TW202105414A

TW202105414A - Method for producing conductive substrate

Info

Publication number: TW202105414A
Application number: TW109110313A
Authority: TW
Inventors: 成田岳史
Original assignee: 日商富士軟片股份有限公司
Priority date: 2019-03-28
Filing date: 2020-03-26
Publication date: 2021-02-01
Also published as: JPWO2020196010A1; WO2020196010A1; CN113677498A

Abstract

The present invention provides a production method for a three-dimensionally shaped electroconductive substrate comprising a decorative layer and a metal layer wherein line width uniformity is excellent. This electroconductive substrate production method comprises: a step 1 of forming a pattern-shaped plating target layer on one surface side of a substrate; a step 2 of forming a decorative layer on the other surface side of the substrate to obtain a decorative layer-equipped substrate; a step 3 of deforming the decorative layer-equipped substrate to obtain a decorative layer-equipped substrate having a three-dimensional shape; a step 4 of performing plating on the pattern-shaped plating target layer on the decorative layer-equipped substrate having the three-dimensional shape to form a metal layer; and a step 5 of forming a protective layer on the substrate in such a manner as to cover the metal layer. The method further comprises a step 6 of providing a plating catalyst or a precursor thereof to the pattern-shaped plating target layer between the step 3 and the step 4; alternatively, the plating target layer precursor layer contains the plating catalyst or the precursor thereof.

Description

導電性基板的製造方法Manufacturing method of conductive substrate

本發明係有關一種導電性基板的製造方法。The present invention relates to a method for manufacturing a conductive substrate.

於基板上配置有金屬層之導電性基板使用於各種用途中。例如，近年來隨著針對行動電話或便攜式遊戲機等的觸控面板的搭載率的上升，能夠進行多點檢測之電容式觸控面板感測器用導電性基板的需求快速擴大。其中，從將具有三維形狀之觸控面板等應用於具有立體形狀之裝置的方面考慮，具有三維形狀之導電性基板備受矚目。The conductive substrate with a metal layer arranged on the substrate is used in various applications. For example, in recent years, with the increase in the mounting rate of touch panels for mobile phones, portable game consoles, and the like, the demand for conductive substrates for capacitive touch panel sensors capable of multi-point detection is rapidly increasing. Among them, from the viewpoint of applying a touch panel having a three-dimensional shape to a device having a three-dimensional shape, a conductive substrate having a three-dimensional shape has attracted attention.

專利文獻1中揭示了一種導電性基板的製造方法，其係使用了圖案狀被鍍層且具有三維形狀。Patent Document 1 discloses a method of manufacturing a conductive substrate that uses a patterned layer to be plated and has a three-dimensional shape.

[專利文獻1]國際公開第2018/034291號[Patent Document 1] International Publication No. 2018/034291

將導電性基板適用於各種用途中時，有時期望設置裝飾層。專利文獻1的實施例中揭示了在形成底漆層之前於基板的一個面上配置裝飾層而製造了導電性基板之情況。該步驟中，在基板上配置裝飾層之後，形成了圖案狀被鍍層。When applying a conductive substrate to various applications, it is sometimes desirable to provide a decorative layer. The example of Patent Document 1 discloses a case where a decorative layer is arranged on one surface of the substrate before the primer layer is formed to manufacture a conductive substrate. In this step, after the decoration layer is arranged on the substrate, the patterned layer to be plated is formed.

另一方面，近年來要求提高導電性基板的圖案狀金屬層的線寬的均勻性。線寬的均勻性是指線寬的偏差少。本發明人等發現在專利文獻1的實施例中具體地揭示之基板上配置裝飾層之後，實施形成圖案狀被鍍層之步驟而製造了導電性基板時，有時圖案狀金屬層的線寬的均勻性不夠充分而需要進一步改善。On the other hand, in recent years, it is required to improve the uniformity of the line width of the patterned metal layer of the conductive substrate. The uniformity of the line width means that the deviation of the line width is small. The inventors of the present invention found that after the decorative layer was specifically disclosed in the examples of Patent Document 1, when the step of forming a patterned layer to be plated was performed to produce a conductive substrate, the line width of the patterned metal layer might be different. The uniformity is not sufficient and needs further improvement.

鑑於上述情況，本發明的目的在於提供一種具有裝飾層和線寬的均勻性優異之金屬層，並具有三維形狀之導電性基板的製造方法。In view of the above situation, the object of the present invention is to provide a method for manufacturing a conductive substrate having a decorative layer and a metal layer with excellent line width uniformity, and having a three-dimensional shape.

本發明人對上述課題進行深入研究之結果，發現能夠藉由以下構成來解決上述課題。As a result of intensive research on the above-mentioned problems, the inventors have found that the above-mentioned problems can be solved by the following configuration.

（1）一種導電性基板的製造方法，其係具有：製程1，係對配置在基板的一個表面側且具有能夠與鍍敷觸媒或其前驅物相互作用之官能基及聚合性基之被鍍層前驅物層實施曝光處理及顯影處理而形成圖案狀被鍍層；製程2，係於基板的另一個表面側形成裝飾層而得到附裝飾層基板；製程3，係使附裝飾層基板變形而得到具有三維形狀之附裝飾層基板；製程4，係對具有三維形狀之附裝飾層基板中的圖案狀被鍍層實施鍍敷處理而形成金屬層；及製程5，係於基板上形成保護層以便覆蓋金屬層；在製程3與製程4之間進而具有對圖案狀被鍍層賦予鍍敷觸媒或其前驅物之製程6，或者被鍍層前驅物層含有鍍敷觸媒或其前驅物。（2）如（1）所述之導電性基板的製造方法，其中保護層係使用光硬化性化合物而形成之層。（3）如（1）或（2）所述之導電性基板的製造方法，其中裝飾層係使用選自包括光硬化性化合物及熱硬化性化合物之群組中之硬化性化合物而形成之層。（4）如（3）所述之導電性基板的製造方法，其中硬化性化合物選自包括胺基甲酸酯（甲基）丙烯酸酯化合物及環氧化合物之群組。（5）如（1）至（4）中任一項所述之導電性基板的製造方法，其係進而具有製程7，係於第1模具及第2模具中的一個模具上以在製程5中得到之導電性基板的裝飾層與其相接之方式配置導電性基板而使第1模具與第2模具合模，向所形成之模穴內射出樹脂而在導電性基板的保護層側上形成樹脂層。（6）如（5）所述之導電性基板的製造方法，其係在製程5與製程7之間進而具有製程8，係於保護層上形成密接層。（7）如（1）至（4）中任一項所述之導電性基板的製造方法，其係進而具有製程9，係於第1模具及第2模具中的一個模具上以在製程5中得到之導電性基板的保護層與其相接之方式配置導電性基板而使第1模具與第2模具合模，向所形成之模穴內射出樹脂而於導電性基板的裝飾層側上形成樹脂層。（8）如（7）所述之導電性基板的製造方法，其係在製程5與製程9之間進而具有製程10，係於裝飾層上形成密接層。 [發明效果](1) A method for manufacturing a conductive substrate, which has: In process 1, the precursor layer of the plated layer, which is arranged on one surface side of the substrate and has functional groups and polymerizable groups capable of interacting with the plating catalyst or its precursor, is subjected to exposure treatment and development treatment to form a patterned substrate. Plating Process 2, forming a decoration layer on the other surface side of the substrate to obtain a substrate with a decoration layer; Process 3 is to deform the substrate with decoration layer to obtain a three-dimensional shape of the substrate with decoration layer; Process 4 is to perform a plating process on the pattern-like plated layer in the substrate with a three-dimensional shape with a decorative layer to form a metal layer; and Process 5 is to form a protective layer on the substrate so as to cover the metal layer; Between the process 3 and the process 4, there is a process 6 of applying a plating catalyst or a precursor thereof to the patterned layer, or the precursor layer of the plating layer contains a plating catalyst or a precursor thereof. (2) The method of manufacturing a conductive substrate as described in (1), wherein The protective layer is a layer formed using a photocurable compound. (3) The method of manufacturing a conductive substrate as described in (1) or (2), wherein The decoration layer is a layer formed using a curable compound selected from the group consisting of a photocurable compound and a thermosetting compound. (4) The method of manufacturing a conductive substrate as described in (3), wherein The hardening compound is selected from the group consisting of urethane (meth)acrylate compounds and epoxy compounds. (5) The method for manufacturing a conductive substrate as described in any one of (1) to (4), which further has a process 7, which is attached to one of the first mold and the second mold to perform the process 5 Arrange the conductive substrate so that the decorative layer of the conductive substrate is in contact with it, the first mold and the second mold are clamped, and the resin is injected into the formed cavity to form on the protective layer side of the conductive substrate Resin layer. (6) The method for manufacturing a conductive substrate as described in (5), which further includes a process 8 between the process 5 and the process 7, which is to form an adhesion layer on the protective layer. (7) The method of manufacturing a conductive substrate as described in any one of (1) to (4), which further has a process 9, which is attached to one of the first mold and the second mold to perform in the process 5 The conductive substrate is placed in contact with the protective layer of the conductive substrate obtained in the process, the first mold and the second mold are clamped, and resin is injected into the formed cavity to form on the decorative layer side of the conductive substrate Resin layer. (8) The method for manufacturing a conductive substrate as described in (7), which further includes a process 10 between the process 5 and the process 9 to form an adhesion layer on the decoration layer. [Effects of the invention]

依本發明，能夠提供一種具有裝飾層和線寬的均勻性優異之金屬層，並具有三維形狀之導電性基板的製造方法。According to the present invention, it is possible to provide a method for manufacturing a conductive substrate having a decorative layer and a metal layer with excellent line width uniformity and a three-dimensional shape.

以下，對本發明進行詳細說明。此外，本說明書中用“～”表示之數值範圍是指，將記載於“～”的前後之數值作為下限值及上限值而含有之範圍。Hereinafter, the present invention will be described in detail. In addition, the numerical range shown with "-" in this specification means the range which contains the numerical value described before and after "-" as a lower limit and an upper limit.

作為本發明的導電性基板的製造方法的特徵，可舉出在形成圖案狀被鍍層之後形成有裝飾層。本發明人等對專利文獻1的步驟中金屬層的線寬的均勻性不夠充分的理由進行了研究之結果，發現裝飾層會影響形成圖案狀被鍍層時的曝光處理。具體而言，對被鍍層前驅物層進行曝光而形成圖案狀被鍍層時，透過被鍍層前驅物層之光的一部分於基板的與被鍍層前驅物層側相反的一側的表面反射而返回到被鍍層前驅物層。此時，若基板的與被鍍層前驅物層側相反的一側存在裝飾層，則於存在裝飾層的區域和不存在裝飾層的區域或裝飾層的顏色不同的區域等中，反射的程度不同，且會對所形成之被鍍層的線寬造成影響。若使用線寬不均勻的圖案狀被鍍層而形成金屬層，則作為結果，所形成之金屬層的線寬亦不均勻。相對於此，本發明中，在形成圖案狀被鍍層之後形成裝飾層，因此不會產生如上問題。As a feature of the manufacturing method of the conductive substrate of the present invention, a decorative layer is formed after forming a patterned layer to be plated. The inventors of the present invention have studied the reason why the line width uniformity of the metal layer is insufficient in the steps of Patent Document 1, and found that the decoration layer affects the exposure process when forming the patterned layer. Specifically, when the patterned layer is formed by exposing the plated precursor layer, part of the light passing through the plated precursor layer is reflected on the surface of the substrate on the opposite side of the plated precursor layer and returns to Precursor layer to be plated. At this time, if there is a decorative layer on the side of the substrate opposite to the precursor layer to be plated, the degree of reflection is different in the area where the decorative layer is present and the area where the decorative layer does not exist, or the area where the color of the decorative layer is different. , And will affect the line width of the formed layer. If the metal layer is formed using a patterned layer with uneven line width, the line width of the formed metal layer will also be uneven as a result. In contrast to this, in the present invention, the decorative layer is formed after the pattern-shaped plated layer is formed, so the above problem does not occur.

作為本發明的導電性基板的製造方法的一實施形態，具有以下製程1～6為較佳。製程1，係對配置在基板的一個表面側，且具有能夠與鍍敷觸媒或其前驅物相互作用之官能基及聚合性基之被鍍層前驅物層實施曝光處理及顯影處理而形成圖案狀被鍍層製程2，係於基板的另一個表面側形成裝飾層而得到附裝飾層基板製程3，係使附裝飾層基板變形而得到具有三維形狀之附裝飾層基板製程6，係對圖案狀被鍍層賦予鍍敷觸媒或其前驅物製程4，係對具有三維形狀之附裝飾層基板中的圖案狀被鍍層實施鍍敷處理而形成金屬層製程5，係於基板上形成保護層以便覆蓋金屬層此外，上述中記載了包括製程6之製造方法，但並不限定於此，只要被鍍層前驅物層含有鍍敷觸媒或其前驅物，則可以不實施製程6。以下，對各製程的步驟進行詳細說明。As an embodiment of the manufacturing method of the conductive substrate of the present invention, it is preferable to have the following processes 1 to 6. In process 1, the precursor layer to be plated, which is arranged on one surface of the substrate and has functional groups and polymerizable groups capable of interacting with the plating catalyst or its precursor, is subjected to exposure treatment and development treatment to form a pattern. To be plated Process 2, a decoration layer is formed on the other surface side of the substrate to obtain a substrate with a decoration layer Process 3 is to deform the substrate with a decorative layer to obtain a three-dimensional shape of the substrate with a decorative layer Process 6 is to apply plating catalyst or its precursor to the patterned layer Process 4 is to perform a plating process on the patterned layer in the substrate with a decorative layer with a three-dimensional shape to form a metal layer Process 5 is to form a protective layer on the substrate to cover the metal layer In addition, the manufacturing method including process 6 is described above, but it is not limited to this. As long as the precursor layer to be plated contains the plating catalyst or its precursor, process 6 may not be implemented. Hereinafter, the steps of each manufacturing process will be described in detail.

>製程1> 製程1係對配置在基板的一個表面側，且具有能夠與鍍敷觸媒或其前驅物相互作用之官能基及聚合性基之被鍍層前驅物層實施曝光處理及顯影處理而形成圖案狀被鍍層之製程。以下，首先對本製程中所使用之部件及材料進行詳細說明。>Process 1> Process 1 is to apply exposure treatment and development treatment to the precursor layer of the plated layer that is arranged on one surface side of the substrate and has functional groups and polymerizable groups that can interact with the plating catalyst or its precursor to form a patterned substrate. The process of plating. Hereinafter, the components and materials used in this process will be described in detail.

（基板）基板具有2個表面（主面），並能夠形成為具有彎曲面之三維形狀，且只要為具有自支撐性者，則其種類並無特別限制。作為基板，透明基板為較佳。透明基板是指，可見光（波長400～700nm）的透過率係60%以上之基板，該透過率係80%以上為較佳，90%以上為更佳。上限並無特別限制，但小於100%之情況多。(Substrate) The substrate has two surfaces (main surfaces) and can be formed into a three-dimensional shape having a curved surface, and as long as it is self-supporting, the type is not particularly limited. As the substrate, a transparent substrate is preferred. A transparent substrate refers to a substrate whose transmittance of visible light (wavelength 400-700nm) is 60% or more. Preferably, the transmittance is 80% or more, and more preferably 90% or more. The upper limit is not particularly limited, but it is often less than 100%.

作為基板，例如可舉出樹脂基板及玻璃基板，樹脂基板為較佳。作為樹脂基板的材料，例如可舉出聚碳酸酯系樹脂、聚丙烯酸系樹脂、聚甲基丙烯酸系樹脂、聚醚碸系樹脂、聚胺基甲酸酯系樹脂、聚酯系樹脂、聚碸系樹脂、聚醯胺系樹脂、聚芳酯系樹脂、聚烯烴系樹脂、纖維素系樹脂、聚氯乙烯系樹脂及環烯烴系樹脂。Examples of the substrate include a resin substrate and a glass substrate, and a resin substrate is preferred. Examples of materials for the resin substrate include polycarbonate resins, polyacrylic resins, polymethacrylic resins, polyether-based resins, polyurethane-based resins, polyester-based resins, and polycarbonate-based resins. Based resins, polyamide resins, polyarylate resins, polyolefin resins, cellulose resins, polyvinyl chloride resins, and cycloolefin resins.

基板的厚度並無特別限制，50μm以上的情況多，從抑制因基於鍍敷浴中的擺動的變形引起之斷線之方面考慮，200μm以上為較佳。上限並無特別限制，但2mm以下為較佳，1mm以下為更佳。又，基板可以為單層結構，亦可以為複數層結構。The thickness of the substrate is not particularly limited. It is often 50 μm or more. From the viewpoint of suppressing wire breakage due to deformation due to swing in the plating bath, 200 μm or more is preferable. The upper limit is not particularly limited, but 2 mm or less is preferable, and 1 mm or less is more preferable. In addition, the substrate may have a single-layer structure or a multiple-layer structure.

（被鍍層前驅物層）被鍍層前驅物層為配置於基板的一個表面側之層，且為用於形成後述圖案狀被鍍層之層。亦即，被鍍層前驅物層為實施硬化處理之前的未硬化狀態的層。此外，被鍍層前驅物層可以配置在基板上以便與基板直接相接，亦可以隔著其他層（例如，底漆層）而配置在基板上。(Precursor layer to be plated) The plated layer precursor layer is a layer arranged on one surface side of the substrate, and is a layer for forming a patterned layer to be plated, which will be described later. That is, the precursor layer to be plated is a layer in an unhardened state before the hardening treatment is performed. In addition, the precursor layer to be plated may be disposed on the substrate so as to directly contact the substrate, or may be disposed on the substrate via other layers (for example, a primer layer).

被鍍層前驅物層具有能夠與鍍敷觸媒或其前驅物相互作用之官能基（以下，還稱為“相互作用性基團”。）及聚合性基。於後面對相互作用性基團及聚合性基的詳細內容進行敘述。The precursor layer to be plated has a functional group capable of interacting with the plating catalyst or its precursor (hereinafter, also referred to as "interactive group") and a polymerizable group. The details of the interactive group and the polymerizable group will be described later.

被鍍層前驅物層的厚度並無特別限制，從所形成之圖案狀被鍍層能夠充分擔載鍍敷觸媒或其前驅物之方面考慮，0.05～2.0μm為較佳，0.1～1.0μm為更佳。The thickness of the precursor layer of the plated layer is not particularly limited. From the aspect that the patterned layer formed can fully support the plating catalyst or its precursor, 0.05-2.0 μm is preferred, and 0.1-1.0 μm is more preferred. good.

被鍍層前驅物層含有以下化合物X或組成物Y為較佳。化合物X：具有相互作用性基團及聚合性基之化合物組成物Y：含有具有相互作用性基團之化合物及具有聚合性基之化合物之組成物The precursor layer of the plated layer preferably contains the following compound X or composition Y. Compound X: a compound with an interactive group and a polymerizable group Composition Y: A composition containing a compound with an interactive group and a compound with a polymerizable group

化合物X係具有相互作用性基團和聚合性基之化合物。相互作用性基團是指，能夠與賦予於圖案狀被鍍層之鍍敷觸媒或其前驅物相互作用之官能團，例如，可舉出能夠與鍍敷觸媒或其前驅物形成靜電相互作用之官能團以及能夠與鍍敷觸媒或其前驅物形成配位之含氮官能團、含硫官能團及含氧官能團。作為相互作用性基團，例如可舉出胺基、醯胺基、醯亞胺基、脲基、三級胺基、銨基、脒基、三𠯤環、***環、苯并***基、咪唑基、苯并咪唑基、喹啉基、吡啶基、嘧啶基、吡𠯤基、唑啉基、喹口咢啉基、嘌呤基、三𠯤基、哌啶基、哌𠯤基、吡咯啶基、吡唑基、苯胺基、含有烷基胺結構的基、含有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、氰酸酯基等含氮官能團；醚基、羥基、酚性羥基、羧基、碳酸酯基、羰基、酯基、含有N-氧化物結構的基團、含有S-氧化物結構的基、含有N-羥基結構的基團等含氧官能團；噻吩基、硫醇基、硫脲基、硫代三聚氰酸基、苯并噻唑基、巰基三𠯤基、硫醚基、硫酮基、亞碸基、碸基、亞硫酸基、含有磺醯亞胺結構的基、含有亞硫鎓鹽結構的基、磺酸基、含有磺酸酯結構的基等含硫官能團；磷酸酯基、磷醯胺基、膦基、含有磷酸酯結構的基等含磷官能團；含有氯原子及溴原子等鹵素原子的基等，於可採用鹽結構的官能團中，亦能夠使用該等官能團的鹽。其中，由於極性高，對鍍敷觸媒或其前驅物等的吸附能高，因此羧酸基、磺酸基、磷酸基及硼酸基等離子性極性基或氰基為較佳，羧酸基或氰基為更佳。化合物X可以具有2種以上的相互作用性基團。Compound X is a compound having an interactive group and a polymerizable group. The interactive group refers to a functional group capable of interacting with the plating catalyst or its precursor provided on the patterned layer. For example, it may be capable of forming an electrostatic interaction with the plating catalyst or its precursor. Functional groups and nitrogen-containing functional groups, sulfur-containing functional groups and oxygen-containing functional groups capable of forming coordination with the plating catalyst or its precursors. As the interactive group, for example, an amine group, an amide group, an imine group, a ureido group, a tertiary amine group, an ammonium group, an amidino group, a tricyclic ring, a triazole ring, and a benzotriazole group are mentioned. , Imidazolyl, benzimidazolyl, quinolinyl, pyridinyl, pyrimidinyl, pyridinyl, oxazolinyl, quinoxinyl, purinyl, trisyl, piperidinyl, piperidine, pyrrolidine Group, pyrazolyl, aniline, alkylamine structure-containing group, isocyanuric acid structure-containing group, nitro group, nitroso group, azo group, diazo group, azide group, cyano group, cyano group Nitrogen-containing functional groups such as acid ester groups; ether groups, hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, carbonate groups, carbonyl groups, ester groups, groups containing N-oxide structure, groups containing S-oxide structure, groups containing N- Oxygen-containing functional groups such as hydroxy structure groups; thienyl, thiol, thiourea, thiocyanurate, benzothiazolyl, mercapto trithiol, thioether, thioketone, sulfenylene Sulfur-containing functional groups such as, sulfide group, sulfite group, sulfimide structure-containing group, sulfonium salt structure-containing group, sulfonic acid group, sulfonate structure-containing group, etc.; phosphate ester group, phosphoamido group Phosphorus-containing functional groups such as phosphine groups and groups containing phosphate structures; groups containing halogen atoms such as chlorine atoms and bromine atoms. Among the functional groups that can adopt salt structures, salts of these functional groups can also be used. Among them, due to its high polarity and high adsorption energy to plating catalysts or their precursors, ionic polar groups or cyano groups are preferred for carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and boric acid groups, and carboxylic acid groups or cyano groups are preferred. Cyano is more preferable. The compound X may have two or more types of interactive groups.

聚合性基係藉由能量賦予而可形成化學鍵之官能基，例如可舉出自由基聚合性基及陽離子聚合性基。其中，從反應性更優異之方面考慮，自由基聚合性基為較佳。作為自由基聚合性基，例如可舉出烯基（例：-C=-C）、丙烯酸酯基（丙烯醯氧基）、甲基丙烯酸酯基（甲基丙烯醯氧基）、衣康酸酯基、巴豆酸酯基，異巴豆酸酯基、順丁烯二酸酯基、苯乙烯基、乙烯基、丙烯醯胺基和甲基丙烯醯胺基。其中，烯基、甲基丙烯醯氧基、丙烯醯氧基、乙烯基、苯乙烯基、丙烯醯胺基或甲基丙烯醯胺基為較佳，甲基丙烯醯氧基、丙烯醯氧基或苯乙烯基為更佳。化合物X中可以具有2種以上的聚合性基。又，化合物X所具有之聚合性基的數並無特別限制，可以為1個，亦可以為2個以上。The polymerizable group is a functional group capable of forming a chemical bond by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group. Among them, a radical polymerizable group is preferred from the viewpoint of being more excellent in reactivity. Examples of radical polymerizable groups include alkenyl groups (example: -C=-C), acrylate groups (acryloxy groups), methacrylate groups (methacryloxy groups), and itaconic acid Ester group, crotonic acid ester group, isocrotonic acid ester group, maleic acid ester group, styryl group, vinyl group, acrylamide group and methacrylamide group. Among them, alkenyl, methacryloxy, acryloxy, vinyl, styryl, acrylamido or methacrylamido are preferred, methacryloxy and acryloxy Or styryl is more preferable. The compound X may have two or more types of polymerizable groups. In addition, the number of polymerizable groups that the compound X has is not particularly limited, and it may be one or two or more.

上述化合物X可以為低分子化合物，亦可以為高分子化合物。低分子化合物是指分子量小於1000的化合物，高分子化合物是指分子量為1000以上的化合物。The aforementioned compound X may be a low-molecular compound or a high-molecular compound. The low-molecular compound refers to a compound with a molecular weight of less than 1,000, and the high-molecular compound refers to a compound with a molecular weight of 1,000 or more.

當上述化合物X為聚合物時，聚合物的重量平均分子量並無特別限制，從溶解性等操作性更優異之方面考慮，1000～700000為較佳，2000～200000為更佳。該種具有聚合性基及相互作用性基團之聚合物的合成方法並無特別限制，使用公知的合成方法（參閱日本特開2009-280905號的[0097]～[0125]段）。When the above-mentioned compound X is a polymer, the weight average molecular weight of the polymer is not particularly limited. From the viewpoint of better handling properties such as solubility, 1,000 to 700,000 is preferable, and 2,000 to 200,000 is more preferable. The synthesis method of the polymer having a polymerizable group and an interactive group is not particularly limited, and a known synthesis method is used (see paragraphs [0097] to [0125] of Japanese Patent Application Publication No. 2009-280905).

組成物Y係含有具有相互作用性基團之化合物及具有聚合性基之化合物之組成物。亦即，組成物Y含有具有相互作用性基團之化合物及具有聚合性基之化合物這2種。相互作用性基團及聚合性基的定義如上所述。具有相互作用性基團之化合物可以為低分子化合物，亦可以為高分子化合物。此外，具有相互作用性基團之化合物可以含有聚合性基。作為具有相互作用性基團之化合物的較佳形態，可舉出包含具有相互作用性基團之重複單元之聚合物（例如，聚丙烯酸）。作為具有相互作用性基團之重複單元的一較佳態樣，可舉出由式（A）表示之重複單元。The composition Y is a composition containing a compound having an interactive group and a compound having a polymerizable group. That is, the composition Y contains two kinds of compounds having an interactive group and a compound having a polymerizable group. The definitions of the interactive group and the polymerizable group are as described above. The compound having an interactive group may be a low-molecular compound or a high-molecular compound. In addition, the compound having an interactive group may contain a polymerizable group. As a preferable aspect of the compound having an interactive group, a polymer (for example, polyacrylic acid) containing a repeating unit having an interactive group can be mentioned. As a preferable aspect of the repeating unit having an interactive group, a repeating unit represented by formula (A) can be cited.

[化學式1]

[Chemical formula 1]

式（A）中，R¹ 表示氫原子或烷基（例如，甲基、乙基等）。 L¹ 表示單鍵或2價連接基。2價連接基的種類並無特別限制，例如可舉出2價烴基（可以為2價飽和烴基，亦可以為2價芳香族烴基。2價飽和烴基可以為直鏈狀、支鏈狀或環狀，碳數1～20為較佳，例如可舉出伸烷基。又，2價芳香族烴基的碳數係5～20為較佳，例如可舉出伸芳基。除此以外，可以為伸烯基、伸炔基。）、2價雜環基、-O-、-S-、-SO₂ -、-NR-、-CO-（-C（=O）-）、-COO-（-C（=O）O-）、-CO-NR-、-SO₃ -、-SO₂ NR-及將該等組合2種以上而成之基團。其中，R表示氫原子或烷基（較佳為碳數1～10）。 Z表示相互作用性基團。相互作用性基團的定義如上所述。In the formula (A), R ¹ represents a hydrogen atom or an alkyl group (for example, a methyl group, an ethyl group, etc.). L ¹ represents a single bond or a divalent linking group. The type of divalent linking group is not particularly limited. For example, a divalent hydrocarbon group (which may be a divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group may be used. The divalent saturated hydrocarbon group may be linear, branched, or cyclic. For example, the carbon number of the divalent aromatic hydrocarbon group is preferably from 5 to 20, and the carbon number of the divalent aromatic hydrocarbon group is preferably from 5 to 20. For example, an aryl group can be mentioned. It is alkenylene and alkynylene.), divalent heterocyclic group, -O-, -S-, -SO ₂ -, -NR-, -CO-(-C(=O)-), -COO- (-C(=O)O-), -CO-NR-, -SO ₃ -, -SO ₂ NR-, and groups formed by combining two or more of these. Among them, R represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms). Z represents an interactive group. The definition of the interactive group is as described above.

作為具有相互作用性基團之重複單元的另一較佳態樣，可舉出源自不飽和羧酸或其衍生物之重複單元。不飽和羧酸是指，具有羧酸基（-COOH基）之不飽和化合物。關於不飽和羧酸的衍生物，例如可舉出不飽和羧酸的酸酐、不飽和羧酸的鹽、不飽和羧酸的單酯。作為不飽和羧酸，例如可舉出丙烯酸、甲基丙烯酸、巴豆酸、異巴豆酸、順丁烯二酸、富馬酸、衣康酸及檸康酸。As another preferable aspect of the repeating unit having an interactive group, a repeating unit derived from an unsaturated carboxylic acid or a derivative thereof can be mentioned. The unsaturated carboxylic acid refers to an unsaturated compound having a carboxylic acid group (-COOH group). As for derivatives of unsaturated carboxylic acids, for example, anhydrides of unsaturated carboxylic acids, salts of unsaturated carboxylic acids, and monoesters of unsaturated carboxylic acids can be cited. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid.

包含具有相互作用性基團之重複單元之聚合物中的具有相互作用性基團之重複單元的含量並無特別限制，從鍍敷析出性的平衡的方面考慮，相對於總重複單元係1～100莫耳%為較佳，10～100莫耳%為更佳。The content of the repeating unit with the interactive group in the polymer containing the repeating unit with the interactive group is not particularly limited, but from the viewpoint of the balance of plating precipitation, it is 1 to 1 relative to the total repeating unit system. 100 mol% is preferable, and 10-100 mol% is more preferable.

作為包含具有相互作用性基團之重複單元之聚合物的較佳態樣，從以較少的能量賦予量（例如，曝光量）輕鬆地形成被鍍層之方面考慮，可舉出具有源自共軛二烯化合物的重複單元及源自不飽和羧酸或其衍生物的重複單元之聚合物X。關於源自不飽和羧酸或其衍生物的重複單元的說明如上述。As a preferable aspect of a polymer containing a repeating unit having an interactive group, from the viewpoint of easily forming the layer to be plated with a small amount of energy imparted (for example, exposure amount), it is possible to include Polymer X which is a repeating unit of a conjugated diene compound and a repeating unit derived from an unsaturated carboxylic acid or its derivative. The description of the repeating unit derived from the unsaturated carboxylic acid or its derivative is as described above.

作為共軛二烯化合物，若為以1個單鍵隔開之、含有具有2個碳-碳雙鍵之分子結構之化合物，則並無特別限制。作為共軛二烯化合物，例如可舉出異戊二烯、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-丁二烯及2-對甲苯基-1,3-丁二烯。The conjugated diene compound is not particularly limited as long as it is a compound separated by a single bond and containing a molecular structure having two carbon-carbon double bonds. Examples of conjugated diene compounds include 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-nonadiene, 2,4- Nonadiene, 3,5-nonadiene, 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 and 2-p-tolyl-1 ,3-Butadiene.

其中，從容易合成聚合物X，且圖案狀被鍍層的特性更加優異之方面考慮，源自共軛二烯化合物的重複單元係源自具有由式（2）表示之丁二烯骨架之化合物的重複單元為較佳。Among them, in terms of easy synthesis of polymer X and better characteristics of the patterned layer, the repeating unit derived from the conjugated diene compound is derived from the compound having the butadiene skeleton represented by formula (2) Repeating units are preferred.

[化學式2]

[Chemical formula 2]

式（2）中，R² 分別獨立地表示氫原子、鹵素原子或烴基。作為烴基，可舉出脂肪族烴基（例如，烷基、烯基等。碳數1～12為較佳。）及芳香族烴基（例如，苯基、萘基等。）。具有複數個之R² 可以彼此相同，亦可以不同。In formula (2), R ² each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group. As the hydrocarbon group, an aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, etc.. The carbon number is preferably 1 to 12) and an aromatic hydrocarbon group (for example, a phenyl group, a naphthyl group, etc.). ^{R 2} having a plurality of R 2 may be the same or different from each other.

作為具有由式（2）表示之丁二烯骨架之化合物（具有丁二烯結構之單體），例如可舉出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。As a compound having a butadiene skeleton represented by the formula (2) (a monomer having a butadiene structure), for example, 1,3-butadiene, isoprene, 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 Diene, 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.

相對於總重複單元，聚合物X中的源自共軛二烯化合物的重複單元的含量係25～75莫耳%為較佳。相對於總重複單元，聚合物X中的源自不飽和羧酸或其衍生物的重複單元的含量係25～75莫耳%為較佳。The content of the repeating unit derived from the conjugated diene compound in the polymer X is preferably 25 to 75 mol% with respect to the total repeating units. The content of the repeating unit derived from the unsaturated carboxylic acid or its derivative in the polymer X is preferably 25 to 75 mol% with respect to the total repeating unit.

具有聚合性基之化合物為所謂單體，從所形成之圖案狀被鍍層的硬度更優異之方面考慮，具有2個以上的聚合性基之多官能單體為較佳。具體而言，多官能單體係具有2～6個聚合性基之單體為較佳。從對反應性造成影響的交聯反應中的分子的流動性的方面考慮，所使用的多官能單體的分子量係150～1000為較佳，200～800為更佳。The compound having a polymerizable group is a so-called monomer, and a polyfunctional monomer having two or more polymerizable groups is preferred from the viewpoint that the hardness of the formed patterned layer to be plated is more excellent. Specifically, a multifunctional monosystem monomer having 2 to 6 polymerizable groups is preferable. From the viewpoint of the fluidity of the molecules in the crosslinking reaction that affects the reactivity, the molecular weight of the polyfunctional monomer used is preferably 150 to 1,000, and more preferably 200 to 800.

作為多官能單體，選自包括多官能丙烯醯胺及多官能甲基丙烯醯胺之群組中之醯胺化合物為較佳。多官能丙烯醯胺含有2個以上的丙烯醯胺基。多官能丙烯醯胺中的丙烯醯胺基的數量並無特別限制，2～10個為較佳，2～5個為更佳，2個為進一步較佳。多官能甲基丙烯醯胺含有2個以上的甲基丙烯醯胺基。多官能甲基丙烯醯胺中的甲基丙烯醯胺基的數量並無特別限制，2～10個為較佳，2～5個為更佳。此外，丙烯醯胺基及甲基丙烯醯胺基分別為由以下式（B）及式（C）表示之基團。*表示鍵結位置。As the multifunctional monomer, an amide compound selected from the group consisting of multifunctional acrylamide and multifunctional methacrylamide is preferred. The polyfunctional acrylamide contains two or more acrylamide groups. The number of acrylamide groups in the multifunctional acrylamide is not particularly limited, and 2 to 10 are preferred, 2 to 5 are more preferred, and 2 is even more preferred. The multifunctional methacrylamide contains two or more methacrylamide groups. The number of methacrylamide groups in the multifunctional methacrylamide is not particularly limited, and 2-10 groups are preferable, and 2-5 groups are more preferable. In addition, the acrylamido group and the methacrylamido group are groups represented by the following formula (B) and formula (C), respectively. * Indicates the position of the bond.

[化學式3]

[Chemical formula 3]

R³ 表示氫原子或取代基。取代基的種類並無特別限制，可舉出公知的取代基（例如，可以含有雜原子之脂肪族烴基、芳香族烴基等。更具體而言，為烷基、芳基等。）。R ³ represents a hydrogen atom or a substituent. The type of the substituent is not particularly limited, and known substituents (for example, an aliphatic hydrocarbon group and an aromatic hydrocarbon group that may contain a hetero atom. More specifically, an alkyl group, an aryl group, etc.) can be mentioned.

多官能丙烯醯胺及多官能甲基丙烯醯胺具有聚氧化烯基為較佳。聚氧化烯基是指，作為重複單元而具有氧化烯基之基團。作為聚氧化烯基，由式（D）表示之基團為較佳。式（D） -（A-O）_q - A表示伸烷基。伸烷基中的碳數並無特別限制，1～4為較佳，2～3為更佳。例如，當A為碳數1的伸烷基時，-（A-O）-表示氧亞甲基（-CH₂ O-），當A為碳數2的伸烷基時，-（A-O）-表示氧伸乙基（-CH₂ CH₂ O-），當A為碳數3的伸烷基時，-（A-O）-表示氧伸丙基（-CH₂ CH（CH₃ ）O-、-CH（CH₃ ）CH₂ O-或-CH₂ CH₂ CH₂ O-）。此外，伸烷基可以是直鏈狀，亦可以是分支鏈狀。The polyfunctional acrylamide and the polyfunctional methacrylamide preferably have a polyoxyalkylene group. The polyoxyalkylene group refers to a group having an oxyalkylene group as a repeating unit. As the polyoxyalkylene group, a group represented by formula (D) is preferred. The formula (D)-(AO) _q -A represents an alkylene group. The number of carbons in the alkylene group is not particularly limited, and 1 to 4 are preferred, and 2 to 3 are more preferred. For example, when A is an alkylene group with carbon number 1, -(AO)- represents an oxymethylene group (-CH ₂ O-), and when A is an alkylene group with carbon number 2, -(AO)- represents Oxyethylene (-CH ₂ CH ₂ O-), when A is an alkylene with carbon number 3, -(AO)- means oxyethylene (-CH ₂ CH(CH ₃ )O-, -CH (CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-). In addition, the alkylene group may be linear or branched.

q表示氧化烯基的重複數，且表示2以上的整數。重複數並無特別限制，其中，2～10為較佳，2～6為更佳。此外，複數個氧化烯基中的伸烷基的碳數可以相同，亦可以不同。又，當含有複數種氧化烯基時，它們的鍵結順序並無特別限制，可以是無規則型，亦可以是嵌段型。q represents the repeating number of an oxyalkylene group, and represents an integer of 2 or more. The number of repetitions is not particularly limited, and among them, 2-10 is preferable, and 2-6 is more preferable. In addition, the number of carbon atoms in the alkylene group in the plurality of oxyalkylene groups may be the same or different. In addition, when a plurality of types of oxyalkylene groups are contained, the order of their bonding is not particularly limited, and it may be a random type or a block type.

被鍍層前驅物層中的化合物X（或組成物Y）的含量並無特別限制，相對於被鍍層前驅物層總質量，50質量%以上為較佳，80質量%以上為更佳。作為上限，可舉出100質量%。當被鍍層前驅物層含有組成物Y時，被鍍層前驅物層中的具有相互作用性基團之化合物的含量並無特別限制，但相對於被鍍層前驅物層總質量，10～90質量%為較佳，25～75質量%為更佳，35～65質量%為進一步較佳。此外，具有相互作用性基團之化合物與具有聚合性基之化合物的質量比（具有相互作用性基團之化合物的質量/具有聚合性基之化合物的質量）並無特別限制，從所形成之圖案狀被鍍層的強度及鍍敷適性的平衡的方面考慮，0.1～10為較佳，0.5～2為更佳。The content of the compound X (or composition Y) in the precursor layer to be plated is not particularly limited. With respect to the total mass of the precursor layer to be plated, 50% by mass or more is preferable, and 80% by mass or more is more preferable. As the upper limit, 100% by mass can be cited. When the precursor layer to be plated contains composition Y, the content of the compound having an interactive group in the precursor layer to be plated is not particularly limited, but relative to the total mass of the precursor layer to be plated, 10 to 90% by mass More preferably, 25 to 75% by mass is more preferable, and 35 to 65% by mass is still more preferable. In addition, the mass ratio of the compound having an interactive group to the compound having a polymerizable group (mass of the compound having an interactive group/mass of the compound having a polymerizable group) is not particularly limited, and it is formed from In consideration of the balance between the strength of the patterned layer and the plating suitability, 0.1-10 is preferable, and 0.5-2 is more preferable.

被鍍層前驅物層可以依需要而含有其他成分（例如，聚合起始劑、增感劑、硬化劑、聚合抑制劑、抗氧化劑、抗靜電劑、填料、阻燃劑滑劑、增塑劑或鍍敷觸媒或其前驅物）。The precursor layer to be plated may contain other ingredients as needed (for example, polymerization initiators, sensitizers, hardeners, polymerization inhibitors, antioxidants, antistatic agents, fillers, flame retardants, lubricants, plasticizers or Plating catalyst or its precursor).

被鍍層前驅物層的形成方法並無特別限制，例如可舉出使含有化合物X或組成物Y之組成物與基板接觸而於基板上形成被鍍層前驅物層之方法。使上述組成物與基板接觸之方法並無特別限制，例如可舉出將組成物塗佈於基板上之方法或將基板浸漬於組成物中之方法。此外，亦可以使上述組成物與基板接觸之後，根據需要為了從被鍍層前驅物層去除溶劑而實施乾燥處理。The method of forming the precursor layer to be plated is not particularly limited. For example, a method of contacting a composition containing compound X or composition Y with the substrate to form a precursor layer to be plated on the substrate can be mentioned. The method of bringing the above-mentioned composition into contact with the substrate is not particularly limited. For example, a method of coating the composition on the substrate or a method of immersing the substrate in the composition can be mentioned. In addition, after the above-mentioned composition is brought into contact with the substrate, a drying process may be performed to remove the solvent from the precursor layer to be plated as needed.

上述組成物可以含有溶劑。溶劑的種類並無特別限制，可舉出水及有機溶劑。作為有機溶劑，可舉出公知的有機溶劑（例如，醇系溶劑、酯系溶劑、酮系溶劑、鹵素系溶劑及烴系溶劑等）。The above composition may contain a solvent. The type of solvent is not particularly limited, and water and organic solvents can be mentioned. Examples of the organic solvent include well-known organic solvents (for example, alcohol-based solvents, ester-based solvents, ketone-based solvents, halogen-based solvents, hydrocarbon-based solvents, etc.).

（製程1的步驟）製程1中，對被鍍層前驅物層實施曝光處理及顯影處理而形成圖案狀被鍍層。曝光處理中，以圖案狀對被鍍層前驅物層照射光，以便得到所希望的圖案狀被鍍層。所使用的光的種類並無特別限制，例如可舉出紫外光及可見光。以圖案狀照射光時，使用具有規定形狀的開口部之遮罩而照射光為較佳。於被鍍層前驅物層的曝光部，被鍍層前驅物層中所含有之聚合性基被活化而產生化合物之間的交聯，並進行層的硬化。此時，為了抑制光暈而於與基板的光照射側（被鍍層前驅物層側）相反的一側的表面設置防光暈層為較佳。進而，能夠剝離防光暈層以便在使後述附裝飾層基板變形之製程及鍍敷處理製程之前去除防光暈層為更佳。(Steps of process 1) In the process 1, an exposure process and a development process are performed on the precursor layer to be plated to form a patterned layer to be plated. In the exposure treatment, the precursor layer to be plated is irradiated with light in a pattern to obtain a desired pattern to be plated. The kind of light used is not particularly limited, and examples include ultraviolet light and visible light. When irradiating light in a pattern, it is preferable to irradiate light using a mask having an opening of a predetermined shape. In the exposed part of the precursor layer to be plated, the polymerizable group contained in the precursor layer to be plated is activated to generate crosslinks between the compounds, and the layer is hardened. In this case, in order to suppress halation, it is preferable to provide an anti-halation layer on the surface of the substrate opposite to the light irradiation side (the side of the precursor layer to be plated). Furthermore, it is more preferable that the anti-halation layer can be peeled off so that the anti-halation layer can be removed before the process of deforming the substrate with a decorative layer and the plating treatment process described later.

接著，對以圖案狀實施了硬化處理之被鍍層前驅物層實施顯影處理，藉此未曝光部被去除而形成圖案狀被鍍層。顯影處理的方法並無特別限制，依所使用的材料的種類實施最佳的顯影處理。作為顯影液，例如可舉出有機溶劑、純水及鹼水溶液。Next, a development process is performed on the to-be-plated precursor layer that has been hardened in a pattern, whereby the unexposed part is removed to form a pattern-like to-be-plated layer. The method of the development treatment is not particularly limited, and the best development treatment is performed according to the type of material used. Examples of the developing solution include organic solvents, pure water, and alkaline aqueous solutions.

藉由上述步驟形成之圖案狀被鍍層為具有與鍍敷觸媒或其前驅物相互作用之官能基之層，且為以規定圖案狀配置之層。圖案狀被鍍層通常含有上述具有相互作用性基團之化合物。作為化合物，聚合物為較佳。亦即，圖案狀被鍍層含有包含具有相互作用性基團之重複單元之聚合物為較佳。當圖案狀被鍍層含有包含具有相互作用性基團之重複單元之聚合物時，上述聚合物的含量相對於圖案狀被鍍層總質量，10質量%以上為較佳，30質量%以上為更佳。上限並無特別限制，可舉出100質量%。The patterned layer to be plated formed by the above steps is a layer having functional groups that interact with the plating catalyst or its precursor, and is a layer arranged in a predetermined pattern. The patterned layer to be plated usually contains the above-mentioned compound having an interactive group. As the compound, polymers are preferred. That is, it is preferable that the patterned layer to be plated contains a polymer containing a repeating unit having an interactive group. When the patterned layer contains a polymer containing a repeating unit having an interactive group, the content of the polymer relative to the total mass of the patterned layer is preferably 10% by mass or more, more preferably 30% by mass or more . The upper limit is not particularly limited, and 100% by mass can be mentioned.

後述鍍敷層沿圖案狀被鍍層的圖案花紋而配置。因此，對應於欲形成之鍍敷層的形狀而將圖案狀被鍍層配置在基板上，藉此形成所希望的形狀的圖案狀被鍍層。此外，圖1中示出圖案狀被鍍層12以網格狀配置在基板10上之形態，但本發明並不限定於該形態，而圖案狀被鍍層可以配置成其他圖案花紋狀（例如，條狀）。The plating layer described later is arranged along the pattern of the patterned layer to be plated. Therefore, the patterned layer to be plated is arranged on the substrate corresponding to the shape of the plating layer to be formed, thereby forming the patterned layer to be plated in a desired shape. In addition, FIG. 1 shows a form in which the patterned layer 12 is arranged on the substrate 10 in a grid pattern, but the present invention is not limited to this form, and the patterned layer may be arranged in other patterns (for example, strips). shape).

圖案狀被鍍層的厚度並無特別限制，從能夠充分擔載鍍敷觸媒或其前驅物，並且防止鍍敷異常之方面考慮，0.05～2.0μm為較佳，0.1～1.0μm為更佳。The thickness of the patterned layer to be plated is not particularly limited. In terms of being able to fully support the plating catalyst or its precursor and preventing plating abnormalities, 0.05 to 2.0 μm is preferable, and 0.1 to 1.0 μm is more preferable.

當圖案狀被鍍層為網格狀時，構成網格之細線部的線寬W並無特別限制，從鍍敷層的導電特性及視覺辨認難度的平衡的方面考慮，30μm以下為較佳，15μm以下為更佳，10μm以下為進一步較佳，5μm以下為特佳，0.5μm以上為較佳，1μm以上為更佳。When the patterned layer is grid-shaped, the line width W of the fine line portion constituting the grid is not particularly limited. From the viewpoint of the balance between the conductive properties of the plating layer and the difficulty of visual recognition, 30μm or less is preferred, 15μm The following is more preferable, 10 μm or less is more preferable, 5 μm or less is particularly preferable, 0.5 μm or more is preferable, and 1 μm or more is more preferable.

當圖案狀被鍍層為網格狀時，網格的開口部（圖1中為開口部14）具有大致菱形形狀為較佳。但，除此以外，亦可以為多邊形狀（例如，三角形、四邊形、六邊形及無規多邊形）。又，可以將一邊的形狀設為直線狀，且其餘設為彎曲狀，亦可以設為圓弧狀。設為圓弧狀時，例如關於相對向的兩邊，可以設為向外側凸出的圓弧狀，且關於其他相對向的兩邊，可以設為向內側凸出的圓弧狀。又，可以將各邊的形狀設為向外側凸出的圓弧與向內側凸出的圓弧連續之波浪線狀。當然，亦可以將各邊的形狀設為正弦曲線。When the pattern-like plated layer is in a grid shape, the opening portion of the grid (the opening portion 14 in FIG. 1) preferably has a substantially rhombus shape. However, in addition to this, it may also be polygonal (for example, triangles, quadrilaterals, hexagons, and random polygons). In addition, the shape of one side may be linear, and the rest may be curved, or it may be arc-shaped. In the case of an arc shape, for example, the two opposing sides may have an arc shape that protrudes outward, and the other opposing sides may be an arc shape that protrudes inward. In addition, the shape of each side may be a wavy line in which an arc projecting outward and an arc projecting inward are continuous. Of course, the shape of each side can also be sinusoidal.

開口部的一邊的長度L並無特別限制，1500μm以下為較佳，1300μm以下為更佳，1000μm以下為進一步較佳，5μm以上為較佳，30μm以上為更佳，80μm以上為進一步較佳。當開口部的邊的長度在上述範圍內時，進而還能夠良好地保持透明性，將導電性基板安裝於顯示裝置的前面時，能夠視覺辨認顯示而無不適感。The length L of one side of the opening is not particularly limited. It is preferably 1500 μm or less, more preferably 1300 μm or less, more preferably 1000 μm or less, preferably 5 μm or more, more preferably 30 μm or more, and even more preferably 80 μm or more. When the length of the side of the opening is within the above-mentioned range, the transparency can be maintained well, and when the conductive substrate is mounted on the front surface of the display device, the display can be visually recognized without discomfort.

又，從透過率的方面考慮，相對於透明基板的所有表面積，形成圖案狀被鍍層之區域係50面積%以下為較佳，40面積%以下為更佳，30面積%以下為進一步較佳。In addition, from the perspective of transmittance, it is preferable that the area where the patterned layer is formed is 50 area% or less, more preferably 40 area% or less, and more preferably 30 area% or less relative to the entire surface area of the transparent substrate.

>製程2> 製程2係於基板的另一個表面側形成裝飾層而得到附裝飾層基板之製程。藉由實施本製程，可得到依次具有圖案狀被鍍層、基板及裝飾層之附裝飾層基板。此外，裝飾層可以配置在基板的另一個表面側的整個面，亦可以配置在其一部分。亦即，裝飾層只要形成於基板的另一個表面側的至少一部分即可。此外，從基板表面的法線方向觀察時，裝飾層僅配置於形成圖案狀被鍍層之區域的一部分之情況多。換言之，於基板的表面方向上，裝飾層被配置成與圖案狀被鍍層的一部分重複之情況多。例如，裝飾層可以以鑲邊狀配置於上述基板的周邊部。此外，裝飾層可以以與基板直接相接之方式配置於基板上，亦可以隔著其他層（例如，底漆層）而配置於基板上。>Process 2> Process 2 is a process of forming a decoration layer on the other surface side of the substrate to obtain a substrate with a decoration layer. By implementing this process, a substrate with a decorative layer having a patterned layer, a substrate, and a decorative layer in sequence can be obtained. In addition, the decoration layer may be arranged on the entire surface of the other surface side of the substrate, or may be arranged on a part of it. That is, the decoration layer may be formed on at least a part of the other surface side of the substrate. In addition, when viewed from the normal direction of the substrate surface, the decorative layer is often arranged only in a part of the area where the patterned layer is formed. In other words, in the surface direction of the substrate, the decoration layer is often arranged to overlap with a part of the patterned layer to be plated. For example, the decorative layer may be arranged on the peripheral portion of the above-mentioned substrate in a border shape. In addition, the decoration layer may be arranged on the substrate in a manner of directly contacting the substrate, or may be arranged on the substrate via another layer (for example, a primer layer).

裝飾層含有著色劑為較佳。此外，裝飾層可以由單一顏色構成，亦可以由複數種顏色構成。由複數種顏色構成是指，例如如裝飾層的一部分區域與其他區域的顏色不同那樣裝飾層具有複數種顏色的區域之情況。The decoration layer preferably contains a coloring agent. In addition, the decoration layer may be composed of a single color, or may be composed of multiple colors. To be constituted by a plurality of colors refers to, for example, a case where the decoration layer has an area with a plurality of colors such as a part of the decoration layer and other areas have different colors.

著色劑並無特別限制，但可舉出顏料及染料。作為顏料，可舉出無機顏料及有機顏料。作為無機顏料，例如可舉出二氧化鈦、氧化鋅、鋅鋇白、輕質碳酸鈣、白碳、氧化鋁、氫氧化鋁及硫酸鈀等白色顏料、以及碳黑、鈦黑、鈦碳、氧化鐵及鉛等黑色顏料。作為白色顏料，例如可舉出日本特開2005-007765號公報的0015段及0114段中所記載之白色顏料。The colorant is not particularly limited, but pigments and dyes can be mentioned. Examples of pigments include inorganic pigments and organic pigments. Examples of inorganic pigments include white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and palladium sulfate, as well as carbon black, titanium black, titanium carbon, and iron oxide. And black pigments such as lead. Examples of white pigments include the white pigments described in paragraphs 0015 and 0114 of JP 2005-007765 A.

作為有機顏料，例如可舉出C.I.Pigment Red 177、179、224、242、254、255、264等紅色顏料、C.I.Pigment Yellow 138、139、150、180、185等黃色顏料、C.I.Pigment Orange 36、38、71等橙色顏料、C.I.Pigment Green 7、36、58等綠色顏料、C.I.Pigment Blue 15:6等藍色顏料、C.I.Pigment Violet 23等紫色顏料。Examples of organic pigments include red pigments such as CIPigment Red 177, 179, 224, 242, 254, 255, 264, yellow pigments such as CIPigment Yellow 138, 139, 150, 180, and 185, and CIPigment Orange 36, 38. , 71 and other orange pigments, CIPigment Green 7, 36, 58 and other green pigments, CIPigment Blue 15:6 and other blue pigments, CIPigment Violet 23 and other purple pigments.

此外，當作為著色劑而使用顏料時，可以依需要而使用分散劑。In addition, when a pigment is used as a colorant, a dispersant may be used as needed.

裝飾層中的著色劑的含量並無特別限制，但相對於裝飾層總質量，1～50質量%為較佳，2～40質量%為更佳。著色劑可以單獨使用1種，亦可以同時使用2種以上。The content of the coloring agent in the decorative layer is not particularly limited, but relative to the total mass of the decorative layer, 1-50% by mass is preferred, and 2-40% by mass is more preferred. A coloring agent may be used individually by 1 type, and may use 2 or more types together.

裝飾層可以含有黏合劑。黏合劑作為用於分散上述著色劑之矩陣而發揮功能。作為黏合劑，可舉出樹脂。樹脂的種類並無特別限制，例如可舉出聚丙烯酸系樹脂、聚甲基丙烯酸系樹脂、矽酮系樹脂、聚酯系樹脂、聚胺基甲酸酯系樹脂、環氧系樹脂及聚烯烴系樹脂。其中，從裝飾層的耐鹼性優異之方面考慮，環氧系樹脂、聚胺基甲酸酯系樹脂為較佳。The decorative layer may contain an adhesive. The binder functions as a matrix for dispersing the above-mentioned colorant. As a binder, resin can be mentioned. The type of resin is not particularly limited. Examples include polyacrylic resins, polymethacrylic resins, silicone resins, polyester resins, polyurethane resins, epoxy resins, and polyolefins. Department resin. Among them, epoxy-based resins and polyurethane-based resins are preferred from the viewpoint of excellent alkali resistance of the decorative layer.

其中，黏合劑使用硬化性化合物而形成為較佳。換言之，裝飾層係使用選自包括光硬化性化合物及熱硬化性化合物之群組中之硬化性化合物而形成之層為較佳。Among them, the binder is preferably formed using a curable compound. In other words, the decorative layer is preferably a layer formed using a curable compound selected from the group consisting of a photocurable compound and a thermosetting compound.

光硬化性化合物為藉由光照射而硬化之化合物。熱硬化性化合物為藉由加熱而硬化之化合物。硬化性化合物的種類並無特別限制，能夠使用公知的硬化性化合物。其中，具有聚合性基之化合物為較佳。作為聚合性基，可舉出以上述被鍍層前驅物層所具有之聚合性基例示之基團。聚合性化合物的分子量並無特別限制，200～3000為較佳，250～2600為更佳。The photocurable compound is a compound that is cured by light irradiation. The thermosetting compound is a compound that is hardened by heating. The type of the curable compound is not particularly limited, and a known curable compound can be used. Among them, compounds having a polymerizable group are preferred. Examples of the polymerizable group include those exemplified by the polymerizable group possessed by the precursor layer to be plated. The molecular weight of the polymerizable compound is not particularly limited, but 200-3000 is preferred, and 250-2600 is more preferred.

作為硬化性化合物，胺基甲酸酯（甲基）丙烯酸酯化合物及環氧化合物為較佳。胺基甲酸酯（甲基）丙烯酸酯化合物為具有胺基甲酸酯鍵之（甲基）丙烯酸酯化合物。此外，（甲基）丙烯酸酯化合物為含有丙烯酸酯化合物及甲基丙烯酸酯化合物之概念。環氧化合物為具有環氧基之化合物。As the curable compound, a urethane (meth)acrylate compound and an epoxy compound are preferable. The urethane (meth)acrylate compound is a (meth)acrylate compound having a urethane bond. In addition, the (meth)acrylate compound is a concept containing an acrylate compound and a methacrylate compound. The epoxy compound is a compound having an epoxy group.

裝飾層中的黏合劑的含量並無特別限制，但相對於裝飾層總質量，50～99質量%為較佳，60～98質量%為更佳。黏合劑可以單獨使用1種，亦可以同時使用2種以上。The content of the binder in the decorative layer is not particularly limited, but relative to the total mass of the decorative layer, 50 to 99% by mass is preferred, and 60 to 98% by mass is more preferred. The binder may be used singly, or two or more of them may be used at the same time.

裝飾層的厚度並無特別限制，0.1～50μm為較佳，1～20μm為更佳。The thickness of the decoration layer is not particularly limited, and 0.1-50 μm is preferred, and 1-20 μm is more preferred.

（製程2的步驟）形成裝飾層之方法並無特別限制，可舉出公知的方法。例如，可舉出使含有著色劑及硬化性化合物之裝飾層形成用組成物與基板接觸而形成塗膜，並對塗膜實施硬化處理（例如，光照射處理及加熱處理）之方法及將形成在偽支撐體上之裝飾層轉印於基板上之方法。此外，裝飾層形成用組成物中可以含有除了著色劑及硬化性化合物以外的其他成分，例如可以含有溶劑及聚合起始劑。又，作為使裝飾層形成用組成物與基板接觸之方法，例如可舉出將裝飾層形成用組成物塗佈於基板上之方法或將基板浸漬於裝飾層形成用組成物中之方法。此外，可以使上述裝飾層形成用組成物與基板接觸之後，根據需要為了從塗膜去除溶劑而實施乾燥處理。(Steps of Process 2) The method of forming the decorative layer is not particularly limited, and known methods can be cited. For example, a method of contacting a composition for forming a decorative layer containing a colorant and a curable compound with a substrate to form a coating film, and applying a curing treatment (for example, light irradiation treatment and heating treatment) to the coating film, and forming A method of transferring the decorative layer on the pseudo support onto the substrate. In addition, the composition for forming a decorative layer may contain components other than the colorant and the curable compound, and may contain, for example, a solvent and a polymerization initiator. Moreover, as a method of bringing the composition for forming a decorative layer into contact with the substrate, for example, a method of applying the composition for forming a decorative layer on the substrate or a method of immersing the substrate in the composition for forming a decorative layer. In addition, after the composition for forming a decorative layer is brought into contact with the substrate, a drying process may be performed in order to remove the solvent from the coating film as necessary.

>製程3> 製程3係使附裝飾層基板變形而得到具有三維形狀之附裝飾層基板之製程。三維形狀係主要具有彎曲面之形狀為較佳。作為三維形狀，更具體而言，可舉出半圓柱形狀、波型形狀、凸凹形狀及圓柱狀等。變形（例如，熱變形）的方法並無特別限制，可舉出公知的方法。作為變形的方法，例如可舉出真空成形、吹塑成形、自由吹塑成形、壓力成形、真空-壓力成形及熱沖壓成形等公知的方法。>Process 3> Process 3 is a process of deforming the substrate with a decoration layer to obtain a three-dimensional shape of the substrate with a decoration layer. The three-dimensional shape is preferably a shape mainly having a curved surface. As a three-dimensional shape, more specifically, a semi-cylindrical shape, a wave shape, a convex-concave shape, a cylindrical shape, etc. are mentioned. The method of deformation (for example, thermal deformation) is not particularly limited, and known methods can be cited. Examples of the method of deformation include known methods such as vacuum forming, blow molding, free blow molding, pressure forming, vacuum-pressure forming, and hot stamping.

圖2中示出附裝飾層基板的一實施形態。圖2為附裝飾層基板的一實施形態的立體圖，圖3為其A-A剖面上的附裝飾層基板的局部放大剖面圖。如圖2～3所示，附裝飾層基板18包括基板10、配置在基板10的一個主面上之圖案狀被鍍層12及配置在基板10的另一個主面上之裝飾層16，且局部具有半球狀三維形狀。Fig. 2 shows an embodiment of a substrate with a decoration layer. Fig. 2 is a perspective view of an embodiment of a substrate with a decoration layer, and Fig. 3 is a partial enlarged cross-sectional view of the substrate with a decoration layer on the A-A section. As shown in Figures 2 to 3, the substrate with a decorative layer 18 includes a substrate 10, a patterned layer 12 arranged on one main surface of the substrate 10, and a decorative layer 16 arranged on the other main surface of the substrate 10, and partially Has a hemispherical three-dimensional shape.

>製程6> 製程6係對圖案狀被鍍層賦予鍍敷觸媒或其前驅物之製程。圖案狀被鍍層具有上述相互作用性基團，因此相互作用性基團依其功能而與被賦予的鍍敷觸媒或其前驅物黏附（吸附）。鍍敷觸媒或其前驅物作為鍍敷處理的觸媒或電極而發揮功能。因此，所使用的鍍敷觸媒或其前驅物的種類可藉由鍍敷處理的種類而適當確定。>Process 6> Process 6 is a process of applying a plating catalyst or its precursor to the patterned layer. The patterned layer to be plated has the above-mentioned interactive group, and therefore the interactive group adheres (adsorbs) to the provided plating catalyst or its precursor according to its function. The plating catalyst or its precursor functions as a plating process catalyst or electrode. Therefore, the type of the plating catalyst or its precursor to be used can be appropriately determined by the type of plating treatment.

鍍敷觸媒或其前驅物係非電解鍍敷觸媒或其前驅物為較佳。關於非電解鍍敷觸媒，若是成為非電解鍍敷時的活性核者，則並無特別限制，例如，可舉出具有自觸媒還原反應的觸媒能之金屬（作為能夠進行離子化傾向比Ni低的非電解鍍敷之金屬而公知者）。具體而言，可舉出Pd、Ag、Cu、Pt、Au及Co。作為該非電解鍍敷觸媒，可以使用金屬膠體。關於非電解鍍敷觸媒前驅物，若為藉由化學反應而成為非電解鍍敷觸媒者，則並無特別限制，例如可舉出作為上述非電解鍍敷觸媒而舉出之金屬的離子。The plating catalyst or its precursor is preferably an electroless plating catalyst or its precursor. Regarding the electroless plating catalyst, there is no particular limitation if it becomes the active nucleus during electroless plating. For example, a metal having a catalytic energy of a self-catalyst reduction reaction (as a catalyst capable of undergoing ionization tendency) Known as a metal lower than Ni for electroless plating). Specifically, Pd, Ag, Cu, Pt, Au, and Co can be mentioned. As the electroless plating catalyst, a metal colloid can be used. Regarding the electroless plating catalyst precursor, if it becomes an electroless plating catalyst by a chemical reaction, it is not particularly limited. For example, the metal exemplified as the electroless plating catalyst can be mentioned. ion.

作為對圖案狀被鍍層賦予鍍敷觸媒或其前驅物之方法，例如可舉出將鍍敷觸媒或其前驅物分散或溶解於溶劑而製備溶液，並將該溶液塗佈於圖案狀被鍍層上之方法或將附裝飾層基板浸漬於該溶液中之方法。作為上述溶劑，例如可舉出水或有機溶劑。As a method of applying a plating catalyst or its precursor to the patterned layer, for example, the plating catalyst or its precursor is dispersed or dissolved in a solvent to prepare a solution, and the solution is applied to the patterned layer. The method of plating on the layer or the method of immersing the substrate with decoration layer in the solution. As said solvent, water or an organic solvent can be mentioned, for example.

>製程4> 製程4係對具有三維形狀之附裝飾層基板中的圖案狀被鍍層實施鍍敷處理而形成金屬層（鍍敷層）之製程。鍍敷處理的方法並無特別限制，例如可舉出非電解鍍敷處理或電解鍍敷處理（電鍍處理）。該製程中，可以單獨實施非電解鍍敷處理，亦可以於實施了非電解鍍敷處理之後進而實施電解鍍敷處理。鍍敷處理的種類並無特別限制，例如可舉出銅鍍敷處理及銀鍍敷處理。>Process 4> Process 4 is a process of performing a plating process on the pattern-shaped plated layer in the substrate with a three-dimensional shape with a decorative layer to form a metal layer (plating layer). The method of the plating treatment is not particularly limited, and for example, an electroless plating treatment or an electrolytic plating treatment (electroplating treatment) can be mentioned. In this process, the electroless plating treatment may be performed alone, or after the electroless plating treatment is performed, the electrolytic plating treatment may be further performed. The type of plating treatment is not particularly limited, and examples include copper plating treatment and silver plating treatment.

金屬層係配置在圖案狀被鍍層上之層。如上所述，金屬層沿圖案狀被鍍層的圖案花紋而配置。例如，當圖案狀被鍍層為網格狀時，所形成之金屬層亦成為網格狀。The metal layer is a layer arranged on the patterned layer to be plated. As described above, the metal layer is arranged along the pattern of the patterned layer to be plated. For example, when the pattern-like plated layer is grid-like, the formed metal layer also becomes grid-like.

當金屬層為網格狀時，構成網格之金屬層的線寬並無特別限制，從金屬層的導電特性及視覺辨認難度的平衡的方面考慮，30μm以下為較佳，15μm以下為更佳，10μm以下為進一步較佳，5μm以下為特佳，0.5μm以上為較佳，1μm以上為更佳。When the metal layer is in the form of a grid, the line width of the metal layer constituting the grid is not particularly limited. From the viewpoint of the balance between the conductive properties of the metal layer and the difficulty of visual recognition, 30μm or less is preferred, and 15μm or less is more preferred. , 10 μm or less is more preferable, 5 μm or less is particularly preferable, 0.5 μm or more is preferable, and 1 μm or more is more preferable.

金屬層的厚度並無特別限制，從電阻更低，並且密接性更優異之方面考慮，0.1～5.0μm為較佳，0.3～3.0μm為更佳。The thickness of the metal layer is not particularly limited. From the viewpoint of lower resistance and better adhesion, 0.1-5.0 μm is preferred, and 0.3-3.0 μm is more preferred.

>製程5> 製程5係於基板上形成保護層以便覆蓋金屬層之製程。保護層主要為有助於金屬層的保護之層。保護層只要以覆蓋金屬層之方式配置即可，通常配置於基板的整個表面之情況多。>Process 5> Process 5 is a process of forming a protective layer on the substrate to cover the metal layer. The protective layer is mainly a layer that contributes to the protection of the metal layer. The protective layer only needs to be arranged so as to cover the metal layer, and it is usually arranged on the entire surface of the substrate in many cases.

構成保護層之材料並無特別限制，但樹脂為較佳。樹脂的種類並無特別限制，可舉出公知的熱塑性樹脂。例如，可舉出聚碳酸酯系樹脂、ABS樹脂（丙烯腈-丁二烯-苯乙烯共聚物）、聚醚碸系樹脂、聚丙烯酸系樹脂、聚甲基丙烯酸系樹脂、聚胺基甲酸酯系樹脂、聚酯系樹脂、聚碸系樹脂、聚醯胺系樹脂、聚丙烯酸酯系樹脂、聚烯烴系樹脂、纖維素系樹脂、聚氯乙烯系樹脂及環烯烴系樹脂。The material constituting the protective layer is not particularly limited, but resin is preferred. The type of resin is not particularly limited, and known thermoplastic resins can be mentioned. For example, polycarbonate resins, ABS resins (acrylonitrile-butadiene-styrene copolymers), polyether-based resins, polyacrylic resins, polymethacrylic resins, and polyurethane Ester resins, polyester resins, polyamide resins, polyamide resins, polyacrylate resins, polyolefin resins, cellulose resins, polyvinyl chloride resins, and cycloolefin resins.

保護層的厚度並無特別限制，1～1000μm為較佳，5～100μm為更佳。The thickness of the protective layer is not particularly limited, and is preferably 1 to 1000 μm, and more preferably 5 to 100 μm.

保護層的形成方法並無特別限制。例如，可舉出使含有上述樹脂和依需要而使用之添加劑（例如，透光性粒子及溶劑等）之保護層形成用組成物與具有金屬層之基板接觸而於金屬層上形成塗膜，並依需要使塗膜硬化而形成保護層之方法。The method of forming the protective layer is not particularly limited. For example, a protective layer forming composition containing the above-mentioned resin and additives (for example, light-transmitting particles and solvents, etc.) used as needed is brought into contact with a substrate having a metal layer to form a coating film on the metal layer. And according to the need to harden the coating film to form a protective layer.

保護層亦可以為使用硬化性化合物而形成之層。作為硬化性化合物，可舉出熱硬化性化合物及光硬化性化合物。其中，從金屬層不易產生斷線之方面考慮，保護層係使用光硬化性化合物而形成之層為較佳。此外，作為硬化性化合物，例如可舉出可形成上述樹脂之單體。The protective layer may also be a layer formed using a curable compound. Examples of the curable compound include thermosetting compounds and photocurable compounds. Among them, in view of the fact that the metal layer is less likely to be disconnected, it is preferable that the protective layer is a layer formed by using a photocurable compound. Moreover, as a curable compound, the monomer which can form the said resin is mentioned, for example.

>其他製程> 本發明的導電性基板的製造方法還可以包括除了上述製程1～6以外的其他製程。>Other processes> The manufacturing method of the conductive substrate of the present invention may also include other processes in addition to the above-mentioned processes 1 to 6.

本發明的導電性基板的製造方法進而可以具有製程7，係於第1模具及第2模具中的一個模具上以在製程5中得到之導電性基板的裝飾層與其相接之方式配置導電性基板而使第1模具與第2模具合模，向所形成之模穴內射出樹脂而在導電性基板的保護層側上形成樹脂層。製程7係實施所謂***成形之製程。The manufacturing method of the conductive substrate of the present invention may further have a process 7, which is to arrange conductivity on one of the first mold and the second mold so that the decorative layer of the conductive substrate obtained in the process 5 is in contact with it. The substrate is closed with the first mold and the second mold, and resin is injected into the formed cavity to form a resin layer on the protective layer side of the conductive substrate. Process 7 implements a process called insert molding.

利用圖4～5對製程7的步驟進行說明。本製程中，如圖4所示，在第1模具20配置（安裝）在製程5中得到之導電性基板24（具有三維形狀之基板）。雖未圖示，但導電性基板24依次具有裝飾層、基板、圖案狀被鍍層、配置在圖案狀被鍍層上之金屬層及以被配置成覆蓋金屬層之保護層。圖4中，導電性基板24中的未圖示之裝飾層被配置成與第1模具20相接。接著，如圖5所示，使第1模具20及第2模具22合模，並從未圖示之射出口向由第1模具20與第2模具22形成之模穴C內射出（射出注入）樹脂。此外，射出時，通常以公知的加熱方式對樹脂進行加熱，並且將所熔融之樹脂注入模穴C。又，模具（第一模具和/或第二模具）亦可以以公知的加熱方式進行加熱。然後，依需要冷卻模具並使樹脂固化而從模具取出成形體。此外，藉由上述步驟可得到於保護層側配置有樹脂層之導電性基板。The steps of process 7 will be described using FIGS. 4 to 5. In this process, as shown in FIG. 4, the conductive substrate 24 (substrate having a three-dimensional shape) obtained in the process 5 is placed (mounted) in the first mold 20. Although not shown, the conductive substrate 24 has a decorative layer, a substrate, a pattern-like plated layer, a metal layer arranged on the pattern-like plated layer, and a protective layer arranged to cover the metal layer in this order. In FIG. 4, a decoration layer (not shown) in the conductive substrate 24 is arranged so as to be in contact with the first mold 20. Next, as shown in FIG. 5, the first mold 20 and the second mold 22 are closed, and an injection port (not shown) is injected into the cavity C formed by the first mold 20 and the second mold 22 (injection injection ) Resin. In addition, during injection, the resin is generally heated by a known heating method, and the molten resin is injected into the cavity C. In addition, the mold (the first mold and/or the second mold) may be heated by a known heating method. Then, the mold is cooled and the resin is cured as necessary, and the molded body is taken out from the mold. In addition, a conductive substrate with a resin layer disposed on the protective layer side can be obtained through the above steps.

此外，模穴是指，使第1模具與第2模具合模而形成之模具內的空間。又，圖4中，第1模具20的形狀為凹狀，第2模具22的形狀為凸狀，但並不限定於該形態，而對應於導電性基板的三維形狀（立體形狀）而選擇最適形狀的模具。In addition, the cavity means the space in the mold formed by clamping the first mold and the second mold. In FIG. 4, the shape of the first mold 20 is concave, and the shape of the second mold 22 is convex. However, it is not limited to this form, and the most suitable one is selected according to the three-dimensional shape (three-dimensional shape) of the conductive substrate. Shape mold.

注入（填充）於模穴之樹脂的種類並無特別限制，可舉出公知的樹脂。作為樹脂，例如可舉出聚醚碸系樹脂、聚丙烯酸系樹脂、聚甲基丙烯酸系樹脂、聚胺基甲酸酯系樹脂、聚酯系樹脂（聚對苯二甲酸乙二酯及聚萘二甲酸乙二酯）、聚碳酸酯系樹脂、聚碸系樹脂、聚醯胺系樹脂、聚丙烯酸酯系樹脂、聚烯烴系樹脂、纖維素系樹脂、聚氯乙烯系樹脂及環烯烴系樹脂。The type of resin injected (filled) in the cavity is not particularly limited, and known resins can be mentioned. Examples of resins include polyether-based resins, polyacrylic resins, polymethacrylic resins, polyurethane resins, and polyester resins (polyethylene terephthalate and polynaphthalene). Ethylene dicarboxylate), polycarbonate resin, polyimide resin, polyamide resin, polyacrylate resin, polyolefin resin, cellulose resin, polyvinyl chloride resin, and cycloolefin resin .

此外，本發明的導電性基板的製造方法亦可以在製程5與製程7之間具有製程8，係於保護層上形成密接層。藉由於保護層上設置密接層，所形成之樹脂層的密接性得以提高。構成密接層之材料並無特別限制，樹脂為較佳。作為樹脂，例示構成上述保護層之樹脂。In addition, the manufacturing method of the conductive substrate of the present invention can also have a process 8 between the process 5 and the process 7, which is to form an adhesion layer on the protective layer. By providing an adhesive layer on the protective layer, the adhesiveness of the formed resin layer can be improved. The material constituting the adhesive layer is not particularly limited, and resin is preferred. As the resin, the resin constituting the above-mentioned protective layer is exemplified.

又，本發明的導電性基板的製造方法進而可以具有製程9，係於第1模具及第2模具中的一個模具上以在製程5中得到之導電性基板的保護層與其相接之方式配置導電性基板而使第1模具與第2模具合模，向所形成之模穴內射出樹脂而於導電性基板的裝飾層側上形成樹脂層。除了改變了導電性基板的配置位置以外，製程9實施與製程7相同的步驟。此外，藉由製程9可得到在裝飾層側配置有樹脂層之導電性基板。In addition, the method for manufacturing a conductive substrate of the present invention may further have process 9, which is arranged on one of the first mold and the second mold so that the protective layer of the conductive substrate obtained in process 5 is in contact with it. The conductive substrate is combined with the first mold and the second mold, and resin is injected into the formed cavity to form a resin layer on the decorative layer side of the conductive substrate. The process 9 performs the same steps as the process 7 except that the arrangement position of the conductive substrate is changed. In addition, a conductive substrate with a resin layer disposed on the side of the decoration layer can be obtained by the process 9.

此外，本發明的導電性基板的製造方法亦可以在製程5與製程9之間具有製程10，係於裝飾層上形成密接層。藉由於裝飾層上設置密接層，所形成之樹脂層的密接性得以提高。In addition, the manufacturing method of the conductive substrate of the present invention may also have a process 10 between the process 5 and the process 9, which is to form an adhesion layer on the decoration layer. By providing an adhesive layer on the decoration layer, the adhesiveness of the formed resin layer can be improved.

又，本發明的導電性基板的製造方法亦可以在製程1之前具有製程11，係於基板的至少一個表面上設置底漆層。底漆層的厚度並無特別限制，0.01～100μm為較佳，0.05～20μm為更佳。底漆層的材料並無特別限制，與基板的密接性良好的樹脂為較佳。底漆層的形成方法並無特別限制，可舉出將必要成分溶解於能夠溶解之溶劑中，並藉由塗佈等方法將所得到之溶液塗佈於基板表面上而形成底漆層之方法。In addition, the manufacturing method of the conductive substrate of the present invention may also have a process 11 before the process 1, which is to provide a primer layer on at least one surface of the substrate. The thickness of the primer layer is not particularly limited, but 0.01-100 μm is preferred, and 0.05-20 μm is more preferred. The material of the primer layer is not particularly limited, but a resin having good adhesion to the substrate is preferable. The method of forming the primer layer is not particularly limited. Examples include a method of dissolving the necessary components in a solvent that can dissolve, and coating the resulting solution on the surface of the substrate by a method such as coating to form the primer layer. .

>用途> 藉由上述製造方法可得到導電性基板。所得到之導電性基板具有三維形狀。三維形狀的例示如上所述。>Uses> A conductive substrate can be obtained by the above-mentioned manufacturing method. The obtained conductive substrate has a three-dimensional shape. The example of the three-dimensional shape is as described above.

本發明的導電性基板能夠適用於各種用途中。例如，能夠應用於觸控面板感測器、半導體晶片、FPC（Flexible printed circuits（撓性印刷電路））、COF（Chip on Film覆晶薄膜）、TAB（Tape Automated Bonding（捲帶式自動接合））、天線、多層配線基板及主機板等各種用途。其中，使用於觸控面板感測器（尤其，電容式觸控面板感測器）為較佳。當將上述導電性基板應用於觸控面板感測器時，金屬層作為觸控面板感測器中的檢測電極或引出配線而發揮功能。該種觸控面板感測器能夠較佳地應用於觸控面板。 [實施例]The conductive substrate of the present invention can be applied to various applications. For example, it can be applied to touch panel sensors, semiconductor chips, FPC (Flexible printed circuits), COF (Chip on Film), TAB (Tape Automated Bonding) ), antennas, multilayer wiring boards and motherboards, etc. for various purposes. Among them, it is better to use in touch panel sensors (especially, capacitive touch panel sensors). When the above-mentioned conductive substrate is applied to a touch panel sensor, the metal layer functions as a detection electrode or a lead wire in the touch panel sensor. This kind of touch panel sensor can be preferably applied to a touch panel. [Example]

以下，基於實施例對本發明進行進一步詳細的說明。以下實施例所示之材料、使用量、比例、處理內容及處理步驟等在不脫離本發明的宗旨之範圍內能夠適當進行變更。因此，本發明的範圍並不應由以下所示之實施例而限定性解釋。Hereinafter, the present invention will be described in further detail based on examples. The materials, usage amount, ratio, processing content, processing steps, etc. shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below.

>實施例1> （底漆層形成用組成物的製備）向AITRON Z-913-3（Aica Kogyo Company, Limited製）添加異丙醇（IPA）及丙二醇單甲醚（MFG）的混合溶劑（IPA:MFG的混合質量比係3:1）並稀釋成固體成分成為4質量%而製備了底漆層形成用組成物。>Example 1> (Preparation of composition for forming primer layer) Add a mixed solvent of isopropanol (IPA) and propylene glycol monomethyl ether (MFG) to AITRON Z-913-3 (manufactured by Aica Kogyo Company, Limited) (the mixing mass ratio of IPA:MFG is 3:1) and dilute to a solid The component was 4% by mass, and a composition for forming a primer layer was prepared.

（前驅物層形成用組成物的製備）將BMA淨重2.5質量份的聚丁二烯順丁烯二酸（丁二烯-順丁烯二酸共聚物）（以下，有時簡稱為“BMA”。）（Wako Pure Chemical Industries,Ltd.製；42質量%水溶液）和通過公開公報2013-502634的[0187]段中所記載之方法合成之2官能丙烯醯胺單體（由下述式（AA）表示之化合物）2.5質量份、Irgacure OXE02（BASF公司製）0.13質量份、丙二醇單甲醚4.2質量份及異丙醇90.67質量份進行混合而得到了前驅物層形成用組成物。(Preparation of composition for forming precursor layer) Polybutadiene maleic acid (butadiene-maleic acid copolymer) having a net weight of 2.5 parts by mass of BMA (hereinafter, sometimes referred to as "BMA") (manufactured by Wako Pure Chemical Industries, Ltd.) ; 42% by mass aqueous solution) and 2.5 parts by mass of a bifunctional acrylamide monomer (compound represented by the following formula (AA)) synthesized by the method described in paragraph [0187] of the publication 2013-502634, Irgacure OXE02 (Manufactured by BASF Corporation) 0.13 parts by mass, 4.2 parts by mass of propylene glycol monomethyl ether, and 90.67 parts by mass of isopropanol were mixed to obtain a composition for forming a precursor layer.

[化學式4]

[Chemical formula 4]

（黑色油墨的製備）以以下所示之比例對各成分進行稱量，並用攪拌機（Awatori Netaro ARV310 THINKY公司製）進行混合而得到了含有胺基甲酸酯丙烯酸酯化合物之黑色油墨1。單體：2-乙基己基丙烯酸酯（TOAGOSEI CO.,LTD.製） 20質量份單體：EBECRYL230（DAICEL-ALLNEX LTD.製） 60質量份（脂肪族胺基甲酸酯丙烯酸酯）黑色顏料：碳黑#52（Mitsubishi Chemical Corporation.製） 5質量份起始劑：Omnirad TPO （IGM Resins公司製） 0.5質量份又，以以下所示之比例對各成分進行稱量，並用攪拌機（Awatori Netaro ARV310 THINKY公司製）進行混合而得到了含有環氧化合物之黑色油墨2。單體：CELOXIDE 8000（Daicel Corporation製） 10質量份（脂環式環氧樹脂）單體：ARON OXETANE OXT213（TOAGOSEI CO.,LTD.製） 60質量份（單官能氧雜環丁烷）起始劑：CPI-410S（San-Apro Ltd.製）1質量份黑色顏料：碳黑#52（Mitsubishi Chemical Corporation.製） 5質量份溶劑：甲基乙基酮 30質量份以以下所示之比例對各成分進行稱量，並用攪拌機（Awatori Netaro ARV310 THINKY公司製）進行混合而得到了含有丙烯酸化合物之黑色油墨3。單體：2-乙基己基丙烯酸酯（TOAGOSEI CO.,Ltd.製） 20質量份單體：聚乙二醇二丙烯酸酯A-1000（Shin-Nakamura Chemical Co.,Ltd.製） 60質量份黑色顏料：碳黑#52（Mitsubishi Chemical Corporation.製） 5質量份起始劑：Omnirad TPO （IGM Resins公司製） 0.5質量份溶劑：甲基乙基酮 20質量份(Preparation of black ink) The components were weighed in the ratio shown below and mixed with a blender (manufactured by Awatori Netaro ARV310 THINKY) to obtain a black ink 1 containing a urethane acrylate compound. Monomer: 20 parts by mass of 2-ethylhexyl acrylate (manufactured by TOAGOSEI CO., LTD.) Monomer: EBECRYL230 (manufactured by DAICEL-ALLNEX LTD.) 60 parts by mass (aliphatic urethane acrylate) Black pigment: Carbon black #52 (manufactured by Mitsubishi Chemical Corporation.) 5 parts by mass Initiator: Omnirad TPO (manufactured by IGM Resins) 0.5 parts by mass In addition, each component was weighed in the ratio shown below and mixed with a blender (manufactured by Awatori Netaro ARV310 THINKY) to obtain black ink 2 containing an epoxy compound. Monomer: CELOXIDE 8000 (manufactured by Daicel Corporation) 10 parts by mass (alicyclic epoxy resin) Monomer: ARON OXETANE OXT213 (manufactured by TOAGOSEI CO., LTD.) 60 parts by mass (monofunctional oxetane) Initiator: 1 part by mass of CPI-410S (manufactured by San-Apro Ltd.) Black pigment: Carbon black #52 (manufactured by Mitsubishi Chemical Corporation.) 5 parts by mass Solvent: 30 parts by mass of methyl ethyl ketone The components were weighed in the ratio shown below and mixed with a blender (manufactured by Awatori Netaro ARV310 THINKY) to obtain acrylic compound-containing black ink 3. Monomer: 20 parts by mass of 2-ethylhexyl acrylate (manufactured by TOAGOSEI CO., Ltd.) Monomer: Polyethylene glycol diacrylate A-1000 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 60 parts by mass Black pigment: carbon black #52 (manufactured by Mitsubishi Chemical Corporation) 5 parts by mass Initiator: Omnirad TPO (manufactured by IGM Resins) 0.5 parts by mass Solvent: 20 parts by mass of methyl ethyl ketone

（導電性基板的作製）將底漆層形成用組成物塗佈於樹脂基板（Teijin Limited製PC（聚碳酸酯）薄膜、PANLITE PC、厚度250μm）上而形成了塗膜。接著，對所得到之塗膜照射紫外光，並使塗膜硬化而形成了厚度0.8μm的底漆層。此外，樹脂基板的可見光（波長400～700nm）的透過率係60%以上。接著，將前驅物層形成用組成物塗佈於所得到之底漆層上而形成了厚度0.8μm的被鍍層前驅物層。接著，經由具有規定條狀開口圖案之光罩，並利用金屬鹵化物光源而對被鍍層前驅物層進行了曝光（200mJ/cm² ）。曝光結束之後，於室溫環境下用水對經曝光之被鍍層前驅物層進行顯影而去除未硬化部分來得到了圖案狀被鍍層。所得到之圖案狀被鍍層由線寬30μm、長度50mm的複數個線狀層構成。接著，於樹脂基板的與配置有圖案狀被鍍層之一側相反的一側的表面上，以硬化後的厚度成為10μm的方式藉由網版印刷對含有胺基甲酸酯丙烯酸酯化合物之黑色油墨1進行滿版印刷，並用金屬鹵化物燈（光源）以成為500mJ/cm² 之方式對所得到之塗膜照射紫外線而形成裝飾層來得到了附裝飾層基板。此外，從樹脂基板表面的法線方向視覺辨認時，在裝飾層的形成區域上以與形成有圖案狀被鍍層之區域的一半區域重複的方式設置有裝飾層。接著，藉由真空成形機Formech508FS（Formech公司製）將所得到之附裝飾層基板真空成形成半球狀而得到了具有三維形狀之附裝飾層基板（參閱圖2）。此外，以於半球面的外側配置裝飾層之方式進行了真空成形（參閱圖3）。接著，於35℃下，將所得到之附裝飾層基板於碳酸鈉1質量%水溶液中浸漬5分鐘，並用純水將所取出之附裝飾層基板清洗了2次。接著，於45℃下，將所得到之附裝飾層基板於Pd觸媒賦予液（RONAMERSE^TM SMT Catalyst CF、Rohm and Haas Electronic Materials製）中浸漬5分鐘之後，用純水將所取出之附裝飾層基板清洗了2次。接著，於35℃下，將所得到之附裝飾層基板於還原液（Circuposit6540Reducer、Rohm and Haas Electronic Materials製）中浸漬5分鐘之後，用純水將所取出之附裝飾層基板清洗了2次。接著，於45℃下，將所得到之附裝飾層基板於無電解鍍敷液（CIRCUPOSIT^TM Electroless Copper 4500、Rohm and Haas Electronic Materials製）中浸漬15分鐘之後，用純水清洗所取出之附裝飾層基板而得到了具有線寬35μm、長度50mm的圖案狀金屬層之基板。接著，在圖案狀金屬層側作為保護層以乾燥後的厚度成為10μm之方式噴塗FUJIHARD HO2972U（FUJIKURA KASEI CO.,Ltd.製），並用70℃烘箱而乾燥了5分鐘。然後，以成為1J/cm² 之方式用高壓水銀燈照射紫外線而形成了保護層。進而，於該保護層上，以乾燥後的厚度成為10μm之方式噴塗了以IMB黏合劑006（Teikoku Printing Inks Mfg. Co.,Ltd.製）成為10質量份之方式將其稀釋於甲苯而成之溶液。用70℃烘箱將所得到之塗膜乾燥15分鐘而形成了密接層。接著，於具有能夠形成模穴之第一模具及第二模具之射出成形機中，在第一模具上將導電性基板配置成所得到之導電性基板中的保護層側朝向模穴（參閱圖4）。換言之，導電性基板被配置成導電性基板中的裝飾層與第1模具相接。此外，第一模具的形狀為與所得到之導電性基板的三維形狀對應之形狀。接著，以成為2mm的縫隙之方式使第一模具及第二模具合模並於所形成之模穴射出成形聚碳酸酯樹脂而得到了含有樹脂層之導電性基板。(Production of conductive substrate) The composition for forming a primer layer was applied on a resin substrate (PC (polycarbonate) film manufactured by Teijin Limited, PANLITE PC, thickness 250 μm) to form a coating film. Next, ultraviolet light was irradiated to the obtained coating film, and the coating film was cured to form a primer layer with a thickness of 0.8 μm. In addition, the transmittance of visible light (wavelength 400 to 700 nm) of the resin substrate is 60% or more. Next, the composition for forming a precursor layer was coated on the resultant primer layer to form a precursor layer of a layer to be plated with a thickness of 0.8 μm. ^{Next, the precursor layer to be plated was exposed (200 mJ/cm 2} ) through a photomask with a predetermined strip-shaped opening pattern and using a metal halide light source. After the exposure is completed, the exposed precursor layer of the plated layer is developed with water in a room temperature environment to remove the unhardened part to obtain a patterned plated layer. The obtained pattern-shaped layer to be plated was composed of a plurality of linear layers with a line width of 30 μm and a length of 50 mm. Next, on the surface of the resin substrate on the side opposite to the side where the patterned layer is arranged, screen printing is performed on the black urethane acrylate compound containing urethane acrylate compound so that the thickness after curing becomes 10 μm. Ink 1 was subjected to full-page printing, and ^{the obtained coating film was irradiated with ultraviolet rays so as to be 500 mJ/cm 2} with a metal halide lamp (light source) to form a decoration layer to obtain a substrate with a decoration layer. In addition, when visually recognized from the normal direction of the surface of the resin substrate, the decoration layer is provided on the formation area of the decoration layer so as to overlap with half of the area where the pattern-like plated layer is formed. Next, the obtained substrate with a decorative layer was vacuum-formed into a hemispherical shape by a vacuum forming machine Formech508FS (manufactured by Formech) to obtain a three-dimensional substrate with a decorative layer (see FIG. 2). In addition, vacuum forming was performed by arranging a decorative layer on the outside of the hemispherical surface (see Figure 3). Next, the obtained substrate with a decorative layer was immersed in a sodium carbonate 1% by mass aqueous solution at 35° C. for 5 minutes, and the removed substrate with a decorative layer was washed twice with pure water. Next, the obtained substrate with decoration layer was immersed in a Pd catalyst-imparting solution (RONAMERSE ^TM SMT Catalyst CF, manufactured by Rohm and Haas Electronic Materials) for 5 minutes at 45°C, and then the removed decoration layer was removed with pure water. The layer substrate was cleaned twice. Next, after immersing the obtained substrate with a decoration layer in a reducing solution (Circuposit6540 Reducer, manufactured by Rohm and Haas Electronic Materials) for 5 minutes at 35° C., the removed substrate with a decoration layer was washed twice with pure water. Next, after immersing the obtained substrate with a decorative layer in an electroless plating solution (CIRCUPOSIT ^TM Electroless Copper 4500, manufactured by Rohm and Haas Electronic Materials) for 15 minutes at 45°C, the removed decorative layer was washed with pure water Layer the substrate to obtain a substrate having a patterned metal layer with a line width of 35 μm and a length of 50 mm. Next, FUJIHARD HO2972U (manufactured by FUJIKURA KASEI CO., Ltd.) was sprayed as a protective layer on the side of the patterned metal layer so that the thickness after drying became 10 μm, and dried in an oven at 70°C for 5 minutes. Then, ultraviolet rays were irradiated with a high-pressure mercury lamp so as to become 1 J/cm ^{2 to form a protective layer.} Furthermore, the protective layer was sprayed with IMB adhesive 006 (manufactured by Teikoku Printing Inks Mfg. Co., Ltd.) so that the thickness after drying became 10 μm and diluted in toluene so that it became 10 parts by mass.的solution. The obtained coating film was dried in an oven at 70°C for 15 minutes to form an adhesive layer. Next, in an injection molding machine with a first mold and a second mold capable of forming a cavity, the conductive substrate is placed on the first mold so that the protective layer side of the resulting conductive substrate faces the mold cavity (see figure 4). In other words, the conductive substrate is arranged so that the decorative layer in the conductive substrate is in contact with the first mold. In addition, the shape of the first mold is a shape corresponding to the three-dimensional shape of the obtained conductive substrate. Next, the first mold and the second mold were clamped so that a gap of 2 mm was formed, and a polycarbonate resin was injected into the formed cavity to obtain a conductive substrate containing a resin layer.

>實施例2～實施例3> 如表1所示變更了形成裝飾層時的黑色油墨的種類，除此以外，按照與實施例1相同的步驟得到了含有樹脂層之導電性基板。>Example 2～Example 3> As shown in Table 1, the type of black ink when forming the decorative layer was changed. Except for this, the same procedure as in Example 1 was followed to obtain a conductive substrate containing a resin layer.

>實施例4> 將保護層的形成方法變更為以下步驟，除此以外，按照與實施例3相同的步驟得到了含有樹脂層之導電性基板。>Example 4> Except for changing the formation method of the protective layer to the following steps, the same procedure as in Example 3 was followed to obtain a conductive substrate containing a resin layer.

（保護層的形成）於圖案狀金屬層側作為保護層以乾燥後的厚度成為10μm之方式噴塗SilFort587C，並用70℃烘箱預乾燥了2小時。然後，用100℃烘箱乾燥1小時而得到了保護層。(Formation of protective layer) SilFort587C was sprayed as a protective layer on the side of the patterned metal layer so that the thickness after drying became 10 μm, and pre-dried in an oven at 70°C for 2 hours. Then, it dried in 100 degreeC oven for 1 hour, and obtained the protective layer.

>比較例1> 在以下（附裝飾層基板的製造）步驟中得到了附裝飾層基板，除此以外，按照與實施例1相同的步驟得到了含有樹脂層之導電性基板。比較例1中，於形成了裝飾層之後進行圖案狀被鍍層的形成。>Comparative example 1> In the following steps (manufacturing of a substrate with a decoration layer), a substrate with a decoration layer was obtained. Except for this, the same procedure as in Example 1 was followed to obtain a conductive substrate containing a resin layer. In Comparative Example 1, the patterned layer to be plated was formed after the decoration layer was formed.

（附裝飾層基板的製造）於樹脂基板（Teijin Limited製PC（聚碳酸酯）薄膜、PANLITE PC、厚度250μm）的一個表面側，以硬化後的厚度成為10μm的方式藉由網版印刷對含有胺基甲酸酯丙烯酸酯化合物之黑色油墨1進行滿版印刷，並用金屬鹵化物燈（光源）以成為500mJ/cm² 之方式對所得到之塗膜照射紫外線而形成了裝飾層。此外，從樹脂基板表面的法線方向視覺辨認時，在裝飾層的形成區域上以與配置在後述步驟中形成之圖案狀被鍍層之區域的一半區域重複的方式設置有裝飾層。於樹脂基板的另一個表面側塗佈底漆層形成用組成物而形成了塗膜。接著，對所得到之塗膜照射紫外光，並使塗膜硬化而形成了厚度0.8μm的底漆層。接著，將前驅物層形成用組成物塗佈於所得到之底漆層上而形成了厚度0.8μm的被鍍層前驅物層。接著，經由具有規定條狀開口圖案之光罩，並利用金屬鹵化物光源而對被鍍層前驅物層進行了曝光（200mJ/cm² ）。曝光結束之後，於室溫環境下用水對經曝光之被鍍層前驅物層進行顯影而去除未硬化部分，從而形成圖案狀被鍍層而得到了附裝飾層基板。所得到之圖案狀被鍍層由複數個線狀層構成。(Manufacture of substrate with decorative layer) On one surface side of a resin substrate (PC (polycarbonate) film manufactured by Teijin Limited, PANLITE PC, thickness 250μm), the cured thickness becomes 10μm by screen printing. The black ink 1 of the urethane acrylate compound was fully printed, and the resulting coating film was irradiated with ultraviolet rays using a metal halide lamp (light source) to become 500 mJ/cm ^{2 to form a decorative layer.} In addition, when visually recognized from the normal direction of the surface of the resin substrate, the decoration layer is provided on the formation area of the decoration layer so as to overlap with half of the area where the pattern-like plated layer formed in the step described later is arranged. The primer layer forming composition was applied to the other surface side of the resin substrate to form a coating film. Next, ultraviolet light was irradiated to the obtained coating film, and the coating film was cured to form a primer layer with a thickness of 0.8 μm. Next, the composition for forming a precursor layer was coated on the resultant primer layer to form a precursor layer of a layer to be plated with a thickness of 0.8 μm. ^{Next, the precursor layer to be plated was exposed (200 mJ/cm 2} ) through a photomask with a predetermined strip-shaped opening pattern and using a metal halide light source. After the exposure, the exposed precursor layer to be plated was developed with water in a room temperature environment to remove the unhardened part, thereby forming a patterned plated layer to obtain a substrate with a decorative layer. The obtained pattern-shaped layer to be plated is composed of a plurality of linear layers.

>評價> （金屬層的均勻性評價）測定5處從樹脂基板的表面的法線方向觀察時，位於與裝飾層重複之區域中之金屬層的線寬而求出其平均值a，進而測定5處位於不與裝飾層重複之區域中之金屬層的線寬而求出了平均值b。接著，求出平均值b相對於平均值a之比（b/a），並沿以下基準進行了評價。 “A”：0.9≤b/a≤1.1 “B”：0.9>b/a或1.1>b/a>Evaluation> (Evaluation of the uniformity of the metal layer) Measure the line width of the metal layer in the area overlapping with the decoration layer when viewed from the normal direction of the surface of the resin substrate at 5 locations to find the average value a, and then measure 5 locations in the area that does not overlap with the decoration layer Calculate the average value b for the line width of the metal layer. Next, the ratio (b/a) of the average value b to the average value a was calculated and evaluated along the following criteria. "A": 0.9≤b/a≤1.1 "B": 0.9>b/a or 1.1>b/a

（耐鹼性評價）對於進行無電解鍍敷而得到之具有圖案狀金屬層之基板的裝飾層，利用基於JIS K 5600-5-6（1999）所示之橫切法對密接性進行了評價。密接切割成寬度15mm、長度70mm之膠帶（CT-18NICHIBAN CO.,Ltd.製），並用手指從上牢固地摩擦。黏合膠帶，並於5分鐘之後以90度的角度一次性剝取。按照密接性的試驗結果的分類，確認膠帶剝離之後的裝飾層，將任意格子中均沒有剝離之情況設為“A”，將藉由切割交叉點觀察到小的剝離之情況設為“B”，將沿切割的交叉點或邊緣剝離之情況設為“C”。(Evaluation of alkali resistance) For the decorative layer of a substrate having a patterned metal layer obtained by electroless plating, the adhesiveness was evaluated by the cross section method based on JIS K 5600-5-6 (1999). Closely cut into a tape with a width of 15mm and a length of 70mm (manufactured by CT-18NICHIBAN CO., Ltd.), and rub it firmly from above with your fingers. Adhere the tape and peel it off at a 90-degree angle after 5 minutes. According to the classification of the adhesion test results, confirm the decorative layer after the tape is peeled off. Set the case where there is no peeling in any grid as "A", and the case where small peeling is observed by cutting the intersection point as "B" , Set the condition of peeling along the intersection or edge of the cut to "C".

表1中，“黑色油墨”欄是指，形成裝飾層時所使用之黑色油墨1～3中的任一個。又，表1中，“步驟”欄中，如本發明的導電性基板的製造方法，將形成圖案狀被鍍層之後形成有裝飾層之情況設為“A”，並將形成裝飾層之後形成有圖案狀被鍍層之情況設為“B”。又，表1中，“保護層的形成形態”欄中，使用光硬化性化合物而形成有保護層之情況設為“光”，並將使用熱硬化性組成物形成有保護層之情況設為“熱”。In Table 1, the "black ink" column refers to any of the black inks 1 to 3 used when forming the decorative layer. In addition, in Table 1, in the "step" column, as in the manufacturing method of the conductive substrate of the present invention, the case where the decorative layer is formed after the patterned layer is formed is referred to as "A", and the decorative layer is formed after the decorative layer is formed. The patterned layer is set to "B". In Table 1, in the column "Formation of protective layer", the case where a protective layer is formed using a photocurable compound is referred to as "light", and the case where a protective layer is formed using a thermosetting composition is referred to as "heat".

[表1] 實施例1 實施例2 實施例3 實施例4 比較例1 黑色油墨黑色油墨1 黑色油墨2 黑色油墨3 黑色油墨3 黑色油墨3 步驟 A A A A B 保護層的形成形態光光光熱光金屬層的均勻性評價 A A A A B 耐鹼性評價 A A B B B [Table 1] Example 1 Example 2 Example 3 Example 4 Comparative example 1 Black ink Black ink 1 Black ink 2 Black ink 3 Black ink 3 Black ink 3 step A A A A B Formation of the protective layer Light Light Light heat Light Evaluation of the uniformity of the metal layer A A A A B Alkali resistance evaluation A A B B B

如表1所示，確認到依本發明的導電性基板的製造方法可得到所希望效果。此外，藉由實施例1、實施例2及實施例3的比較，當裝飾層的形成材料為胺基甲酸酯丙烯酸酯化合物及環氧化合物時，裝飾層的耐鹼性更優異。As shown in Table 1, it was confirmed that the manufacturing method of the conductive substrate according to the present invention can obtain the desired effect. In addition, by comparison of Example 1, Example 2 and Example 3, when the forming material of the decoration layer is a urethane acrylate compound and an epoxy compound, the alkali resistance of the decoration layer is more excellent.

10:基板 12:圖案狀被鍍層 14:開口部 16:裝飾層 18:附裝飾層基板 20:第1模具 22:第2模具 24:導電性基板 C:模穴 L:長度 W:線寬10: substrate 12: Patterned layer 14: Opening 16: decorative layer 18: Substrate with decorative layer 20: The first mold 22: The second mold 24: Conductive substrate C: Mould cavity L: length W: line width

圖1係表示圖案狀被鍍層的一態樣之俯視圖。圖2係附裝飾層基板的一實施形態的立體圖。圖3係附裝飾層基板的局部放大剖面圖。圖4係將導電性基板配置在第1模具上之示意圖。圖5係使第1模具與第2模具合模時的示意圖。Fig. 1 is a plan view showing an aspect of a patterned layer to be plated. Fig. 2 is a perspective view of an embodiment of a substrate with a decoration layer. Figure 3 is a partial enlarged cross-sectional view of a substrate with a decorative layer. Fig. 4 is a schematic diagram of arranging a conductive substrate on a first mold. Fig. 5 is a schematic diagram when the first mold and the second mold are closed.

18:附裝飾層基板 18: Substrate with decorative layer

Claims

一種導電性基板的製造方法，其係具有：製程1，係對配置在基板的一個表面側且具有能夠與鍍敷觸媒或其前驅物相互作用之官能基及聚合性基之被鍍層前驅物層實施曝光處理及顯影處理而形成圖案狀被鍍層；製程2，係於前述基板的另一個表面側形成裝飾層而得到附裝飾層基板；製程3，係使前述附裝飾層基板變形而得到具有三維形狀之附裝飾層基板；製程4，係對前述具有三維形狀之附裝飾層基板中的前述圖案狀被鍍層實施鍍敷處理而形成金屬層；及製程5，係於前述基板上形成保護層以便覆蓋前述金屬層；於前述製程3與前述製程4之間進而具有對前述圖案狀被鍍層賦予鍍敷觸媒或其前驅物之製程6，或者前述被鍍層前驅物層含有鍍敷觸媒或其前驅物。A method for manufacturing a conductive substrate, which has: In process 1, the precursor layer of the plated layer, which is arranged on one surface side of the substrate and has functional groups and polymerizable groups capable of interacting with the plating catalyst or its precursor, is subjected to exposure treatment and development treatment to form a patterned substrate. Plating Process 2, forming a decoration layer on the other surface side of the aforementioned substrate to obtain a substrate with a decoration layer; Process 3 is to deform the aforementioned substrate with decoration layer to obtain a three-dimensional shape of the substrate with decoration layer; Process 4 is to perform a plating process on the pattern-like plated layer in the three-dimensional shape of the substrate with a decorative layer to form a metal layer; and Process 5 is to form a protective layer on the aforementioned substrate so as to cover the aforementioned metal layer; Between the aforementioned process 3 and the aforementioned process 4, there is further a process 6 in which a plating catalyst or its precursor is applied to the patterned layer to be plated, or the plated layer precursor layer contains a plating catalyst or its precursor.

如請求項1所述之導電性基板的製造方法，其中前述保護層係使用光硬化性化合物而形成之層。The method of manufacturing a conductive substrate according to claim 1, wherein The aforementioned protective layer is a layer formed using a photocurable compound.

如請求項1或請求項2所述之導電性基板的製造方法，其中前述裝飾層係使用選自包括光硬化性化合物及熱硬化性化合物之群組中之硬化性化合物而形成之層。The method of manufacturing a conductive substrate according to claim 1 or claim 2, wherein The aforementioned decorative layer is a layer formed by using a curable compound selected from the group consisting of a photocurable compound and a thermosetting compound.

如請求項3所述之導電性基板的製造方法，其中前述硬化性化合物選自包括胺基甲酸酯（甲基）丙烯酸酯化合物及環氧化合物之群組。The method of manufacturing a conductive substrate according to claim 3, wherein The aforementioned curable compound is selected from the group including a urethane (meth)acrylate compound and an epoxy compound.

如請求項1或請求項2所述之導電性基板的製造方法，其係進而具有製程7，係於第1模具及第2模具中的一個模具上以於前述製程5中得到之前述導電性基板的前述裝飾層與其相接之方式配置前述導電性基板而使前述第1模具與前述第2模具合模，向所形成之模穴內射出樹脂而在前述導電性基板的前述保護層側上形成樹脂層。The method for manufacturing a conductive substrate according to claim 1 or claim 2, which further has a process 7, which is applied to one of the first mold and the second mold to obtain the aforementioned conductivity in the foregoing process 5 The conductive substrate is arranged in such a way that the decorative layer of the substrate is in contact with the first mold and the second mold, and resin is injected into the formed cavity on the protective layer side of the conductive substrate Form a resin layer.

如請求項5所述之導電性基板的製造方法，其係於前述製程5與前述製程7之間進而具有製程8，係於前述保護層上形成密接層。The method for manufacturing a conductive substrate according to claim 5, which further includes a process 8 between the aforementioned process 5 and the aforementioned process 7, which is to form an adhesion layer on the aforementioned protective layer.

如請求項1或請求項2所述之導電性基板的製造方法，其係進而具有製程9，係於第1模具及第2模具中的一個模具上以於前述製程5中得到之前述導電性基板的前述保護層與其相接之方式配置前述導電性基板而使前述第1模具與前述第2模具合模，向所形成之模穴內射出樹脂而於前述導電性基板的前述裝飾層側上形成樹脂層。The method for manufacturing a conductive substrate according to claim 1 or claim 2, which further has a process 9, which is applied to one of the first mold and the second mold to obtain the aforementioned conductivity in the foregoing process 5 The conductive substrate is arranged in such a way that the protective layer of the substrate is in contact with the first mold and the second mold, and resin is injected into the formed cavity to be on the decorative layer side of the conductive substrate Form a resin layer.

如請求項7所述之導電性基板的製造方法，其係於前述製程5與前述製程9之間進而具有製程10，係於前述裝飾層上形成密接層。The method for manufacturing a conductive substrate according to claim 7, which is between the aforementioned process 5 and the aforementioned process 9 and further has a process 10, which is to form an adhesion layer on the aforementioned decorative layer.