JP6882721B2 - Electroless plating base material containing highly branched polymer and metal fine particles - Google Patents

Description

The present invention relates to a photosensitive base material containing a hyperbranched polymer, metal fine particles, a polymerizable compound and a photopolymerization initiator.

In recent years, with the miniaturization of devices such as personal computers, mobile phones, and wearable terminals, fine wiring patterns can be easily formed in order to increase the density of patterns and to form wiring with high transmittance and visibility on a transparent substrate. There is a need for a method to do this.

As one of the means for forming fine wiring, a method of patterning an electroless plating catalyst by photolithography and then performing electroless plating is disclosed (Patent Document 1). Specifically, a material in which a metal complex, a metal ion, a metal colloid, etc., which is a catalyst for electroless plating, is mixed with a photosensitive resin is used, and UV exposure through a photomask, development, and any arbitrary shape such as a grid pattern are used. A method for obtaining a conductive pattern by forming a base of a pattern and applying electroless plating to the base is disclosed.

Further, by using a composition containing a hyperbranched polymer having an ammonium group and Pd fine particles as an electroless plating base material, it is electroless by simply immersing it directly in an electroless plating solution without going through an activation step after application. An example in which plating is formed is disclosed (Patent Document 2).

Japanese Unexamined Patent Publication No. 11-170421 International Publication No. 2012/141215 Pamphlet

In Patent Document 1, a protective colloid such as PVP and a surfactant such as dodecylbenzenesulfonic acid are used as a stabilizer for the metal colloid, but the stability of the varnish due to decomposition of the protective colloid and aggregation of the metal colloid. Not only is there a concern, but in the process, it is often difficult to clean the catalyst during development. Another problem is that during electroless plating, plating is deposited in areas other than the target portion. Further, since a water-soluble resist or a metal stabilizer is used, there is a problem in maintaining the pattern shape such as pattern bleeding and line thickening. In the patent document, only the transmittance and the resistance value of the obtained transparent conductive film are discussed, and the line width (shape) of the obtained pattern is not mentioned in detail.

Further, the transparent electrode used for a liquid crystal display element or the like is required to have visibility of an image. However, when metal wiring is formed by electroless plating, the formed metal coating has a metallic luster, which reflects external light, so that the metal wiring is inconspicuous and a clear display device with high image visibility is manufactured. There is a problem that it is difficult to do. Therefore, in the technique of forming a transparent electrode by electroless plating, it is required to suppress metallic luster by blackening the back surface (transparent base material surface) of the formed metal plating film.

Therefore, the present invention focuses on these problems, and as a pretreatment step for electroless plating, which is environmentally friendly, can be easily processed with a small number of steps, and can easily form fine wiring having a width of several μm by photolithography. An object of the present invention is to provide a new electroless plating base material to be used.

As a result of diligent studies to achieve the above object, the present inventors have a hyperbranched polymer having an ammonium group at the molecular end and metal fine particles, and a specific polymerizable compound, a photopolymerization initiator, and an amino group. A photosensitive base material is obtained by combining a compound and a polyfunctional thiol, and the layer obtained by applying this on the base material can be patterned by photolithography, and a patterned base layer of electroless metal plating can be obtained. It has been found that the base layer is excellent in platenability and is a useful layer for improving the adhesion between the metal plating film and the base material to be plated. Further, it was found that when the patterned electroless metal plating base layer is formed on a transparent base material such as glass and a metal plating film is formed on the transparent base material, the back surface of the plating film forming portion is black. It was. In particular, in the above-mentioned photosensitive agent base material, it has been found that the dispersibility and reactivity of metal fine particles can be improved and highly sensitive patterning becomes possible by blending a compound having an amino group and a thiol compound, and the present invention has been completed. I let you.

（式中、Ｒ^１はそれぞれ独立して水素原子又はメチル基を表し、Ｒ^２乃至Ｒ^４はそれぞれ独立して水素原子、炭素原子数１乃至２０の直鎖状、枝分かれ状若しくは環状のアルキル基、炭素原子数７乃至２０のアリールアルキル基又は−（ＣＨ_２ＣＨ_２Ｏ）_ｍＲ^５（式中、Ｒ^５は水素原子又はメチル基を表し、ｍは２乃至１００の整数を表す。）を表す（該アルキル基及びアリールアルキル基は、アルコキシ基、ヒドロキシ基、アンモニウム基、カルボキシ基又はシアノ基で置換されていてもよい。）か、Ｒ^２乃至Ｒ^４のうちの２つの基が一緒になって、直鎖状、枝分かれ状又は環状のアルキレン基を表すか、又はＲ^２乃至Ｒ^４はそれらが結合する窒素原子と一緒になって環を形成してもよく、Ｘ⁻は陰イオンを表し、ｎは繰り返し単位構造の数であって、５乃至１００，０００の整数を表し、Ａ^１は式［２］で表される構造を表す。）

（式中、Ａ^２はエーテル結合又はエステル結合を含んでいてもよい炭素原子数１乃至３０の直鎖状、枝分かれ状又は環状のアルキレン基を表し、Ｙ^１乃至Ｙ^４はそれぞれ独立して水素原子、炭素原子数１乃至２０のアルキル基、炭素原子数１乃至２０のアルコキシ基、ニトロ基、ヒドロキシ基、アミノ基、カルボキシ基又はシアノ基を表す。）
第８観点として、前記（ａ）ハイパーブランチポリマーが、式［３］で表されるハイパーブランチポリマーである、第７観点に記載の感光性下地剤に関する。

（式中、Ｒ^１乃至Ｒ^４及びｎは前記と同じ意味を表す。）
第９観点として、前記（ｂ）金属微粒子が、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、パラジウム（Ｐｄ）、銀（Ａｇ）、スズ（Ｓｎ）、白金（Ｐｔ）及び金（Ａｕ）からなる群より選択される少なくとも一種の金属の微粒子である、第１観点乃至第８観点のうち何れか一つに記載の感光性下地剤に関する。
第１０観点として、前記（ｂ）金属微粒子が、パラジウム微粒子である、第９観点に記載の感光性下地剤に関する。
第１１観点として、前記（ｂ）金属微粒子が、１〜１００ｎｍの平均粒径を有する微粒子である、第１観点乃至第１０観点のうち何れか一つに記載の感光性下地剤に関する。
第１２観点として、フォトリソグラフィーによりパターン形成が可能である、第１観点乃至第１１観点のうち何れか一つに記載の感光性下地剤に関する。
第１３観点として、第１観点乃至第１２観点のうち何れか一つに記載の感光性下地剤からなる、フォトリソグラフィーによるパターン化層である、無電解めっき下地層に関する。
第１４観点として、第１３観点に記載の無電解めっき下地層上に形成された無電解めっき層からなる、金属めっき膜に関する。
第１５観点として、基材と、該基材上に形成された第１３観点に記載の無電解めっき下地層と、該無電解めっき下地層上に形成された第１４観点に記載の金属めっき膜とを具備する、金属被膜基材に関する。
第１６観点として、下記Ａ工程乃至Ｃ工程を含む、金属被膜基材の製造方法に関する。
Ａ工程：第１観点乃至第１２観点のうち何れか一つに記載の感光性下地剤を基材上に塗布し、下地層を具備する工程、
Ｂ工程：フォトリソグラフィーにより所望のパターンの下地層を形成する工程、
Ｃ工程：パターニングされた下地層を具備した基材を無電解めっき浴に浸漬し、金属めっき膜を形成する工程。That is, the present invention is, as a first aspect, a base material for forming a metal plating film on a base material by electroless plating.
(A) A hyperbranched polymer having an ammonium group at the end of the molecule and having a weight average molecular weight of 1,000 to 5,000,000.
(B) Metal fine particles,
(C) It has one or more side chains in the molecule that are polymerizable unsaturated bonds, has 15 to 50 mol of oxyalkylene groups per 100 mol of all repeating units, and has a weight average molecular weight of 10,000. 100,000 high molecular weight compounds,
(D) Photopolymerization initiator,
It relates to (e) a compound having an amino group, and (f) a photosensitive base material containing a polyfunctional thiol.
The second aspect relates to the photosensitive base material according to the first aspect, wherein the polymer compound (c) is a compound having three or more (meth) acryloyl groups in the molecule.
The third aspect relates to the photosensitive base material according to any one of the first aspect and the second aspect, wherein the oxyalkylene group of the polymer compound (c) is a poly (oxyalkylene) group.
As a fourth aspect, the photosensitive base material according to any one of the first to fourth aspects, wherein the weight average molecular weight of the polymer compound (c) is 20,000 to 50,000.
As a fifth aspect, the photosensitive base material according to any one of the first to fourth aspects, wherein the polyfunctional thiol (f) is a tetrafunctional thiol.
The sixth aspect is the photosensitive base material according to any one of the first to fifth aspects, wherein the compound having an amino group (e) is an alkoxysilane compound having an amino group.
As a seventh aspect, the photosensitive base material according to any one of the first to sixth aspects, wherein the hyperbranched polymer (a) is a hyperbranched polymer represented by the formula [1].

(In the formula, R ¹ independently represents a hydrogen atom or a methyl group, and R ^{2 to} R ⁴ independently represent a hydrogen atom and a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, respectively. , An arylalkyl group having 7 to 20 carbon atoms or-(CH ₂ CH ₂ O) _m R ⁵ (in the formula, R ⁵ represents a hydrogen atom or a methyl group, and m represents an integer of 2 to 100). Represent (the alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxy group or a cyano group), or ^{two groups of R 2 to} R ⁴ are combined together. Representing a linear, branched or cyclic alkylene group, or R ^{2 to} R ⁴ may be combined with the nitrogen atom to which they are attached to form a ring, where X ⁻ represents an anion. Represented, n is the number of repeating unit structures, represents an integer of 5 to 100,000, and A ¹ represents the structure represented by the equation [2].)

(In the formula, A ² represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ^{1 to} Y ⁴ are independently hydrogen. Represents an atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxy group or a cyano group).
As an eighth aspect, the photosensitive base material according to the seventh aspect, wherein the hyperbranched polymer (a) is a hyperbranched polymer represented by the formula [3].

(In the formula, ^{R 1} to ^{R 4} and n are as defined above.)
As a ninth viewpoint, the metal fine particles (b) are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum ( The photosensitive base material according to any one of the first to eighth aspects, which is at least one kind of metal fine particles selected from the group consisting of Pt) and gold (Au).
The tenth aspect relates to the photosensitive base material according to the ninth aspect, wherein the metal fine particles (b) are palladium fine particles.
The eleventh viewpoint relates to the photosensitive base material according to any one of the first to tenth viewpoints, wherein the metal fine particles (b) are fine particles having an average particle size of 1 to 100 nm.
The twelfth aspect relates to the photosensitive base material according to any one of the first aspect to the eleventh aspect, which can form a pattern by photolithography.
As a thirteenth viewpoint, the present invention relates to an electroless plating base layer, which is a patterned layer by photolithography, which comprises the photosensitive base material according to any one of the first to twelfth viewpoints.
As the 14th viewpoint, the present invention relates to a metal plating film composed of an electroless plating layer formed on the electroless plating base layer according to the 13th viewpoint.
As the fifteenth viewpoint, the base material, the electroless plating base layer according to the thirteenth viewpoint formed on the base material, and the metal plating film according to the fourteenth viewpoint formed on the electroless plating base layer. The present invention relates to a metal-coated base material.
As a sixteenth viewpoint, the present invention relates to a method for producing a metal film base material, which comprises the following steps A to C.
Step A: A step of applying the photosensitive base material according to any one of the first to twelfth viewpoints onto a base material to provide a base layer.
Step B: A step of forming a base layer of a desired pattern by photolithography,
Step C: A step of immersing a base material having a patterned base layer in an electroless plating bath to form a metal plating film.

The photosensitive base material of the present invention can be easily formed into a patterned electroless metal plating base layer by applying it on a base material and performing photolithography through a mask.
Further, the photosensitive base material of the present invention has an excellent adhesion to the base material without forming a primer layer which was conventionally formed on the base material in order to improve the adhesion to the metal plating film. Can be formed. Further, the photosensitive base material of the present invention can form a patterned plating base layer on the order of μm, and can be suitably used for various wiring techniques.
In particular, the photosensitive base material of the present invention can improve the dispersion stability of the metal fine particles in the base material by blending a compound having an amino group capable of coordinating and bonding to metal fine particles such as palladium to form an ammine complex. Furthermore, the polyfunctional thiol added at the same time plays a role not only as a cross-linking agent but also as a chain transfer agent, so that a patterned electroless metal plating base layer having high sensitivity and excellent developability during photolithography. Can be formed.
Further, the electroless metal plating base layer formed from the photosensitive base material of the present invention can easily form a metal plating film simply by immersing it in an electroless plating bath, and the base material, the base layer, and the metal plating film can be easily formed. A metal-coated base material comprising the above can be easily obtained.
The metal plating film has excellent adhesion to the underlying layer.
That is, by forming the base layer on the base material using the photosensitive base material of the present invention, it is possible to form a metal plating film having excellent adhesion to the base material, so to speak.
Furthermore, when a metal plating film is formed on the photosensitive substrate of the present invention, the back surface thereof is black, so that when these are formed on a transparent substrate such as a glass substrate, the image is highly visible and transparent. Expected to be used as an electrode.

^{FIG. 1 is a diagram showing a 1} H NMR spectrum of a hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular end produced in Production Example 1. ^{FIG. 2 is a diagram showing a 13} C NMR spectrum of the _{hyperbranched polymer (HPS-N (Me) 2} OctCl) having a dimethyloctylammonium group at the molecular end produced in Production Example 2.

前記式［１］中、Ｒ^１は、それぞれ独立して水素原子又はメチル基を表す。
また、Ｒ^２乃至Ｒ^４は、それぞれ独立して、水素原子、炭素原子数１乃至２０の直鎖状、枝分かれ状又は環状のアルキル基、炭素原子数７乃至２０のアリールアルキル基、又は−（ＣＨ_２ＣＨ_２Ｏ）_ｍＲ^５（式中、Ｒ^５は水素原子又はメチル基を表し、ｍは２乃至１００の任意の整数を表す。）を表す。上記アルキル基及びアリールアルキル基は、アルコキシ基、ヒドロキシ基、アンモニウム基、カルボキシ基又はシアノ基で置換されていてもよい。また、Ｒ^２乃至Ｒ^４のうちの２つの基が一緒になって、直鎖状、枝分かれ状又は環状のアルキレン基を表すか、又はＲ^２乃至Ｒ^４並びにそれらが結合する窒素原子が一緒になって環を形成してもよい。
またＸ⁻は陰イオンを表し、ｎは繰り返し単位構造の数であって、５乃至１００，０００の整数を表す。[Base material]
<(A) Hyperbranched polymer>
The (a) hyperbranched polymer used in the photosensitive base material of the present invention is a polymer having an ammonium group at the molecular terminal and having a weight average molecular weight of 1,000 to 5,000,000, specifically. Examples thereof include hyperbranched polymers represented by the following formula [1].

In the above formula [1], R ¹ independently represents a hydrogen atom or a methyl group.
Further, R ^{2 to} R ⁴ are independently hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, or-(. CH ₂ CH ₂ O) _m R ⁵ (in the formula, R ⁵ represents a hydrogen atom or a methyl group, and m represents an arbitrary integer from 2 to 100). The alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxy group or a cyano group. Also, ^{two groups of R 2 to} R ⁴ together represent a linear, branched or cyclic alkylene group, or R ^{2 to} R ^{4 and} the nitrogen atom to which they are attached together. May form a ring.
Further, X ⁻ represents an anion, n is the number of repeating unit structures, and represents an integer of 5 to 100,000.

Examples ^{of the linear alkyl group having 1 to 20 carbon atoms in R 2 to} R ⁴ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group and n. -Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n -Heptadecyl group, n-octadecyl group, n-nonadecil group, n-eicosyl group and the like can be mentioned, and a group having 8 or more carbon atoms is preferable, and n- is particularly preferable in that the base material is difficult to elute into the electroless plating solution. An octyl group is preferred. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like. Examples of the cyclic alkyl group include a cyclopentyl ring and a group having a cyclohexyl ring structure.
Examples of the arylalkyl group having 7 to 20 carbon atoms in R ^{2 to} R ^{4 include a benzyl group and a phenethyl group.}
Further, ^{examples of the linear alkylene group in which two groups of R 2 to} R ⁴ are combined include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group and the like. Examples of the branched alkylene group include a methylethylene group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group and the like. Examples of the cyclic alkylene group include alicyclic aliphatic groups having a cyclic structure having a monocyclic, polycyclic, or crosslinked cyclic structure having 3 to 30 carbon atoms. Specifically, a group having a monocyclo, bicyclo, tricyclo, tetracyclo, pentacyclo structure or the like having 4 or more carbon atoms can be mentioned. These alkylene groups may contain a nitrogen atom, a sulfur atom or an oxygen atom in the group.
Then, the ring nitrogen atom bonded with R ² to R ⁴ as well as their a structure represented by the formula [1] is formed together, the nitrogen atom in the ring, also contain sulfur atom or oxygen atom Frequently, for example, a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, a bipyridyl ring and the like can be mentioned.
Examples ^{of the combination of R 2 to} R ⁴ include [methyl group, methyl group, methyl group], [methyl group, methyl group, ethyl group], [methyl group, methyl group, n-butyl group], and [methyl group]. Group, methyl group, n-hexyl group], [methyl group, methyl group, n-octyl group], [methyl group, methyl group, n-decyl group], [methyl group, methyl group, n-dodecyl group], [Methyl group, methyl group, n-tetradecyl group], [methyl group, methyl group, n-hexadecyl group], [methyl group, methyl group, n-octadecyl group], [ethyl group, ethyl group, ethyl group], [N-butyl group, n-butyl group, n-butyl group], [n-hexyl group, n-hexyl group, n-hexyl group], [n-octyl group, n-octyl group, n-octyl group] Etc., and among them, a combination of [methyl group, methyl group, n-octyl group], [n-octyl group, n-octyl group, n-octyl group] is preferable.
The X ^- is preferably a halogen atom _anion, ^PF 6 -, BF ₄ ^- or perfluoroalkane sulfonate and the like.

上記式［２］中、Ａ^２はエーテル結合又はエステル結合を含んでいてもよい炭素原子数１乃至３０の直鎖状、枝分かれ状又は環状のアルキレン基を表す。
Ｙ^１乃至Ｙ^４は、それぞれ独立して、水素原子、炭素原子数１乃至２０のアルキル基、炭素原子数１乃至２０のアルコキシ基、ニトロ基、ヒドロキシ基、アミノ基、カルボキシ基又はシアノ基を表す。In the above formula [1], A ¹ represents a structure represented by the following formula [2].

In the above formula [2], A ² represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
Y ^{1 to} Y ⁴ independently have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxy group or a cyano group. Represent.

Specific examples of the alkylene group of A ² include linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group and hexamethylene group, methylethylene group, butane-1,3-diyl group and 2 Examples thereof include branched alkylene groups such as −methylpropane-1,3-diyl group. Examples of the cyclic alkylene group include alicyclic aliphatic groups having a cyclic structure having a monocyclic, polycyclic or crosslinked cyclic structure having 3 to 30 carbon atoms. Specifically, a group having a monocyclo, bicyclo, tricyclo, tetracyclo, pentacyclo structure or the like having 4 or more carbon atoms can be mentioned. For example, structural examples (a) to (s) of the alicyclic portion of the alicyclic aliphatic group are shown below.

Examples of the alkyl group of the formula [2] in the Y ¹ to Y ⁴ of 1 to 20 carbon atoms, a methyl group, an ethyl group, an isopropyl group, n- pentyl group, a cyclohexyl group and the like. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an isopropoxy group, an n-pentyloxy group, a cyclohexyloxy group and the like. The Y ¹ to ^{Y 4,} a hydrogen atom or an alkyl group having 1 to 20 carbon atoms are preferred.

前記式［３］中、Ｒ^１、Ｒ^２乃至Ｒ^４及びｎは上記と同じ意味を表す。Preferably, the hyperbranched polymer used in the present invention includes a hyperbranched polymer represented by the following formula [3].

In the above formula [3], R ¹ , R ^{2 to} R ⁴ and n have the same meanings as described above.

The hyperbranched polymer having the ammonium group at the molecular end used in the present invention can be obtained, for example, by reacting an amine compound with the hyperbranched polymer having a halogen atom at the molecular end.
The hyperbranched polymer having a halogen atom at the molecular end can be produced from the hyperbranched polymer having a dithiocarbamate group at the molecular end in accordance with the description in Pamphlet No. 2008/029688. As the hyperbranched polymer having the dithiocarbamate group at the molecular terminal, a commercially available product can be used, and Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd. can be preferably used.

The amine compounds that can be used in this reaction include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, and n as primary amines. -Hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine , N-Hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecilamine, n-eicosylamine and other aliphatic amines; cyclopentylamine, cyclohexylamine and other alicyclic amines; benzylamine, phenethylamine and the like. Aralkylamines; aniline, pn-butylaniline, p-tert-butylaniline, pn-octylaniline, pn-decylaniline, pn-dodecylaniline, pn-tetradecylaniline, etc. Anilines, naphthylamines such as 1-naphthylamine and 2-naphthylamine, aminoanthracenes such as 1-aminoanthracene and 2-aminoanthracene, aminoanthraquinones such as 1-aminoanthraquinone, 4-aminobiphenyl, 2-aminobiphenyl and the like. Aminobiphenyls, 2-aminofluorene, 1-amino-9-fluorenone, 4-amino-9-fluorenone and other aminofluorenes, 5-aminoindane and other aminoindans, 5-aminoisoquinolin and other aminoisoquinolins. , Aromatic amines such as aminophenanthrenes such as 9-aminophenanthrene, and the like. Furthermore, N- (tert-butoxycarbonyl) -1,2-ethylenediamine, N- (tert-butoxycarbonyl) -1,3-propylenediamine, N- (tert-butoxycarbonyl) -1,4-butylenediamine, N -(Tart-butoxycarbonyl) -1,5-pentamethylenediamine, N- (tert-butoxycarbonyl) -1,6-hexamethylenediamine, N- (2-hydroxyethyl) amine, N- (3-hydroxypropyl) ) Amines, N- (2-methoxyethyl) amines, N- (2-ethoxyethyl) amines and other amine compounds can be mentioned.

Secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-n-pentylamine, ethylmethylamine, and methyl-. n-propylamine, methyl-n-butylamine, methyl-n-pentylamine, ethylisopropylamine, ethyl-n-butylamine, ethyl-n-pentylamine, methyl-n-octylamine, methyl-n-decylamine, methyl- n-dodecylamine, methyl-n-tetradecylamine, methyl-n-hexadecylamine, methyl-n-octadecylamine, ethylisopropylamine, ethyl-n-octylamine, di-n-hexylamine, di-n- Aliper amines such as octylamine, di-n-dodecylamine, di-n-hexadecylamine, di-n-octadecylamine; alicyclic amines such as dicyclohexylamine; aralkylamines such as dibenzylamine; Aromatic amines; nitrogen-containing heterocyclic compounds such as phthalimide, pyrrole, piperidine, piperazine, imidazole and the like can be mentioned. Further, bis (2-hydroxyethyl) amine, bis (3-hydroxypropyl) amine, bis (2-ethoxyethyl) amine, bis (2-propoxyethyl) amine and the like can be mentioned.

Examples of tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-octylamine, and tri-n-dodecyl. Amine, dimethylethylamine, dimethyl-n-butylamine, dimethyl-n-hexylamine, dimethyl-n-octylamine, dimethyl-n-decylamine, diethyl-n-decylamine, dimethyl-n-dodecylamine, dimethyl-n-tetradecyl Aliphatic amines such as amines, dimethyl-n-hexadecylamines, dimethyl-n-octadecylamines, dimethyl-n-eicosylamines; pyridine, pyrazine, pyrimidine, quinoline, 1-methylimidazole, 4,4'-bipyridyl, Examples thereof include nitrogen-containing heterocyclic compounds such as 4-methyl-4,4'-bipyridyl.

The amount of the amine compound that can be used in these reactions is 0.1 to 20 molar equivalents, preferably 0.5 to 10 molar equivalents, with respect to 1 mol of the halogen atom of the hyperbranched polymer having a halogen atom at the molecular terminal. It may be preferably 1 to 5 molar equivalents.

The reaction between the hyperbranched polymer having a halogen atom at the end of the molecule and the amine compound can be carried out in water or an organic solvent in the presence or absence of a base. The solvent used is preferably one capable of dissolving a hyperbranched polymer having a halogen atom at the molecular terminal and an amine compound. Further, a hyperbranched polymer having a halogen atom at the molecular end and an amine compound can be dissolved, but a solvent that does not dissolve the hyperbranched polymer having an ammonium group at the molecular end is more preferable because isolation is easy.
The solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and is water; alcohols such as isopropanol; organic acids such as acetic acid; benzene, toluene, xylene, ethylbenzene, 1,2-di. Aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran (THF) and diethyl ether; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and cyclohexanone; chloroform, dichloromethane, 1,2-dichloroethane Halogens such as n-hexane, n-heptane, cyclohexane and other aliphatic hydrocarbons; N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP) and the like. Amids can be used. One of these solvents may be used, or two or more of these solvents may be mixed and used. The amount used is 0.2 to 1,000 times by mass, preferably 1 to 500 times by mass, more preferably 5 to 100 times by mass, most preferably, with respect to the mass of the hyperbranched polymer having a halogen atom at the molecular terminal. It is preferable to use a solvent having a mass of 5 to 50 times.

Suitable bases are generally alkali metal hydroxides and alkaline earth metal hydroxides (eg sodium hydroxide, potassium hydroxide, calcium hydroxide), alkali metal oxides and alkaline earth metal oxides (eg lithium oxide). , Calcium oxide), alkali metal hydrides and alkaline earth metal hydrides (eg sodium hydride, potassium hydride, calcium hydride), alkali metal amides (eg sodium amides), alkali metal carbonates and alkaline earth metal carbonates. Inorganic compounds such as salts (eg lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate), alkali metal bicarbonates (eg sodium bicarbonate), as well as alkali metal alkyls, alkylmagnesium halides, alkali metal alkoxides, alkaline earth metals. Organic metal compounds such as alkoxides and dimethoxymagnesium are used. Particularly preferred are potassium carbonate and sodium carbonate. The amount used is 0.2 to 10 molar equivalents, preferably 0.5 to 10 molar equivalents, most preferably 1 to 5 molar equivalents, relative to 1 mol of the halogen atom of the hyperbranched polymer having a halogen atom at the molecular terminal. It is preferable to use the base of.

In this reaction, it is preferable to sufficiently remove oxygen in the reaction system before the start of the reaction, and it is preferable to replace the inside of the system with an inert gas such as nitrogen or argon. As the reaction conditions, the reaction time is appropriately selected from 0.01 to 100 hours and the reaction temperature is 0 to 300 ° C. The reaction time is preferably 0.1 to 72 hours and the reaction temperature is 20 to 150 ° C.

When a tertiary amine is used, a hyperbranched polymer represented by the formula [1] can be obtained regardless of the presence / absence of a base.
When a primary amine or secondary amine compound is reacted with a hyperbranched polymer having a halogen atom at the molecular terminal in the absence of a base, the corresponding hyperbranched polymer's terminal secondary amine and tertiary are used. An ammonium group-terminated hyperbranched polymer in which a primary amine is protonated is obtained. In addition, even when the reaction is carried out using a base, the terminal secondary amine of the corresponding hyperbranched polymer can be mixed with an aqueous solution of an acid such as hydrogen chloride, hydrogen bromide, or hydrogen iodide in an organic solvent. And an ammonium group-terminated hyperbranched polymer in which a tertiary amine is protonated is obtained.

The hyperbranched polymer has a weight average molecular weight Mw measured by gel permeation chromatography in terms of polystyrene of 1,000 to 5,000,000, more preferably 2,000 to 200,000, and most preferably 2,000 to 200,000. It is 3,000 to 100,000. The dispersity Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, preferably 1.1 to 6.0, and more preferably 1.2 to 5. It is 0.

<(B) Metal fine particles>
The (b) metal fine particles used in the photosensitive base material of the present invention are not particularly limited, and the metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and palladium (Pd). , Silver (Ag), Tin (Sn), Platinum (Pt) and Gold (Au) and alloys thereof, and one kind of these metals may be used, or two or more kinds thereof may be used in combination. Among them, palladium fine particles are mentioned as preferable metal fine particles. The metal oxide may be used as the metal fine particles.

The metal fine particles can be obtained by reducing metal ions by, for example, a method of irradiating an aqueous solution of a metal salt with light by a high-pressure mercury lamp, a method of adding a compound having a reducing action (so-called reducing agent) to the aqueous solution, or the like. For example, a metal ion is added by adding an aqueous solution of a metal salt to the solution in which the hyperbranched polymer is dissolved and irradiating the solution with ultraviolet rays, or by adding an aqueous solution of the metal salt and a reducing agent to the hyperbranched polymer solution. By reducing the above, a base material containing the hyperbranched polymer and the metal fine particles can be prepared while forming a complex of the hyperbranched polymer and the metal fine particles.

Examples of the metal salt include gold chloride acid, silver nitrate, copper sulfate, copper nitrate, copper acetate, tin chloride, first platinum chloride, platinum chloride acid, Pt (dba) ₂ [dba = dibenzylidene acetone], Pt (cod). ₂ [cod = 1,5-cyclooctadiene], Pt (CH ₃ ) ₂ (cod), palladium chloride, palladium acetate (Pd (OC (= O) CH ₃ ) ₂ ), palladium nitrate, Pd ₂ (dba) _3. CHCl ₃ , Pd (dba) ₂ , rhodium chloride, rhodium acetate, ruthenium chloride, ruthenium acetate, Ru (cod) (cot) [cot = cyclooctatriene], iridium chloride, iridium acetate, Ni (cod) _2, etc. Can be mentioned.
The reducing agent is not particularly limited, and various reducing agents can be used, and it is preferable to select the reducing agent according to the metal species and the like contained in the obtained base material. Examples of the reducing agent that can be used include boron hydride metal salts such as sodium boron hydride and potassium boron hydride; aluminum lithium hydride, potassium aluminum hydride, aluminum cesium hydride, aluminum berylium hydride, and hydrogenation. Aluminum hydride salts such as aluminum magnesium and aluminum calcium hydride; hydrazine compounds; citric acid and its salts; succinic acid and its salts; ascorbic acid and its salts; primary or secondary such as methanol, ethanol, isopropanol and polyols. Class alcohols; tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine (TMEDA), ethylenediaminetetraacetic acid (EDTA); hydroxylamine; tri-n-propylphosphine, tri-n- Butylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis (diphenylphosphino) ethane (DPPE), 1,3-bis (diphenylphosphino) propane (DPPP), 1 , 1'-bis (diphenylphosphino) ferrocene (DPPF), 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl (BINAP) and other phosphines.

The average particle size of the metal fine particles is preferably 1 to 100 nm. By setting the average particle size of the metal fine particles to 100 nm or less, the surface area is not reduced and sufficient catalytic activity can be obtained. The average particle size is more preferably 75 nm or less, and particularly preferably 1 to 30 nm.

The amount of the (a) hyperbranched polymer added to the photosensitive base material of the present invention is preferably 50 to 2,000 parts by mass with respect to 100 parts by mass of the (b) metal fine particles. When the amount is 50 parts by mass or more, the metal fine particles can be sufficiently dispersed, and when the amount is 2,000 parts by mass or less, problems such as physical properties due to an increase in the organic matter content can be suppressed. it can. More preferably, it is 100 to 1,000 parts by mass.

<(C) Polymer compound having a side chain whose terminal is a polymerizable unsaturated bond>
The component (c) used in the photosensitive base material of the present invention has one or more side chains having a polymerizable unsaturated bond at the end in the molecule, and contains 15 oxyalkylene groups per 100 mol of all repeating units. It is a polymerizable polymer compound having ~ 50 mol and having a weight average molecular weight of 10,000 to 100,000.
Examples of such a polymer compound having a side chain having a polymerizable unsaturated bond at the end include a polymer compound having two or more side chains in the molecule having a (meth) acryloyl group, and among them are preferable. Examples of the polymer compound having a (meth) acryloyl group and an oxyalkylene group in three or more side chains in the molecule.
As the oxyalkylene group, an oxyalkylene group having 2 to 4 carbon atoms is preferable, and an oxyethylene group [-OCH ₂ CH _2- ] or an oxypropylene group [-OCH ₂ C (CH ₃ ) H-] is preferable. .. The oxyalkylene group may be a poly (oxyalkylene) group in which a plurality of oxyalkylene groups are linked, and in that case, it may have one kind of oxyalkylene group alone, or it may have two or more kinds in combination. May be good. When having a plurality of types of oxyalkylene groups, the bond may be either a block bond or a random bond.
In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

Examples of the polymer compound include polymer compounds containing one or more (meth) acryloyl groups such as urethane acrylics, epoxy acrylics, and various (meth) acrylates, and particularly three or more (meth) acryloyl groups. Examples thereof include polyfunctional polymer compounds.
Among these polymerizable polymer compounds, a compound having three or more (meth) acryloyl groups and an oxyalkylene group in the side chain is preferable.

The weight average molecular weight of the polymer compound of the component (c) is preferably 10,000 to 100,000, more preferably 20,000 to 50,000. If the molecular weight is less than 10,000, the effect of the present invention will not be exhibited. On the other hand, if the molecular weight exceeds 100,000 and is excessive, it may not dissolve in the composition.

As the polymer compound of the component (c), a polyethylene oxide-modified polymer having a polymerizable unsaturated double bond in two or more side chains is preferable. The modification rate at that time is preferably 15% to 50%, more preferably 20% to 40%. If the modification rate is less than 15%, the solubility in the developing solution is lowered, so that the developability may be lowered. If the denaturation rate exceeds 50% and is excessive, a pattern may flow during development.
Examples of the compound as the component (c) include an EO-modified acrylic polymer such as 8KX-078H manufactured by Taisei Fine Chemicals Co., Ltd.

The amount of the (c) polymerizable compound added to the photosensitive base material of the present invention is 100 parts by mass of a composite (or the total mass of the hyperbranched polymer and the metal fine particles) formed of the hyperbranched polymer and the metal fine particles described later. On the other hand, 10 to 10,000 parts by mass is preferable. More preferably, it is 100 to 2,000 parts by mass. (C) If the amount of the polymerizable compound added is less than 10 parts by mass, it becomes difficult to form a pattern of the plating base layer by photolithography described later, and if it is added in excess of 10,000 parts by mass, the base is said. There is a risk that the metal plating film will not be formed on the base layer formed by the agent.

<(D) Photopolymerization initiator>
As the (d) photopolymerization initiator used in the photosensitive base material of the present invention, known ones can be used, and for example, alkylphenones, benzophenones, acylphosphine oxides, and Michler's benzoylbenzoates can be used. , Oxime esters, tetramethylthium monosulfides, thioxanthones and the like.
In particular, a photocleavable photoradical polymerization initiator is preferable. Examples of the photocleavable photoradical polymerization initiator are those described in the latest UV curing technology (page 159, publisher: Kazuhiro Takausu, publisher: Technical Information Association, 1991). ..
Examples of commercially available photoradical polymerization initiators include IRGACURE (registered trademark) 184, 369, 500, 651, 784, 819, 907, 1000, 1300, 1700, and 1800. , 1850, 2959, CGI1700, CGI1750, CGI1850, CG24-61, TPO, Darocur® 1116, 1173, OXE 01 [above, manufactured by BASF Japan Ltd.], ESACURE KIP150 , KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 [all manufactured by Lamberti] and the like, but are not limited thereto. A plurality of types of these polymerization initiators can be used in combination.

The amount of the (d) polymerization initiator added to the photosensitive base material of the present invention is, for example, 0.1 to 100% by mass, preferably 1 to 50% by mass, based on the (c) polymerizable compound. It is preferably 10 to 30% by mass.

<(E) Compound having an amino group>
As the compound having an amino group (e) used in the photosensitive base material of the present invention, known compounds can be used, for example, aliphatic amines such as alkylamines and hydroxyalkylamines. Examples thereof include amines having a cyclic substituent, aromatic amines (arylamines), and alkoxysilane compounds having an amino group. Among these compounds having an amino group, an alkoxysilane compound having an amino group is preferable.
Further, from the viewpoint of improving the storage stability of the plating base material, it is preferable that the amino group of the amine compound is protected by ketones (protection by the alkylidene group), and in the present invention, the amino group is protected by the alkylidene group. Both the amine compound and the amine compound are included in the component (e). When the amine compound protected by the alkylidene group is used as the component (e), the solvent of the base material described later is not an alcohol solvent that removes the protection by the alkylidene group, but ketones, ethers, etc. It is preferable to use an ester solvent.
In the present invention, by blending a compound containing an amino group with a photosensitive base material, dispersion stability in the base material of a composite composed of metal fine particles, specifically, a hyperbranched polymer having metal fine particles and an ammonium group, which will be described later, is stable. The effect of improving the properties can be obtained, and it also contributes to the formation of fine plating patterns.

Examples of the alkylamines include ethylamine (CH ₃ CH ₂ NH ₂ ), propylamine (CH ₃ (CH ₂ ) ₂ NH ₂ ), butylamine (CH ₃ (CH ₂ ) ₃ NH ₂ ), and pentylamine (CH ₃ (CH 3). CH ₂ ) ₄ NH ₂ ), hexylamine (CH ₃ (CH ₂ ) ₅ NH ₂ ), heptylamine (CH ₃ (CH ₂ ) ₆ NH ₂ ), octylamine (CH ₃ (CH ₂ ) ₇ NH ₂ ), Nonylamine (CH ₃ (CH ₂ ) ₈ NH ₂ ), decylamine (CH ₃ (CH ₂ ) ₉ NH ₂ ), undecylamine (CH ₃ (CH ₂ ) ₁₀ NH ₂ ), dodecylamine (CH ₃ (CH ₂ )) ₁₁ NH ₂ ), tridecylamine (CH ₃ (CH ₂ ) ₁₂ NH ₂ ), tetradecylamine (CH ₃ (CH ₂ ) ₁₃ NH ₂ ), pentadecylamine (CH ₃ (CH ₂ ) ₁₄ NH ₂ ), Hexadecylamine (CH ₃ (CH ₂ ) ₁₅ NH ₂ ), heptadecylamine (CH ₃ (CH ₂ ) ₁₆ NH ₂ ), octadecylamine (CH ₃ (CH ₂ ) ₁₇ NH ₂ ), nonadesylamine (CH ₃ (CH 2)) ₂ ) ₁₈ NH ₂ ), icosylamines (CH ₃ (CH ₂ ) ₁₉ NH ₂ ), and primary amines such as structural isomers of these; N, N-dimethylamine, N, N-diethylamine, N, N Secondary amines such as −dipropylamine, N, N-dibutylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine and the like can be mentioned.

Examples of the hydroxyalkylamines (alkanolamines) include methanolamine (OHCH ₂ NH ₂ ), ethanolamine (OH (CH ₂ ) ₂ NH ₂ ), propanol amine (OH (CH ₂ ) ₃ NH ₂ ), and butanol amine. (OH (CH ₂ ) ₄ NH ₂ ), Pentanolamine (OH (CH ₂ ) ₅ NH ₂ ), Hexanolamine (OH (CH ₂ ) ₆ NH ₂ ), Heptanolamine (OH (CH ₂ ) ₇ NH ₂₎ ), Octanolamine (OH (CH ₂ ) ₈ NH ₂ ), Nonanolamine (OH (CH ₂ ) ₉ NH ₂ ), Decanolamine (OH (CH _{2 ) 10} NH ₂ ), Undecanolamine (OH (OH (CH 2)) CH ₂ ) ₁₁ NH ₂ ), dodecanolamine (OH (CH ₂ ) ₁₂ NH ₂ ), tridecanolamine (OH (CH ₂ ) ₁₃ NH ₂ ), tetradecanolamine (OH (CH ₂ ) ₁₄ NH ₂₎ ), Pentadecanolamine (OH (CH ₂ ) ₁₅ NH ₂ ), Hexadecanolamine (OH (CH ₂ ) ₁₆ NH ₂ ), Heptadecanolamine (OH (CH ₂ ) ₁₇ NH ₂ ), Octadecanol Primary amines such as amines (OH (CH ₂ ) ₁₈ NH ₂ ), nonadecanol amines (OH (CH ₂ ) ₁₉ NH ₂ ), ecosadecanol amines (OH (CH ₂ ) ₂₀ NH _2); N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N- Secondary such as methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine and the like. Examples include amines.

Other aliphatic amines include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, and propoxy. Examples thereof include alkoxyalkylamines such as butylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine and butoxybutylamine.

As an example of amines having a cyclic substituent, an amine compound represented by ^{the formula R 11-} R ^12- NH _{2 is preferable.}
In the above formula, R ¹¹ is a monovalent cyclic group having 3 to 10 carbon atoms, preferably 3 to 12 carbon atoms, and may be an alicyclic group, an aromatic group, or a combination thereof. Good. These cyclic groups may be substituted with any substituent, for example, an alkyl group having 1 to 10 carbon atoms. R ¹² represents a single bond or an alkylene group having 1 to 17 carbon atoms, preferably 1 to 3 carbon atoms.

In the present invention, ^{preferred specific examples of the amine compound represented by the formula R 11-} R ^12- NH ₂ include compounds represented by the following formulas (A-1) to (A-10).

Specific examples of aromatic amines (arylamines) include aniline, N-methylaniline, o-, m-, or p-anisidine, o-, m-, or p-toluidine, o-, m-, or. Examples thereof include p-chloroaniline, o-, m-, or p-bromoaniline, o-, m-, or p-iodoaniline.

Specific examples of the alkoxysilane compound having an amino group include N, N'-bis [3- (trimethoxysilyl) propyl] -1,2-ethanediamine and N, N'-bis [3- (triethoxysilyl). Propyl] -1,2-ethanediamine, N- [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N- [3- (triethoxysilyl) propyl] -1,2-ethanediamine, Bis- [3- (trimethoxysilyl) propyl] amine, bis- [3- (triethoxysilyl) propyl] amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxy Silane, 3-aminopropylmethyldiethoxysilane, trimethoxy [3- (methylamino)] propylsilane, 3- (N-allylamino) propyltrimethoxysilane, 3- (N-allylamino) propyltriethoxysilane, 3-( Examples thereof include compounds such as diethylamino) propyltrimethoxysilane, 3- (diethylamino) propyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane, and 3- (phenylamino) propyltriethoxysilane.

Further, in the alkylamines, hydroxyalkylamines, other aliphatic amines, amines having a cyclic substituent, aromatic amines (arylamines), and amine compounds having an alkoxysilyl group, which are specifically mentioned above, Examples thereof include amino compounds in which the amino group is protected by an alkylidene group by ketones such as methyl ethyl ketone and methyl isobutyl ketone.
The content of the compound having an amino group (e) in the photosensitive base material of the present invention is 100, which is a composite formed from the hyperbranched polymer and the metal fine particles described later (or the total mass of the hyperbranched polymer and the metal fine particles) 100. It is preferably 1 part by mass to 100 parts by mass, more preferably 5 parts by mass to 50 parts by mass, and particularly 10 parts by mass to 15 parts by mass.
(E) When the content of the compound having an amino group is less than the above numerical range, the dispersibility of the complex formed from the hyperbranched polymer and the metal fine particles described later and further (f) the polyfunctional thiol described later. -If the solubility stabilizing effect cannot be obtained and the amount is added far beyond the above range (for example, 10 mass times the amount of the above composite), the plating film may have a poor appearance.

<(F) Polyfunctional thiol>
The polyfunctional thiol which is the component (f) used in the photosensitive base material of the present invention is not particularly limited as long as it is a compound having two or more mercapto groups, but for example, two as substituents. As the above hydrocarbons having a mercapto group and other polyfunctional compounds, mercaptocarboxylic acid esters of polyhydric alcohols, for example, polyhydric alcohols (mercaptoacetate), polyhydric alcohols (3-mercaptopro) Pionates), polyhydric alcohol polys (2-mercaptopropionates), polyhydric alcohol polys (3-mercaptobutyrate), polyhydric alcohol polys (3-mercaptoisobutyrate), etc. Can be mentioned.
In the photosensitive base material of the present invention, the polyfunctional thiol plays a role not only as a cross-linking agent but also as a chain transfer agent, and can be said to contribute to the realization of high sensitivity and excellent developability during photolithography.

Specific examples of hydrocarbons having two or more mercapto groups as the substituents include hexane-1,6-dithiol, decane-1,10-dithiol, 1,4-benzenedithiol, and 1,4-bis (). Mercaptomethyl) benzene and the like can be mentioned.

Examples of other bifunctional compounds include ethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), and the like. Ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-Mercaptopropionate), Ethylene Glycolbis (3-Mercaptobutyrate), Diethylene Glycolbis (3-Mercaptobutyrate), Butanediolbis (3-Mercaptobutyrate), Trimethylol Propantris (3-Mercaptobutyrate) Rate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), Butanediol bis (3-mercaptoisobutyrate), octanediolbis (3-mercaptoisobutyrate) and the like can be mentioned.

Trifunctional compounds include glycerintris (mercaptoacetate), trimethylolpropanetris (mercaptoacetate), glycerintris (3-mercaptopropionate), trimethylolpropanetris (3-mercaptopropionate), and trimethylolpropane. Tris (2-mercaptopropionate), trimethylolpropane tris (3-mercaptoisobutyrate), and the like can be mentioned.

Examples of the tetrafunctional compound include pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptoisobutyrate). , Etc. can be mentioned.

As the hexafunctional compound, dipentaerythritol hexakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), dipentaerythritol hexakis (3-Mercaptoisobutyrate), octanediolbis (3-mercaptobutyrate) and the like can be mentioned.

Among these polyfunctional thiols, it is preferable to use a tetrafunctional thiol compound from the viewpoint of improving the developability of the photosensitive base material.
In the present invention, (f) polyfunctional thiol can be used alone or in combination of two or more.

The blending amount of (f) polyfunctional thiol in the photosensitive base material of the present invention is the total mass of the complex (or the total mass of the hyperbranched polymer and the metal fine particles) formed from the hyperbranched polymer and the metal fine particles described later. It is preferably 0.01% by mass to 200% by mass, and preferably 0.05% by mass to 50% by mass. If the blending ratio is less than the above range, the desired effect cannot be obtained, while if it is added beyond the above range, the stability, odor, sensitivity, resolution, developability, adhesion, and plating of the photosensitive base material are obtained. There is a risk that the precipitation property and the like will deteriorate.

<Photosensitive base material>
The photosensitive base material of the present invention comprises the above-mentioned (a) hyperbranched polymer having an ammonium group at the molecular terminal, (b) metal fine particles, (c) polymerizable compound, (d) photopolymerization initiator, and (e) amino group. It contains the compound having (f) polyfunctional thiol and, if desired, other components, and at this time, it is preferable that the hyperbranched polymer and the metal fine particles form a complex.
Here, the complex is a composite in which both coexist in contact with or in close contact with metal fine particles due to the action of the ammonium group at the end of the hyperbranched polymer to form a particulate form, in other words, the hyperbranched polymer. It is expressed as a composite having a structure in which the ammonium group of the polymer is attached or coordinated to the metal fine particles.
Therefore, the "complex" in the present invention includes not only the one in which the metal fine particles and the hyperbranched polymer are bonded to form one complex as described above, but also the metal fine particles and the hyperbranched polymer in the bonded portion. Those that exist independently without forming may also be included.

The formation of a complex of a hyperbranched polymer having an ammonium group and metal fine particles was carried out at the same time as the preparation of the base material containing the hyperbranched polymer and the metal fine particles, and the method was as follows: a metal stabilized to some extent by a lower ammonium ligand. There are a method of exchanging a ligand with a hyperbranched polymer after producing fine particles, and a method of forming a complex by directly reducing metal ions in a solution of a hyperbranched polymer having an ammonium group. For example, a metal ion is added by adding an aqueous solution of a metal salt to the solution in which the hyperbranched polymer is dissolved and irradiating it with ultraviolet rays, or by adding an aqueous solution of the metal salt and a reducing agent to the hyperbranched polymer solution. Complexes can also be formed by reducing.

In the ligand exchange method, metal fine particles stabilized to some extent by a lower ammonium ligand as a raw material can be produced by the method described in Journal of Organometallic Chemistry 1996, 520, 143-162 and the like. The desired metal fine particle composite can be obtained by dissolving a hyperbranched polymer having an ammonium group in the reaction mixed solution of the obtained metal fine particles and stirring at room temperature (about 25 ° C.) or heating.
The solvent used is not particularly limited as long as it is a solvent capable of dissolving the metal fine particles and the hyperbranched polymer having an ammonium group in a required concentration or more, but specifically, alcohols such as ethanol, n-propanol and isopropanol are used. Halogenized hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile and mixed solutions of these solvents can be mentioned. Preferred is tetrahydrofuran.
The temperature at which the reaction mixture of the metal fine particles and the hyperbranched polymer having an ammonium group are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent, preferably at room temperature (approximately 25 ° C.) to 60 ° C. The range.
In the ligand exchange method, the metal fine particles can be stabilized to some extent in advance by using a phosphine-based dispersant (phosphine ligand) in addition to the amine-based dispersant (lower ammonium ligand).

As a direct reduction method, a hyperbranched polymer having a metal ion and an ammonium group is dissolved in a solvent and reduced with primary or secondary alcohols such as methanol, ethanol, isopropanol and polyol to obtain the desired metal. A fine particle composite can be obtained.
As the metal ion source used here, the above-mentioned metal salt can be used.
The solvent used is not particularly limited as long as it is a solvent capable of dissolving a hyperbranched polymer having a metal ion and an ammonium group in a required concentration or more, but specifically, alcohols such as methanol, ethanol, propanol and isopropanol; Halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyl tetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide (DMF), N- Examples thereof include amides such as methyl-2-pyrrolidone (NMP); sulfoxides such as dimethylsulfonate and the like, and a mixed solution of these solvents, preferably alcohols, halogenated hydrocarbons, cyclic ethers and the like. More preferably, ethanol, isopropanol, chloroform, tetrahydrofuran and the like can be mentioned.
The temperature of the reduction reaction can usually be in the range of 0 ° C. to the boiling point of the solvent, preferably in the range of room temperature (approximately 25 ° C.) to 60 ° C.

As another direct reduction method, a desired metal fine particle composite can be obtained by dissolving a hyperbranched polymer having a metal ion and an ammonium group in a solvent and reacting the mixture in a hydrogen gas atmosphere.
Examples of the metal ion source used here include the above-mentioned metal salt, hexacarbonyl chromium [Cr (CO) ₆ ], pentacarbonyl iron [Fe (CO) ₅ ], and octacarbonyl dicobalt [Co ₂ (CO) ₈ ]. , Tetracarbonyl nickel [Ni (CO) ₄ ] and other metal carbonyl complexes can be used. Further, zero-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes can also be used.
The solvent used is not particularly limited as long as it is a solvent capable of dissolving a hyperbranched polymer having a metal ion and an ammonium group in a required concentration or more, but specifically, alcohols such as ethanol and propanol; methylene chloride and chloroform. Halogenated hydrocarbons such as, etc .; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile and butyronitrile and a mixed solution of these solvents are mentioned, and tetrahydrofuran is preferable.
The temperature at which the metal ion and the hyperbranched polymer having an ammonium group are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent.

Further, as a direct reduction method, a desired metal fine particle composite can be obtained by dissolving a hyperbranched polymer having a metal ion and an ammonium group in a solvent and causing a thermal decomposition reaction.
As the metal ion source used here, the above-mentioned metal salt, metal carbonyl complex, other zero-valent metal complex, and metal oxide such as silver oxide can be used.
The solvent used is not particularly limited as long as it can dissolve a hyperbranched polymer having a metal ion and an ammonium group in a concentration higher than the required concentration, but specifically, methanol, ethanol, n-propanol, isopropanol, and ethylene glycol are used. Alcohols such as: Methylene chloride, halogenated hydrocarbons such as chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile and butyronitrile; aromatics such as benzene and toluene Examples thereof include hydrocarbons and the like, and a mixed solution of these solvents, preferably toluene.
The temperature at which the metal ion and the hyperbranched polymer having an ammonium group are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent, preferably near the boiling point of the solvent, for example, 110 ° C. (heating reflux) in the case of toluene. Is.

The complex of the hyperbranched polymer having an ammonium group and the metal fine particles thus obtained can be in the form of a solid substance such as powder through a purification treatment such as reprecipitation.

The photosensitive base material of the present invention comprises the above-mentioned (a) hyperbranched polymer having an ammonium group, (b) metal fine particles (preferably a composite composed of these), the above-mentioned (c) polymerizable compound, and the above-mentioned (d) photopolymerization. It contains an initiator, (e) a compound having an amino group, (f) a polyfunctional thiol, and, if desired, other components, and the photosensitive base material is described in [Electrolytic Plating Base Layer] described later. It may be in the form of a varnish used at the time of formation.

<Other additives>
The photosensitive base material of the present invention further contains additives such as surfactants and various surface conditioners, and additives such as sensitizers, polymerization inhibitors, and polymerization initiators, as long as the effects of the present invention are not impaired. It may be added as appropriate.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether and polyoxy. Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, Solbitan fatty acid esters such as sorbitan trioleate; polyoxyethylene nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate. EF-TOP (registered trademark) EF-301, EF-303, EF-352 [above, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.], Megafuck (registered trademark) F-171, F-173, R -08, R-30 [above, manufactured by DIC Co., Ltd.], Novec (registered trademark) FC-430, FC-431 [above, manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard (registered trademark) AG-710 Fluorine-based surfactants such as [manufactured by Asahi Glass Co., Ltd.] and Surflon (registered trademark) S-382 [manufactured by AGC Seimi Chemical Co., Ltd.] can be mentioned.

Further, as the surface conditioner, a silicone-based leveling agent such as Shin-Etsu Silicone (registered trademark) KP-341 [manufactured by Shin-Etsu Chemical Co., Ltd.]; BYK (registered trademark) -302, 307, 322, 323. , 330, 333, 370, 375, 378 [above, manufactured by Big Chemie Japan Co., Ltd.] and the like.

These additives may be used alone or in combination of two or more. The amount of the additive used is preferably 0.001 to 50 parts by mass, more preferably 0.005 to 10 parts by mass, and 0. 01 to 5 parts by mass is even more preferable.

[Electroless plating base layer]
The above-mentioned photosensitive base material of the present invention can be applied onto a base material to form a thin film, which is then photolithographically formed to form a patterned electroless plating base layer. The underlying layer is also the subject of the present invention.

The base material is not particularly limited, but a non-conductive base material or a conductive base material can be preferably used.
Examples of the non-conductive base material include glass, ceramic, etc .; polyethylene resin, polypropylene resin, vinyl chloride resin, nylon (polyamide resin), polyimide resin, polycarbonate resin, acrylic resin, PEN (polyethylene naphthalate) resin, PET (polyethylene). Telephthalate) resin, PEEK (polyether ether ketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin, etc .; paper and the like can be mentioned. These are preferably used in the form of a sheet, a film, or the like, and the thickness in this case is not particularly limited.
Examples of the conductive substrate include ITO (tin-doped indium oxide), ATO (antimon-doped tin oxide), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide), and the like. Various stainless steels, aluminum alloys such as aluminum and duralumin, iron and iron alloys, copper and brass, copper alloys such as phosphor bronze, white copper and beryllium copper, nickel and nickel alloys, and metals such as silver alloys such as silver and western silver. And so on.
Further, a substrate in which a thin film is formed of these conductive substrates on the non-conductive substrate can also be used.
Further, the base material may be a three-dimensional molded product.

A specific method for forming an electroless plating base layer from the hyperbranched polymer having an ammonium group and a photosensitive base material containing metal fine particles, a polymerizable compound, a photopolymerization initiator, a compound having an amino group and a polyfunctional thiol. First, the hyperbranched polymer having an ammonium group, metal fine particles (preferably a composite composed of these), a polymerizable compound, a photopolymerization initiator, a compound having an amino group, and a polyfunctional thiol are used as appropriate solvents. The varnish is dissolved or dispersed to form a varnish, and the varnish is applied onto a substrate on which a metal plating film is formed by a spin coating method; a blade coating method; a dip coating method; a roll coating method; a bar coating method; a die coating method; Inkjet method; Pen lithography such as fountain pen nanolithography (FPN) and dip pen nanolithography (DPN); typographic printing, flexo printing, resin letterpress printing, contact printing, microcontact printing (μCP), nanoimprinting lithography (NIL) ), Letterpress printing method such as nanotransfer printing (nTP); concave printing method such as gravure printing and engraving; flat plate printing method; stencil printing method such as screen printing and transcript printing; A thin layer is formed by evaporating and drying the solvent.
Among these coating methods, spin coating method, spray coating method, inkjet method, pen lithography, contact printing, μCP, NIL and nTP are preferable. When the spin coating method is used, since it can be applied in a single time, there is an advantage that even a highly volatile solution can be used and a highly uniform application can be performed. When the spray coating method is used, a highly uniform coating can be performed with a very small amount of varnish, which is industrially very advantageous. When the inkjet method, pen lithography, contact printing, μCP, NIL, or nTP is used, it is possible to efficiently form (draw) a fine pattern such as wiring, which is industrially very advantageous.

The solvent used here is a solvent that dissolves or disperses the above-mentioned complex (hyperbranched polymer having an ammonium group and metal fine particles), a polymerizable compound, a photopolymerization initiator, a compound having an amino group, and a polyfunctional thiol. If there is, the present invention is not particularly limited, but for example, water; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and dichlorobenzene; methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, n. Alcohols such as -hexanol, n-octanol, 2-octanol, 2-ethylhexanol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve; propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene Glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol Glycol ethers such as ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), etc. Glycol esters; ethers such as tetrahydrofuran (THF), methyl tetrahydrofuran, 1,4-dioxane, diethyl ether; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclo Ketones such as pentanone and cyclohexanone; aliphatic hydrocarbons such as n-heptane, n-hexane and cyclohexane; halogenated aliphatic hydrocarbons such as 1,2-dichloroethane and chloroform; N-methyl-2-pyrrolidone (NMP), N , N-Dimethylformamide (DMF), N, N-Dimethylacetamide and other amides; dimethyl sulfoxide and the like can be used. These solvents may be used alone or may be a mixture of two or more kinds of solvents. Further, glycols such as ethylene glycol, propylene glycol and butylene glycol may be added for the purpose of adjusting the viscosity of the varnish.
The concentration to be dissolved or dispersed in the solvent is arbitrary, but the solid content concentration in the varnish is 0.005 to 90% by mass, preferably 0.01 to 80% by mass. Here, the solid content is a component in the varnish excluding the solvent.

The method for drying the solvent is not particularly limited, and for example, it may be evaporated using a hot plate or an oven in an appropriate atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or in a vacuum. This makes it possible to obtain a base layer having a uniform film-forming surface. The firing temperature is not particularly limited as long as the solvent can be evaporated, but it is preferably performed at 40 to 250 ° C.

The thin film obtained as described above is then exposed to an exposure amount of ^{about 10 to 3,000 mJ / cm 2} through a mask having a predetermined pattern, and then developed with a developing solution to obtain an exposed portion. Is washed out to obtain a patterned electroless plating base layer.

For the exposure, for example, ultraviolet rays such as a mercury lamp, far ultraviolet rays, electron beams, X-rays and the like are used. As the light source used for ultraviolet irradiation, sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs and the like can be used.

The developing method is not particularly limited, and can be carried out by a known method such as a liquid filling method, a paddle method, a dipping method, a spray method, or a rocking dipping method. The developing temperature is preferably between 20 and 50 ° C., and the developing time is, for example, 10 seconds to 10 minutes.

As the developing solution, an organic solvent, water, an alkaline aqueous solution, or the like can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol and isopropanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether (PGME), 3-methoxy-3-methyl-1-butanol and the like. Glycol ethers; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF), 1,4-dioxane; ether esters such as propylene glycol monomethyl ether acetate (PGMEA); esters such as ethyl acetate and butyl acetate Classes; ketones such as acetone and cyclohexanone; amides such as N-methyl-2-pyrrolidone (NMP) and N, N-dimethylacetamide (DMAc); sulfoxides such as dimethyl sulfoxide and the like.
Examples of the alkaline aqueous solution include an aqueous solution of an alkali metal hydroxide such as potassium hydroxide and sodium hydroxide; an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline; ethanolamine. , Aqueous amine solutions such as propylamine, ethylenediamine and morpholine.
These developers may be used alone or in combination of two or more. As the mixed solution, for example, a PGME / PGMEA mixed solution (mass ratio 7: 3) or the like can be preferably used.
Water; glycols such as ethylene glycol, propylene glycol, and polyethylene glycol may be added to these developers in order to adjust the developability. Further, a surfactant or the like may be added in order to improve the removability of the unexposed portion.
Further, as the developer, a commercially available product can be preferably used, and examples thereof include OK73 thinner [Tokyo Ohka Kogyo Co., Ltd.].

After development, washing with water or a general organic solvent is preferably carried out for, for example, about 20 to 90 seconds. The moisture on the substrate is then removed by air drying with compressed air or compressed nitrogen or by spinning. If necessary, heat-dry it using a hot plate or an oven to obtain a patterned electroless plating base layer.

[Electroless plating, metal plating film, metal film base material]
By electroless plating the electroless plating base layer formed on the base material obtained as described above, a metal plating film is formed on the electroless plating base layer. The metal plating film thus obtained, and the metal coating base material provided on the base material in the order of the electroless plating base layer and the metal plating film are also the objects of the present invention.
The electroless plating treatment (process) is not particularly limited and can be performed by any generally known electroless plating treatment. For example, the plating is performed using a conventionally known electroless plating solution. A general method is to immerse the electroless plating base layer formed on the substrate in a liquid (bath).

The electroless plating solution mainly contains a metal ion (metal salt), a complexing agent, and a reducing agent, and is a pH adjuster, a pH buffer, and a reaction accelerator (second complexing agent) according to other uses. , Stabilizers, surfactants (for imparting gloss to the plating film, for improving the wettability of the surface to be treated, etc.) and the like are appropriately included.
Examples of the metal used for the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold and alloys thereof, which are appropriately selected according to the purpose. Will be done.
Further, the complexing agent and the reducing agent may be appropriately selected according to the metal ions.
A commercially available electroless plating solution may be used as the electroless plating solution. For example, an electroless nickel plating chemical (Melplate (registered trademark) NI series) manufactured by Meltex Co., Ltd. and an electroless copper plating chemical (Melplate (Melplate)) (Registered trademark) CU series); Electroless nickel plating solution (ICP Nicolon (registered trademark) series, Top Piena 650), electroless copper plating solution (OPC-700 electroless copper M-K,) manufactured by Okuno Pharmaceutical Co., Ltd. ATS Ad Copper IW, CT, OPC Copper (registered trademark) AF series, HFS, NCA), electroless tin plating solution (Substar SN-5), electroless gold plating solution (flash gold 330, self gold OTK) -IT), electroless silver plating solution (muden silver); electroless palladium plating solution (pallet II) manufactured by Kojima Chemical Co., Ltd., electroless gold plating solution (dip G series, NC gold series); Sasaki Chemical Electroless silver plating solution manufactured by Yakuhin Co., Ltd. (Sdia AG-40); Electroless nickel plating solution manufactured by Nippon Kanizen Co., Ltd. (Kanizen (registered trademark) series, Schumer (registered trademark) series, Schumaer (registered trademark)) Kani Black (registered trademark) series), electroless palladium plating solution (S-KPD); electroless copper plating solution manufactured by Dow Chemical Co., Ltd. (Cuposit (registered trademark) Coppermix series, Circuposit (registered trademark) series), Electroless palladium plating solution (Palamers (registered trademark) series), electroless nickel plating solution (Duraposit (registered trademark) series), electroless gold plating solution (Aurorectores (registered trademark) series), electroless tin plating solution (Tinposit (registered trademark) series), electroless copper plating solution manufactured by Uemura Kogyo Co., Ltd. (Sulcup (registered trademark) ELC-SP, PSY, PCY, PGT, PSR, PEA), Atotech Japan An electroless copper plating solution (Print Gant (registered trademark) PVE) manufactured by Co., Ltd. can be preferably used.

In the electroless plating step, the formation speed of the metal film is adjusted by adjusting the temperature, pH, immersion time, metal ion concentration, presence / absence of stirring and stirring speed, presence / absence of supply of air / oxygen, supply speed, and the like. And the film thickness can be controlled.

In this way, the metal coating base material of the present invention in which the metal plating film is formed on the base layer obtained by using the photosensitive base material of the present invention is a plating coating when a transparent base material is used as the base material. The surface that can be seen when the transparent base material is observed from the surface opposite to the side on which the transparent substrate is formed can be black.
Therefore, by applying a metal plating film on the base layer patterned by photolithography, a metal coating base material in which the back surface of the patterned plating film forming portion is black can be obtained. It can be used as a highly transparent transparent electrode.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the examples, the physical characteristics of the sample were measured using the following devices under the following conditions.

(1) GPC (Gel Permeation Chromatography)
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Showa Denko Corporation Shodex® GPC KF-804L + KF-803L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: UV (254 nm), RI
(2) ^{1 1} H NMR spectrum device: JNM-L400 manufactured by JEOL Ltd.
Solvent: CDCl ₃
Reference peak: Tetramethylsilane (0.00ppm)
(3) ¹³ C NMR spectrum device: JNM-ECA700 manufactured by JEOL Ltd.
Solvent: CDCl ₃
Relaxation reagent: Trisacetylacetonate chromium (Cr (acac) ₃ )
Reference peak: CDCl ₃ (77.0 ppm)
(4) ICP emission spectrometry (inductively coupled plasma emission spectrometry)
Equipment: ICPM-8500 manufactured by Shimadzu Corporation
(5) TEM (transmission electron microscope) imaging device: H-8000 manufactured by Hitachi High-Technologies Corporation
(6) Pattern exposure (mask aligner)
Equipment: MA6 manufactured by Susu Microtech
(7) Developing device: Small developing device ADE-3000S manufactured by Actes Kyozo Co., Ltd.
(8) Digital microscope imaging device: VHX-2000 manufactured by KEYENCE CORPORATION

The abbreviations used are as follows.
HPS: Hyperbranched polystyrene [Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd.]
8KX-078: Acrylic modified polymer [Acryt (registered trademark) 8KX-078 manufactured by Taisei Fine Chemicals Co., Ltd.]
8KX-078HC: Acrylic-modified ethylene oxide polymer (molecular weight 35,000) [Acryt (registered trademark) 8KX-078HC manufactured by Taisei Fine Chemicals Co., Ltd.]
8KX-078H: Acrylic modified polymer [Acryt (registered trademark) 8KX-078H manufactured by Taisei Fine Chemicals Co., Ltd.]
8KX-128A: Acrylic modified polymer [Acryt (registered trademark) 8KX-128A manufactured by Taisei Fine Chemicals Co., Ltd.]
OXE-01: 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyl oxime)] (photopolymerization initiator) [IRGACURE (registered trademark) OXE 01 manufactured by BASF Japan Ltd.]
IPA: Isopropanol IPE: Diisopropyl ether n-PrOH: n-propanol MIBK: Methyl isobutyl ketone KBM-903: 3-Aminopropyltrimethoxysilane [Shin-Etsu Silicone (registered trademark) KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.]
Karenz MT PE1: Pentaerythritol Tetrakis (3-mercaptobutyrate) [Karens MT (registered trademark) PE1 manufactured by Showa Denko KK)

５００ｍＬの反応フラスコに、塩化スルフリル［キシダ化学（株）製］２７ｇ及びクロロホルム５０ｇを仕込み、撹拌して均一に溶解させた。この溶液を窒素気流下０℃まで冷却した。
別の３００ｍＬの反応フラスコに、ジチオカルバメート基を分子末端に有するハイパーブランチポリマーＨＰＳ１５ｇ及びクロロホルム１５０ｇを仕込み、窒素気流下均一になるまで撹拌した。
前述の０℃に冷却されている塩化スルフリル／クロロホルム溶液中に、窒素気流下、ＨＰＳ／クロロホルム溶液が仕込まれた前記３００ｍＬの反応フラスコから、送液ポンプを用いて、該溶液を反応液の温度が−５〜５℃となるように６０分間かけて加えた。添加終了後、反応液の温度を−５〜５℃に保持しながら６時間撹拌した。
さらにこの反応液へ、シクロヘキセン［東京化成工業（株）製］１６ｇをクロロホルム５０ｇに溶かした溶液を、反応液の温度が−５〜５℃となるように加えた。添加終了後、この反応液をＩＰＡ１，２００ｇに添加してポリマーを沈殿させた。この沈殿をろ取して得られた白色粉末をクロロホルム１００ｇに溶解し、これをＩＰＡ５００ｇに添加してポリマーを再沈殿させた。この沈殿物を減圧ろ過し、真空乾燥して、塩素原子を分子末端に有するハイパーブランチポリマー（ＨＰＳ−Ｃｌ）８．５ｇを白色粉末として得た（収率９９％）。
得られたＨＰＳ−Ｃｌの^１Ｈ ＮＭＲスペクトルを図１に示す。ジチオカルバメート基由来のピーク（４．０ｐｐｍ、３．７ｐｐｍ）が消失していることから、得られたＨＰＳ−Ｃｌは、ＨＰＳ分子末端のジチオカルバメート基がほぼ全て塩素原子に置換されていることが明らかとなった。また、得られたＨＰＳ−ＣｌのＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは１４，０００、分散度Ｍｗ／Ｍｎは２．９であった。[Production Example 1] Production of HPS-Cl

Sulfuryl chloride [manufactured by Kishida Chemical Co., Ltd.] (27 g) and chloroform (50 g) were placed in a 500 mL reaction flask, and the mixture was stirred and uniformly dissolved. The solution was cooled to 0 ° C. under a nitrogen stream.
In another 300 mL reaction flask, 15 g of hyperbranched polymer HPS having a dithiocarbamate group at the end of the molecule and 150 g of chloroform were charged and stirred until uniform under a nitrogen stream.
From the 300 mL reaction flask in which the HPS / chloroform solution was charged under a nitrogen stream in the above-mentioned sulfuryl chloride / chloroform solution cooled to 0 ° C., the solution was subjected to the temperature of the reaction solution using a liquid feed pump. Was added over 60 minutes so that the temperature was -5 to 5 ° C. After completion of the addition, the mixture was stirred for 6 hours while maintaining the temperature of the reaction solution at −5 to 5 ° C.
Further, a solution prepared by dissolving 16 g of cyclohexene [manufactured by Tokyo Chemical Industry Co., Ltd.] in 50 g of chloroform was added to the reaction solution so that the temperature of the reaction solution was −5 to 5 ° C. After completion of the addition, this reaction solution was added to 1,200 g of IPA to precipitate the polymer. The white powder obtained by filtering this precipitate was dissolved in 100 g of chloroform, and this was added to 500 g of IPA to reprecipitate the polymer. The precipitate was filtered under reduced pressure and dried under vacuum to obtain 8.5 g of a hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular terminal as a white powder (yield 99%).
^{The 1} H NMR spectrum of the obtained HPS-Cl is shown in FIG. Since the peak derived from the dithiocarbamate group (4.0 ppm, 3.7 ppm) has disappeared, the obtained HPS-Cl has almost all the dithiocarbamate groups at the terminal of the HPS molecule replaced with chlorine atoms. It became clear. The weight average molecular weight Mw of the obtained HPS-Cl measured by GPC in terms of polystyrene was 14,000, and the dispersity Mw / Mn was 2.9.

冷却器を設置した１００ｍＬの反応フラスコに、製造例１で製造したＨＰＳ−Ｃｌ４．６ｇ（３０ｍｍｏｌ）及びクロロホルム１５ｇを仕込み、均一になるまで撹拌した。この溶液へ、ジメチルオクチルアミン［花王（株）製 ファーミン（登録商標）ＤＭ０８９８］５．０ｇ（３１．５ｍｍｏｌ）をクロロホルム７．５ｇに溶解させた溶液を加え、さらにＩＰＡ７．５ｇを加えた。この混合物を、窒素雰囲気下６５℃で４０時間撹拌した。
液温３０℃まで冷却後、溶媒を留去した。得られた残渣を、クロロホルム６０ｇに溶解し、この溶液をＩＰＥ２９０ｇに添加して再沈精製した。析出したポリマーを減圧ろ過し、５０℃で真空乾燥して、ジメチルオクチルアンモニウム基を分子末端に有するハイパーブランチポリマー（ＨＰＳ−Ｎ（Ｍｅ）_２ＯｃｔＣｌ）９．３ｇを白色粉末として得た。
得られたＨＰＳ−Ｎ（Ｍｅ）_２ＯｃｔＣｌの^１３Ｃ ＮＭＲスペクトルを図２に示す。ベンゼン環のピークと、オクチル基末端のメチル基のピークから、得られたＨＰＳ−Ｎ（Ｍｅ）_２ＯｃｔＣｌは、ＨＰＳ−Ｃｌ分子末端の塩素原子がほぼ定量的にアンモニウム基に置換されていることが明らかとなった。また、ＨＰＳ−ＣｌのＭｗ（１４，０００）及びアンモニウム基導入率（１００％）から算出されるＨＰＳ−Ｎ（Ｍｅ）_２ＯｃｔＣｌの重量平均分子量Ｍｗは２８，０００となった。[Manufacturing Example 2] Production of HPS-N (Me) ₂ OctCl

4.6 g (30 mmol) of HPS-Cl and 15 g of chloroform prepared in Production Example 1 were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. To this solution was added a solution in which 5.0 g (31.5 mmol) of dimethyloctylamine [Farmin (registered trademark) DM0898 manufactured by Kao Corporation] was dissolved in 7.5 g of chloroform, and 7.5 g of IPA was further added. The mixture was stirred at 65 ° C. for 40 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., the solvent was distilled off. The obtained residue was dissolved in 60 g of chloroform, and this solution was added to 290 g of IPE for reprecipitation purification. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 9.3 g of a _{hyperbranched polymer (HPS-N (Me) 2 OctCl) having a dimethyloctylammonium group at the molecular terminal as a white powder.}
The ¹³ C NMR spectrum of the obtained HPS-N (Me) _{2 OctCl is shown in FIG. In the HPS-N (Me) 2} OctCl obtained from the peak of the benzene ring and the peak of the methyl group at the terminal of the octyl group, the chlorine atom at the terminal of the HPS-Cl molecule is almost quantitatively replaced with the ammonium group. Became clear. The weight average molecular weight Mw of _{HPS-N (Me) 2} OctCl calculated from the Mw (14,000) of HPS-Cl and the introduction rate of ammonium groups (100%) was 28,000.

[Production Example 3] Production of HBP-Pd-1 4.2 g of palladium acetate [manufactured by Kawaken Fine Chemicals Co., Ltd.] and 40 g of chloroform were placed in a 100 mL reaction flask equipped with a condenser and stirred until uniform. To this solution, a solution prepared by dissolving 8.0 g of HPS-N (Me) ₂ OctCl produced in Production Example 2 in 100 g of chloroform was added using a dropping funnel. The inside of the dropping funnel was washed into the reaction flask using 20 g of chloroform and 40 g of ethanol. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 2,000 g of an IPE / hexane solution (mass ratio 10: 1) for reprecipitation purification. The precipitated polymer is filtered under reduced pressure and vacuum dried at 50 ° C. to blacken 8.9 g of _{a complex (Pd [HPS-N (Me) 2 OctCl]) of a hyperbranched polymer having an ammonium group at the molecular end and Pd particles.} Obtained as a powder (HBP-Pd-1).
From the result of ICP emission analysis, the Pd content of the obtained Pd [HPS-N (Me) ₂ OctCl] (HBP-Pd-1) was 20% by mass. Further, from the TEM (transmission electron microscope) image, the Pd particle size was about 2 to 4 nm.

[Production Example 4] Production of HBP-Pd-2 2.1 g of palladium acetate [manufactured by Kawaken Fine Chemicals Co., Ltd.] and 20 g of chloroform were placed in a 100 mL reaction flask equipped with a condenser, and the mixture was stirred until uniform. A solution prepared by dissolving 9.0 g of HPS-N (Me) ₂ OctCl prepared in Production Example 2 in 120 g of chloroform was added to this solution using a dropping funnel. The inside of the dropping funnel was washed into the reaction flask using 20 g of chloroform and 40 g of ethanol. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 2,000 g of an IPE / hexane solution (mass ratio 10: 1) for reprecipitation purification. The precipitated polymer is filtered under reduced pressure and vacuum dried at 50 ° C. to blacken 9.3 g of _{a complex (Pd [HPS-N (Me) 2} OctCl]) of a hyperbranched polymer having an ammonium group at the end of the molecule and Pd particles. Obtained as a powder (HBP-Pd-2).
From the result of ICP emission analysis, the Pd content of the obtained Pd [HPS-N (Me) ₂ OctCl] (HBP-Pd-2) was 10% by mass. Further, from the TEM (transmission electron microscope) image, the Pd particle size was about 2 to 4 nm.

[Reference Example 1] Preparation of electroless nickel plating solution 40 mL of Kanigen (registered trademark) Blue Schumer [manufactured by Japan Kanigen Co., Ltd.] was charged in a 2 L beaker, and pure water was further added to bring the total amount of the solution to 200 mL. This solution was stirred to obtain an electroless nickel plating solution.

[Example 1]
[Preparation of photosensitive base material]
8 parts by mass of HBP-Pd-1 produced in Production Example 3 as a Pd catalyst, 1 part by mass of KBM-903 as a compound having an amino group, 86 parts by mass of 8KX-078H shown in Table 1 as a polymerizable polymer compound, many 0.45 parts by mass of Karenz MT PE1 as a functional thiol (also called RSH), 4.54 parts by mass of OXE-01 as a polymerization initiator, and n-PrOH and MIBK as a solvent are mixed at a ratio of 8: 1 to form a non-solvent component (mixture). A photosensitive substrate for electroless plating having a concentration of 5% by mass (all components excluding the solvent inside) was prepared. In order to facilitate uniform mixing of each component, a part of n-PrOH: MIBK = 8: 1 in which each component was dissolved in advance was mixed.
The HBP-Pd-1 used above was previously mixed with a compound having an amino group to form an ammine complex according to the following procedure, and this was mixed with other components of the photosensitive base material.
<Ammonia complex formation>
500 mg of HBP-Pd-1 produced in Production Example 3 was dissolved in n-PrOH: MIBK = 8: 1 (solution 1), the total amount of the solution was 5 g, and the mixture was stirred with a mix rotor for 30 minutes.
On the other hand, 1.25 g of KBM-903 as a compound having an amino group was dissolved in n-PrOH: MIBK = 8: 1 (solution 2), the total amount of this solution was 5 g, and the mixture was stirred with a mix rotor. Further, this solution 2 was diluted 10-fold with n-PrOH: MIBK = 8: 1.
1 g of diluted solution 2 (amino group-containing compound) was added to solution 1 (HBP-PD-1), and n-PrOH: MIBK = 8: 1 was further added to bring the total amount to 10 g.
160 mg of the HBP-PD-1 5.625 mass% solution obtained by this procedure was used.

[Application]
2.5 mL of the above photosensitive base material was applied to the back surface (easily adhesive untreated surface) of a PET film (A4100 manufactured by Toyobo Co., Ltd.) with a bar coater using a bar having a liquid thickness of 25 μm. This base material was allowed to stand for 2 minutes and then dried in an oven at 80 ° C. for 5 minutes to obtain a base material having a base layer on the entire surface of the base material.

[Patterning (exposure and development)]
^{The obtained base layer was exposed to i-line with an illuminance of 11.6 mW / cm 2} and an exposure amount of 600 mJ / cm in an air atmosphere with a mask aligner on which a photomask having a width of 3 μm, 5 μm, 7 μm, and 9 μm was drawn. ^It was irradiated and exposed so as to be 2.
The exposed substrate was developed using a developing apparatus equipped with a shower nozzle. In the development, the base material is rotated at 300 rpm, washed with water for 60 seconds, and then the rotation speed is increased to 1,500 rpm to shake off the water to provide a group having an electroless plating base layer patterned on the base material. I got the wood.

[Electroless plating]
The obtained substrate was immersed in the electroless nickel plating solution prepared in Reference Example 1 heated to 80 ° C. for 2 minutes. Then, the removed base material was washed with water and dried on a hot plate at 100 ° C. for 3 minutes to obtain a plated base material.

[Comparative Examples 1 to 3]
The operation was carried out in the same manner as in Example 1 except that the polymerizable polymer compound was changed to that shown in Table 1.
Each plating substrate obtained from Example 1 and Comparative Examples 1 to 3 was evaluated based on the following criteria.

<Developability evaluation criteria>
○ Developed △ Partially developed × Not developed <Plating formation condition evaluation criteria>
○ The pattern of the base layer is obtained according to the mask pattern, and the plating is deposited on the base layer pattern (a patterned plating film is formed).
× Table 1 shows the results of not forming a patterned plating film.

Further, with respect to the metal plating film on each plating base material obtained by using the electroless plating base materials of Example 1 and Comparative Examples 1 to 3, the plating film formation observed from the back side of the transparent base material. The blackened state of the portion was visually evaluated according to the following criteria. The results are shown in Table 2.

<Evaluation criteria for blackening the back side>
A: Sufficiently blackened B: Looks brown C: No effect

Further, as the plating base material, the surface (easy-adhesion-treated surface) of the PET film (manufactured by Toyo Boseki Co., Ltd., A4100) and the easily-adhesion-treated surface of the PET film (manufactured by Teijin DuPont Film Co., Ltd., HB3) are used. A metal plating film was prepared on each plating substrate by the same method as described above using the electroless plating base material of No. 1 and Comparative Examples 1 to 3. A cellophane tape (registered trademark) [CT-18S manufactured by Nichiban Co., Ltd.] with a width of 18 mm was attached to the obtained metal-plated film portion, and the cellophane tape (registered) was adhered after being firmly rubbed with the fingers of the hand. The trademark) was peeled off at once, and the state of the metal plating film was visually evaluated according to the following criteria. The results are also shown in Table 2.

<Evaluation criteria for substrate adhesion>
◯: Metal plating film peeled off and adhered to the base material △: Metal plating film partially peeled off ×: Most (about 50% or more) metal plating film peeled off and adhered to cellophane tape (registered trademark)

As shown in Table 1, a plating film is formed on a patterned electroless plating base layer obtained by forming a base layer using the above photosensitive base material, exposing the base layer through a mask, and then developing the base layer. When a base material containing a polymerizable polymer compound having no hydrophilic portion was used, the plating was not developed and the plating was not precipitated (Comparative Example 1). Further, when a base material containing a polymerizable polymer compound having a hydrophilic portion of 10% was used, it was partially developed, but almost the entire surface was plated (Comparative Example 2). Further, even when a base material containing a polymerizable polymer compound having a hydrophilic portion of 30% is used, if the compound has a low molecular weight, plating is precipitated in the thick line portion and plating is precipitated in the thin line pattern portion. There was no (Comparative Example 3).
On the other hand, when the photosensitive base material of the present invention containing a polymerizable polymer compound having a high molecular weight and 30% hydrophilic portion was used, plating on the fine wire portion was confirmed (Example 1).
From the above results, it has been clarified that the photosensitive base material of the present invention can form a plating base layer patterned by photolithography and is advantageous in obtaining a fine metal plating film.
Further, as shown in Table 2, the metal plating film obtained by using the photosensitive base material of the present invention has excellent adhesion to the substrate, and the back surface of the metal plating film exhibits a sufficient black color. Can be expected to be used as a transparent electrode with high image visibility when it is formed on a transparent substrate such as a glass substrate.

Claims (16)

A base material for forming a metal plating film on a base material by electroless plating.
(A) A hyperbranched polymer having an ammonium group at the end of the molecule and having a weight average molecular weight of 1,000 to 5,000,000.
(B) Metal fine particles,
(C) It has one or more side chains in the molecule that are polymerizable unsaturated bonds, has 15 to 50 mol of oxyalkylene groups per 100 mol of all repeating units, and has a weight average molecular weight of 10,000. 100,000 high molecular weight compounds,
(D) Photopolymerization initiator,
A photosensitive base material containing (e) a compound having an amino group and (f) a polyfunctional thiol. The photosensitive base material according to claim 1, wherein the polymer compound (c) is a compound having three or more (meth) acryloyl groups in the molecule. The photosensitive base material according to claim 1 or 2, wherein the oxyalkylene group of the polymer compound (c) is a poly (oxyalkylene) group. The photosensitive base material according to any one of claims 1 to 3, wherein the polymer compound (c) is a compound having a weight average molecular weight of 20,000 to 50,000. The photosensitive base material according to any one of claims 1 to 4, wherein the polyfunctional thiol (f) is a tetrafunctional thiol. The photosensitive base material according to any one of claims 1 to 5, wherein the compound having an amino group (e) is an alkoxysilane compound having an amino group. The photosensitive base material according to any one of claims 1 to 6, wherein the hyperbranched polymer (a) is a hyperbranched polymer represented by the formula [1].

(In the formula, R ¹ independently represents a hydrogen atom or a methyl group, and R ^{2 to} R ⁴ independently represent a hydrogen atom and a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, respectively. , An arylalkyl group having 7 to 20 carbon atoms or-(CH ₂ CH ₂ O) _m R ⁵ (in the formula, R ⁵ represents a hydrogen atom or a methyl group, and m represents an integer of 2 to 100). Represent (the alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxy group or a cyano group), or ^{two groups of R 2 to} R ⁴ are combined together. Representing a linear, branched or cyclic alkylene group, or R ^{2 to} R ⁴ may be combined with the nitrogen atom to which they are attached to form a ring, where X ⁻ represents an anion. Represented, n is the number of repeating unit structures, represents an integer of 5 to 100,000, and A ¹ represents the structure represented by the equation [2].)

(In the formula, A ² represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ^{1 to} Y ⁴ are independently hydrogen. Represents an atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxy group or a cyano group). The photosensitive base material according to claim 7, wherein the hyperbranched polymer (a) is a hyperbranched polymer represented by the formula [3].

(In the formula, ^{R 1} to ^{R 4} and n are as defined above.) The metal fine particles (b) are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt) and gold ( The photosensitive base material according to any one of claims 1 to 8, which is at least one kind of metal fine particles selected from the group consisting of Au). The photosensitive base material according to claim 9, wherein the metal fine particles (b) are palladium fine particles. The photosensitive base material according to any one of claims 1 to 10, wherein the metal fine particles (b) are fine particles having an average particle size of 1 to 100 nm. The photosensitive base material according to any one of claims 1 to 11, wherein a pattern can be formed by photolithography. An electroless plating base layer which is a patterned layer by photolithography, which comprises the photosensitive base material according to any one of claims 1 to 12. A metal plating film composed of an electroless plating layer formed on the electroless plating base layer according to claim 13. The base material, the electroless plating base layer according to claim 13 formed on the base material, and the metal plating film according to claim 14 formed on the electroless plating base layer. Metal film base material. A method for producing a metal film base material, which comprises the following steps A to C.
Step A: The photosensitive base material according to any one of claims 1 to 12 is applied onto a base material to provide a base layer. Step B: A base layer having a desired pattern is formed by photolithography. Step C: A step of immersing a base material having a patterned base layer in an electrolytic plating bath to form a metal plating film.

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