被めっき部材の上に形成されためっき膜の被めっき部材に対する密着性を改善したいという要望があるものの、従来の前処理ではめっき膜が形成されたとしてもその密着力は小さく、信頼性に乏しいものであった。 Thus, although there is a desire to improve the adhesion of the plating film formed on the member to be plated having an inert surface such as graphite to the member to be plated, the plating film is formed by the conventional pretreatment. Even so, the adhesion was small and the reliability was poor.
　本発明の主な目的は、めっきに対して不活性な表面を有する被めっき部材の上に形成されためっき膜の被めっき部材に対する密着性を改善することにある。 The main object of the present invention is to improve the adhesion of a plating film formed on a member to be plated having a surface inert to plating to the member to be plated.
　本発明に係るめっき前処理方法では、シランカップリング剤を被めっき部材の表面に化学的に結合させる。めっき膜を構成する金属イオンとキレート錯体を形成可能な多官能化合物の複数の官能基の少なくとも一つをシランカップリング剤に化学的に結合させる。このため、本発明に係るめっき前処理方法により作成されためっき前処理物では、被めっき部材の表面に、めっき膜を構成する金属とキレート錯体可能な官能基が配される。よって、本発明に係るめっき前処理方法を用いることにより、被めっき部材がめっきに対して不活性な表面を有する部材であったとしても、めっき膜の被めっき部材に対する高い密着性、均質なめっき膜の形成を実現することができる。 In the plating pretreatment method according to the present invention, the silane coupling agent is chemically bonded to the surface of the member to be plated. At least one of a plurality of functional groups of a polyfunctional compound capable of forming a chelate complex with a metal ion constituting the plating film is chemically bonded to the silane coupling agent. For this reason, in the plating pretreatment object created by the plating pretreatment method according to the present invention, a functional group capable of chelating complex with the metal constituting the plating film is arranged on the surface of the member to be plated. Therefore, by using the plating pretreatment method according to the present invention, even if the member to be plated is a member having a surface that is inactive to plating, high adhesion to the member to be plated and uniform plating Formation of the film can be realized.
　本発明に係るめっき前処理方法では、多官能化合物が、カルボキシル基を複数有することが好ましい。 In the plating pretreatment method according to the present invention, the polyfunctional compound preferably has a plurality of carboxyl groups.
　本発明に係るめっき前処理方法では、多官能化合物が、めっき膜を構成する金属イオンと結合し得る官能基を３つ以上有することが好ましい。 In the plating pretreatment method according to the present invention, it is preferable that the polyfunctional compound has three or more functional groups capable of binding to metal ions constituting the plating film.
　本発明に係るめっき前処理方法では、多官能化合物が、エチレンジアミン四酢酸、エチレンジアミン－Ｎ，Ｎ’－二酢酸、エチレンジアミン－Ｎ，Ｎ’－二酢酸－Ｎ，Ｎ’－ジプロピオン酸水和物、ヒドロキシエチルエチレンジアミン三酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラミン六酢酸、ジエチレントリアミン五酢酸、ニトリロ三酢酸、ヒドロキシエチルイミノ二酢酸、Ｌ－アスパラギン酸－Ｎ－Ｎ－二酢酸、ヒドロキシイミノジコハク酸、ｔｒａｎｓ－１，２－ジアミノシクロヘキサン－Ｎ，Ｎ，Ｎ’，Ｎ’－四酢酸一水和物、Ｏ，Ｏ’－ビス（２－アミノエチル）エチレングリコール－Ｎ，Ｎ，Ｎ’，Ｎ’－四酢酸からなる群から選ばれた少なくとも１種であることが好ましい。 In the plating pretreatment method according to the present invention, the polyfunctional compound is ethylenediaminetetraacetic acid, ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N′-diacetic acid-N, N′-dipropionic acid hydrate. Hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, L-aspartic acid-NNN-diacetic acid, hydroxyiminodisuccinic acid, trans -1,2-diaminocyclohexane-N, N, N ', N'-tetraacetic acid monohydrate, O, O'-bis (2-aminoethyl) ethylene glycol-N, N, N', N'- It is preferably at least one selected from the group consisting of tetraacetic acid.
　本発明に係るめっき前処理方法では、シランカップリング剤として、鎖中及び末端の少なくとも一方に第一級アミノ基、エポキシ基及びイソシアネート基からなる群から選択された少なくとも１つの官能基を有するシランカップリング剤を用いることが好ましい。 In the plating pretreatment method according to the present invention, as a silane coupling agent, a silane 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 the chain and the terminal It is preferable to use a coupling agent.
　本発明に係るめっき前処理方法では、被めっき部材として、ヒドロキシル基が導入可能な無機部材を用いてもよい。 In the plating pretreatment method according to the present invention, an inorganic member capable of introducing a hydroxyl group may be used as a member to be plated.
　本発明に係るめっき前処理方法では、被めっき部材として、炭素材料、窒化アルミ材料または窒化ケイ素材料を用いてもよい。なお、本発明において、「炭素材料」には、「黒鉛材料」が含まれるものとする。 In the plating pretreatment method according to the present invention, a carbon material, an aluminum nitride material, or a silicon nitride material may be used as a member to be plated. In the present invention, “carbon material” includes “graphite material”.
　本発明に係るめっき方法では、本発明に係るめっきの前処理方法を行う前処理工程を行う。前処理工程を行った被めっき部材の表面にめっきを施すことによりめっき膜を形成するめっき工程を行う。 In the plating method according to the present invention, a pretreatment process for performing the plating pretreatment method according to the present invention is performed. A plating process for forming a plating film is performed by plating the surface of the member to be plated that has undergone the pretreatment process.
　本発明に係るめっき方法では、前処理工程において被めっき部材の表面を酸化する工程を行うことが好ましい。 In the plating method according to the present invention, it is preferable to perform a step of oxidizing the surface of the member to be plated in the pretreatment step.
　本発明に係るめっき前処理物は、被めっき部材と、被めっき部材の表面に化学的に結合したシランカップリング剤と、複数の官能基の少なくとも一つがシランカップリング剤と結合した、めっき膜を構成する金属イオンとキレート錯体を形成可能な多官能化合物とを備える。 The pre-plating product according to the present invention includes a member to be plated, a silane coupling agent chemically bonded to the surface of the member to be plated, and a plating film in which at least one of a plurality of functional groups is bonded to the silane coupling agent. And a polyfunctional compound capable of forming a chelate complex.
　本発明に係るめっき物は、被めっき部材と、被めっき部材の表面に化学的に結合したシランカップリング剤と、複数の官能基の少なくとも一つがシランカップリング剤と結合した、めっき膜を構成する金属イオンとキレート錯体を形成可能な多官能化合物と、多官能器化合物のシランカップリング剤と結合していない複数の官能基と結合しているめっき膜とを備える。 The plated product according to the present invention constitutes a plated film in which a member to be plated, a silane coupling agent chemically bonded to the surface of the member to be plated, and at least one of a plurality of functional groups are bonded to the silane coupling agent. A polyfunctional compound capable of forming a chelate complex with a metal ion to be formed, and a plating film bonded to a plurality of functional groups not bonded to the silane coupling agent of the multifunctional compound.
　本発明によれば、めっきに対して不活性な表面を有する被めっき部材の上に形成されためっき膜の被めっき部材に対する密着性を改善することができる。 According to the present invention, the adhesion of a plating film formed on a member to be plated having a surface inactive to plating to the member to be plated can be improved.
めっき処理工程の一例を示す図である。It is a figure which shows an example of a plating process. 本発明の一実施形態に係るめっき物の模式的断面図である。It is a typical sectional view of a plating thing concerning one embodiment of the present invention.
　以下、本発明を実施した好ましい形態の一例について説明する。但し、下記の実施形態は、単なる例示である。本発明は、下記の実施形態に何ら限定されない。 Hereinafter, an example of a preferable embodiment in which the present invention is implemented will be described. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.
　（めっき法）
　本実施形態において、被めっき部材に対してめっきを行うめっき方法は、キレート剤を被めっき部材の表面に結合させる前処理工程と、キレート剤を結合させた被めっき部材の表面にめっきを施すことによりめっき膜を形成するめっき工程とを備えている。 (Plating method)
In the present embodiment, a plating method for plating a member to be plated includes a pretreatment step of bonding a chelating agent to the surface of the member to be plated, and plating the surface of the member to be plated to which the chelating agent is bonded. And a plating step for forming a plating film.
　＜キレート剤＞
　キレート剤は、めっき膜を構成する金属とキレート錯体を形成可能な多官能化合物からなる。 <Chelating agent>
The chelating agent is composed of a polyfunctional compound capable of forming a chelate complex with the metal constituting the plating film.
　多官能化合物としては、カルボキシル基を複数有するものであることが好ましい。 The polyfunctional compound preferably has a plurality of carboxyl groups.
　多官能化合物は、めっき膜を構成する金属と結合し得る官能基を３つ以上有するものであることが好ましく、４つ以上有するものであることがより好ましい。但し、めっき膜を構成する金属と結合し得る官能基の数が多すぎると、立体障害により金属が好適に配意できなくなるため、めっき膜が好適に形成されなくなる虞がある。従って、キレート錯体を形成可能な化合物は、めっき膜を構成する金属と結合し得る官能基を６つ以下有していることが好ましい。 The polyfunctional compound preferably has three or more functional groups that can bind to the metal constituting the plating film, and more preferably has four or more functional groups. However, if the number of functional groups that can be bonded to the metal constituting the plating film is too large, the metal cannot be properly provided due to steric hindrance, and thus the plating film may not be formed properly. Accordingly, the compound capable of forming a chelate complex preferably has 6 or less functional groups capable of binding to the metal constituting the plating film.
　好ましく用いられる多官能化合物の具体例としては、エチレンジアミン四酢酸、エチレンジアミン－Ｎ，Ｎ’－二酢酸、エチレンジアミン－Ｎ，Ｎ’－二酢酸－Ｎ，Ｎ’－ジプロピオン酸水和物、ヒドロキシエチルエチレンジアミン三酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラミン六酢酸、ジエチレントリアミン五酢酸、ニトリロ三酢酸、ヒドロキシエチルイミノ二酢酸、Ｌ－アスパラギン酸－Ｎ－Ｎ－二酢酸、ヒドロキシイミノジコハク酸、ｔｒａｎｓ－１，２－ジアミノシクロヘキサン－Ｎ，Ｎ，Ｎ’，Ｎ’－四酢酸一水和物、Ｏ，Ｏ’－ビス（２－アミノエチル）エチレングリコール－Ｎ，Ｎ，Ｎ’，Ｎ’－四酢酸等が挙げられる。これらの化合物の１種のみを用いてもよいし、複数種類を用いてもよい。 Specific examples of polyfunctional compounds preferably used include ethylenediaminetetraacetic acid, ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N′-diacetic acid-N, N′-dipropionic acid hydrate, hydroxyethyl Ethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, L-aspartic acid-NNN-diacetic acid, hydroxyiminodisuccinic acid, trans-1, 2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid monohydrate, O, O′-bis (2-aminoethyl) ethylene glycol-N, N, N ′, N′-tetraacetic acid, etc. Is mentioned. Only 1 type of these compounds may be used, and multiple types may be used.
　＜被めっき部材＞
　本発明において、めっきされる部材である被めっき部材は、特に限定されない。被めっき部材として、ヒドロキシル基が導入可能な無機部材を用いてもよい。本発明において、被めっき部材としては、具体的には、例えば、炭素材料や窒化アルミ材料、窒化ケイ材料等が挙げられる。 <Plating material>
In the present invention, the member to be plated which is a member to be plated is not particularly limited. As the member to be plated, an inorganic member into which a hydroxyl group can be introduced may be used. In the present invention, specific examples of the member to be plated include a carbon material, an aluminum nitride material, a silicon nitride material, and the like.
　被めっき部材の形状寸法は、特に限定されない。被めっき部材は、例えば、シート状、粉末状、球状、直方体状、立方体状、柱状等であってもよい。 The shape dimension of the member to be plated is not particularly limited. The member to be plated may be, for example, a sheet shape, a powder shape, a spherical shape, a rectangular parallelepiped shape, a cubic shape, a column shape, or the like.
　＜シランカップリング剤＞
　シランカップリング剤は、被めっき部材及び多官能化合物に応じて適宜選択することができる。被めっき部材が例えば黒鉛である場合に好ましく用いられるシランカップリング剤としては、例えば、エポキシ系シランカップリング剤、アミノ系シランカップリング剤、イソシアネート系シランカップリング剤等が挙げられる。 <Silane coupling agent>
The silane coupling agent can be appropriately selected according to the member to be plated and the polyfunctional compound. Examples of the silane coupling agent preferably used when the member to be plated is graphite include, for example, an epoxy silane coupling agent, an amino silane coupling agent, and an isocyanate silane coupling agent.
　これらのなかでも、鎖中及び末端の少なくとも一方に第一級アミノ基、エポキシ基及びイソシアネート基からなる群より選択された少なくとも１つの官能基を有するシランカップリング剤がより好ましく用いられ、末端にアミノ基を有するアミノ系シランカップリング剤がさらに好ましく用いられる。末端にアミノ基を有するアミノ系シランカップリング剤の具体例としては、例えば、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン等が挙げられる。 Among these, a silane 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 the chain and at least one of the ends is more preferably used. An amino-based silane coupling agent having an amino group is more preferably used. Specific examples of amino-based silane coupling agents having an amino group at the end include, for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Examples include trimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
　上記シランカップリング剤の１種のみを用いてもよいし、複数種類を用いてもよい。 Only one kind of the silane coupling agent may be used, or a plurality of kinds may be used.
　＜縮合剤＞
　シランカップリング剤と多官能化合物との反応を促進するために、縮合剤を用いてもよい。好ましく用いられる縮合剤の具体例としては、例えば、トリアジン系縮合剤、カルボジイミド系縮合剤、イミダゾール系縮合剤、ホスホニウム系縮合剤、ウロニウム系縮合剤、ハロウロニウム系縮合剤等が挙げられる。 <Condensation agent>
In order to promote the reaction between the silane coupling agent and the polyfunctional compound, a condensing agent may be used. Specific examples of the condensing agent preferably used include, for example, a triazine condensing agent, a carbodiimide condensing agent, an imidazole condensing agent, a phosphonium condensing agent, a uronium condensing agent, a hauronium condensing agent, and the like.
　これらのなかでも、トリアジン系縮合剤がより好ましく用いられる。トリアジン系縮合剤の具体例としては、例えば、ＤＭＴ－ＭＭ（４－（４，６－Ｄｉｍｅｔｈｏｘｙ－１，３，５－ｔｒｉａｚｉｎ－２－ｙｌ）－４－ｍｅｔｈｙｌｍｏｒｐｈｏｌｉｎｉｕｍ　Ｃｈｌｏｒｉｄｅ　ｎ－Ｈｙｄｒａｔｅ）等が挙げられる。 Of these, triazine-based condensing agents are more preferably used. Specific examples of the triazine-based condensing agent include, for example, DMT-MM (4- (4,6-Dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholine Chloride n-Hydrate) and the like. .
　＜めっき処理＞
　本実施形態において、被めっき部材に対してめっきを行うに際しては、まず、めっき前処理を行う。具体的には、シランカップリング剤を被めっき部材の表面に化学的に結合させる。めっき膜を構成する金属イオンとキレート錯体を形成可能な多官能化合物の複数の官能基の少なくとも一つをシランカップリング剤に化学的に結合させる。めっき膜を構成する金属と結合し得る官能基が３つ以上形成されるように、多官能化合物を被めっき部材の表面に結合させることが好ましく、めっき膜を構成する金属と結合し得る官能基が４つ以上形成されるように、多官能化合物を被めっき部材の表面に結合させることがより好ましい。 <Plating treatment>
In the present embodiment, when plating is performed on a member to be plated, first, pre-plating treatment is performed. Specifically, the silane coupling agent is chemically bonded to the surface of the member to be plated. At least one of a plurality of functional groups of a polyfunctional compound capable of forming a chelate complex with a metal ion constituting the plating film is chemically bonded to the silane coupling agent. The polyfunctional compound is preferably bonded to the surface of the member to be plated so that three or more functional groups capable of binding to the metal constituting the plating film are formed, and the functional group capable of binding to the metal constituting the plating film More preferably, the polyfunctional compound is bonded to the surface of the member to be plated so that four or more are formed.
　シランカップリング剤を被めっき部材の表面に直接結合させることが困難な場合は、シランカップリング剤による被めっき部材の表面の処理に先立って、被めっき部材の表面の酸化処理を行うことが好ましい。そうすることにより、被めっき部材の表面にヒドロキシル基を配することができるため、シランカップリング剤が結合しやすくなる。酸化処理の方法は、特に限定されない。例えば、硝酸、塩酸、硫酸、それらのうちの２種以上の混酸を用いて湿式酸化処理を行ってもよいし、酸素プラズマ酸化処理を行ってもよい。 When it is difficult to directly bond the silane coupling agent to the surface of the member to be plated, it is preferable to subject the surface of the member to be plated to oxidation prior to the treatment of the surface of the member to be plated with the silane coupling agent. . By doing so, since a hydroxyl group can be arranged on the surface of the member to be plated, the silane coupling agent is easily bonded. The method of oxidation treatment is not particularly limited. For example, wet oxidation treatment may be performed using nitric acid, hydrochloric acid, sulfuric acid, or a mixed acid of two or more thereof, or oxygen plasma oxidation treatment may be performed.
　また、シランカップリング剤と多官能化合物との縮合反応を促進する観点から、上述の縮合剤を用いてもよい。 Further, from the viewpoint of promoting the condensation reaction between the silane coupling agent and the polyfunctional compound, the above-mentioned condensing agent may be used.
　（めっき処理前物）
　上述の工程を行うことにより、めっき処理前物を製造することができる。めっき処理前物は、被めっき部材と、被めっき部材に結合したシランカップリング剤と、シランカップリング剤と結合した、めっき膜を構成する金属イオンとキレート錯体を形成可能な多官能化合物とを備えている。被めっき部材や、シランカップリング剤、めっき膜を構成する多官能化合物の詳細に関しては、前述の通りである。 (Before plating treatment)
By performing the above-described steps, a pre-plating treatment can be manufactured. The pre-plating treatment includes a member to be plated, a silane coupling agent bonded to the member to be plated, and a polyfunctional compound capable of forming a chelate complex with the metal ions constituting the plating film bonded to the silane coupling agent. I have. Details of the member to be plated, the silane coupling agent, and the polyfunctional compound constituting the plating film are as described above.
　最後に、多官能化合物が結合した被めっき部材の表面にめっきを施すことにより、めっき膜を形成する。すなわち、上述した前処理方法を行う前処理工程を行った後に、めっき膜を形成するめっき工程を行う。めっきは、例えば、電解めっき法により行うこともできるし、無電解めっき法により行うこともできる。 Finally, a plated film is formed by plating the surface of the member to be plated to which the polyfunctional compound is bonded. That is, after performing the pretreatment process which performs the pretreatment method mentioned above, the plating process which forms a plating film is performed. The plating can be performed, for example, by an electrolytic plating method or an electroless plating method.
　めっき膜の種類は、特に限定されない。めっき膜は、例えば、Ｃｕめっき膜、Ｎｉめっき膜、Ｆｅめっき膜、Ｃｒめっき膜、Ａｇめっき膜、Ａｕめっき膜、Ｐｄめっき膜、Ｓｎめっき膜やＣｕ，Ｎｉ，Ｆｅ，Ｃｒ，Ａｇ，Ａｕ、Ｐｄ及びＳｎからなる群から選ばれた少なくとも一種の元素を含む合金からなるめっき膜等であってもよい。また、複数のめっき膜の積層体を形成してもよい。 The type of plating film is not particularly limited. The plating film is, for example, Cu plating film, Ni plating film, Fe plating film, Cr plating film, Ag plating film, Au plating film, Pd plating film, Sn plating film, Cu, Ni, Fe, Cr, Ag, Au, It may be a plating film made of an alloy containing at least one element selected from the group consisting of Pd and Sn. Moreover, you may form the laminated body of a some plating film.
　図１に、被めっき部材として黒鉛を、シランカップリング剤として３－アミノプロピルトリメトキシシランを、縮合剤としてＤＭＴ－ＭＭを、多官能化合物としてＥＤＴＡを用いた場合のめっき処理工程を示す。 FIG. 1 shows a plating process in the case of using graphite as a member to be plated, 3-aminopropyltrimethoxysilane as a silane coupling agent, DMT-MM as a condensing agent, and EDTA as a polyfunctional compound.
　（めっき物）
　図２に、製造されためっき物の模式的断面図を示す。図２に示すように、めっき物１は、被めっき部材１０と、被めっき部材１０の表面上に設けられためっき膜１１とを備えている。被めっき部材１０のめっき膜１１が形成されている表面１０ａには、めっき膜１１を構成している金属と多官能化合物が結合している。この多官能化合物により、被めっき部材１０とめっき膜１１との密着性、均一性及び均質性が向上されている。 (Plated material)
FIG. 2 is a schematic cross-sectional view of the manufactured plated product. As shown in FIG. 2, the plated article 1 includes a member to be plated 10 and a plating film 11 provided on the surface of the member to be plated 10. The metal constituting the plating film 11 and the polyfunctional compound are bonded to the surface 10a of the member to be plated 10 on which the plating film 11 is formed. By this polyfunctional compound, the adhesion, uniformity and homogeneity between the member to be plated 10 and the plating film 11 are improved.
　以上説明したように、本実施形態では、めっき膜１１を構成する金属とキレート錯体を形成可能な多官能化合物がめっき前処理物の表面に配される。よって、本実施形態のめっき前処理方法を用いることにより、被めっき部材１０がめっき膜に対して不活性な表面を有する部材であったとしても、めっき膜１１の被めっき部材１０に対する高い密着性、均一かつ均質なめっき膜１１の形成を実現することができる。 As described above, in the present embodiment, the polyfunctional compound capable of forming a chelate complex with the metal constituting the plating film 11 is arranged on the surface of the plating pretreatment object. Therefore, by using the plating pretreatment method of this embodiment, even if the member to be plated 10 is a member having a surface that is inactive with respect to the plating film, the high adhesion of the plating film 11 to the member to be plated 10. A uniform and uniform plating film 11 can be formed.
　めっき膜１１の被めっき部材１０に対するより高い密着性を実現する観点から、キレート錯体を形成可能な多官能化合物が、めっき膜１１を構成する金属と結合し得る官能基を３つ以上有することが好ましく、４つ以上有することがより好ましい。 From the viewpoint of realizing higher adhesion of the plating film 11 to the member 10 to be plated, the polyfunctional compound capable of forming a chelate complex has three or more functional groups capable of binding to the metal constituting the plating film 11. It is preferable to have four or more.
　上記本実施形態のめっき方法によれば、例えば、被めっき部材１０の表面が平滑である場合、すなわち、ＪＩＳ　Ｂ０６０１－２００１で規定される算術平均粗さ（Ｒａ）が小さな場合であっても、高い密着力を有するめっき膜１１を形成することができる。被めっき部材１０の算術平均粗さ（Ｒａ）は、例えば、５μｍ以下であってもよく、３以下であってもよく、１以下であってもよい。 According to the plating method of the present embodiment, for example, when the surface of the member to be plated 10 is smooth, that is, when the arithmetic average roughness (Ra) defined in JIS B0601-2001 is small, The plating film 11 having high adhesion can be formed. The arithmetic average roughness (Ra) of the member to be plated 10 may be, for example, 5 μm or less, 3 or less, or 1 or less.
　以下、本発明について、具体的な実施例に基づいて、さらに詳細に説明するが、本発明は以下の実施例に何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施することが可能である。 Hereinafter, the present invention will be described in more detail on the basis of specific examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented without departing from the scope of the present invention. Is possible.
　（実施例１）
　等方性黒鉛材料（東洋炭素製　ＩＧ－４３：ＣＩＰ－Ａ）を０．５Ｍの硝酸水溶液に室温で１時間浸漬させた後、水洗・乾燥した。次に、１質量％の３－アミノプロピルトリメトキシシラン（シランカップリング剤：ＣＰ－Ａ）を含むメタノール溶液に１時間浸漬させ、アミノプロピル基を導入した。その後、アミノプロピル基が導入された等方性黒鉛材料を１ｍｍｏｌのエチレンジアミン四酢酸（ＥＤＴＡ：キレート剤）と、縮合剤として１．１倍モルのトリアジン系縮合剤（ＤＭＴ－ＭＭ）とを含むメタノール溶液に浸漬し、さらに１時間反応させ、これを希塩酸で洗浄・乾燥して表面にＥＤＴＡが導入された黒鉛材料を得た。このＥＤＴＡが表面に導入された黒鉛材料に対して電解銅めっきを行い、厚さ８μｍの銅めっき膜で被覆された黒鉛材料を得た。めっき膜にむらはなく、めっき膜は、均質な膜質を有していた。得られためっき膜の密着性をＪＩＳ　Ｋ５６００－５－６－１９９９記載のクロスカット試験に準じて直角の格子パターンを切り込んで評価したところ、剥離数は０個／２５マスであった。めっき膜はカットの縁や交差点において剥がれているが、その状態はＪＩＳ記載の分類法に従って２と判断された。 Example 1
An isotropic graphite material (IG-43: CIP-A manufactured by Toyo Tanso Co., Ltd.) was immersed in a 0.5 M nitric acid aqueous solution at room temperature for 1 hour, washed with water and dried. Next, it was immersed in a methanol solution containing 1% by mass of 3-aminopropyltrimethoxysilane (silane coupling agent: CP-A) for 1 hour to introduce aminopropyl groups. Thereafter, methanol containing 1 mmol of ethylenediaminetetraacetic acid (EDTA: chelating agent) and 1.1-fold mol of triazine-based condensing agent (DMT-MM) as a condensing agent is an isotropic graphite material having aminopropyl groups introduced. It was immersed in the solution and allowed to react for another hour, washed with diluted hydrochloric acid and dried to obtain a graphite material having EDTA introduced on the surface. Electrolytic copper plating was performed on the graphite material having the EDTA introduced on the surface thereof to obtain a graphite material coated with a copper plating film having a thickness of 8 μm. There was no unevenness in the plating film, and the plating film had a homogeneous film quality. When the adhesion of the obtained plated film was evaluated by cutting a right-angled lattice pattern in accordance with the crosscut test described in JIS K5600-5-6-1999, the number of peeling was 0/25 cells. The plated film was peeled off at the cut edges and intersections, but the state was judged as 2 according to the classification method described in JIS.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
　（実施例２）
　等方性黒鉛材料をＣＩＰ－Ｂ（東洋炭素製　ＩＳＥＭ－８）に変更する以外は実施例１と同様の方法で表面にＥＤＴＡが導入された黒鉛材料を得た。このＥＤＴＡが表面に導入された黒鉛材料に対して電解銅めっきを行い、銅めっき膜で被覆された黒鉛材料を得た。めっき膜にむらはなく、めっき膜は、均質な膜質を有していた。得られためっき膜のクロスカット試験結果は０／２５、分類は２であった。
Figure JPOXMLDOC01-appb-C000002
(Example 2)
A graphite material having EDTA introduced on the surface was obtained in the same manner as in Example 1 except that the isotropic graphite material was changed to CIP-B (ISEM-8 manufactured by Toyo Tanso Co., Ltd.). Electrolytic copper plating was performed on the graphite material in which EDTA was introduced on the surface to obtain a graphite material coated with a copper plating film. There was no unevenness in the plating film, and the plating film had a homogeneous film quality. The resulting plated film had a crosscut test result of 0/25 and a classification of 2.
　（実施例３）
　ＣＩＰ－Ａを１．０Ｍの硝酸水溶液に室温で１時間浸漬させた後、水洗・乾燥した。次に、１質量％のＣＰ－Ａを含むメタノール溶液に１時間浸漬させ、アミノプロピル基を導入した。その後、アミノプロピル基が導入された等方性黒鉛材料を１ｍｍｏｌのＥＤＴＡと、縮合剤として１．１倍モルのＤＭＴ－ＭＭとを含むメタノール溶液に浸漬し、さらに１時間反応させ、これを希塩酸で洗浄・乾燥して表面にＥＤＴＡが導入された黒鉛材料を得た。このＥＤＴＡが表面に導入された黒鉛材料に対して電解銅めっきを行い、厚さ８μｍの銅めっき膜で被覆された黒鉛材料を得た。めっき膜にむらはなく、めっき膜は、均質な膜質を有していた。得られためっき膜のクロスカット試験結果は０／２５、分類は１であった。 (Example 3)
CIP-A was immersed in a 1.0 M nitric acid aqueous solution at room temperature for 1 hour, 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 aminopropyl groups. Thereafter, the isotropic graphite material into which the aminopropyl group was introduced was immersed in a methanol solution containing 1 mmol of EDTA and 1.1-fold mol of DMT-MM as a condensing agent, and further reacted for 1 hour. After washing and drying, a graphite material having EDTA introduced on the surface was obtained. Electrolytic copper plating was performed on the graphite material having the EDTA introduced on the surface thereof to obtain a graphite material coated with a copper plating film having a thickness of 8 μm. There was no unevenness in the plating film, and the plating film had a homogeneous film quality. The resulting plated film had a crosscut test result of 0/25 and a classification of 1.
　（実施例４）
　ＣＩＰ－Ａを１．０Ｍの硝酸水溶液に室温で１時間浸漬させた後、水洗・乾燥した。次に、１質量％のＮ－２（アミノエチル）３－アミノプロピルメチルジメトキシシラン（シランカップリング剤：ＣＰ－Ｂ）を含むメタノール溶液に１時間浸漬させ、アミノプロピル基を導入した。その後、アミノプロピル基が導入された等方性黒鉛材料を１ｍｍｏｌのｔｒａｎｓ－１，２－ジアミノシクロヘキサン－Ｎ，Ｎ，Ｎ’，Ｎ’－四酢酸一水和物（ＣｙＤＴＡ：キレート剤）と、縮合剤として１．１倍モルのトリアジン系縮合剤（ＤＭＴ－ＭＭ）とを含むメタノール溶液に浸漬し、さらに１時間反応させ、これを希塩酸で洗浄・乾燥して表面にＣｙＤＴＡが導入された黒鉛材料を得た。このＣｙＤＴＡが表面に導入された黒鉛材料に対して電解銅めっきを行い、厚さ８μｍの銅めっき膜で被覆された黒鉛材料を得た。めっき膜にむらはなく、めっき膜は、均質な膜質を有していた。得られためっき膜のクロスカット試験結果は０／２５、分類は０であった。 Example 4
CIP-A was immersed in a 1.0 M nitric acid aqueous solution at room temperature for 1 hour, washed with water and dried. Next, it was immersed in a methanol solution containing 1% by mass of N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane (silane coupling agent: CP-B) for 1 hour to introduce aminopropyl groups. Thereafter, the isotropic graphite material into which the aminopropyl group was introduced was converted to 1 mmol of trans-1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid monohydrate (CyDTA: chelating agent), Graphite in which CyDTA is introduced on the surface by immersing in a methanol solution containing 1.1-fold moles of triazine-based condensing agent (DMT-MM) as a condensing agent, reacting for 1 hour, washing and drying with dilute hydrochloric acid Obtained material. Electrolytic copper plating was performed on the graphite material having CyDTA introduced on the surface thereof to obtain a graphite material coated with a copper plating film having a thickness of 8 μm. There was no unevenness in the plating film, and the plating film had a homogeneous film quality. The resulting plated film had a crosscut test result of 0/25 and a classification of 0.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
　（実施例５）
　シランカップリング剤を３－グリシドキシプロピルトリメトキシシラン（ＣＰ－Ｃ）としたこと以外は実施例３と同様にして銅めっき膜で被覆された黒鉛材料を得た。得られためっき膜のクロスカット試験結果は０／２５、分類は０であった。
Figure JPOXMLDOC01-appb-C000004
(Example 5)
A graphite material coated with a copper plating film was obtained in the same manner as in Example 3 except that 3-glycidoxypropyltrimethoxysilane (CP-C) was used as the silane coupling agent. The resulting plated film had a crosscut test result of 0/25 and a classification of 0.
Figure JPOXMLDOC01-appb-C000005
　（実施例６）
　めっき法を無電解めっきとしたこと以外は実施例４と同様にして銅めっき膜で被覆された黒鉛材料を得た。無電解めっきは、ＣＩＰ－Ａを水洗した後、センシタイザーとなるＳｎＣｌ２とアクティベーターとなるＰｄＣｌ２が添加された前処理液に浸漬し、銅イオン源として硫酸銅を、錯化剤としてＥＤＴＡを用いてホルムアルデヒドで還元することで行った。基材表面には厚さは２μｍの均一な膜厚の銅が被覆された。得られためっき膜のクロスカット試験結果は０／２５、分類は１であった。
（実施例７）
　キレート剤をジエチレントリアミン五酢酸（ＤＴＰＡ）としたこと以外は実施例４と同様にして銅で被覆された黒鉛材料を得た。得られためっき膜のクロスカット試験結果は０／２５、分類は０であった。
（実施例８）
　キレート剤をＯ，Ｏ’－ビス（２－アミノエチル）エチレングリコール－Ｎ，Ｎ，Ｎ’，Ｎ’－四酢酸（ＥＧＴＡ）としたこと以外は実施例４と同様にして銅で被覆された黒鉛材料を得た。得られためっき膜のクロスカット試験結果は０／２５、分類は１であった。
（実施例９）
　キレート剤をトリエチレンテトラミン六酢酸（ＴＴＨＡ）としたこと以外は実施例４と同様にして銅で被覆された黒鉛材料を得た。得られためっき膜のクロスカット試験結果は０／２５、分類は０であった。
Figure JPOXMLDOC01-appb-C000005
(Example 6)
A graphite 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 was washed with water CIP-A, was immersed in the pretreatment solution PdCl 2 as the SnCl 2 and activator as a sensitizer is added, copper sulfate as the source of copper ions, EDTA as a complexing agent Used and reduced with formaldehyde. The substrate surface was coated with copper having a uniform thickness of 2 μm. The resulting plated film had a crosscut test result of 0/25 and a classification of 1.
(Example 7)
A graphite material coated with copper was obtained in the same manner as in Example 4 except that the chelating agent was diethylenetriaminepentaacetic acid (DTPA). The resulting plated film had a crosscut test result of 0/25 and a classification of 0.
(Example 8)
Coated with copper in the same manner as in Example 4 except that the chelating agent was O, O′-bis (2-aminoethyl) ethylene glycol-N, N, N ′, N′-tetraacetic acid (EGTA). A graphite material was obtained. The resulting plated film had a crosscut test result of 0/25 and a classification of 1.
Example 9
A graphite material coated with copper was obtained in the same manner as in Example 4 except that the chelating agent was triethylenetetramine hexaacetic acid (TTHA). The resulting plated film had a crosscut test result of 0/25 and a classification of 0.
　（比較例１）
　ＣＩＰ－Ａを１．０Ｍの硝酸水溶液に室温で１時間浸漬させた後、水洗・乾燥した。次に、１質量％のＣＰ－Ａを含むメタノール溶液に１時間浸漬させ、アミノプロピル基を導入した。ＣＰ－Ａが表面に導入された黒鉛材料に対して電解銅めっきを行い、厚さ８μｍの銅めっき膜で被覆された黒鉛材料を得た。めっき膜にむらはなく、めっき膜は、均質な膜質を有していた。得られためっき膜のクロスカット試験結果は１／２５、分類は３であった。 (Comparative Example 1)
CIP-A was immersed in a 1.0 M nitric acid aqueous solution at room temperature for 1 hour, 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 aminopropyl groups. Electrolytic copper plating was performed on the graphite material having CP-A introduced on the surface to obtain a graphite material coated with a copper plating film having a thickness of 8 μm. There was no unevenness in the plating film, and the plating film had a homogeneous film quality. The resulting plated film had a crosscut test result of 1/25 and a classification of 3.
　（比較例２）
　ＣＩＰ－Ａを１．０Ｍの硝酸水溶液に室温で１時間浸漬させた後、水洗・乾燥した。次に、１質量％のＣＰ－Ｂを含むメタノール溶液に１時間浸漬させ、アミノプロピル基を導入した。ＣＰ－Ｂが表面に導入された黒鉛材料に対して電解銅めっきを行い、銅めっき膜で被覆された黒鉛材料を得た。めっき膜にむらはなく、めっき膜は、均質な膜質を有していた。得られためっき膜のクロスカット試験結果は２／２５、分類は３であった。 (Comparative Example 2)
CIP-A was immersed in a 1.0 M nitric acid aqueous solution at room temperature for 1 hour, 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 aminopropyl groups. Electrolytic copper plating was performed on the graphite material with CP-B introduced on the surface to obtain a graphite material coated with a copper plating film. There was no unevenness in the plating film, and the plating film had a homogeneous film quality. The resulting plated film had a crosscut test result of 2/25 and a classification of 3.
　（比較例３）
　ＣＰ－ＡをＣＰ－Ｃとしたこと以外は実施例５と同様にしてＣＰ－Ｃが表面に導入された黒鉛材料に対して電解銅めっきを行い、銅めっき膜で被覆された黒鉛材料を得た。めっき膜にむらはなく、めっき膜は、均質な膜質を有していた。得られためっき膜のクロスカット試験結果は２／２５、分類は３であった。
（比較例４）
　ＣＩＰ－Ａを０．５Ｍの硝酸水溶液に室温で１時間浸漬させた後、水洗・乾燥してから電解銅めっきを行い、厚さ８μｍの銅めっき膜で被覆された黒鉛材料を得た。得られためっき膜には、部分的なはがれが観察され、めっき膜は、均質な膜質を有していなかった。めっき膜のクロスカット試験結果は１１／２５、分類は３であった。
（比較例５）
　ＣＩＰ－Ａに対して表面処理を行わず、等方性黒鉛材料に対して厚さ８μｍの電解銅めっきを行った。得られためっき膜には、部分的なはがれが観察され、めっき膜は、均質な膜質を有していなかった。めっき膜のクロスカット試験結果は７／２５、分類は４であった。
（比較例６）
　ＣＩＰ－Ａに対して表面処理を行わず、実施例５と同様に無電解銅めっきを行った。めっき膜のクロスカット試験結果は１０／２５、分類は５であった。 (Comparative Example 3)
Except that CP-A was changed to CP-C, electrolytic copper plating was performed on the graphite material on which CP-C was introduced in the same manner as in Example 5 to obtain a graphite material coated with a copper plating film. It was. There was no unevenness in the plating film, and the plating film had a homogeneous film quality. The resulting plated film had a crosscut test result of 2/25 and a classification of 3.
(Comparative Example 4)
CIP-A was immersed in a 0.5 M nitric acid aqueous solution at room temperature for 1 hour, washed with water and dried, and then subjected to electrolytic copper plating to obtain a graphite material coated with a copper plating film having a thickness of 8 μm. Partial peeling was observed in the obtained plated film, and the plated film did not have a homogeneous film quality. The crosscut test result of the plating film was 11/25, and the classification was 3.
(Comparative Example 5)
Surface treatment was not performed on CIP-A, and electrolytic copper plating with a thickness of 8 μm was performed on the isotropic graphite material. Partial peeling was observed in the obtained plated film, and the plated film did not have a homogeneous film quality. The crosscut test result of the plating film was 7/25, and the classification was 4.
(Comparative Example 6)
The surface treatment was not performed on CIP-A, and electroless copper plating was performed in the same manner as in Example 5. The crosscut test result of the plating film was 10/25, and the classification was 5.
　（比較例７）
　ＣＩＰ－Ｂに対して表面処理を行わず、比較例２と同様に無電解銅めっきを行った。めっき膜のクロスカット試験結果は１２／２５、分類は５であった。 (Comparative Example 7)
The surface treatment was not performed on CIP-B, and electroless copper plating was performed in the same manner as in Comparative Example 2. The crosscut test result of the plating film was 12/25, and the classification was 5.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
１　　：めっき物
１０　：被めっき部材
１０ａ：被めっき部材の表面
１１　：めっき膜 1: Plated object 10: Plated member 10a: Surface of the member to be plated 11: Plated film

Claims (11)

  1. 　シランカップリング剤を被めっき部材の表面に化学的に結合させる工程と、
    　めっき膜を構成する金属イオンとキレート錯体を形成可能な多官能化合物の複数の官能基の少なくとも一つをシランカップリング剤に化学的に結合させる工程と、
    　を含む、めっき前処理方法。     Chemically bonding the silane coupling agent to the surface of the member to be plated;
    Chemically bonding at least one of a plurality of functional groups of a polyfunctional compound capable of forming a chelate complex with a metal ion constituting the plating film to a silane coupling agent;
    Including a plating pretreatment method.
  2. 　前記多官能化合物が、カルボキシル基を複数有する、請求項１に記載のめっき前処理方法。 The plating pretreatment method according to claim 1, wherein the polyfunctional compound has a plurality of carboxyl groups.
  3. 　前記多官能化合物が、めっき膜を構成する金属イオンと結合し得る官能基を３つ以上有する、請求項１または２に記載のめっき前処理方法。 The plating pretreatment method according to claim 1 or 2, wherein the polyfunctional compound has three or more functional groups capable of binding to metal ions constituting the plating film.
  4. 　前記多官能化合物が、エチレンジアミン四酢酸、エチレンジアミン－Ｎ，Ｎ’－二酢酸、エチレンジアミン－Ｎ，Ｎ’－二酢酸－Ｎ，Ｎ’－ジプロピオン酸水和物、ヒドロキシエチルエチレンジアミン三酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラミン六酢酸、ジエチレントリアミン五酢酸、ニトリロ三酢酸、ヒドロキシエチルイミノ二酢酸、Ｌ－アスパラギン酸－Ｎ－Ｎ－二酢酸、ヒドロキシイミノジコハク酸、ｔｒａｎｓ－１，２－ジアミノシクロヘキサン－Ｎ，Ｎ，Ｎ’，Ｎ’－四酢酸一水和物、Ｏ，Ｏ’－ビス（２－アミノエチル）エチレングリコール－Ｎ，Ｎ，Ｎ’，Ｎ’－四酢酸からなる群から選ばれた少なくとも１種である、請求項１～３のいずれか一項に記載のめっき前処理方法。 The polyfunctional compound is ethylenediaminetetraacetic acid, ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N′-diacetic acid-N, N′-dipropionic acid hydrate, hydroxyethylethylenediaminetriacetic acid, diethylenetriamine penta Acetic acid, triethylenetetramine hexaacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, L-aspartic acid-NN-diacetic acid, hydroxyiminodisuccinic acid, trans-1,2-diaminocyclohexane-N , N, N ′, N′-tetraacetic acid monohydrate, O, O′-bis (2-aminoethyl) ethylene glycol-N, N, N ′, N′-tetraacetic acid The plating pretreatment method according to any one of claims 1 to 3, wherein the plating pretreatment method is at least one kind.
  5. 　前記シランカップリング剤として、鎖中及び末端の少なくとも一方に第一級アミノ基、エポキシ基及びイソシアネート基からなる群から選択された少なくとも１つの官能基を有するシランカップリング剤を用いる、請求項１～４のいずれか一項に記載のめっきの前処理方法。 The silane 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 the chain and at the end is used as the silane coupling agent. 5. The pretreatment method for plating according to any one of items 1 to 4.
  6. 　前記被めっき部材として、ヒドロキシル基が導入可能な無機部材を用いる、請求項１～５のいずれか一項に記載のめっき前処理方法。 The plating pretreatment method according to any one of claims 1 to 5, wherein an inorganic member capable of introducing a hydroxyl group is used as the member to be plated.
  7. 　前記被めっき部材として、炭素材料、窒化アルミ材料または窒化ケイ素材料を用いる、請求項６に記載のめっき前処理方法。 The plating pretreatment method according to claim 6, wherein a carbon material, an aluminum nitride material, or a silicon nitride material is used as the member to be plated.
  8. 　請求項１～７のいずれか一項に記載のめっき前処理方法を行う前処理工程と、
    　前記前処理工程を行った前記被めっき部材の表面にめっきを施すことによりめっき膜を形成するめっき工程と、
    　を備える、めっき方法。     A pretreatment step of performing the plating pretreatment method according to any one of claims 1 to 7;
    A plating step of forming a plating film by plating the surface of the member to be plated that has undergone the pretreatment step;
    A plating method comprising:
  9. 　前記前処理工程において前記被めっき部材の表面を酸化する工程を行う、請求項８に記載のめっき方法。 The plating method according to claim 8, wherein a step of oxidizing the surface of the member to be plated is performed in the pretreatment step.
  10. 　被めっき部材と、
    　被めっき部材の表面に化学的に結合したシランカップリング剤と、
    　複数の官能基の少なくとも一つが前記シランカップリング剤と結合した、めっき膜を構成する金属イオンとキレート錯体を形成可能な多官能化合物と、
    　を備える、めっき前処理物。     A member to be plated;
    A silane coupling agent chemically bonded to the surface of the member to be plated;
    A polyfunctional compound capable of forming a chelate complex with a metal ion constituting the plating film, wherein at least one of a plurality of functional groups is bonded to the silane coupling agent;
    A pre-plated product.
  11. 　被めっき部材と、
    　被めっき部材の表面に化学的に結合したシランカップリング剤と、
    　複数の官能基の少なくとも一つが前記シランカップリング剤と結合した、めっき膜を構成する金属イオンとキレート錯体を形成可能な多官能化合物と、
    　前記多官能器化合物の前記シランカップリング剤と結合していない複数の官能基と結合しているめっき膜と、
    　を備える、めっき物。     A member to be plated;
    A silane coupling agent chemically bonded to the surface of the member to be plated;
    A polyfunctional compound capable of forming a chelate complex with a metal ion constituting the plating film, wherein at least one of a plurality of functional groups is bonded to the silane coupling agent;
    A plating film bonded to a plurality of functional groups that are not bonded to the silane coupling agent of the multifunctional compound;
    A plated product.
PCT/JP2018/003725 2017-02-13 2018-02-05 Pretreatment method for plating, plating method, article pretreated for plating, and plated article WO2018147205A1 (en)

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