TW201238750A

TW201238750A - Method for manufacturing laminate having patterned metal layer and composition for forming plating layer

Info

Publication number: TW201238750A
Application number: TW101110954A
Authority: TW
Inventors: Takeyoshi Kano; Tetsufumi Takamoto; Shiki Ueki
Original assignee: Fujifilm Corp
Priority date: 2011-03-29
Filing date: 2012-03-29
Publication date: 2012-10-01
Also published as: WO2012133684A1; JP2012214895A

Abstract

The method for manufacturing the laminate having the patterned metal layer includes: a plating layer formation step for forming a plating layer on a substrate by using a composition, wherein the composition for forming the plating layer includes a polymer having specific units; a catalyst applying step for applying a plating catalyst or a precursor thereof to the plating layer; a plating step for forming a metal layer on the plating layer by a plating treatment; a pattern formation step for forming a patterned metal layer using an etchant; an acid solution contacting step for contacting the substrate having the patterned metal layer with an acid solution; and a plating layer removal step for removing the plating layer where the patterned metal layer is not formed by the plasma etching treatment.

Description

201238750 ^υυυ^ριι 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圖案化金屬膜的積層體的製造方法、以及該製造方法中使用的被鍍敷層形成用組成物。【先前技術】自先前以來’於電子零件或半導體元件中廣泛使用金屬配線基板’該金屬配線基板是於絕緣性基板的表面上形成有藉由金屬圖案形成的配線。該金屬圖案材料的製作方法主要使用「減成法 (subtractive process)」。所謂該減成法是指如下方法：在形成於基板表面的金屬膜上設置藉由照射活性光線而感光的感光層，對該感光層進行圖像曝光，然後進行顯影而形成抗蝕劑像，繼而，對金屬膜進行蝕刻而形成金屬圖案，最後剝離抗触劑。利用該方法獲得的金屬圖案中，由於藉由在基板表面設置凹凸喊㈣ϋ著縣（anehw e細），表現出基相與金屬圖案（金屬膜）之間的密著性i此，當將所得# 金屬圖案㈣金屬配線時’由於金屬随的基板界面部纪凹凸而存在高頻特性變差的問題。另外，為了對基板表运進行凹凸化纽，必f利祕酸等_來處理基板表面，因此為了獲得與基板的密著性優異的金屬圖案繁雜步驟的問題。作為解決關題財法，在基板上形絲基板具有高密者性的聚合㈣聚合物層實麵敷，可不使基扬 4 201238750 凹凸化而形成密著性優異的金屬層（專利文獻丨）。依據該方法，能夠在不使基板的表面粗糙化的情況下改良基板^ 金屬膜的密著性。另外’關於該方法，已知可形成對鍍敷觸媒或者其前驅體的吸附性優異的被鍍敷層的被鍍成用組成物（專利文獻2、專利文獻3)。夕 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2009_007662號公報 [專利文獻2]曰本專利特開2〇1〇_248464號公報 [專利文獻3]曰本專利特開2〇〇9·1〇336號公報另一方面，近年來，在印刷配線板等的微細配線中，，配線（金！圖案）的高集成化，要求配線間的絕緣可罪性進-步提高。另外，同時就經濟性的觀點而言，對於進行全面錄且藉由_來形成配線的工法（半加成工法、減成工法）的需求提高。本發明者等人考慮將專利文獻2中記載的包含規定單 _聚合物應餘需求提糾半加拉法或者減成工法，使用該聚合物戦被職層，在賴鍍敷紅製作圖案化 ^屬膜（鑛敷膜）。此時發現，殘存於金屬配線間的被鐘敷 θ與金屬配線間的絕緣可靠性相關。即發現存在如下情 2右形成圖案化金屬膜後，該被錢敷層殘存於配線圖案間，則成為使_化金屬關的絕緣性下降的要因。區Μ本發明者等人為了將未設置有圖案化金屬膜的 -域所存在的讀敷層絲，吨行魏_處理，結果 5 201238750 發現存在以下問題：為了去除被錢敷層而需要長時間的處理時間，或者無法充分去除被鍍敷層。【發明内容】本發明鑒於上述實情，目的在於提供一種具有圖案化金屬膜的積層體的製造方法、以及該製造方法中使用的被鑛敷層形成用組成物’上述製造方法可容易實施被鍍敷層的電漿蝕刻處理，能夠獲得圖案化金屬膜間的絕緣性優異的積層體。本發明者等人對上述課題進行積極研究’結果發現’ 藉由使用具有規定單元的聚合物，並且設置與規定酸性溶液的接觸步驟，能夠解決上述課題。即’本發明者等人發現可藉由以下所示的手段來達成上述目的》 (〇 —種具有圖案化金屬膜的積層體的製造方法，包括以下步驟：被鍍敷層形成步驟，使被鍍敷層形成用組成物接觸於基板上後，對基板上的上述被鍍敷層形成用組成物賦予能量，在基板上形成被鍍敷層，其中該被鍍敷層形成用組成物包含具有後述式（A)所表示的單元、後述式（B)所表示的單元、以及後述式（C)所表示的單元的聚合物；觸媒賦予步驟，對被鍍敷層賦予鍍敷觸媒或者其前驅體；鑛敷步驟’對被賦予鍍敷觸媒或者其前驅體的被鍍敷層進行鑛敷處理’在被鍍敷層上形成金屬膜； 6 201238750. 圖案形成步驟，在鍍敷步驟後，使用包含金屬成分或過氧化氫的蝕刻液來形成圖案化金屬膜；酸性溶液接觸步驟，使具有圖案化金屬膜的基板、與實質上不含金屬成分或過氧化氫的酸性溶液接觸；以及被鍍敷層去除步驟，藉由電漿蝕刻處理而去除未形成圖案化金屬膜的區域的被鍍敷層。 (2) 如（1)所述之具有圖案化金屬膜的積層體的製造方法，其中钮刻液為酸性。 (3) 如（1)或（2)所述之具有圖案化金屬膜的積層體的製造方法，其中金屬成分為銅離子或者鐵離子。 (4) 如（1)至（3)中任一項所述之具有圖案化金屬膜的積層體的製造方法，其中酸性溶液為鹽酸水溶液、硫酸水溶液、或者确酸水溶液。 (5) —種配線基板，包括：利用如（1)至（4)中任一項所述之製造方法來製造的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上的絕緣層。 (6) —種被鍍敷層形成用組成物，包含具有後述式 (A)所表示的單元、後述式（B)所表示的單元、以及後述式（C)所表示的單元的聚合物。 (7) 如（6)所述之被鍵敷層形成用組成物，其中式 (A)所表示的單元為後述式（A-1)所表示的單元。 (8) 如（7)所述之被鍍敷層形成用組成物，其中L1 為可經曱基、乙基或者丙基所取代的碳數1〜6的二價直鏈狀烴基。 201238750 (9)如（6)至（8)中任一項所述之被鍍敷層形成用組成物，其中式（B)所表示的單元為後述式（B-1)所表示的單元、或者後述式（B_2)所表示的單元。 [發明的效果] 依據本發明’能夠提供一種具有圖案化金屬膜的積層體的製造方法、以及該製造方法中使用的被鍍敷層形成用組成=，上述製造方法可容易實施被鍍敷層的電漿蝕刻處理，能夠獲得圖案化金屬膜間的絕緣性優異的積層體。【實施方式】以下，對本發明的具有圖案化金屬膜的積層體的製造 =法:以及該方法巾使㈣被綠層形賴組成物的較佳貫施態樣進行說明。說明首先，對本發明與先前技術相比較的特徵點進行詳細專利人對將藉由先前技術（上述專利文獻1〜去除記載的發明而獲得的積層體中的被錢敷層示時的問逋進行研究，結果發現，殘存於金屬成分造成影響。即，金屬成分殘、x層中的的被_的電_處理存越夕，越會對其後度充分的金屬膜(鍍數膜广並且所二本發明者等人基於上述發現而進仃積極研究，結果發 8 201238750 現’精由使用實質上不含着其笼皆At甘洋舻其#缺甘不3亂基4s旎基，而是具有鲮酸基、二基、她基、或者它們的鹽等相互作用性基，且且有規^絲的聚合物，並且_規定的_液對金屬膜進行触亥'’進而在電襞㈣處理前使被链敷層與酸性溶液接觸，從而獲得所需的效果。更v、體而。，上述竣酸基等相互作用性基具有與鍍敷，媒吸附的特性’但在㈣性賴供給祕子的情況下，容易脫附鍍敷觸媒。即發現，利用酸性溶液，被鍍敷層中的金屬成分被去除’電漿蝕刻處理更良好地進行。此外，在氛基等的情況下，難以產生由氫離子引起的鍍敷觸媒的脫附，無法獲得所需的效果。首先’對本發明的被鍍敷層形成用組成物的構成成分 (聚合物等）進行詳細說明，然後，對使用該組成物的具有圖案化金屬膜的積層體的製造方法進行詳細說明。〈被錢敷層形成用組成物〉 (聚合物）本發明中使用的聚合物至少具有式（A)所表示的單元、式（B)所表示的單元、以及式（c)所表示的單元。藉由聚合物中包含式（A)所表示的單元，則形成聚合物間的交聯，或在基板與聚合物之間形成化學鍵結’所得金屬膜的密著性進一步提高。進而，由於具有（曱基）丙烯醯胺基而可形成耐鹼性高的膜。另外’式（B)所表示的單元中的羧酸基、磺酸基、磷酸基、或者它們的鹽能夠吸附鍍敷觸媒，由此可進行後述的無電解鍍敷等。另外， 201238750 觸媒或者液姑可使吸附於被職層中的鍍敷觸媒難㈣ί 狀金__财職，鍍敷時可所矣-u 矛、被錢敷層。進而’藉由包含式（c) 敷時的驗溶液引起的損傷。解式（Α) R1 式（Β) 式（C)[Technical Field] The present invention relates to a method for producing a laminate having a patterned metal film, and a composition for forming a layer to be plated used in the method of the present invention . [Prior Art] Since the prior art, a metal wiring substrate has been widely used in an electronic component or a semiconductor device. The metal wiring substrate has a wiring formed of a metal pattern on the surface of the insulating substrate. The method of producing the metal pattern material mainly uses a "subtractive process". The subtractive method refers to a method in which a photosensitive layer which is exposed to light by irradiation with 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 a resist image. Then, the metal film is etched to form a metal pattern, and finally the anti-contact agent is peeled off. In the metal pattern obtained by the method, the adhesion between the base phase and the metal pattern (metal film) is exhibited by providing the unevenness on the surface of the substrate (4), and the adhesion between the base phase and the metal pattern (metal film) is obtained. # Metal pattern (4) In the case of metal wiring, there is a problem that the high-frequency characteristics are deteriorated due to the unevenness of the substrate interface portion of the metal. Further, in order to carry out the unevenness of the substrate surface, it is necessary to treat the surface of the substrate by using a sulphuric acid or the like. Therefore, in order to obtain a complicated procedure of the metal pattern excellent in adhesion to the substrate. As a solution to the problem, the filament substrate having a high-density polymerized (four) polymer layer is applied to the substrate, and the metal layer having excellent adhesion can be formed without embossing the base 4 201238750 (Patent Document 丨). According to this method, the adhesion of the substrate to the metal film can be improved without roughening the surface of the substrate. In addition, it is known that a plating composition for forming a plated layer having excellent adhesion to a plating catalyst or a precursor thereof can be formed (Patent Document 2, Patent Document 3). [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-007662 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei No. Hei. On the other hand, in recent years, in the fine wiring such as a printed wiring board, the wiring (gold! pattern) is highly integrated, and the insulation between the wirings is required to be sinful. improve. In addition, from the viewpoint of economy, the demand for a method of semi-addition and semi-addition, which is fully recorded and formed by _, is increased. The inventors of the present invention have considered the use of the polymer ruthenium layer or the subtractive method in the case where the predetermined single-polymer is contained in the patent document 2, and the pattern is formed by using the polymer layer. ^ is a membrane (mineral coating). At this time, it was found that the clocked θ remaining in the metal wiring was related to the insulation reliability between the metal wirings. In other words, it has been found that when the patterned metal film is formed on the right side and the deposited layer is left between the wiring patterns, the insulation property of the metal-based metal is lowered. In order to remove the coated layer of the patterned metal film, the inventors of the present invention found that the presence of the patterned layer of the patterned metal film was not treated. The processing time of the time, or the plating layer cannot be sufficiently removed. In view of the above circumstances, an object of the present invention is to provide a method for producing a laminate having a patterned metal film, and a composition for forming an ore layer used in the method of production. The plasma etching treatment of the cladding layer can obtain a laminate having excellent insulation between the patterned metal films. The inventors of the present invention have conducted active research on the above problems. As a result, it has been found that the above problem can be solved by using a polymer having a predetermined unit and providing a contact step with a predetermined acidic solution. That is, the inventors of the present invention have found that the above object can be attained by the means described below (a method for producing a laminate having a patterned metal film, comprising the steps of: a step of forming a layer to be plated After the composition for forming a plating layer is in contact with the substrate, energy is applied to the composition for forming a layer to be plated on the substrate, and a layer to be plated is formed on the substrate, wherein the composition for forming a layer to be plated includes a unit represented by the formula (A), a unit represented by the formula (B) described later, and a polymer of a unit represented by the formula (C) described later; a catalyst application step of applying a plating catalyst to the layer to be plated or a precursor; a mineralizing step 'mineralizing a plated layer to which a plating catalyst or a precursor thereof is applied' to form a metal film on the layer to be plated; 6 201238750. Pattern forming step in the plating step Thereafter, an etching solution containing a metal component or hydrogen peroxide is used to form a patterned metal film; an acidic solution contacting step, a substrate having a patterned metal film, and an acid substantially free of metal components or hydrogen peroxide Contact with a solution; and a step of removing the plated layer, the plated layer of the region where the patterned metal film is not formed is removed by a plasma etching process. (2) A patterned metal film as described in (1) The method for producing a laminate, wherein the button engraving is acidic. (3) The method for producing a laminate having a patterned metal film according to (1) or (2), wherein the metal component is copper ion or iron ion. (4) The method for producing a laminate having a patterned metal film according to any one of (1) to (3), wherein the acidic solution is an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, or an aqueous acid solution. The substrate includes a laminate having a patterned metal film produced by the production method according to any one of (1) to (4), and an insulating layer provided on the laminate having the patterned metal film. (6) A composition for forming a layer to be plated, comprising a polymer having a unit represented by the following formula (A), a unit represented by the formula (B) described later, and a unit represented by the formula (C) described later. (7) The composition for forming a key layer as described in (6), The unit represented by the formula (A) is a unit represented by the following formula (A-1). (8) The composition for forming a layer to be plated according to (7), wherein L1 is a thiol group or an ethyl group. Or a composition for forming a layer to be plated according to any one of (6) to (8), wherein The unit represented by B) is a unit represented by the following formula (B-1) or a unit represented by the following formula (B_2). [Effects of the Invention] According to the present invention, it is possible to provide a layered body having a patterned metal film. The manufacturing method and the composition for forming a layer to be plated used in the production method = the above-described production method can easily perform plasma etching treatment of the plated layer, and can obtain a layered body excellent in insulation between the patterned metal films . [Embodiment] Hereinafter, a method for producing a laminate having a patterned metal film of the present invention and a method for producing a green layer-formed composition of the present invention will be described. First, the feature points of the present invention in comparison with the prior art will be described in detail by the patentee of the prior art (the above-mentioned Patent Document 1 to the invention of the invention described above) As a result of the research, it has been found that the metal component remains in the metal component, that is, the metal component is left in the x layer, and the metal film is deposited on the night. The second inventor and others based on the above findings and actively researched the results, the results of the 8 201238750 now 'fine use of substantially no cages are at the end of the Gan Yang 舻 # 缺缺缺 # # # # # # 缺缺缺An interactive group having a decanoic acid group, a diyl group, a her group, or a salt thereof, and having a ruthenium-based polymer, and the _prescribed _ liquid is applied to the metal film and further in the electric enthalpy (4) Before the treatment, the chain coating layer is brought into contact with the acidic solution to obtain the desired effect. More v, the body, the above-mentioned interaction group such as a decanoic acid group has the characteristics of plating and medium adsorption, but in the (four) nature In the case of the supply of secrets, it is easy to desorb plating In the case of using an acidic solution, the metal component in the layer to be plated is removed, and the plasma etching treatment is performed more satisfactorily. In the case of an atmosphere or the like, it is difficult to generate a plating catalyst caused by hydrogen ions. The detachment does not provide the desired effect. First, the constituent components (polymer or the like) of the composition for forming a layer to be plated of the present invention will be described in detail, and then, the patterned metal film using the composition will be described. The method for producing a layered product is described in detail. <Polymer layer forming composition> (Polymer) The polymer used in the present invention has at least a unit represented by the formula (A) and a unit represented by the formula (B). And a unit represented by the formula (c). By including a unit represented by the formula (A) in the polymer, crosslinking between the polymers is formed, or a chemical bond is formed between the substrate and the polymer. Further, the adhesion is further improved. Further, the (fluorenyl) acrylamide group can form a film having high alkali resistance. Further, the carboxylic acid group, the sulfonic acid group, and the phosphoric acid group in the unit represented by the formula (B). ,or The salt of the salt can adsorb the plating catalyst, and thus electroless plating, etc., which will be described later, can be performed. In addition, the catalyst or liquid gutta of 201238750 can make the plating catalyst adsorbed in the occupied layer difficult (4) _ _ _ _ In the case of plating, you can use the -u spear and the money layer, and then the damage caused by the test solution containing the formula (c). Solution (Α) R1 Formula (Β) Formula (C)

0’ Z0’ Z

X 表示ί^Α)〜式（c)中’Rl、R2HRW^A& 原子、或者曱基。較佳為氫原子。其R3表示氫原子、甲基、乙基、第三丁基、或者正丁基。 Ϊ面，朗加每單位重量㈣合性基4來提高聚合感度的，以及（曱基）丙烯醯胺基的聚合性的方面而言，較佳馬氧原子。合成V，不單鍵、酯基、醯胺基、或者伸笨基。其中，就的各易度方面以及本發明的效果優異佳為單鍵、喊、或者伸苯基，更佳為醋基。 W表示單鍵、酯基、醯胺基、或者伸苯基。其中，就 201238750 u 增加=位重量的x的含量的觀點而言’較佳為單鍵。明的、|=二價絲。域的魏並無特職制，就本發月的效果更優異的方面而言，較料碳數卜6，更佳 1〜3。煙基的種類可為二價脂肪族烴基（例如亞甲基、伸乙基）、或者二價芳香族烴基（例如伸苯基）中的任一^。此外’脂肪族烴基可為直鏈狀、分支狀、環狀中的任一種，亦可經氧原子或烷基取代。其中，就增加每單位重量的聚合性基量來提高聚合感度的方面而言’L1較佳為可經選自由甲基、乙基及丙基所組成組群中的基團所取代的碳數卜3的二價直鍵狀煙基。 L2表示單鍵、或者二價有機基。二價有機基可列舉：經取代絲經取代的脂肪族煙基 (較佳為碳數1〜8 )、經取代或未經取代的芳香族烴基（較佳為碳數 6〜12)、-〇-、-S-、_s〇r、_n(R)- (R :烷基）、 -CO-、-NH-、-COO-、-CONH-、或者將該些基團組合而成的基團（例如伸烷基氧基、伸烷基氧基羰基（alkylene〇xy carbonyl)、伸烷基羰基氧基等）等。經取代或未經取代的脂肪族烴基較佳為亞甲基、伸乙基、伸丙基、或伸丁基，或者該些基團經甲氧基、氯原子、溴原子、或氟原子等取代的基團。經取代或未經取代的芳香族烴基較佳為未經取代的伸笨基或者經曱氧基、氯原子、溴原子、或氟原子等取代的伸苯基。其中，就聚合物的親水性的方面而言，L2較佳為可經 20123875(^ 選自由曱基、乙基及丙基所組成組群中的基團所取代的碳數1〜6的二價直鏈狀烴基、環氧乙烷基、環氧丙烷基、具有酯基（-COO-)的碳數2〜8的二價烴基、或者單鍵，最佳為單鍵。 X表示叛酸基、續酸基、碟酸基、或者它們的鹽。其中’就合成的容易性的方面而言’較佳為緩酸基、項酸基，就化合物的穩定性的方面而言，更佳為羧酸基。 Z表示-OR7基、或者·N(R8)2基。其中，就耐鹼性方面而言，較佳為-N(R8)2基。 R7表示院基、苯基、或者將它們組合而成的基團。此外’ R中可包含_〇_ (氧原子）。烷基例如可列舉：甲基、乙基、異丙基、正丙基、正丁基、第二丁基、第三丁▲、者2乙基己基。其中，就紐性方面而言，較佳為異丙基、第三丁基。二:步提 (較佳態樣）態樣可列舉式（A-ι)所式（Α)所表示的單元的較佳表示的單元。 12X represents ί^Α)~ in the formula (c), 'Rl, R2HRW^A& atom, or fluorenyl. It is preferably a hydrogen atom. R3 represents a hydrogen atom, a methyl group, an ethyl group, a tert-butyl group, or an n-butyl group. The kneading surface is preferably a horse oxygen atom in terms of the polymerization sensitivity per unit weight (four) of the chelating group 4 and the polymerization property of the (fluorenyl) acrylamide group. Synthesis of V, not a single bond, an ester group, a guanamine group, or a stupid base. Among them, the ease of use and the effect of the present invention are preferably a single bond, a shout, or a phenyl group, and more preferably a vine group. W represents a single bond, an ester group, a guanamine group, or a phenyl group. Among them, from the viewpoint of increasing the content of x of the bit weight of 201238750 u, it is preferably a single bond. Ming, |= divalent silk. Wei of the domain does not have a special system. In terms of the more excellent effect of this month, it is better to compare the number of carbons to 6, preferably 1 to 3. The type of the nicotine group may be any one of a divalent aliphatic hydrocarbon group (for example, a methylene group, an ethyl group) or a divalent aromatic hydrocarbon group (for example, a phenyl group). Further, the 'aliphatic hydrocarbon group' may be any of a linear chain, a branched chain, and a cyclic group, and may be substituted with an oxygen atom or an alkyl group. Wherein, in terms of increasing the amount of polymerizable base per unit weight to increase the polymerization sensitivity, 'L1 is preferably a carbon number which can be substituted with a group selected from the group consisting of methyl, ethyl and propyl groups. Divalent straight-chain cigarette base of Bu3. L2 represents a single bond or a divalent organic group. The divalent organic group may, for example, be an aliphatic nicotyl group substituted with a substituted silk (preferably having a carbon number of 1 to 8), a substituted or unsubstituted aromatic hydrocarbon group (preferably having a carbon number of 6 to 12), 〇-, -S-, _s〇r, _n(R)-(R:alkyl), -CO-, -NH-, -COO-, -CONH-, or a combination of the groups a group (for example, an alkyleneoxy group, an alkylene oxycarbonyl group, an alkylcarbonyloxy group, etc.). The substituted or unsubstituted aliphatic hydrocarbon group is preferably a methylene group, an exoethyl group, a propyl group or a butyl group, or the groups are subjected to a methoxy group, a chlorine atom, a bromine atom, or a fluorine atom. Substituted group. The substituted or unsubstituted aromatic hydrocarbon group is preferably an unsubstituted extended or substituted phenyl group substituted with a decyloxy group, a chlorine atom, a bromine atom, or a fluorine atom. Wherein, in terms of the hydrophilicity of the polymer, L2 is preferably a carbon number of 1 to 6 which may be substituted by a group in the group consisting of a sulfhydryl group, an ethyl group and a propyl group; A straight-chain hydrocarbon group, an oxirane group, an oxypropylene group, a divalent hydrocarbon group having a carbon number of 2 to 8 having an ester group (-COO-), or a single bond, preferably a single bond. X represents a tickic acid. a group, a carboxylic acid group, a dish acid group, or a salt thereof, wherein 'in terms of ease of synthesis' is preferably a slow acid group or an acid group, and is more preferable in terms of stability of the compound. Is a carboxylic acid group. Z represents an -OR7 group or an N(R8)2 group. Among them, in terms of alkali resistance, a -N(R8)2 group is preferred. R7 represents a substituent, a phenyl group, or A group in which they are combined. Further, 'R may contain _〇_ (oxygen atom). Examples of the alkyl group include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, and second butyl group. The base, the third butyl group, and the 2 ethyl hexyl group. Among them, in terms of the kinility, the isopropyl group and the third butyl group are preferred. The second step: the preferred aspect can be enumerated ( A-ι) ) Unit is preferably a unit represented by represented. 12

201238750r - -IT - A 式（A-l)201238750r - -IT - A type (A-l)

i (n :::1、r2、& li的定義如上所述。的容易度的_ 表示氧好、或者视5_基。就合成 :5,靦點而§，γ較佳為氧原子。 R表示氫原子、甲其中，就提高每單位番θΜ基第二丁基、或者正丁基。為氫原子。重1的聚合性基量的方面而言，較佳所表^的/元的較錢樣可列舉：式（Β-1) 3者式（B-2)所表示的單元。The definition of i (n ::: 1, r2, & li is as described above. The ease of _ indicates that oxygen is good, or depends on 5-base. Synthesize: 5, 腼 and §, γ is preferably an oxygen atom R represents a hydrogen atom or a group thereof, and the amount of the second butyl group or the n-butyl group per unit is increased. It is a hydrogen atom. In terms of the amount of the polymerizable group of 1 weight, it is preferable to The unit of the formula (Β-1) 3 (B-2) can be cited.

式（Μ)式 U-2) X $ (Β·υ中，R4、L2及X狀義如上所述。 / (B-1)中，Y表示氧原子、或者NR5基。R5表示 13 201238750 氫原子、曱基、乙基、第三丁基、或者正丁基。其中，就合成的容易度的方面而言，較佳為氧原子。式（B-2)中，R4及X的定義如上所述。此外，式（B-1)與式（B-2)中，式（B-2)為更佳的態樣。式（C)所表示的單元的較佳態樣可列舉式（C-1)所表示的單元。式（C-1) R6 〇人—8)2 式（C-1)中，R6及R8的定義如上所述。以下表示式（A)所表示的單元的一例。 14 201238750Formula (Μ) Formula U-2) X $ (Β·υ, R4, L2 and X are as defined above. In / (B-1), Y represents an oxygen atom or an NR5 group. R5 represents 13 201238750 Hydrogen An atom, a mercapto group, an ethyl group, a tributyl group, or an n-butyl group. Among them, in terms of ease of synthesis, an oxygen atom is preferred. In the formula (B-2), R4 and X are as defined above. Further, in the formula (B-1) and the formula (B-2), the formula (B-2) is a more preferable aspect. The preferred aspect of the unit represented by the formula (C) can be exemplified ( C-1) The unit represented by the formula (C-1) R6 〇人—8) 2 In the formula (C-1), R6 and R8 are as defined above. An example of the unit represented by the formula (A) is shown below. 14 201238750

另外，以下表示式（B)所表示的單元的一例。 15 201238750In addition, an example of the unit represented by the formula (B) is shown below. 15 201238750

η=4-5 η®5*6 另外，以下表示式（c)所表示的單元的一例。η=4-5 η®5*6 Further, an example of a unit represented by the formula (c) is shown below.

16 201238750 聚^巾的式⑷所表示的單元的含有限制，就反應性（硬化性、聚合性）：特別膠，方面而言，相對於«合物〜60莫耳。/。，更佳為5莫耳％〜4G莫;％較佳為5莫耳％另外，聚合物中的式（B)所矣；„ — 無特別限制，就對鑛_媒或者其率並而言，相對於總聚合物單元，較佳為:莫體耳 == 方面更佳為30莫耳％〜8()莫耳％。莫耳M0莫耳％’ 無特別限制聚;::3么(S )所表示的單元的含有率並了於〜聚合物早兀，較佳為5莫 5莫耳❶/。〜50莫耳％。 75莫耳/。，更佳為以上H㈣量平均分子量並無__，較佳為麵乂上70萬以下，尤佳為2000以上、加笼以丁聚合感度的觀點而言，較佳為2_以：萬的凝膠化的_而言，較佳為1G萬以下。物制&成時聚物^去聚合物的聚合度並無特別限制，較佳為使用10 令物以τ尤佳為2〇聚物以上者。另外，較佳為7000 更佳為3000聚物以下’尤佳為2_聚物以下，特佳為1000聚物以下。 ^皮鍍敷層形成用組成物中的聚合物的含量並無特別限 ’相對於組成物總量，較佳為2質量％〜5〇質量％，更，為5質夏％〜3〇質量％。若聚合物的含量在上述範圍内，則組成物的操作性優異，容易控制被鍍敫層的層厚。 17 201238750 〈被鍍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可視需要包含溶劑。可使用的溶劑並無特別限定，例如可列舉：水、曱醇 (methanol)、乙醇（ethanol)、丙醇（propanol)、乙二醇 (ethylene glycol )、甘油（glyCerin )、丙二醇單曱醚 (propylene glycol monomethyl ether)等醇系溶劑，乙酸 (acetic acid )等酸，丙酮（acet〇ne )、甲基乙基酮（methyi ethyl ketone)、環己g同（cyclohexanone)等酮系溶劑，曱醢胺（formamide )、二曱基乙醯胺（dimethyl acetamide )、 N-曱基0比11各咬酮（N-methylpyrrolidone )等醯胺系溶劑，乙腈（acetonitrile)、丙腈（propionitrile)等腈系溶劑，乙酸曱酯（methyl acetate )、乙酸乙酯（ethyl acetate )等 g旨系溶劑’碳酸二曱醋（dimethyl carbonate )、碳酸二乙酉旨 (diethyl carbonate )等碳酸酯系溶劑，除此以外還可列舉醚系溶劑、二醇系溶劑、胺系溶劑、硫醇系溶劑、_素系溶劑等。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、二曱基乙醯胺、甲基乙基酮、環己酮、乙腈、丙腈、]^-甲基°比嘻咬酮、碳酸二曱酯。在被鍍敷層形成用組成物中包含溶劑的情況下，冲目對於組成物總量，溶劑的含量較佳為50質量％〜98質量％，更佳為70質量％〜95質量％。若溶劑的含量在上述範圍 18 201238750t 内，則組成物的操作性優異，容易控制被鍍敷層的層厚等。 (其他添加劑）本發明的被鍍敷層形成用組成物中，可視需要添加其他的添加劑（例如聚合起始劑、單體、增感劑、硬化劑、聚合抑制劑、抗氡化劑、抗靜電劑、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）。〈具有圖案化金屬膜的積層體的製造方法〉藉由使用上述被鍍敷層形成用組成物，可製造具有圖案化金屬膜的積層體。該製造方法主要包括以下6個步驟。 (被鍍敷層形成步驟）使上述被鍍敷層形成用組成物 ^於基板上後’對基板上的被錄層形成馳成物賦予能量，在基板上形成被鍍敷層的步驟； (觸媒賦予步驟）對被鏟敷層賦予職驅體的步驟； / j 数屛、對被賦予鍍敷觸媒或者其前驅體的被鍍敷曰進仃織處理’在被鍍敷層上形成金相的步驟；成步驟)在鍍敷痛，使用包含金屬成分成過軋化虱_刻液來形成圖案化金屬膜的步驟；盘實接觸步驟）使具有随化金屬膜的基板、驟貫質上不3金屬成分或過氧化氫的酸性溶液接觸的步成圖二====:處㈣去除未形以下’對各步驟中使用的材料、以及其操作方法進行 19 201238750 詳細說明。〈被鍍敷層形成步驟〉被鍍敷層形成步驟是使上述被鍍敷層形成用組成物接觸於基板上後’對被鍍敷層形成用組成物賦予能量，在基板上升>成被錄敷層的步驟。藉由該步驟形成的被鍍敷層根據式（B)所表示的單元中的羧酸基、磷酸基、或者確酸基等的功能，在後述觸媒賦予步驟中吸附（附著）鍍敷觸媒或者其則驅體。即，被鍍敷層作為鍍敷觸媒或者其前驅體的良好受容層而發揮功能。另外，式（A)所表示的單元中的一聚合鍵結基用於聚合物彼此的鍵結、或與基板（或者後述的密著輔助層）的化學鍵結。其結果為，在形成於被鍍敷層的表面的金屬膜（鍍敷膜）與基板之間表現出優異的密著性。此外，本步驟令的較佳態樣是被鍍敷層與基板經由化學鍵結而鍵結的態樣。更具體而5，該步驟中，如圖1 (A)所示在基板10 的上部形成被鍍敷層12 ^此外，如下所述，基板10可在其表面具有密著辅助層，在此情況下，被鍍敷層12形成於密著輔助層上。首先，對本步驟中使用的材料（基板、密著輔助層等）進行詳細說明，然後對該步驟的順序進行詳細說明。 (基板）本發明所使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，較佳為上述基板的表面具有可與後述聚合物化學鍵結的功能。具體而 20 201238750 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’或者可在基板上設置藉由能量賦予而與被鍍敷層形成化學鍵結的中間層（例如後述的密著輔助層）。基板的材料並無特別限定，例如可列舉：高分子材料 (例如二乙酸纖維素（cellulose diacetate )、三乙酸纖維素 (cellulose triacetate )、丙酸纖維素（ceuulose pr〇pi〇nate )、丁酸纖維素（cellulose butyrate)、乙酸纖維素（ceuui〇se acetate)、石肖酸纖維素（cellulose nitrate)、聚對苯二甲酸乙二酯（polyethylene terephthalate )、聚乙烯（p〇iyethylene )、聚本乙婦（polystyrene )、聚丙婦（p〇iypr〇pyiene)、聚乙烯縮醛（polyvinyl acetal)、聚醯亞胺（polyimide)、環氧 (epoxy )雙順丁細一酿亞胺樹脂（bismaleinimide resin )、聚苯醚（polyphenylene oxide )、液晶聚合物（Hquid crystalline P〇lymer )、聚四 ι 乙烯（p〇lytetraflu⑽ethylene ) 等）、金屬材料（例如金屬合金、含金屬的材料、純粹金屬、或者與該些材料類似的材料；具體而言為鋁、辞、銅等的混合物、合金、及它們的合金（all〇y))、其他材料（例如紙、層疊有塑膠的紙）、該些材料的組合、或者與該些材料類似的材料等。另外，本發明的積層體可應用於半導體封裝、各種電氣配線基板等。在用於此種用途的情況下，較佳為使用以下所不的包含絕緣性樹脂的基板，具體而言使用包含絕緣性樹脂的基板（絕緣性基板）、或者表面具有絕緣性樹脂的層（絕緣性樹脂層）的基板（帶有絕緣性樹脂層的基板 21 201238750^ 此外’基板可為其表面交替具有金屬配線層及絕緣性樹脂層，且在最表層配置有絕緣性樹脂層的基板。在獲得包含絕緣性樹脂的基板、包含絕緣性樹脂的層的情況下，使用公知的絕緣性樹脂組成物。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，熱硬化性樹知可列舉.環氧樹脂（ep〇Xy resin)、盼樹脂（phen〇i resin )、聚醯亞胺樹脂（p〇iyimide resin )、聚醋樹脂 (polyester resin)、雙順丁稀二酿亞胺樹脂（bismaieimide resin )、聚稀樹脂（p〇iy〇iefin )、異氰酸酯樹脂（is〇cyanate resin )、丙烤腈丁二稀苯乙稀（aCryi〇nitrile butadiene styrene，ABS)樹脂等。環氧樹脂例如可列舉：甲酚酚醛（cres〇l n〇v〇lac)型環氧樹脂、雙齡A (bisphenol A)型環氧樹脂、雙驗F (bisphenolF)型環氧樹脂、苯紛紛搭（phen〇inov〇iac) 型環氧樹脂、烧基苯紛紛酸( 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（dicy clopentadiene )型環氧樹脂、酚類與具有酚性羥基的芳香族醛的縮合物的環氧化物、脂環式環氧樹脂等。該些環氧樹脂可單獨使用，亦可併用2 種以上。熱塑性樹脂例如可列舉：苯氧基樹脂（phen0Xy resin)、聚醚礙（polyether sulfone)、聚硪（p〇iysuifone)、聚苯硬（polyphenylene sulfone)、聚苯硫醚（p〇iyphenyiene 22 201238750 • V V V W 11 sulfide )、聚苯醚（p〇iyphenyiether )、聚醚醯亞胺 (polyetherimide )等 ° (密著輔助層）密著輔助層是可設置於上述基板表面上的任意的層，發揮辅助基板與後述被鍍敷層的密著性的作用。該層^為16 201238750 The content of the unit represented by the formula (4) of the condensed towel is limited, and the reactivity (hardenability, polymerizability): special gel, in terms of the compound, is relative to the compound of 60 to 60. /. More preferably, it is 5 mol%~4G mo; % is preferably 5 mol%. In addition, the formula (B) in the polymer is 矣; „ - no particular limitation, on the mineral or the rate With respect to the total polymer unit, it is preferred that the molar body == aspect is more preferably 30 mol% to 8 () mol%. Mohr M0 mol %' without special restriction poly;::3 ( The content of the unit represented by S) is equal to that of the polymer, preferably 5 moles of 5 moles / 50 mole %. 75 moles /., more preferably the above H (four) amount of average molecular weight and __, preferably 70,000 or less on the enamel, particularly preferably 2,000 or more, and the cage is preferably a gelation of 10,000. The degree of polymerization of the polymer and the polymer to be polymerized is not particularly limited, and it is preferably used as a ruthenium or a ruthenium or the like. More preferably, it is 3,000 or less, and it is more preferably 2 or less, more preferably 1000 or less. The content of the polymer in the composition for forming a skin plating layer is not particularly limited to the total amount of the composition. Quantity, preferably 2 mass When the content of the polymer is within the above range, the handleability of the composition is excellent, and it is easy to control the layer thickness of the ruthenium-plated layer. 17 201238750 〈 Other optional components in the composition for forming a layer to be plated (solvent) The solvent-forming layer-forming composition may optionally contain a solvent. The solvent to be used is not particularly limited, and examples thereof include water and methanol. ), ethanol, propanol, ethylene glycol, glycol (glyCerin), propylene glycol monomethyl ether, alcoholic solvents, acetic acid (acetic acid) and other acids, acetone Ketone solvent such as (acet〇ne), methyi ethyl ketone, cyclohexanone, formamide, dimethyl acetamide, N-oxime a phthalamide solvent such as N-methylpyrrolidone, a nitrile solvent such as acetonitrile or propionitrile, a methyl acetate or ethyl acetate; Solvent solvent Carbonate-based solvents such as dimethyl carbonate and diethyl carbonate may, for example, be an ether solvent, a glycol solvent, an amine solvent, a thiol solvent, or a sulphur-based solvent. Solvents, etc. Among them, 'the preferred one is a guanamine solvent, a ketone solvent, a nitrile solvent, or a carbonate solvent. Specifically, acetone, dimethyl acetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, Propionitrile, ]^-methyl ° is better than bitten ketone or dinonyl carbonate. In the case where a solvent is contained in the composition for forming a layer to be plated, the content of the solvent is preferably from 50% by mass to 98% by mass, and more preferably from 70% by mass to 95% by mass based on the total amount of the composition. When the content of the solvent is within the above range 18 201238750t, the handleability of the composition is excellent, and it is easy to control the layer thickness of the layer to be plated and the like. (Other Additives) In the composition for forming a layer to be plated of the present invention, other additives may be added as needed (for example, a polymerization initiator, a monomer, a sensitizer, a hardener, a polymerization inhibitor, a chelating agent, and an anti-detergent). Electrostatic agents, UV absorbers, fillers, particles, flame retardants, surfactants, lubricants, plasticizers, etc.). <Method for Producing Laminates Having Patterned Metal Films> By using the above-described composition for forming a layer to be plated, a laminate having a patterned metal film can be produced. The manufacturing method mainly includes the following six steps. (Step of forming a layer to be plated), after the composition for forming a layer to be plated is formed on a substrate, a step of applying energy to a layer formed on the substrate, and forming a layer to be plated on the substrate; The catalyst imparting step) is a step of imparting a job to the shovel layer; /j is 屛, and the plating is applied to the plating layer or the precursor to which the plating catalyst or the precursor is applied. a step of metallographically; forming a step of forming a patterned metal film using a metal component into an over-rolled ruthenium-etching solution; a disk-contacting step) causing a substrate having a conformal metal film Steps in which the acidic solution of the metal component or hydrogen peroxide is not in contact with Fig. 2 ====: (4) Removal of the unformed below 'The materials used in each step, and the method of operation thereof are described in detail in 2012 201250. <Step of forming a layer to be plated> The step of forming a layer to be plated is to bring the composition for forming a layer to be plated into contact with the substrate, and then to apply energy to the composition for forming a layer to be plated, and to rise on the substrate. The step of recording the layer. The plated layer formed in this step adsorbs (attaches) the plating touch in the catalyst application step described later according to the function of the carboxylic acid group, the phosphoric acid group, or the acid group in the unit represented by the formula (B). The media or its body. That is, the layer to be plated functions as a plating medium or a good receiving layer of the precursor. Further, a polymerizable bonding group in the unit represented by the formula (A) is used for the bonding of the polymers or the chemical bonding with the substrate (or the adhesion assisting layer described later). As a result, excellent adhesion between the metal film (plating film) formed on the surface of the layer to be plated and the substrate is exhibited. Further, a preferred aspect of this step is a state in which the plated layer and the substrate are bonded by chemical bonding. More specifically, in this step, as shown in FIG. 1(A), a plated layer 12 is formed on the upper portion of the substrate 10. Further, as described below, the substrate 10 may have an adhesion auxiliary layer on its surface, in which case Next, the plated layer 12 is formed on the adhesion assisting layer. First, the materials (substrate, adhesion assisting layer, etc.) used in this step will be described in detail, and the order of the steps will be described in detail. (Substrate) As the substrate to be used in the present invention, any of the previously known substrates can be used as long as it is a substrate having shape retention. Further, it is preferred that the surface of the substrate has a function of being chemically bonded to a polymer to be described later. Specifically, 20 201238750, the substrate itself can form a chemical bond with 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 can be disposed on the substrate (for example, described later) Adhesive layer). The material of the substrate is not particularly limited, and examples thereof include a polymer material (for example, cellulose diacetate, cellulose triacetate, cellulose propionate (ceuulose pr〇pi〇nate), butyric acid). Cellulose butyrate, ceuui〇se acetate, cellulose nitrate, polyethylene terephthalate, polyethylene (p〇iyethylene), polybenz Polystyrene, p〇iypr〇pyiene, polyvinyl acetal, polyimide, epoxy bissuccinimide resin (bismaleinimide resin) ), polyphenylene oxide, liquid crystal polymer (Hquid crystalline P〇lymer), polytetrafluoroethylene (p〇lytetraflu(10)ethylene), etc., metal materials (such as metal alloys, metal-containing materials, pure metals, or Materials similar to those materials; specifically, mixtures of aluminum, rhodium, copper, etc., alloys, and alloys thereof (all〇y)), other materials (examples) Paper, plastic laminated paper), the combination of these materials, or a material similar to the plurality of materials. Further, the laminate of the present invention can be applied to a semiconductor package, various electric wiring boards, and the like. When it is used for such an application, it is preferable to use a substrate containing an insulating resin as described below, specifically, a substrate (insulating substrate) containing an insulating resin or a layer having an insulating resin on its surface ( Substrate (Insulating Resin Layer) Substrate (Substrate 21 with Insulating Resin Layer) The substrate may be a substrate in which an insulating resin layer is disposed on the outermost surface of the substrate in which the metal wiring layer and the insulating resin layer are alternately arranged. When a substrate including an insulating resin or a layer containing an insulating resin is obtained, a known insulating resin composition is used. Specific examples of the insulating resin may be, for example, a thermosetting resin or a thermoplastic resin. A mixture of the resins may be mentioned, for example, an epoxy resin (ep〇Xy resin), a phen〇i resin, a p〇iyimide resin, or a poly Polyester resin, bismaieimide resin, polystyrene resin, isocyanate resin ), acryi〇nitrile butadiene styrene (ABS) resin, etc. Examples of the epoxy resin include: cresol novolac (cres〇ln〇v〇lac) type epoxy resin, double age A (bisphenol A) type epoxy resin, double-accurate F (bisphenolF) type epoxy resin, benzene phen〇inov〇iac type epoxy resin, alkyl phenol novolac type epoxy resin, Biphenol F type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, condensate of phenol and aromatic aldehyde having phenolic hydroxyl group Epoxy resin, alicyclic epoxy resin, etc. These epoxy resins may be used singly or in combination of two or more. Examples of the thermoplastic resin include phenoxy resin (phenOxy resin) and polyether sulfone (polyether sulfone). , polypyrene (p〇iysuifone), polyphenylene sulfone, polyphenylene sulfide (p〇iyphenyiene 22 201238750 • VVVW 11 sulfide ), polyphenylene ether (p〇iyphenyiether), polyetherimide (polyetherimide) Etc. ° (adhesive auxiliary layer) Promoter layer is an optional layer may be provided on the substrate surface, and play an auxiliary substrate to be plated later adhesion effect of the coating. This layer ^ is

對基板與被鍍敷層具有親和性的層，亦可在硬化時^聚合物反應而形成化學鍵結。 D 此外，若基板為板狀物，則可在其兩面形成密著辅助層。密著輔助層較佳為聚合物在硬化時（尤其在光硬化時）產生化學鍵結的層。此種產±化學鍵結的密著辅助層中較佳為導人聚合起始劑。糾，就作#性的無*言，密著輔助層較佳為使用水分散乳膠來形成。密著輔助層較佳為使用與基板的密著性良好的樹脂組成物、以及可藉由曝絲產生自由基的化合物（聚合起始劑）來形成。此外，在構成樹脂組成物的樹脂具有可產^ 自由基的部位的情況τ，衫要另行添加可產生自由化合物。此外，使用先前公知的光聚合起始劑作為藉由曝光而產生自由基的化合物。該光聚合起始劑例如可列舉對第三 (p-tert-butyltrichloroacetophenone)> 2,2'- 二乙苯乙嗣（2,2Ldieth〇XyaCet〇phenone)等。密著辅助層中所含的光聚合起始劑（可藉由曝光而產生自由基的化合物）的量較佳為以固體成分計為0.1質量 %〜50質量％，更佳為1.0質量％〜30質量％。 23 201238750 作為本發明中的密著輔助層，例如在基板包含層積層板、增層基板、或者可撓性基板的材料來使用的二 =絕緣性樹脂的情況下，就與該基板的密著性的觀點二言，作為形成密著輔助層時使用的樹脂組成物，” 用絕緣性樹脂組成物。该馮便以下 ’對基板包含絕緣性樹脂，且密著輔助層由絕性樹脂組成物形成的態樣進行說明。形成密著輔助層時使用的絕緣性樹脂組成物可包含與構成基板的電氣絕緣性樹脂相同的樹脂，亦可包含不同^ 樹脂，較佳為使用玻璃轉移點或彈性模數、熱物性相近的樹脂。具體而言，例如就密著的方面^專較佳為使用麟成純的絕雜触㈣種_絕緣性樹脂。此外，所謂密著輔助層中使用的絕緣性樹脂，是指具有可用於公知絕緣膜的程度的絕緣性的樹脂，即便不是^ 王的絕緣體’只要是具有符合目的之絕緣性的樹脂，則亦可應用於本發明。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/ 生树&可列舉.環氧购旨旨、聚酿亞麟脂、聚醋^脂、雙順丁歸二醯亞胺樹脂、聚烯烴樹脂、異氰酸酯 ^月曰等。，塑性樹脂例如可列舉：苯氧基樹脂、聚喊石風、 ^風、聚苯硬、聚苯硫越、聚苯輕、聚醚醢亞胺、ABS樹月曰等。熱麵樹脂與熱硬化性樹脂可分別單獨使用，亦可 24 201238750. 併用2種以上。本發明中的密著輔助層的厚度通常為〇1师〜的範圍，較佳為0.2 μπι〜5 μιη的範圍。在設置密著辅助声的！:二Ϊ厚度為上述範圍’則獲得與鄰接的基材、i 被鍍敷層的充分的密著強度，另外，雖 _ 接劑相比較，該密著輔助層為薄層層相_㈣性。彳-錢與其黏接劑的密著輔助層是對基材表面應用塗佈法法等公知的層形成方法而形成。 *卩法印刷密著輔助層可視需要，利用印網版犧、柔版印刷法、噴墨印刷法、壓印=刷= 影法（例如濕式姓刻、乾式餘刻、剝韻（abla 2 :的硬化.可塑化(負型/正型)等)等將密著補助層圖: 量來:行卜硬:::助材上後，可賦予某種能電子束等，財料舉光、熱、壓力、载〜300。(；的熱5分鐘〜情況下’較佳為施加著輔===密5著:助層形成後立即進行’若在密理，則可在進行密預備硬化處步驟之後實施。曰$成後所進㈣其他所有的各 (步驟的順序）使上述被鑛敷層形成用組成物接觸於基板上（或者密 25 201238750 著輔助層上）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；或在被鍍敷層形成用組成物為包含溶劑的液狀的情況下，將組成物塗佈於基板上的方法等。就容易控制所得被鍵敷層的厚度的方面而&，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，具體的方法可使用以下的公知方法.利用旋轉塗佈機（Spin c〇ater )、浸潰塗佈機（^ coater )、雙輥塗佈機（double roll coater )、狹縫塗佈機（slit coater)、氣刀塗佈機（air knife coater)、線棒塗佈機（wire bar C〇ater)、滑動漏斗（slide hopper)、喷射塗佈（spray C〇atlng )、刀片塗佈機（blade coater )、刮刀塗佈機（doctor coater )、壓擠塗佈機（squeeze coater )、逆轉輥塗佈機 (reverse roll coater )、轉送輥塗佈機（transfer r〇11 c〇ater)、擠壓式塗佈機（extrusi〇n c〇ater)、簾幕式塗佈機（curtain C〇ater)、模塗佈機（diecoater)、凹版輥（gravureroll)的塗佈法，擠出塗佈法，輥塗佈法等。就操作性或製造效率的觀點而言，較佳為如下態樣：將被鑛敷層开>成用組成物塗佈於基板（或者密著輔助層）上並使其乾燥，去除殘存的溶劑，形成包含聚合物的組成物層。在使被鍍敷層形成用組成物與基板接觸的情況下，就與後述鍍敷觸媒或者其前驅體的充分的相互作用形成性的觀點而言，上述被鍍敷層形成用組成物的塗佈量較佳為以固體成分換算計為〇」g/m2〜1〇g/m2，特佳為〇 5 g/m2〜5 26 201238750 g/m2 〇此外，本步驟中形成被鍍敷層時，亦可於塗佈與乾燥之間在20 C〜4〇°C下放置〇·5小時〜2小時，來去除殘广' 的溶劑。示子 (能量的賦予）對基板上的被鍍敷層形成用組成物賦予能量的方法並無特別限制，例如較佳為使用加熱或曝光等。曝光時使用藉由紫外線（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。放射線有電子束、χ射、^ ' ，子束、遠紅外線等。另外，亦使用g線、丨線、深υν光、高密度能量束（雷射束）。 *通常使用的具體態樣較佳為列舉：藉由紅外線雷射的掃描曝^、4氣放f料的冑照度閃紐曝光、紅曝光等。曝光時間會根據聚合物的反應性以及光源而不同，通常為1〇秒〜5小時之間。曝光能量只要是10mJ〜8_mJ 左右即可，較佳為i〇()m〗〜3_m：r的範圍。此外，在使用加熱作為能量辭的情況下，可使用鼓風乾燥機、、烘箱、紅外線乾燥機、加熱滾筒等。 =得被鍍敷層的厚度並鱗別聞，就金屬The layer having an affinity for the substrate and the layer to be plated may also react with the polymer to form a chemical bond upon hardening. D Further, if the substrate is a plate, an adhesion auxiliary layer may be formed on both surfaces thereof. The adhesion assisting layer is preferably a layer in which the polymer chemically bonds upon hardening, especially during photohardening. Preferably, such a chemically bonded adhesion assisting layer is a donor polymerization initiator. Correction, it is made of #性无言, the adhesion of the auxiliary layer is preferably formed using water-dispersed latex. The adhesion assisting layer is preferably formed using a resin composition having good adhesion to the substrate and a compound (polymerization initiator) which can generate radicals by exposure. Further, in the case where the resin constituting the resin composition has a site capable of generating a radical, τ may be added separately to produce a free compound. Further, a previously known photopolymerization initiator is used as a compound which generates a radical by exposure. The photopolymerization initiator may, for example, be p-tert-butyltrichloroacetophenone > 2,2'-diethyl acetophenone (2,2Ldieth〇XyaCet〇phenone). The amount of the photopolymerization initiator (a compound capable of generating a radical by exposure) contained in the adhesion assisting layer is preferably from 0.1% by mass to 50% by mass, more preferably 1.0% by mass, based on the solid content. 30% by mass. 23 201238750 In the case of the adhesion assisting layer in the present invention, for example, when the substrate comprises a laminated substrate, a build-up substrate, or a material of a flexible substrate, the second insulating resin is adhered to the substrate. Sexual point of view, as a resin composition used when forming an adhesion auxiliary layer, "using an insulating resin composition. The following is a case where the substrate contains an insulating resin, and the adhesion assisting layer is composed of an insulating resin. The insulating resin composition used for forming the adhesion assisting layer may include the same resin as the electrically insulating resin constituting the substrate, or may contain a different resin, preferably using a glass transfer point or elasticity. A resin having a similar modulus and thermal properties. Specifically, for example, in terms of adhesion, it is preferable to use an inert contact (four) type of insulating resin. In addition, the insulation used in the adhesion auxiliary layer is used. The resin is an insulating resin having a degree of insulation that can be used for a known insulating film, and even if it is not an insulating resin, it is a resin having a purpose of insulating properties. The present invention can be applied to, for example, a thermosetting resin, a thermoplastic resin, or a mixture of the resins. The purpose of the invention is to use a phenolic resin, a polystyrene resin, a polyolefin resin, an isocyanate, and the like. Wind, wind, polystyrene, polyphenylene sulfide, polyphenylene light, polyether sulfimine, ABS tree sorghum, etc. Hot surface resin and thermosetting resin can be used separately, or 24 201238750. The thickness of the adhesion assisting layer in the present invention is usually in the range of 〇1 division 〜, preferably in the range of 0.2 μπι to 5 μιη. In the case where the auxiliary sound is set! A sufficient adhesion strength to the adjacent substrate and the i-plated layer is obtained, and the adhesion-preserving layer is a thin layer phase (four) compared to the binder. 彳-money and its adhesive The adhesion assisting layer is a known layer forming method such as a coating method applied to the surface of the substrate. Formed by the law. * The method of printing the adhesion auxiliary layer can be used as needed, using the screen printing, flexographic printing, inkjet printing, imprinting = brushing = shadowing (such as wet type engraving, dry remnant, peeling) Rhyme (abla 2: hardening. Plasticizing (negative/positive), etc.) will be attached to the supplementary layer: Quantity: Line hard::: After the aid is applied, it can be given an electron beam, etc. The materials are light, heat, pressure, load ~300. (The heat of 5 minutes ~ the case is better to apply the auxiliary === dense 5: immediately after the formation of the help layer, if it is in the case of the denseness, then It is carried out after the step of performing the preliminary pre-hardening step. After the 成$ is formed, (4) all other parts (the order of the steps), the above-mentioned composition for forming the mineral layer is brought into contact with the substrate (or on the auxiliary layer of 201238750) The method of directly depositing the composition for forming a layer to be plated on the substrate, or the case where the composition for forming a layer to be plated is a liquid containing a solvent, the composition is A method of coating on a substrate or the like. It is easy to control the aspect of the thickness of the bonded layer to be obtained, and a method of applying the composition onto the substrate is preferred. The method of coating is not particularly limited, and a specific method can be used as follows. A spin coater (Spin C〇ater), a dip coater (^ coater), and a double roll coater (double roll coater) can be used. ), slit coater, air knife coater, wire bar C〇ater, slide hopper, spray coating (spray C〇) Atlng ), blade coater, doctor coater, squeeze coater, reverse roll coater, transfer roll coater (transfer r 〇11 c〇ater), extrusion coater (extrusi〇nc〇ater), curtain coater (curtain C〇ater), die coater (diecoater), gravure roll coating Method, extrusion coating method, roll coating method, and the like. From the viewpoint of workability or manufacturing efficiency, it is preferable to apply the composition to be coated on the substrate (or the adhesion assisting layer) and dry it to remove the remaining The solvent forms a layer of the composition comprising the polymer. When the composition for forming a layer to be plated is brought into contact with the substrate, the composition for forming a layer to be plated is formed from the viewpoint of sufficient interaction with a plating catalyst or a precursor thereof to be described later. The coating amount is preferably 〇"g/m2 to 1〇g/m2 in terms of solid content, particularly preferably 〇5 g/m2 to 5 26 201238750 g/m2 〇 In addition, a plated layer is formed in this step. At the time of application, drying may be carried out at 20 C to 4 ° C for 5 hours to 2 hours to remove the solvent. (Improvement of energy) The method of applying energy to the composition for forming a layer to be plated on the substrate is not particularly limited, and for example, heating or exposure is preferably used. For exposure, light irradiation by an ultraviolet (UV) lamp, visible light, or the like is used. The light source is, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, or the like. The radiation has an electron beam, a ray, a ^', a beam, a far infrared ray, and the like. In addition, g-line, 丨 line, deep υ light, and high-density energy beam (laser beam) are also used. * The specific aspects that are usually used are preferably enumerated: scanning exposure by infrared laser, illuminance exposure of 4 gas discharge, red exposure, and the like. The exposure time will vary depending on the reactivity of the polymer and the source of light, typically between 1 and 5 hours. The exposure energy may be about 10 mJ to 8 mm, preferably a range of i 〇 () m 〜 3 _ m: r. Further, in the case where heating is used as the energy word, a blow dryer, an oven, an infrared dryer, a heating roller, or the like can be used. = the thickness of the layer to be plated and the scale is not smelling, the metal

的密著性方面而言，較佳A 住马0.01 _〜1〇 μπι，更佳為0.05 μηι 〜5 μιη。另外’較佳為以乾燥膜厚計為㈣5咖2〜加咖2，特 27 201238750 佳為 0.1 g/m2〜6 g/m2。進而，就配線形狀以及密著強度的方面而言，被鍍敷層的表面粗糙度（Ra)較佳為0.01 μιη〜0.3 μιη，更佳為 0·02 μιη〜0.15 μιη。此外，表面粗糖度（Ra)是利用非接觸式干涉法，基於JISB 0601 (20010120修訂）中記载的 Ra，使用Surfcom 3〇OOA (東京精密（股）製造）來測定。藉由如上所述使鍍敷觸媒或者其前驅體接觸，可利用藉由如凡得瓦力（vanderWaalsforce)之類的分子間力的相互作用、如離子鍵結之類的靜電相互作用、或者藉由孤立電子對的配位鍵結的相互作用，使鍍敷觸媒或者其前驅體吸附於被鍍敷層中來自式（B)所表示的單元的官能基χ。〈觸媒賦予步驟〉觸媒賦予步驟是對上述步驟中獲得的被鍍敷層賦予錢敷觸媒或者其前驅體的步驟。本步驟中，被鍍敷層中來^ 式（B)所表示的單元的官能基χ (峡基等）根據能而附著（吸附）被賦予的鑛敷觸媒或者其前驅體。、此處’鑛敷觸媒或者其前驅體可列舉後述鍛敷步驟中的作為錄敷處理的觸媒或電極而發揮功能者。因此，或者其前驅體是由鑛敷步驟中的錢敷處理的種類來 1 疋，但較佳為無電解鍍敷觸媒或者其前驅體。、装’對本步财制的材料（無電解織觸媒或者 =體專)進行詳細說明’然後對該步驟的順序進行詳 (無電解鍍敷觸媒） 28 201238750 本步驟中使用的無電解鍍敷觸敷時的活性核的觸媒，則可使用要疋成為無電解錢舉具有自觸媒還原反應的觸媒能力厘，體而έ ’可列 :具體而言，可列舉Pd、Ag、Cu、Ni、pt=:) 八中，就觸麻力的向度而言，特_ Ag、.&以體媒亦可使用金屬膠體。通常，金屬膠體可猎由在存在具有電荷的界面 =金屬膠護劑的溶液中，將金屬離子還 ^或者-有電荷的保可利用其中使用的界面活性製作。金屬朦體的電荷 ⑽解者保護劑來調節。所謂本步驟中使用的無_ 可藉由化學反應而成為無電 == 的金屬離子亦可在被賦予至被鍍敷而轉變為零價金屬來製成無電解鍍敷觸媒。另外=、無電解鍍敷觸媒前驅_狀訂浸潰於無電解織浴中， ::電解鍍敷浴中的還原劑而轉變為金屬(無電解鍍敷屬越媒前驅體的金屬離子較佳為使用金 " 被鍍敷層。所使用的金屬鹽只要溶解於適當 29 201238750 2劑中轉離為金屬離子與鹽基（陰離子），則並無特別，:列舉·· M(N〇3)n、Mcln、M2/n(s〇4)、MPA) (m 聰=貝的金屬原子）#。金屬離子可適#使用上述金屬 ^解離而成_子。例如可跡：Ag離子、⑶離子, :、c。離子、Pt離子、Pd離子n就觸媒能力的面而吕’較佳為Ag離子、Pd離子、Cu離子。 ,本發明中使用的無電解鍍敷觸媒或者其前驅體的較佳，之一可列舉鈀化合物。該鈀化合物作為鍍敷觸媒（鈀）或者其前驅體（鈀離子）來發揮作用，該鍍敷觸媒（鈀）或者其前驅體（鈀離子）在鍍敷處理時成為活性核而發揮，金屬析出的作用。另外，鈀（Pd)由於活性高且可以少 I進行無電解鍵敷，因此具有在電聚姓刻之前難以殘存於聚合物層中的優點。 ' 把化合物只要包含鈀’且在鍍敷處理時作為核而發揮作用’則並無特別限定，例如可列舉鈀（H)鹽、把（"〇) 錯合物、Ιε膠體等。另外，無電解鍍敷觸媒或者其前驅體可列舉銀、At 銀離子作為較佳的其他例子^ 在使用銀離子的情況下，可適當使用如以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：硝峻銀（silver nitrate )、乙酸銀（silver acetate )、硫酸銀（siiver sulfate )、碳酸銀（silver carbonate )、氰化銀（犯乂打 cyanide)、硫氰酸銀（silver thiocyanate)、氣化銀（sUver chloride )、溴化銀（silver bromide )、鉻酸銀（奶乂灯 201238750 chromate)、氯冉酸銀（siiver chloranilate)、水楊酸銀（silver salicylate )、二乙基二硫代胺甲酸銀（siiver diethyldithiocarbamate)、二乙基二硫代胺曱醯胺酸銀、對曱苯績酸銀（silver p-toluenesulfonate)。其中，就水溶性的觀點而言’較佳為确酸銀。上述中最佳為把化合物。 (其他觸媒）本發明中’為了對被鍍敷層不進行無電解鍍敷而是直接進行電解鍍敷所使用的觸媒可使用零價金屬。 (鍍敷觸媒液）如上所述的鍍敷觸媒或者其前驅體較佳為作為分散液或者溶液（鍍敷觸媒液）而賦予至被鍍敷層。鍍敷觸媒液的溶劑是使用水或有機溶劑。藉由含有有，溶劑，鍍敷觸媒或者其前驅體對被鍍敷層的滲透性提尚，可使鍍敷觸媒或者其前驅體效率良好地吸附於官能基 X。In terms of adhesion, it is preferred that A lives 0.01 _~1 〇 μπι, more preferably 0.05 μηι 〜5 μιη. Further, it is preferable that the dry film thickness is (4) 5 coffee 2 to plus 2, and the special 27 201238750 is preferably 0.1 g/m 2 to 6 g/m 2 . Further, the surface roughness (Ra) of the layer to be plated is preferably from 0.01 μm to 0.3 μm, more preferably from 0·02 μm to 0.15 μm, in terms of the wiring shape and the adhesion strength. In addition, the surface roughness (Ra) is measured by using Surfcom 3〇OOA (manufactured by Tokyo Seimi Co., Ltd.) based on Ra described in JIS B 0601 (Revised 20010120) by a non-contact interferometry method. By contacting the plating catalyst or its precursor as described above, it is possible to utilize an interaction of intermolecular forces such as vanderWaalsforce, electrostatic interaction such as ionic bonding, or The plating catalyst or its precursor is adsorbed to the functional group 来自 from the unit represented by the formula (B) in the layer to be plated by the interaction of the coordination bond of the isolated electron pair. <Catalyst Supply Step> The catalyst application step is a step of imparting a solvent or a precursor to the plated layer obtained in the above step. In this step, the functional group χ (the gorge group or the like) of the unit represented by the formula (B) in the layer to be plated adheres (adsorbs) the applied mineralizing catalyst or its precursor according to the energy. Here, the mineralizing catalyst or the precursor thereof may be a function of a catalyst or an electrode as a recording treatment in a forging step described later. Therefore, or the precursor thereof is 1 疋 from the type of money treatment in the mineralizing step, but it is preferably an electroless plating catalyst or a precursor thereof. , install 'Detailed materials for this step (electroless woven media or = body) to explain in detail 'The sequence of this step is detailed (electroless plating catalyst) 28 201238750 Electroless plating used in this step When the catalyst of the active core at the time of the contact is applied, the catalyst having the self-catalytic reduction reaction can be used as the electroless catalyst, and the composition can be listed as "Pd, Ag, and specifically, Pd, Ag, Cu, Ni, pt=:) In the eighth, in terms of the degree of contact with the hemp, the _Ag, .& can also use metal colloids for the body medium. In general, the metal colloid can be made from a solution in which a chargeable interface = a metallizing agent is present, and the metal ions are also OR-charged to utilize the interfacial activity used therein. The charge of the metal steroid (10) is adjusted by a protective agent. The metal ion which is used in this step and which can be rendered non-electric by chemical reaction can be converted into a zero-valent metal by being applied to be electrolessly plated. In addition, the electroless plating catalyst precursor is immersed in the electroless woven bath, and the reducing agent in the electrolytic plating bath is converted into metal (electroless plating is the metal ion of the intermediate precursor). It is better to use gold "coated layer. The metal salt used is not particularly special if it is dissolved in a suitable amount of metal ions and a salt base (anion) in 2 201238750 2: List M·N〇 3) n, Mcln, M2/n (s〇4), MPA) (m 聪 = shell metal atom) #. The metal ion can be used to dissociate the above metal. For example, traces: Ag ions, (3) ions, :, c. The ions, Pt ions, and Pd ions n are preferably Ag ions, Pd ions, and Cu ions. The electroless plating catalyst or the precursor thereof used in the present invention is preferably a palladium compound. The palladium compound functions as a plating catalyst (palladium) or a precursor (palladium ion), and the plating catalyst (palladium) or a precursor thereof (palladium ion) functions as an active core during plating treatment. The role of metal precipitation. Further, since palladium (Pd) has high activity and can be electrolessly bonded with less I, it has an advantage that it is difficult to remain in the polymer layer before electroforming. 'The compound is not particularly limited as long as it contains palladium' and acts as a core during the plating treatment, and examples thereof include palladium (H) salt, ("〇) complex, and Ιε colloid. Further, the electroless plating catalyst or the precursor thereof may be exemplified by silver or At silver ions. When silver ions are used, silver ions dissociated from the silver compound shown below can be suitably used. . Specific examples of the silver compound include silver nitrate, silver acetate, siiver sulfate, silver carbonate, silver cyanide (cyanide), and thiocyanate. Silver thiocyanate, sUver chloride, silver bromide, silver chromate (201238750 chromate), siiver chloranilate, silver salicylate , Siiver diethyldithiocarbamate, silver diethyldithiocarbamate, silver p-toluenesulfonate. Among them, from the viewpoint of water solubility, it is preferred to be acid silver. The best of the above is the compound. (Other catalyst) In the present invention, a zero-valent metal can be used for the catalyst used for electrolytic plating without electroless plating on the layer to be plated. (Plating Catalyst Solution) The plating catalyst or the precursor thereof as described above is preferably applied to the layer to be plated as a dispersion or a solution (plating catalyst liquid). The solvent for plating the catalyst liquid is water or an organic solvent. The plating catalyst or its precursor can be efficiently adsorbed to the functional group X by containing the solvent, the plating catalyst or the precursor thereof to improve the permeability of the layer to be plated.

鑛敷觸媒液中使用的水較佳為不含雜質，就此種觀點而言，較佳為使用逆滲透水（re丽e osmosis water，RO 水）或去離子水、_水、純化水等，特佳為使用去離子水或蒸鶴水。鍛敷觸媒液中使用的有機溶劑只要是可滲透至被鏟敷層中的/合劑’則並無特別限制。例如可使用：丙酉同、乙酿乙酸甲酯（methyi acet〇acetate )、乙醯乙酸乙酯（咖咖嶋㈣）、乙二醇二乙酸醋（ethylene glycol 31 201238750 diacetate )、環己酮、乙醯丙酮（acetylacetone )、苯乙酮 (acetophenone )、2-(1-環己浠基）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 )、二乙二醇二乙酸酯（diethylene glycol diacetate)、二嗔烧 (dioxane)、N-曱基吡咯啶酮、碳酸二甲酯、二曱基溶纖劑（dimethyl cellosolve)等。尤其就與鍍敷觸媒或者其前驅體的相溶性、以及在被鐘敷層中的參透性的觀點而言，較佳為水溶性的有機溶劑，較佳為丙酮、碳酸二甲酯、二甲基溶纖劑、三乙二醇單曱醚、二乙二醇二甲醚、二乙二醇二***。進而，分散液或溶液中可視目的而含有其他添加劑。其他添加劑例如可列舉膨潤劑、或界面活性劑等。 (步驟的順序）特別=敷觸媒或者其前驅體賦予至被鍍敷層的方法並無於、二nr舉以下方法：製備鍍敷觸媒液（將金屬分, =二中的分散液、或者以適當的溶劑溶％而成的金屬離子的溶液)，將錄敷觸細The water used in the mineralizing catalyst liquid is preferably free of impurities. From this point of view, it is preferred to use reverse osmosis water (RO water) or deionized water, water, purified water, or the like. It is especially good to use deionized water or steamed crane water. The organic solvent to be used in the forging catalyst liquid is not particularly limited as long as it is permeable to the compound to be applied to the shovel layer. For example, it can be used: acetamidoacetate (methyi acet〇acetate), ethyl acetate (caffeine (four)), ethylene glycol diacetate (ethylene glycol 31 201238750 diacetate), cyclohexanone, Acetylacetone, acetophenone, 2-(1-cyclohexenylcyclohexanone) 'propylene glycol diacetate, propylene glycol diacetate, three Triacetin, diethylene glycol diacetate, dioxane, N-decyl pyrrolidone, dimethyl carbonate, dimethyl cellosolve )Wait. In particular, from the viewpoint of compatibility with the plating catalyst or the precursor thereof and the permeability in the layer to be coated, a water-soluble organic solvent is preferred, and acetone, dimethyl carbonate, and second are preferred. Methyl cellosolve, triethylene glycol monoterpene ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether. Further, other additives may be contained in the dispersion or solution for the purpose. Examples of other additives include a swelling agent, a surfactant, and the like. (Step of the procedure) Special = The method of applying the catalyst or the precursor to the layer to be plated is not the same as the method of preparing the plating catalyst solution (the metal is divided, the dispersion in the second, Or a solution of a metal ion dissolved in a suitable solvent)

2 、又θ上的方法；或者將形成有被鍍敷層的潰於鑛敷_財付法等。 &纖㈣基板A 分鐘==錄敷觸媒液的接觸時間較佳為30秒〜2 更佳為1分鐘〜1〇分鐘左右。接觸時的鍍敷觸媒液的溫度較佳為听〜6〇以 32 201238750 右，更佳為10°c〜30°C左右。錢敷觸媒或者其前驅體在被鍍敷層中的吸附量（賦予並無特別限制，就後述被鍍敷層去除步驟更良好地進于的方面而s ’較佳為100 mg/m2以下’更佳為5 mg/m2 〜70 mg/m2。藉由如上所述使被鍍敷層接觸鍍敷觸媒或者其前驅體了利用藉由如凡得瓦力之類的分子間力的相互作用、如離子鍵結之類的靜電相互作用、或者藉由孤立電子對的配位鍵結的相互作用，使鍍敷觸媒或者其前驅體吸附於被錢敷層巾來自< (B)所表示的單元的官能基X。〈鍍敷步驟〉一鍍敷步驟是對上述步驟中被賦予鍍敷觸媒或者其前驅體的被，敷層進行鍍敷處理，在被雜層上形成金屬膜的二驟藉由5玄步驟而形成的金屬膜具有優異的導電性、密著性。更具體而言，如圖丨（B)所示，在被鍍敷層12上形成金屬膜14，獲得積層體。曰本步驟中進行的鍍敷處理的種類可列舉無電解鍍敷、電解鍍敷等，上述步驟中，可根據在與被鍍敷層之^形成相互作用的鍍敷觸媒或者其前驅體的功能來選擇。y ^其中，就金屬膜的在、著性提高的方面而言，較佳為進仃無電解鍍敷。另外’為了獲得所該厚的金屬膜W 佳的態樣是在無電解鍍敷之後進一步進行電解鍍敷。，以下，對本步驟中適合進行的鍍敷進行說^。。 (無電解鍍敷） 33 201238750 所謂無電解鍍*：技如下操作：使聽財欲敷而析出的金_子的溶液，藉由化學反應使2鎖 :谷:使用：知的無電解鍍敷浴。此外，作為無電解鍍敷就又取的4度方Φ而言，触為浴（PH值較佳為9〜Μ左右）的情況。…、電解難另外’在將雜予無電解錄顧前雜的基板以益電解鍍敷觸前驅體則愤或者含浸於被職層中的狀^ 次潰於無電解職浴巾的情況τ，將基板水洗而去的剛驅體（金屬鹽等）後’浸潰於無電解職浴中。在此情況下’於無電解鍍敷浴中，進行鍍敷觸媒前驅體的還原，並且繼其之後進行無電解織。此處使㈣無電解錢敷浴亦與上述同樣’可使用公知的無電解鍍敷浴。此外，無電解錢敷觸媒前驅體的還原亦可與如上所述的使用無電解鑛敷液的態樣不同，準備觸媒活性化液（還原液）’作為無電解鍍敷前的另一步驟而進行。觸媒活性化液是溶解有能夠將無電解鍍敷觸媒前驅體（主要是金屬離子）還原為零價金屬的還原劑的溶液，該還原劑相對於溶液整體的濃度較佳為0.1質量％〜50質量％，更佳為1質 1 Α〜質1 %。還原劑可使用如硼氫化納（sodium borohydride)、二曱胺石朋烧（dimethylamine borane)之類的侧系還原劑，甲酸、次鱗酸等還原劑。 34 201238750 觸的二層敷觸媒或者其前驅體所接濃度保持固定，並且媒^者其前驅體的遠攪拌或者搖動一邊浸潰。以外，主又要包含lit的組成除了包含溶劑（例如水）金屬離子的穩定性的^ ^金屬離子、2·還原劑、3.提高上述以外，可勺人"、、加刎（穩定劑）。該鍍敷浴中，除了铲數…dJL已讀數浴的穩定劑等公知的添加物。該方：：f用的有機溶劑必需是可溶於水的溶劑，就醇等醇類:佳為使用丙_賴1醇、乙醇、異丙錫、ί 7難財使㈣金屬__如已知有銅、 -，；佳為鈉金、銀、鈀、铑’其中’就導電性的觀點而 i劑、’添金。另外，根據上述金屬來選擇最佳的還 U上述方式形成的無電解鍍敷的金屬鍍敷浴的金屬離子濃度、在鍍麟中的浸潰時間旱敷冷的温度等來控制，就導電性的觀點而言，較佳為二以上，更佳為0.2 μιη〜2 μιη。 y其中，在將藉由無電解鍍敷的金屬臈作為導通層來進行後述的電解鍍敷的情況下，較佳為均句地賦予至1 μιη以上的膜。 · 另外，在鍍敷浴中的浸潰時間較佳為丨分鐘〜6小時左右，更佳為1分鐘〜;3小時左右。 (電解鍍敷（電鍍）） 35 201238750 本步驟中，在上述步驟中被賦予的驅體具有作為電_魏的情 =2^、前者其前驅體的被職層進行電解錄/破料該觸媒或另外’在上述無電解鍍數德，電極，可進-步進行電解觀。藉此能^ ^金屬膜作為性優異的無電解鍍敷膜為基礎，i易:其上重電解鍍敷，可使金屬膜形成騎合目的鍍敷後進行將金屬膜應用於各種應用。、旱度，因此適合電解鍍敷的方法可使用先前公知的電解鍍敷的金屬可列舉銅、鉻、斜、•、金、】、錫3 整二=2敷而獲得的金屬膜的膜厚可藉由調 1鍵2中所㈣金屬濃度、或者電流密度等來控制。卜，在應用於—般的電氣配線等的情況下，就導電 f的觀而言’金屬膜的膜厚較佳為〇.5 μΓη以上，更佳為 1 μηι〜30 μιη 〇讀配線的線寬變得越窄，即越微細化，則為，電氣配線的厚度變得越薄。因此，藉由電解鍍敷而域的金屬_層厚衫限定於上述，可任意設定。〈圖案形成步驟〉圖^成步驟是在織步驟後，使用包含金屬成分或過氧化朗_液來形成圖案化金屬_步驟。藉由該步 36 201238750η 驟，獲得表面具有圖案化金屬膜的金屬圖案材料。更夏而言，如圖1 (c)所示，藉由使蝕刻液接觸於金屬膜、體的不需要部分而去除該部分，獲得圖案化金屬犋丨6。、14 (飿刻液）首先，以下對本步驟中使用的敍刻液進行說明。本步驟中使用的蝕刻液使金屬膜的金屬成分溶就金屬_去雜峨‘㈣言，㈣錄佳蚀具體而言，ΡΗ值較佳為5以下，更佳為3以下改’2, and the method of θ; or the formation of the layer to be plated in the mineral deposit _ wealth payment method. & Fiber (4) Substrate A minutes == The contact time of the recording medium is preferably 30 seconds to 2 or more preferably 1 minute to 1 minute. The temperature of the plating catalyst liquid at the time of contact is preferably ～6〇 to 32 201238750 right, more preferably 10°c~30°C. The amount of adsorption of the solvent or the precursor in the layer to be plated is not particularly limited, and it is preferably 100 mg/m 2 or less in terms of the step of removing the plating layer to be described later. More preferably, it is 5 mg/m2 to 70 mg/m2. By contacting the plated layer with the plating catalyst or its precursor as described above, mutual interaction by intermolecular forces such as van der Waals is utilized. The action, such as electrostatic interactions such as ionic bonding, or the interaction of coordination bonds of isolated electron pairs, causes the plating catalyst or its precursor to be adsorbed to the money blanket from < (B) The functional group X of the unit shown. <Plating step> A plating step is a step of plating a coating layer to which a plating catalyst or a precursor thereof is applied in the above step, and forming a metal on the impurity layer. The metal film formed by the five steps of the film has excellent conductivity and adhesion. More specifically, as shown in FIG. (B), the metal film 14 is formed on the layer 12 to be plated, Obtaining a laminate. The types of plating treatment performed in this step include electroless plating and electricity. In the above steps, plating or the like can be selected according to the function of the plating catalyst or the precursor of the interaction with the layer to be plated. y ^ Among them, the improvement of the properties of the metal film is improved. In other words, it is preferable to carry out electroless plating in order to obtain the thick metal film W. Further, electrolytic plating is performed after electroless plating. Hereinafter, it is suitable for this step. Plating is said to be ^. (electroless plating) 33 201238750 The so-called electroless plating *: The following operation: a solution of gold _ sub-precipitate deposited by the financial desire, by chemical reaction 2 lock: Valley: use: A known electroless plating bath. In addition, as a 4 degree square Φ taken by electroless plating, it is a case where the bath is touched (the pH value is preferably about 9 to about Μ). The substrate which is mixed with the electroless plating before the electroplating of the precursor is irritated or impregnated in the layer of the service layer, and the substrate is washed with water. After the body (metal salt, etc.) is 'impregnated in the electroless bath. In this case In the electroless plating bath, the reduction of the plating catalyst precursor is carried out, and then electroless woven is performed. Here, the (4) electroless money bath is also the same as described above. A known electroless plating bath can be used. In addition, the reduction of the electrolyte-free pre-catalyst precursor may be different from the use of the electroless ore-like solution as described above, and the catalyst-activated liquid (reducing liquid) is prepared as the other before electroless plating. The catalyst activation liquid is a solution in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly a metal ion) to a zero-valent metal is dissolved, and the concentration of the reducing agent relative to the entire solution is higher. Preferably, it is 0.1% by mass to 50% by mass, more preferably 1% by mass to 1% by mass. The reducing agent may use a side system such as sodium borohydride or dimethylamine borane. A reducing agent, a reducing agent such as formic acid or hypochlorite. 34 201238750 The contact concentration of the two-layer coating medium or its precursor is fixed, and the precursor of the medium is dipped by far stirring or shaking. In addition, the main body must contain the composition of lit in addition to the stability of the metal ion containing solvent (such as water), metal ions, 2, reducing agent, 3. improve the above, can be spooned ",, twisting (stabilizer ). In the plating bath, in addition to the number of shovel... dJL, a well-known additive such as a stabilizer for the bath has been read. The organic solvent used by the party::f must be a solvent soluble in water, such as alcohols such as alcohol: preferably using propylene-l-alcohol, ethanol, isopropyl tin, ί 7 difficult to make (four) metal __ as already It is known that copper, -, ; is preferably sodium gold, silver, palladium, 铑 'where 'in terms of conductivity, i, 'gold.' In addition, the metal ion concentration of the electroless plating metal plating bath formed in the above-described manner is selected according to the above-mentioned metal, and the temperature of the metal plating bath in the plating bath is controlled by the temperature of the coating, and the conductivity is controlled. From the viewpoint of the above, it is preferably two or more, more preferably 0.2 μm to 2 μmη. In the case where electroless plating to be described later is carried out by using a metal crucible which is electrolessly plated as a conduction layer, it is preferable to uniformly apply a film of 1 μm or more. Further, the impregnation time in the plating bath is preferably from about 〜 minute to about 6 hours, more preferably from about 1 minute to about 3 hours. (Electroplating (electroplating)) 35 201238750 In this step, the body to be imparted in the above step has the electric layer as the electric_wei, and the former layer of the precursor is electrolyzed/disassembled. The medium or the other 'in the above electroless plating number, the electrode, can be further stepped on the electrolysis. Therefore, it is possible to use the metal film as an electroless plating film having excellent properties, and it is easy to apply: the metal film is formed into a plating target after plating, and the metal film is applied to various applications. And the degree of dryness, so the method suitable for electrolytic plating can use the previously known electrolytically plated metal, and the thickness of the metal film obtained by copper, chrome, slant, gold, gold, and tin 3 can be used. It can be controlled by adjusting the metal concentration or current density of (4) in the 1 button 2. In the case of application to general electrical wiring, etc., the thickness of the metal film is preferably 〇.5 μΓη or more, more preferably 1 μηη to 30 μηη, of the line of the wiring. The narrower the width is, that is, the thinner the thickness, the thinner the thickness of the electric wiring becomes. Therefore, the metal-layer thick shirt by electrolytic plating is limited to the above, and can be arbitrarily set. <Pattern Forming Step> The drawing step is a step of forming a patterned metal using a metal component or a peroxide-based liquid after the weaving step. By this step 36 201238750η, a metal pattern material having a patterned metal film on its surface is obtained. In the summer, as shown in Fig. 1(c), the etching liquid is brought into contact with the metal film or an unnecessary portion of the body to remove the portion, thereby obtaining the patterned metal crucible 6. , 14 (etching liquid) First, the following description of the engraving liquid used in this step will be described. The etching liquid used in this step dissolves the metal component of the metal film. The metal _ 峨峨 ( ( ( ( ( ( ( ( ( 具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体具体

限並無特別限制，就對被織層等的損傷的方面’下值較佳為〇以上。阳s ’ pH 此外’為了調整pH值而使用的試劑並盈例如可列舉鹽酸、硫酸等。 ’、，刃限制，餘刻液巾使用的賴並無特別限制機溶劑等。賴倾以及射彳性㈣觀點而言，較佳為或有該些成分，可進行金屬類根二離子的種較構成金屬膜的金屬而言佳的金屬，較佳為如在欲蝕刻銅的情況下，、11的金屬的離子，例作為姓刻液，例如可鐵離子等。化氣水混合溶液等，較物===硫酸-過氧性、以及金屬膜的_生方面而言=^限制，就生產毕乂佳為10秒〜10分 37 201238750 • * 在里，更佳為30秒〜3分鐘。 (處理方法） (第1實施態樣）特別= : = =圖而:化金屬膜'6的方法並無第1該方法是基於;謂===:所示的机署碑I ；首先’在金屬膜14上的規定位除未設置遮罩2G的FiW ^ ) 刻液來去心^ 域（遮罩20的非形成區域）的金屬膜14，獲传圖案化金屬膜^ ^ ^ ^ 屬劑材料。然後，如圖2屬(V所;罩=::，、抗姑劑材料的種類並無特別限制，可使用負型、正型、液狀、膜㈣材料。抗侧層的去除方法並無特別限定，可使用公知的方法（藉由驗溶液的絲、乾式餘刻）。 .使蝕刻液接觸於金屬膜14的方法並無特別限定，可列舉：將蝕刻液塗佈（例如喷射塗佈）於金屬膜14上的方法、或將具有金屬膜14的基板浸潰於钮刻液中的方法等。 (第2實施態樣）另外’作為處理方法的其他較佳態樣，較佳為列舉圖 3所示的第2實施態樣。此外，該方法是基於所謂半加成法的方法。在基於該方法的情況下，首先，上述鑛敷步驟中，進行無電解鍍敷後，以在藉由無電解鑛敷而獲得的金屬膜上設置圖案化遮罩，且在未設置遮罩的區域進一步形成金屬 38 201238750ιτ 膜的方式雜電解鍍敷。更具㈣言，如圖3 (Α)所示，藉由無電解鍍敷而在被鍍敷層12上形成金韻*後該金屬膜⑷上設置圖案化的遮罩20(㈣圖3⑻）。 =後’如@ 3 (C)所不’藉由進行電解鑛敷，在未罩2〇的區域（遮罩20的非形成區域）進-步設置金屬膜遮獲得包含凸部22及凹部24的凹凸狀金屬膜_。、解職後’如圖3(D)所示，去除遮罩2卜 € 繼而，對所得的具有凹凸結構的金屬膜14b，使用上纽刻液進行快速_，藉此去除金屬膜_中與配線部對應的凸部22以外的凹部24，獲得圖案化金屬膜16。〈酸性溶液接觸步驟〉 ^酸性溶液接觸步驟是使具有圖案化金屬膜的基板、與 =質上不含金屬成分或過氧化氫的酸性溶液接觸的步驟。藉^實施該步驟，未形成圖案化金屬獏的區域的被鍍敷層與酸性溶液接觸，被鍍敷層中所含的金屬成分（例如鍍敷觸媒、或者構成金屬膜的金屬成分）被去除。藉由經過該步驟，後述電漿蝕刻處理中被鍍敷層的去除效率提高。此外，藉由經過該步驟，在未形成圖案化金屬膜的區車又佳為獲得實質上不含金屬成分的被錢敷層，具體而 °較佳為使被錢敷層中的金屬成分減少至3 me/m2以下的程度。 & ，然首先，對本步驟中使用的酸性溶液進行詳細說明後對步驟_序進行詳細說明。 (酸性溶液） 39 201238750 本步驟中使用的酸性溶液表現出酸性。其中，就被命敷層中的金屬成分的去除性能更優異的方面而言二液的pH值較佳為5以下，更佳為〇〜3。玍令酸性溶液中所含的溶劑通常為水。另外，可包含溶劑（例如乙醇、曱醇、丙二醇單曱趟、異丙醇）。酸性溶液中實質上不含金屬成分或過氧化氮。即用實質上不含金屬成分驗性溶液、實質上不含過氧化氣的H谷II φ使用該酸性溶液，雖然去除被鑛敷層中所含有的金屬成分，但所形成的圖案化金屬賴圖案性以保持。曰此外，此處所§胃的實質上不含，是指相對於酸性溶液總量’金屬成分（或者過氧化氫含量為1質量％以下，較佳為G.1質量％以下。此外，最佳為含量為〇。酸性溶液中所含的酸成分並無特別限制，例如可使用鹽酸、硫酸、硝酸等公知的酸成分。例如可使用鹽酸水溶液、硫酸水溶液、硝酸水溶液等。 (步驟的順序）具有圖案化金屬膜的基板與酸性溶液的接觸方法並無特別限制’可列舉：將酸性溶液塗佈於基板上的方法、或在酸性溶液中浸潰基板的方法等。該基板與酸性溶液的接觸時間是根據所使用的酸性溶液的種轉來適當聰最佳_間，赌躲層中的金屬成分的去除性的觀點而言，較佳為1〇秒〜1〇分鐘，更佳為1分鐘〜5分鐘。 20123875〇ι 〈被鍍敷層去除步驟〉被鍍敷層去除步驟是藉由電漿蝕刻處理而去除未形成圖案化金屬膜的區域的被鍍敷層的步驟。更具體而言，對具有圖案化金屬膜的基板實施電祕刻處理，如圖1 (C) 及圖1 (D)所示’將位於未形成圖案化金屬膜16的區域 30的被鍍敷層12错。藉由去除圖案化金屬膜間的被鑛敷層，配線間（金屬膜間）的絕緣性能進一步提高。此外，在上述經由密著辅助層而將被鍍敷層配置於基板上的情況下，藉由本步驟的電漿蝕刻處理，不僅可去除被鍍敷層，而且亦可將密著辅助層一起去除。 μ 電漿蚀刻處理可實施公知的處理方法壓電浆處理、或者在大氣壓下進行的大氣電4Γ 若對電漿蝕刻處理進行詳細說明，形成步驟完畢後的形成有配線圖案 = 電聚處理裝置的腔室内，使該腔室内產生«，使杨為自由基的中性粒子衝擊基板表面來進行。或本步驟中，由於所形成的圖案化金屬膜自 ϊ 抗㈣㈣發揮魏，故喊由電独刻處ΐ 月匕夠有效地去除在配線間露出而殘存的被鍍敷声^ 二=間的有機物等夾雜物。此外，較佳為利;不j對： =成的配線圖案造成影響的處理條件來進行魏細= 電漿的產生法可應用減壓電裝法一種’較佳為使用廣泛使用的減壓㈣法法中的 201238750 就钱刻速度的觀點而言，實施電漿蚀刻處理時的環境氣壓較佳為100 Pa以下，更佳為1〇Pa以下。此外’若為使用大氣壓電漿法的情況，則無需減塵，因此具有可進行線上（in line)處理等優點，由此可期待生產效率的提高。該處理中，可使用選自由以下氣體所組成組群中的任意1種以上的氣體：選自氦、氬、氪'氣中的惰性氣體；〇2、CF4、C2F4、n2、co2、sf6、CHF3，至少包含〇、N、 F或Cl的反應性氣體。該些氣體可單獨使用，亦可混合使用。所使㈣氣體例如可根據聽理後的基板表面狀態的影響、處理速度或基板溫度的控制等各種條件來適當選定。例如，就處理速度的觀點而言，較佳為氧氣、氮氣、 CF4、以及氧氣及氬氣的混合氣體，更佳為氬氣、氧氣及鼠氣的混合氣體。 ^ 另外，關於使用氧氣作為電漿氣體的情況，該氧氣可使處理表面生成羥基，因此例如當在配線基板上配置以環氧樹脂等為主成分的阻焊劑，使基板表面與阻焊劑進行熱聚合的情況下，可提高基板表面與阻焊劑的密著性。另外，關於使用CF系氣體作為電漿氣體的情況，該 CF糸氣體可提南處理表面的疏水性，因此例如在形成將配線基板積層而成的積層基板的情況下，亦可有效地防止來自界面的水分等侵入至基板間等，可進一步提高配線間的絕緣可靠性。本步驟中’尤其就蝕刻速度、即電漿產生量的方面而 42The limit is not particularly limited, and the lower side of the damage to the woven layer or the like is preferably 〇 or more. In addition, the reagent used for adjusting the pH value may be, for example, hydrochloric acid or sulfuric acid. ',, the blade limit, the use of the residual liquid towel is not particularly limited to machine solvents. From the viewpoint of the immersion and the irradiance (4), it is preferred that the components are selected to be metal which is better than the metal constituting the metal film, preferably as the metal to be etched. In the case, the ion of the metal of 11, for example, a surname engraving, for example, an iron ion or the like. Gas-water mixed solution, etc., compared with ===sulfuric acid-peroxidation, and the metal film's _sheng aspect =^ limit, the production of Bi Yijia is 10 seconds to 10 minutes 37 201238750 • * In, more Good for 30 seconds ~ 3 minutes. (Processing method) (First embodiment) Special = : = = Fig.: The method of forming the metal film '6 is not based on the first method; the system is shown as ===: The prescribed film on the metal film 14 is obtained by dispersing the patterned metal film of the metal film 14 of the mask 2G without the FiW ^ ) engraving of the mask 2G (the non-formation region of the mask 20). material. Then, as shown in Fig. 2 (V; cover =::, the type of the anti-cavity material is not particularly limited, and a negative type, a positive type, a liquid type, or a film (four) material can be used. The method of removing the side layer is not Particularly, a known method (by a solution of a wire or a dry residue) can be used. The method of bringing the etching liquid into contact with the metal film 14 is not particularly limited, and examples thereof include applying an etching solution (for example, spray coating). a method of coating the metal film 14, or a method of immersing the substrate having the metal film 14 in the button engraving liquid, etc. (Second embodiment) Further, as another preferred aspect of the treatment method, it is preferably The second embodiment shown in Fig. 3. The method is based on a so-called semi-additive method. In the case of the method, first, in the above-described mineral depositing step, after electroless plating, A patterned mask is provided on the metal film obtained by electroless ore plating, and a metal 38 201238750 ττ film is further formed in a region where no mask is provided. More (4), as shown in FIG. 3 (Α) ), formed on the layer 12 to be plated by electroless plating After forming a golden rhyme*, a patterned mask 20 is placed on the metal film (4) ((4) Fig. 3(8)). = After 'as @3 (C) is not 'by performing electrolytic mineralization, in the area where the cover is not covered 2 The non-formed region of the cover 20 is further provided with a metal film to obtain a concave-convex metal film _ including the convex portion 22 and the concave portion 24. After the dismissal, as shown in Fig. 3(D), the mask 2 is removed, and then The obtained metal film 14b having a concavo-convex structure is quickly opened using the upper etching liquid, whereby the concave portion 24 other than the convex portion 22 corresponding to the wiring portion in the metal film is removed, and the patterned metal film 16 is obtained. Contact step 〉 ^ The acidic solution contact step is a step of contacting a substrate having a patterned metal film with an acidic solution containing no metal component or hydrogen peroxide. By performing this step, a patterned metal ruthenium is not formed. The plated layer in the region is in contact with the acidic solution, and the metal component (for example, the plating catalyst or the metal component constituting the metal film) contained in the plating layer is removed. By this step, plasma etching treatment will be described later. The removal efficiency of the plated layer is improved. By passing through this step, in the region where the patterned metal film is not formed, it is preferable to obtain a money coating layer substantially free of metal components, and specifically, it is preferable to reduce the metal component in the money coating layer to The degree of 3 me/m2 or less. First, the acidic solution used in this step will be described in detail, and the procedure will be described in detail. (Acid solution) 39 201238750 The acidic solution used in this step exhibits acidity. Among them, the pH of the two liquids is preferably 5 or less, more preferably 〇3 to 3, in terms of the more excellent removal performance of the metal component in the coating layer. The solvent contained in the acidic solution is usually water. In addition, a solvent (for example, ethanol, decyl alcohol, propylene glycol monoterpene, isopropyl alcohol) may be included. The acidic solution contains substantially no metal components or nitrogen peroxide. That is, the acidic solution is used by H Valley II φ which does not substantially contain a metal component test solution and substantially does not contain a peroxidation gas, and the metal component contained in the mineral deposit layer is removed, but the patterned metal layer is formed. Pattern to keep. Further, the term "the stomach substantially does not contain" means the metal component (or the hydrogen peroxide content is 1% by mass or less, preferably G.1% by mass or less based on the total amount of the acidic solution. The acid component contained in the acidic solution is not particularly limited, and for example, a known acid component such as hydrochloric acid, sulfuric acid or nitric acid can be used. For example, an aqueous hydrochloric acid solution, a sulfuric acid aqueous solution, an aqueous nitric acid solution or the like can be used. The method of contacting the substrate having the patterned metal film with the acidic solution is not particularly limited, and examples thereof include a method of applying an acidic solution onto a substrate, a method of impregnating a substrate with an acidic solution, and the like. The contact time is preferably from 1 〜 to 1 〇 minutes, and more preferably from 1 to 1 minute, depending on the nature of the acidic solution to be used, and the detachment of the metal component in the gambling layer. Minutes to 5 minutes. 20123875〇ι <Step of removing the layer to be plated> The step of removing the layer to be plated is to remove the layer to be plated in the region where the patterned metal film is not formed by the plasma etching treatment. More specifically, the substrate having the patterned metal film is subjected to an electro-secret process, as shown in FIG. 1(C) and FIG. 1(D), which will be located in the region 30 where the patterned metal film 16 is not formed. The plating layer 12 is wrong. By removing the mineralized layer between the patterned metal films, the insulation performance between the wirings (between the metal films) is further improved. Further, the layer to be plated is placed on the adhesion assisting layer. In the case of the substrate, the plasma etching treatment in this step can remove not only the plated layer but also the adhesion assisting layer. μ Plasma etching treatment can be carried out by a known processing method. Or atmospheric electricity at atmospheric pressure. If the plasma etching treatment is described in detail, a wiring pattern = electropolymerization processing device is formed in the chamber after the completion of the step, so that the chamber is generated «to make Yang a free radical. Neutral particles are applied to the surface of the substrate. Or, in this step, since the formed patterned metal film is self-reactive (4) and (4), it is effective to remove the exposed wiring in the wiring room. Inclusions such as organic matter and other materials are deposited. In addition, it is preferable to use the same; it is preferable that the processing conditions affecting the wiring pattern are: Piezoelectric method A preferred method of using the widely used decompression (four) method is 201238750. From the viewpoint of the engraving speed, the ambient gas pressure during the plasma etching treatment is preferably 100 Pa or less, more preferably 1 〇Pa or less. In addition, if the atmospheric piezoelectric slurry method is used, there is no need to reduce dust, so that it has the advantage of being able to perform in-line processing, and thus productivity can be expected to be improved. Any one or more gases selected from the group consisting of: a noble gas selected from the group consisting of helium, argon, and argon; 〇2, CF4, C2F4, n2, co2, sf6, and CHF3, including at least 〇, N , F or Cl reactive gases. These gases may be used singly or in combination. The (four) gas can be appropriately selected, for example, according to various conditions such as the influence of the surface state of the substrate after the hearing, the processing speed, and the control of the substrate temperature. For example, from the viewpoint of the processing speed, oxygen, nitrogen, CF4, and a mixed gas of oxygen and argon are preferable, and a mixed gas of argon, oxygen, and rat gas is more preferable. In addition, in the case where oxygen is used as the plasma gas, the oxygen can generate a hydroxyl group on the surface to be treated. Therefore, for example, when a solder resist containing epoxy resin or the like as a main component is disposed on the wiring substrate, the surface of the substrate and the solder resist are heated. In the case of polymerization, the adhesion between the surface of the substrate and the solder resist can be improved. In addition, in the case where a CF-based gas is used as the plasma gas, the CF 糸 gas can improve the hydrophobicity of the surface. Therefore, for example, in the case of forming a laminated substrate in which a wiring board is laminated, it is possible to effectively prevent from coming. The moisture or the like at the interface intrudes into the substrate or the like, and the insulation reliability between the wirings can be further improved. In this step, in particular, the etching rate, that is, the amount of plasma generated.

201238750t _ w W V ^ A X 言，較佳為實施電漿蝕刻處理時的環境氣壓為100 Pa以下，且該處理中，使用選自由氧氣、氬氣、CF4氣體、以及C#4氣體所組成組群中的任意1種以上氣體。〈具有圖案化金屬膜的積層體〉藉由經過上述步驟，可獲得圖案化金屬膜間的被鍍敷層被去除的具有圖案化金屬膜的積層體（圖1 (D))。所付的積層體能夠用於各種用途。例如能夠應用於半導體晶片、各種電氣配線基板（印刷配線基板等）、可撓性印刷電路（flexible print circuit ’ FPC )、晶粒軟膜接合 (chip-cm-film，COF)、捲帶式自動接合（tape邮〇脱二 bonding ’ TAB)、天線、多層配線基板、母板等各種用途。其中，可適合作為配線基板來利用。另外，當與配 -起使用時，視需要亦可在積層體18上設置絕^層4 1(E))。本發明的包含積層體18與絕緣層4〇的配線基板5〇可开7成與平β基板的&、著性優異的配線，高頻特性亦良且即便是微細的高密度配線，配線_絕緣可靠性砰馒異。絕緣膜：Γ可使用公知的材料，例如可列舉公知的層間絕緣膜、阻焊劑等。 [實例] 本發==些;:發明進-步進一 (合成例1 :聚合物1) 43 201238750 159 〇 /的一口 ^瓶中加入乙酸乙脂1 L、2_胺基乙醇以内^ ΐί?。中冷卻。向其中滴下2姻丁醢漠150 g，下的方式進行調節。然後，使内溫上升201238750t _ w WV ^ AX, preferably, the ambient gas pressure during the plasma etching treatment is 100 Pa or less, and in the treatment, a group selected from the group consisting of oxygen, argon, CF 4 gas, and C # 4 gas is used. Any one or more of the gases. <Laminated body having a patterned metal film> By the above steps, a laminated body having a patterned metal film with the plating layer removed between the patterned metal films can be obtained (Fig. 1 (D)). The laminate to be used can be used for various purposes. For example, it can be applied to a semiconductor wafer, various electric wiring boards (printed wiring boards, etc.), flexible printed circuit (FCC), chip-cm-film (COF), and tape-and-tape automatic bonding. (tape postal de-bonding 'TAB), antenna, multilayer wiring board, motherboard, and other uses. Among them, it can be suitably used as a wiring board. Further, when used in conjunction with the dispensing, the layer 4 1 (E) may be provided on the laminated body 18 as needed. In the wiring board 5 including the laminated body 18 and the insulating layer 4, the wiring of the laminated body 18 and the insulating layer 4A can be opened and the wiring of the flat beta substrate is excellent, and the high-frequency characteristics are good, and even the fine high-density wiring is used. _Insulation reliability is very different. As the insulating film: a known material can be used, and examples thereof include a known interlayer insulating film, a solder resist, and the like. [Examples] The present invention == some;:Invention-Step one (Synthesis Example 1: Polymer 1) 43 201238750 159 〇/ of a bottle of ethyl acetate added 1 L, 2_Aminoethanol within ^ ΐί ?? Cooling in the middle. The method of dropping 2 姻丁醢漠150 g into it is adjusted. Then, raise the internal temperature

3m’反應2小時。反應完畢後，追加蒸顧水 300 mL使反應停止。然後’將乙酸乙酿層以策顧水，mL j 4次後’進行硫_賴，蒸料除乙酸乙醋，藉此獲付80 g原料A。繼而，向5〇〇mL的三口燒瓶中加入原料A(47 4 g)、錢（22 g)、乙酸乙醋（15〇 mL)，在冰洛中冷卻。向其 1滴下丙稀醯氣2 5 g ’ u内溫達到2 Q t以下的方式進行調二。然後，提高至室溫’反應3小時。反應完畢後，追加蒸顧水300 mL ’使反應停止。賴，將乙酸乙醋層以蒸顧水300 mL清洗4次後，進行硫酸鎂乾燥，蒸餾去除乙酸乙酉曰，利用管柱層析法將單體A純化而獲得2〇吕。向500 mL的三口燒瓶中加入Ν,Ν-二曱基乙醯胺21 g，在氮氣流下加熱至60。〇向其中以6小時滴下上述所得的單體A : 26.8 g、丙烯酸（東京化成製造）15 6 g、丙烯醯胺3.1 g、V-601 (和光純藥製造）〇 59 g的n，N-二曱基乙醯胺3 4 g溶液。滴下完畢後，進而攪拌3小時。然後，添加N，N-二曱基乙醯胺35 g，將反應溶液冷卻至室溫。向上述反應溶液中添加4-羥基TEMPO(東京化成製造）0.17 g、DBU 105 g，在室溫下進行12小時反應。然後，向反應溶液中添加70質量％曱磺酸水溶液1〇4 g。反應完畢後，以水進行再沈澱’取出固形物，獲得聚合物1 (重量平均 201238750 分子置4.2萬）（21 g)。使用電位差自動滴定裝置（京都電子工業（股）製造）、以及作為滴S液的0.1 Μ氫氧化鈉水>谷液’來測定所得聚合物1的酸值，結果該聚合物1的 S曼值為 4.2 mm〇l/g。將所得聚合物〗利用礙酸氫鈉加以中和使其溶解於重水中，藉由Bruker製造的300 MHz的NMR (AV-300) 進行測定。相當於含聚合性基的單元的波峰是在7.8 PP111-8·1 ppm( 1H 分）、5·8 ppm_5.6 ppm( 1H 分）、5.4 ppm-5.2 PPm ( 1H 刀）、4.2 ppm-3.9 ppm ( 2H 分）、3.5 ppm-3.3 ppm (2H分）、2·5 ppm-0.7 ppm (6H分）寬廣地觀察到，相當於羧酸基單元的波峰是在2.5 ppm-〇.7ppm(3H分）寬廣地觀察到，來自丙烯醯胺單元的波峰是在2.5ppm_〇7ppm (3H分）寬廣地觀察到，確認生成包含具有（甲基)丙烯醯胺基的單元、具有羧酸基的單元、來自丙烯醯胺的單元的聚合物。 (合成例2 :聚合物2) 向500 mL的三口燒瓶中加入N，N•二甲基乙醯胺21 g，在氮氣〃 il下加熱至60 C。向其中以6小時滴下上述所得的單體A:27.9g、丙烯酸（東京化成製造）13丨g、N，N-二曱基丙烯醯胺3.3 g、V-601 (和光純藥製造）〇 59 g的 N，N-二甲基乙醯胺35 g溶液。滴下完畢後，進而撥掉3 時。然後’添加Ν，Ν·4基乙_ ，狀應溶液冷卻至室溫。向上述反應溶液中添加4_羥基TEMp〇 (東京化成製造）0.18 g、DBUlG9g ’在室溫下進行12小時反應。 45 201238750 ▲ 然後’向反應溶液中添加70質量％甲磺酸水溶液1〇8 g。反應完畢後，以水進行再沈澱，取出固形物，獲得聚合物 2 (重量平均分子量4.0萬）（20 g)。使用電位差自動滴定裝置（京都電子工業（股）製造）、以及作為滴定液的〇 ][ Μ氫氧化鈉水溶液，來測定所得聚合物2的酸值，結果該聚合物2的酸值為4.1 mmol/g。將所得聚合物2以碳酸氫鈉加以中和，使其溶解於重水中’藉由Bruker製造的300 MHz的NMR (AV-300)進行測定。相當於含聚合性基的單元的波峰是在7.8 ppm-8.1 ppm ( 1H 分）、5.8 ppi11-5.6 PPm ( 1H 分）、5.4 ppm-5.2 ppm (1H 分）、4.2 ppm-3.9 ppm ( 2H 分）、3.5 ppm-3.3 ppm ( 2H 分）、2.5 ppm-0.7 ppi11 ( 6H分）寬廣地觀察到’相當於叛酸基單元的波峰是在2.5 PPm-0.7 ppm (3H分）寬廣地觀察到，來自二曱基兩稀酿胺單元的波峰是在PPm-2.7 ppm ( 6H 分）、2.5 pPm-〇·7 ppm ( 3H 分）寬廣地觀察到’ 確認生成包含具有（甲基）丙烯醯胺基的單元、具有羧酸基的單元、來自N，N-二乙基丙烯醯胺的單元的聚合物。 (合成例3 :聚合物3) 向500 mL的三口燒瓶中加入N，N-二曱基乙醯胺21 g，在氮氣流下加熱炱6〇°C。向其中以6小時滴下上述所得的單體A: 25.4g、丙烯酸（東京化成製造）12.9g、N，N-二乙基丙烯醯胺（東京化成製造）5.7g、v_601 (和光純藥製造）0.59 g的N，N-二曱基乙醯胺36 g溶浪。滴下完畢後，進而攪拌3小時。然後，添加N，N-二曱基乙酿胺37 g ’將 46 201238750t 反應溶液冷卻至室溫。向上述反應溶液中添加4_經基 TEMPO (東京化成製造）0.17 g、DBU 105 g，在室溫下^ 行12小時反應。然後，向反應溶液中添加70質量〇/〇甲續酸水溶液104 g。反應完畢後，以水進行再沈;殿，取出固形物，獲得聚合物3 (重量平均分子量4.1萬）（23 g)。使用電位差自動滴定裝置（京都電子工業（股）製造）、以及 . 作為滴定液的0.1 Μ氫氧化納水溶液，來測定所得聚合物 3的酸值，結果該聚合物3的酸值為4.2mmol/g。將所得聚合物3以碳酸氫納加以中和，使其溶解於重水中，藉由Bruker製造的300 MHz的NMR (AV-300)進行測定。相當於含聚合性基的單元的波峰是在7,8ppm_8」The reaction was carried out for 3 hours. After the reaction was completed, 300 mL of water was added to steam to stop the reaction. Then, the acetic acid was layered to care for water, and after mL 4 was subjected to sulfur, the steam was removed from the ethyl acetate, whereby 80 g of the starting material A was obtained. Then, a raw material A (47 4 g), money (22 g), and ethyl acetate (15 〇 mL) were placed in a 5 〇〇 mL three-necked flask, and the mixture was cooled in ice. The acrylonitrile 2 5 g ’ u internal temperature was adjusted to 2 Q t or less. Then, it was raised to room temperature to react for 3 hours. After the reaction was completed, 300 mL of water was added to reflux to stop the reaction. Lai, the ethyl acetate layer was washed four times with 300 mL of water, and dried over magnesium sulfate, and the acetic acid was distilled off, and the monomer A was purified by column chromatography to obtain 2 ruthenium. To a 500 mL three-necked flask was placed 21 g of hydrazine, hydrazine-dimercaptoacetamide, and heated to 60 under a nitrogen stream. The monomer A obtained above was dropped in 6 hours, 26.8 g, acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 15 6 g, acrylamide 3.1 g, V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), 59 g of n, N- Dimercaptoacetamide 3 4 g solution. After the completion of the dropwise addition, the mixture was further stirred for 3 hours. Then, 35 g of N,N-dimercaptoacetamide was added, and the reaction solution was cooled to room temperature. To the reaction solution, 0.17 g of 4-hydroxy TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) and 105 g of DBU were added, and the reaction was carried out for 12 hours at room temperature. Then, a solution of 70 mass% hydrazine sulfonic acid in an amount of 1 〇 4 g was added to the reaction solution. After the completion of the reaction, reprecipitation was carried out with water. The solid matter was taken out to obtain a polymer 1 (weight average 201238750 molecule 42,000) (21 g). The acid value of the obtained polymer 1 was measured using a potentiometric auto-titration device (manufactured by Kyoto Electronics Co., Ltd.) and 0.1 Μ sodium hydroxide water > gluten solution as a dropping solution S, and as a result, the polymer 1 was Sman. The value is 4.2 mm〇l/g. The obtained polymer was neutralized with sodium hydrogen sulphate and dissolved in heavy water, and measured by a 300 MHz NMR (AV-300) manufactured by Bruker. The peak corresponding to the unit containing the polymerizable group is 7.8 PP111-8·1 ppm (1H min), 5.8 ppm_5.6 ppm (1H min), 5.4 ppm-5.2 PPm (1H knife), 4.2 ppm-3.9 Ppm (2H), 3.5 ppm-3.3 ppm (2H), and 2. 5 ppm-0.7 ppm (6H) are broadly observed, and the peak corresponding to the carboxylic acid unit is 2.5 ppm-〇.7ppm (3H) It was observed broadly that the peak derived from the acrylamide unit was broadly observed at 2.5 ppm_〇7 ppm (3H), and it was confirmed that a unit having a (meth)acrylamide group and a carboxylic acid group was formed. Unit, polymer from units of acrylamide. (Synthesis Example 2: Polymer 2) To a 500 mL three-necked flask, 21 g of N,N-dimethylacetamide was added, and the mixture was heated to 60 C under a nitrogen gas il. The monomer A obtained above was dropped to the mixture for 2 hours: 27.9 g, acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 13 g, N,N-dimercaptopropenylamine, 3.3 g, V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 59 g of N,N-dimethylacetamide 35 g solution. After the drop is completed, dial 3 times. Then add Ν, Ν·4 base B, and the solution should be cooled to room temperature. To the reaction solution, 4-hydroxyl TEMp (manufactured by Tokyo Chemical Co., Ltd.), 0.18 g, DBUlG9g' was added to carry out a reaction at room temperature for 12 hours. 45 201238750 ▲ Then, 1 〇 8 g of a 70% by mass aqueous methanesulfonic acid solution 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 a polymer 2 (weight average molecular weight: 40,000) (20 g). The acid value of the obtained polymer 2 was measured by using a potentiometric auto-titration device (manufactured by Kyoto Electronics Industry Co., Ltd.) and a hydrazine solution as a titration solution, and the acid value of the polymer 2 was 4.1 mmol. /g. The obtained polymer 2 was neutralized with sodium hydrogencarbonate and dissolved in heavy water, and was measured by 300 MHz NMR (AV-300) manufactured by Bruker. The peak corresponding to the polymerizable group is 7.8 ppm-8.1 ppm (1H min), 5.8 ppi11-5.6 PPm (1H min), 5.4 ppm-5.2 ppm (1H min), 4.2 ppm-3.9 ppm (2H min) ), 3.5 ppm-3.3 ppm (2H points), 2.5 ppm-0.7 ppi11 (6H points) broadly observed that the peak corresponding to the tetamine unit is widely observed at 2.5 PPm-0.7 ppm (3H points). The peaks from the diterpenoid two dilute amine units were observed broadly at PPm-2.7 ppm (6H min), 2.5 pPm-〇·7 ppm (3H min). a unit, a unit having a carboxylic acid group, a polymer derived from a unit of N,N-diethyl acrylamide. (Synthesis Example 3: Polymer 3) To a 500 mL three-necked flask, 21 g of N,N-dimercaptoacetamide was added, and the mixture was heated to 6 ° C under a nitrogen stream. The monomer A obtained above was dropped in 6 hours: 25.4 g, acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 12.9 g, N,N-diethyl acrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.7 g, v_601 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.59 g of N,N-dimercaptoacetamide 36 g was dissolved. After the completion of the dropwise addition, the mixture was further stirred for 3 hours. Then, N,N-dimercaptoacetamide 37 g ' was added to cool the 46 201238750 t reaction solution to room temperature. To the above reaction solution, 0.17 g of TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) and 105 g of DBU were added, and the reaction was carried out for 12 hours at room temperature. Then, 104 g of a 70 mass aqueous solution of hydrazine/hydrazine was added to the reaction solution. After the completion of the reaction, the water was re-sinked; the solid matter was taken out to obtain a polymer 3 (weight average molecular weight 41,000) (23 g). The acid value of the obtained polymer 3 was measured by using a potentiometric auto-titration device (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 Torr sodium hydroxide aqueous solution as a titration solution, and as a result, the acid value of the polymer 3 was 4.2 mmol/ g. The obtained polymer 3 was neutralized with sodium hydrogencarbonate, dissolved in heavy water, and measured by a 300 MHz NMR (AV-300) manufactured by Bruker. The peak corresponding to the unit containing a polymerizable group is at 7,8 ppm_8"

ppm ( 1H 分）、5.8 ppm-5.6 ppm ( 1H 分）、5.4 ppm-5.2 ppm (1H 分）、4.2 ppm-3.9 ppm ( 2H 分）、3.5 ppm-3.3 ppm ( 2H 分）、2.5 ppm-0.7 ppm (6H分）寬廣地觀察到，相當於叛酸基單元的波峰是在2.5 ppm-0.7 ppm (3H分）寬廣地觀察到’來自二乙基丙婦醯胺單元的波峰是在3.4 ppm_3.〇 ppm (4H 分）、2.5 ppm-0.7 ppm (9H 分）寬廣地觀察到，確認生成包含具有（曱基）丙烯醯胺基的單元、具有敌酸基的單元、來自丙烯醯胺的單元的聚合物。 (合成例4 :聚合物4) 向500 mL的三口燒瓶中加入Ν，Ν·二曱基乙醯胺23 g ’在氮氣流下加熱至60它。向其中以6小時滴下上述所得的單體A : 28.1 g、丙烯酸（東京化成製造）129g、丙烯醯基嗎琳（（股）興人製造）5.0g、V-601 (和光純藥製 47 201238750 造）〇.59§的况沁二甲基乙醯胺（東京化成製造）37§溶液。滴下完畢後，進而攪拌3小時。然後，添加N，N-二甲基乙酿胺38 g ’將反應溶液冷卻至室溫。向上述反應溶液中添加‘羥基TEMPO (東京化成製造）0.18 g、DBlJ 1〇8 ^，室溫下進行12小時反應。然後，向反應溶液中添加負K°/〇甲磺酸水溶液1〇8 g。反應完畢後，以水進行再沈搬’取出固形物，獲得聚合物4 (重量平均分子量43 $ 24 g)。使用電位差自動滴定裝置（京都電子工業（股） '4)以及作為滴定液的0.1 Μ氫氧化鈉水溶液，來測定所得聚合物4的酸值，結果該聚合物4的酸值為41 mm〇i/g。將所得聚合物4以碳酸氫納加以中和，使其溶解於重水中’藉由Bruker製造的300 MHz的NMR ( AV-300)進仃剛定。相當於含聚合性基的單元的波峰是在7 8ppm 8」 pPm ( 1H 分）、5.8 ppm-5.6 ppm ( 1H 分）、5 4 ppm_5 2 ppmPpm (1H), 5.8 ppm-5.6 ppm (1H), 5.4 ppm-5.2 ppm (1H), 4.2 ppm-3.9 ppm (2H), 3.5 ppm-3.3 ppm (2H), 2.5 ppm-0.7 The ppm (6H points) was broadly observed, and the peak corresponding to the tetamine unit was broadly observed at 2.5 ppm-0.7 ppm (3H). The peak from the diethyl propyl sulfanamide unit was 3.4 ppm_3. 〇ppm (4H minutes) and 2.5 ppm-0.7 ppm (9H minutes) were widely observed to confirm the formation of a unit containing a (fluorenyl) acrylamide group, a unit having a diacid group, and a unit derived from acrylamide. polymer. (Synthesis Example 4: Polymer 4) To a 500 mL three-necked flask, ruthenium, ruthenium dimercaptoacetamide 23 g ' was heated to 60 Torr under a nitrogen stream. The monomer A obtained above was added dropwise for 6 hours: 28.1 g, acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 129 g, acrylonitrile kiline (manufactured by Konica Minolta), 5.0 g, V-601 (manufactured by Wako Pure Chemical Industries, Ltd., 2012 201238750) Made) 〇.59 § 沁 dimethyl acetamide (made in Tokyo Chemical Industry) 37 § solution. After the completion of the dropwise addition, the mixture was further stirred for 3 hours. Then, N,N-dimethyletheneamine 38 g' was added to cool the reaction solution to room temperature. To the reaction solution, 0.18 g of hydroxy TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) and DB1J 1 〇 8 ^ were added, and the reaction was carried out for 12 hours at room temperature. Then, 1 〇 8 g of a negative K ° / hydrazine methanesulfonic acid aqueous solution was added to the reaction solution. After the completion of the reaction, the mixture was re-sucked with water to remove the solid matter to obtain a polymer 4 (weight average molecular weight: 43 $24 g). The acid value of the obtained polymer 4 was measured using a potentiometric auto-titration device (Kyoto Electronics Industry Co., Ltd. '4) and a 0.1 Μ sodium hydroxide aqueous solution as a titration solution, and as a result, the acid value of the polymer 4 was 41 mm 〇i. /g. The obtained polymer 4 was neutralized with sodium hydrogencarbonate to be dissolved in heavy water' by a 300 MHz NMR (AV-300) manufactured by Bruker. The peak corresponding to the unit containing the polymerizable group is 7 8 ppm 8" pPm (1H min), 5.8 ppm-5.6 ppm (1H min), 5 4 ppm_5 2 ppm

上 1H 分）、4.2 ppm-3.9 ppm ( 2H 分）、3.5 ppm-3.3 ppm ( 2H 分）、2.5 ppm-0.7 ppm (6H分）寬廣地觀察到，相當於綾醆基單元的波峰是在2.5 ppm-0.7 ppm (311分）寬廣地觀察到，來自丙烯醯基嗎啉單元的波峰是在3.7 ppm-3.5 ppm (8只分）、2.8??111-0.7??111(311分）寬廣地觀察到，確認生成包含具有（曱基)丙烯醯胺基的單元、具有羧酸基的單元、來自丙烯醯基嗎啉的單元的聚合物。 (合成例5 :聚合物5) 向2 L的三口燒瓶中加入乙酸乙酯1 L、伸乙基二胺 48 〜ιι 201238750 400 g，在冰洛中冷卻。向其以内溫達到2(rr以丁认士 ^滴下2-溴異丁醯溴200 g，至室溫（25H β 、工進行調節。然後，使内溫上升Upper 1H points), 4.2 ppm-3.9 ppm (2H points), 3.5 ppm-3.3 ppm (2H points), 2.5 ppm-0.7 ppm (6H points) broadly observed, the peak corresponding to the thiol unit is at 2.5 Peptide-0.7 ppm (311 points) broadly observed peaks from acryloyl morpholine units at 3.7 ppm-3.5 ppm (8 points), 2.8??111-0.7??111 (311 points) broadly It was observed that a polymer containing a unit having a (fluorenyl) acrylamide group, a unit having a carboxylic acid group, and a unit derived from acryloyl morpholine was confirmed. (Synthesis Example 5: Polymer 5) To a 2 L three-necked flask was placed 1 L of ethyl acetate and ethyldiamine 48 to 203.387,400 g, and cooled in ice. To the internal temperature of 2 (rr to dibutyl bromide 200 g of 2-bromoisobutyl hydrazine, to room temperature (25H β, work to adjust. Then, make the internal temperature rise

清洗4切、二H酯層以該水300mL 管柱層析法進去除乙酸乙醋，利用的原料Β。传0g僅單末端的胺基進行反應繼而，向漏mL的三口燒瓶中加入原料B (45 g)、二二22 g)、以及乙酸乙醋（15〇虹)，在冰浴中冷卻。向>、中滴下㈣賴25g’關溫達到2叱以下的方行調節。然後，提高至室溫，反應3小時。反應完畢^，，加蒸餾水300 mL使反應停止。然後，將乙酸乙酯層以瘵餾水300 mL清洗4次後，進行硫酸鎂乾燥，蒸餾去除乙酸乙酯，利用管柱層析法將單體B進行純化而獲得3〇以向500 mL的三口燒瓶中加入n，N-二甲基乙醯胺22 g ’在氮氣流下加熱至60°C。向其中以6小時滴下上述所得的單體B : 28.3 g、丙烯酸（東京化成製造）121 g、二乙基丙稀醯胺（東京化成製造）5.7 g、V-601 (和光純藥製造）0.59 g的N，N-二甲基乙醢胺37 g溶液。滴下完畢後，進而授拌3小時。然後，添加N，N-二曱基乙醯胺％ g，將反應溶液冷卻至室溫。向上述反應溶液中添加4-經基 TEMPO (東京化成製造）0.19 g、DBU 105 g ’在室溫下進行12小時反應。然後，向反應溶液中添加70質量％甲續酸水溶液104 g。反應完畢後，以水進行再沈澱，取出固 49 201238750 形物’獲得聚合物5(重量平均分子量3.8萬）（19g)。使用電位差自動滴定裝置（京都電子工業（股）製造）、以及作為滴定液的0.1 Μ氫氧化鈉水溶液，來測定所得聚合物 5的酸值’結果該聚合物5的酸值為4.4 mmol/g。將所得聚合物5以碳酸氫鈉加以中和後，使其溶解於重水中’藉由Bruker製造的300 MHz的NMR ( AV-300) 進行測定。相當於含聚合性基的單元的波峰是在78 PPm-8.1 PPm( 2H 分）、5.8 Ppm-5.6 PPm( 1H 分）、5.4 Ppm-5.2 ppm ( 1H 分）、3.5 ppm-3.3 ppm ( 4H 分）、2.5 ppm-〇.7 ppm (6H分）寬廣地觀察到，相當於羧酸基單元的波峰是在 2.5ppm-0.7Ppm(3H分）寬廣地觀察到，來自二乙基丙烯醯胺單元的波峰是在3.4 ppm-3.0 ppm(4H分）、2.5 ppm_〇 7 ppm (9H分）寬廣地觀察到，確認生成包含具有（曱基)丙烯酿胺基的單元、具有舰基的單元、來自二乙基丙^醯胺的單元的聚合物。 (合成例6 :聚合物6) 向2 L的三口燒瓶中加入乙酸乙酯丨L、夂胺基曱美 -3,5,5-二曱基環己醇446 g，在冰浴中冷卻。向其中滴下2 溴異丁醯溴150 g’以内溫達到2(rc以下的方式進行。· 然後，使内溫上升至室溫（25。〇，反應2小時ϋ 後’追加蒸顧水300 mL使反應停止。然後，將乙層以蒸餾水300 mL清洗4次後，進行硫酸鎮乾广: 去除乙酸乙酯，利用管柱層析法進行純化，藉俨=、原料C。匕筏侍120 g 201238750 繼而’向500 mL的三口燒瓶中加入原料匚（72 g )、。比啶（22 g)、乙酸乙酯（150 mL)，在冰浴中冷卻。向其中滴下丙稀醯風》25 g ’以内溫成為20。〇以下的方式進行調節。然後’提尚至室溫’反應3小時。反應完畢後，追加蒸餾水300 mL使反應停止。然後，將乙酸乙酯層以蒸餾水300 mL清洗4次後，進行硫酸鎂乾燥，蒸餾去除乙酸乙酯，利用管柱層析法將單體C進行純化而獲得25 g。向500 mL的三口燒瓶中加入ν,Ν-二甲基乙醯胺13 g ’在氮氣流下加熱至60°C。向其中以6小時滴下上述所得的單體C : 18.6 g、丙烯酸（東京化成製造）6 g、二乙基丙烯醯胺（東京化成製造）2.1 g、V-601 (和光純藥製造） 0.28 g的N，N-二甲基乙醯胺21 g溶液。滴下完畢後，進而攪拌3小時。然後’添加N，N-二甲基乙醯胺22 g，將反應溶液冷卻至室溫。向上述反應溶液中添加4-羥基TEMPO (東厅、化成製造）0.09 g、DBU 50.1 g，在室溫下進行12 小時反應。然後，向反應溶液中添加7〇質量％甲磺酸水溶液51 g。反應完畢後，以水進行再沈澱，取出固形物，獲得聚合物6 (重量平均分子量4·4萬）（9 g)。使用電位差自動滴定裝置（京都電子工業（股）製造）、以及作為滴定液的〇·1 Μ氫氧化鈉水溶液，來測定所得聚合物6的酸值，結果該聚合物6的酸值為4.5mmol/g。將所得聚合物6以碳酸氫鈉加以中和，使其溶解於重水中’藉由Bruker製造的300 MHz的NMR (AV-300)進行’貝丨义°相當於含聚合性基的單元的波岭是在7.8 ppm-8.1 51 201238750 ppm ( 1H 分）、5.8 ppm-5.6 ppm ( 1H 分）、5 4 ppm 5 2 ppm (1H 分）、4.4 ppm-4.1 ppm ( 2H 分）、3.5 ppm_3 3 ppm ( 2H 分）、2,5ppm-〇.7ppm (21H分）寬廣地觀察到，相當於緩酸基單元的波峰是在2.5 ppm-0.7 ppm (3H分）寬廣地觀察到，來自二乙基丙烯醯胺單元的波峰是在34 ppm 3〇 ??111(411分）、2.5卯111-〇.7?1)111(911分）寬廣地觀察到，確認生成包含具有（甲基）丙烯醯胺基的單元、具有羧酸基的單元、來自二乙基丙烯醯胺的單元的聚合物。土 (合成例7 :聚合物7) 向2 L的三口燒瓶中加入乙酸乙酯1 [、2_(2_胺基乙氧基）乙醇274 g，在冰浴中冷卻。向其中滴下2溴異丁醯溴150 g，以内溫達到20。(：以下的方式進行調節。'麸後·，使内溫上升至室溫（坑），反應2小時。反應完畢後，追加蒸餾水300 mL使反應停止。然後，將乙酸乙酯層以蒸餾水300 mL清洗4次後，進行硫酸鎂乾燥，蒸餾去^ 酸乙酯，藉此獲得90 g原料D。〃繼而，向500 mL的三口燒瓶中加入原料D (57 g)、吡啶（22 g)、乙酸乙酯（15〇 mL)，在冰浴中冷卻。向其中滴下丙烯醯氯25 g ’以内溫達到2〇。〇以下的方式進行^ 節。然後，提高至室溫，反應3小時。反應完畢後，追加蒸餾水300 mL使反應停止。然後，將乙酸乙酯層以蒸餾水300 mL清洗4次後，進行硫酸鎂乾燥，蒸餾去除乙酸乙酯’利用管柱層析法將單體D進行純化而獲得22 g。向500 mL的三口燒瓶中加入N，N二甲基乙醯胺 52 201238¾ g，在氮氣流下加熱至60°C。向其中以6小時滴下上述所得的單體D : 20.5 g、丙烯酸（東京化成製造）8.1 g、二乙基丙烯醯胺2.8 g、V-601 (和光純藥製造）0.37 g的二曱基乙醯胺25 g溶液。滴下完畢後，進而攪拌3小時。然後，添加N，N-二曱基乙醯胺26 g，將反應溶液冷卻至室溫。向上述反應溶液中添加4-羥基TEMPO (東京化成製造）0· 11 g、DBU 68 g，在室溫下進行12小時反應。然後，向反應溶液中添加70質量％甲磺酸水溶液67 g。反應完畢後’以水進行再沈澱，取出固形物，獲得聚合物7 (重量平均分子量3.9萬）（14 g)。使用電位差自動滴定裝置（京都電子工業（股）製造）、以及作為滴定液的0.1 Μ氫氧化鈉水溶液，來測定所得聚合物7的酸值，結果該聚合物7 的酸值為4.4 mmol/g。將所得聚合物7以破酸氫鈉加以中和，使其溶解於重水中，藉由Bruker製造的300 MHz的NMR (AV-300)進行測定。相當於含聚合性基的單元的波峰是在7.8 ppm_8.1The 4 cut and the 2 H ester layer were washed to remove the ethyl acetate by the 300 mL column chromatography of the water, and the raw material used was used. 0 g of only one terminal amino group was reacted. Then, raw material B (45 g), 22 g (22 g), and ethyl acetate (15 〇 rainbow) were added to a three-neck flask of a drain mL, and the mixture was cooled in an ice bath. Adjust to >, drop (4) 赖 25g', turn off the temperature to 2 叱 or less. Then, it was raised to room temperature and reacted for 3 hours. After the reaction was completed, and 300 mL of distilled water was added to stop the reaction. Then, the ethyl acetate layer was washed 4 times with 300 mL of distilled water, dried over magnesium sulfate, and the ethyl acetate was distilled off, and the monomer B was purified by column chromatography to obtain 3 Å to 500 mL. A three-necked flask was charged with n,N-dimethylacetamide 22 g' and heated to 60 ° C under a nitrogen stream. The monomer B obtained above was added dropwise thereto for 6 hours: 28.3 g, acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 121 g, diethyl acrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.7 g, V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.59 g of N,N-dimethylacetamide 37 g solution. After the dripping is completed, the mixture is further mixed for 3 hours. Then, N,N-dimercaptoacetamide % g was added, and the reaction solution was cooled to room temperature. To the above reaction solution, 0.19 g of TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) and DBU 105 g' were added to the reaction solution for 12 hours at room temperature. Then, 104 g of a 70% by mass aqueous solution of m-acid was added to the reaction solution. After the completion of the reaction, reprecipitation was carried out with water, and the solid product was obtained to obtain a polymer 5 (weight average molecular weight: 38,000) (19 g). The acid value of the obtained polymer 5 was measured using a potentiometric auto-titration device (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 Torr sodium hydroxide aqueous solution as a titration solution. As a result, the acid value of the polymer 5 was 4.4 mmol/g. . The obtained polymer 5 was neutralized with sodium hydrogencarbonate and then dissolved in heavy water. The measurement was carried out by 300 MHz NMR (AV-300) manufactured by Bruker. The peak corresponding to the unit containing the polymerizable group is 78 PPm-8.1 PPm (2H min), 5.8 Ppm-5.6 PPm (1H min), 5.4 Ppm-5.2 ppm (1H min), 3.5 ppm-3.3 ppm (4H min) ), 2.5 ppm-〇.7 ppm (6H points) was broadly observed, and the peak corresponding to the carboxylic acid group unit was broadly observed at 2.5 ppm-0.7 Ppm (3H), derived from diethyl acrylamide unit. The peak was observed broadly at 3.4 ppm-3.0 ppm (4H) and 2.5 ppm_〇7 ppm (9H), confirming the formation of a unit containing a (fluorenyl) acrylamide group, a unit having a ship base, A polymer derived from a unit of diethyl propylamine. (Synthesis Example 6: Polymer 6) To a 2 L three-necked flask was placed 446 g of ethyl acetate 丨L, guanamine-amidole-3,5,5-didecylcyclohexanol, and the mixture was cooled in an ice bath. Drop 2 bromoisobutyl hydrazine 150 g' to the internal temperature to 2 (rc or less). Then, raise the internal temperature to room temperature (25. 〇, reaction for 2 hours ' after additional steam 300 mL) The reaction was stopped. Then, the ethyl layer was washed 4 times with 300 mL of distilled water, and then the sulfuric acid was dried. The ethyl acetate was removed and purified by column chromatography, using 俨 =, starting material C. 匕筏 120 120 g 201238750 Then 'Add a raw material 匚 (72 g) to a 500 mL three-necked flask, pyridine (22 g), ethyl acetate (150 mL), and cool in an ice bath. Drop isopropyl hurricane 25 g 'The internal temperature was changed to 20. The following method was adjusted. Then the reaction was carried out for 3 hours. After the reaction was completed, 300 mL of distilled water was added to stop the reaction. Then, the ethyl acetate layer was washed with 300 mL of distilled water. After that, the magnesium sulfate was dried, the ethyl acetate was distilled off, and the monomer C was purified by column chromatography to obtain 25 g. To a 500 mL three-necked flask, ν, Ν-dimethylacetamide 13 was added. g 'heated to 60 ° C under a nitrogen stream. The above was dropped for 6 hours. The obtained monomer C: 18.6 g, acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 6 g, diethyl acrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.1 g, V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.28 g of N, N-dimethyl 21 g of acetalamine. After the completion of the dropwise addition, the mixture was further stirred for 3 hours. Then, 22 g of N,N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxyl group was added to the above reaction solution. 0.09 g of TEMPO (manufactured by Tojo, manufactured by Kasei Kasei Co., Ltd.) and 50.1 g of DBU were reacted at room temperature for 12 hours. Then, 51 g of a 7 mass% methanesulfonic acid aqueous solution was added to the reaction solution. After the completion of the reaction, the reaction was carried out with water. Precipitation, and the solid matter was taken out to obtain a polymer 6 (weight average molecular weight: 44,000) (9 g), using a potentiometric auto-titration device (manufactured by Kyoto Electronics Industry Co., Ltd.), and 〇·1 Μ hydroxide as a titration solution. The acid value of the obtained polymer 6 was measured by an aqueous sodium solution, and as a result, the acid value of the polymer 6 was 4.5 mmol/g. The obtained polymer 6 was neutralized with sodium hydrogencarbonate to dissolve it in heavy water 'by Bruker Manufactured 300 MHz NMR (AV-300) for 'Beiyiyi° equivalent The karst of the polymer-containing unit is 7.8 ppm-8.1 51 201238750 ppm (1H min), 5.8 ppm-5.6 ppm (1H min), 5 4 ppm 5 2 ppm (1H min), 4.4 ppm-4.1 ppm (2H points), 3.5 ppm_3 3 ppm (2H points), 2,5ppm-〇.7ppm (21H points) Widely observed, the peak corresponding to the slow acid-base unit is broad at 2.5 ppm-0.7 ppm (3H points) It was observed that the peak from the diethyl acrylamide unit was broadly observed at 34 ppm 3〇?? 111 (411 points), 2.5卯111-〇.7?1)111 (911 points), confirming the formation. A polymer comprising a unit having a (meth) acrylamide group, a unit having a carboxylic acid group, and a unit derived from diethyl acrylamide. Soil (Synthesis Example 7: Polymer 7) To a 2 L three-necked flask was placed 274 g of ethyl acetate 1 [, 2-(2-aminoethoxy)ethanol, which was cooled in an ice bath. 150 g of 2 bromoisobutyl hydrazine was added thereto to reach an internal temperature of 20. (: The following method was adjusted. After the bran, the internal temperature was raised to room temperature (pit), and the reaction was carried out for 2 hours. After the completion of the reaction, 300 mL of distilled water was added to stop the reaction. Then, the ethyl acetate layer was distilled water 300. After washing 4 times with mL, the mixture was dried over magnesium sulfate, and ethyl acetate was distilled off to obtain 90 g of the starting material D. 继 Next, a raw material D (57 g) and pyridine (22 g) were placed in a 500 mL three-necked flask. Ethyl acetate (15 〇mL) was cooled in an ice bath, and 25 g of propylene hydrazine chloride was added thereto, and the internal temperature was 2 Torr. The enthalpy was carried out in the following manner. Then, the temperature was raised to room temperature, and the reaction was carried out for 3 hours. After completion, 300 mL of distilled water was added to stop the reaction. Then, the ethyl acetate layer was washed 4 times with 300 mL of distilled water, dried over magnesium sulfate, and distilled to remove ethyl acetate. The monomer D was purified by column chromatography. 22 g was added to a 500 mL three-necked flask, and N,N-dimethylacetamide 52 2012383⁄4 g was added, and heated to 60 ° C under a nitrogen stream. The above-obtained monomer D was dropped thereto for 6 hours: 20.5 g , acrylic (made by Tokyo Chemical Industry) 8.1 g, two A solution of 2.8 g of acrylamide, V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), 0.37 g of dimercaptoacetamide, 25 g. After the completion of the dropwise addition, stirring was further carried out for 3 hours. Then, N,N-dimercaptoacetate was added. 6 g of the amine, and the reaction solution was cooled to room temperature. To the above reaction solution, 4-hydroxy TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) 0·11 g, DBU 68 g was added, and the reaction was carried out for 12 hours at room temperature. 67 g of a 70% by mass aqueous methanesulfonic acid solution was added thereto. After the completion of the reaction, 'reprecipitation was carried out with water, and the solid matter was taken out to obtain a polymer 7 (weight average molecular weight: 39,000) (14 g). An automatic titration device using a potential difference (Kyoto Electronics The acid value of the obtained polymer 7 was measured by a 0.1 Μ aqueous sodium hydroxide solution as a titration solution, and as a result, the acid value of the polymer 7 was 4.4 mmol/g. The sodium hydrogen hydride was neutralized and dissolved in heavy water and measured by 300 MHz NMR (AV-300) manufactured by Bruker. The peak corresponding to the unit containing the polymerizable group was 7.8 ppm_8.1

ppm ( 1H 分）、5.8 ppm-5.6 ppm ( 1H 分）、5.4 ppm-5.2 ppm (1H 分）、4·2 ppm-3.9 ppm ( 2H 分）、3.8 ppm-3.3 ppm ( 6H 分）、2.5 ppm-0.7 ppm (6H分）寬廣地觀察到，相當於叛酸基單元的波峰是在2.5 ppm-〇.7 ppm(3H分）寬廣地觀察到’來自二乙基丙烯醯胺單元的波峰是在3.4 ppm-3.0 ppm (4H 分）、2.5 ppm-0.7 ppm ( 9H 分）寬廣地觀察到，確認生成包含具有（曱基）丙烯醯胺基的單元、具有羧酸基的早元、來自一乙基丙稀酿胺的單元的聚合物。 53 201238750 (合成例8 :聚合物8) 向2L·的二口燒瓿中加入乙峻 -甲胺350 g’在冰浴中冷卻。向其中·曰1乙、4_乙烯基苯基 g，以内溫達到2〇t：以下的方式進滴下2、溴異丁醯溴150 上升至室溫（25。〇來反應2小時了調節。然後，使内溫餾水300 mL使反應停止。然後，將反應完畢後，追加蒸 300 mL清洗4次後，進行硫酸鎂乾燥乙，乙醋層以蒸顧水藉此獲得io〇g原料E。、、’蒸餾去除乙酸乙酯，繼而’向500 mL的三口燒拖φ )'乙酸乙醋—在rr冷= 中滴下丙_氣2仏以内溫_耽以下的方式進行調節。然後，提高至室溫，反應3小時。反應完畢後，追加蒸餾水300 mL使反應停止。然後，將乙酸乙酯層以蒸館水300 mL清洗4次後，進行硫酸鎂乾燥，蒸餾去除乙酸乙酯’利用管柱層析法進行純化而獲得27 g單體E。向500 mL的三口燒瓶中加入N，N_二甲基乙醯胺16 g，在氮氣流下加熱至60°C。向其中以6小時滴下上述所得的單體E : 22 g、丙烯酸（東京化成製造）8 g、二乙基丙烯醯胺（東京化成製造）2.8g、V-601 (和光純藥製造） 0.37 g的N，N-二曱基乙醯胺26 g溶液。滴下完畢後’進而攪拌3小時。然後，添加N，N-二曱基乙醯胺27 g，將反應溶液冷卻至室溫。向上述反應溶液中添加4-羥基TEMp〇 (東京化成製造）0.11 g、DBU (67.7 g) ’在室溫下進行 12小時反應。然後，向反應溶液中添加70質量％曱磺酸 54 201238750 水溶液68 g。反應完畢後，以水痛撂平人，丹况叙，取出固形物， (重量平均分子量3·8萬)(i3g)。使用電位定液的’〇r裝置u、都電子工業（股）製造）、以及作為滴信㈣M氫氧⑽水錢，來測定所得聚合物8的酸、、‘。果該聚合物8的酸值為4.3 mmol/g。字所知聚合物8以碳酸氫納加以中和，使其溶解於重一中 a藉由 Bruker 製造的 3〇〇 MHz 的 NMR ( AV-300)進行測定。相當於含聚合性基的單元的波峰是在8丨ppm 7 8PPM (1H min), 5.8 ppm-5.6 ppm (1H min), 5.4 ppm-5.2 ppm (1H min), 4.2 ppm-3.9 ppm (2H min), 3.8 ppm-3.3 ppm (6H min), 2.5 ppm Widely observed at -0.7 ppm (6H), the peak corresponding to the tetamine unit is broadly observed at 2.5 ppm-〇.7 ppm (3H). The peak from the diethyl acrylamide unit is 3.4 ppm-3.0 ppm (4H points) and 2.5 ppm-0.7 ppm (9H points) were widely observed to confirm the formation of a unit containing a (fluorenyl) acrylamide group, a mer radical having a carboxylic acid group, and a A polymer of units of propylene amine. 53 201238750 (Synthesis Example 8: Polymer 8) To a 2 L·two-necked crucible, Ethyl-methylamine 350 g' was added and cooled in an ice bath. To the 曰1, 4, vinyl phenyl g, the internal temperature reached 2 〇 t: or less, and the brominated isobutyl bromo bromo 150 was allowed to rise to room temperature (25. The reaction was adjusted for 2 hours). Then, 300 mL of the internal temperature distilled water was used to stop the reaction. Then, after the completion of the reaction, the mixture was further washed by steaming 300 mL for 4 times, and then dried with magnesium sulfate, and the ethyl acetate layer was evaporated to obtain io〇g starting material E. , , 'Distilled to remove ethyl acetate, and then 'to 500 mL of three mouths tow φ '' acetic acid vinegar - in rr cold = drop _ gas 2 仏 in the internal temperature _ 耽 below the adjustment. Then, it was raised to room temperature and reacted for 3 hours. After the reaction was completed, 300 mL of distilled water was added to stop the reaction. Then, the ethyl acetate layer was washed four times with 300 mL of steaming water, dried over magnesium sulfate, and distilled to remove ethyl acetate. Purified by column chromatography to obtain 27 g of monomer E. 16 g of N,N-dimethylacetamide was added to a 500 mL three-necked flask and heated to 60 ° C under a nitrogen stream. The monomer E obtained above was dropped in 6 hours, 8 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.8 g of diethyl acrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.), and V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.37 g. A solution of N,N-dimercaptoacetamide in 26 g. After the completion of the dropping, the mixture was further stirred for 3 hours. Then, 27 g of N,N-dimercaptoacetamide was added, and the reaction solution was cooled to room temperature. To the reaction solution, 0.11 g of 4-hydroxy TEMp (manufactured by Tokyo Chemical Industry Co., Ltd.) and DBU (67.7 g) were added to carry out a reaction at room temperature for 12 hours. Then, 68 g of a 70% by mass hydrazine sulfonic acid 54 201238750 aqueous solution was added to the reaction solution. After the reaction was completed, the human body was taken out by water, and the solid matter was taken out (weight average molecular weight 38,000) (i3g). The acid of the obtained polymer 8 was measured by using the '〇r device u for potentiometric liquid, manufactured by Totsuka Electronics Co., Ltd., and the Dicense (4) M oxyhydrogen (10) water money. The polymer 8 had an acid value of 4.3 mmol/g. The polymer 8 was neutralized with sodium bicarbonate to dissolve it in the heavy one. a was measured by a 3 〇〇 MHz NMR (AV-300) manufactured by Bruker. The peak corresponding to the unit containing a polymerizable group is at 8 丨 ppm 7 8

=(Η分）、7 5ppm-7.0ppm(4H)、5.8ppm-5.6ppm(lH 刀）5 4 Ppm-5.2 ppm ( 1H 分）、4.6 ppm-4.4 ppm ( 2H 分）、 2.5 ppm_〇 7ppm (6H分）寬廣地觀察到，相當於羧酸基單疋的波峰是在2.5 PPm·0.7 PPm (3H分）寬廣地觀察到，來自一乙基丙稀酿胺單元的波峰是在3.4 ppm-3.0 ppm( 4H 刀）、2.5 ppm-0.7 ppm (9H分）寬廣地觀察到，確認生成包含具有（曱基）丙烯醯胺基的單元、具有羧酸基的單元、來自二乙基丙烯醯胺的單元的聚合物。 (合成例9 :聚合物9) 向500 mL的三口燒瓶中加入ν,Ν-二曱基乙醯胺35 g ’在氮氣流下加熱至60°C。向其中以6小時滴下合成例1 中獲得的單體A : 28.1 g、丙烯醯胺-2-曱基丙磺酸（東京化成製造）37 g、丙烯醯基嗎啉（（股）興人製造）5.0 g、 v-60l (和光純藥製造）0.59 g的N，N-二曱基乙醯胺61 g 洛液。滴下完畢後，進而授拌3小時。然後，添加Ν,Ν-二甲基乙醯胺58 g，將反應溶液冷卻至室溫。向上述反應 55 201238750= (Η), 7 5ppm-7.0ppm (4H), 5.8ppm-5.6ppm (lH knife) 5 4 Ppm-5.2 ppm (1H points), 4.6 ppm-4.4 ppm (2H points), 2.5 ppm_〇7ppm (6H points) Widely observed, the peak corresponding to the carboxylic acid monoterpene was broadly observed at 2.5 PPm·0.7 PPm (3H), and the peak from the ethyl propylamine unit was 3.4 ppm- 3.0 ppm (4H knives) and 2.5 ppm-0.7 ppm (9H points) were broadly observed to confirm the formation of a unit containing a (fluorenyl) acrylamide group, a unit having a carboxylic acid group, and diethyl propylene amide. The unit of the polymer. (Synthesis Example 9: Polymer 9) To a 500 mL three-necked flask, ν, Ν-dimercaptoacetamide 35 g ' was heated to 60 ° C under a nitrogen stream. The monomer A obtained in Synthesis Example 1 was added dropwise thereto for 6 hours: 28.1 g, acrylamide-nonyl mercaptopropanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 37 g, and acryloylmorpholine (manufactured by H. ) 5.0 g, v-60l (manufactured by Wako Pure Chemical Industries, Ltd.) 0.59 g of N,N-dimercaptoacetamide 61 g Lok. After the dropping was completed, the mixture was further mixed for 3 hours. Then, 58 g of hydrazine, hydrazine-dimethylacetamide was added, and the reaction solution was cooled to room temperature. To the above reaction 55 201238750

溶液中添加TEMpQ (東京化成製造）G.18 g、DBU 109 g在至溫下進行12小時反應。然後，向反應溶液中添加70質量％曱續酸水溶液1〇8 g。反應完畢後以水進行再沈殿，取出固形物，獲得聚合物9 (重量平均分子量 4.0，）（45 g)。使用電位差自動滴定裝置（京都電子工業 (股^製造）、以及作為滴定液的〇1M氫氧化鈉水溶液，來測定所得聚合物9的酸值，絲該聚合物9驗值為3.5 mmol/g。將所得聚合物9以碳酸氫鈉加以中和後，使其溶解於重水中，藉由Bruker製造的300 MHz的NMR (AV-300) 進行測定。相當於含聚合性基的單元的波峰是在8.1 ppm-7.8 ppm( 1H 分）、5.8 ppm-5.6 ppm( 1H 分）、5.4 ppm-5.2 ppm ( 1H 刀）、4.2 ppm-3.9 ppm ( 2H 分）、3.5 ppm-3.3 ppm (2H分）、2.5ppm-0.7ppm (6H分）寬廣地觀察到，相當於續I基單元的波峰是在8 1 ppm-7.8 ppm ( 1H分）、3.1 ppm-2.7 ppm (2H 分）、2.5 ppm-0.7 ppm (9H 分）寬廣地觀察到’來自丙烯醯基嗎啉單元的波峰是在3.7 ppm_3 5 ppm ( 8H 分）、2·8 ppm-0.7 ppm ( 3H 分）寬廣地觀察到，確認生成包含具有（曱基）丙烯醯胺基的單元、具有磺酸基的單元、來自丙烯醯基嗎啉的單元的聚合物。 (合成例10 :聚合物10) 向500 mL的三口燒瓶中加入N，N-二曱基乙醯胺49 g，在氮氣流下加熱至60°C。向其中以6小時滴下合成例1 中獲得的單體 A : 28.1 g、Phosmer M ( Uni-Chemical 製造） 56 201238750 66g、丙烯醯基嗎啉（（股）興人製造）5 〇g、v_6〇i (和光純藥製造）0.59 g的N，N-二曱基乙醯胺9〇 g溶液。滴下完畢後，進而攪拌3小時。然後，添加N，N_二曱基乙醯胺 82 g，將反應溶液冷卻至室溫。向上述反應溶液中添加冬羥基TEMPO (東京化成製造）〇·18 g、dBIj 1〇9 g，在室 _ 溫下進行12小時反應。然後，向反應溶液中添加70質量 . %曱磺酸水溶液1〇8 g。反應完畢後，以水進行再沈澱，取出固形物，獲得聚合物10 (重量平均分子量4 8萬）（81 g)。使用電位差自動滴定裝_置（京都電子工業（股）製造）、以及作為滴定液的〇·1 Μ氫氧化納水溶液，來測定所得聚合物10的酸值’結果該聚合物10的酸值為2.0 mmol/g。將所得聚合物10以碳酸氫鈉加以中和，使其溶解於重水中’藉由Bruker製造的300 MHz的NMR ( AV-300)進行測定。相當於含聚合性基的單元的波峰是在8.1 ppm-7.8 ppm ( 1H 分）、5.8 ppm-5.6 ppm ( 1H 分）、5.4 ppm-5.2 ppm (1H 分）、4.2 ppm-3.9 ppm ( 2H 分）、3.5 ppm-3.3 ppm ( 2H 分）、2.5 ppm_〇_7 ppm (6H分）寬廣地觀察到，相當於磷酸基單元的波峰是在4.3 ppm-3.8 ppm(4H分）、2.5 ppm-0.7 PPm (5H分）寬廣地觀察到，來自丙烯醯基嗎啉單元的波峰疋在 3.7 ppm-3.5 ppm ( 8H 分）、2.8 ppm-0.7 ppm ( 3H 分）寬廣地觀察到，確認生成包含具有（甲基)丙烯醯胺基的單元、具有磷酸基的單元、來自丙烯醯基嗎啉的單元的聚合物。 (合成例11 :聚合物11 ) 57 201238750 向500 mL的三口燒瓶中加入ν，Ν·二曱基乙醯胺36 g，在氮氣流下加熱至60°C。向其中以6小時滴下實例1 中獲得的單體A : 28.0 g'NK Ester A-SA (新中村化學製造）38.6g、丙烯醯基嗎啉（（股）興人製造）5〇g、V6〇i (和光純藥製造）0.59 g的N，N-二甲基乙醯胺60 g溶液。滴下完畢後，進而攪拌3小時。然後，添加N，N_:甲基乙醯胺62 g，將反應溶液冷卻至室溫。向上述反應溶液中添加4_經基TEMP0 (東京化成製造）〇.18g、DBUl08g，在室溫下進行12小喊應。織，向反應驗巾添加％質量％甲續酸水溶液刚g。反應完畢後，以水進行再沈澱，取出固形物，獲得聚合物11 (重量平均分子量4.3萬） (3j g)。使用電位差自動滴定裝置（京都電子工業（股）製，）、以及作為滴定液的O.i M氫氧化鈉水溶液，來測定所得聚合物11的酸值，結果該聚合物11的酸值為3.2 mmol/g 〇將所得聚合物11以碳酸氫鈉加以中和，使其溶解於重具中藉由Bruker製造的300 MHz的NMR ( AV-300 )進行測定。彳目當於含聚合性基的單元驗.是在8 ι 8TEMpQ (manufactured by Tokyo Chemical Industry Co., Ltd.) G.18 g and DBU 109 g were added to the solution for 12 hours at room temperature. Then, a solution of 70% by mass of a buffered acid aqueous solution of 1 〇 8 g was added to the reaction solution. After the completion of the reaction, the mixture was again poured out with water, and the solid matter was taken out to obtain a polymer 9 (weight average molecular weight 4.0,) (45 g). The acid value of the obtained polymer 9 was measured using a potentiometric auto-titration device (Kyoto Electronics Industry Co., Ltd.) and a 〇1M sodium hydroxide aqueous solution as a titration solution, and the polymer 9 was found to have a value of 3.5 mmol/g. The obtained polymer 9 was neutralized with sodium hydrogencarbonate, dissolved in heavy water, and measured by 300 MHz NMR (AV-300) manufactured by Bruker. The peak corresponding to the unit containing the polymerizable group was 8.1 ppm-7.8 ppm (1H points), 5.8 ppm-5.6 ppm (1H points), 5.4 ppm-5.2 ppm (1H knives), 4.2 ppm-3.9 ppm (2H points), 3.5 ppm-3.3 ppm (2H points), 2.5ppm-0.7ppm (6H points) broadly observed, the peak corresponding to the continued I base unit is 8 1 ppm-7.8 ppm (1H), 3.1 ppm-2.7 ppm (2H), 2.5 ppm-0.7 ppm (9H points) Widely observed that the peak from the acryloylmorpholine unit was observed broadly at 3.7 ppm_3 5 ppm (8H min) and 2·8 ppm-0.7 ppm (3H min), confirming the formation of the inclusion ( a polymer of a fluorenylamino group, a unit having a sulfonic acid group, or a unit derived from acryloylmorpholine. : Polymer 10) 49 g of N,N-dimercaptoacetamide was added to a 500 mL three-necked flask, and heated to 60 ° C under a nitrogen stream. The monomer A obtained in Synthesis Example 1 was dropped thereto for 6 hours. : 28.1 g, Phosmer M (manufactured by Uni-Chemical) 56 201238750 66g, propylene decylmorpholine (manufactured by Hiroshi) 5 〇g, v_6〇i (made by Wako Pure Chemical Industries, Ltd.) 0.59 g of N, N-II 9 〇g solution of mercaptoacetamide. After the completion of the dropwise addition, the mixture was further stirred for 3 hours. Then, 82 g of N,N-dimercaptoacetamide was added, and the reaction solution was cooled to room temperature. Hydroxy TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) 〇18 g, dBIj 1〇9 g, and reacted at room temperature for 12 hours. Then, 70 g of a mass% aqueous solution of sulfonic acid was added to the reaction solution, and the reaction was completed. After that, it was reprecipitated with water, and the solid matter was taken out to obtain a polymer 10 (weight average molecular weight: 48,000) (81 g), which was automatically titrated using a potential difference (manufactured by Kyoto Electronics Industry Co., Ltd.), and as a titrant solution. 〇·1 Μ aqueous solution of sodium hydroxide to determine the acid value of the obtained polymer 10 An acid number of 10 was 2.0 mmol / g. The resultant polymer 10 and be neutralized with sodium bicarbonate and dissolved in heavy water 'by to 300 MHz NMR (AV-300) Bruker manufactured into line measurement. The peak corresponding to the unit containing the polymerizable group is 8.1 ppm-7.8 ppm (1H min), 5.8 ppm-5.6 ppm (1H min), 5.4 ppm-5.2 ppm (1H min), 4.2 ppm-3.9 ppm (2H min) ), 3.5 ppm-3.3 ppm (2H points), 2.5 ppm_〇_7 ppm (6H points) broadly observed, the peak corresponding to the phosphate unit is 4.3 ppm-3.8 ppm (4H points), 2.5 ppm- 0.7 PPm (5H) broadly observed that the peak 来自 from the acryloylmorpholine unit was widely observed at 3.7 ppm-3.5 ppm (8H min) and 2.8 ppm-0.7 ppm (3H min), confirming that the formation contained A polymer of a (meth)acrylonitrile group, a unit having a phosphate group, or a unit derived from acryloylmorpholine. (Synthesis Example 11: Polymer 11) 57 201238750 To a 500 mL three-necked flask was placed 36 g of ν,nidoctylacetamide, and the mixture was heated to 60 ° C under a nitrogen stream. The monomer A obtained in Example 1 was dropped thereto for 6 hours: 28.0 g of 'NK Ester A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.) 38.6 g, and acryloylmorpholine (manufactured by Xingren) 5 〇 g, V6 〇i (manufactured by Wako Pure Chemical Industries, Ltd.) 0.59 g of N,N-dimethylacetamide 60 g solution. After the completion of the dropwise addition, the mixture was further stirred for 3 hours. Then, 62 g of N,N_:methylacetamide was added, and the reaction solution was cooled to room temperature. To the above reaction solution, 4_base TEMP0 (manufactured by Tokyo Chemical Industry Co., Ltd.) 〇.18g, DBUl08g was added, and 12 shouts were performed at room temperature. Weaving, adding % by mass of aqueous acid solution to the reaction wipes. After completion of the reaction, it was reprecipitated with water, and the solid matter was taken out to obtain a polymer 11 (weight average molecular weight: 43,000) (3 g g). The acid value of the obtained polymer 11 was measured by using a potentiometric auto-titration device (manufactured by Kyoto Electronics Co., Ltd.) and an aqueous solution of Oi M sodium hydroxide as a titration solution. As a result, the acid value of the polymer 11 was 3.2 mmol/ g 所得 The obtained polymer 11 was neutralized with sodium hydrogencarbonate, and dissolved in a weight to be measured by 300 MHz NMR (AV-300) manufactured by Bruker. The order is based on the unit containing the polymerizable group. It is at 8 ι 8

ppm ( 1H ^ . 5.8 ppm-5.6 ppm ( 1H ^ ) ^ 5.4 ppm-5.2 ppm 〔1H 分）、4.2 Ppm-3.9 ppm ( 2H 分）、3.5 ppm_3.3 ppm ( 2H 分）、^.5卯111_0.7卯111(611分）寬廣地觀察到，相當於羧酸基皁元的波峰是在4.2 ppm_3 9 ppm(4H分）、2 8 ppm 〇 7 (7H分）寬廣地觀察到，來自丙烯醯基嗎啉單元的波Ppm ( 1H ^ . 5.8 ppm-5.6 ppm ( 1H ^ ) ^ 5.4 ppm-5.2 ppm [1H points), 4.2 Ppm-3.9 ppm (2H points), 3.5 ppm_3.3 ppm (2H points), ^.5卯111_0 .7卯111 (611 points) Widely observed, the peak corresponding to the carboxylic acid-based soap element was broadly observed at 4.2 ppm_3 9 ppm (4H points) and 28 ppm 〇7 (7H points) from acrylonitrile. Wave of morpholine unit

峰疋在 3.7 ppm_3.5 ppm (8H 分）、2.8 ppm-0.7 ppm (3H 58 201238750 (合成例12 :比較聚合物〇 (早「甲基丙，严胺·丙烯酸2_經乙醋共聚物鈕刀S 5’000,各單疋的莫耳比為62 :16:22) 18 说^ 3^中，添加對苯二㈣化、2_甲i丙氮酸酯19·4 g及二月桂酸二丁基錫心妙下』4小時。所得聚合物的酸值為4.2 meq/g。以1N氫氧錢水溶㈣中和聽，添加於乙酸乙知中使聚合物麟，充分清洗，㈣峨聚合物卜該聚合物中不含式（A)所表示的單元。 (合成例13 :比較聚合物2) 向500 mL的三口燒瓶中加人，氮氣流下加熱至机。向其中以4㈣滴τ上述所得的早體A :14.3 g、丙烯腈（東京化成工業（股）製造）3〇g、内烯酸（東京化成製造）6.5g、ν·65 (和光純藥製造）〇 4 g的Ν，Ν-二甲基乙醯胺8 g溶液。滴下完畢後，進而攪拌 3小時。然後，添加N，N-二甲基乙醯胺41 g，將反應溶液、卻至至>孤。向上述反應溶液中添加4_經基tempo (東厅、化成製造）0.09 g、DBU 5屯8 g，在室溫下進行小時反應。然後，向反應溶液中添加70質量％曱磺酸水溶液 54 g。反應完畢後’以水進行再沈殿，取出固形物，獲得以下結構式的比較聚合物2(重量平均分子量5 3萬）12 g。 59 201238750 使用電位差自動滴定I置（及作為滴定液的W 業（月又）製造）、以聚合物2 虱氧化财料，來啦所得比較 _1/g。^，結果該比較聚合物2的酸值為3.9Peak 疋 at 3.7 ppm_3.5 ppm (8H points), 2.8 ppm-0.7 ppm (3H 58 201238750 (Synthesis Example 12: Comparative Polymer 〇 (early "methyl propyl, succinyl acrylate 2 acetonitrile copolymer button Knife S 5'000, the molar ratio of each single 62 is 62:16:22) 18 says ^ 3^, adding p-phenylene (tetra), 2-methyl i-propionate 19·4 g and dilauric acid The temperature of the obtained polymer was 4 hours. The acid value of the obtained polymer was 4.2 meq/g. It was neutralized with 1N oxyhydroxyl alcohol (4), and added to the acetic acid to make the polymer lin, fully cleaned, (iv) ruthenium polymer The polymer represented by the formula (A) was not contained in the polymer. (Synthesis Example 13: Comparative Polymer 2) A 500 mL three-necked flask was charged, and heated under a nitrogen stream to a machine. Early body A: 14.3 g, acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) 3 〇 g, olefinic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.5 g, ν·65 (manufactured by Wako Pure Chemical Industries, Ltd.) 〇 4 g Ν, Ν - 8 g of dimethylacetamide. After the completion of the dropwise addition, the mixture was further stirred for 3 hours. Then, 41 g of N,N-dimethylacetamide was added, and the reaction solution was allowed to go to > To the liquid, 0.09 g of a base tempo (manufactured by Tosho, Kasei Co., Ltd.) and DBU 5屯8 g were added, and the reaction was carried out at room temperature for an hour. Then, 54 g of a 70% by mass aqueous solution of sulfonic acid was added to the reaction solution. After completion, the water is used to re-deep the temple, and the solid matter is taken out to obtain 12 g of Comparative Polymer 2 (weight average molecular weight of 30,000) of the following structural formula. 59 201238750 Automatic titration of I by potential difference (and W industry as titrant ( Month))), the polymer 2 虱 oxidized material, the comparison is _1 / g. ^, the result of the comparison of the acid value of the polymer 2 is 3.9

較聚定機（（股）堀場製作所製造）進行所得比 ΚΡ5姓曰也鑑定。測定是使聚合物溶解於丙酮中，使用二：：ί進行。IR測定的結果可知，在2240 —附近 ' ’作為腈單元的丙稀腈被導入至聚合物中。另外$由馱值測定，可知丙烯酸作為羧酸單元而導入。另外’ /合解於氘代二甲亞颯（dimethylsulfoxide-d6，氘代 DMS〇)中’藉由 Bruker 製造的 300 MHz 的 NMR( AV-300 ) 進行測定°相當於含氰基的單元的波峰是在2.5 ppm-0.7 ppm (5H分）寬廣地觀察到，相當於含聚合性基的單元的波峰疋在 7.8 ppm-8.1 ppm ( 1H 分）、5.8 ppm-5.6 ppm ( 1H 分）、5.4 ppm-5.2 ppm ( 1H 分）、4.2 ppm-3.9 ppm ( 2H 分）、 3-3 ppm-3.5 ppm ( 2H 分）、2.5 ppm-0.7 ppm ( 6H 分）寬廣地觀察到，相當於叛酸基單元的波峰是在2.5 ppm-0.7 ppm (3H分）寬廣地觀察到，確認生成包含含聚合性基的單 201238750 該聚元、含氰基的單元、以及舰基單元的聚該聚合物巾不含式合物中包含氰基。力r 〈實例1〉 (基底絕緣基板的製作） ” ί玻:= 反(商品名:FR_4，松下電工(股)製 5 賴力下以100°c〜聰的條件，使用真工層豐機進行加熱及加壓’來黏接Aji_otoCompared with the Juding Machine (manufactured by the market), the ratio of 所得5 is also identified. The measurement was carried out by dissolving the polymer in acetone and using two::ί. As a result of the IR measurement, it was found that acrylonitrile which is a nitrile unit in the vicinity of 2240 - is introduced into the polymer. In addition, it was determined from the enthalpy value that acrylic acid was introduced as a carboxylic acid unit. In addition, '/recombination in dimethylsulfoxide-d6 (deuterated DMS) was measured by 300 MHz NMR (AV-300) manufactured by Bruker. The peak corresponding to the unit containing cyano group It is widely observed at 2.5 ppm-0.7 ppm (5H), and the peak equivalent to the polymer-containing unit is 7.8 ppm-8.1 ppm (1H), 5.8 ppm-5.6 ppm (1H), 5.4 ppm. -5.2 ppm (1H min), 4.2 ppm-3.9 ppm (2H min), 3-3 ppm-3.5 ppm (2H min), 2.5 ppm-0.7 ppm (6H min) broadly observed, equivalent to a tetamine unit The peak was observed broadly at 2.5 ppm-0.7 ppm (3H), confirming the formation of a single polymer containing the polymerizable group 201238750, the cyano group-containing unit, and the ship-based unit. A cyano group is included in the formula. Force r <Example 1> (Production of base insulating substrate) ” 玻:= 反 (trade name: FR_4, Panasonic Electric Works (shares) system 5 Lai Li under the conditions of 100 ° c ~ Cong, use the real machine Heat and pressurize 'to bond Aji_oto

Fine_TeChn〇 (股）製造的環氧系絕緣膜（GX_13，45 μιη), 藉此將電氣絕緣層形成於基板上，後，在丨贼下進行i 小時加熱處理，進行該電氣絕緣層的熱層化。 (密著辅助層的形成） θ 在所形成的電氣絕緣層上，以厚度達到15哗的方式利用旋轉塗佈法來塗佈下述組成的密著輔助層形成用組成物，然後在14GC下乾燥30分鐘，形成密著輔助層。對牷著輔助層形成後的基板，進而在下實施％分鐘硬化處理，製作基板A1。 (密著辅助層形成用組成物）將雙紛A型環氧樹脂（環氧當量1 %，Yuka_|§hell Epoxy (股）製造的Epikote 828) 25質量份（以下，調配量全部以質量份表示）、曱酚酚醛型環氧樹脂（環氧當量215，大曰本油墨化學工業（股）製造的Epicr〇nN_673) 45份、苯酚酚醛樹脂（酚性羥基當量1〇5，大日本油墨化學工業（股）製造的Phenolite) 30份，一邊在二乙二醇***乙酸酯20 201238750 份、溶劑;5腦油2G份中麟—邊加熱溶解，冷田然後，向其中添加包含上述Epikote 828與雙盼s的装:。樹脂的環己酮清漆（Yuka_Shdl Ep〇xy (股 ^基 YL6747H30,不揮發分3〇質量％，重量平均分子^的 30份、2-苯基-4,5-雙(輕甲基)味n坐〇 8份、微粉碎 0 ) 2份、矽系消泡劑〇.5份’製作密著辅助層形成用組成物石夕 (被鍍敷層的形成）紙物。、:塵而以厚度達至i 5哗的方式，利用旋轉塗佈法 4述被鍍敷層形成用組成物丨塗佈於基板A1上，鈔在80°C下乾燥。 “ & 繼而’對所塗佈的組成物層，使用曝光機（紫外線照射裝置，UVX-02516S1LP01，牛尾(Ushi〇)電機（股）製造），將波長254 nm的紫外光在室溫下全面曝光2 5分鐘（254 nm下的能量的量：150〇mj)。全面曝光後，為了去除不需要的被鍍敷層形成用組成物，而以〇8 wt%碳酸氫鈉液充分清洗基板。藉此’獲得在基板A1上具有被鍍敷層（清洗後的厚度：0.7 μιη)的基板A2。 (被鐘敷層形成用組成物1) •聚合物1 13.1 g •碳酸氫鈉 0.8 g .水 25.9 g •1-曱氧基-2-丙醇 13.0 g (鍍敷觸媒的賦予） 62 201238750, 將基板A2在硝酸把（Π #量％的水溶液（液溫：坑）浸潰分鐘，織以_水進行清洗。利用感應麵合電聚 (mdUCtively coupledplasma，Icp)發光分析裝置（（股）島孝製作所製造）來測定此時的纪離子的吸附量，结 0.1g/m2〇 ..... (無電解鑛敷處理）將賦予鐘敷觸媒（金屬鹽）之後的基板在以下組成的無電解鍍敷浴（鹼性：pH值12.5)中浸潰1小時，形成厚度0.4 μιη的無電解鍍銅層。 (無電解鍍敷浴成分） •硫酸銅 0.35 g •酒石酸NaK 1.75 g •氫氧化納 0.75 g •甲醛 0.25 g .水 47.8 g (電解鍍敷）將形成有無電解鍍銅層的基板浸潰於以下組成的電解鍍銅浴中，以電流密度3 A/dm2進行約20分鐘的電解鍍An epoxy-based insulating film (GX_13, 45 μm) manufactured by Fine_TeChn®, whereby an electrically insulating layer is formed on the substrate, and then heat-treated for 1 hour under a thief to perform a thermal layer of the electrical insulating layer. Chemical. (Formation of adhesion assisting layer) θ The composition for forming an adhesion assisting layer having the following composition was applied to the formed electrically insulating layer by a spin coating method so as to have a thickness of 15 Å, and then under 14 GC Dry for 30 minutes to form a dense auxiliary layer. The substrate A1 was formed by performing a % minute hardening treatment on the substrate after the formation of the auxiliary layer. (Condensation-adhesive layer-forming composition) 25 parts by mass of an A-type epoxy resin (epoxy equivalent 1%, Epikote 828 manufactured by Yuka_|§hell Epoxy Co., Ltd.) (hereinafter, all the amounts are in parts by mass) )) Phenolic novolac type epoxy resin (epoxy equivalent 215, Epicri〇n N_673 manufactured by Otsuka Ink Chemical Industry Co., Ltd.) 45 parts, phenol novolac resin (phenolic hydroxyl equivalent 1〇5, Dainippon Ink Chemistry 30 parts of Phenolite manufactured by Industrial Co., Ltd., dissolved in diethylene glycol diethyl ether acetate 20 201238750 parts, solvent; 5 brain oil 2G in the middle of the lining - cold field, and then added to the above-mentioned Epikote 828 With the double hope s:: Resin cyclohexanone varnish (Yuka_Shdl Ep〇xy (shared base YL6747H30, nonvolatile content 3 〇 mass%, weight average molecular weight of 30 parts, 2-phenyl-4,5-bis (light methyl) taste n 8 parts, finely pulverized 0) 2 parts, bismuth defoamer 〇. 5 parts 'The composition for forming the adhesion auxiliary layer is formed by Shi Xi (formation of the layer to be plated). Paper: Thickness by dust The coating layer forming composition was applied onto the substrate A1 by a spin coating method, and the banknote was dried at 80 ° C. " & then 'the composition to be applied" The layer is exposed to ultraviolet light at a wavelength of 254 nm at room temperature for 25 minutes (UV at 254 nm) using an exposure machine (UV irradiation device, UVX-02516S1LP01, Ushi〇 motor). Amount: 150 〇mj). After the full exposure, in order to remove the unnecessary composition for forming a layer to be plated, the substrate was sufficiently washed with 〇8 wt% sodium hydrogencarbonate solution. Thus, the obtained substrate was plated with A1. Substrate A2 of the coating layer (thickness after washing: 0.7 μm) (composition material 1 formed by the bell layer) • Polymer 1 13.1 g • Hydrogencarbonate 0.8 g. Water 25.9 g • 1-decyloxy-2-propanol 13.0 g (Improved by plating catalyst) 62 201238750, Dip the substrate A2 in nitric acid (Π#%% aqueous solution (liquid temperature: pit)) In the minute, the woven water was washed with _water. The amount of adsorption of the ion at this time was measured by a mdUCtively coupled plasma (Icp) luminescence analyzer (manufactured by Shimao Manufacturing Co., Ltd.), and the knot was 0.1 g/m2. 〇..... (electroless ore treatment) The substrate after the application of the catalyst (metal salt) was immersed in an electroless plating bath (basic: pH 12.5) having the following composition for 1 hour to form Electroless copper plating layer with a thickness of 0.4 μm. (Electroless plating bath composition) • Copper sulfate 0.35 g • Tartaric acid NaK 1.75 g • Nanoparticles 0.75 g • Formaldehyde 0.25 g. Water 47.8 g (electrolytic plating) Will be formed The substrate of the electrolytic copper plating layer is immersed in an electrolytic copper plating bath having the following composition, and electrolytic plating is performed at a current density of 3 A/dm 2 for about 20 minutes.

電解錢敷後的鍍銅層（金屬膜）的厚度約為18 μπι。 (電解鍍敷浴成分） •硫酸銅 38 g •硫酸 95 g .鹽酸 1 mL •Copper Gleam PCM ( Meltex (股）製造） 3.5 mL 5 63 201238750 500 g .水 (圖案形成步驟）對電解鍍敷後的基板，在17〇。(：下進行丨小時的加熱處理後，在該基板表面層疊乾式抗蝕劑膜（日立化成（股）製造的RY3315，膜厚30 μηι>繼而，使可利用減成法來形成Ι^ = 40μιη/40μιη的梳形圖案的玻璃遮罩，密著於層疊有乾式抗蝕劑膜的基板上，將抗蝕劑的感光區域進行曝光。曝光後，以2 kg/m2的噴射壓賦予溶液，進行顯影處理。然後，對基板進行水洗、乾燥，在鍍銅層上形成抗蝕劑圖案。，形成有抗蝕劑圖案的基板喷淋FeCl2/Hcl水溶液（溫度) (pH值：1.5) 90秒，藉此進行金屬膜的蝕刻，將抗餘劑圖_非形成區域所存在的賴去除。然後，藉 =以2 kg/m2时射壓將Ν_ 4質量％水溶液形成於基板上，剝離抗勉劑圖案。 (酸性溶液處理） =’在魏水溶液（阳值：Q 5)中浸潰1〇分鐘 ^敷層中的金屬成分。利用ICP發光分析裝置(（朋作所製造）來測定此時倾敷層中的_子的吸f 里’、、，口果為檢測極限以下（3mg/m2以下）。 (被鍍敷層去除），有圖案化金屬膜（配線圖案）的基板，以配線{ "二、面與電*照射面相對的方式配置於電*钱刻裝】 )SAMC〇製造，平行平板型電衆處理裝置，PC-100( 64 201238750 的腔室内。將腔室内減壓至jxli^PaOxlO-3!：^)，在氧氣環境下進行1.5分鐘電漿處理。藉由掃描式電子顯微鏡 (scanning electron microscope，SEM)像對處理後的基板表面進行剖面觀察，結果確認配線間的被鍍敷層以及密著輔助層被去除。 (阻焊劑的貼附）對於電漿處理後的基板，以1UTC、0.2 MPa的條件真空層疊阻焊劑（PFR800，太陽油墨製造（股）製造），利用中心波長365 nm的曝光機照射420 mJ的光能量。繼而，對基板進行80°C/l〇分鐘的加熱處理後，以喷射壓2kg/m2將NaHC〇3 : 10%水溶液賦予至基板表面，藉此進行顯影，乾燥。然後，再次利用中心波長365 nm的曝光機對基板照射lOOOmJ的光能量。最後進行15〇。(：/1 hr 的加熱處理，獲得由阻焊劑包覆的配線基板。〈實例2〉除了代替聚合物1而使用聚合物2以外，依據與實例 1相同的順序獲得配線基板。〈實例3〉除了代替聚合物1而使用聚合物3以外，依據與實例 1相同的順序獲得配線基板。〈實例4〉除了代替聚合物1而使用聚合物4以外，依據與實例 1相同的順序獲得配線基板。〈實例5〉 65 201238750 (鍍敷觸媒的賦予）的順序變依據與實例1相同的順序獲得除了將上述實例丨中的更為以下記載的順序以外，配線基板。 (鑛敷觸媒的賦予）中G.1質量％的水溶液（液溫：60。〇) 二又/ 7刀里然後以蒸餘水進行清洗。彻ICP發行 ((股）島津製作所製造）來測定此時把離子對被鍍敷層的吸附量，結果為02g/m2。〈實例6> 除了將上述實例1中的（圖案形成步驟）的使用 FeCl2/HCl 7jc /容液的金屬膜刻處理變更為以下記載的順序以外，依據與貫例丨相同的順序獲得配線基板。 (圖案形成步驟）對於形成有抗蝕劑圖案的基板喷淋CU(NH3)4C12水溶液（溫度37。(：）（pH值：8.5) 90秒，藉此進行金屬膜的名虫刻’將抗蝕劑圖案的非形成區域所存在的鍍銅去除。〈實例7〉除了不實施上述實例1中的（密著辅助層的形成）步驟’而是對（基底絕緣基板的製作）中製作的具有電氣絕緣層的基板實施（被鍍敷層的形成）步驟，在電氣絕緣層上製作被鍍敷層以外，依據與實例1相同的順序獲得配線基板。該實例7中，不經由密著辅助層，將被鍍敷層配置於基板上。 66 201238¾ 〈實例8〉除了代替聚合物1而使用聚合物5，將（被鐘敷層的形成）中的波長254 nm的紫外光在室溫下進行3分鐘全面曝光（254 nm下的能量的量：1800 mJ)以外，依據與實例1相同的順序獲得配線基板。〈實例9〉除了代替聚合物1而使用聚合物6 ’將（被鑛敷層的形成）中的波長254 nm的紫外光在室溫下進行4分鐘全面曝光（254 nm下的能量的量：2400 mJ)以外，依據與實例1相同的順序獲得配線基板。 ~ 〈實例10〉除了代替聚合物1而使用聚合物7，將（被錢敷層的形成）中的波長254 nm的紫外光在室溫下進行4分鐘全面曝光（254 nm下的能量的量：2400 mJ)以外，依據與實例1相同的順序獲得配線基板。 ^ 〈實例11〉除了代替聚合物1而使用聚合物8 ’將（被錢敷層的形成）中的波長254 nm的紫外光在室溫下進行4分鐘全面曝光（254 nm下的能量的量：2400 mJ)以外，依據與實例1相同的順序獲得配線基板。 ~ 〈實例12〉除了代替聚合物丨而使崎合物9 1 (被鍍敷層的形成）中的波長254 nm的紫外光在室溫下進行八二入面曝光（254 nm下的能量的量：6000 mJ)，且將被^敷^ 67 201238750. 形成用組成物中的碳酸氫納的量由G 8 g變更為⑽ 外，依據與實例1相同的順序獲得配線基板。〈實例13〉 /除了代替聚合物1而使用聚合物1〇，將（被鍍敷層的形成）中的波長254 nm的紫外光在室溫下進行1〇分鐘全面曝光（254 nm下的能量的量：6〇〇〇mJ)，且將被鍍敷層形成用組成物中的碳酸氫鈉的量由〇8 g變更為〇38呂以外，依據與實例1相同的順序獲得配線基板。〈實例14〉除了代替聚合物1而使用聚合物11，將（被鍍敷層的形成）中的波長254 nm的紫外光在室溫下進行1〇分鐘全面曝光（254 nm下的能量的量·· 6000 mJ)，且將被鍍敷層形成用組成物中的碳酸氫鈉的量由0.8 g變更為〇6 g以外，依據與實例1相同的順序獲得配線基板。〈比較例1〉除了代替聚合物1而使用比較聚合物2以外，依據角_ 實例1相同的順序獲得配線基板。〈比較例2〉除了代替（被鍵敷層形成用組成物1)而使用以下的 (被鍍敷層形成用組成物2)，且不實施（酸性溶液處理）以及（被鍍敷層去除）步驟以外，依據與實例1相同的順序製造配線基板。藉由SEM像對被鍍敷層去除後的基板表面進行剖面觀察，結果確認殘存有配線間的被鍍敷層。 68 201238750 (被鍍敷層形成用組成物2) •比較聚合物1 0.25 g .水 5g •乙腈 3g 〈比較例3〉除了不實施實例1中的（酸性溶液處理）以外，與實例1相同的順序製造配線基板。〈比較例4〉除了不實施上述實例1中的（被鍍敷層去除）步驟以外’依據與實例1相同的順序獲得配線基板。〈評價方法〉 (絕緣性評價）、上述所得的配線基板的絕緣可靠性試驗是使用電化學遷移评價裝置（（股）Espec公司製造，電化學遷移裝置 AMI及高溫高濕槽Platinous PR_3K)來進行。試驗條件為 =壓30 v，溫濕度環境為85。〇、85%RH，加濕水是使用阻值13 M的蒸餾水，進行至1〇〇〇小時來進行評價。依據以下基準進行評價。將結果示於表1中。 & D」：至小於500小時為止的評價中，配線基板的電卜且值低於1 ΜΩ的情況。「C」：至500小時以上且小於750小時為止的評價中，配線基板的電阻值低於1ΜΩ的情況。「B」：至750小時以上且小於1〇〇〇小時為止的評價中，配線基板的電阻值低於1ΜΩ的情況。 69 201238750 .^rw 「A」：至looo小時為止進行評價，配線基板的電阻值不低於1 ΜΩ的情況。 (電漿姓刻速率）將實例1〜實例14以及比較例1、比較例3中實施的 (被鍍敷層去除）中去除被鍍敷層與密著輔助層時的電漿餘刻的姓刻速率（μπι/min)歸納於表j中。 (密著性評價） =於實例丨〜實例4中獲得的電解鍍敷後所得的具有，屬膜的基板（積層體)，在卿CT進行3()分鐘的烘烤二圖it:/:進時洪烤處理後，使用自動立 ^則圖儀AGS·)((股）島津製作所製造$職屬膜以拉伸強度10 mm/min進行9〇。4 寬金結果歸納於表i中。丁 90剝離強度的測定。將 201238750 J-asoo 寸 ±1 密著性評價 (kN/m) ν〇 d d 00 ο 00 ο I I 1 1 1 1 1 1 1 1 1 I 1 1 啭ε yr) κη cn ΓΛ rn in νΊ 寸 Ο 1 〇 1 絕緣性評價 < < < < CQ OQ m < < < < C < U Q U Q 電漿蝕刻處理的有無 0 〇 Ο 〇 ο Ο 〇〇〇〇〇〇 Ο 〇〇 1 〇 1 酸處理的有無〇 Ο 〇 ο ο 0 ο 〇〇〇〇〇 0 o ο 1 1 0 蝕刻液的種類 < < < < < PQ < < < < < < < < < < < < 鍍敷觸媒吸附條件 < < < < CQ < < < < < < < < < < < < < 密著辅助層的有無〇 Ο 〇〇 ο 〇 1 〇〇〇〇〇〇〇 ο 〇〇〇聚合物的種類聚合物1 聚合物2 聚合物3 聚合物4 聚合物1 聚合物1 聚合物1 聚合物5 聚合物6 聚合物7 聚合物8 聚合物9 聚合物10 聚合物11 比較聚合物2 比較聚合物1 聚合物1 聚合物1 實例1 實例2 實例3 實例4 1實例5 1實例6 卜實例8 |實例9 |實例10 實例11 |實例12 L實例π J 實例14 比較例1 |比較例2 比較例3 寸 £ 201238750 上述表1中，「鐘敷觸媒吸附條件」欄的「A」是指（鍍敷觸媒的賦予）中使用的硝酸鈀〇·ΐ質量％水溶液的液溫為25°C的情況，「b」是指硝酸鈀0,1質量％水溶液的液溫為60°C的情況。「蝕刻液的種類」攔的「A」是指（圖案形成步驟）中使用的蝕刻液為FeCl2/HCl水溶液的情況，「B」是指蝕刻液為Cu(NH3)4C12水溶液的情況。另外，表1中，「-」是指未實施。如實例1〜實例14所示，實施本發明的具有圖案化金屬膜的積層體的製造方法而獲得的配線基板表現出優異的絕緣性能。進而，實例1〜實例14中，被鍍敷層的電漿蝕刻速率亦優異。此外，根據實例1與實例5的比較，被鍍敷層中的鈀離子的吸附量少的實例1的絕緣性更優異。其原因在於：被鍍敷層中的金屬成分量少者在被鍍敷層的蝕刻性方面優異。另外’根據實例1與實例6的比較，確認使用酸性蝕刻液（FeCVHCl水溶液）作為钮刻液者的絕緣性更優異。其原因在於：若使用該蝕刻液，則容易去除被鍍敷層中的金屬成分。另外，根據實例1〜實例4的比較，使用更疏水且耐鹼水解性高的單元作為式（C)所表示的單元者的被鍍敷層的損傷減少，密著力更強。另一方面，使用具有CN基的聚合物的比較例j中， 72 201238750 未有效率地進行被鍍敷層的去除，結果配線間的絕緣性能差。另外’使用聚合性基單元不是規定官能基的聚合物，且不進行酸性溶液處理以及電漿蝕刻處理的比較例2中， f未有效率地進行被鍍敷層的去除，結果配線間的絕緣性能差。、、進而，如比較例3及比較例4所示，在不進行酸性溶液處理或者電漿蝕刻處理的情況下，配線間的絕緣性能差。比較例1〜比較例4中效果差的原因被認為是由於被鍍敷層中所含的金屬成分。 (耐濕性評價）將實例1及比較例2的（電解鍍敷）步驟後獲得的具金屬膜的基袄（積層體）在8(TC、90RH%下放置一週後，依據HS-K5600-5-6 : 1999進行網格剝離試驗。依據以下的基準進行評價。「A」：1〇〇目中殘存95目以上的情況。「B」：1〇〇目中殘存小於95目的情況。「實例1中上述耐濕性評價為「a」，但比較例2中為 B」〇 :為其原因在於：本發明的製造方法中，由於式（A) :表示的單元具有(甲基)丙烯醯胺基，故而難以水解，結果金屬臈的密著性進一步提高。【圖式簡單說明】圖1 (A)〜圖1 (E)分別是依次表示本發明的具有 73 201238750 圖案化金屬膜的積層體的製造方法中的各製造步驟的示意性剖面圖。圖2 (A)〜圖2 (C)是表示圖案形成步驟的一較佳態樣的各步驟圖。圖3 (A)〜圖3 (E)是表示圖案形成步驟的其他較佳態樣的各步驟圖。【主要元件符號說明】 10 :基板 12 :被鍍敷層 14、14a、14b :金屬膜 16 :圖案化金屬膜 18 :積層體 18 :圖案化金屬膜 20 :遮罩 22 :凸部 24 :凹部 30 :未形成圖案化金屬膜的區域 40 :絕緣層 50 :配線基板 74The thickness of the copper plating layer (metal film) after electrolytic deposition is about 18 μm. (electrolytic plating bath components) • Copper sulfate 38 g • Sulfuric acid 95 g. Hydrochloric acid 1 mL • Copper Gleam PCM (Meltex) 3.5 mL 5 63 201238750 500 g. Water (pattern forming step) After electrolytic plating The substrate is at 17 〇. (: After a heat treatment for a few hours, a dry resist film (RY3315 manufactured by Hitachi Chemical Co., Ltd., film thickness: 30 μm) was laminated on the surface of the substrate. Then, a subtractive method was used to form Ι^ = 40 μm a glass mask of a comb pattern of /40 μm is adhered to a substrate on which a dry resist film is laminated, and the photosensitive region of the resist is exposed. After the exposure, the solution is applied at a spray pressure of 2 kg/m 2 . Then, the substrate is washed with water and dried to form a resist pattern on the copper plating layer, and the substrate on which the resist pattern is formed is sprayed with an aqueous solution of FeCl 2 /Hcl (temperature) (pH: 1.5) for 90 seconds. Thereby, the etching of the metal film is performed, and the ruthenium which is present in the non-formation region is removed. Then, the Ν_4 mass% aqueous solution is formed on the substrate by the injection pressure at 2 kg/m2, and the anti-caries agent is peeled off. (acid solution treatment) = 'The metal component in the coating layer was immersed in a Wei aqueous solution (positive value: Q 5) for 1 minute. The ICP luminescence analyzer (manufactured by Friend's Works) was used to measure the tilting at this time. In the layer of the _ sub-sucking in the ',,, mouth It is below the detection limit (3mg/m2 or less). (Removed by the plating layer), the substrate with the patterned metal film (wiring pattern) is placed on the wiring so that the wiring is opposite to the surface. * Money engraving] ) SAMC〇 manufacture, parallel flat type electric mass processing device, PC-100 (64 201238750 chamber. Decompress the chamber to jxli^PaOxlO-3!:^), 1.5 in oxygen environment Minute plasma treatment. The surface of the substrate after the treatment was observed by a scanning electron microscope (SEM) image, and it was confirmed that the plating layer and the adhesion assisting layer between the wirings were removed. Attachment) For the plasma-treated substrate, a solder resist (PFR800, manufactured by Sun Ink Manufacturing Co., Ltd.) was vacuum-laminated at 1 UTC and 0.2 MPa, and 420 mJ of light energy was irradiated by an exposure machine with a center wavelength of 365 nm. After the substrate was subjected to a heat treatment at 80 ° C / l 〇 minutes, a NaHC 〇 3 : 10% aqueous solution was applied to the surface of the substrate at a spray pressure of 2 kg / m 2 to develop and dry. Then, the center wavelength of 365 nm was reused. of The light machine irradiates the substrate with light energy of 1000 mJ. Finally, 15 Å (: / 1 hr of heat treatment is performed to obtain a wiring substrate covered with a solder resist. <Example 2> Except that polymer 2 is used instead of polymer 1, The wiring substrate was obtained in the same order as in Example 1. <Example 3> A wiring substrate was obtained in the same order as in Example 1 except that Polymer 3 was used instead of Polymer 1. <Example 4> Polymerization was used instead of Polymer 1. The wiring substrate was obtained in the same order as in Example 1 except for the object 4. <Example 5> 65 201238750 (Improvement of plating catalyst) The order of the substrate was obtained in the same order as in Example 1 except for the order described below in the above Examples. (Improvement of mineralizing catalyst) An aqueous solution of G.1 mass% (liquid temperature: 60 〇) 2 and / 7 knives were then washed with steamed water. The amount of adsorption of the ion to the plated layer at this time was measured by the ICP release (manufactured by Shimadzu Corporation) and found to be 02 g/m2. <Example 6> A wiring substrate was obtained in the same order as in the example except that the metal film etching treatment using the FeCl2/HCl 7jc/liquid solution in the pattern forming step in the above Example 1 was changed to the order described below. (Pattern forming step) A CU (NH3) 4C12 aqueous solution was sprayed on the substrate on which the resist pattern was formed (temperature 37. (:) (pH: 8.5) for 90 seconds, thereby performing the name of the metal film" The copper plating removed in the non-formation region of the etchant pattern. <Example 7> Except that the step (formation of the adhesion assisting layer) in the above Example 1 was not carried out, the fabrication was performed in (the fabrication of the base insulating substrate). The substrate of the electrical insulating layer was formed (formation of the layer to be plated), and the wiring substrate was obtained in the same order as in Example 1 except that the layer to be plated was formed on the electrically insulating layer. In Example 7, the adhesion assisting layer was not passed. The plating layer is disposed on the substrate. 66 2012383⁄4 <Example 8> In addition to the polymer 5 instead of the polymer 1, the ultraviolet light having a wavelength of 254 nm (formed by the formation of the bell layer) is subjected to room temperature. A wiring substrate was obtained in the same order as in Example 1 except for a full exposure of 3 minutes (amount of energy at 254 nm: 1800 mJ). <Example 9> A polymer 6' was used instead of the polymer 1 In the formation of The wiring substrate was obtained in the same order as in Example 1 except that the ultraviolet light having a wavelength of 254 nm was subjected to full exposure for 4 minutes at room temperature (amount of energy at 254 nm: 2400 mJ). ~ <Example 10> In addition to the replacement of the polymer 1 Using Polymer 7, the ultraviolet light having a wavelength of 254 nm (formed by the formation of the money layer) was subjected to full exposure at room temperature for 4 minutes (amount of energy at 254 nm: 2400 mJ), and Example 1 was used. The wiring substrate was obtained in the same order. ^ <Example 11> In addition to the polymer 1 , the ultraviolet light having a wavelength of 254 nm (formed by the formation of the money layer) was used for 4 minutes at room temperature in place of the polymer 1 ( The wiring substrate was obtained in the same order as in Example 1 except that the amount of energy at 254 nm: 2400 mJ). ~ <Example 12> In addition to the polymer ruthenium, the composition of the composition 9 1 (formation of the layer to be plated) was Ultraviolet light with a wavelength of 254 nm is exposed to octagonal surface exposure at room temperature (amount of energy at 254 nm: 6000 mJ), and will be applied to the amount of sodium bicarbonate in the composition. Changed from G 8 g to (10), according to the same as Example 1. The order of the wiring board was obtained. <Example 13> / In addition to the polymer 1 代替 instead of the polymer 1, the ultraviolet light having a wavelength of 254 nm (formed by the formation of the plating layer) was subjected to full exposure at room temperature for 1 minute. (amount of energy at 254 nm: 6 〇〇〇mJ), and the amount of sodium hydrogencarbonate in the composition for forming a plating layer was changed from 〇8 g to 〇38 碌, according to the same as Example 1. The wiring substrate was sequentially obtained. <Example 14> In addition to the polymer 11 instead of the polymer 1, ultraviolet light having a wavelength of 254 nm (formed by the formation of a plating layer) was subjected to full exposure for 1 minute at room temperature (254 nm). The wiring board was obtained in the same order as in Example 1 except that the amount of the energy of the underlying layer was changed to 〇6 g from 0.8 g to the amount of sodium bicarbonate in the composition for forming a plating layer. <Comparative Example 1> A wiring board was obtained in the same order as the angle_example 1, except that the comparative polymer 2 was used instead of the polymer 1. <Comparative Example 2> The following (the composition for forming a layer 2 to be plated) was used instead of (the composition for forming a layer to be plated), and the (acid solution treatment) and (removal by the plating layer) were not performed. The wiring substrate was manufactured in the same order as in Example 1 except for the steps. The cross-section of the surface of the substrate after the plating layer was removed by the SEM image confirmed that the deposited layer between the wirings remained. 68 201238750 (Composition 2 for plating layer formation) • Comparative polymer 1 0.25 g. Water 5 g • Acetonitrile 3 g <Comparative Example 3> The same as Example 1 except that the (acid solution treatment) in Example 1 was not carried out. The wiring substrate is sequentially manufactured. <Comparative Example 4> A wiring substrate was obtained in the same order as in Example 1 except that the step (removed by the plating layer) in the above Example 1 was not carried out. <Evaluation method> (Insulation evaluation) The insulation reliability test of the wiring board obtained above was carried out using an electrochemical migration evaluation apparatus (manufactured by Espec, Inc., electrochemical migration apparatus AMI, and high temperature and high humidity tank Platinous PR_3K). get on. The test conditions were = pressure 30 v, and the temperature and humidity environment was 85. 〇, 85% RH, and humidified water was evaluated by using distilled water having a resistance of 13 M for 1 hour. The evaluation was based on the following criteria. The results are shown in Table 1. & D": In the evaluation of less than 500 hours, the value of the wiring board was less than 1 ΜΩ. "C": In the evaluation up to 500 hours or more and less than 750 hours, the resistance value of the wiring board was less than 1 Μ Ω. "B": In the evaluation up to 750 hours or more and less than 1 hour, the resistance value of the wiring board is less than 1 Μ Ω. 69 201238750 .^rw "A": Evaluation is performed until the hour of looo, and the resistance value of the wiring board is not less than 1 ΜΩ. (plasma surname rate) The surnames of the remaining plasma in the case of removing the plated layer and the adhesion assisting layer in the examples 1 to 14 and the comparative example 1 and the comparative example 3 (removed by the plating layer) The engraving rate (μπι/min) is summarized in Table j. (Adhesion evaluation) = The substrate (layered body) which is obtained after the electrolytic plating obtained in Example 丨 to Example 4, which is a film (layered body), is baked at 3 () minutes in Qing CT. After the bake-out treatment, the automatic filming apparatus AGS·) (manufactured by Shimadzu Corporation) was used for the tensile strength of 10 mm/min for 9 〇. The results of the 4 wide gold are summarized in Table i. Determination of peel strength of Ding 90. 201238750 J-asoo inch ±1 Adhesion evaluation (kN/m) ν〇dd 00 ο 00 ο II 1 1 1 1 1 1 1 1 1 I 1 1 啭ε yr) κη cn ΓΛ rn in νΊ Ο Ο 1 〇 1 Insulation evaluation <<<<<<<<<<<<<<<<<<<<<<<<> UQUQ Plasma etching treatment with or without 0 〇Ο 〇ο Ο 〇〇〇〇〇〇Ο 〇〇1 〇1 Acid-treated 有ο ο 0 ο 〇〇〇〇〇0 o ο 1 1 0 Type of etching liquid <<<<<< PQ <<<<<<<<<<<<<<<<<<<<<<<<<<<;<<<<<<< Auxiliary layer with or without 〇Ο 〇〇1 〇〇〇〇〇〇〇ο 〇〇〇 Polymer type Polymer 1 Polymer 2 Polymer 3 Polymer 4 Polymer 1 Polymer 1 Polymer 1 Polymer 5 Polymer 6 Polymer 7 Polymer 8 Polymer 9 Polymer 10 Polymer 11 Comparative Polymer 2 Comparative Polymer 1 Polymer 1 Polymer 1 Example 1 Example 2 Example 3 Example 4 1 Example 5 1 Example 6 Example 8 Example 9 | Example 10 Example 11 | Example 12 L example π J Example 14 Comparative Example 1 | Comparative Example 2 Comparative Example 3 Inch £ 201238750 In the above Table 1, the "A" in the "Calibral Catalyst Adsorption Condition" column means ( In the case where the liquid temperature of the palladium nitrate ruthenium ΐ mass % aqueous solution used for the plating catalyst is 25 ° C, "b" means that the liquid temperature of the palladium nitrate 0, 1 mass % aqueous solution is 60 ° C. . "A" in the "type of etching liquid" means that the etching liquid used in the pattern forming step is FeCl2/HCl aqueous solution, and "B" means that the etching liquid is a Cu(NH3)4C12 aqueous solution. In addition, in Table 1, "-" means that it is not implemented. As shown in Examples 1 to 14, the wiring substrate obtained by the method for producing a laminate having a patterned metal film of the present invention exhibits excellent insulating properties. Further, in Examples 1 to 14, the plasma etching rate of the plated layer was also excellent. Further, according to the comparison between Example 1 and Example 5, the insulating property of Example 1 in which the amount of adsorption of palladium ions in the plating layer was small was more excellent. The reason for this is that the amount of the metal component in the layer to be plated is small in terms of the etching property of the layer to be plated. Further, according to the comparison between Example 1 and Example 6, it was confirmed that the use of the acidic etching solution (FeCVHCl aqueous solution) as the button engraving was more excellent in insulation. This is because if the etching liquid is used, the metal component in the layer to be plated can be easily removed. Further, according to the comparison of Examples 1 to 4, the use of a unit which is more hydrophobic and has high alkali hydrolysis resistance as a unit of the formula (C) is less damaged, and the adhesion is stronger. On the other hand, in Comparative Example j using a polymer having a CN group, 72 201238750 was not efficiently removed from the plating layer, and as a result, insulation properties between wirings were inferior. Further, in Comparative Example 2 in which the polymerizable group unit was not a polymer having a predetermined functional group and was not subjected to an acidic solution treatment or a plasma etching treatment, f was not efficiently removed by the plating layer, and as a result, insulation between wirings was obtained. Poor performance. Further, as shown in Comparative Example 3 and Comparative Example 4, the insulating property between the wirings was inferior when the acidic solution treatment or the plasma etching treatment was not performed. The reason why the effect was poor in Comparative Example 1 to Comparative Example 4 was considered to be due to the metal component contained in the plating layer. (Evaluation of Moisture Resistance) The base film (layered body) having a metal film obtained after the (electrolytic plating) step of Example 1 and Comparative Example 2 was placed at 8 (TC, 90 RH% for one week, according to HS-K5600- 5-6 : The grid peeling test was carried out in 1999. The evaluation was carried out according to the following criteria. "A": The case where there are more than 95 mesh in the case of 1 item. "B": The case where 1 item remains less than 95. In the first example, the moisture resistance was evaluated as "a", but in the comparative example 2, it was B": because the unit represented by the formula (A): (meth) propylene was contained in the production method of the present invention. The amidoxime group is difficult to hydrolyze, and as a result, the adhesion of the metal ruthenium is further improved. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (A) to Fig. 1 (E) show, in order, the patterned metal film of the present invention having 73 201238750, respectively. Fig. 2(A) to Fig. 2(C) are diagrams showing the steps of a preferred embodiment of the pattern forming step. Fig. 3(A) to Fig. 3 is a schematic cross-sectional view showing a manufacturing process of the laminated body. 3 (E) is a step diagram showing other preferred aspects of the pattern forming step. [Description of main component symbols] 10 : substrate 12 : plated layer 14 , 14 a , 14 b : metal film 16 : patterned metal film 18 : laminated body 18 : patterned metal film 20 : mask 22 : convex portion 24 : concave portion 30 : no patterning Region 40 of metal film: insulating layer 50: wiring substrate 74

Claims

201238750 七、申請專利範圍： 1. 一種具有圖案化金屬膜的積層體的製造方法，包括：被鍍敷層形成步驟，使被鍍敷層形成用組成物接觸於基板上後，對上述基板上的上述被鑛敷層形成用組成物賦予能量’在上述基板上形成被鍍敷層，其中上述被鍍敷層形成用組成物包含具有式（A)所表示的單元、式（b)所表示的單元以及式（C)所表示的單元的聚合物；觸媒賦予步驟，對上述被鍍敷層賦予鍍敷觸媒或者复前驅體； ~ 〃鍍敷步驟，對被賦予上述鍍敷觸媒或者其前驅體鍍敷層進行鍍敷處理，在上述被鍍敷層上形成金屬膜；、圖案形成步驟’在上述鎌步驟後，使用包含金分或過氧化氫的蝕刻液來形成圖案化金屬膜；驟，使上述具有圖案化金屬膜的基 8成分或過氧化氫的酸性溶液接觸；酸性溶液接觸步板、與實質上不含金；以及上述域==層處理來去除未形成式（A) 式（B) 式（C) 201238750 |^一: A)〜式（C)中，R1、R2、R4及R6分別獨立 L:不i原子或者甲基；r3表示氫原子、甲基、乙基、 *一Ir、或者正τ基；W分別獨立地表示單鍵、醋土、酉=基、或者伸苯基；L1表示二價烴基；L2表示單鍵、或者-h有機基；x絲贿基、雜基、猶基、或者它=的鹽；Z表示视7基、或者卿8)2基；r7表示烧基、 ¥基 ' 或者將它們組合而成的基團；此外，r7中可包含〇· (氧原子），R ”別獨立地表示氫原子、或者可包含办的炫基；此外，R8可相互鍵結而形成環）。 2·如申印專職圍第1項所述之具有圖案化金屬膜的積層體的製造方法’其巾上述_液為酸性。 3.如申請專利範圍第j 金屬膜的積層體的製造方法或者鐵離子。項或第2項所述之具有圖案化，其中上述金屬成分為銅離子 4·如申請專利範圍第丨項至第3項中任—項所述之且有圖案化金屬膜的積層體的製造方法，其中上述酸性溶液為鹽酸水溶液、硫酸水溶液、或者硝酸水溶液。 5· 一種配線基板，包括：利用如申請專利範圍第1項至第4項中任-項所述之製造方法來製造的具有圖案化金屬膜的積層體、及設置於上述具有圖案化金屬膜的積層體卜的級縫廢。 6. —種被鍍敷層形成用組成物，包含具有式（a)所表示的單元、A⑻所表示的單元以及式（c)所表單元的聚合物： 76 201238750 式（A) 式（B) 式（C)201238750 VII. Patent Application Range: 1. A method for manufacturing a laminate having a patterned metal film, comprising: a step of forming a layer to be plated, contacting the substrate forming composition with the substrate, and then applying the composition to the substrate The above-mentioned composition for forming a layer to be plated includes a unit represented by the formula (A) and a layer represented by the formula (b). a cell and a polymer of the cell represented by the formula (C); a catalyst application step of applying a plating catalyst or a complex precursor to the plated layer; ~ 〃 a plating step to which the plating catalyst is applied Or the precursor plating layer is plated to form a metal film on the plated layer; and the pattern forming step 'after the above-described enthalpy step, an etching solution containing gold or hydrogen peroxide is used to form the patterned metal a membrane; contacting the acidic solution of the base 8 component or the hydrogen peroxide having the patterned metal film; the acidic solution contacts the step plate, and substantially does not contain gold; and the domain == layer To remove the unformed formula (A) Formula (B) Formula (C) 201238750 | ^ a: A) ~ In formula (C), R1, R2, R4 and R6 are independent of L: not i atom or methyl; r3 Represents a hydrogen atom, a methyl group, an ethyl group, an *Ir group, or a positive τ group; W independently represents a single bond, a vinegar, a ruthenium group, or a phenyl group; L1 represents a divalent hydrocarbon group; and L2 represents a single bond, Or -h organic group; x brix, hetero group, heptyl, or a salt of it; Z represents a 7 group, or a 8) 2 group; r7 represents a burnt group, a base group or a combination thereof Further, r7 may contain 〇· (oxygen atom), and R ′ independently represents a hydrogen atom, or may contain a leuco group; in addition, R8 may be bonded to each other to form a ring). The method for producing a laminate having a patterned metal film according to the first aspect of the present invention is characterized in that the liquid is acidic. 3. The method for producing a laminate of the jth metal film or the iron ion according to the patent application. Or the patterning according to item 2, wherein the metal component is copper ion 4, as in any of the claims 1-3 to 3 A method for producing a laminate of a patterned metal film, wherein the acidic solution is an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, or an aqueous solution of nitric acid. 5. A wiring substrate comprising: using the first to fourth items of the patent application scope The layered body having the patterned metal film produced by the production method according to any one of the items, and the stepped layer provided on the layered body having the patterned metal film are scrapped. 6. A composition for forming a layer to be plated a polymer comprising a unit represented by the formula (a), a unit represented by A(8), and a unit represented by the formula (c): 76 201238750 Formula (A) Formula (B) Formula (C)

〇 (式（A)〜式（C)中，R1、R2、R4及R6分別獨立地表示氫原子、或者曱基；R3表示氫原子、曱基、乙基、第三丁基、或者正丁基；V及W分別獨立地表示單鍵、酯基、醯胺基、或者伸苯基；L1表示二價烴基；L2表示單鍵、或者二價有機基；X表示羧酸基、磺酸基、磷酸基、或者它們的鹽；Z表示-OR7基、或者-N(R8)2基；R7表示烷基、苯基、或者將它們組合而成的基團；此外，R7中可包含-〇-(氧原子）；R8分別獨立地表示氫原子、或者可包含-0-的烷基；此外，R8可相互鍵結而形成環）。 7.如申請專利範圍第6項所述之被鍍敷層形成用組成物，其中上述式（A)所表示的單元為式（A-1)所表示的單元： 77 2012387501 式（A-l ) R1In the formula (A) to the formula (C), R1, R2, R4 and R6 each independently represent a hydrogen atom or a mercapto group; and R3 represents a hydrogen atom, a mercapto group, an ethyl group, a third butyl group or a n-butyl group; And V and W each independently represent a single bond, an ester group, a decyl group, or a phenyl group; L1 represents a divalent hydrocarbon group; L2 represents a single bond or a divalent organic group; and X represents a carboxylic acid group or a sulfonic acid group. , a phosphate group, or a salt thereof; Z represents a -OR7 group, or a -N(R8)2 group; R7 represents an alkyl group, a phenyl group, or a group in which they are combined; in addition, R7 may contain -〇 - (oxygen atom); R8 each independently represents a hydrogen atom, or may contain an alkyl group of -0-; in addition, R8 may be bonded to each other to form a ring). 7. The composition for forming a layer to be plated according to claim 6, wherein the unit represented by the above formula (A) is a unit represented by the formula (A-1): 77 2012387501 Formula (A-l) R1

Ο 〈A·1)中，R1及R2分別獨立地表示氫 s基二表Ar:者-nrw 甲基乙基第二丁基、或者正了基；L1表示二價煙 8·如Τ π專利範圍第7項所述之被 : 物，其中L1為可經選自由甲基 ^成用組J 的基團所取代的碳數1〜6的二價/鏈狀“組成組群, 9.如申請專利範圍第6項至第 =成用組成物，其中上述式（間所表糾單元、或者式（Β·2)所表*的單元；式（Β·】）式（Β-2) j^L·〈 <A·1), R1 and R2 each independently represent a hydrogen s group, a second table Ar: a -nrw methylethyl second butyl group, or a normal group; L1 represents a divalent smoke 8 such as Τ π patent The above-mentioned item of the above-mentioned item, wherein L1 is a divalent/chain-like "composition group" having a carbon number of 1 to 6 which is substituted with a group selected from the group consisting of methyl group and group J, 9. Patent application No. 6 to the composition of the invention, wherein the above formula (the unit of the table correction unit or the unit of the formula (Β·2)*; the formula (Β·)) (Β-2) j ^L·

X (式⑻）及式（B-2)中，r4分別獨立地表示氣原 78 201238750 子、或者曱基；Y表示氧原子、或者-NR5-基；R5表示氫原子、曱基、乙基、第三丁基、或者正丁基；L2表示可經選自由曱基、乙基及丙基所組成組群中的基團所取代的碳數1〜6的二價直鏈狀烴基、環氧乙烷基、環氧丙烷基，或者具有酯基的碳數2〜8的二價烴基；X表示羧酸基、磺酸基、磷酸基、或者它們的鹽）。 79In X (formula (8)) and formula (B-2), r4 independently represents a gas atom 78 201238750 or a fluorenyl group; Y represents an oxygen atom or an -NR5- group; and R5 represents a hydrogen atom, a thiol group, or an ethyl group. a tributyl or n-butyl group; L2 represents a divalent linear hydrocarbon group having a carbon number of 1 to 6 and a ring which may be substituted with a group selected from the group consisting of a mercapto group, an ethyl group and a propyl group; An oxyethane group, an oxypropylene group, or a divalent hydrocarbon group having 2 to 8 carbon atoms having an ester group; X represents a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a salt thereof). 79