TW201242460A - Laminate having metal layer and method for manufacturing the same, and laminate having patterned metal layer and method for manufacturing the same - Google Patents
Laminate having metal layer and method for manufacturing the same, and laminate having patterned metal layer and method for manufacturing the same Download PDFInfo
- Publication number
- TW201242460A TW201242460A TW101110799A TW101110799A TW201242460A TW 201242460 A TW201242460 A TW 201242460A TW 101110799 A TW101110799 A TW 101110799A TW 101110799 A TW101110799 A TW 101110799A TW 201242460 A TW201242460 A TW 201242460A
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- layer
- substrate
- metal film
- laminate
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
- H05K3/387—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive for electroless plating
-
- 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
- C23C18/1603—Process or apparatus coating on selected surface areas
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
-
- 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
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, 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
- C23C18/18—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
-
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4661—Adding a circuit layer by direct wet plating, e.g. electroless plating; insulating materials adapted therefor
Abstract
Description
201242460 4_2pif 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種具有金屬膜的積層體及其製造方 法、以及具有圖案化金屬膜的積層體及其製造方法。 【先前技術】 先前以來，於電子零件或半導體元件中廣泛使用金屬 配線基板，该金屬配線基板是於絕緣性基板的表面上形成 有金屬圖案的配線。 該金屬圖案材料的製作方法主要是使用「減成法」。所 謂該減成法是指以下方法：在形成於基板表面的金屬膜上 设置藉由活性光線的照射而感光的感光層，對該感光層進 行圖像曝光，然後進行顯影而形成抗㈣彳圖像，繼而，對 金屬膜進行蝕刻而形成金屬圖案，最後剝離抗蝕劑。 利用該方法而獲得的金屬圖案是藉由固著效果 (anchoreffect)來表現出基板與金屬圖案（金屬膜）之間 的密著性，上賴著絲是藉由在基板表面設置凹凸而產 生:因此，將所得的金屬圖_作金屬配線時，有以下問 題.由金屬圖案的基板界面部的凹凸引起高頻特性變差。 L夕:對表面進行凹凸化處理’必須利用鉻酸等 巧二；ίΐ仃處理，因此為了獲得與基板的密著性 U金屬圖案，有需要須雜的步驟的問題。 点』問題的方法，已知以下方法:於基板上形 ㈣合物層，賴聚合物層實施鍍 敷對所付的金屬膜進行钕刻（專利文獻υ。根據該方法， 201242460 可於不使基板的表面粗面化的情況下改良基板與金屬膜的 密著性。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2010_248464號公報 本發明者等人對專利文獻1中記載的先前技術進行了 研究，結果發現，有時於所析出的鍍敷膜（金屬膜）上產 生所谓的突粒（n〇dule )。 另一方面，近年來，為了應對電子機器的小型化、高 功能化的要求，而推進印刷配線板中的微細配線的進一步 的高積體化❶因此，若將此種產生了突粒的積層體用於具 有線間/線寬為100 μηι/1〇〇 μΓη以下的微細導體電路的印刷 配線板的導體電路的形成，則容易導致金屬配線間的短路 不良’使配線板的可靠性下降。 【發明内容】 鑒於上述實際情況，本發明的目的在於提供一種突粒 的產生得到抑制的具有金屬膜的積層體的製造方法。201242460 4_2pif VI. [Technical Field] The present invention relates to a laminated body having a metal film, a method for producing the same, and a laminated body having a patterned metal film and a method for producing the same. [Prior Art] A metal wiring board which is a wiring in which a metal pattern is formed on the surface of an insulating substrate has been widely used in electronic parts or semiconductor elements. The metal pattern material is mainly produced by using a "reduction method". The subtractive method refers to a method in which a photosensitive layer which is exposed to light by irradiation of active light is provided on a metal film formed on a surface of a substrate, and the photosensitive layer is subjected to image exposure, and then developed to form an anti-(four) map. For example, the metal film is then etched to form a metal pattern, and finally the resist is stripped. The metal pattern obtained by this method exhibits the adhesion between the substrate and the metal pattern (metal film) by an anchor effect, which is generated by providing irregularities on the surface of the substrate: Therefore, when the obtained metal pattern is used as a metal wiring, there is a problem that the high frequency characteristics are deteriorated by the unevenness of the substrate interface portion of the metal pattern. L: The surface is subjected to the roughening treatment. It is necessary to use chromic acid or the like. Therefore, in order to obtain the adhesion to the substrate, the U metal pattern has a problem that a complicated step is required. In the method of the problem, a method is known in which a (four) layer is formed on a substrate, and a metal film is etched by plating the polymer layer (Patent Document υ. According to the method, 201242460 may not be used. When the surface of the substrate is roughened, the adhesion between the substrate and the metal film is improved. [Prior Art] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-248464. As a result of the investigation of the prior art, it has been found that so-called swells are formed on the deposited plating film (metal film). In recent years, in order to cope with the miniaturization of electronic equipment. Further, high functionalization is required to promote further high-integration of fine wiring in printed wiring boards. Therefore, if such a laminated body in which bumps are generated is used, the inter-line/line width is 100 μηι/1. In the formation of the conductor circuit of the printed wiring board of the fine conductor circuit of 〇〇μΓη or less, the short-circuit defect between the metal wirings is likely to occur, and the reliability of the wiring board is lowered. Circumstances, an object of the present invention is to provide a manufacturing method to produce a projection of particles is suppressed laminate having a metal film.
另外，本發明的目的亦在於提供一種具有圖案化金 膜的積層體的製造方法及具有圖案化金屬膜的積層體，其 使用由上述製造方法所得的積層體。 S 本發明者荨人對上述課題進行了積極研究，結果發 現’使用規定的聚合物形成被織層後，倾繼層與^ 有規定的成分的鹼性水溶液接觸，藉此可解決上述 即’本發明料人魏’藉由以T構成可解決±述課題。 5 201242460 40002pif (Ο —種具有金屬膜的積層體的製造方法，其包含以 下步驟： 被錢敷層形成步驟，使含有聚合物的被鍍敷層形成用 纽成物接觸於基板上後’對基板上的频敷層形成用組成 物賦予能量’於基板上形成被鍍敷層，上述聚合物具有選 自由後述式（X)所表示的基及（甲基)丙烯醯胺基所組成的 組群中的至少一個基及離子性極性基； 驗性水溶液接觸步驟，使含有胺基醇及界面活性劑且 PH值為ι〇〜14的鹼性水溶液與被鍍敷層接觸； 觸媒賦予步驟，於鹼性水溶液接觸步驟後，對被鍍敷 層賦予鍍敷觸媒或其前驅物；以及 鑛敷步驟’對被賦予了鍍敷觸媒或其前驅物的被鍍敷 層進行鍍敷處理，於被鍍敷層上形成金屬膜。 (2) 如（1)所述之具有金屬膜的積層體的製造方法， 其中鹼性水溶液的液溫為60Ϊ以上。 (3) —種具有金屬膜的積層體，其是由如（丨）或（2) 所述之製造方法而獲得。 (4) 一種具有圖案化金屬膜的積層體的製造方法，其 包含以下步驟：將如（3)所述之積層體中的金屬膜蝕刻成 圖案狀，形成圖案化金屬膜。 (5) —種具有圖案化金屬膜的積層體，其是由如 所述之製造方法而獲得。 (6) —種配線基板’其具備如（5)所述之具有圖案 化金屬膜的積層體、及設置於具有圖案化金屬膜的積層體 201242460 fFurther, another object of the present invention is to provide a method for producing a laminate having a patterned gold film and a laminate having a patterned metal film using the laminate obtained by the above production method. The inventors of the present invention have conducted active research on the above-mentioned problems, and as a result, it has been found that 'after forming a woven layer using a predetermined polymer, the stepping layer is brought into contact with an aqueous alkaline solution having a predetermined component, thereby solving the above-mentioned ' The invention of the present invention can be solved by the composition of T. 5 201242460 40002pif (Ο) A method for producing a laminate having a metal film, comprising the steps of: forming a layer by a money layer, and contacting a substrate for forming a layer containing a polymer onto a substrate; The polymer layer forming composition on the substrate is provided with energy to form a layer to be plated on the substrate, and the polymer has a group selected from the group consisting of a group represented by the following formula (X) and a (meth)acrylamide group. At least one group and an ionic polar group in the group; an aqueous contact step of contacting the alkaline aqueous solution containing the amino alcohol and the surfactant and having a pH of ι 〇 14 to be contacted with the layer to be plated; After the alkaline aqueous solution contacting step, the plating catalyst or its precursor is applied to the plated layer; and the mineralizing step 'plating the plated layer to which the plating catalyst or its precursor is imparted (2) The method for producing a laminate having a metal film according to (1), wherein the liquid temperature of the alkaline aqueous solution is 60 Å or more. (3) The metal film is provided Laminar body Or the manufacturing method according to (2). (4) A method for producing a laminate having a patterned metal film, comprising the steps of: etching a metal film in the laminate according to (3) into a pattern (5) A laminate having a patterned metal film obtained by the manufacturing method as described above. (6) A wiring board having the same as described in (5) a laminate having a patterned metal film and a laminate provided with a patterned metal film 201242460 f
Pii 上的絕緣層。 [發明的效果] , 根據本發明’可提供一種突粒的產生得到抑制的且有 金屬膜的積層體的製造方法。 、 另外’根據本發明，亦可提供一種具有圖案化金屬膜 的積層體的製造方法及具有圖案化金屬膜的積層體，其使 用由上述製造方法所得的積層體。 八 【實施方式】 '以下，對本發明的具有金屬膜的積層體及其製造方 ，、以及具有圖案化金屬膜的積層體及其製造方法的合適 實施態樣加以說明。 ^首先，對本發明與先前技術相比較的特徵點進行詳細 說明。本發明的特徵點可列舉以下方面：使用特定的聚合 物形成被鍍敷層，其後使該被鍍敷層與含有規定的成分的 鹼性水溶液接觸。 本發明者等人對先前技術的問題進行了積極研究，結 果發現，於藉由賦予能量而形成被鍍敷層後，殘存於被鍍 敷層中的未硬化部分、或表面的硬化不充分的成分與突粒 的產生有關。更具體而言發現，若被鍍敷層中存在未硬化 刀或表面的硬化不充分的成分，則於被鍍敷層與錢敷液 的接觸時，未硬化部分或分解物流出至鍍敷液中而污染鍍 敷液，結果引起突粒的產生。根據該發現而反覆進行了研 . 究’結果發現’藉由使用含有胺基醇及界面活性劑且顯示 規定的pH值的鹼性水溶液對以規定的聚合物形成的被鍍 201242460 4UUU2pif 敷層進行清洗’可麟所需效果。 ，本發明的具有金屬膜的制體的製造方法包含被鍍敷 層形成步驟、驗性水溶液接觸步驟、觸媒賦 敷步驟4個步驟。 ^ 以下，對各步驟中使用的材料及各步驟的順序加以詳 述。 〈被鍍敷層形成步驟> 被鍍敷層形成步驟為以下步驟：使含有聚合物的被鍍 敷層开y成用組成物接觸於基板上後，對基板上的被鍍敷層 形成用組成物賦予能量，於基板上形成被鍍敷層 ，上述聚 合物具有選自由式⑻所表示的基及（曱基)丙刺胺基所 組成的組群中的至少一個基及離子性極性基。 更具體而言，於該步驟中，如圖丨（A)所示般準備基 板10，如圖1 (B)所示般於基板1〇的上部形成被鍍敷層 12 ° 藉由該步驟而形成的被鍍敷層根據聚合物中所含的離 子性極性基的功能而於後述觸媒賦予步驟中吸附（附著） 鍍敷觸媒或其前驅物。即，被鍍敷層作為鍍敷觸媒或其前 驅物的良好的接受層而發揮功能。另外，式（X)所表示 的基及（甲基）丙烯醯胺基等聚合性基被用於聚合物彼此的 鍵結、或與基板的化學鍵結。結果，形成於被鍍敷層表面 的金屬膜（鍍敷膜）與基板之間表現出優異的密著性。 首先，對該步驟中使用的材料（基板、聚合物、被鍍 敷層形成用組成物等）加以詳述，其後對步驟的順序加以 201242460 , pit 詳述。 (基板） 本务明令所用的基板可使用先前已知的任一種基板， 只要是具有形狀保持性的基板即可。另外，較佳為其表面 ' 具有可與後述聚合物進行化學鍵結的功能。具體而言，基 板自身可藉由能量賦予（例如曝光）而與聚合物形成化學 鍵結，或亦可於基板上設置可藉由能量賦予而與被鍍敷層 形成化學鍵結的中間層（例如後述密著補助層）。 基板的材料並然特別限定，例如可列舉：高分子材料 (例如二乙酸纖維素（cellul〇se diacetate )、三乙酸纖維素 (cellulose triacetate)、丙酸纖維素（cellul〇se pr〇pi〇nate)、 丁酸纖維素（cellulose butyrate)、乙酸纖維素（cellul〇se acetate )、石肖酸纖維素（ceiiui〇se njtrate )、聚對苯二甲酸乙 二酯（polyethylene terephthalate)、聚乙烯（p〇iyethyiene)、 聚苯乙烯（polystyrene )、聚丙烯（polypr〇pylene )、聚乙 烯縮醛（polyvinyl acetal)、聚醯亞胺（p〇lyimide)、環氧 Μ 月a ( epoxy )、雙順丁 細 ^一 酿亞胺樹脂（bismaleinimide resin)、聚苯醚（polyphenylene oxide)、液晶聚合物（liquid crystalline polymer)、聚四氟乙烯（polytetraflu〇r〇ethylene ) 等）、金屬材料（例如金屬合金、金屬含有材料、純金屬或 該些物質的類似物。具體而言為鋁、鋅、銅等的混合物， 合金或該些物質的摻合物）、其他材料（例如紙、層疊有塑 膠的紙）、該些材料的組合或該些材料的類似物等。 另外’本發明的積層體可應用於半導體封裝、各種電 201242460 4_2pif 氣配線基板等。於用於此種用途的情形時，較佳為使用以 下示出的含有絕緣性樹脂的基板，具體而言為包含絕緣性 樹脂的基板（絕緣性基板）、或於表面具有包含絕緣性樹脂-的層（絕緣性樹脂層）的基板（附有絕緣層的基板）。 於獲得包含絕緣性樹脂的基板、包含絕緣性樹脂的層 的情形時，可使用公知的絕緣性樹脂組成物。 關於絕緣性樹脂的具體例’例如可為熱硬化性樹脂亦 可為熱塑性樹脂，另外亦可為該些樹脂的混合物。例如， 熱硬化性樹脂可列舉環氧樹脂（epoxy resin )、紛樹脂 (phenol resin)、聚醯亞胺樹脂（p〇ly imideresin)、聚醋樹 脂（polyester resin )、雙順丁烯二醯亞胺樹脂（bismaleimide resin )、聚烯烴樹脂（p〇ly〇lefin )、異氰酸酯樹脂（is〇cyanate resin )、丙烯腈_ 丁二烯_苯乙烯共聚物 (Acrylonitrile-Butadiene-Styrene » ABS)樹脂等。 環氧樹脂例如可列舉：曱紛盼酸 ( iS〇Cyanate resin )型 環氧樹脂、雙酚A( bisphenol A)環氧樹脂、雙酚F( bisphenol F)型環氧樹脂、苯紛紛搭（phen〇inov〇iac)型環氧樹脂、 烷基苯酚酚醛（alkyl phenol novolac)型環氧樹脂、聯苯酚 F (biphenol F)型環氧樹脂、萘（naphthalene)型環氧樹 脂、二環戊二烯（dicyclopentadiene)型環氧樹脂、酚類與 具有酰性赵基的芳香族酿的縮合物的環氧化物、異三聚氰 酸三縮水甘油酯、脂環式環氧樹脂等。該些環氧樹脂可單 獨使用，亦可併用兩種以上。 熱塑性樹脂例如可列舉：苯氧基樹脂（phen〇xy 201242460 f _____pif resin 聚醚礙（polyethersulfone)、聚碾（p〇lysulf〇ne)、 聚苯颯（polyphenylene sulfone)、聚苯硫醚 sulfide )、聚苯趟（p〇lyphenylether )、聚醚醯亞胺 C polyetherimide )等。 進而，基板亦可於其單面或兩面具有金屬配線。金屬 配線可對基板的表面以圖案狀而形成，亦可於整個面上妒 成。具代表性的金屬配線可列舉：藉由利用钱刻處理的減 成法所形成者、藉由利用電解鍍敷的半加成法所形成者， 亦可使用藉甴任意方法而形成者。 構成金屬配線的材料例如可列舉銅、銀、錫、鈀、金、 鎳、路、鎢、銦、鋅或鎵等。 孟 具有此種金屬配線的基板例如可使用兩面或 π—㈤L——，叫、或使該覆銅： /板9鋼膜成為圖餘而成料，齡基板可 其 板，亦可為剛性基板。 70性基 絕续Γί 村將於表面依序射金屬配線層及絕緣層的 、==:本發明的基板。另外，該情形時，金屬配 /、、，、邑緣層亦可分別交替積層2層以上。 ’亦可於不損及本發明效果的範圍 =加劑。例如可列舉··無機粒 = 玻璃纖維、二氧切粒子、氧 j = Ϊ合雲母1灰石）或魏系化合物（例Si 交聯苯代^黏ΐΓ)、有機填料（例如硬化環氧樹脂、 —來鼠胺树脂、交聯丙烯酸系聚合物等）、塑化Insulation on the Pii. [Effects of the Invention] According to the present invention, a method for producing a laminate having a metal film and suppressing the generation of the spurs can be provided. Further, according to the present invention, a method for producing a laminate having a patterned metal film and a laminate having a patterned metal film using the laminate obtained by the above-described production method can be provided. [Embodiment] Hereinafter, a suitable embodiment of a laminate having a metal film of the present invention, a manufacturer thereof, a laminate having a patterned metal film, and a method for producing the same will be described. ^ First, the feature points of the present invention compared with the prior art will be described in detail. The features of the present invention include the formation of a layer to be plated using a specific polymer, and thereafter contacting the layer to be plated with an aqueous alkaline solution containing a predetermined component. The present inventors have actively studied the problems of the prior art, and as a result, found that the uncured portion remaining in the layer to be plated or the surface is hardened after the plating layer is formed by the application of energy. The composition is related to the production of neurites. More specifically, it has been found that if there is an uncured blade or a hardened component of the surface in the plated layer, the unhardened portion or the decomposition is discharged to the plating solution when the plated layer is in contact with the money solution. In the middle, the plating solution is contaminated, and as a result, the generation of the granules is caused. Based on this finding, research was carried out. It was found that the 201242460 4UUU2pif coating layer formed of a predetermined polymer was formed by using an alkaline aqueous solution containing an amino alcohol and a surfactant and exhibiting a predetermined pH. Clean the effect of 'Kerlin'. The method for producing a body having a metal film of the present invention comprises four steps of a step of forming a plating layer, a step of contacting an aqueous solution, and a step of adding a catalyst. ^ The following is a detailed description of the materials used in each step and the order of each step. <Step of Forming the Deposited Layer> The step of forming the layer to be plated is a step of forming the layer to be plated with the polymer and contacting the substrate with the composition, and then forming the layer to be plated on the substrate. The composition imparts energy to form a plated layer on the substrate, and the polymer has at least one group selected from the group represented by the formula (8) and a group consisting of (fluorenyl) acrylamide groups and an ionic polar group. . More specifically, in this step, the substrate 10 is prepared as shown in FIG. 1A, and a plated layer 12 is formed on the upper portion of the substrate 1A as shown in FIG. 1(B). The formed layer to be plated adsorbs (adheres) the plating catalyst or its precursor in the catalyst application step described later in accordance with the function of the ionic polar group contained in the polymer. That is, the layer to be plated functions as a good receiving layer of the plating catalyst or its precursor. Further, a polymer group such as a group represented by the formula (X) and a (meth)acrylamide group is used for bonding of the polymers or chemical bonding to the substrate. As a result, the metal film (plating film) formed on the surface of the layer to be plated exhibits excellent adhesion to the substrate. First, the materials used in the step (substrate, polymer, composition for forming a layer to be plated, etc.) will be described in detail, and the order of the steps will be described later in 201242460, pit. (Substrate) Any substrate previously known can be used as the substrate used in the present invention, as long as it is a substrate having shape retention. Further, it is preferred that the surface 'has a function of being chemically bonded to a polymer to be described later. Specifically, the substrate itself may be chemically bonded to the polymer by energy imparting (for example, exposure), or an intermediate layer capable of forming a chemical bond with the plated layer by energy imparting may be disposed on the substrate (for example, described later). Closed subsidy layer). The material of the substrate is particularly limited, and examples thereof include a polymer material (for example, cellulose diacetate, cellulose triacetate, and cellulose propionate (cellul〇se pr〇pi〇nate). ), cellulose butyrate, cellulose acetate, ceiiui〇se njtrate, polyethylene terephthalate, polyethylene (p 〇iyethyiene), polystyrene, polypr〇pylene, polyvinyl acetal, p〇lyimide, epoxy a (epoxy), dicis a bismaleinimide resin, a polyphenylene oxide, a liquid crystalline polymer, a polytetrafluorofluorene (polytetrafluoroethylene), a metal material (for example, a metal alloy, A metal-containing material, a pure metal or an analog of such substances, specifically a mixture of aluminum, zinc, copper, etc., an alloy or a blend of the materials, and other materials (for example) Paper, paper laminated with plastic rubber), the combination of these materials or the like, the plurality of like material. Further, the laminate of the present invention can be applied to a semiconductor package, various electric 201242460 4_2pif gas wiring substrates, and the like. When it is used for such a use, it is preferable to use the substrate containing an insulating resin shown below, specifically, a substrate (insulating substrate) containing an insulating resin, or an insulating resin on the surface - A substrate (insulating resin layer) substrate (substrate with an insulating layer). When a substrate containing an insulating resin or a layer containing an insulating resin is obtained, a known insulating resin composition can be used. Specific examples of the insulating resin, for example, may be a thermosetting resin or a thermoplastic resin, or a mixture of these resins. For example, examples of the thermosetting resin include an epoxy resin, a phenol resin, a p〇ly imideresin, a polyester resin, and a bis-butylene oxide. An amine resin (bismaleimide resin), a polyolefin resin (p〇ly〇lefin), an isocyanate resin, an acrylonitrile-Butadiene-Styrene (ABS) resin, or the like. Examples of the epoxy resin include: iS〇Cyanate resin type epoxy resin, bisphenol A epoxy resin, bisphenol F type epoxy resin, and benzene. 〇inov〇iac) epoxy resin, alkyl phenol novolac epoxy resin, biphenol F epoxy resin, naphthalene epoxy resin, dicyclopentadiene (dicyclopentadiene) type epoxy resin, epoxide of an aromatic aromatic condensate having an acyl group, a triglycidyl isocyanurate, an alicyclic epoxy resin, or the like. These epoxy resins may be used singly or in combination of two or more. Examples of the thermoplastic resin include phenoxy resin (phen〇xy 201242460 f _____pif resin polyethersulfone, polysulfene sulfone, polyphenylene sulfone, polyphenylene sulfide sulfide), P〇lyphenylether, polyetherimide C polyetherimide, and the like. Further, the substrate may have metal wiring on one or both sides thereof. The metal wiring may be formed in a pattern on the surface of the substrate or may be formed on the entire surface. A representative metal wiring may be a person formed by a subtractive method using a money engraving method or a semi-additive method by electrolytic plating, and may be formed by any method. Examples of the material constituting the metal wiring include copper, silver, tin, palladium, gold, nickel, road, tungsten, indium, zinc, or gallium. For example, a substrate having such a metal wiring can be formed by using two sides or π-(f) L-, or by making the copper-clad: /-plate 9 steel film into a sheet material, and the age substrate can be a plate or a rigid substrate. . 70-based substrate Γί Village will sequentially emit metal wiring layers and insulating layers on the surface, ==: the substrate of the present invention. Further, in this case, the metal distribution/, and/or the edge layer may be alternately laminated in two or more layers. 'A range that does not impair the effects of the present invention = additive. For example, inorganic particles = glass fibers, dioxo prior particles, oxygen j = cerium mica 1 gray stone) or Wei compounds (such as Si crosslinked benzoic acid), organic fillers (such as hardened epoxy resin) , - murine amine resin, cross-linked acrylic polymer, etc.), plasticization
II 201242460 4_2pif 劑、界面活性劑、黏度調整劑、著色劑、硬化劑、衝擊強 度改質劑、黏接性賦予劑、抗氧化劑、紫外線吸收劑等。 (被鍍敷層形成用組成物） 被鍍敷層形成用組成物中含有聚合物，該聚合物含有 後述式（X)所表示的基或（甲基)丙烯醯胺基及離子性極性 基。 以下，對該組成物中所含的材料（聚合物等）加以詳 述。 (聚合物） 本發明中使用的聚合物具有選自由式（x)所表示的 基及（曱基）丙婦酿胺基所組成的組群中的至少一個基及離 子性極性基。首先，對所含有的各基加以詳述。II 201242460 4_2pif agent, surfactant, viscosity modifier, colorant, hardener, impact strength modifier, adhesion imparting agent, antioxidant, UV absorber, etc. (The composition for forming a layer to be plated) The composition for forming a layer to be plated contains a polymer containing a group represented by the following formula (X) or a (meth) acrylamide group and an ionic polar group. . Hereinafter, the materials (polymers, etc.) contained in the composition will be described in detail. (Polymer) The polymer used in the present invention has at least one group and an ionic polar group selected from the group consisting of a group represented by the formula (x) and a (fluorenyl) propylamino group. First, each group contained is described in detail.
式（X)中，R12〜R16分別獨立地表示氫原子或者經 取代或未經取代的烷基。未經取代的烷基例如可列舉f 基、^基、丙基或丁基。另外，經取代的烷基例如可列舉 經甲氧基、氯原子、溴原子或氟原子等取代的甲基、+ 丙基、丁基。 巷、 再者，就本發明的效果更優異的方面而言，〜r16 較佳為氫原子。即，式（X)所表示的基較佳為烯丙基。 12 pif 201242460 式（x)所表示的基及（甲基)丙烯醯胺基是藉由能量軾 予而可於聚合物彼此之間或聚合物與基板之間形成化學鍵 結的官能基。藉由聚合物含有該基’藉由能量賦予而硬化 形成的被鍍敷層對後述鹼性水溶液具有充分的耐性（耐鹼 性）。 離子性極性基為與後述織㈣或其前驅物形成相互 作用的基’例如可列舉紐基、魏基、魏基、蝴酸美 ==基的鹽。其中’就適度的酸性（不分解其他官^ 基）的方面而言，較佳為羧酸基。 以上均分子量並無特別限制，較佳為麵 以上70萬以下’更佳為2000以上、2〇苴丨、；π从t β 就聚合感度的觀點而言，較佳為2_以上。、另疋 另外，聚合物的聚合度並無特別限 =以上者’更佳為20聚物以上者== 聚物以下，更佳為3_聚物 雛為7000 下，特佳為刚〇聚物以^ 進而佳為2000聚物以 (合適態樣） 物以態樣可，、 斤表示的具有聚合性基的單 宜稱為聚合性基單元）、及下述式 =以下亦適 £ 13 201242460 40002pif 式式（b)In the formula (X), R12 to R16 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the unsubstituted alkyl group include an f group, a propyl group, a propyl group or a butyl group. Further, examples of the substituted alkyl group include a methyl group substituted with a methoxy group, a chlorine atom, a bromine atom or a fluorine atom, and a + propyl group or a butyl group. Further, in the aspect of the invention, the effect of the present invention is more excellent, and r16 is preferably a hydrogen atom. That is, the group represented by the formula (X) is preferably an allyl group. 12 pif 201242460 The group represented by the formula (x) and the (meth) acrylamide group are functional groups which can form a chemical bond between the polymers or between the polymer and the substrate by energy enthalpy. The plated layer formed by curing the polymer by the energy imparted by the polymer has sufficient resistance (alkali resistance) to the alkaline aqueous solution to be described later. The ionic polar group is a group which interacts with the woven (four) or its precursor described later, and examples thereof include a salt of a neokyl group, a thiol group, a thiol group, and a sulphate group. Among them, a carboxylic acid group is preferred in terms of moderate acidity (not decomposing other groups). The above average molecular weight is not particularly limited, but is preferably from 700,000 or more in the above surface, more preferably from 2,000 or more to 2 Å, and π is preferably from 2 or more from the viewpoint of polymerization sensitivity of tβ. In addition, the degree of polymerization of the polymer is not particularly limited. The above is more preferably 20 or more == below the polymer, more preferably 7000 is the next. The product may be in the form of (the appropriate aspect), and the monomer having a polymerizable group represented by the mass may be referred to as a polymerizable group unit, and the following formula = the following is also applicable. 201242460 40002pif style (b)
中，R1 上述式（a)及式（b) 表示氫原子或甲基。再者， 鹵素原子）取代。 R3表示亂原子或脂肪族煙基、劣 a 一 組合而成的基。脂肪族烴基例如可列&基或將5亥些基 等。其中，較佳為碳數為卜10。=基、烯基、炔基 苯基、萘基等。 烴基例如可列舉 上述式（a)及式（b) + ’ X及¥分別獨立地表示單 鍵或者經取代或未經取代的二價有機基。二價有機基可列 舉=經取代烴基（較佳為碳數為 1〜8)、經取代或未經取代的二價芳香族煙基（較佳為碳數 為 6〜12)、-〇---S-、-S02---N(R)- ( R :烷基）、-CO-、 -NH-、-COO-、-CONH-或將該些基纟且合而成的基（例如伸 烷氧基、伸烷氧基羰基（alkylene oxy carb〇nyi)、伸烷基羰 氧基等）等。 經取代或未經取代的二價脂肪族烴基（例如伸烷基） 201242460 -----Plf 較佳為亞甲基、伸乙基、伸丙基或伸丁基或者該些基經甲 氧基、氯原子、溴原子或I原子等取代而成的基。 經取代或未經取代的二價芳香族烴基較佳為未經取代 的伸笨基或經甲氧基、氯原子、溴原子或氟原子等取代的 ' 伸苯基。 X及γ可較佳地列舉單鍵、酯基（-COO-)、醯胺基 (-CONH-)、醚基（-〇-)、或者經取代或未經取代的二價 方香族炫基寺’更佳為早鍵、醋基（-COO-)、酿胺基 (-CONH-) 〇 上述式（a)及式（b)中’ L1及L2分別獨立地表示單 鍵或者經取代或未經取代的二價有機基。二價有機基的定 義與上述X及Y中所述的二價有機基為相同含意。 L1較佳為單鍵、二價脂肪族烴基、或具有胺基曱酸醋 鍵或脲鍵的二價有機基（例如脂肪族烴基），其中較佳為總 碳數為1〜9。再者’此處所謂L1的總碳數，是指l1所夺 示的經取代或未經取代的二價機基所含的總碳原子數。、 L1的結構更具體而言，較佳為下述式（M)或式（扒2) 所表示的結構。 Η Η Η - 式（ι-l) 式（1-2) 上述式（Μ)及式（1-2)中，Ra&Rb分別獨立地表 示使用選自由碳原子、氫原子及氧原子所組成的組群中^ 15 201242460 4UUUZpif 2個以上的原子形成的二價有機基。較佳可列舉經取代或 未經取代的伸烷基（例如亞甲基、伸乙基、伸丙基或伸丁 基）' 或伸烧氧基或聚氧伸院基（例如氧伸乙基、二(氧伸 乙基)(diethylene oxide)、三（氧伸乙基)(triethylene 〇xide)、 四（氧伸乙基）(tetraethylene oxide)、二（氧伸丙 基X^dipropylene oxide)、三（氧伸丙基)(tripr〇pylene 〇xide)、 四（氧伸丙基)(tetrapropylene oxide))。 ^另外，L2較佳為單鍵或直鏈、分支或環狀的伸烷基、 芳香族基或將該些基組合而成的基。該將伸烷基與芳香族 基組合而成的基亦可進一步介隔醚基、酯基、醯胺基、胺 基甲酸祕、腺基。其中，L、佳為單鍵或總碳數為卜 15，特佳為未經取代。再者，此處所謂a的總碳數，是指 L2所表示的經取代或未經取代的二價有機基所含的總碳 原子數。 具體可列舉亞甲基、伸乙基、伸丙基、伸丁基、伸苯 基及該些基經甲氧基，基、氯原子、_子、氟原子等 取代而成的基’進何W將該些基組合而成的基。 上述式（b)中，w表示離子性極性基。該官能基的 定義與上述定義相同。 上述式（a)所表不的聚合性基單元的合適態樣可列舉 下述式（c)所表示的單元。 201242460pif 式（C)In the above formula (a) and formula (b), a hydrogen atom or a methyl group is represented. Furthermore, a halogen atom is substituted. R3 represents a combination of chaotic atoms or aliphatic nicotine groups and inferior a. The aliphatic hydrocarbon group may be, for example, a column or a group or a group. Among them, the carbon number is preferably 10. = base, alkenyl, alkynylphenyl, naphthyl and the like. Examples of the hydrocarbon group include the above formula (a) and formula (b) + 'X and ¥ each independently representing a single bond or a substituted or unsubstituted divalent organic group. The divalent organic group may be a substituted hydrocarbyl group (preferably having a carbon number of 1 to 8), a substituted or unsubstituted divalent aromatic nicotyl group (preferably having a carbon number of 6 to 12), and -〇- --S-, -S02---N(R)-(R:alkyl), -CO-, -NH-, -COO-, -CONH- or a group formed by combining these groups ( For example, an alkoxy group, an alkylene oxy carb〇nyi, an alkylcarbonyloxy group, and the like. Substituted or unsubstituted divalent aliphatic hydrocarbon group (e.g., alkylene group) 201242460 -----Plf is preferably methylene, ethyl, propyl or butyl or the methoxy group A group substituted with a base, a chlorine atom, a bromine atom or an I atom. The substituted or unsubstituted divalent aromatic hydrocarbon group is preferably an unsubstituted extended or substituted phenyl group substituted with a methoxy group, a chlorine atom, a bromine atom or a fluorine atom. X and γ are preferably exemplified by a single bond, an ester group (-COO-), a decylamino group (-CONH-), an ether group (-〇-), or a substituted or unsubstituted divalent square fragrance. The base temple is more preferably an early bond, a vinegar group (-COO-), or a amide group (-CONH-). In the above formula (a) and formula (b), 'L1 and L2 respectively represent a single bond or a substitution. Or unsubstituted divalent organic groups. The definition of the divalent organic group has the same meaning as the divalent organic group described in the above X and Y. L1 is preferably a single bond, a divalent aliphatic hydrocarbon group, or a divalent organic group having an amino citrate bond or a urea bond (e.g., an aliphatic hydrocarbon group), and preferably having a total carbon number of from 1 to 9. Further, the term "the total carbon number of L1" herein means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by l1. More specifically, the structure of L1 is preferably a structure represented by the following formula (M) or formula (扒2). Η Η Η - Formula (ι-l) Formula (1-2) In the above formula (Μ) and Formula (1-2), Ra&Rb independently represents the use of a group consisting of a carbon atom, a hydrogen atom and an oxygen atom. In the group ^ 15 201242460 4UUUZpif Two or more atoms form a divalent organic group. Preferred are substituted or unsubstituted alkylene groups (e.g., methylene, ethyl, propyl or butyl) or extended alkyl or polyoxyalkylene groups (e.g., oxygen extended ethyl) , diethylene oxide, triethylene 〇xide, tetraethylene oxide, di(oxypropyl)X^dipropylene oxide, Tripirp-pylene 〇xide, tetrapropylene oxide. Further, L2 is preferably a single bond or a linear, branched or cyclic alkyl group, an aromatic group or a group in which the groups are combined. The group in which the alkyl group and the aromatic group are combined may further partition the ether group, the ester group, the guanamine group, the amine formate, and the gland group. Among them, L, preferably a single bond or total carbon number is fi 15, particularly good is unsubstituted. Here, the total carbon number of a here means the total carbon number contained in the substituted or unsubstituted divalent organic group represented by L2. Specific examples thereof include a methylene group, an exoethyl group, a propyl group, a butyl group, a phenyl group, and a group in which the group is substituted with a methoxy group, a chlorine atom, a _ group, a fluorine atom or the like. W is a group in which these groups are combined. In the above formula (b), w represents an ionic polar group. The definition of this functional group is the same as defined above. A suitable aspect of the polymerizable group unit represented by the above formula (a) is a unit represented by the following formula (c). 201242460pif type (C)
>Y^R3 O 式（c)中，R1、R2、R3及L1與式（a)所表示的單元 中的各基的定義相同。Z表示氧原子或NR (R表示氫原子 或烷基，較佳為氫原子或碳數為1〜5的未經取代的烷基）。 另外，於上述式（c)中，L1較佳為未經取代的伸烷 基、或具有胺基甲酸酯鍵或脲鍵的二價有機基（特別是伸 烷基），特佳為總碳數為1〜9。 另外，式（b)所表示的離子性極性基單元的合適態樣 可列舉下述式（d)或式（e)所表示的單元。 式（d) 式（e)>Y^R3 O In the formula (c), R1, R2, R3 and L1 have the same definitions as the respective groups in the unit represented by the formula (a). Z represents an oxygen atom or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having a carbon number of 1 to 5). Further, in the above formula (c), L1 is preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond or a urea bond (particularly an alkylene group), particularly preferably The carbon number is 1 to 9. Further, a suitable aspect of the ionic polar group unit represented by the formula (b) is a unit represented by the following formula (d) or (e). Formula (d) (e)
w 上述式（d)中，W、R4及L2與式（b)所表示的單元 17 s. 201242460 40U02pif 中的各基的定義相同。Q表 子或烧基，較佳為氫原子< 子或NR, (R，表示氫原 基> 次娀數為1〜5的未經取代的烷 另外’式（d)中的L2較 柃其、芒乐4 私仏為直鏈、分支或環狀的伸 说基方麵麵將該絲組合而成的基。 特別於式（d)中，L2 Φ认t 从化社炎s 士士 干的與離子性極性基的連結部 =佳ί :=、分支或環狀的伸院基的二價有機基， ,、Hfe有機基較麵總碳數為卜1〇。 另外，作為其他較佳態樣，式⑷中的[2中的與離 子性極性基的連結雜難為具有芳香祕的二價有機 基，其中’該二價有機基較佳為總礙數為6〜15。 式⑷中’ w及R4與式（b)所表示的單元中的各 基的定義相同。 (合適態樣2) 聚合物的第2較佳態樣可列舉：含有下述式（g)所表 示的具有聚合性基的單元代替第i較佳態樣中的下述式 (a)所表示的具有聚合性基的單元的共聚物。 式（g)w In the above formula (d), W, R4 and L2 are the same as defined in each of the units 17 s. 201242460 40U02pif represented by the formula (b). The Q table or the alkyl group is preferably a hydrogen atom <sub or NR, (R represents a hydrogen primordial group; an unsubstituted alkyl group having a number of times of 1 to 5; and an L2 in the formula (d)柃其,芒乐4 Private 仏 is a linear, branched or ring-shaped base that combines the silk. In particular, in formula (d), L2 Φ recognizes the chemistry of S. The coupling portion with the ionic polar group = the valence of the valence ==, the branched or cyclic divalent organic group, and the total carbon number of the Hfe organic group is 〇1〇. In the aspect, the bonding of the ionic polar group in [2] in the formula (4) is a divalent organic group having a fragrant secret, wherein the divalent organic group preferably has a total hindrance of 6 to 15. In the formula (4) 'w and R4 are the same as the definition of each group in the unit represented by the formula (b). (Appropriate Aspect 2) The second preferred aspect of the polymer includes a formula represented by the following formula (g) The unit of the polymerizable group replaces the copolymer of the unit having a polymerizable group represented by the following formula (a) in the i-th preferred embodiment.
R 12. 13R 12. 13
-R p15-R p15
R R16 18 pif 201242460 •上述式（g)中，R11表示氫原子或者經取代或未經取 代的烷基。未經取代的烷基例如可列舉甲基、乙基、丙基 或丁基。另外，經取代的烷基例如可列舉經甲氧基、氣原 子/臭原子或氟原子等取代的甲基、乙基、丙基、丁基。' 再者’ R11較佳為氫原子、ψ基或_原子取代的甲基。 R〜R的定義如上所述。 X为別獨立表示單鍵、酯基、醯胺基或伸苯基。其中， 就鍵敷性的;T面而言’較佳為縣、醯胺基，就驗性溶液 耐性的方面而言，較佳為酿胺基。 L、表不單鍵或二價有機基。二價有機基與上述又及¥ 中所述的二價有機基為相同含意。 其中，就被鍍敷層的鹼性溶液耐性的方面而言，Lu ^為-C〇Q_以外的二價有機基，進而，就金屬膜的密著 點而Λ ’較佳為具有1個以上的·〇·的碳數為〜 基取^肪再者’刻旨職烴基亦可、雜基等極性 而言總單S，上述聚合性基單元（具體 而含有’更佳為5莫耳％〜”耳％ j 若’财時反紐（硬化性、聚合性）下降， 莫耳％則合成時容易凝膠化而難以合成。 言，才目雜敷觸媒或其前驅物的吸祕的觀點而 佳為以5 麟+性雜基單元較 、 莫耳/〇而含有，更佳為10莫耳％〜 19 f· 201242460 -rv/uv/^pif 85莫耳％。 (其他單元） 醯 媒或其 稱為相互作用性基）。 相互作用性基可使用：能與鑛敷觸媒 配位形成的含氮官能基、含硫官能基、含氧官能基等進仃 相互作用性基例如亦可列舉非解離性官能基（不 離而生成質子的官能基）等。 相互作用性基例如可列舉：胺基、醯胺基、醯亞胺基、 脲基、二級胺基、脒基、三嗪環、***環、苯并***基、 咪唾基、苯并*基、钟基、対基、錢基、吼嗪^、 十V n㈣基、嗓吟基、三嗪基、錢基、旅嘻 基、吡咯啶基、吡唑基、苯胺基、含有烷基胺結構的基、 3有異二聚氰酸結構的基、硝基、亞硝基、偶氮基、重氮 基、S氮基、氰基、氰酸酯基（r_〇_cn)等含氮官能基； =基、碳酸酯基、羰基、酯基、含有N-氧化物結構的基、 含有S-氧化物結構的基等含氧官能基；噻吩基、硫醇基、 硫脲基、硫代三聚氰酸基、苯并噻唑基、巯基三嗪基、硫 醚基、硫氧基、亞砜基、亞硫酸鹽、含有亞砜亞胺結構的 基、含有只小水丰シ二クA鹽結構的基、含有磺酸酯結構 的基等含硫官能基；磷醯胺基、含有磷酸酯結構的基等含 20 -if 201242460 磷官能基；含有氯、溴等鹵素原子的基等，對於 結構的官能基而言亦可使用該些基的鹽。 11採用鹽 其中，較佳細基或氰基，其在於對錢 其前驅物等的吸附能力高。 ^媒或 伸燒Ϊ者，上述醚基較佳為町的式（Υ)所表示的聚氧 式（Υ ) * -(V〇)n-Rc 式（Y)中，v表示伸烷基，Rc表示烷基。 :L0, 鍵結位置。伸烷基較佳為碳數為ί:3， 查’可較佳地列舉伸乙基、伸丙基。 數為1〜1G，具體而言，可較佳地列舉甲基、乙^為反 η表不1〜30的數，較佳為3〜23。 ^ Γ亥數值可藉由公知的方法（核磁共振（二2:= Resonance’NMR))等來測定。 哪咖 再者，上述聚合物亦可含有以下式（f)所表7f•的1右 相互作用性基的單元。 Ρ Λ⑴所表不的具有 R5 hiR R16 18 pif 201242460 • In the above formula (g), R11 represents a hydrogen atom or a substituted or unsubstituted alkyl group. The unsubstituted alkyl group may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group. Further, examples of the substituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a methoxy group, a gas atom, a odor atom, a fluorine atom or the like. Further, R11 is preferably a methyl group substituted with a hydrogen atom, a fluorenyl group or a _ atom. The definitions of R to R are as described above. X is independently represented by a single bond, an ester group, a guanamine group or a phenyl group. Among them, in terms of bondability; the T face is preferably a county or a mercapto group, and in terms of the tolerance of the test solution, it is preferably an amine group. L, the table is not a single bond or a divalent organic group. The divalent organic group has the same meaning as the above-mentioned divalent organic group described in ¥. In the aspect of the alkali solution resistance of the plating layer, Lu ^ is a divalent organic group other than -C〇Q_, and further, the adhesion point of the metal film is preferably '1 The carbon number of the above 〇······························································ %~"ear% j If the 'return time (hardenability, polymerizability) declines, the mole % is easy to gel during synthesis and difficult to synthesize. 言, 目 敷 敷 敷 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其 或其The viewpoint is preferably 5 Å + hetero-hybrid units, more than 10 mol%, and more preferably 10 mol% to 19 f· 201242460 -rv/uv/^pif 85 mol%. (Other units) The medium or its interaction group is used. The interaction group can be used: a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, etc., which can form a coordination with a mineral catalyst. For example, a non-dissociable functional group (a functional group which does not form a proton) may be mentioned. Examples of the interactive group include an amine group, a guanamine group, and the like.醯imino, ureido, secondary amine, sulfhydryl, triazine ring, triazole ring, benzotriazolyl, imilyl, benzo-yl, cyclyl, fluorenyl, ketone, pyridazine ^, ten V n (tetra), fluorenyl, triazinyl, benzyl, sulfhydryl, pyrrolidinyl, pyrazolyl, anilino, alkylamine-containing, 3, isomeric cyanate a nitrogen-containing functional group such as a nitro group, a nitroso group, an azo group, a diazo group, a S nitrogen group, a cyano group or a cyanate group (r_〇_cn); a base group, a carbonate group, a carbonyl group, An oxygen-containing functional group such as an ester group, a group containing an N-oxide structure, a group containing an S-oxide structure, a thienyl group, a thiol group, a thiourea group, a thiotrisocyanate group, a benzothiazolyl group, a mercaptotriazinyl group, a thioether group, a thiol group, a sulfoxide group, a sulfite salt, a group containing a sulfoximine structure, a group containing a structure of only a small water, and a sulfonate-containing structure. a sulfur-containing functional group such as a group; a phosphonium amino group, a phosphate group-containing group, or the like, 20-if 201242460 phosphorus functional group; a group containing a halogen atom such as chlorine or bromine; and the like The salt of some bases. 11 is a salt thereof, preferably a fine group or a cyano group, which has a high adsorption capacity for the precursor of the money, etc. The medium or the above-mentioned ether group is preferably a type of a The polyoxy formula (Υ) * - (V〇) n-Rc represented by the formula (Y), v represents an alkylene group, and Rc represents an alkyl group. : L0, a bonding position. The alkylene group is preferably carbon. The number is ί:3, and the exemplified is preferably an extended ethyl group and a stretched propyl group. The number is 1 to 1 G. Specifically, a methyl group is preferably used, and the ethyl group is a reverse η table of 1 to 30. The number is preferably from 3 to 23. The numerical value can be measured by a known method (nuclear magnetic resonance (2:= Resonance 'NMR)) or the like. Further, the above polymer may also contain the following formula ( f) The unit of the 1 right interactive group of Table 7f•. Ρ Λ (1) does not have R5 hi
U 式（f)U formula (f)
V 式（Ο中，R分別獨立地表示氫原子或者經取代或未 jp·· 芑. 21 201242460 4uuuzpif 烷基例如可列舉 '2 經取代的烧基。燒基較佳為唉 甲基、乙基。 式（f)中，U表示單键式 有機基。二價有機基的定美盘、’昼取代或未經取代的二價 機基為相同含*。1中、表示的二價有 (-coo〇^^&(；c〇nhJ^ ^ 或未經取代的二價芳麵烴基等:、"· (-◦·)、或者經取代 有機=二代及或t:代= 有機基為相同含意。且中，L3 所表不的一仏 基（例如伸院基）。、°較佳地列舉二價脂肪族烴 ί Hi 士中二表不將離子性極性基除外的與鍍敷觸媒 或其丽驅物相互作用的官能基（例如氰基、醚基)。 於=合物中含有式⑴所表示的單元的情形時，就鑛 敷觸媒等的吸附性的方面而言’相對於聚合物中的總單 元，其含量較佳為以10莫耳％〜70莫耳％而含有，更佳 為20莫耳％〜60莫耳％’特佳為30莫耳％〜5〇莫耳％。 關於上述聚合物的具體例，例如具有自由基聚合性基 及離子性極性基的聚合物可使用曰本專利特開 2006-13 5271號公報的段落[〇〇65]〜段落[〇〇70]中記载的聚 合物。具有自由基聚合性基、與鍍敷觸媒或其前驅物形成 相互作用的官能基及離子性極性基的聚合物可使用 US2010-080964號的段落[0030]〜段落[〇1〇8]中記载的聚 合物。 22 201242460 f pif (聚合物的合成方法） 上述聚合物的合成方法並無特別限定，所使用的 亦可為市售品或組合公知的合成方法而合成者。例如可泉 照日本專利公開2009-7662號的段落[〇12〇]〜段落: 中記載的方法等來合成上述聚合物。 ] 被鍍敷層形成用組成物中的聚合物的含量並無特別限 制，相對於组成物總量’較佳為1質量％〜5〇質量。/。，更 佳為5質量％〜30質量％。若在上述範圍内，則組成物的 操作性優異，容易控制被鑛敷層的層厚。 (被鑛敷層形成用組成物中的其他任意成分） (溶劑） 被鍍敷層形成用組成物中，視需要亦可含有溶劑。 可使用的溶齊彳並無特別限定，例如可列舉：水；甲醇 (methanol )、乙醇（ethanol )、丙醇（propanol )、異丙醇 (isopropanol )、乙二醇（ethylene glycol )、甘油（glyCerin )、 丙二醇單甲醚（propylene glycol monomethyl ether )等醇系 溶劑；乙酸（acetic acid)等酸；丙酮（acetone)、甲基乙 基酮（methyl ethyl ketone)、環己酮（cyclohexanone)等 酮系溶劑；二曱基甲蕴胺（dimethyl formamide )、二甲基 乙隨胺（dimethyl acetamide )、N-曱基。比洛咬_等酸胺系溶 劑；乙腈（acetonitrile)、丙腈（propionitrile)等腈系溶劑； 乙酸甲酿（methyl acetate )、乙酸乙醋（ethyl acetate )等酯 系溶劑；碳酸二甲醋（dimethyl carbonate)、碳酸二乙酉旨 (diethyl carbonate )等碳酸醋系溶劑；除此以外，亦可列 23 201242460 4uuu/pif 舉醚系溶劑、二醇系溶劑、胺系溶劑、硫醇系溶 系溶劑等。 困系 其中，較佳為醯胺系溶劑、酮系溶劑、腈系溶劑、碳 酸酯系溶劑，具體而言，較佳為丙酮、二曱基甲醯^= 曱基乙醯胺、甲基乙基酮、環己酮、乙腈、丙腈、N_曱^ σ比洛咬酮、；5炭酸二甲酯。 土 於被鍍敷層形成用組成物中含有溶劑的情形時，相對 於組成物總量’溶劑的含量較佳為5〇質量％〜％質量 %，更佳為70質量％〜95質量％。若在上述範圍内，、則 組成物的操作性優異’容易進行被鍍敷層的層厚的控制等。 (其他添加劑） 本發明的被鍍敷層形成用組成物中，視需要亦可添加 其他添加劑（例如聚合起始劑、增感劑、硬化劑、聚合抑 制劑、抗氧化劑、防靜電劑、紫外線吸收劑、填料、粒子、 阻燃劑、界面活性劑、潤滑劑、塑化劑等）。 (步驟的順序） 使上述被鍍敷層形成用組成物接觸於基板上的方法並 無特別限定，可列舉：將被鍍敷層形成用組成物直接層疊 於基板上的方法；或於被鍍敷層形成用組成物為含有溶劑 的液狀的情形時’將組成物塗佈於基板上的方法等。就容 易控制所得的被鍍敷層的厚度的方面而言，較佳為將組成 物塗佈於基板上的方法。 塗佈的方法並無特別限制，具體方法可使用：利用旋 轉塗佈機（spincoater)、浸潰塗佈機（dipc〇ater)、雙輥塗 24 201242460plf 佈機（double roll coater)、狹缝塗佈機（slit coater)、氣刀 塗佈機（air knife coater )、線棒塗佈機（wire bar coater )、 滑動漏斗（slide hopper )、喷霧塗佈（Spmy coating )、刀片 塗佈機（blade coater)、刮刀塗佈機（doctor coater )、壓摘· 塗佈機（squeeze coater)、反輕塗佈機（reverse roll coater)、 轉送輕塗佈機（transfer roll coater )、播壓式塗佈機 (extrusion coater)、簾幕式塗佈機（curtain eoater)、模塗 佈機（die coater)、凹版輥（gravure roll)的塗佈法，擦出 塗佈法，輥塗佈法等公知方法。 就操作性或製造效率的觀點而言，較佳為以下態樣： 將被鍍敷層形成用組成物塗佈於基板（或密著補助層）上 並使其乾燥，將殘存的溶劑去除， 物層。 形成含有聚合物的組成 、於使被鍍敷層形成用組成物與基板接觸的情形時，其 塗佈1就與後述鍍敷觸媒或其前驅物的充分的相互作用开^ 成性的觀點而言，㈣體成分換料較佳為ai ^ g/m2’ 特佳為 0.5g/m2〜5g/m2。 υ 亦可於塗佈與乾 小時，將殘存的 再者，於該步驟中形成被鍍敷層時， 燥之間於2〇t〜40。(：下放置〇.5小時〜2 溶劑去除。 (能量的賦予） 對基板上的被鑛敷層形成用組成物 ^別限制，例如較佳為使用加熱或曝光等。亚 處理’於被職層形細域物情岭合物^、 25 ☆ 201242460 4UUU2pif 物與基板間的反應進行硬化，形成被鍍敷層。 曝光時，可使用利用紫外線（Ultraviolet，UV)燈、 可見光線等的光照射等。光源例如有水銀燈、金屬鹵化物 燈、氙氣燈、化學燈、碳弧燈等。放射線亦可使用電子束、 X射線、離子束、遠紅外線、g射線、i射線、深紫外 (Deep-UV)光、高密度能量束（雷射束）等。 通常所用的具體態樣可合適地列舉：利用紅外線雷射 的掃描曝光、氙氣放電燈等的高照度閃光曝光、紅外線燈 曝光等。 *光k間疋根據聚合物的反應性及光源而不同，通常 秒鐘〜5小時之間。曝光能量只要為10 mJ〜_ mJ 工右即可，較佳為_m>r〜3_m了的範圍。 風二t 為能量賦予的情形時，可使用鼓 風乾域、…目、紅外線乾職、 所得的被鍍敷層的厚声卄&及冋寺 〇.〇5_〜5jLlm。 1 _〜1〇 μιη，更佳為 。二=厚較佳為。·。一一，特佳為 含量較佳為被鍍敷層中的聚合物的 10〇質量的範圍。° 〇質量％，更佳為10質量％〜 另外，於進行能量騎 予，其後藉由公知的顯，亦旎以圖案狀進行能量賦 理將能量未照射部去除，形成 26 201242460^ 圖案化的被鍍敷層。 <鹼性水溶液接觸步驟> 鹼性水溶液接觸步驟為以下步驟：使上述步驟中形成 的被鍍敷層與含有胺基醇及界面活性劑且pH值為1〇二14 ..的鹼性水溶液接觸，將被鍍敷層的未硬化部分去除。藉由 實施該步驟，後述鍍敷液等的污染得到抑制，突粒的產生 得到抑制。 以下’首先對該步驟中使用的鹼性水溶液的構成成分 加以詳述，其後對步驟的順序加以詳述。 (驗性水溶液） 該步驟中使用的驗性水溶液中含有胺基醇。藉由含有 該化合物，被鍍敷層的未硬化部分、被鍍敷層表面的硬化 不充分的成分的去除性提高。 胺基醇只要為具有胺基及經基的化合物，則並無特別 限制，例如可列舉：單乙醇胺、N-甲基乙醇胺、N-乙基乙 醇胺、N-丁基乙醇胺、N，N-二曱基乙醇胺、N，N-二乙基乙 醇胺、N，N-二丁基乙醇胺等單乙醇胺及其衍生物；二乙醇 胺、N-甲基二乙醇胺、N-丁基二乙醇胺等二乙醇胺及其衍 生物，三乙醇胺、羥基乙基哌嗪等或該些化合物的衍生物 等。 其中，就對被鍍敷層的滲透性優異，進一步抑制突粒 的產生的方面而言’可較佳地列舉單乙醇胺類或二乙醇胺 類。 鹼性水溶液中的胺基醇的含量是根據所使用的種類而In the formula V, R independently represents a hydrogen atom or a substituted or unjp·· 芑. 21 201242460 4uuuzpif alkyl group, for example, a '2 substituted alkyl group. The alkyl group is preferably a methyl group or an ethyl group. In the formula (f), U represents a single-bonded organic group, and a divalent organic group of a succinct disk, a fluorene-substituted or unsubstituted valence group is the same as *. -coo〇^^&(;c〇nhJ^ ^ or unsubstituted divalent aromatic hydrocarbon group, etc.:, "· (-◦·), or substituted organic = second generation and or t: generation = organic The base is the same meaning. In the middle, the one group represented by L3 (for example, the base of the court). ° is preferably listed as a divalent aliphatic hydrocarbon. The second table does not exclude the ionic polar group and plating. a functional group (for example, a cyano group or an ether group) in which the catalyst or the limpetarily interacting material is contained. When the unit represented by the formula (1) is contained in the compound, the adsorption property of the mineralizing catalyst or the like is The content is preferably contained in an amount of from 10 mol% to 70 mol%, more preferably from 20 mol% to 60 mol%, particularly preferably 30 mol%, based on the total unit in the polymer. 5. The specific example of the above polymer, for example, a polymer having a radical polymerizable group and an ionic polar group can be used in the paragraph [〇〇65] of the Japanese Patent Laid-Open Publication No. 2006-13 5271. The polymer described in the paragraph [〇〇70], a polymer having a radical polymerizable group, a functional group which forms an interaction with a plating catalyst or a precursor thereof, and an ionic polar group can be used in US2010-080964. The polymer described in paragraph [0030] to paragraph [〇1〇8] 22 201242460 f pif (method of synthesizing a polymer) The method for synthesizing the above polymer is not particularly limited, and a commercially available product may be used. Or a combination of a known synthesis method, for example, the above-mentioned polymer can be synthesized by the method described in the paragraph [〇12〇] to paragraph: Japanese Patent Publication No. 2009-7662. The content of the polymer in the material is not particularly limited, and is preferably from 1% by mass to 5% by mass based on the total amount of the composition. More preferably, it is from 5% by mass to 30% by mass. The composition is excellent in handleability and easy to control The layer thickness of the mineral deposit layer (other optional components in the composition for forming a mineral deposit layer) (solvent) The composition for forming a layer to be plated may optionally contain a solvent. Specific examples include, for example, water; methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerol (glyCerin), and propylene glycol monomethyl ether ( An alcohol solvent such as propylene glycol monomethyl ether; an acid such as acetic acid; a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone; Dimethyl formamide, dimethyl acetamide, N-fluorenyl. Bilo bite _ acid amine solvent; acetonitrile (acetonitrile), propionitrile and other nitrile solvents; methyl acetate, ethyl acetate and other ester solvents; dimethyl carbonate ( Carbonate-based solvent such as dimethyl carbonate or diethyl carbonate; in addition to 23 201242460 4uuu/pif ether solvent, glycol solvent, amine solvent, thiol solvent, etc. . Among them, a amide-based solvent, a ketone-based solvent, a nitrile-based solvent, and a carbonate-based solvent are preferable, and specifically, acetone, dimercaptomethyl hydrazine, hydrazinylamine, and methyl ethyl ketone are preferable. Ketone, cyclohexanone, acetonitrile, propionitrile, N_曱^ σ pirone, and 5 dimethyl carbonate. In the case where the solvent is contained in the composition for forming a layer to be plated, the content of the solvent is preferably 5% by mass to % by mass, more preferably 70% by mass to 95% by mass based on the total amount of the composition. When it is in the above range, the workability of the composition is excellent. It is easy to control the layer thickness of the layer to be plated. (Other Additives) The composition for forming a layer to be plated of the present invention may optionally contain other additives (for example, a polymerization initiator, a sensitizer, a hardener, a polymerization inhibitor, an antioxidant, an antistatic agent, and an ultraviolet ray). Absorbents, fillers, particles, flame retardants, surfactants, lubricants, plasticizers, etc.). (Step of Step) The method of bringing the composition for forming a layer to be plated into contact with the substrate is not particularly limited, and a method of directly laminating the composition for forming a layer to be plated on the substrate; or plating When the composition for forming a cladding layer is in the form of a liquid containing a solvent, a method of applying a composition onto a substrate or the like. In terms of easily controlling the thickness of the obtained layer to be plated, a method of applying a composition onto a substrate is preferred. The coating method is not particularly limited, and a specific method can be used: using a spin coater, a dipp coating machine (dipc〇ater), a double roll coating 24 201242460plf cloth machine (double roll coater), slit coating Slapping coater, air knife coater, wire bar coater, slide hopper, spray coating (Spmy coating), blade coater ( Blade coater), doctor coater, squeeze coater, reverse roll coater, transfer roll coater, broadcast coating Coating method of extrusion coater, curtain eoater, die coater, gravure roll, wiping coating method, roll coating method, etc. method. From the viewpoint of workability and production efficiency, it is preferred to apply a composition for forming a layer to be plated onto a substrate (or a adhesion support layer), and to dry the solvent, thereby removing the remaining solvent. Layer of matter. When a composition containing a polymer is formed and the composition for forming a layer to be plated is brought into contact with a substrate, the coating 1 is sufficiently interactive with a plating catalyst or a precursor thereof to be described later. In other words, the (IV) body composition refueling is preferably ai ^ g / m2 ' particularly preferably from 0.5 g / m 2 to 5 g / m 2 . υ It can also be applied and dried for a few hours, and the remaining ones will be between 2 〇 t and 40 when the coated layer is formed in this step. (: Placement of 〇5 hours~2 solvent removal. (Energy supply) The composition for forming a layer on the substrate is restricted, and for example, heating or exposure is preferably used. Layered fine-grained ridges ^, 25 ☆ 201242460 4UUU2pif The reaction between the object and the substrate is hardened to form a layer to be plated. When exposed, ultraviolet light (Ultraviolet, UV) lamps, visible light, etc. can be used. The light source may be, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, etc. The radiation may also use an electron beam, an X-ray, an ion beam, a far infrared ray, a g ray, an i ray, or a deep ultraviolet (Deep- UV) light, high-density energy beam (laser beam), etc. Generally, specific examples used may be: scanning exposure using infrared laser, high-illumination flash exposure such as xenon discharge lamp, exposure to infrared light, etc. * The light k varies depending on the reactivity of the polymer and the light source, and is usually between 2 and 5 hours. The exposure energy is preferably 10 mJ to _ mJ, preferably _m>r~3_m. Wind two t is able In the case of the application, it is possible to use a blast dry field, a mesh, an infrared ray, a thick layer of the obtained plated layer, and a 冋 〇 〇. 〇 5_~5jLlm. 1 _~1 〇 μιη, more preferably Preferably, the content is preferably in the range of 10 Å by mass of the polymer in the layer to be plated. 〇% by mass, more preferably 10% by mass. The energy riding is performed, and then the energy-exposed portion is removed by the energy modulation in the form of a pattern, and the patterned coating layer is formed. [2012] The alkaline aqueous solution contact step is performed. The alkaline aqueous solution contacting step is a step of bringing the plated layer formed in the above step into contact with an alkaline aqueous solution containing an amino alcohol and a surfactant and having a pH of 1 Torr. The uncured portion is removed. By performing this step, contamination of the plating solution or the like described later is suppressed, and generation of spurs is suppressed. Hereinafter, the constituent components of the alkaline aqueous solution used in the step will be described in detail first, and then The order of the steps is detailed. (Intestinal aqueous solution) The test aqueous solution used in this step contains an amino alcohol, and by containing the compound, the uncured portion of the plated layer and the component which is insufficiently hardened on the surface of the plated layer are improved. The compound having an amine group and a trans group is not particularly limited, and examples thereof include monoethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N,N-dimercaptoethanolamine, and N. , monoethanolamine such as N-diethylethanolamine or N,N-dibutylethanolamine and derivatives thereof; diethanolamine and its derivatives such as diethanolamine, N-methyldiethanolamine and N-butyldiethanolamine, and triethanolamine And hydroxyethylpiperazine or the like, derivatives of these compounds, and the like. Among them, monoethanolamines or diethanolamines are preferred in terms of excellent permeability to the layer to be plated and further suppression of the generation of spurs. The content of the amino alcohol in the alkaline aqueous solution is based on the type used.
27 S 201242460 4UUUZpif 適宜選擇，相對於鹼性水溶液總量，較佳為0.1質量％〜 5〇質量％，更佳為1質量％〜15質量％。 鹼性水溶液中含有界面活性劑。藉由含有該化合物， 鹼性水溶液的滲透性受到促進，被鍍敷層的未硬化部分及 被鍍敷層表面的硬化不充分的成分的去除性提高。 所使用的界面活性劑的種類並無特別限制，例如可列 舉陰離子系界面活性劑、非離子系界面活性劑、陽離子系 界面活性劑、兩性界面活性劑。 更具體而言，陰離子性界面活性劑例如可列舉：烧基 笨石頁酸鹽、烧基或稀基趟硫酸鹽、烧基或烯基硫酸鹽、烧 基或烯基醚羧酸鹽、胺基酸型界面活性劑、N_醯基胺基酸 型界面活性劑、烷基或烯基磷酸酯或其鹽等。 X非離子系界面活性劑例如可列舉：聚氧伸烷基烷基或 ，基_、聚氧伸乙基絲苯細、高则旨⑽鋪酿胺或 ^氧烧加成物、_脂肪酸s|、烧基糖普、脂肪酸甘油 早酯、烷基胺氧化物等。 陽離子_如可列輕基_子系界面活 ==級陽離子系界面活性劑、醋27 S 201242460 4UUUZpif is suitably selected, and is preferably 0.1% by mass to 5% by mass, more preferably 1% by mass to 15% by mass based on the total amount of the aqueous alkaline solution. The alkaline aqueous solution contains a surfactant. By containing this compound, the permeability of the alkaline aqueous solution is promoted, and the removal property of the unhardened portion of the plating layer and the component which is insufficiently hardened on the surface of the plating layer is improved. The type of the surfactant to be used is not particularly limited, and examples thereof include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. More specifically, the anionic surfactant may, for example, be a pyridyl sulphate, a burnt or a sulfonium sulfate, a burnt or an alkenyl sulfate, a burnt or an alkenyl ether carboxylate, or an amine. A base acid type surfactant, an N-mercapto amino acid type surfactant, an alkyl group or an alkenyl phosphate or a salt thereof. Examples of the X nonionic surfactant include a polyoxyalkylene alkyl group, a group _, a polyoxyethylene benzene benzene fine, a high hydrazine (10) a catalyzed amine or an oxy-fired adduct, and a fatty acid s. |, burnt sugar, fatty acid glyceryl early ester, alkylamine oxide and the like. Cationic _ such as can be listed as light base _ sub-system interface = = grade cationic surfactant, vinegar
如可列輪基型兩性界面活性劑、 石頁基甜采鹼型兩性界面活性劑等。 A 其中’就進-步抑制突粒的 性劑的合適態樣較佳為非離子性界面= 驗性水溶液十的界面活性劑的含量是根據所使用的種 28 pif 201242460 類而適宜選擇，相對於驗性水溶液均、息 %〜10質量％，更佳為1質量％〜=’較佳為ο·1質量 就進一步抑制突粒的產生的貝量％。 舌性齊_醇的重量 二 = 容液中 含量）較佳為10/1〜1/5，更佳為5/ι丞知合1/界面活性劑 驗性水溶液的pH值為10二14。二。。 可抑制突粒產生。其令，就該效=上述範圍内，則 值更佳為12〜14。 優異的方面而言，ρΗ 鹼性水溶液中使用的溶劑通常 要亦可併用有機溶劑（甲醇、乙醇 7 。另外’視需 丙二醇單甲醚等醇系溶劑，乙二醇、乙二醇、甘油、 酸’丙酮、甲基乙基酮等酮系溶劑酸、胺基綾酸等 胺、Ν-甲基π比心定_等酿胺系 昧胺-甲基乙醯 =二甲一— 驗性水溶液切可含有無機驗 制，例如可列舉驗金屬氫氧化物 二種類亚热特別限 鉀、碳酸鈉）等。 虱氧化鈉、氫氧化 無機鹼的含量較佳為於以Η 内調整。 PW值達到上述範圍的範圍 (步驟的順序） 在,層與上述驗性水溶液的接觸方法並益特別限 方法° _可列舉：將具有被鑛敷層的 土板心責於鹼性水溶液中的方法、或將鹼性水溶液塗佈於 29 201242460 40002pif 被鐘敷層上的方法。 被鑛敷層與驗性水溶液的接觸時間是根據所使 = 適輯擇，就生產性及錄㈣制性的方 。#乂佳為1勿鐘〜60分鐘，更佳為2分鐘〜加八 接觸時的祕水溶㈣液溫並無制_，刀硬= 除性、於無電解鍍敷液中容易分解的成分ί去除 ,Γ、的方面而言，較佳為30。°以上，更佳為6CTC以 ’、而佳為60。(：〜80。(：。再者，若為6(rc上 的金屬膜的面狀更優異。 上則所付 再者’於被鑛敷層形成步驟中，於以圖案 =的情形時，藉由實施該步驟，可將硬化; 應聚合物去除，並且進行未曝光部分的去除。 <觸媒賦予步驟> 於觸媒賦付财，對在上錢性水溶液接觸步驟中 未硬化物被去_被錄械讀_媒或其前驅物。 於該步驟中，來源於聚合物的離子性極性基根據豆功 能而附著（吸附）所賦予的_觸媒或其前驅物。更且體 =言’於驗敷層+及被鍍敷層表面域傾敷觸職其 前驅物。 ,此處’鍍敷觸媒或其前驅物可列舉則灸述鑛敷步驟中 作為錢敷處理的觸媒或電極而發揮功能的物質。因此，鐘 ，觸媒或其前驅物是根據魏步财崎敷處理陳類決 定，較佳為無電解鍍敷觸媒或其前驅物。 首先’對5玄步驟中使用的材料（無電解鑛敷觸媒或其 30 201242460 , -----pif 前，媒，對該步驟的順序力，述。 時的活性核’=::二解„媒二，成為無電解鍍敷 還原反應的觸媒能力的人’具體可列舉具有自觸媒 進行孟屬（作為離子化傾向低於Ni的可For example, the columnar type amphoteric surfactant, the stone-based sweet base type amphoteric surfactant, and the like. A suitable form of the agent for inhibiting the granules is preferably a nonionic interface = the content of the surfactant in the aqueous solution is suitably selected according to the species 28 pif 201242460 used, In the case of the test aqueous solution, the % by weight of the aqueous solution is more than 10% by mass, more preferably 1% by mass to ≤1, and the mass % of the granules is further suppressed. The weight of the lignin-alcohol 2 = the content of the liquid is preferably 10/1 to 1/5, more preferably 5 / ι 丞 1 / surfactant The pH of the aqueous solution is 10 2 14 . two. . It can inhibit the production of neurites. Therefore, in the range of the above effect, the value is more preferably 12 to 14. In an excellent aspect, the solvent used in the alkaline aqueous solution of ρΗ is usually also used in combination with an organic solvent (methanol, ethanol 7), and an alcohol solvent such as propylene glycol monomethyl ether, ethylene glycol, ethylene glycol, glycerin, Acids such as ketone-based solvent acids such as acetone and methyl ethyl ketone, amines such as amino phthalic acid, ruthenium-methyl π-pyridinium, etc., and the like, amine amines, guanamine, methyl ethyl hydrazine, dimethyl hydrazine, aqueous solution The cut may contain an inorganic test, and for example, a metal hydroxide may be used, and two types of sub-heats, particularly potassium, sodium carbonate, and the like may be mentioned. The content of sodium ruthenium oxide or hydrogen hydroxide inorganic base is preferably adjusted in Η. The PW value reaches the range of the above range (the order of the steps). The method of contacting the layer with the above-mentioned aqueous solution is particularly limited to the method _ exemplified: the soil plate having the mineralized layer is blamed on the alkaline aqueous solution A method, or a method of applying an aqueous alkaline solution to a 29 201242460 40002 pif-coated layer. The contact time between the mineral coating and the aqueous test solution is based on the choice of = suitable for production and recording (4). #乂佳为1勿钟~60 minutes, more preferably 2 minutes~Adding eight contacts when the secret water dissolves (four) liquid temperature is not made _, knife hard = de-sex, easily decomposed in the electroless plating solution ί In terms of removal, enthalpy, it is preferably 30. Above °, more preferably 6CTC is ‘, and preferably 60. (:~80. (:. In addition, if it is 6 (the surface of the metal film on rc is more excellent. The one that is added on the top is in the step of forming the ore layer, in the case of pattern = By performing this step, the hardening can be performed; the polymer is removed, and the removal of the unexposed portion is performed. <catalyst imparting step> The catalyst is used to make money, and the hardened substance is not subjected to the contacting step in the upper aqueous solution. The ionic group derived from the polymer is attached (adsorbed) to the catalyst or its precursor according to the function of the bean. = 言 'In the test layer + and the surface layer of the plated layer is applied to its precursors. Here, 'plating catalyst or its precursors can be cited as a touch of money in the molybdenum step A substance that functions as a medium or an electrode. Therefore, the clock, catalyst, or precursor thereof is determined according to the treatment of the type by Weibu Fujisaki, preferably an electroless plating catalyst or a precursor thereof. The material used (electroless ore plating catalyst or its 30 201242460, -----pif before, media, the step The order of force, the active core of the time '=:: two solutions „media two, the person who becomes the catalyst ability of the electroless plating reduction reaction' can be exemplified by the self-catalyst to carry out the genus (as a low ionization tendency) Available in Ni
Cu、Ni、A1、Fe、CQ|已知者）导。具體可列舉Pd、Ag、 言，特佳為Ag、Pd。、。其中’就觸媒能力高的方面而 該無電解鍍_媒亦 體可藉由町方式製作.屬I心’金屬膠 護劑存在的溶液中，：全界面活性劑或帶電的保 藉由此處所使用的界面^離子逛原。金屬膠體的帶電可 活性劑或保護劑來調節。 (…、電解鍍敷觸媒前驅物） ，专ι 觸媒前驅物，只要藉 田化予反應可成為無電解 曰 用。主要可使用作為=媒’則可無特別限制地使 金_ +。^ t ，鍍敷觸媒而列舉的金屬的 原反應而成為作為 解鑛敷觸媒前驅物的金屬對=予:為 於無電解織財之俞，h 職層賦予後、次潰 〇價金屬而作為無電解二:另藉由還原反應使其變化為 前驅物直接浸潰於’亦!'將無電解鐘敷觸媒 的還原劑使其變化為㈣”丨糾無電解鍍敷浴中 作為無電解鍍數;。無咖敷觸媒)。 觸媒則驅物的金屬離子較佳為使用金 31 201242460 40002pifCu, Ni, A1, Fe, CQ|known to be). Specific examples thereof include Pd, Ag, and words, and particularly preferably Ag and Pd. ,. Among them, the electroless plating can be produced by the town method in terms of high catalyst capacity. In the solution of the metal core adhesive, the full surfactant or charged The interface used by the place is the original. The metal colloid is charged with a charged surfactant or a protective agent. (..., electrolytic plating catalyst precursor), special catalyst precursor, as long as the use of Tianhua to react can become electroless. It is mainly used as = media, and gold _ + can be made without any particular limitation. ^ t , the original reaction of the metal listed by the plating catalyst becomes the metal pair as the precursor of the demineralized coating medium = for: for the electroless weaving of the money, the h layer is given the post- and post-destruction metal And as electroless two: another change by the reduction reaction into a precursor directly impregnated in 'also!' will reduce the electroless catalyst to reduce the amount of catalyst to (four) "丨 无 electroless plating bath as Electroless plating number; no coffee coating catalyst. Catalysts are preferred to use metal ions 31 201242460 40002pif
屬鹽對被職層賦予。所使用的金屬鹽只要可溶解於適當 的溶劑中並解軸金屬離子與縣（_子），職無特別 限制，可列舉 M(N〇3)n、MCln、M2/n(s〇4)、M3/n(p〇4) (M 表示11½的金屬原子）等。金屬離子可以合適地使用上述 金屬鹽解離所得的離子。關於具體例，例如可列舉Ag離 f、Cu離子、A1離子、Ni離子、Co離子、Fe離子' Pd 離子，其中，較佳為可進行多牙配位的離子，特別是就可 配位的官能基的種類數及觸媒能力的方面而言，較佳為A 離子、Pd離子。 本發明中所用的無電解鍍敷觸媒或其前驅物的較佳例 之二可列舉IG化合物。該把化合物作為職觸媒（把）或 其别驅物（鈀離子）而發揮作用，該鍍敷觸媒（鈀）或其 前驅物（鈀離子）發揮於鍍敷處理時成為活性核而使金^ 析出的作用。鈀化合物只要含有鈀且於鍍敷處理時作為核 而發揮作用’則並無特別限定，例如可列舉把（II):、 銥（〇)錯合物、鈀膠體等。 嚴 另外，無電解鍍敷觸媒或其前驅物可列舉銀或銀離子 作為其他較佳例。 使用銀離子的情形時，可合適地使用如下所示的銀化 合物解離而成的銀離子。銀化合物的具體例可列舉峭酸鋁 (silver nitrate)、乙酸銀（siiver acetate)、硫酸銀（dive sulfate )、碳酸銀（snver carb〇nate )、氰化銀（Mb cyanide)、硫氰酸銀（silver thiocyanate)、氯化銀（sib chloride )、漠化銀（siiver bromide )、絡酸銀（ 32 201242460pif chromate )、氣冉酸銀（Siiver chi〇ranilate )、水楊酸銀（说μ salicylate )、二乙基二硫代胺基甲酸銀（如· diet+hyldithiocarbamate)、二乙基二硫代胺甲醯胺酸銀、對 甲苯石黃酸銀（silver p-toluenesulfonate)。其中，就水、、容性 ' 的觀點而言較佳為硝酸銀。 (其他觸媒） 於本發明中，用於對被鍍敷層直接進行電解鍍敷而不 進行無電解鍍敷的觸媒亦可使用〇價金屬。 (鍍敷觸媒液） 如上所述，鍍敷觸媒或其前驅物較佳為以分散液或溶 液（鍍敷觸媒液）的形式對被鍍敷層賦予。 鍍敷觸媒液的溶劑可使用有機溶劑或水。藉由含有有 機溶劑’鍍敷觸媒或其前驅物對被鍍敷層的滲透性提高， 了使鑛敷觸媒或其纟ij驅物而效地吸附於離子性極性基。 鍍敷觸媒液中所使用的有機溶劑只要為可滲透至被鍍 敷層中的溶劑則並無特別限制，具體而言，可使用丙酮、 乙醯乙酸甲酯（methyl acetoacetate )、乙醯乙酸乙酯（ethyl acetoacetate )、乙二醇二乙酸酉旨（ethylene glycol diacetate )、環己酮、乙蕴丙酮（acetylacetone )、苯乙酮 (acetophenone )、2-(1-環己烯基）環己酮 (2-(1-cyclohexenyl)cyclohexanone )、丙二醇二乙酸酉旨 (propylene glycol diacetate )、三乙酸甘油酯（triacetin )、 • 二乙二醇二乙酸酉旨（diethylene glycol diacetate)、二0惡烧 (dioxane)、N-曱基吡咯啶酮、碳酸二甲酯、二甲基溶纖 33 3. 201242460 40002pif 劑（dimethyl cellosolve)等。 (步驟的順序） 對被鍍敷層賦予錢敷觸媒或其前驅物的方法並無特別 限制。 例如可列舉：製備鑛敷觸媒液（使金屬分散於適當的 分散介質中而成的分散液、或以適當的溶劑溶解金屬鹽而 含有解離而成的金屬離子的溶液），將艘敷觸媒液塗佈於被 鏡敷層上的方法；或將形成有賊敷層的基板浸潰於鑛敷 觸媒液中的方法等。 被鍍敷層與鍍敷觸媒液的接觸時間較佳為3〇秒鐘〜 24小時左右，更佳為1分鐘〜〗小時左右。 接觸時的鍍敷觸媒液的溫度較佳為1(rc〜6〇t>c左 右，更佳為10°C〜30°C左右。 關於被鍍敷層的錄敷觸媒或其前驅物的吸附量，是根 據所使用的鑛敷浴種類、觸媒金屬種類、被錢敷層的離子 性極性基種類、使用方法等而不同，就鍍敷物的析出性的 觀點而言，較佳為5mg/m2〜1000 mg/m2,更佳為10mg/m2 〜800 mg/m2，特佳為 20 mg/m2〜600 mg/m2。 <錢敷步驟> 鑛敷步驟為以下步驟：對觸媒賦予步驟中所得的鍍敷 觸媒或其前驅物所吸附的被鍵敷層進行鑛敷處理，於被鑛 敷層上形成金屬膜。更具體而言，如圖1 (C)所示，於該 步驟中，將金屬膜14形成於被鍍敷層12上，獲得積層體 16 〇 34 201242460 ψιι 電解鍍敷處理的種類可列舉無電解鑛敷、 上述步驟中與被鍍敷層之間形成相 互作用的鍍敷觸媒或其前驅物的功能來選擇。 —其中，就提高金屬膜的密著性的方面而言 解鐘敷。另外，為了獲得所需膜_金_ 141 …-电解鍍敷後進一步進行電解鍍敷為更佳能樣。 、 以下’對該步驟+合適地進行的鑛敷力:以說明。 (無電解鍍敷） 缝是指以下操作：使贿解有欲作為鑛 敷物而析出的金屬離子的溶液，藉由化學反應使金屬析出。 戎步驟中的無電解鍍敷例如是對被賦予了無 觸媒的基板進行水洗㈣錄的無電解職觸（金屬又） 去除後’浸潰於無電解職浴巾而進行。所制的無電解 鍍敷浴:使用公知的無電解綠浴。再者，就容易獲取的 方面而言，無電解鑛敷浴較佳為使用驗性 (pH值為9〜14左右）的情形。 阱又数/口 > “1外，於將被賦予了無電解鍍敷觸媒前驅物的基板以 無電解鍍敷觸媒前驅物吸附或含浸於被鍍敷層中的狀態浸 >貝於然電解鍍敷浴中的情形時，對基板進行水洗而將多餘 的前，，物（金屬歸）錄後，浸潰於無電解錄浴中。' 於該=形時，於無電解鍍敷浴中進行鍍敷觸媒前驅物的還 原及隨後的無電解鍍敷。作為此處所使用的無電解鍍敷 /合，亦可與上述同樣地使用公知的無電解鍵敷浴。 再者’無電解鍍敷觸媒前驅物的還原除了如上所述的 35 201242460 4_2pif 使用無電解鍍敷液的態樣以外，亦可準備觸媒活性化液（還 原液）’作為無電解鍍敷前的其他步驟而進行。觸媒活性化 液為溶解有還原劑的液體，該還原劑可將無電解鍍敷觸媒 月ί驅物（主要為金屬離子）還原成〇價金屬，該還原劑相 對於液體總體的濃度較佳為αΐ質量％〜5〇質量％，更佳 為1質量％〜30質量。/〇。還原劑可使用氫化硼鈉（s〇dium borohydride)、二甲基胺删烧（dimethylamine borane)之類 的棚系還原劑’甲搭’次礙酸等還原劑。 次潰時，較佳為將無電解鑑敷觸媒或其前驅物接觸的 被鍍敷層表面附近的無電解鍍敷觸媒或其前驅物保持於一 定濃度，然後一面施加攪拌或搖晃一面浸潰。 通常的無電解鍍敷浴的組成例如除了溶劑（例如水） 以外，主要含有1.鍵敷用的金屬離子、2.還原劑、3.提高 金屬離子的穩定性的添加劑（穩定劑）^該鍍敷浴中，除了 該些成分以外，亦可含有鍍敷浴的穩定劑等公知的添加物。 鍍敷浴中所用的有機溶劑必須為可溶於水的溶劑，就 該方面而言’可較佳地使用丙酮等酮類，曱醇、乙醇、異 丙醇等醇類。 無電解鍍敷浴中所用的金屬的種類例如已知銅、錫、 鉛、鎳、金、銀、鈀、铑，其中，就導電性的觀點而言， 特佳為銅、金。另外，根據上述金屬來選擇最適合的還原 劑、添加物。 以如上方式形成的由無電解鍍敷所得的金屬膜的膜厚 可藉由鍍敷浴的金屬離子濃度、於鍍敷浴中的浸潰時間或 36 ,pif 201242460 鍍敷浴的溫度等來控制，就導電性 问1以上，更佳為〇.2 μηα〜2 μηι。 ”、， D，較佳為αι 其中，於將由無電解鑛數所得 進行後述電解鐘敷的情形時，較佳為均層來 以上的膜。 口 J J碼丁主少〇.丨μηι 另=，於鑛敷浴中的浸潰時間較佳為】分鐘 左右，更佳為1分鐘〜3小時力 小時 (電解鍍敷（電鍍）) 於該步㈣，於在上述步驟中賦予的職 =士有，為電極的功能的情形時，可對被賦、^觸二 或其則驅物的被鍍敷層進行電解鍍敷。 -觸媒 作為敷Ϊ ’b將所形成的金_The salt is given to the employed layer. The metal salt to be used is not particularly limited as long as it can be dissolved in a suitable solvent and dissociates the metal ion from the county (_), and examples thereof include M(N〇3)n, MCln, and M2/n(s〇4). , M3 / n (p 〇 4) (M means 111⁄2 metal atoms) and so on. As the metal ion, the ion obtained by dissociation of the above metal salt can be suitably used. Specific examples thereof include Ag-free f, Cu ion, A1 ion, Ni ion, Co ion, and Fe ion 'Pd ion. Among them, ions capable of multidentate coordination are preferable, and in particular, it is coordinable. The A ion and the Pd ion are preferred in terms of the number of functional groups and the catalytic ability. Preferred examples of the electroless plating catalyst or the precursor thereof used in the present invention include IG compounds. The compound acts as a catalyst (palladium) or a precursor thereof (palladium ion), and the plating catalyst (palladium) or its precursor (palladium ion) acts as an active core during plating treatment. The effect of gold ^ precipitation. The palladium compound is not particularly limited as long as it contains palladium and acts as a core during the plating treatment, and examples thereof include (II): a ruthenium complex, a palladium colloid, and the like. Further, the electroless plating catalyst or its precursor may be exemplified by silver or silver ions. In the case of using silver ions, silver ions dissociated from the silver compound shown below can be suitably used. Specific examples of the silver compound include silver nitrate, siiver acetate, dive sulfate, silver carbonate (snver carb〇nate), silver cyanide (Mb cyanide), and silver thiocyanate. (silver thiocyanate), silver chloride (sib chloride), desert silver (siiver bromide), silver complex (32 201242460 pif chromate), silver sulphate (Siiver chi〇ranilate), silver salicylate (say μ salicylate) , silver diethyldithiocarbamate (such as · diet + hyldithiocarbamate), diethyl dithiocarbamate, silver, silver p-toluenesulfonate (silver p-toluenesulfonate). Among them, silver nitrate is preferred from the viewpoint of water and capacitance. (Other Catalyst) In the present invention, a ruthenium metal may be used as a catalyst for directly performing electrolytic plating on the plated layer without electroless plating. (Plating Catalyst Solution) As described above, the plating catalyst or its precursor is preferably applied to the layer to be plated in the form of a dispersion or a solution (plating catalyst solution). The solvent for plating the catalyst liquid may be an organic solvent or water. The permeability of the layer to be plated is improved by the inclusion of the organic solvent's plating catalyst or its precursor, and the mineral catalyst or its 纟ij drive is effectively adsorbed to the ionic polar group. The organic solvent to be used in the plating catalyst liquid is not particularly limited as long as it is permeable to the solvent to be plated, and specifically, acetone, methyl acetoacetate, acetamidine acetate can be used. Ethyl (ethyl acetoacetate), ethylene glycol diacetate, cyclohexanone, acetylacetone, acetophenone, 2-(1-cyclohexenyl)cyclohexane Ketone (2-(1-cyclohexenyl)cyclohexanone), propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxin (dioxane), N-decylpyrrolidone, dimethyl carbonate, dimethyl cellosolve 33 3. 201242460 40002 pif (dimethyl cellosolve) and the like. (Sequence of Steps) There is no particular limitation on the method of imparting a money-receiving catalyst or a precursor thereof to the layer to be plated. For example, a mineral-coated catalyst liquid (a dispersion obtained by dispersing a metal in a suitable dispersion medium or a solution in which a metal salt is dissolved in a suitable solvent and containing dissociated metal ions) is prepared. A method in which a vehicle is applied to a coated layer; or a method in which a substrate on which a thief coating is formed is immersed in a mineralizing catalyst liquid. The contact time between the plated layer and the plating catalyst liquid is preferably from about 3 seconds to about 24 hours, more preferably from about 1 minute to about 00 hours. The temperature of the plating catalyst liquid at the time of contact is preferably 1 (rc~6〇t>c or so, more preferably about 10 ° C to 30 ° C. About the coating layer of the coating layer or its precursor The amount of adsorption is different depending on the type of mineral bath used, the type of catalyst metal, the type of ionic polar group of the money coating layer, the method of use, etc., and from the viewpoint of the precipitation property of the plating material, it is preferably 5 mg/m2 to 1000 mg/m2, more preferably 10 mg/m2 to 800 mg/m2, particularly preferably 20 mg/m2 to 600 mg/m2. <Money application step> The mineral application step is as follows: The bonded layer adsorbed by the plating catalyst or the precursor obtained in the step of the medium is subjected to a mineralization treatment to form a metal film on the mineralized layer. More specifically, as shown in FIG. 1(C), In this step, the metal film 14 is formed on the layer 12 to be coated, and the layered body 16 is obtained. 201234 201242460 ψι 1 The type of electrolytic plating treatment can be exemplified by electroless ore plating, and formation between the above-mentioned steps and the layer to be plated. The function of the interacting plating catalyst or its precursor is selected. - Among them, the solution is to improve the adhesion of the metal film. In addition, in order to obtain the desired film _ gold _ 141 ... - electrolytic plating is further performed electrolytic plating is more excellent. The following 'this step + appropriate mineralization force: to illustrate. (electroless plating The seam refers to the following operation: a solution of a metal ion to be precipitated as a mineral deposit, and a metal reaction is precipitated by a chemical reaction. The electroless plating in the step is, for example, imparted with no catalyst. The substrate is washed with water (4) and the electroless contact (metal) is removed. After the removal, it is immersed in an electroless bath towel. The electroless plating bath is made by using a well-known electroless green bath. Moreover, it is easy to obtain. On the other hand, the electroless ore bath is preferably used (at a pH of about 9 to 14). The number of wells is /, > "1, except that the electroless plating catalyst will be imparted. When the substrate of the precursor is immersed in a state in which the electroless plating catalyst precursor is adsorbed or impregnated in the layer to be plated, the substrate is washed with water and excess is used. After the material (metal return) was recorded, it was immersed in an electroless bath.' In the case of this type, the reduction of the plating catalyst precursor and the subsequent electroless plating are carried out in an electroless plating bath. As the electroless plating/combination used herein, it is also known to use the same as described above. The electroless plating bath is used. In addition to the above-mentioned 35 201242460 4_2pif using an electroless plating solution, a catalytically active liquid (reducing liquid) may be prepared. 'Besides the other steps before electroless plating. The catalyst activating solution is a liquid in which a reducing agent is dissolved, and the reducing agent can reduce the electroless plating catalyst (mainly metal ions) into The valence metal preferably has a concentration of the reducing agent relative to the liquid as a mass% to 5% by mass, more preferably 1% by mass to 30% by mass. /〇. As the reducing agent, a reducing agent such as a sulfonate-based borohydride or a dimethylamine borane can be used. In the case of secondary collapse, it is preferred to maintain the electroless plating catalyst or its precursor in the vicinity of the surface of the layer to be plated which is contacted with the electroless plating catalyst or its precursor at a certain concentration, and then apply a stirring or shaking while dipping Crush. The composition of a general electroless plating bath contains, for example, a metal ion for bonding, a reducing agent, and an additive (stabilizer) for improving the stability of metal ions, in addition to a solvent (for example, water). In addition to these components, the plating bath may contain a known additive such as a stabilizer of a plating bath. The organic solvent used in the plating bath must be a solvent which is soluble in water. In this respect, a ketone such as acetone or an alcohol such as decyl alcohol, ethanol or isopropanol can be preferably used. The type of metal used in the electroless plating bath is, for example, copper, tin, lead, nickel, gold, silver, palladium or rhodium. Among them, copper and gold are particularly preferable from the viewpoint of conductivity. Further, the most suitable reducing agent or additive is selected based on the above metal. The film thickness of the metal film obtained by electroless plating formed as described above can be controlled by the metal ion concentration of the plating bath, the dipping time in the plating bath or the temperature of the pif 201242460 plating bath, and the like. The conductivity is 1 or more, and more preferably 2.2 μηα~2 μηι. ”,, D, preferably αι, in the case where the electrolysis is performed by the electroless ore number, it is preferably a film having a uniform layer or more. The mouth JJ code Ding main 〇. 丨μηι Another =, The immersion time in the ore bath is preferably about minutes, more preferably 1 minute to 3 hours of force (electrolytic plating (electroplating)). In the step (4), the job given in the above steps is In the case of the function of the electrode, it is possible to perform electrolytic plating on the plated layer to which the electrode is applied or touched. - The catalyst acts as a coating Ϊ 'b will form the gold _
無電解鍍敷膜作為基底，容易在其上重新形；J 解錢it : = J由如此般於無電解錢敷後進行電 將金屬膜應用於與目標相對應的厚度，故適合 ^解鍍㈣妓可如先前公㈣綠。 鏡敷中所用的金屬例如可列舉銅、絡、錯、錦、全、= ^辞等，就導電性的觀點而言，較佳為銅、金、銀，、更 佳為鋼。 致供ί外i藉由電解锻敷而獲得的金屬膜的膜厚可藉由調 i錄敷浴巾所含的金屬濃度、或電流密度等來控制。 再者’於應用於通常的電氣配線等的情形時，就導電 37 (T·· 201242460 40002pif 性的觀點而言， 1 μπι〜30 帅。 金屬膜的膜厚較佳為0.5 μιη以上，更佳為 <積層體> 備美過上述步驟，可獲得如® 1 (C)所示般依序具 鍍敷層12及金屬膜14的積層體16(附有金 屬膜的積層體）。 ^ 雷^斤Λ的積層體16可用於各種領域，例如可用於電氣· ®無、"^彳二、辰林水產、礦業、建設、食品、纖維、服裝、 石厌、石油、橡膠、皮革、汽車、精密機器、木材、 土木、傢具、印刷、樂器等廣泛的產業領域。 更具體而言，可用於印表機、個人電腦、文字處理機、 鍵皿小型資訊終端機（Personal Digital Assistant，PDA)、 電活機、複印機、傳真機、電子式收銀機（极⑽譲化仏处 Register，ECR)、計算器、電子記賬薄、卡、托架、文具 等事務機器’辦公自動化（Office Automation，OA)機器， 洗衣機 '冰箱、吸塵器、微波爐、照明器具、遊戲機、熨 斗被爐專豕電機器，電視（Television，TV)、磁帶錄影 機（Video Tape Recorder，VTR)、攝影機、收錄音機、磁 帶錄音機、迷你光碟、壓縮光碟（c〇mpactDisk，CD)播 放器、揚聲器、液晶顯示器等音頻視頻（Audi〇vide〇, AV) 機器，連接器、繼電器、電容器、開關、印刷基板、繞線 言、半導體岔封材料、發光二極體（Light Emitting Diode， LED)密封材料、電線、電纜、變壓器、偏向磁軛、分電 盤、半導體晶片、各種電氣配線板、可撓性印刷電路板 38 pif 201242460 (Flexible Print Circuit，FPC)、晶粒軟膜接合（chip on Film，COF)、捲帶自動接合（Tape Automated Bonding， TAB)、雙層 CCL (Copper Clad Laminate)材料、電氣配 線用材料、多層配線基板、母板、天線、防電磁波膜、鐘 錶等電氣•電子零件及通信機器等用途。 特別疋由於金屬膜與被鑛敷層的界面的平滑性得到改 良’故例如可應用於裝飾品（眼鏡框、汽車裝飾品j珠寶 飾品、遊戲機外殼、西餐餐具、水管配件、照明器具等） 或必須確保高頻傳送的用途（例如配線基板用、印刷配線 基板用）等各種用途。 <任思步驟：圖案形成步驟> ㈣要’村對上述所得的制體實施將金屬膜钱刻 成圖案狀，形成圖案化金屬膜的步驟。 更具體而言，如圖1⑼所示，於該步驟中，藉由將 ==膜的不需要部分去除，藉此而生成所需的 可使用任何方法而形成該 的減成法(於金屬膜上設置圖案化的遮 膜的方法)、半加成法 金屬 將遮罩去除，和Hi丨;t金屬朗方式進行職處理， 進仃關處理，形成圖案化的金屬膜的方The electroless plating film is used as a substrate and is easily reshaped on it; J. J. Money: = J is applied to the thickness corresponding to the target by electrolessly applying the electroless carbon, so it is suitable for deplating. (4) You can be as green as the previous (four). Examples of the metal used in the mirror coating include copper, complex, error, brocade, total, and ruthenium. From the viewpoint of conductivity, copper, gold, silver, and more preferably steel. The film thickness of the metal film obtained by electrolytic forging can be controlled by adjusting the metal concentration, current density, and the like contained in the bath towel. In addition, when it is applied to a normal electric wiring or the like, it is electrically conductive 37 (T·· 201242460 40002 pif property, 1 μπι to 30 is handsome. The film thickness of the metal film is preferably 0.5 μm or more, more preferably By the above steps, the layered body 16 (the layered body with the metal film) having the plating layer 12 and the metal film 14 as shown in the paragraph (1) can be obtained. The laminated body 16 of Lei Jin can be used in various fields, for example, it can be used in electrical ® no, "^彳2, Chenlin aquatic products, mining, construction, food, fiber, clothing, stone, oil, rubber, leather, A wide range of industrial fields such as automobiles, precision machinery, wood, civil engineering, furniture, printing, musical instruments, etc. More specifically, it can be used in printers, personal computers, word processors, and small digital information terminals (Personal Digital Assistant, PDA). ), electric activity machine, copier, fax machine, electronic cash register (Postal (10) 譲 仏 Register Register, ECR), calculator, electronic accounting book, card, bracket, stationery, etc. Office Automation (Office Automation) , OA) machine, Clothes dryer 'refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game consoles, iron ovens, special motors, televisions (TVs), video tape recorders (VTRs), video cameras, tape recorders, tape recorders, mini Audio, video, audio, etc. (Audi〇vide〇, AV) machines, connectors, relays, capacitors, switches, printed circuit boards, wire-wound, semiconductor packages Materials, Light Emitting Diode (LED) sealing materials, wires, cables, transformers, deflection yokes, distribution boards, semiconductor wafers, various wiring boards, flexible printed circuit boards 38 pif 201242460 (Flexible Print Circuit, FPC), chip on film (COF), Tape Automated Bonding (TAB), double layer CCL (Copper Clad Laminate) material, electrical wiring material, multilayer wiring board, mother board , antennas, anti-electromagnetic waves, watches, and other electrical and electronic parts and communication equipment, etc. The smoothness of the interface of the mineral coating is improved. Therefore, it can be applied, for example, to decorations (eyeglass frames, car decorations, jewelry, game machine casings, western tableware, water pipe fittings, lighting fixtures, etc.) or high frequency transmission must be ensured. Various uses such as applications (for wiring boards, printed wiring boards). <Renith Step: Pattern Forming Step> (4) The step of forming a patterned metal film by patterning the metal film into a pattern on the body obtained as described above. More specifically, as shown in FIG. 1 (9), in this step, the unnecessary portion of the film is removed by ==, thereby generating a desired subtractive method (in the metal film) which can be formed by any method. The method of setting the patterned mask on the surface), the semi-additive metal to remove the mask, and the Hi丨;t metal lang method for the post treatment, and the process of forming the patterned metal film
S 39 201242460 wuuzpif 法）。 所謂減成法’具體是指以下方法：於所形成的金屬膜 ^置抗鋪層，藉由圖案曝光、顯影而形成與金屬膜圖 案#同的圖案，將抗蝕劑圖案作為遮罩，利用蝕刻處理 將金屬膜去除，形成圖案化的金屬膜。 抗钱劑可使用任何材料，可使用負型、正型 術法，製造印刷配線基板時所使 用的方法均可使用，可使賴式侧、乾絲刻等，只要 任意選f即可。於作麵操作方面，賴置等的簡便性的 方面而言較佳顧式_。#職例如可使 化鐵等的水溶液。 乳 能#更具體而言’於圖2中示出使職成法的網步驟的 首先，進行上述鍍敷步驟，藉此準備圖2(A)所示的 積層體’該積層體具備基板1G、絕緣性樹脂層22、被錢敷 層12及金屬膜14。再者，於圖2 (A)中，於基板⑺表 面上及其内部具備金屬配線2〇。絕緣性樹脂層22、金屬配 線20為視需要追加的構成構件。另外，於圖2 (A)中， 可於基板1G的單面設置金屬骐14，亦可設置於兩面。 繼而，如圖2 (B)所示，於金屬膜14上設置圖案化 的遮罩24。 '、 其，，如圖2 (C)所示’藉由蝕刻處理（例如乾式蝕 刻、濕至蝕刻）將未設置遮罩的區域的金屬膜14去除，獲 得圖案化的金屬膜18。最後，去除料24，獲得本發明二 201242460 積層體（參照圖2 (D))。 所謂半加成法，具體是指以下方法：於所 膜上設置抗_層’藉㈣轉光、顯影㈣彡成全= 膜圖案部相同的圖案，將抗钱劑圖案作為遮罩進_ = 敷，去除抗触劑圖案後實施快速钕刻，將金屬膜去 案狀，It此形成圖案化的金屬膜。 抗钱劑、餘刻液等可使用與減成法相同的 電解鍍敷方法可使用上述記载的方法。 为外’ 更具體而言’於圖3中示出使用本* 士、 的態樣。 出使用+加成法的蝕刻步驟 首^，準備如圖3 (A)所示的積層體， 具有金屬配線20的基板10、絕緣性樹脂声 曰广備 及金屬膜14。 θ 破鑛敷層 繼而’如圖3 (Β)所示，於金屬 的遮罩24。 、 、 上设置圖案化 然後’如圖3 (C)所示，進行電解錄， 罩24的區域中形成金屬膜，獲得金屬膜14b。、未5又置遮 -後如圖3 (D)所示，去除遮罩％ 及凹部的凹凸狀的金屬膜14b進行 ^有凸部 刻:濕式餘刻），將凸部以外的凹部去=列如乾式蝕 所不般具備圖案化的金屬膜18的積層體。A如圖3 (E) 再者，亦可於去除金屬膜的同時， 乾式蝕刻）等將被鍍敷層一起去除。9 a α的方法（例 上述所得的具有圖案化金屬膜的積層體可用於各種用 41 201242460 40002pif =·ι如可用於半導體晶片、各種電氣配線板、Frc、cQF、 TAB、天線、多層配線基板、 合適地用伽、祕m 4種用途。其中，可 亦可於積層體上設置絕緣層。 t优而要 含有本發明的積層體及絕 滑的AMs & 層的線基板可形成與平 在者性優異的配線’高頻特性亦良好，並且即 更為此細的南密度配線，配線間的絕緣 。 絕緣層可使用公知的材料，例如可列舉公知的層 緣膜、阻焊劑層等。 [實例] ’但本發明 以下，藉由實例對本發明加以更詳細說明 不限定於該些實例。 (合成例1 :聚合物Α) 於2 L的二口燒般中加入乙酸乙醋i L、2_胺基 59 g，利用冰浴進行冷卻。向其中以内溫成為2〇它以 的方式調節並滴加2·溴'異丁15G g。其後，使内溫上 升至室溫（25。〇並反應2小時。反應結束後，追加 ^ 300mL使反應停止。其後，以蒸餾水3〇〇11^將乙酸乙 酉曰層清洗4次後，以硫酸鎂乾燥，進而將乙酸乙酯蒸 除，藉此獲得80 g原料A。 ' 繼而，於500 mL的三口燒瓶中加入原料A 47.4 g、吡 。疋22 g、乙酸乙酯15〇mL，利用冰浴進行冷卻。向其中以 内溫成為20°C以下的方式調節並滴加丙烯酸& 2s g。其 唆，提高至室溫並反應3小時。反應結束後，追加蒸餾水 42 201242460 300mL使反應停止。其後’以蒸餾水3〇〇mL將乙酸乙酯 層清洗4次後，以硫酸鎂乾燥，進而將乙酸乙酯蒸餾去除胃。 其後，利用管柱層析儀將以下的單體Ml純化，獲得2〇 g。S 39 201242460 wuuzpif method). The "reduction method" specifically refers to a method in which an anti-layer is formed on the formed metal film, and a pattern similar to the metal film pattern # is formed by pattern exposure and development, and the resist pattern is used as a mask. The etching process removes the metal film to form a patterned metal film. Any material can be used for the anti-money agent, and a negative type or a positive type method can be used, and any method used for manufacturing a printed wiring board can be used, and the Lai side, the dry wire can be used, and the like can be selected arbitrarily. In terms of the ease of handling, it is preferable to use the aspect of simplicity. For example, an aqueous solution such as iron can be used. In the first step, the above-described plating step is performed to prepare the layered body shown in FIG. 2(A). The layered body includes the substrate 1G. The insulating resin layer 22, the money coating layer 12, and the metal film 14. Further, in Fig. 2(A), metal wiring 2 is provided on the surface of the substrate (7) and inside thereof. The insulating resin layer 22 and the metal wiring 20 are constituent members that are added as needed. Further, in FIG. 2(A), the metal crucible 14 may be provided on one surface of the substrate 1G, or may be provided on both surfaces. Then, as shown in Fig. 2(B), a patterned mask 24 is provided on the metal film 14. ', as shown in Fig. 2(C), the metal film 14 in the region where the mask is not provided is removed by an etching treatment (e.g., dry etching, wet to etching) to obtain a patterned metal film 18. Finally, the material 24 is removed to obtain the 201242460 laminate of the present invention (refer to Fig. 2(D)). The semi-additive method specifically refers to a method in which an anti-layer layer is provided on the film, and the same pattern is formed on the film pattern portion, and the anti-money agent pattern is used as a mask. After removing the anti-contact agent pattern, a rapid engraving is performed, and the metal film is removed, and this forms a patterned metal film. The above-described method can be used as the anti-money agent, the residual liquid, or the like, which can be used in the same electrolytic plating method as the subtractive method. For the sake of the 'more specifically', the aspect of using this is shown in FIG. An etching step using the +addition method is performed, and a laminate having the metal wiring 20, an insulating resin squeegee, and a metal film 14 are prepared as shown in Fig. 3(A). The θ-deposited coating is then shown in Figure 3 (Β) in a metal mask 24. Patterning is performed on the upper side, and as shown in Fig. 3(C), electrolytic recording is performed, and a metal film is formed in the region of the cover 24 to obtain a metal film 14b. As shown in FIG. 3(D), the metal film 14b having the unevenness of the mask % and the concave portion is removed to have a convex portion: wet residual, and the concave portion other than the convex portion is removed. The column has a laminated body of the patterned metal film 18 as in dry etching. A (Fig. 3(E)) Further, the plated layer may be removed together with the removal of the metal film, dry etching or the like. 9 a α method (Example of the above-mentioned laminated body having a patterned metal film can be used for various purposes. 201224260 40002 pif =·ι such as can be used for semiconductor wafers, various electrical wiring boards, Frc, cQF, TAB, antenna, multilayer wiring substrate It is suitable to use four kinds of applications, such as gamma and secret m. Among them, an insulating layer may be provided on the laminated body. The wire substrate containing the laminated body of the present invention and the slippery AMs & layer may be formed and flattened. The wiring of the wiring which is excellent in the high-frequency characteristics is also excellent, that is, the south density wiring which is finer, and the insulation between the wirings. The insulating layer can be a known material, and examples thereof include a well-known interlayer film and a solder resist layer. [Examples] In the following, the present invention will be described in more detail by way of examples without limitation to the examples. (Synthesis Example 1: Polymer oxime) Ethyl acetate i L is added to a 2-L two-burner 2 g of an amine group, 59 g, was cooled by an ice bath, and 2 bromo-isobutyl 15 Gg was adjusted and added dropwise so that the internal temperature became 2 Torr. Thereafter, the internal temperature was raised to room temperature (25). 〇 and react for 2 hours. After the reaction is over, After adding 300 mL, the reaction was stopped. Thereafter, the ethyl acetate layer was washed 4 times with distilled water, dried over magnesium sulfate, and then ethyl acetate was evaporated to give 80 g of material A. In a 500 mL three-necked flask, a raw material A 47.4 g, pyridinium, 22 g, and ethyl acetate 15 mL were added, and the mixture was cooled in an ice bath, and the acrylic acid was adjusted and the internal temperature was adjusted to 20 ° C or less. 2s g. After that, it was raised to room temperature and reacted for 3 hours. After the reaction was completed, distilled water 42 201242460 300 mL was added to stop the reaction. Thereafter, the ethyl acetate layer was washed 4 times with 3 mL of distilled water, followed by sulfuric acid. The magnesium was dried, and the ethyl acetate was distilled off to remove the stomach. Thereafter, the following monomer M1 was purified by a column chromatography to obtain 2 μg.
單體Ml 於500 mL的三口燒瓶中加入Ν,Ν-二曱基乙醯胺8 g， 於氮氣流下加熱至65°C。向其中用4小時滴加上述所得的 單體Ml 14.3 g、丙烯腈（東京化成工業（股）製造）3.〇 g、 丙烯酸（東京化成製造）g、V-65 (和光純藥製造）〇 4 g的Ν,Ν-二甲基乙驢胺8 g溶液。滴加結束後，進而授拌 3小時。其後’添加N，N-二甲基乙酸胺41 g，將反應溶液 冷卻至室溫。於上述反應溶液中添加4-羥基-2,2,6,6-四曱 基 β辰 淀 -1- 氧 自 由 基 (4，Hydroxy-2,2,6,6-tetramethylpiperidine-l-〇xyl，4-經基 -TEMPO)(東京化成製造）〇_〇9g、1,8-二氮雜二環[5.4.0] 十一碳-7-烯（l,8-Diazabicyclo[5.4.0]undec-7-ene ’ DBU) 54.8 g，於室溫下進行12小時反應。其後’於反應溶液中 添加70質量％曱磺酸水溶液54 g。反應結束後，以水進 行再沈澱，取出固形物’獲得聚合物A (重量平均分子量 為5.3萬）12 g。使用電位差自動滴定裝置（京都電子工 業（股）製造）及作為滴定液的0·1 M氫氧化鈉水溶液對 43 201242460 4UUU2pif 所得聚合物A的酸價進行測定，結果該聚合物A的酸價為 3.9 mmol/g。 使用紅外（Infrared，IR)測定機（囉場製作所（股） 製造）進行所得聚合物A的鑑定。測定是將聚合物溶解於 丙酮中並使用KBr結晶來進行。IR測定的結果為，於2240 cm“附近觀測到波峰，得知聚合物中導入了作為腈單元的 丙烯腈。另外’藉由酸價測定而得知導入了丙烯酸作為竣 酸單元。另外’使其溶解於氘代DMSO (二曱基亞砜）中， 利用布魯克（Broker)製造的300 MHz的核磁共振儀 (Nuclear Magnetic Resonance，NMR) (AV-300)進行剛 定。於2.5-0.7 ppm (5H)觀察到寬的相當於含有腈基的單 元的波峰，於 7.8-8.1 ppm( iH)、5 8_5 6 ppm( m)、5 4_5 2 ppm ( 1H) > 4.2-3.9 ppm ( 2H) > 33-3.5 ppm ( 2H) > 2^5-0^ ppm( 6H)觀察到寬的相當於含有聚合性基的單元的波 於2.5-0.7 PPm (3H)觀察到寬的相當於紐基單元 峰，得知含有聚合縣的單元：義 單元=25:28:47(莫耳（瓜〇1)比）。 竣义基Monomer M1 To a 500 mL three-necked flask was placed 8 g of hydrazine, hydrazine-dimercaptoacetamide, and heated to 65 ° C under a nitrogen stream. Into the above, the monomer M1, 14.3 g, acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), 〇g, acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise thereto over 4 hours. 4 g of Ν, Ν-dimethylacetamide 8 g solution. After the completion of the dropwise addition, the mixture was further mixed for 3 hours. Thereafter, 41 g of N,N-dimethylacetic acidamine was added, and the reaction solution was cooled to room temperature. To the above reaction solution, 4-hydroxy-2,2,6,6-tetradecyl-β-n-hydroxyl radical (4,Hydroxy-2,2,6,6-tetramethylpiperidine-l-〇xyl, 4-Phenyl-TEMPO) (manufactured by Tokyo Chemical Industry Co., Ltd.) 〇_〇9g, 1,8-diazabicyclo[5.4.0] undec-7-ene (1,8-Diazabicyclo[5.4.0]undec -7-ene 'DBU) 54.8 g, reacted at room temperature for 12 hours. Thereafter, 54 g of a 70% by mass aqueous solution of sulfonic acid was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, and the solid matter was taken out to obtain 12 g of a polymer A (weight average molecular weight: 53,000). The acid value of the polymer A obtained by the use of a potentiometric auto-titration device (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M aqueous sodium hydroxide solution as a titration solution for 43 201242460 4UUU2pif was measured, and as a result, the acid value of the polymer A was 3.9 mmol/g. The identification of the obtained polymer A was carried out using an infrared (IR) measuring machine (manufactured by Horiba, Ltd.). The measurement was carried out by dissolving the polymer in acetone and using KBr crystals. As a result of IR measurement, a peak was observed in the vicinity of 2240 cm, and it was found that acrylonitrile as a nitrile unit was introduced into the polymer. Further, it was found that acrylic acid was introduced as a tannic acid unit by acid value measurement. It was dissolved in deuterated DMSO (dimercaptosulfoxide) and subjected to a rigid set using a 300 MHz Nuclear Magnetic Resonance (NMR) (AV-300) manufactured by Brooke. At 2.5-0.7 ppm ( 5H) A broad peak corresponding to a nitrile-containing unit was observed at 7.8-8.1 ppm(iH), 5 8_5 6 ppm(m), 5 4_5 2 ppm (1H) > 4.2-3.9 ppm ( 2H) > ; 33-3.5 ppm ( 2H) > 2^5-0^ ppm( 6H) A wide wave equivalent to a unit containing a polymerizable group was observed at 2.5-0.7 PPm (3H). The unit peak is known to contain the unit of the polymerization county: the unit = 25:28:47 (mole (guar 1) ratio).
(合成例2 :聚合物 44 201242460pif 於川uumL的(Synthesis Example 2: Polymer 44 201242460pif Yu Chuan uumL
Ui ㈣g、第三丁基甲基醚225 g' :用丙=酸鹽⑼g、 其中丙為耽以下的方式調節並二U向3 二V5 g。其後，提高至室溫並反應3小時。及 應結束後，追加蒸館水300 mL使反應停止1夺反 镏水刚mL將第三丁基曱基醚層清洗2次後，、、行= 鎮乾燥’將第三丁基甲基贿料除，利^^ 單體D純化，磐6G g。 析儀將Ui (tetra) g, third butyl methyl ether 225 g': adjusted with propionate (9) g, wherein c is 耽 or less and two U to 3 two V5 g. Thereafter, it was raised to room temperature and reacted for 3 hours. After the end of the process, add 300 mL of steaming water to stop the reaction. 1 镏 镏 刚 mL mL mL 将 mL mL 清洗 将 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 清洗 第三 第三 第三 第三 第三 第三 第三 第三, Li ^ ^ monomer D purification, 磐 6G g. Analyzer
單體D 於500mL的三口燒瓶中加入1-曱氧基-2-丙醇14〇g， 於氮氣流下加熱至7(TC。向其中用2.5小時滴加上述所得 的單體D9.0g、丙烯酸（東京化成製造）5 84 g、v_65 (= 光純藥製造）1.20g、1-甲氧基_2_丙醇14〇g溶液。滴加結 束後，進一步攪拌2小時。其後，將反應溶液冷卻至室溫， 以己烧/乙酸乙醋進行再沈澱，取出固形物，獲得以下結構 式的聚合物B (重量平均分子量為12萬）5 g。使用電位 差自動滴定裝置（京都電子工業（股）製造）及作為滴定 液的0·1 Μ氫氧化鈉水溶液對所得聚合物B的酸價進行測 定，結果該聚合物B的酸價為4.48 mmol/g。 •W' 45 201242460 4UUUZpifMonomer D was added to a 500 mL three-necked flask, 14 〇g of 1-nonoxy-2-propanol, and heated to 7 (TC) under a nitrogen stream. The above-obtained monomer D 9.0 g, acrylic acid was added dropwise thereto over 2.5 hours. (manufactured by Tokyo Chemical Industry Co., Ltd.) 5 84 g, v_65 (made by Wako Pure Chemical Industries, Ltd.) 1.20 g, and 1-methoxy-2-propanol 14 〇g solution. After the completion of the dropwise addition, the mixture was further stirred for 2 hours. Thereafter, the reaction solution was prepared. After cooling to room temperature, reprecipitation was carried out with hexane/ethyl acetate, and the solid matter was taken out to obtain 5 g of polymer B (weight average molecular weight: 120,000) of the following structural formula. Automated titration apparatus using potential difference (Kyoto Electronics Industry Co., Ltd. The acid value of the obtained polymer B was measured by a 0. 1 hydrazine aqueous solution as a titration solution, and the acid value of the polymer B was 4.48 mmol/g. • W' 45 201242460 4UUUZpif
使所得聚合物B溶解於DMSO中，利用IR測定機（艰 場製作所（股）製造）使用KBr結晶進行測定。IR測定的 結果為，於224(^11^1附近未觀測到波峰，得知聚合物b不 含氰基。另外，藉由酸價測定而得知導入了丙浠酸作為竣 酸單元。進而’使其溶解於氘代DMSO (二甲基亞砜）中， 利用布魯克製造的300MHz的NMR(AV-300)進行測定。 於 5.9-5.7 ppm( lH)、5.2-5.0 ppm(2H)、3.8-3.7 ppm(2H)、 2.5-0.7 ppm (3H)觀察到寬的相當於含有聚合性基的單元 的波峰，於2.5-0.7ppm (3H)觀察到寬的相當於羧酸基單 元的波峰，得知含有聚合性基的單元：緩酸基單元=58 : 42 ( mol 比）。 (合成例3 :聚合物C) 於500 mL的三口燒瓶中加入聚丙烯酸（和光純藥工 業（股）製造，M.W = 25,000) 30 g、4-羥基-TEMPO(0.07 g)、三乙基苄基氯（東京化成工業（股）製造）l.〇g、烯 丙基縮水甘油醚（東京化成工業（股）製造）31.53 g、1_ 曱氧基-2-丙醇143 g，加熱至100。(：，攪拌12小時。其後， 將反應溶液冷卻至室溫，以水進行再沈澱，取出固形物， 獲得以下結構式的聚合物C (重量平均分子量為4.5萬）8 46 201242460yif g 仗用電位差自動滴疋裝置（京都電子工業（股 滴定液的化納水溶液對所得聚合物c的 W貝進仃败，M果該，合物c _價為4 31咖响。The obtained polymer B was dissolved in DMSO, and the measurement was carried out using a KBr crystal by an IR measuring machine (manufactured by Ryuchang Seisakusho Co., Ltd.). As a result of the IR measurement, no peak was observed in the vicinity of 224 (^11^1), and it was found that the polymer b did not contain a cyano group. Further, it was found that a propionic acid was introduced as a tannic acid unit by acid value measurement. 'It was dissolved in deuterated DMSO (dimethyl sulfoxide) and measured using a 300 MHz NMR (AV-300) manufactured by Bruker. 5.9-5.7 ppm (1H), 5.2-5.0 ppm (2H), 3.8 -3.7 ppm (2H), 2.5-0.7 ppm (3H), a broad peak corresponding to a unit containing a polymerizable group was observed, and a broad peak corresponding to a carboxylic acid group unit was observed at 2.5-0.7 ppm (3H). The unit containing a polymerizable group was found: a buffer base unit = 58: 42 (mol ratio) (Synthesis Example 3: Polymer C) Polyacrylic acid was added to a 500 mL three-necked flask (Wako Pure Chemical Industries, Ltd.) , MW = 25,000) 30 g, 4-hydroxy-TEMPO (0.07 g), triethylbenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) l. g, allyl glycidyl ether (Tokyo Chemical Industry Co., Ltd. Manufactured) 31.53 g, 1_ methoxy-2-propanol 143 g, heated to 100. (:, stirring for 12 hours. Thereafter, the reaction solution was cooled to room temperature, and then re-hydrated with water. Precipitation, the solid matter was taken out, and the polymer C of the following structural formula was obtained (weight average molecular weight was 45,000). 8 46 201242460yif g 电位Automatic drip device with potential difference (Kyoto Electronics Industry (aqueous solution of the solution of the titration solution) W Beyin defeated, M fruit, the compound c _ price is 4 31 coffee.
使所得聚合物c溶解於丙酮中，利用IR測定機（崛 場製作所（股）製造）使用KBr結晶進行測定。汉測定的 結果為’於2240 cm-1附近未觀測到波峰，得知聚合物c 不含氰基。另外’藉由酸價測定而得知導入了丙烯酸作為 羧酸單元。進而，使其溶解於氘代DMSO (二曱基亞;ε風） 中，利用布魯克製造的300 MHz的NMR (AV_3〇〇)進行 測定。於 5.9-5.7 ppm( 1H)、5.3-5.2 ppm(2H)、4.1-3.9 ppm (4H)、3.8-3.7 ppm ( 1H)、3.4-3.3 ppm (2H)、2.5-0.7 ppm (3H)觀察到寬的相當於含有聚合性基的單元的波峰，於 2.5-0.7ppm (3H)觀察到寬的相當於羧酸基單元的波峰， 得知含有聚合性基的單元：叛酸基单元=58 : 42( mol比）。 (合成例4 :比較聚合物1) 於500 mL的三口燒瓶中加入1-甲氧基-2-丙醇28.7 g，於氮氣流下加熱至65°C。向其中用4小時滴加丙烯腈 (東京化成工業（股）製造）5.9g、丙烯酸（東京化成工 47 r^ 201242460 ^uuuzpif 業（股）製造^ 18.7g、V_65 (和光純藥工業（股）製造） 0.74 g的1·甲氧基·2·丙醇28.7 g溶液。滴加結束後，進而 擾拌,3小其後’添加1_甲氧基·2_轉41 g，將反應溶 液冷卻至至/孤於上述反應溶液中添加4-經基-TEMPO 0.06 g、三乙基苄基氣（東京化成工業（股）製造）i7g、 甲基丙烯酸縮水甘油酯（東京化成工業（股）製造）816g， 加熱至95 C反應4小時。反應結束後’以乙酸乙酯進行再 沈澱，取出固形物，獲得比較聚合物1 (重量平均分子量 為2.7萬）21 g。利用與合成例丨相同的方法對所得的比 較聚合物1的酸價進行測定，結果該比較聚合物1的酸價 為 5.4 mmol/g。The obtained polymer c was dissolved in acetone, and the measurement was performed using KBr crystals using an IR measuring machine (manufactured by Horiba Seisakusho Co., Ltd.). As a result of the measurement, no peak was observed near 2240 cm-1, and it was found that the polymer c contained no cyano group. Further, it was found that acrylic acid was introduced as a carboxylic acid unit by acid value measurement. Further, it was dissolved in deuterated DMSO (dimercapto; ε wind) and measured by 300 MHz NMR (AV_3〇〇) manufactured by Bruker. Observed at 5.9-5.7 ppm (1H), 5.3-5.2 ppm (2H), 4.1-3.9 ppm (4H), 3.8-3.7 ppm (1H), 3.4-3.3 ppm (2H), 2.5-0.7 ppm (3H) A broad peak corresponding to a unit containing a polymerizable group, a broad peak corresponding to a carboxylic acid group unit was observed at 2.5 to 0.7 ppm (3H), and a unit containing a polymerizable group was known: a tetacid unit = 58: 42 (mol ratio). (Synthesis Example 4: Comparative Polymer 1) To a 500 mL three-necked flask, 28.7 g of 1-methoxy-2-propanol was added, and the mixture was heated to 65 ° C under a nitrogen stream. 5.9 g of acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd. 47 r^201242460 ^uuuzpif Co., Ltd.) 18.7 g, V_65 (Wako Pure Chemical Industries Co., Ltd.) Manufactured) 0.74 g of 1·methoxy-2-propanol 28.7 g solution. After the addition was completed, the mixture was further scrambled, and after 3 hours, '1 methoxy·2· to 41 g was added, and the reaction solution was cooled. To the above reaction solution, 4-ion-TEMPO 0.06 g, triethylbenzyl gas (manufactured by Tokyo Chemical Industry Co., Ltd.), i7 g, glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 816 g, heated to 95 C for 4 hours. After the reaction was completed, 'reprecipitated with ethyl acetate, and the solid matter was taken out to obtain 21 g of Comparative Polymer 1 (weight average molecular weight: 27,000). The same as in the synthesis example. The acid value of the obtained comparative polymer 1 was measured, and as a result, the acid value of the comparative polymer 1 was 5.4 mmol/g.
^ Jcir^ Jcir
4n cA)H 比較聚合物1 <實例1> [底層絕緣基板的製作] 於玻璃環氧基板（商品名：FR-4，松下電工（股）製 造）上，以0.2 MPa的壓力於l〇〇°C〜110 C的條件下，使 用真空層疊機進行加熱及加壓’ 黏接味之素精密技術 (Ajinomoto Fine-Techno )(股）製邊的環氧系絕緣膜 48 201242460# (GX-13,45^)，藉此於基板上形成 於170Ϊ下進行1小時加熱處理，進、费巴:彖層。其後， 層化，獲得基板Α卜 μ電乳絕緣層的熱 [被鐘敷層形成] 繼而，以厚度成為1·0 μπι的方式於基板〜上利用旋 轉塗佈法塗佈後述被鍍敷層形成用組成物，然後於80它〜 120°C下乾燥。 ' 然後，對基板A1上的被鑛敷層形成用組成物層使用 曝光機（紫外線照射裝置，UVX-02516S1LP01，牛尾(ushio) 電機（股）製造）’以波長為254 nm的紫外光於室溫下進 行2分鐘全面曝光（能量：5 全面曝光後，為了將不 需要的被鑛敷層形成用組成物去除，將附有被鍍敷層的基 板於以下組成的鹼性水溶液A (液溫：60°C，pH值：13.6) 中浸潰5分鐘，將被鍍敷層的未硬化部分清洗去除。 藉此’獲得具有基板A1及被鍍敷層（清洗後的厚度： 0.6 μιη)的基板 A2。 (被錢敷層形成用組成物） ^聚合物A 3.1 g '碳酸氫鈉 2.0 g |水 24.6 g 甲氧基-2-丙醇 12.3 g (鹼性水溶液A) 2-胺基乙醇 3g t(氧伸乙基)辛基苯基轉 2g4n cA)H Comparative Polymer 1 <Example 1> [Production of Underlying Insulating Substrate] On a glass epoxy substrate (trade name: FR-4, manufactured by Matsushita Electric Works Co., Ltd.) at a pressure of 0.2 MPa at 10 Torr 〇 °C ~ 110 C, using a vacuum laminator for heating and pressing 'Ajinomoto Fine-Techno' (Ajinomoto Fine-Techno) edge of the epoxy-based insulating film 48 201242460# (GX- 13,45^), thereby forming a heat treatment on the substrate at 170 Torr for 1 hour, and entering, Fiba: enamel layer. Thereafter, stratification is performed to obtain heat of the substrate μ 电 电 绝缘 绝缘 [ [ 被 被 被 被 被 被 被 被 [ [ [ [ [ [ [ [ [ [ [ [ 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热The layer was formed into a composition and then dried at 80 ° C to 120 ° C. Then, an exposure machine (UV irradiation device, UVX-02516S1LP01, manufactured by ushio motor) was used for the composition layer for forming a layer on the substrate A1 to emit ultraviolet light at a wavelength of 254 nm. Full exposure for 2 minutes at a temperature (energy: 5) After the full exposure, in order to remove the unnecessary composition for forming a layer, the substrate with the layer to be plated is placed in an alkaline aqueous solution A (liquid temperature) : 60 ° C, pH: 13.6) After immersing for 5 minutes, the unhardened portion of the plated layer was cleaned and removed. Thus, the substrate A1 and the plated layer (thickness after cleaning: 0.6 μm) were obtained. Substrate A2 (Constituent for forming a layer of money) ^Polymer A 3.1 g 'Sodium hydrogencarbonate 2.0 g |Water 24.6 g Methoxy-2-propanol 12.3 g (alkaline aqueous solution A) 2-Aminoethanol 3g t (oxyethyl) octylphenyl to 2g
49 S 201242460 4UUUZpif (和光純藥公司製造） •氫氧化鈉 •水 93 g [鐘敷觸媒賦予] 將基板A2於硝酸鈀0.1質量％的水溶液中浸潰1〇分 名里’然後以療顧水清洗。利用感應耦合電漿（Inductivdy49 S 201242460 4UUUZpif (manufactured by Wako Pure Chemical Co., Ltd.) • Sodium hydroxide • Water 93 g [Calculation of the catalyst] The substrate A2 was immersed in a 0.1% by mass aqueous solution of palladium nitrate in a 1 minute name. Water cleaning. Using inductively coupled plasma (Inductivdy
Coupled Plasma ’ Icp)發光分析裝置（島津製作所（股） 製造）對此時的鈀離子的吸附量進行測定’結果為0.10 g/m ° [無電解鎮敷處理] 將賦予鍍敷觸媒（金屬鹽）後的基板A2於以下組成 的無電解鍍敷浴（鹼性：pH值為12.5)中浸潰6小時，形 成厚度為0.4 μιη的無電解鍍鋼層。 (無電解鍍敷浴成分） •硫酸銅 0.35 g •酒石酸鈉鉀 1.75 g •氫氧化鈉 0.75 g •甲醛 0.25 g •水 47.8 g [電解鍍敷處理] 將形成有無電解鍍銅層的基板浸潰於以下組成的電_ 鍍銅浴，於電流密度為3 A/dm2的條件下進行約20分轎的 電解鎮敷。電解鍍敷後的鍍銅層（金屬膳）的厚度為約18 μιη 〇 50 201242460〆The Coupled Plasma ' Icp ) luminescence analyzer (manufactured by Shimadzu Corporation) is used to measure the amount of palladium ion adsorbed. The result is 0.10 g/m ° [electroless-free treatment] The plating catalyst (metal) is applied. The substrate A2 after the salt was immersed in an electroless plating bath (basic: pH: 12.5) having the following composition for 6 hours to form an electroless plated steel layer having a thickness of 0.4 μm. (electroless plating bath composition) • Copper sulfate 0.35 g • Sodium potassium tartrate 1.75 g • Sodium hydroxide 0.75 g • Formaldehyde 0.25 g • Water 47.8 g [Electroplating treatment] Submerged the substrate on which the electroless copper plating layer is formed In the electro_copper bath of the following composition, electrolysis was carried out for about 20 minutes under the condition of a current density of 3 A/dm2. The thickness of the copper plating layer (metal meal) after electrolytic plating is about 18 μm 〇 50 201242460〆
38 g 95 g 1 mL (電解鍍敷浴成分） »硫酸銅 *硫酸 •鹽酸38 g 95 g 1 mL (electrolytic bath composition) » copper sulfate * sulfuric acid • hydrochloric acid
•Copper Gleam PCM ( Meltex (股）製造）3.5 mL •水 500 g [圖案形成步驟] 對電解鍍敷後的基板於170°C下進行1小時的加熱處 理後’於該基板表面層疊乾式抗姓劑膜（日立化成（股） 衣1^_的RY3315，膜厚為30 μιη)。繼而，於層疊有乾式抗 姓劑膜的基板上’使可利用減成法而形成L/s；=5〇 μπι梳形圖案的玻璃遮罩密著，對抗蝕劑的感光區域進行 曝光。曝光後，以2 kg/m2的喷霧壓力賦予NaHC03水溶 液，進行顯影處理。其後，對基板進行水洗、乾燥，於鍍 銅層上形成抗钕劑圖案。 將形成有抗蝕劑圖案的基板浸潰於FeCl2/Hcl水溶液 宏為WC )中，藉此進行金屬膜的钱刻，將抗餘劑圖 ’2形成區域中存在的鍍銅去除。其後，於5〇。〇下以2 :圖的宰喷^力賦予_4質量％水溶液2分鐘，將抗 案剝離’獲得圖案化的金屬膜。 [版焊劑的貼附] 件^有目案化金膜的積層體於llG°C、().2MPa的條 利財^疊阻焊劑（舰_，太陽油墨製造（股）製造）， 長為365 nm的曝光機照射42〇 mJ的光能量。 51 201242460 4UUU^pif 繼而，對基板實施8(rc/i〇分鐘的加熱處理後，以2 kg/m2的喷霧壓力對基板表面賦予NaHC〇3的10%水溶 液，藉此進行顯影，加以乾燥。其後，再次利用中心波長 為365 nm的曝光機對基板照射100〇111：[的光能量。最後^ 行150°C/1 hr的加熱處理，獲得經阻焊劑被覆的配線基板。 <實例2> 將鹼性水溶液的液溫變更為45Ϊ：，將被鍍敷層的未硬 化部分清洗去除，除此以外，按照與實例丨相同的順序獲 得配線基板。 <實例3、實例4、實例5> 根據表1的記載來變更醇胺及界面活性劑的種類，除 此以外’按照與實例1相同的順序獲得配線基板。再者， 所使用的界面活性劑為聚氧伸乙基聚氧丙二醇（花王股份 有限公司製造，EmulgenPP-290)、月桂酸鈉（和光純藥公 司製造）。 <實例6> 使用鹼性水溶液B，該鹼性水溶液B是利用30%HC1 水溶液將[被鍍敷層形成]中使用的鹼性水溶液A調整為p Η 值= 10.0而成，除此以外，按照與實例1相同的順序獲得 配線基板。 <實例7> 使用以下組成的鹼性水溶液C (pH值：13.6)代替鹼 性水溶液A ’除此以外’按照與實例1相同的順序獲得配 線基板。 52 201242460 (鹼性水溶液c) 胺基乙醇 '聚(氧伸乙基)辛基苯基醚 (和光純藥公司製造） 2g 87 g 氫氧化鈉 水 <實例8> 將[被鍍敷層形成]中使用的被鍍敷層形成用組成物中 的聚合物A換成聚合物B，且將鹼性水溶液中的聚(氧伸乙 基)辛基苯基醚換成山梨糖醇酐單硬脂酸酯（花王股份有限 公司製造’ Rheodol AS-10V) ’除此以外，按照與實例1 相同的順序獲得配線基板。 <實例9> 將[被鍍敷層形成]中使用的被鍍敷層形成用組成物中 的聚合物A換成聚合物C，除此以外，按照與實例1相同 的順序獲得配線基板。 <比較例1> 使用以下的鹼性水溶液D (pH值：11.6)代替[被鍍敷 層形成]中使用的驗性水溶液A，除此以外，按照與實例1 相同的順序獲得配線基板 (驗性水溶液D) •碳酸納 1 g •水 99 g <比較例2>• Copper Gleam PCM (manufactured by Meltex) 3.5 mL • Water 500 g [Pattern forming step] After the electrolytically plated substrate is heated at 170 ° C for 1 hour, the dry anti-surname is stacked on the surface of the substrate. The film of the film (RY3315 of Hitachi Chemical Co., Ltd.) has a film thickness of 30 μm. Then, on the substrate on which the dry anti-surname film is laminated, a glass mask which can be formed into a L/s by a subtractive method; a comb pattern of 5 〇 μπι is adhered, and the photosensitive region of the resist is exposed. After the exposure, the NaHCO03 aqueous solution was applied at a spray pressure of 2 kg/m2 to carry out development treatment. Thereafter, the substrate was washed with water and dried to form an anti-caries agent pattern on the copper plating layer. The substrate on which the resist pattern was formed was immersed in the FeCl2/Hcl aqueous solution macro (WC), whereby the metal film was burned, and the copper plating existing in the region where the anti-residue pattern was formed was removed. Thereafter, at 5 〇. The underside of the figure was given a _4 mass% aqueous solution for 2 minutes, and the resist was peeled off to obtain a patterned metal film. [attachment of the flux] The layered body of the gold film with a mesh of gold is deposited at llG ° C, (). 2 MPa, and the solder resist (ship _, manufactured by Sun Ink Manufacturing Co., Ltd.), The 365 nm exposure machine illuminates 42 〇mJ of light energy. 51 201242460 4UUU^pif Then, after the substrate was subjected to 8 (r/i 〇 minute heat treatment, a 10% aqueous solution of NaHC〇3 was applied to the surface of the substrate at a spray pressure of 2 kg/m 2 to develop and dry the substrate. Thereafter, the substrate is again irradiated with 100 〇 111: [light energy by an exposure machine having a center wavelength of 365 nm. Finally, heat treatment at 150 ° C / 1 hr is performed to obtain a solder resist-coated wiring substrate. Example 2> The liquid crystal of the alkaline aqueous solution was changed to 45 Å: the uncured portion of the plated layer was washed and removed, and the wiring substrate was obtained in the same order as in Example &. Example 3, Example 4 Example 5> The wiring substrate was obtained in the same order as in Example 1 except that the types of the alcohol amine and the surfactant were changed according to the description of Table 1. Further, the surfactant used was polyoxyethylene extension. Oxypropylene glycol (manufactured by Kao Co., Ltd., Emulgen PP-290), sodium laurate (manufactured by Wako Pure Chemical Industries, Ltd.) <Example 6> An alkaline aqueous solution B was used, which was treated with a 30% aqueous HCl solution. Plating layer formation The wiring board was obtained in the same order as in Example 1 except that the alkaline aqueous solution A used in the above was adjusted to have a p Η value = 10.0. <Example 7> An alkaline aqueous solution C of the following composition was used (pH: 13.6) Instead of the alkaline aqueous solution A 'except this', the wiring substrate was obtained in the same order as in Example 1. 52 201242460 (alkaline aqueous solution c) Aminoethanol 'poly(oxyethyl) octylphenyl ether (and pure light) Manufactured by a pharmaceutical company) 2 g of 87 g of sodium hydroxide water <Example 8> The polymer A in the composition for forming a layer to be formed used in the formation of a layer to be plated is replaced with the polymer B, and is alkaline. Poly(oxyethylidene) octylphenyl ether in aqueous solution was replaced with sorbitan monostearate (manufactured by Kao Co., Ltd. 'Rheidodol AS-10V)' except for the same procedure as in Example 1. The wiring board was obtained. <Example 9> The same procedure as in Example 1 was carried out except that the polymer A in the composition for forming a layer to be plated used in the formation of the layer to be plated was replaced with the polymer C. A wiring board was obtained. <Comparative Example 1> The following alkaline water solution was used. D (pH: 11.6) was used instead of the aqueous solution A used in the formation of the plated layer, except that the wiring substrate (the aqueous solution D) was obtained in the same order as in Example 1. • 1 g of carbonate • water 99 g <Comparative Example 2>
53 S 201242460 40002pif 使用鹼性水溶液E ( pH值：13 6 )代替[被鍍敷層形成] 中使用的祕水溶液A，除此以外，按照與實例丨相同的 順序獲得配線基板。再者，於驗性水溶液E巾不含界面活 性劑。 3g 2 g 95 g (鹼性水溶液E) •2-胺基乙醇 •氫氧化鈉 •水 <比較例3 > 使用鹼性水溶液F (pH值：13 6)代替[被鍍敷層形成] 中使用的驗性水溶液A，除此以外，按照與實例丨相同的 順序獲得配線基板。再者，於驗性水溶液F中不含胺基醇。 (鹼性水溶液F) •聚(氧伸乙基)辛基苯基醚 2g •氫氧化鈉 2g •水 96 g <比較例4> 使用鹼性水溶液G’該鹼性水溶液G是於[被鍍敷層形 成]中使用的鹼性水溶液A中添加30%HC1水溶液而調整 為pH值= 9.0而成，除此以外，按照與實例丨相同的順 獲得配線基板。 、 <比較例5> 將[被鍍敷層形成]中使用的被鍍敷層形成用組成物中 的聚合物A換成比較聚合物1，除此以外，按照與實例】 54 201242460 相同的順序獲得配線基板。 <面狀評價> 所各貫例及比較射，準備上述[無電解錄處理]後 =具有金屬賴積频2° w彳崎描式電子顯微鏡 10000倍），對每1片於任意位置各以5視場觀察 该金屬膜（鍍細）的面狀，觀察所產生的硬塊狀或半球 凸，的大粒的個數（合計100視場）。將所觀察的視場内有 長徑為1·0 μιη以上的硬塊狀或半球凸狀的突粒的情形判 定為不良，計算出不良率（％) {(被判斷為不良的視場數 /100) Χ100}。按照以下基準進行評價。將結果匯總示於表 1中。於實用方面，較佳為「Aj、「B」。 「A」：不良率為〇%以上、小於 「B」：不良率為10%以上、小於2〇% 「C」：不良率為2〇〇/0以上、小於3〇% 「D」：不良率為30%以上 表1中，pH值是指所使用的鹼性水溶液的pH值。 55 20124246053 S 201242460 40002 pif A wiring board was obtained in the same order as in Example 使用 except that the aqueous solution A (pH: 13 6 ) was used instead of the aqueous solution A used in [formation of the layer to be plated]. Further, the aqueous solution E-injection does not contain an interface active agent. 3 g 2 g 95 g (basic aqueous solution E) • 2-aminoethanol • sodium hydroxide • water <Comparative Example 3 > Alkaline aqueous solution F (pH: 13 6) was used instead of [formed by plating layer] A wiring substrate was obtained in the same order as in Example 除 except for the aqueous solution A used in the above. Further, the test aqueous solution F does not contain an amino alcohol. (Basic aqueous solution F) • Poly(oxyethyl) octylphenyl ether 2 g • Sodium hydroxide 2 g • Water 96 g <Comparative Example 4> The alkaline aqueous solution G' was used as the alkaline aqueous solution G In the alkaline aqueous solution A used for the formation of the plating layer, a 30% HCl aqueous solution was added to adjust the pH to 9.0, and the wiring board was obtained in the same manner as in Example 。. <Comparative Example 5> The same procedure as in Example 54 201242460 except that the polymer A in the composition for forming a layer to be plated used in the formation of the layer to be plated was replaced with the comparative polymer 1 The wiring substrate is obtained in order. <Surface evaluation> Each of the examples and the comparison shots were prepared after the above [electroless recording process] = 10,000 times with a metal reticle frequency of 2° w彳 描 描 电子 电子 , , , , , , , , , The surface of the metal film (thinned) was observed in five fields of view, and the number of large particles (total 100 fields of view) of the hard block or hemispherical convexity generated was observed. The case where the lumps of the hard block shape or the hemispherical shape having a long diameter of 1·0 μm or more in the observed field of view were judged to be defective, and the defective ratio (%) {(the number of fields of view judged to be bad/ 100) Χ100}. The evaluation was performed according to the following criteria. The results are summarized in Table 1. In practical terms, it is preferably "Aj, "B". "A": The defect rate is 〇% or more and less than "B": the defect rate is 10% or more and less than 2〇%. "C": The defect rate is 2〇〇/0 or more and less than 3〇%. "D": Bad The rate is 30% or more. In Table 1, the pH value means the pH value of the alkaline aqueous solution used. 55 201242460
Jasi 面狀評價 < PQ DQ < PQ DQ CQ < < Q Ο Q Q Q pH值 13.6 13.6 13.6 13.6 !^_] 〇 1 13.6 13.6 13.6 〇· 13.6 j 13.6 〇 〇\ 13,6 驗性水溶液的液溫 60°C 45 °C 60°C 60°C 60°C 60°C 60°C 60°C 60°C 60°C 60°C 60°C 60°C 60°C 無機驗 NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH | Na2C〇3 1 NaOH NaOH NaOH NaOH 界面活性劑 聚(氧伸乙基)辛基苯基醚 聚(氧伸乙基)辛基笨基醚 聚(氧伸乙基)辛基苯基醚 聚氧伸乙基聚氧丙二醇 月桂酸鈉 聚(氧伸乙基)辛基苯基醚 聚(氧伸乙基)辛基苯基 山梨糖醇酐單硬脂酸酯 聚(氧伸乙基)辛基笨基醚 1 1 聚(氧伸乙基)辛基苯基醚 聚(氧伸乙基)辛基苯基醚 聚(氧伸乙基)辛基苯基醚 胺基醇 2-胺基乙醇 2-胺基乙醇 三乙醇胺 2-胺基乙醇 2-胺基乙醇 2-胺基乙醇 2-胺基乙醇 2-胺基乙醇 2-胺基乙醇 1 2-胺基乙醇 1 2-胺基乙醇 2-胺基乙醇 聚合物的種類 聚合物A 聚合物A 聚合物A 聚合物A 聚合物A 聚合物A 聚合物A 聚合物B 聚合物C 聚合物A 聚合物A 聚合物A 聚合物A 比較聚合物 實例1 實例2 實例3 實例4 實例5 實例6 實例7 實例8 實例9 比較例I 比較例2 比較例3 |比較例4 比較例5 201242460 如表1所示，於實例1〜實例9中，所得的積層體中 的金屬膜的面狀優異。 特別是根據實例1與實例2的比較而確認到，於所使 用的驗性水溶液的溫度為6(TC以上的情形時，金屬膜的面 狀更優異。 另外’根據實例1與實例3的比較而確認到，若使用 單乙醇胺作為所使用的醇胺，則金屬膜的面狀更優異。 另外，根據實例1與實例5的比較而確認到，於使用 非離子糸界面活性劑作為界面活性劑的情形時，金屬膜的 面狀更優異。可推測其原因在於，非離子系界面活性劑以 外的界面活性劑容易吸附於被鍍敷層，容易流出至鍍敷液 中。 另外，根據實例1與實例6的比較而確認到，於鹼性 水溶液的pH值更高（特別是pH值為12以上）的情形時， 金屬膜的面狀更優異。 進而’根據實例1與實例7的比較而確認到，界面活 性劑的含量在1質量％〜5質量％的範圍内的情況下，金 屬膜的面狀更優異。可推測其原因在於，若界面活性劑的 量過多，則於鐘敷液中的流出增多。 另一方面，如比較例1〜比較例3所示，於鹼性水溶 液中不含醇胺或界面活性劑的情形時，無法獲得所需效果。 另外，如比較例4所示，若驗性水溶液的值不在 規定範圍内’則無法獲得所需效果。 進而，如比較例5所示，若使用不具有規定的官能基 57 201242460 4UUU/pif 的聚合物，則與鹼性水溶液接觸後被鍍敷層的膜減少 大，所得的金屬膜的面狀亦差。 玉度 【圖式簡單說明】 圖 1 CA) ^ .回I )为別為依序表示本發明的積展 體及具有圖案化金屬_積層體的製造方法中的各^造^ 驟的自基板至積層體為止的示意性剖面圖。 衣 2 (A)〜11 2 (D)是依序表示本發明的積層雜^ 蝕刻乂驟的一態樣的示意性剖面圖。 、 ^丨^⑷〜11 3 (Ε)是依序表示本發明的積層雜^ 飯刻步驟的其萄樣的示意㈣_。 【主要元件符號說明】 10 ： 基板 12 ： 被鍍敷層 14、 14b :金屬膜 16 ： 積層體 18 ： 圖案化金屬膜 20 : 金屬配線 22 : 絕緣性樹脂層 24 ： 遮罩 58Jasi Face Evaluation < PQ DQ < PQ DQ CQ << Q Ο QQQ pH 13.6 13.6 13.6 13.6 !^_] 〇1 13.6 13.6 13.6 〇· 13.6 j 13.6 〇〇\ 13,6 Authentic aqueous solution Liquid temperature 60 ° C 45 ° C 60 ° C 60 ° C 60 ° C 60 ° C 60 ° C 60 ° C 60 ° C 60 ° C 60 ° C 60 ° C 60 ° C 60 ° C inorganic test NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH | Na2C〇3 1 NaOH NaOH NaOH NaOH Surfactant Poly(oxyethyl) octylphenyl ether poly(oxyethyl) octyl phenyl ether poly(oxyethyl) octyl Phenyl ether polyoxyethylene ethyl polyoxypropylene glycol sodium laurate poly(oxyethyl) octyl phenyl ether poly(oxyethyl) octyl phenyl sorbitan monostearate poly(oxygen extension) Ethyl) octyl phenyl ether 1 1 poly(oxyethyl) octyl phenyl ether poly(oxyethyl) octyl phenyl ether poly(oxyethyl) octyl phenyl ether amino alcohol 2 -aminoethanol 2-aminoethanol triethanolamine 2-aminoethanol 2-aminoethanol 2-aminoethanol 2-aminoethanol 2-aminoethanol 2-aminoethanol 1 2-aminoethanol 1 2- Aminoethanol 2-Aminoethanol Polymer Type Polymer A Polymer A Polymer A Polymer A Polymer A Polymer A Polymer A Polymer B Polymer C Polymer A Polymer A Polymer A Polymer A Comparative Polymer Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example I Comparative Example 2 Comparative Example 3 | Comparative Example 4 Comparative Example 5 201242460 As shown in Table 1, in the examples 1 to 9, the metal film in the obtained laminate was excellent in surface shape. In particular, it was confirmed from the comparison between Example 1 and Example 2 that the surface of the metal film was more excellent when the temperature of the aqueous solution to be used was 6 (TC or more. Further, 'Comparation between Example 1 and Example 3> It was confirmed that when monoethanolamine was used as the alcoholamine to be used, the surface of the metal film was more excellent. Further, it was confirmed by comparison with Example 1 and Example 5 that a nonionic cerium surfactant was used as a surfactant. In the case of the metal film, the surface of the metal film is more excellent. It is presumed that the surfactant other than the nonionic surfactant is easily adsorbed on the layer to be plated, and is likely to flow out into the plating solution. In comparison with Example 6, it was confirmed that the surface of the metal film was more excellent when the pH of the alkaline aqueous solution was higher (particularly, the pH was 12 or more). Further, 'Comparative Example 1 and Example 7 When the content of the surfactant is in the range of 1% by mass to 5% by mass, the surface of the metal film is more excellent. It is presumed that if the amount of the surfactant is too large, On the other hand, as shown in Comparative Example 1 to Comparative Example 3, when the alcoholic solution or the surfactant was not contained in the alkaline aqueous solution, the desired effect could not be obtained. Further, as in Comparative Example 4 As shown in the figure, if the value of the aqueous test solution is not within the predetermined range, the desired effect cannot be obtained. Further, as shown in Comparative Example 5, if a polymer having no predetermined functional group 57 201242460 4UUU/pif is used, the base is used. After the contact of the aqueous solution, the film of the plated layer is greatly reduced, and the surface of the obtained metal film is also poor. Jade degree [simple description of the drawing] Fig. 1 CA) ^. Back I) is the product of the present invention A schematic cross-sectional view of the structure and the layered body from the substrate and the method for producing the patterned metal-layered body. The garments 2 (A) to 11 2 (D) are schematic cross-sectional views sequentially showing one aspect of the laminated etching process of the present invention. And 丨^(4) to 11 3 (Ε) are schematic (4) _ which sequentially show the sample of the laminated layer of the present invention. [Description of main component symbols] 10 : Substrate 12 : Plating layer 14 , 14b : Metal film 16 : Laminated body 18 : Patterned metal film 20 : Metal wiring 22 : Insulating resin layer 24 : Mask 58
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011073168 | 2011-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201242460A true TW201242460A (en) | 2012-10-16 |
Family
ID=46931015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW101110799A TW201242460A (en) | 2011-03-29 | 2012-03-28 | Laminate having metal layer and method for manufacturing the same, and laminate having patterned metal layer and method for manufacturing the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2012214889A (en) |
| TW (1) | TW201242460A (en) |
| WO (1) | WO2012133297A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018034291A1 (en) * | 2016-08-19 | 2018-02-22 | 富士フイルム株式会社 | Composition for forming plated layer, plated layer, substrate provided with plated layer, electroconductive film, touch panel sensor, and touch panel |
| JP7160554B2 (en) * | 2018-05-07 | 2022-10-25 | 株式会社日本触媒 | RESIN COMPOSITION FOR OPTICAL MATERIAL AND USES THEREOF |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4365114B2 (en) * | 2003-02-28 | 2009-11-18 | トヨタ自動車株式会社 | Pretreatment method of electroless plating material, manufacturing method of plating coated member, and plated component |
| JP5448524B2 (en) * | 2008-04-23 | 2014-03-19 | 富士フイルム株式会社 | Laminated film for plating, surface metal film material production method and surface metal film material |
| JP2010229536A (en) * | 2009-03-30 | 2010-10-14 | Nippon Mining & Metals Co Ltd | Pretreatment agent for electroless plating, and pretreatment method for electroless plating using the same |
| JP2010239080A (en) * | 2009-03-31 | 2010-10-21 | Fujifilm Corp | Method of forming conductive film, method of manufacturing printed wiring board, and conductive film material |
-
2012
- 2012-03-26 WO PCT/JP2012/057739 patent/WO2012133297A1/en active Application Filing
- 2012-03-28 TW TW101110799A patent/TW201242460A/en unknown
- 2012-03-28 JP JP2012073386A patent/JP2012214889A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012133297A1 (en) | 2012-10-04 |
| JP2012214889A (en) | 2012-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5419441B2 (en) | Method for forming multilayer wiring board | |
| KR101625421B1 (en) | Surface metal film material, process for producing surface metal film material, process for producing metal pattern material, and metal pattern material | |
| TWI503383B (en) | Composition for forming plating layer and method for producing laminate having metal film | |
| WO2008050715A1 (en) | Metal-film-coated material and process for producing the same, metallic-pattern-bearing material and process for producing the same, composition for polymer layer formation, nitrile polymer and method of synthesizing the same, composition containing nitrile polymer, and layered product | |
| WO2012046615A1 (en) | Laminate production process | |
| JP2010185128A (en) | Photosensitive resin composition for plating, laminate, method of producing surface metal film material using the same, surface metal film material, method of producing metal pattern material, metal pattern material, and wiring board | |
| CN103828497B (en) | Attached aperture layer stack and manufacture method, the manufacture method of multilager base plate, printed circuit board and bottom formation compositions | |
| JP5579160B2 (en) | Method for producing a laminate having a metal film | |
| JP2010077322A (en) | Composition for forming plated layer, production method for metal pattern material and metal pattern material obtained thereby, and production method for surface metal film material and surface metal film material obtained thereby | |
| WO2012133684A1 (en) | Production method for laminate having patterned metal films, and plating layer-forming composition | |
| TW201242460A (en) | Laminate having metal layer and method for manufacturing the same, and laminate having patterned metal layer and method for manufacturing the same | |
| WO2012073814A1 (en) | Method for producing laminate having metal film | |
| WO2013065628A1 (en) | Method for producing laminate having metal layer | |
| WO2011118797A1 (en) | Composition for forming plating layer, surface metal film material and method for producing same, and metal pattern material and method for producing same | |
| JP2012031447A (en) | Composition for forming layer to be plated, material for surface metal film and method for producing the same, and material for metal pattern and method for producing the same | |
| TW201244576A (en) | Method for manufacturing printed wiring board and IC package substrate | |
| TW201643655A (en) | Method for producing conductive film for touch panel sensor, conductive film for touch panel sensor, and touch panel | |
| WO2012133032A1 (en) | Production method for laminate having patterned metal films, and plating layer-forming composition | |
| JP2012180561A (en) | Laminated body having metal film and method for producing the same, and laminated body having patterned metal film and method for producing the same | |
| WO2012029865A1 (en) | Method for manufacturing multilayer wiring board | |
| TW201132795A (en) | Method of plate pretreatment and production method of surface metal film material | |
| JP2012207258A (en) | Composition for forming layered to be plated, and method for producing laminate having metal film | |
| JP2008274390A (en) | Process for producing metal-film-coated substrate, metal-film-coated substrate, process for producing metallic-pattern material, and metallic-pattern material | |
| JP2012246535A (en) | Lamination stack having metal film and method for manufacturing the same, and lamination stack having patterned metal film and method for manufacturing the same | |
| JP2011190484A (en) | Composition for forming the layer to be plated, surface metal film material, method for producing the same, metal pattern material and method for producing the same |