TW201902956A - Photosensitive transfer material and method of manufacturing circuit wiring - Google Patents

Photosensitive transfer material and method of manufacturing circuit wiring Download PDF

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TW201902956A
TW201902956A TW107100159A TW107100159A TW201902956A TW 201902956 A TW201902956 A TW 201902956A TW 107100159 A TW107100159 A TW 107100159A TW 107100159 A TW107100159 A TW 107100159A TW 201902956 A TW201902956 A TW 201902956A
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Taiwan
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group
resin composition
photosensitive
transfer material
resin
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TW107100159A
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Chinese (zh)
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藤本進二
佐藤守正
片山晃男
漢那慎一
篠田克己
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日商富士軟片股份有限公司
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Publication of TW201902956A publication Critical patent/TW201902956A/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

This photosensitive transferring material comprises a temporary support, an intermediate layer, and a photosensitive resin composition layer in this order. The photosensitive resin composition layer includes: a polymer including a constituent unit including an acid group protected by an acid-degradable group; and a photoacid generator. The intermediate layer is water-soluble or alkali-soluble, and includes a resin C including a constituent unit including a phenolic hydroxyl group or an alcoholic hydroxyl group that is not directly bonded to the main chain. Also provided is a method for producing a circuit wiring using said photosensitive transferring material.

Description

感光性轉印材料以及電路配線之製造方法Method for manufacturing photosensitive transfer material and circuit wiring

本公開係有關一種感光性轉印材料以及電路配線之製造方法。The present disclosure relates to a photosensitive transfer material and a method for manufacturing circuit wiring.

在靜電電容型輸入裝置等具備觸控面板之顯示裝置（有機電發光（EL）顯示裝置以及液晶顯示裝置等）中，在觸控面板內部設置有相當於可見部的感測器之電極圖案、邊緣配線部分以及引出配線部分的配線等導電性層圖案。 通常在已圖案化之層的形成中，用於獲得所需之圖案形狀之製程數量少，因此廣泛使用對使用感光性轉印材料在任意基板上設置之感光性樹脂組成物的層，經由具有所希望的圖案之遮罩進行曝光後顯影之方法。In display devices (such as organic electroluminescence (EL) display devices and liquid crystal display devices) provided with a touch panel, such as an electrostatic capacitance type input device, the electrode pattern corresponding to the sensor of the visible part is provided inside the touch panel, Conductive layer patterns such as the wiring at the edge wiring part and the lead-out wiring part. Generally, in the formation of a patterned layer, the number of processes for obtaining a desired pattern shape is small, and therefore, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material is widely used. A method of developing a mask of a desired pattern after exposure.

例如在日本特開2015-118202號公報中，公開有一種感光性轉印材料，其特徵在於，具有支撐體和感光性樹脂組成物層，上述感光性樹脂組成物層含有（A）包含聚合物之聚合物成分以及（B）光酸產生劑，前述聚合物包含具有被酸分解性基保護之酸基之構成單元（a1），上述感光性樹脂組成物不具有乙烯***聯結構。For example, Japanese Patent Laid-Open No. 2015-118202 discloses a photosensitive transfer material characterized by having a support and a photosensitive resin composition layer, the photosensitive resin composition layer containing (A) containing a polymer The polymer component and (B) a photo-acid generator. The polymer contains a structural unit (a1) having an acid group protected by an acid-decomposable group, and the photosensitive resin composition does not have an ethylenic cross-linked structure.

本發明的一實施形態欲解決之課題在於提供一種所獲得之圖案形狀的變形少的感光性轉印材料。 並且，本發明的另一實施形態欲解決之課題在於提供一種使用了上述感光性轉印材料之電路配線之製造方法。The problem to be solved by one embodiment of the present invention is to provide a photosensitive transfer material with less distortion in the pattern shape obtained. In addition, a problem to be solved by another embodiment of the present invention is to provide a method for manufacturing circuit wiring using the photosensitive transfer material.

用於解決上述課題之手段包含以下態樣。 ＜1＞一種感光性轉印材料，依次具有偽支撐體、中間層、感光性樹脂組成物層，上述感光性樹脂組成物層含有聚合物和光酸產生劑，前述聚合物包含具有被酸分解性基保護之酸基之構成單元，上述中間層含有樹脂C，前述樹脂C為水溶性或鹼溶性，且包含具有酚性羥基或未直接連結於主鏈之醇性羥基之構成單元。 ＜2＞如上述＜1＞所述之感光性轉印材料，其中在上述偽支撐體和上述中間層之間進一步具有熱塑性樹脂層。 ＜3＞如上述＜1＞或＜2＞所述之感光性轉印材料，其中上述樹脂C係選自由酚醛清漆樹脂、改質纖維素樹脂以及具有羥基之丙烯酸樹脂組成的群之至少1種樹脂。 ＜4＞如上述＜1＞～＜3＞中任一個所述之感光性轉印材料，其中上述中間層進一步含有除上述樹脂C以外的水溶性或鹼溶性之樹脂D。 ＜5＞如上述＜4＞所述之感光性轉印材料，其中上述樹脂D係選自由聚丙烯酸、聚丙烯酸鈉、聚丙烯醯胺、聚環氧乙烷、聚伸乙亞胺、聚乙烯醇以及聚乙烯吡咯啶酮組成的群之至少1種樹脂。 ＜6＞如上述＜4＞或＜5＞所述之感光性轉印材料，其中上述樹脂D係選自由聚乙烯醇以及聚乙烯吡咯啶酮組成的群之至少1種樹脂。 ＜7＞如上述＜4＞～＜6＞中任一個所述之感光性轉印材料，其中上述中間層中之上述樹脂C和上述樹脂D的含有質量比係樹脂C:樹脂D=5:1～1:2。 ＜8＞如上述＜7＞所述之感光性轉印材料，其中上述中間層中之上述樹脂C和上述樹脂D的含有質量比係樹脂C:樹脂D=4:1～2:1。 ＜9＞如上述＜1＞～＜8＞中任一個所述之感光性轉印材料，其中具有被上述酸分解性基保護之酸基之構成單元係以下述式A表示之構成單元。The means for solving the above problems include the following. <1> A photosensitive transfer material having a pseudo support, an intermediate layer, and a photosensitive resin composition layer in this order, the photosensitive resin composition layer containing a polymer and a photoacid generator, the polymer containing acid decomposability The structural unit of the acid group protected by the group, the intermediate layer contains a resin C, which is water-soluble or alkali-soluble, and contains a structural unit having a phenolic hydroxyl group or an alcoholic hydroxyl group not directly linked to the main chain. <2> The photosensitive transfer material according to the above <1>, further comprising a thermoplastic resin layer between the dummy support and the intermediate layer. <3> The photosensitive transfer material according to the above <1> or <2>, wherein the resin C is at least one selected from the group consisting of novolak resin, modified cellulose resin, and acrylic resin having a hydroxyl group Resin. <4> The photosensitive transfer material according to any one of <1> to <3>, wherein the intermediate layer further contains a water-soluble or alkali-soluble resin D other than the resin C. <5> The photosensitive transfer material according to the above <4>, wherein the resin D is selected from polyacrylic acid, sodium polyacrylate, polypropylene amide, polyethylene oxide, polyethyleneimine, polyethylene At least one resin of the group consisting of alcohol and polyvinylpyrrolidone. <6> The photosensitive transfer material according to the above <4> or <5>, wherein the resin D is at least one resin selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone. <7> The photosensitive transfer material according to any one of the above <4> to <6>, wherein the content ratio of the resin C and the resin D in the intermediate layer is based on the mass ratio resin C: resin D = 5: 1 ～ 1: 2. <8> The photosensitive transfer material according to the above <7>, wherein the content ratio of the resin C and the resin D in the intermediate layer is resin C: resin D = 4: 1 to 2: 1. <9> The photosensitive transfer material according to any one of the above <1> to <8>, wherein the structural unit having an acid group protected by the acid-decomposable group is a structural unit represented by the following formula A.

[化學式1] [Chemical Formula 1]

式A中，R31 以及R32 分別獨立地表示氫原子、烷基或芳基，R31 以及R32 中之至少一者係烷基或芳基，R33 表示烷基或芳基，R31 或R32 可與R33 連結而形成環狀醚，R34 表示氫原子或甲基，X0 表示單鍵或伸芳基。In formula A, R 31 and R 32 independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 represents an alkyl group or an aryl group, R 31 Or R 32 may be linked to R 33 to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or an aryl group.

＜10＞如上述＜1＞～＜9＞中任一個所述之感光性轉印材料，其中上述感光性樹脂組成物層中之上述聚合物的玻璃轉移溫度為90℃以下。 ＜11＞一種電路配線之製造方法，依次包含以下製程：對於基板，使上述＜1＞～＜10＞中任一個所述之感光性轉印材料的上述感光性樹脂組成物層與上述基板接觸並貼合之製程；對上述貼合製程後的上述感光性轉印材料的上述感光性樹脂組成物層進行圖案曝光之製程；對上述進行曝光之製程後的上述感光性樹脂組成物層進行顯影並形成圖案之製程；以及對未配置有上述圖案之區域中之上述基板進行蝕刻處理之製程。 ＜12＞一種電路配線之製造方法，依次包含以下製程：對於基板，使上述＜1＞～＜10＞中任一個所述之感光性轉印材料的上述感光性樹脂組成物層與上述基板接觸並貼合之製程；剝離上述感光性轉印材料的偽支撐體之製程；對上述感光性樹脂組成物層進行圖案曝光之製程；對上述感光性樹脂組成物層進行顯影並形成圖案之製程；以及對未配置有上述圖案之區域中之上述基板進行蝕刻處理之製程。 [發明效果]<10> The photosensitive transfer material according to any one of the above <1> to <9>, wherein the glass transition temperature of the polymer in the photosensitive resin composition layer is 90 ° C. or lower. <11> A method for manufacturing circuit wiring, which sequentially includes the following processes: For a substrate, the photosensitive resin composition layer of the photosensitive transfer material according to any one of the above <1> to <10> is brought into contact with the substrate And the lamination process; the process of pattern exposing the photosensitive resin composition layer of the photosensitive transfer material after the lamination process; the development of the photosensitive resin composition layer after the exposure process And a process of forming a pattern; and a process of etching the substrate in the area where the pattern is not configured. <12> A method of manufacturing circuit wiring, which sequentially includes the following processes: For a substrate, the photosensitive resin composition layer of the photosensitive transfer material according to any one of the above <1> to <10> is brought into contact with the substrate The process of laminating; the process of peeling the pseudo-support of the photosensitive transfer material; the process of pattern exposing the photosensitive resin composition layer; the process of developing the photosensitive resin composition layer and forming the pattern; And a process of etching the substrate in the area where the pattern is not arranged. [Effect of invention]

依本發明的一實施形態，能夠提供一種所獲得之圖案形狀的變形少的感光性轉印材料。 並且，依本發明的另一實施形態，能夠提供一種使用了上述感光性轉印材料之電路配線之製造方法。According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material with little distortion of the obtained pattern shape. Furthermore, according to another embodiment of the present invention, it is possible to provide a method for manufacturing circuit wiring using the above-mentioned photosensitive transfer material.

以下，對本公開的內容進行說明。另外，雖參閱圖式進行說明，但有時省略元件符號。 並且，在本說明書中使用“～”表示之數值範圍表示將記載於“～”的前後之數值作為下限值以及上限值而包含在內之範圍。 並且，在本說明書中，“（甲基）丙烯酸”表示丙烯酸以及甲基丙烯酸兩者或任一者，“（甲基）丙烯酸酯”表示丙烯酸酯以及甲基丙烯酸酯兩者或任一者。 而且，在本說明書中關於組成物中的各成分的量，當在組成物中存在複數種相當於各成分之物質時，只要沒有特別的說明則表示在組成物中存在之相應之複數種物質的總計量。 在本說明書中“製程”一詞不僅表示獨立之製程，即使在無法與其他製程明確區分的情況下，只要能達成製程的預期目的，則包含於本用語。 在本說明書中之基團（原子團）的標記中，未標有取代以及未取代之標記包含具有取代基者和不具有取代基者。例如“烷基”為不僅包含不具有取代基之烷基（未取代烷基），亦包含具有取代基之烷基（取代烷基）者。 並且，本說明書中之化學結構式有時會記載成省略了氫原子之簡略結構式。 在本公開中，“質量%”與“重量%”的含義相同，“質量份”與“重量份”的含義相同。 並且，在本公開中，2個以上的較佳態樣的組合係更佳的態樣。 並且，本公開中之重量平均分子量（Mw）以及數均分子量（Mn）只要沒有特別的說明則係以使用了TSKgel GMHxL、TSKgel G4000HxL、TSKgel G2000HxL（均為TOSOH CORPORATION製的產品名）的管柱之凝膠滲透層析法（GPC）分析裝置，藉由溶劑THF（四氫呋喃）、差示折射計進行檢測，並將聚苯乙烯作為標準物質進行換算之分子量。The content of the present disclosure will be described below. In addition, although the description is made with reference to the drawings, the component symbols are sometimes omitted. In addition, the numerical range represented by "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In addition, in this specification, "(meth) acrylic acid" means both or either acrylic acid and methacrylic acid, and "(meth) acrylate" means both or any one of acrylate and methacrylate. In addition, in this specification, regarding the amount of each component in the composition, when a plurality of substances corresponding to each component exist in the composition, unless otherwise specified, it indicates the corresponding plurality of substances present in the composition Total measurement. In this specification, the term "process" not only means an independent process, but even if it cannot be clearly distinguished from other processes, as long as the intended purpose of the process can be achieved, it is included in this term. In the labeling of groups (atomic groups) in this specification, unlabeled and unsubstituted labels include those with substituents and those without substituents. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). In addition, the chemical structural formula in this specification may be described as a simplified structural formula in which a hydrogen atom is omitted. In the present disclosure, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning. Also, in the present disclosure, a combination of two or more preferred aspects is a better aspect. In addition, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in this disclosure are columns using TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all product names manufactured by TOSOH CORPORATION) The gel permeation chromatography (GPC) analyzer uses a solvent THF (tetrahydrofuran) and a differential refractometer to detect molecular weights converted from polystyrene as a standard substance.

（感光性轉印材料） 本公開之感光性轉印材料依次具有偽支撐體、中間層、感光性樹脂組成物層，上述感光性樹脂組成物層含有聚合物和光酸產生劑，前述聚合物包含具有被酸分解性基保護之酸基之構成單元，上述中間層含有樹脂C，前述樹脂C為水溶性或鹼溶性，且包含具有酚性羥基或未直接連結於主鏈之醇性羥基之構成單元。(Photosensitive transfer material) The photosensitive transfer material of the present disclosure has a pseudo support, an intermediate layer, and a photosensitive resin composition layer in this order. The photosensitive resin composition layer contains a polymer and a photoacid generator, and the polymer contains A structural unit having an acid group protected by an acid-decomposable group, the intermediate layer contains a resin C, the resin C is water-soluble or alkali-soluble, and contains a phenolic hydroxyl group or an alcoholic hydroxyl group not directly linked to the main chain unit.

輥對輥（roll-to-roll）製程可考慮在被傳送之基材上連續地實施轉印製程-曝光製程-顯影製程後捲取到輥上之製程，但本發明人發現存在以下問題，亦即實際在實施生產時，當在任意製程中發生故障時，不得不停止基材的傳送，此時，在轉印製程、顯影製程中停止之部分的性能明顯劣化而不得不廢棄。 並且，在曝光製程中，技術上還無法實現一邊以恆定速度傳送基材一邊經由遮罩進行曝光，需要組裝局部性地停止基材的傳送之裝置等複雜的裝置。並且，本發明人等推斷，分別獨立地配置轉印、曝光以及顯影的各製程，並在各製程的前後嵌入了開捲以及捲取之製程在現有技術的範圍內是比較理想的。 然而，本發明人等發現在包含該種轉印、曝光以及顯影的各製程之方法中，若圖像形成使用了化學增幅正型感光性樹脂組成物之層，則有時產生所獲得之圖案的變形。另外，當使用除了化學增幅正型感光性樹脂組成物以外的以往的阻劑時，未發現上述現象。 本發明人等進行深入研究之結果，發現該現象係使用化學增幅正型樹脂組成物時的特徵性現象，發現藉由設為上述構成的感光性轉印材料，所獲得之圖案形狀的變形減少。 雖然上述效果的詳細的發現機構不明確，但所獲得之圖案形狀的變形尤其在使用化學增幅正型樹脂組成物時顯現，藉此本發明人等推斷係由基於已產生之酸之酸分解性基的脫離反應、以及來自於之後脫離之酸分解性基之化合物的擴散而引起之現象。而且，本發明人等推斷中間層藉由含有為水溶性或鹼溶性且包含具有酚性羥基或未直接連結於主鏈之醇性羥基之構成單元之樹脂C，將來自於已脫離之酸分解性基之化合物藉由中間層中之上述羥基進行捕捉，藉此相對地減少來自於已脫離之酸分解性基之化合物向相近畫素擴散，並抑制基於與上述擴散相伴之體積變化之膜中的內部應力的產生，藉此抑制所獲得之圖案形狀的變形。The roll-to-roll process may be considered as a process of continuously performing the transfer process-exposure process-development process on the substrate to be transported, and the process of winding on the roll after the development process, but the inventor found that the following problems exist, That is to say, in actual production, when a failure occurs in any process, the conveyance of the substrate has to be stopped. At this time, the performance of the part stopped during the transfer process and the development process is significantly deteriorated and has to be discarded. Furthermore, in the exposure process, it is technically impossible to realize exposure through a mask while transferring the substrate at a constant speed, and it is necessary to assemble a complicated device such as a device that locally stops the transfer of the substrate. Furthermore, the inventors concluded that the processes of transfer, exposure, and development are independently arranged, and the processes of unwinding and winding are embedded before and after each process, which is ideal within the scope of the prior art. However, the present inventors found that in the method including each process of transfer, exposure, and development, if an image is formed using a layer of a chemically amplified positive photosensitive resin composition, the obtained pattern may sometimes occur Deformation. In addition, when a conventional resist other than the chemically amplified positive photosensitive resin composition is used, the above phenomenon is not found. As a result of intensive studies conducted by the present inventors, it was found that this phenomenon is a characteristic phenomenon when a chemically amplified positive resin composition is used, and it is found that the deformation of the obtained pattern shape is reduced by using the photosensitive transfer material of the above-mentioned configuration . Although the detailed discovery mechanism of the above effect is not clear, the deformation of the obtained pattern shape appears especially when a chemically amplified positive-type resin composition is used, from which the present inventors infer that the acid decomposability is based on the generated acid Phenomenon caused by the reaction of radical detachment and the diffusion of compounds from acid-decomposable radicals that detach later. Furthermore, the inventors inferred that the intermediate layer decomposes the acid derived from the resin by containing a resin unit that is water-soluble or alkali-soluble and contains a structural unit having a phenolic hydroxyl group or an alcoholic hydroxyl group not directly linked to the main chain. The compound of the sex group is captured by the above-mentioned hydroxyl group in the intermediate layer, thereby relatively reducing the diffusion of the compound from the acid-decomposable group that has been detached to a similar pixel, and suppressing the film based on the volume change accompanying the above diffusion Generation of internal stress, thereby suppressing deformation of the obtained pattern shape.

以下，對本公開之感光性轉印材料進行詳細地說明。Hereinafter, the photosensitive transfer material of the present disclosure will be described in detail.

圖1概略性地表示本公開之感光性轉印材料的層結構的一例。圖1所示之感光性轉印材料100中依次積層有偽支撐體10、中間層12、感光性樹脂組成物層14以及覆蓋膜16。 中間層12含有樹脂C，前述樹脂C係水溶性或鹼溶性，且包含具有酚性羥基或未直接連結於主鏈之醇性羥基之構成單元。 感光性樹脂組成物層14含有聚合物和光酸產生劑，前述聚合物包含具有被酸分解性基保護之酸基之構成單元。 以下，對本公開之感光性轉印材料的構成材料等進行說明。另外，在本說明書中，有時如下稱呼本公開中之上述構成。 有時將包含具有被酸分解性基保護之酸基之構成單元之聚合物稱作“特定聚合物”。 上述感光性樹脂組成物層係正型感光性樹脂組成物層，有時稱作“正型感光性樹脂組成物層”。FIG. 1 schematically shows an example of the layer structure of the photosensitive transfer material of the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a pseudo support 10, an intermediate layer 12, a photosensitive resin composition layer 14 and a cover film 16 are sequentially stacked. The intermediate layer 12 contains a resin C, which is water-soluble or alkali-soluble, and includes a structural unit having a phenolic hydroxyl group or an alcoholic hydroxyl group that is not directly connected to the main chain. The photosensitive resin composition layer 14 contains a polymer and a photoacid generator. The polymer contains a structural unit having an acid group protected by an acid-decomposable group. Hereinafter, constituent materials and the like of the photosensitive transfer material of the present disclosure will be described. In addition, in this specification, the above-mentioned configuration in the present disclosure is sometimes referred to as follows. A polymer containing a structural unit having an acid group protected by an acid-decomposable group is sometimes called a "specific polymer". The above-mentioned photosensitive resin composition layer is a positive photosensitive resin composition layer, and is sometimes referred to as a "positive photosensitive resin composition layer".

＜偽支撐體＞ 偽支撐體係支撐中間層以及感光性樹脂組成物層，且能夠從中間層或感光性樹脂組成物層剝離之支撐體。 在本公開中使用之偽支撐體從在對感光性樹脂組成物層進行圖案曝光時能夠經由偽支撐體對感光性樹脂組成物層進行曝光之觀點來看，具有透光性為較佳。 具有透光性表示在圖案曝光中使用之光的主波長的透過率為50%以上，在圖案曝光中使用之光的主波長的透過率從提高曝光靈敏度之觀點來看，60%以上為較佳，70%以上為更佳。另外，上述透過率的上限值為100%。作為透過率的測量方法，可舉出利用Otsuka Electronics Co.,Ltd.製MCPD Series進行測量之方法。 作為偽支撐體，可舉出玻璃基板、樹脂薄膜、紙等，從強度以及撓性等觀點來看，樹脂薄膜為特佳。作為樹脂薄膜，可舉出聚對酞酸乙二酯薄膜、三乙酸纖維素薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜等。其中，雙軸拉伸聚對酞酸乙二酯薄膜為特佳。<Pseudo Support> The pseudo support system supports the intermediate layer and the photosensitive resin composition layer and can be peeled from the intermediate layer or the photosensitive resin composition layer. The dummy support used in the present disclosure is preferably light-transmissive from the viewpoint that the photosensitive resin composition layer can be exposed via the dummy support when the photosensitive resin composition layer is pattern exposed. Transparency means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is more than 60% from the viewpoint of improving the exposure sensitivity Good, more than 70% is even better. In addition, the upper limit of the transmittance is 100%. As a method of measuring the transmittance, a method of measuring with MCPD Series manufactured by Otsuka Electronics Co., Ltd. can be mentioned. Examples of the pseudo support include glass substrates, resin films, and paper. From the viewpoint of strength and flexibility, resin films are particularly preferred. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among them, the biaxially stretched polyethylene terephthalate film is particularly preferred.

偽支撐體的厚度沒有特別的限定，5μm～200μm的範圍為較佳，從操作容易性、通用性等觀點來看，10μm～150μm的範圍為更佳。 偽支撐體的厚度從作為支撐體之強度、與電路配線形成用基板的貼合所要求之撓性、最初的曝光製程中所要求之透光性等觀點來看，根據材質選擇即可。The thickness of the pseudo support is not particularly limited, and the range of 5 μm to 200 μm is preferable, and the range of 10 μm to 150 μm is more preferable from the viewpoints of ease of handling and versatility. The thickness of the dummy support may be selected according to the strength of the support, flexibility required for bonding to the circuit wiring forming substrate, and light transmittance required in the initial exposure process.

關於偽支撐體的較佳態樣例如在日本特開2014-85643號公報的0017段～0018段中有記載，該公報的內容編入於本說明書中。A preferred form of the pseudo-support is described in paragraphs 0017 to 0018 of Japanese Patent Laid-Open No. 2014-85643, and the contents of this publication are incorporated in this specification.

＜中間層＞ 本公開之感光性轉印材料在偽支撐體和感光性樹脂組成物層之間具有含有樹脂C之中間層，前述樹脂C係水溶性或鹼溶性，且包含具有酚性羥基或未直接連結於主鏈之醇性羥基之構成單元（亦簡單稱作“樹脂C”。）。 另外，本發明人等發現當僅使用包含具有直接連結於主鏈之醇性羥基之構成單元之樹脂例如如聚乙烯醇的樹脂時，產生所獲得之圖案形狀的變形。本發明人等推斷，在直接連結於主鏈之醇性羥基中，由於主鏈的立體障礙，無法藉由上述羥基來捕捉來自於已脫離之酸分解性基之化合物，從而無法獲得充分的效果。 並且，在本公開中，“主鏈”表示在構成樹脂之高分子化合物的分子中相對最長的鍵結鏈，“側鎖”表示從主鏈支化之碳鏈。<Intermediate layer> The photosensitive transfer material of the present disclosure has an intermediate layer containing a resin C between the pseudo-support and the photosensitive resin composition layer. The aforementioned resin C is water-soluble or alkali-soluble and contains a phenolic hydroxyl group or Constituent units of alcoholic hydroxyl groups that are not directly linked to the main chain (also simply called "Resin C"). In addition, the present inventors have found that when only a resin containing a structural unit having an alcoholic hydroxyl group directly connected to the main chain, such as a resin such as polyvinyl alcohol, is used, a deformation of the obtained pattern shape occurs. The inventors inferred that in the alcoholic hydroxyl group directly linked to the main chain, due to the steric hindrance of the main chain, the compound derived from the acid-decomposable group that has been detached cannot be captured by the above-mentioned hydroxyl group, and sufficient effects cannot be obtained. . Also, in the present disclosure, "main chain" means a relatively longest bonding chain among molecules of a polymer compound constituting a resin, and "sidelock" means a carbon chain branched from the main chain.

-樹脂C- 樹脂C係水溶性或鹼溶性，且包含具有酚性羥基或未直接連結於主鏈之醇性羥基之構成單元之樹脂，重複包含上述構成單元之樹脂為較佳。作為構成單元，藉由在樹脂C中具有大量上述羥基，更加抑制所獲得之圖案形狀的變形。 另外，在本公開中，“水溶性”表示在25℃中在pH7.0的水中可溶，“鹼溶性”表示在25℃中在pH8.5以上的鹼水溶液中可溶。 並且，上述“水溶性或鹼溶性”可為水溶性或鹼溶性中之任一種，亦可為水溶性且鹼溶性。-Resin C- Resin C is a water-soluble or alkali-soluble resin and contains a structural unit having a phenolic hydroxyl group or an alcoholic hydroxyl group that is not directly linked to the main chain, and a resin containing the above structural unit repeatedly is preferably. As a structural unit, by having a large number of the above-mentioned hydroxyl groups in the resin C, the deformation of the obtained pattern shape is more suppressed. In addition, in the present disclosure, “water-soluble” means soluble in water at pH 7.0 at 25 ° C., and “alkali-soluble” means soluble in alkaline aqueous solution at pH 8.5 or higher at 25 ° C. In addition, the "water-soluble or alkali-soluble" may be either water-soluble or alkali-soluble, or may be water-soluble and alkali-soluble.

作為樹脂C，可舉出包含具有酚性羥基之構成單元之樹脂、以及包含具有未直接連結於主鏈之醇性羥基之構成單元之樹脂。 作為包含具有酚性羥基之構成單元之樹脂，例如可舉出苯酚甲醛樹脂、間甲酚甲醛樹脂、對甲酚甲醛樹脂、m-/p-混合甲酚甲醛樹脂、苯酚/甲酚（可為m-、p-或m-/p-混合中之任一種）混合甲醛樹脂等酚醛清漆樹脂、鄰苯三酚丙酮樹脂、聚羥基苯乙烯樹脂等。 作為包含具有未直接連結於主鏈之醇性羥基之構成單元之樹脂，可舉出改質纖維素樹脂、具有羥基之丙烯酸樹脂（例如羥烷基（甲基）丙烯酸酯的單獨聚合物或共聚物）、淀粉類、糖原類、甲殼素類、瓊脂糖類、卡拉膠類、普魯闌多糖類、***膠、大豆膠等。As the resin C, a resin containing a structural unit having a phenolic hydroxyl group and a resin containing a structural unit having an alcoholic hydroxyl group not directly linked to the main chain can be mentioned. Examples of the resin containing a structural unit having a phenolic hydroxyl group include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, and phenol / cresol (can be m-, p- or m- / p-mixing) mixed with novolak resins such as formaldehyde resins, pyrogallol acetone resins, polyhydroxystyrene resins, etc. Examples of the resin containing a structural unit having an alcoholic hydroxyl group not directly linked to the main chain include modified cellulose resins, acrylic resins having a hydroxyl group (for example, individual polymers or copolymers of hydroxyalkyl (meth) acrylates) Substances), starches, glycogen, chitins, agaroses, carrageenans, pullulan, gum arabic, soy gum, etc.

在該等之中，從抑制圖案形狀的變形之觀點來看，樹脂C係選自由酚醛清漆樹脂、改質纖維素樹脂以及具有羥基之丙烯酸樹脂組成的群之至少1種樹脂為較佳，選自由改質纖維素樹脂以及具有羥基之丙烯酸樹脂組成的群之至少1種樹脂為更佳，改質纖維素樹脂為進一步較佳。 並且，作為改質纖維素樹脂，從抑制圖案形狀的變形之觀點來看，羥烷基化纖維素為較佳。 作為羥烷基化纖維素，可較佳地舉出羥甲基纖維素、羥乙基纖維素、聚羥乙基化纖維素、羥丙基纖維素、羥丙基甲基纖維素、乙二醛化羥丙基甲基纖維素、羥丙基甲基纖維素鄰苯二甲酸酯等。 其中，從抑制圖案形狀的變形之觀點來看，選自由羥丙基纖維素以及羥丙基甲基纖維素組成的群之至少1種樹脂為較佳，羥丙基甲基纖維素為更佳。Among these, from the viewpoint of suppressing the deformation of the pattern shape, the resin C is preferably at least one resin selected from the group consisting of novolak resin, modified cellulose resin, and acrylic resin having a hydroxyl group. At least one resin of the group consisting of free modified cellulose resin and acrylic resin having hydroxyl group is more preferable, and modified cellulose resin is more preferable. In addition, as the modified cellulose resin, hydroxyalkylated cellulose is preferred from the viewpoint of suppressing the deformation of the pattern shape. As the hydroxyalkylated cellulose, preferably hydroxymethyl cellulose, hydroxyethyl cellulose, polyhydroxyethylated cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, ethylene glycol Hydroxypropyl methyl cellulose, hydroxypropyl methyl cellulose phthalate, etc. Among them, from the viewpoint of suppressing the deformation of the pattern shape, at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropyl methyl cellulose is preferred, and hydroxypropyl methyl cellulose is more preferred .

樹脂C的重量平均分子量從抑制圖案形狀的變形、以及曝光後的顯影液中的溶解性以及轉印性的觀點來看，1,000以上為較佳，2,000～100,000為更佳，10,000～50,000為進一步較佳。The weight average molecular weight of the resin C is preferably 1,000 or more, preferably 2,000 to 100,000, and more preferably 10,000 to 50,000 from the viewpoint of suppressing the deformation of the pattern shape and the solubility and transferability in the developer after exposure. Better.

上述中間層可單獨含有1種樹脂C，亦可含有2種以上。 中間層中的樹脂C的含量從抑制圖案形狀的變形、以及曝光後的顯影液中的溶解性以及轉印性的觀點來看，相對於中間層的總質量為10質量%以上100質量%以下為較佳，20質量%以上100質量%以下為更佳，40質量%以上100質量%以下為進一步較佳，65質量%以上85質量%以下為特佳。The intermediate layer may contain one kind of resin C alone or two or more kinds. The content of the resin C in the intermediate layer is 10% by mass or more and 100% by mass or less relative to the total mass of the intermediate layer from the viewpoint of suppressing the deformation of the pattern shape and the solubility and transferability in the developer after exposure. Preferably, 20 mass% or more and 100 mass% or less is more preferable, 40 mass% or more and 100 mass% or less is more preferably, and 65 mass% or more and 85 mass% or less is particularly preferable.

-樹脂D- 本公開之感光性轉印材料從曝光後的顯影液中的溶解性以及轉印性的觀點來看，進一步含有除了上述樹脂C以外的水溶性或鹼溶性之樹脂D為較佳。 作為樹脂D，可舉出除了樹脂C以外的聚醯胺樹脂、環氧樹脂、聚縮醛樹脂、丙烯酸樹脂、聚苯乙烯樹脂、聚氨酯樹脂、聚乙烯醇、聚乙烯醇縮甲醛、聚酯樹脂、聚伸乙亞胺、聚烯丙基胺、聚亞烷基二醇等。 其中，作為樹脂D，從曝光後的顯影液中的溶解性以及轉印性的觀點來看，選自由聚丙烯酸、聚丙烯酸鈉、聚丙烯醯胺、聚環氧乙烷、聚伸乙亞胺、聚乙烯醇以及聚乙烯吡咯啶酮組成的群之至少1種樹脂為較佳，選自由聚乙烯醇以及聚乙烯吡咯啶酮組成的群之至少1種樹脂為更佳。-Resin D- From the viewpoint of the solubility and transferability in the developer after exposure, the photosensitive transfer material of the present disclosure further preferably contains a water-soluble or alkali-soluble resin D other than the above-mentioned resin C . Examples of the resin D include polyamide resins other than resin C, epoxy resins, polyacetal resins, acrylic resins, polystyrene resins, polyurethane resins, polyvinyl alcohol, polyvinyl formal, and polyester resins. , Polyethyleneimine, polyallylamine, polyalkylene glycol, etc. Among them, the resin D is selected from the group consisting of polyacrylic acid, sodium polyacrylate, polyacrylamide, polyethylene oxide, and polyethyleneimine from the viewpoint of solubility and transferability in the developer after exposure. At least one resin of the group consisting of polyvinyl alcohol and polyvinylpyrrolidone is preferred, and at least one resin selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone is more preferred.

樹脂D的重量平均分子量從曝光後的顯影液中的溶解性以及轉印性的觀點來看，1,000以上為較佳，2,000～100,000為更佳，10,000～50,000為進一步較佳。From the viewpoint of solubility and transferability in the developer after exposure, the weight average molecular weight of the resin D is preferably 1,000 or more, more preferably 2,000 to 100,000, and even more preferably 10,000 to 50,000.

上述中間層可單獨含有1種樹脂D，亦可含有2種以上。 中間層中的樹脂D的含量從抑制圖案形狀的變形、以及曝光後的顯影液中的溶解性以及轉印性的觀點來看，相對於中間層的總質量為1質量%以上80質量%以下為較佳，5質量%以上50質量%以下為更佳，10質量%以上40質量%以下為進一步較佳，15質量%以上35質量%以下為特佳。 並且，中間層中的樹脂D的含量從抑制圖案形狀的變形之觀點來看，以質量換算為樹脂C的含量以下為較佳。The intermediate layer may contain one kind of resin D alone or two or more kinds. The content of the resin D in the intermediate layer is 1% by mass or more and 80% by mass or less relative to the total mass of the intermediate layer from the viewpoint of suppressing the deformation of the pattern shape and the solubility and transferability in the developer after exposure. Preferably, 5 mass% or more and 50 mass% or less are more preferable, 10 mass% or more and 40 mass% or less are more preferably, and 15 mass% or more and 35 mass% or less are particularly preferable. In addition, the content of the resin D in the intermediate layer is preferably the content of the resin C or less in terms of mass from the viewpoint of suppressing the deformation of the pattern shape.

並且，上述中間層中之樹脂C和樹脂D的含有質量比從抑制圖案形狀的變形、以及曝光後的顯影液中的溶解性以及轉印性的觀點來看，樹脂C:樹脂D=5:1～1:2為較佳，4:1～2:1為更佳，3.5:1～2.5:1為進一步較佳。In addition, the content ratio of the resin C and the resin D in the intermediate layer is from the viewpoint of suppressing the deformation of the pattern shape and the solubility and transferability in the developer after exposure, and the resin C: resin D = 5: 1 to 1: 2 is preferred, 4: 1 to 2: 1 is more preferred, and 3.5: 1 to 2.5: 1 is further preferred.

-其他添加劑- 本公開中之上述中間層除了樹脂C以及樹脂D以外，還能夠根據需要包含公知的添加劑。 作為其他添加劑，可較佳地舉出後述之在感光性樹脂組成物層中使用之其他添加劑。-Other Additives- The above-mentioned intermediate layer in the present disclosure may contain well-known additives in addition to the resin C and the resin D as needed. As other additives, other additives used in the photosensitive resin composition layer described later can be preferably mentioned.

-中間層的厚度- 上述中間層的厚度從抑制圖案形狀的變形之觀點來看，0.1μm～10μm為較佳，0.2μm～8μm為更佳，0.5μm～5μm為特佳。 並且，上述中間層的厚度比上述感光性樹脂組成物層的厚度薄為較佳。-Thickness of the intermediate layer- From the viewpoint of suppressing the deformation of the pattern shape, the thickness of the intermediate layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 8 μm, and particularly preferably 0.5 μm to 5 μm. Furthermore, the thickness of the intermediate layer is preferably thinner than the thickness of the photosensitive resin composition layer.

-中間層的形成方法- 中間層的形成方法沒有特別的限定，能夠將各成分以及溶劑以特定比例且以任意方法進行混合，並進行攪拌溶解來製備用於形成中間層之中間層形成用組成物（亦稱作“中間層組成物”。）。例如，亦能夠製成使各成分分別預先溶解於溶劑中之溶液後，將所獲得之溶液以特定比例進行混合來製備組成物。如上製備之組成物能夠在使用孔徑5μm的過濾器等進行過濾後提供於使用。-Method for forming the intermediate layer- The method for forming the intermediate layer is not particularly limited, and the components and the solvent can be mixed in a specific ratio and in any method, and stirred and dissolved to prepare an intermediate layer forming composition for forming the intermediate layer Thing (also called "intermediate layer composition."). For example, it is also possible to prepare a solution in which each component is dissolved in a solvent in advance, and then mix the obtained solution at a specific ratio to prepare a composition. The composition prepared as described above can be provided for use after filtration using a filter with a pore size of 5 μm or the like.

藉由將中間層組成物塗佈於偽支撐體並使其乾燥，能夠容易地在偽支撐體上形成中間層。 塗佈方法沒有特別的限定，能夠以狹縫塗佈、旋塗、簾塗、噴墨塗佈等公知的方法進行塗佈。 另外，亦能夠在偽支撐體上形成後述其他層（例如熱塑性樹脂層等）並在之上塗佈中間層。By applying the intermediate layer composition to the dummy support and drying it, the intermediate layer can be easily formed on the dummy support. The coating method is not particularly limited, and can be applied by a well-known method such as slit coating, spin coating, curtain coating, and inkjet coating. In addition, it is also possible to form another layer (for example, a thermoplastic resin layer, etc.) described later on the dummy support and apply an intermediate layer thereon.

＜感光性樹脂組成物層＞ 本公開之感光性轉印材料依次具有偽支撐體、中間層、感光性樹脂組成物層，上述感光性樹脂組成物層含有聚合物和光酸產生劑，前述聚合物包含具有被酸分解性基保護之酸基之構成單元。 並且，本公開中之感光性樹脂組成物層係正型感光性樹脂組成物層，化學增幅正型感光性樹脂組成物層為較佳。 後述之鎓鹽或肟磺酸鹽化合物等光酸產生劑中，感應活性放射線（光化射線）而生成之酸對上述特定聚合物中的被保護之酸基的脫保護作為觸媒發揮作用，因此以1個光量子的作用生成之酸有助於多數的脫保護反應，量子產率超過1成為例如10的數次方那樣大的值，作為所謂化學增幅的結果，可獲得高靈敏度。 另一方面，作為感應活性放射線之光酸產生劑而使用了醌二疊氮化合物時，藉由逐次型光化學反應而生成羧基，其量子產率一定為1以下，但在化學增幅型中並非如此。<Photosensitive resin composition layer> The photosensitive transfer material of this disclosure has a pseudo support, an intermediate layer, and a photosensitive resin composition layer in this order, and the said photosensitive resin composition layer contains a polymer and a photo-acid generator, the said polymer Consists of constituent units with acid groups protected by acid-decomposable groups. In addition, the photosensitive resin composition layer in the present disclosure is a positive photosensitive resin composition layer, and the chemically amplified positive photosensitive resin composition layer is preferable. In a photoacid generator such as an onium salt or an oxime sulfonate compound described later, the acid generated by induction of active radiation (actinic rays) deprotects the protected acid group in the specific polymer as a catalyst, Therefore, the acid generated by the action of one light quantum contributes to most deprotection reactions, and the quantum yield exceeds 1 to a value as large as a power of 10, for example. As a result of so-called chemical amplification, high sensitivity can be obtained. On the other hand, when a quinonediazide compound is used as a photoacid generator for inductively active radiation, the carboxyl group is generated by successive photochemical reactions, and its quantum yield must be 1 or less, but it is not in the chemical amplification type in this way.

-含有包含具有被酸分解性基保護之酸基之構成單元之聚合物之聚合物成分- 上述感光性樹脂組成物層包含聚合物（亦稱作“特定聚合物”。），前述聚合物包含具有被酸分解性基保護之酸基之構成單元（亦稱作“構成單元A”。）。 並且，上述感光性樹脂組成物層中除了具有構成單元A之聚合物以外，還可以包含其他聚合物。在本公開中，亦將具有構成單元A之聚合物以及其他聚合物統稱為“聚合物成分”。 上述特定聚合物藉由由曝光產生之觸媒量的酸性物質的作用，特定聚合物中的具有被酸分解性基保護之酸基之構成單元A受到脫保護反應而成為酸基。藉由該酸基，能夠進行固化反應。 以下對構成單元A的較佳態樣進行說明。-A polymer component containing a polymer containing a structural unit having an acid group protected by an acid-decomposable group- The above-mentioned photosensitive resin composition layer contains a polymer (also referred to as "specific polymer".), And the aforementioned polymer contains Constituent units with acid groups protected by acid-decomposable groups (also called "constituent unit A"). Furthermore, the photosensitive resin composition layer may contain other polymers in addition to the polymer having the structural unit A. In the present disclosure, the polymer having the constituent unit A and other polymers are also collectively referred to as "polymer component". The specific polymer has an acid group protected by an acid-decomposable group, and the structural unit A in the specific polymer is deprotected by the action of an acidic substance in the amount of catalyst generated by exposure to become an acid group. With this acid group, a curing reaction can proceed. Hereinafter, preferred aspects of the constituent unit A will be described.

上述感光性樹脂組成物層可進一步含有除了包含具有被酸分解性基保護之酸基之構成單元之聚合物以外的聚合物。 並且，上述聚合物成分中所含之全部聚合物分別係至少包含後述之具有酸基之構成單元之聚合物為較佳。 並且，上述化學增幅正型感光性樹脂組成物可進一步包含除該等以外的聚合物。本公開中之上述聚合物成分只要沒有特別的說明，則表示包含根據需要添加之其他聚合物者。另外，相當於後述之交聯劑以及分散劑之化合物設為即使係高分子化合物亦不包含於上述聚合物成分者。The photosensitive resin composition layer may further contain a polymer other than the polymer containing a structural unit having an acid group protected by an acid-decomposable group. In addition, it is preferable that all of the polymers contained in the above-mentioned polymer components each include at least a structural unit having an acid group described later. In addition, the chemically amplified positive photosensitive resin composition may further contain polymers other than these. Unless otherwise specified, the above-mentioned polymer component in the present disclosure means that it contains other polymers added as necessary. In addition, the compounds corresponding to the crosslinking agent and the dispersing agent described later are not included in the above-mentioned polymer component even if it is a polymer compound.

特定聚合物係加成聚合型樹脂為較佳，具有來自於（甲基）丙烯酸或其酯之構成單元之聚合物為更佳。另外，亦可以具有除了來自於（甲基）丙烯酸或其酯之構成單元以外的構成單元，例如來自於苯乙烯之構成單元或來自於乙烯基化合物之構成單元等。A specific polymer is preferably an addition polymerization type resin, and a polymer having a structural unit derived from (meth) acrylic acid or its ester is more preferable. In addition, it may have a structural unit other than the structural unit derived from (meth) acrylic acid or its ester, for example, a structural unit derived from styrene or a structural unit derived from a vinyl compound.

上述感光性樹脂組成物層從抑制圖案形狀的變形、以及顯影液中的溶解性以及轉印性的觀點來看，作為聚合物成分，包含作為上述構成單元A具有以下述式A1表示之構成單元A1之聚合物為較佳，作為聚合物成分包含作為上述構成單元A具有以下述式A1表示之構成單元A1，且玻璃轉移溫度為90℃以下之特定聚合物為較佳，作為聚合物成分包含作為上述構成單元A具有以下述式A1表示之構成單元A1以及後述之具有酸基之構成單元B，且玻璃轉移溫度為90℃以下之特定聚合物為進一步較佳。 上述感光性樹脂組成物層中所含之特定聚合物可僅為1種，亦可為2種以上。The above-mentioned photosensitive resin composition layer contains the structural unit represented by the following formula A1 as the above-mentioned structural unit A as the polymer component from the viewpoint of suppressing the deformation of the pattern shape and the solubility and transferability in the developer. The polymer of A1 is preferable, and as the polymer component, a specific polymer having the above-mentioned structural unit A having a structural unit A1 represented by the following formula A1 and having a glass transition temperature of 90 ° C. or less is preferable. As the above-mentioned structural unit A, a specific polymer having a structural unit A1 represented by the following formula A1 and a structural unit B having an acid group to be described later, and having a glass transition temperature of 90 ° C. or lower, is more preferable. The specific polymer contained in the photosensitive resin composition layer may be only one kind, or two or more kinds.

＜＜構成單元A＞＞ 上述聚合物成分包含聚合物，前述聚合物至少包含具有被酸分解性基保護之酸基之構成單元A。藉由上述聚合物成分包含具有構成單元A之聚合物，能夠製成靈敏度極高的化學增幅正型感光性樹脂組成物層。 本公開中之“被酸分解性基保護之酸基”能夠使用作為酸基以及酸分解性基公知者，並沒有特別的限定。作為具體的酸基可較佳地舉出羧基以及酚性羥基。並且，作為被酸分解性基保護之酸基，能夠使用比較容易藉由酸分解之基（例如被以式A1表示之基保護之酯基、四氫吡喃酯基或四氫呋喃酯基等縮醛系官能基）或比較難以藉由酸分解之基（例如叔丁酯基等三級烷基、碳酸叔丁酯基等碳酸三級烷基酯基）。 在該等之中，作為上述酸分解性基，具有以縮醛的形態被保護之結構之基團為較佳。<< Constitutional unit A >> The polymer component includes a polymer, and the polymer includes at least a structural unit A having an acid group protected by an acid-decomposable group. By including the polymer having the structural unit A in the polymer component, a chemically amplified positive photosensitive resin composition layer with extremely high sensitivity can be produced. The “acid group protected by an acid-decomposable group” in the present disclosure can be used as well-known as an acid group and an acid-decomposable group, and is not particularly limited. Specific acid groups preferably include carboxyl groups and phenolic hydroxyl groups. In addition, as the acid group protected by an acid-decomposable group, an acetal such as an ester group protected by a group represented by Formula A1, a tetrahydropyranyl group, or a tetrahydrofuran ester group can be used, which is relatively easily decomposed by an acid It is a functional group) or a group that is relatively difficult to be decomposed by acid (for example, tertiary alkyl group such as tert-butyl ester group, tertiary alkyl carbonate group such as tert-butyl carbonate group). Among these, as the acid-decomposable group, a group having a structure protected in the form of an acetal is preferred.

＜＜構成單元A＞＞ 上述具有被酸分解性基保護之酸基之構成單元A從靈敏度以及解析度的觀點來看，以下述式A1表示之構成單元A1為較佳。<< Constitutional Unit A >> The structural unit A having an acid group protected by an acid-decomposable group is preferably a structural unit A1 represented by the following formula A1 from the viewpoint of sensitivity and resolution.

[化學式2] [Chemical Formula 2]

在式A1中，R31 以及R32 分別獨立地表示氫原子、烷基或芳基，R31 以及R32 中之至少一者係烷基或芳基，R33 表示烷基或芳基，R31 或R32 可與R33 連結而形成環狀醚，R34 表示氫原子或甲基，X0 表示單鍵或伸芳基。In formula A1, R 31 and R 32 independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 represents an alkyl group or an aryl group, R 31 or R 32 may be linked to R 33 to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or an aryl group.

在式A1中，當R31 或R32 為烷基時，碳原子數為1～10的烷基為較佳。當R31 或R32 為芳基時，苯基為較佳。R31 以及R32 分別為氫原子或碳原子數1～4的烷基為較佳。 在式A1中，R33 表示烷基或芳基，碳原子數1～10的烷基為較佳，碳原子數1～6的烷基為更佳。 並且，R31 ～R33 中之烷基以及芳基可具有取代基。 在式A1中，R31 或R32 可與R33 連結而形成環狀醚，R31 或R32 與R33 連結而形成環狀醚為較佳。環狀醚的環元數沒有特別的限定，5或6為較佳，5為更佳。 在式A1中，X0 表示單鍵或伸芳基，單鍵為較佳。伸芳基可具有取代基。 以上述式A1表示之構成單元A1係具有被酸分解性基保護之羧基之構成單元。特定聚合物包含以式A1表示之構成單元A1，藉此在圖案形成時的靈敏度優異，並且解析度更優異。In formula A1, when R 31 or R 32 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. When R 31 or R 32 is an aryl group, phenyl is preferred. R 31 and R 32 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In formula A1, R 33 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. In addition, the alkyl group and the aryl group in R 31 to R 33 may have a substituent. In Formula A1, R 31 or R 32 may be linked to R 33 to form a cyclic ether, and R 31 or R 32 to R 33 may be linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, and 5 or 6 is preferred, and 5 is more preferred. In formula A1, X 0 represents a single bond or an aryl group, and a single bond is preferred. The arylene group may have a substituent. The structural unit A1 represented by the above formula A1 is a structural unit having a carboxyl group protected by an acid-decomposable group. The specific polymer includes the structural unit A1 represented by the formula A1, whereby the sensitivity at the time of pattern formation is excellent, and the resolution is more excellent.

在式A1中，R34 表示氫原子或甲基，從能夠更加降低特定聚合物的Tg之觀點來看，氫原子為較佳。 更具體而言，相對於在特定聚合物中所含之構成單元A1的總量，式A中之R34 為氫原子之構成單元為20質量%以上為較佳。 另外，構成單元A1中的式A1中之R34 為氫原子之構成單元的含量（含有比例:質量比）能夠藉由依據13 C-核磁共振（NMR）測量並以常規方法算出之峰值強度的強度比來確認。In Formula A1, R 34 represents a hydrogen atom or a methyl group, and from the viewpoint of being able to further lower the Tg of a specific polymer, a hydrogen atom is preferred. More specifically, it is preferable that the structural unit in which R 34 in the formula A is a hydrogen atom is 20% by mass or more with respect to the total amount of the structural unit A1 contained in the specific polymer. In addition, the content of the structural unit in which R 34 in the structural unit A1 is a hydrogen atom (content ratio: mass ratio) can be measured by 13 C-nuclear magnetic resonance (NMR) and calculated by a conventional method of peak intensity Strength ratio to confirm.

以式A1表示之構成單元A1中，從進一步提高圖案形成時的靈敏度之觀點來看，以下述式A2表示之構成單元亦為更佳。In the structural unit A1 represented by the formula A1, the structural unit represented by the following formula A2 is also preferable from the viewpoint of further improving the sensitivity at the time of pattern formation.

[化學式3] [Chemical Formula 3]

在式A2中，R34 表示氫原子或甲基，R35 ～R41 分別獨立地表示氫原子或碳原子數1～4的烷基。 在式A2中，R34 為氫原子為較佳。 在式A2中，R35 ～R41 為氫原子為較佳。In formula A2, R 34 represents a hydrogen atom or a methyl group, and R 35 to R 41 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In formula A2, R 34 is preferably a hydrogen atom. In formula A2, R 35 to R 41 are preferably hydrogen atoms.

作為以式A1表示之具有被酸分解性基保護之羧基之構成單元A1的較佳具體例，能夠例示下述構成單元。另外，R34 表示氫原子或甲基。As a preferred specific example of the structural unit A1 represented by the formula A1 having a carboxyl group protected by an acid-decomposable group, the following structural units can be exemplified. In addition, R 34 represents a hydrogen atom or a methyl group.

[化學式4] [Chemical Formula 4]

並且，作為上述構成單元A，從抑制圖案形狀的變形的觀點來看，以下述式A3表示之構成單元為較佳。In addition, as the above-mentioned structural unit A, a structural unit represented by the following formula A3 is preferable from the viewpoint of suppressing the deformation of the pattern shape.

[化學式5] [Chemical Formula 5]

在式A3中，RB1 以及RB2 分別獨立地表示氫原子、烷基或芳基，RB1 以及RB2 中之至少一者係烷基或芳基，RB3 表示烷基或芳基，RB1 或RB2 可與RB3 連結而形成環狀醚，RB4 表示氫原子或甲基，XB 表示單鍵或二價的連接基團，RB12 表示取代基，n表示0～4的整數。In formula A3, R B1 and R B2 independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R B1 and R B2 is an alkyl or aryl group, and R B3 represents an alkyl or aryl group, R B1 or R B2 can be linked to R B3 to form a cyclic ether, R B4 represents a hydrogen atom or a methyl group, X B represents a single bond or a divalent linking group, R B12 represents a substituent, n represents an integer of 0 to 4 .

在式A3中，當RB1 或RB2 為烷基時，碳原子數為1～10的烷基為較佳。當RB1 或RB2 為芳基時，苯基為較佳。RB1 以及RB2 分別為氫原子或碳原子數1～4的烷基為較佳。 在式A3中，RB3 表示烷基或芳基，碳原子數1～10的烷基為較佳，碳原子數1～6的烷基為更佳。 並且，RB1 ～RB3 中之烷基以及芳基可具有取代基。 在式A3中，RB1 或RB2 可與RB3 連結而形成環狀醚，RB1 或RB2 與RB3 連結而形成環狀醚為較佳。環狀醚的環元數沒有特別的限定，5或6為較佳，5為更佳。 在式A3中，XB 表示單鍵或二價的連接基團，單鍵或伸烷基、-C（=O）O-、-C（=O）NRN -、-O-或該等的組合為較佳，單鍵為更佳。伸烷基可以係直鏈狀且可具有分叉亦可具有環狀結構，亦可具有取代基。伸烷基的碳原子數為1～10為較佳，1～4為更佳。當XB 包含-C（=O）O-時，在-C（=O）O-中所含之碳原子和與RB4 鍵結之碳原子直接鍵結之態樣為較佳。當XB 包含-C（=O）NRN -時，-C（=O）NRN -中所含之碳原子和與RB4 鍵結之碳原子直接鍵結之態樣為較佳。RN 表示烷基或氫原子，碳原子數1～4的烷基或氫原子為較佳，氫原子為更佳。 在式A3中，包含RB1 ～RB3 之基團和XB 以亙相對位鍵結為較佳。 在式A3中，RB12 表示取代基、烷基或鹵素原子為較佳。烷基的碳原子數為1～10為較佳，1～4為更佳。 在式A3中，n表示0～4的整數，0或1為較佳，0為更佳。In formula A3, when R B1 or R B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. When R B1 or R B2 is an aryl group, phenyl is preferred. R B1 and R B2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In formula A3, R B3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. In addition, the alkyl group and the aryl group in R B1 to R B3 may have a substituent. In formula A3, R B1 or R B2 may be linked to R B3 to form a cyclic ether, and R B1 or R B2 and R B3 may be linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, and 5 or 6 is preferred, and 5 is more preferred. In formula A3, X B represents a single bond or a divalent linking group, a single bond or an alkylene group, -C (= O) O-, -C (= O) NR N- , -O- or these Is better, and single bonds are better. The alkylene group may be linear and may have a branch or a cyclic structure, or may have a substituent. The number of carbon atoms of the alkylene group is preferably 1-10, and more preferably 1-4. When X B contains -C (= O) O-, the carbon atom contained in -C (= O) O- and the carbon atom bonded to R B4 are directly bonded. When X B contains -C (= O) NR N- , the carbon atom contained in -C (= O) NR N -is directly bonded to the carbon atom bonded to R B4 . R N represents an alkyl group or a hydrogen atom. An alkyl group having 1 to 4 carbon atoms or a hydrogen atom is preferred, and a hydrogen atom is more preferred. In formula A3, it is preferable that the group including R B1 to R B3 and X B be bonded in a relative position. In formula A3, R B12 preferably represents a substituent, an alkyl group, or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1-10, and more preferably 1-4. In formula A3, n represents the integer of 0-4, 0 or 1 is preferable, and 0 is more preferable.

在式A3中，RB4 表示氫原子或甲基，從更加降低特定聚合物的Tg之觀點來看，氫原子為較佳。 更具體而言，相對於特定聚合物中所含之構成單元A的總含量，式A3中之RB4 為氫原子之構成單元為20質量%以上為較佳。 另外，構成單元A中的式A3中之RB4 為氫原子之構成單元的含量（含有比例:質量比）能夠藉由依據13 C-核磁共振（NMR）測量並以常規方法算出之峰值強度的強度比來確認。In Formula A3, R B4 represents a hydrogen atom or a methyl group, and from the viewpoint of further reducing the Tg of a specific polymer, a hydrogen atom is preferred. More specifically, it is preferable that the structural unit in which R B4 in the formula A3 is a hydrogen atom is 20% by mass or more with respect to the total content of the structural unit A contained in the specific polymer. Further, in the constituting unit A of the formula A3, R B4 is a hydrogen atom content of the constituent units (content ratio: mass ratio) of the peak intensity can be 13 C- nuclear magnetic resonance (NMR) measurements and is calculated according to the conventional manner by the Strength ratio to confirm.

以式A3表示之構成單元中，從抑制圖案形狀的變形之觀點來看，以下述式A4表示之構成單元亦為更佳。Among the structural units represented by the formula A3, the structural unit represented by the following formula A4 is also preferable from the viewpoint of suppressing the deformation of the pattern shape.

[化學式6] [Chemical Formula 6]

在式A4中，RB4 表示氫原子或甲基，RB5 ～RB11 分別獨立地表示氫原子或碳原子數1～4的烷基，RB12 表示取代基，n表示0～4的整數。 在式A4中，RB4 為氫原子為較佳。 在式A4中，RB5 ～RB11 為氫原子為較佳。 在式A4中，RB12 表示取代基，烷基或鹵素原子為較佳。烷基的碳原子數為1～10為較佳，1～4為更佳。 在式A4中，n表示0～4的整數，0或1為較佳，0為更佳。In Formula A4, R B4 represents a hydrogen atom or a methyl group, R B5 to R B11 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R B12 represents a substituent, and n represents an integer of 0 to 4. In formula A4, R B4 is preferably a hydrogen atom. In formula A4, R B5 to R B11 are preferably hydrogen atoms. In formula A4, R B12 represents a substituent, and an alkyl group or a halogen atom is preferred. The number of carbon atoms of the alkyl group is preferably 1-10, and more preferably 1-4. In formula A4, n represents the integer of 0-4, 0 or 1 is preferable, and 0 is more preferable.

作為以式A4表示之構成單元A4的較佳具體例，能夠例示下述構成單元。另外，RB4 表示氫原子或甲基。As a preferable specific example of the structural unit A4 represented by the formula A4, the following structural units can be exemplified. In addition, R B4 represents a hydrogen atom or a methyl group.

[化學式7] [Chemical Formula 7]

在特定聚合物中所含之構成單元A可以係1種，亦可以係2種以上。 特定聚合物中之構成單元A的含量相對於特定聚合物的總質量為20質量%以上為較佳，20質量%～90質量%為更佳，30質量%～70質量%為進一步較佳。 特定聚合物中之構成單元A的含量（含有比例:質量比）能夠藉由依據13 C-NMR測量並以常規方法算出之峰值強度的強度比來確認。 並且，在將全部的聚合物成分分解成構成單元（單體單元）之基礎上，構成單元A的比例相對於聚合物成分的總質量為5質量%～80質量%為較佳，10質量%～80質量%為更佳，30質量%～70質量%為特佳。The structural unit A contained in the specific polymer may be one kind, or two or more kinds. The content of the structural unit A in the specific polymer is preferably 20% by mass or more relative to the total mass of the specific polymer, more preferably 20% by mass to 90% by mass, and still more preferably 30% by mass to 70% by mass. The content (content ratio: mass ratio) of the constituent unit A in the specific polymer can be confirmed by the intensity ratio of the peak intensity measured by 13 C-NMR and calculated by a conventional method. Furthermore, after decomposing all the polymer components into structural units (monomer units), the proportion of the structural unit A is preferably 5% to 80% by mass relative to the total mass of the polymer components, and 10% by mass ～ 80% by mass is better, and 30% to 70% by mass is particularly good.

＜＜構成單元B＞＞ 上述特定聚合物包含具有酸基之構成單元B為較佳。 構成單元B係包含未被保護基例如酸分解性基保護之酸基，亦即不具有保護基之酸基之構成單元。特定聚合物包含構成單元B，藉此在圖案形成時的靈敏度變得良好，在圖案曝光後的顯影製程中變得易溶解於鹼性的顯影液中，能夠實現顯影時間的縮短。 本說明書中之酸基表示pKa為12以下的質子解離性基團。酸基利用能夠形成酸基之單體，作為包含酸基之構成單元（構成單元B）而嵌入到聚合物中為較佳。從提高靈敏度的觀點來看，酸基的pKa為10以下為較佳，6以下為更佳。並且，酸基的pKa為-5以上為較佳。<< Constitutional Unit B >> It is preferable that the specific polymer contains a structural unit B having an acid group. The constituent unit B is a constituent unit that includes an acid group that is not protected by a protective group such as an acid-decomposable group, that is, an acid group that does not have a protective group. The specific polymer contains the constituent unit B, whereby the sensitivity at the time of pattern formation becomes good, it becomes easily soluble in an alkaline developer in the development process after pattern exposure, and the development time can be shortened. The acid group in this specification means a proton dissociative group with a pKa of 12 or less. As the acid group, a monomer capable of forming an acid group is used, and it is preferable to be embedded in the polymer as a structural unit (constituent unit B) containing an acid group. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. In addition, the pKa of the acid group is preferably -5 or more.

特定聚合物將構成單元A和具有未被保護基保護之酸基之構成單元B作為共聚成分而包含在內，藉由將玻璃轉移溫度設為90℃以下，含有特定聚合物之正型感光性樹脂組成物層在將轉印性以及從偽支撐體的剝離性維持在良好的水平之同時，圖案形成時的解析度以及靈敏度變得更良好。The specific polymer contains the structural unit A and the structural unit B having an acid group that is not protected by a protective group as a copolymerization component. By setting the glass transition temperature to 90 ° C. or lower, the positive sensitivity containing the specific polymer The resin composition layer maintains the transferability and the peelability from the pseudo support at a good level, and the resolution and sensitivity at the time of pattern formation become better.

作為上述酸基，可例示出羧基、磺醯胺基、膦酸基、磺酸基、酚性羥基以及磺醯亞胺基等。其中，選自由羧酸基以及酚性羥基組成的群之至少1種酸基為較佳。 朝向特定聚合物之包含酸基之構成單元的導入能夠藉由使具有酸基之單體共聚合來進行。 作為構成單元B之包含酸基之構成單元為相對於來自於苯乙烯之構成單元或來自於乙烯基化合物之構成單元取代了酸基之構成單元、或來自於（甲基）丙烯酸之構成單元為更佳。Examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonimide group. Among them, at least one acid group selected from the group consisting of carboxylic acid groups and phenolic hydroxyl groups is preferred. The introduction of structural units containing an acid group into a specific polymer can be carried out by copolymerizing a monomer having an acid group. The structural unit containing the acid group as the structural unit B is a structural unit in which an acid group is substituted with respect to a structural unit derived from styrene or a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid is Better.

作為構成單元B，從更加提高圖案形成時的靈敏度之觀點來看，具有羧酸基之構成單元或具有酚性羥基之構成單元為較佳。 能夠形成構成單元B之具有酸基之單體並不限定於已述的例子。As the structural unit B, a structural unit having a carboxylic acid group or a structural unit having a phenolic hydroxyl group is preferred from the viewpoint of further improving the sensitivity during pattern formation. The monomer having an acid group capable of forming the constituent unit B is not limited to the examples described above.

特定聚合物中所含之構成單元B可僅為1種，亦可為2種以上。 特定聚合物中，相對於特定聚合物的總質量包含0.1質量%～20質量%的具有酸基之構成單元（構成單元B）為較佳，包含0.5質量%～15質量%為更佳，包含1質量%～10質量%為進一步較佳。若為上述範圍，則圖案形成性變得更良好。 特定聚合物中之構成單元B的含量（含有比例:質量比）能夠藉由依據13 C-NMR測量並以常規方法算出之峰值強度的強度比來確認。The structural unit B contained in the specific polymer may be only one kind, or two or more kinds. In the specific polymer, it is preferable to contain 0.1% to 20% by mass of a structural unit (constituent unit B) having an acid group with respect to the total mass of the specific polymer, and more preferably to contain 0.5% to 15% by mass. 1% by mass to 10% by mass is further preferable. Within the above range, the pattern formability becomes better. The content (content ratio: mass ratio) of the constituent unit B in the specific polymer can be confirmed by the intensity ratio of the peak intensity measured by 13 C-NMR and calculated by a conventional method.

＜＜其他構成單元＞＞ 在不損害本公開之感光性轉印材料的效果之範圍內，特定聚合物除了已述的構成單元A以及構成單元B以外還可以包含其他構成單元（以下有時稱作構成單元C。）。 作為形成構成單元C之單體沒有特別的限定，例如能夠舉出苯乙烯類、（甲基）丙烯酸烷酯、（甲基）丙烯酸環狀烷酯、（甲基）丙烯酸芳酯、不飽和二羧酸二酯、雙環不飽和化合物、馬來醯亞胺化合物、不飽和芳香族化合物、共軛二烯系化合物、不飽和單羧酸、不飽和二羧酸、不飽和二羧酸酐、具有脂肪族環式骨架之基團以及其他不飽和化合物。 藉由使用構成單元C來調整種類以及含量中之至少任一種，能夠調整特定聚合物的諸特性。尤其藉由適當使用構成單元C，能夠容易地將特定聚合物的Tg調整為90℃以下。 特定聚合物可僅包含1種構成單元C，亦可包含2種以上。<< Other structural units >> Within the range that does not impair the effect of the photosensitive transfer material of the present disclosure, the specific polymer may include other structural units (hereinafter sometimes referred to as hereinafter referred to as structural unit A and structural unit B). As constituent unit C.). The monomer forming the structural unit C is not particularly limited, and examples thereof include styrene, alkyl (meth) acrylate, cyclic alkyl (meth) acrylate, aryl (meth) acrylate, and unsaturated dimethacrylate. Carboxylic diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, with fats Group of cyclic skeletons and other unsaturated compounds. By using the structural unit C to adjust at least any one of the kind and the content, various characteristics of the specific polymer can be adjusted. In particular, by appropriately using the structural unit C, the Tg of the specific polymer can be easily adjusted to 90 ° C or lower. The specific polymer may include only one type of structural unit C, or two or more types.

構成單元C具體而言能夠舉出將苯乙烯、叔丁氧基苯乙烯、甲基苯乙烯、α-甲基苯乙烯、乙醯氧基苯乙烯、甲氧基苯乙烯、乙氧基苯乙烯、氯苯乙烯、乙烯基苯甲酸甲酯、乙烯基苯甲酸乙酯、（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸異丙酯、（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥丙基、（甲基）丙烯酸芐酯、（甲基）丙烯酸異冰片酯、丙烯腈或乙二醇單乙醯乙酸酯（甲基）丙烯酸酯等進行聚合而形成之構成單元。此外，還能夠舉出在日本特開2004-264623號公報的0021段～0024段中記載的化合物。Specific examples of the structural unit C include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, and ethoxystyrene. , Chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate Propyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile or ethylene glycol monoethyl A structural unit formed by polymerization of acetyl acetate (meth) acrylate and the like. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 can also be mentioned.

並且，作為構成單元C，從提高所獲得之轉印材料的電特性之觀點來看，具有芳香環之構成單元或具有脂肪族環式骨架之構成單元為較佳。作為形成該等構成單元之單體，具體而言可舉出苯乙烯、叔丁氧基苯乙烯、甲基苯乙烯、α-甲基苯乙烯、二環戊基（甲基）丙烯酸酯、環己基（甲基）丙烯酸酯、（甲基）丙烯酸異冰片酯以及芐基（甲基）丙烯酸酯等。其中，作為構成單元C，可較佳地舉出來自於環己基（甲基）丙烯酸酯之構成單元。In addition, as the structural unit C, from the viewpoint of improving the electrical characteristics of the obtained transfer material, a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton is preferable. Specific examples of the monomers that form these structural units include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentyl (meth) acrylate, and cyclic Hexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Among them, the structural unit C preferably includes a structural unit derived from cyclohexyl (meth) acrylate.

並且，作為形成構成單元C之單體，從密合性的觀點來看，例如（甲基）丙烯酸烷酯為較佳。其中，具有碳原子數4～12的烷基之（甲基）丙烯酸烷酯從密合性的觀點來看為較佳。具體而言，可舉出（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸正丁酯以及（甲基）丙烯酸2-乙基己酯。In addition, as the monomer forming the constituent unit C, from the viewpoint of adhesion, for example, alkyl (meth) acrylate is preferable. Among them, alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. ester.

構成單元C的含量相對於特定聚合物的總質量為70質量%以下為較佳，60質量%以下為更佳，50質量%以下為進一步較佳。作為下限值可為0質量%，但1質量%以上為較佳，5質量%以上為更佳。若為上述範圍，則解析度以及密合性更加提高。The content of the structural unit C is preferably 70% by mass or less relative to the total mass of the specific polymer, more preferably 60% by mass or less, and further preferably 50% by mass or less. The lower limit may be 0% by mass, but 1% by mass or more is preferable, and 5% by mass or more is more preferable. Within the above range, the resolution and adhesion are further improved.

特定聚合物中，從相對於顯影液之溶解性、以及使上述感光性樹脂組成物層的物理物性最優化之觀點來看，作為構成單元C而包含具有上述構成單元B中之酸基的酯之構成單元亦較佳。 其中，特定聚合物中作為構成單元B而包含具有羧酸基之構成單元，進一步地將包含羧酸酯基之構成單元C作為共聚成分而包含在內為較佳，例如，包含來自於（甲基）丙烯酸之構成單元B、以及來自於（甲基）丙烯酸環己基、（甲基）丙烯酸2-乙基己酯或（甲基）丙烯酸正丁酯之構成單元C之聚合物為更佳。 以下，舉出本公開中之特定聚合物的較佳例，但本公開並不限定於以下例示。另外，下述例示化合物中之構成單元的比率、重量平均分子量為了能夠獲得較佳物性而適當地被選擇。The specific polymer contains an ester having an acid group in the above-mentioned structural unit B as the structural unit C from the viewpoint of optimizing the solubility with respect to the developer and optimizing the physical properties of the photosensitive resin composition layer The constituent unit is also preferable. Among them, it is preferable to include a structural unit having a carboxylic acid group as a structural unit B in a specific polymer, and further include a structural unit C including a carboxylic acid ester group as a copolymerization component. For example, The polymer of the structural unit B of the base) acrylic acid and the structural unit C derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate is more preferred. Hereinafter, preferred examples of the specific polymer in the present disclosure are given, but the present disclosure is not limited to the following examples. In addition, the ratio of the constituent units and the weight-average molecular weight of the exemplified compounds described below are appropriately selected in order to obtain better physical properties.

[化學式8] [Chemical Formula 8]

＜＜聚合物的玻璃轉移溫度：Tg＞＞ 本公開中之特定聚合物的玻璃轉移溫度（Tg）為90℃以下為較佳。藉由Tg為90℃以下，上述感光性樹脂組成物層具有高密合性，轉印性更優異。 上述Tg為60℃以下為更佳，40℃以下為進一步較佳。 並且，上述Tg的下限值沒有特別的限定，-20℃以上為較佳，-10℃以上為更佳。藉由特定聚合物的Tg為-20℃以上，可維持良好的圖案形成性，並且例如在使用覆蓋膜時，抑制剝離覆蓋膜時的剝離性的下降。 而且，從轉印性的觀點來看，本公開中之上述聚合物成分總體的玻璃轉移溫度（Tg）為90℃以下為較佳，60℃以下為更佳，40℃以下為進一步較佳。<< Glass transition temperature of polymer: Tg >> The glass transition temperature (Tg) of the specific polymer in the present disclosure is preferably 90 ° C. or lower. When the Tg is 90 ° C. or lower, the photosensitive resin composition layer has high adhesion and the transferability is more excellent. The above Tg is more preferably 60 ° C or lower, and further preferably 40 ° C or lower. In addition, the lower limit of the above-mentioned Tg is not particularly limited, but -20 ° C or higher is more preferable, and -10 ° C or higher is more preferable. When the Tg of the specific polymer is -20 ° C. or higher, good pattern formability can be maintained, and, for example, when a cover film is used, a decrease in peelability when the cover film is peeled off is suppressed. From the viewpoint of transferability, the glass transition temperature (Tg) of the entire polymer component in the present disclosure is preferably 90 ° C. or lower, more preferably 60 ° C. or lower, and further preferably 40 ° C. or lower.

聚合物的玻璃轉移溫度能夠利用差示掃描量熱（DSC）來進行測量。 具體的測量方法依在JIS K 7121（1987年）或JIS K 6240（2011年）中記載的方法依次進行。本說明書中之玻璃轉移溫度使用外推玻璃轉移起始溫度（Extrapolated Glass Transition Onset Temperature，以下有時稱作Tig）。 對玻璃轉移溫度的測量方法進行更具體的說明。 求玻璃轉移溫度時，以比預想之聚合物的Tg低約50℃的溫度保持至裝置穩定為止後，以加熱速度：20℃/分鐘加熱至比玻璃轉移結束之溫度高約30℃的溫度為止，並描畫DTA曲線或DSC曲線。 外推玻璃轉移起始溫度（Tig）亦即本說明書中之玻璃轉移溫度Tg作為將DTA曲線或DSC曲線中之低溫側的基線延長至高溫側之直線與在玻璃轉移的階梯狀變化部分的曲線的梯度成為最大的點上畫出之切線的交點的溫度而求出。The glass transition temperature of a polymer can be measured using differential scanning calorimetry (DSC). The specific measurement method is carried out sequentially in accordance with the method described in JIS K 7121 (1987) or JIS K 6240 (2011). The glass transition temperature in this specification uses an extrapolated glass transition onset temperature (hereinafter sometimes referred to as Tig). The method for measuring the glass transition temperature will be described more specifically. When determining the glass transition temperature, keep the temperature about 50 ° C lower than the expected Tg of the polymer until the device is stable, and then heat it at a heating rate of 20 ° C / min to a temperature about 30 ° C higher than the temperature at which the glass transition ends. , And draw the DTA curve or DSC curve. The extrapolated glass transition starting temperature (Tig), which is the glass transition temperature Tg in this specification, is a curve that extends the baseline of the low temperature side of the DTA curve or DSC curve to the high temperature side and the stepwise change part of the glass transition The gradient becomes the temperature at the intersection of the tangent lines drawn at the point where the maximum is obtained.

作為將聚合物的Tg調整為己述的較佳範圍之方法，例如能夠依據作為目標之聚合物的各構成單元的單獨聚合物的Tg和各構成單元的質量比，將FOX式作為指南，控制特定聚合物的目標Tg。 關於FOX式 將聚合物中所含之第1構成單元的單獨聚合物的Tg設為Tg1，將第1構成單元的共聚物中之質量分數設為W1，將第2構成單元的單獨聚合物的Tg設為Tg2，並將第2構成單元的共聚物中之質量分數設為W2時，包含第1構成單元和第2構成單元之共聚物的Tg0（K）能夠按照以下式來推斷。 FOX式：1/Tg0=（W1/Tg1）+（W2/Tg2） 利用己述的FOX式，並調整共聚物中所含之各構成單元的種類和質量分數，藉此能夠獲得具有所希望的Tg之共聚物。 並且，藉由調整聚合物的重量平均分子量，亦能夠調整聚合物的Tg。As a method of adjusting the Tg of the polymer to the preferred range described above, for example, the FOX formula can be used as a guide to control based on the Tg of the individual polymer of each constituent unit of the target polymer and the mass ratio of each constituent unit Target Tg for specific polymers. Regarding the FOX formula, the Tg of the individual polymer of the first constitutional unit contained in the polymer is Tg1, the mass fraction of the copolymer of the first constitutional unit is W1, and the individual polymer of the second constitutional unit When Tg is Tg2 and the mass fraction in the copolymer of the second constitutional unit is W2, Tg0 (K) of the copolymer including the first constitutional unit and the second constitutional unit can be estimated according to the following formula. FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2) Using the FOX formula described above, and adjusting the types and mass fractions of the constituent units contained in the copolymer, it is possible to obtain the desired Tg copolymer. Moreover, by adjusting the weight average molecular weight of the polymer, the Tg of the polymer can also be adjusted.

＜＜聚合物的分子量：Mw＞＞ 特定聚合物的分子量以聚苯乙烯換算重量平均分子量計為60,000以下為較佳。藉由特定聚合物的重量平均分子量為60,000以下，能夠將感光性樹脂組成物層的熔融黏度抑制為較低，在與上述基板貼合時實現低溫（例如130℃以下）貼合。 並且，特定聚合物的重量平均分子量為2,000～60,000為較佳，3,000～50,000為更佳。 另外，聚合物的重量平均分子量能夠藉由GPC（凝膠滲透層析法）來測量，作為測量裝置，能夠使用各種市售的裝置，裝置的詳細內容以及測量技術係同行業人員公知的。 藉由凝膠滲透層析法（GPC）之重量平均分子量的測量中，作為測量裝置能夠使用HLC（註冊商標）-8220GPC（TOSOH CORPORATION製），作為管柱能夠使用將TSKgel（註冊商標）Super HZM-M（4.6mmID×15cm，TOSOH CORPORATION製）、Super HZ4000（4.6mmID×15cm，TOSOH CORPORATION製）、Super HZ3000（4.6mmID×15cm，TOSOH CORPORATION製）、Super HZ2000（4.6mmID×15cm，TOSOH CORPORATION製）的各一個串聯連接者，作為溶析液能夠使用THF（四氫呋喃）。 並且，作為測量條件，能夠將試樣濃度設為0.2質量%，將流速設為0.35ml/min，將樣品注入量設為10μl，且將測量溫度設為40℃，並利用示差折射率（RI）檢測器來進行。 校準曲線能夠利用TOSOH CORPORATION製的“標準試樣TSK standard，polystyrene”：“F-40”、“F-20”、“F-4”、“F-1”、“A-5000”、“A-2500”以及“A-1000”該7個樣品中之任一個來製作。<< Molecular weight of polymer: Mw >> The molecular weight of the specific polymer is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. When the weight-average molecular weight of the specific polymer is 60,000 or less, the melt viscosity of the photosensitive resin composition layer can be suppressed to be low, and bonding at a low temperature (for example, 130 ° C. or less) can be achieved when bonding to the substrate. In addition, the weight average molecular weight of the specific polymer is preferably 2,000 to 60,000, and more preferably 3,000 to 50,000. In addition, the weight-average molecular weight of the polymer can be measured by GPC (gel permeation chromatography). As a measuring device, various commercially available devices can be used. The details of the device and the measurement technique are well known to those in the industry. In the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by TOSOH CORPORATION) can be used as the measuring device, and TSKgel (registered trademark) Super HZM can be used as the column -M (4.6mmID × 15cm, manufactured by TOSOH CORPORATION), Super HZ4000 (4.6mmID × 15cm, manufactured by TOSOH CORPORATION), Super HZ3000 (4.6mmID × 15cm, manufactured by TOSOH CORPORATION), Super HZ2000 (4.6mmID × 15cm, manufactured by TOSOH CORPORATION) ) In series connection, THF (tetrahydrofuran) can be used as the eluent. Furthermore, as the measurement conditions, the sample concentration can be set to 0.2% by mass, the flow rate to 0.35 ml / min, the sample injection volume to 10 μl, and the measurement temperature to 40 ° C., using differential refractive index (RI ) The detector. The calibration curve can use "standard sample TSK standard, polystyrene" manufactured by TOSOH CORPORATION: "F-40", "F-20", "F-4", "F-1", "A-5000", "A -2500 "and" A-1000 "are made of any of the seven samples.

特定聚合物的數均分子量與重量平均分子量之比（分散度）為1.0～5.0為較佳，1.05～3.5為更佳。The ratio (dispersion degree) of the number average molecular weight to the weight average molecular weight of the specific polymer is preferably 1.0 to 5.0, and more preferably 1.05 to 3.5.

＜＜特定聚合物之製造方法＞＞ 特定聚合物之製造方法（合成法）沒有特別的限定，舉一例，能夠在包含用於形成以式A表示之構成單元A1之聚合性單體以及用於形成具有酸基之構成單元B之聚合性單體，且根據需要包含用於形成其他構成單元C之聚合性單體之有機溶劑中，藉由利用聚合引發劑進行聚合來合成。並且，亦能夠以所謂高分子反應來進行合成。＜< Specific polymer manufacturing method >> The specific polymer manufacturing method (synthesis method) is not particularly limited, and for example, the polymerizable monomer for forming the structural unit A1 represented by the formula A and The polymerizable monomer forming the structural unit B having an acid group, and, if necessary, is contained in an organic solvent used to form the polymerizable monomer of the other structural unit C, and is synthesized by polymerization using a polymerization initiator. Furthermore, synthesis can also be carried out by a so-called polymer reaction.

本公開中之上述感光性樹脂組成物層從相對於上述基板顯現良好的密合性之觀點來看，相對於感光性樹脂組成物層的總固體成分以50質量%～99.9質量%的比例包含上述聚合物成分為較佳，以70質量%～98質量%的比例包含為更佳。 並且，上述感光性樹脂組成物層從相對於上述基板顯現良好的密合性之觀點來看，相對於感光性樹脂組成物層的總固體成分以50質量%～99.9質量%的比例包含上述特定聚合物為較佳，以70質量%～98質量%的比例包含為更佳。The above-mentioned photosensitive resin composition layer in the present disclosure is included in a ratio of 50% by mass to 99.9% by mass with respect to the total solid content of the photosensitive resin composition layer from the viewpoint of showing good adhesion to the substrate. The above-mentioned polymer component is preferable, and it is more preferable to be contained in a proportion of 70% by mass to 98% by mass. In addition, from the viewpoint of showing good adhesion to the substrate, the photosensitive resin composition layer contains the above-mentioned specificity at a ratio of 50% by mass to 99.9% by mass relative to the total solid content of the photosensitive resin composition layer. The polymer is preferable, and it is more preferable to be included in a ratio of 70% by mass to 98% by mass.

＜＜其他聚合物＞＞ 在不損害本公開之感光性轉印材料的效果之範圍內，上述感光性樹脂組成物層中作為聚合物成分除了特定聚合物以外，可進一步包含不含有以式A表示之構成單元（a）之聚合物（有時稱作“其他聚合物”。）。當上述感光性樹脂組成物層包含其他聚合物時，其他聚合物的配合量在總聚合物成分中為50質量%以下為較佳，30質量%以下為更佳，20質量%以下為進一步較佳。<< Other Polymers >> The polymer component in the photosensitive resin composition layer described above may further contain, in addition to the specific polymer, the formula A in addition to the effect of the effect of the photosensitive transfer material of the present disclosure. The polymer represented as the constituent unit (a) (sometimes called "other polymer"). When the photosensitive resin composition layer contains other polymers, the blending amount of other polymers is preferably 50% by mass or less in the total polymer component, more preferably 30% by mass or less, and further more than 20% by mass. good.

上述感光性樹脂組成物層可除了特定聚合物以外僅包含1種其他聚合物，亦可包含2種以上。 作為其他聚合物，例如能夠使用聚羥基苯乙烯，亦能夠使用市售之SMA 1000P、SMA 2000P、SMA 3000P、SMA 1440F、SMA 17352P、SMA 2625P以及SMA 3840F（以上，Sartomer Company, Inc製）、ARUFON UC-3000、ARUFON UC-3510、ARUFON UC-3900、ARUFON UC-3910、ARUFON UC-3920以及ARUFON UC-3080（以上，TOAGOSEI CO., LTD.製）以及Joncryl 690、Joncryl 678、Joncryl l67以及Joncryl 586（以上，BASF JAPAN LTD.製）等。The above-mentioned photosensitive resin composition layer may contain only one kind of other polymer than the specific polymer, or may contain two or more kinds. As other polymers, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer Company, Inc), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080 (above, manufactured by TOAGOSEI CO., LTD.) And Joncryl 690, Joncryl 678, Joncryl l67 and Joncryl 586 (above, manufactured by BASF JAPAN LTD.), Etc.

-光酸產生劑- 上述感光性樹脂組成物層含有光酸產生劑。 作為在本公開中使用之光酸產生劑，係能夠藉由照射紫外線、遠紫外線、X射線以及帶電粒子束等放射線來產生酸之化合物。 作為在本公開中使用之光酸產生劑，感應波長300nm以上、較佳為波長300nm～450nm的光化射線，且產生酸之化合物為較佳，但其化學結構沒有限定。並且，即便係不直接感應波長300nm以上的光化射線之光酸產生劑，只要係藉由併用增感劑來感應波長300nm以上的光化射線並產生酸之化合物，則能夠與增感劑組合來較佳地使用。 作為在本公開中使用之光酸產生劑，產生pKa為4以下的酸之光酸產生劑為較佳，產生pKa為3以下的酸之光酸產生劑為更佳，產生pKa為2以下的酸之光酸產生劑為特佳。pKa的下限值沒有特別的限定，但例如為-10.0以上為較佳。-Photoacid generator- The photosensitive resin composition layer contains a photoacid generator. As the photoacid generator used in the present disclosure, it is a compound capable of generating an acid by irradiating radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. As the photo-acid generator used in the present disclosure, actinic rays with a wavelength of 300 nm or more, preferably with a wavelength of 300 nm to 450 nm are induced, and a compound that generates an acid is preferable, but its chemical structure is not limited. Furthermore, even if it is a photoacid generator that does not directly induce actinic rays with a wavelength of 300 nm or more, as long as it is a compound that induces actinic rays with a wavelength of 300 nm or more and generates an acid by using a sensitizer in combination, it can be combined with a sensitizer To better use. As the photoacid generator used in the present disclosure, a photoacid generator that generates an acid with a pKa of 4 or less is preferred, and a photoacid generator that generates an acid with a pKa of 3 or less is more preferred, and a photoacid generator that generates a pKa of 2 or less The acid photoacid generator is particularly good. The lower limit value of pKa is not particularly limited, but for example, it is preferably -10.0 or more.

作為光酸產生劑，能夠舉出離子性光酸產生劑和非離子性光酸產生劑。 並且，作為光酸產生劑，從靈敏度以及解析度的觀點來看，包含選自由後述之鎓鹽化合物以及後述之肟磺酸鹽化合物組合的群之至少1種化合物為較佳，包含肟磺酸鹽化合物為更佳。Examples of the photoacid generator include ionic photoacid generators and nonionic photoacid generators. Further, as the photoacid generator, from the viewpoint of sensitivity and resolution, it is preferable to include at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later, and include an oxime sulfonic acid Salt compounds are more preferred.

作為非離子性光酸產生劑的例子，能夠舉出三氯甲基均三類、重氮甲烷化合物、醯亞胺磺酸酯化合物以及肟磺酸鹽化合物等。在該等之中，從靈敏度、解析度以及密合性的觀點來看，光酸產生劑為肟磺酸鹽化合物為較佳。該等光酸產生劑能夠單獨使用1種或組合2種以上來使用。作為三氯甲基均三類以及重氮甲烷衍生物的具體例，能夠例示在日本特開2011-221494號公報的0083段～0088段中記載的化合物。Examples of the nonionic photoacid generator include trichloromethyl mesitane, diazomethane compounds, amide imine sulfonate compounds, and oxime sulfonate compounds. Among these, from the viewpoint of sensitivity, resolution, and adhesion, it is preferable that the photoacid generator is an oxime sulfonate compound. These photoacid generators can be used alone or in combination of two or more. As specific examples of trichloromethyl mesitanes and diazomethane derivatives, the compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be exemplified.

作為肟磺酸鹽化合物亦即具有肟磺酸鹽結構之化合物，具有以下述式（B1）表示之肟磺酸鹽結構之化合物為較佳。As the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure, a compound having an oxime sulfonate structure represented by the following formula (B1) is preferable.

[化學式9] [Chemical Formula 9]

在式（B1）中，R21 表示烷基或芳基，＊表示與其他原子或其他基團的鍵結部位。In formula (B1), R 21 represents an alkyl group or an aryl group, and * represents a bonding site with other atoms or other groups.

具有以式（B1）表示之肟磺酸鹽結構之化合物的任一基團均可被取代，R21 中之烷基可為直鏈狀，亦可具有分叉結構，亦可具有環結構。被允許之取代基在以下進行說明。 作為R21 的烷基，碳原子數1～10的直鏈狀或分叉狀烷基為較佳。R21 的烷基可以被碳原子數6～11的芳基、碳原子數1～10的烷氧基、環烷基（包含7,7-二甲基-2-氧代降冰片基等橋接式脂環基，雙環烷基等為較佳）或鹵素原子取代。 作為R21 的芳基，碳原子數6～18的芳基為較佳，苯基或萘基為更佳。R21 的芳基可被選自由碳原子數1～4的烷基、烷氧基以及鹵素原子組成的群之1種以上的基團取代。Any group of the compound having the oxime sulfonate structure represented by formula (B1) may be substituted, and the alkyl group in R 21 may be linear, may have a branched structure, or may have a ring structure. The allowed substituents are described below. The alkyl group of R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R 21 may be bridged with an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (including 7,7-dimethyl-2-oxonorbornyl group, etc.) Formula alicyclic group, bicycloalkyl group, etc. are preferred) or halogen atom substitution. The aryl group of R 21 is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R 21 may be substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups, and halogen atoms.

具有以式（B1）表示之肟磺酸鹽結構之化合物，在日本特開2014-85643號公報的0078～0111段中記載之肟磺酸鹽化合物亦較佳。The compound having the oxime sulfonate structure represented by the formula (B1) is also preferably the oxime sulfonate compound described in paragraphs 0078 to 0111 of Japanese Patent Laid-Open No. 2014-85643.

作為離子性光酸產生劑的例子，能夠舉出二芳基錪鎓鹽類以及三芳基鋶鹽化合物類等鎓鹽化合物、四級銨鹽類等。在該等之中，鎓鹽化合物為較佳，三芳基鋶鹽類以及二芳基錪鎓鹽類為特佳。Examples of the ionic photoacid generators include onium salt compounds such as diarylionium salts and triarylammonium salt compounds, and quaternary ammonium salts. Among these, onium salt compounds are preferred, and triaryl alkoxide salts and diaryl sulfonium salts are particularly preferred.

作為離子性光酸產生劑，亦能夠較佳地使用日本特開2014-85643號公報的0114～0133段中記載的離子性光酸產生劑。As the ionic photoacid generator, the ionic photoacid generator described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

光酸產生劑可單獨使用1種，亦可併用2種以上。 上述感光性樹脂組成物層中之光酸產生劑的含量從靈敏度、解析度的觀點來看，相對於上述感光性樹脂組成物層的總質量為0.1質量%～10質量%為較佳，0.5質量%～5質量%為更佳。One type of photoacid generator may be used alone, or two or more types may be used in combination. The content of the photoacid generator in the photosensitive resin composition layer is preferably 0.1% by mass to 10% by mass relative to the total mass of the photosensitive resin composition layer from the viewpoint of sensitivity and resolution, and 0.5 The mass% to 5 mass% is better.

-溶劑- 上述感光性樹脂組成物層可包含溶劑。 並且，形成上述感光性樹脂組成物層之感光性樹脂組成物為了容易地形成上述感光性樹脂組成物層，先含有溶劑來調節感光性樹脂組成物的黏度，再將包含溶劑之感光性樹脂組成物進行塗佈以及乾燥，藉此能夠較佳地形成上述感光性樹脂組成物層。 作為在本公開中使用之溶劑，能夠使用公知的溶劑。作為溶劑，能夠例示乙二醇單烷基醚類、乙二醇二烷基醚類、乙二醇單烷基醚乙酸酯類、丙二醇單烷基醚類、丙二醇二烷基醚類、丙二醇單烷基醚乙酸酯類、二甘醇二烷基醚類、二甘醇單烷基醚乙酸酯類、二丙二醇單烷基醚類、二丙二醇二烷基醚類、二丙二醇單烷基醚乙酸酯類、酯類、酮類、醯胺類、以及內酯類等。並且，作為溶劑的具體例亦可舉出在日本特開2011-221494號公報的0174～0178段中記載的溶劑，將該等內容編入於本說明書中。-Solvent- The photosensitive resin composition layer may contain a solvent. In addition, in order to easily form the photosensitive resin composition layer, the photosensitive resin composition forming the photosensitive resin composition layer contains a solvent to adjust the viscosity of the photosensitive resin composition, and then the photosensitive resin composition containing the solvent By coating and drying the material, the photosensitive resin composition layer can be preferably formed. As the solvent used in the present disclosure, a known solvent can be used. As the solvent, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol mono Alkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetic acid Esters, esters, ketones, amides, and lactones. In addition, as specific examples of the solvent, the solvents described in paragraphs 0174 to 0178 of Japanese Patent Laid-Open No. 2011-221494 can also be cited, and these contents are incorporated in this specification.

並且，在己述的溶劑中，能夠進一步根據需要添加苄基***、二己醚、乙二醇單苯醚乙酸酯、二甘醇單甲醚、二甘醇單***、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、苄醇、苯甲醚、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、碳酸乙二酯或碳酸丙二酯等溶劑。 溶劑可僅使用1種，亦可以使用2種以上。 能夠在本公開中使用之溶劑可單獨使用1種，併用2種為更佳。當使用2種以上的溶劑時，例如丙二醇單烷基醚乙酸酯類和二烷基醚類的併用、二乙酸酯類和二甘醇二烷基醚類的併用、或酯類和丁二醇烷基醚乙酸酯類的併用為較佳。In addition, in the solvent described above, benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, Hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate or propylene carbonate Diester and other solvents. Only one type of solvent may be used, or two or more types may be used. Solvents that can be used in the present disclosure may be used alone, and it is more preferable to use two kinds. When two or more solvents are used, for example, the combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, the combined use of diacetates and diethylene glycol dialkyl ethers, or the combination of esters and butylene glycol The combined use of alkyl ether acetates is preferred.

並且，作為溶劑，沸點130℃以上且小於160℃的溶劑、沸點160℃以上的溶劑或該等的混合物為較佳。 作為沸點130℃以上且小於160℃的溶劑，能夠例示丙二醇單甲醚乙酸酯（沸點146℃）、丙二醇單***乙酸酯（沸點158℃）、丙二醇甲基-正丁醚（沸點155℃）以及丙二醇甲基-正丙醚（沸點131℃）。 作為沸點160℃以上的溶劑，能夠例示乙氧基丙烯酸酯（沸點170℃）、二甘醇甲基***（沸點176℃）、丙二醇單甲醚丙酸酯（沸點160℃）、二丙二醇甲醚乙酸酯（沸點213℃）、3-甲氧基丁醚乙酸酯（沸點171℃）、二甘醇二***（沸點189℃）、二甘醇二甲醚（沸點162℃）、丙二醇二乙酸酯（沸點190℃）、二甘醇單***乙酸酯（沸點220℃）、二丙二醇二甲醚（沸點175℃）以及1,3-丁二醇二乙酸酯（沸點232℃）。In addition, as the solvent, a solvent having a boiling point of 130 ° C. or higher and less than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture of these are preferred. Examples of solvents having a boiling point of 130 ° C or higher and less than 160 ° C include propylene glycol monomethyl ether acetate (boiling point 146 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), and propylene glycol methyl-n-butyl ether (boiling point 155 ° C) ) And propylene glycol methyl-n-propyl ether (boiling point 131 ℃). Examples of solvents having a boiling point of 160 ° C or higher include ethoxy acrylate (boiling point 170 ° C), diethylene glycol methyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), and dipropylene glycol methyl ether Acetate (boiling point 213 ℃), 3-methoxybutyl ether acetate (boiling point 171 ℃), diethylene glycol diethyl ether (boiling point 189 ℃), diethylene glycol dimethyl ether (boiling point 162 ℃), propylene glycol di Acetate (boiling point 190 ℃), diethylene glycol monoethyl ether acetate (boiling point 220 ℃), dipropylene glycol dimethyl ether (boiling point 175 ℃) and 1,3-butanediol diacetate (boiling point 232 ℃) .

作為塗佈感光性樹脂組成物時之溶劑的含量，感光性樹脂組成物中的總固體成分的每100質量份為50質量份～1,900質量份為較佳，100質量份～900質量份為更佳。 並且，上述感光性樹脂組成物層中之溶劑的含量相對於上述感光性樹脂組成物層的總質量為2質量%以下為較佳，1質量%以下為更佳，0.5質量%以下為進一步較佳。As the content of the solvent when coating the photosensitive resin composition, 50 parts by mass to 1,900 parts by mass per 100 parts by mass of the total solid content in the photosensitive resin composition is more preferable, and 100 parts by mass to 900 parts by mass is more good. Further, the content of the solvent in the photosensitive resin composition layer is preferably 2% by mass or less relative to the total mass of the photosensitive resin composition layer, more preferably 1% by mass or less, and further preferably 0.5% by mass or less good.

-其他添加劑- 本公開中之上述感光性樹脂組成物層中除了特定聚合物以及光酸產生劑以外，能夠根據需要包含公知的添加劑。-Other Additives-The above-mentioned photosensitive resin composition layer in the present disclosure may contain well-known additives in addition to specific polymers and photoacid generators as needed.

〔塑化劑〕 上述感光性樹脂組成物層可以以改良塑性為目的而含有塑化劑。 上述塑化劑的重量平均分子量小於特定聚合物為較佳。 塑化劑的重量平均分子量從賦予塑性的觀點來看500以上且小於10,000為較佳，700以上且小於5,000為更佳，800以上且小於4,000為進一步較佳。 塑化劑只要為與特定聚合物相容而顯現塑性之化合物則沒有特別的限定，從賦予塑性之觀點來看，塑化劑在分子中具有伸烷氧基為較佳。在塑化劑中所含之伸烷氧基具有下述結構為較佳。[Plasticizer] The photosensitive resin composition layer may contain a plasticizer for the purpose of improving plasticity. It is preferable that the weight average molecular weight of the plasticizer is less than that of a specific polymer. From the viewpoint of imparting plasticity, the weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and even more preferably 800 or more and less than 4,000. The plasticizer is not particularly limited as long as it is a compound compatible with a specific polymer and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer preferably has an alkoxy group in the molecule. The alkoxy group contained in the plasticizer preferably has the following structure.

[化學式10] [Chemical Formula 10]

在上述式中，R係碳原子數2～8的伸烷基，n表示1～50的整數，＊表示與其他原子的鍵結部位。In the above formula, R is an alkylene group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and * represents a bonding site with other atoms.

另外，例如即使為具有上述結構的伸烷氧基之化合物（設為“化合物X”。），當混合了化合物X、特定聚合物以及光酸產生劑而獲得之化學增幅正型感光性樹脂組成物與不包含化合物X而形成之化學增幅正型感光性樹脂組成物相比塑性未提高時，不符合本公開中之塑化劑。例如，任意添加之界面活性劑通常不會以使感光性樹脂組成物帶有塑性之量使用，因此不符合本說明書中之塑化劑。In addition, for example, even if it is an alkoxylated compound having the above structure (set to "Compound X"), the chemically amplified positive photosensitive resin composition obtained by mixing Compound X, a specific polymer, and a photoacid generator When the plasticity of the chemically amplified positive photosensitive resin composition formed without the compound X is not improved, the plasticizer in the present disclosure is not satisfied. For example, arbitrarily added surfactants are usually not used in an amount to impart plasticity to the photosensitive resin composition, and therefore do not comply with the plasticizer in this specification.

作為上述塑化劑，例如可舉出具有下述結構之化合物，但並非限定於該等者。Examples of the plasticizer include compounds having the following structures, but they are not limited thereto.

[化學式11] [Chemical Formula 11]

塑化劑的含量從密合性的觀點來看，相對於上述感光性樹脂組成物層的總質量為1質量%～50質量%為較佳，2質量%～20質量%為更佳。 上述感光性樹脂組成物層可僅包含1種塑化劑，亦可包含2種以上。From the viewpoint of adhesion, the content of the plasticizer is preferably 1% by mass to 50% by mass relative to the total mass of the photosensitive resin composition layer, and more preferably 2% by mass to 20% by mass. The photosensitive resin composition layer may contain only one kind of plasticizer, or may contain two or more kinds.

〔增感劑〕 上述感光性樹脂組成物層還能夠包含增感劑。 增感劑吸收光化射線而成為電子激發狀態。成為電子激發狀態之增感劑與光酸產生劑接觸而產生電子移動、能量移動以及發熱等作用。藉此光酸產生劑產生化學變化而分解並生成酸。 藉由含有增感劑，能夠提高曝光靈敏度。[Sensitizer] The photosensitive resin composition layer may further contain a sensitizer. The sensitizer absorbs actinic rays and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with the photoacid generator to produce electron movement, energy movement and heat generation. Thereby, the photoacid generator chemically decomposes and generates acid. By containing a sensitizer, exposure sensitivity can be improved.

作為增感劑，選自由蒽衍生物、吖啶酮衍生物、氧硫口星衍生物、香豆素衍生物、鹼性苯乙烯衍生物以及二苯乙烯基苯衍生物組成的群之化合物為較佳，蒽衍生物為更佳。 作為蒽衍生物，蒽、9,10-二丁氧基蒽、9,10-二氯蒽、2-乙基-9,10-二甲氧基蒽、9-羥甲基蒽、9-溴蒽、9-氯蒽、9,10-二溴蒽、2-乙基蒽或9,10-二甲氧基蒽為較佳。As a sensitizer, a compound selected from the group consisting of anthracene derivatives, acridinone derivatives, oxythiopin derivatives, coumarin derivatives, basic styrene derivatives, and distyrylbenzene derivatives is Preferably, anthracene derivatives are more preferred. As anthracene derivatives, anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromo Anthracene, 9-chloroanthracene, 9,10-dibromoanthracene, 2-ethylanthracene or 9,10-dimethoxyanthracene is preferred.

作為上述增感劑，能夠舉出在國際公開第2015/093271號的0139～0141段中記載的化合物。Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/093271.

增感劑的含量相對於上述感光性樹脂組成物層的總質量為0質量%～10質量%為較佳，0.1質量%～10質量%為更佳。The content of the sensitizer is preferably 0% by mass to 10% by mass relative to the total mass of the photosensitive resin composition layer, and more preferably 0.1% by mass to 10% by mass.

〔鹼性化合物〕 上述感光性樹脂組成物層進一步包含鹼性化合物為較佳。 作為鹼性化合物，能夠從在化學增幅阻劑中使用之鹼性化合物中任意地選用。例如可舉出脂肪族胺、芳香族胺、雜環式胺、四級氫氧化銨以及羧酸的四級銨鹽等。作為該等的具體例，可舉出在日本特開2011-221494號公報的0204段～0207段中記載的化合物，該等內容編入於本說明書中。[Basic Compound] The photosensitive resin composition layer preferably further contains a basic compound. As the basic compound, it can be arbitrarily selected from the basic compounds used in the chemical amplifier. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxide, and quaternary ammonium salts of carboxylic acids. As specific examples of these, the compounds described in paragraphs 0204 to 0207 of Japanese Patent Laid-Open No. 2011-221494 can be cited, and these contents are incorporated in this specification.

具體而言，作為脂肪族胺，例如可舉出三甲基胺、二乙基胺、三乙基胺、二正丙基胺、三正丙基胺、二正戊基胺、三正戊基胺、二乙醇胺、三乙醇胺、二環己基胺基以及二環己基甲胺等。 作為芳香族胺，例如可舉出苯胺、苄胺、N,N-二甲基苯胺以及二苯胺等。 作為雜環式胺，例如可舉出吡啶、2-甲基吡啶、4-甲基吡啶、2-乙基吡啶、4-己基吡啶、2-苯基吡啶、4-苯基吡啶、N-甲基-4-苯基吡啶、4-二甲胺基吡啶、咪唑、苯并咪唑、4-甲基咪唑、2-苯基苯并咪唑、2,4,5-三苯基咪唑、煙鹼、煙酸、煙醯胺、喹啉、8-氧喹啉、吡、吡唑、噠、嘌呤、吡咯烷、哌啶、哌、嗎啉、4-甲基嗎啉、1,5-二氮雜雙環[4.3.0]-5-壬烯以及1,8-二氮雜雙環[5.3.0]-7-十一碳烯等。 作為四級氫氧化銨，例如可舉出氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四正丁基銨等以及氫氧化四-正己基銨等。 作為羧酸的四級銨鹽，例如可舉出四甲基乙酸銨、四甲基苯甲酸銨、四正丁基乙酸銨以及四正丁基苯甲酸銨等。Specifically, examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, and tri-n-pentyl group. Amine, diethanolamine, triethanolamine, dicyclohexylamino, dicyclohexylmethylamine, etc. Examples of aromatic amines include aniline, benzylamine, N, N-dimethylaniline, and dianiline. Examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-hexylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, Niacin, nicotinamide, quinoline, 8-oxoquinoline, pyridine, pyrazole, pyridine, purine, pyrrolidine, piperidine, piper, morpholine, 4-methylmorpholine, 1,5-diaza Bicyclo [4.3.0] -5-nonene and 1,8-diazabicyclo [5.3.0] -7-undecene etc. Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide. Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

上述鹼性化合物可單獨使用1種，亦可以併用2種以上。 鹼性化合物的含量相對於上述感光性樹脂組成物層的總質量為0.001質量%～5質量%為較佳，0.005質量%～3質量%為更佳。These basic compounds may be used alone or in combination of two or more. The content of the basic compound is preferably 0.001% by mass to 5% by mass relative to the total mass of the photosensitive resin composition layer, and more preferably 0.005% by mass to 3% by mass.

〔雜環狀化合物〕 本公開中之感光性樹脂組成物層能夠包含雜環狀化合物。 對本公開中之雜環狀化合物沒有特別的限定。例如能夠在以下所述之分子內添加具有環氧基或氧雜環丁基之化合物、含烷氧基甲基之雜環狀化合物、其他各種環狀醚、環狀酯（內酯）等含酸素單體、環狀胺、噁唑啉基這種含氮單體，進一步能夠添加矽、硫、膦等具有帶有d電子之原子之含雜原子環單體等。[Heterocyclic Compound] The photosensitive resin composition layer in the present disclosure can contain a heterocyclic compound. The heterocyclic compound in the present disclosure is not particularly limited. For example, compounds containing epoxy groups or oxetanyl groups, heterocyclic compounds containing alkoxymethyl groups, other various cyclic ethers, cyclic esters (lactones), etc. can be added to the molecules described below Nitrogen-containing monomers such as acid monomers, cyclic amines, and oxazoline groups can be further added with heteroatom-containing ring monomers having atoms with d electrons, such as silicon, sulfur, and phosphine.

當添加雜環狀化合物時，感光性樹脂組成物層中之雜環狀化合物的添加量相對於上述感光性樹脂組成物層的總質量為0.01質量%～50質量%為較佳，0.1質量%～10質量%為更佳，1質量%～5質量%為進一步較佳。若為上述範圍，則從密合性以及蝕刻耐性的觀點來看為較佳。雜環狀化合物可僅使用1種，亦能夠併用2種以上。When the heterocyclic compound is added, the addition amount of the heterocyclic compound in the photosensitive resin composition layer is preferably 0.01% by mass to 50% by mass relative to the total mass of the photosensitive resin composition layer, and 0.1% by mass -10% by mass is more preferable, and 1% by mass to 5% by mass is even more preferable. Within the above range, it is preferable from the viewpoint of adhesion and etching resistance. Only one type of heterocyclic compound may be used, or two or more types may be used in combination.

作為在分子內具有環氧基之化合物的具體例，能夠舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、脂肪族環氧樹脂等。Specific examples of the compound having an epoxy group in the molecule include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, Aliphatic epoxy resin, etc.

在分子內具有環氧基之化合物能夠作為市售品來購入。例如可舉出JER828、JER1007、JER157S70（Mitsubishi Chemical Corporation製）、JER157S65（Mitsubishi Chemical Holdings Co., Ltd.製）等、以及在日本特開2011-221494號公報的0189段中記載的市售品等。 作為其他市售品，可舉出ADEKA RESIN EP-4000S、ADEKA RESIN EP-4003S、ADEKA RESIN EP-4010S、ADEKA RESIN EP-4011S（以上，ADEKA Corporation製）、NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502（以上，ADEKA Corporation製）、DENACOL EX-611、EX-612、EX-614、EX-614B、EX-622、EX-512、EX-521、EX-411、EX-421、EX-313、EX-314、EX-321、EX-211、EX-212、EX-810、EX-811、EX-850、EX-851、EX-821、EX-830、EX-832、EX-841、EX-911、EX-941、EX-920、EX-931、EX-212L、EX-214L、EX-216L、EX-321L、EX-850L、DLC-201、DLC-203、DLC-204、DLC-205、DLC-206、DLC-301、DLC-402、EX-111、EX-121、EX-141、EX-145、EX-146、EX-147、EX-171、EX-192（以上Nagase ChemteX Corporation製）、YH-300、YH-301、YH-302、YH-315、YH-324、YH-325（以上，NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.製）、CELLOXIDE 2021P、2081、2000、3000、EHPE3150、Epolead GT400、CELVENUS B0134、B0177（Daicel Corporation製）等。 在分子內具有環氧基之化合物可單獨使用1種，亦可併用2種以上。Compounds having epoxy groups in the molecule can be purchased as commercial products. Examples include JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), etc., and commercially available products described in paragraph 0189 of Japanese Patent Laid-Open No. 2011-221494. . As other commercially available products, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC- 7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), DENACOL EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX- 830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201 DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX- 171, EX-192 (manufactured by Nagase ChemteX Corporation above), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD. ), CELLOXIDE 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, CELVENUS B0134, B0177 (made by Daicel Corporation), etc. The compound having an epoxy group in the molecule may be used alone or in combination of two or more.

在分子內具有環氧基之化合物之中，可更佳地舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂以及脂肪族環氧樹脂，可尤為佳地舉出脂肪族環氧樹脂。Among the compounds having an epoxy group in the molecule, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin can be more preferably mentioned, especially Good examples include aliphatic epoxy resins.

作為在分子內具有氧雜環丁基之化合物的具體例，能夠使用Aron Oxetane OXT-201、OXT-211、OXT-212、OXT-213、OXT-121、OXT-221、OX-SQ、PNOX（以上，TOAGOSEI CO., LTD.製）。As specific examples of compounds having oxetanyl groups in the molecule, Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX ( Above, manufactured by TOAGOSEI CO., LTD.).

並且，包含氧雜環丁基之化合物單獨或與包含環氧基之化合物混合使用為較佳。Furthermore, the compound containing oxetanyl group is preferably used alone or in combination with the compound containing epoxy group.

在本公開中之感光性樹脂組成物層中，雜環狀化合物係具有環氧基之化合物，從蝕刻耐性以及線寬穩定性的觀點來看為較佳。In the photosensitive resin composition layer in the present disclosure, the heterocyclic compound is a compound having an epoxy group, which is preferable from the viewpoint of etching resistance and line width stability.

〔烷氧基矽烷化合物〕 上述感光性樹脂組成物層可含有烷氧基矽烷化合物。作為烷氧基矽烷化合物，可較佳地舉出三烷氧基矽烷化合物。 作為烷氧基矽烷化合物，例如可舉出γ-胺丙基三甲氧基矽烷、γ-胺丙基三乙氧基矽烷、γ-環氧丙氧基丙基烷氧基矽烷、γ-環氧丙氧基丙基烷基二烷氧基矽烷、γ-甲基丙烯醯氧基丙基三烷氧基矽烷、γ-甲基丙烯醯氧基丙基烷基二烷氧基矽烷、γ-氯丙基三烷氧基矽烷、γ-巰丙基三烷氧基矽烷、β-（3,4-環氧基環己基）乙基三烷氧基矽烷、乙烯三烷氧基矽烷。在該等之中，γ-環氧丙氧基丙基烷氧基矽烷或γ-甲基丙烯醯氧基丙基三烷氧基矽烷為更佳，γ-環氧丙氧基丙基烷氧基矽烷進一步較佳，3-環氧丙氧基丙基三甲氧基矽烷為特佳。該等能夠單獨使用1種或組合2種以上來使用。[Alkoxysilane compound] The photosensitive resin composition layer may contain an alkoxysilane compound. As the alkoxysilane compound, a trialkoxysilane compound is preferably mentioned. Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropylalkoxysilane, and γ-epoxy Propoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloro Propyl trialkoxy silane, γ-mercaptopropyl trialkoxy silane, β- (3,4-epoxycyclohexyl) ethyl trialkoxy silane, ethylene trialkoxy silane. Among these, γ-glycidoxypropylalkoxysilane or γ-methacryloxypropyltrialkoxysilane is better, γ-glycidoxypropylalkoxy Silane is further preferred, and 3-glycidoxypropyltrimethoxysilane is particularly preferred. These can be used alone or in combination of two or more.

〔界面活性劑〕 上述感光性樹脂組成物層從膜厚均勻性的觀點來看，含有界面活性劑為較佳。作為界面活性劑，能夠使用陰離子系、陽離子系、非離子系（nonionic）或兩性中之任一種，但較佳的界面活性劑係非離子界面活性劑。 作為非離子系界面活性劑的例子，能夠舉出聚氧乙烯高級烷基醚類、聚氧乙烯高級烷基苯基醚類、聚氧乙二醇的高級脂肪酸二酯類、聚矽氧系、氟系界面活性劑。並且，能夠舉出以下KP（Shin-Etsu Chemical Co., Ltd.製）、Polyflow（Kyoeisha Chemical Co., Ltd.製）、EFTOP（Japan Electronic Monetary Claim Organization製）、Megaface（DIC Corporation製）、Fluorad（Sumitomo 3M Limited製）、AsahiGuard、Surflon（Asahi Glass Co., Ltd.製）、PolyFox（OMNOVA SOLUTIONS INC.製）以及SH-8400（Dow Corning Toray Co.,Ltd.製）等產品名之各系列。 並且，作為界面活性劑，能夠將包含以下述式I-1表示之構成單元A以及構成單元B，且將四氫呋喃（THF）作為溶劑時以凝膠滲透層析法測量之聚苯乙烯換算的重量平均分子量（Mw）為1,000以上10,000以下之共聚物作為較佳例來舉出。[Surfactant] The photosensitive resin composition layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, polysilicone, Fluorine surfactant. In addition, the following KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Japan Electronic Monetary Claim Organization), Megaface (manufactured by DIC Corporation), Fluorad can be cited. (Sumitomo 3M Limited), AsahiGuard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA SOLUTIONS INC.) And SH-8400 (manufactured by Dow Corning Toray Co., Ltd.) and other product names . In addition, as a surfactant, the weight of polystyrene measured by gel permeation chromatography including the structural unit A and the structural unit B represented by the following formula I-1 and using tetrahydrofuran (THF) as a solvent can be measured Copolymers having an average molecular weight (Mw) of 1,000 or more and 10,000 or less are cited as preferred examples.

[化學式12] [Chemical Formula 12]

在式（I-1）中，R401 以及R403 分別獨立地表示氫原子或甲基，R402 表示碳原子數1以上4以下的直鏈伸烷基，R404 表示氫原子或碳原子數1以上4以下的烷基，L表示碳原子數3以上6以下的伸烷基，p以及q係表示聚合比之質量百分率，p表示10質量%以上80質量%以下的數值，q表示20質量%以上90質量%以下的數值，r表示1以上18以下的整數，s表示1以上10以下的整數，＊表示與其他結構的鍵結部位。In formula (I-1), R 401 and R 403 each independently represent a hydrogen atom or a methyl group, R 402 represents a linear alkylene group having 1 to 4 carbon atoms, and R 404 represents a hydrogen atom or the number of carbon atoms Alkyl groups of 1 or more and 4 or less, L represents an alkylene group having a carbon number of 3 or more and 6 or less, p and q represent mass percentages of polymerization ratio, p represents a value of 10% by mass or more and 80% by mass or less, and q represents 20% Values of% or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, s represents an integer of 1 or more and 10 or less, and * represents a bonding site with another structure.

L為以下述式（I-2）表示之分叉伸烷基為較佳。式（I-2）中之R405 表示碳原子數1以上4以下的烷基，從相容性和相對於被塗佈面之潤濕性的觀點來看，碳原子數1以上3以下的烷基為較佳，碳原子數2或3的烷基為更佳。p與q之和（p+q）為p+q=100亦即100質量%為較佳。L is preferably a bifurcated alkylene group represented by the following formula (I-2). R 405 in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and from the viewpoint of compatibility and wettability with respect to the coated surface, 1 to 3 carbon atoms The alkyl group is preferable, and the alkyl group having 2 or 3 carbon atoms is more preferable. The sum of p and q (p + q) is preferably p + q = 100, that is, 100% by mass.

[化學式13] [Chemical Formula 13]

共聚物的重量平均分子量（Mw）為1,500以上5,000以下為更佳。The weight average molecular weight (Mw) of the copolymer is preferably 1,500 or more and 5,000 or less.

此外，還能夠使用日本專利第4502784號公報的0017段、日本特開2009-237362號公報的0060段～0071段中記載的界面活性劑。Moreover, the surfactant described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Laid-Open No. 2009-237362 can also be used.

界面活性劑可單獨使用1種，亦可以併用2種以上。 界面活性劑的添加量相對於上述感光性樹脂組成物層的總質量為10質量%以下為較佳，0.001質量%～10質量%為更佳，0.01質量%～3質量%為進一步較佳。One type of surfactant may be used alone, or two or more types may be used in combination. The added amount of the surfactant is preferably 10% by mass or less relative to the total mass of the photosensitive resin composition layer, more preferably 0.001% by mass to 10% by mass, and further preferably 0.01% by mass to 3% by mass.

〔其他成分〕 在本公開中之感光性樹脂組成物層中，能夠進一步添加金屬氧化物粒子、抗氧化劑、分散劑、酸增殖劑、顯影促進劑、導電性纖維、著色劑、熱自由基聚合引發劑、熱產酸劑、紫外線吸收劑、增黏劑、交聯劑以及有機或無機的沉淀防止劑等公知的添加劑。 其他成分的較佳態樣分別記載於日本特開2014-85643號公報的0165～0184段，該公報的內容編入於本說明書中。[Other Components] In the photosensitive resin composition layer of the present disclosure, metal oxide particles, antioxidants, dispersants, acid multiplication agents, development accelerators, conductive fibers, colorants, thermal radical polymerization can be further added Known additives such as initiators, thermal acid generators, ultraviolet absorbers, tackifiers, crosslinking agents, and organic or inorganic precipitation inhibitors. Preferred aspects of other components are described in paragraphs 0165 to 0184 of Japanese Patent Laid-Open No. 2014-85643, and the contents of this bulletin are incorporated in this specification.

〔感光性樹脂組成物層的形成方法〕 能夠將各成分以及溶劑以任意比例且以任意方法進行混合，並進行攪拌溶解來製備用於形成感光性樹脂組成物層之感光性樹脂組成物。例如，亦能夠將各成分分別預先溶解於溶劑中來製成溶液後，將所獲得之溶液以特定的比例進行混合來製備組成物。如上製備之組成物亦能夠以孔徑0.2μm的過濾器等進行過濾後提供於使用。[Method for Forming Photosensitive Resin Composition Layer] The components and the solvent can be mixed in any ratio and in any method, and stirred and dissolved to prepare a photosensitive resin composition for forming the photosensitive resin composition layer. For example, after dissolving each component in a solvent in advance to prepare a solution, the obtained solution can be mixed at a specific ratio to prepare a composition. The composition prepared as described above can also be used after being filtered through a filter with a pore size of 0.2 μm or the like.

藉由將感光性樹脂組成物塗佈在中間層上並使其乾燥，能夠獲得在偽支撐體上具有感光性樹脂組成物層之本公開之感光性轉印材料。 塗佈方法沒有特別的限定，能夠以狹縫塗佈、旋塗、簾塗、噴墨塗佈等公知的方法進行塗佈。 另外，亦能夠在中間層上形成後述的其他層後，在之上塗佈感光性樹脂組成物層。By coating and drying the photosensitive resin composition on the intermediate layer, the photosensitive transfer material of the present disclosure having the photosensitive resin composition layer on the dummy support can be obtained. The coating method is not particularly limited, and can be applied by a well-known method such as slit coating, spin coating, curtain coating, and inkjet coating. In addition, after forming another layer described later on the intermediate layer, a photosensitive resin composition layer may be coated thereon.

＜其他層＞ 本公開之感光性轉印材料可具有除上述感光性樹脂組成物層以外的層（以下，有時稱作“其他層”）。作為其他層，能夠舉出對比度增強層、覆蓋膜、熱塑性樹脂層等。<Other Layers> The photosensitive transfer material of the present disclosure may have layers other than the above-mentioned photosensitive resin composition layer (hereinafter, sometimes referred to as “other layers”). Examples of other layers include a contrast enhancement layer, a cover film, and a thermoplastic resin layer.

-熱塑性樹脂層、覆蓋膜等- 本公開之感光性轉印材料從轉印性的觀點來看，在上述偽支撐體和上述中間層之間進一步具有熱塑性樹脂層為較佳。 並且，本公開之感光性轉印材料可以以保護上述感光性樹脂組成物層為目的來具有覆蓋膜。 關於熱塑性樹脂層的較佳態樣在日本特開2014-85643號公報的0189～0193段、關於其他層的較佳態樣在日本特開2014-85643號公報的0194～0196段中分別有記載，該公報的內容編入於本說明書中。 其中，從轉印性的觀點來看，熱塑性樹脂層包含選自由丙烯酸樹脂以及苯乙烯/丙烯酸共聚物組成的群之至少1種熱塑性樹脂為較佳。-Thermoplastic resin layer, cover film, etc.-From the viewpoint of transferability, the photosensitive transfer material of the present disclosure preferably further has a thermoplastic resin layer between the dummy support and the intermediate layer. In addition, the photosensitive transfer material of the present disclosure may have a cover film for the purpose of protecting the photosensitive resin composition layer. The preferred aspects of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of Japanese Patent Laid-Open No. 2014-85643, and the preferred aspects of the other layers are described in paragraphs 0194 to 0196 of Japanese Patent Laid-Open No. 2014-85643, respectively. The contents of this bulletin are incorporated in this specification. Among them, it is preferable that the thermoplastic resin layer contains at least one thermoplastic resin selected from the group consisting of acrylic resin and styrene / acrylic copolymer from the viewpoint of transferability.

當本公開之感光性轉印材料具有熱塑性樹脂層等其他層時，能夠遵照在日本特開2006-259138號公報的0094～0098段中記載的感光性轉印材料的製作方法來製作。 例如，當製作具有熱塑性樹脂層之本公開之感光性轉印材料時，在偽支撐體上將溶解有熱塑性有機高分子和添加劑之溶解液（熱塑性樹脂層用塗佈液）進行塗佈並使其乾燥來設置熱塑性樹脂層後，在所獲得之熱塑性樹脂層上將在不使熱塑性樹脂層溶解之溶劑中添加樹脂以及添加劑而製備之製備液（中間層組成物）進行塗佈並使其乾燥來積層中間層。在已形成之中間層上進一步將使用不使中間層溶解之溶劑來製備之感光性樹脂組成物進行塗佈並使其乾燥來積層感光性樹脂組成物層，藉此能夠較佳地製作本公開之感光性轉印材料。When the photosensitive transfer material of the present disclosure has other layers such as a thermoplastic resin layer, it can be produced in accordance with the production method of the photosensitive transfer material described in paragraphs 094 to 0098 of JP-A 2006-259138. For example, when manufacturing the photosensitive transfer material of the present disclosure having a thermoplastic resin layer, a dissolving solution (coating solution for thermoplastic resin layer) in which a thermoplastic organic polymer and additives are dissolved is applied on a pseudo support and the After drying to provide a thermoplastic resin layer, a preparation liquid (intermediate layer composition) prepared by adding resin and additives to a solvent that does not dissolve the thermoplastic resin layer is applied and dried on the obtained thermoplastic resin layer To build up the middle layer. The photosensitive resin composition prepared by using a solvent that does not dissolve the intermediate layer is further coated and dried on the formed intermediate layer, thereby laminating the photosensitive resin composition layer, whereby the present disclosure can be preferably produced The photosensitive transfer material.

-對比度增強層- 本公開之感光性轉印材料除了上述感光性樹脂組成物層以外，還能夠具備對比度增強層。 對比度增強層（Contrast Enhancement Layer；CEL）在曝光前對曝光波長之吸收大，但隨著被曝光而逐漸變小，亦即係含有光的透過率變高之材料（稱作光消色性色素成分）之層。作為光消色性色素成分，已知有重氮鹽、苯乙烯基吡啶鎓（stilbazolium）鹽、芳基亞硝基鹽類等。作為覆膜形成成分，使用酚系樹脂等。 此外，作為對比度增強層，能夠使用在日本特開平6-97065號公報的0004段～0051段、日本特開平6-332167號公報的0012段～0055段、光聚合物手冊、光聚合座談會編、工業調査會（1989）、光聚合・技術（Technology）、山崗、永松編、THE NIKKAN KOGYO SHIMBUN,LTD.（1988）中記載的材料。-Contrast Enhancement Layer-The photosensitive transfer material of the present disclosure can include a contrast enhancement layer in addition to the above-mentioned photosensitive resin composition layer. The Contrast Enhancement Layer (CEL) absorbs a large amount of exposure wavelength before exposure, but gradually becomes smaller as it is exposed, that is, it contains a material with a higher transmittance of light (called achromatic pigment Ingredients). As photochromic pigment components, diazonium salts, styryl pyridinium (stilbazolium) salts, aryl nitroso salts and the like are known. As a film forming component, a phenol resin or the like is used. In addition, as the contrast enhancement layer, paragraphs 0004 to 0051 of Japanese Patent Laid-Open No. 6-97065, paragraphs 0012 to 0055 of Japanese Patent Laid-Open No. 6-332167, photopolymer handbook, photopolymerization symposium can be used , Industrial Investigation Association (1989), Photopolymerization Technology (Technology), Yamagata, Yongsong, THE NIKKAN KOGYO SHIMBUN, LTD. (1988) described in the material.

（電路配線之製造方法） 本公開之電路配線之製造方法只要係使用了本公開之感光性轉印材料之製造方法則沒有特別的限定，依次包含以下製程為較佳：相對於基板，使本公開之感光性轉印材料的上述感光性樹脂組成物層與上述基板接觸並貼合之製程；對上述貼合製程後的上述感光性轉印材料的上述感光性樹脂組成物層進行圖案曝光之製程；對上述進行曝光之製程後的上述感光性樹脂組成物層進行顯影來形成圖案之製程、以及對未配置有上述圖案之區域中之上述基板進行蝕刻處理之製程。 並且，本公開之電路配線之製造方法依次包含以下製程為較佳：相對於基板，使本公開之感光性轉印材料的上述感光性樹脂組成物層與上述基板接觸並貼合之製程；剝離上述感光性轉印材料的偽支撐體之製程；對上述感光性樹脂組成物層進行圖案曝光之製程；對上述感光性樹脂組成物層進行顯影來形成圖案之製程；以及對未配置有上述圖案之區域中之上述基板進行蝕刻處理之製程。(Manufacturing method of circuit wiring) The manufacturing method of circuit wiring of the present disclosure is not particularly limited as long as the manufacturing method of the photosensitive transfer material of the present disclosure is used, and it is preferable to sequentially include the following processes: The process of contacting and laminating the photosensitive resin composition layer of the disclosed photosensitive transfer material with the substrate; pattern exposing the photosensitive resin composition layer of the photosensitive transfer material after the lamination process Process; a process of developing the photosensitive resin composition layer after the exposure process to form a pattern, and a process of etching the substrate in the area where the pattern is not arranged. In addition, the manufacturing method of the circuit wiring of the present disclosure sequentially includes the following processes: It is preferable that the photosensitive resin composition layer of the photosensitive transfer material of the present disclosure is in contact with and bonded to the substrate relative to the substrate; peeling The process of the dummy support of the photosensitive transfer material; the process of pattern exposing the photosensitive resin composition layer; the process of developing the pattern of the photosensitive resin composition layer to form a pattern; The above-mentioned substrate in the region is subjected to an etching process.

以往，感光性樹脂組成物根據感光系統的不同而分成將照射光化射線之部分作為圖像而殘留之負型、以及將未照射光化射線之部分作為圖像而殘留之正型。在正型中藉由照射光化射線，例如使用照射光化射線來產生酸之感光劑等來提高曝光部的溶解性，因此當在圖案曝光時刻曝光部以及未曝光部均未固化，所獲得之圖案形狀為不良時，能夠藉由全面曝光等來對基板進行再利用（再加工）。因此，從所謂再加工性優異之觀點來看，正型為較佳。並且，對殘留之感光性樹脂組成物層進行再度曝光來製作不同之圖案之技術如果不是感光性樹脂組成物層則無法實現，因此在本公開之電路配線之製造方法中，可較佳地舉出進行2次以上的曝光之態樣。Conventionally, the photosensitive resin composition is divided into a negative type in which a part irradiated with actinic rays remains as an image and a positive type in which a part not irradiated with actinic rays remains as an image, depending on the photosensitive system. In the positive type, by irradiating actinic rays, for example, using a sensitizer that irradiates actinic rays to generate an acid, etc., the solubility of the exposed portion is improved. Therefore, when the pattern is exposed, neither the exposed portion nor the unexposed portion is cured. When the pattern shape is defective, the substrate can be reused (reprocessed) by full exposure or the like. Therefore, from the viewpoint of so-called excellent reworkability, the positive type is preferable. In addition, the technique of re-exposure of the remaining photosensitive resin composition layer to produce different patterns cannot be achieved unless it is a photosensitive resin composition layer. Therefore, in the manufacturing method of the circuit wiring of the present disclosure, it is preferable to Appeared to perform two or more exposures.

＜貼合製程＞ 本公開之電路配線之製造方法包含相對於基板，使本公開之感光性轉印材料的上述感光性樹脂組成物層與上述基板接觸並貼合之製程（貼合製程）為較佳。 在上述貼合製程中，使上述感光性轉印材料與具備導電性層之基材接觸並貼合為較佳。 並且，在上述貼合製程中，使上述導電性層和上述感光性樹脂組成物層接觸之方式壓接為較佳。若為上述態樣，則能夠將曝光以及顯影後的圖案形成之感光性樹脂組成物層較佳地用作對導電性層進行蝕刻時的蝕刻阻劑。 作為將上述基材和上述感光性轉印材料進行壓接之方法沒有特別的限定，能夠使用公知的轉印方法以及積層方法。 具體而言，例如將上述感光性轉印材料的感光性樹脂組成物層側重疊在導電性層上並藉由基於輥等之加壓、或加壓以及加熱來進行為較佳。在貼合中，能夠使用積層、真空積層以及能夠更加提高生產性之自動切割積層（Auto-Cut laminator）等公知的積層。 上述貼合製程中之壓接壓力以及溫度沒有特別的限定，能夠依據導電性層以及感光性樹脂組成物層的材質、傳送速度以及所使用之壓接機等來適當地設定。並且，在感光性轉印材料的感光性樹脂組成物層上具有覆蓋膜時，從感光性樹脂組成物層除去覆蓋膜後進行壓接即可。 當上述基材為樹脂薄膜時，可進行輥對輥方式的壓接。<Lamination process> The manufacturing method of the circuit wiring of the present disclosure includes a process (lamination process) in which the photosensitive resin composition layer of the photosensitive transfer material of the present disclosure is in contact with the substrate and bonded to the substrate as: Better. In the above-mentioned bonding process, it is preferable that the photosensitive transfer material is brought into contact with the substrate provided with a conductive layer and bonded. In addition, in the above-mentioned bonding process, it is preferable that the conductive layer and the photosensitive resin composition layer are brought into contact with each other by pressure bonding. In the above-mentioned aspect, the photosensitive resin composition layer formed by the pattern after exposure and development can be preferably used as an etching resist when etching the conductive layer. The method of pressure-bonding the base material and the photosensitive transfer material is not particularly limited, and a known transfer method and lamination method can be used. Specifically, for example, it is preferable to superimpose the photosensitive resin composition layer side of the photosensitive transfer material on the conductive layer and apply pressure by a roller or the like, or pressurization and heating. For lamination, well-known build-ups such as build-up, vacuum build-up, and auto-cut laminator that can further improve productivity can be used. The pressure pressure and temperature in the above-mentioned bonding process are not particularly limited, and can be appropriately set according to the materials, the transmission speed of the conductive layer and the photosensitive resin composition layer, the pressure bonding machine used, and the like. In addition, when a cover film is provided on the photosensitive resin composition layer of the photosensitive transfer material, the cover film may be removed from the photosensitive resin composition layer and then pressure-bonded. When the above substrate is a resin film, roll-to-roll type pressure bonding can be performed.

〔基材〕 在基材上積層有複數個導電性層之基板中，基材為玻璃基材或薄膜基材為較佳，薄膜基材為更佳。本公開之電路配線之製造方法中，當為觸控面板用電路配線時，基材為片狀樹脂組成物為特佳。 並且，基材為透明為較佳。 基材的折射率為1.50～1.52為較佳。 基材可由玻璃基材等透光性基材構成，能夠使用以Corning Incorporated Co.,Ltd.的大猩猩玻璃（Gorilla Glass）為代表之強化玻璃等。並且，作為前述透明基材，能夠較佳地使用在日本特開2010-86684號公報、日本特開2010-152809號公報以及日本特開2010-257492號公報中使用之材料。 作為基材使用薄膜基材時，使用沒有光學應變之基材、以及透明度高的基材為更佳，具體的素材能夠舉出聚對酞酸乙二酯（polyethyleneterephthalate；PET）、聚萘二甲酸乙二醇酯、聚碳酸酯、三乙醯纖維素、環烯烴聚合物。[Substrate] Among the substrates in which a plurality of conductive layers are laminated on the substrate, the substrate is preferably a glass substrate or a film substrate, and the film substrate is more preferable. In the manufacturing method of the circuit wiring of this disclosure, when it is circuit wiring for touch panels, it is especially preferable that the base material is a sheet-like resin composition. Moreover, it is preferable that the base material is transparent. The refractive index of the substrate is preferably 1.50 to 1.52. The base material may be made of a light-transmitting base material such as a glass base material, and tempered glass typified by Gorilla Glass of Corning Incorporated Co., Ltd. can be used. In addition, as the transparent substrate, materials used in Japanese Patent Laid-Open No. 2010-86684, Japanese Patent Laid-Open No. 2010-152809, and Japanese Patent Laid-Open No. 2010-257492 can be preferably used. When using a film substrate as the substrate, a substrate without optical strain and a substrate with high transparency are better. Specific materials include polyethylene terephthalate (PET) and polynaphthalene dicarboxylic acid. Ethylene glycol ester, polycarbonate, triethyl cellulose, cycloolefin polymer.

〔導電性層〕 作為在基材上形成之複數個導電性層，能夠舉出在一般的電路配線或觸控面板配線中使用之任意的導電性層。 作為導電性層的材料，能夠舉出金屬以及金屬氧化物等。 作為金屬氧化物，能夠舉出ITO（Indium Tin Oxide，氧化銦錫）、IZO（Indium Zinc Oxide，氧化銦鋅）、SiO2 等。作為金屬，能夠舉出Al、Zn、Cu、Fe、Ni、Cr、Mo等。[Conductive Layer] As the plurality of conductive layers formed on the base material, any conductive layer used in general circuit wiring or touch panel wiring can be mentioned. Examples of materials for the conductive layer include metals and metal oxides. Examples of metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 . Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, and Mo.

本公開之電路配線之製造方法中，複數個導電性層中之至少一個導電性層包含金屬氧化物為較佳。 作為導電性層，相當於在靜電電容型觸控面板中使用之可見部的感測器之電極圖案或邊緣引出部的配線為較佳。In the method for manufacturing circuit wiring of the present disclosure, it is preferable that at least one of the plurality of conductive layers contains a metal oxide. As the conductive layer, the electrode pattern of the sensor corresponding to the visible portion used in the capacitance-type touch panel or the wiring of the edge extraction portion is preferable.

〔電路配線形成用基板〕 在本公開中使用之電路配線形成用基板係在基材的表面上具有導電性層之基板為較佳。藉由對導電性層進行圖案形成來設為電路配線。在本例子中，在PET等薄膜基材上設置有金屬氧化物或金屬等複數個導電性層者為較佳。[Substrate for Circuit Wiring Formation] The substrate for circuit wiring formation used in the present disclosure is preferably a substrate having a conductive layer on the surface of the base material. The circuit wiring is formed by patterning the conductive layer. In this example, it is preferable to provide a plurality of conductive layers such as metal oxide or metal on a film substrate such as PET.

＜曝光製程＞ 本公開之電路配線之製造方法中，包含對上述貼合製程後的上述感光性轉印材料的上述感光性樹脂組成物層進行圖案曝光之製程（曝光製程）為較佳。 在上述曝光製程中，在設置有塗膜之基板上，經由具有特定圖案之遮罩來照射光化射線為較佳。在該製程中，光酸產生劑分解而產生酸。藉由所產生之酸的觸媒作用，在塗膜成分中所含之酸分解性基進行加水分解，生成酸基例如羧基或酚性羥基。 在本公開中，圖案的詳細配置以及具體尺寸沒有特別的限定。為了提高具備具有在本公開中製造之電路基板之輸入裝置之顯示裝置（例如觸控面板）的顯示品質，並且盡可能縮小引出配線所佔之面積，圖案的至少一部分（尤其觸控面板的電極圖案以及引出配線的部分）為100μm以下的細線為較佳，70μm以下的細線為更佳。 並且，上述曝光製程中之曝光可為經由遮罩之曝光，亦可為利用了雷射等之數碼曝光，但經由曝光用遮罩之曝光為較佳。 本公開的附圖案之基材之製造方法在上述貼合製程和上述曝光製程之間包含使上述感光性轉印材料和曝光用遮罩接觸之製程為較佳。若為上述態樣，則所獲得之圖案的解析度更優異。 而且，本公開之電路配線之製造方法在上述貼合製程和上述曝光製程之間包含剝離上述感光性轉印材料的偽支撐體之製程為較佳。此時，上述感光性轉印材料的表面成為中間層，但亦能夠使中間層和曝光用遮罩接觸來進行曝光，亦能夠隔著數十μm以下的距離進行曝光。尤其使中間層和曝光用遮罩接觸來進行曝光為較佳。<Exposure process> In the manufacturing method of the circuit wiring of the present disclosure, a process (exposure process) including pattern exposure of the photosensitive resin composition layer of the photosensitive transfer material after the lamination process is preferred. In the above exposure process, it is preferable to irradiate actinic rays through a mask having a specific pattern on a substrate provided with a coating film. In this process, the photoacid generator decomposes to generate acid. By the catalyst action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to generate an acid group such as carboxyl group or phenolic hydroxyl group. In the present disclosure, the detailed configuration and specific size of the pattern are not particularly limited. In order to improve the display quality of a display device (such as a touch panel) equipped with an input device having a circuit board manufactured in the present disclosure, and minimize the area occupied by the lead wiring, at least a part of the pattern (especially the electrodes of the touch panel The pattern and the portion where the wiring is drawn) are preferably thin lines of 100 μm or less, and more preferably thin lines of 70 μm or less. In addition, the exposure in the above-mentioned exposure process may be exposure through a mask, or digital exposure using a laser or the like, but exposure through a mask for exposure is preferable. The method for manufacturing a patterned substrate of the present disclosure preferably includes a process of bringing the photosensitive transfer material into contact with the exposure mask between the laminating process and the exposure process. With the above-mentioned aspect, the resolution of the obtained pattern is more excellent. Furthermore, the method for manufacturing a circuit wiring of the present disclosure is preferably a process including a dummy support for peeling the photosensitive transfer material between the bonding process and the exposure process. At this time, the surface of the photosensitive transfer material becomes an intermediate layer, but the intermediate layer and the exposure mask can be brought into contact for exposure, and exposure can also be performed at a distance of tens of μm or less. In particular, it is preferable to expose the intermediate layer in contact with the exposure mask.

作為光化射線，可舉出可見光、紫外光以及電子束，但可見光或紫外光為較佳，紫外線為特佳。 作為基於光化射線之曝光光源，能夠使用低壓水銀燈、高壓水銀燈、超高壓水銀燈、熒光燈、發光二極體（LED）光源、準分子雷射發生裝置等，能夠較佳地使用g射線（436nm）、i射線（365nm）、h射線（405nm）等具有波長300nm以上450nm以下的波長之光化射線。並且，根據需要，亦能夠通過長波長截止濾波器、短波長截止濾波器、帶通濾波器之類的分光濾波器來調整照射光。 作為曝光裝置，能夠使用鏡面投影對準曝光器（mirror projection aligner）、步進機、掃描儀、近接式（proximity）、接觸式（contact）、微透鏡陣列、雷射曝光等各種方式的曝光機。 曝光量依據所使用之感光性樹脂組成物層來適當選擇即可，但5mJ/cm2 ～200mJ/cm2 為較佳，10mJ/cm2 ～100mJ/cm2 為更佳。 並且，在曝光後以提高圖案的矩形性、直線性為目的而在顯影前進行熱處理亦較佳。藉由所謂被稱作PEB（Post Exposure Bake，曝光後烘烤）之製程，能夠降低由曝光時在感光性樹脂組成物層中產生之駐波導致之圖案邊緣的粗糙。Examples of actinic rays include visible light, ultraviolet light, and electron beams, but visible light or ultraviolet light is preferred, and ultraviolet light is particularly preferred. As an exposure light source based on actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a fluorescent lamp, a light-emitting diode (LED) light source, an excimer laser generator, etc. can be used, and a g-ray (436 nm) can be preferably used , I-ray (365nm), h-ray (405nm) and other actinic rays with a wavelength of 300nm to 450nm. Furthermore, if necessary, the irradiation light can be adjusted by a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a band-pass filter. As the exposure device, various types of exposure machines such as mirror projection aligner, stepper, scanner, proximity, contact, microlens array, laser exposure, etc. can be used . The use of an exposure amount based on the photosensitive resin composition layer may be appropriately selected, but 5mJ / cm 2 ~ 200mJ / cm 2 is preferred, 10mJ / cm 2 ~ 100mJ / cm 2 is more preferred. Furthermore, it is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. The so-called PEB (Post Exposure Bake) process can reduce the roughness of the pattern edges caused by standing waves generated in the photosensitive resin composition layer during exposure.

另外，圖案曝光可在將偽支撐體從中間層以及感光性樹脂組成物層剝離後進行，亦可在剝離偽支撐體之前經由偽支撐體進行曝光，之後剝離偽支撐體。為了防止基於中間層和遮罩的接觸之遮罩污染、以及避免附著於遮罩之異物對曝光產生之影響，不剝離偽支撐體而進行曝光為較佳。另外，圖案曝光可以係經由遮罩之曝光，亦可以係利用了雷射等之數碼曝光。In addition, the pattern exposure may be performed after peeling the dummy support from the intermediate layer and the photosensitive resin composition layer, or may be exposed through the dummy support before peeling the dummy support, and then the dummy support may be peeled off. In order to prevent mask contamination based on the contact between the intermediate layer and the mask, and to avoid the influence of foreign objects attached to the mask on exposure, it is preferable to perform exposure without peeling off the dummy support. In addition, the pattern exposure may be exposure through a mask, or digital exposure using a laser or the like.

＜顯影製程＞ 本公開之電路配線之製造方法包含對上述進行曝光之製程後的上述感光性樹脂組成物層進行顯影來形成圖案之製程（顯影製程）為較佳。 並且，在顯影製程中，被曝光之部分的中間層與被曝光之感光性樹脂組成物層一起被除去。 而且，在顯影製程中，未曝光部的中間層亦以在顯影液中溶解或分散之形式被去除。 上述顯影製程中之被曝光之上述感光性樹脂組成物層的顯影能夠利用顯影液來進行。 作為顯影液，只要能夠去除上述感光性樹脂組成物層的曝光部分則沒有特別的限定，例如能夠使用在日本特開平5-72724號公報中記載的顯影液等公知的顯影液。另外，顯影液為使上述感光性樹脂組成物層的曝光部分進行溶解型顯影行為之顯影液為較佳。作為顯影液，鹼水溶液為較佳，例如將pKa=7～13的化合物以0.05mol/L（升）～5mol/L的濃度包含之鹼水溶液為更佳。顯影液可進一步含有與水具有混合性之有機溶劑、界面活性劑等。作為在本公開中較佳地使用之顯影液，例如可舉出國際公開第2015/093271號的0194段中記載的顯影液。<Development Process> A process for manufacturing a circuit wiring of the present disclosure includes a process (development process) in which the photosensitive resin composition layer after the exposure process is developed to form a pattern (development process). In addition, in the development process, the exposed intermediate layer is removed together with the exposed photosensitive resin composition layer. Moreover, in the development process, the intermediate layer of the unexposed portion is also removed in the form of dissolution or dispersion in the developer. The development of the exposed photosensitive resin composition layer in the development process can be performed using a developer. The developer is not particularly limited as long as it can remove the exposed portion of the photosensitive resin composition layer. For example, a known developer such as the developer described in Japanese Patent Application Laid-Open No. 5-72724 can be used. In addition, the developer is preferably a developer in which the exposed portion of the photosensitive resin composition layer undergoes a dissolution-type development behavior. As the developing solution, an alkaline aqueous solution is preferable, and for example, an alkaline aqueous solution containing a compound having a pKa = 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is more preferable. The developer may further contain an organic solvent and surfactant that are miscible with water. Examples of the developer that is preferably used in the present disclosure include the developer described in paragraph 0194 of International Publication No. 2015/093271.

作為顯影方式沒有特別的限定，可為旋覆浸沒顯影、噴淋顯影、噴淋及旋轉顯影、浸漬顯影等的任一種。在此，對噴淋顯影進行說明，藉由噴淋將顯影液噴吹到曝光後的感光性樹脂組成物層以及中間層，能夠去除曝光部分。並且，在顯影後，將清潔劑等藉由噴淋來進行噴吹，一邊用刷子等進行擦拭一邊去除顯影殘渣為較佳。顯影液的液溫為20℃～40℃為較佳。 並且，從曝光至顯影為止的時間長的態樣可更加發揮抑制本公開中之圖案形狀的變形之效果。可在曝光後立即進行顯影，但在從曝光至顯影為止的時間較佳為從曝光起經過0.5小時以上，更佳為經過1小時以上，進一步較佳為經過6小時以上後進行顯影之態樣中，更加發揮抑制本公開中之圖案形狀的變形之效果。 並且，本公開的附圖案之基材之製造方法可包含在顯影後藉由水等進行清洗之製程、或將所獲得之附圖案之基材進行乾燥之製程等公知的製程。The development method is not particularly limited, and may be any of rotary immersion development, shower development, shower and rotary development, and immersion development. Here, shower development will be described. By spraying the developer solution onto the exposed photosensitive resin composition layer and the intermediate layer, the exposed portion can be removed. In addition, after development, it is preferable to spray cleaning agents and the like by spraying, and to remove development residues while wiping with a brush or the like. The liquid temperature of the developer is preferably 20 ° C to 40 ° C. In addition, the long time from exposure to development can further exert the effect of suppressing the deformation of the pattern shape in the present disclosure. Development can be performed immediately after exposure, but the time from exposure to development is preferably 0.5 hours or more after exposure, more preferably 1 hour or more, and even more preferably 6 hours or more. In addition, the effect of suppressing the deformation of the pattern shape in the present disclosure is more exerted. In addition, the method for manufacturing a patterned substrate of the present disclosure may include known processes such as a process of washing with water or the like after development, or a process of drying the obtained patterned substrate.

而且，可具有對進行顯影而獲得之圖案進行加熱處理之後烘烤製程。 後烘烤的加熱在8.1kPa～121.6kPa的環境下進行為較佳，在50.66kPa以上的環境下進行為更佳。另一方面，在111.46kPa以下的環境下進行為更佳，在101.3kPa以下的環境下進行為特佳。 後烘烤的溫度為80℃～250℃為較佳，110℃～170℃為更佳，130℃～150℃為特佳。 後烘烤的時間為1分鐘～30分鐘為較佳，2分鐘～10分鐘為更佳，2分鐘～4分鐘為特佳。 後烘烤可在空氣環境下進行，亦可在氮取代環境下進行。Moreover, it may have a baking process after heat-processing the pattern obtained by development. Post-baking heating is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably performed in an environment of 50.66 kPa or more. On the other hand, it is better to perform in an environment of 111.46 kPa or less, and particularly preferably in an environment of 101.3 kPa or less. The post-baking temperature is preferably 80 ° C to 250 ° C, more preferably 110 ° C to 170 ° C, and particularly preferably 130 ° C to 150 ° C. The post-baking time is preferably from 1 minute to 30 minutes, more preferably from 2 minutes to 10 minutes, and particularly preferably from 2 minutes to 4 minutes. Post-baking can be carried out in an air environment, or in a nitrogen replacement environment.

本公開之電路配線之製造方法中之各製程時之上述基材的傳送速度沒有特別的限定，除去曝光時為0.5m/min～10m/min為較佳，除去曝光時為2.0m/min～8.0m/min為更佳。The conveying speed of the above-mentioned base material in each process in the manufacturing method of the circuit wiring of the present disclosure is not particularly limited, and it is preferably 0.5 m / min to 10 m / min when removing exposure, and 2.0 m / min to when removing exposure 8.0m / min is better.

＜蝕刻製程＞ 本公開之電路配線之製造方法包含對未配置有上述圖案之區域中之上述基板進行蝕刻處理之製程（蝕刻製程）為較佳。 在上述蝕刻製程中，將藉由上述顯影製程由上述感光性樹脂組成物層形成之圖案用作蝕刻阻劑來進行上述基板的蝕刻處理。 上述基板的蝕刻能夠以在日本特開2010-152155號公報的0048段～0054段等中記載的方法、基於公知的等離子體蝕刻等乾式蝕刻之方法等公知的方法來應用蝕刻。 例如，作為蝕刻方法，可舉出通常進行之在蝕刻液中浸漬之濕式蝕刻法。在濕式蝕刻中使用之蝕刻液依據蝕刻對象來適當地選擇酸性類型或鹼性類型的蝕刻液。 作為酸性類型的蝕刻液，可例示出鹽酸、硫酸、硝酸、乙酸、氟酸、草酸或磷酸等單獨的酸性成分的水溶液、酸性成分和氯化鐵、氟化銨或過錳酸鉀等鹽的混合水溶液等。酸性成分可使用組合了複數種酸性成分之成分。 作為鹼性類型的蝕刻液，可例示出氫氧化鈉、氫氧化鉀、氨、有機胺或氫氧化四甲基銨之類的有機胺的鹽等單獨的鹼成分的水溶液、鹼成分和過錳酸鉀等鹽的混合水溶液等。鹼成分可使用組合了複數種鹼成分之成分。<Etching Process> The manufacturing method of the circuit wiring of the present disclosure includes a process (etching process) in which the above substrate in the region where the above pattern is not arranged is subjected to an etching process (etching process). In the etching process, the pattern formed by the photosensitive resin composition layer through the development process is used as an etching resist to perform the etching process of the substrate. The etching of the above substrate can be applied by a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155, etc., and a dry etching method based on a known plasma etching. For example, as an etching method, a wet etching method which is usually performed by immersing in an etching solution can be mentioned. The etching liquid used in the wet etching appropriately selects an acid type or alkaline type etching liquid according to the etching target. Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, or phosphoric acid, acidic components, and salts of ferric chloride, ammonium fluoride, or potassium permanganate. Mixed aqueous solution, etc. As the acid component, a combination of plural acid components can be used. Examples of alkaline type etching solutions include aqueous solutions of alkaline components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, or salts of organic amines such as tetramethylammonium hydroxide, alkaline components, and permanganese. Mixed aqueous solutions of salts such as potassium acid. As the alkali component, a combination of a plurality of alkali components can be used.

蝕刻液的溫度沒有特別的限定，但45℃以下為較佳。在本公開中，用作蝕刻遮罩（蝕刻圖案）之圖案尤其對45℃以下的溫度區域中之酸性以及鹼性的蝕刻液發揮優異之耐性為較佳。因此，防止上述圖案在蝕刻製程中剝離，不存在上述圖案之部分選擇性地被蝕刻。The temperature of the etching solution is not particularly limited, but it is preferably 45 ° C or lower. In the present disclosure, it is preferable that the pattern used as an etching mask (etching pattern) exhibits excellent resistance to acidic and alkaline etching solutions in a temperature region of 45 ° C. or lower. Therefore, the above pattern is prevented from peeling off during the etching process, and portions where the above pattern does not exist are selectively etched.

在上述蝕刻製程後，為防止製程線的污染，可根據需要進行清洗上述基板之製程（清洗製程）以及對上述基板進行乾燥之製程（乾燥製程）。關於清洗製程，例如可舉出在常溫（10℃～35℃）中以純水對基板進行10秒～300秒之清洗。關於乾燥製程，例如使用鼓風機並適當調整鼓風機壓力（0.1kg/cm2 ～5kg/cm2 程度）來進行乾燥即可。After the above etching process, in order to prevent contamination of the process line, a process of cleaning the substrate (cleaning process) and a process of drying the substrate (drying process) may be performed as needed. Regarding the cleaning process, for example, the substrate may be cleaned with pure water at normal temperature (10 ° C to 35 ° C) for 10 seconds to 300 seconds. Regarding the drying process, for example, a blower may be used, and the pressure of the blower (approximately 0.1 kg / cm 2 to 5 kg / cm 2 ) may be adjusted for drying.

＜剝離製程＞ 本公開之電路配線之製造方法在上述蝕刻製程之後，包含將上述感光性樹脂組成物層使用剝離液進行剝離之製程（剝離製程）為較佳。 在上述蝕刻製程結束後，殘留有已圖案形成之上述感光性樹脂組成物層。若不需要上述感光性樹脂組成物層，則去除殘留之全部上述感光性樹脂組成物層即可。 作為使用剝離液進行剝離之方法，例如可舉出以較佳為30℃～80℃，更佳為50℃～80℃在攪拌中的剝離液中將具有上述感光性樹脂組成物層等之基材浸漬5分鐘～30分鐘之方法。 作為剝離液，例如可舉出將氫氧化鈉或氫氧化鉀等無機鹼成分、或叔胺或四級銨鹽等有機鹼成分溶解於水、二甲基亞碸、N-甲基吡咯啶酮或該等混合溶液中之剝離液。可使用剝離液，藉由噴霧法、噴淋法或旋覆浸沒法等進行剝離。<Peeling Process> The method for manufacturing a circuit wiring of the present disclosure is preferably a process (peeling process) including peeling the photosensitive resin composition layer using a peeling liquid after the etching process. After the etching process is completed, the patterned photosensitive resin composition layer remains. If the above-mentioned photosensitive resin composition layer is not required, all the remaining above-mentioned photosensitive resin composition layer may be removed. As a method of peeling using a peeling liquid, for example, a base having the above-mentioned photosensitive resin composition layer and the like in a stirring peeling liquid of preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. can be mentioned. The method of immersing the material for 5 minutes to 30 minutes. Examples of the stripping liquid include an inorganic base component such as sodium hydroxide or potassium hydroxide, or an organic base component such as tertiary amine or quaternary ammonium salt dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone Or the stripping solution in these mixed solutions. The peeling liquid can be used for peeling by a spray method, a spray method, or a rotary immersion method.

並且，本公開之電路配線之製造方法可根據需要將曝光製程、顯影製程以及蝕刻製程重複2次以上。 作為本公開中之曝光製程、顯影製程以及其他製程的例子，在日本特開2006-23696號公報的0035段～0051段中記載的方法在本公開中亦能夠較佳地使用。Moreover, the manufacturing method of the circuit wiring of the present disclosure may repeat the exposure process, the development process, and the etching process twice or more as needed. As examples of the exposure process, the development process, and other processes in the present disclosure, the methods described in paragraphs 0035 to 0051 of Japanese Patent Laid-Open No. 2006-23696 can also be preferably used in the present disclosure.

本公開之電路配線之製造方法可包含其他任意製程。例如，可舉出如下製程，但並不限定於該等製程。The manufacturing method of the circuit wiring of the present disclosure may include any other manufacturing process. For example, the following processes may be mentioned, but not limited to these processes.

＜降低可見光線反射率之製程＞ 本公開之電路配線之製造方法能夠包含進行降低基材例如基材所具有之導電性層的一部分或全部的可見光線反射率之處理之製程。 作為降低可見光線反射率之處理，能夠舉出氧化處理等。例如，對銅進行氧化處理來製成氧化銅，從而進行黑化，藉此能夠降低可見光線反射率。 關於降低可見光線反射率之處理的較佳態樣，在日本特開2014-150118號公報的0017段～0025段、以及日本特開2013-206315號公報0041段、0042段、0048段以及0058段中有記載，該公報的內容編入於本說明書中。<Process for Reducing Visible Light Reflectivity> The manufacturing method of the circuit wiring of the present disclosure can include a process for reducing the visible light reflectance of a part or all of the conductive layer of the substrate, such as the substrate. As the treatment for reducing the reflectance of visible rays, oxidation treatment and the like can be mentioned. For example, copper is oxidized to make copper oxide, which is blackened, thereby reducing the visible light reflectance. For preferred aspects of the treatment for reducing the reflectance of visible light, see paragraphs 0017 to 0025 of Japanese Patent Laid-Open No. 2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Laid-Open No. 2013-206315 There is a description in it, and the contents of this bulletin are incorporated in this specification.

＜在被蝕刻之上述基板上形成絶緣膜之製程、以及在絶緣膜上形成新的導電性層之製程＞ 本公開之電路配線之製造方法包含在上述基板上例如在已形成之電路配線（被蝕刻之上述導電性層）上形成絶緣膜之製程、以及在絶緣膜上形成新的導電性層之製程亦較佳。 形成絶緣膜之製程沒有特別的限定，能夠舉出公知的形成永久膜之方法。並且，亦可使用具有絶緣性之感光性材料，藉由光微影法來形成所希望的圖案的絶緣膜。 在絶緣膜上形成新的導電性層之製程沒有特別的限定。可使用具有導電性之感光性材料，藉由光微影法來形成所希望的圖案的新的導電性層。<The process of forming an insulating film on the etched substrate described above, and the process of forming a new conductive layer on the insulating film> The manufacturing method of the circuit wiring of the present disclosure includes, for example, the circuit wiring formed on the substrate The process of forming the insulating film on the etched conductive layer) and the process of forming a new conductive layer on the insulating film are also preferred. The process of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be mentioned. In addition, an insulating film with a desired pattern may be formed by photolithography using an insulating photosensitive material. The process of forming a new conductive layer on the insulating film is not particularly limited. A photosensitive material having conductivity can be used to form a new conductive layer of a desired pattern by photolithography.

並且，本公開之電路配線之製造方法可以對上述新的導電性層藉由與上述相同的方法形成蝕刻阻劑並進行蝕刻，亦可另外藉由公知的方法來進行蝕刻。 藉由本公開之電路配線之製造方法獲得之電路基板可在上述基板上僅具有1層電路配線，亦可具有2層以上的電路配線。In addition, the method of manufacturing a circuit wiring of the present disclosure may form an etching resist on the above-mentioned new conductive layer by the same method as described above and etch it, or may perform etching by another known method. The circuit board obtained by the method of manufacturing a circuit wiring of the present disclosure may have only one layer of circuit wiring on the substrate, or may have two or more layers of circuit wiring.

並且，本公開之電路配線之製造方法中，基材在兩側的表面上分別具有複數個導電性層，對在基材的兩側的表面上形成之導電性層逐次或同時形成電路亦較佳。藉由該種構成，能夠形成在基材的一側的表面上形成有第一導電圖案（第一電路配線）且在另一側的表面上形成有第二導電圖案（第二電路配線）之電路配線，較佳為形成觸控面板用電路配線。Moreover, in the method for manufacturing circuit wiring of the present disclosure, the substrate has a plurality of conductive layers on the surfaces on both sides, and it is also more convenient to form circuits on the surfaces of the substrate on both sides sequentially or simultaneously. good. With this configuration, the first conductive pattern (first circuit wiring) can be formed on one surface of the substrate and the second conductive pattern (second circuit wiring) can be formed on the surface on the other side. The circuit wiring is preferably formed as a circuit wiring for a touch panel.

（電路配線以及電路基板） 本公開之電路配線係藉由本公開之電路配線之製造方法製造之電路配線。 本公開之電路基板係具有藉由本公開之電路配線之製造方法製造之電路配線之基板。 本公開之電路基板的用途沒有特別的限定，例如觸控面板用電路基板為較佳。(Circuit wiring and circuit board) The circuit wiring of this disclosure is the circuit wiring manufactured by the manufacturing method of the circuit wiring of this disclosure. The circuit substrate of the present disclosure is a substrate having circuit wiring manufactured by the method of manufacturing a circuit wiring of the present disclosure. The use of the circuit board of the present disclosure is not particularly limited, and for example, a circuit board for a touch panel is preferable.

（輸入裝置以及顯示裝置） 作為具備藉由本公開之電路配線之製造方法製造之電路配線之裝置，可舉出輸入裝置。 本公開之輸入裝置只要為至少具有藉由本公開之電路配線之製造方法製造之電路配線之輸入裝置即可，靜電電容型觸控面板為較佳。 本公開之顯示裝置具備本公開之輸入裝置為較佳。本公開之顯示裝置為有機EL顯示裝置以及液晶顯示裝置等圖像顯示裝置為較佳。(Input device and display device) As a device provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring of this disclosure, an input device can be mentioned. The input device of the present disclosure may be any input device having at least circuit wiring manufactured by the circuit wiring manufacturing method of the present disclosure, and an electrostatic capacitance type touch panel is preferred. It is preferable that the display device of the present disclosure is provided with the input device of the present disclosure. The display device of the present disclosure is preferably an image display device such as an organic EL display device and a liquid crystal display device.

（觸控面板以及觸控面板顯示裝置） 本公開之觸控面板係至少具有藉由本公開之電路配線之製造方法製造之電路配線之觸控面板。並且，本公開之觸控面板至少具有透明基板、電極、以及絶緣層或保護層為較佳。 本公開之觸控面板顯示裝置係至少具有藉由本公開之電路配線之製造方法製造之電路配線之觸控面板顯示裝置，具有本公開之觸控面板之觸控面板顯示裝置為較佳。 作為本公開之觸控面板以及本公開之觸控面板顯示裝置中之檢測方法，可為電阻膜方式、靜電電容方式、超音波方式、電磁感應方式以及光學方式等公知的方式中的任一種。其中，靜電電容方式為較佳。(Touch Panel and Touch Panel Display Device) The touch panel of the present disclosure is a touch panel having at least circuit wiring manufactured by the method of manufacturing a circuit wiring of the present disclosure. Moreover, it is preferable that the touch panel of the present disclosure has at least a transparent substrate, electrodes, and an insulating layer or a protective layer. The touch panel display device of the present disclosure is a touch panel display device having at least the circuit wiring manufactured by the circuit wiring manufacturing method of the present disclosure, and the touch panel display device having the touch panel of the present disclosure is preferred. As the detection method in the touch panel of the present disclosure and the touch panel display device of the present disclosure, any one of known methods such as a resistive film method, an electrostatic capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among them, the electrostatic capacitance method is preferred.

作為觸控面板型，能夠舉出所謂內嵌型（例如在日本特表2012-517051號公報的圖5、圖6、圖7、圖8中記載者）、所謂外嵌型（例如在特開2013-168125號公報的圖19中記載者、在日本特開2012-89102號公報的圖1和圖5中記載者）、OGS（One Glass Solution，單片玻璃觸控）型、TOL（Touch-on-Lens，鏡片觸控）型（例如在日本特開2013-54727號公報的圖2中記載者）、其他構成（例如在日本特開2013-164871號公報的圖6中記載者）、各種外掛型（所謂GG、G1・G2、GFF、GF2、GF1、G1F等）。As the touch panel type, a so-called in-cell type (for example, those described in FIG. 5, FIG. 6, FIG. 7, and FIG. 8 of Japanese Patent Publication No. 2012-517051), and a so-called in-cell type (for example, in JP 19 described in FIG. 19 of 2013-168125, and described in FIGS. 1 and 5 of JP 2012-89102), OGS (One Glass Solution) type, TOL (Touch- on-Lens (lens touch) type (for example, described in FIG. 2 of JP-A-2013-54727), other configurations (for example described in FIG. 6 of JP-A-2013-164871), various Plug-in type (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.).

作為本公開之觸控面板以及本公開之觸控面板顯示裝置，能夠應用在“最新觸控面板技術”（2009年7月6日，Techno Times Co.,Ltd.發行），三谷雄二主編，“觸控面板的技術和開發”（2004年12月，CMC出版）、FPD International 2009 Forum T-11講演教科書、Cypress Semiconductor Corporation應用註釋（application note）AN2292等中公開之構成。 [實施例]As the touch panel of the present disclosure and the touch panel display device of the present disclosure, it can be applied to "the latest touch panel technology" (published on July 6, 2009 by Techno Times Co., Ltd.), edited by Mitsuo Yuji, " The technology and development of touch panel "(published by CMC in December 2004), FPD International 2009 Forum T-11 lecture textbook, Cypress Semiconductor Corporation application note AN2292, etc. [Example]

以下舉出實施例對本發明的實施形態進行更具體的說明。以下實施例中所示之材料、使用量、比例、處理內容以及處理順序等只要不脫離本發明的實施形態的主旨則能夠適當進行改變。因此，本發明的實施形態的範圍並不限定於以下所示之具體例。另外，只要沒有特別的說明，則“份”、“%”為質量基準。The embodiments of the present invention will be described more specifically below with examples. The materials, usage amounts, ratios, processing contents, and processing order shown in the following examples can be appropriately changed as long as they do not depart from the gist of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are based on mass.

〔感光性樹脂組成物層中之聚合物〕 在以下例子中，以下略語分別表示以下化合物。 ATHF：2-四氫呋喃基丙烯酸酯（合成品） MATHF：2-四氫呋喃基甲基丙烯酸酯（合成品） MAEVE：1-甲基丙烯酸乙氧基乙酯（Wako Pure Chemical Industries, Ltd.製） PHSTHF：4-（2-四氫呋喃基氧基）苯乙烯（合成品） PHSEVE：1-乙氧基乙基氧基苯乙烯（合成品） PHS：對羥基苯乙烯（合成品） AA：丙烯酸（Tokyo Chemical Industry Co., Ltd.製） CHA：丙烯酸環己基（Tokyo Chemical Industry Co., Ltd.製） PGMEA（丙二醇單甲醚乙酸酯）：（SHOWA DENKO K.K.製） V-601：二甲基2,2’-偶氮雙（2-甲基丙酸酯）（Wako Pure Chemical Industries, Ltd.製）[Polymer in photosensitive resin composition layer] In the following examples, the following abbreviations represent the following compounds, respectively. ATHF: 2-tetrahydrofuryl acrylate (synthetic product) MATHF: 2-tetrahydrofuran methacrylate (synthetic product) MAEVE: Ethoxyethyl 1-methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) PHSTHF: 4- (2-Tetrahydrofuranyloxy) styrene (synthetic product) PHSEVE: 1-ethoxyethyloxystyrene (synthetic product) PHS: p-hydroxystyrene (synthetic product) AA: acrylic acid (Tokyo Chemical Industry Co., Ltd.) CHA: cyclohexyl acrylate (Tokyo Chemical Industry Co., Ltd.) PGMEA (propylene glycol monomethyl ether acetate): (manufactured by SHOWA DENKO KK) V-601: dimethyl 2,2 '-Azobis (2-methyl propionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

＜ATHF的合成＞ 在3口燒瓶中加入丙烯酸（72.1份，1.0莫耳當量）、己烷（72.1份）並冷卻至20℃。滴落樟腦磺酸（0.0070份，0.03毫莫耳當量）、2-二氫呋喃（70.1份，1.0莫耳當量）並在20℃±2℃中攪拌1.5小時後，升溫至35℃並進行了2小時攪拌。在吸濾器中依次舖滿Kyoward 200（氫氧化鋁吸附劑，Kyowa Chemical Industry Co., Ltd.製）、Kyoward 1000（水滑石系吸附劑，Kyowa Chemical Industry Co., Ltd.製）後，藉由將反應液進行過濾而獲得了過濾液。在所獲得之過濾液中加入氫醌單甲醚（MEHQ，0.0012份）後，藉由在40℃中進行減壓濃縮，獲得了作為無色油狀之丙烯酸四氫呋喃-2-基（ATHF）140.8份（收率99.0%）。<Synthesis of ATHF> Acrylic acid (72.1 parts, 1.0 mole equivalent) and hexane (72.1 parts) were added to a 3-necked flask and cooled to 20 ° C. After dripping camphorsulfonic acid (0.0070 parts, 0.03 millimolar equivalent) and 2-dihydrofuran (70.1 parts, 1.0 molar equivalent) and stirring at 20 ℃ ± 2 ℃ for 1.5 hours, the temperature was raised to 35 ℃ and carried out Stir for 2 hours. After the suction filter is covered with Kyoward 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) in this order, by The reaction liquid was filtered to obtain a filtrate. After adding hydroquinone monomethyl ether (MEHQ, 0.0012 parts) to the obtained filtrate, by concentration under reduced pressure at 40 ° C, 140.8 parts of tetrahydrofuran-2-yl acrylate (ATHF) was obtained as a colorless oil. (Yield 99.0%).

＜MATHF的合成＞ 在3口燒瓶中加入甲基丙烯酸（86.1份，1.0莫耳當量）、己烷（86.1份）並冷卻至20℃。滴落樟腦磺酸（0.0070份，0.03毫莫耳當量）、2-二氫呋喃（70.1份，1.0莫耳當量）並在20℃±2℃中攪拌1.5小時後，升溫至35℃並進行了2小時攪拌。在吸濾器中依次舖滿Kyoward 200、Kyoward 1000後，藉由將反應液進行過濾而獲得了過濾液。在所獲得之過濾液中加入MEHQ（0.0012份）後，藉由在40℃中進行減壓濃縮，獲得了作為無色油狀物之甲基丙烯酸四氫呋喃-2-基（MATHF）156.2份（收率98.0%）。<Synthesis of MATHF> In a 3-necked flask, methacrylic acid (86.1 parts, 1.0 molar equivalent) and hexane (86.1 parts) were added and cooled to 20 ° C. After dripping camphorsulfonic acid (0.0070 parts, 0.03 millimolar equivalent) and 2-dihydrofuran (70.1 parts, 1.0 molar equivalent) and stirring at 20 ℃ ± 2 ℃ for 1.5 hours, the temperature was raised to 35 ℃ Stir for 2 hours. After the suction filter was covered with Kyoward 200 and Kyoward 1000 in this order, the filtered solution was obtained by filtering the reaction solution. After MEHQ (0.0012 parts) was added to the obtained filtrate, it was concentrated under reduced pressure at 40 ° C to obtain 156.2 parts (yield) of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oil. 98.0%).

＜PHS的合成＞ 在3口燒瓶中加入乙酸4-乙烯基苯酯（25.0份，0.154莫耳當量）、乙酸乙酯（34.2份）並冷却至5℃。滴落28%甲醇鈉甲醇溶液（59.5份）後進行了2小時攪拌。加入乙酸乙酯（100份）、水（200份）、氯化銨（33.0份），進行分液操作來提取了有機層。將所獲得之有機層依序以飽和氯化銨水溶液、飽和食鹽水進行清洗，藉由在40℃中進行減壓濃縮，獲得了作為黄色油狀物之對羥基苯乙烯（PHS）17.0份（收率91.9%）。<Synthesis of PHS> In a 3-necked flask, 4-vinylphenyl acetate (25.0 parts, 0.154 mole equivalent) and ethyl acetate (34.2 parts) were added and cooled to 5 ° C. After dripping 28% sodium methoxide methanol solution (59.5 parts), it stirred for 2 hours. Ethyl acetate (100 parts), water (200 parts) and ammonium chloride (33.0 parts) were added, and a liquid separation operation was performed to extract the organic layer. The obtained organic layer was washed sequentially with saturated ammonium chloride aqueous solution and saturated brine, and concentrated under reduced pressure at 40 ° C to obtain 17.0 parts of p-hydroxystyrene (PHS) as a yellow oil ( Yield 91.9%).

＜PHSTHF的合成＞ 在3口燒瓶中加入對羥基苯乙烯（120.0份，1.0莫耳當量）、己烷（86.1份）並冷卻至20℃。滴落樟腦磺酸（0.0070份，0.03毫莫耳當量）、2-二氫呋喃（70.1份，1.0莫耳當量）並在20℃±2℃中攪拌1.5小時後，升溫至35℃並進行了2小時攪拌。在吸濾器中依次舖滿Kyoward 200、Kyoward 1000後，藉由將反應液進行過濾而獲得了過濾液。在所獲得之過濾液中加入MEHQ（0.0012份）後，藉由在40℃中進行減壓濃縮，獲得了作為無色油狀物之4-（2-四氫呋喃基氧基）苯乙烯（PHSTHF）186.3份（收率98.0%）。<Synthesis of PHSTHF> In a 3-necked flask, p-hydroxystyrene (120.0 parts, 1.0 molar equivalent) and hexane (86.1 parts) were added and cooled to 20 ° C. After dripping camphorsulfonic acid (0.0070 parts, 0.03 millimolar equivalent) and 2-dihydrofuran (70.1 parts, 1.0 molar equivalent) and stirring at 20 ℃ ± 2 ℃ for 1.5 hours, the temperature was raised to 35 ℃ and carried out Stir for 2 hours. After the suction filter was covered with Kyoward 200 and Kyoward 1000 in this order, the filtered solution was obtained by filtering the reaction solution. After MEHQ (0.0012 parts) was added to the obtained filtrate, it was concentrated under reduced pressure at 40 ° C to obtain 4- (2-tetrahydrofuryloxy) styrene (PHSTHF) 186.3 as a colorless oil. Portion (yield 98.0%).

＜PHSEVE的合成＞ 在3口燒瓶中加入對羥基苯乙烯（120.0份，1.0莫耳當量）、己烷（86.1份）並冷卻至20℃。滴落樟腦磺酸（0.0070份，0.03毫莫耳當量）、乙基乙烯基醚（72.1份，1.0莫耳當量）並在20℃±2℃中攪拌1.5小時後，升溫至35℃並進行了2小時攪拌。在吸濾器中依次舖滿Kyoward 200、Kyoward 1000後，藉由將反應液進行過濾而獲得了過濾液。在所獲得之過濾液中加入MEHQ（0.0012份）後，藉由在40℃中進行減壓濃縮，獲得了作為無色油狀物之1-乙氧基乙基氧基苯乙烯（PHSEVE）188.2份（收率98.0%）。<Synthesis of PHSEVE> In a 3-necked flask, p-hydroxystyrene (120.0 parts, 1.0 molar equivalent) and hexane (86.1 parts) were added and cooled to 20 ° C. After dripping camphorsulfonic acid (0.0070 parts, 0.03 millimolar equivalent) and ethyl vinyl ether (72.1 parts, 1.0 molar equivalent) and stirring at 20 ° C ± 2 ° C for 1.5 hours, the temperature was raised to 35 ° C and carried out Stir for 2 hours. After the suction filter was covered with Kyoward 200 and Kyoward 1000 in this order, the filtered solution was obtained by filtering the reaction solution. After MEHQ (0.0012 parts) was added to the obtained filtrate, it was concentrated under reduced pressure at 40 ° C to obtain 188.2 parts of 1-ethoxyethyloxystyrene (PHSEVE) as a colorless oil. (Yield 98.0%).

＜聚合物A-1的合成例＞ 在3口燒瓶中加入PGMEA（75.0份），在氮環境下升溫至90℃。將混合了ATHF（38.70份）、AA（1.47份）、CHA（59.83份）、V-601（4.1份）、PGMEA（75.0份）之溶液花費2小時滴落到了維持在90℃±2℃之3口燒瓶溶液中。滴落結束後，藉由在90℃±2℃中攪拌2小時而獲得了聚合物A-1（固體成分濃度40.0質量%）。<Synthesis Example of Polymer A-1> PGMEA (75.0 parts) was added to a 3-necked flask, and the temperature was raised to 90 ° C under a nitrogen atmosphere. The solution mixed with ATHF (38.70 parts), AA (1.47 parts), CHA (59.83 parts), V-601 (4.1 parts), PGMEA (75.0 parts) was dripped to maintain the temperature at 90 ℃ ± 2 ℃ for 2 hours 3-neck flask solution. After completion of the dripping, the polymer A-1 (solid content concentration 40.0% by mass) was obtained by stirring at 90 ° C ± 2 ° C for 2 hours.

＜聚合物A-2～A-5的合成例＞ 將單體的種類等如下述表中所示那樣進行變更，其他條件則以與A-1相同的方法進行了合成。將聚合物的固體成分濃度設為了40質量%。表1的各構成單元（將各單體聚合而成之單體單元）的含量單位為mol%。<Synthesis Examples of Polymers A-2 to A-5> The types of monomers and the like were changed as shown in the following table, and other conditions were synthesized by the same method as A-1. The solid content concentration of the polymer was set to 40% by mass. The content unit of each structural unit (monomer unit which polymerized each monomer) of Table 1 is mol%.

[表1] [Table 1]

［光酸產生劑］ B-1：BASF JAPAN LTD.製Irgacure PAG-103，下述化合物[Photoacid generator] B-1: Irgacure PAG-103 manufactured by BASF JAPAN LTD., The following compounds

[化學式14] [Chemical Formula 14]

B-2：下述所示之結構的化合物（係在日本特開2013-47765號公報的0227段中記載的化合物，且依照在0227段中記載的方法進行了合成。）B-2: The compound of the structure shown below (the compound described in paragraph 2227 of JP-A-2013-47765 and synthesized according to the method described in paragraph 2227.)

[化學式15] [Chemical Formula 15]

B-3：下述所示之結構的化合物（依照在國際公開第2014/020984號的0160段中記載的方法進行了合成。）B-3: Compounds of the structure shown below (Synthesized according to the method described in paragraph 0160 of International Publication No. 2014/020984.)

[化學式16] [Chemical Formula 16]

B-4：下述所示之結構的化合物（係在日本特開2012-163937號公報的0208段中記載的化合物，且依照在0212段中記載的方法進行了合成。）B-4: A compound of the structure shown below (the compound described in paragraph 0208 of Japanese Unexamined Patent Publication No. 2012-163937, and synthesized according to the method described in paragraph 0212.)

[化學式17] [Chemical Formula 17]

［增感劑］ E-1：Kawasaki Kasei Chemicals Ltd.製ANTHRACURE（註冊商標）UVS-1331，下述化合物（另外，Bu表示丁基。）[Sensitizer] E-1: ANTHRACURE (registered trademark) UVS-1331 manufactured by Kawasaki Kasei Chemicals Ltd., the following compound (In addition, Bu represents butyl.)

[化學式18] [Chemical Formula 18]

［界面活性劑］ E-1：下述所示之結構的化合物[Surfactant] E-1: Compound with the structure shown below

[化學式19] [Chemical Formula 19]

［鹼性化合物］ D-1：下述所示之結構的化合物（CMTU）[Basic compound] D-1: Compound of the structure shown below (CMTU)

[化學式20] [Chemical Formula 20]

＜聚合物C-1的合成例＞ 在以下例子中，以下略語分別表示以下化合物。 AANa：丙烯酸鈉（Tokyo Chemical Industry Co., Ltd.製） HEMA：甲基丙烯酸2-羥基乙酯（Tokyo Chemical Industry Co., Ltd.製） PGME：丙二醇單甲醚（SHOWA DENKO K.K.製）<Synthesis Example of Polymer C-1> In the following examples, the following abbreviations represent the following compounds, respectively. AANa: sodium acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) HEMA: 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) PGME: propylene glycol monomethyl ether (manufactured by SHOWA DENKO K.K.)

在3口燒瓶中加入PGME（75.0份），在氮環境下升溫至90℃。將混合了AANa（45.37份）、HEMA（54.63份）、V-601（4.1份）、PGME（75.0份）之溶液花費2小時滴落到了維持在90℃±2℃之3口燒瓶溶液中。滴落結束後，藉由在90℃±2℃中攪拌2小時而獲得了聚合物C-1（固體成分濃度40.0質量%）。PGME (75.0 parts) was added to the 3-necked flask, and the temperature was raised to 90 ° C under a nitrogen atmosphere. A solution mixed with AANa (45.37 parts), HEMA (54.63 parts), V-601 (4.1 parts), and PGME (75.0 parts) was dropped into a 3-neck flask solution maintained at 90 ° C ± 2 ° C over 2 hours. After completion of dripping, the polymer C-1 (solid content concentration 40.0% by mass) was obtained by stirring at 90 ° C ± 2 ° C for 2 hours.

（實施例1） ＜中間層組成物的製備＞ 按照以下組成進行混合、溶解，並以孔徑5.0μm的聚四氟乙烯製過濾器進行過濾，從而獲得了中間層組成物（固體成分濃度5.0質量%）。 離子交換水：47.5質量份 甲醇：47.5質量份 羥丙基甲基纖維素（HPMC，Shin-Etsu Chemical Co., Ltd.製TC-5E）：5.0質量份(Example 1) <Preparation of intermediate layer composition> Mix and dissolve according to the following composition, and filter with a polytetrafluoroethylene filter having a pore diameter of 5.0 μm to obtain an intermediate layer composition (solid content concentration 5.0 mass %). Ion-exchanged water: 47.5 parts by mass Methanol: 47.5 parts by mass Hydroxypropyl methyl cellulose (HPMC, TC-5E manufactured by Shin-Etsu Chemical Co., Ltd.): 5.0 parts by mass

＜感光性樹脂組成物的製備＞ 按照以下組成進行調配，並以孔徑0.2μm的聚四氟乙烯製過濾器進行過濾，從而獲得了感光性樹脂組成物。 PGMEA：424.5質量份 聚合物A-1：237.0質量份 光酸產生劑B-1：5.0質量份 界面活性劑E-1：0.1質量份 鹼性化合物D-1：0.1質量份<Preparation of photosensitive resin composition> It was prepared according to the following composition, and filtered through a filter made of polytetrafluoroethylene with a pore diameter of 0.2 μm to obtain a photosensitive resin composition. PGMEA: 424.5 parts by mass Polymer A-1: 237.0 parts by mass Photoacid generator B-1: 5.0 parts by mass Surfactant E-1: 0.1 parts by mass Basic compound D-1: 0.1 parts by mass

＜感光性轉印材料的製作＞ 在成為偽支撐體之厚度50μm的聚對酞酸乙二酯薄膜（以下亦稱作“PET（A）”。）上，將中間層組成物利用狹縫狀噴嘴以乾燥膜厚成為1.0μm之方式進行了塗佈。之後，在100℃的對流烘箱（convection oven）中乾燥了2分鐘，接著將感光性樹脂組成物利用狹縫狀噴嘴以乾燥膜厚成為3.0μm之方式進行了塗佈。之後，在100℃的對流烘箱中乾燥了2分鐘，最後作為覆蓋膜而將聚乙烯薄膜（Tredegar Co., Ltd.,製，OSM-N）進行了壓接，從而製作了感光性轉印材料。<Preparation of photosensitive transfer material> On a 50 μm-thick polyethylene terephthalate film (hereinafter also referred to as “PET (A)”) that becomes a pseudo-support, the intermediate layer composition is made into a slit shape The nozzle was coated so that the dry film thickness became 1.0 μm. After that, it was dried in a convection oven at 100 ° C. for 2 minutes, and then the photosensitive resin composition was applied with a slit-shaped nozzle so that the dry film thickness became 3.0 μm. After that, it was dried in a convection oven at 100 ° C for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Co., Ltd., OSM-N) was pressure-bonded as a cover film to produce a photosensitive transfer material .

（實施例2） 以固體成分中的含量的質量比成為表2所記載的組成之方式製作了中間層組成物，除此以外以與實施例1相同的方式製作了感光性轉印材料。(Example 2) A photosensitive transfer material was produced in the same manner as in Example 1 except that the intermediate layer composition was prepared so that the mass ratio of the content in the solid content became the composition described in Table 2.

（實施例3～25以及27～31） ＜熱塑性樹脂組成物H1的製備＞ 甲醇：11.1質量份 丙二醇單甲醚乙酸酯：6.36質量份 甲基己基酮：52.4質量份 甲基丙烯酸甲酯/2-乙基己基丙烯酸酯/甲基丙烯酸苄酯/甲基丙烯酸共聚物（共聚組成比（莫耳比）=55/11.7/4.5/28.8，分子量=10万，Tg≒70℃）：5.83質量份 苯乙烯/丙烯酸共聚物（共聚組成比（莫耳比）=63/37，重量平均分子量=1万，Tg≒100℃）：13.6質量份 單體1（環氧乙烷（EO）改質雙酚A二甲基丙烯酸酯（EO10莫耳當量），產品名：BPE-500，Shin-Nakamura Chemical Co., Ltd.製）：9.1質量份 氟系聚合物：0.54質量份 上述氟系聚合物係40份C6 F13 CH2 CH2 OCOCH=CH2 和55份H（OCH（CH3 ）CH2 ）7 OCOCH=CH2 和5份H（OCHCH2 ）7 OCOCH=CH2 的共聚物、重量平均分子量為3万、甲基己基酮30質量%溶液（產品名：Megaface F780F，DIC Corporation製）。(Examples 3 to 25 and 27 to 31) <Preparation of thermoplastic resin composition H1> Methanol: 11.1 parts by mass of propylene glycol monomethyl ether acetate: 6.36 parts by mass of methylhexyl ketone: 52.4 parts by mass of methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (mole ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ℃): 5.83 mass Parts styrene / acrylic acid copolymer (copolymerization composition ratio (mole ratio) = 63/37, weight average molecular weight = 10,000, Tg ≒ 100 ° C): 13.6 parts by mass of monomer 1 (ethylene oxide (EO) modification) Bisphenol A dimethacrylate (EO10 molar equivalent), product name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 9.1 parts by mass of fluorine-based polymer: 0.54 parts by mass of the above-mentioned fluorine-based polymer Copolymer of 40 parts C 6 F 13 CH 2 CH 2 OCOCH = CH 2 and 55 parts H (OCH (CH 3 ) CH 2 ) 7 OCOCH = CH 2 and 5 parts H (OCHCH 2 ) 7 OCOCH = CH 2 A solution having a weight average molecular weight of 30,000 and a methylhexyl ketone 30% by mass solution (product name: Megaface F780F, manufactured by DIC Corporation).

＜中間層組成物的製備＞ 以固體成分中的含量的質量比成為表2所記載的組成之方式製作了中間層組成物，除此以外以與實施例1相同的方式進行了混合、溶解，並以孔徑5.0μm的聚四氟乙烯製過濾器進行了過濾，藉此分別獲得了實施例3～25以及27～31的中間層組成物（固體成分濃度5.0質量%）。<Preparation of the intermediate layer composition> The intermediate layer composition was prepared so that the mass ratio of the content in the solid content became the composition described in Table 2, except that the intermediate layer composition was mixed and dissolved in the same manner as in Example 1. It was filtered with a polytetrafluoroethylene filter having a pore size of 5.0 μm, and thereby the intermediate layer compositions (solid content concentration 5.0% by mass) of Examples 3 to 25 and 27 to 31 were obtained, respectively.

＜感光性轉印材料的製作＞ 在成為偽支撐體之厚度50μm的聚對酞酸乙二酯薄膜（PET（A））上，將熱塑性樹脂組成物H1利用狹縫狀噴嘴以乾燥膜厚成為5.0μm之方式進行了塗佈。之後，在100℃的對流烘箱中乾燥了2分鐘，之後將中間層組成物利用狹縫狀噴嘴以乾燥膜厚成為1.0μm之方式進行了塗佈。之後，在100℃的對流烘箱中乾燥了2分鐘，接著將感光性樹脂組成物利用狹縫狀噴嘴以乾燥膜厚成為3.0μm之方式進行了塗佈。之後，在100℃的對流烘箱中乾燥了2分鐘，最後作為覆蓋膜而將聚乙烯薄膜（Tredegar Co., Ltd.,製，OSM-N）進行了壓接，從而製作了感光性轉印材料。<Preparation of photosensitive transfer material> On a polyethylene terephthalate film (PET (A)) with a thickness of 50 μm that becomes a pseudo support, the thermoplastic resin composition H1 was dried with a slit-shaped nozzle to a thickness of The coating was carried out in the manner of 5.0 μm. After that, it was dried in a convection oven at 100 ° C. for 2 minutes, and then the intermediate layer composition was applied with a slit-shaped nozzle so that the dried film thickness became 1.0 μm. After that, it was dried in a convection oven at 100 ° C. for 2 minutes, and then the photosensitive resin composition was applied with a slit-shaped nozzle so that the dried film thickness became 3.0 μm. After that, it was dried in a convection oven at 100 ° C for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Co., Ltd., OSM-N) was pressure-bonded as a cover film to produce a photosensitive transfer material .

（實施例26） 作為光酸產生劑使用B-4，並且添加了5.0質量份的增感劑，且將聚合物的添加量減少了5.0質量份，除此以外以與實施例23相同的方式製作了感光性轉印材料。(Example 26) B-4 was used as a photoacid generator, and 5.0 parts by mass of a sensitizer was added, and the amount of polymer added was reduced by 5.0 parts by mass, in the same manner as Example 23 except that A photosensitive transfer material was produced.

（實施例32以及33） 作為熱塑性樹脂組成物分別使用了下述熱塑性樹脂組成物H2或H3，除此以外以與實施例17相同的方式製作了實施例32以及33的感光性轉印材料。(Examples 32 and 33) As the thermoplastic resin composition, the following thermoplastic resin compositions H2 or H3 were used, respectively, and the photosensitive transfer materials of Examples 32 and 33 were produced in the same manner as in Example 17.

＜熱塑性樹脂組成物H2的製備＞ 甲醇：11.1質量份 丙二醇單甲醚乙酸酯：6.36質量份 甲基己基酮：52.4質量份 苯乙烯/丙烯酸共聚物（共聚組成比（莫耳比）=63/37，重量平均分子量=1万，Tg≒100℃）：19.43質量份 單體1（產品名：BPE-500，Shin-Nakamura Chemical Co., Ltd.製）：9.1質量份 氟系聚合物（產品名：Megaface F780F，DIC Corporation製）：0.54質量份<Preparation of thermoplastic resin composition H2> Methanol: 11.1 parts by mass of propylene glycol monomethyl ether acetate: 6.36 parts by mass of methylhexyl ketone: 52.4 parts by mass of styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63 / 37, weight average molecular weight = 10,000, Tg ≒ 100 ℃): 19.43 parts by mass of monomer 1 (product name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 9.1 parts by mass of fluorine-based polymer ( Product name: Megaface F780F, manufactured by DIC Corporation): 0.54 parts by mass

＜熱塑性樹脂組成物H3的製備＞ 甲醇：11.1質量份 丙二醇單甲醚乙酸酯：6.36質量份 甲基己基酮：52.4質量份 甲基丙烯酸甲酯/2-乙基己基丙烯酸酯/甲基丙烯酸苄酯/甲基丙烯酸共聚物（共聚組成比（莫耳比）=55/11.7/4.5/28.8，分子量=10万，Tg≒70℃）：19.43質量份 單體1（產品名：BPE-500，Shin-Nakamura Chemical Co., Ltd.製）：4.6質量份 氟系聚合物（產品名：Megaface F780F，DIC Corporation製）：0.54質量份<Preparation of thermoplastic resin composition H3> Methanol: 11.1 parts by mass of propylene glycol monomethyl ether acetate: 6.36 parts by mass of methylhexyl ketone: 52.4 parts by mass of methyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid Benzyl ester / methacrylic acid copolymer (copolymer composition ratio (mole ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ℃): 19.43 parts by mass of monomer 1 (product name: BPE-500 , Manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.6 parts by mass of fluorine-based polymer (product name: Megaface F780F, manufactured by DIC Corporation): 0.54 parts by mass

（比較例1以及5～8） 不塗佈熱塑性樹脂組成物以及中間層組成物而分別塗佈下述表2中所記載的感光性樹脂組成物，除此以外以與實施例1相同的方式分別製作了比較例1以及5～8的感光性轉印材料。(Comparative Examples 1 and 5 to 8) In the same manner as in Example 1, except that the thermoplastic resin composition and the intermediate layer composition were not applied but the photosensitive resin compositions described in Table 2 below were applied separately. The photosensitive transfer materials of Comparative Examples 1 and 5 to 8 were prepared respectively.

（比較例2～4） 分別使用下述表2中記載的中間層組成物，除此以外以與實施例3相同的方式分別製作了比較例2～4的感光性轉印材料。(Comparative Examples 2 to 4) The photosensitive transfer materials of Comparative Examples 2 to 4 were prepared in the same manner as in Example 3, except that the intermediate layer compositions described in Table 2 below were used, respectively.

［性能評價］ 使用了在厚度188μm的聚對酞酸乙二酯（PET）薄膜上以厚度500nm藉由濺射法製作有銅層之附銅層之PET基板。[Performance Evaluation] A PET substrate with a copper layer and a copper layer was prepared by a sputtering method on a polyethylene film of polyethylene terephthalate (PET) with a thickness of 188 μm and a thickness of 500 nm.

＜轉印性評價＞ 將已製作之感光性轉印材料切割成50cm見方，剝掉覆蓋膜，以輥溫度90℃、線壓0.6MPa、線速度3.6m/min的積層條件在附銅層之PET基板上進行了積層。測量感光性樹脂組成物層與銅層密合之面積，藉由感光性樹脂組成物層所密合之面積/切割之轉印材料的面積（%）求出了密合之面積比例。 5：95%以上 4：90%以上且小於95% 3：85%以上且小於90% 2：80%以上且小於85% 1：小於80%<Evaluation of transferability> The prepared photosensitive transfer material was cut into 50 cm squares, the cover film was peeled off, and the copper layer was deposited under the stacking conditions of roller temperature 90 ° C., line pressure 0.6 MPa, line speed 3.6 m / min. Lamination was carried out on the PET substrate. The area where the photosensitive resin composition layer and the copper layer are closely adhered was measured, and the area ratio of the adhesion was determined from the area where the photosensitive resin composition layer was adhered / the area of the cut transfer material (%). 5: 95% or more 4: 90% or more and less than 95% 3: 85% or more and less than 90% 2: 80% or more and less than 85% 1: less than 80%

＜畫素變形評價＞ 將已製作之感光性轉印材料以線壓0.6MPa、線速度（積層速度）3.6m/min的積層條件在附銅層之PET基板上進行了積層。另外，當在輥溫度90℃下上述轉印性評價為4以下時，直到上述轉印性評價成為判定5為止，提高輥溫度來製作了試樣。 不剝離偽支撐體而經由線寬3μm～20μm的線與空間圖案（line-and-space pattern）（佔空比（duty ratio）1:1）遮罩以超高壓水銀燈進行曝光後，在23℃下放置6小時後剝離偽支撐體來進行了顯影。顯影使用28℃的1.0質量%碳酸鈉水溶液，以噴淋顯影進行了40秒鐘。藉由上述方法形成10μm的線與空間圖案，求出線寬和空間寬度之比成為1:1之曝光量，藉由掃描型電子顯微鏡（SEM）觀察其曝光量中之5μm的線與空間圖案的前端的變形量，進行了畫素變形的評價。3以上為能夠實際使用之等級。 5：未觀察到畫素變形 4：畫素變形小於0.5μm 3：畫素變形為0.5μm以上且小於1.0μm 2：畫素變形為1.0μm以上且小於3.0μm 1：畫素變形為3.0μm以上或無畫素的殘留<Evaluation of Pixel Deformation> The prepared photosensitive transfer material was laminated on a PET substrate with a copper layer under the laminating conditions of a linear pressure of 0.6 MPa and a linear speed (laminating speed) of 3.6 m / min. In addition, when the above transferability evaluation was 4 or less at a roller temperature of 90 ° C., until the above transferability evaluation became judgment 5, the roller temperature was increased to prepare a sample. Without exposing the dummy support, after exposing with a line-and-space pattern (duty ratio 1: 1) with a line width of 3 μm to 20 μm and an ultra-high pressure mercury lamp, at 23 ° C. After being left for 6 hours, the dummy support was peeled off and developed. The development was carried out using a 1.0% by mass sodium carbonate aqueous solution at 28 ° C. for 40 seconds by spray development. The 10 μm line and space pattern was formed by the above method, the exposure amount at which the ratio of line width and space width was 1: 1 was obtained, and the 5 μm line and space pattern in the exposure amount was observed by scanning electron microscope (SEM) The amount of deformation of the front end was evaluated for pixel deformation. 3 or more is a level that can be actually used. 5: No pixel distortion is observed 4: Pixel distortion is less than 0.5 μm 3: Pixel distortion is 0.5 μm or more and less than 1.0 μm 2: Pixel distortion is 1.0 μm or more and less than 3.0 μm 1: Pixel distortion is 3.0 μm Above or no pixel residue

＜顯影液溶解性評價＞ 將已製作之感光性轉印材料以線壓0.6MPa、線速度（積層速度）3.6m/min的積層條件在附銅層之PET基板上進行了積層。另外當在輥溫度90℃下上述轉印性評價為4以下時，直到上述轉印性評價成為判定5為止，提高輥溫度來製作了試樣。 不剝離偽支撐體而以300mJ/cm2 的曝光量進行了全面曝光，在23℃中放置1小時後剝離偽支撐體，使用28℃的1.0質量%碳酸鈉水溶液，一邊改變顯影時間一邊進行了噴淋顯影。藉由求出從顯影開始至殘膜消失為止的時間來進行了顯影液溶解性的評價。 5：從顯影開始至殘膜消失為止的時間小於5秒 4：從顯影開始至殘膜消失為止的時間為5秒以上且小於10秒 3：從顯影開始至殘膜消失為止的時間為10秒以上且小於30秒 2：從顯影開始至殘膜消失為止的時間為30秒以上且小於60秒 1：從顯影開始至殘膜消失為止的時間為60秒以上<Evaluation of Solubility of Developer> The prepared photosensitive transfer material was laminated on a PET substrate with a copper layer under the laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminating speed) of 3.6 m / min. In addition, when the above-mentioned transferability evaluation was 4 or less at a roller temperature of 90 ° C., until the above-mentioned transferability evaluation became judgment 5, the roller temperature was increased to prepare a sample. Full exposure was carried out at an exposure of 300 mJ / cm 2 without peeling off the dummy support, and the dummy support was peeled off after being left at 23 ° C. for 1 hour, and a 28 ° C. 1.0% by mass sodium carbonate aqueous solution was used while changing the development time. Spray development. The solubility of the developer was evaluated by determining the time from the start of development until the residual film disappeared. 5: The time from the start of development to the disappearance of the residual film is less than 5 seconds 4: The time from the start of development to the disappearance of the residual film is 5 seconds or more and less than 10 seconds 3: The time from the start of development to the disappearance of the residual film is 10 seconds Above and less than 30 seconds 2: The time from the start of development until the residual film disappears is 30 seconds or more and less than 60 seconds 1: The time from the start of development to the disappearance of residual film is 60 seconds or more

[表2] [Table 2]

另外，表2中之中間層的各樹脂的含量（質量%）的值表示在上述中間層組成物中使用之樹脂5.0質量份中的比例。In addition, the value of the content (mass%) of each resin of the intermediate layer in Table 2 represents the ratio in 5.0 parts by mass of the resin used in the intermediate layer composition.

並且，表2中記載的略號的詳細內容如下。 HPMC：羥丙基甲基纖維素，Shin-Etsu Chemical Co., Ltd.製TC-5E 低分子量類型 HPMCH：羥丙基甲基纖維素，Shin-Etsu Chemical Co., Ltd.製TC-5S 高分子量類型 HPC：羥丙基纖維素，NIPPON SODA CO.,LTD.製Nisso HPC SSL 分子量40,000 HPCH：羥丙基纖維素，NIPPON SODA CO.,LTD.製Nisso HPC L 分子量140,000 PhNv：苯酚酚醛清漆樹脂，ASAHI YUKIZAI CORPORATION製RM-25 PA：丙烯酸樹脂（聚合物C-1），丙烯酸鈉/丙烯酸羥乙酯共聚物（莫耳比=50:50），分子量20,000 PVA：聚乙烯醇，Kuraray Co.,Ltd.製KURARAY PVA-205 PVP：聚乙烯吡咯啶酮，NIPPON SHOKUBAI CO., LTD.製聚乙烯吡咯啶酮K-30 PAA：聚丙烯酸，TOAGOSEI CO., LTD.製Aron A-10SL PAANa：聚丙烯酸鈉，TOAGOSEI CO., LTD.製Aron A-210 PEO：聚環氧乙烷，MEISEI CHEMICAL WORKS, LTD.製ALK0X L-6 PEI：聚伸乙亞胺，NIPPON SHOKUBAI CO., LTD.製EPOMIN SP-018The details of the abbreviations described in Table 2 are as follows. HPMC: Hydroxypropyl methylcellulose, TC-5E manufactured by Shin-Etsu Chemical Co., Ltd. Low molecular weight type HPMCH: Hydroxypropyl methylcellulose, TC-5S manufactured by Shin-Etsu Chemical Co., Ltd. High Molecular weight type HPC: Hydroxypropyl cellulose, Nisso HPC SSL manufactured by NIPPON SODA CO., LTD. Molecular weight 40,000 HPCH: Hydroxypropyl cellulose, Nisso HPC L manufactured by NIPPON SODA CO., LTD. Molecular weight 140,000 PhNv: Phenol novolak resin , RM-25 PA manufactured by ASAHI YUKIZAI CORPORATION: acrylic resin (polymer C-1), sodium acrylate / hydroxyethyl acrylate copolymer (mole ratio = 50: 50), molecular weight 20,000 PVA: polyvinyl alcohol, Kuraray Co. , Ltd. KURARAY PVA-205 PVP: polyvinylpyrrolidone, NIPPON SHOKUBAI CO., LTD. Polyvinylpyrrolidone K-30 PAA: polyacrylic acid, TOAGOSEI CO., LTD. Aron A-10SL PAANa: Sodium polyacrylate, manufactured by TOAGOSEI CO., LTD. Aron A-210 PEO: polyethylene oxide, manufactured by MEISEI CHEMICAL WORKS, LTD. ALK0X L-6 PEI: polyethylenimine, manufactured by NIPPON SHOKUBAI CO., LTD. EPOMIN SP-018

（實施例41） 將使用了在實施例1中記載的中間層以及感光性樹脂組成物之感光性轉印材料以實施例1中記載的方法進行了製作，並在畫素變形評價以及顯影液溶解性評價中進行了下述變更，除此以外均進行了相同的性能評價。(Example 41) A photosensitive transfer material using the intermediate layer and the photosensitive resin composition described in Example 1 was prepared by the method described in Example 1, and evaluated for pixel distortion and developer The following changes were made in the solubility evaluation, and the same performance evaluation was carried out except for the following.

＜畫素變形評價＞ 將已製作之感光性轉印材料以線壓0.6MPa、線速度（積層速度）3.6m/min的積層條件在附銅層之PET基板上進行了積層。另外，在該積層中，直到上述轉印性評價成為判定5為止，提高輥溫度來製作了試樣。 剝離了偽支撐體後，使線寬3μm～20μm的線與空間圖案（Duty比1:1）遮罩與中間層接觸，以超高壓水銀燈進行曝光後，在23℃中放置6小時後進行了顯影。顯影使用28℃的1.0質量%碳酸鈉水溶液，以噴淋顯影進行了40秒鐘。藉由上述方法形成10μm的線與空間圖案，求出線寬和空間寬度之比成為1:1之曝光量，藉由掃描型電子顯微鏡（SEM）觀察其曝光量中之5μm的線與空間圖案的前端的變形量，進行了畫素變形的評價。3以上為能夠實際使用之等級。 5：未觀察到畫素變形 4：畫素變形小於0.5μm 3：畫素變形為0.5μm以上且小於1.0μm 2：畫素變形為1.0μm以上且小於3.0μm 1：畫素變形為3.0μm以上或無畫素殘留<Evaluation of Pixel Deformation> The prepared photosensitive transfer material was laminated on a PET substrate with a copper layer under the laminating conditions of a linear pressure of 0.6 MPa and a linear speed (laminating speed) of 3.6 m / min. In addition, in this buildup, until the above transferability evaluation became determination 5, the roller temperature was increased to prepare a sample. After peeling off the dummy support, the line with a line width of 3 μm to 20 μm was brought into contact with the space pattern (Duty ratio 1: 1) mask and the intermediate layer, and exposed with an ultra-high pressure mercury lamp, and then placed at 23 ° C for 6 hours. development. The development was carried out using a 1.0% by mass sodium carbonate aqueous solution at 28 ° C. for 40 seconds by spray development. The 10 μm line and space pattern was formed by the above method, the exposure amount at which the ratio of line width and space width was 1: 1 was obtained, and the 5 μm line and space pattern in the exposure amount was observed with a scanning electron microscope (SEM) The amount of deformation of the front end was evaluated for pixel deformation. 3 or more is a level that can be actually used. 5: No pixel distortion is observed 4: Pixel distortion is less than 0.5 μm 3: Pixel distortion is 0.5 μm or more and less than 1.0 μm 2: Pixel distortion is 1.0 μm or more and less than 3.0 μm 1: Pixel distortion is 3.0 μm Above or no pixel residue

＜顯影液溶解性評價＞ 將已製作之感光性轉印材料以線壓0.6MPa、線速度（積層速度）3.6m/min的積層條件在附銅層之PET基板上進行了積層。另外當在輥溫度90℃下上述轉印性評價為4以下時，直到上述轉印性評價成為判定5為止，提高輥溫度來製作了試樣。 剝離偽支撐體後，以300mJ/cm2 的曝光量進行了全面曝光，在23℃中放置1小時間後，使用28℃的1.0質量%碳酸鈉水溶液，一邊改變顯影時間一邊進行了噴淋顯影。藉由求出從顯影開始至殘膜消失為止的時間來進行了顯影液溶解性的評價。 5：從顯影開始至殘膜消失為止的時間小於5秒 4：從顯影開始至殘膜消失為止的時間為5秒以上且小於10秒 3：從顯影開始至殘膜消失為止的時間為10秒以上且小於30秒 2：從顯影開始至殘膜消失為止的時間為30秒以上且小於60秒 1：從顯影開始至殘膜消失為止的時間為60秒以上<Evaluation of Solubility of Developer> The prepared photosensitive transfer material was laminated on a PET substrate with a copper layer under the laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminating speed) of 3.6 m / min. In addition, when the above-mentioned transferability evaluation was 4 or less at a roller temperature of 90 ° C., until the above-mentioned transferability evaluation became judgment 5, the roller temperature was increased to prepare a sample. After peeling off the dummy support, it was fully exposed at an exposure of 300 mJ / cm 2 , and after standing at 23 ° C for 1 hour, a 28 ° C 1.0% by mass sodium carbonate aqueous solution was used to perform spray development while changing the development time. . The solubility of the developer was evaluated by determining the time from the start of development until the residual film disappeared. 5: The time from the start of development to the disappearance of the residual film is less than 5 seconds 4: The time from the start of development to the disappearance of the residual film is 5 seconds or more and less than 10 seconds 3: The time from the start of development to the disappearance of the residual film is 10 seconds Above and less than 30 seconds 2: The time from the start of development until the residual film disappears is 30 seconds or more and less than 60 seconds 1: The time from the start of development to the disappearance of residual film is 60 seconds or more

（實施例42～44） 將使用了在實施例2～4中記載的中間層以及感光性樹脂組成物之感光性轉印材料以實施例1中記載的方法進行了製作，在畫素變形評價以及顯影液溶解性評價中，進行了與實施例41的評價相同的變更，除此以外均進行了相同的性能評價。(Examples 42 to 44) A photosensitive transfer material using the intermediate layer and the photosensitive resin composition described in Examples 2 to 4 was prepared by the method described in Example 1 and evaluated for pixel distortion In addition, in the evaluation of the solubility of the developer, the same changes as those in Example 41 were carried out, and all the same performance evaluations were carried out.

[表3] [table 3]

（實施例101） 在100μm厚PET基材上，作為第2層的導電性層而將氧化銦錫（ITO）藉由濺射以150nm厚進行了成膜，在之上作為第1層的導電性層而將銅藉由真空蒸鍍法以200nm厚進行了成膜，藉此製成了電路形成基板。 在銅層上積層了在實施例1中獲得之感光性轉印材料1（線壓0.8MPa，線速度3.0m/min，輥溫度90℃）。不剝離偽支撐體而使用設置有具有沿單向連結有導電性層襯墊之構成之圖2所示之圖案（以下亦稱作“圖案A”。）之光罩進行了接觸圖案曝光。 另外，圖2所示之圖案A中，實線部SL以及灰色部G係遮光部，虛線部DL為假設性地表示對準的框者。 之後將偽支撐體進行剝離、顯影、水洗來獲得了圖案A。接著使用銅蝕刻液（KANTO CHEMICAL CO.,INC.製Cu-02）對銅層進行了蝕刻後，使用ITO蝕刻液（KANTO CHEMICAL CO.,INC.製ITO-02）對ITO層進行了蝕刻，藉此獲得了由銅（實線部SL）和ITO（灰色部G）一同描繪出圖案A之基板。(Example 101) On a 100-μm-thick PET substrate, indium tin oxide (ITO) was formed as a second-layer conductive layer by sputtering at a thickness of 150 nm, and the first layer was conductive The copper layer was formed into a 200 nm thick layer by vacuum evaporation method as a conductive layer, thereby forming a circuit-forming substrate. The photosensitive transfer material 1 obtained in Example 1 (linear pressure 0.8 MPa, linear speed 3.0 m / min, roller temperature 90 ° C.) was laminated on the copper layer. The contact pattern exposure was performed using the photomask provided with the pattern shown in FIG. 2 (hereinafter also referred to as “pattern A”) having a configuration in which a conductive layer pad was connected in one direction without peeling the dummy support. In addition, in the pattern A shown in FIG. 2, the solid line portion SL and the gray portion G are light-shielding portions, and the broken line portion DL is a frame that tentatively indicates alignment. After that, the dummy support was peeled, developed, and washed with water to obtain the pattern A. Next, the copper layer was etched using a copper etching solution (Cu-02 made by KANTO CHEMICAL CO., INC.), And then the ITO layer was etched using an ITO etching solution (ITO-02 made by KANTO CHEMICAL CO., INC.). This obtained a substrate in which the pattern A was drawn by copper (solid line portion SL) and ITO (gray portion G) together.

接著，使用以對準之狀態設置有圖3所示之圖案（以下亦稱作“圖案B”。）的開口部之光罩進行了圖案曝光、顯影、水洗。 另外，圖3所示之圖案B中，灰色部G係遮光部，虛線部DL為假設性地表示對準的框者。 之後，使用Cu-02對銅層進行蝕刻，並使用剝離液（10質量%氫氧化鈉水溶液）來剝離剩餘之感光性樹脂組成物層而獲得了電路配線基板。 藉此獲得了電路配線基板。以顯微鏡進行觀察時，無剝落和缺失等，係完美的圖案。Next, pattern exposure, development, and water washing were performed using the photomask in which the pattern shown in FIG. 3 (hereinafter also referred to as “pattern B”) was provided in an aligned state. In the pattern B shown in FIG. 3, the gray portion G is a light-shielding portion, and the broken line portion DL is a frame that tentatively indicates alignment. Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive resin composition layer was stripped using a stripping solution (10% by mass sodium hydroxide aqueous solution) to obtain a circuit wiring board. Thereby, a circuit wiring board was obtained. When observed with a microscope, there is no flaking or missing, which is a perfect pattern.

（實施例102～133） 分別使用在實施例2～33中獲得之感光性轉印材料進行了與實施例101相同的評價，結果無剝落和缺失等，係完美的圖案。(Examples 102 to 133) The photosensitive transfer materials obtained in Examples 2 to 33 were used to perform the same evaluation as in Example 101. As a result, there was no peeling, missing, etc., and they were perfect patterns.

（實施例141） 在100μm厚PET基材上作為第2層的導電性層而將氧化銦錫（ITO）藉由濺射以150nm厚進行了成膜，在其之上作為第1層的導電性層而將銅藉由真空蒸鍍法以200nm厚進行了成膜，藉此製成了電路形成基板。 在銅層上積層了在實施例1中獲得之感光性轉印材料1（線壓0.8MPa，線速度3.0m/min，輥溫度90℃）。剝離偽支撐體並使用設置有圖案A的構成之光罩進行了接觸圖案曝光。如此在剝離偽支撐體後進行圖案曝光，除此以外進行了與實施例101相同的評價。 藉此獲得了電路配線基板。以顯微鏡進行觀察時，無剝落和缺失等，係完美的圖案。(Example 141) An indium tin oxide (ITO) film was formed by sputtering at a thickness of 150 nm on a 100-μm-thick PET substrate as a conductive layer of the second layer, and a conductive layer of the first layer was formed thereon. The copper layer was formed into a 200 nm thick layer by vacuum evaporation method as a conductive layer, thereby forming a circuit-forming substrate. The photosensitive transfer material 1 obtained in Example 1 (linear pressure 0.8 MPa, linear speed 3.0 m / min, roller temperature 90 ° C.) was laminated on the copper layer. The dummy support was peeled off, and contact pattern exposure was performed using the photomask provided with the pattern A. The pattern exposure was carried out after peeling the dummy support body in this way, and the same evaluation as in Example 101 was performed except for this. Thereby, a circuit wiring board was obtained. When observed with a microscope, there is no flaking or missing, which is a perfect pattern.

（實施例142～144） 分別使用在實施例2～4中獲得之感光性轉印材料進行了與實施例141相同的評價，結果無剝落或缺失等，係完美的圖案。(Examples 142 to 144) The photosensitive transfer materials obtained in Examples 2 to 4 were used to perform the same evaluation as in Example 141. As a result, there was no peeling, missing, etc., and they were perfect patterns.

10‧‧‧偽支撐體10‧‧‧Pseudo support

12‧‧‧中間層12‧‧‧ middle layer

14‧‧‧感光性樹脂組成物層14‧‧‧Photosensitive resin composition layer

16‧‧‧覆蓋膜16‧‧‧covering film

100‧‧‧感光性轉印材料100‧‧‧Photosensitive transfer material

SL‧‧‧實線部SL‧‧‧Solid line department

G‧‧‧灰色部G‧‧‧Gray

DL‧‧‧虛線部DL‧‧‧ dotted line

圖1係表示本公開之感光性轉印材料的層結構的一例之概要圖。 圖2係表示圖案A之概要圖。 圖3係表示圖案B之概要圖。FIG. 1 is a schematic diagram showing an example of the layer structure of the photosensitive transfer material of the present disclosure. FIG. 2 is a schematic diagram showing the pattern A. FIG. FIG. 3 is a schematic diagram showing pattern B. FIG.

Claims (12)

一種感光性轉印材料，依次具有： 偽支撐體； 中間層；以及 感光性樹脂組成物層， 前述感光性樹脂組成物層含有聚合物和光酸產生劑，前述聚合物包含具有被酸分解性基保護之酸基之構成單元， 前述中間層含有樹脂C，前述樹脂C係水溶性或鹼溶性，且包含具有酚性羥基或未直接連結於主鏈之醇性羥基之構成單元。A photosensitive transfer material comprising: a pseudo-support; an intermediate layer; and a photosensitive resin composition layer, the photosensitive resin composition layer containing a polymer and a photoacid generator, and the polymer containing an acid-decomposable group The structural unit of the protected acid group, the intermediate layer contains resin C, and the resin C is water-soluble or alkali-soluble, and includes a structural unit having a phenolic hydroxyl group or an alcoholic hydroxyl group not directly linked to the main chain. 如申請專利範圍第1項所述之感光性轉印材料，其中 在前述偽支撐體和前述中間層之間，進一步具有熱塑性樹脂層。The photosensitive transfer material as described in item 1 of the patent application range, wherein a thermoplastic resin layer is further provided between the dummy support and the intermediate layer. 如申請專利範圍第1項或第2項所述之感光性轉印材料，其中 前述樹脂C係選自由酚醛清漆樹脂、改質纖維素樹脂以及具有羥基之丙烯酸樹脂組成的群之至少1種樹脂。The photosensitive transfer material according to item 1 or 2 of the patent application, wherein the resin C is at least one resin selected from the group consisting of novolak resins, modified cellulose resins, and acrylic resins having hydroxyl groups . 如申請專利範圍第1項或第2項所述之感光性轉印材料，其中 前述中間層進一步含有除了前述樹脂C以外的水溶性或鹼溶性之樹脂D。The photosensitive transfer material according to item 1 or 2 of the patent application, wherein the intermediate layer further contains a water-soluble or alkali-soluble resin D other than the resin C. 如申請專利範圍第4項所述之感光性轉印材料，其中 前述樹脂D係選自由聚丙烯酸、聚丙烯酸鈉、聚丙烯醯胺、聚環氧乙烷、聚伸乙亞胺、聚乙烯醇以及聚乙烯吡咯啶酮組成的群之至少1種樹脂。The photosensitive transfer material as described in item 4 of the patent application, wherein the resin D is selected from the group consisting of polyacrylic acid, sodium polyacrylate, polypropylene amide, polyethylene oxide, polyethyleneimine, and polyvinyl alcohol And at least one resin of the group consisting of polyvinylpyrrolidone. 如申請專利範圍第4項所述之感光性轉印材料，其中 前述樹脂D係選自由聚乙烯醇以及聚乙烯吡咯啶酮組成的群之至少1種樹脂。The photosensitive transfer material as described in item 4 of the patent application, wherein the resin D is at least one resin selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone. 如申請專利範圍第4項所述之感光性轉印材料，其中 前述中間層中之前述樹脂C和前述樹脂D的含有質量比係樹脂C:樹脂D=5:1～1:2。The photosensitive transfer material as described in item 4 of the patent application range, wherein the content ratio of the resin C and the resin D in the intermediate layer is resin C: resin D = 5: 1 to 1: 2. 如申請專利範圍第7項所述之感光性轉印材料，其中 前述中間層中之前述樹脂C和前述樹脂D的含有質量比係樹脂C:樹脂D=4:1～2:1。The photosensitive transfer material as described in Item 7 of the patent application range, wherein the content ratio of the resin C and the resin D in the intermediate layer is resin C: resin D = 4: 1 to 2: 1. 如申請專利範圍第1項或第2項所述之感光性轉印材料，其中 前述具有被酸分解性基保護之酸基之構成單元係以下述式A表示之構成單元，式A中，R31 以及R32 分別獨立地表示氫原子、烷基或芳基，R31 以及R32 中之至少一者係烷基或芳基，R33 表示烷基或芳基，R31 或R32 可與R33 連結而形成環狀醚，R34 表示氫原子或甲基，X0 表示單鍵或伸芳基。The photosensitive transfer material as described in Item 1 or Item 2 of the patent application, wherein the structural unit having an acid group protected by an acid-decomposable group is a structural unit represented by the following formula A, In formula A, R 31 and R 32 independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 represents an alkyl group or an aryl group, R 31 Or R 32 may be linked to R 33 to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or an aryl group. 如申請專利範圍第1項或第2項所述之感光性轉印材料，其中 前述感光性樹脂組成物層中之前述聚合物的玻璃轉移溫度係-20℃以上且90℃以下。The photosensitive transfer material according to item 1 or 2 of the patent application, wherein the glass transition temperature of the polymer in the photosensitive resin composition layer is -20 ° C or higher and 90 ° C or lower. 一種電路配線之製造方法，依次具有以下製程： 相對於基板，使申請專利範圍第1項或第2項所述之感光性轉印材料的前述感光性樹脂組成物層與前述基板接觸並進行貼合之製程； 對前述貼合製程後的前述感光性轉印材料的前述感光性樹脂組成物層進行圖案曝光之製程； 對前述進行曝光之製程後的前述感光性樹脂組成物層進行顯影並形成圖案之製程；以及 對未配置有前述圖案之區域中之前述基板進行蝕刻處理之製程。A method for manufacturing circuit wiring, which has the following processes in sequence: With respect to a substrate, the photosensitive resin composition layer of the photosensitive transfer material described in item 1 or 2 of the patent application scope is brought into contact with and pasted to the substrate A combined process; a process of pattern exposing the photosensitive resin composition layer of the photosensitive transfer material after the lamination process; developing and forming the photosensitive resin composition layer after the exposure process The process of the pattern; and the process of etching the substrate in the area where the pattern is not configured. 一種電路配線之製造方法，依次包含以下製程： 相對於基板，使申請專利範圍第1項或第2項所述之感光性轉印材料的前述感光性樹脂組成物層與前述基板接觸並進行貼合之製程； 剝離前述感光性轉印材料的偽支撐體之製程； 對前述感光性樹脂組成物層進行圖案曝光之製程； 對前述感光性樹脂組成物層進行顯影並形成圖案之製程；以及 對未配置有前述圖案之區域中之前述基板進行蝕刻處理之製程。A method of manufacturing a circuit wiring, which includes the following processes in sequence: With respect to a substrate, the photosensitive resin composition layer of the photosensitive transfer material described in item 1 or 2 of the patent application scope is brought into contact with and pasted to the substrate The combined process; the process of peeling off the dummy support of the photosensitive transfer material; the process of pattern exposing the photosensitive resin composition layer; the process of developing and patterning the photosensitive resin composition layer; and The etching process of the substrate in the area where the pattern is not configured.
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