200837217 九、發明說明 【發明所屬之技術領域】 本發明’係關於一種具有與基材之密合性優里之金屬 鑛敷膜，該膜之表面無露出部（斑點）而均一*，可藉化學 鍍敷法製造之鍍敷物及其製造方法。 【先前技術】 於基材上形成導電性筒分子層並於該導電性高分子層 上實施鍍敷，藉此製作電氣電路之化學鍍敷法，曾有數個 被提出。 專利文獻1，揭示：於基板上形成含有具藉由光照射 使單體之氧化聚合性消失或減少之性質之氧化齊υ的觸媒層 ，於該觸媒層上將導電性高分子聚合後，於該導電性高子 上由化學鍍敷液將金屬膜化學鍍敷之方法。 專利文獻2，揭示一種金屬物質之製造方法，其特徵 係，金屬化之物質被施以含聚苯胺之被覆，聚苯胺藉還原 而活性化，以及，將被施以被覆之物質與含有金屬離子的 溶液接觸，藉此，以非電氣化學之方法使金屬附著於物質 上。 專利文獻1 :日本專利第3 069942號說明書 專利文獻2 :日本專利第3 20873 5號說明書 【發明內容】 然而，於專利文獻1所揭示之方法，於導電性高子聚 -4- 200837217 合時所使用之氧化劑，無法去除，故將導電性高分子氧化 聚合、再實施化學鍍敷之後’該氧化劑亦殘留於導電性高 分子層之下。而該殘留之氧化劑，會將以化學鍍敷形成之 金屬鍍敷膜（銅、鎳等）氧化，其結果，該金屬鍍敷膜會 劇烈地腐鈾，因此，金屬鍍敷膜與基材膜之密合性會變得 非常弱，而難以承受中〜長期之使用。 以專利文獻1記載之方法所製得之金屬鍍敷膜，於金 屬鍍敷膜之重要評價項目之一之與基材膜之密合性，爲非 常弱者。密合性低之主要原因，係如上述，可考量爲金屬 鍍敷膜因氧化劑而腐鈾之故，除此之外，亦可考量爲由於 爲基材膜-氧化劑層-導電性高分子層-金屬鍍敷膜之多 層構造，故容易產生各層間之剝離之故。 專利文獻2，係如專利文獻1之於基材上將單體聚合 以形成導電性高分子層者，而揭示一種使用聚苯胺等之已 聚合之導電性高分子之金屬物質之製造方法。該製造方法 ，由於係使用已聚合之導電性高分子故不使用氧化觸媒， 因此，不會產生專利文獻1之問題，亦即，因殘留之氧化 劑所致之金屬鍍敷膜腐鈾之問題、因多層構造使金屬鍍敷 膜之密合性不足所致之易剝離性之問題。 然而，專利文獻2所記載之製造方法，於以非電氣化 學之方法（=化學）於導電性高分子上進行鍍敷使金屬附 著之前，必須將該導電性高分子以聯胺等化學還原劑還原 (=脫摻雜）以活性化，並且，脫摻雜後，由於不使用 Pd等觸媒進行鍍敷以使金屬附著，故必須塗布很厚的導 -5- 200837217 電性局分子層。其結果’該導電性筒分子之化學還原（= 脫摻雜），必須於氫氧化鈉等強鹼中以室溫浸漬2 4小時 之長時間作成還原（=脫摻雜）狀態。因此，僅能使用可 長時間承受該鹼處理液之基材膜，其可使用之基材僅限定 於特定者，且，由於該處理使聚苯胺本身塗膜之強度降低 、與基材膜之密合性降低，是其問題， 本發明之課題在於提供一種鍍敷物及其製造方法，其 於上述之化學鍍敷法中，沒有金屬鍍敷膜之密合性降低之 問題，亦即，金屬鍍敷膜與基材之密合性優，此外，金屬 鍍敷膜之表面無露出部（斑點）而均一，而可藉化學鍍敷 法製造。 本發明人等，爲了解決上述課題而努力探討的結果發 現，若於用以形成金屬鍍敷膜之塗膜層使用還原性高分子 微粒子與特定量之黏結劑，則可增高以化學鍍敷所形成之 金屬鍍敷膜的密合性，增加該塗膜表面上之觸媒金屬之吸 附量’藉此，可使塗膜上所形成之金屬鍍敷膜爲無露出部 (斑點）而均一之膜表面，又，於進行該化學鍍敷之際， 於該還原性高分子微粒子上會還原、吸附鈀等觸媒金屬， 而藉此該還原性高分子微粒子，成爲導電性之高分子微粒 子’再者’於形成該塗膜層之際，使塗膜層之上側半部之 中存在有該導電性高分子微粒子中之60%以上之粒子， 則可更提高金屬鍍敷膜之密合性，此外，即使於薄的塗膜 層’塗膜上所形成之金屬鍍敷膜亦可爲無露出部（斑點） 而均一之膜表面，而完成本發明。 -6- 200837217 亦即，本發明，係關於 1. 一種鍍敷物，係於基材表面上形成含導電性高分 子微粒子與黏結劑之塗膜層，而於該塗膜層上以化學鍍敷 法形成有金屬鍍敷膜之鍍敷物， 該黏結劑，對於該導電性高分子微粒子1質量份以 〇·1至10質量份存在，該塗膜層之厚度爲20至500nm。 2 ·如上述1所記載之鍍敷物，其中，於該塗膜層之 上側半部中，存在有該導電性高分子微粒子中之60 %以 上之粒子。 3. 如上述1所記載之鍍敷物，其中，該導電性高分 子微粒子之平均粒徑爲10至100nm。 4. 一種方法，係藉由化學鍍敷液將金屬膜化學鍍敷 之鍍敷物之製造方法，其係由下述A )步驟及B )步驟所 構成， A)於基材上，塗布含有還原性高分子微粒子與對該 還原性高分子微粒子1質量份之〇. 1至1 〇質量份之黏結 劑的塗料，形成厚度爲20至50Onm、表面上可吸附之觸 媒金屬量爲0.1 // g/cm2以上、且層之上側半部中存在有 該還原性高分子微粒子中之60 %以上之粒子所形成的塗 膜層之步驟， B )於該塗膜層，由化學鍍敷液將金屬膜化學鍍敷之 步驟。 5. 如上述4所記載之方法，其中，該還原性高分子 微粒子，係使用將導電性高分子微粒子進行脫摻雜（ -7- 200837217200837217 IX. OBJECTS OF THE INVENTION [Technical Field] The present invention relates to a metal ore coating having a good adhesion to a substrate, the surface of which has no exposed portion (spot) and is uniform*, and can be chemically A plating method produced by a plating method and a method for producing the same. [Prior Art] Several types of electroless plating methods for electrical circuits have been formed by forming a conductive cylinder molecular layer on a substrate and performing plating on the conductive polymer layer. Patent Document 1 discloses that a catalyst layer containing oxidized ruthenium having a property of eliminating or reducing oxidative polymerization property of a monomer by light irradiation is formed on a substrate, and a conductive polymer is polymerized on the catalyst layer. A method of chemically plating a metal film from an electroless plating solution on the conductive high-order. Patent Document 2 discloses a method for producing a metal substance characterized in that a metallized substance is coated with a polyaniline-containing coating, polyaniline is activated by reduction, and a substance to be coated and a metal ion-containing substance are applied. The solution is contacted whereby the metal is attached to the material in a non-electrochemical manner. Patent Document 1: Japanese Patent No. 3 069 942, Patent Document 2: Japanese Patent No. 3 20873 5 [Invention] However, the method disclosed in Patent Document 1 is used in the case of high conductivity poly-4- 200837217. Since the oxidizing agent cannot be removed, the oxidizing agent remains under the conductive polymer layer after oxidative polymerization of the conductive polymer and chemical plating. The residual oxidizing agent oxidizes a metal plating film (copper, nickel, etc.) formed by electroless plating, and as a result, the metal plating film violently uranizes, and therefore, the metal plating film and the base film The adhesion will become very weak and it will be difficult to withstand the use of medium to long term. The metal plating film obtained by the method described in Patent Document 1 is very weak in adhesion to the substrate film in one of the important evaluation items of the metal plating film. The reason for the low adhesion is as follows. It can be considered that the metal plating film is rusted with uranium due to the oxidizing agent, and in addition, it may be considered as a substrate film-oxidizing agent layer-conductive polymer layer. - The multilayer structure of the metal plating film is liable to cause peeling between the layers. Patent Document 2 discloses a method for producing a metal material using a polymerized conductive polymer such as polyaniline, in which a monomer is polymerized on a substrate to form a conductive polymer layer. In this production method, since the polymerized conductive polymer is used, the oxidation catalyst is not used, so that the problem of Patent Document 1 is not caused, that is, the problem of the metal plated film uranium due to the residual oxidant. The problem of easy peelability due to insufficient adhesion of the metal plating film due to the multilayer structure. However, in the production method described in Patent Document 2, it is necessary to chemically polymerize the conductive polymer to a chemical reducing agent such as hydrazine before the metal is adhered to the conductive polymer by a non-electrochemical method (=chemistry). Reduction (=de-doping) is activated, and after dedoping, since plating is not performed using a catalyst such as Pd to adhere the metal, it is necessary to apply a very thick conductive layer of the conductive layer-5-200837217. As a result, chemical reduction (= dedoping) of the conductive cylinder molecules must be carried out in a reduced (= dedoped) state by immersing in a strong alkali such as sodium hydroxide at room temperature for 24 hours. Therefore, it is only possible to use a substrate film which can withstand the alkali treatment liquid for a long period of time, and the substrate which can be used is limited to a specific one, and the strength of the polyaniline coating film is lowered by the treatment, and the substrate film is The problem of the adhesion is lowered, and an object of the present invention is to provide a plating material and a method for producing the same, wherein in the above electroless plating method, there is no problem that the adhesion of the metal plating film is lowered, that is, the metal The plating film is excellent in adhesion to the substrate, and the surface of the metal plating film is uniform without an exposed portion (spot), and can be produced by an electroless plating method. As a result of intensive studies to solve the above problems, the present inventors have found that when a reducing polymer fine particle and a specific amount of a binder are used for a coating layer for forming a metal plating film, an electroless plating can be used. The adhesion of the formed metal plating film increases the amount of adsorption of the catalyst metal on the surface of the coating film. Thus, the metal plating film formed on the coating film can be made uniform without spots (spots). On the surface of the film, when the electroless plating is performed, a catalytic metal such as palladium is reduced and adsorbed on the reducing polymer fine particles, whereby the reducing polymer fine particles become conductive polymer microparticles. In addition, when the coating layer is formed, when 60% or more of the conductive polymer fine particles are present in the upper half of the coating layer, the adhesion of the metal plating film can be further improved. Further, the metal plating film formed on the coating film of the thin coating layer may be a film surface having no exposed portion (spot) and uniform, and the present invention has been completed. -6- 200837217 That is, the present invention relates to a plating material which forms a coating layer containing conductive polymer microparticles and a binder on a surface of a substrate, and is electrolessly plated on the coating layer. In the method, a plating material having a metal plating film is formed, and the binder is present in an amount of from 1 to 10 parts by mass per 1 part by mass of the conductive polymer fine particles, and the thickness of the coating layer is from 20 to 500 nm. (2) The plating material according to the above aspect, wherein more than 60% of the conductive polymer fine particles are present in the upper half of the coating layer. 3. The plating material according to the above 1, wherein the conductive high molecular fine particles have an average particle diameter of 10 to 100 nm. 4. A method for producing a plating material for electroless plating of a metal film by an electroless plating solution, which comprises the following steps A) and B), wherein A) is coated on the substrate to contain a reduction The polymer microparticles and the coating material of 1 to 1 part by mass of the binder of the reducing polymer microparticles are formed to have a thickness of 20 to 50 nm, and the amount of the catalyst metal adsorbed on the surface is 0.1 // a step of forming a coating layer formed by particles of 60% or more of the reducing polymer fine particles in the upper half of the layer, and B) in the coating layer, which is formed by the electroless plating solution The step of metal film electroless plating. 5. The method according to the above 4, wherein the reducing polymer microparticles are subjected to dedoping of the conductive polymer microparticles (-7-200837217)
Dedoping)處理以作成還原性之微粒子。 本發明之鍍敷物，係於基材表面上形成含導電性高分 子微粒子與黏結劑之塗膜層，而於該塗膜層上以化學鍍敷 法形成有金屬鍍敷膜者，於該塗膜層，係使用已聚合之微 粒子，故未使用聚合觸媒之氧化劑，而無專利文獻1所示 之腐蝕的問題， 又，於以下說明，該塗膜層中之還原性高分子微粒子 ，藉化學鍍敷法而最終成爲導電性高分子微粒子。 又，藉由使用黏結劑，可提昇金屬鍍敷膜與基材之密 合性。 此時，所形成之金屬鍍敷膜，可爲無露出部（斑點） 而均一者。 本發明之鍍敷物之較佳狀態，塗膜層，係以使其上側 半部中存在有還原性高分子微粒子中之60%以上之粒子 的方式形成，因此，塗膜層之下側半部，黏結劑的存在比 增高而提昇基材與塗膜層之密合性，結果，更進一步地提 昇金屬鍍敷膜與基材之密合性。 又，由於靠近塗膜層之表面還原性高分子微粒子之存 在比增高，故表面上之觸媒金屬之吸附量增加，藉此，所 形成之金屬鍍敷膜，即使爲薄的塗膜層，亦可成爲無露出 部（斑點）而均一者。 本發明之鑛敷物’不僅速原性筒分子微粒子，即使使 用導電性高分子微粒子亦可同樣地製造。於該場合，於進 行化學鍍敷之前，必須將導電性高分子微粒子脫摻雜成爲 -8 - 200837217 還原性，本發明之鍍敷物，與上述同樣的，即使於薄的層 (導電性高分子微粒子層），亦可維持優異之密合性及均 一性。 而由於可將導電性高分子微粒子層變薄，故即使短時 間之鹼處理亦可達成該脫摻雜作成塗膜層，藉此，可避免 專利文獻2所記載之長時間之鹼處理所致之密合性降低的 問題。 又，於塗膜層之上側半部中存在有高分子微粒子中之 60%以上之粒子之構造，僅要對將含還原性高分子微粒子 或導電性高分子微粒子與黏結劑之塗料塗布於基材上後之 乾燥溫度與時間下工夫即可容易地達成。 又，本發明之鍍敷物，例如，可藉由於形成於基材上 之含還原性高分子微粒子之塗膜層上，使鈀等觸媒金屬還 原、吸附，於吸附該鈀等觸媒金屬之塗膜層上形成金屬鍍 敷膜來製造，而此時，鈀等觸媒金屬對還原性高分子微粒 子之吸附，例如，當爲聚吡咯時，可推測爲下圖所示之狀 態。 [化1] H uDedoping) is treated to make reducing microparticles. The plating material of the present invention is formed by forming a coating layer containing conductive polymer microparticles and a binder on the surface of the substrate, and forming a metal plating film by electroless plating on the coating layer. In the film layer, since the polymerized fine particles are used, the oxidizing agent of the polymerization catalyst is not used, and there is no problem of corrosion as shown in Patent Document 1, and the reducing polymer fine particles in the coating layer are described below. The electroless plating method finally becomes a conductive polymer fine particle. Further, by using a binder, the adhesion between the metal plating film and the substrate can be improved. At this time, the formed metal plating film may be uniform without an exposed portion (spot). In a preferred embodiment of the plating material of the present invention, the coating layer is formed such that 60% or more of the reducing polymer fine particles are present in the upper half portion, and therefore, the lower half of the coating layer is formed. When the presence ratio of the binder is increased, the adhesion between the substrate and the coating layer is improved, and as a result, the adhesion between the metal plating film and the substrate is further improved. Further, since the ratio of the amount of the reducing polymer fine particles on the surface close to the coating layer is increased, the amount of the catalyst metal adsorbed on the surface is increased, whereby the formed metal plating film is a thin coating layer. It can also be uniform without exposure (spots). The mineral deposits of the present invention are not only produced by using the pyrogenic microparticles, but also by using the conductive polymer microparticles. In this case, it is necessary to de-doping the conductive polymer fine particles to -8 - 200837217 before the electroless plating, and the plating material of the present invention is the same as the above, even in a thin layer (conductive polymer) Microparticle layer) also maintains excellent adhesion and uniformity. Further, since the conductive polymer fine particle layer can be thinned, even if the alkali treatment is performed for a short period of time, the dedoping can be achieved to form a coating layer, thereby avoiding the long-time alkali treatment described in Patent Document 2. The problem of reduced adhesion. Further, in the upper half of the coating layer, 60% or more of the particles of the polymer fine particles are present, and only the coating material containing the reducing polymer fine particles or the conductive polymer fine particles and the binder is applied to the base. The drying temperature and time after the material can be easily achieved. In addition, the plating material of the present invention can be reduced or adsorbed by a catalytic metal such as palladium or the like by adsorbing the catalytic metal such as palladium on the coating layer containing the reducing polymer fine particles formed on the substrate. When a metal plating film is formed on the coating layer, the adsorption of the catalytic metal such as palladium to the reducing polymer fine particles, for example, when it is polypyrrole, can be estimated as shown in the following figure. [Chemical 1] H u
9- 200837217 亦即，還原性之高分子微粒子（聚吡咯）藉由將鈀離 子還原，於高分子微粒子上吸附鈀（金屬），藉此， 高分子微粒子（聚吡咯）被離子化，亦即，成爲以鈀 摻雜之狀態，結果展現導電性。 【實施方式】 更詳細地說明本發明。 本發明之鍍敷物，係藉由 A )於基材上，塗布含有還原性高分子微粒子與對該 還原性高分子微粒子1質量份之0.1至10質量份之黏結 劑的塗料，形成厚度爲20至5 OOnm、表面上可吸附之觸 媒金屬量爲0.1 // g/cm2以上，較佳爲，層之上側半部中 存在有該還原性高分子微粒子中之6 0 %以上之粒子所形 成的塗膜層， B )於該塗膜層，由化學鍍敷液將金屬膜化學鍍敷來 製造。 本發明所使用之還原性高分子微粒子，係於將有機溶 劑與水與陰離子系界面活性劑及非離子系界面活性劑混合 攪拌所成之0/W型之乳化液中，添加具有；τ -共軛雙鍵之 單體，將該單體氧化聚合，藉此來製造。 具有π-共軛雙鍵之單體，只要是用以製造導電性高 分子所使用之單體即可，並無特別限定，可舉例如吡咯、 N —甲基吡咯、N —乙基吡咯、N —苯基吡咯、N —萘基吡 -10- 200837217 咯、N —甲基一 3 —甲基吡咯、N —甲基一3 —乙基吡咯、N —苯基一3 —甲基吡咯、N—苯基—3 —乙基吡咯、3 -甲 基吡咯、3 —乙基吡咯、3 —正丁基吡咯、3 —甲氧基吡咯 、3 —乙氧基吡咯、3 —正丙氧基吡咯、3 -正丁氧基吡咯 、3 -苯基P比略、3 —甲苯基卩比略、3 —萘基啦略、3 —苯氧 基吡咯、3 —甲基苯氧基吡咯、3 -胺基吡咯、3 -二甲基 胺基吡咯、3 -二乙基胺基吡咯、3 -二苯基胺基吡咯、3 -甲基苯基胺基吡咯及3 -苯基萘基胺基吡咯等吡咯衍生 物、苯胺、對氯苯胺、間氯苯胺、鄰氯苯胺、對甲氧基苯 胺、間甲氧基苯胺、鄰甲氧基苯胺、對乙氧基苯胺、間乙 氧基苯胺、鄰乙氧基苯胺、對甲基苯胺、間甲基苯胺、鄰 甲基苯胺等苯胺衍生物、噻吩、3-甲基噻吩、3 —正丁基 噻吩、3 -正戊基噻吩、3 -正己基噻吩、3 -正庚基噻吩 、3 -正戊基噻吩、3 —正壬基噻吩、3 -正癸基噻吩、3 — 正十一基噻吩、3 -正十二基噻吩、3 -甲氧基噻吩、3 — 萘氧基噻吩及3,4 _乙烯二氧噻吩等噻吩衍生物，較佳爲 ，吡咯、苯胺、噻吩及3，4 一乙烯二氧噻吩等，更佳爲， 吡咯。 又，上述製造所使用之陰離子系界面活性劑，可使用 各種者，但較佳爲具有複數個疏水性末端者（例如，於疏 水基具有分枝構造者、或具有複數個疏水基者）。藉由使 用如此具有複數個疏水性末端之陰離子系界面活性劑，可 形成安定之微胞，於聚合後之水相與有機溶劑相的分離可 平順地進行，容易取得分散於有機溶劑相之還原性高分子 -11 - 200837217 微粒子。 具有複數個疏水性末端之陰離 較佳爲使用磺基琥珀酸二一 2 -乙3 性末端）、磺基琥珀酸二一 2 -乙塞 性末端）及分枝鏈型烷基苯磺酸鹽 〇 反應系中之陰離子系界面活僧 軛雙鍵之單體 lmol，以未滿 0 0.005mol 〜O.Olmol。當爲 0.05mol 子性界面活性劑作爲摻雜劑產生作 生導電性，故爲了使用其進行化學 〇 非離子系界面活性劑，可舉例 烷基醣苷類、甘油脂肪酸酯類、山 聚氧乙烯山梨糖醇酐脂肪酸酯、聚 肪酸烷醇醯胺、聚氧乙烯烷基苯醚 種或或複數種混合使用。特別以形 者爲佳。 反應系中之非離子系界面活性 軛雙鍵之單體lmol，非離子系界面 爲佳、更佳爲 0.05〜0.15mol。當ί 及分散安定性降低，另一方面，當 聚合後水相與有機溶劑相之分離變 得到於有機溶劑相中之還原性高分 子系界面活性劑之中’ I己基鈉（有4個疏水 g辛基鈉（有4個疏水 (有2個疏水性末端） :劑的量，對具有^ -共 .05mol爲佳、更佳爲 以上時，所添加之陰離 用，所得之微粒子會產 鍍敷需要脫摻雜之步驟 如聚氧乙烯烷基醚類、 梨糖醇酐脂肪酸酯類、 氧乙烯脂肪酸酯類、脂 類等。亦可將該等之一 成安定之0/W型乳膠 :劑的量，對具有7Γ -共 丨活性劑以〇.2mol以下 长滿 0.05mol時，收率 爲 0.2mol以上時，於 得困難，且會變得無法 子微粒子，故不佳。 -12- 200837217 上物製造中之形成乳化液之有機相之有機溶劑，以疏 水性爲佳。其中，芳香族系之有機溶劑之甲苯或二甲苯， 由0/W型乳膠之安定性及與具有7Γ -共軛雙鍵之單體之親 和性的觀點考量較佳。兩性溶劑，亦可進行具有V -共軛 雙鍵之單體的聚合，但於回收所生成之還原性高分子微粒 子之際難以分離有機相與水相。 於乳化液之有機相與水相之比例，較佳爲，水相爲 75體積％以上。當水相爲20體積％以下時，具有7Γ -共 軛雙鍵之單體的溶解量變少、生產效率變差。 上述製造所使用之氧化劑，可使用例如硫酸、鹽酸、 硝酸及氯磺酸等無機酸、烷基苯磺酸及烷基萘磺酸等有機 酸、過硫酸鉀、過硫酸銨及過氧化氫等過氧化物。該等可 單獨使用、亦可倂用兩種以上。氯化鐵等路易士酸亦可聚 合具有7Γ-共軛雙鍵之單體，但所生成之粒子會有凝集、 無法微分散之情形。特佳之氧化劑，係過硫酸銨等過硫酸 鹽。 反應系中氧化劑的量，對具有7Γ -共軛雙鍵之單體 lmol，較佳爲 O.lmol以上、〇.8mol以下、更佳爲0.2〜 0.6mol。當未滿O.lmol時，單體之聚合度降低、難以將 高分子微粒子分液回收，另一方面，當0.8mol以上時， 會凝集使高分子微粒子之粒徑增大、分散安定性變差。 該高分子微粒子之製造方法，例如可藉以下之步驟進 行： (a )將陰離子系界面活性劑、非離子系界面活性劑 -13- 200837217 、有機溶劑及水混合攪拌，以調製乳 (b )使具有7Γ -共軛雙鍵之單體 驟、 (C )使單體氧化聚合之步驟、 (d )將有機相分液以回收高分3 上述各步驟，可利用該技術領域 段進行。例如，乳化液之調製時所進 特別限定，可適當選擇例如磁攪拌器 來進行。又，聚合溫度爲〇〜25 °C、 聚合溫度若超過25 °C，則會引起副反 若停止氧化聚合反應，則反應系 相兩相，而此時未反應之單體、氧化 中而殘存。此處，將有機相分液回收 數次，即可取得分散於有機溶劑之還 以上述之製造法所製得之高分子 7Γ -共軛雙鍵之單體衍生物之聚合物j 子系界面活性劑及非離子系界面活性 係，具有微細之粒徑、可分散於有機 高分子微粒子係球形之微粒子， 〜100nm爲佳。 藉由作成如上述之平均粒徑小之 之表面積爲極大，即使同一質量之微 觸媒金屬，藉此可使塗膜層薄膜化。 所得高分子微粒子之導電率爲未 化液之步驟、 分散於乳化液中之步 1微粒子之步驟。 所屬之業者已知之手 行之混合攪拌，並無 、攪拌機、均質機等 較佳爲2 0以下°C。 應，故不佳。 會分離成有機相與水 劑或鹽會溶解於水相 ，以離子交換水洗淨 原性高分子微粒子。 微粒子，主要由具有 听形成，而含有陰離 劑之微粒子。其特徵 溶劑中。 其平均粒徑，以1 0 微粒子，可使微粒子 粒子，可吸附更多之 滿0.0 1 S / c m，較佳爲 -14- 200837217 0.005 S/cm 以下。 如此所得之分散於有機溶劑之還 可直接濃縮、或乾燥作爲塗料之還原 使用。 又’即使非如上述所製造之還原 可將例如市售可取得之還原性高分子 分使用。 本發明所使用之塗料，係含有還 黏結劑之塗料。 黏結劑’可舉例如聚氯乙烯、聚 聚甲基丙烯酸甲酯、聚酯、聚颯、聚 (N-乙烯咔唑）、烴樹脂、酮樹脂、 乙基纖維素、乙酸乙烯酯、ABS樹脂 、三聚氰胺樹脂、不飽和聚酯樹脂、 、矽樹脂等。 所使用之黏結劑量，對還原性高 爲0.1至10質量份。黏結劑若超過 不會析出，而黏結劑若未滿0.1質量 性減弱。 又’本發明所使用之塗料含有有 機溶劑，只要不會損傷微粒子、可使 並無特別限定，較佳可舉例如苯、甲 烴類。 再者，本發明所使用之塗料，可 原性高分子微粒子， 性高分子微粒子成分 性高分子微粒子，亦 微粒子作爲塗料之成 原性高分子微粒子與 碳酸酯、聚苯乙嫌、 苯醚、聚丁二烯、聚 苯氧樹脂、聚醯胺、 、聚胺基甲酸酯樹脂 醇酸樹脂、乙氧樹脂 分子微粒子1質量份 1 0質量份則金屬鍍敷 份，則對基材之密合 機溶劑。所使用之有 微粒子分散者.即可， 苯、二甲苯等芳香族 視用途及塗布對象物 -15- 200837217 等之需要，添加分散安定劑、增黏劑、油墨黏結劑等樹脂 〇 將上述所調製之塗料塗布於基材上以形成塗膜層，較 佳爲，以使層之上側半部中，存在有還原性高分子微粒子 中之60%以上之粒子的方式形成塗膜層。 基材，並無特別限定，可舉例如聚對苯二甲酸乙二醇 酯或聚乳酸等聚酯樹脂、聚甲基丙烯酸甲酯等丙烯酸樹脂 、聚丙烯樹脂、聚碳酸酯樹脂、聚苯乙烯樹脂、聚氯乙烯 樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚甲醛樹脂、聚醚醚 酮樹脂、環狀聚烯烴樹脂、聚乙烯樹脂、聚苯硫樹脂、液 晶聚合物、變性聚苯醚樹脂、聚礪樹脂、PC/ABS (聚碳 酸酯ABS )樹脂、ASA/PC (丙烯腈苯乙烯丙烯酸酯/聚碳 酸酯）樹脂、ABS (丙烯腈丁二烯苯乙烯）樹脂、玻璃等 〇 又，基材’可爲具有自我黏著性之軟質合成樹脂，可 舉例如聚烯烴彈性體、聚乙烯彈性體、聚胺基甲酸酯彈性 體、矽樹脂、丁基橡膠、軟質聚氯乙烯、氟系樹脂等。 再者，基材之形狀並無特別限定，可舉例如板狀、薄 膜狀。 另外，基材，可舉例如以射出成形等將樹脂成形之樹 脂成形品。而藉由於該樹脂成形品設置本發明之鍍敷物， 可製作成例如汽車之裝飾鑛敷品’或者，藉由於聚釀亞胺 樹脂所構成之膜上，將本發明之鍍敷物以成圖型狀的方式 設置，可製作成例如電氣電路品。 -16- 200837217 於基材之塗布方法亦無特別限定，例如，可使用照相 凹板印刷機、噴墨印刷機、浸漬、噴霧、旋塗、輥塗、網 版印刷機等，進行印刷或塗布。 塗膜層之上側半部中存在有還原性高分子微粒子中之 6 〇 %以上之粒子之構成，可藉由於塗料之塗布後，以緩和 條件花費時間進行乾燥來達成。 具體之方法，例如，可藉由以3 0至6 0 °C之低溫長時 間乾燥、由3 0至6 0 °C之低溫緩緩提升溫度進行乾躁、以 30至60°C之低溫與較其高之溫度（例如，100至130°C ) 之2階段、或與以上相異之溫度（例如，3 0至6 0 °C — 6 5 至90°C - 100至130°C )進行乾燥來達成。 以2階段之相異溫度乾燥時，例如當使用甲苯作爲有 機溶劑時，以40°C乾燥10分鐘後，以8(TC乾燥1〇分鐘 ，之後，以1 2 0 °C乾燥1 〇分鐘，藉此，可作成塗膜層之 上側半部中存在有微粒子中之60%以上之粒子之構成。 塗膜層之厚度，爲20至500nm。 厚度若未滿20nm則金屬不會析出而無法形成鍍敷膜 ’而若厚度超過500nm則塗膜強度降低。 塗膜層之表面上可吸附之觸媒金屬的量爲0.1/zg/cm2 以上。 該吸附量若未滿〇· 1 // g/cm2，則無法得到均一之金屬 鍍敷膜、或金屬未析出而無法形成鍍敷膜。 本發明之鍍敷物，藉由使用將導電性高分子微粒子進 行脫摻雜處理作成還原性之微粒子作爲該還原性高分子微 -17- 200837217 粒子，亦可同樣地製造。 所使用之導電性高分子微粒子，例如，可藉由於將有 機溶劑與水與陰離子系界面活性劑混合攪拌所成之0/W 型乳化液中，添加具有具有7Γ -共軛雙鍵之單體，將該單 體氧化聚合以製造。 具有7Γ-共軛雙鍵之單體及陰離子系界面活性劑，可 舉例如與還原性高分子微粒子之製造時所例示者相同，而 較佳爲吡咯、苯胺、噻吩及3，4 -乙烯二氧噻吩等，更佳 爲，吡咯。 反應系中之陰離子系界面活性劑的量，對具有7Γ -共 軛雙鍵之單體 lmol，以未滿 0.2mol爲佳、更佳爲 0.05mol〜0.15mol。當未滿 0.05mol時，收率及分散安定 性低，另一方面，當爲0.2mol以上時，所得之導電性高 分子微粒子會產生導電性之溫度依存性。 上述製造中形成乳化液之有機相之有機溶劑以疏水性 爲佳。其中，芳香族系之有機溶劑之甲苯或二甲苯，由 0/W型乳膠之安定性及與單體之親和性的觀點考量較佳。 兩性溶劑，亦可進行具有7Γ -共軛雙鍵之單體的聚合，但 於回收所生成之導電性高分子微粒子之際難以分離有機相 與水相。 乳化液中之有機相與水相之比例，較佳爲，水相爲 75體積％以上。當水相爲20體積％以下時，具有7Γ -共 軛雙鍵之單體的溶解量變少、生產效率變差。 上述製造所使用之氧化劑，可舉例如與還原性高分子 -18- 200837217 之製造時所例示者相同。特佳之氧化劑，係過硫酸銨等過 硫酸鹽。 反應系中氧化劑的量，對具有7Γ-共軛雙鍵之單體 lmol，較佳爲 O.lmol以上、0.8mol以下、更佳爲 0.2〜 0.6m〇l。當未滿0.1 mol時，單體之聚合度降低、難以將 局分子微粒子分液回收，另一方面，當0.8mol以上時， 會凝集使高分子微粒子之粒徑增大、分散安定性變差。 該導電性高分子微粒子之製造方法，例如可藉以下之 步驟進行： (a )將陰離子系界面活性劑、有機溶劑及水混合攪 拌，以調製乳化液之步驟、 (b )使具有7Γ -共軛雙鍵之單體分散於乳化液中之步 驟、 (c )將單體氧化聚合，使高分子微粒子接觸吸附於 陰離子系界面活性劑之步驟、 (d )將有機相分液以回收導電性高分子微粒子之步 驟。 上述各步驟，可利用該技術領域所屬之業者已知之手 段進行。例如，乳化液之調製時所進行之混合攪拌，並無 特別限定，可適當選擇例如磁攪拌器、攪拌機、均質機等 來進行。又，聚合溫度爲0〜25°C、較佳爲20以下°C。 聚合溫度若超過25 °C，則會引起副反應，故不佳。 若停止氧化聚合反應，則反應系會分離成有機相與水 相兩相，而此時未反應之單體、氧化劑或鹽會溶解於水相 -19- 200837217 中而殘存。此處，將有機相分液回收’以離子交換水洗淨 數次，即可取得分散於有機溶劑之導電性高分子微粒子。 以上述之製造法所製得之導電性高分子微粒子，主要 由具有7Γ -共軛雙鍵之單體衍生物之聚合物所形成，而含 有陰離子系界面活性劑之微粒子。其特徵係，具有微細之 粒徑、可分散於有機溶劑中。 高分子微粒子係球形之微粒子，其平均粒徑，以10 〜100nm爲佳。 藉由作成如上述之平均粒徑小之微粒子，可使微粒子 之表面積爲極大，即使同一質量之微粒子，進行脫摻雜處 理作成還原性之際，可吸附更多之觸媒金屬，藉此可使塗 膜層薄膜化。 如此所得之分散於有機溶劑之導電性高分子微粒子， 可直接濃縮、或乾燥作爲塗料之導電性高分子微粒子成分 使用。 又，即使非如上述所製造之導電性高分子微粒子，亦 可將例如市售可取得之導電性高分子微粒子作爲塗料之成 分使用。 將含有上述導電性高分子微粒子與黏結劑之塗料塗布 於基材上，形成塗膜層後，藉由進行用以將微粒子作成還 原性之脫摻雜處理，可形成存在有還原性高分子微粒子之 塗膜層，而較佳爲，將含有上述導電性高分子微粒子與黏 結劑之塗料塗布於基材上，形成層之上側半部中存在有導 電性高分子微粒子中之60 %以上之粒子之層後，藉由進 -20- 200837217 行用以將微粒子作成還原性之脫摻雜處理’可形成層之上 側半部中存在有60 %以上之還原性高分子微粒子之塗膜 層。 黏結劑，可舉例如與上述例示相同者，其使用量，對 導電性高分子微粒子1質量份爲0」至10質量份。黏結 劑若超過1 〇質量份則金屬鍍敷不會析出，而黏結劑若未 滿0.1質量份，則對基材之密合性減弱。 又，上述塗料含有有機溶劑。所使用之有機溶劑，只 要不會損傷微粒子、可使微粒子分散者即可，並無特別限 定，較佳可舉例如苯、甲苯、二甲苯等芳香族烴類。 再者，上述塗料，可視用途及塗布對象物等之需要， 添加分散安定劑、增黏劑、油墨黏結劑等樹脂。 將上述所調製之塗料塗布於基材上以形成塗膜層，較 佳爲，形成層之上側半部中存在有導電性高分子微粒子中 之60%以上之粒子之層。 基材，可舉例如與上述例示相同者，其之形狀並無特 別限定，可舉例如板狀、薄膜狀。 於基材之塗布方法亦無特別限定，例如，可使用照相 凹板印刷機、噴墨印刷機、浸漬、旋塗、輥塗等，進行印 刷或塗布。 層之上側半部中存在有導電性高分子微粒子中之6 0 %以上之粒子之構成，可藉由於塗料之塗布後，以緩和條 件花費時間進行乾燥來達成。 具體之方法，例如，可藉由以30至60 °c之低溫長時 -21 - 200837217 間乾燥、由30至60 °C之低溫緩緩提升溫度進行乾躁、 3 0至6 0 °C之低溫與較其高之溫度（例如，1 0 0至1 3 0 °C 之2階段、或與以上相異之溫度（例如，30至60 °C — 至90 °C — 1〇〇至130 °C )進行乾燥來達成。 以2階段之相異溫度乾燥時，例如當使用甲苯作爲 機溶劑時，以40 °C乾燥1〇分鐘後，以80 °C乾燥10分 ，之後，以120°C乾燥1〇分鐘，藉此，可作成層之上 半部中存在有微粒子中之60%以上之粒子之構成。 層之厚度，爲20至500nm。 厚度若未滿20nm則金屬不會析出而無法形成鍍敷 ，而若厚度超過50 Onm則塗膜強度降低。 特別是，使用導電性高分子微粒子所形成之層，爲 將微粒子作成還原性進行鹼處理等脫摻雜處理以作成塗 層，而若厚度超過500nm，則上述之處理需長時間，因 膜強度降低，結果，所得之金屬鍍敷膜，與基材之密合 降低。 上述之使用導電性高分子微粒子所形成之層，爲了 微粒子作成還原性而進行脫摻雜處理。 脫摻雜處理，可舉例如以含有還原劑（例如，氫化 鈉、氫化硼鉀等氫化硼化合物、二甲基胺硼烷、二乙基 硼烷、三甲基胺硼烷、三乙基胺硼烷等烷基胺硼烷、及 胺等）之溶液進行處理以還原之方法，或者，以鹼性溶 進行處理之方法。 由操作性及經濟性的觀點考量，以鹼性溶液進行處 以 ) 65 有 鐘 側 膜 了 膜 此 性 將 硼 胺 聯 液 理 -22- 200837217 較佳。 特別是，使用導電性高分子微粒子所形成之層，厚度 爲20至5 OOnm爲非常薄，故可藉由於緩和條件下之短時 間之鹼處理達成脫摻雜。 例如，於1M氫氧化鈉水溶液中，以20至5 Ot、較 佳爲30至40 °C之溫度處理1至30分鐘、較佳爲3至10 分鐘。 於藉由該脫摻雜處理使微粒子爲還原性之塗膜層之表 面上可吸附之觸媒金屬之量，爲0.1// g/cm2以上。 該吸附量若未滿0.1 # g/cm2，則無法得到均一之金屬 鍍敷膜、或金屬未析出而無法形成鍍敷膜。 將形成有如上述所製造之塗膜層之基材藉由化學鍍敷 法作成鍍敷物，該化學鍍敷法，可根據一般周知之方法進 行。 亦即，可將該基材浸漬於用以使氯化鈀等觸媒金屬附 著之觸媒液後，進行水洗等，藉由浸漬於化學鍍敷液製得 鍍敷物。 觸媒液，係含有對化學鍍敷具有觸媒活性之貴重金屬 (觸媒金屬）之溶液，觸媒金屬’可舉例如鈀、金、鉑、 鍺等，該等金屬可爲單體或化合物，由含觸媒金屬之安定 性的觀點考量，以鈀化合物較佳，其中以氯化鈀爲特佳。 具體之觸媒液，較佳可舉例如〇 · 〇 2 %氯化鈀一 0 · 0 1 % 鹽酸水溶液（pH3 )。 處理溫度，爲20至50°C、較佳爲30至40°C，處理 -23- 200837217 時間，爲0.1至20分鐘、較佳爲1至10分鐘。 藉由上述之操作，塗膜中之還原性高分子微粒子，結 果，變成導電性高分子微粒子。 以上述處理之基材，浸漬於用以使金屬析出之鍍敷液 ，藉此形成化學鍍敷膜。 鍍敷液，只要一般之化學鍍敷所使用之鍍敷液即可， 並無特別限定。 亦即，於化學鍍敷可使用之金屬、銅、金、銀、鎳、 鉻等，皆可使用，而以銅較佳。 化學鍍敷浴之具體例，可舉例如ATS亞德卡帕IW浴 (奧野製藥工業（股）公司製）等。 處理溫度，爲20至50°C、較佳爲30至40°C，處理 時間，爲1至3 0分鐘、較佳爲5至15分鐘。 如上所述，塗膜中之還原性高分子微粒子，結果，成 爲導電性高分子微粒子，故藉由以上之操作，可製造一種 鍍敷物，係於基材表面上形成含導電性高分子微粒子與黏 結劑之塗膜層，而於該塗膜層上以化學鍍敷法形成有金屬 鍍敷膜之鍍敷物， 該黏結劑，對於該導電性高分子微粒子1質量份以 0.1至10質量份存在，該塗膜層之厚度爲20至500 nm， 較佳爲，於該塗膜層之上側半部中，存在有該導電性高分 子微粒子中之60%以上之粒子。 如上述之塗膜層上所形成之金屬鍍敷膜之厚度，較佳 爲 100 至 3000nm 。 -24- 200837217 金屬鑛敷0吴之厚度若未滿1 0 0 n m，則電磁波屏敝性谷 易減弱，若超過3 00 Onm，則金屬鍍敷膜（金屬層）難以 追隨膜之彎曲、折曲，而容易由基材膜剝離。 本發明之鍍敷物，可再層合其他層作成三明治構造， 例如’可於設置有金屬鍍敷膜之膜再層合其他膜、或將設 置有金屬鍍敷膜之自我黏著膜黏著於玻璃作成三明治構造 實施例 接著，以實施例更詳細地說明本發明，但本發明並不 限於實施例。 製造例1 :含還原性聚吡咯微粒子之塗料（塗料1〜6 )之 調製 添加陰離子性界面活性劑貝雷克斯0T_P (花王股份 有限公司製）0.42mmol、聚氧乙烯烷基醚系非離子界面活 性劑艾瑪魯給409P (花王股份有限公司製）2.1 mmol、甲 苯5 0mL、離子交換水i〇0mL，於保持於20。(：之下攪拌至 乳化爲止。於所得之乳化液加入吡咯單體21 jmmol，攪 拌1小時’接著，加入過硫酸銨6mmol進行聚合反應2 小時。反應結束後，回收有機相，以離子交換水洗淨數次 ’製得分散於甲苯之具有還原性能之還原性聚吡咯微粒子 〇 上述所得之甲苯分散液中之還原性聚吡咯微粒子之固 -25- 200837217 體成分，約1 .3 %，此處，將黏結劑A、B以各自之質量 份添加，調製成表1所示之含還原性聚吡咯微粒子之塗料 〇 此處，表1中之黏結劑A、B係指以下者，又，黏結 劑之使用量，係表示對還原性聚吡咯微粒子1質量份所使 用之黏結劑之質量份數。 A:超貝卡名 J-820:三聚氰胺系（大日本油墨化學 工業（股）公司製） B :拜龍240 :聚酯系（東洋紡績（股）公司製） [表1] 塗料編號 黏結劑 種類 使用量 1 A 0.5 2 A 0.1 3 A 10 4 B 0.5 5 A 0.067 6 A 15 製造例2 :含導電性聚吡咯微粒子之塗料（塗料7 )之調 製 添加陰離子性界面活性劑貝雷克斯OT-P (花王股份 有限公司製）1.5mmol、甲苯50mL、離子交換水l〇〇mL， 於保持於20 °C之下攪拌至乳化爲止。於所得之乳化液加 入吡咯單體2 1.2mmol，攪拌1小時，接著，加入過硫酸 銨6mmol進行聚合反應2小時。反應結束後，回收有機 -26- 200837217 相，以離子交換水洗淨數次，製得分散於甲苯之具有還原 性能之還原性聚吡略微粒子。此處所得之甲苯分散液中之 導電性聚吡咯微粒子之固體成分，約1.2 %，此處，對導 電性聚吡咯微粒子1質量份，添加黏結劑之超貝卡名J -820 (大日本油墨化學工業（股）公司製）1質量份作成 塗料7。 製造例3 :含還原性聚苯胺微粒子之塗料（塗料8)之調 製 添加陰離子性界面活性劑貝雷克斯OT-P (花王股份 有限公司製）0.42mm〇l、山梨糖醇酐脂肪酸酯系非離子界 面活性劑雷歐德魯 SP-O30V (花王股份有限公司製） 0.424mmol與聚氧乙烯山梨糖醇酐月旨肪酸酯2.12mmol (花 王股份有限公司製）、甲苯50mL、離子交換水100mL， 於保持於2 (TC之下攪拌至乳化爲止。於所得之乳化液加 入吡咯單體21.2mmol，攪拌1小時，接著，加入過硫酸 銨4mmol進行聚合反應2小時。反應結束後，回收有機 相，以離子交換水洗淨數次，製得分散於甲苯之具有還原 性能之還原性聚苯胺微粒子。此處所得之甲苯分散液中之 還原性聚苯胺微粒子之固體成分，約1.4%，此處，對還 原性聚苯胺微粒子1質量份，添加黏結劑之超貝卡名J-820 (大日本油墨化學工業（股）公司製）1質量份作成 塗料8。 -27- 200837217 製造例4 ··塗膜層之形成 使用軟質薄膜C、D作爲基材’於該基材上塗布上述 所調製之塗料1至8，製造成形成有具有表2所示之各種 膜厚之塗膜層之軟質薄膜。 又，於表2中之塗膜1至7及9至13，係於塗料塗 布後，以4 0 °C乾燥1 〇分鐘後以8 0 °C乾燥1 0分鐘，之後 以1 2 0 °C乾燥1 〇分鐘，使塗膜層之上側半部中所存在之 微粒子爲60 %以上，於塗膜8亦進行同樣的操作，使導 電性高分子微粒層之上側半部中所存在之微粒子爲6 0 % 以上。 又’於表2中之塗膜14及1 5，係於塗料塗布後，以 1 2 0 °C乾燥5分鐘，作成微粒子均勻分散之塗膜層。 表中之軟質薄膜C、D係指以下所述者。 C :樹脂P E T、商品名寇斯摩協影a 4 1 0 0、東洋紡績 (股）公司製 D :樹脂PP、商品名OP U-0、東協羅（股）公司製 -28- 200837217 [表2] 塗膜編號 塗料編號 軟質薄膜 膜厚（n m ) 1 1 C 100 2 1 C 400 3 1 C 30 4 2 C 100 5 3 C 100 6 4 C 100 7 1 D 100 8 7 C 100 9 8 C 100 10 1 C 600 11 1 C 10 12 5 C 100 13 6 C 100 14 1 C 100 15 3 C _ 100 製造例5 :以化學鍍敷法之鍍敷物之製造 將上述所製造之形成有塗膜層之薄膜（塗膜1至7及 9至15)，於0.02%氯化鈀一〇.〇1%鹽酸水溶液中以35 °C浸漬5分鐘後，以自來水水洗。接著，將該薄膜浸漬於 化學鍍銅浴ATS亞德卡帕IW浴（奧野製藥工業（股）公 司製），以3 5 °C浸漬1 〇分鐘以實施鍍銅。又，塗膜8， 係於1 Μ氫氧化鈉水溶液中以3 5 °C浸漬5分鐘，進行表面 處理作成塗膜層後進行同樣的操作。將由塗膜1至9所製 造之鍍敷物分別視爲實施例1至9，由塗膜1 0至1 5所製 造之鍍敷物分別視爲比較例1 1 6 ° 又，以透過型電子顯微鏡（日本電子（股）公司製： -29- 200837217 JEM- 1 200 EXM)攝影實施例1至9之鍍敷物的截面圖所 得之照片之模式化者示於圖1，以透過型電子顯微鏡（日 本電子（股）公司製：JEM- 1 200 EXM )攝影比較例5、6 之鍍敷物的截面圖所得之照片之模式化者示於圖2。 試驗例1 對上述所製造之實施例1至9及比較例1至6之鍍敷 物，進行各種評價試驗，並將其之結果整理示於表3。 又，評價試驗項目及其評價方法、評價基準，係如以 下所示。 • P d量 將試樣裁切成約3cmx4cm，以硝酸（1+9 )萃取鈀後 ，以無火焰式原子吸收光譜法定量。 •鍍敷外觀 以目視觀察鍍敷皮膜之狀態，測定基材露出面積。 又，評價基準係如以下所示。 〇：完全被覆，基材無露出 △:有50%左右之基材露出 X: 100%基材露出 •鍍敷膜厚 以電解式膜厚計CT-1 ((股）電測公司製）測定鍍 -30- 200837217 敷面之3點，以平均値作爲膜厚。 •膠帶試驗 2mm邊長之 根據JIS H8504試驗方法，以刀片作成 條痕1 〇 〇個後，以膠帶實施撕下試驗。 又，評價基準係如以下所示。 〇：沒有剝離 △:有50%左右之剝離 X : 90%以上剝離 •剝離強度 根據JIS C674 1實施測定。 •還原性微粒子存在比 超薄切片機S 電子顯微鏡（ 聶影截面部之 ，製作1 〇個 之値。 使用超薄切片機（萊卡（股）公司製： )將塗膜切割成60nm之寬度，由以透過型 日本電子（股）公司製：JEM-1200 EXM) 影像，求出粒子部與黏結部之面積比率。又 樣品，使用以相同方式測定後求出之平均値 -31 - 200837217 表3 ] 實施例 編號 塗膜 編號 Pd量 (pg/cm2) 鍍敷 外觀 鍍敷膜厚 (μιη) 膠帶 試驗 剝離強度 (kgf/cm) 還原性微粒子存在 比(上層/下層） 實施例1 1 1.1 〇 0.3 〇 2.5 65/35 實施例2 2 2.1 〇 0.3 〇 1.5 70/30 實施例3 3 0.2 〇 0.2 〇 2.3 60/40 實施例4 4 1.3 〇 0.5 〇 1.1 70/30 實施例5 5 0.8 〇 0.1 〇 2.4 60/40 實施例6 6 1.0 〇 0.3 〇 1.9 65/35 實施例7 7 0.9 〇 0.3 〇 2.2 65/35 實施例8 8 1.0 〇 0.3 〇 2.3 65/35 實施例9 9 0.9 〇 0.3 〇 1.8 65/35 比較例1 10 4.2 〇 0.5 Δ 0.3 70/30 比較例2 11 0.04 △ 0.1 〇 2.0 60/40 比較例3 12 1.6 〇 0.3 △ 0.4 65/35 比較例4 13 0.05 △ 0.1 〇 2.1 65/35 比較例5 14 0.5 〇 0.2 X 0.05 50/50 比較例6 15 0.01 X - - - 45/55 【圖式簡單說明】 圖1，係將實施例1至9之鍍敷物之截面圖之透過型 電子顯微照片模式化之圖。 圖2，係將比較例5、6之鍍敷物之截面圖之透過型 電子顯微照片模式化之圖。 【主要元件符號說明】 1 :基材膜 2 :塗膜層 3 :金屬鍍敷膜 -32- 200837217 4 :還原性高分子微粒子 -33-9-200837217 That is, the reducing polymer microparticles (polypyrrole) are ionized by adsorbing palladium (metal) on the polymer microparticles by reducing palladium ions, that is, the polymer microparticles (polypyrrole) are ionized, that is, It is in a state of being doped with palladium, and as a result, conductivity is exhibited. [Embodiment] The present invention will be described in more detail. In the plating material of the present invention, a coating material containing 0.1 to 10 parts by mass of the reducing polymer fine particles and 1 to 10 parts by mass of the reducing polymer fine particles is applied to the substrate to form a thickness of 20 The amount of the catalyst metal adsorbable on the surface is 0.1 // g/cm 2 or more, preferably, more than 60% of the particles of the reducing polymer microparticles are present in the upper half of the layer. The coating layer, B) is produced by electroless plating a metal film on the coating layer by an electroless plating solution. The reducing polymer fine particles used in the present invention are added to an emulsion of 0/W type in which an organic solvent and water are mixed with an anionic surfactant and a nonionic surfactant, and are added; The monomer of the conjugated double bond is produced by oxidative polymerization of the monomer. The monomer having a π-conjugated double bond is not particularly limited as long as it is used for producing a conductive polymer, and examples thereof include pyrrole, N-methylpyrrole, and N-ethylpyrrole. N-phenylpyrrole, N-naphthylpyrrole-10-200837217, R-N-methyl-3-methylpyrrole, N-methyl-3-ethylpyrrole, N-phenyl-3-methylpyrrole, N-phenyl-3-ethylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-butylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-n-propoxy Pyrrole, 3-n-butoxypyrrole, 3-phenyl P ratio, 3-tolylhydrazine, 3-naphthyl, 3-phenoxypyrrole, 3-methylphenoxypyrrole, 3 -aminopyrrole, 3-dimethylaminopyrrole, 3-diethylaminopyrrole, 3-diphenylaminopyrrole, 3-methylphenylaminopyrrole and 3-phenylnaphthylamino Pyrrole derivatives such as pyrrole, aniline, p-chloroaniline, m-chloroaniline, o-chloroaniline, p-methoxyaniline, m-methoxyaniline, o-methoxyaniline, p-ethoxyaniline, m-ethoxyaniline, Neighbor B Aniline derivatives such as aniline, p-methylaniline, m-methylaniline, o-methylaniline, thiophene, 3-methylthiophene, 3-n-butylthiophene, 3-n-pentylthiophene, 3-n-hexylthiophene, 3-n-heptylthiophene, 3-n-pentylthiophene, 3-n-decylthiophene, 3-n-decylthiophene, 3-n-nonylthiophene, 3-n-dodecylthiophene, 3-methoxythiophene Further, a thiophene derivative such as 3-naphthyloxythiophene or 3,4-ethylenedioxythiophene is preferably pyrrole, aniline, thiophene or 3,4-ethylenedioxythiophene, and more preferably pyrrole. Further, the anionic surfactant used in the above production may be used in various forms, but it is preferably one having a plurality of hydrophobic terminals (for example, those having a branching structure in a hydrophobic group or having a plurality of hydrophobic groups). By using such an anionic surfactant having a plurality of hydrophobic terminals, stable micelles can be formed, and the separation of the aqueous phase and the organic solvent phase after the polymerization can be carried out smoothly, and the reduction in the organic solvent phase can be easily achieved. Polymer-11 - 200837217 Microparticles. Preferably, the anion having a plurality of hydrophobic terminals is a di- 2 -ethyl 3-terminal end of sulfosuccinate, a di- 2 -ethyl end of sulfosuccinate, and a branched chain alkylbenzene sulfonic acid The anion-based interface in the salt hydrazine reaction system is 1 mol of the monomer of the yoke double bond, which is less than 0 0.005 mol to 1.0 mol. When 0.05 mol of the surfactant is used as a dopant to produce bioconductivity, in order to use the chemical antimony nonionic surfactant, alkyl glycosides, glycerin fatty acid esters, and mountain polyoxyethylene sorbes can be exemplified. A sugar anhydride fatty acid ester, a polyalkylene decanoate, a polyoxyethylene alkyl phenyl ether or a plurality of them are used in combination. Especially the shape is better. The nonionic interfacial activity in the reaction system is 1 mol of the monomer of the yoke double bond, and the nonionic interface is preferably 0.05 to 0.15 mol. When the dispersion stability is lowered, on the other hand, the separation of the aqueous phase and the organic solvent phase after polymerization becomes into the reducing polymer surfactant in the organic solvent phase, 'I-hexyl sodium (4 hydrophobic) G octyl sodium (4 hydrophobic (with 2 hydrophobic ends): the amount of the agent, when it is preferably - more than .05 mol, more preferably, the added cation is used, and the obtained microparticles are produced. Plating requires a step of dedoping such as polyoxyethylene alkyl ethers, sorbitan fatty acid esters, oxyethylene fatty acid esters, lipids, etc. One of these may be stabilized as a 0/W type latex. When the amount of the agent is 7 Γ - 丨 丨 丨 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 - 200837217 The organic solvent for forming the organic phase of the emulsion in the manufacture of the upper material is preferably hydrophobic. Among them, the aromatic organic solvent toluene or xylene has the stability of the 0/W type latex and has 7Γ. The viewpoint of the affinity of the monomer of the conjugated double bond is preferred. The amphoteric solvent It is also possible to carry out polymerization of a monomer having a V-conjugated double bond, but it is difficult to separate the organic phase from the aqueous phase when recovering the produced reduced polymer fine particles. The ratio of the organic phase to the aqueous phase in the emulsion, Preferably, the aqueous phase is 75% by volume or more. When the aqueous phase is 20% by volume or less, the amount of the monomer having a 7 Γ-conjugated double bond is reduced, and the production efficiency is deteriorated. The oxidizing agent used in the above production may be used. For example, inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and chlorosulfonic acid, organic acids such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid, peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide can be used. Two or more types may be used or used. The Lewis acid such as ferric chloride may also polymerize a monomer having a 7-conjugated double bond, but the particles formed may be aggregated and not slightly dispersed. The persulfate such as ammonium persulfate is used. The amount of the oxidizing agent in the reaction system is 1 mol, preferably 0.1 mol% or more, 〇.8 mol or less, more preferably 0.2 to 0.6 mol, of the monomer having a 7 Γ-conjugated double bond. When less than 0.1 mol, the polymerization degree of the monomer is lowered, and it is difficult to When the amount of the polymer fine particles is 0.8 mol or more, the particle size of the polymer fine particles is increased and the dispersion stability is deteriorated. The method for producing the polymer fine particles can be carried out, for example, by the following steps. : (a) mixing an anionic surfactant, a nonionic surfactant-13-200837217, an organic solvent, and water to prepare a milk (b) to form a monomer having a 7 Γ-conjugated double bond. The step of oxidatively polymerizing the monomer, (d) separating the organic phase to recover the high score 3 The above steps can be carried out by using the technical field. For example, the preparation of the emulsion is particularly limited, and for example, it can be appropriately selected. Magnetic stirrer is used to carry out. Further, when the polymerization temperature is 〇25 ° C and the polymerization temperature exceeds 25 ° C, the oxidative polymerization reaction is stopped, and the reaction phase is two phases, and the unreacted monomer remains in the oxidation at this time. . Here, by collecting the organic phase liquid several times, a polymer j-substrate interface of a monomer derivative of a polymer 7 Γ -conjugate double bond which is obtained by the above-mentioned production method, which is dispersed in an organic solvent, can be obtained. The active agent and the nonionic interfacial activity system have fine particle diameters and can be dispersed in the spherical particles of the organic polymer fine particles, preferably 〜100 nm. By making the surface area as small as the above-mentioned average particle diameter extremely large, even if the same amount of the microcatalyst metal is used, the coating film layer can be made thin. The step of obtaining the fine particles of the obtained polymer fine particles is a step of dispersing the liquid, and dispersing the fine particles in the emulsion. Mixing and stirring by hand, known as the manufacturer, without a mixer, homogenizer, etc., preferably below 20 °C. Should be, it is not good. The organic phase and the water or salt are dissolved in the aqueous phase, and the original polymer microparticles are washed with ion-exchanged water. The microparticles are mainly composed of microparticles having an anion formation and containing an anion agent. Its characteristics are in the solvent. The average particle size, with 10 microparticles, allows the microparticle particles to adsorb more than 0.01 1 S / c m, preferably -14-200837217 0.005 S/cm or less. The dispersion thus obtained can be directly concentrated or dried as a coating for reduction. Further, even if it is not the reduction produced as described above, for example, a commercially available reducing polymer can be used. The coating used in the present invention is a coating containing a binder. The binder may, for example, be polyvinyl chloride, polymethyl methacrylate, polyester, polyfluorene, poly(N-vinylcarbazole), hydrocarbon resin, ketone resin, ethyl cellulose, vinyl acetate, ABS resin. , melamine resin, unsaturated polyester resin, enamel resin, and the like. The bonding dose to be used is 0.1 to 10 parts by mass for the reducing property. If the binder exceeds, it will not precipitate, and if the binder is less than 0.1, the quality will be weakened. Further, the coating material used in the present invention contains an organic solvent, and is not particularly limited as long as it does not damage the fine particles, and is preferably benzene or a hydrocarbon. Further, the coating used in the present invention may be a raw polymer microparticle, a polymer microparticle-component polymer microparticle, or a microparticle as a pigment-forming polymer microparticle and a carbonate, a polyphenylene benzene, a phenyl ether, or Polybutadiene, polyphenylene oxide resin, polydecylamine, polyurethane resin alkyd resin, ethoxy resin molecular microparticles, 1 part by mass, 10 parts by mass, metal plating, then dense to the substrate Machine solvent. The microparticle dispersion is used. For example, benzene, xylene, and the like, and the object to be coated, -15-200837217, etc., may be added with a resin such as a dispersion stabilizer, a tackifier, or an ink binder. The prepared coating material is applied onto a substrate to form a coating layer. Preferably, the coating layer is formed so that 60% or more of the reducing polymer fine particles are present in the upper half of the layer. The substrate is not particularly limited, and examples thereof include polyester resins such as polyethylene terephthalate or polylactic acid, acrylic resins such as polymethyl methacrylate, polypropylene resins, polycarbonate resins, and polystyrene. Resin, polyvinyl chloride resin, polyamide resin, polyimide resin, polyacetal resin, polyether ether ketone resin, cyclic polyolefin resin, polyethylene resin, polyphenylene sulfide resin, liquid crystal polymer, denatured polyphenylene Ether resin, polyfluorene resin, PC/ABS (polycarbonate ABS) resin, ASA/PC (acrylonitrile styrene acrylate/polycarbonate) resin, ABS (acrylonitrile butadiene styrene) resin, glass, etc. Further, the base material 'may be a soft synthetic resin having self-adhesive properties, and examples thereof include a polyolefin elastomer, a polyethylene elastomer, a polyurethane elastomer, an anthracene resin, a butyl rubber, and a soft polyvinyl chloride. Fluorine resin or the like. Further, the shape of the substrate is not particularly limited, and examples thereof include a plate shape and a film shape. Further, the base material may, for example, be a resin molded article obtained by molding a resin by injection molding or the like. Further, since the resin molded article is provided with the plating material of the present invention, it can be produced, for example, as a decorative ore dressing for automobiles. Or, by using a film composed of a polyimide resin, the plating material of the present invention can be patterned. It can be made into, for example, an electrical circuit product. -16- 200837217 The coating method for the substrate is also not particularly limited, and for example, printing or coating can be performed using a gravure printing machine, an inkjet printer, dipping, spraying, spin coating, roll coating, screen printing machine, or the like. . The composition of the particles in the upper half of the coating layer in which at least 6 % by mass of the reducing polymer fine particles are present can be achieved by drying the coating material after the application of the coating material. The specific method can be carried out, for example, by drying at a low temperature of 30 to 60 ° C for a long time, slowly elevating from a low temperature of 30 to 60 ° C, and drying at a low temperature of 30 to 60 ° C. 2 stages of higher temperature (for example, 100 to 130 ° C), or temperatures different from the above (for example, 30 to 60 ° C - 6 5 to 90 ° C - 100 to 130 ° C) Dry to achieve. When drying at a different temperature of two stages, for example, when toluene is used as an organic solvent, it is dried at 40 ° C for 10 minutes, dried at 8 (TC for 1 minute, and then dried at 120 ° C for 1 minute, Thereby, it is possible to form a structure in which 60% or more of the fine particles are present in the upper half of the coating layer. The thickness of the coating layer is 20 to 500 nm. If the thickness is less than 20 nm, the metal does not precipitate and cannot be formed. When the thickness exceeds 500 nm, the coating film strength is lowered. The amount of the catalyst metal adsorbable on the surface of the coating layer is 0.1/zg/cm2 or more. If the adsorption amount is less than 〇·1 // g/ In the case of cm2, a uniform metal plating film or a metal is not precipitated, and a plating film cannot be formed. The plating material of the present invention is obtained by using a conductive polymer fine particle by dedoping treatment to obtain a reducing particle. The reducing polymer micro-17-200837217 particles can be produced in the same manner. The conductive polymer microparticles used can be, for example, 0/W by mixing an organic solvent with water and an anionic surfactant. Type emulsion A monomer having a 7 Γ-conjugated double bond and oxidatively polymerizing the monomer to produce the monomer having a 7 Γ-conjugated double bond and an anionic surfactant, for example, when the reducing polymer fine particles are produced The same is exemplified, and is preferably pyrrole, aniline, thiophene, and 3,4-ethylenedioxythiophene, etc., more preferably, pyrrole. The amount of the anionic surfactant in the reaction system has a Γ-conjugated double 1 mol of the monomer of the bond is preferably less than 0.2 mol, more preferably 0.05 mol to 0.15 mol. When less than 0.05 mol, the yield and dispersion stability are low, and on the other hand, when it is 0.2 mol or more, the yield is obtained. The conductive polymer microparticles have a temperature dependence of conductivity. The organic solvent forming the organic phase of the emulsion in the above production is preferably hydrophobic. Among them, the aromatic organic solvent toluene or xylene is 0// The viewpoint of the stability of the W-type latex and the affinity with the monomer is preferable. The amphoteric solvent can also carry out polymerization of a monomer having a 7 Γ-conjugated double bond, but recovers the generated conductive polymer fine particles. Difficult to separate organic phase and The ratio of the organic phase to the aqueous phase in the emulsion is preferably, the aqueous phase is 75% by volume or more. When the aqueous phase is 20% by volume or less, the amount of the monomer having a 7 Γ-conjugated double bond is changed. The oxidizing agent used in the above production is, for example, the same as those exemplified in the production of the reducing polymer -18-200837217. Particularly preferred oxidizing agents are persulfates such as ammonium persulfate. The amount of the oxidizing agent is 1 mol of the monomer having a 7 Γ-conjugated double bond, preferably 0.1 mol or more, 0.8 mol or less, more preferably 0.2 to 0.6 m 〇l. When less than 0.1 mol, polymerization of the monomer When the degree is lowered, it is difficult to collect the local fine particles, and on the other hand, when it is 0.8 mol or more, the particle size of the polymer fine particles is increased and the dispersion stability is deteriorated. The method for producing the conductive polymer microparticles can be carried out, for example, by the following steps: (a) mixing and stirring an anionic surfactant, an organic solvent, and water to prepare an emulsion, and (b) having a total of 7 Å - a step of dispersing a monomer of the yoke double bond in the emulsion, (c) oxidatively polymerizing the monomer, contacting the polymer microparticles with the anionic surfactant, and (d) separating the organic phase to recover conductivity. The step of polymer microparticles. The above steps can be carried out using means known to those skilled in the art. For example, the mixing and stirring performed at the time of preparation of the emulsion is not particularly limited, and can be suitably selected, for example, by using a magnetic stirrer, a stirrer, a homogenizer or the like. Further, the polymerization temperature is 0 to 25 ° C, preferably 20 or less ° C. If the polymerization temperature exceeds 25 ° C, side reactions may occur, which is not preferable. When the oxidative polymerization reaction is stopped, the reaction system separates into an organic phase and an aqueous phase, and at this time, the unreacted monomer, oxidizing agent or salt is dissolved in the aqueous phase -19-200837217 and remains. Here, the organic phase liquid separation is recovered by washing with ion-exchanged water several times to obtain conductive polymer fine particles dispersed in an organic solvent. The conductive polymer fine particles obtained by the above-described production method are mainly composed of a polymer having a monomer derivative of a 7 Γ-conjugated double bond and containing fine particles of an anionic surfactant. It is characterized by having a fine particle size and being dispersible in an organic solvent. The polymer microparticles are spherical microparticles, and the average particle diameter thereof is preferably 10 to 100 nm. By forming the fine particles having a small average particle diameter as described above, the surface area of the fine particles can be made extremely large, and even if the fine particles of the same mass are subjected to the de-doping treatment to form a reducing property, more catalyst metal can be adsorbed. The coating film layer is made thin. The conductive polymer fine particles dispersed in the organic solvent thus obtained can be directly concentrated or dried to be used as a conductive polymer fine particle component as a coating material. Further, even if it is not the conductive polymer fine particles produced as described above, for example, commercially available conductive polymer fine particles can be used as a component of the coating material. A coating material containing the conductive polymer fine particles and a binder is applied onto a substrate to form a coating layer, and then de-doping treatment for reducing the fine particles is performed to form a reducing polymer microparticle. In the coating layer, it is preferable that a coating material containing the conductive polymer fine particles and a binder is applied to a substrate to form 60% or more of the conductive polymer particles in the upper half of the layer. After the layer, the coating layer for reducing the amount of the reducing polymer microparticles present in the upper half of the layer can be formed by the de-doping treatment for reducing the fine particles by the step -20-200837217. The binder is, for example, the same as the above-described examples, and the amount thereof is from 0" to 10 parts by mass based on 1 part by mass of the conductive polymer fine particles. If the amount of the binder exceeds 1 part by mass, the metal plating does not precipitate, and if the binder is less than 0.1 part by mass, the adhesion to the substrate is weakened. Further, the above coating material contains an organic solvent. The organic solvent to be used is not particularly limited as long as the fine particles are not damaged, and is not particularly limited. Preferred examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene. Further, the above-mentioned coating material may be added with a resin such as a dispersion stabilizer, a tackifier or an ink binder as needed for the purpose of application and application of the object. The coating material prepared as described above is applied onto a substrate to form a coating layer. Preferably, a layer of particles of 60% or more of the conductive polymer microparticles is present in the upper half of the layer. The substrate may be, for example, the same as the above-described examples, and the shape thereof is not particularly limited, and examples thereof include a plate shape and a film shape. The coating method of the substrate is not particularly limited, and for example, printing or coating can be carried out using a gravure printing machine, an ink jet printer, dipping, spin coating, roll coating, or the like. The composition of the particles in the upper half of the layer in which 60% or more of the conductive polymer fine particles are present can be obtained by drying the coating material after the coating is applied, and it takes time to dry. The specific method can be dried, for example, by drying at a low temperature of 30 to 60 ° C for a long period of time -21 - 3737217, and slowly raising the temperature from a low temperature of 30 to 60 ° C, 30 to 60 ° C. Low temperature and higher temperature (for example, phase 2 of 100 to 130 °C, or temperature different from the above (for example, 30 to 60 °C - to 90 °C - 1 to 130 °) C) Drying is achieved. When drying at a different temperature of 2 stages, for example, when toluene is used as the organic solvent, it is dried at 40 ° C for 1 minute, then dried at 80 ° C for 10 minutes, and then at 120 ° C. After drying for 1 minute, it is possible to form a particle in which 60% or more of the fine particles are present in the upper half of the layer. The thickness of the layer is 20 to 500 nm. If the thickness is less than 20 nm, the metal does not precipitate and cannot be formed. When the thickness is more than 50 Onm, the coating film strength is lowered. In particular, the layer formed by using the conductive polymer fine particles is subjected to de-doping treatment such as alkali treatment for reducing the fine particles to form a coating layer. If the thickness exceeds 500 nm, the above treatment takes a long time, and the film strength is lowered, and as a result, The metal plating film is reduced in adhesion to the substrate. The layer formed using the conductive polymer fine particles described above is subjected to dedoping treatment for reducing the fine particles. The dedoping treatment may, for example, contain a reduction. (for example, a hydrogenated boron compound such as sodium hydride or potassium borohydride, an alkylamine borane such as dimethylamine borane, diethylborane, trimethylamine borane or triethylamine borane, and an amine The solution of the solution is treated by reduction, or by alkaline treatment. From the viewpoint of operability and economy, it is treated with an alkaline solution. Amine hydrazine -22- 200837217 is preferred. In particular, the layer formed using the conductive polymer fine particles has a thickness of 20 to 5,000 nm which is very thin, so that dedoping can be achieved by a short-time alkali treatment under mildening conditions. For example, it is treated in a 1 M aqueous sodium hydroxide solution at a temperature of 20 to 5 Ot, preferably 30 to 40 ° C for 1 to 30 minutes, preferably 3 to 10 minutes. The amount of the catalyst metal adsorbable on the surface of the coating layer on which the fine particles are reduced by the de-doping treatment is 0.1 / / g / cm 2 or more. If the amount of adsorption is less than 0.1 # g/cm2, a uniform metal plating film cannot be obtained, or the metal is not precipitated, and a plating film cannot be formed. The substrate on which the coating layer produced as described above is formed is formed into a plating by electroless plating, and the electroless plating method can be carried out according to a generally known method. In other words, the substrate may be immersed in a catalyst liquid for attaching a catalytic metal such as palladium chloride to water, or the like, and then immersed in an electroless plating solution to obtain a plating material. The catalyst liquid is a solution containing a noble metal (catalyst metal) having catalytic activity for electroless plating, and the catalyst metal may be, for example, palladium, gold, platinum, rhodium or the like, and the metals may be monomers or compounds. From the viewpoint of the stability of the catalytic metal, a palladium compound is preferred, and palladium chloride is particularly preferred. The specific catalyst liquid is preferably, for example, 〇·〇 2% palladium chloride-0.1% hydrochloric acid aqueous solution (pH 3). The treatment temperature is 20 to 50 ° C, preferably 30 to 40 ° C, and the treatment time is -23 to 200837217, which is 0.1 to 20 minutes, preferably 1 to 10 minutes. By the above operation, the reducing polymer fine particles in the coating film are turned into conductive polymer fine particles. The substrate treated as described above is immersed in a plating solution for depositing a metal to form an electroless plating film. The plating solution is not particularly limited as long as it is a plating solution used for general chemical plating. That is, metals, copper, gold, silver, nickel, chromium, and the like which can be used for electroless plating can be used, and copper is preferred. Specific examples of the electroless plating bath include, for example, ATS Yadecapa IW bath (manufactured by Okuno Pharmaceutical Co., Ltd.). The treatment temperature is 20 to 50 ° C, preferably 30 to 40 ° C, and the treatment time is 1 to 30 minutes, preferably 5 to 15 minutes. As described above, the reducing polymer fine particles in the coating film are formed into conductive polymer fine particles. Therefore, by the above operation, a plating material can be produced, and the conductive polymer microparticles are formed on the surface of the substrate. a coating layer of a binder, wherein a plating material of a metal plating film is formed by electroless plating on the coating layer, and the binder is present in an amount of 0.1 to 10 parts by mass based on 1 part by mass of the conductive polymer microparticles. The coating layer has a thickness of 20 to 500 nm, and preferably 60% or more of the conductive polymer fine particles are present in the upper half of the coating layer. The thickness of the metal plating film formed on the coating layer as described above is preferably from 100 to 3,000 nm. -24- 200837217 If the thickness of metal ore 0 is less than 100 nm, the electromagnetic wave screen is easy to weaken. If it exceeds 300 ounces, the metal plating film (metal layer) is difficult to follow the bending and folding of the film. It is easy to peel off from the base film. In the plating material of the present invention, the other layers may be laminated to form a sandwich structure, for example, 'the film may be laminated on the film provided with the metal plating film, or the self-adhesive film provided with the metal plating film may be adhered to the glass. Sandwich Construction Example Next, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. Production Example 1: Preparation of a coating containing a reducing polypyrrole fine particle (coatings 1 to 6), an anionic surfactant, Berex 0T_P (manufactured by Kao Co., Ltd.), 0.42 mmol, and a polyoxyethylene alkyl ether-based nonionic solution were added. The surfactant Amyru was supplied to 409P (manufactured by Kao Co., Ltd.) 2.1 mmol, toluene 50 mL, and ion-exchanged water i〇0 mL, and kept at 20. (: stirring until emulsification. 21 μmmol of pyrrole monomer was added to the obtained emulsion, and stirred for 1 hour. Then, 6 mmol of ammonium persulfate was added to carry out polymerization for 2 hours. After the reaction was completed, the organic phase was recovered to ion-exchange water. Washing several times to obtain a reducing polypyrrole fine particle having a reducing property dispersed in toluene, and a reducing polypyrrole fine particle in the toluene dispersion obtained above, a solid component of -25. Wherein, the binders A and B are added in respective parts by mass to prepare a coating containing the reducing polypyrrole particles shown in Table 1. Here, the binders A and B in Table 1 mean the following, The amount of the binder used is the mass fraction of the binder used for 1 part by mass of the reduced polypyrrole microparticles. A: Super Beka name J-820: melamine system (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) B: Bailong 240: Polyester (manufactured by Toyobo Co., Ltd.) [Table 1] Paint No. Coaming agent type Usage 1 A 0.5 2 A 0.1 3 A 10 4 B 0.5 5 A 0.067 6 A 15 Manufacturing Example 2: Conductive polypyrrole In the preparation of the particle coating (coating 7), 1.5 mmol of anionic surfactant Bereks OT-P (manufactured by Kao Co., Ltd.), 50 mL of toluene, and 100 mL of ion-exchanged water were added to maintain the coating at 20 °C. The mixture was stirred until emulsification, and 1.2 mmol of the pyrrole monomer was added to the obtained emulsion, and the mixture was stirred for 1 hour, and then 6 mmol of ammonium persulfate was added to carry out polymerization for 2 hours. After the completion of the reaction, the organic -26-200837217 phase was recovered as an ion. The exchanged water is washed several times to obtain a reduced polypyrrole fine particle having a reducing property dispersed in toluene. The solid content of the conductive polypyrrole fine particles in the toluene dispersion obtained here is about 1.2%, here, 1 part by mass of the conductive polypyrrole fine particles, and 1 part by mass of the super-Beca name J-820 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) to be added as a coating material 7. Production Example 3: Reducing polyaniline-containing fine particles Preparation of coating (coating 8) Adding anionic surfactant Berex OT-P (made by Kao Co., Ltd.) 0.42 mm 〇l, sorbitan fatty acid ester type nonionic surfactant Leo Drew SP-O30V (manufactured by Kao Co., Ltd.) 0.424 mmol and polyoxyethylene sorbitan ester fatty acid ester 2.12 mmol (manufactured by Kao Co., Ltd.), toluene 50 mL, and ion-exchanged water 100 mL, kept at 2 ( The mixture was stirred under TC until emulsification. 21.2 mmol of the pyrrole monomer was added to the obtained emulsion, and the mixture was stirred for 1 hour, and then 4 mmol of ammonium persulfate was added to carry out polymerization for 2 hours. After the reaction was completed, the organic phase was recovered and washed with ion-exchanged water. A few times, a reducing polyaniline fine particle having a reducing property dispersed in toluene was obtained. The solid content of the reducing polyaniline fine particles in the toluene dispersion obtained herein is about 1.4%. Here, for the amount of the reducing polyaniline fine particles of 1 part by mass, the superbeca name J-820 (large Japanese ink) is added with a binder. 1 part by mass of Chemical Industry Co., Ltd. was used as the coating material 8. -27-200837217 Production Example 4 · Formation of Coating Layer Using the soft films C and D as the substrate 'The above-mentioned prepared coating materials 1 to 8 were applied to the substrate, and various types shown in Table 2 were produced. A soft film of a film thickness of the film thickness. Further, the coating films 1 to 7 and 9 to 13 in Table 2 were dried at 40 ° C for 1 〇 minutes after coating, and then dried at 80 ° C for 10 minutes, and then at 1 20 ° C. After drying for 1 minute, the fine particles present in the upper half of the coating layer were 60% or more, and the same operation was performed on the coating film 8, so that the fine particles present in the upper half of the conductive polymer fine particle layer were More than 60%. Further, the coating films 14 and 15 in Table 2 were dried at 120 ° C for 5 minutes after application of the coating material to form a coating layer in which fine particles were uniformly dispersed. The soft films C and D in the table refer to the following. C: Resin PET, trade name 寇斯摩协影 a 4 1 0 0, Toyo Textile Co., Ltd. company D: Resin PP, trade name OP U-0, ASEAN Royce Co., Ltd. -28- 200837217 [ Table 2] Film No. Coating No. Soft Film Thickness (nm) 1 1 C 100 2 1 C 400 3 1 C 30 4 2 C 100 5 3 C 100 6 4 C 100 7 1 D 100 8 7 C 100 9 8 C 100 10 1 C 600 11 1 C 10 12 5 C 100 13 6 C 100 14 1 C 100 15 3 C _ 100 Production Example 5: Production of a plating material by electroless plating method A coating layer formed as described above was formed. The film (coating films 1 to 7 and 9 to 15) was immersed in a 0.02% palladium chloride monohydrate solution at 35 ° C for 5 minutes, and then washed with tap water. Next, the film was immersed in an electroless copper plating bath ATS Yadekapa IW bath (manufactured by Okuno Pharmaceutical Co., Ltd.), and immersed at 35 ° C for 1 〇 minute to carry out copper plating. Further, the coating film 8 was immersed in a 1 Torr sodium hydroxide aqueous solution at 35 ° C for 5 minutes to carry out a surface treatment to form a coating layer, and the same operation was carried out. The plating materials produced by the coating films 1 to 9 were regarded as Examples 1 to 9, respectively, and the plating materials manufactured by the coating films 10 to 15 were regarded as Comparative Example 1 1 6 °, respectively, by a transmission electron microscope ( Japanese Electronics Co., Ltd.: -29- 200837217 JEM-1200 EXM) A cross-sectional view of the plating examples of the photographic examples 1 to 9 is shown in Fig. 1 as a transmission electron microscope (Japan Electronics) (Stock) company: JEM-1200 EXM) The pattern of the photograph obtained by photographing the comparative examples 5 and 6 is shown in Fig. 2. Test Example 1 The plating compositions of Examples 1 to 9 and Comparative Examples 1 to 6 produced above were subjected to various evaluation tests, and the results thereof are shown in Table 3. Further, the evaluation test item, its evaluation method, and evaluation criteria are as follows. • P d amount The sample was cut into about 3 cm x 4 cm, and palladium was extracted with nitric acid (1+9) and quantified by flameless atomic absorption spectrometry. • Appearance of plating The state of the plating film was visually observed, and the exposed area of the substrate was measured. Moreover, the evaluation criteria are as follows. 〇: completely covered, the substrate is not exposed △: about 50% of the substrate is exposed X: 100% of the substrate is exposed. The thickness of the plating film is measured by an electrolytic film thickness gauge CT-1 (manufactured by Co., Ltd.) Plating -30- 200837217 3 points of the face, with the average 値 as the film thickness. • Tape test 2mm side length According to the JIS H8504 test method, after the streaks are made of 1 〇, the tearing test is carried out with tape. Moreover, the evaluation criteria are as follows. 〇: No peeling △: peeling of about 50% X: 90% or more peeling • Peeling strength The measurement was carried out in accordance with JIS C674 1. • Reducing microparticles are present in an ultra-thin microtome S (electron microscopy). The Nie shadow section is made up of 1 値. The film is cut into a width of 60 nm using an ultramicrotome (made by Leica). The area ratio of the particle portion to the bonded portion was determined from the image of JEM-1200 EXM manufactured by Transmitted Japan Electronics Co., Ltd. Further, the sample was measured by the same method and found to be the average 値-31 - 200837217. Table 3] Example No. Coating film number Pd amount (pg/cm2) Plating appearance plating film thickness (μιη) Tape test peeling strength (kgf /cm) Reducing fine particle existence ratio (upper/lower layer) Example 1 1 1.1 〇0.3 〇2.5 65/35 Example 2 2 2.1 〇0.3 〇1.5 70/30 Example 3 3 0.2 〇0.2 〇2.3 60/40 Implementation Example 4 4 1.3 〇0.5 〇1.1 70/30 Example 5 5 0.8 〇0.1 〇2.4 60/40 Example 6 6 1.0 〇0.3 〇1.9 65/35 Example 7 7 0.9 〇0.3 〇2.2 65/35 Example 8 8 1.0 〇0.3 〇2.3 65/35 Example 9 9 0.9 〇0.3 〇1.8 65/35 Comparative Example 1 10 4.2 〇0.5 Δ0.3 70/30 Comparative Example 2 11 0.04 △ 0.1 〇2.0 60/40 Comparative Example 3 12 1.6 〇0.3 △ 0.4 65/35 Comparative Example 4 13 0.05 △ 0.1 〇2.1 65/35 Comparative Example 5 14 0.5 〇0.2 X 0.05 50/50 Comparative Example 6 15 0.01 X - - - 45/55 [Simple diagram] 1, a schematic diagram of a transmission electron micrograph of a cross-sectional view of the platings of Examples 1 to 9. Fig. 2 is a view showing a transmission electron micrograph of a cross-sectional view of the plating materials of Comparative Examples 5 and 6. [Explanation of main component symbols] 1 : Substrate film 2 : Coating film layer 3 : Metal plating film -32- 200837217 4 : Reducing polymer microparticles -33-