JP2014071300A - Photosensitive resin composition, production method of cured film using the composition, cured film, liquid crystal display device and organic electroluminescence display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition having high sensitivity and excellent contact hole stability.SOLUTION: The photosensitive resin composition comprises: a polymer component having (a1) a structural unit having a group in which an acid group is protected by an acid decomposable group and (a3) a structural unit having a thiirane ring; (B) a photo-acid generator; and (C) a solvent.

Description

  The present invention relates to a photosensitive resin composition, a method for forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device. More specifically, a photosensitive resin composition suitable for forming a planarizing film, a protective film, and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state image sensor, and the use thereof The present invention relates to a method for forming a cured film. In particular, the present invention relates to a positive photosensitive resin composition.

  An organic EL display device, a liquid crystal display device, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.

  In addition to the properties of the cured film, such as insulating properties, solvent resistance, heat resistance, hardness, and indium tin oxide (ITO) sputtering suitability, the interlayer insulating film in the above display device is desired to have high transparency. Yes. For this reason, it has been attempted to use an acrylic resin having excellent transparency as a film-forming component. For example, those described in Patent Document 1 are known.

JP 2011-215580 A

  However, as a result of investigation by the present inventor, it has been found that the contact hole uniformity is insufficient in the photosensitive resin composition described in Patent Document 1. The present invention aims to solve such problems, and an object thereof is to provide a photosensitive resin composition capable of forming a uniform contact hole while maintaining high sensitivity and transparency after heat resistance. And

（一般式（Ｉ）中、Ｘは−ＣＯＯ−、−ＣＯＮＨ−、または、フェニレン基を表し、Ｒ⁴は、水素原子またはメチル基を表し、Ｌ¹は、原子数が１以上の２〜５価の連結基を表し、Ｌ²は、単結合、または原子数が１以上の２価の連結基を表し、Ｓは、チイラン環構造を含む１価の基である。ｐは１〜４の整数を表す。）
＜５＞（ａ３）チイラン環を有する構成単位が、一般式（i）〜(ｉｖ)で表される構成単位のいずれか１種以上である、＜１＞〜＜４＞のいずれかに記載の感光性樹脂組成物。

（一般式（ｉ）〜（ｉｖ）中、Ｘは、−ＣＯＯ−、−ＣＯＮＨ−、または、フェニレン基を表し、Ｒ⁴は、水素原子またはメチル基を表し、Ｌ¹は、原子数が１以上の２〜５価の連結基を表し、Ｌ²は、単結合、または原子数が１以上の２価の連結基を表し、Ｒ¹〜Ｒ³は、それぞれ、水素原子、ハロゲン原子、水酸基または炭素数１〜３のアルキル基を表し、Ｒ^xは、ハロゲン原子、水酸基または炭素数１〜３のアルキル基を表す。ｎは、０〜９の整数を表し、ｍは０〜２の整数を表し、ｐは１〜４の整数を表す。）
＜６＞Ｌ¹が２価の連結基であり、ｐが１である、＜４＞または＜５＞に記載の感光性樹脂組成物。
＜７＞Ｘは、−ＣＯＯ−または−ＣＯＮＨ−を表す、＜４＞または＜５＞に記載の感光性樹脂組成物。
＜８＞前記構成単位（ａ１）が、一般式（Ａ２’）で表される構成単位である、＜１＞〜＜７＞のいずれかに記載の感光性樹脂組成物。
一般式（Ａ２’）

（一般式（Ａ２’）中、Ｒ¹およびＲ²は、それぞれ、水素原子、アルキル基またはアリール基を表し、少なくともＲ¹およびＲ²のいずれか一方がアルキル基またはアリール基であり、Ｒ³は、アルキル基またはアリール基を表し、Ｒ¹またはＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子またはメチル基を表し、Ｘは単結合またはアリーレン基を表す。）
＜９＞（ａ３）チイラン環を有する構成単位の少なくとも１種が、（ａ１）酸基が酸分解性基で保護された基を有する構成単位および／または（ａ２）架橋性基を有する構成単位との共重合体である、＜１＞〜＜８＞のいずれかに記載の感光性樹脂組成物。
＜１０＞（１）＜１＞〜＜９＞のいずれかに記載の感光性樹脂組成物を基板上に塗布する工程、
（２）塗布された感光性樹脂組成物から溶剤を除去する工程、
（３）溶剤が除去された感光性樹脂組成物を活性光線により露光する工程、
（４）露光された感光性樹脂組成物を水性現像液により現像する工程、および、
（５）現像された感光性樹脂組成物を熱硬化するポストベーク工程、を含む硬化膜の製造方法。
＜１１＞前記現像工程後、ポストベーク工程前に、全面露光する工程を含む、＜１０＞に記載の硬化膜の製造方法。
＜１２＞＜１０＞または＜１１＞に記載の方法により形成された硬化膜。
＜１３＞層間絶縁膜である、＜１２＞に記載の硬化膜。
＜１４＞＜１２＞または＜１３＞に記載の硬化膜を有する有機ＥＬ表示装置または液晶表示装置。 As a result of investigations by the present inventors under such circumstances, it has been found that a uniform contact hole can be formed while maintaining high sensitivity by using a polymer having a structural unit having a thiirane ring. Although this mechanism is not clear, it is considered that when a thiirane ring is inserted, the hydrophilic component is likely to volatilize during baking and a uniform contact hole can be formed.
Means for solving the above-mentioned problems are the following means <1>, preferably the following means <2> to <14>.
<1> (A) a polymer component containing a polymer that satisfies at least one of the following (1) or (2) (1) (a1) a structural unit having an acid group protected by an acid-decomposable group, and (A3) a polymer having a structural unit having a thiirane ring,
(2) (a1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a3) a polymer having a structural unit having a thiirane ring,
A photosensitive resin composition containing (B) a photoacid generator and (C) a solvent.
<2> The photosensitive resin composition according to <1>, wherein the polymer component (A) is a polymer component satisfying at least one of the following (1 ′) to (5 ′).
(1 ′) (a1) a structural unit having an acid group protected by an acid-decomposable group, (a2) a structural unit having a crosslinkable group, and (a3) a polymer having a structural unit having a thiirane ring,
(2 ′) (a1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a2) a polymer having a structural unit having a crosslinkable group, and (a3) a thiirane ring. A polymer having structural units having,
(3 ′) (a1) a polymer having a structural unit in which an acid group is protected by an acid-decomposable group, (a2) a structural unit having a crosslinkable group, and (a3) a structural unit having a thiirane ring A polymer having
(4 ′) (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a2) a polymer having a structural unit having a crosslinkable group, and (a3) a structural unit having a thiirane ring A polymer having
(5 ′) (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a3) a polymer having a structural unit having a thiirane ring, and (a2) a structural unit having a crosslinkable group A polymer having
A photosensitive resin composition containing (B) a photoacid generator and (C) a solvent.
<3> (a2) The structural unit having a crosslinkable group is an epoxy group, an oxetanyl group, and —NH—CH (R ₁ ) —OR ₂ (R ₁ and R ₂ are each a hydrogen atom or carbon, The photosensitive resin composition as described in <2> selected from the structural unit which has an alkyl group of several 1-20.
<4> (a3) The photosensitive resin composition according to any one of <1> to <3>, wherein the structural unit having a thiirane ring is a structural unit represented by the general formula (I).
Formula (I)

(In General Formula (I), X represents —COO—, —CONH—, or a phenylene group, R ⁴ represents a hydrogen atom or a methyl group, and L ¹ represents 2 to 5 having 1 or more atoms. L ² represents a single bond or a divalent linking group having 1 or more atoms, S is a monovalent group containing a thiirane ring structure, and p is 1 to 4. Represents an integer.)
<5> (a3) The structural unit having a thiirane ring is any one or more of structural units represented by general formulas (i) to (iv), and any one of <1> to <4> Photosensitive resin composition.

(In the general formulas (i) to (iv), X represents —COO—, —CONH—, or a phenylene group, R ⁴ represents a hydrogen atom or a methyl group, and L ¹ has ¹ atom. The above-mentioned divalent to pentavalent linking groups are represented, L ² represents a single bond or a divalent linking group having 1 or more atoms, and R ^{1 to} R ³ represent a hydrogen atom, a halogen atom, and a hydroxyl group, respectively. Or an alkyl group having 1 to 3 carbon atoms, wherein R ^x represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, n represents an integer of 0 to 9, and m represents an integer of 0 to 2. And p represents an integer of 1 to 4.)
<6> The photosensitive resin composition according to <4> or <5>, wherein L ¹ is a divalent linking group and p is 1.
<7> X is the photosensitive resin composition as described in <4> or <5> in which -COO- or -CONH- is represented.
<8> The photosensitive resin composition according to any one of <1> to <7>, wherein the structural unit (a1) is a structural unit represented by the general formula (A2 ′).
General formula (A2 ')

(In the general formula (A2 '), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, either one of at least R ¹ and R ² is an alkyl group or an aryl group, R ³ Represents an alkyl group or an aryl group, and 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 represents a single bond or Represents an arylene group.)
<9> (a3) At least one of the structural units having a thiirane ring is (a1) a structural unit in which an acid group is protected by an acid-decomposable group and / or (a2) a structural unit having a crosslinkable group. The photosensitive resin composition in any one of <1>-<8> which is a copolymer with these.
<10> (1) The process of apply | coating the photosensitive resin composition in any one of <1>-<9> on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for producing a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.
<11> The method for producing a cured film according to <10>, including a step of exposing the entire surface after the development step and before the post-bake step.
<12> A cured film formed by the method according to <10> or <11>.
<13> The cured film according to <12>, which is an interlayer insulating film.
<14> An organic EL display device or a liquid crystal display device having the cured film according to <12> or <13>.

  According to the present invention, a positive photosensitive resin composition excellent in high sensitivity and contact hole stability and having a low dielectric constant, a method for producing a pattern, an organic EL display device, a method for producing a liquid crystal display device, and a cured film are provided. Can be provided.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. 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. Moreover, the organic EL display device in the present invention refers to an organic electroluminescence display device (organic electroluminescence element).
Furthermore, (meth) acrylic acid means acrylic acid and / or methacrylic acid.
In the present invention, the term “alkali-soluble” means that a compound (resin) film (thickness 3 μm) 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. means 0.01 μm / second or more. “Alkali insoluble” means that a compound (resin) solution is applied on a substrate, The dissolution rate of a compound (resin) film (thickness 3 μm) formed by heating at 90 ° C. for 2 minutes in a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. is less than 0.01 μm / second. Say something.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) is preferably used as a positive photosensitive resin composition.
The photosensitive resin composition of the present invention contains (A) a polymer component containing a polymer satisfying at least one of the following (1) or (2), (B) a photoacid generator, and (C) a solvent. It is characterized by doing.
(1) (a1) a polymer having a structural unit having an acid group protected by an acid-decomposable group and (a3) a structural unit having a thiirane ring,
(2) (a1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a3) a polymer having a structural unit having a thiirane ring,
According to the present invention, it is possible to provide a positive photosensitive resin composition excellent in contact hole stability while maintaining high sensitivity.
Hereinafter, the composition of the present invention will be described in detail.

<(A) Polymer component>
The composition of the present invention comprises (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a3) a structural unit having a thiirane ring as the polymer component. Including. In particular,
(1) (a1) a polymer having a structural unit having an acid group protected by an acid-decomposable group and (a3) a structural unit having a thiirane ring,
(2) (a1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a3) a polymer having a structural unit having a thiirane ring,
At least one of the above.
Preferred embodiments of the present invention include polymer components that satisfy at least one of the following (1 ′) to (5 ′).
(1 ′) (a1) a structural unit having an acid group protected by an acid-decomposable group, (a2) a structural unit having a crosslinkable group, and (a3) a polymer having a structural unit having a thiirane ring,
(2 ′) (a1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a2) a polymer having a structural unit having a crosslinkable group, and (a3) a thiirane ring. A polymer having structural units having,
(3 ′) (a1) a polymer having a structural unit in which an acid group is protected by an acid-decomposable group, (a2) a structural unit having a crosslinkable group, and (a3) a structural unit having a thiirane ring A polymer having
(4 ′) (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a2) a polymer having a structural unit having a crosslinkable group, and (a3) a structural unit having a thiirane ring A polymer having
(5 ′) (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a3) a polymer having a structural unit having a thiirane ring, and (a2) a structural unit having a crosslinkable group Further, a polymer other than these may be included. The polymer component (A) in the present invention (hereinafter referred to as “component (A)”) is the above (1) or (2), or (1 ′) to (5 ′), unless otherwise specified. In addition to any of them, it means one containing other polymers added as necessary.
Further, for example, in the polymer (3 ′), the polymer having (a2) a structural unit having a crosslinkable group and (a3) a structural unit having a thiirane ring is (a1) the acid group is an acid-decomposable group. It does not exclude having a structural unit having a protected group. The same applies to other polymer components.

<< Structural Unit (a1) >>
Component A has (a1) at least a structural unit having a group in which an acid group is protected with an acid-decomposable group. When the component (A) has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited. Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group. The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group). A functional group) or a group that is relatively difficult to be decomposed by an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).

(A1) The structural unit having a group in which the acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group protected with an acid-decomposable group, or a protected phenolic group protected with an acid-decomposable group. A structural unit having a hydroxyl group is preferred.
Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in this order. To do.

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

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

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

<<<< acid-decomposable group that can be used for the structural unit (a1-1) >>>>
As the acid-decomposable group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group, the above-mentioned acid-decomposable group can be used.
Among these acid-decomposable groups, it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. Basic properties of the photosensitive resin composition, in particular, sensitivity and pattern shape, contact hole formation, photosensitive resin It is preferable from the viewpoint of the storage stability of the composition. Furthermore, it is more preferable from a viewpoint of a sensitivity that a carboxyl group is a protected carboxyl group protected in the form of the acetal represented with the following general formula (a1-10) among acid-decomposable groups. In addition, when the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10), the entire protected carboxyl group is — (C═O) —O—CR ^101. The structure is R ¹⁰² (OR ¹⁰³ ).

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

(In formula (a1-10), R ¹⁰¹ and R ¹⁰² each represent a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms, and R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.)

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

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

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

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable, More preferably, it is C6-C12, Specifically, a phenyl group, (alpha) -methylphenyl group, a naphthyl group etc. can be illustrated. Examples of the entire alkyl group substituted with an aryl group, that is, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
As said alkoxy group, a C1-C6 alkoxy group is preferable, More preferably, it is C1-C4, and a methoxy group or an ethoxy group is more preferable.
In addition, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is linear Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

In the general formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. preferable. The aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a cumenyl group, and a 1-naphthyl group.

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

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

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

（一般式（Ａ２’）中、Ｒ¹およびＲ²は、それぞれ、水素原子、アルキル基またはアリール基を表し、少なくともＲ¹およびＲ²のいずれか一方がアルキル基またはアリール基であり、Ｒ³は、アルキル基またはアリール基を表し、Ｒ¹またはＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子またはメチル基を表し、Ｘは単結合またはアリーレン基を表す。）
Ｒ¹およびＲ²がアルキル基の場合、炭素数は１〜１０のアルキル基が好ましい。Ｒ¹およびＲ²がアリール基の場合、フェニル基が好ましい。Ｒ¹およびＲ²は、それぞれ、水素原子または炭素数１〜４のアルキル基が好ましい。
Ｒ³は、アルキル基またはアリール基を表し、炭素数１〜１０のアルキル基が好ましく、１〜６のアルキル基がより好ましい。
Ｘは単結合またはアリーレン基を表し、単結合が好ましい。 A first preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following general formula (A2 ′).

(In the general formula (A2 '), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, either one of at least R ¹ and R ² is an alkyl group or an aryl group, R ³ Represents an alkyl group or an aryl group, and 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 represents a single bond or Represents an arylene group.)
When R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferred.

（式中、Ｒ¹²¹は水素原子または炭素数１〜４のアルキル基を表し、Ｌ¹はカルボニル基またはフェニレン基を表し、Ｒ¹²²〜Ｒ¹²⁸はそれぞれ、水素原子または炭素数１〜４のアルキル基を表す。）
Ｒ¹²¹は水素原子またはメチル基が好ましい。
Ｌ¹はカルボニル基が好ましい。
Ｒ¹²²〜Ｒ¹²⁸は、水素原子が好ましい。 The 2nd preferable aspect of the structural unit (a1-1) which has the protected carboxyl group protected by the said acid-decomposable group is a structural unit of the following general formula.

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

  Preferable specific examples of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group include the following structural units. R represents a hydrogen atom or a methyl group.

<<< (a1-2) Structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group >>>>
The structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic component in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a hydroxyl group.

<<<< (a1-2-1) Structural unit having phenolic hydroxyl group >>>>
Examples of the structural unit having a phenolic hydroxyl group include a structural unit in a hydroxystyrene-based structural unit and a novolac-based resin. Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene is, It is preferable from the viewpoint of sensitivity. Moreover, as a structural unit having a phenolic hydroxyl group, a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.

（一般式（ａ１−２０）中、Ｒ²²⁰は水素原子またはメチル基を表し、Ｒ²²¹は単結合または二価の連結基を表し、Ｒ²²²はハロゲン原子または炭素数１〜５の直鎖または分岐鎖状のアルキル基を表し、ａは１〜５の整数を表し、ｂは０〜４の整数を表し、ａ＋ｂは５以下である。なお、Ｒ²²²が２以上存在する場合、これらのＲ²²²は相互に異なっていてもよいし同じでもよい。） Formula (a1-20)

(In General Formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and R ²²² represents a halogen atom or a straight chain having 1 to 5 carbon atoms or Represents a branched alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less, and when R ²²² is 2 or more, these R ²²² may be different from each other or the same.)

In the general formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ²²¹ represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved. The divalent linking group of R ²²¹ may be exemplified alkylene groups, specific examples R ²²¹ is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group, etc. are mentioned. Among these, it is preferable that R ²²¹ is a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Moreover, although a represents the integer of 1-5, from the viewpoint of the effect of this invention and the point that manufacture is easy, it is preferable that a is 1 or 2, and it is more preferable that a is 1. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R ²²¹ is defined as the reference (first position).
R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples include fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4;

<<<< acid-decomposable group that can be used for the structural unit (a1-2) >>>>
The acid-decomposable group that can be used for the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group has a protected carboxyl group protected with the acid-decomposable group. Similarly to the acid-decomposable group that can be used for the unit (a1-1), a known one can be used and is not particularly limited. Among the acid-decomposable groups, the structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability. Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10). When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of the acetal represented by the general formula (a1-10), the entire protected phenolic hydroxyl group is -Ar-O-CR ¹⁰¹ R. The structure is ¹⁰² (OR ¹⁰³ ). Ar represents an arylene group.

Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group.

Moreover, as a radically polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of acetal, for example, paragraph number 0042 of JP2011-215590A is disclosed. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

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

  As the radical polymerizable monomer used to form the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group, a commercially available one may be used, or a known method may be used. What was synthesize | combined by can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.

  Preferable specific examples of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group include the following structural units, but the present invention is not limited thereto.

<<< Preferred Aspect of Structural Unit (a1) >>>
When the polymer containing the structural unit (a1) does not substantially contain the structural unit (a2), the structural unit (a1) is 20 to 100 in the polymer containing the structural unit (a1). The mol% is preferable, and 30 to 90 mol% is more preferable.
When the polymer containing the structural unit (a1) contains the following structural unit (a2), the single structural unit (a1) is contained in the polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, 3-70 mol% is preferable, and 10-60 mol% is more preferable. In particular, when the acid-decomposable group that can be used for the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, 20 to 50 mol% is preferable.

The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred when developing quickly. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred when developing quickly. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

<< (a2) Structural Unit Having Crosslinkable Group >>
(A2) The structural unit having a crosslinkable group is preferably a structural unit derived from a compound having a cyclic ether group and —NH—CH (R ₁ ) —OR ₂ (R ₁ and R ₂ are each represented by , A hydrogen atom or an alkyl group having 1 to 20 carbon atoms), more preferably an epoxy group, an oxiranyl group, an oxetanyl group, or —NH—CH (R ₁ ) —OR ₂ (R ₁ and R ₂ is a structural unit having a crosslinkable group selected from a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
The compound having an oxiranyl group and / or an oxetane group is more preferably a structural unit composed of a radical polymerizable monomer represented by any one of the following general formulas (3) to (5). In addition, as a structural unit having —NH—CH (R ₁ ) —OR ₂ (R ₁ and R ₂ are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), the following general formula (2 Is also preferred.
One type of crosslinkable group may be sufficient, and two or more types may be sufficient as it.
The crosslinkable group used in the present invention is more preferably an oxiranyl group and / or an oxetanyl group.

In General Formulas (3) to (5), X represents a divalent linking group, and examples thereof include organic groups such as —O—, —S—, —COO—, and —OCH ₂ COO—. X is preferably —COO—.
R ⁷ represents a hydrogen atom, a methyl group or a halogen atom, preferably a hydrogen atom or a methyl group.
R ⁸ to R ¹⁵ each independently represent a hydrogen atom, an alkyl group. Preferably it represents a hydrogen atom or a methyl group.
n is an integer of 1 to 10, preferably an integer of 1 to 3, and more preferably 1.

  Specific examples of the radical polymerizable monomer used to form the structural unit containing an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl acrylate, and 3,4-methacrylic acid 3,4- Epoxybutyl, acrylic acid 4,5-epoxypentyl, methacrylic acid 4,5-epoxypentyl, acrylic acid 6,7-epoxyheptyl, methacrylic acid 6,7-epoxyheptyl, 3,4-epoxycyclohexylmethyl acrylate, 3, (Meth) acrylates such as 4-epoxycyclohexylmethyl methacrylate; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl -Vinylbenzyl glycidyl ethers such as m-vinylbenzyl glycidyl ether and α-methyl-p-vinylbenzyl glycidyl ether; Vinylphenyls such as o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether and p-vinylphenyl glycidyl ether Glycidyl ethers. Glycidyl acrylate, glycidyl methacrylate, p-vinylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate are preferable, and glycidyl acrylate and glycidyl methacrylate are particularly preferable.

In another embodiment, the structural unit having a crosslinkable group is preferably a structural unit composed of a radical polymerizable monomer represented by the following general formula (6) or (7), alone or in combination of two or more. Can be used. The molecular weight of the radical polymerizable monomer represented by the general formula (6) or (7) is preferably 100 to 500, more preferably 150 to 200.

In General Formulas (6) and (7), X represents a divalent linking group, and examples thereof include organic groups such as —O—, —S—, —COO—, and —OCH ₂ COO—. X is preferably —COO—.
R ⁷ represents a hydrogen atom, a methyl group or a halogen atom, preferably a hydrogen atom or a methyl group.
R ⁸ to R ¹⁵ each independently represent a hydrogen atom, an alkyl group. Preferably it represents a hydrogen atom or a methyl group.
n is an integer of 1 to 10, preferably an integer of 1 to 3, and more preferably 1.

  Examples of the radical polymerizable monomer used to form such a structural unit having an oxetanyl group include the oxiranyl group in the above specific example of the radical polymerizable monomer containing an oxiranyl group. And (meth) acrylic acid ester having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953.

  As the radical polymerizable monomer used for forming the structural unit having a crosslinkable group, a commercially available one may be used, or one synthesized by a known method may be used. For example, Osaka Organic Chemical Industrial OXE series and the like can be mentioned.

Preferable specific examples of the structural unit having a functional group capable of reacting with a carboxyl group to form a covalent bond include the following structural units.

The structural unit having a crosslinkable group is a structural unit having —NH—CH (R ₁ ) —OR ₂ (R ₁ and R ₂ are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). (A2-2) is also preferable. By having the structural unit (a2-2), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained.
R ₁ and R ₂ are each preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, and a hydrogen atom or 1 carbon atom. More preferred are ˜4 alkyl groups. The alkyl group may be a linear, branched or cyclic alkyl group, and is preferably a linear or branched alkyl group.
The alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, an aryl group, and an alkoxy group.

As the structural unit (a2-2) having —NH—CH (R ₁ ) —OR ₂ (R ₁ and R ₂ are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), A structural unit having a group represented by the formula (2) is preferred.

（上記式中、Ｒ¹は水素原子またはメチル基を表し、Ｒ²は炭素数１〜２０のアルキル基を表す。）

(In the above formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms.)

R ² is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.

  In the structural unit constituting the component (A), the content of the structural unit (a2) is preferably 1 to 95 mol%, more preferably 5 to 70 mol%, still more preferably 10 to 50 mol%, and more preferably 20 to 50 mol%. More preferably, mol% is more preferable, and 30-50 mol% is especially preferable. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

<<< Preferred Aspect of Structural Unit (a2) >>>
When the polymer containing the structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a2) is 5 to 90 in the polymer containing the structural unit (a2). Mol% is preferable and 20-80 mol% is more preferable.
When the polymer containing the structural unit (a2) contains the structural unit (a1), the single structural unit (a2) is contained in the polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of chemical resistance, 3-70 mol% is preferable, and 10-60 mol% is more preferable.
In this invention, it is preferable to contain 3-70 mol% of structural units (a2) in all the structural units of (A) component irrespective of any aspect, and it is more preferable to contain 10-60 mol%. preferable.

（一般式（Ｉ）中、Ｘは−ＣＯＯ−、−ＣＯＮＨ−、または、フェニレン基を表し、Ｒ⁴は、水素原子またはメチル基を表し、Ｌ¹は、原子数が１以上の２〜５価の連結基を表し、Ｌ²は、単結合、または原子数が１以上の２価の連結基を表し、Ｓは、チイラン環構造を含む１価の基である。ｐは１〜４の整数を表す。） << (a3) structural unit having thiirane ring >>
The component A has a structural unit (a3) having a thiirane ring. By having a thiirane ring, CH stability can be improved while maintaining sensitivity. In addition, the dielectric constant can be lowered. The structural unit having a thiirane ring is not particularly limited as long as it has at least one thiirane ring. As a preferred embodiment of the structural unit having a thiirane ring, a structure in which a thiirane ring is bonded to the side chain of the structural unit derived from (meth) acrylate is preferable, and the structural unit having a thiirane ring represented by the following general formula (I) More preferably.
Formula (I)

(In General Formula (I), X represents —COO—, —CONH—, or a phenylene group, R ⁴ represents a hydrogen atom or a methyl group, and L ¹ represents 2 to 5 having 1 or more atoms. L ² represents a single bond or a divalent linking group having 1 or more atoms, S is a monovalent group containing a thiirane ring structure, and p is 1 to 4. Represents an integer.)

  X represents —COO—, —CONH—, or a phenylene group, preferably —COO— or —CONH—, more preferably —COO—.

R ⁴ represents a hydrogen atom or a methyl group, and a methyl group is preferable.

L ¹ represents a divalent to pentavalent linking group having 1 or more atoms. 1-50 are preferable and, as for the number of atoms of a 2-5 valent coupling group whose number of atoms is 1 or more, 1-30 are more preferable except for a hydrogen atom. The valence of the divalent to pentavalent linking group having 1 or more atoms is preferably divalent or trivalent, and more preferably divalent.
Examples of the divalent to pentavalent linking group having 1 or more atoms include a hydrocarbon group (preferably an alkylene group and / or an arylene group), and these, —O—, —O—SO ₂ —, —O. A group selected from the group consisting of —C (═O) —, —C (═O) —O—, —S—, —C (═O) —, and a group represented by the following formula (v); Or the group which consists of 2 or more combinations is illustrated.

（一般式（ｖ）中、ｚは０〜５までの整数を表す。）
Ｚは、０〜５が好ましく、２〜３がより好ましく、３が特に好ましい。 Formula (v)

(In general formula (v), z represents an integer of 0 to 5.)
Z is preferably 0 to 5, more preferably 2 to 3, and particularly preferably 3.

The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms. Further preferred. The alkylene group may have a substituent, but preferably does not have a substituent. The alkylene group may be any of linear, branched or cyclic, but a linear alkylene group is preferred. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a t-butylene group, a pentylene group, and a hexylene group. In the present invention, a methylene group, an ethylene group, a propylene group, and a butylene group are particularly preferable.
As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, an alkylene group having 6 to 14 carbon atoms is more preferable, an arylene group having 6 to 10 carbon atoms is further preferable, and a phenylene group is further more preferable. The arylene group may have a substituent. 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, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, and naphthylene group are particularly preferable, and 1,3-phenylene group, 1,4-phenylene group, and naphthylene group are more preferable. . The arylene group may have a substituent, but preferably does not have a substituent.

  Examples of the substituent that the alkylene group and the arylene 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.

L ² represents a single bond or a divalent linking group having 1 or more atoms, and may have a substituent. When L ² is a divalent linking group having 1 or more atoms, the number of atoms is preferably 1-50, and more preferably 1-30, excluding hydrogen atoms. Examples of the divalent linking group having 1 or more carbon atoms include an alkylene group and an arylene group.
The alkylene group has the same meaning as the alkylene group for L ^1, a preferred range is also the same. The arylene group has the same meaning as the arylene group for L ^1, a preferred range is also the same.
The substituent that the alkylene group and arylene group may have is the same as the substituent that the alkyl group or aryl group may have.

S is a monovalent group containing a thiirane ring structure, and the thiirane ring may be a single ring or a condensed ring with another ring. In the case of a condensed ring, it may be condensed with either an aromatic ring or an aliphatic ring. In this case, the aromatic ring and the aliphatic ring are 4- to 8-membered rings, preferably 5-membered rings or 6-membered rings.
The substituent that the aromatic ring and the aliphatic ring may have is the same as the substituent that the alkyl group or aryl group may have. The group S containing a thiirane ring structure preferably consists only of a cyclic structure.

p represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1. When p is 2 or more, the groups represented by two or more -L ² -S present in one structural unit may be the same or different.

  The structural unit having a thiirane ring represented by the general formula (I) is preferably a structural unit represented by the general formulas (i) to (iv). Especially, it is preferable that the composition of this invention contains the structural unit represented by general formula (i) from a dielectric constant viewpoint.

（一般式（ｉ）〜（ｉｖ）中、Ｘは、−ＣＯＯ−、−ＣＯＮＨ−、または、フェニレン基を表し、Ｒ⁴は、水素原子またはメチル基を表し、Ｌ¹は、原子数が１以上の２〜５価の連結基を表し、Ｌ²は、単結合、または原子数が１以上の２価の連結基を表し、Ｒ¹〜Ｒ³は、それぞれ、水素原子、ハロゲン原子、水酸基または炭素数１〜３のアルキル基を表し、Ｒ^xは、ハロゲン原子、水酸基または炭素数１〜３のアルキル基を表す。ｎは、０〜９の整数を表し、ｍは０〜２の整数を表し、ｐは１〜４の整数を表す。）

(In the general formulas (i) to (iv), X represents —COO—, —CONH—, or a phenylene group, R ⁴ represents a hydrogen atom or a methyl group, and L ¹ has ¹ atom. The above-mentioned divalent to pentavalent linking groups are represented, L ² represents a single bond or a divalent linking group having 1 or more atoms, and R ^{1 to} R ³ represent a hydrogen atom, a halogen atom, and a hydroxyl group, respectively. Or an alkyl group having 1 to 3 carbon atoms, wherein R ^x represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, n represents an integer of 0 to 9, and m represents an integer of 0 to 2. And p represents an integer of 1 to 4.)

X, R ^4, L ^1, L ² and p have the general formula (1) in X, it has the same meaning as R ^4, L ^1, L ² and p, preferred ranges are also the same.
R ^{1 to} R ³ each represents a hydrogen atom, a halogen atom (preferably a chlorine atom or a fluorine atom), a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom, a hydroxyl group or a methyl group, Is more preferable.
R ^x represents a halogen atom (preferably a chlorine atom or a fluorine atom), a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and an alkyl group is preferred.

n represents an integer of 0 to 9, an integer of 0 to 4 is preferable, 0 or 1 is more preferable, and 0 is more preferable.
m represents an integer of 0 to 2, 0 or 1 is preferable, and 0 is more preferable.

Specific examples of the structural unit having a thiirane ring represented by formula (I) include the following structures, but the present invention is not limited to the following structures.

  (A3) Various methods for synthesizing a structural unit having a thiirane ring are known. For example, in the above (a-1), glycidyl methacrylate is dropped into a mixed solution of thiourea, ammonium acetate, and methanol. -It can be synthesized by stirring.

  In the structural unit constituting the component (A), (a3) the content of the structural unit having a thiirane ring is preferably 0.1 to 30 mol%, preferably 0.1 to 15 mol% of the structural units of all resin components. Is more preferable, and 0.1-10 mol% is further more preferable. When the content is 0.1 mol% or more, an effect that the stability of the contact hole is excellent is obtained, and when it is 30 mol% or less, it is preferable in terms of improving developability.

  The weight average molecular weight (Mw) of the polymer having the structural unit (a3) having a thiirane ring is preferably in the range of 3000 to 300000, more preferably 4000 to 100,000, and still more preferably 8000 to 50000. . By setting it to 3000 or more, the effect of improving the remaining film ratio is obtained, and by setting it to 300000 or less, the effect of high sensitivity is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

<< (a4) Other structural units >>
In addition to the structural units (a1) to (a3), the component (A) may include a polymer having a structural unit (a4) derived from another monomer. The structural unit (a4) may also be copolymerized. Apart from the polymer component (1) or (2) or (1 ′) to (5 ′), a polymer having substantially no (a1) to (a3) and having another structural unit (a4) When the component is included, the blending amount of the polymer component is preferably 60% by mass or less, more preferably 40% by mass or less, and further preferably 20% by mass or less in the total polymer component. preferable.

  There is no restriction | limiting in particular as a monomer used as another structural unit (a4), For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to. Moreover, you may have the structural unit which has an acid group so that it may mention later. The monomer which becomes another structural unit (a4) can be used individually or in combination of 2 or more types.

  Although preferable embodiment of the polymer component of this invention is given to the following, this invention is not limited to these.

(First embodiment)
The aspect in which any one of the polymer component (1) or (2) or (1 ′) to (5 ′) further has one or more other structural units (a4).

(Second Embodiment)
An embodiment in which any one of the polymer components (1) or (2) or (1 ′) to (5 ′) is a combination of two or more.

(Third embodiment)
In any one of the first and second embodiments, the other structural unit (a4) includes a structural unit containing at least an acid group.

(Fourth embodiment)
Apart from the polymer component (1) or (2) or (1 ′) to (5 ′), it further has another structural unit (a4) which does not substantially contain (a1) to (a3). Embodiment with polymer.

(Fifth embodiment)
The form which consists of two or more combinations of the said 1st-4th embodiment.

  The structural unit (a4) is specifically styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid. Ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid Isopropyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate Mention may be made of a structural unit due. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  Further, as other structural unit (a4), styrenes and groups having an alicyclic skeleton are preferable from the viewpoint of electrical characteristics. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.

  Furthermore, (meth) acrylic acid alkyl ester is preferable as another structural unit (a4) from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable. In the structural unit constituting the polymer (A), the content of the structural unit (a4) is preferably 60 mol% or less, more preferably 50 mol% or less, and further 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.

As the other structural unit (a4), an acid group is preferably included. 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 Amide groups, sulfonylimide groups and the like are exemplified, 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. .

  In the present invention, it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.

  The structural unit containing an acid group is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, still more preferably 5 to 40 mol%, and particularly preferably 5 to 30 mol% of the structural units of all polymer components. 5 to 20 mol% is particularly preferable.

  In the present invention, apart from the polymer component (1) or (2) or (1 ′) to (5 ′), the other structural unit (a4) is substantially free of (a1) to (a3). The polymer which has this may be included.

  As such a polymer, a resin having a carboxyl group in the side chain is preferable. 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 copolymer, 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 copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Copolymer and the like.
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, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON are commercially available as these polymers. UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncry 690, Joncry 678, Joncry 67, Joncry 586 (above, made by BASF) You can also.

[Molecular weight of component (A)]
The weight average molecular weight (Mw) of the component (A) is preferably in the range of 3000 to 300000, more preferably 4000 to 100,000, and still more preferably 8000 to 50000. By setting it to 3000 or more, the effect of improving the remaining film ratio is obtained, and by setting it to 300000 or less, the effect of high sensitivity is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

<< (A) Component Production Method >>
Various methods for synthesizing the component (A) are known. To give an example, the component (A) is used to form at least the structural units represented by the above (a1) to (a3). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator.

<(B) Photoacid generator>
The photosensitive resin composition of the present invention contains (B) a photoacid generator. As the photoacid generator (also referred to as “component (B)”) used in the present invention, a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable. The chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.

  Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-221494A. It can be illustrated.

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

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

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

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

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

（式（Ｂ２）中、Ｒ⁴²は、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。）

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

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
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.

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

（式（Ｂ３）中、Ｒ⁴³は式（Ｂ２）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。）

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

R ⁴³ in the general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and 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.
As n4, 0-2 are preferable and 0-1 are especially preferable.

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

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

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

In the general formula (OS-1), 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.
As R ^{121 to} R ¹²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, 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 preferable. 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 more preferably a compound represented by the following general formula (OS-2).

In the general formula (OS-2), R ¹⁰¹ , R ¹⁰² , R ^{121 to} R ¹²⁴ are respectively synonymous with those in the formula (OS-1), and preferred examples are also the same.
Among these, an embodiment in which R ¹⁰¹ in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2). And R ¹⁰¹ is most preferably a cyano group, a phenyl group or a naphthyl group.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  In the photosensitive resin composition of the present invention, (B) the photoacid generator is based on 100 parts by mass of all resin components (preferably a solid content, more preferably a total of copolymers) in the photosensitive resin composition. 0.1 to 10 parts by mass is preferably used, and 0.5 to 10 parts by mass is more preferably used. Two or more kinds can be used in combination.

<(C) Solvent>
The photosensitive resin composition of the present invention contains (C) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and optional components described below are dissolved in the solvent (C).
As the solvent (C) used in the photosensitive resin composition of the present invention, 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 Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like. Specific examples of the solvent (C) used in the photosensitive resin composition of the present invention include the solvents described in JP-A-2011-221494, paragraph numbers 0174 to 0178, and the contents thereof are described in the present specification. Embedded in the book.

  In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is 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.

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

  The content of the solvent (C) in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, preferably 60 to 90 parts by mass, per 100 parts by mass of all resin components in the photosensitive resin composition. More preferably it is.

<Other ingredients>
In addition to the above components, the photosensitive resin composition of the present invention includes (D) an alkoxysilane compound, (E) a crosslinking agent, (F) a sensitizer, (G) a surfactant, H) a basic compound and (I) an antioxidant can be preferably added. Furthermore, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added.

(D) Alkoxysilane compound (adhesion improver)
The photosensitive resin composition of the present invention is characterized by containing (D) an alkoxysilane compound (also referred to as “(D) component”). When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do. As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. As for carbon number of the alkoxy group which an alkoxysilane compound has, 1-5 are preferable.
The (D) alkoxysilane compound that can be used in the photosensitive resin 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, gold, copper, molybdenum, titanium, or aluminum. A compound that improves the adhesion between the metal and the like and the insulating film is preferable. Specifically, a known silane coupling agent or the like is also effective.
Examples of the silane coupling agent 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. These can be used alone or in combination of two or more.

The following compounds can also be preferably employed.

  In the above, Ph is a phenyl group.

The (D) alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited, and a known one can be used.
As for content of (D) alkoxysilane compound in the photosensitive resin composition of this invention, 0.1-30 mass parts is preferable with respect to 100 mass parts of total solid in a photosensitive composition, 0.5- 20 parts by mass is more preferable.

(E) Crosslinking agent It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat. (Excluding component A). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can be added.
It is preferable that the addition amount of the crosslinking agent in the photosensitive resin composition of this invention is 0.01-50 mass parts with respect to 100 mass parts of total solids of the photosensitive resin composition, 0.1-30 It is more preferable that it is a mass part, and it is still more preferable that it is 0.5-20 mass parts. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.

<Compound having two or more epoxy groups or oxetanyl groups in the molecule>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.

These are available as commercial products. For example, the commercial item etc. of paragraph number 0189 of Unexamined-Japanese-Patent No. 2011-221494, such as JER157S70, JER157S65, JER1007 (made by Mitsubishi Chemical Holdings Corporation), etc. are mentioned.
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX- 832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX- 14L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase Chemtech), YH -300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by NS Daicel), and the like.
These can be used alone or in combination of two or more.

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

  As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.

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

  As other crosslinking agents, alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A and compounds having at least one ethylenically unsaturated double bond are also preferably used. The contents of which are incorporated herein by reference. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

<Block isocyanate compound>
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. Moreover, it is preferable that the said block isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90 to 250 degreeC.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic. Polyisocyanate may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1 , 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate , Isocyanation of hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, etc. A compound and a prepolymer type skeleton compound derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

  The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (and above) , Manufactured by Asahi Kasei Chemicals Corporation, Death Module BL 100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) and the like are preferably used can do.

(F) Sensitizer The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (B) a photoacid generator. 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, acriflavine), 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 photosensitive resin composition of the present invention is preferably 0 to 1000 parts by mass, and 10 to 500 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition. It is more preferable that it is 50-200 mass parts.
Two or more kinds can be used in combination.

(G) Surfactant The photosensitive resin composition of the present invention may contain (G) a surfactant. As the surfactant (G), any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by JEMCO), Mega Fuck (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Manufactured by Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following general formula (G-1), and 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（Ｇ−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 (G-1)

(In the formula (G-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 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% by mass to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

The L is preferably a branched alkylene group represented by the following general formula (G-2). R ⁴⁰⁵ in the general formula (H-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 (G-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.
The addition amount of the (G) surfactant in the photosensitive resin composition of the present invention 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. It is more preferable that it is -10 mass parts, and it is still more preferable that it is 0.01-3 mass parts.

(H) Basic compound The photosensitive resin composition of the present invention may contain (H) a basic compound. (H) The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraph numbers 0204 to 0207 of JP2011-221494A.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

  The basic compounds that can be used in the present invention may be used singly or in combination of two or more.

  The content of the basic compound (H) in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, it is 0.005 to 1 part by mass.

(I) Antioxidant The photosensitive resin 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, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Among these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. 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 AO-60, ADK STAB AO-70, ADK STAB AO-80, 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 PEP-36Z, ADK STAB HP-1 , ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS 90, ADK STAB ZS 90 -91 (above, manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Co., Ltd.), and the like. Among these, ADK STAB AO-60, ADK STAB AO-80, Irganox 1726, Irganox 1035, and Irganox 1098 can be preferably used.

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. It is particularly preferably 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.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

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、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。 [Acid multiplication agent]
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used 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.
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 dissolution contrast between the exposed part and the unexposed part. Preferably, the amount is 20 to 500 parts by mass.

[Development accelerator]
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, the description of paragraph numbers 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.
The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 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. 1-20 mass parts is more preferable, and it is most preferable that it is 0.5-10 mass parts.
In addition, as other additives, a thermal radical generator described in paragraph Nos. 0120 to 0121 of JP2012-8223A, a nitrogen-containing compound and a thermal acid generator described in WO2011 / 136074A1, 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.

[Method for producing cured film]
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the photosensitive resin composition of this invention on a board | substrate;
(2) A step of removing the solvent from the applied photosensitive resin composition;
(3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays;
(4) A step of developing the exposed photosensitive resin composition with an aqueous developer;
(5) A post-baking step of thermosetting the developed photosensitive resin composition.
Each step will be described below in order.

In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin 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 inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound These substrates which may be mentioned are less if used while the above embodiment, normally, depending on the form of the final product, for example, multi-layered structure such as a TFT element is formed.
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 pret method as described in JP 2009-145395 A.
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 solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and 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), h-line ( 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.

In the developing step (4), a polymer 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 a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. 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.
Preferred examples of the developer include 0.4% aqueous solution, 0.5% aqueous solution, 0.7% aqueous solution and 2.38% aqueous solution of tetraethylammonium hydroxide.
The pH of the developer is preferably 10.0 to 14.0.
The developing time is preferably 30 to 500 seconds, and the developing method may be any of a liquid piling method and a dipping method. After development, washing with running water is usually 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 post-baking step of (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and then crosslinked with a crosslinkable group, a crosslinking agent or the like. A cured film can be formed. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on a hot plate, 30 to 120 minutes for an oven. It is preferable to By proceeding with such a crosslinking reaction, it is possible to form a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

  Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

[Curing film]
The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.

[Liquid Crystal Display]
The liquid crystal display device of the present invention comprises the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures. An apparatus 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.
In addition, as a liquid crystal driving method that can be taken by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. 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, or JP-A-2005 -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. 1 is a conceptual cross-sectional view showing an example of an active matrix 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. Further, it can be made flexible, and can be used as the second interphase insulating film (48) of JP 2011-145686 A or the interphase insulating film (520) of JP 2009-258758 A.

[Organic EL display device]
The organic EL display device of the present invention comprises the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device 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. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
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. 2, 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 second 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 photosensitive resin composition of the present invention is excellent in curability and cured film characteristics, a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part. 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.

  Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) described in FIG. 4A of 9793, and the bank layer (221) and third interlayer insulating film (216b) described in FIG. 10 of JP 2010-27591A. ), Second interlayer insulating film (125) and third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12) and a pixel isolation insulating film (14).

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

In the following synthesis examples, the following symbols represent the following compounds, respectively.
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-601: Dimethyl-2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
MAEVE: 1-ethoxyethyl methacrylate MATHF: tetrahydro-2H-furan-2-yl methacrylate MATHP: tetrahydro-2H-pyran-2-yl methacrylate NBMA: n-butoxymethylacrylamide (NBMA, manufactured by Tokyo Chemical Industry Co., Ltd.)
GMA: glycidyl methacrylate St: styrene MMA: methyl methacrylate MAA: methacrylic acid EDM: diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Industry, Hisolv EDM)
OXE-30: Methyl methacrylate (3-ethyloxetane-3-yl) methyl (Osaka Organic Chemical Industry Co., Ltd.)
DCPM: Methacrylic acid (tricyclo [5.2.1.0 ^2,6 ] decan-8-yl)

Compounds (a-1) to (a-25):

<Synthesis of a-1>
Thiourea (49.1 g, 0.645 mol), ammonium acetate (1.5 g, 0.019 mol), and methanol 200 g were added to a 500 ml three-necked flask. Cool to 0 ° C. and add glycidyl methacrylate (45.9 g, 0.322 mol) dropwise. After dropwise addition, the mixture was stirred at room temperature for 4 hours, extracted with ethyl acetate (500 mL), washed with water (500 mL) four times, dried over magnesium sulfate, filtered, and concentrated under reduced pressure at 40 ° C. or lower to give a cyclic glycidyl methacrylate. 40.2g of compound (a-1) by which the ether part was substituted by the thiirane ring was obtained.

<Synthesis of a-2 to a-25>
Compounds (a-2) to (a-25) were obtained in the same manner except that glycidyl methacrylate was replaced with the corresponding cyclic ether compound in the synthesis example of (a-1).

<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.

  Monomers and the like were changed as shown in the following table, and other polymers were synthesized. In the following table, all solvents used PGMEA.

(Preparation of photosensitive resin composition)
Each component was dissolved and mixed in a solvent described later so as to have a solid content ratio shown in the following table, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain a photosensitive resin composition. The solvent is a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol ethyl methyl ether / 1,3-butylene glycol diacetate = 60/37/3 (weight ratio), and the viscosity is adjusted to 5 mPa · s. did.

  The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.

<Photo acid generator>
B-1: CGI-1397 (manufactured by BASF)

<Adhesion improver>
D-1: KBM-403 (trade name, 3-glycidoxypropyltrimethoxysilane, structure shown below, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Crosslinking agent>
E-1: JER157S65 (trade name, phenol novolac type epoxy resin, manufactured by Japan Epoxy Resins Co., Ltd.)

<Basic compound>
H-1: 1,5-diazabicyclo [4.3.0] -5-nonene H-2: N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea

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

<Evaluation of contact hole (CH) uniformity>
Each photosensitive resin composition was spin-coated on a 550 mm × 650 mm glass substrate, pre-baked on a hot plate (90 ° C. × 2 minutes), and then i-line (365 nm) was applied at 25 mJ / cm from the mask using a high-pressure mercury lamp. ² After irradiation (energy intensity 20 mW / cm ² ), development was performed with an alkaline aqueous solution to form a contact hole (CH) pattern. Prepare 10 such substrates with CH pattern, 50 points for each substrate, and how much difference there is with respect to the set CH size of 10 μm with optical measuring instrument ZYGO New View 7200 (manufactured by ZYGO corp.) The size was measured. The evaluation criteria are as follows, and D or higher is a practical level.
A: Average CH size difference is 0.2 μm or less B: Average CH size difference is greater than 0.2 μm and 0.4 μm or less C: Average CH size difference is greater than 0.4 μm and 0.6 μm or less D: Average CH size difference is larger than 0.6 μm and 0.8 μm or less E: Average CH size difference is larger than 0.8 μm

<Evaluation of sensitivity>
Each photosensitive resin composition was slit-coated on a 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 volatilize the solvent. A photosensitive resin composition layer having a thickness of 4.0 μm was formed.
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 (0.4 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
The optimum i-line exposure (Eopt) when resolving a 5 μm hole by these operations was taken as the sensitivity. C and above are practical levels.
A: 20mJ / cm ² less B: 20mJ / cm ² or more, 40 mJ / cm ² less than C: 40mJ / cm ² or more, 80 mJ / cm ² less than D: 80mJ / cm ² or more, 160 mJ / cm ² less than E: 160 mJ / cm ² or more

  As is clear from the above results, the photosensitive resin composition of the present invention obtained a photosensitive composition excellent in CH stability while maintaining high sensitivity. On the other hand, it was found that the photosensitive resin composition of the comparative example was inferior in sensitivity.

<Example 40>
Example 40 was performed in the same manner as in Example 1, except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The evaluation of sensitivity was the same level as in Example 1.

<Example 41>
Example 41 was carried out in the same manner as in Example 1, except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a 355 nm laser exposure machine and 355 nm laser exposure was performed. Here, as the 355 nm laser exposure machine, “AEGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR.
The evaluation of sensitivity was the same level as in Example 1.

<Example 42>
In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 52 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film.

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

<Example 43>
A liquid crystal display device similar to that of Example 42 was obtained by changing only the following coating process. That is, after the photosensitive resin composition of Example 1 was applied by a slit coating method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 μm. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was good as in Example 52.

<Example 44>
Example 44 was carried out in the same manner as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a UV-LED light source exposure machine. The evaluation of sensitivity was the same level as in Example 1.

  As described above, it was found that the photosensitive resin compositions of the examples were excellent in the shape of the formed pattern regardless of the substrate and the exposure machine.

<Example 45>
A liquid crystal display device similar to that of Example 42 was obtained by changing only the following coating process. That is, after the photosensitive resin composition of Example 1 was applied by a slit and spin method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 μm. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was good as in Example 52.

<Example 46>
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
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 of Example 16 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating 45 mJ / cm ² (energy intensity 20 mW / cm ² ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C./30 minutes.
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, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). 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 of Example 1 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.

  Furthermore, 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 active matrix type organic EL display device in which each organic EL element is connected to the 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.

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

Claims (14)

(A) a polymer component containing a polymer satisfying at least one of the following (1) or (2) (1) (a1) a structural unit having a group in which an acid group is protected with an acid-decomposable group, and (a3) A polymer having a structural unit having a thiirane ring,
(2) (a1) a polymer having a structural unit in which an acid group is protected by an acid-decomposable group, and (a3) a polymer having a structural unit having a thiirane ring,
A photosensitive resin composition containing (B) a photoacid generator and (C) a solvent. The photosensitive resin composition according to claim 1, wherein the polymer component (A) is a polymer component satisfying at least one of the following (1 ′) to (5 ′).
(1 ′) (a1) a structural unit having an acid group protected by an acid-decomposable group, (a2) a structural unit having a crosslinkable group, and (a3) a polymer having a structural unit having a thiirane ring,
(2 ′) (a1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a2) a polymer having a structural unit having a crosslinkable group, and (a3) a thiirane ring. A polymer having structural units having,
(3 ′) (a1) a polymer having a structural unit in which an acid group is protected by an acid-decomposable group, (a2) a structural unit having a crosslinkable group, and (a3) a structural unit having a thiirane ring A polymer having
(4 ′) (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a2) a polymer having a structural unit having a crosslinkable group, and (a3) a structural unit having a thiirane ring A polymer having
(5 ′) (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, (a3) a polymer having a structural unit having a thiirane ring, and (a2) a structural unit having a crosslinkable group Polymer having (A2) The structural unit having a crosslinkable group is an epoxy group, an oxetanyl group, and —NH—CH (R ₁ ) —OR ₂ (R ₁ and R ₂ are each a hydrogen atom or a carbon number of 1 to The photosensitive resin composition according to claim 2, which is selected from structural units having 20 alkyl groups). (A3) The photosensitive resin composition of any one of Claims 1-3 whose structural unit which has a thiirane ring is a structural unit represented by general formula (I).
Formula (I)

(In General Formula (I), X represents —COO—, —CONH—, or a phenylene group, R ⁴ represents a hydrogen atom or a methyl group, and L ¹ represents 2 to 5 having 1 or more atoms. L ² represents a single bond or a divalent linking group having 1 or more atoms, S is a monovalent group containing a thiirane ring structure, and p is 1 to 4. Represents an integer.) (A3) The photosensitivity according to any one of claims 1 to 4, wherein the structural unit having a thiirane ring is at least one of the structural units represented by the general formulas (i) to (iv). Resin composition.

(In the general formulas (i) to (iv), X represents —COO—, —CONH—, or a phenylene group, R ⁴ represents a hydrogen atom or a methyl group, and L ¹ has ¹ atom. The above-mentioned divalent to pentavalent linking groups are represented, L ² represents a single bond or a divalent linking group having 1 or more atoms, and R ^{1 to} R ³ represent a hydrogen atom, a halogen atom, and a hydroxyl group, respectively. Or an alkyl group having 1 to 3 carbon atoms, wherein R ^x represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, n represents an integer of 0 to 9, and m represents an integer of 0 to 2. And p represents an integer of 1 to 4.) The photosensitive resin composition according to claim 4 or 5, wherein L ¹ is a divalent linking group and p is 1. The photosensitive resin composition according to claim 4 or 5, wherein X represents -COO- or -CONH-. The photosensitive resin composition of any one of Claims 1-7 whose said structural unit (a1) is a structural unit represented by general formula (A2 ').
General formula (A2 ')

(In the general formula (A2 '), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, either one of at least R ¹ and R ² is an alkyl group or an aryl group, R ³ Represents an alkyl group or an aryl group, and 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 represents a single bond or Represents an arylene group.) (A3) At least one of the structural units having a thiirane ring is a combination of (a1) a structural unit having an acid group protected with an acid-decomposable group and / or (a2) a structural unit having a crosslinkable group. The photosensitive resin composition of any one of Claims 1-8 which is a polymer. (1) The process of apply | coating the photosensitive resin composition of any one of Claims 1-9 on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for producing a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition. The manufacturing method of the cured film of Claim 9 including the process of exposing the whole surface after the said image development process and before a post-baking process. A cured film formed by the method according to claim 10 or 11. The cured film according to claim 12, which is an interlayer insulating film. An organic EL display device or a liquid crystal display device having the cured film according to claim 12 or 13.

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