WO2014200013A1 - Photosensitive resin composition, method for producing pattern, method for manufacturing organic el display device or liquid crystal display device, and cured film - Google Patents

Abstract

Provided are: a photosensitive resin composition which has excellent sensitivity, line width stability, resolution, rectangularity and adhesion to a substrate; a method for producing a pattern; a method for manufacturing an organic EL display device or a liquid crystal display device; and a cured film. A photosensitive resin composition which contains (A) a polymer having a group that is protected by an acid-decomposable group, (B) a compound represented by general formula (3), and (C) a solvent.

Description

Photosensitive resin composition, method for producing pattern, method for producing organic EL display device or liquid crystal display device, and cured film

The present invention relates to a photosensitive resin composition and a method for producing a pattern using the same. Furthermore, the present invention relates to a method for manufacturing an organic EL display device or a liquid crystal display device including the pattern manufacturing method. Furthermore, it is related with the cured film formed by hardening | curing the photosensitive resin composition.

The TFT (Thin Film Transistor) substrate used in flat panel display devices such as organic EL display devices and liquid crystal display devices has an insulating inorganic transparent film such as SiOx and SiNx, and an oxide transparent conductive film such as ITO and IZO. , Al, Mo, Ti, Cu, W, a metal film made of a laminated film thereof, and a semiconductor film such as Si or an oxide semiconductor are provided in a pattern. For pattern formation of these functional inorganic films, a photosensitive resin composition (etching resist) is applied and dried (solvent removal), pattern exposure and development on each functional inorganic film, and the formed resist pattern is masked. Etching and processing methods are widely known.

In recent years, in order to make organic EL display devices and liquid crystal display devices have high-definition display characteristics, high resolution of functional inorganic film processing is required. In order to finely process a functional inorganic film with high definition, high resolution of a photosensitive resin composition that functions as a mask during etching is required. For this reason, the photosensitive resin composition from which a high-definition and fine pattern shape is obtained is examined (for example, patent document 1, patent document 2, etc.).

JP 9-325473 A Japanese Patent Laid-Open No. 10-326015

However, in recent years, in order to produce a high-definition display panel substrate with high productivity, production using a large-area glass substrate has become common, and the photosensitive resin composition used therefor The object is required to have further improved characteristics with respect to sensitivity. In addition, there are a wide variety of types of functional inorganic films that form patterns by etching, and etching resists having excellent adhesion to various functional inorganic films are required. The object of the present invention is to solve such a demand, and an object of the present invention is to provide a photosensitive resin composition having further improved sensitivity.

Under such circumstances, the inventor of the present application has intensively studied, and as a result, a photosensitive resin composition capable of obtaining a pattern with high sensitivity can be obtained by adding a photoacid generator having a predetermined structure to the photosensitive resin composition. The present invention has been completed.

一般式（１）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、Ｒ¹およびＲ²の少なくとも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；

一般式（２）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、Ｒ¹およびＲ²の少なくとも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し、Ｘ⁰は単結合またはアリーレン基を表す；

一般式（３）中、Ｒ¹は、アルキル基またはアリール基を表し、Ｒ²は、アルキル基、アリール基、またはヘテロアリール基を表す；Ｒ³～Ｒ⁶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す；但し、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵またはＲ⁵とＲ⁶が互いに結合して脂環または芳香環を形成してもよい；Ｘは、－Ｏ－または－Ｓ－を表す。
＜２＞一般式（３）中のＲ¹が、炭素数が３～１０のアルキル基または炭素数が６～１２のアリール基である、＜１＞に記載の感光性樹脂組成物。
＜３＞一般式（３）中のＲ¹が、分岐構造を有するアルキル基、環状のアルキル基、またはフェニル基である、＜１＞または＜２＞に記載の感光性樹脂組成物。
＜４＞一般式（３）で表される化合物が、下記化合物から選択される、＜１＞～＜３＞のいずれかに記載の感光性樹脂組成物；

＜５＞（Ａ）重合体成分が、（Ａ１）一般式（１）で表される構成単位（ａ１）を有する重合体、および、（Ａ２）一般式（２）で表される構成単位（ａ２）を有する重合体、の両方を含む、＜１＞～＜４＞のいずれかに記載の感光性樹脂組成物。
＜６＞（Ｄ）一般式（４）で表される化合物をさらに含有する、＜１＞～＜５＞のいずれかに記載の感光性樹脂組成物；

一般式（４）中、Ｒ¹は窒素原子を少なくとも１つ以上含む基を表し、Ａは２価の連結基を表し、Ｒ²は有機基を表す。
＜７＞（Ｅ）脂環式エポキシ化合物をさらに含有する、＜１＞～＜６＞のいずれかに記載の感光性樹脂組成物。
＜８＞（Ｃ）溶剤が、（Ｃ１）分子内にアセテート構造を２つ以上含有する溶剤と、（Ｃ１）分子内にアセテート構造を２つ以上含有する溶剤と異なる他の溶剤（Ｃ２）とを含む、＜１＞～＜７＞のいずれかに記載の感光性樹脂組成物。
＜９＞ディスプレイパネル基板形成に用いられるエッチングレジスト用感光性樹脂組成物である、＜１＞～＜８＞のいずれかに記載の感光性樹脂組成物。
＜１０＞エッチングレジスト用感光性樹脂組成物である、＜１＞～＜９＞のいずれかに記載の感光性樹脂組成物。
＜１１＞＜１＞～＜１０＞のいずれかに記載の感光性樹脂組成物を硬化してなる硬化膜。
＜１２＞（１）基板の少なくとも一方の面に、＜１＞～＜１０＞のいずれかに記載の感光性樹脂組成物を塗布する工程、
（２）乾燥により有機溶剤を揮発させ、感光性樹脂組成物層を形成する工程、
（３）感光性樹脂組成物層を露光する工程、
（４）露光された感光性樹脂組成物層を現像する工程、を含むパターンの製造方法。
＜１３＞＜１２＞に記載の方法でパターンを形成する工程、得られたパターンをエッチング用レジストとして用いてエッチングを行う工程、およびエッチングを行ったパターンをプラズマ処理または薬品処理により除去する工程、を含む、パターンの製造方法。
＜１４＞＜１２＞に記載のパターンの製造方法または＜１３＞に記載のパターンの製造方法を含む、有機ＥＬ表示装置または液晶表示装置の製造方法。 Specifically, the above-mentioned problem has been solved by the following means <1>, preferably <2> to <14>.
<1> (A) (A1) A polymer having a structural unit (a1) represented by the following general formula (1) and / or (A2) a structural unit (a2) represented by the following general formula (2) A polymer component comprising a polymer comprising
(B) a compound represented by the following general formula (3), and
(C) solvent,
Containing a photosensitive resin composition;

In general formula (1), 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 an aryl group, 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 (2), 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, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group;

In general formula (3), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group, or a heteroaryl group; R ³ to R ⁶ each independently represent a hydrogen atom, Represents an alkyl group, an aryl group, or a halogen atom; provided that R ³ and R ⁴ , R ⁴ and R ⁵ or R ⁵ and R ⁶ may be bonded to each other to form an alicyclic ring or an aromatic ring; , -O- or -S-.
<2> The photosensitive resin composition according to <1>, wherein R ¹ in the general formula (3) is an alkyl group having 3 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms.
<3> The photosensitive resin composition according to <1> or <2>, wherein R ¹ in the general formula (3) is an alkyl group having a branched structure, a cyclic alkyl group, or a phenyl group.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the compound represented by the general formula (3) is selected from the following compounds:

<5> (A) The polymer component has (A1) a polymer having the structural unit (a1) represented by the general formula (1), and (A2) a structural unit represented by the general formula (2) ( The photosensitive resin composition according to any one of <1> to <4>, comprising both a polymer having a2).
<6> (D) The photosensitive resin composition according to any one of <1> to <5>, further containing a compound represented by the general formula (4);

In general formula (4), R ¹ represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R ² represents an organic group.
<7> The photosensitive resin composition according to any one of <1> to <6>, further comprising (E) an alicyclic epoxy compound.
<8> (C) the solvent is (C1) a solvent containing two or more acetate structures in the molecule, and (C1) another solvent (C2) different from the solvent containing two or more acetate structures in the molecule; The photosensitive resin composition according to any one of <1> to <7>, comprising:
<9> The photosensitive resin composition according to any one of <1> to <8>, which is a photosensitive resin composition for an etching resist used for forming a display panel substrate.
<10> The photosensitive resin composition according to any one of <1> to <9>, which is a photosensitive resin composition for an etching resist.
<11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <10>.
<12> (1) A step of applying the photosensitive resin composition according to any one of <1> to <10> to at least one surface of the substrate,
(2) a step of volatilizing an organic solvent by drying to form a photosensitive resin composition layer,
(3) a step of exposing the photosensitive resin composition layer;
(4) A process for producing a pattern comprising a step of developing the exposed photosensitive resin composition layer.
<13> A step of forming a pattern by the method described in <12>, a step of etching using the obtained pattern as an etching resist, and a step of removing the etched pattern by plasma treatment or chemical treatment, A method for manufacturing a pattern, comprising:
<14> A method for producing an organic EL display device or a liquid crystal display device, comprising the method for producing a pattern according to <12> or the method for producing a pattern according to <13>.

The present invention makes it possible to provide a photosensitive resin composition with high sensitivity.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. 1 is a schematic cross-sectional view of an active matrix substrate in a liquid crystal display device. It is the figure which showed typically an example of the exposure form using a halftone phase difference mask.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL display device in the present invention refers to an organic electroluminescence display device. The polydispersity in the present invention refers to the value of Mw / Mn.

In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Furthermore, (meth) acrylic acid means acrylic acid and / or methacrylic acid.
The solid content in the present invention refers to a solid content at 25 ° C.

In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene converted values by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgelｇSuper AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

（一般式（１）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、Ｒ¹およびＲ²の少なくとも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。）

（一般式（２）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、Ｒ¹およびＲ²の少なくとも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し、Ｘ⁰は単結合またはアリーレン基を表す。）

（一般式（３）中、Ｒ¹は、アルキル基またはアリール基を表し、Ｒ²は、アルキル基、アリール基、またはヘテロアリール基を表す。Ｒ³～Ｒ⁶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す。但し、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵またはＲ⁵とＲ⁶が互いに結合して脂環または芳香環を形成してもよい。Ｘは、－Ｏ－または－Ｓ－を表す。）
　本発明の組成物は、化学増幅型ポジ型感光性樹脂組成物として好ましく用いられる。特に、エッチングレジスト用感光性樹脂組成物（例えばディスプレイパネル基板形成に用いられるエッチングレジスト用感光性樹脂組成物）として好ましく用いられる。
　以下、本発明の組成物について詳細に説明する。 The composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) includes (A) (A1) a polymer having a structural unit (a1) represented by the following general formula (1), and / Or (A2) a polymer component including a polymer containing the structural unit (a2) represented by the following general formula (2),
(B) a compound represented by the following general formula (3), and
(C) It contains a solvent.

(In the general formula (1), 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. A group or an aryl group, 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 the general formula (2), R ¹ and R ² each independently represents 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 an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group. .)

(In General Formula (3), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group, or a heteroaryl group. R ³ to R ⁶ each independently represents a hydrogen atom. Represents an alkyl group, an aryl group, or a halogen atom, provided that R ³ and R ⁴ , R ⁴ and R ^5, or R ⁵ and R ⁶ may be bonded to each other to form an alicyclic ring or an aromatic ring. Represents —O— or —S—.
The composition of the present invention is preferably used as a chemically amplified positive photosensitive resin composition. In particular, it is preferably used as a photosensitive resin composition for an etching resist (for example, a photosensitive resin composition for an etching resist used for forming a display panel substrate).
Hereinafter, the composition of the present invention will be described in detail.

<Polymer component (A)>
The composition of the present invention comprises (A1) a polymer component having the structural unit (a1) represented by the general formula (1) and / or (A2) the following general formula (2) as the polymer component (A). The polymer component which has a structural unit (a2) represented by this is included. (A1) The polymer component may contain a polymer other than the structural unit (a1) represented by the general formula (1). Moreover, (A2) polymer component may contain polymers other than the structural unit (a2) represented by General formula (2). The composition of the present invention contains at least one of (A1) polymer and (A2) polymer, and may contain only one type or two or more types.

The polymer component in the composition of the present invention is preferably alkali-insoluble, and the structural unit represented by the general formula (1) and / or the acid-decomposable group of the structural unit represented by the general formula (2) It is preferable that the resin be alkali-soluble when decomposed. Here, in the present invention, “alkali-soluble” means a coating film (thickness 3 μm) of a compound (resin) formed by applying a compound (resin) solution on a substrate and heating at 90 ° C. for 2 minutes. The dissolution rate in a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. is 0.01 μm / second or more. “Alkali insoluble” means that a compound (resin) solution is applied onto a substrate. The dissolution rate of the coating film (thickness 3 μm) of the compound (resin) formed by heating at 90 ° C. for 2 minutes with respect to a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. is 0.01 μm / It means less than a second.
Hereinafter, these polymer components will be described.

（一般式（１）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、Ｒ¹およびＲ²の少なくとも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。） << Polymer Component (A1) >>
The (A1) polymer component in the present invention is a polymer component including a polymer having the structural unit (a1) represented by the general formula (1). When the component (A1) has the structural unit (a1), a photosensitive resin composition excellent in resolving power and rectangularity can be obtained. The structural unit (a1) represented by the general formula (1) is a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected with an acid-decomposable group. The protected phenolic hydroxyl group can be produced by the decomposition of the protecting group with an acid.

(In the general formula (1), 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. A group or an aryl group, 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.)

R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. The alkyl group may have a substituent. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. The aryl group may have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

Examples of the substituent that the alkyl group and aryl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, and a cyano group. And halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. These substituents may further have a substituent.

Among these, R ¹ and R ² are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, one of R ¹ and R ² is a methyl group, and the other is a hydrogen atom. Particularly preferred is an atom.

R ³ represents an alkyl group or an aryl group. The alkyl group and aryl group represented by R ³ have the same meanings as the alkyl group and aryl group in R ¹ and R ² . R ³ is preferably a methyl group, an ethyl group, or a propyl group, and more preferably an ethyl group or a propyl group.

R ³ may be linked to R ¹ or R ² to form a cyclic ether. The cyclic ether formed by linking to R ¹ or R ² is preferably a 3- to 6-membered cyclic ether, more preferably a 5- to 6-membered cyclic ether.

Hereinafter, specific examples of the structural unit (a1) represented by the general formula (1) include the following structures, but the present invention is not limited to the following structures.

Among the structural units constituting the polymer (A1), the structural unit represented by the general formula (1) is preferably 5 to 40 mol%, more preferably 10 to 40 mol% of the structural unit of the polymer component (A1). Preferably, 20 to 35 mol% is more preferable.

（一般式（５）中、Ｒ⁴は水素原子またはメチル基である。） (A1) The polymer component preferably contains a polymer having a structural unit (a4) represented by the following general formula (5) in addition to the structural unit (a1) from the viewpoint of high sensitivity.
General formula (5)

(In general formula (5), R ⁴ is a hydrogen atom or a methyl group.)

R ⁴ is preferably a hydrogen atom.
The OH group may be any of p-, m-, and o-, but is preferably bonded to the p-position.

The structural unit represented by the general formula (5) is preferably 50 to 80 mol%, more preferably 60 to 70 mol% of the structural unit of the polymer component (A1). By setting it to 50 mol% or more, the effect of the present invention is more effectively exhibited, and by setting it to 80 mol% or less, it is possible to suppress excessive sensitivity and to make the exposure process margin more appropriate. be able to.

(A1) The polymer may contain other structural units in addition to the structural unit represented by the general formula (1) and the structural unit represented by the general formula (5). As such a structural unit, the other structural unit (a3) mentioned later is illustrated. The proportion of the other structural unit (a3) in the polymer (A1) is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less. As a lower limit, although 0 mol% may be sufficient, it can be set as 1 mol% or more, for example, Furthermore, it can be set as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

(A1) The protection rate of the polymer is preferably 1 to 60%, more preferably 5 to 50%, and still more preferably 10 to 40%. By setting it as such a range, an image disk and a sensitivity, resolution, and rectangularity will become favorable. The protection rate refers to the molar ratio of the acid-protected structural unit, where the total of the acidic structural unit and the acid-protected structural unit in the polymer (A1) is 100 mol%.

The weight average molecular weight (Mw) of the polymer (A1) is preferably in the range of 2000 to 15000, more preferably 5000 to 12000, and still more preferably 7500 to 12000. By setting it to 2000 or more, an effect that the formed pixel can maintain rectangularity after heating by post-baking is obtained, and by setting it to 15000 or less, an effect that sensitivity and line width stability are improved is obtained.

The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (A1) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. 0 to 1.5 is more preferable. By setting it as such a range, the rectangularity of a pixel becomes favorable.

<< polymer component (A2) >>
The (A2) polymer component in the present invention is a polymer component including a polymer having the structural unit (a2) represented by the general formula (2). When the component (A2) has the structural unit (a2), a photosensitive resin composition having excellent sensitivity can be obtained. The structural unit (a2) represented by the general formula (2) is a structural unit having a protected carboxyl group in which the carboxyl group is protected with an acid-decomposable group. The protected carboxyl group can be generated by the decomposition of the protective group with an acid.

（一般式（２）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、Ｒ¹およびＲ²の少なくとも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し、Ｘ⁰は単結合またはアリーレン基を表す。） Examples of the structural unit having a protected carboxyl group protected by an acid-decomposable group include the structural unit having a protected carboxyl group protected by an acid-decomposable group described in paragraphs 0021 to 0055 of JP2012-155288A. Examples of the structural unit having a protected carboxyl group protected with an acid-decomposable group described in paragraphs 0020 to 0052 of JP 2012-133301 A are exemplified, the contents of which are incorporated herein. Among them, the polymer component (A2) is preferably a polymer component having a structural unit (a2) having a group in which an acid group having a structure represented by the following general formula (2) is protected with an acid-decomposable group. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. 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 such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer. When the component (A2) has the structural unit (a2), a highly sensitive photosensitive resin composition can be obtained.
General formula (2)

(In the general formula (2), R ¹ and R ² each independently represents 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 an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group. .)

When R ¹ and R ² are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. 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.
R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
X ⁰ represents a single bond or an arylene group, and a single bond is preferable.

Preferable specific examples of the structural unit represented by the general formula (2) include the following structural units. R represents a hydrogen atom or a methyl group.

The structural unit represented by the general formula (2) is preferably 10 to 80 mol%, more preferably 20 to 80 mol%, and more preferably 30 to 70 mol% of the structural unit of the polymer component (A2).

(A2) In the constituent units constituting the polymer component, the content of constituent units other than the constituent unit represented by the general formula (2) is preferably 60 mol% or less, more preferably 50 mol% or less, 40 mol% or less is more preferable. As a lower limit, although 0 mol% may be sufficient, it can be set as 1 mol% or more, for example, Furthermore, it can be set as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

(A2) The protection ratio of the polymer component is preferably 20 to 100%, more preferably 40 to 90%, and still more preferably 60 to 90%. By setting it as such a range, a sensitivity improves and the difference (discrimination) of the solubility of an exposed part and an unexposed part becomes favorable. The protection rate refers to the molar ratio of the acid-protected structural unit, where the total of the acidic structural unit and the acid-protected structural unit in the polymer (A2) is 100 mol%.

The weight average molecular weight (Mw) of the polymer component (A2) is preferably in the range of 2000 to 50000, more preferably 5000 to 20000, and further preferably 7500 to 15000. By setting it to 2000 or more, an effect that the formed pixel can maintain rectangularity after heating by post-baking is obtained, and by setting it to 50000 or less, an effect that sensitivity and PED characteristics are improved is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

The polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer component (A2) is preferably 1.0 to 4.0, more preferably 1.2 to 3.0. More preferably, it is 5 to 2.0. By setting it as such a range, the characteristic excellent in the sensitivity and the rectangularity can be acquired.

-Mixing ratio of component (A1) and component (A2)-
It is preferable that the composition of this invention contains both (A1) and (A2) as a polymer component. These mass ratios are preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3, and still more preferably 4: 6 to 6: 4. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.

<< polymer component >>
In the present invention, the component (A) may have another structural unit (a3) in addition to the structural units (a1) and (a2). These structural units may contain either one of the polymer components (A1) and (A2), or both. In addition to the polymer component (A1) or (A2), the polymer component (A3) having substantially only (a1) and / or (a2) and having only the other structural unit (a3). You may have. In addition to the polymer component (A1) or (A2), the polymer component (A3) having substantially only (a1) and / or (a2) and having only another structural unit (a3) is included. In this case, the blending amount of the polymer component is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in the total polymer component.

There is no restriction | limiting in particular as a monomer used as 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 Examples include 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. it can. 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.

Specifically, the structural unit (a3) is styrene, methyl styrene, hydroxy styrene, α-methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxy Benzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, N-cyclohexylmaleimide, acrylonitrile, ethylene glycol monoa It can be mentioned a structural unit due preparative acetate mono (meth) acrylate. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

As the other structural unit (a3), it is preferable to include a repeating unit containing an acid group. By containing an acid group, it becomes easy to dissolve 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 of less than 7. 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 such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Examples include amide 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 in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. . For example, compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein. Of these, structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferred.

The structural unit containing an acid group is preferably 1 to 80% by mole, more preferably 1 to 50% by mole, and still more preferably 5 to 40% by mole of the structural unit of all polymer components.

In the present invention, as described above, in addition to the polymer component (A1) or (A2), the weight having only the other structural unit (a3) without substantially including (a1) and / or (a2). The coalescence component (A3) may be included.

Such a polymer is preferably a resin having a carboxyl group in the side chain. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

For example, benzyl (meth) acrylate / (meth) acrylic acid co-A-2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid co-A-2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid co-A-2-hydroxyethyl Methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer A-2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer It is below.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.
These polymers may contain only 1 type and may contain 2 or more types.

SMA 1000P, SMA2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC are commercially available as these polymers. -3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncry 690, Joncry 678, Joncry
67, Joncryl 586 (manufactured by BASF) or the like can also be used.

The composition of the present invention preferably contains the polymer component in a proportion of 60% by mass or more, more preferably 80% by mass or more, based on the total solid content.

（一般式（３）中、Ｒ¹は、アルキル基またはアリール基を表し、Ｒ²は、アルキル基、アリール基、またはヘテロアリール基を表す。Ｒ³～Ｒ⁶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す。但し、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵またはＲ⁵とＲ⁶が互いに結合して脂環または芳香環を形成してもよい。Ｘは、－Ｏ－または－Ｓ－を表す。） <(B) Compound Represented by General Formula (3)>
The composition of this invention contains the compound represented by (B) general formula (3), and the compound represented by (B) general formula (3) functions as a photo-acid generator.

(In General Formula (3), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group, or a heteroaryl group. R ³ to R ⁶ each independently represents a hydrogen atom. Represents an alkyl group, an aryl group, or a halogen atom, provided that R ³ and R ⁴ , R ⁴ and R ^5, or R ⁵ and R ⁶ may be bonded to each other to form an alicyclic ring or an aromatic ring. Represents —O— or —S—.

R ¹ represents an alkyl group or an aryl group. The alkyl group is preferably a branched alkyl group or a cyclic alkyl group. The alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable, and when the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable. Examples of the alkyl group include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. , 2-ethylhexyl group, cyclohexyl group, cyclopentyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group. The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.

In the composition of the present invention, R ¹ is preferably an alkyl group from the viewpoint of transparency, and R ¹ is an alkyl group having a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity. An alkyl group having a cyclic structure having 5 to 7 carbon atoms or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. By adopting such a bulky group (particularly a bulky alkyl group) as R ¹ , it becomes possible to further improve the transparency.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.

R ² represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R ² is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group, and preferably a methyl group It is.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, and a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable. Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R ² may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R1 represents may have.
R ² is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.

R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom). The alkyl group represented by R ³ to R ⁶ has the same meaning as the alkyl group represented by R ² , and the preferred range is also the same. The aryl group represented by R ³ to R ⁶ has the same meaning as the aryl group represented by R ¹ , and the preferred range is also the same.
Among R ³ to R ⁶ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form a ring, and the ring may form an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
R ³ to R ⁶ are each a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ^6. A benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring Is more preferable.
Preferred embodiments of R ³ to R ⁶ are as follows.
(Aspect 1) Preferably, at least one is a hydrogen atom and at least two are hydrogen atoms.
(Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is 3 or less in total. Preferably it is one or less.
(Aspect 3) R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring.
(Aspect 4) An aspect satisfying the above aspects 1 and 2 and / or an aspect satisfying the above aspects 1 and 3.

X represents -O- or -S-.

Specific examples of the general formula (3) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

In the composition of the present invention, (B) the compound represented by the general formula (3) is 100 parts by mass of the total resin components (preferably the total solid content, more preferably the total of the polymer) in the photosensitive resin composition. In contrast, 0.1 to 10 parts by mass is preferably used, and 0.5 to 5 parts by mass is more preferably used. Two or more kinds can be used in combination.

In the present invention, other photoacid generators may be included. As another photoacid generator, an oxime sulfonate compound is preferable. Hereinafter, the oxime sulfonate compound preferably used in the present invention will be described.

（式（Ｂ１－２）中、Ｒ⁴²は、置換されていても良いアルキル基またはアリール基を表し、Ｘ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Ｘは同一でも異なっていてもよい。） The first embodiment of the oxime sulfonate compound as another photoacid generator that can be used in the present invention is an oxime sulfonate compound represented by the general formula (B1-2).
General formula (B1-2)

(In the formula (B1-2), R ⁴² represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents 0-3. Represents an integer, and when m4 is 2 or 3, a plurality of Xs may be the same or different.

Preferred ranges of R ^42, the same as the preferable range of the R ^21.
The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Further, the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1. In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

（式（Ｂ１－３）中、Ｒ⁴³は式（Ｂ１－２）におけるＲ⁴²と同義であり、Ｘ¹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。） A second embodiment of the oxime sulfonate compound as another photoacid generator that can be used in the present invention is an oxime sulfonate compound represented by the general formula (B1-3).
General formula (B1-3)

(In Formula (B1-3), R ⁴³ has the same meaning as R ⁴² in Formula (B1-2), and X ¹ is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the above general formula (B1-3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n—. A propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
As specific examples of the compound represented by the general formula (B1-3) and preferable examples of the oxime sulfonate compound, the description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to, and the contents thereof are described in this application. Incorporated in the description.

A third embodiment of the oxime sulfonate compound as another photoacid generator that can be used in the present invention is a compound represented by the general formula (OS-1).

In the general formula (OS-1), R ¹⁰¹ 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. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ² —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ¹⁰⁵ to R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ¹²¹ to R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.
R ¹²¹ to R ¹²⁴ are preferably a hydrogen atom, a halogen atom and an alkyl group, and an embodiment in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R ¹²¹ to R ¹²⁴ 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, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is hereby incorporated by reference.

（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。）
　上記一般式（ＯＳ－３）～（ＯＳ－５）については、例えば、特開２０１２－１６３９３７号公報の段落番号００９８～０１１５の記載を参酌でき、この内容は本願明細書に組み込まれる。 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 b-34), but the present invention is not limited thereto.
In the present invention, the fourth embodiment of the oxime sulfonate compound as another photoacid generator that can be used in the present invention is represented by the following general formula (OS-3), general formula (OS-4), or An oxime sulfonate compound represented by the general formula (OS-5) is preferable.

(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; 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.)
Regarding the above general formulas (OS-3) to (OS-5), for example, the description of paragraph numbers 0098 to 0115 of JP2012-163937A can be referred to, and the contents thereof are incorporated in the present specification.

In addition, a fifth embodiment of the oxime sulfonate compound as another photoacid generator that can be used in the present invention is described in, for example, paragraph 0117 of JP2012-163937A. A compound represented by any one of (OS-6) to (OS-11), the contents of which are incorporated herein.
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. The contents of which are incorporated herein by reference.
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. The contents of which are incorporated herein by reference. The present invention is not limited to these.

（一般式（Ｂ１－４）中、Ｒ¹は、アルキル基またはアリール基を表し、Ｒ²は、アルキル基、アリール基、またはヘテロアリール基を表す。Ｒ³～Ｒ⁶は、それぞれ、水素原子、アルキル基、アリール基、ハロゲン原子を表す。但し、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、またはＲ⁵とＲ⁶が結合して脂環または芳香環を形成してもよい。Ｘは、－Ｏ－またはＳ－を表す。） The sixth embodiment of the oxime sulfonate compound as another photoacid generator that can be used in the present invention is an oxime sulfonate compound represented by the general formula (B1-4).
General formula (B1-4)

(In the general formula (B1-4), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group, or a heteroaryl group. R ³ to R ⁶ each represents a hydrogen atom. Represents an alkyl group, an aryl group, or a halogen atom, provided that R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form an alicyclic ring or aromatic ring. , -O- or S-.

R ¹ represents an alkyl group or an aryl group. The alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
The alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable, and when the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
Examples of the alkyl group include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.

In the photosensitive resin composition of the present invention, R ¹ is preferably an alkyl group from the viewpoint of transparency, and R ¹ has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity. An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. . By adopting such a bulky group (particularly a bulky alkyl group) as R ¹ , it becomes possible to further improve the transparency.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.

R ² represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R ² is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R ² may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R < ¹ > may have.
R ² is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.

R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom). The alkyl group represented by R ³ to R ⁶ has the same meaning as the alkyl group represented by R ² , and the preferred range is also the same. The aryl group represented by R ³ to R ⁶ has the same meaning as the aryl group represented by R ¹ , and the preferred range is also the same.
Among R ³ to R ⁶ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form a ring, and the ring may form an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
R ³ to R ⁶ are each a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ^6. A benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring Is more preferable.
Preferred embodiments of R ³ to R ⁶ are as follows.
(Aspect 1) At least two are hydrogen atoms.
(Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is one or less.
(Aspect 3) R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring.
(Aspect 4) An aspect satisfying the above aspects 1 and 2 and / or an aspect satisfying the above aspects 1 and 3.
X represents —O— or S—.

When the composition of the present invention contains other acid generators in addition to the compound represented by the general formula (3), the blending amount thereof is the total resin component (preferably the total solid content) in the photosensitive resin composition. More preferably, the total of the polymer) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight. Two or more kinds can be used in combination.

<(C) Solvent>
The composition of the present invention contains (C) a solvent containing two or more acetate structures in the molecule as the (C) solvent. By blending such a solvent, it becomes a plasticizer for an appropriate coating film, and by promoting the appropriate capture of an acid by a quencher and an alicyclic epoxy compound described later, sensitivity and line width stability It becomes possible to improve resolution and rectangularity. It is preferable that the composition of this invention is prepared as a solution which melt | dissolved the essential component of this invention and the arbitrary component of the below-mentioned in (C) solvent.

(C1) The solvent containing two or more acetate structures in the molecule is not particularly limited as long as it contains two or more acetate structures in the molecule, but the number of acetate structures in the molecule is preferably 2 to 4 Two are more preferred.
Further, (C1) the solvent containing two or more acetate structures in the molecule is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 300 ° C., preferably a solvent having a boiling point of 180 ° C. or higher and lower than 270 ° C., and 200 ° C. or higher and lower than 270 ° C. Those are more preferred. The boiling point is a boiling point at 1 atm unless otherwise specified. Further, in the case of a solvent mixture containing two or more kinds of solvents, the boiling point is a weighted average of the boiling points of the respective solvents with respect to the total solvent at respective weight ratios.

(C1) Examples of the solvent containing two or more acetate structures in the molecule include 1,2-ethylenediol diacetate, 1,2-propanediol diacetate, 1,3-propanediol diacetate, Examples include 1,2-butanediol diacetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, triacetin, and the like. (C1) The solvent which contains two or more acetate structures in a molecule | numerator can be used individually by 1 type or in mixture of 2 or more types.

In the composition of the present invention, the content of the solvent (C1) having two or more acetate structures in the molecule is preferably 1 to 10 parts by mass per 100 parts by mass of the photosensitive resin composition. More preferably, it is part by mass.

In addition, it is preferable that (C2) another solvent is further added to the solvent (C1) containing two or more acetate structures in the molecule, if necessary, to obtain a mixed solvent. In the case of a mixed solvent, it is preferable to select (C2) another solvent so that the weighted average of the boiling points of the respective solvents with respect to the total solvent is 130 ° C. or higher and lower than 300 ° C. (C2) Other solvents may be used alone or in combination of two or more.

(C2) The other solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., or a solvent having a boiling point of 160 ° C. or higher. Specifically, propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol mono Solvents containing one acetate structure in the molecule, such as ethyl ether acetate (boiling point 158 ° C); propylene glycol methyl-n-butyl ether (boiling point 155 ° C), propylene glycol methyl-n-propyl ether (boiling point 131 ° C) it can.
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), diethylene glycol monoethyl ether acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (Boiling point 175 ° C.).

In addition to the other solvents, known solvents can be used, such as 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 glycol monoalkyl ether acetates, esters, ketones And amides and lactones. Further, specific examples of the (C2) solvent used in the composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP 2011-221494A, the contents of which are incorporated herein. It is.

If necessary, 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-nonal, benzyl alcohol, Solvents such as anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate 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 a single type or a combination of two types, 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 ether acetates are more preferably used in combination.

The content of the (C2) solvent in the composition of the present invention is preferably 70 to 95 parts by mass, more preferably 80 to 95 parts by mass per 100 parts by mass of the photosensitive resin composition.

The amount of the (C) solvent in the present invention is preferably 70% by mass or more of the photosensitive resin composition, more preferably 85% by mass or more, and particularly preferably 90% by mass or more. The upper limit is preferably 99% by mass or less.
In the present invention, the blending ratio (mass ratio) of the (C1) solvent and the (C2) solvent is preferably 0.1 to 10: 99.9 to 90, more preferably 0.5 to 5: 99.5 to 95. . The viscosity of the photosensitive resin composition used in the present invention is preferably in the range of 2.0 to 8 mPa · s, more preferably in the range of 2.5 to 6 mPa · s. Moreover, the viscosity in this invention shall be a viscosity in 25 degreeC.

<Basic compound>
The composition of the present invention may contain 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 JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
These basic compounds may be used alone or in combination of two or more.

（一般式（４）中、Ｒ¹は窒素原子を少なくとも１つ以上含む基を表し、Ａは２価の連結基を表し、Ｒ²は有機基を表す。） It is preferable that the composition of this invention contains the compound represented by (D) following General formula (4).
General formula (4)

(In general formula (4), R ¹ represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R ² represents an organic group.)

R ¹ represents a group containing at least one nitrogen atom, preferably a group containing 1 to 3 nitrogen atoms, and more preferably a group represented by —NR ³ R ⁴ .
R ¹ is preferably a group composed of 1 to 10 carbon atoms, an oxygen atom, and 1 to 3 heteroatoms including at least one nitrogen atom. In this case, examples of the hetero atom include an oxygen atom and a sulfur atom, and an oxygen atom is preferable. R ¹ is preferably a cyclic group, more preferably a 5-membered or 6-membered cyclic group.
R ³ and R ⁴ each represents an organic group. As the organic group, an alkyl group, an alkenyl group, or a group composed of at least one of —O—, —S— and —N— is preferable. R ³ and R ⁴ are each preferably a group having 1 to 3 carbon atoms. R ³ and R ⁴ may be bonded to each other to form a ring, and preferably forms a ring.

Preferred embodiments of R ¹ include the following embodiments.
(1) An embodiment in which R ¹ is a group represented by —NR ³ R ⁴ and R ³ and R ⁴ are bonded to each other to form a ring, or R ³ and R ⁴ are each The aspect which is an aliphatic hydrocarbon group.
(2) Embodiment in which R ¹ is a group represented by —NR ³ R ⁴ and R ³ and R ⁴ are bonded to each other to form a 5-membered or 6-membered ring, or R ³ and R ⁴ Are each a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms.
(3) R ¹ is a group represented by —NR ³ R ⁴ , and R ³ and R ⁴ are bonded to each other to form two or more heteroatoms (at least one is a nitrogen atom and the rest are oxygen atoms or A mode in which a 5-membered ring or a 6-membered ring is formed, or a straight-chain aliphatic hydrocarbon group having 1 to 4 carbon atoms, each of R ³ and R ⁴ The aspect which is.

Specific examples of R ¹ include, for example, morpholino group, hydrazino group, pyridyl group, imidazolyl group, quinolyl group, piperidyl group, pyrrolidinyl group, pyrazonyl group, oxazolyl group, thiazolyl group, benzoxazolyl group, benzimidazolyl group, A benzthiazolyl group, a pyrazinyl group, a diethylamino group, etc. are mentioned. Of these, a morpholino group is preferable.

R ² represents an organic group. The organic group is preferably a hydrocarbon group or a group comprising a hydrocarbon group and at least one of —O— and —C (═O) —. R ² preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
R ² is more preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, or a group composed of these and at least one of —O— and —C (═O) —. These groups may have a substituent, and examples of the substituent include a halogen atom.
When R ² is an alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group is preferable. When R ² is a cyclic alkyl group, a 5-membered or 6-membered cyclic alkyl group is preferred.
When R ² is an aryl group, a phenyl group and a naphthyl group are exemplified, and a phenyl group is more preferable.

Preferred embodiments of R ² include the following embodiments.
(1) A mode of being a straight-chain alkylene group having 1 to 4 carbon atoms (preferably 2 or 3).

A represents a divalent linking group, preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and further preferably a hydrocarbon group having 2 to 6 carbon atoms. Examples of the hydrocarbon group include an alkylene group and an arylene group, and an alkylene group is preferable.
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a cyclohexylene group, and a cyclopentylene group. Examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and a naphthylene group. In the present invention, a methylene group, an ethylene group, and a propylene group are particularly preferable, and an ethylene group or a propylene group is more preferable.

Preferred embodiments of A include the following embodiments.
(1) An embodiment in which the alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms, a 5- or 6-membered cyclic alkyl group, or a phenyl group.

In the compound represented by the general formula (4), a preferred embodiment of R ^1, a preferred embodiment of R ^{2 and} a preferred embodiment of A are exemplified as a particularly preferred embodiment.

The compound represented by the general formula (4) is preferably represented by the general formula (4-2).

（一般式（４－２）中、Ｒ²は有機基を表し、Ａは２価の連結基を表す。）
　Ｒ²は、一般式（４）におけるＲ²と同義であり、好ましい範囲も同義である。
　Ａは、一般式（４）におけるＡと同義であり、好ましい範囲も同義である。
　特に、一般式（４－２）において、以下の態様が好ましい。
（１）Ａは炭素数１～４の直鎖のアルキレン基であり、Ｒ²は、直鎖、分岐、または環状のアルキル基である態様。
（２）Ａは炭素数２または３のアルキレン基であり、Ｒ²は、炭素数２～６の直鎖、分岐、または環状のアルキル基である態様。 Formula (4-2)

(In the general formula (4-2), R ² represents an organic group, and A represents a divalent linking group.)
R ² has the same meaning as R ² in the general formula (4), the preferred range is also the same.
A is synonymous with A in General formula (4), and its preferable range is also synonymous.
In particular, in the general formula (4-2), the following embodiments are preferable.
(1) An embodiment in which A is a linear alkylene group having 1 to 4 carbon atoms, and R ² is a linear, branched, or cyclic alkyl group.
(2) A mode in which A is an alkylene group having 2 or 3 carbon atoms, and R ² is a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms.

Specific examples of the general formula (4) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Et represents an ethyl group.

The composition of the present invention preferably contains the component (D) in a proportion of 0.001 to 5 parts by mass, more preferably 0.003 to 2 parts by mass with respect to 100 parts by mass of the total solid content. The content is preferably 0.005 to 1 part by mass. (D) Only 1 type may be sufficient as a component and 2 or more types may be sufficient as it. In the case of two or more types, the total is preferably in the above range.

<(E) Alicyclic epoxy compound>
The composition of the present invention preferably contains an alicyclic epoxy compound as a crosslinking agent. Since the alicyclic epoxy compound quickly traps the acid generated by the acid generator, the compound is considered to be a photosensitive resin composition excellent in sensitivity, line width stability, resolution and rectangularity. It is done.
The alicyclic epoxy group possessed by the alicyclic epoxy compound used in the present invention is not particularly limited, and examples thereof include an alicyclic epoxy group directly added to a cyclic aliphatic hydrocarbon. Is preferably a 3- to 10-membered ring, and more preferably a 5- to 6-membered ring. Among them, preferred is an alicyclic epoxy group represented by the following.

（一般式（６）中、ｎは１～４の整数を表す。Ｒ¹は炭素数１～１５の有機基を表す。） The alicyclic epoxy compound is preferably represented by the following general formula (6).

(In general formula (6), n represents an integer of 1 to 4. R ¹ represents an organic group having 1 to 15 carbon atoms.)

R ¹ represents an organic group having 1 to 15 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond. R ¹ is an n-valent linking group.

The number of carbon atoms in the organic group represented by R ¹ is preferably 1-8, and more preferably 1-6. The organic group is a hydrocarbon group, a hydrocarbon group, a silyl group, —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). ) Is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.

When the epoxy group in the alicyclic epoxy compound is opened, when the acid is generated by the acid generator, the opened epoxy group is bonded to the functional group of the polymer and the degree of freedom of the alicyclic epoxy compound is lost. May be. For this reason, it is preferable that the number of epoxy groups is small. n represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.

（一般式（６－２）中、Ｒ²は炭素数１～１５の有機基を表す。）
　Ｒ²は炭素数１～１５の有機基を表し、分岐していても不飽和結合を有していてもよく、脂肪族環または芳香環の環状構造を有してもよい。また、これらの基は、酸素、硫黄、窒素、リン、ホウ素、ハロゲン原子を有していてもよい。また、置換基を有していてもよく、置換基同士が互いに結合を形成していても良い。また、Ｒ²は２価の連結基である。 A preferred embodiment of the alicyclic epoxy compound is exemplified by a compound represented by the following general formula (6-2).

(In the general formula (6-2), R ² represents an organic group having 1 to 15 carbon atoms.)
R ² represents an organic group having 1 to 15 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic ring or an aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond. R ² is a divalent linking group.

The organic group of R ² preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group. The hydrocarbon group is preferably an alkylene group.

（一般式（６－３）中、Ｒ³は炭素数１～１５の有機基を表す。）
　Ｒ³は炭素数１～１５の有機基を表し、分岐していても不飽和結合を有していてもよく、脂肪族環または芳香環の環状構造を有してもよい。また、これらの基は、酸素、硫黄、窒素、リン、ホウ素、ハロゲン原子を有していてもよい。また、置換基を有していてもよく、置換基同士が互いに結合を形成していても良い。また、Ｒ³は２価の連結基である。 As a preferred embodiment of the alicyclic epoxy compound, a compound represented by the following general formula (6-3) is also exemplified.

(In the general formula (6-3), R ³ represents an organic group having 1 to 15 carbon atoms.)
R ³ represents an organic group having 1 to 15 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond. R ³ is a divalent linking group.

The number of carbon atoms in the organic group of R ³ is preferably 1-8, and more preferably 1-6. The organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group. The hydrocarbon group is preferably an alkylene group.

Specific examples of the above formulas (6) to (6-3) include the following compounds, but the present invention is not particularly limited thereto.

The production method of the alicyclic epoxy compound used in the present invention is not limited. For example, Maruzen KK Publishing, 4th Edition Experimental Chemistry Course 20 Organic Synthesis II, 213-, 1992, Ed. by Alfred Hasfner, The chemistry of heterocyclic compounds-Small Ring Heterocycles part3 oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, adhesive, Vol. 29 No. 12, 32,1985, Yoshimura, adhesive, Vol. 30, No. 5 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, JP-A-1-100388, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.

The molecular weight of the alicyclic epoxy compound used in the present invention is preferably less than 1000, and more preferably less than 500. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively. The lower limit is not particularly defined, but is usually 100 or more.

The addition amount of the alicyclic epoxy compound in the composition of the present invention is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition, preferably 0.1 to 3 The amount is more preferably part by mass, and further preferably 0.1 to 1.5 parts by mass. A plurality of alicyclic epoxy compounds may be used in combination, and in that case, all the alicyclic epoxy compounds are added together to calculate the content.

<Other ingredients>
In addition to the above-described components, the composition of the present invention includes (F) an alkoxysilane compound, (G) a crosslinking agent, (H) a sensitizer, (J) a surfactant, and (K) an oxidation, as necessary. An inhibitor can be preferably added. Further, the composition of the present invention includes known acid proliferating agents, development accelerators, plasticizers, thermal radical generators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors. Additives can be added. Examples of other components include compounds described in [0180] [0228] of JP2011-221494A.

(F) Alkoxysilane Compound The composition of the present invention preferably contains (F) an alkoxysilane compound (also referred to as “(F) component”). When the alkoxysilane compound is used, the adhesion between the film formed from the composition of the present invention and the substrate can be further improved, and the properties of the film formed from the composition of the present invention can be adjusted. As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. The alkoxy group contained in the alkoxysilane compound preferably has 1 to 5 carbon atoms.
The (F) alkoxysilane compound that can be used in the composition of the present invention is an inorganic material serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. Preferably, the compound improves the adhesion between the insulating film and the insulating film. Specifically, a known silane coupling agent or the like is also effective.
Examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred.

The following compounds can also be preferably employed.

In the above, Ph is a phenyl group.

The (F) alkoxysilane compound in the composition of the present invention is not limited to the above, and a known one can be used. An alkoxysilane compound can be used individually by 1 type or in combination of 2 or more types.
The content of the (F) alkoxysilane compound in the composition of the present invention is preferably 0.1 to 30 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition. Is more preferable. When 2 or more types are included, the total amount is preferably within the above range.

(G) Crosslinking agent It is preferable that the composition of this invention contains crosslinking agents other than the compound mentioned above as needed. By adding a crosslinking agent, the cured film obtained by the composition of the present invention can be made a stronger film.
As the cross-linking agent, reference can be made to the incorporated description in paragraphs 0157 to 0168 of JP2013-210607A, the contents of which are incorporated herein.

(H) Sensitizer The composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with the compound represented by (B) the general formula (3). 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. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavin), acridones (eg, acridone, 10-butyl-2-chloroacridone, 10-butylacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryl , Base styryls (eg 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (eg 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2 , 3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolidine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

The addition amount of the sensitizer in the composition of the present invention is preferably 0 to 1000 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition, and is 10 to 500 parts by mass. Is more preferably 50 to 200 parts by mass.
A sensitizer may be used individually by 1 type and can also use 2 or more types together.

(J) Surfactant The composition of the present invention may contain (J) a surfactant. (J) As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, 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) Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
In addition, the surfactant contains the structural unit A and the structural unit B represented by the following general formula (J-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 (Mw) of 1,000 or more and 10,000 or less can be given as a preferred example.

　（式（Ｊ－１）中、Ｒ⁴⁰¹およびＲ⁴⁰³はそれぞれ、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。） General formula (J-1)

(In the formula (J-1), R ⁴⁰¹ and R ⁴⁰³ each represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or a carbon number. 1 represents 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 a numerical value of 10 mass% to 80 mass%. 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 (J-2). R ⁴⁰⁵ in formula (J-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.

General formula (J-2)

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

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
In the composition of the present invention, the amount of (J) surfactant added is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. The amount is more preferably 001 to 10 parts by mass, and further preferably 0.01 to 3 parts by mass.

(K) Antioxidant The composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Among these, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur oxidations, in particular, from the viewpoint of coloring of the cured film and reduction of film thickness Inhibitors are preferred. These may be used individually by 1 type and may mix 2 or more types.
Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40, and ADK STAB AO. -50, ADK STAB AO-51, ADK STAB LA-52, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB LA-81, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A -611, ADK STAB A-612, ADK STAB A-613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB P-10-Z, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP, ADK STAB CDA-6, ADK STAB CDA-6S 27, ADK STAB ZS-90, ADK STAB ZS-91 (manufactured by ADEKA), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irga Knox 1330, Irganox 1520L, Irganox 3114, Irganox 1726 Irgafos 168, Irugamoddo 295, (manufactured by BASF (Ltd.)) Tinuvin 144, Santonox R (Monsanto Co., Ltd.). In addition, compounds described in paragraphs 0108 to 0116 of JP 2011-227106 A can also be mentioned. Among these, ADK STAB AO-60, ADK STAB AO-80, Irganox 1726, Irganox 1035, and Irganox 1098 are listed.
Can be preferably used.

When blended, the content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. The content is preferably 0.5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
Further, as an additive other than the antioxidant, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators and the like are used in the composition of the present invention. You may add to.

(L) Ultraviolet absorber An ultraviolet absorber can be used for the composition of this invention. By using the ultraviolet absorber, the linearity of the resist pattern during patterning on a substrate having a non-smooth surface is improved.
As the ultraviolet absorber that can be used in the present invention, a known one can be used as long as it has absorbance at the photosensitive wavelength of the photoacid generator.
As the ultraviolet absorber, benzotriazole, benzophenone, triazine, stilbene, coumarin, anthracene, azo dye, pararosolic acid, curcumin and the like can be used. Among these, benzophenone series, azo dyes, curcumin, and the like are preferable from the viewpoints of solubility and developability of materials.
As specific examples of the ultraviolet absorber, for example, the description in paragraph 0080 of JP 2010-059267 A can be referred to, and the contents thereof are incorporated in the present specification.
When the photosensitive resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition, 0.1 Is more preferably 5 parts by mass, and further preferably 0.5-2 parts by mass.
An ultraviolet absorber may be used individually by 1 type, and may mix 2 or more types. When two or more types of ultraviolet absorbers are included, the total amount is preferably within the above range.

　等を挙げることができる。
　酸増殖剤の感光性組成物への含有量は、配合する場合、光酸発生剤１００質量部に対して、１０～１，０００質量部とするのが、露光部と未露光部との溶解コントラストの観点から好ましく、２０～５００質量部とするのがさらに好ましい。酸増殖剤は、１種類のみ含んでいても良いし、２種類以上含んでいても良い。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 [Acid multiplication agent]
The composition of the present invention can use an acid proliferating agent for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
Specific examples of the acid proliferating agent include paragraph numbers 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39 of JP-T 9-512498. The compounds described on line 12 to page 47, line 2 can be mentioned, the contents of which are incorporated herein.
Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
In particular

Etc.
When blended, the content of the acid proliferating agent in the photosensitive composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator. From the viewpoint of contrast, it is more preferably 20 to 500 parts by mass. Only one type of acid proliferating agent may be included, or two or more types thereof may be included. When two or more types are included, the total amount is preferably within the above range.

[Development accelerator]
The composition of the present invention can contain a development accelerator.
As the development accelerator, the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.

A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
When blended, the development accelerator in the composition of the present invention is preferably 0 to 30 parts by mass, preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition from the viewpoint of sensitivity and residual film ratio. 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable. When two or more types of development accelerators are included, the total amount is preferably within the above range.
In addition, as other additives, thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1, can be used. Is incorporated herein by reference.

<Method for preparing photosensitive resin composition>
Each component is mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio. 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.

[Pattern manufacturing method]
Next, the pattern manufacturing method of the present invention will be described.
The pattern manufacturing method of the present invention includes at least the following steps.
(1) Step of applying the photosensitive resin composition for use in the present invention to at least one surface of the substrate (2) Step of volatilizing the organic solvent by drying to form a photosensitive resin composition layer (3) The above photosensitive Step of exposing the photosensitive resin composition layer (4) Step of developing the exposed photosensitive resin composition layer

Furthermore, the present invention also discloses a pattern manufacturing method in which a pattern is formed by etching using the pattern obtained by the pattern manufacturing method. That is, a step of forming a pattern by the above pattern manufacturing method, (5) a step of etching using the obtained pattern as an etching resist, and (6) a plasma treatment or a chemical treatment of the etched pattern. Disclosed is a method for manufacturing a pattern.

In the coating step (1), it is preferable to apply the composition of the present invention on a substrate to form a wet film containing a solvent. Before applying the photosensitive resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include an inorganic substrate, a resin, and a resin composite material. For example, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, a tungsten film, a tungsten alloy film, and an oxide doped with tin oxide. Metal substrates such as indium (ITO, IZO) film, tin oxide film, Ni, Cu, Fe, Al, etc .; quartz (SiOx), glass, silicon nitride film, silicone, silicone nitride, polysilicon, silicone oxide, amorphous silicone film IGZO and other oxide semiconductor films, SOG, silicon substrates such as glass square substrates for manufacturing liquid crystal elements; polymer substrates such as paper, polyester film, polycarbonate film, polyimide film, and other polymer substrates used in organic EL display devices ; Ceramic material, Ti substrate, Al substrate Etc. can be used. Among them, in the present invention, an ITO substrate, a molybdenum substrate, a silicon substrate, a SiOx substrate, a SiNx substrate, a Cu substrate, or an Al substrate is preferable, and an ITO substrate, a molybdenum substrate, a SiOx substrate, a SiNx substrate, or a silicon substrate is preferable. It is more preferable.
The shape of the substrate may be a plate shape or a roll shape. Moreover, there is no limitation on the thickness of the inorganic film to be etched, and the film may be a film with only a few nm of the ideogram or the material of the whole substrate. Moreover, the case where the base-material surface is the composite surface of the said material (board | substrate) may be sufficient.
The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 μm.

In the drying step (2), the heating conditions of the drying step of removing the solvent from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate are preferably 70. The temperature is about 130 ° C. for about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.

In the exposure step (3), the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used, and g-line (436 nm), i-line (365 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, since the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group, PEB is not necessarily performed. A positive image can also be formed by development.

When exposure is performed using a mask, a halftone mask can be used in addition to a normal mask.
<Halftone phase difference mask>
The halftone (HT) phase difference mask is a mask that cancels the diffracted light to the periphery of the pattern at the time of exposure with light having an opposite phase. As the halftone (HT) phase difference mask 30, a transparent substrate 32 provided with a phase shifter portion (phase change film 31) having a specific transmittance on the outer periphery of an exposure pattern is used. An exposure mode using this is schematically shown in FIG. In FIG. 3, s indicates a transmission part, k indicates an exposure part (substrate), 33 indicates a light intensity distribution, 34 indicates a light amplitude distribution (positive phase), and 35 indicates a light amplitude distribution (reverse phase). Yes. As can be seen from this figure, according to this exposure mode, the light whose waveforms are inverted are irradiated adjacent to each other, so that the difference in the amount of light at the edge portion of the pattern is increased and the exposure resolution can be improved. A processing method employing such an exposure method is known, and for example, the procedures and conditions described in JP 2010-8868 A and JP 2007-241136 A can be referred to. The form of the halftone phase difference mask applied to the present invention is not particularly limited. For example, a laminated mask in which the phase shifter layer is divided into a transmittance adjustment layer and a phase adjustment layer may be used.
As described above, a halftone phase difference mask refers to a mask having a transmission part and a phase shifter part. In the present invention, in addition to a mask having a transmission part and a phase shifter part, a transmission part, a phase You may use the mask which has a shifter part and a light-shielding part.

In the developing step (4), a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having an acid group that easily dissolves in an alkaline developer, such as a carboxyl group or a phenolic hydroxyl group.
The developer used in the development step preferably contains an aqueous solution of a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; alcohol amines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] Cycloaliphatic amines such as -5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably from 9.0 to 15.0, more preferably from 10.0 to 14.0. The concentration of the developer is preferably from 0.1 to 20% by mass, more preferably from 0.1 to 5.0% by mass.
The development time is preferably 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method, a shower method, and the like. After development, washing with running water can be performed for 30 to 300 seconds to form a desired pattern. A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

In the step (5), the method for etching the substrate using the resist pattern as a mask is not particularly limited, and a known method can be used.

The pattern manufacturing method of the present invention may include (6) a step of removing the resist pattern. There is no restriction | limiting in particular as a method of removing the said resist pattern, A well-known method can be used. The removal of the resist pattern is preferably performed by plasma treatment or chemical treatment.

[Curing film]
In the present invention, (4) after the developing step, the pattern corresponding to the unexposed area obtained by development is predetermined at a predetermined temperature, for example, 100 to 250 ° C., using a heating device such as a hot plate or an oven. A cured film having excellent hardness and the like can be formed by performing the heat treatment for 5 to 60 minutes on a hot plate, and 30 to 90 minutes on an oven.
Moreover, when performing heat processing, transparency of a cured film can also be improved by performing in nitrogen atmosphere.
Prior to the heat treatment, the substrate on which the cured film is formed in a pattern can be re-exposed with actinic rays and then heated.

The exposure in the re-exposure step may be performed by the same means as in the exposure step. In the re-exposure step, the entire surface of the substrate on which the film is formed by the composition of the present invention is exposed. It is preferable. A preferable exposure amount for the re-exposure step is 100 to 1,000 mJ / cm ² .

[pattern]
The pattern of the present invention is a pattern obtained by etching the substrate using a resist pattern obtained by curing the composition of the present invention as a mask. The pattern of the present invention is preferably ITO, molybdenum, silicon, SiOx, SiNx, Cu, or Al, and more preferably ITO, molybdenum, SiOx, SiNx, or silicon.
Since the composition of the present invention is excellent in sensitivity, resolution, and exposure margin, and has excellent adhesion to materials on various substrate surfaces, a resist pattern having excellent rectangularity can be obtained. Since the pattern of the present invention is obtained by the method for producing a pattern of the present invention using the resist pattern, it can be finely processed, and an organic EL display device or a liquid crystal display device can have high definition display characteristics.

[Liquid Crystal Display]
The liquid crystal display device of the present invention comprises a pattern of a functional inorganic film formed using the photosensitive resin composition of the present invention. That is, it has the pattern manufactured by the pattern manufacturing method of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a pattern of a functional inorganic film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures are used. Can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, the liquid crystal driving methods that can be adopted by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of JP-A-2005-284291, -346054 can be used as the organic insulating film (212).
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. It is also possible to make it flexible.

[Organic EL display device]
The organic EL display device of the present invention includes a functional inorganic film pattern formed using a photosensitive resin composition. That is, it has the pattern manufactured by the pattern manufacturing method of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a pattern of a functional inorganic film formed using the photosensitive resin composition, and various known organic EL display devices having various structures. And a liquid crystal display device.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 1 is a conceptual diagram of a configuration of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

Since the composition of the present invention has good pixel rectangularity, a resist pattern formed using the composition of the present invention is used as a partition wall of a MEMS device. Examples of such MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

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.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
MAEVE: 1-ethoxyethyl methacrylate MATH: Tetrahydro-2H-furan-2-yl methacrylate PHS: parahydroxystyrene BzMA: (benzyl methacrylate) (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
EDM: (diethylene glycol ethyl methyl ether) (manufactured by Toho Chemical Industry Co., Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries)
V-601: Dimethyl-2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries)

<(A) Polymer component>
<< Synthesis Example 1: Synthesis of A-1 >>
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 p-toluenesulfonic acid were added and stirred at room temperature for 1 hour. Thereto, 0.28 g of triethylamine was added to stop the reaction. Ethyl acetate was added to the reaction solution, and the mixture was further washed with water. Then, ethyl acetate, water, and azeotropic PGMEA were removed by distillation under reduced pressure to obtain an alkali-soluble resin A-1 protected with an acid-decomposable group. It was. The weight average molecular weight of the obtained resin was 11,000. The polydispersity was 1.13.
The structure of A-1 is a 1-ethoxyethyl protected body of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%).

<< Synthesis Example 2: Synthesis of A-2 >>
15.6 g of 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 and distilled under reduced pressure to distill off water and PGMEA azeotropically. After confirming that the water content was sufficiently low, 2.7 g of 2,3-dihydrofuran and 0.015 g of p-toluenesulfonic 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. Then, ethyl acetate and water were distilled off under reduced pressure to obtain A-2 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 A-2 is a 2-tetrahydrofuranyl protected product of p-hydroxystyrene / p-hydroxystyrene copolymer (30 mol% / 70 mol%).

<< Synthesis of A-3 >>
A-3 as a copolymer was synthesized as follows.
To 144.2 parts (2 molar equivalents) of ethyl vinyl ether, 0.5 part of phenothiazine was added, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower. ) For 4 hours. After adding 5.0 parts of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. To the reaction solution, 5 parts of sodium bicarbonate and 5 parts of sodium sulfate were added, and the mixture was stirred at room temperature for 1 hour. Insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower. .) 134.0 parts of 1-ethoxyethyl methacrylate (MAEVE) fraction of 43-45 ° C./7 mmHg was obtained as a colorless oil.
1-Ethoxyethyl methacrylate (63.28 parts (0.4 molar equivalent)), BzMA (52.83 parts (0.3 molar equivalent)), MAA (8.61 parts (0.1 molar equivalent) )), HEMA (26.03 parts (0.2 molar equivalent)) and EDM (110.8 parts) were heated to 70 ° C. under a stream of nitrogen. While stirring this mixed solution, a mixed solution of radical polymerization initiator V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., 4 parts) and EDM (100.0 parts) was added dropwise over 2.5 hours. did. After completion of the dropping, the reaction was carried out at 70 ° C. for 4 hours to obtain an EDM solution of polymer (solid content concentration: 40%).
The weight average molecular weight of the obtained A-3 measured by gel permeation chromatography (GPC) was 15,000.

(Synthesis of MATHF)
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-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 afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.

<< Synthesis of A-4 >>
Similar to the synthesis of A-3, A-4 was also synthesized.
A-4

<< Synthesis of other polymers >>
Other copolymers were synthesized in the same manner as the synthesis of the polymer A-3, except that the monomers used and the amounts used thereof were changed to those shown in the following table.

<(B) Compound Represented by General Formula (3)>
<< Synthesis of B-1 >>
5.0 g of o-aminothiophenol (manufactured by Wako Pure Chemical Industries) and 5.0 g of pivaloyl acetonitrile (manufactured by Tokyo Chemical Industry) were mixed and stirred at 120 ° C. for 2 hours. After allowing to cool, the crude product was purified by silica gel column chromatography to obtain 5.7 g of intermediate B-1A.
THF (3 mL) and B-1A (5.6 g) were mixed, 24 mL of 2M hydrochloric acid / THF solution was added dropwise under ice cooling, and then isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (3.4 g) was added dropwise. Stir for another 2 hours. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated to obtain intermediate intermediate B-1B.
After mixing intermediate crude B-1B with acetone (20 mL), triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (4.9 g) and p-toluenesulfonyl chloride (manufactured by Tokyo Chemical Industry) (5.9 g) were added under ice cooling. The mixture was warmed to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture to separate it, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-1. Crude B-1 was reslurried with methanol, filtered and dried to obtain B-1 (6.0 g).

The ¹ H-NMR spectrum (300 MHz, CDCl 3) of B-1 is δ = 8.1-8.0 (m, 1H), 7.9 (d, 2H), 7.9-7.8 ( m, 1H), 7.6-7.5 (m, 2H), 7.4 (d.2H), 2.4 (s, 3H), 1.4 (s, 9H).

<< Synthesis of B-2 >>
B-2 was synthesized in the same manner as B-1, except that pivaloyl acetonitrile in the synthesis of B-1 was changed to benzoyl acetonitrile (manufactured by Tokyo Chemical Industry).

The ¹ H-NMR spectrum (300 MHz, CDCl 3) of B-2 is δ = 8.0 (m, 1H), 7.9-7.8 (m, 5H), 7.7-7.6 ( m, 1H), 7.5-7.4 (m, 4H), 7.4 (d.2H), 2.4 (s, 3H).

<< Synthesis of B-3 to B-5, B-13 to B-15 >>
Following the synthesis of B-1, it was synthesized according to a conventional method.

<<< Synthesis of B-6 >>>
3.0 g of 2-aminophenol (manufactured by Tokyo Chemical Industry) and 8.7 g of methyl 4,4-dimethyl-3-oxovalerate (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and p-toluenesulfonic acid monohydrate (Wako Pure Chemical Industries, Ltd.) was mixed. 0.5 g) was added and heated at 120 ° C. for 2 hours under a nitrogen atmosphere. After allowing to cool, the crude product was purified by silica gel column chromatography to obtain 4.4 g of Intermediate B-6A.
B-6A (2.0 g) and p-xylene (10 mL) were mixed, 0.3 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated at 140 ° C. for 6 hours. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated. The organic phase was dried over magnesium sulfate, filtered and concentrated to give crude B-6B.
THF (1.5 mL) and the whole amount of crude B-6B were mixed, and 8.5 mL of 2M hydrochloric acid / THF solution and then isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (1.2 g) were added dropwise under ice cooling. The mixture was stirred for 2 hours after warming. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered, and concentrated to obtain Intermediate Intermediate B-6C.
Intermediate crude B-6C (1.0 g) was mixed with acetone (10 mL), and triethylamine (manufactured by Wako Pure Chemical Industries) (0.74 g) and p-toluenesulfonyl chloride (manufactured by Tokyo Chemical Industry) (1. 0 g) was added, and the mixture was warmed to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture to separate it, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-6. Crude B-6 was reslurried with methanol, filtered and dried to obtain B-6 (1.0 g).

The ¹ H-NMR spectrum (300 MHz, CDCl 3) of B-6 is δ = 8.0-7.9 (m, 2H), 7.8-7.7 (m, 1H), 7.7- 7.6 (m, 1H), 7.5-7.4 (m, 1H), 7.4-7.3 (m.3H), 2.4 (s, 3H), 1.3 (s, 9H).

<<< Synthesis of B-7 >>>
B-7 was synthesized in the same manner as B-1, except that o-aminothiophenol in the synthesis of B-1 was changed to 2-amino-4-chlorobenzenethiol (manufactured by Tokyo Chemical Industry).

<<< Synthesis of B-8 >>>
B-8 was synthesized in the same manner as B-6 except that 2-aminophenol in the synthesis of B-6 was changed to 2-amino-1-naphthol hydrochloride (manufactured by Tokyo Chemical Industry).

<<< Synthesis of B-9 >>>
4.0 g of 1-amino-2-naphthol hydrochloride (Tokyo Kasei) is suspended in 16 g of N-methylpyrrolidone (Wako Pure Chemical Industries), and 3.4 g of sodium hydrogen carbonate (Wako Pure Chemical Industries) is added. Then, 4.9 g of methyl 4-dimethyl-3-oxovalerate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise and heated at 120 ° C. for 2 hours in a nitrogen atmosphere. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-9A. Crude B-9A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-9A.
B-9A (1.7 g) and p-xylene (6 mL) were mixed, 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated at 140 ° C. for 2 hours. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated. The organic phase was dried over magnesium sulfate, filtered and concentrated to give crude B-9B.
THF (2 mL) and the whole amount of crude B-9B were mixed, and 2 mL hydrochloric acid / THF solution 6.0 mL was added dropwise under ice cooling, followed by dropwise addition of isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g). Stir for 2 hours. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated to obtain Intermediate Intermediate B-9C.
Mix the entire amount of intermediate crude B-9C with acetone (10 mL), and add triethylamine (Wako Pure Chemicals) (1.2 g) and p-toluenesulfonyl chloride (Tokyo Kasei) (1.4 g) under ice cooling. Then, it heated up to room temperature and stirred for 1 hour.
Water and ethyl acetate were added to the obtained reaction mixture to separate it, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-9. Crude B-9 was reslurried with cold methanol, filtered and dried to obtain B-9 (1.2 g).

The ¹ H-NMR spectrum (300 MHz, CDCl 3) of B-9 is δ = 8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7- 7.6 (m, 2H), 7.6-7.5 (m, 1H), 7.4 (d, 2H), 2.4 (s, 3H), 1.4 (s, 9H) It was.

<< Synthesis of B-10 to B-12 >>
Following the synthesis of B-6, it was synthesized according to a conventional method.

<<< Synthesis of B-16 >>>
B-16 was synthesized in the same manner as B-1, except that p-toluenesulfonyl chloride in the synthesis of B-1 was changed to 2-thiophenesulfonyl chloride (manufactured by Tokyo Chemical Industry).

<< Synthesis of B-17, B-20, B-21 >>
Following the synthesis of B-6, it was synthesized according to a conventional method.

<< Synthesis of B-18, B-22, B-25 >>
Following the synthesis of B-1, it was synthesized according to a conventional method.

<<< Synthesis of B-23 >>>
5.0 g of 1- (1-naphthyl) -2-thiourea (manufactured by Wako Pure Chemical Industries, Ltd.) is suspended in 100 mL of acetic acid, 9.6 g of benzyltrimethylammonium tribromide (manufactured by Tokyo Chemical Industry Co., Ltd.) is added in portions, and 8 at room temperature is added. Stir for hours. The reaction mixture was added dropwise to a saturated aqueous sodium hydrogen carbonate solution (1.6 L) in an ice bath, and the mixture was partitioned with ethyl acetate (300 mL). The organic phase was dried over magnesium sulfate, filtered and concentrated to give crude B- 23A (4.9 g) was obtained.
The obtained crude B-23A (4.9 g) was added to ethylene glycol (50 mL), a 50% aqueous solution of sodium hydroxide (12.2 g) was added, and the mixture was heated to reflux for 48 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was added to a mixture of acetic acid (40 mL) and water (120 mL) with ice cooling, and the mixture was partitioned with diethyl ether (150 mL). The organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-23B.
The total amount of the obtained crude B-23B was mixed with pivaloylacetonitrile (manufactured by Tokyo Chemical Industry) and stirred at 140 ° C. for 6 hours. After allowing to cool, the crude product was purified by silica gel column chromatography to obtain 2.1 g of Intermediate B-23C.
THF (3 mL) and B-23C (2.0 g) were mixed. Under ice-cooling, 2 M hydrochloric acid / THF solution 7.1 mL was added dropwise, and then isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (1.0 g) was added dropwise to room temperature. It stirred for 2 hours after temperature rising. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated to obtain Intermediate Intermediate B-23D.
After mixing intermediate crude B-23D with acetone (10 mL) and adding ice-cooled triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (1.1 g) and p-toluenesulfonyl chloride (manufactured by Tokyo Chemical Industry) (1.35 g) The mixture was warmed to room temperature and stirred for 1 hour.
Water and ethyl acetate were added to the obtained reaction mixture to separate it, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-23. Crude B-23 was reslurried with cold methanol, filtered and dried to obtain B-23 (1.7 g).

The ¹ H-NMR spectrum (300 MHz, CDCl 3) of B-23 is δ = 8.7-8.6 (m, 1H), 8.0-7.9 (m, 3H), 7.9- 7.8 (m, 2H), 7.7-7.65 (m, 1H), 7.65-7.6 (m, 1H), 7.4 (d.2H), 2.4 (s, 3H), 1.4 (s, 9H).

<<< Synthesis of B-19 >>>
Following the synthesis of B-23, it was synthesized according to a conventional method.

<< Synthesis of B-24 >>
B-24 was synthesized in the same manner as B-6 except that 2-aminophenol in the synthesis of B-6 was changed to 3-amino-2-naphthol (manufactured by Tokyo Chemical Industry).
<< Synthesis of B-26 >>
B-26 was synthesized in the same manner as B-6 except that 2-aminophenol in the synthesis of B-6 was changed to 6-amino-2,4-dichloro-3-methylphenol (Wako Pure Chemical Industries, Ltd.).

<< Synthesis of B-27 >>
B-27 was synthesized in the same manner as B-6 except that 2-aminophenol in the synthesis of B-6 was changed to 2-amino-4-phenylphenol (manufactured by Tokyo Chemical Industry).

<< Synthesis of B-28 >>
B-28 was prepared in the same manner as B-9 except that methyl 4,4-dimethyl-3-oxovalerate in the synthesis of B-9 was changed to methyl 4-methyl-3-oxovalerate (manufactured by Tokyo Chemical Industry). Was synthesized.

<< Synthesis of B-29 >>
B-29 was synthesized in the same manner as B-9 except that methyl 4,4-dimethyl-3-oxovalerate in the synthesis of B-6 was changed to ethyl benzoyl acetate (manufactured by Tokyo Chemical Industry).

<Photoacid generator other than the compound represented by the general formula (3)>
<< Synthesis of B'-30 >>
The compound was synthesized according to the description in paragraph number 0108 of JP-T-2002-528451.

<< Synthesis of B'-31 >>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain the B′-31 compound (the above structure) (2.3 g). .
The ¹ H-NMR spectrum (300 MHz, CDCl 3) of B′-31 has δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

<(C) Solvent>
PGMEA: Methoxypropyl acetate (manufactured by Showa Denko)
PGDA: 1,2-propanediol diacetate (boiling point 190 ° C., manufacturer: manufactured by Daicel Corporation, product number: PGDA)
1,3-BGDA: 1,3-butanediol diacetate (boiling point 232 ° C., manufacturer: manufactured by Daicel Corporation, product number: 1,3-BGDA)
1,6-HDDA: 1,6-hexanediol diacetate (boiling point 260 ° C., manufacturer: manufactured by Daicel Corporation, product number: 1,6-HDDA)
DRA-150: Triacetin (boiling point 260 ° C., manufacturer: manufactured by Daicel Corporation, product number: DRA-150)

Ｄ－４：ＤＢＮ（１，５－ジアザビシクロ［４，３，０］－５－ノネン（東京化成工業（株）製））
Ｄ－５：ＴＰＩ（２，４，５－トリフェニルイミダゾール（東京化成工業（株）製））） <(D) Basic compound>
D-1: Structure shown below D-2: Structure shown below D-3: Structure shown below

D-4: DBN (1,5-diazabicyclo [4,3,0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.))
D-5: TPI (2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)))

Ｅ－２：下記化合物（製造元：信越化学工業株式会社製、品番：ＫＢＭ－３０３）

Ｅ－３：下記化合物（製造元：ダイセル化学工業株式会社製、品番：セロキサイド２０８１）

Ｅ－４：下記化合物（製造元：ダイセル化学工業株式会社製、品番：エポリードＧＴ－４０１）

<(E) Alicyclic epoxy compound>
E-1: The following compound (manufacturer: manufactured by Daicel Chemical Industries, Ltd., product number: Celoxide 2021P)

E-2: The following compound (manufacturer: Shin-Etsu Chemical Co., Ltd., product number: KBM-303)

E-3: The following compound (manufacturer: Daicel Chemical Industries, product number: Celoxide 2081)

E-4: The following compound (manufacturer: manufactured by Daicel Chemical Industries, Ltd., product number: Epolide GT-401)

<Sensitizer>
H-1: 9,10-dibutoxyanthracene

　Ｌ－２：下記化合物（製造元：和光純薬工業株式会社製）

　Ｌ－３：下記化合物（製造元：和光純薬工業株式会社製）

　Ｌ－４：下記化合物（製造元：和光純薬工業株式会社製）

　Ｌ－５：下記化合物（製造元：和光純薬工業株式会社製）

<Ultraviolet absorber>
L-1: The following compound (manufacturer: Wako Pure Chemical Industries, Ltd., product number)

L-2: The following compound (manufacturer: Wako Pure Chemical Industries, Ltd.)

L-3: The following compound (manufacturer: Wako Pure Chemical Industries, Ltd.)

L-4: The following compound (manufacturer: Wako Pure Chemical Industries, Ltd.)

L-5: The following compound (manufacturer: Wako Pure Chemical Industries, Ltd.)

<Adjustment of photosensitive resin composition (1)>
Each component was dissolved and mixed so as to have the composition shown in the following table, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm. Examples 1 to 49, 53 to 55, 57, 59, 62, 63 67 photosensitive resin compositions were obtained. The blending ratio was as shown in the following table.
(A) Polymer: (A1) and (A2) were blended at the ratio (mass ratio) shown in the table.
-(B) Compound represented by the general formula (3): 1.5 parts by mass with respect to 100 parts by mass of the polymer (A)-(C2) Solvent: The composition has a nonvolatile content of 20% by weight. Prepared.
-(C1) Solvent: (C1) When adding a solvent, it is 3.0 mass parts with respect to 100 mass parts of all the solvents.-(D) Compound represented by General formula (4): Polymer (A) 100 0.2 parts by mass / (E) alicyclic epoxy compound: 100 parts by mass of polymer (A) 0.5 parts by mass / (H) sensitizer: sensitizer is added to parts by mass. In this case, 1.5 parts by mass with respect to 100 parts by mass of the polymer (A).

<Adjustment of photosensitive resin composition (2)>
Each component was dissolved and mixed so as to have the composition shown in the following table, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm. Examples 50 to 52, 56, 58, 60, 61, 64 to 66 68 and Comparative Examples 1 to 10 were obtained. The blending ratio was as shown in the following table.
(A) Polymer: (A1) and (A2) were blended at the ratio (mass ratio) shown in the table.
-(B) Compound represented by general formula (3): 0.5 part by mass with respect to 100 parts by mass of polymer (A)-(B ') Acid generator other than general formula (3): Polymer ( A) 1.0 mass part with respect to 100 mass parts. (C2) solvent: It prepared so that the non volatile matter of a composition might be 20 weight%.
-(C1) Solvent: (C1) When adding a solvent, it is 3.0 mass parts with respect to 100 mass parts of all the solvents.-(D) Compound represented by General formula (4): Polymer (A) 100 0.2 parts by mass with respect to parts by mass. (E) Alicyclic epoxy compound: 0.5 parts by mass with respect to 100 parts by mass of polymer (A)

<Adjustment of photosensitive resin composition (3)>
Each component was dissolved and mixed so as to have the composition shown in the following table, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of Examples 69 to 73 and Comparative Example 11. It was. The blending ratio was as shown in the following table.
(A) Polymer: (A1) and (A2) were blended at the ratio (mass ratio) shown in the table.
-(B) Compound represented by general formula (3): 0.5 part by mass with respect to 100 parts by mass of polymer (A)-(B ') Acid generator other than general formula (3): Polymer ( A) 1.0 mass part with respect to 100 mass parts. (C2) solvent: It prepared so that the non volatile matter of a composition might be 20 weight%.
-(C1) Solvent: (C1) When adding a solvent, it is 3.0 mass parts with respect to 100 mass parts of all the solvents.-(D) Compound represented by General formula (4): Polymer (A) 0.2 parts by mass with respect to 100 parts by mass. (E) Alicyclic epoxy compound: polymer (A) 0.5 parts by mass with respect to 100 parts by mass. (L) UV absorber: polymer (A) 1.0 part by mass with respect to 100 parts by mass

Each evaluation shown below was performed about the photosensitive resin composition of each Example and each comparative example obtained by the above.

<Evaluation of sensitivity>
Each photosensitive resin composition is slit-coated on a cleaned, HMDS-treated glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then pre-baked on a hot plate at 95 ° C. for 140 seconds to remove the solvent. The photosensitive resin composition layer having a film thickness of 1.3 μm was formed by volatilization.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (extra high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
The sensitivity was evaluated with the exposure amount at which the 10 μm line and space pattern was exactly 10 μm as the optimum exposure amount. Three or more are practical levels.
1: An exposure dose of 50 mJ / cm ² or more is required 2: An exposure dose of 20 mJ / cm ² or more and less than 50 mJ is required 3: An exposure dose of 15 mJ / cm ² or more and less than 20 mJ is required 4: 10 mJ / cm ² or more and less than 15 mJ Exposure amount 5: Exposure amount less than 10 mJ / cm ²

<Evaluation of line width stability>
After spin-coating with a film thickness of 1.3 μm on a cleaned, HMDS-treated 550 mm × 650 mm glass substrate, prebaking on a hot plate (95 ° C. × 140 seconds), Canon Inc. MPA 5500CF (Ultra High Pressure Mercury Lamp) After exposure at an exposure amount such that a 10 μm line-and-space pattern is exactly 10 μm through a predetermined mask, an alkaline developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) is used at 23 ° C./60. Develop for 10 seconds and prepare 10 substrates with such a line and space pattern, measure 10 μm line width with an optical measuring instrument ZYGO New View 7200 (manufactured by ZYGO Corp.) for each substrate, The standard deviation (σ) of 100 measured line widths was calculated. The evaluation criteria are as follows, and 3 or more are practical levels.
1: Standard deviation σ is 0.4 μm or more 2: Standard deviation σ is 0.2 μm or more and less than 0.4 μm 3: Standard deviation σ is 0.15 μm or more and less than 0.25 μm 4: Standard deviation σ is 0.1 μm or more , Less than 0.15 μm 5: standard deviation σ is less than 0.1 μm

<Evaluation of resolution>
Each photosensitive resin composition is slit-coated on a cleaned, HMDS-treated glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then pre-baked on a hot plate at 95 ° C. for 140 seconds to remove the solvent. The photosensitive resin composition layer having a film thickness of 1.3 μm was formed by volatilization.
Next, using the MPA 5500CF (extra-high pressure mercury lamp) manufactured by Canon Inc., the obtained photosensitive resin composition layer is exposed to an exposure amount at which a 10 μm line and space pattern is exactly 10 μm through a predetermined mask. And exposed. The exposed photosensitive resin composition layer was developed with an alkali developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. Three or more are practical levels.
1: Resolution is 5 μm or more 2: 3.0 μm is resolved, but 2.5 μm is not resolved 3: 2.5 μm is resolved but 2.0 μm is not resolved 4: 2.0 μm is resolved 1.5 μm does not resolve 5: 1.5 μm resolves.

<Evaluation of rectangularity>
After spin coating on a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) treated with HMDS and having a film thickness of 1.3 μm, pre-baking (95 ° C. × 140 seconds) on a hot plate, Canon ( Using an MPA 5500CF (extra-high pressure mercury lamp) manufactured by Co., Ltd., after exposure at an exposure amount such that a 10 μm line and space pattern is exactly 10 μm through a predetermined mask, an alkali developer (2.38 mass% tetra) A substrate formed by developing with a methylammonium hydroxide aqueous solution (23 ° C./60 seconds) was post-baked at a temperature of 140 ° C. for 3 minutes using a hot plate, and the taper angle of a 3 μm L & S pixel was measured to obtain a rectangular shape. It was. Three or more are practical levels.
1: The taper angle is less than 30 ° 2: The taper angle is 30 ° or more and less than 45 ° 3: The taper angle is 45 ° or more and less than 60 ° 4: The taper angle is 60 ° or more and less than 75 ° 5: The taper angle is 75 ° or more

<Evaluation of substrate adhesion>
It is applied to a washed Mo-coated glass substrate with a film thickness of 1.3 μm, and exposed and developed at an exposure amount such that a 10 μm line-and-space pattern is exactly 10 μm through a mask. The line and space pattern was observed to determine the pixel substrate adhesion. Three or more are practical levels.
1: Pixels do not adhere at all.
2: An L & S pattern having a line width of 10 μm or more is in close contact.
3: L & S pattern having a line width of 5 μm or more is in close contact.
4: An L & S pattern having a line width of 3 μm or more is in close contact.
5: An L & S pattern having a line width of 2 μm is in close contact.

<Evaluation of linearity>
Apply the washed Mo / Al / Mo to the glass substrate coated in this order with a film thickness of 1.3 μm, and expose and develop through a mask with an exposure amount that makes a 10 μm line and space pattern exactly 10 μm. The line and space pattern in the bright field of the formed substrate was observed by SEM (Scanning Electron Microscopy) to determine the linearity of the pixels. Three or more are practical levels.
1: The difference between the maximum value and the minimum value when the line width is measured 10 times is 1.0 μm or more 2: The difference between the maximum value and the minimum value when the line width is measured 10 times is 0.5 μm or more to 1.0 μm Less than 3: The difference between the maximum value and the minimum value when the line width is measured 10 times is 0.3 μm or more to less than 0.5 μm 4: The difference between the maximum value and the minimum value when the line width is measured 10 times is 0. 1 μm to less than 0.3 μm 5: The difference between the maximum value and the minimum value when the line width is measured 10 times is less than 0.1 μm

As shown in the above table, the photosensitive resin composition of each example had excellent results for evaluation of either sensitivity or substrate adhesion in comparison with the photosensitive resin composition of each comparative example. I found out. Furthermore, the photosensitive resin composition excellent also in evaluation of line width stability, resolution, and rectangularity was obtained. Moreover, it turned out that the photosensitive resin composition which was notably excellent comprehensively by using (A1) and (A2) together as a polymer component especially.

(Example 74)
<Organic EL display device>
An organic EL display device having an ITO pattern was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition described in Example 1 of JP-A-2009-98616 on a substrate and pre-baking (90 ° C. × 90 ° C.) on a hot plate. 2 minutes), after irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a high-pressure mercury lamp from above the mask, developing with an alkaline aqueous solution to form a pattern at 230 ° C. A heat treatment for 60 minutes was performed.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, the photosensitive resin composition of Example 8 was spin-coated on an ITO substrate, pre-baked on a hot plate (90 ° C. × 2 minutes), and then subjected to i-line (365 nm) using a high-pressure mercury lamp from the mask at 20 mJ. After irradiation with / cm ² (illuminance 20 mW / cm ² ), the pattern was formed by developing with an alkaline aqueous solution. Then, the post-baking heat processing for 3 minutes were performed at 140 degreeC before the etching process. Using this resist pattern as a mask, ITO was patterned by wet etching by dipping in an ITO etchant (3% aqueous oxalic acid solution) at 40 ° C./1 min. Thereafter, the resist pattern was peeled off by being immersed in a resist stripping solution (MS2001, manufactured by Fuji Film Electronics Materials Co., Ltd.) at 70 ° C. for 7 minutes. The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition described in Example 1 of JP2009-98616A was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

Further, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

As described above, an organic EL display device having an active matrix type ITO pattern formed by connecting each organic EL element to TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 75)
<Liquid crystal display device>
A liquid crystal display device having an ITO pattern was produced by the following method.
In the active matrix liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, the pixel electrode 4 was formed using the photosensitive resin composition of Example 1 as a mask, and the liquid crystal display device of Example 75 was obtained.
That is, the pixel electrode 4 was formed by the same method as the method for forming the first electrode 5 of the organic EL display device in Example 74.

When a drive voltage was applied to the obtained liquid crystal display device having the ITO pattern, it was found that the liquid crystal display device showed good display characteristics and high reliability.

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter 30 Halftone mask 32 Transparent base material 31 Phase shifter part (phase change film)
33, 34, 35 Exposure intensity curve s: Transmission part k: Exposure part (substrate)
33: Light intensity distribution 34: Light amplitude distribution (positive phase)
35: Light amplitude distribution (antiphase)

Claims (14)

(A) (A1) a polymer having a structural unit (a1) represented by the following general formula (1) and / or (A2) a structural unit (a2) represented by the following general formula (2) A polymer component comprising a polymer,
(B) a compound represented by the following general formula (3), and
(C) solvent,
Containing a photosensitive resin composition;

In general formula (1), 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 an aryl group, 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 (2), 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, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group;

In general formula (3), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group, or a heteroaryl group; R ³ to R ⁶ each independently represent a hydrogen atom, Represents an alkyl group, an aryl group, or a halogen atom; provided that R ³ and R ⁴ , R ⁴ and R ⁵ or R ⁵ and R ⁶ may be bonded to each other to form an alicyclic ring or an aromatic ring; , -O- or -S-. 2. The photosensitive resin composition according to claim 1, wherein R ¹ in the general formula (3) is an alkyl group having 3 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. The photosensitive resin composition according to claim 1 or 2, wherein R ¹ in the general formula (3) is an alkyl group having a branched structure, a cyclic alkyl group, or a phenyl group. The photosensitive resin composition according to any one of claims 1 to 3, wherein the compound represented by the general formula (3) is selected from the following compounds.

(A) The polymer component is (A1) a polymer having the structural unit (a1) represented by the general formula (1), and (A2) a structural unit (a2) represented by the general formula (2). The photosensitive resin composition according to any one of claims 1 to 4, which comprises both of a polymer having). (D) The photosensitive resin composition according to any one of claims 1 to 5, further comprising a compound represented by the general formula (4);

In general formula (4), R ¹ represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R ² represents an organic group. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (E) an alicyclic epoxy compound. The (C) solvent includes (C1) a solvent containing two or more acetate structures in the molecule, and (C1) another solvent (C2) different from the solvent containing two or more acetate structures in the molecule. The photosensitive resin composition according to any one of claims 1 to 7. The photosensitive resin composition according to any one of claims 1 to 8, which is a photosensitive resin composition for an etching resist used for forming a display panel substrate. The photosensitive resin composition according to any one of claims 1 to 9, which is a photosensitive resin composition for an etching resist. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 10. (1) a step of applying the photosensitive resin composition according to any one of claims 1 to 10 to at least one surface of a substrate;
(2) a step of volatilizing an organic solvent by drying to form a photosensitive resin composition layer,
(3) a step of exposing the photosensitive resin composition layer;
(4) A method for producing a pattern, comprising developing the exposed photosensitive resin composition layer. A step of forming a pattern by the method according to claim 12, a step of etching using the obtained pattern as an etching resist, and a step of removing the etched pattern by plasma treatment or chemical treatment. , Pattern manufacturing method. An organic EL display device or a liquid crystal display device manufacturing method comprising the pattern manufacturing method according to claim 12 or the pattern manufacturing method according to claim 13.

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