JP2017078852A - Dry film resist, method for producing circuit wiring, circuit wiring, input device and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dry film resist which makes it possible to produce circuit wiring having high pattern linearity.SOLUTION: The present invention provides a positive dry film resist having a resist layer on a temporary support, with the temporary support having a total light beam haze of 0.3% or less; a method for producing circuit wiring; circuit wiring; an input device; and a display device.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a dry film resist, a method for manufacturing circuit wiring, circuit wiring, an input device, and a display device.

In a display device (such as an organic Electro Luminescence (EL) display device or a liquid crystal display device) having a touch panel such as a capacitance type input device, an electrode pattern corresponding to a sensor of a visual recognition part, a peripheral wiring portion, and a wiring of a take-out wiring portion Etc. are provided in the touch panel.
In general, a patterned conductive layer is formed by using a dry film resist as a photosensitive transfer material and a resist provided on an arbitrary circuit formation substrate because the number of steps for obtaining a required pattern shape is small. A layer (photosensitive resin composition layer) is exposed through a mask having a desired pattern, the resist layer is partially cured or dissolved, and developed to obtain a circuit pattern, and then etched to form a conductive layer In addition, a method of forming a circuit pattern by transfer is widely used.

  Here, the resist layer is roughly classified into a negative type and a positive type from a reaction method with light or an electron beam. When exposed to a negative resist layer, the solubility in the developer decreases, leaving an exposed portion after development. When the positive resist layer is exposed, the solubility in the developer increases, and the exposed portion is removed after development. Since there is an advantage that a high-resolution pattern can be easily formed as compared with a negative resist, a positive dry film resist is required.

  As a positive dry film resist, for example, positive dry film resists described in Patent Documents 1 and 2 are known.

  Patent Document 1 describes a multilayer resist in which an intermediate layer having photobleachability and / or light absorption is provided between a lower photoresist layer and an upper photoresist layer. Patent Document 1 also describes providing a multilayer resist with improved multi-contrast exposure controllability and improved multi-contrast exposure effect.

  Patent Document 2 describes a film-type photodegradable transfer material including a support film; a photodegradable photoresist layer; and a reflection suppressing layer formed on a surface to be laminated on a circuit forming substrate.

Japanese Patent Laid-Open No. 5-66568 JP 2009-282522 A

  When the present inventors examined circuit formation using the positive-type dry film resists described in Patent Documents 1 and 2, when pattern exposure was performed without peeling off the temporary support, exposure was caused by light diffusion caused by the temporary support. It was found that light diffuses and the pattern linearity of the resulting pattern is degraded. In the positive dry film resist, the exposed portion dissolves to form a mask image, so that the remaining pattern portion is not cured, and peeling is likely to occur particularly in a thin line pattern when the pattern linearity is lowered. Therefore, circuit quality degradation, circuit disconnection, and short circuit may occur. Therefore, it has been found that the decrease in pattern linearity is a more prominent problem when a high resolution pattern is formed using a positive dry film resist than when a high resolution pattern is formed using a negative resist. .

The problem to be solved by the present invention is to provide a dry film resist that is capable of producing a circuit wiring having a high pattern linearity that is easy to form a high resolution pattern.
Further, the problem to be solved by the present invention is to provide a positive wiring pattern that can easily form a high-resolution pattern, and a circuit wiring having high pattern linearity and a method for manufacturing the circuit wiring.
Another problem to be solved by the present invention is to provide an input device using the circuit wiring and a display device including the input device.

As a result of intensive studies by the present inventors, it has been found that the above problem can be solved by using a temporary support having a low haze.
Moreover, it discovered that the said subject could be similarly solved by using the resist layer containing the binder which has a specific structural unit.
On the other hand, Patent Document 1 does not describe the transparency and haze of a multilayer resist support, and uses a commercially available binder made of novolac resin as a binder for the resist layer. In Patent Document 2, there is a description that the support film of the film-type transfer material is not particularly limited as long as it satisfies the transparency that does not impair the light transmission, and there is no description about haze. Among the alkali-soluble resins, it is described that a novolak resin is used.
The present invention, which is a specific means for solving the above problems, and preferred ranges of the present invention are as follows.

一般式Ａ３中、Ｒ³¹およびＲ³²はそれぞれ独立に水素原子、アルキル基またはアリール基を表し、少なくともＲ³¹およびＲ³²のいずれか一方がアルキル基またはアリール基であり、Ｒ³³はアルキル基またはアリール基を表し、Ｒ³¹またはＲ³²と、Ｒ³³とが連結して環状エーテルを形成してもよく、Ｒ³⁴は水素原子またはメチル基を表し、Ｘ⁰は単結合またはアリーレン基を表し、Ｙは窒素原子、硫黄原子または酸素原子を表す。
［３］ ［１］に記載のドライフィルムレジストは、レジスト層が、（Ａ）成分および（Ｂ）光酸発生剤を含み、
（Ａ）成分が、酸基が酸分解性基で保護された酸構成単位ａ０を有する重合体であり、
酸構成単位ａ０が、下記一般式Ａ３で表される構成単位を有することが好ましい；
一般式Ａ３

一般式Ａ３中、Ｒ³¹およびＲ³²はそれぞれ独立に水素原子、アルキル基またはアリール基を表し、少なくともＲ³¹およびＲ³²のいずれか一方がアルキル基またはアリール基であり、Ｒ³³はアルキル基またはアリール基を表し、Ｒ³¹またはＲ³²と、Ｒ³³とが連結して環状エーテルを形成してもよく、Ｒ³⁴は水素原子またはメチル基を表し、Ｘ⁰は単結合またはアリーレン基を表し、Ｙは窒素原子、硫黄原子または酸素原子を表す。
［４］ ［２］または［３］に記載のドライフィルムレジストは、一般式Ａ３中、Ｘ⁰が単結合であることが好ましい。
［５］ ［２］〜［４］のいずれか一つに記載のドライフィルムレジストは、一般式Ａ３中、Ｙが酸素原子であることが好ましい。
［６］ ［１］に記載のドライフィルムレジストは、レジスト層が、（Ａ）成分および（Ｂ）光酸発生剤を含み、
（Ａ）成分が、酸基が酸分解性基で保護された酸構成単位ａ０を有する重合体であり、
酸構成単位ａ０が、カルボキシ基またはフェノール性水酸基がアセタールの形で保護された酸構成単位ａ１であることが好ましい。
［７］ ［６］に記載のドライフィルムレジストは、酸構成単位ａ１が、下記一般式Ａ１で表される構成単位を有することが好ましい；
一般式Ａ１

一般式Ａ１中、Ｒ¹およびＲ²はそれぞれ独立に水素原子、アルキル基またはアリール基を表し、少なくともＲ¹およびＲ²のいずれか一方がアルキル基またはアリール基であり、Ｒ³はアルキル基またはアリール基を表し、Ｒ¹またはＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は水素原子またはメチル基を表す。
［８］ ［６］に記載のドライフィルムレジストは、酸構成単位ａ１が、下記一般式Ａ２で表される構成単位を有することが好ましい；
一般式Ａ２

一般式Ａ２中、Ｒ¹¹およびＲ¹²はそれぞれ独立に水素原子、アルキル基またはアリール基を表し、少なくともＲ¹¹およびＲ¹²のいずれか一方がアルキル基またはアリール基であり、Ｒ¹³はアルキル基またはアリール基を表し、Ｒ¹¹またはＲ¹²と、Ｒ¹³とが連結して環状エーテルを形成してもよく、Ｒ¹⁴はそれぞれ独立に、水素原子、水酸基、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、アリール基、アラルキル基、アルコキシカルボニル基、ヒドロキシアルキル基、アリールカルボニル基またはシクロアルキル基を表す。
［９］ ［１］および［３］〜［８］のいずれか一つに記載のドライフィルムレジストは、レジスト層が、酸基が酸分解性基で保護された酸構成単位ａ０を有する重合体を２種類以上含有することが好ましい。
［１０］ ［１］に記載のドライフィルムレジストは、レジスト層がナフトキノンジアジド化合物およびフェノール性水酸基を有する樹脂を含むことが好ましい。
［１１］ ［１］〜［１０］のいずれか一つに記載のドライフィルムレジストは、レジスト層が、さらにヘテロ環状化合物を含むことが好ましい。
［１２］ ［１］〜［１１］のいずれか一つに記載のドライフィルムレジストは、レジスト層が、さらに塩基性化合物を含むことが好ましい。
［１３］ ［１］〜［１２］のいずれか一つに記載のドライフィルムレジストは、レジスト層が、さらに放射線吸収剤を含むことが好ましい。
［１４］ ［１］〜［１３］のいずれか一つに記載のドライフィルムレジストは、以下の条件（１）および条件（２）の少なくとも一つを満たすことが好ましい；
条件（１）：仮支持体が、レジスト層の露光主波長に対して８０％以下の透過率を有する；
条件（２）：仮支持体およびレジスト層の間にレジスト層の露光主波長に対して８０％以下の透過率を有する光吸収層を有する。
［１５］ 下記（ａ）工程、（ｂ）工程、（ｃ）工程および（ｄ）工程、を含む回路配線の製造方法；
（ａ） 基材と導電層とを有する回路形成基板の上へ［１］〜［１４］のいずれか一つに記載のドライフィルムレジストをラミネートするラミネート工程；
（ｂ） ドライフィルムレジストの仮支持体を剥離せずに、パターン露光用パターンでコンタクトパターン露光するパターン露光工程；
（ｃ） 仮支持体を剥離後、現像してレジスト層にパターン露光用パターンを形成する現像工程；
（ｄ） エッチングにより、回路形成基板にパターン露光用パターンを形成するエッチング工程。
［１６］ ［１５］に記載の回路配線の製造方法は、（ｂ）工程が下記（ｂ１）工程であり、
（ｃ）工程が下記（ｃ１）工程であり、
（ｄ）工程が下記（ｄ１）工程であり、
さらに下記（ｅ１）工程、（ｆ１）工程および（ｇ）工程を含むことが好ましい；
（ｂ１） ドライフィルムレジストの仮支持体を剥離せずに、第１のパターンでコンタクトパターン露光するパターン露光工程；
（ｃ１） 仮支持体を剥離後、現像してレジスト層に第１のパターンを形成する現像工程；
（ｄ１） エッチングにより、回路形成基板に第１のパターンを形成するエッチング工程；
（ｅ１） （ｃ１）工程で第１のパターンを形成したレジスト層を剥離することなく、第２のパターンでコンタクトパターン露光するパターン露光工程；
（ｆ１） 現像してレジスト層に第１のパターンとは異なる第２のパターンを形成する現像工程；
（ｇ） エッチングにより、回路形成基板に第２のパターンを形成するエッチング工程。
［１７］ ［１５］に記載の回路配線の製造方法は、（ｂ）工程が下記（ｂ１）工程であり、
（ｃ）工程が下記（ｃ１）工程であり、
（ｄ）工程が下記（ｄ２）工程であり、
さらに（ｅ２）工程、（ｆ２）工程および（ｇ）工程を含むことが好ましい；
（ｂ１） ドライフィルムレジストの仮支持体を剥離せずに、第１のパターンでコンタクトパターン露光するパターン露光工程；
（ｃ１） 仮支持体を剥離後、現像してレジスト層に第１のパターンを形成する現像工程；
（ｄ２） エッチングにより、回路形成基板に第１のパターンを形成したのち、（ｃ１）工程で第１のパターンを形成したレジスト層を剥離することなく、残りのレジスト層の上にカバーフィルムを貼り付けるエッチング工程；
（ｅ２） （ｄ２）工程で貼り付けたカバーフィルムを剥離せずに、第２のパターンでコンタクトパターン露光するパターン露光工程；
（ｆ２） （ｄ２）工程で貼り付けたカバーフィルムを剥離した後、現像してレジスト層に第１のパターンとは異なる第２のパターンを形成する現像工程；
（ｇ） エッチングにより、回路形成基板に第２のパターンを形成するエッチング工程。［１８］ ［１５］〜［１７］のいずれか一つに記載の回路配線の製造方法では、現像工程で使用する現像液のｐＨが１２．５以下であることが好ましい。
［１９］ ［１５］〜［１８］のいずれか一つに記載の回路配線の製造方法で製造された回路配線。
［２０］ ［１９］に記載の回路配線を用いた入力装置。
［２１］ ［２０］に記載の入力装置は、入力装置が静電容量型タッチパネルであることが好ましい。
［２２］ ［２０］または［２１］に記載の入力装置を備える、表示装置。 [1] A positive dry film resist having a resist layer on a temporary support,
A dry film resist in which the total light haze of the temporary support is 0.3% or less.
[2] A positive dry film resist having a resist layer on a temporary support,
The resist layer contains (A) component and (B) photoacid generator,
The component (A) is a polymer having an acid structural unit a0 in which an acid group is protected with an acid-decomposable group,
A dry film resist in which the acid structural unit a0 has a structural unit represented by the following general formula A3;
Formula A3

In general formula A3, R ³¹ and R ³² each 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 is an alkyl group or Represents an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, X ⁰ represents a single bond or an arylene group, Y represents a nitrogen atom, a sulfur atom or an oxygen atom.
[3] In the dry film resist according to [1], the resist layer includes a component (A) and a photoacid generator (B).
The component (A) is a polymer having an acid structural unit a0 in which an acid group is protected with an acid-decomposable group,
The acid structural unit a0 preferably has a structural unit represented by the following general formula A3;
Formula A3

In general formula A3, R ³¹ and R ³² each 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 is an alkyl group or Represents an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, X ⁰ represents a single bond or an arylene group, Y represents a nitrogen atom, a sulfur atom or an oxygen atom.
[4] In the dry film resist described in [2] or [3], X ⁰ in the general formula A3 is preferably a single bond.
[5] In the dry film resist according to any one of [2] to [4], in general formula A3, Y is preferably an oxygen atom.
[6] In the dry film resist according to [1], the resist layer includes a component (A) and a photoacid generator (B).
The component (A) is a polymer having an acid structural unit a0 in which an acid group is protected with an acid-decomposable group,
The acid structural unit a0 is preferably an acid structural unit a1 in which a carboxy group or a phenolic hydroxyl group is protected in the form of an acetal.
[7] In the dry film resist according to [6], the acid structural unit a1 preferably has a structural unit represented by the following general formula A1;
General formula A1

In general formula A1, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, and R ⁴ represents a hydrogen atom or a methyl group.
[8] In the dry film resist according to [6], the acid structural unit a1 preferably has a structural unit represented by the following general formula A2.
General formula A2

In general formula A2, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, and R ¹³ is an alkyl group or Represents an aryl group, and R ¹¹ or R ¹² and R ¹³ may combine to form a cyclic ether, and each R ¹⁴ independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group. Represents a group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group or a cycloalkyl group.
[9] The dry film resist according to any one of [1] and [3] to [8], wherein the resist layer has a polymer having an acid structural unit a0 in which an acid group is protected by an acid-decomposable group. It is preferable to contain 2 or more types.
[10] In the dry film resist according to [1], the resist layer preferably contains a naphthoquinonediazide compound and a resin having a phenolic hydroxyl group.
[11] In the dry film resist according to any one of [1] to [10], the resist layer preferably further includes a heterocyclic compound.
[12] In the dry film resist according to any one of [1] to [11], the resist layer preferably further contains a basic compound.
[13] In the dry film resist according to any one of [1] to [12], it is preferable that the resist layer further includes a radiation absorber.
[14] The dry film resist according to any one of [1] to [13] preferably satisfies at least one of the following conditions (1) and (2):
Condition (1): The temporary support has a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer;
Condition (2): A light absorption layer having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer is provided between the temporary support and the resist layer.
[15] A circuit wiring manufacturing method including the following steps (a), (b), (c) and (d);
(A) A laminating step of laminating the dry film resist according to any one of [1] to [14] on a circuit forming substrate having a base material and a conductive layer;
(B) a pattern exposure step of exposing a contact pattern with a pattern for pattern exposure without peeling off the temporary support of the dry film resist;
(C) a development step in which the temporary support is peeled and then developed to form a pattern exposure pattern on the resist layer;
(D) An etching step of forming a pattern exposure pattern on the circuit forming substrate by etching.
[16] In the circuit wiring manufacturing method according to [15], the step (b) is the following step (b1),
(C) The process is the following (c1) process,
(D) The process is the following (d1) process,
Further, it preferably includes the following steps (e1), (f1) and (g);
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form a first pattern on the resist layer;
(D1) an etching step of forming a first pattern on the circuit forming substrate by etching;
(E1) A pattern exposure step of exposing the contact pattern with the second pattern without removing the resist layer on which the first pattern has been formed in the step (c1);
(F1) A development step of developing and forming a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming the second pattern on the circuit formation substrate by etching.
[17] In the circuit wiring manufacturing method according to [15], the step (b) is the following step (b1),
(C) The process is the following (c1) process,
(D) The process is the following (d2) process,
Furthermore, it is preferable to include a step (e2), a step (f2) and a step (g);
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form a first pattern on the resist layer;
(D2) After forming the first pattern on the circuit formation substrate by etching, a cover film is pasted on the remaining resist layer without peeling off the resist layer on which the first pattern was formed in the step (c1). Attaching etching process;
(E2) A pattern exposure step of exposing the contact pattern with the second pattern without peeling off the cover film attached in the step (d2);
(F2) A development step in which the cover film attached in step (d2) is peeled and then developed to form a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming the second pattern on the circuit formation substrate by etching. [18] In the circuit wiring manufacturing method according to any one of [15] to [17], the pH of the developer used in the development step is preferably 12.5 or less.
[19] A circuit wiring manufactured by the method for manufacturing a circuit wiring according to any one of [15] to [18].
[20] An input device using the circuit wiring according to [19].
[21] In the input device according to [20], the input device is preferably a capacitive touch panel.
[22] A display device comprising the input device according to [20] or [21].

ADVANTAGE OF THE INVENTION According to this invention, the dry film resist which can manufacture the circuit wiring which is a positive type which is easy to form a high resolution pattern, and has high pattern linearity can be provided.
In addition, according to the present invention, it is possible to provide a positive-type circuit wiring that can easily form a high-resolution pattern and a high pattern linearity and a method for manufacturing the circuit wiring.
Further, according to the present invention, it is possible to provide an input device using the circuit wiring and a display device including the input device.

It is a schematic diagram which shows an example of the manufacturing method of circuit wiring. It is a cross-sectional schematic diagram of an example of circuit wiring which is one of the embodiments of the present invention obtained when x is 2. It is a schematic diagram of an example of circuit wiring which is one of the embodiments of the present invention obtained when x is 2. 4 is a schematic diagram showing a pattern A. FIG. 4 is a schematic diagram showing a pattern B. FIG. 6 is a schematic diagram showing a pattern C. FIG. It is a cross-sectional schematic diagram which shows an example of arrangement | positioning of the connection part of a 1st electrode pattern, and a 2nd electrode pattern. It is a schematic diagram which shows an example of arrangement | positioning of the pad part and connection part of a 1st electrode pattern, and a 2nd electrode pattern. It is a cross-sectional schematic diagram which shows a structure of an example of the input device of this invention.

Hereinafter, a dry film resist, a method for manufacturing circuit wiring, circuit wiring, an input device, in particular, an input device that is a touch panel, and a display device using the input device will be described.
The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to the embodiments and specific examples. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

一般式Ａ３中、Ｒ³¹およびＲ³²はそれぞれ独立に水素原子、アルキル基またはアリール基を表し、少なくともＲ³¹およびＲ³²のいずれか一方がアルキル基またはアリール基であり、Ｒ³³はアルキル基またはアリール基を表し、Ｒ³¹またはＲ³²と、Ｒ³³とが連結して環状エーテルを形成してもよく、Ｒ³⁴は水素原子またはメチル基を表し、Ｘ⁰は単結合またはアリーレン基を表し、Ｙは窒素原子、硫黄原子または酸素原子を表す。
上記の構成であるため、本発明のドライフィルムレジストは、高解像度のパターンを形成しやすいポジ型であり、パターン直線性が高い回路配線を製造できる。ここで、ドライフィルムレジストは仮支持体越しに露光を行った場合に仮支持体に起因する露光光の光拡散でパターン直線性が低下する。いかなる理論に拘泥するものでもないが、パターン直線性が低下する問題は、主として、仮支持体内および／または表面に存在するフィラーやその他の仮支持体に起因する露光光の光拡散が原因と推定される。仮支持体によって拡散された後の露光光のエネルギーが、レジスト感度（レジスト層の感光剤の活性化エネルギー、すなわち必要露光量）を超える場合、所望のパターンでは未露光部となるべき部分が拡散光で露光されてしまい、パターン直線性が低下する。それに対し、拡散後の露光光エネルギーが、レジスト感度（必要露光量）を超えない場合、所望のパターンでは未露光部となるべき部分は事実上、拡散光で露光されず、パターン直線性の低下を抑制できる。
仮支持体での露光光の光拡散に起因するパターン直線性低下を回避するには、（ｉ）例えば仮支持体のヘイズを抑制すること等に起因する仮支持体での光拡散抑制、（ｉｉ）仮支持体を通過する拡散光が仮支持体内またはレジスト層に到達するまでに配置された他の部材での吸収、（ｉｉｉ）レジスト層の低感度化などの手法が考えられる。
本発明のドライフィルムレジストの第１の態様では、上記（ｉ）例えば仮支持体のヘイズを抑制すること等に起因する仮支持体での光拡散抑制の手法に着目した構成によりパターン直線性の低下を抑制できる。
本発明のドライフィルムレジストの第２の態様では、よりアルカリ溶解速度を向上することが出来、特に現像工程で使用する現像液のｐＨ（ｐｏｗｅｒ ｏｆ Ｈｙｄｒｏｇｅｎ）が１２．５以下の弱アルカリである場合にパターン直線性が良好となり好ましい。
なお、上記（ｉ）から（ｉｉｉ）の複数の観点を組み合わせることにより直線性低下を抑制することも、好ましい手段として用いられ得る。 [Dry film resist]
The first aspect of the dry film resist of the present invention is a positive dry film resist having a resist layer on a temporary support,
A dry film resist having a total light haze of a temporary support of 0.3% or less.
The second aspect of the dry film resist of the present invention is a positive dry film resist having a resist layer on a temporary support,
The resist layer contains (A) component and (B) photoacid generator,
The component (A) is a polymer having an acid structural unit a0 in which an acid group is protected with an acid-decomposable group,
The acid film forming unit a0 is a dry film resist having a structural unit represented by the following general formula A3.
Formula A3

In general formula A3, R ³¹ and R ³² each 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 is an alkyl group or Represents an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, X ⁰ represents a single bond or an arylene group, Y represents a nitrogen atom, a sulfur atom or an oxygen atom.
Since it is said structure, the dry film resist of this invention is a positive type which is easy to form a high resolution pattern, and can manufacture circuit wiring with high pattern linearity. Here, when the dry film resist is exposed through the temporary support, the pattern linearity is lowered by the light diffusion of the exposure light caused by the temporary support. Although not bound by any theory, the problem that the pattern linearity decreases is presumably caused mainly by light diffusion of exposure light caused by fillers and other temporary supports in the temporary support and / or the surface. Is done. When the energy of the exposure light after being diffused by the temporary support exceeds the resist sensitivity (activation energy of the photosensitizer of the resist layer, that is, the required exposure amount), the portion that should be the unexposed portion in the desired pattern is diffused The pattern is exposed to light and the pattern linearity is lowered. On the other hand, if the exposure light energy after diffusion does not exceed the resist sensitivity (necessary exposure amount), the portion that should be an unexposed part in the desired pattern is not actually exposed with the diffused light, and the pattern linearity decreases. Can be suppressed.
In order to avoid a decrease in pattern linearity due to light diffusion of exposure light on the temporary support, (i) suppression of light diffusion on the temporary support due to, for example, suppressing haze of the temporary support, It is conceivable to use a method such as ii) absorption of the diffused light passing through the temporary support in the temporary support or another member disposed before reaching the resist layer, and (iii) reducing the sensitivity of the resist layer.
In the first aspect of the dry film resist of the present invention, pattern linearity is achieved by the above configuration (i) focusing on the method of suppressing light diffusion in the temporary support due to, for example, suppressing haze of the temporary support. Reduction can be suppressed.
In the second aspect of the dry film resist of the present invention, the alkali dissolution rate can be further improved, and particularly when the developer used in the development step is a weak alkali having a pH (power of hydrogen) of 12.5 or less. In addition, the pattern linearity is good and preferable.
In addition, it can also be used as a preferable means to suppress the linearity degradation by combining a plurality of aspects (i) to (iii).

<Configuration>
The dry film resist of the present invention has at least a resist layer on a temporary support. The dry film resist of the present invention preferably further has a light absorption layer having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer between the temporary support and the resist layer.
The dry film resist of the present invention preferably has a temporary support, a thermoplastic resin layer, and a resist layer in this order, and may further have other layers such as a protective film and an intermediate layer. The dry film resist of the present invention preferably has a temporary support, a thermoplastic resin layer, an intermediate layer, and a resist layer in this order. Regarding preferable modes of the thermoplastic resin layer, [0189] to [0193] of JP-A-2014-85643, and for preferable modes of other layers, refer to [0194] to [0196] of JP-A-2014-85643, respectively. The contents of this publication are incorporated herein.

The dry film resist of the present invention is a positive dry film resist in which exposed portions are dissolved in a developer. A positive dry film resist has an advantage that a high-resolution pattern can be easily formed as compared with a negative resist.
Further, in the positive type, by irradiating actinic light, for example, a photosensitive agent that generates acid upon irradiation with actinic light is used to increase the solubility of the exposed part. None of them are cured, and when the obtained pattern shape is defective, the circuit-formed substrate can be reused (reworked) by full exposure or the like. Therefore, the positive type is preferably used from the viewpoint of excellent so-called reworkability.
Further, the technique of reexposing the remaining resist to produce different patterns can only be realized with a positive type.

The dry film resist of the present invention preferably satisfies at least one of the following conditions (1) and (2).
Condition (1): The temporary support has a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer;
Condition (2): A light absorption layer having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer is provided between the temporary support and the resist layer.
When the condition (1) is satisfied, it is particularly preferable that the following condition (1A) is satisfied.
Condition (1A): The temporary support has a transmittance of more than 10% and 80% or less with respect to the exposure main wavelength of the resist layer.
When the condition (2) is satisfied, it is particularly preferable that the following condition (2A) is satisfied.
Condition (2A): A light absorption layer having a transmittance of more than 10% and 80% or less with respect to the exposure main wavelength of the resist layer is provided between the temporary support and the resist layer.
When the condition (2) or the condition (2A) is satisfied, the temporary support, the light absorbing layer, and the light-receiving layer are formed from the side opposite to the laminate surface in contact with the target substrate when the dry film resist is laminated (for example, transferred) to the target substrate. A resist layer can be provided in this order.
Here, JP 2009-282522 A describes that the reflection suppression layer preferably has an absorptance of 90% or more for light having a wavelength in the range of 200 nm to 700 nm. In the temporary support or the light absorption layer, if the light absorption at the exposure dominant wavelength of the resist layer is excessive, the resist design requires compression or a large amount of exposure due to containing a large amount of the photosensitive agent in the resist layer. In practice, it is preferable to use a temporary support or a light absorption layer having a transmittance of more than 10% and 80% or less with respect to the exposure main wavelength of the resist layer.

(Temporary support)
The dry film resist of the present invention has a temporary support.
In the first aspect of the dry film resist of the present invention, the total light haze (also referred to as haze) of the temporary support is 0.3% or less, preferably 0.20% or less, and preferably 0.18% or less. Is more preferable, and 0.16% or less is particularly preferable. In the second aspect of the dry film resist of the present invention, the total light haze of the temporary support is preferably 0.3% or less, more preferably 0.20% or less, and 0.18% or less. It is particularly preferable that it is 0.16% or less. The lower limit of the total light haze of the temporary support is not particularly limited. For example, in the case of a PET film, a filler added to the film or coated on the film surface is a major haze source. If the amount is too small, problems such as poor handling and blocking during storage will occur. Therefore, considering that the minimum filler is necessary, it is practical to be 0.05% or more. Needless to say, in films other than PET, the minimum total light ray haze in practical use can take different values, and therefore is not limited to the above value of 0.05% or more in any sense.
As means for reducing the haze of the temporary support, in addition to selecting the polymer type of the temporary support, there are reductions in the amount of filler such as silica particles used as a slipping agent, reduction in surface irregularities, and the addition of a refractive index adjustment layer. Can be mentioned. In particular, when the temporary support is polyethylene terephthalate (PET), reducing the amount of filler is an effective means. However, if the amount of the filler as the slip agent is too small, problems such as the above-described deterioration in handling property and storage property and generation of static electricity are caused. Therefore, it is desirable to adjust so that these problems do not occur. The filler may be added at the time of film formation and dispersed in the temporary support, or the functional layer containing the filler may be applied and disposed on the surface of the temporary support after film formation. The haze reduction effect resulting from filler amount reduction is acquired.
As the temporary support, in addition to having a low haze, a solvent coating property is good, a material that transmits ultraviolet rays and can be exposed to ultraviolet rays, and has little abnormal birefringence can be preferably used. In this invention, the film which is not used as a temporary support body of a normal dry film resist can be used as a temporary support body. Moreover, in this invention, the film which reduced haze rather than the film for normal optical use can be used as a temporary support body.
The temporary support preferably has a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer, more preferably has a transmittance of 60% or less, and particularly preferably has a transmittance of 50% or less. preferable. However, in the present invention, if the haze is within the above range, the pattern linearity is good even if the resist layer has a transmittance of more than 80% with respect to the exposure main wavelength.
Examples of such a temporary support include a polyethylene terephthalate film, a cellulose acetate film, a polypropylene film, etc. Among them, a polyethylene terephthalate film with reduced haze is particularly preferable.
Other preferred embodiments of the temporary support are described in JP-A-2014-85643 [00].
17] to [0018], and the contents of this publication are incorporated herein.

(Resist layer)
The dry film resist of the present invention has a resist layer.
In the first aspect of the dry film resist, the resist layer preferably contains a photosensitizer.
In the second aspect of the dry film resist of the present invention, the resist layer contains (B) a photoacid generator as a photosensitive agent.
Examples of the photosensitizer include a naphthoquinone diazide compound described below and a photoacid generator described below.

As a preferred embodiment of the resist layer in the first embodiment of the dry film resist of the present invention, the first preferred embodiment containing a naphthoquinonediazide compound and a resin having a phenolic hydroxyl group, the resist layer comprises (A) component and (B And a photoacid generator, and the component (A) is a polymer having a group in which an acid group is protected with an acid-decomposable group. The second preferred embodiment is more preferable than the first preferred embodiment from the viewpoint of improving the linearity of the pattern by improving the solubility of the resist layer resulting from the chemical amplification type.
On the other hand, the resist layer in the second aspect of the dry film resist of the present invention is, in the second preferred aspect of the resist layer in the first aspect of the dry film resist of the present invention, the component (A) is an acid group. This is a polymer having an acid structural unit a0 protected with an acid-decomposable group, and the acid structural unit a0 has a structural unit represented by the general formula A3.
Hereinafter, the material of the resist layer used in each preferred embodiment will be described. The preferable aspect of the resist layer in the second aspect of the dry film resist of the present invention will be described collectively in the item of the second preferable aspect of the resist layer in the first aspect of the dry film resist of the present invention.

-First preferred embodiment of resist layer-
First, the 1st preferable aspect of a resist layer is demonstrated.
In the first aspect of the dry film resist of the present invention, the resist layer preferably contains a naphthoquinonediazide compound and a resin having a phenolic hydroxyl group. Especially, it is especially preferable that a resist layer contains two types, a cresol novolak resin and a naphthoquinone diazide derivative, from a viewpoint with wide development latitude.

--Resin having phenolic hydroxyl group--
Examples of the resin having a phenolic hydroxyl group include a phenol novolac resin and a cresol novolac resin.

The phenol novolac resin preferably has a molar ratio of formaldehyde to phenol of about 0.5 to 1.0, and more preferably about 0.8 to 1.0 from the viewpoint of developability and image sticking. Moreover, as a weight average molecular weight of the said phenol novolak resin, 300-4000 are preferable and 400-800 are especially preferable.
The phenol novolac resin may be a derivative thereof.
The phenol novolac resin may be used alone or in combination of two or more different weight average molecular weights, and other cresol novolac resins may be used as long as the object of the present invention is not impaired. You may mix and use resin.
As content of the said phenol novolak resin, it is preferable that it is 40-90 mass% with respect to the total solid in a positive resist layer, and it is more preferable that it is 60-80 mass%.

The cresol novolac resin preferably has a molar ratio of formaldehyde content to cresol of about 0.7 to 1.0, and more preferably about 0.8 to 1.0. Moreover, as a weight average molecular weight of the said cresol novolak resin, 800-8,000 are preferable and 1000-6000 are more preferable.
The isomer ratio (ortho / meta / para molar ratio) of the cresol novolak resin is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of improving developability, the para isomer with respect to all isomers. Is preferably 10 mol% or more, more preferably 20 mol% or more.

The said cresol novolak resin may be used individually by 1 type, and can be used as a 2 or more types of mixture. In this case, it may be used by mixing with other resins such as phenol novolac.
In the present invention, as the cresol novolak resin, a derivative of a cresol novolak resin such as a reaction product with naphthoquinone diazide sulfonate may be used.
As the usage-amount of the said cresol novolak resin, 0.1-10 g / m < ² > is preferable and 0.5-5 g / m < ² > is more preferable.

--Naphthoquinonediazide compound--
The naphthoquinonediazide compound is not particularly limited and may be appropriately selected depending on the intended purpose, but it is particularly preferable to use in combination with a cresol novolac resin. The naphthoquinonediazide compound may be a monofunctional compound, a bifunctional or higher functional compound, and a mixture thereof.
Examples of the monofunctional naphthoquinonediazide compound include naphthoquinone-4-sulfonic acid chloride or an ester compound obtained by reacting naphthoquinone-5-sulfonic acid chloride with a substituted phenol.

As the bifunctional or higher naphthoquinone diazide compound, for example, an ester compound obtained by reacting naphthoquinone-4-sulfonic acid chloride or naphthoquinone-5-sulfonic acid chloride with a compound having a plurality of phenolic hydroxyl groups is preferable. Examples of the compound having a plurality of phenolic hydroxyl groups include polyphenols such as bisphenols, trisphenols and tetraquinosphenols; polyfunctional phenols such as dihydroxybenzene and trihydroxybenzene; bis-type or tris-type dihydroxybenzene or Examples thereof include trihydroxybenzene, asymmetric polynuclear phenol, and a mixture thereof.
Examples of the compound having a plurality of phenolic hydroxyl groups include 4-t-butylphenol, 4-isoamylphenol, 4-t-octylphenol, 2-isopropyl-5-methylphenol, 2-acetylphenol, 4-hydroxybenzophenone, 3 -Chlorophenol, 4-benzyloxycarbonylphenol, 4-dodecylphenol, resorcinol, 4- (1-methyl-1-phenylethyl) -1,3-benzenediol, phloroglucinol, 4,4'-dihydroxybenzophenone, Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) methane, 2,3,4,4′-tetrahydroxy Benzophenone, 4,4 '-[ 4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], and the like.

  Examples of the naphthoquinonediazide compound include 4′-t-octylphenylnaphthoquinonediazide-4-sulfonate, 4′-t-octylphenylnaphthoquinonediazide-5-sulfonate, 4′-benzoylphenylnaphthoquinonediazide-5-sulfonate, , 3,4,4′-tetrahydroxybenzophenone and a reaction product of 1,2-naphthoquinonediazide-5-sulfonic acid chloride. These may be used alone or in combination of two or more. The naphthoquinone diazide compound described in JP-A-4-22955 may be used, and the contents of this publication are incorporated herein.

  The amount of the naphthoquinone diazide compound added in the resist layer is preferably 1 to 200 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the cresol novolac resin.

In the first preferred embodiment of the other resist layer, materials described in [0072] to [0083] of Japanese Patent Application Laid-Open No. 2007-24969 may be used as an additive. Incorporated into.
Moreover, you may use the material as described in the 2nd preferable aspect of the below-mentioned resist layer for the 1st preferable aspect of a resist layer.

-Second preferred embodiment of resist layer-
A second preferred embodiment of the resist layer will be described.
In the first aspect of the dry film resist of the present invention, it is preferable that the resist layer contains the component (A) and the photoacid generator (B), and the component (A) is protected with an acid-decomposable group. It is preferable that the polymer has a group formed.
In a second aspect of the dry film resist of the present invention, the resist layer contains (A) component and (B) a photoacid generator, and (A) component is an acid in which an acid group is protected with an acid-decomposable group. It is a polymer having a structural unit a0, and the acid structural unit a0 has a structural unit represented by the general formula A3.

<(A) component: a polymer having an acid structural unit a0 in which an acid group is protected by an acid-decomposable group>
The component (A) is preferably a polymer having an acid structural unit a0 in which an acid group is protected with an acid-decomposable group.
Further, in the dry film resist of the present invention, the component (A) is a polymer component containing a polymer having an acid structural unit a1 in which a carboxy group or a phenolic hydroxyl group is protected in the form of an acetal, or represented by the general formula A3. More preferably, the polymer component includes a polymer having a structural unit. In the structural unit represented by the general formula A3, the carboxy group is protected in an acetal form (when Y described below is an oxygen atom) or other forms (when Y described below is a nitrogen atom or a sulfur atom). Since it is an acid structural unit, it has a part which is not contained in the part contained in the acid structural unit a1 in which the carboxy group or the phenolic hydroxyl group is protected in the form of an acetal.
The resist layer may further contain a polymer other than these.

<< Group in which acid group is protected with acid-decomposable group >>
The component (A) includes a polymer having an acid structural unit a0 in which an acid group is protected with an acid-decomposable group, preferably an acid structural unit a1 in which a carboxy group or a phenolic hydroxyl group is protected in the form of an acetal. Or a polymer having a structural unit represented by the general formula A3 can be used to form an extremely sensitive resist layer.
As the acid group and acid-decomposable group in the “acid structural unit a0 in which the acid group is protected with an acid-decomposable group” in the present invention, those known as acid groups and acid-decomposable groups can be used, and are not particularly limited. Specific examples of the acid group preferably include a carboxy group and a phenolic hydroxyl group. Examples of the acid-decomposable group include groups that are relatively easily decomposed by an acid (for example, an ester structure of a group represented by the following general formula A1, general formula A2, or general formula A3, a tetrahydropyranyl ester group, or a tetrahydrofuran group). An acetal functional group such as a nyl ester group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group). Can be used.

The acid structural unit a0 in which the acid group is protected with an acid-decomposable group is a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group or a protected carboxy group protected with an acid-decomposable group Preferably it is a unit.
The acid structural unit a0 in which the acid group is protected with an acid-decomposable group is an acid structural unit a1 in which a carboxy group or a phenolic hydroxyl group is protected in the form of an acetal, or a structural unit represented by the general formula A3. It is more preferable.
Hereinafter, the structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group and the structural unit having a protected carboxy group protected with an acid-decomposable group will be described in order.

<<< Structural Unit Having Protected Phenolic Hydroxyl Group Protected with Acid-Decomposable Group >>>
The structural unit having a protected phenolic hydroxyl group protected by an acid-decomposable group is a structural unit having a protected phenolic hydroxyl group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. It is.
As the structural unit having a phenolic hydroxyl group, a structural unit in which the hydroxyl group of a structural unit derived from hydroxystyrene or α-methylhydroxystyrene (for example, a structural unit in a novolak resin) is protected by an acid-decomposable group is used. The polymer having a structural unit represented by the following general formula A1 is more preferable from the viewpoint of further improving the resolution, and is a polymer having a structural unit represented by the following general formula A1 or A2. It is particularly preferred that In other words, in the first aspect of the dry film resist of the present invention, the acid structural unit a1 preferably has a structural unit represented by the following general formula A1. Similarly, in the 1st aspect of the dry film resist of this invention, it is preferable that the acid structural unit a1 has a structural unit represented by the following general formula A2.

一般式Ａ１中、Ｒ¹およびＲ²はそれぞれ独立に水素原子、アルキル基またはアリール基を表し、少なくともＲ¹およびＲ²のいずれか一方がアルキル基またはアリール基であり、Ｒ³はアルキル基またはアリール基を表し、Ｒ¹またはＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は水素原子またはメチル基を表す。
上記一般式Ａ１中、Ｒ¹およびＲ²がアルキル基の場合、炭素数１〜１０のアルキル基が好ましい。Ｒ¹およびＲ²がアリール基の場合、フェニル基が好ましい。Ｒ¹およびＲ²は、それぞれ、水素原子または炭素数１〜４のアルキル基が好ましく、少なくとも一方が水素原子であることがより好ましい。
上記一般式Ａ１中、Ｒ³はアルキル基またはアリール基を表し、炭素数１〜１０のアルキル基が好ましく、１〜６のアルキル基がより好ましい。
Ｒ¹またはＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ¹またはＲ²と、
Ｒ³とが連結して環状エーテルを形成することが好ましい。上記環状エーテルの環員数は特に制限はないが、５または６であることが好ましく、５であることがより好ましい。
上記一般式Ａ１中、Ｒ⁴は水素原子またはメチル基を表し、水素原子であることが好ましい。 General formula A1

In general formula A1, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, and R ⁴ represents a hydrogen atom or a methyl group.
In General Formula A1, when R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably at least one is a hydrogen atom.
In the general formula A1, R ³ 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.
R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ¹ or R ² and
R ³ is preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In the general formula A1, R ⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

一般式Ａ２中、Ｒ¹¹およびＲ¹²はそれぞれ独立に水素原子、アルキル基またはアリール基を表し、少なくともＲ¹¹およびＲ¹²のいずれか一方がアルキル基またはアリール基であり、Ｒ¹³はアルキル基またはアリール基を表し、Ｒ¹¹またはＲ¹²と、Ｒ¹³とが連結して環状エーテルを形成してもよく、Ｒ¹⁴はそれぞれ独立に、水素原子、水酸基、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、アリール基、アラルキル基、アルコキシカルボニル基、ヒドロキシアルキル基、アリールカルボニル基またはシクロアルキル基を表す。
上記一般式Ａ２中、Ｒ¹¹およびＲ¹²がアルキル基の場合、炭素数１〜１０のアルキル基が好ましい。Ｒ¹¹およびＲ¹²がアリール基の場合、フェニル基が好ましい。Ｒ¹¹およびＲ¹²は、それぞれ、水素原子または炭素数１〜４のアルキル基が好ましく、少なくとも一方が水素原子であることがより好ましい。
上記一般式Ａ２中、Ｒ¹³はアルキル基またはアリール基を表し、炭素数１〜１０のアルキル基が好ましく、１〜６のアルキル基がより好ましい。
Ｒ¹¹またはＲ¹²と、Ｒ¹³とが連結して環状エーテルを形成してもよい。
上記一般式Ａ２中、Ｒ¹⁴は水素原子またはメチル基を表し、水素原子であることが好ましい。 General formula A2

In general formula A2, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, and R ¹³ is an alkyl group or Represents an aryl group, and R ¹¹ or R ¹² and R ¹³ may combine to form a cyclic ether, and each R ¹⁴ independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group. Represents a group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group or a cycloalkyl group.
In the general formula A2, when R ¹¹ and R ¹² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹¹ and R ¹² are aryl groups, phenyl groups are preferred. R ¹¹ and R ¹² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably at least one is a hydrogen atom.
In the general formula A2, R ¹³ 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.
R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether.
In the general formula A2, R ¹⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

As the acid-decomposable group that can be used for the structural unit having a protected phenolic hydroxyl group protected with the acid-decomposable group, a known one can be used, and is not particularly limited. Among the acid-decomposable groups, a structural unit having a protected phenolic hydroxyl group protected with acetal is preferable from the viewpoint of basic physical properties of the resist layer, particularly sensitivity, pattern shape, and storage stability of the resist layer. Furthermore, among the acid-decomposable groups, the phenolic hydroxyl group is preferably a protected phenolic hydroxyl group protected in the form of an acetal represented by the following general formula (a1-10) from the viewpoint of sensitivity. In addition, when the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the following general formula (a1-10), the entire protected phenolic hydroxyl group is -Ar-O-CR ¹⁰¹ R. The structure is ¹⁰² (OR ¹⁰³ ). In addition,
Ar represents an arylene group.

（一般式（ａ１−１０）中、Ｒ¹⁰¹およびＲ¹⁰²は、それぞれ独立に水素原子またはアルキル基を表し、但し、Ｒ¹⁰¹とＲ¹⁰²とが共に水素原子の場合を除く。Ｒ¹⁰³は、アルキル基を表す。Ｒ¹⁰¹またはＲ¹⁰²と、Ｒ¹⁰³とが連結して環状エーテルを形成してもよい。） Formula (a1-10)

(In the general formula (A1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, provided that, .R ¹⁰³ except in the case of the R ¹⁰¹ and R ¹⁰² are both hydrogen atoms, alkyl R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.

In the general formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, and R ¹⁰³ represents an alkyl group. The alkyl group may be linear, branched or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

In the general formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.

  The cyclic alkyl group is preferably a cyclic alkyl group having 3 to 12 carbon atoms, more preferably a cyclic alkyl group having 4 to 8 carbon atoms, and a cyclic alkyl group having 4 to 6 carbon atoms. Is more preferable. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When having a halogen atom as a substituent, R ¹⁰¹ ,
When R ¹⁰² and R ¹⁰³ are haloalkyl groups and have an aryl group as a substituent, R ¹⁰¹ ,
R ¹⁰² and R ¹⁰³ are an aralkyl group. An aralkyl group is an entire alkyl group substituted with an aryl group. Examples of the aralkyl group include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable, More preferably, it is a C6-C12 aryl group. Specific examples include a phenyl group, an α-methylphenyl group, and a naphthyl group.
As said alkoxy group, a C1-C6 alkoxy group is preferable, More preferably, it is C1-C4, and a methoxy group or an ethoxy group is more preferable.
When the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is linear. Or when it is a branched alkyl group, it may have a C3-C12 cycloalkyl group as a substituent.

  These substituents may be further substituted with the above substituents.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be connected to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ^103, or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.

In the general formula (a1-10), it is preferable that any one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

Preferred examples of the acetal ester structure of a phenolic hydroxyl group are: R ¹⁰¹ = methyl group, R ¹⁰² = hydrogen atom, R ¹⁰³ = ethyl group, R ¹⁰¹ = methyl group, R ¹⁰² = hydrogen atom, R ¹⁰³ = ethyl group And when R ¹⁰¹ and R ¹⁰³ are connected to each other to form a 5-membered ring, or when R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl The case of a group can be illustrated.

Examples of the polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include, for example, paragraph No. 0042 of JP2011-215590A. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

  Specific examples of the acetal protecting group for the phenolic hydroxyl group include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group. 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned. These may be used alone or in combination of two or more.

  As the polymerizable monomer used to form the structural unit having a protected phenolic hydroxyl group protected by the acid-decomposable group, a commercially available monomer may be used, or a monomer synthesized by a known method may be used. You can also. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.

  Preferable specific examples of the structural unit having a protected phenolic hydroxyl group protected with the acid-decomposable group include the following structural units, but the present invention is not limited thereto.

The copolymerization ratio of the structural unit having a protected phenol group protected by an acid-decomposable group in the polymer having an acid structural unit a0 in which the acid group is protected by an acid-decomposable group was protected by this acid-decomposable group. 10-50 mol% is preferable with respect to the polymer containing the structural unit which has a protected phenol group, 20-40 mol% is more preferable, and 25-40 mol% is especially preferable.
In addition, all the polymer components (when the polymer component is a mixture of two or more polymers, all polymers included) are decomposed into structural units (monomer units) and then all the components The proportion of the structural unit having a protected phenol group in which the acid group is protected with an acid-decomposable group with respect to the number of moles of the unit is preferably 0 to 40 mol%, and more preferably 10 to 35 mol%. It is especially preferable that it is 15-30 mol%.

<<< Structural Unit Having Protected Carboxy Group Protected with Acid-Decomposable Group >>>
The structural unit having a protected carboxy group protected with an acid-decomposable group is a structural unit in which the carboxy group of the structural unit having a carboxy group has a protected carboxy group protected by an acid-decomposable group described in detail below. It is.
There is no restriction | limiting in particular as a structural unit which has the said carboxy group which can be used for the structural unit which has the protected carboxy group protected by the said acid-decomposable group, A well-known structural unit can be used. For example, the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid, Examples include a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride, and a structural unit represented by General Formula A3.
Hereinafter, a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule, an ethylenically unsaturated group, and an acid, which are used as the structural unit having the carboxy group. The structural unit (a1-1-2) having both an anhydride-derived structure and the structural unit represented by General Formula A3 will be described in order.

<<<<< Structural Unit (a1-1-1) Derived from Unsaturated Carboxylic Acid Having at least One Carboxy Group in the Molecule >>>>
Examples of the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule include those listed below. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Examples include hexahydrophthalic acid and 2- (meth) acryloyloxyethylphthalic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxy group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyl) succinate. Oxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. Moreover, as unsaturated carboxylic acid, acrylic acid 2-carboxyethyl ester, methacrylic acid 2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene, etc. can also be used.
Among these, from the viewpoint of developability, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule, acrylic acid, methacrylic acid, Use of 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, or an anhydride of unsaturated polyvalent carboxylic acid Preferably, acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid are more preferably used.
The structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule may be composed of one kind alone or two or more kinds. May be.

<<<<< Structural Unit (a1-1-2) Having Both Ethylenically Unsaturated Group and Acid Anhydride Structure >>>>
The structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride reacts a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride. A unit derived from the obtained monomer is preferred.
As the acid anhydride, known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride and succinic anhydride are preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

The acid-decomposable group that can be used for the structural unit having a protected carboxy group protected by the acid-decomposable group is used for a structural unit having a protected phenol group protected by the acid-decomposable group. Possible acid-decomposable groups can be used.
Among these acid-decomposable groups, a protected carboxy group in which the carboxy group is protected in the form of an acetal is preferable from the viewpoint of basic physical properties of the resist layer, particularly sensitivity and pattern shape, and storage stability of the resist layer. Furthermore, it is more preferable from a viewpoint of a sensitivity that a carboxy group is a protected carboxy group protected in the form of the acetal represented with the said general formula (a1-10) among acid-decomposable groups. In addition, when the carboxy group is a protected carboxy group protected in the form of an acetal represented by the above general formula (a1-10), the entire protected carboxy group is-(C = O) -O-CR ^101. The structure is R ¹⁰² (OR ¹⁰³ ).

  As the polymerizable monomer used for forming the structural unit having a protected carboxy group represented by the general formula (a1-10), a commercially available monomer may be used, or one synthesized by a known method. Can also be used. For example, it can be synthesized by the synthesis method described in paragraph numbers 0037 to 0040 of JP2011-221494A.

一般式Ａ３中、Ｒ³¹およびＲ³²はそれぞれ独立に水素原子、アルキル基またはアリール基を表し、少なくともＲ³¹およびＲ³²のいずれか一方がアルキル基またはアリール基であり、Ｒ³³はアルキル基またはアリール基を表し、Ｒ³¹またはＲ³²と、Ｒ³³とが連結して環状エーテルを形成してもよく、Ｒ³⁴は水素原子またはメチル基を表し、Ｘ⁰は単結合またはアリーレン基を表し、Ｙは窒素原子、硫黄原子または酸素原子を表す。
上記一般式Ａ３中、Ｒ³¹およびＲ³²がアルキル基の場合、炭素数１〜１０のアルキル基が好ましい。Ｒ³¹およびＲ³²がアリール基の場合、フェニル基が好ましい。Ｒ³¹およびＲ³²は、それぞれ、水素原子または炭素数１〜４のアルキル基が好ましい。
上記一般式Ａ３中、Ｒ³³は、アルキル基またはアリール基を表し、炭素数１〜１０のアルキル基が好ましく、１〜６のアルキル基がより好ましい。
上記一般式Ａ３中、Ｒ³¹またはＲ³²と、Ｒ³³とが連結して環状エーテルを形成してもよく、Ｒ³¹またはＲ³²と、Ｒ³³とが連結して環状エーテルを形成することが好ましい。上記環状エーテルの環員数は特に制限はないが、５または６であることが好ましく、５であることがより好ましい。
上記一般式Ａ３中、Ｒ³⁴は水素原子またはメチル基を表し、水素原子であることが好ましい。
上記一般式Ａ３中、Ｘ⁰は単結合またはアリーレン基を表し、本発明のドライフィルムレジストは、一般式Ａ３中、Ｘ⁰が単結合であることが好ましい。
上記一般式Ａ３中、Ｙは窒素原子、硫黄原子または酸素原子を表し、本発明のドライフィルムレジストは、一般式Ａ３中、Ｙが酸素原子であることが好ましい。 <<< Structural Unit Represented by General Formula A3 >>>
Among the acid structural unit a0 in which the acid group is protected with an acid-decomposable group, the component (A) has an alkaline dissolution in the development step that the acid structural unit a0 has a structural unit represented by the following general formula A3. The speed can be further improved, which is preferable.
The acid structural unit a0 in which the acid group is protected with an acid-decomposable group is an acid structural unit in which the carboxy group is protected with an acid-decomposable group (the structural unit having a protected carboxy group protected with the acid-decomposable group. ), It is preferable to have a structural unit represented by the following general formula A3 from the viewpoint of increasing sensitivity. In the dry film resist of the present invention, the resist layer may contain two or more types of the component (A) and a polymer having a structural unit represented by the following general formula A3 as the component (A). preferable.

In general formula A3, R ³¹ and R ³² each 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 is an alkyl group or Represents an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, X ⁰ represents a single bond or an arylene group, Y represents a nitrogen atom, a sulfur atom or an oxygen atom.
In the general formula A3, when R ³¹ and R ³² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ³¹ and R ³² are aryl groups, a phenyl group is preferred. R ³¹ and R ³² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the general formula A3, 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 the general formula A3, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, or R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether. preferable. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In the general formula A3, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the general formula A3, X ⁰ represents a single bond or an arylene group, and in the dry film resist of the present invention, X ⁰ in the general formula A3 is preferably a single bond.
In the general formula A3, Y represents a nitrogen atom, a sulfur atom, or an oxygen atom. In the dry film resist of the present invention, it is preferable that Y in the general formula A3 is an oxygen atom.

（式中、Ｒ¹²¹は水素原子または炭素数１〜４のアルキル基を表し、Ｒ¹²²〜Ｒ¹²⁸はそれぞれ独立に、水素原子または炭素数１〜４のアルキル基を表す。）
上記一般式Ａ３−１中、Ｒ¹²¹は水素原子またはメチル基が好ましい。
上記一般式Ａ３−１中、Ｒ¹²²〜Ｒ¹²⁸は、水素原子が好ましい。 Among the structural units represented by the general formula A3, the structural unit represented by the following general formula A3-1 is more preferable from the viewpoint of further increasing the sensitivity.

(In the formula, R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{122 to} R ¹²⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
In the general formula A3-1, R ¹²¹ is preferably a hydrogen atom or a methyl group.
In the general formula A3-1, R ^{122 to} R ¹²⁸ are preferably hydrogen atoms.

  Preferable specific examples of the structural unit having a protected carboxy group protected with the acid-decomposable group include the following structural units. R represents a hydrogen atom or a methyl group.

The copolymerization ratio of the structural unit having a protected carboxy group protected by an acid-decomposable group in the polymer having an acid structural unit a0 in which the acid group is protected by an acid-decomposable group was protected by this acid-decomposable group. 5-60 mol% is preferable with respect to the polymer containing the structural unit which has a protected carboxy group, 10-50 mol% is more preferable, and 30-50 mol% is especially preferable.
Moreover, after decomposing all the polymer components into structural units (monomer units), the ratio of the structural unit having a protected carboxy group in which the acid group is protected with an acid-decomposable group with respect to the number of moles of all the structural units is 0 to 60 mol% is preferable, 10 to 50 mol% is more preferable, and 15 to 25 mol% is particularly preferable.

<< Other structural units (a3) >>
The component (A) of the resist layer may have another structural unit (a3) other than these in addition to the acid structural unit a0 in which the acid group is protected with an acid-decomposable group. These other structural units (a3) contain, as a copolymerization component, a polymer used for the component (A), that is, a polymer having an acid structural unit a0 in which an acid group is protected with an acid-decomposable group. May be. Moreover, apart from the polymer containing the acid structural unit a0 in which the acid group used in the component (A) is protected with an acid-decomposable group, the acid structure in which the acid group is substantially protected with an acid-decomposable group The polymer which does not contain unit a0 and has another structural unit may have the other structural unit (a3).

  There is no restriction | limiting in particular as a monomer used as another structural unit (a3), For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to. Moreover, you may have the structural unit which has an acid group so that it may mention later. The monomer which becomes another structural unit (a3) can be used individually or in combination of 2 or more types.

  The structural unit (a3) is specifically styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid. Ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid Isopropyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate Mention may be made of the structural units derived from such. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  Moreover, the group which has styrenes and an aliphatic cyclic skeleton as another structural unit (a3) is preferable from a viewpoint of an electrical property. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.

Furthermore, (meth) acrylic acid alkyl ester is preferable as another structural unit (a3) from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
In the structural unit constituting the polymer containing the acid structural unit a0 in which the acid group is protected with an acid-decomposable group, the content of the structural unit (a3) is preferably 60 mol% or less, and 50 mol% or less. Is more preferable, and 40 mol% or less is still more preferable. The lower limit may be 0 mol%,
For example, it can be 1 mol% or more, and further can be 5 mol% or more. If the numerical value is within the above range, various characteristics of the resist layer are improved.

It is preferable to have a structural unit containing an acid group as the other structural unit (a3). When the component (A) has a structural unit containing an acid group, the component (A) is easily dissolved in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa (power of Ka; Ka is an acid dissociation constant) of 10 or less. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including the structural unit containing an acid group in the polymer, the component (A) tends to be easily dissolved in an alkaline developer.
As the acid group of the structural unit containing an acid group used for the above other structural units, those derived from a carboxylic acid group, those derived from a sulfonamide group, those derived from a phosphonic acid group, those derived from a sulfonic acid group Examples thereof include those derived from phenolic hydroxyl groups, sulfonamide groups, sulfonylimide groups and the like, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used for the above other structural units is a structural unit obtained by substituting an acid group for a structural unit derived from styrene or a structural unit derived from a vinyl compound, or (meth) acrylic acid. More preferably, it is a structural unit derived from.

  Furthermore, it is preferable to have a structural unit containing an ester of an acid group from the viewpoint of optimizing the solubility in a developer and the physical properties of the film.

In the present invention, it is particularly preferable from the viewpoint of sensitivity that the other structural unit (a3) contains a structural unit having a carboxy group or a structural unit having a phenolic hydroxyl group.
As the acid structural unit a0 in which the acid group is protected with an acid-decomposable group, the polymer having a structural unit having a protected phenol group protected with the acid-decomposable group is among the other structural units (a3). It is preferable that the structural unit derived from a phenolic hydroxyl group is included as a copolymerization component. The polymer having a structural unit having a protected phenol group protected with an acid-decomposable group as the acid structural unit a0 in which the acid group is protected with an acid-decomposable group is derived from hydroxystyrene or α-methylhydroxystyrene. It is more preferable to include a structural unit as a copolymerization component, and it is particularly preferable to include a structural unit derived from hydroxystyrene as a copolymerization component.
In the polymer having a structural unit having a protected phenol group protected with an acid-decomposable group, the copolymerization ratio of the structural unit containing an acid group is protected by this acid-decomposable group when the acid group is a phenolic hydroxyl group. 50-90 mol% is preferable with respect to the polymer which has the structural unit which has the protected phenol group made, and 60-75 mol% is more preferable.
Moreover, when an acid group is a carboxylic acid group, 0-30 mol% is preferable with respect to the polymer which has a structural unit which has the protection phenol group protected by this acid-decomposable group, and 5-10 mol% is More preferred.
The copolymerization ratio of the structural unit containing an ester of an acid group in the polymer having a structural unit having a protected phenol group protected with an acid-decomposable group is a structure having a protected phenol group protected with this acid-decomposable group. 0-30 mol% is preferable with respect to the polymer which has a unit, 0-10 mol% is more preferable, and 0 mol% is especially preferable.

The polymer having a structural unit having a protected carboxy group protected with an acid-decomposable group as the acid structural unit a0 in which the acid group is protected with an acid-decomposable group is among the other structural units (a3). It is preferable to include a structural unit derived from a carboxylic acid group and / or an ester thereof as a copolymerization component. As the acid structural unit a0 in which the acid group is protected with an acid-decomposable group, a polymer having a structural unit having a protected carboxy group protected with the acid-decomposable group is (meth) acrylic acid or (meth) acrylic. More preferably, a structural unit derived from benzyl acid or 2-hydroxyethyl (meth) acrylate is included as a copolymerization component.
In the polymer having a structural unit having a protected carboxy group protected with an acid-decomposable group, the copolymerization ratio of the structural unit containing an acid group is protected by this acid-decomposable group when the acid group is a phenolic hydroxyl group. 50-90 mol% is preferable with respect to the polymer which has the structural unit which has the made carboxy group, and 60-75 mol% is more preferable.
Moreover, when an acid group is a carboxylic acid group, 0-30 mol% is preferable with respect to the polymer which has a structural unit which has a carboxy group protected by this acid-decomposable group, and 5-10 mol% is more. preferable.
The copolymerization ratio of the structural unit containing an ester of an acid group in the polymer having a structural unit having a protected carboxy group protected with an acid-decomposable group is a structure having a protected carboxy group protected with this acid-decomposable group. 10-80 mol% is preferable with respect to the polymer which has a unit, 30-70 mol% is more preferable, and 40-60 mol% is especially preferable.

<Preferred embodiment of polymer component>
The structural unit having a protected carboxy group protected with an acid-decomposable group develops faster (development speed) than the structural unit having a protected phenolic hydroxyl group protected with the acid-decomposable group. Therefore, when it is desired to develop the resist layer rapidly after exposure, it is preferable to use a structural unit having a protected carboxy group protected with an acid-decomposable group. Conversely, when it is desired to slow development, it is preferable to use a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.

In the resist layer, the polymer having the acid structural unit a0 in which the acid group is protected by an acid-decomposable group in the component (A) may be one type or two or more types.
First, the case where the resist layer of the dry film resist contains one type of polymer having an acid structural unit a0 in which an acid group is protected by an acid-decomposable group will be described. When the resist layer contains one type of polymer having the acid structural unit a0 in which the acid group is protected with an acid-decomposable group as the polymer component, the component (A) is an acid-decomposable group. A polymer component containing the acid structural unit a0 protected by the above, wherein the acid structural unit a0 has a structural unit represented by the general formula A3, from the viewpoint of improving pattern linearity, particularly a developer used in the development step It is preferable from the viewpoint of improving the pattern linearity when the pH is 12.5 or less.
When the resist layer contains one type of polymer having an acid structural unit a0 in which an acid group is protected by an acid-decomposable group, 60 of the acid structural units a0 in which the acid group is protected by an acid-decomposable group ~ 100 mol% is preferably a structural unit represented by the general formula A3, more preferably 70 to 100 mol% is a structural unit represented by the general formula A3, and 100 mol% is represented by the general formula A3. The structural unit represented is particularly preferable.
When the resist layer contains one type of polymer having an acid structural unit a0 in which the acid group is protected with an acid-decomposable group, the acid group contained in the resist layer has a group protected with an acid-decomposable group. Among the polymers, the polymer component having the structural unit represented by Formula A3 is preferably 70 to 100% by mass, more preferably 90 to 100% by mass, and 100% by mass. (That is, having no other polymer component other than the polymer having the structural unit represented by Formula A3) is particularly preferable.

Next, in the dry film resist of the present invention, the resist layer may contain two or more types of polymers having an acid structural unit a0 in which an acid group is protected with an acid-decomposable group. When the resist layer contains two or more kinds of polymers having an acid structural unit a0 in which an acid group is protected by an acid-decomposable group, a heavy polymer having an acid structural unit a0 in which the acid group is protected by an acid-decomposable group. As a coalescence component, a polymer having a structural unit having a protected phenolic hydroxyl group protected by the acid-decomposable group, and a polymer containing a structural unit having a protected carboxy group protected by the acid-decomposable group It is more preferable to contain.
When the resist layer contains two or more kinds of polymers having an acid structural unit a0 in which an acid group is protected by an acid-decomposable group, the acid group has an acid structural unit a0 in which the acid group is protected by an acid-decomposable group. As the polymer, it is particularly preferable from the viewpoint of increasing the sensitivity that a polymer having a structural unit represented by the general formula A3 is contained. That is, in the dry film resist of the present invention, the resist layer contains two or more types of the component (A) and a polymer having a structural unit represented by the general formula A3 as the component (A). Is preferred.
When the resist layer contains two or more kinds of polymers having an acid structural unit a0 in which an acid group is protected by an acid-decomposable group, the acid group has an acid structural unit a0 in which the acid group is protected by an acid-decomposable group. Sensitivity to contain at least one of the polymers having the structural unit represented by the general formula A1 or the general formula A2 and the polymer having the structural unit represented by the general formula A3 as the polymer. In particular, it is more preferable from the viewpoint of increasing the resolution. From the viewpoint of enhancing both sensitivity and resolution, it is preferable to contain at least one of the polymers having the structural unit represented by the general formula A1 and the polymer having the structural unit represented by the general formula A3. Particularly preferred.
When the resist layer contains two or more kinds of polymers having an acid structural unit a0 in which an acid group is protected by an acid-decomposable group, the resist layer has a structural unit having a protected phenolic hydroxyl group protected by the acid-decomposable group. The ratio of the polymer and the polymer containing the structural unit having a protected carboxy group protected by the acid-decomposable group is preferably 10:90 to 100: 0 by mass ratio, and 30:70 to 60: 40 is more preferable, and 1: 1 is particularly preferable.

<< Molecular Weight of Polymer Containing Acid Constituent Unit a0 Protected with Acid-Decomposable Group >>
The weight average molecular weight of the polymer containing the acid structural unit a0 in which the acid group is protected with an acid-decomposable group is a polystyrene-equivalent weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000. It is in the range of ~ 50,000. Various characteristics are favorable in the range of said numerical value.
The ratio (dispersion degree) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

<< (A) Component Production Method >>
Various methods for synthesizing the component (A) are also known. As an example, a polymerizable unit comprising at least the acid structural unit a0 in which the acid group is protected with an acid-decomposable group and the polymerizable monomer used to form the structural unit represented by (a3) above. It can be synthesized by polymerizing the monomer mixture in an organic solvent using a polymerization initiator. It can also be synthesized by a so-called polymer reaction.

  The resist layer preferably contains the component (A) in a proportion of 50 to 99.9 parts by mass, more preferably 70 to 98 parts by mass with respect to 100 parts by mass of the total solid content.

<< Other polymer components >>
Moreover, apart from the polymer containing the acid structural unit a0 in which the acid group used in the component (A) is protected with an acid-decomposable group, the acid structure in which the acid group is substantially protected with an acid-decomposable group You may have the polymer which does not contain the unit a0 and has another structural unit. In addition to the polymer used for the component (A), when a polymer having other structural units is contained substantially without the acid structural unit a0 in which the acid group is protected by an acid-decomposable group, The blending amount of the coal is preferably 60% by mass or less, more preferably 40% by mass or less, particularly preferably 20% by mass or less, and particularly preferably 3% by mass or less in all polymer components. More particularly preferred. Most preferably, it is 0 mass%.

  The resist layer may contain only one type of polymer having another structural unit (a3) without including the acid structural unit a0 in which the acid group is substantially protected by an acid-decomposable group. Two or more types may be included.

  For example, polyhydroxystyrene can be used as a polymer having other structural unit (a3) without containing acid structural unit a0 whose acid group is substantially protected by an acid-decomposable group, and is commercially available. SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (Sartomer) ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, manufactured by BASF) can also be used. The

<(B) component: Photoacid generator>
The resist layer preferably contains (B) a photoacid generator. As the photoacid generator (also referred to as “component (B)”) used in the present invention, an acid can be generated by irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. A compound. The photoacid generator (B) used in the present invention is preferably a compound that generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm. (B) The chemical structure of the photoacid generator is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The pKa value of the acid generated upon irradiation with radiation is preferably 4.0 or less, more preferably 3.0 or less. The lower limit is not particularly defined, but can be set to -10.0 or more, for example.

  Examples of the (B) photoacid generator include ionic photoacid generators and nonionic photoacid generators.

  Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, from the viewpoint of insulating properties, it is preferable that the (B) photoacid generator in the resist layer is an oxime sulfonate compound. These photoacid generators can be used alone or in combination of two or more. Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-221494A, the contents of which are incorporated herein.

  Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1).

（一般式（Ｂ１）中、Ｒ²¹は、アルキル基またはアリール基を表す。波線は他の基との結合を表す。） General formula (B1)

(In the general formula (B1), R ²¹ represents an alkyl group or an aryl group. A wavy line represents a bond with another group.)

Any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
As the alkyl group for R ^21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group represented by R ²¹ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

  The compound containing an oxime sulfonate structure represented by the general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B2).

（一般式（Ｂ２）中、Ｒ⁴²は、アルキル基またはアリール基を表し、Ｘ¹⁰は、アルキル基、アルコキシ基、または、ハロゲン原子を表し、ｍ４は、０〜３の整数を表し、ｍ４が２または３であるとき、複数のＸ¹⁰は同一でも異なっていてもよい。）

(In the general formula (B2), R ⁴² represents an alkyl group or an aryl group, X ¹⁰ represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents an integer of 0 to 3, and m4 represents When it is 2 or 3, the plurality of X ¹⁰ may be the same or different.)

The alkyl group as X ¹⁰ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X ¹⁰ is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X ¹⁰ is preferably a chlorine atom or a fluorine atom. m4 is preferably 0 or 1. In the general formula (B2), m4 is 1, X ¹⁰ is a methyl group, the substitution position of X ¹⁰ is an ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound that is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

  The compound containing an oxime sulfonate structure represented by the general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B3).

（一般式（Ｂ３）中、Ｒ⁴³は一般式（Ｂ２）におけるＲ⁴²と同義であり、Ｘ¹¹は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、シアノ基またはニトロ基を表し、ｎ４は０〜５の整数を表す。）

(In General Formula (B3), R ⁴³ has the same meaning as R ⁴² in General Formula (B2), and X ¹¹ is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Represents a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, paratolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.
X ¹¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As n4, 0-2 are preferable and 0-1 are especially preferable.

  Specific examples of the compound represented by the general formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino). ) Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4- Methoxyphenyl] acetonitrile, α-[(4- Toluene sulfonyl) -4-methoxyphenyl] can be mentioned acetonitrile.

  Specific examples of preferred oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used singly or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

  The compound containing an oxime sulfonate structure represented by the general formula (B1) is also preferably a compound represented by the following general formula (OS-1).

In the general formula (OS-1), ^R411 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. R ⁴¹² represents an alkyl group or an aryl group.
X ⁴⁰¹ represents —O—, —S—, —NH—, —NR ⁴¹⁵ —, —CH ₂ —, —CR ⁴¹⁶ H—, or —CR ⁴¹⁵ R ⁴¹⁷ —, and R ^{415 to} R ⁴¹⁷ are alkyl groups. Or an aryl group.
R ^{421 to} R ⁴²⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group, Or an aryl group is represented. Two of R ^{421 to} R ⁴²⁴ may be connected to each other to form a ring.
As R ^{421 to} R ⁴²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and an embodiment in which at least two of R ^{421 to} R ⁴²⁴ are connected to each other to form an aryl group is also preferable. Among these, an embodiment in which R ^{421 to} R ⁴²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

  The compound represented by the general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).

In the general formula ^{(OS-2), R 411} , R 412 and R ⁴²¹ to R ⁴²⁴ are respectively synonymous with R ^411, R ⁴¹² and R ⁴²¹ to R ⁴²⁴ in formula (OS-1), preferably The example is similar.
Among these, the aspect in which R ⁴¹¹ in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and the general formula (OS-2)
And R ⁴¹¹ is most preferably a cyano group, a phenyl group or a naphthyl group.

  In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

  Specific examples of the compound represented by the general formula (OS-1) that can be suitably used in the present invention include compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to 1). b-34), but the present invention is not limited thereto.

  In the present invention, the compound containing the oxime sulfonate structure represented by the general formula (B1) is represented by the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5). It is preferable that it is an oxime sulfonate compound represented by these.

（一般式（ＯＳ−３）〜一般式（ＯＳ−５）中、Ｒ²²、Ｒ²⁵およびＲ²⁸はそれぞれ独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ²³、Ｒ²⁶およびＲ²⁹はそれぞれ独立に水素原子、アルキル基、アリール基またはハロゲン原子を表し、Ｒ²⁴、Ｒ²⁷およびＲ³⁰はそれぞれ独立にハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基またはアルコキシスルホニル基を表し、Ｘ¹〜Ｘ³はそれぞれ独立に酸素原子または硫黄原子を表し、ｎ¹〜ｎ³はそれぞれ独立に１または２を表し、ｍ¹〜ｍ³はそれぞれ独立に０〜６の整数を表す。）

(In the general formula (OS-3) to general formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represents 1 or 2, and m ^{1 to} m ³ each independently represents an integer of 0 to 6 Represents.)

In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.

In the general formulas (OS-3) to (OS-5), as the aryl group in R ²² , R ²⁵ and R ^28, an aryl group having 6 to 30 carbon atoms which may have a substituent may be used. preferable.

Further, in the above general formula (OS-3) ~ (OS -5), as the heteroaryl group in R ^1, heteroaryl group having a total carbon number of 4-30 which may have a substituent is preferable.

In the general formulas (OS-3) to (OS-5), at least one ring of the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be a heteroaromatic ring. For example, a heteroaromatic ring and benzene The ring may be condensed.

In the general formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. preferable.
In the general formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in the compound are an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.

The alkyl group for R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.

In the general formulas (OS-3) to (OS-5), X ^{1 to} X ³ each independently represents O or S, and is preferably O.
In the general formulas (OS-3) to (OS-5), the ring containing X ^{1 to} X ³ as a ring member is a 5-membered ring or a 6-membered ring.
In the general formulas (OS-3) to (OS-5), n ^{1 to} n ³ each independently represent 1 or 2, and when X ^{1 to} X ³ are O, n ^{1 to} n ³ are each independently 1 is preferable, and when X ^{1 to} X ³ are S, n ^{1 to} n ³ are preferably 2 each independently.

In the general formulas (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. Represent. Among them, R ²⁴ , R ²⁷ and R ³⁰ are preferably each independently an alkyl group or an alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.
In the general formulas (OS-3) to (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. It is preferable.

In the general formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. Preferably there is.

In the general formulas (OS-3) to (OS-5), m ^{1 to} m ³ each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.
Further, with respect to each of the substituents of (OS-3) to (OS-5), the substitution of (OS-3) to (OS-5) described in paragraph numbers 0092 to 0109 of JP2011-221494A. The preferred range of groups is likewise preferred.

  Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. However, the present invention is not limited to these.

  The compound containing the oxime sulfonate structure represented by the general formula (B1) is particularly an oxime sulfonate compound represented by any one of the following general formulas (OS-6) to (OS-11). preferable.

（一般式（ＯＳ−６）〜（ＯＳ−１１）中、Ｒ³⁰¹〜Ｒ³⁰⁶はアルキル基、アリール基またはヘテロアリール基を表し、Ｒ³⁰⁷は、水素原子または臭素原子を表し、Ｒ³⁰⁸〜Ｒ³¹⁰、
Ｒ³¹³、Ｒ³¹⁶およびＲ³¹⁸はそれぞれ独立に水素原子、炭素数１〜８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基またはクロロフェニル基を表し、Ｒ³¹¹およびＲ³¹⁴はそれぞれ独立に水素原子、ハロゲン原子、メチル基またはメトキシ基を表し、Ｒ³¹²、Ｒ³¹⁵、Ｒ³¹⁷およびＲ³¹⁹はそれぞれ独立に水素原子またはメチル基を表す。）

(In General Formulas (OS-6) to (OS-11), R ^{301 to} R ³⁰⁶ represent an alkyl group, an aryl group, or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ^{308 to} R ³¹⁰ ,
R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group; ³¹¹ and R ³¹⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group. )

  Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. It is the same.

  In the resist layer, (B) the photoacid generator is 0.1 to 10 parts by mass with respect to 100 parts by mass of all resin components (preferably the total solid content, more preferably the total polymer) in the resist layer. It is preferable to use it, and it is more preferable to use 0.5-10 mass parts. Two or more types can be used in combination.

  Examples of the ionic photoacid generator include diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts and the like. Of these, triarylsulfonium salts and diaryliodonium salts are preferred.

（一般式（１）中、Ｒ⁵⁰⁵、Ｒ⁵⁰⁶及びＲ⁵⁰⁷は、それぞれ、置換基を有していてもよい、
アルキル基又は芳香族基を表し、アルキル基の場合、互いに連結して環を形成してもよい；Ｘ^-は共役塩基を表す。） Triarylsulfonium salts used as an ionic photoacid generator are represented by the following general formula (1).
General formula (1)

(In the general formula (1), R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ may each have a substituent,
Represents an alkyl group or an aromatic group, and in the case of an alkyl group, they may be linked to each other to form a ring; X ⁻ represents a conjugate base. )

The alkyl group for R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ is preferably an alkyl group having 1 to 10 carbon atoms and may have a substituent. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, and octyl group. Can be mentioned. Of these, a methyl group, an ethyl group, and a tertiary butyl group are preferable. In addition, when two or more of R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ are alkyl groups, it is preferable that the two or more alkyl groups are connected to each other to form a ring. A 5-membered ring (thiacyclopentane) and a 6-membered ring (thiacyclohexane) are preferred in a form containing atoms.
The aromatic group in R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ is preferably an aromatic group having 6 to 30 carbon atoms and may have a substituent. Examples of the aromatic group having 6 to 30 carbon atoms include phenyl group, naphthyl group, 4-methoxyphenyl group, 4-chlorophenyl group, 4-methylphenyl group, 4-tertiarybutylphenyl group, 4-phenylthiophenyl group, Examples include 2,4,6-trimethylphenyl group, 4-methoxy-1-naphthyl group, and 4- (4′-diphenylsulfoniophenylthio) phenyl group.
The ionic photoacid generator represented by the general formula (1) may be bonded to each other at any one of R ^{505 to} R ⁵⁰⁷ to form a multimer such as a dimer. For example, the 4- (4′-diphenylsulfoniophenylthio) phenyl group is an example of a dimer, and the counter anion in the 4- (4′-diphenylsulfoniophenylthio) phenyl group is the same as X ^−. It is.

The substituent which the alkyl group and aromatic group in R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ may have is preferably an aromatic group, specifically a phenyl group, 4-methoxyphenyl group, 4-chlorophenyl group. 4- (4′-diphenylsulfoniophenylthio) phenyl group is particularly preferred. These substituents may be further substituted with the above substituents.

As the conjugate base represented by X ⁻ , a conjugate base of alkylsulfonic acid, a conjugate base of arylsulfonic acid, BY ₄ ⁻ (Y represents a halogen atom, the same applies to the following), PY ₆ ⁻ , AsY ₆ ^−. , SbY ₆ ⁻ , or a monovalent anion represented by the following general formula (3) or general formula (4) is preferable, a conjugate base of alkylsulfonic acid, a conjugate base of arylsulfonic acid, PY ₆ ⁻ , or The monovalent anion represented by the general formula (3) is particularly preferable.

As the conjugated base of alkyl sulfonic acid and aryl sulfonic acid, a conjugated base of alkyl sulfonic acid having 1 to 7 carbon atoms is preferable, and a conjugated base of alkyl sulfonic acid having 1 to 4 carbon atoms is more preferable, and expressed in acid form. For example, methanesulfonic acid, trifluoromethanesulfonic acid, n-propanesulfonic acid, and heptanesulfonic acid are particularly preferable.
Examples of the conjugate base of the aryl sulfonic acid include benzene sulfonic acid, chlorobenzene sulfonic acid, and paratoluene sulfonic acid when expressed in the form of an acid.

Y in BY ₄ ⁻ , PY ₆ ⁻ , AsY ₆ ⁻ and SbY ₆ ^— in X ⁻ is preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom.

（一般式（３）及び一般式（４）中、Ｒ⁵²¹、Ｒ⁵²²及びＲ⁵²³はそれぞれ独立に、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のフッ素原子を有するアルキル基、又は、Ｒ⁵²¹とＲ⁵²²とが互いに炭素原子数２〜６のアルキレン基若しくは炭素原子数２〜６のフッ素原子を有するアルキレン基で結合した環を表す。）

(In General Formula (3) and General Formula (4), R ⁵²¹ , R ⁵²² and R ⁵²³ are each independently an alkyl group having 1 to 10 carbon atoms and an alkyl group having a fluorine atom having 1 to 10 carbon atoms. Alternatively, R ⁵²¹ and R ⁵²² represent a ring in which the alkylene group having 2 to 6 carbon atoms or the alkylene group having 2 to 6 carbon atoms is bonded to each other.

1 to 1 carbon atoms in R ⁵²¹ , R ⁵²² and R ⁵²³ in general formula (3) and general formula (4)
Examples of the 0 alkyl group include a methyl group, an ethyl group, a butyl group, a tertiary butyl group, a cyclohexyl group, and an octyl group. Examples of the alkyl group having a fluorine atom having 1 to 10 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a dodecafluoropentyl group, and a perfluorooctyl group. Can be mentioned. Among these, R ⁵²¹ , R ⁵²² and R ⁵²³ are preferably alkyl groups having 1 to 10 carbon atoms and particularly preferably alkyl groups having 1 to 6 carbon atoms.
In general formula (3) and general formula (4), when ^R521 and ^R522 are connected to each other to form a ring, the alkylene group having 2 to 6 carbon atoms includes an ethylene group, a propylene group, and a butylene group. , Pentylene group, hexylene group and the like. Examples of the alkylene group having 2 to 6 carbon atoms include a tetrafluoroethylene group, a hexafluoropropylene group, an octafluorobutylene group, a decafluoropentylene group, and an undecafluorohexylene group. it can. Among these, when R ⁵²¹ and R ⁵²² are connected to each other to form a ring, they are preferably bonded with an alkylene group having 2 to 6 carbon atoms, particularly 2 to 4 carbon atoms. Bonding with an alkylene group having a fluorine atom is preferred.

（一般式（５）中、Ｒ⁵¹⁰、Ｒ⁵¹¹、Ｒ⁵¹²及びＲ⁵¹³はそれぞれ独立に、置換基を有していてもよい、アルキル基又は芳香族基を表し、Ａｒ³及びＡｒ⁴はそれぞれ独立に、置換基を有していてもよい二価の芳香族基を表し、Ｘ^1-及びＸ^2-はそれぞれ独立に、共役塩基を表す。） The ionic photoacid generator represented by the general formula (1) is preferably a photoacid generator represented by the following general formula (5).

(In General Formula (5), R ⁵¹⁰ , R ⁵¹¹ , R ⁵¹² and R ⁵¹³ each independently represents an alkyl group or an aromatic group which may have a substituent, and Ar ³ and Ar ⁴ are each Independently, it represents a divalent aromatic group which may have a substituent, and X ¹⁻ and X ²⁻ each independently represents a conjugate base.

The alkyl group and aromatic group in R ⁵¹⁰ , R ⁵¹¹ , R ⁵¹² and R ⁵¹³ are synonymous with the alkyl group and aromatic group represented by R ⁵⁰⁵ , R ⁵⁰⁶ and R ^{507 in} formula (1), and preferred embodiments are also included. It is the same. Moreover, the substituent which may have is the same.

The conjugate base represented by X ¹⁻ and X ²⁻ has the same meaning as the conjugate base represented by X ^{− in the} general formula (1), and the preferred embodiment is also the same.

The divalent aromatic group in Ar ³ and Ar ⁴ is preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group.

Specific examples of triarylsulfonium salts used as ionic photoacid generators include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyl. Examples thereof include diphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, and 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.
Commercially available compounds include TPS-102, 103, 105, 106, 109, 300, 1000, MDS-103, 105, 109, 205, 209, BDS-109, DTS-103, 105, MNPS-109, HDS-109 (above, Midori Chemical Co., Ltd.), GSID-26-1, Cyracure UVI-6976 (above, BASF Corp.).

（一般式（２）中、Ｒ⁵⁰⁸及びＲ⁵⁰⁹はそれぞれ独立に、置換基を有していてもよい芳香族基を表し、Ｘ^-は共役塩基を表す。） The diaryl iodonium salts used as the ionic photoacid generator are represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ⁵⁰⁸ and R ⁵⁰⁹ each independently represents an aromatic group which may have a substituent, and X ⁻ represents a conjugate base.)

In General Formula (2), the aromatic group represented by R ⁵⁰⁸ and R ⁵⁰⁹ has the same meaning as the aromatic group represented by R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ in General Formula (1), and the preferred embodiment is also the same.
In the general formula (2), X ^- conjugate base represents the general formula (1) X ^- has the same meaning as conjugate bases represented, preferable embodiments thereof are also the same.
Moreover, the photo-acid generator represented by General formula (2) may couple ^| bond together with ^R508 and ^R509 , and may form multimers, such as a dimer. For example, the 4- (4′-diphenylsulfoniophenylthio) phenyl group is an example of a dimer, and the counter anion in the 4- (4′-diphenylsulfoniophenylthio) phenyl group is the above X ⁻ and It is the same thing.

Specific examples of diaryliodonium salts used as ionic photoacid generators include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trioxide. Fluoroacetate, phenyl, 4- (2′-hydroxy-1′-tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2′-hydroxy-1′-tetradecaoxy) phenyliodonium hexafluoroantimonate, phenyl , 4- (2′-hydroxy-1′-tetradecaoxy) phenyliodonium-paratoluenesulfonate and the like.
Commercially available compounds include DPI-105, 106, 109, 201, BI-105, MPI-105, 106, 109, BBI-102, 103, 105, 106, 109, 110, 201, 300, 301 ( As mentioned above, Midori Chemical Co., Ltd.) can be mentioned.

  Specific examples of quaternary ammonium salts used as an ionic photoacid generator include tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (parachlorophenyl) borate, tetramethylammonium Hexyltris (3-trifluoromethylphenyl) borate, benzyldimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (parachlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-tri Fluoromethylphenyl) borate and the like.

In addition to the specific examples described above, specific examples of the component (B) include the following compounds, but the present invention is not limited thereto.

The content of Component B in the resist layer is preferably 0.1 to 10 parts by mass and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer component. When the content of component B is 0.1 parts by mass or more, desired sensitivity (higher sensitivity) is easily obtained, and when it is 10 parts by mass or less, the transparency of the coating film is easily secured.
Moreover, it is preferable that the addition amount of a nonionic photoacid generator is 1 mass% or less, and the aspect which does not contain a nonionic photoacid generator substantially is preferable.

<Solvent>
The photosensitive resin composition for forming the resist layer is preferably prepared as a solution in which a predetermined component is dissolved in a solvent (component (D)).
As the solvent used in the photosensitive resin composition for forming the resist layer, known solvents can be used, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, Propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene Examples include glycol monoalkyl ether acetates, esters, ketones, amides, lactones, etc. That. In addition, specific examples of the solvent used in the photosensitive resin composition for forming the resist layer include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A. Incorporated in the description.

  In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol as required for these solvents. , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ethers. It is more preferable to use together with acetates.

Component D is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.

  The content of the solvent in the resist layer for forming the resist layer is preferably 50 to 95 parts by weight, and preferably 60 to 90 parts by weight, per 100 parts by weight of the total resin components in the photosensitive resin composition. Is more preferable.

<Sensitizer>
It is also preferred that the resist layer further contains a sensitizer. The resist layer can contain a sensitizer in order to promote its decomposition in combination with the (B) photoacid generator, and in particular when using a nonionic photoacid generator, It is preferable to contain. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid.
By including a sensitizer, the exposure sensitivity is further improved, and when a nonionic photoacid generator having a low visible light absorption rate is used, the exposure light source is a mixed line of g-line and h-line. It is particularly effective.

As the sensitizer, anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives, and distyrylbenzene derivatives are preferable, and anthracene derivatives are more preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-dibromoanthracene, 2-ethylanthracene and 9,10-dimethoxyanthracene are preferred.
As an acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone and N-ethyl-2-methoxyacridone are preferable.
As the thioxanthone derivative, thioxanthone, diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2-chlorothioxanthone are preferable.
As the coumarin derivative, coumarin-1, coumarin-6H, coumarin-110 and coumarin-102 are preferable.
Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole, and 2- (4-dimethylaminostyryl) naphthothiazole.
Examples of the distyrylbenzene derivative include distyrylbenzene, di (4-methoxystyryl) benzene, and di (3,4,5-trimethoxystyryl) benzene.

  Specific examples of the sensitizer include the following, but the present invention is not limited thereto. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

  The content of the sensitizer in the resist layer is preferably 0.1 to 10 parts by mass and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymerizable component. Desirable sensitivity can be easily obtained by setting the content of the sensitizer to 0.1 parts by mass or more, and transparency of the coating film can be easily ensured by setting the content to 10 parts by mass or less.

<Basic compound>
In the dry film resist of the present invention, the resist layer preferably further contains a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraph numbers 0204 to 0207 of JP2011-221494A, the contents of which are incorporated herein.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. And ethanolamine, dicyclohexylamine, dicyclohexylmethylamine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea (abbreviation CHMETU), and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene (abbreviation DBN), 1,8-diazabicyclo [5.3. 0] -7-undecene etc. That.
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.

  The basic compound which can be used for this invention may be used individually by 1 type, or may use 2 or more types together.

  The content of the basic compound in the resist layer is preferably 0.001 to 3 parts by mass and more preferably 0.005 to 1 part by mass with respect to 100 parts by mass of the total solid content in the resist layer. preferable.

<(C): Heterocyclic compound>
In the dry film resist of the present invention, the resist layer preferably contains (C) a heterocyclic compound. By adding a heterocyclic compound, the cured film obtained from the resist layer can be made stronger.
There is no restriction | limiting in particular as a heterocyclic compound except a polymer component. For example, compounds having an epoxy group or oxetanyl group in the molecule described below, alkoxymethyl group-containing heterocyclic compounds, other oxygen-containing monomers such as various types of cyclic ethers and cyclic esters (lactones), cyclic amines and oxazolines Nitrogen-containing monomers and heterocyclic monomers having d electrons such as silicon, sulfur and phosphorus can be added.

  The addition amount of the heterocyclic compound in the resist layer is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the resist layer. 1 to 5 parts by mass is more preferable. By adding in this range, a cured film having excellent mechanical strength can be obtained, and a cured film having excellent chemical resistance can be obtained. A plurality of heterocyclic compounds can be used in combination, and in that case, the heterocyclic compounds are added together to calculate the content.

  Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.

These are available as commercial products. Examples thereof include commercially available products described in paragraph number 0189 of JP2011-221494A, such as JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation), and the like.
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, 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- 14L, 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), YH-300, YH-301, YH-302, YH-315, Examples thereof include YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.), Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolide GT400, Cellbiners B0134, B0177 (manufactured by Daicel Corporation).
These can be used alone or in combination of two or more.

  Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, aliphatic epoxy, and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.

  Specific examples of the compound having an oxetanyl group in the molecule include Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd.) Can be used.

  Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

  Among these, the (C) heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability.

  A compound having both an alkoxysilane structure and a heterocyclic structure in the molecule can also be suitably used for the resist layer. Examples include γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane. Of these, γ-glycidoxypropyltrialkoxysilane is more preferred. These can be used alone or in combination of two or more.

<Surfactant>
The resist layer may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants 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, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M (Manufactured by Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
Further, as a surfactant, it contains a structural unit A and a structural unit B represented by the following general formula (I-1), and is converted to polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A copolymer having a weight average molecular weight of 1,000 or more and 10,000 or less can be mentioned as a preferred example.

（式（Ｉ−１）中、Ｒ⁴⁰¹およびＲ⁴⁰³はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ⁴⁰²は炭素数１以上４以下の直鎖状のアルキレン基を表し、Ｒ⁴⁰⁴は水素原子または炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐおよびｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。） Formula (I-1)

(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 hydrogen. Represents an atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. The following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

L is preferably a branched alkylene group represented by the following general formula (I-2). R ⁴⁰⁵ in the general formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. A number 2 or 3 alkyl group is more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

Formula (I-2)

  The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

  In addition, surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362 can also be used.

These surfactants can be used alone or in combination of two or more.
The addition amount of the surfactant in the resist layer is preferably 10 parts by mass or less, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the resist layer. More preferably, it is 0.01-3 mass parts.

<Radiation absorber>
The resist layer also preferably contains a radiation absorber. As the radiation absorber, an ultraviolet absorber is preferable. Those exhibiting so-called photobleaching properties in which the absorbance is reduced by ultraviolet absorption are more preferred. Specifically, photobleachable materials such as naphthoquinonediazide derivatives, nitrones and diazonium salts (for example, JP-B-62-40697, M. Sasano et al., SPIE Symp. Proc., 631, 321 (1986)). Described compounds).
The radiation absorber is used for the purpose of averaging the light intensity distribution in the resist layer, and brings about the so-called internal enhancement type CEL (Contrast Enhancement Lithography) effect, thereby making the pattern rectangular and pattern linearity (line edge). Roughness can be improved (see Semiconductor Process Materials and Chemicals, supervised by Masanori Sakamoto, CM Publishing (2006)).

<Other ingredients>
In addition to the above components, the resist layer further includes metal oxide particles, cross-linking agents other than heterocyclic compounds, alkoxysilane compounds, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, and colorants. Known additives such as plasticizers, thermal radical generators, thermal acid generators, thickeners, and organic or inorganic suspending agents can be added.
Preferred embodiments of the other components are described in JP-A-2014-85643, [0165] to [0184], respectively, and the contents of this publication are incorporated herein.

<Compound having an ethylenically unsaturated bond>
In the dry film resist, the amount of the compound having an ethylenically unsaturated bond in the resist layer is preferably 0% by mass from the viewpoint of resolution. Note that 0 mass% may include an aspect that is contained in a minute amount (for example, 1 mass% or less in the resist layer) to the extent that the resolution effect is not impaired.

<Resist layer thickness>
The film thickness of the resist layer is preferably 0.5 to 10 μm. When the film thickness of the resist layer is 10 μm or less, the resolution of the pattern is good, and when it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity.
As a film thickness of a resist layer, 0.8-5 micrometers is still more preferable, and 1.0-3.0 micrometers is especially preferable.

<Method for forming resist layer>
A photosensitive resin composition for forming a resist layer can be prepared by mixing each component at a predetermined ratio and by any method, stirring and dissolving. For example, a resin composition can be prepared by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

(Light absorption layer)
The dry film resist can have a light absorption layer having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer between the temporary support and the resist layer.
The light absorption layer preferably has a transmittance of 60% or less, and more preferably has a transmittance of 55% or less.

The light absorption layer will be described. The light absorption layer is preferably provided between the resist layer and the temporary support in order to absorb unnecessary light out of the exposure light diffused by the temporary support and suppress resist exposure.
The light absorption layer preferably contains a light absorber and a resin.

The light absorber is selected from ultraviolet absorbers, dyes, and the like, and may or may not have photobleaching properties. Photobleaching refers to a property that absorbs exposure light and decreases the absorbance.
As a substance to be photobleached, photobleachable materials such as naphthoquinone diazide derivatives, nitrones and diazonium salts (for example, Japanese Patent Publication No. Sho 62-40697, M. Sasano et al., SPIE Symp. Proc., 631, 321 (1986) ), Stilbazolium salts, aryl nitroso salts, formazan dyes, oxonol dyes, and the like. More specific examples include formazan dyes such as nitro blue tetrazolium, MTT formazan, 1,3,5-triphenyl formazan and INT formazan, and oxonol dyes such as oxonol yellow K and oxonol 805 blue.
As a light absorber that is not photobleached, a known ultraviolet absorber or the like can be used. Typical examples of the structure of the light absorber not to be photobleached include benzotriazole, benzophenone, triazine, cyanoacrylate, oxanilide, formamidine and the like. More specific examples of light absorbers that are not photobleached include benzotriazoles such as TINUVIN 384, 900, and 928 (all manufactured by BASF), ADK STAB LA-29, and LA-36 (all manufactured by ADEKA), Examples thereof include triazine-based compounds such as TINUVIN 400 and 460 (all manufactured by BASF) and Adeka Stub LA-46 (manufactured by ADEKA), and benzophenone-based compounds such as Adeka Stub 1413 (manufactured by ADEKA).

Since the resin constituting the light absorption layer needs to disappear by alkali development together with the resist layer, an alkali-soluble resin is preferable. The alkali-soluble resin is preferably a linear organic polymer and is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of the linear organic high molecular polymer include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, The methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer described in JP-A-59-53836 and JP-A-59-71048 Examples thereof include polymers and partially esterified maleic acid copolymers. Similarly, acidic cellulose derivatives having a carboxylic acid in the side chain are useful.
In addition to those described above, alkali-soluble resins include those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched Or linear butyl (meth) acrylate or phenoxyhydroxypropyl (meth) acrylate.

  In addition to the above substances, substances such as surfactants, antioxidants, antifoaming agents, development accelerators, and plasticizers may be added to the light absorption layer for improving the properties.

<Dry film resist manufacturing method>
The dry film resist can be produced according to the method for producing a photosensitive transfer material described in paragraphs [0094] to [0098] of JP-A No. 2006-259138. The resist layer is preferably formed using a positive photosensitive resin composition.
In the first aspect of the dry film resist of the present invention, a low-haze temporary support having a total light haze of 0.3% or less is used. In the case of producing a dry film resist using such a low haze temporary support, it is preferable that a step of neutralizing the temporary support is included in the step of forming the resist layer. That is, the dry film resist of the present invention is preferably formed by forming a resist layer on the temporary support that has been neutralized. When the low-haze temporary support is, for example, a temporary support with a low filler content inside or on the surface of the temporary support, static electricity tends to be generated when the temporary support is unwound from the roll-shaped temporary support. The neutralization of the temporary support is preferably performed for the purpose of removing static electricity from the temporary support. In the case where the resist layer is formed by application of a resist layer coating solution, the application property of the resist layer can be improved by removing static electricity. Moreover, when forming a resist layer by application | coating of the solvent-type resist layer coating liquid, the safety | security of the application | coating process in a solvent atmosphere can also be improved by removing static electricity. The step of neutralizing the temporary support may be included before the formation of the resist layer, during the formation of the resist layer, or after the formation of the resist layer. From the viewpoint of improving the coating property and safety, the formation of the resist layer is performed. It is preferable that the step of previously removing the charge is included at least once.
Specifically, when forming a dry film resist having an intermediate layer, a solution (addition liquid for thermoplastic resin layer) in which an additive is dissolved together with a thermoplastic organic polymer is applied on a temporary support, After drying and providing a thermoplastic resin layer, a preparation liquid (intermediate layer coating liquid) prepared by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer on this thermoplastic resin layer is applied, It is preferably produced by laminating and laminating an intermediate layer, and further applying a resist layer coating solution prepared using a solvent that does not dissolve the intermediate layer, and laminating the resist layer by drying. can do.

[Method of manufacturing circuit wiring]
The circuit wiring manufacturing method of the present invention is a circuit wiring manufacturing method including the following steps (a), (b), (c) and (d).
(A) a laminating step of laminating the dry film resist of the present invention on a circuit-forming substrate having a base material and a conductive layer;
(B) a pattern exposure step of exposing a contact pattern with a pattern exposure pattern (preferably a photomask having a pattern exposure pattern shape) without peeling off the temporary support of the dry film resist;
(C) A development step of forming a pattern exposure pattern (preferably a resist pattern having a pattern exposure pattern shape) on the resist layer by developing after peeling the temporary support;
(D) An etching step of forming a pattern exposure pattern (preferably a conductive layer pattern (circuit wiring) having a pattern exposure pattern shape) on the circuit forming substrate by etching.
In the present specification, “pattern exposure pattern” means “pattern exposure pattern shape” unless otherwise specified. When the pattern exposure pattern is developed on the resist layer after pattern exposure, it means that a resist pattern having the same shape as the “pattern exposure pattern shape” used for pattern exposure is formed. When a pattern exposure pattern is formed on a circuit forming substrate by etching, this means that a conductive layer pattern having the same shape as the “pattern exposure pattern shape” used for pattern exposure is formed.
The circuit wiring of the present invention is suitable for an input device, particularly for a touch panel. In the circuit wiring manufacturing method of the present invention, the circuit wiring is preferably a circuit wiring of the input device. Furthermore, in the method for manufacturing circuit wiring of an input device according to the present invention, the input device is preferably a touch panel.
Hereinafter, a preferable aspect of the method for manufacturing a circuit wiring of the present invention will be described.

In the method for manufacturing a circuit wiring of the present invention, the step (b) is the following step (b1),
(C) The process is the following (c1) process,
(D) The process is the following (d1) process,
Further, the following steps (e1), (f1) and (g) are preferably included from the viewpoint of forming a circuit wiring including a conductive layer having two types of patterns;
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form a first pattern on the resist layer;
(D1) an etching step of forming a first pattern on the circuit formation substrate (substantially a conductive layer of the circuit formation substrate) by etching;
(E1) A pattern exposure step of exposing the contact pattern with the second pattern without removing the resist layer to which the first pattern is transferred in the step (c1);
(F1) A development step of developing and forming a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming a second pattern on the circuit formation substrate (substantially a conductive layer of the circuit formation substrate) by etching.

In the method for manufacturing a circuit wiring of the present invention, the step (b) is the following step (b1),
(C) The process is the following (c1) process,
(D) The process is the following (d2) process,
Furthermore, it is preferable to include the step (e2), the step (f2), and the step (g) from the viewpoint of forming a circuit wiring including a conductive layer having two types of patterns and more easily suppressing process contamination;
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form a first pattern on the resist layer;
(D2) After transferring the first pattern to the circuit formation substrate (substantially the conductive layer of the circuit formation substrate) by etching, without removing the resist layer on which the first pattern was formed in the step (c1) An etching step of attaching a cover film on the remaining resist layer;
(E2) A pattern exposure step of exposing the contact pattern with the second pattern without peeling off the cover film attached in the step (d2);
(F2) A development step in which the cover film attached in step (d2) is peeled and then developed to form a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming a second pattern on the circuit formation substrate (substantially a conductive layer of the circuit formation substrate) by etching.

  In the method for producing circuit wiring, it is also preferable that the substrate has conductive layers on both surfaces, and the circuit is sequentially or simultaneously formed on the conductive layers formed on both surfaces of the substrate. With this configuration, it is possible to form the touch panel circuit wiring in which the first electrode pattern is formed on one surface of the substrate and the second electrode pattern is formed on the other surface. Moreover, it is also preferable to form the circuit wiring for touch panels of this structure from both surfaces of a base material by roll-to-roll.

A case where a conductive pattern of a capacitive input device is obtained using a resist layer as an etching resist (etching pattern) will be described.
The capacitance-type input device has a base material (also referred to as a front plate) and at least the following elements (2) to (5) on the non-contact surface side of the base material: (2), (3) It is preferable that at least one of (5) is formed by the circuit wiring manufacturing method of the present invention.
(2) A plurality of first electrode patterns formed by extending a plurality of pad portions in a first direction via connecting portions. (3) The first electrode patterns are electrically insulated from the first electrode patterns, and the first A plurality of second electrode patterns including a plurality of pad portions and connection portions formed extending in a direction crossing one direction; and (4) electrically connecting the first electrode pattern and the second electrode pattern. Electrically insulating layer (5) electrically connected to at least one of the first electrode pattern and the second electrode pattern, and having a different conductivity from the first electrode pattern and the second electrode pattern Hereinafter, details of each step will be described.

<(A) Process>
(A) A laminating process for laminating the dry film resist of the present invention on a circuit forming substrate having a base material and a conductive layer will be described.
Lamination (transfer, bonding) of the dry film resist onto the circuit forming substrate is carried out by applying the resist layer on the circuit forming substrate (preferably on the conductive layer, and when there are two or more conductive layers, the first layer of the conductive layer is formed. It is preferably carried out using a method of layering, pressing and heating on the layer). For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.

(Base material)
The substrate is preferably a glass substrate or a film substrate, and more preferably a film substrate. When the circuit wiring manufacturing method of the present invention is a circuit wiring for a touch panel, the substrate is particularly preferably a sheet-shaped resin composition.
Moreover, it is preferable that a base material is transparent.
In the present specification, transparent means that the average transmittance of visible light having a wavelength of 400 nm to 700 nm is 80% or more. Therefore, the transparent layer refers to a layer having an average transmittance of visible light having a wavelength of 400 nm to 700 nm of 80% or more. The average transmittance of visible light having a wavelength of 400 nm to 700 nm of the transparent layer is preferably 90% or more.
The refractive index of the substrate is particularly preferably 1.50 to 1.52.
The substrate may be composed of a transparent substrate such as a glass substrate. As the base material, tempered glass represented by Corning gorilla glass can be used. Moreover, as the above-mentioned transparent substrate, the materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
When a film substrate is used as the substrate, it is more preferable to use a material that is not optically distorted or highly transparent. Specific examples of the material include polyethylene terephthalate (PET) and polyethylene naphthalate. , Polycarbonate, triacetyl cellulose, and cycloolefin polymer.

(Conductive layer)
As a conductive layer, the arbitrary conductive layers used for general circuit wiring and touch-panel wiring can be mentioned.
Examples of the material for the conductive layer include metals and metal oxides.
The multilayer conductive layers may be made of the same material or different materials, but preferably contain different materials.

It is preferable that at least one of the multilayer conductive layers contains a metal oxide.
Examples of the metal oxide used in this case include metal oxide films such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . The metal oxide will be described later.
The conductive layer is preferably a material for a first electrode pattern, a second electrode pattern, and another conductive element described below, which are used in a capacitive input device described later.
Other preferred modes of the conductive layer will be described later in the description of the capacitive input device.

<(B) Process>
(B) A pattern exposure process for exposing a contact pattern with a pattern for pattern exposure without peeling off the temporary support of the dry film resist will be described.
The step (b) is preferably a pattern exposure step in which the contact pattern is exposed with the first pattern without peeling the temporary support of (b1) dry film resist.

  As examples of the exposure step, the development step (c) described later, and other steps, the method described in paragraphs [0035] to [0051] of JP-A-2006-23696 is also suitable in the present invention. Can be used.

Specifically, above the resist layer formed on the circuit forming substrate (preferably on the conductive layer, or on the first layer of the conductive layer if there are two or more conductive layers), and temporarily support Examples include a method in which a predetermined mask is arranged at a position in direct contact with the body, and then a contact pattern is exposed from a light source above the mask through the mask and a temporary support.
In the present invention, the detailed arrangement and specific size of the pattern are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) including the input device of the present invention and to reduce the area occupied by the extraction wiring as much as possible, at least a part of the pattern (particularly the electrode pattern of the touch panel and the extraction wiring portion). ) Is preferably a fine wire of 100 μm or less, more preferably 70 μm or less, and particularly preferably 10 μm or less.
Here, as the light source for the exposure, a light source capable of irradiating light in a wavelength region (for example, 365 nm, 405 nm, etc.) that allows the exposed portion of the resist layer to be dissolved in the developer is appropriately selected and used. it can. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.
It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and pattern linearity of the pattern after exposure. By this process called so-called PEB (Post Exposure Bake), it is possible to reduce the roughness of the resist pattern edge due to standing waves generated in the resist layer during exposure.

  The pattern exposure is performed before the temporary support is peeled off. Thereafter, the support may be peeled off. Exposure through a mask or digital exposure using a laser or the like may be used. The pattern exposure is preferably exposure through a mask. When exposure is performed through a mask, the pattern exposure pattern is also referred to as a mask pattern.

<(C) Process>
A development process for forming a pattern exposure pattern on the resist layer after peeling off the temporary support will be described.
The step (c) is preferably a development step (c1) in which the temporary support is peeled and then developed to form a first pattern on the resist layer.

The development step is a step of developing the pattern-exposed resist layer.
The development can be performed using a developer. The developer is not particularly limited, and known developers such as those described in JP-A-5-72724 can be used. The developer is preferably one in which the resist layer has a dissolution type development behavior. For example, pKa =
A compound containing 7 to 13 compounds at a concentration of 0.05 to 5 mol / L is preferred, but a small amount of an organic solvent miscible with water may be added. Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

The development method may be any of paddle development, shower development, shower & spin development, dip development, and the like. Here, the shower development will be described. The exposed portion can be removed by spraying a developing solution onto the resist layer after exposure. When a thermoplastic resin layer or an intermediate layer is provided, a cleaning solution having a low solubility of the resist layer may be sprayed by a shower or the like before development to remove the thermoplastic resin layer or the intermediate layer. preferable. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The temperature of the developer is preferably 20 ° C to 40 ° C.
Further, the pH of the developer can be selected from, for example, more than 7 and 13.5 or less, but by using the dry film resist of the present invention, the pH of the developer used in the development process is 12.5 or less. Also in this case, the pattern linearity is good. In particular, the component (A) is a polymer component including a polymer having an acid structural unit a1 in which a carboxy group or a phenolic hydroxyl group is protected in the form of an acetal, and the acid structural unit a1 is represented by the general formula A3. In the case of a dry film resist having a structural unit, the pattern linearity is further improved when the pH of the developer used in the development step is 12.5 or less. For this reason, by using the dry film resist of the present invention, it is possible to use a weak alkali developer having a small process load and environmental load, and the advantage of widening the selectivity of the developer can be obtained.

Further, it may have a post-baking step of heat-treating the pattern including the resist layer obtained by the development, and obtained by the development after the step of removing the thermoplastic resin layer and the intermediate layer. A step of performing post-baking for heat-treating the pattern made of the resist layer may be included.
By the post-baking step, elimination of the protecting group using an acid in the resist layer can be promoted. In the acid structural unit a0 in which the acid group in the resist layer is protected with an acid-decomposable group, protecting the carboxy group with an acetal reduces activation energy for protecting group elimination and avoids heat treatment after exposure. From the viewpoint of

  (C) You may have other processes, such as a post exposure process, before or after a process.

<(D) Process>
(D) An etching process for forming a pattern exposure pattern on the circuit forming substrate by etching will be described.
Step (d) includes (d1) etching to form a first pattern on the circuit formation substrate, or (d2) etching to form the first pattern on the circuit formation substrate and then the remaining resist. It is preferable that it is an etching process which affixes a cover film on a layer.
(D2) After the first pattern is formed on the circuit forming substrate by etching, the cover film is formed on the remaining resist layer without peeling off the resist layer on which the first pattern is formed in the above-described step (c1). In the etching step of attaching the film, it is preferable to use again the temporary support once peeled off in the step (c) as the cover film.

  For the etching, a known etching method such as the method described in paragraphs [0048] to [0054] of JP 2010-152155 A can be applied.

  For example, as an etching method, a commonly performed wet etching method in which the substrate is immersed in an etching solution can be used. As an etching solution used for wet etching, an acid type or an alkaline type may be appropriately selected according to an object to be etched. Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid; mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, etc. Is done. As the acidic component, a combination of a plurality of acidic components may be used. In addition, alkaline type etching solutions include aqueous solutions containing only alkali components such as salts of organic amines such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, tetramethylammonium hydroxide; alkaline components and potassium permanganate, etc. A mixed aqueous solution of a salt of A combination of a plurality of alkali components may be used as the alkali component.

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. The resist layer used as an etching mask (etching pattern) in the present invention preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in the above temperature range. Therefore, the resist layer is prevented from being peeled off during the etching process, and the portion where the resist layer does not exist is selectively etched.
After the etching, a cleaning process and / or a drying process may be performed as necessary to prevent line contamination. For the cleaning step, for example, the base material is cleaned for 10 to 300 seconds at room temperature, and for the drying step, an air blow is used and an air blow pressure (about 0.1 to 5 kg / cm ² ) is appropriately set. Adjust and do.

<(E1) step and (e2) step>
(E1) a pattern exposure step of exposing the contact pattern with the second pattern without peeling off the resist layer on which the first pattern has been formed in the step (c1), and (e2) in the step (d2). A pattern exposure process for exposing the contact pattern with the second pattern without peeling off the attached cover film will be described.
For the contact pattern exposure in the steps (e1) and (e2), the same method as the contact pattern exposure in the step (b) can be used.

<(F1) process and (f2) process>
(F1) a development step of developing and forming a second pattern different from the first pattern on the resist layer; and (f2) the cover film attached in the step (d2) is peeled off and then developed. A developing process for forming a second pattern different from the first pattern on the resist layer will be described.
The development in step (f1) and (f2) can use the same method as the development in step (c).

<(G) Process>
(G) An etching process for forming the second pattern on the circuit formation substrate by etching will be described.
For the etching in the step (g), the same method as the etching in the step (d) can be used.
In step (g), it is preferable to selectively etch fewer conductive layers than in step (d), depending on the desired pattern.

<Method for Forming Circuit Wiring Containing Two Types of Conductive Layers>
When forming a circuit wiring including a conductive layer having at least two types of patterns, the following (Xa) process, (Xb) process, (Xc) process, (Xd) process, (Xe) process, and (Xz) process are performed as follows. It is also preferable to implement in combination with each step of the method for manufacturing a circuit wiring of the invention.
(Xa) where x is an integer of 2 or more, the first layer of the conductive layer with respect to the circuit forming substrate having the base material and the conductive layers from the x-th layer to the first layer in order from one surface of the base material A laminating step for forming a resist layer in which the exposed portion is dissolved in a developer;
(Xb) A pattern exposure and development process in which a resist layer is formed into a first pattern by pattern exposure and development on the circuit-formed substrate on which the resist layer is formed;
(Xc) An etching process for etching from the first layer to the i-th layer of the conductive layer in the region where the resist layer having the first pattern in the (Xb) process is not formed, where i is an integer of 1 to x ;
(Xd) A pattern exposure and development step in which the resist layer remaining in the step (Xb) is subjected to pattern exposure and development in a pattern different from that of the remaining resist layer, and the resist layer is used as a second pattern;
(Xe) An etching process in which j is an integer of 1 or more and less than i, and etching is performed from the first layer to the jth layer of the conductive layer in the region where the resist layer formed as the second pattern in the (Xd) process is not formed. ;
(Xz) A remaining resist layer removing step of removing all remaining resist layers to form circuit wiring including conductive layers having at least two types of patterns.

FIG. 1 shows an example of a method for manufacturing a circuit wiring for a touch panel when forming a circuit wiring including a conductive layer having at least two types of patterns.
In the example of the method for manufacturing the circuit wiring for touch panel shown in FIG. 1, in addition to the (Xa) process, the (Xb) process, the (Xc) process, the (Xd) process, the (Xe) process, and the (Xz) process, Step (Xf) is described.
In the step (Xa), a resist layer is formed on the first layer of the conductive layer. This resist layer remains at least partially in the subsequent (Xa) step, (Xb), (Xc), (Xd), (Xe), and (Xf), and finally remains in the (Xz) step. All the resist layers to be removed are removed to form a circuit wiring including at least two types of conductive layers. That is, a circuit wiring including a plurality of types of conductive layers can be formed by a single resist formation.
In step (Xb), pattern exposure and development are performed to make the resist layer the first pattern.
In the step (Xc), the first layer to the i-th layer of the conductive layer in the region where the resist layer having the first pattern in the step (Xb) is not formed are etched. In FIG. 1, i = x is set in step (Xc), and all the conductive layers from the first layer to the x-th layer are etched and removed.
The pattern from the first layer to the i-th layer of the conductive layer obtained in the (Xc) process does not remain when all the resist layers are removed by going to the (Xz) process, and in the (Xe) process. Etching in step (Xf), which can be performed as needed, forms another pattern. In the configuration shown in FIG. 1, the pattern from the first layer to the i-th layer of the conductive layer obtained in the step (Xc) is described as seven columns, but the third, fourth, and fifth columns from the right Is a different pattern in the etching in the (Xe) process, and the first, second and sixth pillars from the right also have a different pattern in the etching in the (Xf) process, and the final (Xz) When all the resist layers are removed through the steps, only the seventh column from the right is a pattern from the first layer to the i-th layer of the conductive layer.
In the step (Xd), the resist layer remaining in the step (Xb) is subjected to pattern exposure and development in a pattern different from that of the remaining resist layer, so that the resist layer becomes a second pattern.
In the (Xe) process, the first to jth layers of the conductive layer in the region where the resist layer having the second pattern formed in the (Xd) process is not formed are etched. In FIG. 1, in step (Xe), j = x−1 and j = i−1, and the conductive layers from the first layer to the x−1th layer (jth layer) are removed by etching. Only the x layer is left.
Although details of the (Xf) process are omitted in FIG. 1, the (Xf) process can be repeated as many times as necessary.
In the step (Xz), all remaining resist layers are removed to form circuit wiring including conductive layers having at least two types of patterns. FIG. 1 shows that the entire resist layer was finally removed after the (Xz) step.

(Step (Xa))
(Xa) Step: The first conductive layer is formed on a circuit-formed substrate having a base material and conductive layers from the x-th layer to the first layer in order from one surface of the base material, where x is an integer of 2 or more. A laminating process for laminating a resist layer in which a portion exposed on the layer is dissolved in a developer will be described.

  The step (Xa) is preferably a step of laminating the resist layer of the dry film resist from which the protective film has been removed on the first layer of the conductive layer.

x is an integer of 2 or more, preferably 2 or 3, and more preferably 2.
FIG. 2 shows a schematic cross-sectional view of an example of circuit wiring for a touch panel, which is one of the embodiments of the present invention obtained when x is 2. In FIG. 2, the first electrode pattern 3 is formed on the base material 1, and another conductive element 6 is formed on the first electrode pattern. The circuit wiring for the touch panel shown in FIG. 2 has two types of patterns: a conductive layer laminate in which another conductive element is formed with the first electrode pattern 3 and a conductive layer having only the first electrode pattern 3. The circuit wiring includes a conductive layer.
FIG. 3 shows the circuit wiring for the touch panel in FIG. In the example of the circuit wiring for the touch panel shown in FIG. 3, the dotted line part in FIG. Is a conductive layer having only the first electrode pattern 3. As shown in FIG. 3, among the conductive layers having different types of patterns included in the circuit wiring, the conductive layer having at least one type of pattern includes a conductive layer stack of two or more layers sharing the same circuit pattern. Is preferred.

(Step (Xb))
Process (Xb): A pattern exposure and development process in which a resist layer is formed into a first pattern by pattern exposure and development on a circuit-formed substrate on which a resist layer is formed will be described.
The pattern exposure and development in the step (Xd) can use the same methods as the pattern exposure and development in the steps (b) and (c).

(Step (Xc))
(Xc) Process: Etching is performed from the first layer to the i-th layer of the conductive layer in the region where the resist layer having the first pattern in the (Xb) process is not formed, where i is an integer of 1 to x. The etching process will be described.
For the etching process in the step (Xc), the same method as the etching process in the process (d) can be used.

(Step (Xd))
Process (Xd): The pattern exposure and development process in which the resist layer remaining in the process (Xb) is subjected to pattern exposure and development in a pattern different from the remaining resist layer to make the resist layer a second pattern will be described.
The pattern exposure and development in the step (Xd) can use the same methods as the pattern exposure and development in the step (Xb).

(Step (Xe))
(Xe) Process: Etching is performed from the first layer to the jth layer of the conductive layer in the region where the resist layer having the second pattern in the (Xd) process is not formed, where j is an integer of 1 or more and less than i. The etching process will be described.
The same method as the etching in the (Xc) process can be used for the etching in the (Xe) process.
In step (Xe), it is preferable to selectively etch fewer conductive layers than in step (Xc), depending on the desired pattern.

(Step (Xf))
It is preferable that the method for manufacturing circuit wiring further includes the following step (Xf).
Step (Xf): pattern exposure and development of the remaining resist layer in a pattern different from the remaining resist layer, and any less than j from the first layer of the conductive layer in the region where the resist layer is not formed after development Pattern exposure and development process in which the conductive layer is patterned by etching up to the layer.
Hereinafter, the step (Xf) will be described.
In the method for manufacturing a circuit wiring of the present invention, it is also preferable not to perform the step (Xf). That is, in the method for manufacturing a circuit wiring of the present invention, it is preferable that the circuit wiring includes a conductive layer having only two types of patterns.
The number of steps (Xf) is not particularly limited, and can be repeated according to the desired pattern shape. Among them, the number of steps (Xf) is preferably one.
In the method for manufacturing a circuit wiring of the present invention, it is preferable that the (Xf) step includes the following (Xf1) step and (Xf2) step, and includes a conductive layer having at least three types of patterns.
(Xf1) A pattern exposure and development process in which the resist layer remaining in the (Xe) process is subjected to pattern exposure and development in a pattern different from the remaining resist layer, and the resist layer is used as a third pattern;
(Xf2) Pattern exposure in which k is an integer of 1 or more and less than j, and etching is performed from the first layer to the k-th layer of the conductive layer in the region where the resist layer formed as the third pattern in the step (f1) is not formed And development process.
Other preferred embodiments of the step (Xf) are the same as those in the steps (Xd) and (Xe).

((Xz) process)
Step (Xz): The remaining resist layer removing step for removing all the remaining resist layers and forming circuit wiring including conductive layers having at least two types of patterns will be described.
Although there is no restriction | limiting in particular as a method of removing all the resist layers which remain | survive after the said etching process, The method of removing by a chemical process can be mentioned.
Examples of the method for removing the resist layer include a method of immersing a substrate having a resist layer or the like in a stripping solution being stirred at 30 to 80 ° C., preferably 50 to 80 ° C. for 5 to 30 minutes. The resin pattern used as an etching mask may exhibit excellent chemical resistance at 45 ° C. or lower, but preferably exhibits a property of swelling with an alkaline stripping solution when the chemical temperature is 50 ° C. or higher. Due to the above properties, when the stripping process is performed using a stripping solution of 50 to 80 ° C., there are advantages that the process time is shortened and the stripping residue of the resist layer is reduced. That is, by providing a difference in chemical temperature between the etching step and the step of removing the resist layer, the resist layer used as an etching mask exhibits good chemical resistance in the etching step, while the removal step In this case, good releasability is exhibited, and both contradictory properties of chemical resistance and releasability can be satisfied.

  Examples of the stripping solution include inorganic alkali components such as sodium hydroxide and potassium hydroxide, organic alkali components such as tertiary amine and quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or these. What was melt | dissolved in this mixed solution is mentioned. You may peel by the spray method, the shower method, the paddle method etc. using said peeling liquid.

[Circuit wiring]
The circuit wiring of the present invention is a circuit wiring manufactured by the circuit wiring manufacturing method of the present invention. The circuit wiring of the present invention is preferably a touch panel circuit wiring. A preferable aspect of the circuit wiring for the touch panel will be described later in the description of the capacitive input device.

[Input device and display device]
The input device of the present invention is an input device using the circuit wiring of the present invention. In the present invention, the input device is preferably a capacitive touch panel.
The display device of the present invention includes the input device of the present invention. The display device of the present invention is preferably an image display device.

<Capacitive Input Device and Image Display Device Comprising Capacitive Input Device>
A capacitive input device which is a preferred embodiment of the input device and display device of the present invention, and an image display device including this capacitive input device as a constituent element are “latest touch panel technology” (July 6, 2009). (Published by Techno Times, Inc.), Yuji Mitani, Yoshio Itakura, "Technology and Development of Touch Panel" (CMC Publishing, 2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292 The configuration disclosed in the above can be applied.

  First, the configuration of the capacitive input device will be described. FIG. 9 is a cross-sectional view showing the configuration of the capacitive input device. In FIG. 9, the capacitive input device 10 includes a base material 1, a mask layer 2, a first electrode pattern 3, a second electrode pattern 4, an insulating layer 5, and another conductive element 6. , And a transparent protective layer 7.

  In FIG. 9, the side where each element of the base material 1 is provided is referred to as a non-contact surface. In the capacitance-type input device 10, input is performed by bringing a finger or the like into contact with the contact surface of the substrate 1 (the surface opposite to the non-contact surface). Hereinafter, the base material may be referred to as a “front plate”.

A mask layer 2 is provided on the non-contact surface of the substrate 1. The mask layer 2 is a frame-like pattern around the display area formed on the non-contact surface side of the base material 1 (for example, the touch panel front plate), and is formed so as to hide the lead wiring and the like.
The capacitive input device 10 may be provided with a mask layer 2 so as to cover a partial region of the substrate 1. Furthermore, the base material 1 can be provided with an opening in part. A mechanical switch that operates by pressing can be installed in the opening.

On the contact surface of the substrate 1, a plurality of first electrode patterns 3 formed by extending a plurality of pad portions in the first direction via connection portions, and the first electrode pattern 3 and the electrical A plurality of second electrode patterns 4 including a plurality of pad portions and connection portions that are insulated from each other and extend in a direction crossing the first direction, and the first electrode pattern 3 and the second electrode An insulating layer 5 that electrically insulates the pattern 4 is formed. The said 1st electrode pattern 3, the 2nd electrode pattern 4, and another electroconductive element 6 mentioned later can be produced with a transparent conductive film, for example. Examples of the conductive film include metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as ITO, IZO, and SiO ₂ . At this time, the film thickness of each element can be 10 to 200 nm. In addition, the electrical resistance can be reduced by changing the amorphous ITO film to a polycrystalline ITO film by firing.
The first electrode pattern 3 and the second electrode pattern 4 are preferably formed using a resist layer as an etching resist (etching pattern). For the formation of the second electrode layer for forming the second electrode pattern, a known method can be used in addition to photolithography using a resist including the resist layer used in the present invention. In addition, it can also manufacture using the photosensitive transfer material which has the photosensitive resin composition using an electroconductive fiber. When the first electrode pattern or the like is formed of ITO or the like, paragraphs [0014] to [0016] of Japanese Patent No. 4506785 can be referred to.

  In addition, at least one of the first electrode pattern 3 and the second electrode pattern 4 is disposed across both the non-contact surface of the base material 1 and the surface of the mask layer 2 opposite to the base material 1. be able to. FIG. 9 shows an aspect in which the second electrode pattern 4 is disposed across both the non-contact surface of the substrate 1 and the surface of the mask layer 2 opposite to the substrate 1. Yes.

  The first electrode pattern and the second electrode pattern 4 will be described with reference to FIGS. 7 and 8 are also explanatory diagrams showing examples of the first electrode pattern and the second electrode pattern. As shown in FIG. 8, the first electrode pattern is formed such that the pad portion 3a extends in the first direction via the connection portion 3b. The second electrode pattern 4 is electrically insulated by the first electrode pattern and the insulating layer 5 and is formed to extend in a direction intersecting the first direction (second direction). It is composed of a plurality of pad portions. Here, when the first electrode pattern 3 is formed, the pad portion 3a and the connection portion 3b may be manufactured integrally, or only the connection portion 3b is manufactured, and the pad portion 3a and the second electrode are formed. The pattern 4 may be integrally formed (patterned). When the pad portion 3a and the second electrode pattern 4 are integrally formed (patterned), as shown in FIGS. 7 and 8, a part of the connection portion 3b and one of the pad portions 3a (not shown in FIG. 7). Each layer is formed such that the first electrode pattern 3 and the second electrode pattern 4 are electrically insulated by the insulating layer 5.

  In FIG. 9, another conductive element 6 is installed on the side of the mask layer 2 opposite to the base 1. Another conductive element 6 is electrically connected to at least one of the first electrode pattern 3 and the second electrode pattern 4 and is different from the first electrode pattern 3 and the second electrode pattern 4. Is an element. FIG. 9 shows a diagram in which another conductive element 6 is connected to the second electrode pattern 4.

Moreover, in FIG. 9, the transparent protective layer 7 which covers all of each component is installed. The transparent protective layer 7 may be configured to cover only a part of each component. The insulating layer 5 and the transparent protective layer 7 may be made of the same material or different materials. As the material constituting the insulating layer 5 and the transparent protective layer 7, those having high surface hardness and high heat resistance are preferable, and known photosensitive siloxane resin materials, acrylic resin materials, and the like are used, which are known to those skilled in the art. is there.
As a method for patterning the insulating layer, a known method such as ink jet or screen can be used in addition to the photolithography method.

  In the method of manufacturing the capacitance-type input device, at least one of the first electrode pattern 3, the second electrode pattern 4, and another conductive element 6 is formed by etching a resist layer (etching pattern). It is preferable to form by etching using. In addition, at least one element of the black mask layer 2, the insulating layer 5, and, if necessary, the transparent protective layer 7 also has a temporary support, a thermoplastic resin layer, and a photocurable resin layer in this order. It is also preferable to form using a film.

At least one of the first electrode pattern 3, the second electrode pattern 4, and another conductive element 6 is preferably formed by etching using a resist layer as an etching resist (etching pattern). .
When the first electrode pattern 3, the second electrode pattern 4, and another conductive element 6 are formed by etching, black is first formed on the non-contact surface of the substrate 1 on which the black mask layer 2 is formed. An inorganic insulating layer is provided at least on the portion where the mask layer 2 is provided, and a transparent electrode layer such as ITO is formed on the non-contact surface of the substrate 1 or on the inorganic insulating layer by sputtering. Next, an etching pattern is formed by exposure and development using a resist layer having a photocurable resin layer for etching as a photocurable resin layer on the transparent electrode layer. Thereafter, the transparent electrode layer is etched to pattern the transparent electrode, and the etching pattern is removed, whereby the first electrode pattern 3 and the like can be formed.

  When forming the 1st electrode pattern 3, the 2nd electrode pattern 4, and another electroconductive element 6 using the photosensitive film which has a photocurable resin layer containing an electroconductive material, on the surface of the base material 1 In addition, at least an inorganic insulating layer is provided on the portion where the black mask layer 2 is provided, and a photocurable resin layer containing a conductive material is transferred onto the non-contact surface of the substrate 1 or onto the inorganic insulating layer (lamination ) Or the like.

  The mask layer 2, the insulating layer 5, and the transparent protective layer 7 can be formed by transferring a photocurable resin layer to the substrate 1 using a photosensitive film. For example, when the black mask layer 2 is formed, the black photocurable resin layer is transferred onto the surface of the substrate 1 using a photosensitive film having a black photocurable resin layer as the photocurable resin layer. Can be formed. When the insulating layer 5 is formed, the surface of the substrate 1 on which the first or second electrode pattern is formed using a photosensitive film having an insulating photocurable resin layer as the photocurable resin layer. It can be formed by transferring a photocurable resin layer to the film. When the transparent protective layer 7 is formed, a photocurable resin layer is used on the surface of the substrate 1 on which each element is formed using a photosensitive film having a transparent photocurable resin layer as the photocurable resin layer. It can be formed by transferring.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.
The following symbols represent the following compounds, respectively.
MATHF: 2-tetrahydrofuranyl methacrylate MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
PHS: parahydroxystyrene PHS-EVE: 1-ethoxyethyl protector of parahydroxystyrene PHS-THF: 2-tetrahydrofuranyl protector of parahydroxystyrene PGMEA: propylene glycol monomethyl ether acetate

[Evaluation method of material properties]
Below, the evaluation method of a material characteristic is described.

<Total light haze of temporary support>
Using a haze meter HZ-2 manufactured by Suga Test Instruments Co., Ltd., the total light haze (%) of a small piece of a temporary support was measured according to JIS (Japan Industrial Standards) K7136.

<Transmittance of temporary support or light absorption layer>
A transmission spectrum of a sample of a temporary support or a light absorption layer sample prepared by peeling a temporary support from a laminate in which a light absorption layer is formed on the temporary support, is converted into an 8453 ultraviolet-visible spectrophotometer ( The transmittance at a wavelength of 365 nm which is the same as the exposure main wavelength of the resist layer was determined.

[Example 1]
A positive photosensitive resin composition was prepared according to the following formulation.
Novolak resin (metacresol: paracresol = 30: 70, molecular weight 5,500): 79.9 parts ) Compound (1): 20 parts Surfactant (Surfactant 1 below): 0.1 part PGMEA: 900 parts Surfactant 1: F-554, perfluoroalkyl group-containing nonion represented by the following structural formula Surfactant (manufactured by DIC)

The photosensitive resin composition is placed on a 100 μm-thick polyethylene terephthalate film (hereinafter referred to as PET (A)) serving as a temporary support so that the dry film thickness becomes 2.0 μm using a slit nozzle. Applied. Thereafter, the film was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (manufactured by Tredegar, OSM-N) was pressure bonded as a protective film to prepare a dry film resist. The obtained dry film resist was used as the dry film resist of Example 1.
In addition, PET (A) does not contain a filler as a slipping agent, and the total light haze was 0.3%.

Next, copper was formed as a conductive layer with a thickness of 200 nm on a PET substrate having a thickness of 100 μm by a vacuum deposition method to obtain a circuit formation substrate.
After peeling the protective film from the dry film resist of Example 1, the (a) laminating step described later was performed. The dry film resist of Example 1 was laminated and transferred onto the copper layer to produce a positive resist layer (a) A lamination process was performed.
The resist layer is exposed to a contact pattern using a photomask provided with a line-and-space wiring pattern having a line width of 4 μm (opening portion: light-shielding portion width ratio is 1: 1) without peeling off the temporary support. (B) A pattern exposure process was performed. For the exposure, a high pressure mercury lamp having i-line (365 nm) as an exposure dominant wavelength was used.
After removing the temporary support from the exposed circuit-formed substrate, development using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) and washing with water to obtain a resist layer on which a wiring pattern is formed (c) A development step was performed. The pH of TMAH 2.38 mass% aqueous solution is 13.3.
Next, an etching (d) process for forming a pattern exposure pattern on the circuit forming substrate by etching the copper layer using a copper etching solution (Cu-02, manufactured by Kanto Chemical Co., Ltd.) was performed to obtain a copper wiring substrate. . The obtained circuit wiring was used as the circuit wiring of Example 1.

[Example 2]
A dry film resist of Example 2 was prepared in the same manner as in Example 1 except that the temporary support used was PET having a film thickness of 75 μm and a total light haze of 0.16% (hereinafter referred to as PET (B)). Further, a copper wiring board as a circuit wiring of Example 2 was obtained in the same manner as in Example 1 except that the dry film resist of Example 2 was used as the dry film resist.

[Example 3]
A dry film resist of Example 3 was prepared in the same manner as in Example 1 except that the temporary support used was a polypropylene film (hereinafter referred to as PP (a)) having a film thickness of 25 μm and a total light haze of 0.20%. Further, a copper wiring board as a circuit wiring of Example 3 was obtained in the same manner as in Example 1 except that the dry film resist of Example 3 was used as the dry film resist.

[Example 4]
A dry film resist of Example 4 was prepared in the same manner as in Example 1 except that the temporary support used was a cellulose triacetate film (hereinafter referred to as TAC) having a film thickness of 40 μm and a total light haze of 0.30%. Further, a copper wiring board as a circuit wiring of Example 4 was obtained in the same manner as in Example 1 except that the dry film resist of Example 4 was used as the dry film resist.

[Example 5]
<Synthesis Example 1: Synthesis of PHS-EVE>
20 g of alkali-soluble resin (VP-8000 manufactured by Nippon Soda Co., Ltd.) and 320 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask and distilled under reduced pressure, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 24 g of ethyl vinyl ether and 0.35 g of paratoluenesulfonic acid were added and stirred at room temperature for 1 hour. Thereto, 0.28 g of triethylamine was added to stop the reaction. After adding ethyl acetate to the reaction solution and further washing with water, ethyl acetate, water and azeotropic PGMEA were distilled off by distillation under reduced pressure to obtain PHS-EVE which is an alkali-soluble resin protected with an acid-decomposable group. It was. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 1.21.
The structure of PHS-EVE is as follows, and is a 1-ethoxyethyl protector / parahydroxystyrene copolymer (30 mol% / 70 mol%) of parahydroxystyrene.

Using the synthesized PHS-EVE, a positive photosensitive composition was prepared according to the following formulation.
-PHS-EVE: 97.9 parts-Photoacid generator (following PAG-1): 2 parts-Surfactant (the above-mentioned surfactant 1): 0.1 part-PGMEA: 900 parts PAG-1: WO2014 / Compound B-9 according to 020984.
The positive photosensitive composition is slit-coated on PET (A) as a temporary support to a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally as a protective film A dry film resist was prepared by pressure-bonding a polyethylene film (Tradegar, OSM-N). The obtained dry film resist was used as the dry film resist of Example 5.
A copper wiring board as the circuit wiring of Example 5 was produced in the same manner as in Example 1 except that the dry film resist of Example 5 was used as the dry film resist.

[Example 6]
A dry film resist of Example 6 was produced in the same manner as in Example 5 except that PET (B) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 6 was produced in the same manner as in Example 1 except that the dry film resist of Example 6 was used as the dry film resist.

[Example 7]
A dry film resist of Example 7 was produced in the same manner as in Example 5 except that PP (a) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 7 was produced in the same manner as in Example 1 except that the dry film resist of Example 7 was used as the dry film resist.

[Example 8]
A dry film resist of Example 8 was produced in the same manner as Example 5 except that TAC was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 8 was produced in the same manner as in Example 1 except that the dry film resist of Example 8 was used as the dry film resist.

[Example 9]
<Synthesis Example 2: Synthesis of PHS-THF>
15.6 g of an alkali-soluble resin (VP-8000 manufactured by Nippon Soda Co., Ltd.) and 100 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask, distilled under reduced pressure, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 2.7 g of 2,3-dihydrofuran and 0.015 g of paratoluenesulfonic acid were added and stirred at room temperature for 2 hours. Thereto was added 0.090 g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution and the mixture was further washed with water, and then ethyl acetate and water were distilled off under reduced pressure to obtain PHS-THF which is a soluble resin having a protection rate of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 1.13.
The structure of PHS-THF is shown below, and is a 2-tetrahydrofuranyl protected form of parahydroxystyrene / parahydroxystyrene copolymer (30 mol% / 70 mol%).

Using the synthesized PHS-THF, a positive photosensitive composition was prepared with the following formulation.
PHS-THF: 97.9 parts Photoacid generator (PAG-2 below): 2 parts Surfactant (surfactant 1 above): 0.1 part PGMEA: 900 parts PAG-2: JP Compound A-1 described in [0227] of JP2013-047765A

The positive photosensitive composition is slit-coated on PET (A) as a temporary support to a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally as a protective film A dry film resist was prepared by pressure-bonding a polyethylene film (Tradegar, OSM-N). The obtained dry film resist was used as the dry film resist of Example 9.
A copper wiring board as the circuit wiring of Example 9 was produced in the same manner as in Example 5 except that the dry film resist of Example 9 was used as the dry film resist.

[Example 10]
A dry film resist of Example 10 was produced in the same manner as Example 9 except that PET (B) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 10 was produced in the same manner as in Example 9 except that the dry film resist of Example 10 was used as the dry film resist.

[Example 11]
A dry film resist of Example 11 was produced in the same manner as Example 9 except that PP (a) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 11 was produced in the same manner as in Example 9 except that the dry film resist of Example 11 was used as the dry film resist.

[Example 12]
A dry film resist of Example 12 was produced in the same manner as Example 9 except that TAC was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 12 was produced in the same manner as in Example 9 except that the dry film resist of Example 12 was used as the dry film resist.

[Example 13]
<Synthesis Example 3: Synthesis of polymer novolak-EVE (1-ethoxyethyl protected product)>
A polymer novolak-EVE (1-ethoxyethyl protector) was synthesized in the same manner as in Example 1 of JP-A-2003-98671. The weight average molecular weight of the obtained resin was 5,000. The polydispersity was 7.0. The structure of polymer novolak-EVE (1-ethoxyethyl protector) is shown below (the numerical values in the structural formula are molar ratios).

Using the synthesized polymer novolak-EVE, a positive photosensitive composition was prepared according to the following formulation.
-Polymer novolak-EVE: 97.9 parts-Photoacid generator (PAG-2 above): 2 parts-Surfactant (surfactant 1 above): 0.1 part-PGMEA: 900 parts

The positive photosensitive composition is slit-coated on PET (A) as a temporary support to a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally as a protective film A dry film resist was prepared by pressure-bonding a polyethylene film (Tradegar, OSM-N). The obtained dry film resist was used as the dry film resist of Example 13.
A copper wiring board as the circuit wiring of Example 13 was produced in the same manner as in Example 5 except that the dry film resist of Example 13 was used as the dry film resist.

[Example 14]
A dry film resist of Example 14 was produced in the same manner as Example 13 except that PET (B) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 14 was produced in the same manner as in Example 13 except that the dry film resist of Example 14 was used as the dry film resist.

[Example 15]
A dry film resist of Example 15 was produced in the same manner as in Example 13 except that PP (a) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 15 was produced in the same manner as in Example 13 except that the dry film resist of Example 15 was used as the dry film resist.

[Example 16]
A dry film resist of Example 16 was produced in the same manner as Example 13 except that TAC was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 16 was produced in the same manner as in Example 13 except that the dry film resist of Example 16 was used as the dry film resist.

[Example 17]
<Synthesis Example 4: Synthesis of MATHF copolymer>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C. and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure gave 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (boiling point: 54-56 ° C./3.5 mmHg) (yield: 80 mol%).
Using this, the following MATH copolymer was synthesized by the method described in [0248] to [0249] of JP2013-61616A. The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained MATH copolymer was 14,000. The structure of the MATHH copolymer was as shown below (the numerical values in the structural formula are molar ratios). Of the acid structural unit a1 in which the carboxy group or phenolic hydroxyl group contained in the MATHF copolymer is protected in the form of an acetal, 100 mol% is the structural unit represented by the general formula A3, and is represented by the general formula A1. The structural unit was 0 mol%.

Using the synthesized MATHF copolymer, a positive photosensitive composition was prepared with the following formulation. Among the polymers having a group in which the acid group contained in the positive photosensitive composition (A) is protected with an acid-decomposable group, as the acid structural unit a1 in which the carboxy group or the phenolic hydroxyl group is protected in the form of an acetal The polymer component having the structural unit represented by General Formula A3 was 100% by mass.
-MATH copolymer: 97.9 parts-Photoacid generator (PAG-2): 2 parts-Surfactant (surfactant 1): 0.1 part-PGMEA: 900 parts

The positive photosensitive composition is slit-coated on PET (A) as a temporary support to a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally as a protective film A dry film resist was prepared by pressure-bonding a polyethylene film (Tradegar, OSM-N). The obtained dry film resist was used as the dry film resist of Example 17.
The dry film resist of Example 17 was used as a dry film resist, and development using a 1.0 mass% aqueous solution of sodium carbonate, which is a pH 11.2 developer, was performed instead of development using a 2.38 mass% aqueous solution of TMAH. Otherwise, a copper wiring board that was the circuit wiring of Example 17 was produced in the same manner as in Example 5.

[Example 18]
A dry film resist of Example 18 was produced in the same manner as Example 17 except that PET (B) was used as a temporary support. Further, a copper wiring board as the circuit wiring of Example 18 was produced in the same manner as in Example 17 except that the dry film resist of Example 18 was used as the dry film resist.

[Example 19]
A dry film resist of Example 19 was produced in the same manner as Example 17 except that PP (a) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 19 was produced in the same manner as in Example 17 except that the dry film resist of Example 19 was used as the dry film resist.

[Example 20]
A dry film resist of Example 20 was produced in the same manner as in Example 17 except that TAC was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 20 was produced in the same manner as in Example 17 except that the dry film resist of Example 20 was used as the dry film resist.

[Example 21]
A positive photosensitive composition was prepared according to the following formulation.
-MATH copolymer: 69.1 parts-PHS-THF: 28.8 parts-Photoacid generator (PAG-2): 2 parts-Surfactant (surfactant 1): 0.1 / PGMEA: 900 parts

The positive photosensitive composition is slit-coated on PET (A) as a temporary support to a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally as a protective film A dry film resist was prepared by pressure-bonding a polyethylene film (Tradegar, OSM-N). The obtained dry film resist was used as the dry film resist of Example 21.
A copper wiring board as the circuit wiring of Example 21 was produced in the same manner as in Example 5 except that the dry film resist of Example 21 was used as the dry film resist.

[Example 22]
A dry film resist of Example 22 was produced in the same manner as Example 21 except that PET (B) was used as a temporary support. Further, a copper wiring board as the circuit wiring of Example 22 was produced in the same manner as in Example 21 except that the dry film resist of Example 22 was used as the dry film resist.

[Example 23]
A dry film resist of Example 23 was produced in the same manner as in Example 21 except that PP (a) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 23 was produced in the same manner as in Example 21 except that the dry film resist of Example 23 was used as the dry film resist.

[Example 24]
A dry film resist of Example 24 was produced in the same manner as Example 21 except that TAC was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 24 was produced in the same manner as in Example 21 except that the dry film resist of Example 24 was used as the dry film resist.

[Example 25]
A positive photosensitive composition was prepared according to the following formulation.
-MATH copolymer: 97.7 parts-Photoacid generator (PAG-2): 2 parts-Basic compound (N-cyclohexyl-N '-[2- (4-morpholinyl) ethyl] thiourea Abbreviation CHMETU): 0.2 parts Surfactant (Surfactant 1): 0.1 parts PGMEA: 900 parts

The positive photosensitive composition is slit-coated on PET (B) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally as a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (Tradegar, OSM-N). The obtained dry film resist was used as the dry film resist of Example 25.
A copper wiring board, which is the circuit wiring of Example 25, was produced in the same manner as Example 17 except that the dry film resist of Example 25 was used as the dry film resist.

[Example 26]
A positive photosensitive composition was prepared according to the following formulation.
-MATH copolymer: 97.8 parts-Photoacid generator (PAG-2): 2 parts-Basic compound (1,5-diazabicyclo [4.3.0] -5-nonene, abbreviation DBN): 0.1 part ・ Surfactant (Surfactant 1): 0.1 part ・ PGMEA: 900 parts

The positive photosensitive composition is slit-coated on PET (B) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally as a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (Tradegar, OSM-N). The obtained dry film resist was used as the dry film resist of Example 26.
A copper wiring board as the circuit wiring of Example 26 was produced in the same manner as in Example 17 except that the dry film resist of Example 26 was used as the dry film resist.

[Example 27]
A positive photosensitive composition was prepared according to the following formulation.
-MATH copolymer: 93.1 parts-Photoacid generator (PAG-2): 2 parts-Surfactant (surfactant 1): 0.1 part-Heterocyclic compound (Denacol EX-321L) (Manufactured by Nagase ChemteX Corporation)): 4.8 parts, PGMEA: 900 parts

The positive photosensitive composition is slit-coated on PET (B) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally as a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (Tradegar, OSM-N).
A copper wiring board was produced in the same manner as in Example 5 except that this dry film resist was used. The obtained dry film resist was used as the dry film resist of Example 27.
A copper wiring board as the circuit wiring of Example 27 was produced in the same manner as in Example 17 except that the dry film resist of Example 27 was used as the dry film resist.

[Example 28]
A positive photosensitive composition was prepared according to the following formulation.
-MATHH copolymer: 93.0 parts-Photoacid generator (PAG-2): 2 parts-Surfactant (surfactant 1): 0.1 part-Heterocyclic compound (3-glycid Xylpropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd.)): 4.8 parts, PGMEA: 900 parts

The positive photosensitive composition is slit-coated on PET (B) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally as a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (Tradegar, OSM-N). The obtained dry film resist was used as the dry film resist of Example 28.
A copper wiring board as the circuit wiring of Example 28 was produced in the same manner as in Example 17 except that the dry film resist of Example 28 was used as the dry film resist.

[Example 29]
A positive photosensitive composition was prepared according to the following formulation.
-MATH copolymer: 97.8 parts-Photoacid generator (PAG-2): 2 parts-UV absorber (UV absorber 1 having the following structure): 0.1 parts-Surfactant (above interface) Activator 1): 0.1 part PGMEA: 900 parts UV absorber 1

The positive photosensitive composition is slit-coated on PET (B) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally as a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (Tradegar, OSM-N). The obtained dry film resist was used as the dry film resist of Example 29.
A copper wiring board as the circuit wiring of Example 29 was produced in the same manner as in Example 17 except that the dry film resist of Example 29 was used as the dry film resist.

[Example 30]
A dry film resist was produced in the same manner as in Example 17 except that PET (C) having a haze of 0.16% and a light transmittance of 70% was used as the temporary support. The obtained dry film resist was used as the dry film resist of Example 30.
A copper wiring board as the circuit wiring of Example 30 was produced in the same manner as in Example 17 except that the dry film resist of Example 30 was used as the dry film resist.
PET (C) was prepared by adding a UV-absorbing dye based on PET (B).

[Example 31]
The composition for light absorption layers was prepared with the following compositions.
・ 1,3,5-triphenylformazan: 12 parts ・ Copolymer polymer of polyvinyl pyrrolidone 60 mol% and polyacrylic acid 40 mol%: 88 parts ・ Pure water: 900 parts

On the PET (B), the light absorbing layer composition was slit coated so as to have a dry film thickness of 1.0 μm, and dried in a convection oven at 100 ° C. for 5 minutes to prepare a light absorbing layer. The transmittance of the manufactured light absorption layer with respect to light having a wavelength of 365 nm was 70%.
On this light absorption layer, the positive photosensitive composition used in Example 17 was slit coated so as to have a dry film thickness of 2.0 μm, and dried in a convection oven at 100 ° C. for 5 minutes. Finally, a polyethylene film (Tradegar, OSM-N) was pressure bonded as a protective film to prepare a dry film resist. The obtained dry film resist was used as the dry film resist of Example 31.
A copper wiring board as the circuit wiring of Example 31 was produced in the same manner as in Example 17 except that the dry film resist of Example 31 was used as the dry film resist.

[Example 32]
On a PET substrate having a thickness of 100 μm, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by vacuum evaporation to a thickness of 200 nm. A film was formed with a film thickness to obtain a circuit forming substrate.
After the protective film was peeled off from the dry film resist of Example 18, the dry film resist of Example 18 was laminated on the copper layer to produce a positive resist layer (a) A lamination process was performed.
A photomask provided with the pattern A (first pattern) shown in FIG. 4 having a configuration in which the shape of the pad portion of the electrode pattern is connected in one direction without peeling off the temporary support on the resist layer. (B1) A pattern exposure step for exposing the contact pattern was performed. In the pattern A shown in FIG. 4, the solid line portion and the gray portion are light shielding portions, the other portions are openings, and the dotted line portion virtually shows an alignment alignment frame. For the exposure, a high pressure mercury lamp having i-line (365 nm) as an exposure dominant wavelength was used.
Thereafter, the temporary support is peeled off, and development using a 1.0 mass% aqueous solution of sodium carbonate, which is a pH 11.2 developer, and washing with water to obtain a resist layer on which pattern A is formed (c1) is performed. It was.
Next, after etching the first layer (copper layer) using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the second layer using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.). The (IT1 layer) was etched to form a first pattern on the circuit formation substrate (d1). By etching in this way, the first to second layers of the conductive layer in the region where the resist layer is not formed are etched, and the first pattern in the region where the resist layer having the first pattern is not formed. A circuit-formed substrate was obtained in which both the first layer (copper layer) and the second layer (ITO layer) were drawn with a first pattern (a pattern having a shape of a region (negative) in which no pattern A was present).
Next, a pattern exposure step (e1) was performed in which pattern exposure was performed using a photomask provided with openings of the pattern B (second pattern) shown in FIG. In the pattern B shown in FIG. 5, the gray portion is a light shielding portion, the other portion is an opening portion, and the dotted line portion virtually shows an alignment alignment frame. For the exposure, a high pressure mercury lamp having i-line (365 nm) as an exposure dominant wavelength was used.
Thereafter, development using a 1.0 mass% aqueous solution of sodium carbonate, which is a developer having a pH of 11.2, and washing with water are performed, so that a second pattern different from the first pattern (the light shielding portion of pattern A and the light shielding of pattern B) is obtained. (F1) A development step was performed to obtain a resist layer to which the pattern of the overlapping portion) was transferred.
Thereafter, by etching only the wiring of the first layer (copper layer) using Cu-02, the first layer of the conductive layer in the region where the resist layer having the second pattern is not formed is etched. (G) The etching process which forms the pattern for pattern exposure on a circuit formation board | substrate was performed. By etching in this way, a circuit forming substrate including a conductive layer having only two types of patterns was obtained. Specifically, the obtained conductive layer has a pattern A (existence of the first pattern) in which both the first layer (copper layer) and the second layer (ITO layer) in the region where the resist layer having the second pattern is formed. The second layer (ITO layer) in the region where the resist layer which is the second pattern is not formed and the second pattern is not present is drawn. It was drawn with a pattern having the shape of (negative).
The remaining resist layer was removed by peeling using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.), and a circuit wiring including a conductive layer of two types of patterns was formed on the substrate. 32 circuit wirings were obtained. The circuit wiring of Example 32 has the circuit wiring of the pattern C shown in FIG. The wiring portion included in the gray region in FIG. 6 is in a state where the second layer (ITO wiring) is exposed. A dotted line portion in FIG. 6 virtually shows an alignment alignment frame. The other part is a peripheral wiring part and has a structure including two or more conductive layer laminates in which the first layer (copper wiring) is laminated on the second layer (ITO wiring) and shares the same circuit pattern. ing. FIGS. 2 and 3 are schematic diagrams showing a structure including two or more conductive layer stacks sharing the same circuit pattern. In the circuit wiring of Example 32, the first layer (copper wiring) overlapped the second layer (ITO wiring) in the dotted line portion of FIG.

[Example 33]
On a PET substrate having a thickness of 100 μm, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by vacuum evaporation to a thickness of 200 nm. A film was formed with a film thickness to obtain a circuit forming substrate.
After the protective film was peeled off from the dry film resist of Example 18, the dry film resist used in Example 18 was laminated on the copper layer to produce a positive resist layer (a) A lamination process was performed.
A temporary support using a photomask provided with a pattern A (first pattern) having a configuration in which the shape of the pad portion of the electrode pattern is connected in one direction to the resist layer without peeling off the temporary support. (B1) A pattern exposure step was performed in which a photomask was contacted to expose the contact pattern. For the exposure, a high pressure mercury lamp having i-line (365 nm) as an exposure dominant wavelength was used.
Thereafter, the temporary support is peeled off, and development using a 1.0% by mass aqueous solution of sodium carbonate, which is a pH 11.2 developer, and washing with water is performed to obtain a resist layer on which pattern A is formed (c1) went.
Next, after etching the first layer (copper layer) using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the second layer using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.). By etching (ITO layer), the pattern exposure pattern was transferred to the circuit forming substrate. By etching in this way, the first to second layers of the conductive layer in the region where the resist layer is not formed are etched, and the first pattern in the region where the resist layer having the first pattern is not formed. A circuit-formed substrate was obtained in which both the first layer (copper layer) and the second layer (ITO layer) were drawn with a first pattern (a pattern having a shape of a region (negative) in which no pattern A was present). Next, an etching process was performed (d2) in which PET (B) used as a temporary support as a cover film was again laminated on the remaining resist.
(D2) Contact the photomask with the cover film using the photomask provided with the opening of the pattern B (second pattern) in a state where the alignment is aligned in a state where the cover film attached in the step is not peeled off (E2) A pattern exposure step was performed. For the exposure, a high pressure mercury lamp having i-line (365 nm) as an exposure dominant wavelength was used.
(D2) After the cover film attached in the etching process is peeled off, development using a 1.0% by weight aqueous solution of sodium carbonate, which is a developer having a pH of 11.2, and washing with water are performed. (F2) The development process was performed to obtain a resist layer to which the pattern (the pattern of the portion where the light shielding part of pattern A and the light shielding part of pattern B overlap) was transferred.
Thereafter, by etching only the wiring of the first layer (copper layer) using Cu-02, the first layer of the conductive layer in the region where the resist layer having the second pattern is not formed is etched. (G) The etching process which forms the pattern for pattern exposure on a circuit formation board | substrate was performed.
The remaining resist layer was removed by peeling using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.), and a circuit wiring including a conductive layer of two types of patterns was formed on the substrate. 33 circuit wirings were obtained. The circuit wiring of Example 33 has the circuit wiring of the pattern C shown in FIG.

[Example 34]
<Preparation of composition for thermoplastic resin layer>
A composition for a thermoplastic resin layer was prepared according to the following formulation.
Methyl ethyl ketone: 82.0 parts PGMEA: 12.8 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 /28.8, weight average molecular weight = 100,000, glass transition temperature (Tg) ≈70 ° C.): 3.5 parts / monomer (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 1.5 parts fluorine-based polymer: 0.2 parts the above fluorine-based polymer, and _{C 6 F 13 CH 2 CH 2} OCOCH = CH 2 40 parts of _{H (OCH (CH 3) CH} 2) 7 OCOCH = CH 2 55 parts H in (OCHCH _{2) 7} copolymer of OCOCH = CH ₂ 5 parts, weight average molecular weight 30,000, methyl ethyl ketone 30 wt% solution (trade name: Megafac F780F, DIC Co., Ltd.))

<Preparation of composition for intermediate layer>
A composition for an intermediate layer was prepared according to the following formulation.
Distilled water: 39.0 parts Methanol: 58.0 parts Polyvinyl alcohol (trade name: PVA205, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550): 1.5 parts Hydroxypropylmethylcellulose ( Product name: TC-5, manufactured by Shin-Etsu Chemical Co., Ltd.): 1.5 parts

<Preparation of positive photosensitive composition>
A positive photosensitive composition was prepared according to the following formulation.
MATH copolymer: 97.9 parts Photoacid generator (PAG-2): 2 parts Surfactant (surfactant 1): 0.1 part PGMEA: 900 parts

The thermoplastic resin layer composition was slit coated on a temporary support PET (A) so as to have a dry film thickness of 1.0 μm, and dried in a convection oven at 100 ° C. for 2 minutes. Thereafter, the intermediate layer composition was slit coated on the thermoplastic resin layer so as to have a dry film thickness of 0.5 μm and dried in a convection oven at 100 ° C. for 2 minutes. Finally, after slit coating the positive photosensitive composition so as to have a dry film thickness of 3.0 μm, it was dried in a convection oven at 100 ° C. for 2 minutes, and a polyethylene film (OSM-N, manufactured by Tredegar) was used as a protective film. A dry film resist was prepared by pressure bonding.
A copper wiring board, which is the circuit wiring of Example 34, was produced in the same manner as Example 5 except that this dry film resist was used.

[Example 35]
A copper wiring board, which is the circuit wiring of Example 35, was produced in the same manner as Example 34 except that PET (B) was used as a temporary support.

[Comparative Example 1]
A positive-type photosensitive resin composition prepared in the same manner as in Example 5 was dried on a 25 μm-thick PET (hereinafter referred to as PET (D)) serving as a temporary support using a slit-like nozzle. It was applied so as to be 0.0 μm. Thereafter, the film was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (manufactured by Tredegar, OSM-N) was pressure bonded as a protective film to prepare a dry film resist. The obtained dry film resist was used as the dry film resist of Comparative Example 1. In addition, PET (D) with a film thickness of 25 μm had a total light haze of 0.48%.
A copper wiring board as a circuit wiring of Comparative Example 1 was produced in the same manner as in Example 5 except that the dry film resist of Comparative Example 1 was used as the dry film resist.

[Comparative Example 2]
A dry film resist of Comparative Example 2 was prepared in the same manner as Comparative Example 1 except that the temporary support used was PET having a film thickness of 40 μm and a total light haze of 1.10% (hereinafter referred to as PET (E)). Furthermore, the copper wiring board which is the circuit wiring of the comparative example 2 was obtained like the comparative example 1 except having used the dry film resist of the comparative example 2 as a dry film resist.

[Comparative Example 3]
A dry film resist of Comparative Example 3 was prepared in the same manner as Comparative Example 1 except that the temporary support used was PP (hereinafter referred to as PP (b)) having a film thickness of 50 μm and a total light haze of 0.50%. Further, a copper wiring board as a circuit wiring of Comparative Example 3 was obtained in the same manner as Comparative Example 1 except that the dry film resist of Comparative Example 3 was used as the dry film resist.

[Comparative Example 4]
A copper wiring substrate as a circuit wiring of Comparative Example 4 was obtained in the same manner as in Comparative Example 1 except that the temporary support was peeled off during contact pattern exposure and the photomask was brought into contact with the resist layer to perform contact pattern exposure. .

[Evaluation]
<Pattern linearity (LWR)>
Twenty pattern widths were measured at locations selected at random from the line and space pattern of the circuit wiring board having the circuit wirings of the obtained examples and comparative examples. A standard deviation σ was determined from the obtained line width data, and a value obtained by multiplying the standard deviation σ by 3 was defined as LWR (Line Width Roughness), which was used as an index of pattern linearity.
By definition, the smaller the LWR, the smaller the line width variation, which is preferable. For a 4 μm line width pattern, the LWR value is evaluated as follows.
Evaluation D 1.0 ≦ LWR: Line width variation is large, leading to circuit failure, and cannot be used as a circuit wiring board.
Evaluation C 0.5 ≦ LWR <1.0: Although it can be used as a circuit wiring board, there is a possibility of occurrence of defects, which is not preferable.
Evaluation B 0.3 ≦ LWR <0.5: Preferred as a circuit wiring board.
Evaluation A LWR <0.3: Very preferable as a circuit wiring board.
Of the above evaluations, evaluations A and B are practically necessary to obtain a circuit wiring board having good performance, and evaluation A is preferable.
The evaluation results are shown in Table 1 below.

<Process contamination>
It was visually determined whether or not deposits could be seen on the photomask after the exposure process, and process contamination related to photomask contamination caused by resist transfer to the photomask during exposure was evaluated according to the following criteria.
A: No deposits are seen on the photomask after the exposure process.
B: Deposits are seen on the photomask after the exposure process.
The evaluation results are shown in Table 1 below.

From Table 1 above, it was found that according to the dry film resist of the present invention, it is possible to provide a dry film resist that is capable of producing a circuit wiring that is easy to form a high-resolution pattern and has high pattern linearity. The circuit wiring having high pattern linearity is suitable as the circuit wiring for the input device and the display device. Moreover, according to the circuit wiring manufacturing method of the present invention, it was found that circuit wiring with high pattern linearity can be manufactured without process contamination.
As shown in Comparative Examples 1 to 3, when pattern exposure through a temporary support having a haze greater than 0.3% is performed, the linearity tends to decrease according to the haze value and is used as a circuit wiring board. Something that was possible but unfavorable quality or could not be used at all.
Further, as shown in Comparative Example 4, although high pattern linearity can be obtained if exposure is performed by peeling the temporary support, mask contamination occurs due to direct contact between the photomask and the resist, resulting in process contamination. Therefore, it was not preferable in the process.

1: Base material 2: Mask layer 3: 1st electrode pattern 3a: Pad part 3b: Connection part 4: 2nd electrode pattern 5: Insulating layer 6: Another conductive element (peripheral wiring part and extraction wiring part)
7: Transparent protective layer 10: Capacitance type input device

Claims (22)

It is a positive dry film resist having a resist layer on a temporary support,
The dry film resist whose total light haze of the said temporary support body is 0.3% or less. It is a positive dry film resist having a resist layer on a temporary support,
The resist layer contains (A) component and (B) photoacid generator,
The component (A) is a polymer having an acid structural unit a0 in which an acid group is protected with an acid-decomposable group,
A dry film resist in which the acid structural unit a0 has a structural unit represented by the following general formula A3;
Formula A3

In the general formula A3, R ³¹ and R ³² each 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 is an alkyl group. Or an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group. , Y represents a nitrogen atom, a sulfur atom or an oxygen atom. The resist layer contains (A) component and (B) photoacid generator,
The component (A) is a polymer having an acid structural unit a0 in which an acid group is protected with an acid-decomposable group,
The dry film resist according to claim 1, wherein the acid structural unit a0 has a structural unit represented by the following general formula A3;
Formula A3

In the general formula A3, R ³¹ and R ³² each 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 is an alkyl group. Or an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group. , Y represents a nitrogen atom, a sulfur atom or an oxygen atom. 4. The dry film resist according to claim 2, wherein X ⁰ in the general formula A3 is a single bond.   In said general formula A3, Y is an oxygen atom, The dry film resist as described in any one of Claims 2-4. The resist layer contains (A) component and (B) photoacid generator,
The component (A) is a polymer having an acid structural unit a0 in which an acid group is protected with an acid-decomposable group,
The dry film resist according to claim 1, wherein the acid structural unit a0 is an acid structural unit a1 in which a carboxy group or a phenolic hydroxyl group is protected in the form of an acetal. The dry film resist according to claim 6, wherein the acid structural unit a1 has a structural unit represented by the following general formula A1.

In the general formula A1, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group Alternatively, it represents an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, and R ⁴ represents a hydrogen atom or a methyl group. The dry film resist according to claim 6, wherein the acid structural unit a1 has a structural unit represented by the following general formula A2.

In the general formula A2, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, and R ¹³ is an alkyl group Or an aryl group, and R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, and each R ¹⁴ independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, An alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group or a cycloalkyl group is represented.   The dry film resist as described in any one of Claim 1 and 3-8 in which the said resist layer contains 2 or more types of polymers which have the acid structural unit a0 in which the acid group was protected by the acid-decomposable group.   The dry film resist according to claim 1, wherein the resist layer contains a naphthoquinone diazide compound and a resin having a phenolic hydroxyl group.   The dry film resist according to claim 1, wherein the resist layer further contains a heterocyclic compound.   The dry film resist according to claim 1, wherein the resist layer further contains a basic compound.   The dry film resist according to claim 1, wherein the resist layer further contains a radiation absorber. The dry film resist according to any one of claims 1 to 13, which satisfies at least one of the following conditions (1) and (2):
Condition (1): The temporary support has a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer;
Condition (2): A light absorption layer having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer is provided between the temporary support and the resist layer. A circuit wiring manufacturing method including the following steps (a), (b), (c) and (d);
(A) A laminating step of laminating the dry film resist according to any one of claims 1 to 14 on a circuit forming substrate having a base material and a conductive layer;
(B) A pattern exposure step of exposing a contact pattern with a pattern for pattern exposure without peeling off the temporary support of the dry film resist;
(C) A development step of peeling off the temporary support and developing to form the pattern exposure pattern on the resist layer;
(D) An etching step of forming the pattern exposure pattern on the circuit forming substrate by etching. The step (b) is the following step (b1),
The step (c) is the following step (c1),
The step (d) is the following step (d1),
Furthermore, the manufacturing method of the circuit wiring of Claim 15 including the following (e1) process, (f1) process, and (g) process;
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form the first pattern on the resist layer;
(D1) an etching step of forming the first pattern on the circuit forming substrate by etching;
(E1) A pattern exposure step of exposing a contact pattern with a second pattern without peeling off the resist layer on which the first pattern has been formed in the step (c1);
(F1) A development step of developing and forming a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming the second pattern on the circuit forming substrate by etching. The step (b) is the following step (b1),
The step (c) is the following step (c1),
The step (d) is the following step (d2),
Furthermore, the manufacturing method of the circuit wiring of Claim 15 including the process (e2), the process (f2), and the process (g);
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form the first pattern on the resist layer;
(D2) After the first pattern is formed on the circuit forming substrate by etching, the resist layer on which the first pattern is formed in the step (c1) without peeling off the remaining resist layer. Etching process to attach a cover film on top;
(E2) A pattern exposure step of exposing the contact pattern with a second pattern without peeling off the cover film attached in the step (d2);
(F2) A development step in which the cover film attached in the step (d2) is peeled and then developed to form a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming the second pattern on the circuit forming substrate by etching.   The method for manufacturing a circuit wiring according to any one of claims 15 to 17, wherein a pH of a developer used in the developing step is 12.5 or less.   The circuit wiring manufactured with the manufacturing method of the circuit wiring as described in any one of Claims 15-18.   An input device using the circuit wiring according to claim 19.   The input device according to claim 20, wherein the input device is a capacitive touch panel.   A display device comprising the input device according to claim 20 or 21.

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