TWI548513B - Laminate and method for manufacturing the same, printed wiring board, and composition for forming underlayer - Google Patents

Description

積層體及其製造方法、印刷配線基板、以及底層形成用組成物 Laminated body, manufacturing method thereof, printed wiring substrate, and composition for forming underlayer

本發明是有關於一種具有金屬層的積層體及其製造方法、以及該方法所使用的底層形成用組成物。 The present invention relates to a laminate having a metal layer, a method for producing the same, and a composition for forming a primer layer used in the method.

先前以來，在絕緣性基板的表面形成金屬圖案的配線的金屬配線基板，廣泛用於電子零件或半導體元件。 A metal wiring board in which a wiring of a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic parts or semiconductor elements.

該金屬配線基板的製造方法主要使用「減成法(subtractive process)」。該減成法是如下的方法：在形成於基板表面的金屬層上，設置藉由活性光線的照射而感光的感光層，將該感光層成像曝光，然後進行顯影而形成光阻圖像(resist image)，接著將金屬層蝕刻而形成金屬圖案，最後將光阻圖像剝離。另外，作為下一代的金屬配線基板的製造方法，主要使用「半加成法(semi-additive process)」。該半加成法是如下的方法：在形成於基板表面的無電鍍敷金屬層上，設置藉由活性光線的照射而感光的感光層，將該感光層成像曝光，然後進行顯影形成光阻圖像，在 未形成光阻圖像的區域形成電鍍而成的金屬層，接著，將光阻圖像剝離後，將無電鍍敷金屬層的膜厚部分蝕刻而形成金屬圖案。 The method of manufacturing the metal wiring board mainly uses a "subtractive process". The subtractive method is a method in which a photosensitive layer which is photosensitive by irradiation of active light is provided on a metal layer formed on a surface of a substrate, and the photosensitive layer is imagewise exposed, and then developed to form a resist image (resist Image), the metal layer is then etched to form a metal pattern, and finally the photoresist image is peeled off. Further, as a method of manufacturing a metal wiring board of the next generation, a "semi-additive process" is mainly used. The semi-additive method is a method in which a photosensitive layer which is photosensitive by irradiation of active light is disposed on an electroless plating metal layer formed on a surface of a substrate, and the photosensitive layer is imagewise exposed, and then developed to form a photoresist pattern. feels like A region where the resist image is not formed forms a plated metal layer. Then, after the photoresist image is peeled off, the film thickness portion of the electroless plated metal layer is etched to form a metal pattern.

在藉由這些方法而得的金屬圖案中，由於藉由在基板表面設置凹凸而產生的錨定效果(anchor effect)，而表現出基板與金屬層之間的密接性。因此，由於所得的金屬圖案的基板界面部的凹凸，而有用作金屬配線時的高頻特性變差的問題。另外為了對基板表面進行凹凸化處理，而需要藉由鉻酸等強酸對基板表面進行處理，因此亦有為了獲得金屬層與基板的密接性優異的金屬圖案，而需要繁雜的步驟的問題。 In the metal pattern obtained by these methods, the adhesion between the substrate and the metal layer is exhibited by an anchor effect which is formed by providing irregularities on the surface of the substrate. Therefore, there is a problem that the high-frequency characteristics when used as a metal wiring are deteriorated due to the unevenness of the substrate interface portion of the obtained metal pattern. Further, in order to perform the roughening treatment on the surface of the substrate, it is necessary to treat the surface of the substrate with a strong acid such as chromic acid. Therefore, in order to obtain a metal pattern having excellent adhesion between the metal layer and the substrate, a complicated step is required.

作為解決該問題的方法，專利文獻1中提出在絕緣性基板的表面塗佈包含丙烯腈丁二烯橡膠(acrylonitrile butadiene rubber，NBR)的無電鍍敷用底層黏接劑的方法。 As a method for solving this problem, Patent Document 1 proposes a method of applying an electroless plating underlayer adhesive containing acrylonitrile butadiene rubber (NBR) to the surface of an insulating substrate.

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開昭62-250086號公報 [Patent Document 1] Japanese Patent Laid-Open No. 62-250086

另一方面，近年來，為了應對電子設備的小型化、高功能化的要求，而在印刷配線板等中進行配線的進一步微細化及高積體化。隨之要求基板與金屬層的密接性的進一步提高。 On the other hand, in recent years, in order to cope with the demand for miniaturization and high functionality of electronic equipment, wiring has been further miniaturized and integrated in a printed wiring board or the like. Further, the adhesion between the substrate and the metal layer is required to be further improved.

此外，將金屬層製成微細配線時，維持其表面的淨化性成為重要的課題。特別是若在金屬層表面存在包含構成金屬層的金屬離子以外的其他成分的異物等，則在將該金屬層圖案化而形成微細配線時，產生配線的尺寸精度降低、隨之導致印刷配線板 自身的性能降低的問題。 Further, when the metal layer is made into a fine wiring, it is an important subject to maintain the cleanability of the surface. In particular, when a foreign material or the like containing a component other than the metal ion constituting the metal layer exists on the surface of the metal layer, when the metal layer is patterned to form fine wiring, the dimensional accuracy of the wiring is lowered, and the printed wiring board is caused. The problem of its own performance degradation.

本發明者等人參照專利文獻1所揭示的發明，使用包含NBR的無電鍍敷用底層黏接劑製造具有金屬層的積層體。 The inventors of the present invention have made a laminate having a metal layer by using an undercoating agent for electroless plating containing NBR, with reference to the invention disclosed in Patent Document 1.

然而可知，所得的金屬層的密接性及表面的淨化性無法滿足近來所要求的水準。 However, it is understood that the adhesion of the obtained metal layer and the cleanability of the surface cannot satisfy the level required recently.

本發明鑒於上述實際情況而成，目的是提供一種金屬層的密接性優異、金屬層表面的淨化性亦優異的積層體及其製造方法。 The present invention has been made in view of the above circumstances, and an object of the invention is to provide a laminate having excellent adhesion of a metal layer and excellent surface cleanability of a metal layer, and a method for producing the same.

另外，本發明的目的亦是提供一種該積層體的製造方法中所使用的底層形成用組成物。 Further, another object of the present invention is to provide a composition for forming a primer layer used in the method for producing a laminate.

本發明者等人對上述課題進行銳意研究，結果發現，藉由使用特定粒徑的金屬氧化物粒子形成底層，並且使用鹼性鍍敷觸媒液，而可達成上述目的。 The inventors of the present invention conducted intensive studies on the above problems and found that the above object can be attained by forming a primer layer using metal oxide particles having a specific particle diameter and using an alkaline plating catalyst liquid.

即發現，藉由以下所示的方法可達成上述目的。 That is, it was found that the above object can be attained by the method shown below.

(1)一種積層體的製造方法，其包括：底層形成步驟，形成包含具有可氫化的共軛二烯化合物單元的聚合物、以及平均粒徑為400 nm以下的金屬氧化物粒子的底層；觸媒提供步驟，使包含鍍敷觸媒或其前驅物且為鹼性的鍍敷觸媒液、與上述底層接觸，而在上述底層上提供鍍敷觸媒或其前驅物；以及 鍍敷步驟，對提供了上述鍍敷觸媒或其前驅物的上述底層進行鍍敷，而在上述底層上形成金屬層。 (1) A method for producing a laminate comprising: a primer layer forming step of forming a polymer comprising a polymer having a hydrogenated conjugated diene compound unit and a metal oxide particle having an average particle diameter of 400 nm or less; Providing a step of contacting a plating catalyst liquid comprising a plating catalyst or a precursor thereof and being alkaline, in contact with the underlayer, to provide a plating catalyst or a precursor thereof on the underlayer; In the plating step, the underlayer provided with the plating catalyst or the precursor thereof is plated to form a metal layer on the underlayer.

(2)如上述(1)所述的積層體的製造方法，其中上述金屬氧化物粒子的平均粒徑為100 nm以下。 (2) The method for producing a layered product according to the above aspect, wherein the metal oxide particles have an average particle diameter of 100 nm or less.

(3)如上述(1)或(2)所述的積層體的製造方法，其中上述底層中的上述金屬氧化物粒子的含量，相對於上述聚合物與上述金屬氧化物粒子的合計質量為25質量%~45質量%。 (3) The method for producing a layered product according to the above aspect, wherein the content of the metal oxide particles in the underlayer is 25 or less based on the total mass of the polymer and the metal oxide particles. Mass%~45% by mass.

(4)如上述(1)至(3)中任一項所述的積層體的製造方法，其中上述聚合物是進一步具有含有相互作用性基的單元的聚合物。 (4) The method for producing a layered product according to any one of the above aspects, wherein the polymer is a polymer further having a unit containing an interactive group.

(5)如上述(1)至(4)中任一項所述的積層體的製造方法，其中上述聚合物是丙烯腈與丁二烯的共聚物或其氫化產物(hydrogenated product)，上述金屬氧化物粒子為氧化矽粒子(silica particle)。 (5) The method for producing a laminate according to any one of the above aspects, wherein the polymer is a copolymer of acrylonitrile and butadiene or a hydrogenated product thereof, the metal The oxide particles are silica particles.

(6)如上述(1)至(5)中任一項所述的積層體的製造方法，其中進一步包括：將上述金屬層蝕刻為圖案狀的步驟。 The method for producing a layered product according to any one of the above aspects, further comprising the step of etching the metal layer into a pattern.

(7)一種印刷配線基板，其具有藉由如上述(1)至(6)中任一項所述的製造方法而製造的積層體。 (7) A printed wiring board having a laminate produced by the production method according to any one of the above (1) to (6).

(8)一種底層形成用組成物，其包含具有可氫化的共軛二烯化合物單元的聚合物、以及平均粒徑為400 nm以下的金屬氧化物粒子，且藉由上述底層形成用組成物而形成的底層用於與包含 鍍敷觸媒或其前驅物且為鹼性的鍍敷觸媒液接觸。 (8) A composition for forming an underlayer comprising a polymer having a hydrogenatable conjugated diene compound unit and metal oxide particles having an average particle diameter of 400 nm or less, and comprising the composition for forming an underlayer The bottom layer formed is used to contain The plating catalyst or its precursor is contacted with an alkaline plating catalyst solution.

(9)如上述(8)所述的底層形成用組成物，其中上述金屬氧化物粒子的平均粒徑為100 nm以下。 (9) The composition for forming an underlayer according to the above (8), wherein the metal oxide particles have an average particle diameter of 100 nm or less.

(10)如上述(8)或(9)所述的底層形成用組成物，其中上述金屬氧化物粒子的含量，相對於上述聚合物與上述金屬氧化物粒子的合計質量為25質量%~45質量%。 (10) The composition for forming an underlayer according to the above (8), wherein the content of the metal oxide particles is 25% by mass to 45 based on the total mass of the polymer and the metal oxide particles. quality%.

(11)如上述(8)至(10)中任一項所述的底層形成用組成物，其中上述聚合物是進一步具有含有相互作用性基的單元的聚合物。 The composition for forming an underlayer according to any one of the above aspects, wherein the polymer is a polymer further having a unit containing an interactive group.

(12)如上述(8)至(11)中任一項所述的底層形成用組成物，其中上述聚合物是丙烯腈與丁二烯的共聚物或其氫化產物，上述金屬氧化物粒子為氧化矽粒子。 The composition for forming an underlayer according to any one of the above-mentioned (8), wherein the polymer is a copolymer of acrylonitrile and butadiene or a hydrogenated product thereof, and the metal oxide particles are Antimony oxide particles.

(13)一種積層體，其具有底層、以及與上述底層鄰接的金屬層，該底層含有具有可氫化的共軛二烯化合物單元的聚合物及平均粒徑為400 nm以下的金屬氧化物粒子，且對上述積層體的剖面進行掃描型電子顯微鏡(Scanning Electron Microscope，SEM)觀察時，自上述底層與上述金屬層的界面起在上述底層側方向的500 nm的表層區域中存在金屬部分，在上述表層區域中金屬部分的面積率為5%以上。 (13) A laminate having a primer layer and a metal layer adjacent to the primer layer, the primer layer comprising a polymer having a hydrogenatable conjugated diene compound unit and metal oxide particles having an average particle diameter of 400 nm or less. When the cross section of the laminate is observed by a scanning electron microscope (SEM), a metal portion exists in a surface region of 500 nm from the interface between the underlayer and the metal layer in the bottom layer side direction. The area ratio of the metal portion in the surface layer region is 5% or more.

(14)如上述(13)所述的積層體，其中上述金屬部分的面積率為5%~30%。 (14) The laminate according to the above (13), wherein an area ratio of the metal portion is 5% to 30%.

(15)如上述(13)或(14)所述的積層體，其中上述 聚合物是丙烯腈與丁二烯的共聚物或其氫化產物，上述金屬氧化物粒子為氧化矽粒子。 (15) The laminate according to the above (13) or (14), wherein The polymer is a copolymer of acrylonitrile and butadiene or a hydrogenated product thereof, and the above metal oxide particles are cerium oxide particles.

根據本發明，可提供一種金屬層的密接性優異、金屬層表面的淨化性亦優異的積層體及其製造方法。 According to the present invention, it is possible to provide a laminate having excellent adhesion of a metal layer and excellent surface cleanability of a metal layer, and a method for producing the same.

另外，根據本發明，可提供一種在該積層體的製造方法中所使用的底層形成用組成物。 Further, according to the present invention, a composition for forming a primer layer used in the method for producing a laminate can be provided.

10‧‧‧基板 10‧‧‧Substrate

12‧‧‧底層 12‧‧‧ bottom layer

14‧‧‧金屬層 14‧‧‧metal layer

16‧‧‧積層體 16‧‧‧Layer

18‧‧‧圖案狀金屬層 18‧‧‧patterned metal layer

圖1中的(A)~(C)是分別依序表示本發明的積層體的製造方法中的各製造步驟的自基板至具有圖案狀金屬層的積層體為止的示意性剖面圖。 (A) to (C) in Fig. 1 are schematic cross-sectional views showing the respective steps from the substrate to the layered body having the patterned metal layer in the respective manufacturing steps in the method for producing a layered product of the present invention.

圖2是金屬層表面上的異物的SEM照片。 2 is a SEM photograph of a foreign matter on the surface of a metal layer.

圖3是實施例2中所得的積層體的剖面SEM圖。 3 is a cross-sectional SEM image of the layered body obtained in Example 2. FIG.

圖4是將實施例2中所得的積層體的剖面SEM圖進行解析而得的圖。 4 is a view showing a cross-sectional SEM image of the layered product obtained in Example 2. FIG.

圖5是實施例18中所得的配線基板的SEM照片。 Fig. 5 is a SEM photograph of the wiring board obtained in Example 18.

以下，對本發明的積層體及其製造方法、以及該製造方法中所使用的底層形成用組成物的較佳實施方式進行說明。 Hereinafter, preferred embodiments of the laminate of the present invention, a method for producing the same, and a composition for forming a primer layer used in the method of production will be described.

首先，對本發明的與現有技術比較的特徵點進行詳細敍述。 First, the feature points of the present invention which are compared with the prior art will be described in detail.

本發明中，在使用包含特定粒徑的金屬氧化物粒子的底層、與鹼性鍍敷觸媒液的方面具有特徵。若使該底層與鍍敷觸媒液接觸，則鍍敷觸媒或其前驅物容易自底層表面滲透至內部。因此，在鍍敷處理時形成於底層上的金屬層容易侵入至底層內部，結果金屬層對底層的錨定效果更優異，金屬層的密接性提高，並且亦維持金屬層表面的淨化性。 In the present invention, it is characterized in that a primer layer containing metal oxide particles having a specific particle diameter and an alkaline plating catalyst liquid are used. When the underlayer is brought into contact with the plating catalyst liquid, the plating catalyst or its precursor easily penetrates from the surface of the bottom layer to the inside. Therefore, the metal layer formed on the underlayer at the time of the plating treatment easily intrudes into the inside of the underlayer, and as a result, the anchoring effect of the metal layer on the underlayer is more excellent, the adhesion of the metal layer is improved, and the cleanability of the surface of the metal layer is also maintained.

本發明的積層體的製造方法的較佳實施方式包括：形成底層的底層形成步驟、使底層與鹼性溶液接觸的鹼性溶液接觸步驟、在底層上提供鍍敷觸媒或其前驅物的觸媒提供步驟、以及對底層實施鍍敷處理的鍍敷步驟。另外，如後述般，鹼性溶液接觸步驟是根據需要而設置的任意的步驟。 A preferred embodiment of the method for producing a laminate of the present invention comprises: a bottom layer forming step of forming a bottom layer, an alkaline solution contacting step of contacting the bottom layer with an alkaline solution, and a contact of a plating catalyst or a precursor thereof on the bottom layer. The medium supply step and a plating step of performing a plating treatment on the bottom layer. Further, as will be described later, the alkaline solution contacting step is an optional step provided as needed.

以下，對各步驟中所使用的材料(底層形成用組成物等)及其順序進行詳細敍述。首先，對底層形成步驟進行詳細敍述。 Hereinafter, the materials used in the respective steps (the composition for forming the underlayer, etc.) and the order thereof will be described in detail. First, the underlayer forming step will be described in detail.

<底層形成步驟> <Under layer forming step>

底層形成步驟是形成包含具有可氫化的共軛二烯化合物單元的聚合物、與平均粒徑為400 nm以下的金屬氧化物粒子的底層的步驟。藉由該步驟而形成的底層，在觸媒提供步驟中吸附(附著)鍍敷觸媒或其前驅物。即，底層發揮出作為鍍敷觸媒或其前驅物的良好的接受層(被鍍敷層)的功能。 The underlayer forming step is a step of forming a primer layer comprising a polymer having a hydrogenatable conjugated diene compound unit and a metal oxide particle having an average particle diameter of 400 nm or less. The underlayer formed by this step adsorbs (attaches) the plating catalyst or its precursor in the catalyst supply step. That is, the underlayer functions as a good receiving layer (plated layer) as a plating catalyst or a precursor thereof.

更具體而言，藉由該步驟，而例如圖1中的(A)所示般在基板10上形成底層12。另外，圖1中的(A)中，在基板10上形成底層12，但亦可不使用基板10而形成底層12。 More specifically, by this step, the underlayer 12 is formed on the substrate 10 as shown, for example, in (A) of FIG. Further, in (A) of FIG. 1, the underlayer 12 is formed on the substrate 10, but the underlayer 12 may be formed without using the substrate 10.

首先，對本步驟中所使用的材料(聚合物、金屬氧化物粒子等)進行詳細敍述，然後對該步驟的順序進行詳細敍述。 First, the materials (polymer, metal oxide particles, and the like) used in this step will be described in detail, and the order of the steps will be described in detail.

(聚合物) (polymer)

聚合物具有可氫化的共軛二烯化合物單元。本聚合物藉由具有該共軛二烯化合物單元，而作為底層的應力緩和層的功能進一步提高，結果，金屬層的密接性進一步提高。 The polymer has a hydrogenatable conjugated diene compound unit. The polymer has a function as a stress relaxation layer of the underlayer by having the conjugated diene compound unit, and as a result, the adhesion of the metal layer is further improved.

以下，對聚合物中所含的單元進行說明。 Hereinafter, the unit contained in the polymer will be described.

(可氫化的共軛二烯化合物單元) (hydrogenizable conjugated diene compound unit)

共軛二烯化合物單元是指源自共軛二烯化合物的重複單元。共軛二烯化合物若為具有藉由一個單鍵隔開、且具有二個碳-碳雙鍵的分子結構的化合物，則並無特別限制。 The conjugated diene compound unit means a repeating unit derived from a conjugated diene compound. The conjugated diene compound is not particularly limited as long as it has a molecular structure separated by one single bond and has a molecular structure of two carbon-carbon double bonds.

例如可列舉：異戊二烯、1,3-丁二烯、1,3-戊二烯、2,4-己二烯、1,3-己二烯、1,3-庚二烯、2,4-庚二烯、1,3-辛二烯、2,4-辛二烯、3,5-辛二烯、1,3-壬二烯、2,4-壬二烯、3,5-壬二烯、1,3-癸二烯、2,4-癸二烯、3,5-癸二烯、2,3-二甲基-丁二烯、2-甲基-1,3-戊二烯、3-甲基-1,3-戊二烯、4-甲基-1,3-戊二烯、2-苯基-1,3-丁二烯、2-苯基-1,3-戊二烯、3-苯基-1,3-戊二烯、2,3-二甲基-1,3-戊二烯、4-甲基-1,3-戊二烯、2-己基-1,3-丁二烯、3-甲基-1,3-己二烯、2-苄基-1,3-丁二烯、2-對甲苯基-1,3-丁二烯等各種二烯化合物。 For example, isoprene, 1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 2 , 4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-decadiene, 2,4-decadiene, 3,5 -decadiene, 1,3-decadiene, 2,4-decadiene, 3,5-decadiene, 2,3-dimethyl-butadiene, 2-methyl-1,3- Pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1, 3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2- Hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene, etc. Various diene compounds.

其中，就聚合物的合成容易、且作為底層的應力緩和層的功能進一步提高的方面而言，共軛二烯化合物單元較佳為藉由下述式(2)所示的具有丁二烯骨架的化合物發生聚合反應而生成 的重複單元(源自式(2)所示的具有丁二烯骨架的化合物的重複單元)。 In particular, the conjugated diene compound unit preferably has a butadiene skeleton represented by the following formula (2) in terms of the ease of synthesis of the polymer and the further improvement of the function of the stress relaxation layer of the underlayer. The compound is polymerized to form A repeating unit (derived from a repeating unit of a compound having a butadiene skeleton represented by the formula (2)).

式(2)中，R²表示氫原子、鹵素原子或烴基。烴基可列舉：脂肪族烴基(例如烷基、烯基等。較佳為碳數1~12)、或芳香族烴基(例如苯基、萘基等)。多個R²可相同亦可不同。 In the formula (2), R ² represents a hydrogen atom, a halogen atom or a hydrocarbon group. The hydrocarbon group may, for example, be an aliphatic hydrocarbon group (for example, an alkyl group or an alkenyl group, preferably having a carbon number of 1 to 12) or an aromatic hydrocarbon group (for example, a phenyl group or a naphthyl group). A plurality of R ^{2 's} may be the same or different.

式(2)所示的具有丁二烯骨架的化合物(具有丁二烯結構的單體)的具體例例如可列舉：1,3-丁二烯、異戊二烯、2-乙基-1,3-丁二烯、2-正丙基-1,3-丁二烯、2,3-二甲基-1,3-丁二烯、1-苯基-1,3-丁二烯、1-α-萘基-1,3-丁二烯、1-β-萘基-1,3-丁二烯、2-氯-1,3-丁二烯、1-溴-1,3-丁二烯、1-氯丁二烯、2-氟-1,3-丁二烯、2,3-二氯-1,3-丁二烯、1,1,2-三氯-1,3-丁二烯、2-氰基-1,3-丁二烯。 Specific examples of the compound having a butadiene skeleton represented by the formula (2) (monomer having a butadiene structure) include, for example, 1,3-butadiene, isoprene, and 2-ethyl-1. , 3-butadiene, 2-n-propyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1-bromo-1,3- Butadiene, 1-chlorobutadiene, 2-fluoro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1,1,2-trichloro-1,3 - Butadiene, 2-cyano-1,3-butadiene.

這些中，特佳為1,3-丁二烯、異戊二烯、2-氯-1,3-丁二烯。 Among these, 1,3-butadiene, isoprene, and 2-chloro-1,3-butadiene are particularly preferred.

源自具有丁二烯骨架的化合物的重複單元的具體例例如可列舉：以下式(3)或式(4)所示的重複單元。 Specific examples of the repeating unit derived from the compound having a butadiene skeleton include a repeating unit represented by the following formula (3) or formula (4).

上述式(3)、式(4)中的R²的定義與上述R²相同。 The definition of R ² in the above formulas (3) and (4) is the same as the above R ² .

另外，上述共軛二烯化合物單元可進行氫化，在包含該經氫化的共軛二烯化合物單元時，金屬層的密接性進一步提高，且耐熱性進一步提高，而較佳。即，源自共軛二烯化合物的重複單元中的雙鍵可進行氫化。具體而言，在上述式(3)中的R²為氫原子時，經氫化的重複單元成為丁烯單元。 Further, the conjugated diene compound unit can be hydrogenated, and when the hydrogenated conjugated diene compound unit is contained, the adhesion of the metal layer is further improved, and the heat resistance is further improved, which is preferable. That is, the double bond in the repeating unit derived from the conjugated diene compound can be hydrogenated. Specifically, when R ² in the above formula (3) is a hydrogen atom, the hydrogenated repeating unit becomes a butene unit.

可氫化的共軛二烯化合物單元的含量在聚合物中的全部單元(全部重複單元)中，較佳為90莫耳%以下，更佳為80莫耳%以下，特佳為40莫耳%~75莫耳%。若可氫化的共軛二烯化合物單元的含量為該範圍，則金屬層的密接性進一步提高。 The content of the hydrogenatable conjugated diene compound unit is preferably 90 mol% or less, more preferably 80 mol% or less, and particularly preferably 40 mol%, based on all units (all repeating units) in the polymer. ~75 mol%. When the content of the hydrogenatable conjugated diene compound unit is in this range, the adhesion of the metal layer is further improved.

(具有相互作用性基的單元) (unit with interactive basis)

聚合物可進一步具有含有與鍍敷觸媒或其前驅物相互作用的官能基(以下亦適當稱為相互作用性基)的單元。藉由聚合物具有相互作用性基，而在底層上可高效地附著鍍敷觸媒或其前驅物。 The polymer may further have a unit containing a functional group (hereinafter also referred to as an interactive group as appropriate) which interacts with the plating catalyst or its precursor. The plating catalyst or its precursor can be efficiently attached to the underlayer by the polymer having an interactive group.

具有相互作用性基的單元是指具有相互作用性基的重複單元。 A unit having an interactive group means a repeating unit having an interactive group.

相互作用性基若與後述的鍍敷觸媒或其前驅物相互作用，則可為任意的官能基，例如可使用：可與鍍敷觸媒或其前驅物形成靜電相互作用的官能基、或可與鍍敷觸媒或其前驅物形成配位的含氮官能基、含硫官能基、含氧官能基等。 The interactive group may be any functional group if it interacts with a plating catalyst or a precursor thereof to be described later, and for example, a functional group capable of electrostatically interacting with a plating catalyst or a precursor thereof, or A nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, or the like which can form a coordination with a plating catalyst or a precursor thereof.

相互作用性基例如亦可列舉：非解離性官能基(藉由解離而不生成質子的官能基)等。 Examples of the interactive group include a non-dissociable functional group (a functional group which does not generate a proton by dissociation) and the like.

相互作用性基更具體可列舉：胺基、醯胺基、醯亞胺基、脲基、三級胺基、銨基、脒基(amidino)、三嗪環、***環、苯并***基、咪唑基、苯并咪唑基、喹啉基、吡啶基、嘧啶基、吡嗪基、喹唑啉基、喹噁啉基、嘌呤基、三嗪基、哌啶基、哌嗪基、吡咯啶基、吡唑基、苯胺基、含烷基胺結構的基、含異三聚氰酸結構的基、硝基、亞硝基、偶氮基、重氮基、疊氮基、氰基、氰酸酯基(R-O-CN)等含氮官能基；醚基、羥基、酚性羥基、羧基、碳酸酯基、羰基、酯基、含N-氧化物結構的基、含S-氧化物結構的基、含N-羥基結構的基等含氧官能基；噻吩基、硫醇基、硫脲基、硫代三聚氰酸基、苯并噻唑基、巰基三嗪基、硫醚基、硫氧基、亞碸基、碸基、硫醚基、含磺醯亞胺(sulfoximine)結構的基、含磺酸鹽結構的基、磺酸基、含磺酸酯結構的基等含硫官能基；磷酸酯基、磷醯胺基、膦基、含磷酸酯結構的基等含磷官能基；氯、溴等含鹵素原子的基等，可形成鹽結構的官能基中，亦 可使用這些的鹽。 More specifically, the interactive group may be exemplified by an amine group, a guanamine group, a guanidino group, a ureido group, a tertiary amine group, an ammonium group, an amidino group, a triazine ring, a triazole ring, and a benzotriazole. Base, imidazolyl, benzimidazolyl, quinolyl, pyridyl, pyrimidinyl, pyrazinyl, quinazolinyl, quinoxalinyl, fluorenyl, triazinyl, piperidinyl, piperazinyl, pyrrole Pyridyl, pyrazolyl, anilino, alkylamine-containing, hetero-cyanate-containing, nitro, nitroso, azo, diazonium, azide, cyano, a nitrogen-containing functional group such as a cyanate group (RO-CN); an ether group, a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, a carbonate group, a carbonyl group, an ester group, an N-oxide-containing group, and an S-containing structure. Oxygen-containing functional group such as an N-hydroxyl group-containing group; thienyl group, thiol group, thiourea group, thiotrisocyanate group, benzothiazolyl group, mercaptotriazinyl group, thioether group, sulfur a sulfur-containing functional group such as an oxy group, a fluorenylene group, a fluorenyl group, a thioether group, a sulfoximine-containing group, a sulfonate-containing group, a sulfonic acid group, or a sulfonate-containing group Phosphate group Phosphorus acyl group, a phosphino group, phosphate structure-containing group of the phosphorus-containing functional group; functional group chlorine and bromine atoms, a halogen-containing group, may form a salt structure, but also Salts of these can be used.

其中，就極性高、對鍍敷觸媒或其前驅物等的吸附能力高的方面而言，特佳為羧基、磺酸基、磷酸基、及硼酸基等離子性極性基，或醚基，或氰基；特別是氰基進而更佳。 Among them, in terms of high polarity, high adsorption capacity to a plating catalyst or a precursor thereof, etc., a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group polar polar group, or an ether group, or Cyano; especially cyano is further preferred.

作為相互作用性基的這些官能基在聚合物中可包含2種以上。 These functional groups as an interactive group may contain two or more types in the polymer.

作為具有相互作用性基的單元，就聚合物的合成更容易、且金屬層的密接性進一步提高的方面而言，較佳為以下式(1)所示的重複單元。 The unit having an interactive group is preferably a repeating unit represented by the following formula (1) in terms of facilitating the synthesis of the polymer and further improving the adhesion of the metal layer.

式(1)中，R¹表示氫或烷基(例如甲基、乙基等)。 In the formula (1), R ¹ represents hydrogen or an alkyl group (e.g., methyl group, ethyl group, etc.).

式(1)中，L¹表示單鍵或二價連結基。二價連結基可列舉：經取代或未經取代的二價脂肪族烴基(較佳為碳數1~8。例如亞甲基、伸乙基、伸丙基等伸烷基)、經取代或未經取代的二價芳香族烴基(較佳為碳數6~12，例如伸苯基)、-O-、S-、-SO₂-、-N(R)-(R：烷基)、-CO-、-NH-、-COO-、-CONH-、或將這些基組合而成的基(例如伸烷氧基、伸烷氧羰基、伸烷基羰氧基等) 等。就後述的X基的每單位體積的官能基量提高的方面而言，L¹較佳為單鍵。 In the formula (1), L ¹ represents a single bond or a divalent linking group. The divalent linking group may be exemplified by a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having a carbon number of 1 to 8. for example, a methylene group, an ethyl group, a propyl group or the like), substituted or Unsubstituted divalent aromatic hydrocarbon group (preferably having a carbon number of 6 to 12, such as a phenyl group), -O-, S-, -SO ₂ -, -N(R)-(R:alkyl), -CO-, -NH-, -COO-, -CONH-, or a group in which these groups are combined (for example, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, etc.). L ^{1 is} preferably a single bond in terms of an increase in the amount of the functional group per unit volume of the X group described later.

式(1)中，X表示相互作用性基。相互作用性基的定義如上所述。 In the formula (1), X represents an interactive group. The definition of the interactive group is as described above.

另外，進一步具有上述相互作用性基的聚合物，亦可為在具有可氫化的共軛二烯化合物單元的聚合物中接枝共聚合具有相互作用性基與聚合性基的單體而成的聚合物。此處，相互作用性基的定義及較佳的形態如上所述。另外，聚合性基例如可列舉：自由基聚合性基、陽離子聚合性基等，其中較佳為：甲基丙烯醯基、丙烯醯基、衣康酸酯基、丁烯酸酯基、異丁烯酸酯基、順丁烯二酸酯基、苯乙烯基、乙烯基、烯丙基、丙烯醯胺基、甲基丙烯醯胺基。 Further, the polymer further having the above-mentioned interactive group may be obtained by graft-polymerizing a monomer having an interactive group and a polymerizable group in a polymer having a hydrogenatable conjugated diene compound unit. polymer. Here, the definition and preferred form of the interactive group are as described above. Further, examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group. Among them, a methacryl oxime group, an acryl fluorenyl group, an itaconate group, a butenoate group, and a methacrylic acid are preferable. Ester group, maleate group, styryl group, vinyl group, allyl group, acrylamide group, methacrylamide group.

具有相互作用性基與聚合性基的單體例如可列舉：丙烯酸、甲基丙烯酸、順丁烯二酸、反丁烯二酸、四氫鄰苯二甲酸、衣康酸、檸康酸、丁烯酸、耐地酸(nadic acid)等。具有相互作用性基與聚合性基的單體亦可為：順丁烯二酸酐、衣康酸酐、檸康酸酐等具有聚合性基、且藉由水解而生成相互作用性基者。具有相互作用性基與聚合性基的單體，就金屬層的密接性更優異的理由而言，較佳為順丁烯二酸、順丁烯二酸酐。 Examples of the monomer having an interactive group and a polymerizable group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, and butyl. Oleic acid, nadic acid, and the like. The monomer having an interactive group and a polymerizable group may be a polymerizable group such as maleic anhydride, itaconic anhydride or citraconic anhydride, and an interactive group formed by hydrolysis. The monomer having an interactive group and a polymerizable group is preferably maleic acid or maleic anhydride for the reason that the adhesion of the metal layer is more excellent.

具有相互作用性基的單元(重複單元)的含量，在聚合物中的全部單元(全部重複單元)中，較佳為10莫耳%以上，更佳為20莫耳%以上，特佳為25莫耳%~60莫耳%。若具有相互作 用性基的單元(重複單元)的含量為該範圍，則金屬層的密接性進一步提高。 The content of the unit (repeating unit) having an interactive group is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 25 in all units (all repeating units) in the polymer. Mole%~60% by mole. If they have mutual interaction When the content of the unit (repeating unit) of the usable group is in this range, the adhesion of the metal layer is further improved.

另外，在聚合物中亦可包含上述以外的重複單元。 Further, a repeating unit other than the above may be contained in the polymer.

例如可具有源自以下單體的重複單元：芳香族乙烯基單體(例如苯乙烯、α-甲基苯乙烯、二乙烯苯等)、含醯胺基的(甲基)丙烯酸系單體(例如丙烯醯胺、甲基丙烯醯胺、N-(甲基)丙烯醯基嗎福啉、N-乙烯基-2-吡咯烷酮等)、不飽和羧酸單體(例如反丁烯二酸、順丁烯二酸、丙烯酸、甲基丙烯酸等)、或其他單體(例如乙烯、丙烯、氯乙烯、偏二氯乙烯、乙酸乙烯酯、乙基乙烯醚、丁基乙烯醚等)。其中，就金屬層的密接性更優異的理由而言，較佳為源自芳香族乙烯基單體(較佳為苯乙烯)及/或不飽和羧酸單體(較佳為順丁烯二酸)的重複單元。 For example, it may have a repeating unit derived from an aromatic vinyl monomer (for example, styrene, α-methylstyrene, divinylbenzene, etc.), a mercaptoamine-containing (meth)acrylic monomer ( For example, acrylamide, methacrylamide, N-(methyl) propylene decyl porphyrin, N-vinyl-2-pyrrolidone, etc.), unsaturated carboxylic acid monomers (for example, fumaric acid, cis Butylene diacid, acrylic acid, methacrylic acid, etc., or other monomers (for example, ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl acetate, ethyl vinyl ether, butyl vinyl ether, etc.). Among them, the reason why the adhesion of the metal layer is more excellent is preferably derived from an aromatic vinyl monomer (preferably styrene) and/or an unsaturated carboxylic acid monomer (preferably, butylene). Repeat unit of acid).

聚合物的較佳的形態可列舉：丙烯腈丁二烯橡膠(NBR)、丙烯腈-丁二烯-異戊二烯橡膠(NBIR)、丙烯腈-丁二烯-苯乙烯共聚物(ABS樹脂)、苯乙烯丁二烯共聚物、或這些的氫化產物(例如氫化丙烯腈丁二烯橡膠)、或這些的羧酸改質物(例如含羧基的丁腈橡膠(carboxylated nitrile rubber，XNBR)、順丁烯二酸改質氫化苯乙烯丁二烯共聚物(例如使順丁烯二酸酐接枝共聚合而成的氫化苯乙烯丁二烯共聚物))等。其中，就熱處理時的形狀穩定性及/或密接性更高的理由而言，較佳為丙烯腈與丁二烯的共聚物、苯乙烯與丁二烯的共聚物、或這些的氫化產物、或這些的羧酸改質物。 Preferred examples of the polymer include acrylonitrile butadiene rubber (NBR), acrylonitrile-butadiene-isoprene rubber (NBIR), and acrylonitrile-butadiene-styrene copolymer (ABS resin). a styrene butadiene copolymer, or a hydrogenated product of these (for example, hydrogenated acrylonitrile butadiene rubber), or a carboxylic acid modification of these (for example, a carboxylated nitrile rubber (XNBR), cis A butadiene-modified hydrogenated styrene butadiene copolymer (for example, a hydrogenated styrene butadiene copolymer obtained by graft-copolymerizing maleic anhydride)). Among them, a copolymer of acrylonitrile and butadiene, a copolymer of styrene and butadiene, or a hydrogenated product of these may be preferred for reasons of higher shape stability and/or adhesion during heat treatment. Or a carboxylic acid modification of these.

就金屬層的應力緩和的觀點而言，聚合物的孟納黏度(Mooney viscosity)[ML₁₊₄(100℃)]較佳為10~90，更佳為25~80。聚合物的孟納黏度(中心值)是基於JIS K 6300-1「未硫化橡膠-物理特性-第1部：藉由孟納黏度計的黏度及焦化時間(Scorch time)的求法」而測定者。 The Mooney viscosity [ML ₁₊₄ (100 ° C)] of the polymer is preferably from 10 to 90, more preferably from 25 to 80, from the viewpoint of stress relaxation of the metal layer. The Mona viscosity (central value) of the polymer is determined based on JIS K 6300-1 "Unvulcanized rubber - physical properties - Part 1: Evaluation by viscosity and Scorch time of a Monner viscosity meter".

本發明的聚合物的合成方法並無特別限制，可使用公知的方法(例如自由基聚合、陽離子聚合等)。例如可列舉：使上述具有丁二烯骨架的單體與其他乙烯基化合物(丙烯腈等)共聚合的方法等。 The method for synthesizing the polymer of the present invention is not particularly limited, and a known method (for example, radical polymerization, cationic polymerization, or the like) can be used. For example, a method of copolymerizing a monomer having a butadiene skeleton and another vinyl compound (such as acrylonitrile) may be mentioned.

(金屬氧化物粒子) (metal oxide particles)

藉由在底層中包含金屬氧化物粒子，而底層的彈性模數提高，金屬層的密接性提高，並且由於粒子表面上的親水基的影響而金屬層容易進入底層中，而容易形成良好的錨定結構。 By including metal oxide particles in the underlayer, the elastic modulus of the underlayer is improved, the adhesion of the metal layer is improved, and the metal layer easily enters the underlayer due to the influence of the hydrophilic group on the surface of the particles, and a good anchor is easily formed. Structure.

金屬氧化物粒子的種類並無特別限制，例如可列舉：包含選自由週期表第4A族元素、第5A族元素、第3B族元素、第4B族元素、及第8族元素所組成的組群中的至少1種金屬元素的金屬氧化物粒子。其中，就可廉價的獲得、且本發明的效果更優異的方面而言，較佳為可列舉：包含選自由矽、鋁、鈦、及鐵所組成的組群中的至少1種金屬元素的金屬氧化物粒子；更佳為可列舉：包含矽的金屬氧化物粒子。 The type of the metal oxide particles is not particularly limited, and examples thereof include a group selected from the group consisting of a Group 4A element, a Group 5A element, a Group 3B element, a Group 4B element, and a Group 8 element of the periodic table. Metal oxide particles of at least one metal element. Among them, in terms of being inexpensively obtained and having more excellent effects of the present invention, it is preferable to include at least one metal element selected from the group consisting of ruthenium, aluminum, titanium, and iron. Metal oxide particles; more preferably, metal oxide particles containing ruthenium are mentioned.

另外，金屬氧化物粒子的具體例例如可列舉：氧化鈦、氧化鋅、氧化矽(silica)、氧化鉛、氧化鎢、氧化錫、氧化銦、氧 化鈮、氧化鎘、氧化鉍、氧化鋁、氧化鎵(III)、氧化亞鐵等。 Further, specific examples of the metal oxide particles include titanium oxide, zinc oxide, silica, lead oxide, tungsten oxide, tin oxide, indium oxide, and oxygen. Antimony, cadmium oxide, antimony oxide, aluminum oxide, gallium oxide (III), ferrous oxide, and the like.

金屬氧化物粒子的平均粒徑為400 nm以下，更佳為300 nm以下，尤佳為200 nm以下，最佳為100 nm以下。平均粒徑的下限並無特別限制，就金屬氧化物粒子的合成上的容易性的方面而言，較佳為3 nm以上。若平均粒徑為上述範圍，則金屬層的密接性優異。 The average particle diameter of the metal oxide particles is 400 nm or less, more preferably 300 nm or less, and particularly preferably 200 nm or less, and most preferably 100 nm or less. The lower limit of the average particle diameter is not particularly limited, and is preferably 3 nm or more in terms of ease of synthesis of the metal oxide particles. When the average particle diameter is in the above range, the adhesion of the metal layer is excellent.

另一方面，在平均粒徑超過400 nm時，金屬層的密接性劣化。 On the other hand, when the average particle diameter exceeds 400 nm, the adhesion of the metal layer is deteriorated.

金屬氧化物粒子的粒徑的測定方法，是藉由利用掃描型電子顯微鏡(SEM)的觀察，測定至少100個以上的金屬氧化物粒子的粒徑，將這些粒徑值進行算術平均而求出粒徑。另外，在金屬氧化物粒子的形狀不為球狀時(例如為橢圓狀時)，將其長徑設為粒徑。 The method for measuring the particle diameter of the metal oxide particles is obtained by measuring the particle diameter of at least 100 metal oxide particles by observation using a scanning electron microscope (SEM), and arithmetically averaging the particle diameter values. Particle size. Further, when the shape of the metal oxide particles is not spherical (for example, in the case of an elliptical shape), the long diameter is defined as the particle diameter.

(任意成分：螯合劑(chelating agent)) (optional ingredient: chelating agent)

底層中可包含螯合劑。藉由使用螯合劑，而可進一步抑制因底層中所存在的金屬離子等雜質引起的異物的產生。 A chelating agent can be included in the bottom layer. By using a chelating agent, the generation of foreign matter due to impurities such as metal ions present in the underlayer can be further suppressed.

特別是本發明者等人對現有技術中妨礙金屬層的淨化的原因進行研究，結果發現，專利文獻1中所使用的NBR等中所微量含有的脂肪酸等乳化劑會造成大的影響，上述脂肪酸含有Ca或Al等的金屬離子。根據該發現而發現，藉由在底層中混合螯合劑，而捕捉底層或鍍敷觸媒液中所含的金屬離子等微量的雜質，結果在金屬層表面上進一步抑制異物等的產生，並維持其淨化性。 In particular, the inventors of the present invention have studied the cause of the deterioration of the metal layer in the prior art, and as a result, it has been found that an emulsifier such as a fatty acid contained in a small amount of NBR or the like used in Patent Document 1 has a large influence. Contains metal ions such as Ca or Al. According to this finding, it is found that a small amount of impurities such as metal ions contained in the underlayer or the plating catalyst liquid are trapped by mixing the chelating agent in the underlayer, and as a result, the generation of foreign matter or the like is further suppressed on the surface of the metal layer and maintained. Its purification.

螯合劑若對金屬離子具有螯合物形成能力，則並無特別限定，可為單牙配位的化合物，亦可為多牙配位的化合物。 The chelating agent is not particularly limited as long as it has a chelate forming ability to metal ions, and may be a monodentate-coordinated compound or a polydentate-coordinated compound.

就進一步抑制異物的產生的方面而言，較佳為在螯合劑中不含氮原子。而且，就進一步抑制異物的產生的方面而言，較佳為在螯合劑中包含選自由羧酸基、磺酸基、膦酸基及二酮基所組成的組群中的至少一種官能基或其鹽。即，螯合劑較佳為：羧酸系螯合劑(分子內具有羧酸基(-COOH)或其鹽的螯合劑)、磺酸系螯合劑(分子內具有磺酸基(-SO₂OH)或其鹽的螯合劑)、膦酸系螯合劑(分子內具有膦酸基(-OPO(OH)₂)或其鹽的螯合劑)、二酮系螯合劑(分子內具有二酮基的螯合劑)。 In terms of further suppressing the generation of foreign matter, it is preferred that the chelating agent does not contain a nitrogen atom. Further, in terms of further suppressing the generation of foreign matter, it is preferred to include at least one functional group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, and a diketone group in the chelating agent or Its salt. That is, the chelating agent is preferably a carboxylic acid-based chelating agent (a chelating agent having a carboxylic acid group (-COOH) or a salt thereof in the molecule) or a sulfonic acid-based chelating agent (having a sulfonic acid group (-SO ₂ OH) in the molecule) a chelating agent of a salt thereof, a phosphonic acid chelating agent (a chelating agent having a phosphonic acid group (-OPO(OH) ₂ ) or a salt thereof), and a diketone chelating agent (a chelate having a diketone group in the molecule) mixture).

另外，就可進一步抑制異物的產生、且在有機溶劑中的溶解性更優異的方面而言，較佳為二酮系螯合劑(包含二酮基的螯合劑)。 In addition, a diketone-based chelating agent (a chelating agent containing a diketone group) is preferable because it can further suppress the generation of foreign matter and is more excellent in solubility in an organic solvent.

螯合劑的具體例例如可列舉：聚磷酸酯類(例如三聚磷酸鈉、六偏磷酸、酸性焦磷酸鈉、焦磷酸鈉、焦磷酸四鈉、六偏磷酸鈉、偏磷酸鈉)；胺基羧酸類(例如乙二胺四乙酸(EDTA)、1,2-雙(2-胺基-苯氧基)乙烷-N,N,N'N'-四乙酸(EGTA)、伸乙基二(氧基伸乙基氮川基)四乙酸(BAPTA)、N-(羥基乙基)-乙二胺三乙酸(HEDTA)、二伸乙基三胺五乙酸(DTPA)、N-二羥基乙基甘胺酸(2-HxG)、伸乙基二(羥基苯基-甘胺酸)(EHPG)、麩胺酸、天冬醯胺酸、甘胺酸、離胺酸)；1,3-二酮類(例如乙醯丙酮、4,4,4-三氟-1-苯基-1,3-丁烷二酮、三氟乙醯丙酮、噻吩甲醯三氟丙酮、 抗壞血酸)；羥基羧酸類(例如酒石酸、檸檬酸、蘋果酸、葡萄糖酸、阿魏酸(ferulic acid)、乳酸、葡萄糖醛酸(glucuronic acid))；聚胺類(例如二伸乙基三胺、三伸乙基三胺)；胺基醇類(例如三乙醇胺、N-羥基乙二胺、胺基乙基乙醇胺(AEEA)；酚類(例如二磺基鄰苯二酚、鉻變酸(Chromotropic acid))；胺基酚類(例如8-羟基喹啉磺酸(oxine sulphonic acid))；希夫鹼(例如二柳醛1,2-丙二亞胺)；四吡咯類(例如四苯基卟吩、酞菁)；硫化合物(例如乙基黃原酸鉀(potassium ethyl xanthate)、二乙基二硫代胺基甲酸鈉(sodium diethyldithiocarbamate)、二乙基二硫代磷酸、硫脲、硫酸鎂)；合成大環式化合物(例如六甲基-[14]-4,11-二烯N₄、2.2.2-穴狀化合物(cryptate))；磷酸類(例如、氮川基三亞甲基磷酸、乙二胺四-(亞甲基磷酸)、羥基亞乙基二磷酸、十二烷基磷酸)；磺酸類(例如十二烷基苯磺酸)等。 Specific examples of the chelating agent include polyphosphates (for example, sodium tripolyphosphate, hexametaphosphoric acid, sodium acid pyrophosphate, sodium pyrophosphate, tetrasodium pyrophosphate, sodium hexametaphosphate, sodium metaphosphate); Carboxylic acids (such as ethylenediaminetetraacetic acid (EDTA), 1,2-bis(2-amino-phenoxy)ethane-N,N,N'N'-tetraacetic acid (EGTA), ethylidene (oxyl-ethylidene) tetraacetic acid (BAPTA), N-(hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA), di-ethyltriaminepentaacetic acid (DTPA), N-dihydroxyethyl Glycine (2-HxG), ethyl bis(hydroxyphenyl-glycine) (EHPG), glutamic acid, aspartic acid, glycine, lysine; 1,3- Ketones (eg, acetamidine, 4,4,4-trifluoro-1-phenyl-1,3-butanedione, trifluoroacetone, thiophene trifluoroacetone, ascorbic acid); hydroxycarboxylic acids (eg tartaric acid, citric acid, malic acid, gluconic acid, ferulic acid, lactic acid, glucuronic acid); polyamines (eg di-ethyltriamine, tri-ethyltriamine) ); amino alcohols (eg, triethanolamine, N-hydroxyethylenediamine, aminoethylethanolamine (AEEA); phenolics) (e.g., disulfocatechol, Chromotropic acid); aminophenols (e.g., oxine sulphonic acid); Schiff bases (e.g., diamylaldehyde 1, 2) - propylenediamine); tetrapyrroles (such as tetraphenyl porphin, phthalocyanine); sulfur compounds (such as potassium ethyl xanthate, sodium diethyldithiocarbamate) ), diethyldithiophosphoric acid, thiourea, magnesium sulfate); synthesis of macrocyclic compounds (eg hexamethyl-[14]-4,11-diene N ₄ , 2.2.2-cryptate (cryptate) )); phosphoric acid (for example, nitrilotrimethylenephosphoric acid, ethylenediaminetetrakis-(methylenephosphoric acid), hydroxyethylidene diphosphate, dodecylphosphoric acid); sulfonic acid (for example, dodecyl) Benzenesulfonic acid) and the like.

(底層形成步驟的順序) (the order of the bottom layer forming steps)

形成底層的方法並無特別限定，可使用公知的方法。例如可列舉：將包含上述聚合物及金屬氧化物粒子的底層形成用組成物塗佈於基板上的方法；在底層形成用組成物中浸漬基板的方法；將底層形成用組成物層壓於基板上的方法；將底層形成用組成物直接成形為板狀或膜狀的方法等。就容易控制所得的底層的厚度的方面而言，較佳為將底層形成用組成物塗佈於基板上的方法。 The method of forming the underlayer is not particularly limited, and a known method can be used. For example, a method of applying a composition for forming a primer layer containing the polymer and metal oxide particles to a substrate, a method of immersing a substrate in a composition for forming a primer layer, and a composition for forming a primer layer on a substrate can be mentioned. The above method; a method of directly forming a composition for forming an underlayer into a plate shape or a film shape. In terms of easily controlling the thickness of the obtained underlayer, a method of applying a composition for forming an underlayer onto a substrate is preferred.

另外，關於底層形成用組成物及基板的實施方式，於後 段進行詳細敍述。 In addition, the embodiment of the composition for forming the underlayer and the substrate are as follows. The paragraph is described in detail.

在基板上塗佈底層形成用組成物的方法並無特別限制，具體的方法可使用：藉由旋塗機、雙輥塗佈機、狹縫塗佈機、氣刀塗佈機、線棒塗佈機、滑板漏斗(slide hopper)、噴塗、刀片塗佈機、刮刀塗佈機、擠壓塗佈機、逆輥塗佈機、轉移輥塗佈機、擠壓塗佈機(extrusion coater)、淋幕式塗佈機、浸塗機、模塗機、凹版輥的塗敷法，擠出塗佈法，輥塗法等公知的方法。 The method of coating the composition for forming the underlayer on the substrate is not particularly limited, and a specific method can be used: by a spin coater, a twin roll coater, a slit coater, an air knife coater, and a wire bar coating. Cloth machine, slide hopper, spray coating, blade coater, knife coater, extrusion coater, reverse roll coater, transfer roll coater, extrusion coater, A known method such as a coating method of a curtain coater, a dip coater, a die coater, a gravure roll, an extrusion coating method, and a roll coating method.

另外，在基板上塗佈底層形成用組成物後，根據需要，為了除去溶劑而可實施乾燥處理。進行乾燥處理時的溫度並無特別限制，就基板的耐熱性的觀點而言，較佳為在80℃~180℃下實施。 Further, after the composition for forming the underlayer is applied onto the substrate, if necessary, a drying treatment may be performed to remove the solvent. The temperature at the time of the drying treatment is not particularly limited, and is preferably from 80 ° C to 180 ° C from the viewpoint of heat resistance of the substrate.

(底層形成用組成物(被鍍敷層形成用組成物)) (The composition for forming the underlayer (the composition for forming a layer to be plated))

底層形成用組成物含有上述聚合物及金屬氧化物粒子。另外，由該組成物形成的底層如後述般，用於與包含鍍敷觸媒或其前驅物且為鹼性的鍍敷觸媒液接觸，而在底層上提供鍍敷觸媒或其前驅物。 The composition for forming the underlayer contains the above polymer and metal oxide particles. Further, the underlayer formed of the composition is used to provide a plating catalyst or a precursor thereof on the underlayer, as described later, in contact with a plating catalyst liquid containing a plating catalyst or a precursor thereof and being alkaline. .

底層形成用組成物中的聚合物的含量並無特別限制，就組成物的操作性優異、可更簡便地形成特定厚度的底層的方面而言，相對於組成物總量，較佳為0.1質量%~90質量%，更佳為1質量%~80質量%。 The content of the polymer in the composition for forming the underlayer is not particularly limited, and is preferably 0.1 mass in terms of the handleability of the composition and the formation of the underlayer having a specific thickness more easily. %~90% by mass, more preferably 1% by mass to 80% by mass.

底層形成用組成物中的金屬氧化物粒子的含量並無特別限制，相對於聚合物與金屬氧化物粒子的合計質量，較佳為15 質量%~65質量%，更佳為25質量%~45質量%。若金屬氧化物粒子的含量為該範圍，則金屬層的密接性優異。 The content of the metal oxide particles in the composition for forming the underlayer is not particularly limited, and is preferably 15 based on the total mass of the polymer and the metal oxide particles. The mass % to 65 mass%, more preferably 25 mass% to 45 mass%. When the content of the metal oxide particles is in this range, the adhesion of the metal layer is excellent.

在底層形成用組成物中包含螯合劑時，組成物中的螯合劑的含量並無特別限制，相對於聚合物100質量份，較佳為0.05質量份~20質量份，更佳為0.1質量份~10質量份。若螯合劑的含量為該範圍，則金屬層的密接性優異。 When the chelating agent is contained in the composition for forming the underlayer, the content of the chelating agent in the composition is not particularly limited, and is preferably 0.05 parts by mass to 20 parts by mass, more preferably 0.1 part by mass, per 100 parts by mass of the polymer. ~10 parts by mass. When the content of the chelating agent is in this range, the adhesion of the metal layer is excellent.

底層形成用組成物中，根據需要可包含溶劑。藉由含有溶劑，而組成物的操作性提高。 The composition for forming the underlayer may contain a solvent as needed. By containing a solvent, the handleability of the composition is improved.

可使用的溶劑並無特別限定，例如可列舉：水、甲醇、乙醇、丙醇、乙二醇、甘油、丙二醇單甲醚等醇系溶劑，乙酸等酸，丙酮、甲基乙基酮、環己酮等酮系溶劑，甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等醯胺系溶劑，乙腈、丙腈等腈系溶劑，乙酸甲酯、乙酸乙酯等酯系溶劑，碳酸二甲酯、碳酸二乙酯等碳酸酯系溶劑，苯、甲苯、二甲苯等芳香族烴系溶劑，此外亦可列舉：醚系溶劑、二醇系溶劑、胺系溶劑、硫醇系溶劑、鹵素系溶劑等。 The solvent to be used is not particularly limited, and examples thereof include an alcohol solvent such as water, methanol, ethanol, propanol, ethylene glycol, glycerin or propylene glycol monomethyl ether, an acid such as acetic acid, acetone, methyl ethyl ketone or a ring. a ketone solvent such as ketone or a guanamine solvent such as formamide, dimethylacetamide or N-methylpyrrolidone; a nitrile solvent such as acetonitrile or propionitrile; or an ester solvent such as methyl acetate or ethyl acetate; A carbonate-based solvent such as dimethyl carbonate or diethyl carbonate, or an aromatic hydrocarbon-based solvent such as benzene, toluene or xylene, and examples thereof include an ether solvent, a glycol solvent, an amine solvent, and a thiol solvent. , halogen solvent, etc.

其中，較佳為醯胺系溶劑、酮系溶劑、腈系溶劑、碳酸酯系溶劑、芳香族烴系溶劑，具體而言，較佳為丙酮、二甲基乙醯胺、甲基乙基酮、環己酮、乙腈、丙腈、N-甲基吡咯烷酮、碳酸二甲酯、甲苯。 Among them, a guanamine solvent, a ketone solvent, a nitrile solvent, a carbonate solvent, and an aromatic hydrocarbon solvent are preferable, and specifically, acetone, dimethylacetamide, and methyl ethyl ketone are preferable. , cyclohexanone, acetonitrile, propionitrile, N-methylpyrrolidone, dimethyl carbonate, toluene.

底層形成用組成物中的溶劑的含量並無特別限制，相對於組成物總量，較佳為50質量%~98質量%，更佳為90質量%~ 97質量%。若溶劑的含量為上述範圍內，則組成物的操作性優異，容易進行底層的層厚的控制等。 The content of the solvent in the composition for forming the underlayer is not particularly limited, and is preferably 50% by mass to 98% by mass, and more preferably 90% by mass based on the total amount of the composition. 97% by mass. When the content of the solvent is within the above range, the handleability of the composition is excellent, and it is easy to control the layer thickness of the underlayer.

底層形成用組成物中，根據需要可含有分散劑(界面活性劑)。藉由含有分散劑，而可抑制金屬氧化物粒子的凝聚，並且底層形成用組成物的保存穩定性提高。 The composition for forming the underlayer may contain a dispersing agent (surfactant) as needed. By containing a dispersing agent, aggregation of metal oxide particles can be suppressed, and the storage stability of the composition for forming an underlayer can be improved.

分散劑的種類並無特別限定，例如可使用高分子系分散劑。高分子系分散劑例如可列舉：鹼性高分子系分散劑、中性高分子系分散劑、酸性高分子系分散劑等。此種高分子系分散劑例如可列舉：包含丙烯酸系、改質丙烯酸系共聚物的分散劑，磷酸系分散劑，胺基甲酸酯系分散劑，包含聚胺基醯胺鹽、聚醚酯、脂肪族聚醚、脂肪族多元羧酸等的分散劑等。其中，由於磷酸系分散劑對金屬或金屬氧化物的吸附性優異，與氧化矽的相容性亦非常佳，因此就底層形成用組成物的保存穩定性更優異的方面而言，較佳為磷酸系分散劑。 The type of the dispersant is not particularly limited, and for example, a polymer dispersant can be used. Examples of the polymer-based dispersant include a basic polymer-based dispersant, a neutral-polymer dispersant, and an acidic polymer-based dispersant. Examples of such a polymer-based dispersant include a dispersant containing an acrylic-based or modified acrylic copolymer, a phosphate-based dispersant, and a urethane-based dispersant, and a polyamine guanamine salt or a polyether ester. A dispersant such as an aliphatic polyether or an aliphatic polycarboxylic acid. In particular, since the phosphate-based dispersant is excellent in the adsorptivity to a metal or a metal oxide, and has excellent compatibility with cerium oxide, it is preferable that the storage stability of the composition for forming the underlayer is more excellent. Phosphoric acid dispersant.

分散劑例如可列舉：艾菲西亞(Avecia)股份有限公司製造的SOLSPERSE3000、SOLSPERSE9000、SOLSPERSE17000、SOLSPERSE18000、SOLSPERSE21000、SOLSPERSE24000、SOLSPERSE24000GR、SOLSPERSE28000、SOLSPERSE32000、SOLSPERSE35100、SOLSPERSE36000、SOLSPERSE41000，埃夫卡助劑(EFKA Additives)公司製造的EFKA6230、EFKA4009、EFKA4046、EFKA4047、EFKA4080、EFKA4010、EFKA4015、EFKA4050、EFKA4055、EFKA4060、EFKA4330、EFKA4300、 EFKA7462，味之素精細化學(Ajinomoto Fine-Techno)股份有限公司製造的Ajisper PB821、Ajisper PB711、Ajisper PB822、Ajisper PN411、Ajisper PA111，日本科寧(Cognis Japan)股份有限公司製造的TEXAPHORUV20等。 Examples of the dispersing agent include: SOLSPERSE 3000, SOLSPERSE 9000, SOLSPERSE 17000, SOLSPERSE 18000, SOLSPERSE 21000, SOLSPERSE 24000, SOLSPERSE 24000 GR, SOLSPERSE 28000, SOLSPERSE 32000, SOLSPERSE 35100, SOLSPERSE 36000, SOLSPERSE 41000, EFKA Additives manufactured by Avecia Co., Ltd. EFKA6230, EFKA4009, EFKA4046, EFKA4047, EFKA4080, EFKA4010, EFKA4015, EFKA4050, EFKA4055, EFKA4060, EFKA4330, EFKA4300, manufactured by the company, EFKA7462, Ajisper PB821, Ajisper PB711, Ajisper PB822, Ajisper PN411, Ajisper PA111 manufactured by Ajinomoto Fine-Techno Co., Ltd., TEXAPHORUV20 manufactured by Cognis Japan Co., Ltd., and the like.

(基板) (substrate)

本步驟中可使用的基板亦可使用現有已知的任意基板(例如絕緣性基板)，較佳為可承受後述的處理條件者。例如可列舉：塑膠基板、玻璃環氧樹脂基板、玻璃基板、陶瓷基板、金屬基板等。 Any substrate known in the art (for example, an insulating substrate) may be used as the substrate which can be used in this step, and it is preferable to be able to withstand the processing conditions described later. For example, a plastic substrate, a glass epoxy substrate, a glass substrate, a ceramic substrate, a metal substrate, etc. are mentioned.

塑膠基板的材料可列舉：熱硬化性樹脂(例如環氧樹脂、酚樹脂、聚醯亞胺樹脂、聚酯樹脂等)或熱塑性樹脂(例如苯氧樹脂、聚醚碸、聚碸、聚苯碸(Polyphenylene sulfone)等)。 Examples of the material of the plastic substrate include thermosetting resins (for example, epoxy resins, phenol resins, polyimide resins, polyester resins, etc.) or thermoplastic resins (for example, phenoxy resins, polyether oximes, polyfluorenes, polyphenylenes). (Polyphenylene sulfone), etc.).

陶瓷基板的材料例如可列舉：氧化鋁、氮化鋁、氧化鋯、矽、氮化矽、碳化矽等。 Examples of the material of the ceramic substrate include alumina, aluminum nitride, zirconium oxide, ruthenium, tantalum nitride, tantalum carbide, and the like.

玻璃基板的材料例如可列舉：鈉玻璃、鉀玻璃、硼矽酸玻璃、石英玻璃、鋁矽酸玻璃、鉛玻璃等。 Examples of the material of the glass substrate include soda glass, potassium glass, borosilicate glass, quartz glass, aluminosilicate glass, lead glass, and the like.

金屬基板的材料例如可列舉：鋁、鋅、銅等。 Examples of the material of the metal substrate include aluminum, zinc, copper, and the like.

另外，基板亦可為上述塑膠基板、玻璃基板、陶瓷基板、金屬基板等積層2層以上而成的結構。 Further, the substrate may have a structure in which two or more layers of the plastic substrate, the glass substrate, the ceramic substrate, and the metal substrate are laminated.

另外，基板可在其單面或兩面具有金屬層。即，可使用附金屬層的基板。金屬層可在基板的表面形成為圖案狀，亦可形成於整個面上。代表性的可列舉：藉由利用蝕刻處理的減成法形 成者、或藉由利用電鍍的半加成法形成者，亦可使用藉由任一方法形成者。 In addition, the substrate may have a metal layer on one or both sides thereof. That is, a substrate with a metal layer can be used. The metal layer may be formed in a pattern on the surface of the substrate or may be formed on the entire surface. Representative examples include a subtractive form by etching treatment The former, or formed by a semi-additive method using electroplating, may also be formed by any method.

構成金屬層的材料例如可列舉：銅、銀、錫、鈀、金、鎳、鉻、鎢、銦、鋅、或鎵等。 Examples of the material constituting the metal layer include copper, silver, tin, palladium, gold, nickel, chromium, tungsten, indium, zinc, or gallium.

(底層) (bottom layer)

所形成的底層包含上述聚合物及金屬氧化物粒子。 The underlayer formed includes the above polymer and metal oxide particles.

底層的厚度並無特別限制，就金屬層的密接性及厚度的均勻性更優異的方面而言，較佳為0.05 μm~50 μm，更佳為0.01 μm~10 μm，尤佳為0.1 μm~5 μm。 The thickness of the underlayer is not particularly limited, and is preferably 0.05 μm to 50 μm, more preferably 0.01 μm to 10 μm, and particularly preferably 0.1 μm, in terms of the adhesion of the metal layer and the uniformity of the thickness. 5 μm.

底層中金屬氧化物粒子的含量相對於金屬氧化物粒子與聚合物的合計質量，並無特別限制，其較佳的範圍較佳為15質量%~65質量%，更佳為25質量%~45質量%。若金屬氧化物粒子的含量為該範圍，則金屬層的密接性優異。 The content of the metal oxide particles in the underlayer is not particularly limited with respect to the total mass of the metal oxide particles and the polymer, and the preferred range thereof is preferably 15% by mass to 65% by mass, more preferably 25% by mass to 45% by mass. quality%. When the content of the metal oxide particles is in this range, the adhesion of the metal layer is excellent.

底層中螯合劑的含量相對於聚合物100質量份並無特別限制，較佳為0.05質量份~20質量份，更佳為0.1質量份~10質量份。若螯合劑的含量為該範圍，則金屬層的密接性優異。 The content of the chelating agent in the underlayer is not particularly limited with respect to 100 parts by mass of the polymer, and is preferably from 0.05 part by mass to 20 parts by mass, more preferably from 0.1 part by mass to 10 parts by mass. When the content of the chelating agent is in this range, the adhesion of the metal layer is excellent.

<鹼性溶液接觸步驟> <Alkaline solution contact step>

鹼性溶液接觸步驟是使上述底層與鹼性溶液接觸的步驟。藉由實施該步驟，而將底層表面活化，並且後述的鍍敷觸媒或其前驅物容易附著於底層。另外，在底層已具有所期望的特性時，可不實施本步驟。 The alkaline solution contacting step is a step of bringing the above underlayer into contact with an alkaline solution. By performing this step, the underlying surface is activated, and the plating catalyst or its precursor described later is likely to adhere to the underlayer. In addition, this step may not be performed when the bottom layer already has the desired characteristics.

以下，對本步驟中所使用的材料(鹼性溶液等)進行詳 細敍述，然後對步驟的順序進行詳細敍述。 Hereinafter, the materials (alkaline solution, etc.) used in this step will be detailed. Describe in detail, and then detail the order of the steps.

(鹼性溶液) (alkaline solution)

鹼性溶液若pH值為鹼性，則其種類並無特別限定。 When the pH of the alkaline solution is alkaline, the type thereof is not particularly limited.

就金屬層的密接性更高的理由而言，鹼性溶液的pH值較佳為10~14，更佳為12~14。 The pH of the alkaline solution is preferably from 10 to 14, more preferably from 12 to 14, for the reason that the adhesion of the metal layer is higher.

另外，該鹼性溶液中不含鍍敷觸媒或其前驅物。 In addition, the alkaline solution does not contain a plating catalyst or a precursor thereof.

鹼性溶液中所使用的溶劑通常使用水。另外，根據需要可併用：有機溶劑(甲醇、乙醇、丙醇、乙二醇、甘油、丙二醇單甲醚、2-胺基乙醇等醇系溶劑，乙酸、羥基乙酸、胺基羧酸等酸，丙酮、甲基乙基酮等酮系溶劑，甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等醯胺系溶劑，乙腈、丙腈等腈系溶劑，碳酸二甲酯、碳酸二乙酯等碳酸酯系溶劑，二醇系溶劑，二伸乙基三胺等胺系溶劑，或2種以上這些溶劑的混合物等)。 The solvent used in the alkaline solution usually uses water. Further, if necessary, it may be used in combination: an organic solvent (an alcohol such as methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether or 2-aminoethanol; an acid such as acetic acid, glycolic acid or aminocarboxylic acid; A ketone solvent such as acetone or methyl ethyl ketone; a guanamine solvent such as formamide, dimethylacetamide or N-methylpyrrolidone; a nitrile solvent such as acetonitrile or propionitrile; dimethyl carbonate and carbonic acid; A carbonate solvent such as ethyl ester, a glycol solvent, an amine solvent such as diethyltriamine or a mixture of two or more of these solvents.

另外，鹼性溶液可進一步包含界面活性劑。界面活性劑的種類並無特別限制，可列舉：非離子系界面活性劑、兩性界面活性劑、陰離子系界面活性劑、陽離子系界面活性劑等。其中，就鍍敷的析出性更優異的方面而言，較佳為陰離子系界面活性劑。 Additionally, the alkaline solution may further comprise a surfactant. The type of the surfactant is not particularly limited, and examples thereof include a nonionic surfactant, an amphoteric surfactant, an anionic surfactant, and a cationic surfactant. Among them, an anionic surfactant is preferred in terms of more excellent deposition properties of the plating.

非離子系界面活性劑例如可列舉：聚乙二醇衍生物、聚丙二醇衍生物。兩性界面活性劑例如可列舉：長鏈烷基的甜菜鹼類。陰離子系界面活性劑例如可列舉：長鏈烷基硫酸銨鹽、烷基芳基硫酸銨鹽、烷基芳基磺酸銨鹽、烷基磷酸銨鹽、聚羧酸系高分子的銨鹽等。陽離子系界面活性劑例如可列舉：長鏈烷基胺乙 酸鹽等。 Examples of the nonionic surfactant include a polyethylene glycol derivative and a polypropylene glycol derivative. Examples of the amphoteric surfactant include long-chain alkyl betaines. Examples of the anionic surfactant include long-chain alkyl ammonium sulfate, alkyl aryl ammonium sulfate, alkyl aryl sulfonate ammonium salt, alkyl ammonium phosphate salt, ammonium salt of polycarboxylic acid polymer, and the like. . Examples of the cationic surfactant include long-chain alkylamine B. Acid salt, etc.

作為鹼性溶液，其種類並無特別限制，例如可列舉：氫氧化鋰水溶液、氫氧化鈉水溶液、氫氧化鉀水溶液、碳酸鋰水溶液、碳酸鈉水溶液、碳酸鉀水溶液、碳酸氫鋰水溶液、碳酸氫鈉水溶液、碳酸氫鉀水溶液、氫氧化鈣水溶液、氫氧化鍶水溶液、氫氧化鋇水溶液、碳酸鈣水溶液、碳酸鍶水溶液、碳酸鋇水溶液等。 The type of the alkaline solution is not particularly limited, and examples thereof include a lithium hydroxide aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a lithium carbonate aqueous solution, a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a lithium hydrogencarbonate aqueous solution, and hydrogencarbonate. A sodium aqueous solution, an aqueous solution of potassium hydrogencarbonate, an aqueous solution of calcium hydroxide, an aqueous solution of barium hydroxide, an aqueous solution of barium hydroxide, an aqueous solution of calcium carbonate, an aqueous solution of barium carbonate, an aqueous solution of barium carbonate, or the like.

(鹼性溶液接觸步驟的順序) (Order sequence of alkaline solution contact steps)

底層與鹼性溶液的接觸方法並無特別限制，可使用公知的方法。例如可列舉：將鹼性溶液塗佈於底層上的方法(噴霧塗佈、旋塗、印刷法等)、或在鹼性溶液中浸漬具有底層的基板的方法(浸泡浸漬(dipping))等，就處理的簡便性、處理時間的調整的容易性而言，較佳為浸泡浸漬、噴霧塗佈。 The contact method of the underlayer with the alkaline solution is not particularly limited, and a known method can be used. For example, a method of applying an alkaline solution to a primer layer (spray coating, spin coating, printing method, or the like), or a method of immersing a substrate having a primer layer in an alkaline solution (dipping), or the like, The ease of the treatment and the ease of adjustment of the treatment time are preferably soaking and spraying.

接觸時的鹼性溶液的液溫並無特別限制，就金屬層的密接性更優異的理由而言，較佳為20℃~90℃的範圍，更佳為25℃~60℃的範圍。 The liquid temperature of the alkaline solution at the time of contact is not particularly limited, and is preferably in the range of 20 ° C to 90 ° C, and more preferably in the range of 25 ° C to 60 ° C, for the reason that the adhesion of the metal layer is more excellent.

就金屬層的密接性更高的理由而言，底層與鹼性溶液的接觸時間較佳為5秒~30分鐘的範圍，更佳為30秒~25分鐘的範圍，尤佳為1分鐘~20分鐘的範圍。 For the reason that the adhesion of the metal layer is higher, the contact time of the underlayer and the alkaline solution is preferably in the range of 5 seconds to 30 minutes, more preferably in the range of 30 seconds to 25 minutes, and particularly preferably 1 minute to 20 minutes. The range of minutes.

另外，就金屬層的密接性更優異的理由而言，較佳為在與鹼性溶液接觸後，藉由純水等清洗附著於底層的鹼性溶液。 Further, for the reason that the adhesion of the metal layer is more excellent, it is preferred to wash the alkaline solution adhering to the underlayer by pure water or the like after contact with the alkaline solution.

<觸媒提供步驟> <Catalyst supply step>

觸媒提供步驟是使包含鍍敷觸媒或其前驅物且為鹼性的鍍敷觸媒液與底層接觸，在底層上提供鍍敷觸媒或其前驅物的步驟。 The catalyst providing step is a step of contacting the plating catalyst liquid containing the plating catalyst or its precursor and being alkaline with the underlayer to provide a plating catalyst or a precursor thereof on the underlayer.

此處，鍍敷觸媒或其前驅物可列舉：後述的鍍敷步驟中發揮出作為鍍敷處理的觸媒或電極的功能者。因此，鍍敷觸媒或其前驅物根據鍍敷步驟中的鍍敷處理的種類而確定，就金屬層的密接性更優異的方面而言，較佳為無電鍍敷觸媒或其前驅物。 Here, the plating catalyst or its precursor may be a function of a catalyst or an electrode that functions as a plating treatment in a plating step to be described later. Therefore, the plating catalyst or its precursor is determined according to the type of the plating treatment in the plating step, and the electroless plating catalyst or its precursor is preferable in terms of the adhesion of the metal layer being more excellent.

首先，對本步驟中所使用的材料(鍍敷觸媒、鍍敷觸媒液等)進行詳細敍述，然後對該步驟的順序進行詳細敍述。 First, the materials (plating catalyst, plating catalyst liquid, etc.) used in this step will be described in detail, and the order of the steps will be described in detail.

(無電鍍敷觸媒) (electroless plating catalyst)

本步驟中可使用的無電鍍敷觸媒若是成為無電鍍敷時的活性核者，則亦可使用任意者，具體可列舉：具有自我觸媒還原反應的觸媒能力的金屬(作為離子化傾向低於Ni且可無電鍍敷的金屬而已知者)等。具體可列舉：Pd、Ag、Cu、Ni、Pt、Au、Co等。其中，就高的觸媒能力而言，特佳為Ag、Pd、Pt、Cu。 If the electroless plating catalyst which can be used in this step is an active core in the case of electroless plating, any one may be used, and specific examples thereof include a metal having a catalytic ability of a self-catalyst reduction reaction (as an ionization tendency) It is known that it is lower than Ni and can be electrolessly plated. Specific examples thereof include Pd, Ag, Cu, Ni, Pt, Au, Co, and the like. Among them, in terms of high catalyst capacity, it is particularly preferable to be Ag, Pd, Pt, and Cu.

該無電鍍敷觸媒可使用金屬膠體。通常，金屬膠體可藉由在帶電的界面活性劑或帶電的保護劑存在的溶液中將金屬離子還原而製作。金屬膠體的帶電可藉由此處所使用的界面活性劑或保護劑進行調節。 The electroless plating catalyst can use a metal colloid. Typically, the metal colloid can be made by reducing metal ions in a solution in the presence of a charged surfactant or a charged protective agent. The charging of the metal colloid can be adjusted by the surfactant or protective agent used herein.

(無電鍍敷觸媒前驅物) (electroless plating catalyst precursor)

本步驟中可使用的無電鍍敷觸媒前驅物，若為藉由化學反應而可成為無電鍍敷觸媒者，則可無特別限制地使用。主要可 使用作為上述無電鍍敷觸媒而列舉的金屬的金屬離子。作為無電鍍敷觸媒前驅物的金屬離子藉由還原反應而成為作為無電鍍敷觸媒的0價金屬。作為無電鍍敷觸媒前驅物的金屬離子被提供至底層後，在無電鍍敷浴中的浸漬前，可另外藉由還原反應使其變化為0價金屬而製成無電鍍敷觸媒。另外，亦可以無電鍍敷觸媒前驅物的狀態浸漬於無電鍍敷浴中，藉由無電鍍敷浴中的還原劑而變化為金屬(無電鍍敷觸媒)。 The electroless plating catalyst precursor which can be used in this step can be used without any particular limitation if it can be an electroless plating catalyst by a chemical reaction. Mainly available A metal ion of a metal exemplified as the above electroless plating catalyst is used. The metal ions which are precursors of the electroless plating catalyst become a zero-valent metal which is an electroless plating catalyst by a reduction reaction. After the metal ions as the precursor of the electroless plating catalyst are supplied to the underlayer, an electroless plating catalyst can be prepared by additionally changing to a zero-valent metal by a reduction reaction before the immersion in the electroless plating bath. Alternatively, the electroless plating precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

作為無電鍍敷觸媒前驅物的金屬離子，較佳為使用金屬鹽而提供至底層。所使用的金屬鹽若為溶解於恰當的溶劑中而解離成金屬離子與鹼(陰離子)者，則並無特別限制，可列舉：M(NO₃)_n、MCl_n、M_2/n(SO₄)、M_3/n(PO₄)(M表示n價金屬原子)等。金屬離子可較佳地使用上述金屬鹽解離而成者。例如可列舉：Ag離子、Cu離子、Ni離子、Co離子、Pt離子、Pd離子。其中較佳為可多牙配位者，特別是就可配位的官能基的種類數及觸媒能力的方面而言，較佳為Ag離子、Pd離子、Cu離子。 The metal ion as the electroless plating catalyst precursor is preferably supplied to the underlayer using a metal salt. The metal salt to be used is not particularly limited as long as it is dissolved in a suitable solvent and is dissociated into a metal ion and a base (anion), and examples thereof include M(NO ₃ ) _n , MCl _n , and M _2/n (SO). ₄ ), M _3/n (PO ₄ ) (M represents an n-valent metal atom), and the like. The metal ion can be preferably obtained by dissociating the above metal salt. For example, Ag ion, Cu ion, Ni ion, Co ion, Pt ion, and Pd ion are mentioned. Among them, a polydentate ligand is preferable, and in particular, in terms of the number of kinds of functional groups that can be coordinated and the catalytic ability, Ag ions, Pd ions, and Cu ions are preferable.

作為無電鍍敷觸媒或其前驅物的較佳例之一，可列舉鈀化合物。該鈀化合物發揮出在鍍敷處理時成為活性核而使金屬析出的作用，並發揮出作為鍍敷觸媒(鈀)或其前驅物(鈀離子)的作用。作為鈀化合物，若包含鈀、且在鍍敷處理時發揮出作為核的作用，則並無特別限定，例如可列舉：鈀(II)鹽、鈀(0)錯合物、鈀膠體等。 One of preferable examples of the electroless plating catalyst or its precursor is a palladium compound. This palladium compound acts to form an active nucleus during the plating treatment to precipitate a metal, and functions as a plating catalyst (palladium) or a precursor thereof (palladium ion). The palladium compound is not particularly limited as long as it contains palladium and functions as a core during the plating treatment, and examples thereof include a palladium (II) salt, a palladium (0) complex, and a palladium colloid.

另外，作為無電鍍敷觸媒或其前驅物，可列舉銀、或銀 離子作為較佳的其他例。 In addition, as an electroless plating catalyst or a precursor thereof, silver or silver may be mentioned. Ions are preferred examples.

在使用銀離子時，可較佳地使用如以下所示的銀化合物解離而成者。銀化合物的具體例可列舉：硝酸銀、乙酸銀、硫酸銀、碳酸銀、氰化銀、硫氰酸銀、氯化銀、溴化銀、鉻酸銀、氯冉酸銀、水楊酸銀、二乙基二硫代胺基甲酸銀、對甲苯磺酸銀。其中，就水溶性的觀點而言，較佳為硝酸銀。 When silver ions are used, it is preferred to use a silver compound as shown below to dissociate. Specific examples of the silver compound include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, silver chloroantimonate, silver salicylate, Silver diethyl diethyldithiocarbamate and silver p-toluenesulfonate. Among them, from the viewpoint of water solubility, silver nitrate is preferred.

(其他觸媒) (other catalysts)

本步驟中，作為用於不進行無電鍍敷而直接進行電鍍的觸媒，亦可使用上述以外的0價金屬。 In this step, as the catalyst for directly performing electroplating without electroless plating, a zero-valent metal other than the above may be used.

(鍍敷觸媒液) (plating catalyst liquid)

鍍敷觸媒液是使上述鍍敷觸媒或其前驅物分散或溶解於溶劑中而成的分散液或溶液。 The plating catalyst liquid is a dispersion or solution obtained by dispersing or dissolving the plating catalyst or its precursor in a solvent.

鍍敷觸媒液中所使用的溶劑可使用有機溶劑及/或水。藉由鍍敷觸媒液含有有機溶劑，而鍍敷觸媒液對底層的滲透性提高，並使相互作用性基高效地吸附鍍敷觸媒或其前驅物。 An organic solvent and/or water may be used as the solvent used in the plating catalyst. When the plating catalyst liquid contains an organic solvent, the permeability of the plating catalyst liquid to the underlayer is improved, and the interactive group is efficiently adsorbed to the plating catalyst or its precursor.

鍍敷觸媒液中可使用的有機溶劑若為可滲透至底層的溶劑，則並無特別限制，具體可使用：丙酮、乙醯乙酸甲酯、乙醯乙酸乙酯、乙二醇二乙酸酯、環己酮、乙醯丙酮、苯乙酮、2-(1-環己烯基)環己酮、丙二醇二乙酸酯、三乙酸甘油酯、二乙二醇二乙酸酯、二噁烷、N-甲基吡咯烷酮、碳酸二甲酯、二甲基溶纖劑等。 The organic solvent which can be used in the plating catalyst liquid is not particularly limited as long as it is a solvent which can penetrate into the underlayer. Specifically, acetone, ethyl acetate, ethyl acetate, ethylene glycol diacetic acid can be used. Ester, cyclohexanone, acetoacetone, acetophenone, 2-(1-cyclohexenyl)cyclohexanone, propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxins Alkane, N-methylpyrrolidone, dimethyl carbonate, dimethyl cellosolve, and the like.

鍍敷觸媒液中的鍍敷觸媒及其前驅物的含量並無特別 限制，就附著量的控制更容易的方面、及生產性的方面而言，相對於觸媒液總量，較佳為0.01質量%~1質量%。 There is no special content of plating catalyst and its precursor in the plating catalyst. The limitation is preferably from 0.01% by mass to 1% by mass based on the total amount of the catalyst liquid in terms of easier control of the amount of adhesion and productivity.

鍍敷觸媒液的pH值顯示鹼性。由於顯示鹼性，而該鍍敷觸媒液可進一步浸漬於底層中，結果金屬層的密接性進一步提高。其中，就金屬層的密接性進一步提高的方面而言，pH值較佳為9以上，更佳為10以上。pH值的上限並無特別限制，就抑制底層的分解的方面而言，較佳為13以下。 The pH of the plating catalyst liquid is alkaline. Since the plating catalyst liquid is further immersed in the underlayer due to the alkalinity, the adhesion of the metal layer is further improved. In particular, the pH is preferably 9 or more, and more preferably 10 or more, from the viewpoint of further improving the adhesion of the metal layer. The upper limit of the pH is not particularly limited, and is preferably 13 or less from the viewpoint of suppressing decomposition of the underlayer.

另外，為了調整鍍敷觸媒液的pH值，可在鍍敷觸媒液中添加公知的鹼成分(例如氫氧化鈉、氫氧化鉀等)。 Further, in order to adjust the pH of the plating catalyst liquid, a known alkali component (for example, sodium hydroxide, potassium hydroxide or the like) may be added to the plating catalyst liquid.

而且，鍍敷觸媒液中根據目的可含有其他添加劑。其他添加劑例如可列舉：膨潤劑、或界面活性劑等。 Further, the plating catalyst liquid may contain other additives depending on the purpose. Examples of other additives include a swelling agent, a surfactant, and the like.

(觸媒附著步驟的順序) (The order of the catalyst attachment steps)

將鍍敷觸媒或其前驅物提供至底層的方法並無特別限制。 The method of supplying the plating catalyst or its precursor to the underlayer is not particularly limited.

例如可列舉：將鍍敷觸媒液塗佈於底層上的方法、或者在鍍敷觸媒液中浸漬形成有底層的基板的方法等。 For example, a method of applying a plating catalyst liquid to a primer layer or a method of immersing a substrate having a primer layer in a plating catalyst liquid may be mentioned.

作為底層與鍍敷觸媒液的接觸時間，較佳為30秒~24小時左右，更佳為1分鐘~1小時左右。 The contact time between the underlayer and the plating catalyst liquid is preferably from about 30 seconds to about 24 hours, more preferably from about 1 minute to about 1 hour.

接觸時的鍍敷觸媒液的溫度較佳為5℃~80℃左右，更佳為15℃~60℃左右。 The temperature of the plating catalyst liquid at the time of contact is preferably about 5 ° C to 80 ° C, more preferably about 15 ° C to 60 ° C.

底層中的鍍敷觸媒或其前驅物的吸附量並無特別限制，就金屬層的均勻性及/或密接性更優異的理由而言，較佳為1 mg/m²~200 mg/m²，更佳為5 mg/m²~100 mg/m²。 The amount of adsorption of the plating catalyst or its precursor in the underlayer is not particularly limited, and is preferably 1 mg/m ² to 200 mg/m for the reason that the metal layer is more excellent in uniformity and/or adhesion. ² , more preferably 5 mg/m ² ~ 100 mg/m ² .

<鍍敷步驟> <plating step>

鍍敷步驟是對在觸媒提供步驟中提供了鍍敷觸媒或其前驅物的底層進行鍍敷，而在底層上形成金屬層的步驟。藉由該步驟而形成的金屬層具有優異的導電性、密接性。更具體而言，如圖1中的(B)所示般，在底層12上形成金屬層14，而獲得積層體16。 The plating step is a step of plating the underlayer which provides the plating catalyst or its precursor in the catalyst supply step, and forms a metal layer on the underlayer. The metal layer formed by this step has excellent conductivity and adhesion. More specifically, as shown in (B) of FIG. 1, the metal layer 14 is formed on the underlayer 12, and the laminated body 16 is obtained.

本步驟中所進行的鍍敷處理的種類可列舉：無電鍍敷、電鍍等，在上述觸媒提供步驟中，可根據吸附於底層的鍍敷觸媒或其前驅物的功能進行選擇。 The type of the plating treatment to be carried out in this step may be, for example, electroless plating or electroplating, and in the catalyst supply step, it may be selected according to the function of the plating catalyst adsorbed on the underlayer or a precursor thereof.

其中，就金屬層的密接性更優異的方面而言，較佳為進行無電鍍敷。另外，為了獲得所期望的層厚的金屬層，更佳的實施方式是在無電鍍敷後進一步進行電鍍。 Among them, in terms of more excellent adhesion of the metal layer, electroless plating is preferably performed. Further, in order to obtain a metal layer having a desired layer thickness, a more preferable embodiment is to further perform electroplating after electroless plating.

以下，對本步驟中可較佳地進行的鍍敷進行說明。 Hereinafter, plating which can be preferably performed in this step will be described.

(無電鍍敷) (electroless plating)

無電鍍敷是指使用溶解有在鍍敷時欲析出的金屬離子的溶液，藉由化學反應使金屬析出的操作。 The electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which a metal ion to be precipitated at the time of plating is dissolved.

本步驟中的無電鍍敷例如較佳為：將提供了無電鍍敷觸媒的基板進行水洗並將多餘的無電鍍敷觸媒(金屬)除去後，浸漬於無電鍍敷浴中而進行。所使用的無電鍍敷浴可使用公知的無電鍍敷浴。 In the electroless plating in this step, for example, it is preferable to carry out water washing of the substrate provided with the electroless plating catalyst and remove excess electroless plating catalyst (metal), followed by immersion in an electroless plating bath. A well-known electroless plating bath can be used for the electroless plating bath used.

另外，在將提供了無電鍍敷觸媒前驅物的基板，以無電 鍍敷觸媒前驅物吸附或含浸於底層的狀態浸漬於無電鍍敷浴中時，較佳為將基板水洗而將多餘的前驅物(金屬鹽等)除去後，浸漬於無電鍍敷浴中。此時，在無電鍍敷浴中，進行鍍敷觸媒前驅物的還原以及後續的無電鍍敷。此處所使用的無電鍍敷浴與上述同樣亦可使用公知的無電鍍敷浴。 In addition, a substrate that will provide an electroless plating catalyst precursor will be provided without electricity. When the plating catalyst precursor is adsorbed or impregnated in the underlayer, the substrate is washed with water to remove excess precursor (metal salt or the like), and then immersed in an electroless plating bath. At this time, in the electroless plating bath, the reduction of the plating catalyst precursor and the subsequent electroless plating were performed. As the electroless plating bath used herein, a known electroless plating bath can be used in the same manner as described above.

另外，無電鍍敷觸媒前驅物的還原與使用如上述的無電鍍敷液的形態不同，亦可準備觸媒活化液(還原液)，作為無電鍍敷前的另外步驟而進行。觸媒活化液是溶解有可將無電鍍敷觸媒前驅物(主要是金屬離子)還原為0價金屬的還原劑而成的溶液，相對於溶液整體，該還原劑的濃度較佳為0.1質量%~50質量%，更佳為1質量%~30質量%。還原劑可使用：如氫化硼鈉、二甲基胺硼烷的硼系還原劑，甲醛，次亞磷酸等。 Further, the reduction of the electroless plating catalyst precursor may be carried out by using a catalyst activating liquid (reducing liquid) as a separate step before electroless plating, unlike the use of the above-described electroless plating solution. The catalyst activating solution 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 is preferably 0.1 mass with respect to the entire solution. %~50% by mass, more preferably 1% by mass to 30% by mass. As the reducing agent, for example, sodium borohydride, a boron-based reducing agent of dimethylamine borane, formaldehyde, hypophosphorous acid or the like can be used.

浸漬時，較佳為在將無電鍍敷觸媒或其前驅物所接觸的底層表面附近的無電鍍敷觸媒或其前驅物的濃度保持為固定的基礎上，一邊施加攪拌或揺動一邊浸漬。 In the case of immersion, it is preferred to keep the concentration of the electroless plating catalyst or its precursor in the vicinity of the surface of the underlayer which is contacted by the electroless plating catalyst or its precursor, and to impregnate while stirring or stirring. .

通常的無電鍍敷浴的組成例如除了溶劑(例如水)外，主要包括：1.鍍敷用金屬離子、2.還原劑、3.使金屬離子的穩定性提高的添加劑(穩定劑)。該鍍敷浴中，除了這些外，亦可包含鍍敷浴的穩定劑等公知的添加物。 The composition of a general electroless plating bath includes, for example, a metal ion for plating, a reducing agent, and an additive (stabilizer) for improving the stability of metal ions, in addition to a solvent (for example, water). In addition to these, the plating bath may contain a known additive such as a stabilizer of a plating bath.

鍍敷浴中可使用的有機溶劑必須是可溶解於水的溶劑，就該方面而言，較佳為使用丙酮等酮類，甲醇、乙醇、異丙醇等醇類。 The organic solvent which can be used in the plating bath must be a solvent which can be dissolved in water. In this respect, it is preferred to use a ketone such as acetone or an alcohol such as methanol, ethanol or isopropyl alcohol.

無電鍍敷浴中可使用的金屬的種類已知：銅、錫、鉛、鎳、金、銀、鈀、銠，其中就導電性的觀點而言，特佳為銅、金。另外，可根據上述金屬而選擇最佳的還原劑、添加物。 The types of metals which can be used in the electroless plating bath are known: copper, tin, lead, nickel, gold, silver, palladium, rhodium, and among them, copper and gold are particularly preferable from the viewpoint of conductivity. Further, an optimum reducing agent or additive can be selected depending on the above metal.

如此形成的藉由無電鍍敷的金屬層的層厚，可藉由鍍敷浴的金屬離子濃度、在鍍敷浴中的浸漬時間、或鍍敷浴的溫度等進行控制，就導電性的觀點而言，較佳為0.1 μm以上，更佳為0.2 μm~2 μm。 The layer thickness of the metal layer by electroless plating thus formed can be controlled by the metal ion concentration of the plating bath, the immersion time in the plating bath, or the temperature of the plating bath, etc., and the viewpoint of conductivity In particular, it is preferably 0.1 μm or more, and more preferably 0.2 μm to 2 μm.

但是，在將無電鍍敷而成的金屬層作為導通層，進行後述的電鍍時，較佳為均勻地提供至少0.1 μm以上的層。 However, when a metal layer which is not electrolessly plated is used as a conduction layer, and plating to be described later is performed, it is preferable to uniformly provide a layer of at least 0.1 μm or more.

另外，作為在鍍敷浴中的浸漬時間，較佳為1分鐘~6小時左右，更佳為1分鐘~3小時左右。 Further, the immersion time in the plating bath is preferably from about 1 minute to about 6 hours, more preferably from about 1 minute to about 3 hours.

(電鍍) (plating)

本步驟中，在觸媒提供步驟中所提供的鍍敷觸媒或其前驅物具有作為電極的功能時，可對提供了該觸媒或其前驅物的底層進行電鍍。 In this step, when the plating catalyst or its precursor provided in the catalyst supplying step has a function as an electrode, the underlayer which provides the catalyst or its precursor can be plated.

另外，在前述的無電鍍敷後，將所形成的金屬層作為電極，可進一步進行電鍍。藉此可將與基板的密接性優異的無電鍍敷層作為基礎，於其上容易形成新的具有任意厚度的金屬層。如此，在無電鍍敷後，進行電鍍，藉此可將金屬層形成為與目的相對應的厚度，因此適合將金屬層應用於各種用途。 Further, after the electroless plating described above, the formed metal layer is used as an electrode, and further plating can be performed. Thereby, it is possible to form a new metal layer having an arbitrary thickness on the basis of the electroless plating layer having excellent adhesion to the substrate. Thus, after electroless plating, electroplating is performed, whereby the metal layer can be formed to have a thickness corresponding to the purpose, and thus it is suitable to apply the metal layer to various uses.

電鍍的方法可使用現有公知的方法。另外，電鍍所用的金屬可列舉：銅、鉻、鉛、鎳、金、銀、錫、鋅等，就導電性的 觀點而言，較佳為銅、金、銀，更佳為銅。 The method of electroplating can use a conventionally known method. In addition, metals used for electroplating include copper, chromium, lead, nickel, gold, silver, tin, zinc, etc., and are electrically conductive. From the viewpoint, copper, gold, and silver are preferable, and copper is more preferable.

另外，藉由電鍍而得的金屬層的層厚，可藉由調整鍍敷浴中所含的金屬濃度、或電流密度等進行控制。 Further, the layer thickness of the metal layer obtained by electroplating can be controlled by adjusting the metal concentration or current density contained in the plating bath.

另外，在應用於通常的電氣配線等時，就導電性的觀點而言，金屬層的層厚較佳為0.5 μm以上，更佳為1 μm~30 μm。 Further, when applied to ordinary electric wiring or the like, the layer thickness of the metal layer is preferably 0.5 μm or more, and more preferably 1 μm to 30 μm from the viewpoint of conductivity.

另外，為了維持縱橫比(aspect ratio)，電氣配線的線寬越變窄、即越微細化，則電氣配線的厚度越會變薄。因此，藉由電鍍而形成的金屬層的層厚並不限定於以上所述，可任意設定。 Further, in order to maintain the aspect ratio, the line width of the electric wiring becomes narrower, that is, the finer the electric wiring, the thinner the thickness of the electric wiring. Therefore, the layer thickness of the metal layer formed by electroplating is not limited to the above, and can be arbitrarily set.

<積層體> <Laminated body>

藉由經過上述步驟，而如圖1中的(B)所示般，可獲得依序包括基板10、底層12、金屬層14的積層體16(具有金屬層的積層體)。 By the above steps, as shown in FIG. 1(B), a laminate 16 (a laminate having a metal layer) including the substrate 10, the underlayer 12, and the metal layer 14 in this order can be obtained.

所得的積層體16例如使用於金屬配線基板用途，更具體而言，可應用於：印刷配線板、抗電磁波膜、塗佈膜、2層覆銅板(Copper Clad Laminate，CCL)材料、電氣配線用材料等各種電子裝置用途。 The obtained laminated body 16 is used for, for example, a metal wiring board, and more specifically, it can be applied to a printed wiring board, an electromagnetic wave resistant film, a coating film, a copper clad laminate (CCL) material, and an electric wiring. Various electronic device uses such as materials.

本發明的積層體中，藉由相對於積層體的金屬層的垂直面中的剖面的SEM觀察，自底層與金屬層的界面起在底層側方向至500 nm為止的表層區域中存在金屬部分，在表層區域中金屬部分的面積率為5%以上。藉由底層中包含特定量的金屬成分，而可表現本發明的效果(金屬層的密接性、金屬層表面的淨化性)。其中，就本發明的效果更優異的方面而言，金屬部分的面積率較佳 為5%~30%。較佳為包含特定量的金屬部分的詳細的理由仍不明，但推測：在底層的表層區域中金屬成分形成連成樹木狀的結構，藉由該結構而發揮所期望的效果。 In the laminate of the present invention, by the SEM observation of the cross section in the vertical plane of the metal layer of the laminate, a metal portion exists in the surface layer region from the bottom layer side to the 500 nm from the interface between the underlayer and the metal layer. The area ratio of the metal portion in the surface layer region is 5% or more. The effect of the present invention (adhesiveness of the metal layer, cleanability of the surface of the metal layer) can be expressed by including a specific amount of the metal component in the underlayer. Among them, in terms of the effect of the present invention being more excellent, the area ratio of the metal portion is preferably It is 5%~30%. Although the reason for including a specific amount of the metal portion is not known, it is presumed that the metal component forms a tree-like structure in the surface layer region of the underlayer, and the desired effect is exhibited by the structure.

在金屬部分的面積率小於5%時，金屬層的密接性、或者金屬層表面的淨化性的至少一者劣化。 When the area ratio of the metal portion is less than 5%, at least one of the adhesion of the metal layer or the cleanability of the surface of the metal layer is deteriorated.

另外，金屬成分的面積率的測定方法並無特別限制，例如有：使用公知的圖像解析軟體(例如winROOF)對可進行SEM觀察的照片進行圖像解析，測定底層的表層區域的金屬成分的面積的方法。另外，在SEM觀察中亦可同時進行元素分析，進行成分的確定。另外，金屬成分的面積率是觀察積層體的任意3個部位，對每張照片測定面積率並進行平均而得的值。 In addition, the method of measuring the area ratio of the metal component is not particularly limited. For example, a photo analysis of a SEM-observable photograph is performed using a well-known image analysis software (for example, winROOF), and the metal component of the surface layer region of the underlayer is measured. The method of area. In addition, elemental analysis can be performed simultaneously in the SEM observation to determine the composition. In addition, the area ratio of the metal component is a value obtained by observing an arbitrary area of the laminated body and measuring the area ratio for each photograph.

另外，在底層的厚度超過500 nm時，表層區域是指自底層與金屬層的界面起在底層側方向至500 nm為止的區域，在底層的厚度為500 nm以下時，表層區域是指整個底層。 In addition, when the thickness of the underlayer exceeds 500 nm, the surface region refers to the region from the bottom layer to the metal layer at the bottom side direction to 500 nm, and when the thickness of the underlayer is 500 nm or less, the surface region refers to the entire underlayer. .

<具有圖案狀金屬層的積層體及其製造方法> <Laminate body having a patterned metal layer and method for producing the same>

藉由進行將上述積層體中的金屬層蝕刻為圖案狀的步驟，而可製造具有圖案狀金屬層的積層體。 By laminating the metal layer in the above-mentioned laminated body into a pattern, a laminated body having a patterned metal layer can be produced.

以下對該蝕刻步驟的順序進行詳細敍述。 The order of the etching step will be described in detail below.

<蝕刻步驟> <etching step>

蝕刻步驟是將上述中所形成的金屬層(鍍敷膜)蝕刻為圖案狀的步驟。即，本步驟中，藉由蝕刻將所形成的金屬層的不需要部分去除，而可形成所期望的金屬圖案。更具體而言，如圖1 中的(C)所示般，在本步驟中，形成圖案狀金屬層18。 The etching step is a step of etching the metal layer (plating film) formed in the above into a pattern. That is, in this step, an unnecessary portion of the formed metal layer is removed by etching to form a desired metal pattern. More specifically, as shown in Figure 1. As shown in (C), in this step, the patterned metal layer 18 is formed.

該金屬圖案的形成亦可使用任意的方法，具體而言，可使用通常已知的減成法、半加成法。 Any method can be used for the formation of the metal pattern. Specifically, a generally known subtractive method or semi-additive method can be used.

所謂減成法，是如下的方法：在所形成的金屬層上設置乾膜抗蝕劑層，藉由圖案曝光、顯影形成與金屬圖案部相同的圖案，將乾膜抗蝕劑圖案作為遮罩藉由蝕刻液除去金屬層，而形成金屬圖案。乾膜抗蝕劑亦可使用任意的材料，可使用負型、正型、液狀、膜狀者。另外，作為蝕刻方法，在印刷配線基板的製造時所使用的方法均可使用，可使用濕式蝕刻、乾式蝕刻等，任意選擇即可。在作業的操作上，濕式蝕刻在裝置等的簡便性的方面較佳。蝕刻液例如可使用：氯化銅、氯化鐵等的水溶液。 The subtractive method is a method in which a dry film resist layer is provided on the formed metal layer, and the same pattern as that of the metal pattern portion is formed by pattern exposure and development, and the dry film resist pattern is used as a mask. The metal layer is removed by an etching solution to form a metal pattern. Any material may be used as the dry film resist, and a negative type, a positive type, a liquid form, or a film type may be used. Further, as the etching method, any method used in the production of the printed wiring board can be used, and it can be arbitrarily selected by wet etching, dry etching, or the like. In the operation of the work, wet etching is preferable in terms of simplicity of the apparatus and the like. As the etching liquid, for example, an aqueous solution of copper chloride or ferric chloride can be used.

另外，所謂半加成法，是如下的方法：在所形成的金屬層上設置乾膜抗蝕劑層，藉由圖案曝光、顯影形成與非金屬圖案部相同的圖案，將乾膜抗蝕劑圖案作為遮罩進行電鍍，將乾膜抗蝕劑圖案除去後實施快速蝕刻，以圖案狀除去金屬層，藉此形成金屬圖案的方法。乾膜抗蝕劑、蝕刻液等可使用與減成法相同的材料。另外，電鍍方法可使用上述記載的方法。 Further, the semi-additive method is a method in which a dry film resist layer is provided on the formed metal layer, and the same pattern as that of the non-metal pattern portion is formed by pattern exposure and development, and the dry film resist is used. The pattern is formed by plating as a mask, removing the dry film resist pattern, performing rapid etching, and removing the metal layer in a pattern to form a metal pattern. A dry film resist, an etching solution, or the like can be used in the same material as the subtractive method. Further, the method described above can be used for the plating method.

另外，圖1中的(A)中，底層設置於基板的整個面上，根據需要可設置為圖案狀。在圖案狀底層配置於基板上時，藉由實施上述的步驟，而僅在圖案狀底層上形成金屬層，並獲得金屬圖案材料。 Further, in (A) of FIG. 1, the underlayer is provided on the entire surface of the substrate, and may be provided in a pattern shape as needed. When the patterned underlayer is disposed on the substrate, the metal layer is formed only on the patterned underlayer by performing the above steps, and a metal pattern material is obtained.

[用途] [use]

具有所得的圖案狀金屬層的積層體例如可應用於：半導體晶片、各種電氣配線板(例如印刷配線基板)、柔性印刷電路(Flexible Printed Circuit，FPC)、薄膜覆晶(Chip On Film，COF)、捲帶自動結合(Tape Automated Bonding，TAB)、天線、多層配線基板、母板等各種用途。其中，較佳為用作配線基板的用途。 The laminate having the obtained patterned metal layer can be applied, for example, to a semiconductor wafer, various electrical wiring boards (for example, printed wiring boards), flexible printed circuits (FPC), and chip on film (COF). , Tape Automated Bonding (TAB), antenna, multilayer wiring board, motherboard, and other applications. Among them, it is preferably used as a wiring board.

[實施例] [Examples]

以下，藉由實施例對本發明進行更詳細地說明，但本發明並不限定於這些實施例。 Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to these examples.

(氧化矽分散液的製備) (Preparation of cerium oxide dispersion)

根據以下的表1，在1000 ml的PP製瓶中添加特定量的各成分，使用TK公司製造的HomoDisper均勻分散機，以8000 rpm分散30分鐘，而獲得氧化矽分散液S01~氧化矽分散液S05。 According to the following Table 1, a specific amount of each component was added to a 1000 ml PP bottle, and a HomoDisper uniform disperser manufactured by TK Corporation was used, and dispersed at 8000 rpm for 30 minutes to obtain a cerium oxide dispersion S01 to cerium oxide dispersion. S05.

(底層形成用組成物的製備) (Preparation of composition for forming the underlayer)

根據以下的表2，將各成分混合，而製備底層形成用組成物P01~底層形成用組成物P19。 Each of the components was mixed according to the following Table 2 to prepare a composition for forming the underlayer P01 to a composition for forming the underlayer P19.

另外，表2中，化合物X是4,4,4-三氟-1-苯基-1,3-丁烷二酮，溶劑Y是環己酮。 Further, in Table 2, the compound X is 4,4,4-trifluoro-1-phenyl-1,3-butanedione, and the solvent Y is cyclohexanone.

另外，編號14中所使用的聚合物以外的編號1~編號13、編號15~編號19中所使用的聚合物，包括共軛二烯化合物單元(或經氫化的共軛二烯化合物單元)。 Further, the polymer used in No. 1 to No. 13 and No. 15 to No. 19 other than the polymer used in No. 14 includes a conjugated diene compound unit (or a hydrogenated conjugated diene compound unit).

<編號1~編號19(實施例1~實施例17、比較例1~比較例2)> <No. 1 to No. 19 (Examples 1 to 17 and Comparative Examples 1 to 2)

將底層形成用組成物P01~底層形成用組成物P19的任一種滴加至帝人杜邦(Teijin Dupont)製造的Kapton 100EN的表面上，以1000 rpm旋塗20秒。然後，以180℃烘烤15分鐘而獲 得附底層的基板S01~附底層的基板S19。 Any one of the underlayer forming composition P01 to the underlayer forming composition P19 was dropped onto the surface of Kapton 100EN manufactured by Teijin Dupont, and spin-coated at 1000 rpm for 20 seconds. Then, baking at 180 ° C for 15 minutes The substrate S01 of the bottom layer is attached to the substrate S19 of the bottom layer.

在50℃下將基板S01~基板S19的任一種於0.1%的NaOH溶液中浸漬5分鐘，藉由純水清洗2次。然後，在室溫下在Pd觸媒提供液MAT-2(上村工業)中浸漬5分鐘，藉由純水清洗2次。 Any one of the substrate S01 to the substrate S19 was immersed in a 0.1% NaOH solution at 50 ° C for 5 minutes, and washed twice with pure water. Then, it was immersed in Pd catalyst supply liquid MAT-2 (Shangcun Industrial) for 5 minutes at room temperature, and washed twice with pure water.

另外，Pd觸媒提供液MAT-2相當於本發明的鍍敷觸媒液，其pH值為11。 Further, the Pd catalyst supply liquid MAT-2 corresponds to the plating catalyst liquid of the present invention, and has a pH of 11.

接著，在36℃下將實施了上述處理的基板於還原劑MAB(上村工業)中浸漬5分鐘，藉由純水清洗2次。然後，在室溫下進一步將基板於活化處理液MEL-3(上村工業)中浸漬5分鐘，不進行清洗而在室溫下在無電鍍敷液Through-Cupper PEA(上村工業)中浸漬60分鐘，在底層上形成無電鍍敷層(厚度：1 μm)。 Next, the substrate subjected to the above treatment was immersed in a reducing agent MAB (Uemura Industries) at 36 ° C for 5 minutes, and washed twice with pure water. Then, the substrate was further immersed in the activation treatment liquid MEL-3 (Shangcun Industrial) for 5 minutes at room temperature, and immersed in an electroless plating solution, Through-Cupper PEA (Shangcun Industrial), at room temperature for 60 minutes without washing. An electroless plating layer (thickness: 1 μm) was formed on the underlayer.

接著，使用水1283 g、硫酸銅五水合物135 g、98%濃硫酸342 g、36%濃鹽酸0.25 g、ET-901M(羅門哈斯(Rohm & Haas))39.6 g的混合溶液作為電解鍍敷液，將形成有無電鍍敷層的基板與銅板安裝於固定器上與電源連接，以3 A/dm²進行45分鐘的電解鍍銅處理，而獲得具有約18 μm的鍍銅層(金屬層)的積層體(編號1~編號19)。 Next, a mixed solution of water 1283 g, copper sulfate pentahydrate 135 g, 98% concentrated sulfuric acid 342 g, 36% concentrated hydrochloric acid 0.25 g, and ET-901M (Rohm & Haas) 39.6 g was used as the electrolytic plating. The liquid is applied, and the substrate on which the electroless plating layer is formed and the copper plate are mounted on the holder and connected to the power source, and electrolytic copper plating is performed at 3 A/dm ² for 45 minutes to obtain a copper plating layer (metal layer) having about 18 μm. The layered body (number 1 to number 19).

(密接性評價(之一)) (Adhesion evaluation (one))

將編號1~編號19(實施例及比較例)中所得的積層體以180℃烘烤15分鐘。在所得的樣品的金屬層上隔開10 mm的間 隔，平行地切入130 mm的切口，藉由裁刀於其端部切入切口並提昇10 mm。抓住經剝離的端部並使用TENSILON(島津(SHIMAZU))測定剝離強度(拉伸速度50 mm/min)。將結果匯總示於表3。 The laminate obtained in No. 1 to No. 19 (Examples and Comparative Examples) was baked at 180 ° C for 15 minutes. Separating 10 mm between the metal layers of the resulting sample Separately, cut a 130 mm incision in parallel, and cut the incision at the end by a cutter and lift it by 10 mm. The peeled end was grasped and the peel strength (tensile speed 50 mm/min) was measured using TENSILON (SHIMAZU). The results are summarized in Table 3.

另外，將密接性為0.8 kN/m以上的情形設為「A」，將密接性為0.6 kN/m以上且小於0.8 kN/m的情形設為「B」，將密接性小於0.6 kN/m的情形設為「C」。實用上，只要為A或B即可。 In addition, the case where the adhesion is 0.8 kN/m or more is "A", the case where the adhesion is 0.6 kN/m or more and less than 0.8 kN/m is "B", and the adhesion is less than 0.6 kN/m. The situation is set to "C". Practically, it is only required to be A or B.

(異物觀察) (foreign object observation)

藉由日立高新技術(Hitachi High-Technologies)公司製造的S-3000，觀察具有金屬層的積層體(編號1~編號19)的金屬層表面，並評價異物的有無。另外，異物的判斷例如如圖2所示般，在金屬表面上觀測物質(凸上物)，且進行能量色散X射線能譜(Energy Dispersive X-ray spectroscopy，EDX)分析，在包含Ca或Al等構成金屬層的金屬離子以外的成分的情形，判斷為異物。將結果匯總示於表3。 The surface of the metal layer of the layered body (No. 1 to No. 19) having a metal layer was observed by S-3000 manufactured by Hitachi High-Technologies Co., Ltd., and the presence or absence of foreign matter was evaluated. In addition, as shown in FIG. 2, for example, a foreign matter is observed on a metal surface, and an energy dispersive X-ray spectroscopy (EDX) analysis is performed on the surface of the metal, and Ca or Al is contained. In the case of a component other than the metal ion constituting the metal layer, it is determined as a foreign matter. The results are summarized in Table 3.

(剖面觀察) (section observation)

將1 cm²(1 cm×1 cm)的積層體(編號1~編號19)固定於壓克力塊(Acrylic Block)，放入至專用模具，將丙烯酸系樹脂Acrylic One(丸都(MARUTO)股份有限公司)注入至模具後，藉由曝光裝置ONE LIGHT(丸都股份有限公司)進行2小時曝光使丙烯酸系樹脂硬化。硬化後，藉由丙酮清洗，藉由研磨裝置ML-160A(丸都股份有限公司)使用#400的研磨紙進行研磨直至 露出基板表面為止，然後藉由Baikaloy1.0CR(貝考基國際公司(BAIKOWSKI INTERNATIONAL CORPORATION))進行研磨直至成為鏡面為止。然後，在表面蒸鍍防帶電(charge up)用金後，藉由日立高新技術S-3000觀察積層體的剖面(相對於金屬層而垂直面的剖面)。 Fix a 1 cm ² (1 cm × 1 cm) laminate (No. 1 to No. 19) to an Acrylic Block and place it in a special mold. Acrylic One (MARUTO) After the injection into the mold, the acrylic resin was cured by exposure to ONE LIGHT (Maru Co., Ltd.) for 2 hours. After hardening, it was washed with acetone, and ground by a grinding apparatus ML-160A (Maru Co., Ltd.) using #400 abrasive paper until the surface of the substrate was exposed, and then by Baikaloy 1.0 CR (BAIKOWSKI) INTERNATIONAL CORPORATION)) Grinding until it becomes a mirror. Then, after vapor deposition of gold for charge up on the surface, the cross section of the laminate (cross section perpendicular to the metal layer) was observed by Hitachi High-Tech S-3000.

另外，底層的表層區域中的金屬部分的面積率，是使用圖像解析軟體「winROOF」對剖面SEM圖進行解析而算出。 In addition, the area ratio of the metal portion in the surface layer region of the bottom layer is calculated by analyzing the cross-sectional SEM image using the image analysis software "winROOF".

表3中，「氰基率」表示聚合物中的具有氰基的重複單元的含量(莫耳%)。「氧化矽粒徑」表示底層中的氧化矽粒子的平均粒徑。「氧化矽濃度」表示底層中相對於聚合物與氧化矽粒子(金屬氧化物粒子)的合計質量的氧化矽粒子的含量(質量%)。 In Table 3, "cyano group rate" means the content (% by mole) of a repeating unit having a cyano group in the polymer. The "cerium oxide particle diameter" means the average particle diameter of the cerium oxide particles in the underlayer. The "cerium oxide concentration" indicates the content (% by mass) of the cerium oxide particles in the underlayer relative to the total mass of the polymer and the cerium oxide particles (metal oxide particles).

另外，表3中，「表面的異物的有無」是指金屬層表面的異物的有無。 In addition, in Table 3, "the presence or absence of foreign matter on the surface" means the presence or absence of foreign matter on the surface of the metal layer.

如表3所示般，在實施例1~實施例17中，在所得的金屬層的表面未觀察到異物，且金屬層的密接性亦優異。 As shown in Table 3, in Examples 1 to 17, no foreign matter was observed on the surface of the obtained metal layer, and the adhesion of the metal layer was also excellent.

其中，如根據實施例1~實施例5的比較可知般，金屬氧化物粒子的含量相對於金屬氧化物粒子與聚合物的合計質量，為25質量%~45質量%時(實施例2及實施例3)，確認到金屬層的密接性更優異。 In the case of the comparison of Examples 1 to 5, the content of the metal oxide particles is from 25% by mass to 45% by mass based on the total mass of the metal oxide particles and the polymer (Example 2 and implementation) In Example 3), it was confirmed that the adhesion of the metal layer was more excellent.

另外，如根據實施例6~實施例8的比較可知般，在金屬氧化物粒子的平均粒徑為100 nm以下時，確認到金屬層的密接性更優異。 In addition, as is clear from the comparison of Example 6 to Example 8, when the average particle diameter of the metal oxide particles is 100 nm or less, it is confirmed that the adhesion of the metal layer is more excellent.

另外，如根據實施例9~實施例12的比較可知般，在聚合物中的具有相互作用性基的單元的含量為20莫耳%以上時，確認到金屬層的密接性更優異。 Further, as is clear from the comparison of Examples 9 to 12, when the content of the unit having an interactive group in the polymer is 20 mol% or more, it is confirmed that the adhesion of the metal layer is more excellent.

另一方面，本發明的範圍外的比較例1~比較例2中，鍍敷未析出。 On the other hand, in Comparative Example 1 to Comparative Example 2 outside the scope of the present invention, plating did not precipitate.

另外，在實施例2中所得的積層體的剖面SEM圖(圖3)中，金屬成分自金屬層向底層延伸，而確認到錨定結構。根據該結構，而推測金屬層的密接性提高。 Further, in the cross-sectional SEM image (Fig. 3) of the layered product obtained in Example 2, the metal component was extended from the metal layer to the bottom layer, and the anchor structure was confirmed. According to this configuration, it is estimated that the adhesion of the metal layer is improved.

另外，圖4表示使用圖像解析軟體「winROOF」，對圖3的剖面SEM圖解析自連續的金屬界面起位於500 nm以內的金屬部分的面積的圖。 In addition, FIG. 4 is a view showing an area of a metal portion located within 500 nm from a continuous metal interface of the cross-sectional SEM image of FIG. 3 using the image analysis software "winROOF".

<實施例18> <Example 18>

對實施例4中所得的具有無電鍍敷金屬層的積層體進行 150℃/15分鐘的熱處理後，在該積層體的金屬層表面，藉由真空貼合機(名機製作所(股)製造：MVLP-600)，以70℃、0.2 MPa層壓乾式抗蝕劑膜(日立化成(股)製造；RY3315、膜厚15 μm)。接著，在層壓了乾式抗蝕劑膜的積層體上，密接可形成JPCA-ET01所規定的梳型配線(依據JPCA-BU01-2007)的玻璃遮罩，藉由中心波長405 nm的曝光機對抗蝕劑膜照射70 mJ的光能量。對曝光後的積層體以0.2 MPa的噴霧壓噴附1%Na₂CO₃水溶液，而進行顯影。然後，對積層體進行水洗、乾燥，而在金屬層上形成半加成法用抗蝕劑圖案。 After the laminate having the electroless plated metal layer obtained in Example 4 was subjected to a heat treatment at 150 ° C for 15 minutes, the surface of the metal layer of the laminate was produced by a vacuum laminator (Made Machine Co., Ltd.): MVLP-600), a dry resist film (manufactured by Hitachi Chemical Co., Ltd.; RY3315, film thickness: 15 μm) was laminated at 70 ° C and 0.2 MPa. Next, on the laminated body on which the dry resist film is laminated, a glass mask which can form a comb type wiring (according to JPCA-BU01-2007) prescribed by JPCA-ET01 is adhered, by an exposure machine having a center wavelength of 405 nm. The resist film was irradiated with light energy of 70 mJ. The exposed laminate was sprayed with a 1% Na ₂ CO ₃ aqueous solution at a spray pressure of 0.2 MPa to develop. Then, the laminate is washed with water and dried to form a resist pattern for a semi-additive method on the metal layer.

在形成了抗蝕劑圖案的積層體的抗蝕劑圖案外形成10 μm電鍍銅，在積層體上以0.2 MPa的噴霧壓噴附3%NaOH水溶液，藉此將抗蝕劑圖案膨潤剝離。藉由硫酸/過氧化氫水溶液(蝕刻液)進行蝕刻，將無電鍍敷厚部分的金屬層除去，藉此獲得梳型配線(圖案狀金屬層)(參照圖5)。所得的配線為L/S=10 μm/10 μm。 10 μm of electroplated copper was formed outside the resist pattern of the laminate in which the resist pattern was formed, and a 3% aqueous NaOH solution was sprayed on the laminate at a spray pressure of 0.2 MPa to swell and peel the resist pattern. The metal layer of the electroless thick portion is removed by etching with a sulfuric acid/hydrogen peroxide aqueous solution (etching liquid) to obtain a comb-shaped wiring (pattern metal layer) (see FIG. 5). The resulting wiring was L/S = 10 μm/10 μm.

(底層形成用組成物的製備) (Preparation of composition for forming the underlayer)

根據以下的表4將各成分混合，而製備底層形成用組成物Y1~底層形成用組成物Y9及底層形成用組成物X1~底層形成用組成物X2。另外，對於底層形成用組成物Y4、底層形成用組成物Y5及底層形成用組成物Y9，在調液後進行30分鐘以上攪拌。表4所記載的各成分的詳細內容如以下所述。另外，表4中的數值表示質量%。 The components for the underlayer formation Y1 to the underlayer formation composition Y9 and the underlayer formation composition X1 to the underlayer formation composition X2 were prepared by mixing the respective components according to the following Table 4. In addition, the composition for forming the underlayer Y4, the composition for forming the underlayer Y5, and the composition for forming the underlayer Y9 are stirred for 30 minutes or more after the liquid adjustment. The details of each component described in Table 4 are as follows. In addition, the numerical values in Table 4 represent the mass %.

‧聚合物1：Tuftec M1943(使順丁烯二酸酐接枝共聚合而成的氫化苯乙烯丁二烯共聚物、旭化成製造) ‧ Polymer 1: Tuftec M1943 (hydrogenated styrene butadiene copolymer obtained by graft copolymerization of maleic anhydride, manufactured by Asahi Kasei)

‧聚合物2：Tuftec H1052X(氫化苯乙烯丁二烯共聚物、旭化成製造) ‧Polymer 2: Tuftec H1052X (hydrogenated styrene butadiene copolymer, manufactured by Asahi Kasei)

‧聚合物3：Zetpol 0020(氫化丙烯腈丁二烯橡膠、日本瑞翁製造) ‧Polymer 3: Zetpol 0020 (hydrogenated acrylonitrile butadiene rubber, manufactured by Ryan, Japan)

‧聚合物4：丙烯腈-苯乙烯共聚合樹脂(AS樹脂)(商品No：182869、阿爾多里奇(Aldrich)公司製造) ‧ polymer 4: acrylonitrile-styrene copolymer resin (AS resin) (product No. 182869, manufactured by Aldrich)

‧氧化鋁：氧化鋁(粒徑：40 nm~50 nm、和光純藥製造) ‧Alumina: Alumina (particle size: 40 nm~50 nm, manufactured by Wako Pure Chemical Industries, Ltd.)

‧氧化鐵：氧化鐵(III)(氧化鐵、粒徑：20 nm~40 nm、和光純藥製造) ‧ Iron Oxide: Iron (III) oxide (iron oxide, particle size: 20 nm~40 nm, manufactured by Wako Pure Chemical Industries, Ltd.)

‧氧化矽：Silfil NSS-4N(粒徑：90 nm、德山製造) ‧Oxide: Silfil NSS-4N (particle size: 90 nm, manufactured by Tokuyama)

‧分散劑1：SOLSPERSE36000(路博潤製造) ‧Dispersant 1: SOLSPERSE36000 (made by Lubrizol)

‧分散劑2：SOLSPERSE24000(路博潤製造) ‧ Dispersant 2: SOLSPERSE 24000 (made by Lubrizol)

‧PR54046(甲酚酚醛清漆樹脂、住友貝克萊特(SUMITOMO BAKELITE)製造) ‧PR54046 (cresol novolac resin, manufactured by SUMITOMO BAKELITE)

‧KBM-5103(矽烷偶合劑、信越化學工業製造) ‧KBM-5103 (decane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.)

<實施例19~實施例27及比較例3~比較例4> <Example 19 to Example 27 and Comparative Example 3 to Comparative Example 4>

根據以下的表5，藉由旋塗法在基板上塗佈底層形成用組成物，並以180℃乾燥60分鐘。藉此在基板上形成底層(厚度：2.8 μm)。 According to the following Table 5, the composition for forming a primer layer was applied onto the substrate by spin coating, and dried at 180 ° C for 60 minutes. Thereby, a bottom layer (thickness: 2.8 μm) was formed on the substrate.

接著，在50℃下將形成有底層的基板於Alkapp ACL(2-胺基乙醇：4.9質量%、二伸乙基三胺：2.4質量%、界面活性劑：4.9質量%、上村工業(股)製造)95 g與氫氧化鈉5 g的混合液(pH值：14)中浸漬5分鐘，然後進行水洗。接著，在26℃下於作為Pd觸媒提供液的Alkapp MAT-2(上村工業(股)製造)中浸漬5分鐘，然後在37℃下於作為還原劑的Alkapp MAB(上村工業(股)製造)中浸漬3分鐘，然後進行水洗。接著，在26℃下於作為活化處理液的Alkapp MEL(上村工業(股)製造)中浸漬1分鐘，然後在37℃下於作為無電鍍敷液的Through-Cupper PEA中浸漬30分鐘，並進行無電鍍敷。藉此在底層上形成無電鍍敷層(厚度：約0.7 μm)。 Next, the substrate on which the underlayer was formed was subjected to Alkapp ACL at 50 ° C (2-aminoethanol: 4.9% by mass, di-ethyltriamine: 2.4% by mass, surfactant: 4.9% by mass, and Shangcun Industrial Co., Ltd.) Manufactured) A mixture of 95 g and 5 g of sodium hydroxide (pH: 14) was immersed for 5 minutes and then washed with water. Next, it was immersed in Alkapp MAT-2 (manufactured by Uemura Industrial Co., Ltd.) as a Pd catalyst supply liquid at 26 ° C for 5 minutes, and then at 37 ° C in Alkapp MAB (Shang Cun Industrial Co., Ltd.) as a reducing agent. Immersed for 3 minutes and then washed with water. Subsequently, it was immersed in Alkapp MEL (manufactured by Uemura Kogyo Co., Ltd.) as an activation treatment liquid at 26 ° C for 1 minute, and then immersed in a through-coat PEA as an electroless plating solution at 37 ° C for 30 minutes, and was carried out. Electroless plating. Thereby, an electroless plating layer (thickness: about 0.7 μm) was formed on the underlayer.

接著，將所形成的無電鍍敷層設為供電層，使用下述組成的電鍍銅浴，在3 A/dm²的條件下進行30分鐘電鍍，而獲得具有金屬層的積層體。電鍍銅層的厚度為13 μm。 Next, the formed electroless plating layer was used as a power supply layer, and electroplating was performed for 30 minutes under conditions of 3 A/dm ² using an electroplating copper bath having the following composition to obtain a layered body having a metal layer. The thickness of the electroplated copper layer is 13 μm.

另外，Pd觸媒提供液Alkapp MAT-2相當於本發明的鍍敷觸媒液，其pH值為鹼性。 Further, the Pd catalyst supply liquid Alkapp MAT-2 corresponds to the plating catalyst liquid of the present invention, and its pH is alkaline.

(電鍍浴的組成) (composition of electroplating bath)

‧硫酸銅：38 g ‧ Copper sulfate: 38 g

‧硫酸：95 g ‧ sulfuric acid: 95 g

‧鹽酸：1 mL ‧ Hydrochloric acid: 1 mL

‧Copper Gleam PCM(美錄德(Meltex)(股)製造)：3 mL ‧Copper Gleam PCM (Meltex (manufactured)): 3 mL

‧水：500 g ‧Water: 500 g

(異物觀察) (foreign object observation)

對於實施例19~實施例27及比較例3~比較例4中所得的積層體，藉由目視對金屬層表面進行異物觀察，並評價異物的有無。將結果匯總示於表5。 With respect to the laminates obtained in Examples 19 to 27 and Comparative Examples 3 to 4, foreign matter was observed by visual observation of the surface of the metal layer, and the presence or absence of foreign matter was evaluated. The results are summarized in Table 5.

(密接性評價(之二)) (Adhesion evaluation (Part 2))

將實施例19~實施例27及比較例3~比較例4中所得的積層體在180℃下保持1小時後，在金屬層上隔開5 mm的間隔，並平行地切入130 mm的切口，藉由裁刀於其端部切入切口並提昇10 mm。使用拉伸試驗機(A&D(股)製造、RTM-100)，抓住經剝離的金屬層端部並測定90°剝離強度(拉伸速度10 mm/min)。將結果匯總示於表5。實用上，較佳為0.50 kN/m以上。 The laminates obtained in Examples 19 to 27 and Comparative Examples 3 to 4 were held at 180 ° C for 1 hour, and then a gap of 5 mm was placed on the metal layer, and a slit of 130 mm was cut in parallel. Cut the incision at its end by a knife and raise it by 10 mm. The end of the peeled metal layer was grasped using a tensile tester (manufactured by A&D Co., Ltd., RTM-100), and the 90° peel strength (tensile speed: 10 mm/min) was measured. The results are summarized in Table 5. Practically, it is preferably 0.50 kN/m or more.

表5中，「金屬氧化物濃度」表示底層中相對於聚合物與金屬氧化物粒子的合計質量的金屬氧化物粒子的含量(質量%)。 In Table 5, the "metal oxide concentration" indicates the content (% by mass) of the metal oxide particles in the underlayer relative to the total mass of the polymer and the metal oxide particles.

另外，表5中，「表面的異物的有無」是指金屬層表面的異物的有無。 In addition, in Table 5, "the presence or absence of the foreign matter on the surface" means the presence or absence of the foreign material on the surface of the metal layer.

如表5所示般，在實施例19~實施例27中，在所得的金屬層的表面未觀察到異物，且金屬層的密接性亦優異。 As shown in Table 5, in Examples 19 to 27, no foreign matter was observed on the surface of the obtained metal layer, and the adhesion of the metal layer was also excellent.

根據實施例24與實施例25的比較確認到，聚合物具有氰基的實施例25的金屬層的密接性更優異。根據實施例25與實施例26的比較確認到，金屬氧化物粒子包含矽的實施例25的金 屬層的密接性更優異。 According to the comparison between Example 24 and Example 25, it was confirmed that the metal layer of Example 25 in which the polymer had a cyano group was more excellent in adhesion. According to the comparison between Example 25 and Example 26, it was confirmed that the metal oxide particles contained the gold of Example 25 of ruthenium. The adhesion of the genus layer is more excellent.

另一方面，底層不含金屬氧化物粒子的比較例3中，鍍敷未析出。另外，聚合物不含共軛二烯化合物單元的比較例4中，金屬層的密接性不充分。 On the other hand, in Comparative Example 3 in which the underlayer contained no metal oxide particles, plating did not precipitate. Further, in Comparative Example 4 in which the polymer did not contain the conjugated diene compound unit, the adhesion of the metal layer was insufficient.

<實施例28~實施例34> <Example 28 to Example 34>

使用擺動碾壓機(rocking mill)RM-05(成和技研(Seiwa Giken)(股))，在投入樣品量60 g(使用200 mL PP瓶)、0.5 mmφ的氧化鋯珠100 g、50 Hz、30 min的條件下，使根據以下的表6的比率而投入的樣品分散，而獲得氧化矽分散液W1~氧化矽分散液W7。 Using a rocking mill RM-05 (Seiwa Giken), a sample volume of 60 g (using a 200 mL PP bottle), 0.5 mmφ zirconia beads 100 g, 50 Hz Under the conditions of 30 min, the sample charged according to the ratio of Table 6 below was dispersed to obtain a cerium oxide dispersion W1 to cerium oxide dispersion W7.

另外，表6中的「Aerosil 200」是使用艾羅西爾公司製造。 In addition, "Aerosil 200" in Table 6 was manufactured using Aerosil.

根據以下的表7，將各成分混合，使用擺動碾壓機RM-05(成和技研(股))，在投入量60 g(使用200 mL PP瓶)、0.5 mmφ的氧化鋯珠100 g、50 Hz、30 min的條件下進行分散，而製備底 層形成用組成物Y10~底層形成用組成物Y16。 According to the following Table 7, the components were mixed, using a oscillating roller compactor RM-05 (Chenghe Technology Co., Ltd.), an input amount of 60 g (using a 200 mL PP bottle), a 0.5 mmφ zirconia bead 100 g, Dispersion at 50 Hz, 30 min, and preparation The layer forming composition Y10 to the underlayer forming composition Y16.

另外，表7中，「Zetpol 0020」是使用日本瑞翁公司製造。 In addition, in Table 7, "Zetpol 0020" is manufactured by the Japanese company.

使用上述中所製造的底層形成用組成物Y10~底層形成用組成物16，代替編號1~編號19(實施例1~實施例17、比較例1~比較例2)中所使用的底層形成用組成物P01~底層形成用組成物P19，除此以外，根據與編號1~編號19相同的順序，製造具有鍍銅層(金屬層)的積層體，並進行密接性評價(之二)及異物觀察。將結果匯總示於表8。另外，表8中，「底層形成用組成物」欄表示各實施例中所使用的組成物的種類。 The underlayer forming composition Y10 to the underlayer forming composition 16 produced in the above was used instead of the underlayer forming used in the numbers 1 to 19 (Examples 1 to 17 and Comparative Examples 1 to 2). In the same procedure as No. 1 to No. 19, a laminate having a copper plating layer (metal layer) was produced, and the adhesion evaluation (Part 2) and foreign matter were performed, except for the composition P01 to the underlayer formation composition P19. Observed. The results are summarized in Table 8. In addition, in the column of "the composition for forming an underlayer" in Table 8, the type of the composition used in each Example is shown.

如表8所示般，在使用底層形成用組成物Y10~底層形成用組成物16而製造的積層體中，在金屬層的表面未觀察到異物，且金屬層的密接性亦優異。 As shown in Table 8, in the laminate produced by using the composition for forming the underlayer formation Y10 to the underlayer formation composition 16, no foreign matter was observed on the surface of the metal layer, and the adhesion of the metal layer was also excellent.

(分散穩定性評價) (Dispersion stability evaluation)

在5℃條件下，將底層形成用組成物Y10~底層形成用組成物Y16靜置保管10天。 The composition for forming the underlayer layer Y10 to the composition for forming the underlayer Y16 was allowed to stand still for 10 days under the conditions of 5 °C.

在不含分散劑(界面活性劑)的底層形成用組成物Y10中，隨著時間的經過，確認到氧化矽粒子的凝聚物(以下亦稱為氧化矽凝聚物)。但是藉由定期振盪底層形成用組成物Y10，而可抑制氧化矽凝聚物的生成。 In the composition Y10 for forming the underlayer containing no dispersant (surfactant), agglomerates of cerium oxide particles (hereinafter also referred to as cerium oxide agglomerates) were observed as time passed. However, by periodically oscillating the composition for forming the underlayer Y10, generation of cerium oxide agglomerates can be suppressed.

另一方面，在含分散劑(界面活性劑)的底層形成用組成物Y11~底層形成用組成物Y16中，未確認到氧化矽凝聚物的存在，而確認到保存穩定性優異。另外，在底層形成用組成物Y16中，即便是靜置保管30天的情況下，亦未確認到氧化矽凝聚物的存在，而表現優異的保存穩定性。 On the other hand, in the composition for forming the underlayer layer Y11 to the underlayer forming composition Y16 containing a dispersing agent (surfactant), the presence of the cerium oxide agglomerate was not confirmed, and it was confirmed that the storage stability was excellent. Further, in the composition for forming the underlayer Y16, even when it was left to stand for 30 days, the presence of cerium oxide agglomerates was not confirmed, and excellent storage stability was exhibited.

10‧‧‧基板 10‧‧‧Substrate

12‧‧‧底層 12‧‧‧ bottom layer

14‧‧‧金屬層 14‧‧‧metal layer

16‧‧‧積層體 16‧‧‧Layer

18‧‧‧圖案狀金屬層 18‧‧‧patterned metal layer

Claims (15)

一種積層體的製造方法，其包括：底層形成步驟，形成包含具有可氫化的共軛二烯化合物單元的聚合物、以及平均粒徑為400 nm以下的金屬氧化物粒子的底層；觸媒提供步驟，使包含鍍敷觸媒或其前驅物且為鹼性的鍍敷觸媒液、與上述底層接觸，而在上述底層上提供鍍敷觸媒或其前驅物；以及鍍敷步驟，對提供了上述鍍敷觸媒或其前驅物的上述底層進行鍍敷，而在上述底層上形成金屬層。 A method for producing a laminate comprising: a primer formation step of forming a polymer comprising a polymer having a hydrogenatable conjugated diene compound unit, and a metal oxide particle having an average particle diameter of 400 nm or less; a catalyst supply step Providing a plating catalyst liquid containing a plating catalyst or a precursor thereof and being alkaline, contacting the underlying layer, and providing a plating catalyst or a precursor thereof on the underlayer; and a plating step, provided The underlayer of the plating catalyst or its precursor is plated to form a metal layer on the underlayer. 如申請專利範圍第1項所述的積層體的製造方法，其中上述金屬氧化物粒子的平均粒徑為100 nm以下。 The method for producing a layered product according to claim 1, wherein the metal oxide particles have an average particle diameter of 100 nm or less. 如申請專利範圍第1項或第2項所述的積層體的製造方法，其中上述底層中的上述金屬氧化物粒子的含量，相對於上述聚合物與上述金屬氧化物粒子的合計質量為25質量%~45質量%。 The method for producing a laminate according to the above aspect, wherein the content of the metal oxide particles in the underlayer is 25 masses based on the total mass of the polymer and the metal oxide particles. %~45% by mass. 如申請專利範圍第1項或第2項所述的積層體的製造方法，其中上述聚合物是進一步具有含有相互作用性基的單元的聚合物。 The method for producing a laminate according to the first or second aspect of the invention, wherein the polymer is a polymer further having a unit containing an interactive group. 如申請專利範圍第1項或第2項所述的積層體的製造方法，其中上述聚合物是丙烯腈與丁二烯的共聚物或其氫化產物，上述金屬氧化物粒子為氧化矽(silica)粒子。 The method for producing a laminate according to the above aspect, wherein the polymer is a copolymer of acrylonitrile and butadiene or a hydrogenated product thereof, and the metal oxide particles are silica. particle. 如申請專利範圍第1項或第2項所述的積層體的製造方 法，其中進一步包括：將上述金屬層蝕刻為圖案狀的步驟。 The manufacturer of the laminate as described in claim 1 or 2 The method further includes the step of etching the metal layer into a pattern. 一種印刷配線基板，其具有藉由如申請專利範圍第1項至第6項中任一項所述的製造方法而製造的積層體。 A printed wiring board having a laminate produced by the production method according to any one of the first to sixth aspects of the invention. 一種底層形成用組成物，其包含具有可氫化的共軛二烯化合物單元的聚合物、以及平均粒徑為400 nm以下的金屬氧化物粒子，且藉由上述底層形成用組成物而形成的底層用於與包含鍍敷觸媒或其前驅物且為鹼性的鍍敷觸媒液接觸。 A composition for forming an underlayer comprising a polymer having a hydrogenatable conjugated diene compound unit, and a metal oxide particle having an average particle diameter of 400 nm or less and a bottom layer formed by the composition for forming the underlayer Used in contact with a plating catalyst solution containing a plating catalyst or its precursor and being alkaline. 如申請專利範圍第8項所述的底層形成用組成物，其中上述金屬氧化物粒子的平均粒徑為100 nm以下。 The composition for forming an underlayer according to claim 8, wherein the metal oxide particles have an average particle diameter of 100 nm or less. 如申請專利範圍第8項或第9項所述的底層形成用組成物，其中上述金屬氧化物粒子的含量，相對於上述聚合物與上述金屬氧化物粒子的合計質量為25質量%~45質量%。 The composition for forming a primer layer according to Item 8 or 9, wherein the content of the metal oxide particles is 25 mass% to 45 mass based on the total mass of the polymer and the metal oxide particles. %. 如申請專利範圍第8項或第9項所述的底層形成用組成物，其中上述聚合物是進一步具有含有相互作用性基的單元的聚合物。 The composition for forming a primer layer according to Item 8 or 9, wherein the polymer is a polymer further having a unit having an interactive group. 如申請專利範圍第8項或第9項所述的底層形成用組成物，其中上述聚合物是丙烯腈與丁二烯的共聚物或其氫化產物，上述金屬氧化物粒子為氧化矽粒子。 The composition for forming a primer layer according to Item 8 or 9, wherein the polymer is a copolymer of acrylonitrile and butadiene or a hydrogenated product thereof, and the metal oxide particles are cerium oxide particles. 一種積層體，其具有底層、以及與上述底層鄰接的金屬層，上述底層含有具有可氫化的共軛二烯化合物單元的聚合物及平均粒徑為400 nm以下的金屬氧化物粒子，且 對上述積層體的剖面進行掃描型電子顯微鏡(SEM)觀察時，自上述底層與上述金屬層的界面起在上述底層側方向的500 nm的表層區域中存在金屬部分，在上述表層區域中上述金屬部分的面積率為5%以上。 A laminate having a bottom layer and a metal layer adjacent to the underlayer, the underlayer comprising a polymer having a hydrogenatable conjugated diene compound unit and metal oxide particles having an average particle diameter of 400 nm or less, and When the cross section of the laminate is observed by a scanning electron microscope (SEM), a metal portion exists in a surface region of 500 nm from the interface between the underlayer and the metal layer in the bottom layer side direction, and the metal is present in the surface layer region. The area ratio of the part is 5% or more. 如申請專利範圍第13項所述的積層體，其中上述金屬部分的面積率為5%~30%。 The laminate according to claim 13, wherein the area ratio of the metal portion is 5% to 30%. 如申請專利範圍第13項或第14項所述的積層體，其中上述聚合物是丙烯腈與丁二烯的共聚物或其氫化產物，上述金屬氧化物粒子為氧化矽粒子。 The laminate according to claim 13 or 14, wherein the polymer is a copolymer of acrylonitrile and butadiene or a hydrogenated product thereof, and the metal oxide particles are cerium oxide particles.