TW201132795A - Method of plate pretreatment and production method of surface metal film material - Google Patents

Method of plate pretreatment and production method of surface metal film material Download PDF

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Publication number
TW201132795A
TW201132795A TW099145688A TW99145688A TW201132795A TW 201132795 A TW201132795 A TW 201132795A TW 099145688 A TW099145688 A TW 099145688A TW 99145688 A TW99145688 A TW 99145688A TW 201132795 A TW201132795 A TW 201132795A
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Taiwan
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group
substrate
plating
solvent
layer
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TW099145688A
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Chinese (zh)
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Hideo Nagasaki
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Fujifilm Corp
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Publication of TW201132795A publication Critical patent/TW201132795A/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Abstract

The invention relates to a method of plate pretreatment that sequentially implements the following steps: a step (A): forming a resin layer containing a copolymer comprising a unit represented by the following formula (1) and a unit represented by the following formula (2) over a substrate; a step (B): providing a plate catalyst or its precursor; and a step (C) implemented before or after the step (B): providing a pretreatment liquid having at least one organic solvent selected from a group consisting of an ether based solvent, an alcohol based solvent, an ester based solvent and an ketone based solvent to the resin layer. In the following formulas (1) and (2), R.sup.1 to R.sup.5 each represents a hydrogen atom, alkyl group, X, Y and Z each represents a single bond, a divalent organic group, an ester group, an amide group, or an ether group. L.sup.1 represents a divalent organic group, and L.sup.2 represents the single bond or a divalent organic group.

Description

201132795 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種適合於表面金屬膜材料製作之鍍敷 前處理方法及包含該鍍敷前處理方法之表面金屬膜材料之 製作方法。 【先前技術】 習知，在絕緣性基板之表面形成因金屬圖案所獲得之 配線的金屬配線基板已廣泛使用於電子構件或半導體元 件。 如此之金屬圖案材料之製作方法主要使用「相減法」。 所謂此相減法係在基板表面所形成的金屬膜上，設置藉由 活性光線之照射而進行感光的感光層，進行此感光層之影 像圖案曝光，其後進行顯影而形成光阻圖像，接著，蝕刻 金屬膜而形成金屬圖案，最後剝離光阻之方法。 於藉由此方法所獲得之金屬圖案中，藉由在基板表面 設置凹凸而產生固定效果，藉此顯現基板與金屬膜之間的 緊貼性。因此，起因於所獲得之金屬圖案的基板界面部之 凹凸，具有作爲金屬配線使用之際的高頻特性將變差的問 題點。另外，爲了在基板表面進行凹凸化處理，必須利用 鉻酸等之強酸處理基板表面，爲了獲得金屬膜與基板之緊 貼性優異的金屬圖案，而有繁雜之步驟爲必要的問題點。 爲了解決此問題，有人提案如下之方法：在基板之表 面進行電漿處理，藉由將聚合起始基導入基板表面，從其 -4- 201132795 聚合起始基而使單體聚合，進行使具有極性基之表面接枝 聚合物生成於基板表面之表面處理，並不會粗面化基板之 表面而使基板與金屬膜之緊貼性改良（例如，參閱非專利文 獻1。）。然而，若根據此方法，由於接枝聚合物具有極性 基，根據溫度或濕度變化，水分之吸收或脫離將容易發生， 其結果，具有所形成的金屬膜或基板將變形的問題。 另外，於將利用此方法所獲得之金屬圖案作爲金屬配 線基板之配線而使用之際，在基板界面部分殘存具有極性 基之接枝聚合物，由於變得容易保持水分或離子而對溫/濕 度依賴性或配線間之耐離子遷移性或形狀變化則具有憂 慮。尤其適用於印刷配線板等之微細配線之際，配線（金屬 圖案）間之高的絕緣性爲必要，也要求配線間之絕緣信賴性 的更進一步提高。 於此，本申請案發明人等提案一種表面金屬膜材料之 製作方法，其係藉由特定物性-尤其將銨敷接受性之樹脂 層作成疏水性，對於平滑之基材，具優越之金屬膜緊貼性， 因濕度變化所造成的緊貼力之變動少（例如，參閱專利文獻 1 ° ) ° 若根據此方法，雖然可形成適合使用於絕緣信賴性所 要求的用途之金屬膜材料，但是由於樹脂層具優越之疏水 性而具有難以進行鍍敷析出之問題，期望鍍敷金屬析出效 率的提高。 非專利文獻 1: Advanced Materials 2000 年 20 號 1481-1494 201132795 專利文獻1 :日本特開2009-7662號公報 【發明內容】 〔發明所欲解決之技術問題〕 本發明係提供一種有效率地形成具有優異的緊貼性且 無不均之均勻金屬膜的鍍敷前處理方法、及採用該鍍敷前 處理方法的表面金屬膜材料之製作方法。 〔解決問題之技術手段〕 本發明人等有鑒於該課題而鑽硏探討的結果，發現藉 由以下所示之手段而可達成該目的。 亦即，本發明之鍍敷前處理方法，其特徵係含有下列 步驟··步驟（A )··形成含有包含以下式（丨）所代表之單位及 以下式（2)所代表之單位的共聚物之樹脂層：步驟（B):賦予 鑛敷觸媒或其先質；及在該步驟（B)之前或之後含有步驟 (C):將包含由醚系溶劑、醇系溶劑、酯系溶劑及酮系溶劑 所構成之族群中所選出的至少一種有機溶劑的前處理液賦 予該樹脂層中；BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pre-plating treatment method suitable for surface metal film material fabrication and a method of fabricating a surface metal film material comprising the pre-plating treatment method. [Prior Art] Conventionally, a metal wiring substrate in which wiring obtained by a metal pattern is formed on the surface of an insulating substrate has been widely used for an electronic component or a semiconductor element. The method of manufacturing such a metal pattern material mainly uses a "subtraction method". The subtractive method is to provide a photosensitive layer that is exposed to light by irradiation of active light on a metal film formed on the surface of the substrate, and to expose the image pattern of the photosensitive layer, and then develop to form a photoresist image, and then form a photoresist image. A method of etching a metal film to form a metal pattern and finally stripping the photoresist. In the metal pattern obtained by this method, a fixing effect is produced by providing irregularities on the surface of the substrate, whereby the adhesion between the substrate and the metal film is revealed. Therefore, the unevenness of the interface portion of the substrate due to the obtained metal pattern has a problem that the high frequency characteristics are deteriorated when used as a metal wiring. Further, in order to perform the roughening treatment on the surface of the substrate, it is necessary to treat the surface of the substrate with a strong acid such as chromic acid, and a complicated step is necessary in order to obtain a metal pattern excellent in adhesion between the metal film and the substrate. In order to solve this problem, a method has been proposed in which a plasma treatment is carried out on the surface of a substrate, and a polymerization starting group is introduced onto the surface of the substrate, and a monomer is polymerized from the polymerization starting group of -4-201132795 to carry out polymerization. The surface-grafted polymer of the polar group is formed on the surface of the substrate, and the adhesion between the substrate and the metal film is not improved by roughening the surface of the substrate (see, for example, Non-Patent Document 1). However, according to this method, since the graft polymer has a polar group, absorption or detachment of moisture easily occurs depending on temperature or humidity, and as a result, there is a problem that the formed metal film or substrate is deformed. In addition, when the metal pattern obtained by the method is used as a wiring of a metal wiring board, a graft polymer having a polar group remains at the interface of the substrate, and it is easy to maintain moisture or ions to maintain temperature/humidity. Dependence or resistance to ion mobility or shape change between wirings is a concern. In particular, when it is applied to fine wiring such as a printed wiring board, high insulation between wirings (metal patterns) is necessary, and insulation reliability between wirings is required to be further improved. Herein, the inventors of the present application have proposed a method for producing a surface metal film material which is made of a specific material property, in particular, an ammonium resin-receptive resin layer, and a superior metal film for a smooth substrate. Tightness, little change in the adhesion due to humidity change (for example, refer to Patent Document 1 °) ° According to this method, although a metal film material suitable for use in applications required for insulation reliability can be formed, Since the resin layer has a superior hydrophobicity and has a problem that it is difficult to perform plating deposition, it is desired to improve the deposition efficiency of the plating metal. Non-Patent Document 1: Advanced Materials 2000 No. 20 1481-1494 201132795 Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-7662 [Draft of the Invention] [Technical Problem to be Solved by the Invention] The present invention provides an efficient formation with A pre-plating treatment method for a uniform metal film having excellent adhesion and no unevenness, and a method for producing a surface metal film material using the pre-plating treatment method. [Technical means for solving the problem] The present inventors have found out the results of the discussion in view of the above problems, and have found that the object can be achieved by the means described below. That is, the pre-plating treatment method of the present invention is characterized by the following steps: Step (A): forming a copolymer containing a unit represented by the following formula (丨) and a unit represented by the following formula (2) Resin layer: step (B): imparting a mineralizing catalyst or a precursor thereof; and containing step (C) before or after the step (B): containing an ether solvent, an alcohol solvent, an ester solvent And a pretreatment liquid of at least one organic solvent selected from the group consisting of a ketone solvent is imparted to the resin layer;

201132795 (上式（1)及式（2)中，R1至R5係表示各自獨立之氫原子、或 取代或者未取代之烷基，X、Y及Z係表示各自獨立之單 鍵、或取代或者未取代之二價有機基、酯基、醯胺基 '或 醚基’ L 1係表示取代或者未取代之二價有機基，L2係表示 單鍵、或取代或者未取代之二價有機基）。 於此’前處理液中之有機溶劑含有率較佳爲1質量％ 以上且50質量％以下，另外，較佳的形態係於該前處理液 中，除了該有機溶劑之外，更含有金屬鹽。 於本發明之鏟敷前處理方法中，賦予前處理液之步驟 可以於賦予該鍍敷觸媒或其先質的步驟之前予以實施，也 可以於之後予以實施，從析出效率提高之觀點，較佳於賦 予鑛敷觸媒或其先質的步驟之後予以實施。 有關本發明之申請專利範圍第9項之表面金屬膜材料 之製作方法，其特徵係在實施該本發明之鍍敷前處理方法 後，對該鍍敷觸媒或其先質進行鍍敷之步驟。 還有，進行該鍍敷之步驟係無電鍍敷之步驟（D)，基於 控制金屬膜的厚度等之目的下，也可以於無電鍍敷步驟之 後，進一步進行電鍍步驟（E)。 於本發明中，銨敷觸媒或其先質接受層之該樹脂層係 含有包含以下式（1)所代表之單位及以下式（2)所代表之單 位的共聚物。亦即，由於該樹脂層係藉由具有與鍍敷觸媒 或其先質形成相互作用之官能基、及聚合性基之聚合物所 形成，因此具有疏水性之物性’且與下層之基板具有優異 201132795 的緊貼性’效率佳地接受鍍敷觸媒或其先質。因此，所形 成的鍍敷金屬膜係與樹脂層具有優異的緊貼性。另外，藉 由實施本發明之鍍敷前處理方法，由於對存在於基材上之 疏水性樹脂層的鍍敷液之親和性將提高，以樹脂層中所賦 予的鍍敷觸媒等爲基點’效率良好地形成均勻的鍍敷膜。201132795 (In the above formulas (1) and (2), R1 to R5 represent each independently a hydrogen atom, or a substituted or unsubstituted alkyl group, and X, Y and Z are each a single bond or a substitution or An unsubstituted divalent organic group, an ester group, a decylamino group or an ether group 'L 1 means a substituted or unsubstituted divalent organic group, and L2 means a single bond, or a substituted or unsubstituted divalent organic group) . The content of the organic solvent in the pretreatment liquid is preferably 1% by mass or more and 50% by mass or less, and a preferred embodiment is in the pretreatment liquid, and further contains a metal salt in addition to the organic solvent. . In the pretreatment method of the present invention, the step of applying the pretreatment liquid may be carried out before the step of imparting the plating catalyst or its precursor, or may be carried out later, from the viewpoint of improvement in precipitation efficiency. It is preferred to carry out the step of imparting a mineralizing catalyst or its precursor. The method for producing a surface metal film material according to claim 9 of the present invention is characterized in that, after performing the pre-plating treatment method of the present invention, the plating catalyst or its precursor is plated. . Further, the step of performing the plating is the step (D) of electroless plating, and the plating step (E) may be further performed after the electroless plating step for the purpose of controlling the thickness of the metal film or the like. In the present invention, the resin layer of the ammonium catalyst or its precursor receiving layer contains a copolymer comprising a unit represented by the following formula (1) and a unit represented by the following formula (2). In other words, since the resin layer is formed of a polymer having a functional group that interacts with a plating catalyst or a precursor thereof and a polymerizable group, it has hydrophobic physical properties and has a substrate with a lower layer. Excellent 201132795's closeness 'Efficiently accepts plating catalyst or its precursors. Therefore, the formed metal plating film has excellent adhesion to the resin layer. In addition, by performing the pre-plating method of the present invention, the affinity for the plating solution of the hydrophobic resin layer present on the substrate is improved, and the plating catalyst or the like provided in the resin layer is used as a base point. 'Efficiently form a uniform plating film.

上式（1)及式（2)中，R1至R5係表示各自獨立之氫原 子、或取代或者未取代之烷基，X、Y及Z係表示單鍵、或 取代或者未取代之二價有機基、酯基、醯胺基、或醚基， L1係表示取代或者未取代之二價有機基，L2係表示單鍵' 或取代或者未取代之二價有機基。 由於藉由本發明之表面金屬膜材料之製作方法所獲得 之表面金屬膜材料係鍍敷膜之析出性無不均且均勻，且與 樹脂層具有優異的緊貼性，各種的應用爲可能。 201132795 例如’對於利用本發明表面金屬膜材料之製作方法所 獲得之表面金屬膜材料的鍍敷膜（金屬膜），藉由實施触刻 成圖案狀之步驟而製作金屬圖案材料，或是藉由在金屬構 件或塑膠構件之表面製作本發明之表面金屬膜材料，也可 應用於鏟敷構件表面之用途。 發明之效果 若根據本發明，能夠提供一種有效率地形成具有優異 的緊貼性且無不均之均勻金屬膜的鍍敷前處理方法、及採 用該鑛敷前處理方法的表面金屬膜材料之製作方法。 【實施方式】 以下，詳細說明本發明。 <鍍敷前處理方法> 本發明之鍍敷前處理方法係在基板上經由鍍敷處理而 用以形成金屬膜之鍍敷前處理方法。 〔步驟（A)〕 步驟（A)係形成含有以式（1)所代表之單位、及以下式（2) 所代表之單位的共聚物之樹脂層的步驟。 有關本發明之樹脂層係含有以式（1)所代表之單位 '及 以下式（2)所代表之單位的共聚物（以下，適合稱爲特定共聚 物）。 針對在基板上形成樹脂層，首先將含有特定共聚物的 樹脂層形成用組成物賦予基板，該特定共聚物係具有與鍍 敷觸媒或其先質形成相互作用之官能基’且可與該基板進 201132795 行可直接化學鍵結之聚合物。 所形成的樹脂層較佳爲符合下列1至2之全部條件。 條件1 : 2 5。(： - 5 0 %相對濕度環境下之飽和吸水率爲〇 · 0 1 至1 0質量％。 條件2 : 2 5 °C - 5 0 %相對濕度環境下’滴下蒸餾水5 //L， 15秒鐘靜置後之表面接觸角爲50度至150度。 所形成的樹脂層係即使高溫高濕下’吸水性爲低，且 外疏水性爲高者。 因此，將鍍敷觸媒等賦予此樹脂層後〔步驟（B)〕，藉 由使用它而進行無電鍍敷〔步驟（D)〕’能夠獲得與樹脂層 具有優異的緊貼性之金屬膜，將此金屬膜蝕刻成圖案狀而 獲得金屬圖案之'丨胃形，即使樹脂層露出於該金屬圖案之非 形成區域之狀態，所露出的樹脂層部分既不吸水且不會導 致起因於此之絕緣性的降低。其結果，藉由利用本發明之 方法所形成的金屬材料所獲得之金屬圖案材料係成爲具有 優異的金屬圖案之非形成區域的絕緣信賴性者。還有，於 本發明中，於〔步驟（B)〕之前或之後，由於進行將含有以 下所詳述的有機溶劑之前處理液的步驟〔步驟（C)〕’與無 電鍍敷液之親和性將提高，可效率佳地形成均勻之鑛敷 膜。 以下，針對有關本發明之樹脂層的較佳條件之該1至 2之各條件加以說明。 條件1中之飽和吸水率，甚至條件2中之表面接觸角 -10- 201132795 皆能夠利用日本特開2009-7662號公報中揭示之方法而測 定。 另外，於本發明中，該樹脂層符合下列1 ’至2 ’之全部 條件爲更佳的形態。 條件1’ ： 25°C-50%相對濕度環境下之飽和吸水率爲 〇. 〇 1至5質量％。 條件2’ ： 25°C-50%相對濕度環境下，滴下蒸餾水5//L， 15秒鐘靜置後之表面接觸角爲55度至150度》 於本發明中，由於含有以下所詳述的特定單位之共聚 物係吸水性低，具有優異的疏水性，形成有符合該條件之 樹脂層。 首先，在基板上具有與鍍敷觸媒或其先質形成相互作 用的官能基（以下，有時簡稱爲「相互作用性基」），且可 與該基板進行直接化學鍵結的聚合物。利用含有特定共聚 物之樹脂層形成用組成物，進行形成樹脂層之樹脂層形成 步驟。 此樹脂層形成步驟〔步驟（A)〕之較佳的形態係包含下 列之步驟：在基板上，首先製作形成含有（A-1)聚合起始 劑、或具有能夠聚合起始官能基之聚合起始層的基板之步 驟；與在（A-2)該聚合起始層，使式（1)所代表之單位、及式 (2)所代表之單位的共聚物直接化學鍵結而形成樹脂層之 步驟。 另外，（A-2)步驟-亦即使共聚物直接化學鍵結於聚合 -11- 201132795 起始層之步驟較佳爲藉由使含有式（1)所代表之單位、及式 (2)所代表之單位的共聚物接觸於該聚合起始層上之後，賦 予能量而使該共聚物直接化學鍵結於該整體基板表面（整 體聚合起始層表面）之步驟。 (表面接枝） 基板上之樹脂層的形成係使用一般稱爲表面接枝聚合 之手段。所謂表面接枝聚合係將活性種賦予高分子化合物 鏈上，藉此而使起始聚合之其他單體進一步聚合，合成接 枝聚合物之方法。尤其於賦予活性種之高分子化合物形成 固體表面時，被稱爲表面接枝聚合。 本發明所適用的表面接枝聚合法能夠使用文獻揭示之 任一種習知方法。例如，在新高分子實驗學1〇、高分子學 會編、19 94年、共立出版（股）發行、p_i35中，作爲表面接 枝聚合法，記載有光接枝聚合法、電漿照射接枝聚合法。 另外’吸附技術便覽、N T S (股）、竹內監修、1 9 9 9 · 2發行、 ρ·203、p.695中’記載有厂線、電子線等之放射線照射接枝 聚合法。 光接枝聚合法之具體方法能夠使用在日本特開昭 63-92658號公報、特開平10-296895號公報及特開平 11-1194 13號公報記載之方法。 於形成本發明中之樹脂層之際，除了上述之表面接枝 法以外，也能夠採用將三烷氧矽烷基、異氰酸酯基、胺基、 經基、羧基等之反應性官能基賦予特定共聚物之末端，依 -12- 201132795 照此等基與存在於基板表面之官能基之偶合反應而使其鍵 結之方法。 此等方法之中，從生成更多的接枝聚合物之觀點，較 佳爲使用光接枝聚合法，尤其是利用UV光所進行的光接 枝聚合法而形成樹脂層。 〔基板〕 所謂本發明中之「基板」係指其表面具有可以直接化 學鍵結之狀態形成特定共聚物的機能者，可以爲蕋板本身 具有如此之表面特性者，另外，也可以在該基材上設置另 種中間層（例如，所後述的聚合起始層），該中間層具有如 此之特性者。 (基材、基板） 本發明所使用的基材較佳爲尺寸安定之板狀物，例 如，包括紙、塑膠（例如，聚乙烯' 聚丙烯、聚苯乙烯等） 所積層的紙、金屬板（例如，鋁、鋅、銅等）、塑膠薄膜（例 如’二醋酸纖維素、三醋酸纖維素、丙酸纖維素、丁酸纖 維素、醋酸纖維素、硝酸纖維素、聚對苯二甲酸乙二酯、 聚乙烯、聚苯乙烯、聚丙烯、聚碳酸酯、聚乙烯縮醛、聚 醯亞胺樹脂、環氧樹脂、雙順丁烯二醯亞胺樹脂、聚苯醚、 液晶聚合物、聚四氟乙烯等）、積層或蒸鍍有如上所述之金 屬的紙或塑膠薄膜等。本發明所使用的基材較佳爲環氧樹 脂、或聚醯亞胺樹脂。 還有，此等之基材表面係具有可形成直接化學鍵結具 -13- 201132795 有與鍍敷觸媒或其先質形成相互作用之官能基的聚合物之 狀態的機能之情形下，也可以將其基材本身作爲基板使用。 作爲於本發明中之基板’也能夠使用日本特開 2005-281350號公報之段落編號〔〇〇28〕至〔〇〇88〕中記載 之含有在骨架中具有聚合起始部位之聚醯亞胺的基材。 另外’將利用本發明之表面金屬膜之製作方法所獲得 之表面金屬膜材料應用於半導體組件、各種電配線基板等 之情形下’較佳爲使用由如日本特開2009-7662號公報段 落編號〔 0039〕至〔〇〇46〕中所記載之絕緣性樹脂組成物 所形成的基板。 用於如此用途之情形的基板，具體而言，較佳爲由i GHz中之介電常數（比介電常數）爲3.5以下之絕緣性樹脂 所構成的基板’或是在基材上具有由該絕緣性樹脂所構成 的層之基板。另外，較佳爲由1 GHz中之介電正接爲〇.〇1 以下之絕緣性樹脂所構成的基板，或是在基材上具有由該 絕緣性樹脂所構成的層之基板。 絕緣性樹脂之介電常數及介電正接係已被記載於該公 報中。 如此方式，於本發明中，從介電常數或介電正切之觀 點，選擇絕緣樹脂材料也爲有用。介電常數爲3.5以下， 介電正接爲0.01以下之絕緣性樹脂，可舉例：液晶聚合物、 聚醯亞胺樹脂、氟樹脂、聚苯醚樹脂、氰酸酯樹脂、雙（雙 伸苯基）乙烷樹脂等，進一步也含有此等之改性樹脂。 -14- 201132795 若考量對半導體組件、各種電配線基板等之用途時， 本發明所用之基板的表面凹凸較·佳爲500 nm以下，更佳爲 1 00 nm以下’進一步較佳爲50 nm以下，最好爲20 nm以 下。較佳爲此基板之表面凹凸（設置有中間層或聚合起始層 之情形係其層之表面凹凸）變得越小，將所獲得之金屬圖案 材料應用於配線等之情形下，高頻送電時之電損失將變得 越少。 於本發明中，若基板爲板狀物，例如樹脂薄膜（塑膠薄 膜）的話，能夠在其兩面形成樹脂層。 如此方式，在樹脂薄膜（基板）之兩面形成有樹脂層之 情形下，藉由對此樹脂層進行鍍敷前處理步驟及鏟敷步 驟，能夠獲得在兩面形成有金屬膜的表面金屬膜材料。 於本發明中，採用將活性種賦予基板表面，以此作爲 起點而使接枝聚合物生成的表面接枝聚合法之情形，於接 枝聚合物生成之際，較佳爲使用在基材上形成含有聚合起 始層或具有能夠聚合起始之官能基的聚合起始層而成之基 板。藉由使用此基板，能夠使活性點效率佳地發生，使更 多的接枝聚合物生成。 以下，針對本發明中之聚合起始層加以說明。還有， 若基材爲板狀物的話，也可以在其雙面形成聚合起始層。 (聚合起始層） 本發明中之聚合起始層可舉例：含有高分子化合物與 聚合起始層之層、或含有聚合性化合物與聚合起始劑之 -15- 201132795 層、具有能夠聚合起始的官能基之層。 本發明中之聚合起始層係藉由將必要的成分溶解於能 夠溶解之溶劑中，利用塗布等之方法而設置於基材表面， 經由加熱或光照射來硬化薄膜而能夠形成。詳言之，藉由 日本特開2009-7662號公報段落編號〔 0052〕至〔 0056〕 所記載的方法來予以形成。 從顯現充分聚合起始能力及維持膜性而防止膜剝離之 觀點而言’在基材上形成聚合起始層之情形的塗布量係以 乾燥後之質量計，較佳爲〇· 1 g/m2至20 g/m2，更佳爲0.1 g/m2 至 15 g/m2，進一步較佳爲 0.1 g/m2 至 2 g/m2。 於本發明中，如上所述，較佳爲藉由利用塗布等而將 上述之聚合起始層形成用之組成物配置於基材上，去除溶 劑而使其成膜後形成聚合起始層，此時，進行加熱及/或光 照射而硬化薄膜。尤其，藉由加熱而加以乾燥之後，一旦 進行光照射而事先預備硬膜時，因爲預先進行聚合性化合 物某種程度之硬化，所以能夠有效地抑制在聚合起始層上 生成接枝聚合物之後，連聚合起始層一倂脫落之事態，因 此爲較佳的。 從適當製造之觀點，加熱溫度與時間最好選擇塗布溶 劑能夠充分乾燥之條件，較佳選擇溫度爲1 0(TC以下、乾燥 時間爲30分鐘以內，更佳選擇乾燥溫度爲40t至80 °C、乾 燥時間爲1 0分鐘以內之範圍的加熱條件。 加熱乾燥後，依照期望而所進行的光照射能夠使用用 -16- 201132795 於所後述的接枝聚合物之生成反應的光源。於接著所進行 的接枝聚合物生成步驟，從不阻礙藉由能量賦予所發生的 聚合起始層活性點與接枝聚合物生成之觀點，於硬化聚合 性化合物之際，即使進行自由基聚合，存在於聚合起始層 中之聚合起始劑也較佳爲未完全消耗之程度下進行光照 射。關於光照射時間係因光源之強度而不同，一般而言， 較佳爲30分鐘以內。如此之預備硬化的目標可舉例：溶劑 洗淨後之膜殘存率成爲80%以下，且預備硬化後之起始劑 殘存率爲1%以上。 另外’除了含有上述之聚合性化合物及聚合起始劑之 聚合起始層以外，使用日本特開20〇4-161995號公報中記 載之聚合起始基懸垂在側鏈上而成之聚合物的聚合起始層 亦爲較佳。具體而言，此聚合物係在側鏈上具有聚合起始 能力之官能基（聚合起始基）及交聯性基之聚合物（以下，適 宜稱爲聚合起始聚合物。），依照此聚合物而能夠形成具有 鍵結於聚合物鏈之聚合起始基，且其聚合物鏈是藉交聯反 應予以固定化之形態的聚合起始層。 進行如此方式所形成的聚合起始層也適合作爲本申請 案之聚合起始層。 於此所用之聚合起始聚合物可舉例：日本特開 2004-161995號公報之段落編號〔0011〕至〔〇158〕中記載 者 '特開2009-7662號公報之段落編號〔〇〇62〕至〔 0063〕 中記載者等。 -17- 201132795 一聚合起始層之成膜一 本發明中之使用聚合起始聚合物所構成的聚合起始層 係藉由將上述之聚合起始聚合物溶解於適當之溶劑中而調 製塗布液，利用塗布等而將其塗布液配置於基材上，除去 溶劑，進行交聯反應而成膜。亦即，藉由進行此交聯反應 而使聚合起始聚合物予以固定化。關於藉此交聯反應所致 的固定化，可舉例：使用聚合起始聚合物之自縮合反應的 方法、及倂用交聯劑的方法，較佳使用交聯劑。使用聚合 起始聚合物之自縮合反應的方法係例如交聯性基爲-NCO 之情形，利用藉由加熱而進行自縮合反應的性質。藉由進 fT此自縮合反應而能夠形成交聯結構。 倂用交聯劑之方法所用之交聯劑能夠使用如山下信二 編「交聯劑手冊」所揭示的習知物。 聚合起始聚合物中之交聯性基與交聯劑之較佳的組合 係已記載於日本特開2009-7662號公報段落編號〔 0065〕， 較佳的交聯劑之具體例可舉例：同一公報段落編號〔〇〇67〕 中所記載者。 如此之交聯劑係於聚合起始層成膜之際添加於含有上 述之聚合起始聚合物的塗布液中。其後，藉由塗膜加熱乾 燥時之熱而進行交聯反應，能夠形成牢固之交聯結構。針 對此反應之詳細內容及聚合起始層之製膜，已記載於曰本 特開2009-7662號公報段落編號〔0068〕至〔〇〇71〕中。 從表面接枝聚合之起始能力或膜性之觀點，由使用聚 -18- 201132795 合起始聚合物所構成的聚合起始層的塗布量係以乾燥後之 質量計’較佳爲0.1g/m2至20g/m2，進一步較佳爲lg/m2 至 1 5 g/m2。 再者’於本發明中，如上所述，使用在基材上具有由 絕緣性樹脂而成之層的基板之情形，較佳爲由此絕緣性樹 脂所構成的層中，含有習知之聚合起始劑而作成絕緣性之 聚合起始層。於此絕緣性聚合起始層中所含之聚合起始 劑，並無特別之限制，例如，能夠使用上述之熱聚合起始 劑、光聚合起始劑（自由基聚合起始劑、陰離子聚合起始 劑、陽離子聚合起始劑）、或在日本特開平9-77891號、特 開平1 0-4 5927號記載之在側鏈具有活性羰基之高分子化合 物，甚至在側鏈上具有聚合起始能力之官能基及交聯性基 之聚合物（聚合起始聚合物）等。 一般而言，於絕緣層中以固形物計，絕緣性之聚合起 始層中所含之聚合起始劑的量較佳爲〇 · 1至5 0質量％左 右，更佳爲1.0至30.0質量％左右。 (接枝聚合物之生成） 於步驟（A)中之接枝聚合物的生成形態，如上所述，能 夠採用：利用存在於基板表面之官能基與高分子化合物在 其末端或側鏈上所具有的反應性官能基之偶合反應的方 法、或光接枝聚合法。 於本發明中，較佳爲如下之形態〔（al-2)步驟〕：使用 在基材上形成有聚合起始層之基板，在該聚合起始層上具 -19- 201132795 有與鑛敷觸媒或其先質形成相互作用之官能基（相互作用 性基）’且由形成與該聚合起始層進行直接化學鍵結之聚合 物所構成的聚合物層。進一步較佳爲如下之形態：在聚合 起始層上’於使具有聚合性基及相互作用性基之聚合物接 觸之後’藉由賦予能量而使該聚合物直接化學鍵結於該整 體基板表面（整體聚合起始層表面）的形態。亦即，一邊使 含有具有聚合性基及相互作用性基之化合物的組成物接觸 於聚合起始層表面，一邊藉由生成該聚合起始層表面之活 性層而使其直接鍵結。 該接觸可以藉由將形成有聚合起始層之基板浸漬於具 有聚合性基及相互作用性基之化合物的液狀組成物（本發 明之聚合物層形成用組成物）中而進行，從操作性或製造效 率之觀點，如後所述，較佳爲利用塗布法，在基板表面（聚 合起始層表面）形成含有具有聚合性基及相互作用性基之 化合物的組成物（本發明之聚合物層形成用組成物）所構成 的層。 於本發明中，針對利用表面接枝聚合法而用於使接枝 聚合物生成之情形的具有聚合性基及相互作用性基之化合 物而加以說明。 本發明中之具有聚合性基及相互作用性基之化合物係 由於由所生成的接枝聚合物所構成的樹脂層含有該特定共 聚物，成爲全部符合該1至2之條件者。 於本發明中，具有聚合性基及相互作用性基之聚合物 -20- 201132795 單位 可使用含有下式（1)所代表之單位、及下式（2)所代表之 的共聚物。In the above formulas (1) and (2), R1 to R5 represent each independently hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y and Z represent a single bond, or a substituted or unsubstituted divalent group. An organic group, an ester group, a decylamino group, or an ether group, L1 represents a substituted or unsubstituted divalent organic group, and L2 represents a single bond 'or a substituted or unsubstituted divalent organic group. The surface metal film material-based plating film obtained by the method for producing a surface metal film material of the present invention has no unevenness and uniformity in precipitation, and has excellent adhesion to the resin layer, and various applications are possible. 201132795 For example, a plating film (metal film) of a surface metal film material obtained by the method for producing a surface metal film material of the present invention is formed by performing a step of patterning a metal pattern, or by using a step of performing a patterning process. The surface metal film material of the present invention can be produced on the surface of a metal member or a plastic member, and can also be applied to the surface of a scooping member. Advantageous Effects of Invention According to the present invention, it is possible to provide a pre-plating treatment method for efficiently forming a uniform metal film having excellent adhesion without unevenness, and a surface metal film material using the pre-mineral treatment method. Production Method. [Embodiment] Hereinafter, the present invention will be described in detail. <Pre-plating treatment method> The pre-plating treatment method of the present invention is a pre-plating treatment method for forming a metal film on a substrate by a plating treatment. [Step (A)] The step (A) is a step of forming a resin layer containing a copolymer represented by the formula (1) and a unit represented by the following formula (2). The resin layer of the present invention contains a copolymer represented by the unit represented by the formula (1) and a unit represented by the following formula (2) (hereinafter, it is suitably referred to as a specific copolymer). In order to form a resin layer on a substrate, first, a composition for forming a resin layer containing a specific copolymer having a functional group which forms an interaction with a plating catalyst or a precursor thereof is provided, and The substrate enters the 201132795 line of polymers that can be directly chemically bonded. The resin layer to be formed preferably satisfies all of the following conditions 1 to 2. Condition 1: 2 5. (: - 50 % relative humidity, saturated water absorption 〇 · 0 1 to 10% by mass. Condition 2 : 2 5 °C - 50% relative humidity environment 'drip distilled water 5 / L, 15 seconds The surface contact angle after standing still is 50 to 150 degrees. The resin layer formed is low in water absorption and high in external hydrophobicity even under high temperature and high humidity. Therefore, a plating catalyst or the like is imparted thereto. After the resin layer [Step (B)], by using it, electroless plating [Step (D)]' can obtain a metal film having excellent adhesion to the resin layer, and the metal film is etched into a pattern. The 'stomach shape of the metal pattern is obtained, and even if the resin layer is exposed to the non-formation region of the metal pattern, the exposed resin layer portion does not absorb water and does not cause a decrease in insulation property due to this. The metal pattern material obtained by the metal material formed by the method of the present invention is an insulation reliability having an excellent non-formation region of the metal pattern. Also, in the present invention, before [step (B)] Or after that, due to carry out will contain the following The step of the organic solvent pretreatment liquid (step (C)]' will be described in detail, and the affinity with the electroless plating solution will be improved, and a uniform ore film can be formed efficiently. Hereinafter, the resin layer of the present invention is more specifically described. The conditions of the conditions 1 to 2 of the preferred conditions are explained. The saturated water absorption rate in the condition 1, even the surface contact angle in the condition 2 - 10, 2011, 830, can be determined by the method disclosed in Japanese Patent Laid-Open Publication No. 2009-7662. Further, in the present invention, the resin layer satisfies all of the following conditions of 1 ' to 2 ' as a more preferable condition. Condition 1': saturated water absorption ratio in the case of 25 ° C - 50% relative humidity 〇. 〇 1 To 5 mass%. Condition 2': 25 ° C - 50% relative humidity environment, dripping distilled water 5 / / L, surface contact angle after standing for 15 seconds is 55 degrees to 150 degrees" In the present invention, The copolymer containing a specific unit as described below is low in water absorbability, has excellent hydrophobicity, and is formed with a resin layer satisfying the above conditions. First, it has an interaction with a plating catalyst or a precursor thereof on a substrate. Functional group (hereinafter, sometimes referred to as short A polymer which can be directly chemically bonded to the substrate, and a resin layer forming step of forming a resin layer by using a composition for forming a resin layer containing a specific copolymer. [The preferred embodiment of the step (A)] comprises the steps of: first forming a substrate comprising (A-1) a polymerization initiator or a polymerization starting layer capable of polymerizing a starting functional group on a substrate. And a step of forming a resin layer by directly chemically bonding the copolymer represented by the formula (1) and the unit represented by the formula (2) to the polymerization starting layer (A-2). (A-2) Step - even if the copolymer is directly chemically bonded to the starting layer of the polymerization-11-201132795, preferably by including the unit represented by the formula (1) and the unit represented by the formula (2) After the copolymer is contacted with the polymerization starting layer, energy is applied to directly bond the copolymer to the surface of the unitary substrate (the surface of the overall polymerization starting layer). (Surface Grafting) The formation of the resin layer on the substrate is generally referred to as means of surface graft polymerization. The surface graft polymerization is a method in which an active species is added to a polymer compound chain, whereby another monomer which is initially polymerized is further polymerized to synthesize a graft polymer. In particular, when a polymer compound which imparts an active species forms a solid surface, it is called surface graft polymerization. The surface graft polymerization method to which the present invention is applied can use any of the conventional methods disclosed in the literature. For example, in the new polymer experiment 1〇, the Society of Polymers, 19 94, Co-published (issued), p_i35, as a surface graft polymerization method, photo-graft polymerization, plasma irradiation graft polymerization is described. law. In addition, a radiation irradiation graft polymerization method such as a factory line or an electron line is described in the 'Adsorption technology manual, N T S (share), Takeuchi supervision, 1989, ρ·203, and p.695. For the specific method of the photo-grafting polymerization method, the method described in JP-A-63-92658, JP-A-10-296895, and JP-A No. Hei 11-119413 can be used. In forming the resin layer in the present invention, in addition to the surface grafting method described above, a reactive copolymer having a trialkoxyalkyl group, an isocyanate group, an amine group, a trans group, a carboxyl group or the like can be imparted to the specific copolymer. At the end, according to -12-201132795, a method of bonding these groups with a coupling reaction of a functional group existing on the surface of the substrate. Among these methods, from the viewpoint of producing more graft polymer, it is preferred to form a resin layer by photo-graft polymerization, in particular, photo-bundling polymerization using UV light. [Substrate] The term "substrate" as used in the present invention means a function of forming a specific copolymer in a state where it can be directly chemically bonded, and may have such a surface characteristic as the raft itself, or may be on the substrate. An additional intermediate layer (for example, a polymerization starting layer described later) is provided thereon, and the intermediate layer has such characteristics. (Substrate, Substrate) The substrate used in the present invention is preferably a plate having a stable size, for example, a paper or a metal plate including paper, plastic (for example, polyethylene 'polypropylene, polystyrene, etc.). (eg, aluminum, zinc, copper, etc.), plastic film (eg 'diacetate cellulose, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate, nitrocellulose, polyethylene terephthalate Diester, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, polyimide resin, epoxy resin, bis-xenylenediamine resin, polyphenylene ether, liquid crystal polymer, Polytetrafluoroethylene or the like, a paper or a plastic film which is laminated or vapor-deposited with the metal as described above. The substrate used in the present invention is preferably an epoxy resin or a polyimide resin. Further, in the case where the surface of the substrate has a function of forming a state in which a direct chemical bond has a polymer having a functional group which interacts with a plating catalyst or a precursor thereof, it can also be used. The substrate itself is used as a substrate. As the substrate in the present invention, it is also possible to use the polyimine which has a polymerization initiation site in the skeleton as described in paragraphs [〇〇28] to [〇〇88] of JP-A-2005-281350. Substrate. Further, in the case where the surface metal film material obtained by the method for producing a surface metal film of the present invention is applied to a semiconductor component, various electric wiring substrates, etc., it is preferable to use the paragraph number as disclosed in Japanese Patent Laid-Open Publication No. 2009-7662. A substrate formed of the insulating resin composition described in [0393] to [46]. The substrate used in such a case is preferably a substrate made of an insulating resin having a dielectric constant (specific permittivity) of 3.5 or less in i GHz or has a substrate A substrate of a layer composed of the insulating resin. Further, it is preferably a substrate made of an insulating resin having a dielectric of 1 GHz or less, or a layer having a layer made of the insulating resin on a substrate. The dielectric constant and dielectric positive interface of an insulating resin have been described in the publication. In this manner, in the present invention, it is also useful to select an insulating resin material from the viewpoint of dielectric constant or dielectric tangent. An insulating resin having a dielectric constant of 3.5 or less and a positive dielectric connection of 0.01 or less may, for example, be a liquid crystal polymer, a polyimide resin, a fluororesin, a polyphenylene ether resin, a cyanate resin, or a bis(bisphenylene) group. An ethane resin or the like further contains such a modified resin. -14-201132795 When considering the use of a semiconductor component or various electric wiring boards, the surface roughness of the substrate used in the present invention is preferably 500 nm or less, more preferably 100 nm or less, and further preferably 50 nm or less. It is preferably below 20 nm. It is preferable that the surface unevenness of the substrate (the case where the intermediate layer or the polymerization starting layer is provided is the surface unevenness of the layer) becomes smaller, and the obtained metal pattern material is applied to wiring or the like, and the high frequency power is supplied. The electric loss will become less. In the present invention, if the substrate is a plate-like material such as a resin film (plastic film), a resin layer can be formed on both surfaces thereof. In such a manner, in the case where a resin layer is formed on both surfaces of the resin film (substrate), the surface metal film material having the metal film formed on both surfaces can be obtained by performing the plating pretreatment step and the squeezing step on the resin layer. In the present invention, the surface graft polymerization method in which the active species is applied to the surface of the substrate as a starting point for the formation of the graft polymer is preferably used on the substrate when the graft polymer is formed. A substrate comprising a polymerization starting layer or a polymerization starting layer having a functional group capable of polymerization initiation is formed. By using this substrate, the active site can be efficiently produced, and more graft polymer can be formed. Hereinafter, the polymerization starting layer in the present invention will be described. Further, if the substrate is a plate, a polymerization starting layer may be formed on both sides thereof. (Polymerization starting layer) The polymerization starting layer in the present invention may, for example, be a layer containing a polymer compound and a polymerization starting layer, or a layer containing a polymerizable compound and a polymerization initiator, -15-201132795, capable of being polymerized The layer of the initial functional group. The polymerization starting layer in the present invention can be formed by dissolving a necessary component in a solvent which can be dissolved, and applying it to the surface of the substrate by a method such as coating, and curing the film by heating or light irradiation. More specifically, it is formed by the method described in paragraphs [0502] to [0056] of JP-A-2009-7662. The coating amount in the case where the polymerization starting layer is formed on the substrate from the viewpoint of exhibiting sufficient polymerization initiation ability and maintaining film property to prevent film peeling is preferably 〇·1 g/ by mass after drying. M2 to 20 g/m2, more preferably 0.1 g/m2 to 15 g/m2, still more preferably 0.1 g/m2 to 2 g/m2. In the present invention, as described above, it is preferred that the composition for forming a polymerization starting layer described above is disposed on a substrate by coating or the like, and the solvent is removed to form a polymerization starting layer. At this time, the film is cured by heating and/or light irradiation. In particular, when it is dried by heating, when the hard film is prepared in advance by light irradiation, since the polymerizable compound is hardened to some extent in advance, it is possible to effectively suppress the formation of the graft polymer on the polymerization starting layer. It is preferable to have a state in which the initial layer of the polymerization is detached. From the viewpoint of proper production, the heating temperature and time are preferably selected so that the coating solvent can be sufficiently dried. Preferably, the temperature is 10 (below TC, the drying time is 30 minutes or less, and the drying temperature is preferably 40 to 80 ° C). The drying time is a heating condition within a range of 10 minutes. After heating and drying, a light source which is subjected to a reaction of the graft polymer described later in -16 to 201132795 can be used as the light irradiation desired. The graft polymer formation step is carried out so as to prevent the formation of the polymerization starting layer active point and the formation of the graft polymer by energy imparting, and to effect the radical polymerization even when the polymerizable compound is cured. The polymerization initiator in the polymerization starting layer is also preferably subjected to light irradiation to the extent that it is not completely consumed. The light irradiation time varies depending on the intensity of the light source, and is generally preferably within 30 minutes. The target of hardening is exemplified by a film residual ratio of 80% or less after solvent washing, and a residual agent residual ratio of 1% or more after preliminary hardening. In addition to the polymerization starting layer of the above-mentioned polymerizable compound and polymerization initiator, the polymerization initiation of the polymer in which the polymerization starting group described in JP-A No. 20-14-161995 is suspended on the side chain is used. Further, the layer is preferably a polymer having a functional group (polymerization initiator) and a crosslinkable group having a polymerization initiation ability in a side chain (hereinafter, suitably referred to as polymerization initiation polymerization) According to the polymer, a polymerization starting layer having a polymerization starting group bonded to a polymer chain and having a polymer chain immobilized by a crosslinking reaction can be formed. The polymerization starting layer is also suitable as the polymerization starting layer of the present application. The polymerization starting polymer used herein can be exemplified by the paragraph numbers [0011] to [〇158] of JP-A-2004-161995. The method described in paragraphs [〇〇62] to [0063] of JP-A-2009-7662. -17- 201132795 Film formation of a polymerization starting layer - Polymerization starting polymer used in the present invention Polymerization initiation layer The coating liquid is prepared by dissolving the above-mentioned polymerization starting polymer in a suitable solvent, and the coating liquid is placed on a substrate by coating or the like, and the solvent is removed to form a film by crosslinking reaction. The crosslinking reaction is carried out to immobilize the polymerization starting polymer. The immobilization by the crosslinking reaction can be exemplified by a method of using a self-condensation reaction of a polymerization starting polymer, and a crosslinking agent for crosslinking. Preferably, a crosslinking agent is used. A method of using a self-condensation reaction of a polymerization starting polymer is, for example, a case where the crosslinking group is -NCO, and the property of self-condensation by heating is employed. This self-condensation reaction can form a crosslinked structure. The cross-linking agent used in the method of using a cross-linking agent can be a conventional one as disclosed in Yamato Shinji, "Handbook of Crosslinking Agent". A preferred combination of the crosslinkable group and the crosslinking agent in the polymerization starting polymer is described in JP-A-2009-7662, Paragraph No. [0065], and specific examples of preferred crosslinking agents are exemplified by: The same as that stated in the paragraph number of the same bulletin [〇〇67]. Such a crosslinking agent is added to the coating liquid containing the above-mentioned polymerization starting polymer at the time of film formation of the polymerization starting layer. Thereafter, the crosslinking reaction is carried out by heating the coating film while heating the heat to form a strong crosslinked structure. The details of the reaction and the film formation of the polymerization starting layer are described in paragraphs [0068] to [〇〇71] of JP-A-2009-7662. From the viewpoint of the initial ability of the surface graft polymerization or the film property, the coating amount of the polymerization starting layer composed of the starting polymer using poly-18-201132795 is preferably 0.1 g based on the mass after drying. From /m2 to 20g/m2, further preferably from lg/m2 to 15 g/m2. In the present invention, as described above, in the case of using a substrate having a layer made of an insulating resin on a substrate, it is preferred that the layer composed of the insulating resin contains a conventional polymerization. The starting agent is used as an insulating polymerization starting layer. The polymerization initiator contained in the insulating polymerization starting layer is not particularly limited, and for example, the above-mentioned thermal polymerization initiator, photopolymerization initiator (radical polymerization initiator, anionic polymerization) can be used. a starting compound, a cationic polymerization initiator, or a polymer compound having a reactive carbonyl group in a side chain as described in JP-A-H09-77891, JP-A No. Hei. A functional group and a crosslinkable group polymer (polymerization starting polymer) of the starting ability. In general, the amount of the polymerization initiator contained in the insulating polymerization starting layer in the insulating layer is preferably from about 1 to about 50% by mass, more preferably from 1.0 to 30.0% by mass based on the solid content. %about. (Formation of Graft Polymer) The formation form of the graft polymer in the step (A), as described above, can be carried out by using a functional group and a polymer compound present on the surface of the substrate at the end or side chain thereof. A method of coupling reaction of a reactive functional group or a photograft polymerization method. In the present invention, the following form is preferred [(al-2) step]: using a substrate having a polymerization starting layer formed on a substrate, and having -19-201132795 on the polymerization starting layer The catalyst or its precursor forms an interactive functional group (interactive group)' and is formed of a polymer layer formed by a polymer that is directly chemically bonded to the polymerization starting layer. Further preferably, it is preferably in the form of: after contacting the polymer having a polymerizable group and an interactive group on the polymerization starting layer, the polymer is directly chemically bonded to the surface of the unit substrate by imparting energy ( The morphology of the surface of the overall polymerization starting layer). That is, while the composition containing the polymerizable group and the interactive group is brought into contact with the surface of the polymerization starting layer, the active layer on the surface of the polymerization starting layer is directly bonded. This contact can be carried out by immersing the substrate on which the polymerization starting layer is formed in a liquid composition (the polymer layer-forming composition of the present invention) having a polymerizable group and an interactive group. From the viewpoint of the property or the production efficiency, as described later, it is preferred to form a composition containing a compound having a polymerizable group and an interactive group on the surface of the substrate (the surface of the polymerization initiation layer) by a coating method (polymerization of the present invention) A layer composed of a composition for forming a layer of matter. In the present invention, a compound having a polymerizable group and an interactive group in the case where a graft polymer is produced by a surface graft polymerization method will be described. The compound having a polymerizable group and an interactive group in the present invention is such that the resin layer composed of the produced graft polymer contains the specific copolymer, and all of them satisfy the conditions of 1 to 2. In the present invention, a polymer having a polymerizable group and an interactive group -20 - 201132795 unit A copolymer represented by the following formula (1) and a copolymer represented by the following formula (2) can be used.

式（2) 上式（1)與式（2)中，R1至R5係表示各自獨立之 子、或取代或者未取代之直鏈、分枝或環狀之烷基， 與2係表示各自獨立之單鍵、或取代或者未取代之二 機基、酯基、醯胺基、或醚基，L1係表示取代或者未 之一價有機基’ L2係表示單鍵、或取代或者未取代之 有機基。 k1 S R5彳系取代或者未取代之直鏈、分枝或環狀之 之丨η形’較佳爲碳數丨至*之取代或者未取代之直鏈 枝或環狀之院基’未取代之直鏈、分枝或環狀之烷基 例.甲基、乙基、丙基 '正丁基、第二丁基、第三丁 氫原 < ' Υ 價有 取代 二價 烷基 、分 可舉 基， -21 - 201132795 另外，取代直鏈烷基可舉例：被甲氧基、羥基、氯原子、 氟原子等所取代的甲基、乙基、丙基、丁基。 還有’ R1較佳爲氫原子、甲基、或被羥基或溴原子所 取代的甲基。 R2較佳爲氫原子、甲基、或是被羥基或溴原子所取代 的甲基。 R3較佳爲氫原子。 R4較佳爲氫原子。 R5較佳爲氫原子、甲基、或是被羥基或溴原子所取代 的甲基。 X、Y與Z爲取代或者未取代之二價有機基之情形，該 二價有機基可舉例：取代或者未取代之脂肪族烴基、取代 或者未取代之芳香族烴基。 取代或者未取代之脂肪族烴基較佳爲碳數1至4者， 較佳爲亞甲基、伸乙基、伸丙基、伸丁基'或此等之基被 甲氧基、羥基、氯原子、溴原子、氟原子等所取代者。 取代或者未取代之芳香族烴基較佳爲未取代之苯基， 或是被甲氧基、羥基、氯原子、溴原子、氟原子等所取代 的苯基。 其中，較佳爲一（CH2)n-(n係1至3之整數），更佳爲 -CH2- 〇 L較佳爲具有胺甲酸酯鍵或脲鍵之二價有機基，更佳 爲具有胺甲酸酯鍵之二價有機基，其中，總碳數較佳爲ι -22- 201132795 至9。還有，於此所謂L1之總碳數係意指以Ll所代表之取 代或者未取代之二價有機基中所含之總碳原子數。In the above formula (1) and formula (2), R1 to R5 represent each independently, or a substituted or unsubstituted linear, branched or cyclic alkyl group, and the two systems are independent of each other. A single bond, or a substituted or unsubstituted dienyl group, an ester group, a decylamino group, or an ether group, and L1 means a substituted or unsubstituted organic group 'L2 means a single bond, or a substituted or unsubstituted organic group . K1 S R5 is a substituted or unsubstituted linear, branched or cyclic 丨n-shaped 'preferably substituted or unsubstituted straight or branched nominee' of the carbon number * to * a linear, branched or cyclic alkyl group. methyl, ethyl, propyl 'n-butyl, second butyl, tert-butyl hydrogen < ' Υ valence substituted divalent alkyl, sub Further, -21 - 201132795 Further, the substituted linear alkyl group may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group substituted with a methoxy group, a hydroxyl group, a chlorine atom or a fluorine atom. Further, 'R1 is preferably a hydrogen atom, a methyl group or a methyl group substituted by a hydroxyl group or a bromine atom. R2 is preferably a hydrogen atom, a methyl group or a methyl group substituted by a hydroxyl group or a bromine atom. R3 is preferably a hydrogen atom. R4 is preferably a hydrogen atom. R5 is preferably a hydrogen atom, a methyl group or a methyl group substituted by a hydroxyl group or a bromine atom. Where X, Y and Z are a substituted or unsubstituted divalent organic group, the divalent organic group may, for example, be a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group. The substituted or unsubstituted aliphatic hydrocarbon group is preferably a carbon number of 1 to 4, preferably a methylene group, an exoethyl group, a propyl group, a butyl group or a methoxy group, a hydroxyl group or a chlorine group. Atom, bromine, fluorine, etc. are replaced. The substituted or unsubstituted aromatic hydrocarbon group is preferably an unsubstituted phenyl group or a phenyl group substituted by a methoxy group, a hydroxyl group, a chlorine atom, a bromine atom, a fluorine atom or the like. Preferably, it is preferably (CH2)n- (n is an integer of 1 to 3), more preferably -CH2-〇L is preferably a divalent organic group having a urethane bond or a urea bond, more preferably A divalent organic group having a urethane bond, wherein the total carbon number is preferably from ι -22 to 201132795 to 9. Further, the total carbon number of L1 herein means the total number of carbon atoms contained in the divalent organic group substituted or unsubstituted by L1.

Ll之結構較佳爲下式（1-1)或式（1_2)所代表之結構。The structure of L1 is preferably a structure represented by the following formula (1-1) or formula (1_2).

上式（1-1)及式（1-2)中，1^及Rb係各自獨立地使用由 碳原子、氫原子、及氧原子所構成之族群中所選出的二個 以上原子所形成的二價有機基，可舉例：較佳爲取代或者 未取代之亞甲基、伸乙基、伸丙基或伸丁基、氧化伸乙基、 二氧化伸乙基、三氧化伸乙基、四氧化伸乙基、二氧化伸 丙基、三氧化伸丙基、及四氧化伸丙基。 另外，L2較佳爲單鍵、直鏈、分枝、或環狀之伸烷基、 芳香族基、或組合此等之基。組合該伸烷基與芳香族基之 基也可以進一步使醚基 '酯基、醯胺基、胺甲酸酯基、脲 基、胺基介於中間。較佳的形態之一可舉例：L2係總碳數 爲1至1 5，特佳爲未取代。還有’於此所謂L2之總碳數係 意指以L2所代表之取代或者未取代之二價有機基中所含之 總碳數。 具體而言，可舉例：亞甲基、伸乙基、伸丙基、伸丁 -23- 201132795 基、伸苯基、及此等之基被甲氧基、羥基、氯原子 '溴原 子、氟原子等所取代者，進一步組合此等之基。 另外’ L2爲單鍵之情形也較佳，於本形態中，也具有 相對於共聚物之分子量之氰基的含有率將提高之優點。 於本發明中之含有氰基的聚合性聚合物，較佳爲係以 該式（1)所代表之單位是以該式（3 )所代表之單位。In the above formula (1-1) and formula (1-2), 1 and R are each independently formed using two or more selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom. The divalent organic group may, for example, be a substituted or unsubstituted methylene group, an ethyl group, a propyl group or a butyl group, an oxidized ethyl group, a diethyl epoxide group, a triethyl sulphate group or a tetra group. Oxidized ethyl, diexex extended propyl, trioxylated propyl, and tetraisolated propyl. Further, L2 is preferably a single bond, a linear chain, a branched chain, or a cyclic alkyl group, an aromatic group, or a combination thereof. The combination of the alkyl group and the aromatic group may further have an ether group 'ester group, a mercapto group, a carbamate group, a urea group, and an amine group interposed therebetween. One of the preferred forms is exemplified by an L2 system having a total carbon number of from 1 to 15 and particularly preferably unsubstituted. Further, the total carbon number referred to herein as L2 means the total carbon number contained in the divalent organic group substituted or unsubstituted by L2. Specifically, a methylene group, an ethyl group, a propyl group, a butyl group, a phenyl group, a phenyl group, a phenyl group, a hydroxy group, a chlorine atom, a bromine atom, and a fluorine atom are exemplified. Those substituted by atoms, etc., further combine these bases. Further, it is also preferable that L2 is a single bond, and in the present aspect, it also has an advantage that the content of the cyano group relative to the molecular weight of the copolymer is improved. The cyano group-containing polymerizable polymer in the present invention is preferably a unit represented by the formula (1) in the unit represented by the formula (3).

L1L1

Wy〇 入2 式（3〉 上式（3)中，R1及R2係表示各自獨立之氫原子、或取 代或者未取代之直鏈、分枝或環狀之烷基，較佳爲未取代 之直鏈或分枝的烷基，總碳數較佳爲1至5»Z係表示單鍵、 或取代或者未取代之二價有機基、酯基、醯胺基、或醚基， W係表示氧原子或NR(R係表示氫原子、或烷基，較佳爲 -24- 201132795 氫原子或碳數1至5的未取代之烷基。），ι/係表示取代或 者未取代之二價有機基。 式（3)中之R1及R2係與該式（1)中之R1及R2爲同義， 較佳例也爲相同。 式（3)中之Ζ係與該式（1)中之ζ爲同義，較佳例也爲 相同。 另外’式（3)中之L1也與該式（1)中之L1爲同義，較佳 例也爲相同。 本發明中之含有氰基的聚合性聚合物，較佳爲以該式 (3 )所代表之單位爲以下式（4)所代表之單位。Wy is in the formula (3). In the above formula (3), R1 and R2 represent independently hydrogen atoms, or substituted or unsubstituted linear, branched or cyclic alkyl groups, preferably unsubstituted. a linear or branched alkyl group having a total carbon number of preferably 1 to 5»Z represents a single bond, or a substituted or unsubstituted divalent organic group, an ester group, a decylamino group, or an ether group, and the W system represents An oxygen atom or NR (R represents a hydrogen atom or an alkyl group, preferably a -24-201132795 hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms), and ι/line represents a substituted or unsubstituted divalent group. The R1 and R2 in the formula (3) are synonymous with R1 and R2 in the formula (1), and the preferred examples are also the same. The oxime in the formula (3) and the formula (1) ζ is synonymous, and preferred examples are also the same. Further, L1 in the formula (3) is also synonymous with L1 in the formula (1), and preferred examples are also the same. The cyano group-containing polymerizable property in the present invention The polymer preferably has a unit represented by the formula (3) as a unit represented by the following formula (4).

R2八 式（4) 式（4)中，R1及R2係表示各自獨立之氫原子、或取代 或者未取代之直鏈、分枝或環狀之烷基，V及W係袠禾& -25- 201132795 自獨立之氧原子、或NR(R係表示氫原子、或直鏈、分枝 或環狀之烷基’較佳爲氫原子或碳數丨至5之未取代之直 鏈烷基）’ L1係表示取代或者未取代之二價有機基。 式（4)中之R1及R2係與該式（1)中之Ri及R2爲同義， 較佳例也爲相同。 式（4)中之V及W較佳爲氧原子、或NR(R較佳爲表示 氫原子）。 式（4)中之L1係與該式（1)中之L1爲同義，較佳例也爲 相同。 於該式（3)及式（4)中’ W較佳爲氧原子、或NR(R較佳 爲表示氫原子）。 另外’於該式（3)及式（4)中’ L1較佳爲未取代之伸烷 基、或具有胺甲酸酯鍵或脲鍵之二價有機基，更佳爲具有 胺甲酸酯鍵之二價有機基，此等之中特佳爲總碳數1至9 者。 另外’本發明中之含有氰基的聚合性聚合物，較佳爲 以該式（2)所代表之單位爲以下式（5)所代表之單位。R2 VIII (4) In the formula (4), R1 and R2 represent a hydrogen atom independently of each other, or a substituted or unsubstituted linear, branched or cyclic alkyl group, and V and W are both && 25- 201132795 From an independent oxygen atom, or NR (R represents a hydrogen atom, or a linear, branched or cyclic alkyl group) is preferably a hydrogen atom or an unsubstituted linear alkyl group having a carbon number of 丨5 ) 'L1 represents a substituted or unsubstituted divalent organic group. R1 and R2 in the formula (4) are synonymous with Ri and R2 in the formula (1), and preferred examples are also the same. V and W in the formula (4) are preferably an oxygen atom or NR (R preferably represents a hydrogen atom). The L1 in the formula (4) is synonymous with L1 in the formula (1), and the preferred examples are also the same. In the formulae (3) and (4), 'W is preferably an oxygen atom or NR (R preferably represents a hydrogen atom). Further, 'in the formula (3) and the formula (4), 'L1 is preferably an unsubstituted alkylene group, or a divalent organic group having a urethane bond or a urea bond, more preferably having a carbamate. The divalent organic group of the bond, especially among those having a total carbon number of 1 to 9. Further, the polymerizable polymer containing a cyano group in the present invention is preferably a unit represented by the following formula (5) represented by the formula (2).

Q U -26- 201132795 該式（5)中，R5係表示氫原子、或取代或者未取代之烷 基，U係氧原子、或NR，（R，係表示氫原子、或直鏈分枝 或環狀之烷基。）’ L2係表示單鍵或取代或者未取代之二價 有機基。 式（5)中之R5係與該式（〗）中之尺1及R2爲同義，較佳 爲氫原子。 另外’式（5)中之u較佳爲NR，，該R’較佳爲氫原子、 或碳數1至5之直鏈 '分枝或環狀之烷基，更佳爲分枝之 院基’最好爲第三丁基。 另外’式（5)中之L2係與該式（1)中之l2爲同義，較佳 爲單鍵或是直鏈、分枝或環狀之伸院基、芳香族基或組合 此等之基。 尤其，式（5)中’與L2中之與氰基的連結部位較佳爲單 鍵或是具有直鏈、分枝或環狀之伸院基的二價有機基，於 前者中，共聚物之每單位重量的氰基含有率將提高；後者 之情形，從親疏水性平衡之觀點，此二價有機基之總碳數 較佳爲1至10。再者，從分子運動性之觀點，更佳爲直鏈 且總碳數爲2至6。 另外，其他較佳的形態係與在式（5 )的L2中之氰基的連 結部位較佳爲具有芳香族基之二價有機基，其中，該二價 有機基之總碳數較佳爲6至1 5。 本發明中之含有氰基的特定共聚物係含有以該式（1) 至式（5)所代表之單位所構成者’在側鏈上具有聚合性基與 -27- 201132795 氰基之聚合物。 本發明中之含有氰基的聚合性聚合物係依照1 )形成聚 合物主鏈之聚合形態與在側鏈上所導入的聚合性基之聚合 形態爲不同之情形，與2)形成聚合物主鏈之聚合形態與在 側鏈上所導入的聚合性基之聚合形態爲相同之情形，其合 成方法不同。關於此合成方法之詳細內容，已詳細記載於 曰本特開2009-7662號公報之段落編號〔0120〕至〔0164〕， 能夠將記載於此的方法應用於本發明。 依照該公報之記載所合成的本發明中之含有氰基的聚 合性聚合物，相對於整體共聚物而言，較佳係含有聚合性 基之單位、含有氰基之單位的比例爲以下之範圍。 亦即，相對於整體共聚合成分而言，含有聚合性基之 單位較佳爲含有5至5 0 m ο 1 %，更佳爲5至4 0 m ο 1 %。5 m ο 1 % 以下之情形，反應性（硬化性、聚合性）將降低；5 0 m ο 1 %以 上之情形，於合成之際容易凝膠化而難以合成。 另外，從對鍍敷觸媒的吸附性之觀點，相對於整體共 聚合成分而言，含有氰基之單位較佳爲含有5至95mol %， 更佳爲1 〇至9 5 m ο 1 %。 還有’本發明中之含有氰基的聚合性聚合物除了含有 氰基之單位、含有聚合性基之單位以外，也可以含有其他 之單位。用以形成其他單位所用之單體，只要爲不損害本 發明之效果，也能夠使用任何的單體。 用以形成其他的單位所用之單體，具體而言，可舉例 -28- 201132795 能形成下列之主鏈骨架的單體：丙烯酸樹脂骨架、苯乙稀 樹脂骨架、苯酚樹脂（苯酚-甲醛樹脂）骨架、三聚氰胺樹脂 (三聚氰胺與甲醛之聚縮合物）骨架、尿素樹脂（尿素與甲醛 之聚縮合物）骨架、聚酯樹脂骨架、聚胺甲酸酯骨架、聚酿 亞胺骨架、聚烯烴骨架、聚環烯烴骨架、聚苯乙烯骨架、 聚丙烯酸骨架、ABS樹脂（丙烯腈、丁二烯、苯乙烯之聚合 物）骨架、聚醯胺骨架、聚縮醛骨架、聚碳酸酯骨架、聚苯 醚骨架、聚苯硫醚骨架、聚颯骨架、聚醚颯骨架、聚芳香 酯骨架、聚醚醚酮骨架、聚醯胺醯亞胺骨架等。 另外，此等之主鏈骨架也可以爲含有氰基之單位或含 有聚合性基之單位的主鏈骨架。 但是，如上所述，使聚合性基與聚合物反應而導入之 情形，由於1 00%導入爲困難之際，少量之反應性部分將殘 留，此情形也有成爲第3單位之可能性。 針對可成爲第3單位之單體，能夠使用於日本特開 2009-7662號公報段落編號〔0166〕至〔0167〕所記載的單 體。 本發明中之含有氰基的特定共聚物之重量平均分子量 較佳爲1000以上且70萬以下，更佳爲2000以上且20萬 以下。尤其，從聚合感度之觀點，本發明中之含有氰基的 聚合性共聚物的重量平均分子量較佳爲20000以上。 另外，本發明中之含有氰基的特定共聚物的聚合度較 佳爲10量體以上者，更佳爲20量體以上者。另外，較佳 -29- 201132795 爲7 000量體以下，更佳爲3〇〇〇量體以下，進—步較佳爲 2000量體以下’特佳爲1000量體以下。 本發明中可用之特定共聚物的具體例可舉例：曰本特 開2 009-7662號公報段落編號〔0170〕至〔〇丨78〕所目己載 断限定 ° 遺 者，及具有以下所示之結構者’但並不受此 方 炸爲3〇〇0至 有，上述具體例之重量平均分子量任一種白 1 00000之範圍。 -30- 201132795QU -26- 201132795 In the formula (5), R5 represents a hydrogen atom, or a substituted or unsubstituted alkyl group, a U-based oxygen atom, or NR, (R represents a hydrogen atom, or a linear branch or a ring Alkyl.) 'L2 represents a single bond or a substituted or unsubstituted divalent organic group. The R5 in the formula (5) is synonymous with the ruthenium 1 and R2 in the formula (I), and is preferably a hydrogen atom. Further, u in the formula (5) is preferably NR, and the R' is preferably a hydrogen atom, or a linear 'branched or cyclic alkyl group having 1 to 5 carbon atoms, more preferably a branching branch. The base 'is preferably a third butyl group. Further, the L2 in the formula (5) is synonymous with the l2 in the formula (1), and is preferably a single bond or a linear, branched or cyclic stretching group, an aromatic group or a combination thereof. base. In particular, in the formula (5), the linking site with the cyano group in L2 is preferably a single bond or a divalent organic group having a linear, branched or cyclic stretching group. In the former, the copolymer The cyano group content per unit weight will increase; in the latter case, the total carbon number of the divalent organic group is preferably from 1 to 10 from the viewpoint of the balance of hydrophilicity and hydrophobicity. Further, from the viewpoint of molecular mobility, it is more preferably linear and has a total carbon number of 2 to 6. Further, the other preferred embodiment is preferably a divalent organic group having an aromatic group at a linking portion with a cyano group in L2 of the formula (5), wherein the total carbon number of the divalent organic group is preferably 6 to 1 5. The specific copolymer containing a cyano group in the present invention contains a polymer having a polymerizable group in the side chain and a cyano group of -27-201132795 in a unit represented by the formula (1) to the formula (5). . The polymerizable polymer containing a cyano group in the present invention is different from the case where the polymerization form of the polymer main chain formed by 1) is different from the polymerization form of the polymerizable group introduced in the side chain, and 2) the polymer main is formed. The polymerization form of the chain is the same as the polymerization form of the polymerizable group introduced in the side chain, and the synthesis method is different. The details of this synthesis method are described in detail in paragraphs [0120] to [0164] of JP-A-2009-7662, and the method described herein can be applied to the present invention. The cyano group-containing polymerizable polymer of the present invention synthesized in accordance with the description of the above-mentioned publication preferably has a ratio of a unit containing a polymerizable group to a unit containing a cyano group as a whole in the range of the following copolymer. . That is, the unit containing a polymerizable group preferably contains 5 to 50 m ο 1 %, more preferably 5 to 40 m ο 1 %, with respect to the entire copolymerization component. In the case of 5 m ο 1 % or less, the reactivity (hardenability, polymerizability) is lowered; in the case of 50 m ο 1 % or more, it is easy to gel at the time of synthesis and it is difficult to synthesize. Further, from the viewpoint of the adsorptivity to the plating catalyst, the unit containing a cyano group preferably contains 5 to 95 mol%, more preferably 1 to 9 5 m ο 1 %, based on the total copolymerization component. Further, the polymerizable polymer containing a cyano group in the present invention may contain other units in addition to the unit containing a cyano group or a unit containing a polymerizable group. Any monomer used to form other units can be used as long as it does not impair the effects of the present invention. For the monomers used for forming other units, specifically, -28-201132795 can form monomers of the following main chain skeleton: acrylic resin skeleton, styrene resin skeleton, phenol resin (phenol-formaldehyde resin) Skeleton, melamine resin (polycondensate of melamine and formaldehyde) skeleton, urea resin (polycondensate of urea and formaldehyde) skeleton, polyester resin skeleton, polyurethane skeleton, polyaniline skeleton, polyolefin skeleton, Polycycloolefin skeleton, polystyrene skeleton, polyacrylic acid skeleton, ABS resin (polymer of acrylonitrile, butadiene, styrene) skeleton, polyamine skeleton, polyacetal skeleton, polycarbonate skeleton, polyphenylene ether Skeleton, polyphenylene sulfide skeleton, polyfluorene skeleton, polyether fluorene skeleton, polyarylate skeleton, polyetheretherketone skeleton, polyamidoximine skeleton, and the like. Further, the main chain skeleton of these may be a main chain skeleton containing a unit of a cyano group or a unit containing a polymerizable group. However, as described above, when the polymerizable group is introduced into the polymer and introduced into the polymer, it is difficult to introduce 100%, and a small amount of the reactive portion remains, and in this case, the third unit may be used. For the monomer which can be the third unit, the monomer described in paragraphs [0166] to [0167] of JP-A-2009-7662 can be used. The weight average molecular weight of the specific copolymer containing a cyano group in the present invention is preferably 1,000 or more and 700,000 or less, more preferably 2,000 or more and 200,000 or less. In particular, the weight average molecular weight of the cyano group-containing polymerizable copolymer in the present invention is preferably 20,000 or more from the viewpoint of polymerization sensitivity. Further, the degree of polymerization of the specific copolymer containing a cyano group in the present invention is preferably 10 or more, more preferably 20 or more. Further, it is preferably -29-201132795 which is 7 000 or less, more preferably 3 〇〇〇 or less, and the step is preferably 2000 or less, and particularly preferably 1000 or less. Specific examples of the specific copolymer which can be used in the present invention can be exemplified by the following paragraphs: [0170] to [〇丨78] of the Japanese Patent Publication No. 2 009-7662. The structure of the structure is not limited to 3 to 0, and the weight average molecular weight of the above specific examples is in the range of 1,000,000. -30- 201132795

本發明中之特定共聚物係除了聚合性基與相互作用性 基之外，若所形成的聚合物層爲符合該1至2之全部條件 的範圍，也可以具有極性基。 藉由具有極性基，依照後述之步驟而形成金屬膜之 後，例如，設置保護層之情形下，能夠在聚合物層與保護 層之接觸區域而使緊貼力提高。 -31 - 201132795 如上所述，爲了形成本發明中之樹脂層，較佳爲使用 具有聚合性基與相互作用性基之聚合物等之含有具有聚合 性基及相互作用性基之化合物的液狀組成物，亦即含有具 有聚合性基與相互作用性基之化合物、與可溶解該化合物 之溶劑的組成物（較佳爲含有如下組成的本發明之聚合物 層形成用組成物：具有氰基或以一0-(CH2)n — 〇- (n係1至 5之整數）所代表之構造及具有聚合性基之聚合物、與可溶 解該聚合物之溶劑）。 還有’相對於整體聚合物而言，具有聚合性基與相互 作用性基之化合物（例如，含有氰基的聚合性共聚物）之組 成物中的含量較佳爲2質量％至5 0質量％。 使用於該組成物之溶劑只要爲組成物之主成分且能夠 溶解具有聚合性基及相互作用性基之化合物的話，並無特 別之限制。也可以進一步將界面活性劑添加於溶劑中。 能夠使用之溶劑，例如，可舉例：如甲醇、乙醇、丙 醇、乙二醇、甘油、丙二醇單甲基醚之醇系溶劑；如醋酸 之酸；如丙酮、甲基乙基酮、環己酮之酮系溶劑；如甲酿 胺、二甲基乙醯胺、Ν-甲基吡咯啶酮之醯胺系溶劑；如乙 腈、丙腈之腈系溶劑；如醋酸甲酯、醋酸乙酯之酯系溶劑； 如二甲基碳酸酯、二乙基碳酸酯之碳酸酯系溶劑等。 於此等溶劑之中’作成使用含有氰基之聚合性聚合物 的組成物之情形下，較佳爲醯胺系、酮系、腈系溶劑、碳 酸酯系溶劑’具體而言，較佳爲丙酮、二甲基乙醯胺、甲 -32- 201132795 基乙基酮、環己酮、乙腈、丙腈、N-甲基吡咯啶酮、二甲 基碳酸酯。 另外，塗布含有具有氰基之聚合性聚合物的組成物之 情形，從容易處理之觀點，較佳爲50至150°C之溶劑。還 有，此等之溶劑可以使用單一種，也可以混合而使用。 另外，於本發明中，將含有具有聚合性基與相互作用 性基之化合物的組成物塗布於基板或聚合起始層上之情 形，能夠選擇基板或聚合起始層之吸溶劑率成爲5至25% 之溶劑。此吸溶劑率能夠將基板或形成聚合起始層之基材 浸漬於溶劑中，從在1 000分鐘後提起時的質量變化而求 出。 另外，將含有具有聚合性基與相互作用性基之化合物 的組成物塗布於基板或聚合起始層上之情形，也可以選擇 基板或聚合起始層之膨潤率成爲1 0至4 5 %之溶劑。此膨潤 率能夠將基板或形成聚合起始層之基材浸漬於溶劑中，從 在1〇〇〇分鐘後提起時的厚度變化而求出。 必要時，能夠添加於溶劑中之界面活性劑只要爲溶解 於溶劑中者即可。另外，必要時也能夠添加可塑劑。能夠 使用的可塑劑可舉例一般之可塑劑。 ‘ 於含有特定共聚物之組成物中，必要時，爲了進行聚 合抑制劑、聚合起始層之硬化，也可以適當添加硬化劑及/ 或硬化促進劑等。 另外，也可以進一步添加橡膠成分（例如，CTBN)、難 -33- 201132795 燃化劑（例如，磷系難燃化劑）、稀釋劑或觸變減黏化劑、 顏料、消泡劑、平坦劑、偶合劑等。另外’此等之添加劑 必要時也可以添加於聚合起始層中。 藉由使用適當混合特定共聚物與各種添加劑之組成物 而能夠最適切地設定所形成的樹脂層之物性，例如熱膨脹 係數、玻璃轉移溫度、楊氏模數、帕松（Poisson)比、斷裂 應力、屈服應力、熱分解溫度等。尤其，針對斷裂應力、 屈服應力、熱分解溫度越高者越佳。 所獲得之樹脂層能夠藉由溫度循環試驗或隨時間經過 之熱試驗、回流試驗等而能夠測定熱耐久性，例如關於熱 分解，若於200°C環境曝露1小時的情形之質量減少爲20% 以下時，能夠評估具有充分之熱耐久性。 接觸含有特定共聚物之組成物之情形下，從與鍍敷觸 媒或其先質的充分相互作用形成性之觀點，以固形物換 算，其塗布量較佳爲0.1至10 g/m2,特佳爲0.5至5 g/m2 ° 還有，將含有具有聚合性基與相互作用性基之化合物 的組成物塗布於基板上，使其乾燥而形成具有聚合性基與 相互作用性基之化合物層之情形，也可以於塗布與乾燥之 間，在2 0至4 0 °C使其放置0.5至2小時而去除所殘存的溶 劑。 (能量之賦予） 對基板表面之能量賦予方法，例如能夠使用加熱或曝 光等之輻射線照射。例如，使用UV燈、可見光等所進行 -34- 201132795 的光照射' 使用熱板等之加熱等爲可能。例如，光源可舉 例：水銀燈、金屬鹵化物燈、氙燈、化學燈、碳弧燈等。 放射線可舉例：電子線、X線、離子束、遠紅外線等。另 外’也使用g線、i線、Deep-UV光、高密度能量束（雷射 束）。 一般所用之具體形態可適當舉例：使用熱記錄頭等所 進行的直接影像圖案記錄、使用紅外線所進行的掃瞄曝 光、氙放電燈等之高照度快閃曝光或紅外線燈曝光等。 能量賦予所需要的時間係因依照作爲目的之接枝聚合 物的生成量及光源而異，通常爲10秒鐘至5小時之間。 還有’利用曝光而進行能量賦予之情形，其曝光功率 係用以使接枝聚合容易進行，另外，爲了抑制所生成的接 枝聚合物之分解，較佳爲10 mJ/cm2至5000 mJ/cm2之範 圍，更佳爲50 mJ/cm2至3 000 mJ/cm2之範圍。 另外，具有聚合性基與相互作用性基之化合物，若使 用平均分子量2萬以上、聚合度2 00量體以上之聚合物時， 由於利用低能量之曝光容易進行接枝聚合，能夠進一步抑 制所生成的接枝聚合物之分解。 依照以上所說明之步驟（A)，在基板上形成有由具有接 受鍍敷觸媒等之相互作用性基的接枝聚合物而成之樹脂層 (接枝聚合物層）。 所獲得之樹脂層添加於例如pH 1 2之鹼性溶液中，1 小時攪拌後之聚合性基部位的分解爲5 0%以下之情形，能 -35- 201132795 夠對該樹脂層進行使用強鹼性溶液的洗淨。 〔步驟（B)〕 在步驟（B)，將鍍敷觸媒或其先質賦予於該步驟（A)所 形成的樹脂層中。於本步驟中，構成樹脂層之接枝聚合物 所具有的相互作用性基（氰基）係按照其機能而附著（吸附） 所賦予的鍍敷觸媒或其先質。 於此，鍍敷觸媒或其先質可舉例：所後述的（D)無電鍍 敷步驟中之發揮作爲鍍敷觸媒或電極之機能者。因此，鍍 敷觸媒或其先質係依照（D)鍍敷步驟中之鍍敷種類所決定。 還有於此，在本步驟中所用之鑛敷觸媒或其先質係無 電鍍敷觸媒或其先質。 (無電鍍敷觸媒） 本發明中所用之無電鍍敷觸媒只要係成爲無電鏟敷時 之活性核者的話，能夠使用任何之無電鍍敷觸媒，具體而 言，無電鍍敷觸媒可舉例：具有自我觸媒還原反應觸媒能 力之金屬等，具體而言，可舉例：Pd、Ag、Cu、Ni、A1、 Fe、Co等。其中，較佳爲能夠多處配位者，尤其，從能夠 配位之官能基的種類數目、觸媒能力高低之觀點，特佳爲 Pd ° 此無電鍍敷觸媒亦可做爲金屬膠體使用，一般而言， 金屬膠體可以在具有電荷之界面活性劑或是具有電荷之保 護劑所存在的溶液中，藉由還原金屬離子而製作。金屬膠 體之電荷能夠藉由此處所使用的界面活性劑或保護劑而調 -36- 201132795 節。 (無電鍍敷觸媒先質） 本步驟所用之無電鑛敷觸媒先質係指若爲藉由化學反 應而能夠成爲無電鍍敷觸媒者的話，能夠無特別限制地使 用。主要可使用作爲該無電鍍敷觸媒所舉出的金屬之金屬 離子。無電鍍敷觸媒先質之金屬離子係藉由還原反應而成 爲無電鍍敷觸媒之〇價金屬。無電鍍敷觸媒先質之金屬離 子可以於對聚合物層之賦予後，於對無電鍍敷浴之浸漬 前，藉由其他途徑之還原反應而使其變化成〇價金屬來形 成無電鍍敷觸媒；也可以維持無電鍍敷觸媒先質之狀態下 浸漬於無電鑛敷浴中，藉由無電鍍敷浴中之還原劑而使其 變化成金屬（無電鍍敷觸媒）。 實際上，無電鍍敷先質之金屬離子係使用金屬鹽而賦 予在聚合物層上。所使用的金屬鹽只要爲溶解於適當的溶 劑中而予以解離成金屬離子與鹼（陰離子）的話，並無特別 之限制，可舉例：M(N03)n、MCln、M2/n(S04)、Μ3/η(Ρ04)(Μ 係表示n價之金屬原子）等。金屬原子能夠適合使用上述之 金屬鹽解離而成者。例如，具體例可舉例：Ag離子、Cu 離子、A1離子' Ni離子、Co離子、Fe離子、Pd離子，其 中，較佳爲能夠多處配位者，基於能夠配位的官能基之種 類數目及觸媒能力之觀點，特佳爲Pd離子。 將無電鍍敷觸媒之金屬、或無電鍍敷觸媒之金屬鹽賦 予至聚合物層之方法’最好是調製將金屬分散於適當之分 -37- 201132795 散劑的分散液中、或是使用適當之溶劑溶解金屬鹽而含有 解離的金屬離子之溶液，將該分散液或溶液塗布於聚合物 層上或是將形成有聚合物層之基板浸漬於該分散液或溶液 中 〇 另外，於步驟（A)中，利用表面接枝聚合法之情形，使 含有具有聚合性基及相互作用性基（氰基）之化合物的組成 物接觸於基板上，也可以利用將無電鍍敷觸媒或其先質添 加於此組成物中之方法。使含有具有聚合性基及相互作用 性基（氰基）之化合物、與無電鍍敷觸媒或其先質之組成物 接觸於基板上，藉由採用表面接枝聚合法而能夠形成含有 具有相互作用性基（氰基）且與基板進行直接化學鍵結之聚 合物、與鍍敷觸媒或其先質之樹脂層。還有，若使用此方 法的話，本發明中之步驟（A)與步驟（B)成爲以一個步驟而 可以進行，此情形下，步驟（C)係於步驟（B)之後進行。 還有，在基材之兩面形成樹脂層之情形下，爲了使無 電鍍敷觸媒或其先質同時對其兩面之樹脂層進行接觸，較 佳爲使用上述之浸漬法》 如上所述，藉由使無電鍍敷觸媒或其先質接觸，樹脂 層中之相互作用性基（氰基）上，利用依照如凡得瓦力之分 子間力所導致的相互作用，或是利用依照因孤立電子對所 形成的配位鍵所導致的相互作用，能夠使無電鏟敷觸媒或 其先質吸附。 從使如此之吸附充分進行之觀點，分散液、溶液、組 -38- 201132795 成物中之金屬濃度或溶液中之金屬離子濃度較佳爲0.001 至50質量％之範圍，更佳爲0.005至30質量％之範圍。另 外，接觸時間較佳爲3 0秒鐘至2 4小時左右，更佳爲1分 鐘至1小時左右。 藉由經過以上所說明之步驟（B )，能夠於聚合物層中之 相互作用性基（氰基）與鑛敷觸媒或其先質之間形成相互作 用。 〔步驟（C)〕 於本發明中，具有於該步驟（B)之前或之後，將含有由 醚系溶劑、醇系溶劑、酯系溶劑及酮系溶劑所構成之族群 中所選出的至少一種有機溶劑之前處理液的步驟（C)。 前處理液中所含之有機溶劑係由醚系溶劑、醇系溶 劑、酯系溶劑及酮系溶劑所構成之族群中所選出的水溶性 有機溶劑之至少一種。於此，水溶性有機溶劑係指1質量 %以上溶解於水中之溶劑。 醚系溶劑可舉例：雙（2-乙氧基乙基）醚、雙〔2-(2-羥 基乙氧基）乙基〕醚、1，2-雙（2-甲氧基乙氧基）乙烷、雙〔2-(2-甲氧基乙氧基）乙基〕醚、雙（2-甲氧基乙基）醚、2-(2-丁氧 基乙氧基）乙醇、2-〔 2-(2-氯乙氧基）乙氧基〕乙醇、2-乙 氧基乙醇、2-(2 -乙氧基乙氧基）乙醇、2-異丁氧基乙醇、2·(2-異丁氧基乙氧基）乙醇、2_異丙氧基乙醇、2-〔2-(2-.甲氧基 乙氧基）乙氧基〕乙醇、2_ (2-甲氧基乙氧基）乙醇、卜乙氧 基-2-丙醇、1-甲氧基-2-丙醇、三丙二醇單甲基醚、甲氧基 -39- 201132795 醋酸、2_甲氧基乙醇等。 醇系溶劑可舉例：乙醇、異丙醇、正丙醇、3 -乙醯基 -1-丙醇' 2-(稀丙氧基）乙醇、2_胺基乙醇、2_胺基-2_甲基 _1_丙醇、（±)·2-胺基-1-丙醇、3-胺基-1-丙醇、2-二甲胺基 乙醇、2，3-環氧-丨_丙醇、乙二醇、2_氟乙醇、二丙酮醇' 2-甲基環己醇、4_羥基_4_甲基-2_戊酮、甘油、2,2，，2，，_氰基 三乙醇、2-吡啶甲醇、2,2,3,3_四氟-!•丙醇、2_(2·胺基乙 氧基）乙醇、2-〔 2-(苄氧基）乙氧基〕乙醇、2,3-丁二醇、2_ 丁氧基乙醇、2,2，-硫二乙醇、1，3-丁二醇、1，4-丁二醇、2，3-丁二醇' 2-甲基-2,4_戊二醇、13-丙二醇、二甘油、2,2，_ 甲亞胺基二乙醇、1，2 -戊二醇等。 酯系溶劑可舉例：醋酸乙酯、醋酸-2-(2-乙氧基乙氧基） 乙酯、乙二醇單甲基醚醋酸酯、二乙二醇單乙基醚醋酸酯、 甲基溶纖素醋酸酯、丙烯酸-2-羥乙酯、丙烯酸羥丙酯、乙 醇酸甲酯、乙醇酸乙酯等。 酮系溶劑可舉例：丙酮、4-羥基-4-甲基-2-戊酮、γ-丁 內酯、羥基丙酮等。 從因觸媒金屬所造成的氧化之擔憂爲少的觀點，於上 述之水溶性有機溶劑之中，其較佳的實施形態之一較佳爲 不含有醇之有機溶劑；從溶液保存性之觀點’較佳爲酮系 溶劑、酯系溶劑、醚系溶劑。更具體而言’較佳爲丙酮、 二甲基碳酸酯、乙二醇二甲基醚、醋酸-2_ (2_乙氧基乙氧基） 乙酯、1-乙醯氧基_2·甲氧基乙烷、雙（2·乙氧基乙基）醚（別 -40- 201132795 稱：二乙二醇二乙基醚）、1,2-雙（2-甲氧基乙氧基）乙烷、 雙〔2-(2-甲氧基乙氧基）乙基〕醚、雙（2-甲氧基乙基）醚（別 稱：二乙二醇二甲基醚）等。其中，另外從對本發明使用之 聚合物的親和性或溶解性之觀點，更佳爲醚系溶纖素，適 合爲雙（2-甲氧基乙基）醚等。 前處理液中所含之有機溶劑可以僅爲一種或倂用二種 以上，含量係前處理液中所含之有機溶劑的總量較佳爲1 質量％以上且50質量％以下，更佳爲5質量％以上且45質 量％以下。另外，於不損害本發明效果之範圍內，也可以 供給該有機溶劑以外之有機溶劑。 於前處理液中，更佳爲含有金屬鹽。 所使用的金屬鹽只要爲溶解於適切之溶劑中而被解離 成金屬離子與鹼（陰離子）者的話，並無特別之限制，可舉 例：M(N03)n、MCln、M2/n(S04)、M3/n(P04)、M(OAc)n(M 係表示n價之金屬原子，Ac係表示乙醯基）等。金屬離子 能夠適合使用上述之金屬鹽解者。例如，具體例可舉例： Ag離子、Cu離子、A1離子、Ni離子、Co離子、Fe離子、 Pd離子，其中，較佳爲能夠多處配位者，尤其，基於能夠 配位之官能基的種類數目、及觸媒能力之觀點，較佳爲Pd 離子、銅離子，更佳爲銅離子。另外，關於陰離子，基於 對水或酸性水溶液的溶解性之觀點，較佳爲ΝΟΓ、（〇 Ac) _、 及C「’更佳爲NO,及（OAc)—。在步驟（C)使用金屬鹽 之情形，其金屬鹽較佳爲與在步驟（B)所賦予的觸媒或其 -41- 201132795 先質不同。 相對於前處理液之金屬鹽的含量較佳爲ο·〗質量％以 上且10質量％以下，更佳爲0.5質量％以上且5質量％以下。 於前處理液中，除了該有機溶劑、較佳的倂用成分之 金屬鹽、主要溶劑之水以外，於不損害本發明效果之範圍 內，能夠按照目的而含有其他之添加劑。 其他添加劑可舉例以下所示者。 例如，可舉例：酸（鹽酸、硝酸等之無機酸；醋酸、檸 檬酸等之有機酸）、膨潤劑（酮、醛、醚、酯類等之有機化 合物等）、或界面活性劑（陰離子性、陽離子性、雙性、非 離子性及低分子性或高分子性等）等。 針對將前處理液賦予樹脂層中，最好使樹脂層形成面 與該前處理液接觸，從操作簡易性之觀點，較佳爲採取將 具備樹脂層之基板浸漬於前處理液中的方法。 從效果之觀點，與前處理液之接觸時間較佳爲3 0秒鐘 至2 4小時左右，更佳爲1分鐘至1小時左右。接觸時之前 處理液溫度可以爲常溫（25 °C )，另外，從確保滲透性之觀 點，更佳爲3 0 °C至5 0 °C之範圍。 與前處理液之接觸，亦即步驟（C)可以在該步驟（B)之 前，亦即於具有在步驟（A)所形成的相互作用性基之樹脂層 中，首先賦予前處理液，其後，實施步驟（B)而賦予鍍敷觸 媒等，另外，也可以在步驟（B)，首先將鍍敷觸媒賦予樹脂 層中之後，接著，實施步驟（C)而賦予前處理液。藉由與前 -42- 201132795 處理液之接觸，於接著所進行的無電鍍敷觸媒步驟（D)中， 無電鍍敷液與樹脂層之親和性將提高，鍍敷處理將均勻且 效率佳地進行。 從對樹脂層之親和性提高效果之觀點，步驟（C)較佳爲 在步驟（B)之後所進行。 藉由於鑛敷處理之前，實施具有該步驟（A)、步驟（B)、 及步驟（C)的本發明之鍍敷前處理方法，使得有效地形成具 有優異的緊貼性、無不均之均勻金屬膜的鍍敷膜之形成將 成爲可能。 <表面金屬膜材料之製作方法> 實施該本發明之鍍敷前處理方法後，對於賦予有鍍敷 觸媒或其先質之樹脂層，藉由進行無電鍍敷而形成有表面 金屬膜材料。 亦即’本發明之表面金屬膜材料之製作方法之特徵係 具有於實施該本發明之鍍敷前處理方法後，對該樹脂層所 賦予的鍍敷觸媒或其先質進行無電鍍敷之步驟（D)。 〔步驟（D)〕 於步驟（D)中，藉由對賦予有無電鍍敷觸媒或其先質的 聚合物層進行無電鑛敷而形成有鍍敷膜。所形成的鍍敷膜 係具有優異的導電性、緊貼性。 於本步驟所進行的無電鍍敷係於該步驟（C)中，以在聚 合物層之間形成相互作用之鏟敷觸媒或其先質爲基點而形 成有鍍敷膜（金屬膜）。於本發明中，藉由樹脂層中所顯現 -43- 201132795 的混成結構之形成，形成具有優異的緊貼性之無電鍍敷 膜。另外，爲了獲得所期望的膜厚之鏟敷層，於無電鍵敷 之後，如後所述，進一步進行電鍍〔步驟（E )〕爲更佳的形 態。 以下，針對本步驟中之無電鍍敷而加以說明。 (無電鍍敷） 所謂無電鍍敷係意指鍍敷係使用溶解欲使其析出的金 屬離子的溶液，經由化學反應而使金屬析出的操作。 本步驟中之無電鍍敷係例如水洗賦予有無電鍍敷觸媒 之基板而去除無電鍍敷觸媒（金屬）後，浸漬於無電鍍敷浴 中而進行。所使用的無電鍍敷浴能夠使用一般所習知的無 電鍍敷浴。 另外，無電鍍敷觸媒先質爲吸附或含浸於聚合物層中 之狀態下，將賦予有無電鍍敷觸媒先質的基板浸漬於無電 鍍敷浴中之情形下，水洗基板而去除多餘之先質（金屬鹽等） 後，予以浸漬於無電鍍敷浴中。此情形下，於無電鏟敷浴 中，進行鍍敷觸媒先質之還原與接續此還原之無電鍍敷。 即使於此所使用的無電鍍敷浴也能夠與上述同樣地使用一 般所習知的無電鍍敷浴。 還有，無電鑛敷先質之還原係與使用如上所述之無電 鍍敷液之形態不同，也能夠準備觸媒活化液（還原液）’以 無電鍍敷前之其他步驟的方式而進行。觸媒活化液係溶解 能夠將無電鍍敷觸媒先質（主要爲金屬離子）還原成0價金 -44 - 201132795 屬之還原劑的溶液且可以爲 0.1 %至50%，較佳爲1%至 3 0 %。還原劑能夠使用如氫化硼鈉、二甲胺基硼烷之硼系 還原劑、甲醛、次磷酸等之還原劑。 一般之無電鍍敷浴之組成係主要含有1.鏟敷用之金屬 離子、2.還原劑、3.使金屬離子之安定性提高的添加劑（安 定劑）。此等之外，也可以含有鑛敷浴之安定劑等之習知添 加物。 可用於無電鍍敷浴之金屬種類，習知爲銅、錫、鉛、 鎳、金、鈀、鍺，其中，從導電性之觀點，特佳爲銅、金。 另外，配合該金屬而具有最適之還原劑、添加物。例 如，銅之無電鑛敷係含有：作爲銅鹽之CuS04;作爲還原 劑之HCOH ;作爲添加劑之銅離子安定劑的EDTA或羅謝 爾（Rochelle)鹽等之螯合劑；三烷醇胺等。另外，於CoNiP 之無電鍍敷所使用的鍍敷浴中含有：作爲其金屬鹽之硫酸 鈷、硫酸鎳；作爲還原劑之次磷酸鈉；作爲錯化劑之丙二 酸鈉、蘋果酸鈉、琥珀酸鈉。另外，鈀之無電鍍敷浴係含 有：作爲其金屬離子之（Pd(NH3)4)Cl2;作爲還原劑之NH3、 H2NNH2 ;作爲安定化劑之EDTA。於此等之鍍敷浴中，也 可以加入上述成分以外之成分。 藉由進行如此方式所形成的無電鍍敷所獲得之鍍敷膜 的膜厚能夠依照鍍敷浴之金屬離子濃度、對鍍敷浴之浸漬 時間、或鍍敷浴之溫度等而控制，從導電性之觀點，較佳 爲0.2 μπι以上，更佳爲1 μιη以上。 -45 - 201132795 另外’對鍍敷浴之浸漬時間較佳爲1分鐘至6小時左 右，更佳爲1分鐘至3小時左右。 於本發明中’依照源自上述之鍍敷觸媒、鍍敷觸媒先 質之金屬或金屬鹽、及/或無電鍍敷，藉由聚合物層中所析 出的金屬係作成在該層中之碎形的微細構造物所形成，能 夠進一步使金屬膜與聚合物層之緊貼性提高。 存在於聚合物層中之金屬量係使用金屬顯微鏡而照相 拍攝基板截面時，從聚合物層之最外表面起至深度0.5 μηι 之區域所佔有之金屬的比例爲5至5 0面積％，聚合物層與 金屬界面之算術平均粗糙度Ra(JISB0633-2001)爲0.05μm 至0.5 μιη之情形下，顯現更強的緊貼力。 〔步驟（Ε)〕 (電鍍） 於本步驟中，能夠將在步驟（D)所形成的鍍敷膜作爲電 極而進一步進行電鍍。藉此，將作成與基板具有優異的緊 貼性之無電鍍敷膜作爲基底，於其上能夠容易地形成新的 任意厚度之金屬膜。如此方式，於無電鑛敷之後，由於藉 由進行電鍍而可將金屬膜形成按照目的之厚度，故適合將 本發明之金屬膜適用於各種之應用。 本發明中之電鍍方法能夠利用習知之方法。還有，可 用於本步驟之電鍍的金屬，可舉例：銅、鉻、鉛、鎳、金、 銀、錫、鋅等，從導電性之觀點，較佳爲銅、金、銀，更 佳爲銅。 -46 - 201132795 另外，針對藉由電鍍所獲得之金屬膜的膜厚，其係按 照用途而異，藉由調整鍍敷浴中所含之金屬濃度或電流密 度等而能夠控制。還有，從導電性之觀點，用於一般之電 配線等之情形的膜厚較佳爲〇. 5 μπι以上，更佳爲3 μιη以 上。 藉由經歷本發明之表面金屬膜材料之製作方法的各步 驟，能夠獲得表面金屬膜材料。還有，藉由在基材之兩面 形成樹脂層，能夠獲得在兩面形成有金屬膜之表面金屬膜 材料。 利用表面金屬膜材料之製作方法所獲得之表面金屬膜 材料即使於高溫高濕下，也具有金屬膜之緊貼力的變動爲 少的效果。此表面金屬膜材料能夠適用於例如抗電磁波 膜、塗布膜、2層CCL材料、電配線用材料等之各種用途。 另外，由於該表面金屬膜材料係基材與金屬膜具有優 異的緊貼性，也可適合使用於將金屬膜圖案化之用途。亦 即’藉由進行將利用本發明之方法所獲得之表面金屬膜材 料的鍍敷膜鈾刻成圖案狀之步驟（F)，也能夠獲得金屬圖案 材料。 以下，針對此步驟（F)而加以說明。 〔步驟（F)〕 於步驟（F)中，藉由上述步驟（D)及依需求所進行的步 驟（Ε)所形成的鍍敷膜（金屬膜）蝕刻成圖案狀。亦即，於本 步驟中，藉由利用蝕刻而去除在整體基板表面所形成的鍍 -47- 201132795 敷膜之不要部分而能夠形成所期望的金屬圖案。 針對此金屬圖案之形成，也能夠使用任意之手法，具 體而言，一般所習知之相減法、半相加法。 所謂相減法係指將乾膜光阻層設置於所形成的鍍敷膜 上，藉由圖案曝光、顯影而形成與金屬圖案部相同的圖案， 將乾膜光阻圖案作爲遮罩而使用蝕刻液來去除鍍敷膜，形 成金屬圖案之方法。也能夠將任意之材料作爲乾膜光阻而 使用’能夠使用負型、正型、液狀、膜狀者。另外，也能 夠使用印刷配線板製造時所使用的任一種方法作爲蝕刻方 法，能夠使用濕式蝕刻、乾式蝕刻等，最好任意選擇。作 業之操作上’由於濕式蝕刻之裝置等爲簡便而較诖。鈾刻 液能夠使用例如氯化銅、氯化鐵等之水溶液。 另外’所謂半相加法係指藉由將乾膜光阻層設置於所 形成的鍍敷膜上’依照圖案曝光、顯影而與非金屬圖案部 形成相同圖案’將乾燥膜光阻圖案作爲遮罩而進行電鍍， 於去除乾膜光阻圖案之後實施快速蝕刻，將鍍敷膜去除成 圖案狀而形成金屬圖案的方法。乾燥膜光阻、蝕刻液等能 夠使用與相減法同樣的材料。另外，電鍍手法能夠使用上 述記載的手法。 如上所述’實施本發明之表面金屬膜材料形成方法 後’進一步經由步驟（F)而製作具有所期望的金屬圖案的金 屬圖案材料。 3 ~方面’例如藉由控制曝光方法等而將在步驟（Α) -48- 201132795 所獲得之樹脂層形成圖案狀，且藉由對圖案狀之 行步驟（B)、步驟（C)、及步驟（D)，進一步依期望 驟（E)，也能夠製作金屬圖案材料（半相加技術）。 將在步驟（A)所獲得之樹脂層形成圖案狀之方 而言，藉由將於形成樹脂層之際所賦予的能量 狀，利用顯影而去除未賦予能量之部分，能夠形 之樹脂層。 還有，顯影方法係藉由浸漬於可溶解用以形 合性基及相互作用性基（氰基）的化合物等之聚合 料之溶劑中所進行。所浸漬的時間較佳爲1分鐘至 另外，步驟（A)中之樹脂層的形成也可以藉由 凹版、噴墨法、使用光罩之噴灑塗布法等習知之 來直接將樹脂組成物賦予圖案上之後，賦予能量 藉由進行顯影而形成。 爲了在形成圖案狀之樹脂層上形成鍍敷{ (B)、步驟（C)、及步驟（D)最好與上述之方法同樣 藉由本發明之上述方法所獲得之金屬圖案材 金屬圖案材料之樹脂層的吸水性低，由於疏水性 脂層之露出部（金屬圖案之非形成區域）係具有優 信賴性。 金屬圖案材料係表面之凹凸較佳爲5 00 nm J 爲100 nm以下）之基板的整面或局部上設置金力 膜）。另外，基板與金屬圖案之緊貼性較佳爲0.2 樹脂層進 而進行步 法，具體 作成圖案 成圖案狀 成具有聚 物層的材 3 0分鐘。 利用照相 塗布方法 ，其後， 漠之步驟 地進行。 料係構成 局，此樹 異的絕緣 d下（更佳 團膜（鍍敷 kN/m 以 -49- 201132795 上。亦即，以基板表面爲平滑、同時基板與金屬圖案也具 優越之緊貼性爲特徵。 還有，基板表面之凹凸係相對於基板表面而垂直地切 斷基板表面，藉由利用s Ε Μ而觀察其截面所測定之値。 更詳言之，依照Π S Β 0 6 0 1所測定的R ζ，亦即「指定 面上之從最大至第5號爲止之山頂的Ζ資料平均値、與從 最小至第5號爲止之谷底的平均値之差」較佳爲500nm以 下。 另外，基板與金屬膜之緊貼性的値係在金屬膜（金屬圖 案）之表面，使用環氧系接著劑（Araldite Ciba-Geigy製）而 接著銅板（厚度：0.1 mm)，於140 °C乾燥4小時之後，根據 JIS C 6M1而進行90度剝離實驗，或是直接剝取金屬膜本 身之端部，根據〗IS C 648 1而進行90度剝離實驗後所獲得 之値。 利用本發明之金屬圖案材料之製作方法所獲得之金屬 圖案材料能夠適用於例如半導體晶片、各種電配線板、 FPC、COF、TAB、天線、多層配線基板、母板、表面金屬 裝飾構件等之各種用途。 實施例 以下，藉由實施例而詳細說明本發明，但是本發明並 不受此等實施例所限定。還有，只要無特別申明，「％」、 「份」係質量基準。 <合成例1 :具有聚合性基及相互作用性基之特定共聚物： -50- 201132795 聚合物A之合成> 於1000ml之三口燒瓶中，加入35g之N，N -二甲基乙 醯胺，於氮氣氣流下，加熱直到75°C。再將6.60g之丙烯 酸-2-羥乙酯（市售品、東京化成製）、28.4 g之丙烯酸-2-氰 乙酯、0.65 g之V-601(和光純藥製）的35 g之N，N-二甲基 乙醯胺溶液，花費2.5小時而滴入其中。滴入結束後，加 熱直到80°C，進一步攪拌3小時。之後，將反應溶液冷卻 直到室溫。 於上述之反應溶液中，添加0.29 g之二第三丁基氫 醌、0.29g之二丁基二月桂酸錫、18.56g之KarenzAOI(昭 和電工（股份有限公司）製）、19 g之N，N-二甲基乙醯胺，於 5 5 °C進行4小時反應。其後，將3 · 6 g之甲醇加入反應液中， 進一步進行1 . 5小時反應。反應結束後’以醋酸乙酯：己 烷=1: 1進行再沉澱，取出固形物，獲得32g之具有聚合 性基及相互作用性基之聚合物A(重量平均分子量6.2萬）。The specific copolymer in the present invention may have a polar group in addition to a polymerizable group and an interactive group, if the polymer layer formed is in a range satisfying all of the conditions 1 to 2. After the metal film is formed in accordance with the procedure described later by having a polar group, for example, in the case where a protective layer is provided, the adhesion can be improved in the contact region between the polymer layer and the protective layer. -31 - 201132795 As described above, in order to form the resin layer in the present invention, it is preferred to use a liquid having a polymerizable group and an interactive group, such as a polymer having a polymerizable group and an interactive group. The composition, that is, a composition containing a polymerizable group and an interactive group, and a solvent capable of dissolving the compound (preferably, a composition for forming a polymer layer of the present invention having the following composition: having a cyano group Or a structure represented by 0-(CH2)n- 〇- (n is an integer of 1 to 5) and a polymer having a polymerizable group, and a solvent capable of dissolving the polymer). Further, the content of the compound having a polymerizable group and an interactive group (for example, a polymerizable copolymer containing a cyano group) is preferably from 2% by mass to 50% by mass relative to the entire polymer. %. The solvent to be used in the composition is not particularly limited as long as it is a main component of the composition and is capable of dissolving a compound having a polymerizable group and an interactive group. It is also possible to further add a surfactant to the solvent. The solvent which can be used is, for example, an alcohol solvent such as methanol, ethanol, propanol, ethylene glycol, glycerin or propylene glycol monomethyl ether; an acid such as acetic acid; such as acetone, methyl ethyl ketone or cyclohexane. a ketone ketone solvent; a guanamine solvent such as amide, dimethyl acetamide or hydrazine-methylpyrrolidone; a nitrile solvent such as acetonitrile or propionitrile; such as methyl acetate or ethyl acetate An ester solvent; for example, a dimethyl carbonate, a carbonate solvent of diethyl carbonate, or the like. In the case where a composition using a polymerizable polymer containing a cyano group is used as the solvent, a guanamine type, a ketone type, a nitrile type solvent, or a carbonate type solvent is preferable. Specifically, it is preferably Acetone, dimethylacetamide, methyl-32-201132795 ethyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N-methylpyrrolidone, dimethyl carbonate. Further, in the case of coating a composition containing a polymerizable polymer having a cyano group, a solvent of 50 to 150 ° C is preferable from the viewpoint of easy handling. Further, these solvents may be used singly or in combination. Further, in the present invention, when a composition containing a compound having a polymerizable group and an interactive group is applied onto a substrate or a polymerization starting layer, the solvent absorption rate of the substrate or the polymerization starting layer can be selected to be 5 to 25% solvent. This solvent absorption rate can be obtained by immersing the substrate or the substrate on which the polymerization starting layer is formed in a solvent, and changing the mass when it is lifted up after 1000 minutes. Further, in the case where a composition containing a compound having a polymerizable group and an interactive group is applied onto a substrate or a polymerization starting layer, the swelling ratio of the substrate or the polymerization starting layer may be selected to be 10 to 45 %. Solvent. This swelling ratio can be obtained by immersing the substrate or the substrate on which the polymerization starting layer is formed in a solvent, and changing the thickness when lifted after 1 minute. If necessary, the surfactant which can be added to the solvent may be dissolved in a solvent. In addition, a plasticizer can also be added as necessary. The plasticizer which can be used can be exemplified by a general plasticizer. In the composition containing a specific copolymer, if necessary, a curing agent and/or a curing accelerator may be appropriately added in order to cure the polymerization inhibitor or the polymerization starting layer. Further, a rubber component (for example, CTBN), a hard-to-33-201132795 oxidizing agent (for example, a phosphorus-based flame retardant), a diluent or a thixotropic visbreaking agent, a pigment, an antifoaming agent, and a flat may be further added. Agents, coupling agents, and the like. Further, such additives may be added to the polymerization starting layer as necessary. The physical properties of the formed resin layer can be optimally set by appropriately mixing a specific copolymer with a composition of various additives, such as a coefficient of thermal expansion, a glass transition temperature, a Young's modulus, a Poisson ratio, and a fracture stress. , yield stress, thermal decomposition temperature, etc. In particular, the higher the fracture stress, the yield stress, and the thermal decomposition temperature, the better. The obtained resin layer can be measured for thermal durability by a temperature cycle test or a thermal test, a reflow test or the like which passes over time, for example, regarding thermal decomposition, and if the temperature is exposed to an environment of 200 ° C for 1 hour, the mass is reduced to 20 When it is less than %, it can be evaluated to have sufficient thermal durability. In the case of contacting a composition containing a specific copolymer, the coating amount is preferably from 0.1 to 10 g/m2 in terms of solid content from the viewpoint of sufficient interaction with the plating catalyst or its precursor. It is preferably 0.5 to 5 g/m 2 °. Further, a composition containing a compound having a polymerizable group and an interactive group is applied onto a substrate and dried to form a compound layer having a polymerizable group and an interactive group. In this case, it is also possible to remove the residual solvent by allowing it to stand at 20 to 40 ° C for 0.5 to 2 hours between coating and drying. (Improvement of Energy) The method of imparting energy to the surface of the substrate can be irradiated with radiation such as heating or exposure. For example, light irradiation of -34-201132795 is performed using a UV lamp, visible light, or the like, and heating by a hot plate or the like is possible. For example, the light source can be exemplified by a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, or the like. The radiation can be exemplified by an electron beam, an X-ray, an ion beam, a far infrared ray, or the like. In addition, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) are also used. The specific form to be used generally may be, for example, direct image recording using a thermal recording head, scanning exposure using infrared rays, high-intensity flash exposure such as a xenon discharge lamp, or infrared lamp exposure. The time required for energy imparting varies depending on the amount of the graft polymer to be produced and the light source, and is usually from 10 seconds to 5 hours. Further, in the case where energy is applied by exposure, the exposure power is used to facilitate graft polymerization, and in order to suppress decomposition of the produced graft polymer, it is preferably from 10 mJ/cm 2 to 5000 mJ / The range of cm2 is more preferably in the range of 50 mJ/cm2 to 3 000 mJ/cm2. In addition, when a polymer having a polymerizable group and an interactive group is used, when a polymer having an average molecular weight of 20,000 or more and a polymerization degree of 200 or more is used, graft polymerization can be easily performed by exposure with low energy, and the polymerization can be further suppressed. Decomposition of the resulting graft polymer. According to the step (A) described above, a resin layer (graft polymer layer) made of a graft polymer having an interactive group that receives a plating catalyst or the like is formed on the substrate. The obtained resin layer is added to, for example, an alkaline solution of pH 1 2, and the decomposition of the polymerizable base portion after stirring for 1 hour is 50% or less, and the resin layer can be used for a strong base at -35 to 201132795. Wash the solution. [Step (B)] In the step (B), a plating catalyst or a precursor thereof is imparted to the resin layer formed in the step (A). In this step, the interactive group (cyano group) of the graft polymer constituting the resin layer adheres (adsorbs) the plating catalyst or its precursor according to its function. Here, the plating catalyst or the precursor thereof may be exemplified as a function of a plating catalyst or an electrode in the (D) electroless plating step described later. Therefore, the plating catalyst or its precursor is determined according to the type of plating in the (D) plating step. Further, the mineralizing catalyst used in this step or its precursor is an electroless plating catalyst or a precursor thereof. (Electroless plating catalyst) The electroless plating catalyst used in the present invention can be any electroless plating catalyst as long as it is an active core in the absence of electric shovel. Specifically, the electroless plating catalyst can be used. For example, a metal having a self-catalyst reduction reaction catalyst ability, and the like, specifically, Pd, Ag, Cu, Ni, A1, Fe, Co, and the like. Among them, it is preferred to be able to have multiple ligands, and in particular, from the viewpoint of the number of kinds of functional groups capable of coordination and the catalyst ability, particularly preferably Pd °, the electroless plating catalyst can also be used as a metal colloid. In general, the metal colloid can be produced by reducing metal ions in a solution in which a charged surfactant or a protective agent having a charge is present. The charge of the metal colloid can be adjusted by the surfactant or protectant used herein -36-201132795. (Electroless plating catalyst precursor) The electroless mineralization catalyst used in this step means that it can be used as an electroless plating catalyst by chemical reaction, and can be used without particular limitation. Metal ions of the metal exemplified as the electroless plating catalyst can be mainly used. The metal ions of the electroless plating catalyst precursor are formed into an valence metal of an electroless plating catalyst by a reduction reaction. The metal ion of the electroless plating catalyst precursor can be formed into an electroless plating layer after being applied to the polymer layer and then being changed into a valence metal by a reduction reaction of the other route before the impregnation of the electroless plating bath. The catalyst can also be immersed in the electroless mineral bath in the state of the electroless plating catalyst precursor, and can be changed into a metal (electroless plating catalyst) by the reducing agent in the electroless plating bath. In fact, the metal ions of the electroless plating precursor are imparted to the polymer layer using a metal salt. The metal salt to be used is not particularly limited as long as it is dissolved in a suitable solvent to form a metal ion and a base (anion), and examples thereof include M(N03)n, MCln, and M2/n (S04). Μ3/η(Ρ04) (Μ indicates a metal atom of n valence) and the like. The metal atom can be suitably obtained by dissociating the above metal salt. For example, a specific example can be exemplified by Ag ions, Cu ions, A1 ions 'Ni ions, Co ions, Fe ions, Pd ions, and among them, it is preferable to be able to coordinate at a plurality of positions, based on the number of kinds of functional groups capable of coordination And the viewpoint of catalyst capacity, especially Pd ions. A method of imparting a metal of an electroless plating catalyst or a metal salt of an electroless plating catalyst to a polymer layer is preferably prepared by dispersing a metal in a dispersion of a suitable dispersion of -37-201132795 or using a solution in which a suitable solvent dissolves the metal salt and contains the dissociated metal ion, and the dispersion or solution is applied onto the polymer layer or the substrate on which the polymer layer is formed is immersed in the dispersion or solution. (A), in the case of surface graft polymerization, a composition containing a compound having a polymerizable group and an interactive group (cyano group) is brought into contact with a substrate, and an electroless plating catalyst or A method of adding a precursor to this composition. Contacting a compound containing a polymerizable group and an interactive group (cyano group) with a composition of an electroless plating catalyst or a precursor thereof on a substrate, and forming a mixture containing each other by surface graft polymerization A functional group (cyano group) which is directly chemically bonded to a substrate, and a plating catalyst or a resin layer thereof. Further, if this method is used, the steps (A) and (B) in the present invention can be carried out in one step, in which case the step (C) is carried out after the step (B). Further, in the case where a resin layer is formed on both surfaces of the substrate, in order to bring the electroless plating catalyst or the precursor thereof into contact with the resin layers on both sides thereof, it is preferred to use the above-described impregnation method as described above. By contacting the electroless plating catalyst or its precursor, the interaction group (cyano group) in the resin layer is utilized by an interaction according to an intermolecular force such as van der Waals force, or The interaction between the electrons on the coordination bond formed can cause the electrosurgical squeegee or its precursor to adsorb. The metal concentration in the dispersion, the solution, the group-38-201132795 or the metal ion concentration in the solution is preferably in the range of 0.001 to 50% by mass, more preferably 0.005 to 30, from the viewpoint of allowing such adsorption to proceed sufficiently. The range of mass %. Further, the contact time is preferably from about 30 seconds to about 24 hours, more preferably from about 1 minute to about 1 hour. By the step (B) described above, it is possible to form an interaction between the interactive group (cyano group) in the polymer layer and the mineralizing catalyst or its precursor. [Step (C)] In the present invention, at least one selected from the group consisting of an ether solvent, an alcohol solvent, an ester solvent, and a ketone solvent is used before or after the step (B). Step (C) of treating the liquid with an organic solvent. The organic solvent contained in the pretreatment liquid is at least one selected from the group consisting of an ether solvent, an alcohol solvent, an ester solvent, and a ketone solvent. Here, the water-soluble organic solvent means a solvent which is dissolved in water in an amount of 1% by mass or more. The ether solvent can be exemplified by bis(2-ethoxyethyl)ether, bis[2-(2-hydroxyethoxy)ethyl]ether, 1,2-bis(2-methoxyethoxy). Ethane, bis[2-(2-methoxyethoxy)ethyl]ether, bis(2-methoxyethyl)ether, 2-(2-butoxyethoxy)ethanol, 2- [2-(2-Chloroethoxy)ethoxy]ethanol, 2-ethoxyethanol, 2-(2-ethoxyethoxy)ethanol, 2-isobutoxyethanol, 2·(2 -isobutoxyethoxy)ethanol, 2-isopropyloxyethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol, 2-(2-methoxyethoxy) Ethyl alcohol, ethoxylated 2-propanol, 1-methoxy-2-propanol, tripropylene glycol monomethyl ether, methoxy-39-201132795 acetic acid, 2-methoxyethanol, and the like. The alcohol solvent can be exemplified by ethanol, isopropanol, n-propanol, 3-ethylidene-1-propanol '2-(dipropoxy)ethanol, 2-aminoethanol, 2-amino-2_ Methyl-1-propanol, (±)·2-amino-1-propanol, 3-amino-1-propanol, 2-dimethylaminoethanol, 2,3-epoxy-丨-prop Alcohol, ethylene glycol, 2-fluoroethanol, diacetone alcohol '2-methylcyclohexanol, 4-hydroxy-4-methyl-2-pentanone, glycerin, 2,2,,2,,-cyano Triethanol, 2-pyridinemethanol, 2,2,3,3_tetrafluoro-!•propanol, 2-(2-aminoethoxy)ethanol, 2-[2-(benzyloxy)ethoxy] Ethanol, 2,3-butanediol, 2-butoxyethanol, 2,2,-thiodiethanol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol' 2 -methyl-2,4-pentanediol, 13-propanediol, diglycerin, 2,2,-methyliminodiethanol, 1,2-pentanediol, and the like. Examples of the ester solvent include ethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and methyl group. Cellulose acetate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl glycolate, ethyl glycolate, and the like. The ketone solvent can be exemplified by acetone, 4-hydroxy-4-methyl-2-pentanone, γ-butyrolactone, hydroxyacetone or the like. From the viewpoint of less concern of oxidation by the catalyst metal, among the above-mentioned water-soluble organic solvents, one of the preferred embodiments is preferably an organic solvent containing no alcohol; from the viewpoint of solution preservability 'It is preferably a ketone solvent, an ester solvent, or an ether solvent. More specifically, 'preferably acetone, dimethyl carbonate, ethylene glycol dimethyl ether, acetic acid-2_(2-ethoxyethoxy)ethyl ester, 1-ethyloxyl-2. Oxyethane, bis(2·ethoxyethyl)ether (Di-40-201132795: diethylene glycol diethyl ether), 1,2-bis(2-methoxyethoxy)B Alkane, bis[2-(2-methoxyethoxy)ethyl]ether, bis(2-methoxyethyl)ether (other name: diethylene glycol dimethyl ether), and the like. Further, from the viewpoint of affinity or solubility to the polymer used in the present invention, it is more preferably ether-based cellulase, and is preferably bis(2-methoxyethyl)ether or the like. The organic solvent contained in the pretreatment liquid may be used alone or in combination of two or more. The total amount of the organic solvent contained in the pretreatment liquid is preferably 1% by mass or more and 50% by mass or less, more preferably 5 mass% or more and 45 mass% or less. Further, an organic solvent other than the organic solvent may be supplied to the extent that the effects of the present invention are not impaired. More preferably, it contains a metal salt in the pretreatment liquid. The metal salt to be used is not particularly limited as long as it is dissolved in a suitable solvent to be dissociated into a metal ion and a base (anion), and may be exemplified by M(N03)n, MCln, M2/n (S04). M3/n(P04), M(OAc)n (M represents a metal atom of n valence, and Ac represents an acetamyl group). The metal ion can be suitably used in the above metal salt solution. For example, specific examples can be exemplified by Ag ions, Cu ions, A1 ions, Ni ions, Co ions, Fe ions, Pd ions, among which, it is preferred to be capable of multiple coordination, in particular, based on functional groups capable of coordination The viewpoint of the number of species and the catalytic ability is preferably Pd ion, copper ion, and more preferably copper ion. Further, as for the anion, from the viewpoint of solubility in water or an acidic aqueous solution, yttrium, (〇Ac) _, and C"' are more preferably NO, and (OAc)-. In the step (C), a metal is used. In the case of a salt, the metal salt is preferably different from the catalyst given in the step (B) or its -41 to 201132795. The content of the metal salt relative to the pretreatment liquid is preferably ο· mass% or more. 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less. In the pretreatment liquid, the organic solvent, the metal salt of the preferred hydrazine component, and the water of the main solvent are not impaired. In the range of the effects of the invention, other additives may be contained according to the purpose. Other additives may be exemplified below. For example, an acid (organic acid such as hydrochloric acid or nitric acid; an organic acid such as acetic acid or citric acid) may be swelled. Agents (organic compounds such as ketones, aldehydes, ethers, esters, etc.) or surfactants (anionic, cationic, amphoteric, nonionic, low molecular or polymeric), etc. Liquid imparting resin layer Preferably, the resin layer forming surface is brought into contact with the pretreatment liquid, and from the viewpoint of ease of handling, a method of immersing the substrate having the resin layer in the pretreatment liquid is preferred. From the viewpoint of effect, pretreatment The contact time of the liquid is preferably from about 30 seconds to about 24 hours, more preferably from about 1 minute to about one hour. The temperature of the treatment liquid before the contact may be normal temperature (25 ° C), and from the viewpoint of ensuring permeability. More preferably, it is in the range of 30 ° C to 50 ° C. The contact with the pretreatment liquid, that is, the step (C) can be formed before the step (B), that is, having the step (A) In the resin layer of the interactive group, the pretreatment liquid is first applied, and then the step (B) is applied to provide a plating catalyst or the like. Alternatively, in the step (B), the plating catalyst may be first applied to the resin layer. After that, the step (C) is carried out to provide the pretreatment liquid. By contact with the pre-42-201132795 treatment liquid, in the subsequent electroless plating catalyst step (D), the electroless plating solution and The affinity of the resin layer will be improved, and the plating treatment will be uniform and efficient. From the viewpoint of the effect of improving the affinity of the resin layer, the step (C) is preferably carried out after the step (B). By the step of the mineral deposit treatment, the step (A), the step (B), And the pre-plating treatment method of the present invention of the step (C) makes it possible to form a plating film which is effective in forming a uniform metal film having excellent adhesion and no unevenness. <Surface metal film material [Production Method] After the plating pretreatment method of the present invention is carried out, a surface metal film material is formed by electroless plating on a resin layer to which a plating catalyst or a precursor thereof is applied. The method for producing a surface metal film material is characterized in that the plating catalyst or the precursor thereof is subjected to a step (D) of electroless plating after the plating method of the present invention is carried out. [Step (D)] In the step (D), a plating film is formed by electrolessly mineralizing a polymer layer to which an electroplating catalyst or a precursor thereof is applied. The formed plating film has excellent conductivity and adhesion. The electroless plating performed in this step is carried out in the step (C), and a plating film (metal film) is formed by using a shovel coating medium or a precursor thereof which forms an interaction between the polymer layers. In the present invention, an electroless plating film having excellent adhesion is formed by the formation of a mixed structure of -43 to 201132795 which is exhibited in the resin layer. Further, in order to obtain a desired coating layer having a film thickness, electroplating [step (E)] is further performed after electroless bonding, as will be described later. Hereinafter, the electroless plating in this step will be described. (Electroless plating) The electroless plating means an operation of depositing a metal by a chemical reaction using a solution in which a metal ion to be precipitated is dissolved. The electroless plating in this step is performed, for example, by washing with a substrate having or without an electroplating catalyst, removing the electroless plating catalyst (metal), and then immersing it in an electroless plating bath. The electroless plating bath used can use a commonly known electroless plating bath. In addition, in the state where the electroless plating catalyst precursor is adsorbed or impregnated in the polymer layer, the substrate to which the electroless plating precursor is applied is immersed in the electroless plating bath, and the substrate is washed to remove excess After the precursor (metal salt, etc.), it is immersed in an electroless plating bath. In this case, in the electroless shovel bath, the plating catalyst precursor is reduced and the electroless plating is continued. Even in the electroless plating bath used herein, a conventionally known electroless plating bath can be used in the same manner as described above. Further, the reduction system of the electroless ore deposit is different from the form of the electroless plating solution as described above, and the catalyst activation liquid (reducing liquid) can be prepared in such a manner as to carry out the other steps before the electroplating. The catalyst activation liquid solution can reduce the electroless plating catalyst precursor (mainly metal ions) into a solution of the reducing agent of the zero-valent gold-44 - 201132795 and can be 0.1% to 50%, preferably 1%. Up to 30%. As the reducing agent, a reducing agent such as sodium borohydride, a boron-based reducing agent of dimethylaminoborane, formaldehyde, hypophosphorous acid or the like can be used. The composition of the general electroless plating bath mainly includes 1. metal ions for shovel application, 2. a reducing agent, and an additive (safety agent) for improving the stability of metal ions. In addition to these, a conventional additive such as a stabilizer for a mineral bath may be contained. The type of metal that can be used in the electroless plating bath is conventionally known as copper, tin, lead, nickel, gold, palladium, and rhodium. Among them, from the viewpoint of conductivity, copper and gold are particularly preferred. Further, the metal is blended to have an optimum reducing agent or additive. For example, the electroless ore deposit of copper contains: CuS04 as a copper salt; HCOH as a reducing agent; chelating agent such as EDTA or Rochelle salt as a copper ion stabilizer of an additive; trialkanolamine or the like. In addition, the plating bath used for electroless plating of CoNiP contains: cobalt sulfate as a metal salt thereof, nickel sulfate; sodium hypophosphite as a reducing agent; sodium malonate or sodium malate as a neutralizing agent; Sodium succinate. Further, the electroless plating bath of palladium contains: (Pd(NH3)4)Cl2 as its metal ion; NH3 and H2NNH2 as a reducing agent; and EDTA as a stabilizer. In the plating baths of these, it is also possible to add components other than the above components. The film thickness of the plating film obtained by performing the electroless plating formed in this manner can be controlled according to the metal ion concentration of the plating bath, the immersion time of the plating bath, or the temperature of the plating bath, etc., from the conductive The viewpoint of sex is preferably 0.2 μπι or more, more preferably 1 μιη or more. -45 - 201132795 Further, the immersion time for the plating bath is preferably from about 1 minute to about 6 hours, more preferably from about 1 minute to about 3 hours. In the present invention, 'the metal or metal salt derived from the above-mentioned plating catalyst, plating catalyst precursor, and/or electroless plating is formed in the layer by the metal system precipitated in the polymer layer. The fractured fine structure is formed, and the adhesion between the metal film and the polymer layer can be further improved. The amount of metal present in the polymer layer is a photomicrograph of a substrate cross section using a metal microscope, and the ratio of the metal occupied from the outermost surface of the polymer layer to a region having a depth of 0.5 μm is 5 to 50% by area. In the case where the arithmetic mean roughness Ra (JISB0633-2001) of the object layer and the metal interface is 0.05 μm to 0.5 μm, a stronger adhesion is exhibited. [Step (Ε)] (Electroplating) In this step, the plating film formed in the step (D) can be further plated as an electrode. Thereby, an electroless plating film having excellent adhesion to the substrate is used as a substrate, and a new metal film of any thickness can be easily formed thereon. In this manner, after the electroless ore deposit, since the metal film can be formed into a thickness according to the purpose by electroplating, the metal film of the present invention is suitable for various applications. The plating method in the present invention can utilize a conventional method. Further, the metal which can be used for the plating in this step may, for example, be copper, chromium, lead, nickel, gold, silver, tin, zinc, etc., from the viewpoint of conductivity, preferably copper, gold, silver, more preferably copper. Further, the film thickness of the metal film obtained by electroplating varies depending on the application, and can be controlled by adjusting the metal concentration or current density contained in the plating bath. Further, from the viewpoint of conductivity, the film thickness used in the case of general electric wiring or the like is preferably μ 5 μπι or more, more preferably 3 μιη or more. The surface metal film material can be obtained by the steps of the method of producing the surface metal film material of the present invention. Further, by forming a resin layer on both surfaces of the substrate, a surface metal film material having a metal film formed on both surfaces can be obtained. The surface metal film material obtained by the method for producing a surface metal film material has an effect of less variation in the adhesion force of the metal film even under high temperature and high humidity. The surface metal film material can be suitably used for various applications such as an electromagnetic wave resistant film, a coating film, a two-layer CCL material, and a material for electrical wiring. Further, since the surface metal film material-based substrate and the metal film have excellent adhesion, they can be suitably used for patterning a metal film. That is, the metal pattern material can also be obtained by performing the step (F) of patterning the uranium plating film of the surface metal film material obtained by the method of the present invention into a pattern. Hereinafter, this step (F) will be described. [Step (F)] In the step (F), the plating film (metal film) formed by the above step (D) and the step (Ε) performed as required is etched into a pattern. That is, in this step, a desired metal pattern can be formed by removing unnecessary portions of the plating film formed on the surface of the entire substrate by etching. Any method can be used for the formation of the metal pattern, and a subtractive method or a semi-additive method which is generally known in the art. The subtractive method refers to a method in which a dry film photoresist layer is provided on a formed plating film, and a pattern similar to a metal pattern portion is formed by pattern exposure and development, and an etching liquid is used as a mask. A method of removing a plating film to form a metal pattern. Any material can also be used as a dry film photoresist. A negative type, a positive type, a liquid form, or a film type can be used. Further, any method used in the production of a printed wiring board can be used as the etching method, and wet etching, dry etching, or the like can be used, and it is preferable to arbitrarily select it. The operation of the operation is relatively simple due to the ease of the device such as wet etching. The uranium engraving can use an aqueous solution such as copper chloride or ferric chloride. In addition, the term "semi-phase addition means that the dry film resist layer is provided on the formed plating film", and the same pattern is formed as the non-metal pattern portion in accordance with pattern exposure and development. The cover is plated, and after the dry film resist pattern is removed, rapid etching is performed, and the plating film is removed into a pattern to form a metal pattern. A dry film resist, an etching solution, or the like can be used in the same manner as the subtractive method. Further, the plating method can use the method described above. After the method of forming the surface metal film material of the present invention is carried out as described above, a metal pattern material having a desired metal pattern is further produced via the step (F). 3 to the aspect 'the resin layer obtained in the step (Α) -48- 201132795 is patterned by controlling the exposure method or the like, and the step (B), the step (C), and the step of patterning are performed. In step (D), a metal pattern material (semi-additive technique) can also be produced according to the desired step (E). In the case where the resin layer obtained in the step (A) is patterned, the portion to which no energy is applied can be removed by development by the energy imparted when the resin layer is formed, whereby the resin layer can be formed. Further, the developing method is carried out by immersing in a solvent which can dissolve a polymer such as a compound for a complex group and an interactive group (cyano group). The immersion time is preferably from 1 minute to the other, and the formation of the resin layer in the step (A) can be directly applied to the pattern by a gravure, an inkjet method, a spray coating method using a photomask, or the like. After the above, energy is imparted by development. In order to form plating {(B), step (C), and step (D) on the patterned resin layer, it is preferable that the metal pattern metal pattern material obtained by the above method of the present invention is the same as the above method. The water absorption of the resin layer is low, and the exposed portion of the hydrophobic grease layer (non-formation region of the metal pattern) has excellent reliability. The surface of the metal pattern material is preferably a gold film formed on the entire surface or partially of the substrate of 500 nm J (100 nm or less). Further, the adhesion between the substrate and the metal pattern is preferably 0.2 resin layer, and the pattern is patterned into a material having a polymer layer for 30 minutes. The photographic coating method is used, and thereafter, the steps are carried out in a deserted manner. The material system constitutes a bureau, and this tree has different insulation d (better film (plating kN/m is on -49-201132795. That is, the substrate surface is smooth, and the substrate and the metal pattern are also superior. Further, the unevenness of the surface of the substrate is perpendicular to the surface of the substrate, and the surface of the substrate is cut perpendicularly, and the enthalpy measured by the cross section is observed by s Ε 値. More specifically, according to Π S Β 0 6 The R ζ measured by 0 1 , that is, the “average 値 of the Ζ data from the top to the 5th on the designated surface, and the average 値 from the smallest to the bottom of the 5th” is preferably 500 nm. In addition, the adhesion between the substrate and the metal film is on the surface of the metal film (metal pattern), and an epoxy-based adhesive (manufactured by Araldite Ciba-Geigy) is used followed by a copper plate (thickness: 0.1 mm) at 140. After drying at ° C for 4 hours, a 90-degree peeling test was carried out in accordance with JIS C 6M1, or the end portion of the metal film itself was directly peeled off, and the obtained product was subjected to a 90-degree peeling test according to IS C 648 1. Obtained by the method for producing the metal pattern material of the invention The metal pattern material can be applied to various applications such as a semiconductor wafer, various electric wiring boards, FPC, COF, TAB, antenna, multilayer wiring board, mother board, surface metal decorative member, etc. Examples Hereinafter, the details will be described by way of examples. The present invention is not limited to these examples, and "%" and "parts" are quality standards unless otherwise specified. <Synthesis Example 1: Polymerizable group and interactive group Specific copolymer: -50- 201132795 Synthesis of Polymer A> In a 1000 ml three-necked flask, 35 g of N,N-dimethylacetamide was added and heated under nitrogen gas until 75 ° C. 6.60 g of 2-hydroxyethyl acrylate (commercial product, manufactured by Tokyo Chemical Industry Co., Ltd.), 28.4 g of 2-cyanoethyl acrylate, 0.65 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), 35 g of N, N a solution of dimethyl acetamide, which was dropped into it over 2.5 hours. After the completion of the dropwise addition, it was heated to 80 ° C and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature. In the above reaction solution, Add 0.29 g of di-tert-butylhydroquinone, 0.29 g of dibutyltin dilaurate, 18.56 g of Karenz AOI (manufactured by Showa Denko Co., Ltd.), and 19 g of N,N-dimethylacetamide were reacted at 55 ° C for 4 hours. After that, 3 · 6 g of methanol was added to the reaction liquid, and the reaction was further carried out for 1.5 hours. After the completion of the reaction, 'reprecipitation was carried out with ethyl acetate:hexane = 1:1, and the solid matter was taken out to obtain 32 g of the polymerization. Polymer A and a reactive group of polymers A (weight average molecular weight 62,000).

聚合物A -51- 201132795 <合成例2:具有聚合性基及相互作用性基之特定共聚物： 聚合物B之合成> 於3 00 ml之三口燒瓶中，加入73 g之第二丁基胺（市 售品' Aldrich製）、7.3 g之水，加熱直到45°C。再將53 g 之丙烯腈（市售品、和光純藥製）滴入其中。滴入結束後， 使其反應3小時後，利用減壓蒸餾而獲得8 1 g之N-第三丁 基氰基乙胺。 接著，於300 ml之三口燒瓶中，加入80 g之N-第三 丁基氰基乙胺' 5 0 0 g之醋酸乙酯，冷卻直到5 °C。再將4 3 g之丙烯醯氯（市售品、東京化成工業（股）製）。滴入結束後， 回到室溫使其反應3小時。其後，使用醋酸乙酯萃取反應 物，使用小蘇打水、鹽水而洗淨，使用硫酸鎂而使其乾燥 一晚。其後，利用蒸發而獲得粗生成物，使用異丙醇進行 再結晶而獲得44 g之N_第三丁基氰乙基丙烯醯胺。 接著，於300 ml之三口燒瓶中，加入22 g之二甲基 碳酸酯，於氮氣氣流下，加熱直到6 5 °C。再將3.7 2 g之丙 烯酸-2-羥乙酯（市售品、東京化成工業（股）製）、25.63 g之 N-第三丁基氰乙基丙烯醯胺、及〇.397g之V-65(和光純藥 製）的22 g之二甲基碳酸酯溶液，花費4小時而滴入其中。 滴入結束後，進一步攪拌3小時。之後，將反應溶液冷卻 直到室溫。 於上述之反應溶液中，添加0.093 g之TEMPO(東京化 成工業（股）製）、0.277 g之U-600(日東化成工業（股）製）、 -52- 201132795 8.4 g之Karenz AOI(昭和電工（股）製）、及8.4 g之二甲基 碳酸酯，於45 °C進行6小時反應。之後，將1_1 g之水加 入反應液中，進一步進行1 .5小時反應。反應結束後’以 醋酸乙酯：己烷=1 : 3進行再沉澱，取出固形物’獲得1 〇 g之有關本發明之特定共聚物的含有氰基之聚合性聚合物 B ° 含有氰基之聚合性聚合物B之構造的鑑定係使用 NMR(Bruker製400 MHz)而使聚合物溶解於d-DMSO中， 於加熱至5(TC之狀態下’使用1H-NMR確認。分子量之測 定方法係使聚合物溶解於NMP中，使用Tosoh(股）製高速 GPC(HLC-8 220GPC)而進行分子量之測定。還有，分子量係 利用聚苯乙烯換算而計算。含有氰基之聚合性聚合物B之 重量平均分子量爲2.3萬。Polymer A-51-201132795 <Synthesis Example 2: Specific copolymer having a polymerizable group and an interactive group: Synthesis of Polymer B> In a three-necked flask of 300 ml, 73 g of a second butyl group was added. The base amine (commercial product 'made by Aldrich'), 7.3 g of water, was heated until 45 °C. Further, 53 g of acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped into it. After completion of the dropwise addition, the mixture was reacted for 3 hours, and then distilled under reduced pressure to obtain 81 g of N-t-butyl cyanoethylamine. Next, 80 g of N-tert-butylcyanoethylamine '500 g of ethyl acetate was added to a 300 ml three-necked flask, and cooled to 5 °C. Further, 4 3 g of acrylonitrile chloride (commercial product, manufactured by Tokyo Chemical Industry Co., Ltd.). After the completion of the dropwise addition, the mixture was returned to room temperature for 3 hours. Thereafter, the reaction mixture was extracted with ethyl acetate, washed with sodium bicarbonate and brine, and dried over magnesium sulfate overnight. Thereafter, a crude product was obtained by evaporation, and recrystallization was carried out using isopropyl alcohol to obtain 44 g of N-t-butylcyanoethyl acrylamide. Next, 22 g of dimethyl carbonate was placed in a 300 ml three-necked flask, and heated to 65 ° C under a nitrogen stream. Further, 3.7 2 g of 2-hydroxyethyl acrylate (commercial product, manufactured by Tokyo Chemical Industry Co., Ltd.), 25.63 g of N-t-butylcyanoethyl acrylamide, and 397.397 g of V- A solution of 65 g of dimethyl carbonate in 65 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped into it over 4 hours. After the completion of the dropwise addition, the mixture was further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature. In the above reaction solution, 0.093 g of TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.277 g of U-600 (made by Nitto Chemical Industry Co., Ltd.), -52-201132795 8.4 g of Karenz AOI (Showa Electric Works) were added. (manufactured by the company), and 8.4 g of dimethyl carbonate, reacted at 45 ° C for 6 hours. Thereafter, 1_1 g of water was added to the reaction liquid, and the reaction was further carried out for 1.5 hours. After completion of the reaction, 'reprecipitation was carried out with ethyl acetate:hexane = 1:3, and the solid matter was taken out to obtain 1 〇g of a cyano group-containing polymerizable polymer B ° containing a specific copolymer of the present invention containing a cyano group. Identification of the structure of the polymerizable polymer B was carried out by using NMR (400 MHz manufactured by Bruker) to dissolve the polymer in d-DMSO, and heating to 5 (TC state) was confirmed by 1H-NMR. The polymer was dissolved in NMP, and the molecular weight was measured using a high-speed GPC (HLC-8 220 GPC) manufactured by Tosoh Co., Ltd. The molecular weight was calculated by polystyrene conversion. The polymerizable polymer B containing a cyano group was used. The weight average molecular weight is 23,000.

聚合物B -53- 201132795 〔實施例1〕 〔基板之製作〕 在玻璃環氧基板上，進行作爲電絕緣層之味之素Fine Techno公司製之環氧系絕緣膜GX-13(膜厚40 μιη)之加 熱、加壓，使用真空積層機，依照以0.5MPa之壓力、100°C 至1 1 0 °C之條件而接著後獲得基材。 接著，在基材之上，利用旋轉塗布法而成爲厚度3微 米的方式來塗布含有下列組成之聚合起始劑的絕緣性組成 物，於30°C放置1小時而去除溶劑後，於140°C乾燥30分 鐘而形成聚合起始層（絕緣性之聚合起始層）。 (含有聚合起始劑之絕緣性組成物） —邊攪拌且一邊使20質量份之雙酚A型環氧樹脂（環 氧當量 185、油化 Shell Epoxy(股）製 Epicoat 828 )、45 質 量份之甲酚酚醛型環氧樹脂（環氧當量215、大日本油墨化 學工業股份有限公司製EpiclonN-673)、30質量份之酚酚 醛樹脂（酚性羥基當量105、大曰本油墨化學工業股份有限 公司製Phenolite)加熱溶解於20份之乙基二甘醇醋酸酯 及2 0份之溶劑石腦油中’冷卻直到室溫後’於其中添加 3〇質量份之該Epicoat 8 2 8與雙酚S所構成的苯氧基樹脂 之環己酮蠟（油化 Shell Epoxy 股份有限公司製 YL6747H30、不揮發成分30質量％、重量平均分子量 47〇00)、0.8質量份之2-苯基_4,5-雙（羥甲基）咪唑、2質量 份之微粉碎二氧化矽、0.5質量份之矽系消泡劑，進一步添 -54- 201132795 加1 〇份之利用下列方法所合成的聚合起始聚合物p，獲得 含有聚合起始劑之絕緣性組成物。 (聚合起始聚合物p之合成） 於3 00 ml之三口燒瓶中，加入30 g之丙二醇單甲基 醚（MFG)後加熱至75度。於其中，將8.1 g之溴化〔2-(丙 烯醯氧）乙基〕（4-苯甲醯苄基）二甲基銨、9.9g之甲基丙烯 酸-2-羥乙酯、13.5 g之甲基丙烯酸異丙酯、0.43 g之二甲 基-2,2’-偶氮二（2-甲基丙酸酯）、30g之MFG的溶液，花費 2.5小時而滴下。其後，將反應溫度上升至80t，進一步使 其反應2小時，獲得具有聚合起始基之聚合物P。 形成如上述之聚合起始層後，於180°C實施30分鐘硬 化處理。藉此，獲得基板A1。此基板A1之表面凹凸（Rz) 爲 0 · 2 μιη。 〔樹脂層之形成〕 (塗布溶液之調製） 攪拌混合1 0.5質量份之在該合成例1所獲得之聚合物 A、73.3質量份之丙酮、33.9質量份之甲醇及4.8質量份之 N，N-二甲基乙醯胺而調製塗布溶液。 (接枝聚合物之生成） 在該基板A1之聚合起始層上，成爲厚度1 μιη的方式 來利用旋轉塗布法而塗布所調製的塗布溶液，在80°C乾燥 3〇分鐘後，使用三永電機製之 UV曝光機（型號： UVF-520S' 燈·· UXM-501MD)，利用 1.5mW/cm2 之照射功 -55- 201132795 率（Ushio電機製紫外線累積光量計UIT150-受光感測器 -U V D - S 2 5 4進行照射功率測定），使其照射6 6 0秒鐘而使接 枝聚合物生成於整面基板A1之聚合起始層。於此，累積曝 光量爲990 mJ。 其後，於攪拌的狀態之丙酮中，浸漬生成有接枝聚合 物之基板5分鐘，接著，使用蒸餾水而洗淨。 藉此，獲得具有樹脂層之基板A。 (樹脂層之物性測定） •於25°C-5 0%相對濕度環境下之飽和吸水率：〗.2質量％ .於25°C-50%相對濕度環境下，滴下蒸餾水5//L，15 秒鐘靜置後之表面接觸角：7 0.3度 〔鏟敷觸媒之賦予〕 於將0.25 %之醋酸鈀溶解於硝酸/二乙醇二乙基醚/水 = 1/2/2(重量比）之溶液的鍍敷觸媒液中，浸漬具有樹脂層之 基板A 3 0分鐘。 〔前處理液之賦予〕 調整40質量％之醚系溶劑的二乙醇二乙基醚水溶液， 將此水溶液作爲前處理液（1 )，於2 5 °C、浸漬由賦予該鍍敷 觸媒而成之基板A5分鐘後，藉由水洗而去除多餘的前處理 液，進行下一個步驟。 〔無電鍍敷及鑛敷膜析出性之評估〕 進行如上述方式而賦予鍍敷觸媒，對於具有賦予前處 理液之樹脂層的基板A，使用下列組成之無電鍍敷浴，進 -56 - 201132795 行無電鍍敷。 此時’對於賦予觸媒、實施鍍敷前處理方法之5 cm正 方形基板A2 ’實施無電鍍敷，測定基板被100 %銅所被覆 爲止之時間。於實施例1中，利用2 5分鐘完成被覆。 還有於此’最多直到60分鐘實施無電鍍敷，60分鐘 結束時’未整面被覆之情形，藉由以下之方法而測定60分 鐘無電鍍敷結束時之銅被覆率。 <金屬被覆率之測定方法> 即使進行60分鐘之無電鍍敷處理，也未整面被覆之情 形，利用縱橫5 mm正方形棋盤格子而將5 cm見方的基板 分割成1 〇〇個區塊，以目視觀察各自的區劃而判定銅是否 析出於此，即使於區劃內之一部分具有未析出的部分之情 形，判斷爲未析出，數出其棋盤格子，從棋盤格子之數目 而算出被覆率。 所形成的無電鍍敷膜之厚度爲0.5 μπι。 (無電鍍敷浴之組成·上村工業（股）製Thrucup PGT) 蒸餾水 約6 0容量％ PGT-A 9.0 容量 ％ P G T - B 6.0 容量 ％ PGT-C 3.5 容量 ％ 甲醛水溶液* 2.3容量％ 最後’以全部量成爲1 00容量％的方式來利用蒸餾水 而調整液面。 -57· 201132795 *此處，所用之甲醛水係和光純藥工業（股）製之甲醛水 溶液（特級）。 利用氫氧化鈉及硫酸而將以上組成的鍍敷液之pH調 整成 12.6(26 t)。 〔電鍍〕 接著，將無電鍍敷膜作爲供電層，使用下列組成之銅 電鍍浴，以3 A/dm2之條件下，進行30分鐘之電鍍。所表 示的銅電鍍膜之厚度爲18 μπι。 (電鍍浴之組成） •硫酸銅•五水合物 38g •硫酸 95 gPolymer B-53-201132795 [Example 1] [Production of substrate] On the glass epoxy substrate, an epoxy-based insulating film GX-13 (film thickness 40) manufactured by Fine Techno Co., Ltd., which is an electrically insulating layer, was used. The substrate was heated and pressurized, and a substrate was obtained by using a vacuum laminator under the conditions of a pressure of 0.5 MPa and a temperature of 100 ° C to 110 ° C. Next, an insulating composition containing a polymerization initiator having the following composition was applied onto the substrate by a spin coating method to a thickness of 3 μm, and the mixture was allowed to stand at 30 ° C for 1 hour to remove the solvent, and then at 140 °. C was dried for 30 minutes to form a polymerization starting layer (initial polymerization starting layer). (Insulating composition containing a polymerization initiator) - 20 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 185, oil-coated Shell Epoxy Epicoat 828), 45 parts by mass while stirring Cresol novolac type epoxy resin (epoxy equivalent 215, Epiclon N-673 manufactured by Dainippon Ink and Chemicals Co., Ltd.), 30 parts by mass of phenolic phenolic resin (phenolic hydroxyl equivalent of 105, Otsuka ink chemical industry limited stock) Phenolite manufactured by the company is heated and dissolved in 20 parts of ethyl diglycol acetate and 20 parts of solvent naphtha. After cooling to room temperature, 3 parts by mass of the Epicoat 8 2 8 and bisphenol are added thereto. a cyclohexanone wax of phenoxy resin composed of S (YL6747H30 manufactured by Oily Shell Epoxy Co., Ltd., 30% by mass of a nonvolatile matter, a weight average molecular weight of 47〇00), and 0.8 parts by mass of 2-phenyl-4. 5-bis(hydroxymethyl)imidazole, 2 parts by mass of finely divided ceria, 0.5 parts by mass of an antimony defoamer, further added -54-201132795 plus 1 part by weight of the polymerization starting by the following method Polymer p, obtained with a polymerization initiator Edges of the composition. (Synthesis of polymerization starting polymer p) In a 300 ml three-necked flask, 30 g of propylene glycol monomethyl ether (MFG) was added and heated to 75 °C. Among them, 8.1 g of brominated [2-(propenyloxy)ethyl](4-benzylidenebenzyl)dimethylammonium, 9.9 g of 2-hydroxyethyl methacrylate, 13.5 g A solution of isopropyl methacrylate, 0.43 g of dimethyl-2,2'-azobis(2-methylpropionate), and 30 g of MFG was dropped over 2.5 hours. Thereafter, the reaction temperature was raised to 80 t, and further reacted for 2 hours to obtain a polymer P having a polymerization starting group. After forming the polymerization starting layer as described above, it was subjected to a hardening treatment at 180 ° C for 30 minutes. Thereby, the substrate A1 is obtained. The surface unevenness (Rz) of the substrate A1 was 0 · 2 μmη. [Formation of Resin Layer] (Preparation of Coating Solution) 1 part by mass of the polymer A obtained in the synthesis example 1, 73.3 parts by mass of acetone, 33.9 parts by mass of methanol, and 4.8 parts by mass of N, N were stirred and mixed. - Dimethylacetamide to prepare a coating solution. (Formation of a graft polymer) The prepared coating solution was applied by a spin coating method to a thickness of 1 μm on the polymerization starting layer of the substrate A1, and dried at 80 ° C for 3 minutes, and then used. UV exposure machine for Yongdeng mechanism (Model: UVF-520S' lamp · UXM-501MD), using 1.5mW/cm2 of illumination work -55- 201132795 rate (Ushio electromechanical ultraviolet cumulative light meter UIT150 - light sensor - The UVD-S 2 5 4 was subjected to irradiation power measurement), and the graft polymer was formed for 6 60 seconds to form a graft polymer on the polymerization starting layer of the entire surface substrate A1. Here, the cumulative exposure is 990 mJ. Thereafter, the substrate on which the graft polymer was formed was immersed in acetone in a stirred state for 5 minutes, and then washed with distilled water. Thereby, the substrate A having the resin layer was obtained. (Measurement of physical properties of resin layer) • Saturated water absorption rate in the environment of 25 ° C - 5 0 % relative humidity: 〖. 2 mass %. In the environment of 25 ° C - 50% relative humidity, drip distilled water 5 / / L, Surface contact angle after standing for 15 seconds: 7 0.3 ° [giving of shovel catalyst] Dissolving 0.25% palladium acetate in nitric acid / diethanol diethyl ether / water = 1/2 / 2 (weight ratio) In the plating catalyst solution of the solution, the substrate A having the resin layer was immersed for 30 minutes. [Improvement of pretreatment liquid] A 40% by mass aqueous solution of an ethereal solvent of diethanol diethyl ether was adjusted, and this aqueous solution was used as a pretreatment liquid (1), and impregnation was carried out at 25 ° C to impart the plating catalyst. After 5 minutes from the substrate A, the excess pretreatment liquid was removed by washing with water, and the next step was carried out. [Evaluation of Electroless Plating and Mineral Film Precipitability] The plating catalyst was applied as described above, and the substrate A having the resin layer to which the pretreatment liquid was applied was subjected to an electroless plating bath of the following composition. 201132795 Lines are electroless. At this time, electroless plating was applied to the 5 cm square substrate A2' to which the catalyst was applied and the pre-plating treatment method was applied, and the time until the substrate was covered with 100% copper was measured. In Example 1, the coating was completed in 25 minutes. Further, in the case where electroless plating was carried out up to 60 minutes, and the entire surface was covered at the end of 60 minutes, the copper coverage at the end of the electroless plating for 60 minutes was measured by the following method. <Method for Measuring Metal Coverage Rate> Even if the surface is not coated with the electroless plating treatment for 60 minutes, the substrate of 5 cm square is divided into 1 block by the vertical and horizontal 5 mm square checkerboard grid. By visually observing the respective divisions, it was determined whether or not copper was precipitated. Even if one of the divisions had an unexposed portion, it was judged that it was not precipitated, the checkerboard grid was counted, and the coverage ratio was calculated from the number of checkerboard grids. The thickness of the formed electroless plating film was 0.5 μm. (Composition of electroless plating bath · Thrucup PGT made by Uemura Industrial Co., Ltd.) Distilled water approximately 60% by volume PGT-A 9.0 Capacity % PGT - B 6.0 Capacity % PGT-C 3.5 Capacity % Formaldehyde solution * 2.3% by volume Last ' The amount of the whole amount was changed to 100% by volume, and the liquid level was adjusted by using distilled water. -57· 201132795 *In this case, the formaldehyde water system and the formaldehyde water solution (special grade) made by Wako Pure Chemical Industries Co., Ltd. are used. The pH of the plating solution of the above composition was adjusted to 12.6 (26 t) using sodium hydroxide and sulfuric acid. [Electroplating] Next, an electroless plating film was used as a power supply layer, and plating was performed for 30 minutes under the conditions of 3 A/dm 2 using a copper plating bath having the following composition. The copper plating film shown has a thickness of 18 μm. (Composition of electroplating bath) • Copper sulfate • Pentahydrate 38g • Sulfuric acid 95 g

•鹽酸 1 mL• Hydrochloric acid 1 mL

•Copperglim PCM(Meltex(股）製） 3 mL •水 5 0 0 g (緊貼性評估） 對於所獲得之鍍敷膜，使用拉伸試驗機（島津製作所 (股）製、Autograph AGS-])，針對5 mm寬度，以拉伸強度 10 mm/min，進行90°剝離強度之測定後，爲0.7 kN/mm。 〔金屬圖案之形成、焊錫光阻之貼附及絕緣信賴性試驗〕 對於電鍍後之基板進行1 8 0°C /1小時之熱處理後，使甩 真空積層機（名機製作所（股）製：MVLP-600)，於該基板之 表面上以7〇°C、0.2 MPa積層乾光阻膜（日立化成（股）製： RY33 15、膜厚15 μιη)。接著，使能夠形成JPCA-ET01所 -58- 201132795 定的 L/S = 75 μιη/75 μιη 之梳子型配線（依據 JPCA-BU01-2007、圖案FB)之玻璃遮罩緊貼於積層有乾光 阻膜之基板，使用中心波長405 nm之曝光機而將70 mJ之 光能量照射光阻。 以0.2 MPa之噴壓而將l%Na2C03水溶液噴附於曝光 後之基板，進行顯像。其後，進行基板之水洗/乾燥，在銅 鍍敷膜上，形成相減法用之光阻圖案。 藉由在40°C，將形成光阻圖案之基板浸漬於FeCl3/HCl 水溶液（蝕刻液）中而進行蝕刻，除去存在於光阻圖案之非 形成區域的銅鍍敷層。其後，藉由以0.2 MPa之噴壓而將 3 %NaOH水溶液噴附於基板上，膨潤剝離光阻圖案，使用 1 〇 %硫酸水溶液而進行中和處理、進行水洗而獲得上述之 梳子型配線。 進一步以 70°C、0.2 MPa之條件而將焊錫光阻 (PFR8 00;太陽墨水製造（股）製）真空積層於梳子型配線 上，使用中心波長3 65 nm之曝光機而照射420 mJ之光能 量。此時，關於其後之絕緣信賴性試驗中所賦予焊錫的部 分，使用遮光膠帶而作成遮罩。接著，對基板實施80 °C/10 分鐘之加熱處理後，以0.2 MPa之噴壓而將1 %之Na2C03 水溶液噴附於基板表面，進行顯像、水洗、乾燥。其後， 再度使用中心波長3 65 nm之曝光機而將1 000 mJ之光能量 對基板進行照射。最後，進行150°C/lhr之加熱處理。獲得 用以測定被焊錫光阻所被覆之線間絕緣信賴性的梳子形配 -59- 201132795 線（金屬圖案材料）。 對於此梳子形配線基板，根據JPCA規格印刷配線板 環境試驗方法JPCA-ET01(通則）及ET07(高溫/高濕/正常不 飽和加壓水蒸氣試驗）而進行絕緣信賴性試驗。使用ESPEC 製 HAST 試驗機（AMI-150S-25(EHS-211-MD))，以 13 0°C-85%相對濕度（不飽和）、外加電壓20V而進行200小 時試驗，觀察試驗槽內絕緣電阻（Ω)。其結果，槽內絕緣電 阻爲1 〇6以上，絕緣性並無問題。 〔實施例2至1 2〕 除了將在實施例1所用之前處理液（1)變更爲下表1記 載的前處理液（2)至前處理液（1 2)之外，進行與實施例1同 樣地形成表面金屬膜材料。與實施例1同樣地評估所獲得 之金屬膜材料。將結果顯示於下表2。 〔比較例1〕 除了不利用在實施例1所用之前處理液（1)進行前處理 之外，進行與實施例1同樣地形成表面金屬膜材料。與實 施例1同樣地評估所獲得之金屬膜材料。將結果顯示於下 表2。 -60- 201132795 【表1】 溶劑 溶劑濃度 (質量％) 金屬鹽 金屬鹽濃度 (質量％) 前處理液（1) 二乙二醇二乙基醚 40 — — 前處理液(2) 30 — — 前處理液(3) 30 硫酸銅· 5水合物 1 前處理液(4) 醋酸-2-(2-乙氧基 乙氧基）乙酯 40 — — 前處理液(5) 30 — — 前處理液(6) 30 硫酸銅· 5水合物 1 前處理液(7) 产丁內酯 40 — — 前處理液（8) 30 — — 前處理液(9) 30 硫酸銅· 5水合物 1 前處理液（10) 4-羥基-4-甲基-2-戊酮 40 — — 前處理液（11) 30 — — 前處理液（12) 30 硫酸銅· 5水合物 1 【表2】 基板 評估結果 無電鍍敷膜 90°c剝離試 驗緊貼力 (kN/m) 絕緣信賴性 絕緣電阻 (Ω) 前處理液 100%金屬 被覆時間 (分鐘） 金屬被 覆率(％) 實施例1 處理液01 15 100 0.75 3.9xl06 實施例2 處理液02 20 100 0.72 2.7xl06 實施例3 處理液03 10 100 0.73 2.6χ106 實施例4 處理液04 15 100 0.75 2.8xl06 實施例5 處理液05 20 100 0.71 2.6xl06 實施例6 處理液06 10 100 0.72 2.5χ106 實施例7 基板A 處理液07 15 100 0.74 2.8xl06 實施例8 處理液08 20 100 0.73 2.8χ106 實施例9 處理液09 10 100 0.73 2.6χ106 實施例10 處理液10 20 100 0.7 2.4xl06 實施例11 處理液11 15 100 0.71 2.5xl06 實施例12 處理液12 10 100 0.73 2.0xl06 比較例1 4τττ. m 30 100 0.7 2.7xl06 -61- 201132795 由該表2之結果，得知藉由進行本發明 方法，所用之有機溶劑中任一種，均勻且效 疏水性之基板也具有優異的緊貼性之金屬膜 在前處理液中更含有金屬鹽而發現改善之效 〔實施例1 3〕 使用在實施例1所製作的形成有聚合 A1，進行如下方式而製作表面金屬膜材料。 (塗布溶液之調整） 混合攪拌在合成例2所獲得之聚合物B 異丙醇：.73.3質量份、甲醇：33.9質量份' 乙醯胺4.8質量份，調製塗布溶液。 (接枝聚合物之生成） 利用旋轉塗布器，使厚度成爲Ιμπι的方 的塗布溶液，藉由旋轉塗布法而塗布於該基电 始層上，在80 °C乾燥5分鐘後，使用三永電 光機（型號：UVF-502S、燈：UXM-501MD)， 之照射功率（使用Ushio電機製紫外線累積货 受光感測器UVD-S254測定照射功率），使; 鐘，使接枝聚合物生成於基板A1之聚合起免 此，累積曝光量爲990 mJ。 其後，使生成有接枝聚合物之基板於擾 中浸漬5分鐘，接著，利用蒸餾水洗淨。 藉此，獲得具有聚合物層之基板B。 之鍍敷前處理 率佳地形成對 。另外，藉由 果。 起始層之基板 :7.9質量份、 及N，N-二甲基 式來將所調製 5 A1之聚合起 :機製之UV曝 以 1 .5 mW/cm2 5 量計 U IT 1 5 0 -其照射6 0 0秒 3層的整面。於 拌狀態之甲醇 -62- 201132795 (聚合物層之物性測定） •於2 5 °C - 5 〇 %相對濕度環境下之飽和吸水率：0.8質量％ •於25°C-50%相對濕度環境下，滴下蒸餾水5//L, 15 秒鐘靜置後之表面接觸角：83.9度 接著，對具有此聚合物層之基板B，利用與實施例1 同樣之方法，進行〔鍍敷觸媒之賦予〕、〔前處理液之賦 予〕、〔無電鍍敷〕、及〔電鍍〕，同樣地進行評估。將 結果顯不於下表3。 〔實施例1 4至2 4〕 除了將在實施例14所使用的前處理液（1)取代成該表i 記載的前處理液（2)至前處理液（12)之外，進行與實施例14 同樣的方式來形成表面金屬膜材料。與實施例1同樣地評 估所獲得之金屬膜材料。將結果顯示於下表3。 〔比較例' 2〕 除了未進行藉由在實施例14所使用的前處理液（1)所 造成的前處理之外’進行相同於實施例14的方式而形成表 ® 材·料* °與實施例1同樣地評估所獲得之金屬膜材 料。將結果顯示於下表3。 -63- 201132795 【表3】 基板 評估結果 無電鍍敷膜 90°C剝離 試驗 緊貼力 (kN/m) 絕緣信 賴性絕 緣電阻 (Ω) 前處理液 100%金屬被 覆時間 (分鐘） 金屬被覆 率(％) 實施例13 處理液01 40 100 0.72 3.4xl〇7 實施例14 處理液02 60 100 0.70 2.5xl〇7 實施例15 處理液03 30 100 0.71 2.1M07 實施例16 處理液04 50 100 0.70 2.5xl07 實施例Π 處理液05 60 90 0.62 2.1χ1〇7 實施例18 處理液06 45 100 0.71 2.〇xl〇7 實施例19 基板B 處理液07 60 100 0.72 3.0χ107 實施例20 處理液08 60 75 0.54 2.2χ107 實施例21 處理液09 50 100 0.73 2.〇χΙ〇7 實施例22 處理液10 55 100 0.71 3.0χ107 實施例23 處理液11 60 80 0.82 2.4xl07 實施例24 處理液12 40 100 0.72 2.2χ1〇7 比較例2 無 60 25 0.32 2.5xl〇7 由該表3之結果，得知藉由進行本發明之鍍敷前處理 方法，與用於前處理液之有機溶劑的種類無關，無不均勻 且效率佳地形成對疏水性之基板也具有優異的緊貼性之金 屬膜。再者，也得知藉由濃度之提高、金屬鹽之添加而改 善本發明之效果。 另外，由表2與表3之對比，得知使用具有優異的更 疏水性的基板之情形下，本發明之鍍敷前處理方法之效果 將顯著。 【圖式簡單說明】 【主要元件符號說明】 ^ffF 〇 -64-• Copperglim PCM (Meltex) 3 mL • Water 500 g (Adhesive evaluation) For the obtained plating film, a tensile tester (Shimadzu Corporation, Autograph AGS-] was used. For a 5 mm width, the tensile strength was 10 mm/min, and after measuring 90° peel strength, it was 0.7 kN/mm. [Formation of metal pattern, solder resist adhesion, and insulation reliability test] After the electroplated substrate was subjected to heat treatment at 180 ° C / 1 hour, the 积 vacuum laminator (Made Machine Manufacturing Co., Ltd.: MVLP-600), a dry photoresist film (made by Hitachi Chemical Co., Ltd.: RY33 15 and a film thickness of 15 μm) was deposited on the surface of the substrate at 7 ° C and 0.2 MPa. Next, a glass mask capable of forming a comb-type wiring (according to JPCA-BU01-2007, pattern FB) of L/S = 75 μm/75 μm defined by JPCA-ET01-58-201132795 is adhered to the laminated dry light. The substrate of the resist film irradiated the light with a light energy of 70 mJ using an exposure machine with a center wavelength of 405 nm. The 1% Na2C03 aqueous solution was sprayed onto the exposed substrate at a spray pressure of 0.2 MPa to perform development. Thereafter, the substrate was washed with water/dried, and a photoresist pattern for the subtractive method was formed on the copper plating film. The substrate on which the photoresist pattern was formed was immersed in an aqueous FeCl3/HCl solution (etching solution) at 40 ° C to perform etching to remove the copper plating layer existing in the non-formation region of the photoresist pattern. Thereafter, a 3% aqueous solution of NaOH was sprayed onto the substrate by a spray pressure of 0.2 MPa, and the resist pattern was swollen and peeled off, and a neutralization treatment was carried out using a 1% by weight aqueous sulfuric acid solution, followed by washing with water to obtain the comb-type wiring described above. . Furthermore, solder photoresist (PFR8 00; manufactured by Sun Ink Co., Ltd.) was vacuum-laminated on the comb-type wiring at 70 ° C and 0.2 MPa, and the light was irradiated at 420 mJ using an exposure machine with a center wavelength of 3 65 nm. energy. At this time, the portion to which the solder was applied in the subsequent insulation reliability test was formed into a mask using a light-shielding tape. Next, the substrate was subjected to heat treatment at 80 ° C for 10 minutes, and then a 1% Na 2 CO 3 aqueous solution was sprayed onto the surface of the substrate at a spray pressure of 0.2 MPa, and developed, washed with water, and dried. Thereafter, the substrate was irradiated with an optical energy of 1 000 mJ using an exposure machine having a center wavelength of 3 65 nm. Finally, heat treatment at 150 ° C / lhr was carried out. A comb-shaped wire (metal pattern material) for measuring the reliability of the insulation between the wires covered by the solder resist was obtained. This comb-shaped wiring board was subjected to an insulation reliability test in accordance with JPCA specifications printed wiring board environmental test method JPCA-ET01 (General Rules) and ET07 (high temperature/high humidity/normal unsaturated pressurized water vapor test). Use the ESPEC HAST test machine (AMI-150S-25 (EHS-211-MD)) to conduct a 200-hour test at 13 0 ° C - 85% relative humidity (unsaturated) and an applied voltage of 20 V. Observe the insulation in the test cell. Resistance (Ω). As a result, the insulation resistance in the tank is 1 〇 6 or more, and there is no problem in insulation. [Examples 2 to 2] Except that the pretreatment liquid (1) used in Example 1 was changed to the pretreatment liquid (2) to the pretreatment liquid (1 2) described in Table 1 below, and Example 1 was carried out. The surface metal film material is formed in the same manner. The obtained metal film material was evaluated in the same manner as in Example 1. The results are shown in Table 2 below. [Comparative Example 1] A surface metal film material was formed in the same manner as in Example 1 except that the pretreatment was carried out without using the treatment liquid (1) used in Example 1. The obtained metal film material was evaluated in the same manner as in Example 1. The results are shown in Table 2 below. -60- 201132795 [Table 1] Solvent solvent concentration (% by mass) Metal salt metal salt concentration (% by mass) Pretreatment liquid (1) Diethylene glycol diethyl ether 40 — — Pretreatment liquid (2) 30 — — Pretreatment liquid (3) 30 Copper sulfate · 5 hydrate 1 Pretreatment liquid (4) Acetic acid 2-(2-ethoxyethoxy)ethyl ester 40 — — Pretreatment liquid (5) 30 — — Pretreatment Liquid (6) 30 copper sulfate · 5 hydrate 1 pretreatment liquid (7) butyrolactone 40 — — pretreatment liquid (8) 30 — — pretreatment liquid (9) 30 copper sulfate · 5 hydrate 1 pretreatment Liquid (10) 4-hydroxy-4-methyl-2-pentanone 40 — — pretreatment liquid (11) 30 — — pretreatment liquid (12) 30 copper sulfate · 5 hydrate 1 [Table 2] Substrate evaluation results Electroless plating film 90°c peel test adhesion force (kN/m) Insulation reliability insulation resistance (Ω) Pretreatment liquid 100% metal coating time (minutes) Metal coverage rate (%) Example 1 Treatment liquid 01 15 100 0.75 3.9xl06 Example 2 Treatment liquid 02 20 100 0.72 2.7xl06 Example 3 Treatment liquid 03 10 100 0.73 2.6χ106 Example 4 Treatment liquid 04 15 100 0.75 2.8xl06 Implementation 5 Treatment liquid 05 20 100 0.71 2.6xl06 Example 6 Treatment liquid 06 10 100 0.72 2.5χ106 Example 7 Substrate A Treatment liquid 07 15 100 0.74 2.8xl06 Example 8 Treatment liquid 08 20 100 0.73 2.8χ106 Example 9 Treatment liquid 09 10 100 0.73 2.6χ106 Example 10 Treatment liquid 10 20 100 0.7 2.4xl06 Example 11 Treatment liquid 11 15 100 0.71 2.5xl06 Example 12 Treatment liquid 12 10 100 0.73 2.0xl06 Comparative example 1 4τττ. m 30 100 0.7 2.7xl06 - 61-201132795 From the results of Table 2, it is found that any of the organic solvents used by carrying out the method of the present invention, the uniform and hydrophobic substrate also has excellent adhesion to the metal film in the pretreatment liquid. The effect of improvement was found by containing a metal salt [Example 13] Using the formation of the polymerization A1 produced in Example 1, the surface metal film material was produced as follows. (Adjustment of Coating Solution) Polymer B isopropyl alcohol obtained in Synthesis Example 2: 7.33 parts by mass, methanol: 33.9 parts by mass of 4.8 parts by mass of acetamidine was mixed and stirred to prepare a coating solution. (Formation of Graft Polymer) A coating solution having a thickness of Ιμm was applied to the base electric layer by a spin coating method using a spin coater, and dried at 80 ° C for 5 minutes, and then used for three times. Electro-optical machine (model: UVF-502S, lamp: UXM-501MD), the irradiation power (Using Ushio electro-mechanical ultraviolet accumulating light sensor UVD-S254 to measure the irradiation power), so that the graft polymer is formed The polymerization of the substrate A1 was avoided, and the cumulative exposure amount was 990 mJ. Thereafter, the substrate on which the graft polymer was formed was immersed for 5 minutes, and then washed with distilled water. Thereby, the substrate B having the polymer layer is obtained. The pre-plating treatment rate is well formed. In addition, by virtue. The substrate of the starting layer: 7.9 parts by mass, and N,N-dimethyl form to polymerize the prepared 5 A1: the mechanism of UV exposure is 1.5 mW/cm 2 5 U IT 1 5 0 - Irradiate the entire surface of the 3 layers of 600 seconds. Methanol in mixed state-62- 201132795 (Measurement of physical properties of polymer layer) • Saturated water absorption at 25 °C - 5 〇% relative humidity: 0.8% by mass • At 25 °C - 50% relative humidity Next, the distilled water was dropped 5//L, and the surface contact angle after standing for 15 seconds was 83.9 degrees. Then, the substrate B having the polymer layer was subjected to the same method as in Example 1 (plating catalyst) The evaluation, the [application of the pretreatment liquid], the [electroless plating], and the [electroplating] were carried out in the same manner. The results are not shown in Table 3 below. [Examples 1 to 4 4] Except that the pretreatment liquid (1) used in Example 14 was replaced with the pretreatment liquid (2) to the pretreatment liquid (12) described in Table i, Example 14 A surface metal film material was formed in the same manner. The obtained metal film material was evaluated in the same manner as in Example 1. The results are shown in Table 3 below. [Comparative Example 2 2] The same procedure as in Example 14 was carried out except that the pretreatment by the pretreatment liquid (1) used in Example 14 was not carried out to form the surface material *° and Example 1 The obtained metal film material was evaluated in the same manner. The results are shown in Table 3 below. -63- 201132795 [Table 3] Substrate evaluation results Electroless plating film 90°C peeling test adhesion force (kN/m) Insulation reliability insulation resistance (Ω) Pretreatment liquid 100% metal coating time (minutes) Metal coverage rate (%) Example 13 Treatment liquid 01 40 100 0.72 3.4xl〇7 Example 14 Treatment liquid 02 60 100 0.70 2.5xl〇7 Example 15 Treatment liquid 03 30 100 0.71 2.1M07 Example 16 Treatment liquid 04 50 100 0.70 2.5 Xl07 Example Π Treatment liquid 05 60 90 0.62 2.1χ1〇7 Example 18 Treatment liquid 06 45 100 0.71 2. 〇 xl 〇 7 Example 19 Substrate B Treatment liquid 07 60 100 0.72 3.0 χ 107 Example 20 Treatment liquid 08 60 75 0.54 2.2χ107 Example 21 Treatment liquid 09 50 100 0.73 2.〇χΙ〇7 Example 22 Treatment liquid 10 55 100 0.71 3.0χ107 Example 23 Treatment liquid 11 60 80 0.82 2.4×l07 Example 24 Treatment liquid 12 40 100 0.72 2.2 Χ1〇7 Comparative Example 2 No 60 25 0.32 2.5xl〇7 From the results of Table 3, it is found that the pre-plating treatment method of the present invention is independent of the type of the organic solvent used for the pretreatment liquid, Uniform and efficient formation of hydrophobicity It has excellent substrate adhesion of the metal film. Further, it has been found that the effect of the present invention is improved by an increase in concentration and addition of a metal salt. Further, from the comparison between Table 2 and Table 3, it is known that the effect of the pre-plating treatment method of the present invention is remarkable in the case of using a substrate having excellent more hydrophobicity. [Simple description of the diagram] [Explanation of main component symbols] ^ffF 〇 -64-

Claims (1)

201132795 七、申請專利範圍·· 1. 一種鍍敷前處理方法，其係依序實施下列步驟： 步驟（A):在基板上形成含有包含以下式（1)所代表 之單位與以下式（2)所代表之單位的共聚物之樹脂層；步 驟（B):賦予鍍敷觸媒或其先質；及在該步驟（B)之前或 之後實施步驟（C):將包含由醚系溶劑、醇系溶劑、酯系 溶劑與酮系溶劑所構成之族群中所選出的至少一種有 機溶劑的前處理液賦予該樹脂層中；201132795 VII. Patent Application Range·· 1. A pre-plating treatment method, which performs the following steps in sequence: Step (A): forming a unit on the substrate containing the formula represented by the following formula (1) and the following formula (2) a resin layer of a copolymer of the unit represented; a step (B): imparting a plating catalyst or a precursor thereof; and performing the step (C) before or after the step (B): comprising an ether solvent, a pretreatment liquid of at least one organic solvent selected from the group consisting of an alcohol solvent, an ester solvent and a ketone solvent is imparted to the resin layer; (上式（1)與式（2)中，R1至R5係表示各自獨立之氫原子' 或取代或者未取代之烷基，X、Y與Z係表示單鍵、或 取代或者未取代之二價有機基、酯基 '酿胺基、或醚基， L1係表示取代或者未取代之二價有機基，L2係表示單 鍵、或取代或者未取代之二價有機基）。 2.如申請專利範圍第1項之鍍敷前處理方法，其中該基板 爲具有聚合起始層之基板。 -65- 201132795 3_如申請專利範圍第1或2項之鍍敷前處理方法，其中該 前處理液之有機溶劑含有率爲1質量％以上且5〇質量％ 以下。 4.如申請專利範圍第1或2項之鍍敷前處理方法，其中該 前處理液之有機溶劑至少爲醚系溶劑。 5_如申請專利範圍第1或2項之鍍敷前處理方法，其中該 前處理液更含有與在步驟（B)所賦予的鏟敷觸媒或其先 質不同的金屬鹽。 6.如申請專利範圍第1或2項之鍍敷前處理方法，其中賦 予該前處理液之步驟（C)係於賦予該鑛敷觸媒或其先質 之步驟（B)後所實施。 7·如申請專利範圍第6項之鍍敷前處理方法，其中該前處 理液不含有金屬鹽。 8. 如申請專利範圍第6項之鑛敷前處理方法，其中該前處 理液係含有硫酸銅，該鍍敷觸媒或其先質爲含有鈀。 9. 一種表面金屬膜材料之製作方法，其係具有在實施如申 請專利範圍第1或2項之鍍敷前處理方法後，對該樹脂 層中所賦予的鍍敷觸媒或其先質進行無電鍍敷之步驟 (D)。 10.如申請專利範圍第9項之表面金屬膜材料之製作方法， 其中於進行該無電鎞敷之步驟（D)後，更具有進行電鍍 之步驟（E)。 -66 - 201132795 四、指定代表圖： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件符號簡單說明： 無 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：(In the above formulas (1) and (2), R1 to R5 represent a hydrogen atom which is independent or a substituted or unsubstituted alkyl group, and X, Y and Z represent a single bond, or a substituted or unsubstituted one. The valent organic group, the ester group 'bristylamino group, or the ether group, L1 represents a substituted or unsubstituted divalent organic group, and L2 represents a single bond, or a substituted or unsubstituted divalent organic group). 2. The pre-plating treatment method of claim 1, wherein the substrate is a substrate having a polymerization starting layer. In the pre-plating treatment method of the first or second aspect of the invention, the organic solvent content of the pretreatment liquid is 1% by mass or more and 5% by mass or less. 4. The pre-plating treatment method according to claim 1 or 2, wherein the organic solvent of the pretreatment liquid is at least an ether solvent. 5_ The pre-plating treatment method according to claim 1 or 2, wherein the pretreatment liquid further contains a metal salt different from the shovel catalyst or the precursor imparted in the step (B). 6. The pre-plating treatment method according to claim 1 or 2, wherein the step (C) of imparting the pretreatment liquid is carried out after the step (B) of imparting the mineralization catalyst or its precursor. 7. The pre-plating treatment method of claim 6, wherein the pre-treatment liquid does not contain a metal salt. 8. The pre-mineral treatment method of claim 6, wherein the pre-treatment liquid contains copper sulfate, and the plating catalyst or precursor thereof contains palladium. A method for producing a surface metal film material, which comprises performing a plating pretreatment method according to the first or second aspect of the patent application, the plating catalyst or the precursor thereof imparted in the resin layer. Step (D) of electroless plating. 10. The method for producing a surface metal film material according to claim 9, wherein the step (D) of performing the electroless plating is further performed by the step (E) of performing electroplating. -66 - 201132795 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
TW099145688A 2010-03-31 2010-12-24 Method of plate pretreatment and production method of surface metal film material TW201132795A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI566057B (en) * 2011-10-11 2017-01-11 默克專利有限公司 Method for treating resist pattern and method for producing resist pattern using thereof, and composition for forming cover layer used in the same
CN110493950A (en) * 2019-07-24 2019-11-22 广东东溢新材料科技有限公司 A kind of substrate and preparation process of the flex circuit application on lithium battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI566057B (en) * 2011-10-11 2017-01-11 默克專利有限公司 Method for treating resist pattern and method for producing resist pattern using thereof, and composition for forming cover layer used in the same
CN110493950A (en) * 2019-07-24 2019-11-22 广东东溢新材料科技有限公司 A kind of substrate and preparation process of the flex circuit application on lithium battery

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