JP2006256031A - Substrate for electroless plating, electroless-plated substrate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate for electroless plating having a metal film uniform in a nano-level by highly smoothing the surface of the substrate modified by organic matter, uniformly dispersing the adsorption sites of plating nuclei and enhancing the chemical stability of the substrate with respect to a plating bath, and an electroless-plated substrate due to electroless plating. <P>SOLUTION: The electroless-plated substrate is constituted by coating the substrate with at least one monomolecular film of a random copolymer containing a hydrophobic repeating unit 1 and a repeating unit 2 containing a functional group having an adsorbing function of metal nanoparticles and electroless-plating the coated substrate using the metal nanoparticles, which are adsorbed on functional group having the adsorbing function of the metal nanoparticles, as plating nuclei. The manufacturing method of the electroless-plated substrate is also disclosed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electroless plating substrate, an electroless plated substrate, and a method for manufacturing the same.

  In the case of a printed wiring board in which fine wiring is formed on a substrate, it is indispensable to form via holes that conduct both surfaces of the printed wiring board. Therefore, such a printed wiring board is usually subjected to circuit formation through a laser via hole forming process, a desmear process, a catalyst application process, an electroless copper plating process, and the like. Furthermore, circuit formation may be performed by a subtractive method using etching, or may be performed by a semi-additive method or an additive method. Therefore, in the printed wiring board on which the fine wiring as described above is formed, the adhesion between the wiring circuit and the polymer film needs to withstand these processes.

  Several methods have been studied as an attempt to improve the adhesive force between a metal thin film formed by a dry method such as sputtering or vapor deposition and a polyimide resin [for example, JP 2002-113812 A (Patent Document 1)]. . On the other hand, as a method for realizing strong adhesion between the metal foil and the polyimide resin, a method in which the surface of the copper metal foil is surface-treated in advance has been reported [for example, JP 2002-208768 A (Patent Document 2). ]]. In Non-Patent Document 1, for example, after the copper foil surface is sequentially treated with a polybenzimidazole solution and a 4-aminophenyl disulfide solution, a film of polyamic acid that is a precursor of a polyimide resin is formed, and this is heated. It is disclosed that strong adhesion can be realized between copper foil and polyimide resin by using polyimide resin.

  On the other hand, as a wet process used for a printed wiring board, that is, as a method of directly forming an electroless plating film on a resin material, a method of forming electroless plating on a roughened surface of an epoxy resin surface is disclosed. [For example, JP 2000-198907 A (Patent Document 3)]. Further, as a method of forming an electroless plating film on a polyimide resin, a method of treating with a solution containing an organic disulfide compound having a primary amino group and / or an organic thiol compound having a primary amino group in a solution containing caustic alkali Is disclosed.

In the field of electronic devices typified by VLSI obtained by integrating and forming a large number of thin films, the thickness of the constituent thin films has become extremely small with the miniaturization of integrated circuit devices. In the field of fine wiring technology using an electroless plating method, the importance of forming a microcircuit composed of a nano-level ultrathin film is increasing. However, when an electroless plating film is formed on the surface of the substrate, a film thickness that can ignore the influence of the roughening layer (scratch layer) is required. The scratch layer is an important layer for improving the adhesion at the interface between the plating film and the base material. However, when a nano-level metal thin film is formed, the scratch layer peaks and valleys on the order of several microns are formed. There are problems such as hindering conduction of the metal nano thin film. Therefore, in order to form a uniform metal thin film on the surface of various substrates while having a function as a scratch layer and having a nano-level film thickness, a high flattening process on the surface of the scratch layer is important. .
However, in the conventional method, since there is no suitable method for the high planarization treatment at the nano level, it has been difficult to obtain a uniform metal film at the nano level.

On the other hand, a liquid crystal alignment film in which a monomolecular film of an organic polymer containing a group having active hydrogen is formed on a glass substrate has been known [for example, Japanese Patent Application Laid-Open No. 2004-101782 (Patent Document 4)]. However, it has never been known to plate metal on the glass substrate having such a configuration.
JP 2002-113812 A JP 2002-208768 A Japanese Patent Laid-Open No. 2000-198907 JP 2004-101782 A K. Arisumi, F. Feng, T. Miyashita, and H. Ninomiya, Langmuir, 14, 5555 (1998)

The present invention, for example, as a high planarization treatment on various substrates, after forming an organic thin film containing a functional group capable of adsorbing metal nanoparticles whose film thickness is controlled at the nano level, An object of the present invention is to obtain a metal thin film that is highly smoothed on various substrates by adsorbing the resulting metal nanoparticles and further performing electroless plating using this as a core.
Another object of the present invention is, for example, to form a nano-order metal thin film on various substrates and to arbitrarily control the film thickness of the thin film.
Furthermore, the present invention provides, for example, an electroless plating substrate having a uniform metal film at the nano level, an electroless plated substrate, etc. by uniformly dispersing the adsorption sites of the plating nuclei on the organic thin film. The purpose is to do.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors relate to a substrate for electroless plating coated with a monomolecular film having a predetermined functional group, a substrate subjected to electroless plating, and the like. The present invention has been completed.

（式中、Ｒ_１は互いに同一または異なってもよく水素原子もしくはメチル基を表し、Ｚ_１は互いに同一または異なってもよく−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、ｎは２〜２０の整数である。）で表される繰り返し単位１と、金属ナノ粒子が吸着する機能を有する機能団を含む下記一般式（２）

（式中、Ｗは活性水素を有する基であり、Ｒ_２は互いに同一または異なってもよく水素原子もしくはメチル基を表し、Ｚ_２は同一または異なってもよく−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、ｍは１〜５の整数である。）で表される繰り返し単位２を含有するランダム共重合体Ａの単分子膜、および、
下記一般式（３）

（式中、Ｒ_３は互いに同一または異なってもよく水素原子もしくはメチル基を表し、Ｚ_３は互いに同一または異なってもよく−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、ｒは２〜２０の整数である。）で表される繰り返し単位３と、金属ナノ粒子が吸着する機能を有する機能団を含む下記一般式（４）

（式中、Ｖは活性水素を有する基であり、Ｒ_４は互いに同一または異なってもよく水素原子もしくはメチル基を表し、Ｚ_４は同一または異なってもよく−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、ｐは１〜５の整数である。）で表される繰り返し単位４と、光もしくは熱によって３次元架橋構造体を形成する機能を有する機能団を含む下記一般式（５）

（式中、Ｘは−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、Ｒ_５は互いに同一または異なってもよく水素原子もしくはメチル基を表し、Ｒ_６は水素、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基もしくは炭素数２〜２０のアルキニル基であり、Ｚ₅は互いに同一または異なってもよく−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、ｑは１〜５の整数である。）で表される繰り返し単位５とを含有するランダム共重合体Ｂの単分子膜からなる群から選択される１種以上の単分子膜であることができる。
上記一般式、（１）〜（５）において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ_４およびＲ_５は、水素原子を表し、Ｒ₆は互いに同一または異なってもよくメチル基または水素原子であり、Ｚ₁、Ｚ₂、Ｚ₃、Ｚ₄およびＺ₅が共に−ＮＨ−であり、Ｗがアミノ基であり、ｍおよびｑが２であり、ｎおよびｒが８〜１４であることが好ましい。 The first aspect of the present invention is a substrate for electroless plating coated with one or more monomolecular films of a copolymer containing a functional group having a function of adsorbing metal nanoparticles. This monomolecular film has the following general formula (1)

(In the formula, R ₁ may be the same or different from each other, and represents a hydrogen atom or a methyl group; Z ₁ may be the same or different from each other; —NH—, —O— or —S—; The following general formula (2), which includes a repeating unit 1 represented by the following formula (2) and a functional group having a function of adsorbing metal nanoparticles:

Wherein W is a group having active hydrogen, R ₂ may be the same or different from each other and represents a hydrogen atom or a methyl group, Z ₂ may be the same or different, —NH—, —O— or — A monomolecular film of random copolymer A containing repeating unit 2 represented by S-, m is an integer of 1 to 5, and
The following general formula (3)

(In the formula, R ₃ may be the same or different from each other and represents a hydrogen atom or a methyl group; Z ₃ may be the same or different from each other; —NH—, —O— or —S—; The following general formula (4) including a repeating unit 3 represented by the formula (4) and a functional group having a function of adsorbing metal nanoparticles:

(In the formula, V is a group having active hydrogen, R ₄ may be the same or different from each other and represents a hydrogen atom or a methyl group, and Z ₄ may be the same or different, —NH—, —O— or — S-, p is an integer of 1 to 5), and a functional group having the function of forming a three-dimensional crosslinked structure by light or heat, and the following general formula (5)

(In the formula, X is —NH—, —O— or —S—, R ₅ may be the same or different from each other, and represents a hydrogen atom or a methyl group; R ₆ is hydrogen, alkyl having 1 to 20 carbon atoms; A alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, Z ₅ may be the same or different from each other, and is —NH—, —O— or —S—, and q is 1 to It is an integer of 5. It can be 1 or more types of monomolecular films selected from the group consisting of monomolecular films of random copolymer B containing repeating unit 5 represented by:
In the general formulas (1) to (5), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom, and R ₆ may be the same or different from each other, and may be a methyl group or a hydrogen atom. Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ are all —NH—, W is an amino group, m and q are 2, and n and r are 8 to 14. preferable.

  Moreover, it is preferable that the monomolecular film of the random copolymer B including a functional group having a function of forming a three-dimensional crosslinked structure by light or heat is a film irradiated with ultraviolet rays. The monomolecular film is preferably a Langmuir-Blodgett film. Moreover, it is preferable that the surface of the board | substrate with which a monomolecular film is coat | covered is glass, a silicon wafer, or a plastic.

  The random copolymer A preferably has a weight average molecular weight of 8,000 to 50,000, and the random copolymer B preferably has a weight average molecular weight of 8,000 to 50,000. In the method for producing an electroless plating substrate, the monomolecular film is preferably coated with one or more layers. Moreover, it is preferable that a monomolecular film is produced by the Langmuir-Blodgett method. The surface of the substrate on which the monomolecular film is coated is preferably glass, a silicon wafer or plastic. Moreover, the process of irradiating the monomolecular film of the random copolymer B containing the functional group having the function of forming a three-dimensional crosslinked structure by light or heat may be included.

The second aspect of the present invention is a plating substrate obtained by electrolessly plating the electroless plating substrate of the first aspect using metal nanoparticles adsorbed on a functional group having a function of adsorbing metal nanoparticles as a plating nucleus. .
In this plated substrate, the plating nucleus is preferably gold nanoparticles and copper is preferably plated.

（式中、Ｒ_１は互いに同一または異なってもよく水素原子もしくはメチル基を表し、Ｚ_１は互いに同一または異なってもよく−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、ｎは２〜２０の整数である。）で表される繰り返し単位１と、金属ナノ粒子が吸着する機能を有する機能団を含む下記一般式（２）

（式中、Ｗは活性水素を有する基であり、Ｒ_２は互いに同一または異なってもよく水素原子もしくはメチル基を表し、Ｚ_２は同一または異なってもよく−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、ｍは１〜５の整数である。）で表される繰り返し単位２を含有するランダム共重合体Ａの単分子膜、および、
下記一般式（３）

（式中、Ｒ_３は互いに同一または異なってもよく水素原子もしくはメチル基を表し、Ｚ_３は互いに同一または異なってもよく−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、ｒは２〜２０の整数である。）で表される繰り返し単位３と、金属ナノ粒子が吸着する機能を有する機能団を含む下記一般式（４）

（式中、Ｖは活性水素を有する基であり、Ｒ_４は互いに同一または異なってもよく水素原子もしくはメチル基を表し、Ｚ_４は同一または異なってもよく−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、ｐは１〜５の整数である。）で表される繰り返し単位４と、光もしくは熱によって３次元架橋構造体を形成する機能を有する機能団を含む下記一般式（５）

（式中、Ｘは−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、Ｒ_５は互いに同一または異なってもよく水素原子もしくはメチル基を表し、Ｒ_６は水素、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基もしくは炭素数２〜２０のアルキニル基であり、Ｚ₅は互いに同一または異なってもよく−ＮＨ−、−Ｏ−もしくは−Ｓ−であり、ｑは１〜５の整数である。）で表される繰り返し単位５とを含有するランダム共重合体Ｂの単分子膜からなる群から選択される１種以上の単分子膜であることができる。
上記一般式、（１）〜（５）において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ_４およびＲ_５は、水素原子を表し、Ｒ₆は互いに同一または異なってもよくメチル基または水素原子であり、Ｚ₁、Ｚ₂、Ｚ₃、Ｚ₄およびＺ₅が共に−ＮＨ−であり、Ｗがアミノ基であり、ｍおよびｑが２であり、ｎおよびｒが８〜１４であることが好ましい。
また、光もしくは熱によって３次元架橋構造体を形成する機能を有する機能団を含むランダム共重合体Ｂの単分子膜に紫外線を照射する工程を含むことが好ましい。単分子膜を２層以上被覆することが好ましい。単分子膜がラングミュア・ブロジェット法によって作成されることが好ましい。単分子膜が被覆される基板の表面がガラス、シリコンウェーハまたはプラスチックであることが好ましい。 A third aspect of the present invention is a method for producing a substrate for electroless plating, including a step of coating a monomolecular film of a copolymer containing a functional group having a function of adsorbing metal nanoparticles. This monomolecular film has the following general formula (1)

(In the formula, R ₁ may be the same or different from each other, and represents a hydrogen atom or a methyl group; Z ₁ may be the same or different from each other; —NH—, —O— or —S—; The following general formula (2), which includes a repeating unit 1 represented by the following formula (2) and a functional group having a function of adsorbing metal nanoparticles:

Wherein W is a group having active hydrogen, R ₂ may be the same or different from each other and represents a hydrogen atom or a methyl group, Z ₂ may be the same or different, —NH—, —O— or — A monomolecular film of random copolymer A containing repeating unit 2 represented by S-, m is an integer of 1 to 5, and
The following general formula (3)

(In the formula, R ₃ may be the same or different from each other and represents a hydrogen atom or a methyl group; Z ₃ may be the same or different from each other; —NH—, —O— or —S—; The following general formula (4) including a repeating unit 3 represented by the formula (4) and a functional group having a function of adsorbing metal nanoparticles:

(In the formula, V is a group having active hydrogen, R ₄ may be the same or different from each other and represents a hydrogen atom or a methyl group, and Z ₄ may be the same or different, —NH—, —O— or — S-, p is an integer of 1 to 5), and a functional group having the function of forming a three-dimensional crosslinked structure by light or heat, and the following general formula (5)

(In the formula, X is —NH—, —O— or —S—, R ₅ may be the same or different from each other, and represents a hydrogen atom or a methyl group; R ₆ is hydrogen, alkyl having 1 to 20 carbon atoms; A alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, Z ₅ may be the same or different from each other, and is —NH—, —O— or —S—, and q is 1 to It is an integer of 5. It can be 1 or more types of monomolecular films selected from the group consisting of monomolecular films of random copolymer B containing repeating unit 5 represented by:
In the general formulas (1) to (5), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom, and R ₆ may be the same or different from each other, and may be a methyl group or a hydrogen atom. Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ are all —NH—, W is an amino group, m and q are 2, and n and r are 8 to 14. preferable.
Moreover, it is preferable to include a step of irradiating the monomolecular film of the random copolymer B containing a functional group having a function of forming a three-dimensional crosslinked structure by light or heat with ultraviolet rays. It is preferable to coat two or more monomolecular films. It is preferable that the monomolecular film is produced by the Langmuir-Blodgett method. The surface of the substrate on which the monomolecular film is coated is preferably glass, a silicon wafer or plastic.

  The random copolymer A preferably has a weight average molecular weight of 8,000 to 20,000, and the random copolymer B preferably has a weight average molecular weight of 8,000 to 50,000. In the method for producing an electroless plating substrate, the monomolecular film is preferably coated with one or more layers. Moreover, it is preferable that a monomolecular film is produced by the Langmuir-Blodgett method. The surface of the substrate on which the monomolecular film is coated is preferably a silicon wafer or plastic. Moreover, the process of irradiating the monomolecular film of the random copolymer B containing the functional group having the function of forming a three-dimensional crosslinked structure by light or heat may be included.

A fourth aspect of the present invention is a method for producing a plated substrate, comprising a step of adsorbing metal nanoparticles to a functional group and a step of electrolessly plating a metal on the plating substrate produced in the third aspect. .
Moreover, it is preferable that the process of electrolessly plating a metal is performed by electroless copper plating using gold nanoparticles adsorbed on a functional group having a function of adsorbing metal nanoparticles as a plating nucleus.
The fourth aspect of the present invention includes a step of coating a plurality of monomolecular films of random copolymer B, and irradiating the monomolecular film with ultraviolet rays, and then coating the monomolecular film of random copolymer A. It is a method for producing a plated substrate including a step of adsorbing gold nanoparticles to a functional group and a step of plating copper by electroless copper plating using the gold nanoparticles as a plating nucleus.

  In the present specification, examples of the “group having active hydrogen” include an amino group, a carboxyl group, a sulfonic acid group, a hydroxy group, a hydroxyphenyl group, an amide group, a hydrazino group, a hydrazinocarbonyl group, and a mercapto group.

In the present specification, the “C ₁ -C ₂₀ alkyl group” is a linear or branched alkyl group. Preferably _"C 1 _{-C 20} alkyl group" is a _C 1 _{-C 10} alkyl _group, more preferably a C 1 -C ₆ alkyl group. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, dodecanyl, etc., with methyl being most preferred .
In the present specification, the “C ₂ -C ₂₀ alkenyl group” is a linear or branched alkenyl group. _"C 2 _{-C 20} alkenyl group" _is preferably C 2 _{-C 10} alkenyl _group, more preferably a C 2 -C ₆ alkenyl group. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylallyl, 2-butenyl and the like.
In the present specification, the “C ₂ -C ₂₀ alkynyl group” is a linear or branched alkenyl group. "C ₂ -C ₂₀ alkynyl group" _is preferably C 2 _{-C 10} alkynyl _group, more preferably a C 2 -C ₆ alkynyl group. Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, butynyl, and the like.

According to the preferred embodiment of the present invention, the plating substrate, the plating substrate, and the manufacturing method thereof can adsorb metal nanoparticles whose film thickness is controlled at the nano level as a high planarization treatment on various substrates, for example. Highly smoothed metal on various substrates by forming organic thin films containing possible functional groups, adsorbing metal nanoparticles as plating nuclei, and performing electroless plating using them as cores A thin film can be obtained.
According to the preferred embodiment of the present invention, the plating substrate, the plating substrate, and the manufacturing method thereof, for example, can form a nano-order metal thin film on various substrates, and can arbitrarily control the film thickness of the thin film. it can.
According to the preferred embodiment of the present invention, the plating substrate and the plating substrate, and their manufacturing method, for example, uniformly disperse the adsorption sites of the plating nuclei on the organic thin film, thereby forming a nano-level uniform metal film. Electrolytic plating substrates, electroless plated substrates and the like can be obtained.

1. Random Copolymer Containing Functional Group Having Function for Adsorbing Metal Nanoparticles Random copolymer containing a functional group having a function for adsorbing metal nanoparticles of the present invention includes the above general formula (1) and the above general formula ( 2) is a random copolymer of repeating units (hereinafter, also referred to as “random copolymer A”).

The random copolymer A is a copolymer having two different repeating units. The side chain of the repeating unit 1 represented by the general formula (1) is a structural unit exhibiting hydrophobicity, and the side chain of the repeating unit 2 represented by the general formula (2) is a structural unit exhibiting hydrophilicity. Therefore, in the random copolymer A, the hydrophobicity of the random copolymer A increases as the proportion of the repeating unit 1 increases, and the hydrophilicity increases as the proportion of the repeating unit 2 increases.
Moreover, the repeating unit 2 of the random copolymer A has a functional group having a function of adsorbing metal nanoparticles. For example, when an amino group is provided at the end of the repeating unit 2, the amino group strongly adsorbs the metal nanoparticles.
In the random copolymer A, the preferred proportion of both structural units is such that the number of moles a of the repeating unit 1 and the number of moles b of the repeating unit 2 are both in the range of 100b / (a + b) from 0.01 to 99.99. More preferably, it is 0.03-50, More preferably, it is 1-25.

  If the molecular weight of the random copolymer A is too small or too large, it becomes difficult to form an LB film described later. Therefore, when expressed in terms of weight average molecular weight, the range of 8,000 to 20,000 is preferable, and more preferably 10,000 to 100,000.

The random copolymer A is obtained, for example, by introducing a group having active hydrogen into a copolymer pDDA-SuOA obtained by copolymerization of N-dodecylacrylamide (DDA) and N-acryloxysuccinimide (SuOA).
Specifically, using a known method described in “K. Arisumi, F. Feng, T. Miyashita, and H. Ninomiya, Langmuir, 14, 5555 (1998)” (Non-Patent Document 1) and the like. N-dodecylacrylamide (DDA) and N-acryloxysuccinimide (SuOA) are synthesized, DDA and SuOA thus synthesized are dissolved in purified toluene, and a predetermined amount of a polymerization initiator is added to the solution. Thereafter, oxygen is removed from the reaction system and polymerization is performed to obtain a copolymer pDDA-SuOA. The obtained pDDA-SuOA can be dissolved in chloroform and dropped into an (ethylenedioxy) bis (ethylamine) DADOO / chloroform solution having a predetermined concentration to obtain a random copolymer A.

2. Copolymer containing a functional group having a function of forming a three-dimensional cross-linked structure by light or heat A random copolymer containing a functional group having a function of forming a three-dimensional cross-linked structure by light or heat of the present invention, It is a random copolymer of repeating units represented by the above general formula (3), the above general formula (4) and the above general formula (5) (hereinafter also referred to as “random copolymer B”).
Examples of the functional group having a function of forming a three-dimensional crosslinked structure include (meth) acryl group, glycidyl group, oxetanyl group, amino group, hydroxyl group, carboxyl group and the like.
In the present specification, “(meth) acrylic group” is used as a general term for methacrylic group and acrylic group.

The random copolymer B includes the repeating unit 3 represented by the general formula (3) and the repeating unit 5 represented by the general formula (5), and optionally includes the repeating unit 4 represented by the general formula (4). It is a copolymer containing. Among the three repeating units, the repeating unit 3 is a structural unit exhibiting hydrophobicity, and the repeating unit 4 is a structural unit including a functional group having hydrophilicity and a function of adsorbing metal nanoparticles. The repeating unit 5 is a structural unit having a functional group having a function of forming a three-dimensional crosslinked structure by light or heat.
Therefore, when the proportion of the repeating unit 3 of the random copolymer B increases, the copolymer has a strong hydrophobic property, and when the proportion of the repeating unit 4 increases, the hydrophilic property appears strongly.
The repeating unit 4 of the random copolymer B has a functional group having a function of adsorbing metal nanoparticles. For example, when an amino group is provided at the terminal of the repeating unit 4, the amino group highly adsorbs the metal nanoparticles.
The repeating unit 5 of the random copolymer B has a functional group having a function of forming a three-dimensional crosslinked structure by light or heat. Specifically, the terminal (meth) acryl group of the repeating unit 5 is A radical coupling reaction is caused by light or heat to form a three-dimensional crosslinked structure.

  In the random copolymer B, the preferable proportion of both structural units is such that the number of moles c of the repeating unit 3, the number of moles d of the repeating unit 4, and the number of moles e of the repeating unit 5 are both 0.01e to 100e / (c + d + e). The numerical value is in the range of 99.99, more preferably 0.03 to 50, and still more preferably 1 to 25. Moreover, in the random copolymer B, the presence or absence of the repeating unit 4 is arbitrary. That is, d may be 0.

The random copolymer B is obtained by introducing a (meth) acryl group into a part or all of the repeating units 2 of the random copolymer A.
Compared with the repeating unit 2 of the random copolymer A, if there are more compounds having (meth) acrylic groups that react with the random copolymer A, the repeating unit 2 of the random copolymer A has a higher proportion of (meth) acrylic. A group is introduced. If the compound having a (meth) acrylic group that reacts with the random copolymer A is made excessive compared to the repeating unit 2 of the random copolymer A, all of the repeating units 2 of the random copolymer A will have ( ) An acrylic group is introduced.
On the other hand, if the compound having the (meth) acryl group is less than the repeating unit 2 of the random copolymer A, a part of the repeating unit 2 of the random copolymer A is a repeating unit 4 of the random copolymer B. As a result, random copolymer B in which three repeating units of repeating unit 3, repeating unit 4 and repeating unit 5 are randomly copolymerized is obtained.

3-1 Coating of LB film using LB method In the present invention, the substrate on which the monomolecular film of random copolymer A, random copolymer B or both is accumulated is, for example, silicon wafer, gallium arsenide plate, quartz plate Inorganic substrates such as glass plates, ceramic plates, calcium fluoride plates, and organic substrates such as polyamide, polysulfone, polyester, polycarbonate, fluororesin, polyimide, polyethersulfone, acetal resin, polyphenylene sulfide, polyphenylene oxide, etc. Can be mentioned. The substrate for plating is prepared by coating these substrates with one or more layers of the random copolymer A, the random copolymer B, or both.

  Although the substrate can be used by coating the monomolecular film as it is, the substrate surface can be pretreated before the coating of the monomolecular film, if necessary. For example, when a silicon wafer is used as the substrate, it is preferable that the surface of the silicon substrate is used after being pretreated with a silane coupling agent such as dimethyldichlorosilane, hexamethylcisilazane, octyltrichlorosilane, or the like. Silane treatment is classified into hydrophobic treatment and reactive functional group treatment, and can be appropriately selected depending on the material of the substrate and the material of the monomolecular film to be coated thereafter. Moreover, when using a plastic for a board | substrate, it is preferable to perform the pre-processing which wash | cleans with organic solvents, such as chloroform. This cleaning is preferably ultrasonic cleaning.

  One or more monolayers of random copolymer A, random copolymer B, or both are coated on the pretreated substrate to produce a plating substrate. The monomolecular film is coated as follows using the Langmuir-Blodgett method (LB method). In this specification, a monomolecular film formed by using the LB method is also referred to as “Langmuir-Blodget film (LB film)”.

Random copolymer A or random copolymer B is dissolved in an organic solvent, and a required amount of this solution is dropped on the water surface to form a monomolecular film on the water surface.
The organic solvent that dissolves the random copolymer A or the random copolymer B is preferably one that dissolves the polymer and completely evaporates after forming a film on the water surface and does not remain on the film surface. Examples of preferred organic solvents are halogenated hydrocarbons, aromatic compounds, aliphatic hydrocarbons, esters and the like. Specific examples of halogenated hydrocarbons include chloroform. Specific examples of the aromatic compound include toluene. Specific examples of the aliphatic hydrocarbon include hexane. Specific examples of esters include ethyl acetate and the like. Further, halogenated hydrocarbons are preferable from the viewpoint of solvent evaporation rate at the time of forming a monomolecular film, and specifically chloroform is preferable.

  After completely evaporating the organic solvent, this monomolecular film is compressed at a constant speed using a fluororesin-processed member to obtain a monomolecular film in which polymer chains are densely packed on the water surface. . When the random copolymer A or the random copolymer B is spread on the water surface, the main chain of the random copolymer tends to be arranged on the water surface, and the side chain tends to be arranged in a direction perpendicular to the substrate. For example, as shown in FIG. 1, in the random copolymer A, the main chain of the random copolymer is arranged on the water surface, and the side chain of the repeating unit 1 represented by the general formula (1) indicating hydrophobicity Faces in the air, and the side chain of the repeating unit 2 represented by the general formula (2) showing hydrophilicity faces in water.

  While maintaining the surface pressure of the random copolymer developed on the water surface at a predetermined value, the pretreated substrate is lowered from the air to the water at a predetermined speed so that the monomolecular film adheres to the substrate. Raise into the air at a predetermined speed. The LB film is obtained by repeating this and accumulating the monomolecular film on the substrate one by one. At this time, the LB film that adheres only when the substrate is raised may be accumulated, or the LB film that adheres only when the substrate is lowered may be accumulated.

  Whether or not the LB film is formed can be determined by measuring the occupied area per molecule calculated from the film area and the surface pressure. The surface pressure of the film at the time of coating may be a surface pressure in a range where the film forms a solid condensed film in the surface thickness (π) -area (A) curve. However, if the pressure is too high, the membrane-constituting molecules overlap, while if the pressure is too low, it cannot be stably accumulated. In order to form a multi-layered cumulative film by performing good coating a plurality of times, it is preferable to use a surface pressure of 10 to 40 mN / m, preferably 25 to 30 mN / m.

  The concentration of the polymer dissolved in the solvent is preferably 0.0001 to 0.005 mol / L, more preferably 0.01 to 0.02 mol / L. In particular, a polymer concentration of 0.005 mol / L or less is preferable because a good monomolecular film can be obtained without forming a polymer aggregate. On the other hand, if the polymer concentration is 0.0001 mol / L or more, contamination of the water tank can be prevented.

  When the monomolecular film is accumulated and coated, the LB film is accumulated on both sides of the substrate by moving the substrate up and down. By repeating this operation, the accumulated film can have a desired thickness. The thickness is 1-1000 layers, Preferably it is 2-200 layers, More preferably, it is 50-100 layers. In addition, monomolecular films having different compositions may be accumulated and coated.

3-2 Fixing the LB film to the substrate When the LB film is accumulated and coated on the substrate using the LB method, it is preferable that the LB film coated on the substrate is firmly fixed to the substrate.

  Therefore, for example, when the substrate is glass, a pretreatment with a silane coupling agent, an epoxy group is fixed on the glass surface, and the ring-opened epoxy group and the random copolymer A constituting the LB film are repeated. The LB film and the glass substrate can be fixed by bonding the active hydrogen group of the unit 2 or the repeating unit 4 of the random copolymer B. FIG. 2 shows a state in which the LB film of the random copolymer A is fixed to the glass substrate. This group having active hydrogen is also a functional group having a function of adsorbing metal nanoparticles.

  When the substrate is polyimide, the surface of the polyimide substrate ultrasonically cleaned with chloroform is coated with a random copolymer B and irradiated with light such as ultraviolet rays, or a polyimide substrate using a hot plate or the like. By heating the surface to 70 to 90 ° C., the repeating unit 5 of the random copolymer B forms a three-dimensional crosslinked structure, and the LB film of the random copolymer B can be firmly fixed to the polyimide substrate. .

4). An electroless metal film forming step of forming an electroless metal plating film on the substrate coated with the electroless metal plating LB film is performed. As the electroless plating film, an electroless copper plating film, an electroless nickel plating film, and an electroless gold plating film are preferably used, and an electroless copper plating film can be most preferably used. For example, when electroless copper is used as the electroless metal, (1) substrate pretreatment, (2) catalyst support (3) water washing, (4) reduction, (5) water washing, (6) electroless copper An electroless copper plating film can be formed by performing each step of plating and (7) washing in this order.

A monomolecular film of random copolymer A or random copolymer B exists on the surface of the electroless plating substrate of the present invention, in which one or more LB films are coated on the substrate, and these monomolecular films are formed. There are groups having active hydrogen at the terminals of the repeating unit 2 of the random copolymer A and the repeating unit 4 of the random copolymer B. The group having active hydrogen is also a functional group having a function of adsorbing metal nanoparticles. Examples of the functional group include an amino group, a carboxyl group, a sulfonic acid group, a hydroxy group, a hydroxyphenyl group, an amide group, a hydrazino group, a hydrazinocarbonyl group, and a mercapto group, and an amino group is particularly preferable.
The electroless plating substrate having such a configuration is immersed in a metal nanoparticle solution, and the metal nanoparticles (plating nuclei) are adsorbed on the functional group. Among metal nanoparticles, it is preferable to use gold or copper nanoparticles. These nanoparticles are preferably covered with citric acid.

  By immersing the substrate in which the metal nanoparticles (plating nuclei) are dispersed on the surface in the plating bath, the metal dissolved in the plating bath is plated over the substrate using the metal nanoparticles dispersed in the entire substrate as the plating nuclei. . Since the metal nanoparticles adsorbed on the functional group having the function of adsorbing metal nanoparticles are dispersed throughout the substrate, plating using the metal nanoparticles as plating nuclei is uniformly performed on the entire substrate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these.

[Synthesis Example 1] Synthesis of pDDA-DADOO The synthesis of pDDA-DADOO, which is random copolymer A, will be described.

<Synthesis of monomer and polymer>
N-dodecylacrylamide (DDA) monomer was synthesized by reacting N-dodecylamine and acrylic acid chloride in the presence of triethylamine at room temperature for 8 hours using chloroform as a solvent (Scheme 1-1).

Similarly, an N-acryloyloxysuccinimide (SuOA) monomer was synthesized by reacting N-hydroxysuccinimide and acrylic acid chloride in the presence of a chloroform solvent and triethylamine at room temperature for 8 hours (Scheme 1-2).

Next, a predetermined amount of DDA monomer and SuOA monomer were dissolved in purified toluene in a polymerization tube to prepare a solution having a concentration of 0.2 M / L. 0.012 equivalents of 2,2′-azobisisobutyronitrile (AIBN) as an initiator was added to the solution and dissolved. Next, in order to remove oxygen in the reaction system, freeze deaeration was repeated several times, followed by polymerization in a water bath at 60 ° C. for 12 hours. At room temperature, the reaction product was concentrated, and the reaction product was dropped into about 20-fold amount of acetonitrile to precipitate a copolymer pDDA-SuOA (Scheme 1-3). In pDDA-SuOA, two repeating units derived from each monomer are randomly copolymerized. That is, the synthesized pDDA-SuOA is a random copolymer.

<Polymer reaction>
The copolymer pDDA-DADOO having an amino group at the end of the side chain is obtained by polymerizing the copolymer pDDA-SuOA and 2,2 ′-(ethylenedioxy) bis (ethylamine) (DADOO) at room temperature for 48 hours. (Scheme 1-4). In order to prevent the resulting copolymer from gelling, a dilute chloroform solution of the copolymer pDDA-SuOA was slowly added dropwise to the concentrated solution of DADOO. Moreover, about 20 equivalents of DADOO was added to the succinyl group and reacted at room temperature for 2 days. In addition, chloroform was used for the solvent. The copolymer pDDA-DADOO after the reaction was reprecipitated several times with acetonitrile to remove excess DADOO. The two repeating units constituting pDDA-DADOO are randomly copolymerized random copolymers.

  When the composition ratio of the obtained copolymer pDDA-DADOO was determined by NMR, the content of DADOO was 12%. Further, from the molecular weight measurement by gel permeation chromatography (GPC), the number average molecular weight was 30,000 and the molecular weight distribution (Mw / Mn) was about 1.5.

[Synthesis Example 2] Synthesis of pDDA-DADOO-M The synthesis of random copolymer B, pDDA-DADOO-M, will be described.

The pDDA-DADOO synthesized in Synthesis Example 1 was dissolved in CHCl ₃ to prepare a 0.1M pDDA-DADOO solution. This 0.1M pDDA-DADOO solution was added dropwise to 5M 2-methacryloyloxyethyl isocyanate (MOI, approximately 20 times equivalent of amino group) in CHCl ₃ and stirred overnight at room temperature. Thereafter, the solution was removed under reduced pressure at room temperature, and reprecipitation was performed twice with acetonitrile to recover pDDA-DADOO-M (Scheme 2). When the obtained copolymer pDDA-DADOO-M was examined by NMR, all DADOO had reacted. Therefore, a methacryl group was introduced into all the repeating units having an amino group contained in pDDA-DADOO.

Example 1 Copper Plated Substrate Using Glass Substrate An epoxy silane (GTS) solution (80 ° C.), which is a silane coupling agent dissolved in toluene, is applied to glass substrate 7 for pretreatment, and the surface of the substrate Was provided with an epoxy group. Next, the pDDA-DADOO (the number of moles of hydrophobic repeating units and the number of moles of hydrophilic repeating units having an amino group is determined by synthesizing the glass substrate 7 using the LB method. 8: 2), a multilayer accumulation 5 (one layer) of monomolecular films was provided, and a plating substrate was prepared.

Gold nanoparticles (having a diameter of about 30 nm) 3 covered with citric acid were electrostatically adsorbed to the amino group of pDDA-DADOO on this plating substrate. Thereafter, this substrate is immersed in a plating bath (70 ° C.) having the following composition for 40 seconds to perform electroless copper plating, copper plating 4 using gold nanoparticles as a plating nucleus is applied, and copper using a glass substrate 7 is used. A plated substrate 70 was produced (FIG. 3).
(Composition of plating bath)
CuSO ₄ ; 6 g / L (0.038 M)
(CH ₂ O) n: 3 g / L (0.10 M)
KOH: 27 g / L (0.48M)
EDTA: 15g / L (0.051M)

  The plating thickness of the obtained copper plating substrate was about 120 nm. The volume resistivity of the copper plating film on the substrate was about 2.87 (μΩ · cm).

[Examples 2 to 5] Copper plated substrate using polyimide substrate The surface of the polyimide substrate 8 was subjected to ultrasonic cleaning in chloroform and pretreated. Next, pDDA-DADOO-M synthesized in Synthesis Example 2 using the LB method on the polyimide substrate 8 (the ratio of the number of moles of hydrophobic repeating units to the number of moles of repeating units having a methacryl group is 78:22) Multilayer accumulation of monomolecular film 5 [24 layers (Example 2), 50 layers (Example 3), 74 layers (Example 4), 100 layers (Example 5)] is provided for plating. A substrate was produced.

Subsequently, this substrate was irradiated with deep UV (70 mW / cm ² , 20 minutes), and a pDDA-DADOO two-layer accumulation 5 synthesized in Synthesis Example 1 was provided. Thereafter, gold nanoparticles 3 (having a diameter of about 30 nm) having a structure in which gold is covered with citric acid were electrostatically adsorbed. Thereafter, this substrate is immersed in a plating bath (70 ° C.) having the following composition for 30 seconds to perform electroless copper plating, copper plating 4 using gold nanoparticles as a plating nucleus is performed, and copper using polyimide substrate 8 is applied. A plated substrate 80 was produced (FIG. 4).

  From the viewpoint that the plating layer is difficult to peel off, the copper plating substrates of Examples 3 to 5 (50 layers, 74 layers, 100 layers) were preferred. That is, when 50 to 100 layers of pDDA-DADOO-M were accumulated, the plating layer was most difficult to peel off.

[Example 6] Copper plated substrate using polyimide substrate A copper plated substrate using a polyimide substrate was prepared in the same procedure as in Example 5 except that the immersion time in the plating bath was 10 minutes (Example) 6). When the plating thickness of this copper-plated substrate was measured with a stylus profilometer, the average plating thickness was 1.9 μm.

  As a method of utilizing the present invention, for example, a highly integrated circuit that requires highly fine wiring can be cited.

It is a schematic diagram which shows the state which can be taken when the random copolymer A expand | deploys on the water surface. It is a schematic diagram which shows the state by which the LB film | membrane of the random copolymer A is fixed to a glass substrate. Copper plated substrate using glass substrate Copper plated substrate using polyimide substrate

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Side chain 2 of repeating unit 1 Side chain 3 of repeating unit 2 Gold nanoparticle 4 Copper plating 5 Multilayer accumulation of monomolecular film of pDDA-DADOO 6 Multilayer accumulation of monomolecular film of pDDA-DADOO-M 7 Glass substrate 70 Glass Copper plating substrate 8 using substrate Polyimide substrate 80 Copper plating substrate using polyimide substrate

Claims (18)

  A substrate for electroless plating coated with one or more monomolecular films of a copolymer containing a functional group having a function of adsorbing metal nanoparticles. The following general formula (1)

(In the formula, R ₁ may be the same or different from each other, and represents a hydrogen atom or a methyl group; Z ₁ may be the same or different from each other; —NH—, —O— or —S—; The following general formula (2), which includes a repeating unit 1 represented by the following formula (2) and a functional group having a function of adsorbing metal nanoparticles:

Wherein W is a group having active hydrogen, R ₂ may be the same or different from each other and represents a hydrogen atom or a methyl group, Z ₂ may be the same or different, —NH—, —O— or — A monomolecular film of random copolymer A containing repeating unit 2 represented by S-, m is an integer of 1 to 5, and
The following general formula (3)

(In the formula, R ₃ may be the same or different from each other and represents a hydrogen atom or a methyl group; Z ₃ may be the same or different from each other; —NH—, —O— or —S—; The following general formula (4) including a repeating unit 3 represented by the formula (4) and a functional group having a function of adsorbing metal nanoparticles:

(In the formula, V is a group having active hydrogen, R ₄ may be the same or different from each other and represents a hydrogen atom or a methyl group, and Z ₄ may be the same or different, —NH—, —O— or — S-, p is an integer of 1 to 5), and a functional group having the function of forming a three-dimensional crosslinked structure by light or heat, and the following general formula (5)

(In the formula, X is —NH—, —O— or —S—, R ₅ may be the same or different from each other, and represents a hydrogen atom or a methyl group; R ₆ is hydrogen, alkyl having 1 to 20 carbon atoms; A alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, Z ₅ may be the same or different from each other, and is —NH—, —O— or —S—, and q is 1 to 1 or more monomolecular films selected from the group consisting of monomolecular films of random copolymer B containing repeating unit 5 represented by the following formula: A substrate for electroless plating. The following general formula (1)

(Wherein R ₁ represents a hydrogen atom, Z ₁ is —NH—, and n is an integer of 8 to 14), and the metal nanoparticle has a function of adsorbing. The following general formula (2) including functional groups

(Wherein W is an amino group, R ₂ represents a hydrogen atom, Z ₂ is —NH—, and m is 2). Monomolecular film, and
The following general formula (3)

(Wherein R ₃ represents a hydrogen atom, Z ₃ is —NH—, and r is an integer of 8 to 14), and the metal nanoparticles have a function of adsorbing. Following general formula (4) including functional group

(Wherein, V is an amino group, R ₄ represents a hydrogen atom, Z ₄ is —NH—, and p is an integer of 1 to 5), The following general formula (5) including a functional group having a function of forming a three-dimensional crosslinked structure by heat

(Wherein, X is -NH -, - a O- or -S-, _{R 5} represents a hydrogen atom, _{R 6} represents a hydrogen atom or a methyl group may be the same or different from each other, Z ₅ is - NH- and q is 2.) One or more monomolecular films selected from the group consisting of monomolecular films of random copolymer B containing repeating unit 5 represented by: A substrate for electroless plating coated with two or more layers.   The substrate for electroless plating according to claim 2 or 3, wherein the monomolecular film of random copolymer B containing a functional group having a function of forming a three-dimensional crosslinked structure by light or heat is a film irradiated with ultraviolet rays. .   The substrate for electroless plating according to any one of claims 1 to 4, wherein the monomolecular film is a Langmuir-Blodgett film.   The substrate for electroless plating according to any one of claims 1 to 5, wherein the surface of the substrate on which the monomolecular film is coated is glass, silicon wafer or plastic.   A plated substrate obtained by electrolessly plating the electroless plating substrate according to claim 1, wherein the metal nanoparticles adsorbed on a functional group having a function of adsorbing metal nanoparticles are used as plating nuclei.   The plated substrate according to claim 7, wherein the plating nucleus is gold nanoparticles and copper is plated.   The manufacturing method of the board | substrate for electroless plating including the process of coat | covering the monomolecular film of the copolymer containing the functional group which has a function which a metal nanoparticle adsorb | sucks. The following general formula (1)

(In the formula, R ₁ may be the same or different from each other, and represents a hydrogen atom or a methyl group; Z ₁ may be the same or different from each other; —NH—, —O— or —S—; The following general formula (2), which includes a repeating unit 1 represented by the following formula (2) and a functional group having a function of adsorbing metal nanoparticles:

Wherein W is a group having active hydrogen, R ₂ may be the same or different from each other and represents a hydrogen atom or a methyl group, Z ₂ may be the same or different, —NH—, —O— or — A monomolecular film of random copolymer A containing repeating unit 2 represented by S-, m is an integer of 1 to 5, and
The following general formula (3)

(In the formula, R ₃ may be the same or different from each other and represents a hydrogen atom or a methyl group; Z ₃ may be the same or different from each other; —NH—, —O— or —S—; The following general formula (4) including a repeating unit 3 represented by the formula (4) and a functional group having a function of adsorbing metal nanoparticles:

(In the formula, V is a group having active hydrogen, R ₄ may be the same or different from each other and represents a hydrogen atom or a methyl group, and Z ₄ may be the same or different, —NH—, —O— or — S-, p is an integer of 1 to 5), and a functional group having the function of forming a three-dimensional crosslinked structure by light or heat, and the following general formula (5)

(In the formula, X is —NH—, —O— or —S—, R ₅ may be the same or different from each other, and represents a hydrogen atom or a methyl group; R ₆ is hydrogen, alkyl having 1 to 20 carbon atoms; A alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, Z ₅ may be the same or different from each other, and is —NH—, —O— or —S—, and q is 1 to An electroless process comprising a step of coating one or more monomolecular films selected from the group consisting of monomolecular films of random copolymer B containing repeating unit 5 represented by: A method for manufacturing a plating substrate. The following general formula (1)

(Wherein R ₁ represents a hydrogen atom, Z ₁ is —NH—, and n is an integer of 8 to 14), and the metal nanoparticle has a function of adsorbing. The following general formula (2) including functional groups

(Wherein W is an amino group, R ₂ represents a hydrogen atom, Z ₂ is —NH—, and m is 2). Monomolecular film, and
The following general formula (3)

(Wherein R ₃ represents a hydrogen atom, Z ₃ is —NH—, and r is an integer of 8 to 14), and the metal nanoparticles have a function of adsorbing. Following general formula (4) including functional group

(Wherein, V is an amino group, R ₄ represents a hydrogen atom, Z ₄ is —NH—, and p is an integer of 1 to 5), The following general formula (5) including a functional group having a function of forming a three-dimensional crosslinked structure by heat

(Wherein, X is -NH -, - a O- or -S-, _{R 5} represents a hydrogen atom, _{R 6} represents a hydrogen atom or a methyl group may be the same or different from each other, Z ₅ is - NH— and q is 2. The step of coating one or more monomolecular films selected from the group consisting of monomolecular films of random copolymer B containing repeating unit 5 represented by The manufacturing method of the board | substrate for electroless plating containing this.   The production of a plating substrate according to claim 10 or 11, comprising a step of irradiating the monomolecular film of the random copolymer B containing a functional group having a function of forming a three-dimensional crosslinked structure by light or heat, with ultraviolet rays. Method.   The method for producing a substrate for electroless plating according to any one of claims 9 to 12, wherein two or more monomolecular films are coated.   The method for producing a substrate for electroless plating according to any one of claims 9 to 13, wherein the monomolecular film is prepared by the Langmuir-Blodgett method.   The method for producing a substrate for electroless plating according to any one of claims 9 to 14, wherein the surface of the substrate on which the monomolecular film is coated is glass, a silicon wafer or plastic.   A method for producing a plated substrate, comprising: a step of adsorbing metal nanoparticles to a functional group on a substrate for plating produced by the method of claims 9 to 15; and a step of electrolessly plating a metal.   The method for producing a plated substrate according to claim 16, wherein the step of electrolessly plating a metal is performed by electroless copper plating using gold nanoparticles adsorbed on a functional group having a function of adsorbing metal nanoparticles as a plating nucleus. To the substrate whose surface is polyimide,
The following general formula (3)

(In the formula, R ₃ may be the same or different from each other and represents a hydrogen atom or a methyl group; Z ₃ may be the same or different from each other; —NH—, —O— or —S—; The following general formula (4) including a repeating unit 3 represented by the formula (4) and a functional group having a function of adsorbing metal nanoparticles:

(In the formula, V is a group having active hydrogen, R ₄ may be the same or different from each other and represents a hydrogen atom or a methyl group, and Z ₄ may be the same or different, —NH—, —O— or — S-, p is an integer of 1 to 5), and a functional group having the function of forming a three-dimensional crosslinked structure by light or heat, and the following general formula (5)

(In the formula, X is —NH—, —O— or —S—, R ₅ may be the same or different from each other, and represents a hydrogen atom or a methyl group; R ₆ is hydrogen, alkyl having 1 to 20 carbon atoms; A alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, Z ₅ may be the same or different from each other, and is —NH—, —O— or —S—, and q is 1 to A plurality of monomolecular films of random copolymer B containing repeating unit 5 represented by the following formula (5)), and after irradiating the monomolecular film with ultraviolet rays, the following general formula (1)

(In the formula, R ₁ may be the same or different from each other, and represents a hydrogen atom or a methyl group; Z ₁ may be the same or different from each other; —NH—, —O— or —S—; The following general formula (2), which includes a repeating unit 1 represented by the following formula (2) and a functional group having a function of adsorbing metal nanoparticles:

Wherein W is a group having active hydrogen, R ₂ may be the same or different from each other and represents a hydrogen atom or a methyl group, Z ₂ may be the same or different, —NH—, —O— or — A step of coating a monomolecular film of random copolymer A containing repeating unit 2 represented by: S-, m is an integer of 1 to 5.
A method for producing a plated substrate, comprising: a step of adsorbing gold nanoparticles to a functional group; and a step of plating copper by electroless copper plating using the gold nanoparticles as a plating nucleus.

Images