JP2016045248A - Photosensitive resin composition, production method of cured film, cured film, liquid crystal display device, organic electroluminescence display device and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having high sensitivity and capable of improving display unevenness, a production method of a cured film, a cured film, a liquid crystal display device, an organic electroluminescence display device and a touch panel.SOLUTION: The photosensitive resin composition comprises: a polymer component containing a polymer having a structural unit having a group in which an acid group is protected by an acid decomposable group; a photoacid generator that generates an acid having a pKa of 3 or less; a compound represented by General Formula (I) below; and a solvent. In Formula (I), Rrepresents an n-valent organic group; Rto Reach independently represent a hydrogen atom or an alkyl group; and n represents an integer of 1 or more.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition. More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film, an interlayer insulating film, and the like of electronic components such as a liquid crystal display device, an organic electroluminescence display device, a touch panel, an integrated circuit element, and a solid-state imaging element About. The present invention also relates to a method for producing a cured film, a cured film obtained by curing a photosensitive resin composition, a liquid crystal display device using the cured film, an organic electroluminescence display device, and an image display device such as a touch panel.

  Image display devices such as organic electroluminescence display devices, liquid crystal display devices, and touch panels are provided with a patterned interlayer insulating film. In forming an interlayer insulating film, a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.

An attempt has been made to use an acrylic resin as a film forming component for an interlayer insulating film in an image display device. As an interlayer insulating film using an acrylic resin, for example, the one described in Patent Document 1 is known.
Patent Document 2 discloses a positive photosensitive resin composition containing a carbamate-based thermal base generator.
Patent Document 3 discloses a photosensitive resin composition containing a urea-based thermal base generator.
Patent Document 4 discloses a chemically amplified resist material containing carbamoyloxime.

JP2011-221494A International publication WO2011 / 136074 pamphlet JP 2008-31324 A JP 2008-286924 A

  In recent years, in order to produce a high-definition display panel substrate with high productivity, production using a large-area glass substrate has become common. The photosensitive resin composition used for this is required to further improve the sensitivity. Furthermore, when the image display device is used, further improvement in display unevenness is demanded.

  An object of the present invention is to provide a photosensitive resin composition which has a high sensitivity and can improve display unevenness. Moreover, it aims at providing the manufacturing method of the cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel.

式（Ｉ）において、Ｒ¹は、水素原子またはｎ価の有機基を表し、Ｒ²〜Ｒ⁵は、それぞれ独立に、水素原子またはアルキル基を表し、ｎは、１以上の整数を表す。
＜２＞ 酸基を有する構成単位を有する重合体を含有する重合体成分と、キノンジアジド化合物と、下記一般式（Ｉ）で表される化合物と、溶剤と、を含有する感光性樹脂組成物；

式（Ｉ）において、Ｒ¹は、水素原子またはｎ価の有機基を表し、Ｒ²〜Ｒ⁵は、それぞれ独立に、水素原子またはアルキル基を表し、ｎは、１以上の整数を表す。
＜３＞ 一般式（Ｉ）において、Ｒ¹が芳香族環基である、＜１＞または＜２＞に記載の感光性樹脂組成物。
＜４＞ 一般式（Ｉ）において、Ｒ²〜Ｒ⁵が水素原子である、＜１＞〜＜３＞のいずれかに記載の感光性樹脂組成物。
＜５＞ 重合体成分が、架橋性基を有する構成単位を有する重合体を含有する、＜１＞〜＜４＞のいずれかに記載の感光性樹脂組成物。
＜６＞ 重合体成分が、下記（１−１）および（１−２）の少なくとも一方を満たす重合体成分である、＜１＞に記載の感光性樹脂組成物；
（１−１）（ａ１−１）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（ａ１−２）架橋性基を有する構成単位を有する重合体、
（１−２）（ａ１−１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体、および（ａ１−２）架橋性基を有する構成単位を有する重合体。
＜７＞ 構成単位（ａ１−１）が、下記式（Ａ２’）で表される構成単位である、＜６＞に記載の感光性樹脂組成物；

式（Ａ２’）中、Ｒ²¹およびＲ²²は、それぞれ独立に、水素原子、アルキル基またはアリール基を表し、Ｒ²¹およびＲ²²の少なくとも一方がアルキル基またはアリール基であり、Ｒ²³は、アルキル基またはアリール基を表し、Ｒ²¹またはＲ²²と、Ｒ²³とが連結して環状エーテルを形成してもよく、Ｒ²⁴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。
＜８＞ 架橋性基が、エポキシ基、オキセタニル基、および、−ＮＨ−ＣＨ₂−ＯＲで表される基から選ばれる１種以上である＜５＞〜＜７＞のいずれかに記載の感光性樹脂組成物；但し、Ｒは水素原子または炭素数１〜２０のアルキル基である。
＜９＞ 感光性樹脂組成物が、化学増幅型ポジ型感光性樹脂組成物である、＜１＞に記載の感光性樹脂組成物。
＜１０＞ 光酸発生剤が、オキシムスルホネート化合物および／またはオニウム塩化合物である、＜１＞に記載の感光性樹脂組成物。
＜１１＞ 光酸発生剤が、オキシムスルホネート化合物である、＜１＞に記載の感光性樹脂組成物。
＜１２＞ ＜１＞〜＜１１＞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と、塗布された感光性樹脂組成物から溶剤を除去する工程と、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と、露光された感光性樹脂組成物を現像液により現像する工程と、現像された感光性樹脂組成物を熱硬化する工程とを含む硬化膜の製造方法。
＜１３＞ 現像する工程後、熱硬化する工程前に、現像された感光性樹脂組成物を露光する工程を含む、＜１２＞に記載の硬化膜の製造方法。
＜１４＞ ＜１＞〜＜１１＞のいずれかに記載の感光性樹脂組成物を硬化してなる硬化膜。
＜１５＞ 層間絶縁膜である、＜１４＞に記載の硬化膜。
＜１６＞ ＜１４＞または＜１５＞に記載の硬化膜を有する、液晶表示装置。
＜１７＞ ＜１４＞または＜１５＞に記載の硬化膜を有する、有機エレクトロルミネッセンス表示装置。
＜１８＞ ＜１４＞または＜１５＞に記載の硬化膜を有する、タッチパネル。 As a result of investigations by the inventors, it has been found that the above-mentioned problems can be solved by incorporating a compound represented by the general formula (I) described later into the photosensitive resin composition. That is, the present invention provides the following.
<1> A polymer component containing a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, a photoacid generator that generates an acid having a pKa of 3 or less, and the following general formula ( A photosensitive resin composition comprising a compound represented by I) and a solvent;

In the formula (I), R ¹ represents a hydrogen atom or an n-valent organic group, R ^{2 to} R ⁵ each independently represents a hydrogen atom or an alkyl group, and n represents an integer of 1 or more.
<2> A photosensitive resin composition containing a polymer component containing a polymer having a structural unit having an acid group, a quinonediazide compound, a compound represented by the following general formula (I), and a solvent;

In the formula (I), R ¹ represents a hydrogen atom or an n-valent organic group, R ^{2 to} R ⁵ each independently represents a hydrogen atom or an alkyl group, and n represents an integer of 1 or more.
<3> The photosensitive resin composition according to <1> or <2>, wherein R ¹ is an aromatic ring group in the general formula (I).
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein R ^{2 to} R ⁵ are hydrogen atoms in the general formula (I).
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the polymer component contains a polymer having a structural unit having a crosslinkable group.
<6> The photosensitive resin composition according to <1>, wherein the polymer component is a polymer component satisfying at least one of the following (1-1) and (1-2);
(1-1) (a1-1) a polymer having a structural unit having an acid group protected by an acid-decomposable group, and (a1-2) a structural unit having a crosslinkable group,
(1-2) (a1-1) A polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group.
<7> The photosensitive resin composition according to <6>, wherein the structural unit (a1-1) is a structural unit represented by the following formula (A2 ′);

In formula (A2 ′), R ²¹ and R ²² each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, and R ²³ is: Represents an alkyl group or an aryl group, and R ²¹ or R ²² and R ²³ may combine to form a cyclic ether, R ²⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. Represents.
<8> The photosensitivity according to any one of <5> to <7>, wherein the crosslinkable group is one or more selected from an epoxy group, an oxetanyl group, and a group represented by —NH—CH ₂ —OR. Wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
<9> The photosensitive resin composition according to <1>, wherein the photosensitive resin composition is a chemically amplified positive photosensitive resin composition.
<10> The photosensitive resin composition according to <1>, wherein the photoacid generator is an oxime sulfonate compound and / or an onium salt compound.
<11> The photosensitive resin composition according to <1>, wherein the photoacid generator is an oxime sulfonate compound.
<12> The step of applying the photosensitive resin composition according to any one of <1> to <11> on the substrate, the step of removing the solvent from the applied photosensitive resin composition, and the solvent are removed. A cured film comprising a step of exposing the exposed photosensitive resin composition with actinic rays, a step of developing the exposed photosensitive resin composition with a developer, and a step of thermally curing the developed photosensitive resin composition Manufacturing method.
<13> The method for producing a cured film according to <12>, including a step of exposing the developed photosensitive resin composition after the step of developing and before the step of thermosetting.
<14> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <11>.
<15> The cured film according to <14>, which is an interlayer insulating film.
<16> A liquid crystal display device having the cured film according to <14> or <15>.
<17> An organic electroluminescence display device having the cured film according to <14> or <15>.
<18> A touch panel having the cured film according to <14> or <15>.

  The present invention can provide a photosensitive resin composition having high sensitivity and capable of improving display unevenness. Moreover, it became possible to provide the manufacturing method of the cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel.

1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. 1 shows a conceptual diagram of a configuration of an example of an organic EL display device. It is sectional drawing which shows the structural example of an electrostatic capacitance type input device. It is explanatory drawing which shows an example of a front plate. It is explanatory drawing which shows an example of a 1st transparent electrode pattern and a 2nd transparent electrode pattern.

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.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In this specification, solid content is solid content in 25 degreeC.

本発明の感光性樹脂組成物は、化学増幅型ポジ型感光性樹脂組成物として好ましく用いることができる。
以下本発明を詳細に説明する。 The photosensitive resin composition of the present invention includes a polymer component having a structural unit having a group in which an acid group is protected by an acid-decomposable group, a photoacid generator that generates an acid having a pKa of 3 or less, and will be described later. A composition (first embodiment) containing a compound represented by general formula (I) and a solvent, or a polymer component having a structural unit having an acid group, a quinonediazide compound, and a general formula (described later) It is a composition (2nd aspect) containing the compound represented by I), and a solvent.
Although an example of the mechanism of the effect expression of this invention is estimated as follows, if the same effect is acquired, it will not specifically limit. That is, the compound represented by the general formula (I) is a compound having a carboxyl group, and has an acidic property in a normal state. For this reason, in the state before a heating, especially in an exposure stage, a composition can be made into an acidic state, generation | occurrence | production of the carboxyl group and phenolic hydroxyl group by exposure advances favorably, and the outstanding sensitivity is achieved. In the compound represented by the general formula (I), the carboxyl group is decarboxylated or dehydration-cyclized and lost by heating, so that the amine site that has been neutralized and inactivated becomes active and becomes basic. . That is, in the heating for curing after exposure, when the compound represented by the general formula (I) is heated, the reaction of the following formula proceeds to generate a base. And the acid etc. which are liberated in the cured film can be neutralized by the base generated from the compound represented by the general formula (I). For this reason, the metal discoloration in an electrode part etc. by the influence of an acid can be suppressed and the display nonuniformity at the time of setting it as an image display apparatus etc. can be improved.

The photosensitive resin composition of the present invention can be preferably used as a chemically amplified positive photosensitive resin composition.
The present invention will be described in detail below.

式（Ｉ）において、Ｒ¹は、水素原子またはｎ価の有機基を表し、Ｒ²〜Ｒ⁵は、それぞれ独立に、水素原子またはアルキル基を表し、ｎは、１以上の整数を表す。 [First Aspect of the Present Invention]
The photosensitive resin composition according to the first aspect of the present invention includes (A1) a polymer component having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (B1) an acid having a pKa of 3 or less. A photoacid generator that generates (C), a compound represented by the following general formula (I), and (D) a solvent.

In the formula (I), R ¹ represents a hydrogen atom or an n-valent organic group, R ^{2 to} R ⁵ each independently represents a hydrogen atom or an alkyl group, and n represents an integer of 1 or more.

<(A1) Polymer component>
The photosensitive resin composition of the 1st aspect of this invention has a polymer component containing the polymer which has a structural unit (a1-1) which has the group in which the acid group was protected by the acid-decomposable group.
The “group in which an acid group is protected with an acid-decomposable group” in the present invention is a group that causes a deprotection reaction using an acid as a catalyst (or an initiator) to generate an acid group, a regenerated acid, and a decomposed structure. Means. A well-known thing can be used as an acid group and an acid-decomposable group, It does not specifically limit. (A1) When a polymer component has the said structural unit (a1-1), it can be set as a highly sensitive photosensitive resin composition.
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. Specific acid-decomposable groups include groups that are relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group, which will be described later), or an acid. Examples include groups that are relatively difficult to decompose (for example, tertiary alkyl groups such as tert-butyl ester groups and tertiary alkyl carbonate groups such as tert-butyl carbonate groups).

In the present invention, the (A1) polymer component preferably contains a crosslinkable group, and more preferably contains a polymer having a structural unit (a1-2) having a crosslinkable group. According to this aspect, a cured film having excellent surface hardness can be obtained. Furthermore, display unevenness in an image display device or the like can be improved.
The crosslinkable group is not particularly limited as long as it is a group having a crosslinking reaction starting temperature of 100 ° C. or higher during heat treatment at 1 atm. The initiation temperature of the cross-linking reaction can be analyzed using a known method, for example, by a method using DSC measurement (Differential scanning calorimetry). As a preferred embodiment of the structural unit having a crosslinkable group, an epoxy group, an oxetanyl group, a group represented by —NH—CH ₂ —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene And a structural unit containing at least one selected from the group consisting of an unsaturated group. It is preferably at least one selected from the group represented by an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Among them, in the photosensitive resin composition of the present invention, it is preferable that the (A1) polymer component includes a structural unit including at least one of an epoxy group and an oxetanyl group.

The structural unit (a1-2) may be contained in a polymer having the structural unit (a1-1), or may be a polymer different from the polymer having the structural unit (a1-1). It may be included. That is, in the present invention, the (A1) polymer component preferably satisfies at least one of the following (1-1) and (1-2).
(1-1) (a1-1) a polymer having a structural unit having an acid group protected by an acid-decomposable group, and (a1-2) a structural unit having a crosslinkable group,
(1-2) (a1-1) A polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group.
Hereinafter, the structural unit (a1-1) having a group in which an acid group is protected with an acid-decomposable group is also referred to as a structural unit (a1-1). In addition, the structural unit (a1-2) having a crosslinkable group is also referred to as a structural unit (a1-2).
(A1) Unless otherwise stated, a polymer component means what contains the other polymer added as needed in addition to the said polymer.

  The above-described aspect (1-1) is an aspect including at least one type of polymer, the polymer having the structural unit (a1-1) and the structural unit (aI1-2). This polymer may further contain other repeating units. In addition, the structural unit (a1-1) and the structural unit (a1-2) may each include two or more types. Moreover, the other structural unit (a1-3) mentioned later may be included.

In the above aspect (1-2), at least two types of polymers are included, at least one of the polymers has the structural unit (a1-1), and at least one other type of polymer is the structural unit. This is an embodiment having (a1-2). In the aspect of (1-2), the polymer containing the structural unit (a1-1) may further contain the structural unit (a1-2) or another structural unit. Similarly, the polymer containing the structural unit (a1-2) may contain the structural unit (a1-1) or another structural unit. In such a case, the embodiment satisfies both (1-1) and (1-2).
In the case of the above (1-2), the mass ratio of the polymer having the structural unit (a1-1) and the polymer having the structural unit (a1-2) is 95: 5 to 5:95. Preferably, 80:20 to 20:80 is more preferable, and 70:30 to 30:70 is more preferable.

  The (A1) polymer component is preferably an addition polymerization type polymer, more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc. The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”.

<< (a1-1) Structural unit having a group in which an acid group is protected by an acid-decomposable group >>
(A1) The polymer component has at least a structural unit (a1-1) having a group in which an acid group is protected with an acid-decomposable group.
The structural unit (a1-1) is preferably a structural unit having a protected carboxyl group protected with an acid-decomposable group or a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group. Hereinafter, the structural unit (a1-1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group Each will be described in turn.

<<< (a1-1-1) Structural unit having a protected carboxyl group protected with an acid-decomposable group >>>>
The structural unit (a1-1-1) is a structural unit having a protected carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described below.
There is no restriction | limiting in particular as a structural unit which has a carboxyl group, A well-known structural unit can be used. For example, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid (a1-1-1-1) Is mentioned. Hereinafter, the structural unit (a1-1-1-1) will be described.

<<<<< (a1-1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>>
As unsaturated carboxylic acid, the following are used.
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, 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.
Further, the unsaturated polyvalent carboxylic acid used for obtaining the structural unit having a carboxyl group may be an acid anhydride. 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 these, from the viewpoint of developability, in order to form the structural unit (a1-1-1-1), acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meta ) It is preferable to use acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or an anhydride of unsaturated polyvalent carboxylic acid. Acrylic acid, methacrylic acid, 2- (meta It is more preferable to use acryloyloxyethyl hexahydrophthalic acid.
The structural unit (a1-1-1-1) may be composed of one type alone, or may be composed of two or more types.

<<<< acid-decomposable group that can be used for the structural unit (a1-1-1) >>>>
As the acid-decomposable group that can be used for the structural unit (a1-1-1), the acid-decomposable groups described above can be used.
Among these acid-decomposable groups, a group having a structure protected in the form of an acetal is preferable. For example, the protected carboxyl group in which the carboxyl group is protected in the form of an acetal means that the basic physical properties of the photosensitive resin composition, in particular the sensitivity and pattern shape, the formation of contact holes, and the storage stability of the photosensitive resin composition From the viewpoint of Furthermore, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the general formula (a1-10). 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、それぞれ独立に、水素原子、アルキル基またはアリール基を表す。但し、Ｒ¹⁰¹とＲ¹⁰²とが共に水素原子の場合を除く。Ｒ¹⁰³は、アルキル基またはアリール基を表す。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 independently represents a hydrogen atom, an alkyl group or an aryl group. However, the case where both R ¹⁰¹ and R ¹⁰² are hydrogen atoms is excluded. R ¹⁰³ represents an alkyl group or an aryl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.

The alkyl group represented by R ^{101 to} R ¹⁰³ 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.
Moreover, when the said alkyl group is a cyclic | annular alkyl group, you may have a C1-C10 linear or branched alkyl group as a substituent. Moreover, when an alkyl group is a linear or branched alkyl group, you may have a C3-C12 cyclic alkyl group as a substituent.
These substituents may be further substituted with the above substituents.

The aryl group represented by R ^{101 to} R ¹⁰³ is preferably an aryl group having 6 to 12 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may have a substituent, and the substituent is preferably an alkyl group having 1 to 6 carbon atoms. Specific examples of the aryl group include a phenyl group, a tolyl group, a xylyl 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 synthesize | combine with the synthesis | combining method etc. of Paragraph Nos. 0037-0040 of Unexamined-Japanese-Patent No. 2011-221494, The content is integrated in this-application specification.

  A first preferred embodiment of the structural unit (a1-1-1) is a structural unit represented by the following general formula (A2 ′).

式（Ａ２’）中、Ｒ²¹およびＲ²²は、それぞれ独立に、水素原子、アルキル基またはアリール基を表し、Ｒ²¹およびＲ²²の少なくとも一方がアルキル基またはアリール基であり、Ｒ²³は、アルキル基またはアリール基を表し、Ｒ²¹またはＲ²²と、Ｒ²³とが連結して環状エーテルを形成してもよく、Ｒ²⁴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。

In formula (A2 ′), R ²¹ and R ²² each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, and R ²³ is: Represents an alkyl group or an aryl group, and R ²¹ or R ²² and R ²³ may combine to form a cyclic ether, R ²⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. Represents.

When R ²¹ and R ²² are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferable. When R ²¹ and R ²² are aryl groups, a phenyl group is preferred. R ²¹ and R ²² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ²³ 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.

  A second preferred embodiment of the structural unit (a1-1-1) is a structural unit represented by the following general formula (1-12).

式（１−１２）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はそれぞれ独立に、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。 Formula (1-12)

In formula (1-12), 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 independently represents a hydrogen atom or a carbon atom. The alkyl group of number 1-4 is represented.
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 (a1-1-1) include the following structural units. In the structural units below, R represents a hydrogen atom or a methyl group.

<<< (a1-1-2) Structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group >>>
The structural unit (a1-1-2) is a structural unit (a1-1-2-1) in which a structural unit having a phenolic hydroxyl group has a protected phenolic hydroxyl group protected by an acid-decomposable group described in detail below. ).

<<<<< (a1-1-2-1) 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 linear or branched group having 1 to 5 carbon atoms. A chain alkyl group is represented, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less. In addition, when two or more ^R222 exists, these ^R222 may mutually differ or may be 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. .
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 (a1-1-2) >>>>
The acid-decomposable group that can be used for the structural unit (a1-1-2) is the same as the acid-decomposable group that can be used for the structural unit (a1-1-1). It 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 the basic physical property of the photosensitive resin composition, particularly the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, and the formation of contact holes. From the viewpoint of sex. Furthermore, among 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, R ¹⁰³ = benzyl group and the like.
Examples of the radical 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 an acetal are described in paragraph No. 0042 of JP2011-215590A. And so on.
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.

  A commercially available thing may be used for the radically polymerizable monomer used in order to form a structural unit (a1-1-2), and what was synthesize | combined by the well-known method 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 (a1-1-2) include the following structural units, but the present invention is not limited thereto.

<<< Preferred Aspect of Structural Unit (a1-1) >>>
When the polymer containing the structural unit (a1-1) is substantially free of the structural unit (a1-2), the content of the structural unit (a1-1) is 20 to 100 in the polymer. The mol% is preferable, and 30 to 90 mol% is more preferable.
When the polymer containing the structural unit (a1-1) contains the structural unit (a1-2), the content of the single structural unit (a1-1) is 3 to 70 mol% in the polymer. Preferably, 10 to 60 mol% is more preferable. Moreover, when a structural unit (a1-1) is a structural unit which has the protected carboxyl group in which the carboxyl group was protected in the form of an acetal, 20-50 mol% is preferable.

  The structural unit (a1-1-1) is characterized by faster development than the structural unit (a1-1-2). Therefore, when it is desired to develop quickly, the structural unit (a1-1-1) is preferable. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-1-2).

<< (a1-2) Structural Unit Having a Crosslinkable Group >>
(A1) The polymer component preferably has a structural unit (a1-2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. What was mentioned above is mentioned. At least one selected from an epoxy group, an oxetanyl group, and a group represented by —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) is preferable. Of these, an epoxy group and / or an oxetanyl group are preferable.
Examples of the structural unit having a crosslinkable group include the following.

<<< (a1-2-1) Structural Unit Having Epoxy Group and / or Oxetanyl Group >>>
(A1) The polymer component preferably contains a structural unit having an epoxy group and / or an oxetanyl group (hereinafter also referred to as a structural unit (a1-2-1)).
The structural unit (a1-2-1) may have at least one epoxy group or oxetanyl group in one structural unit. Although not particularly limited, it preferably has 1 to 3 epoxy groups and / or oxetanyl groups in total, more preferably 1 or 2, more preferably 1 epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic And compounds containing epoxy backbone can be cited, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Examples thereof include acrylate esters and compounds described in paragraph No. 0027 of JP2012-088459A, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit (a1-2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylate structure and an acrylate ester. A monomer containing a structure is preferred.

  Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl are preferred. Ether, acrylic acid (3-ethyloxetane-3-yl) methyl, and methacrylic acid (3-ethyloxetane-3-yl) methyl are preferred from the viewpoints of copolymerization reactivity and improved properties of the cured film. These structural units can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit (a1-2-1) include the following structural units. In the structural units below, R represents a hydrogen atom or a methyl group.

<<< (a1-2-2) Structural unit having an ethylenically unsaturated group >>>
As one of the structural units (a1-2) having a crosslinkable group, there may be mentioned a structural unit (a1-2-2) having an ethylenically unsaturated group. As the structural unit (a1-2-2), a structural unit having an ethylenically unsaturated group in the side chain is preferable, a structural unit having an ethylenically unsaturated group at the terminal and a side chain having 3 to 16 carbon atoms. Is more preferable.
In addition, as for the structural unit (a1-2-2), compounds described in paragraph numbers 0072 to 0090 of JP2011-215580A and paragraph numbers 0013 to 0031 of JP2008-256974A are preferable. The contents of which are incorporated herein by reference.

<<< constituent unit having a group represented by (a1-2-3) -NH—CH ₂ —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>
As one of the structural units (a1-2) having a crosslinkable group, a structure having a group represented by —NH—CH ₂ —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The unit (a1-2-3) is also preferable. By having the structural unit (a1-2-3), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. R 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. The structural unit (a1-2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).

一般式（ａ２−３０）中、Ｒ¹は水素原子またはメチル基を表し、Ｒ²は水素原子または炭素数１〜２０のアルキル基を表す。
Ｒ²は、炭素数１〜９のアルキル基が好ましく、炭素数１〜４のアルキル基がさらに好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。
Ｒ²の具体例としては、メチル基、エチル基、ｎ−ブチル基、ｉｓｏ−ブチル基、シクロヘキシル基、およびｎ−ヘキシル基を挙げることができる。中でもｉｓｏ−ブチル基、ｎ−ブチル基、メチル基が好ましい。 Formula (a2-30)

In General Formula (a2-30), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or 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 iso-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, an iso-butyl group, an n-butyl group, and a methyl group are preferable.

<<< Preferred Aspect of Structural Unit Having (a1-2) Crosslinkable Group >>>
When the polymer containing the structural unit (a1-2) is substantially free of the structural unit (a1-1), the content of the structural unit (a1-2) is 5 to 90 in the polymer. Mol% is preferable and 20-80 mol% is more preferable.
When the polymer containing the structural unit (a1-2) contains the structural unit (a1-1), the content of the structural unit (a1-2) is 3 in the polymer from the viewpoint of chemical resistance. -70 mol% is preferable and 10-60 mol% is more preferable.
In the present invention, the content of the structural unit (a1-2) is preferably 3 to 70 mol% in all the structural units of the polymer component (A1) regardless of any embodiment. More preferably, it is mol%. By setting it within the above numerical range, a cured film having excellent characteristics can be formed.

<< (a1-3) Other structural units >>
(A1) In addition to the structural unit (a1-1) and / or the structural unit (a1-2), the polymer component may have another structural unit (a1-3) other than these. The structural unit (a1-3) may contain a polymer having at least one structural unit selected from the structural unit (a1-1) and the structural unit (a1-2). Moreover, the polymer which does not contain a structural unit (a1-1) and a structural unit (a1-2) substantially may be contained.

  There is no restriction | limiting in particular as a monomer used as another structural unit (a1-3), 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, other unsaturated compounds Can be mentioned. 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 (a1-3) can be used individually or in combination of 2 or more types.

  Specific examples of the structural unit (a1-3) include styrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4 -Hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, N-cyclohexylmaleimide, acrylonitrile, ethylene glycol mono It can be mentioned a structural unit due Seto acetate mono (meth) acrylate. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  The other structural unit (a1-3) is preferably a structural unit having a styrene or an aliphatic cyclic skeleton from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and the like.

  The other structural unit (a1-3) is preferably a (meth) acrylic acid alkyl ester 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.

  The other structural unit (a1-3) preferably has a structural unit containing an acid group. By containing an acid group, it becomes easy to dissolve in an alkaline developer. 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 derived from carboxylic acid groups, derived from sulfonamide groups, derived from phosphonic acid groups, derived from sulfonic acid groups, derived from phenolic hydroxyl groups, sulfonamide groups, sulfonylimides Examples include groups derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups.
The structural unit containing an acid group is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid and / or an ester thereof. For example, the compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein. Of these, structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferred.

As a method for introducing the structural unit containing an acid group, it can be introduced into the same polymer as the structural unit (a1-1) and / or the structural unit (a1-2), or (a1-1) the structural unit and ( a1-2) It can also be introduced as a structural unit of a polymer different from the structural unit.
As the polymer having a structural unit containing an acid group, a resin having a carboxyl group in the side chain is preferred. 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.

  Examples of commercially available products include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Cray Valley), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3510, and ARUFON UC-3510. ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (manufactured by Toagosei Co., Ltd.), Joncry 690, Joncryl 678, Joncryl 67, Joncry 586 (manufactured by BASF), etc. can also be used.

  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. For example, the compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.

  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 25 mol% is particularly preferable.

Hereinafter, preferred embodiments of the polymer component (A1) will be described, but the present invention is not limited thereto.
(First embodiment)
In the aspect of (1-1) described above, the polymer having the structural unit (a1-1) and the structural unit (a1-2) is further one or more other structural units (a1-3). The aspect which has.
(Second Embodiment)
In the aspect of (1-2) described above, the polymer having the structural unit (a1-1) further has one or more other structural units (a1-3).
(Third embodiment)
In the aspect of (1-2) described above, the polymer having the structural unit (a1-2) further has one or more other structural units (a1-3).
(Fourth embodiment)
In any one of the first to third embodiments, the other structural unit (a1-3) includes a structural unit containing at least an acid group.
(Fifth embodiment)
In the above-mentioned embodiment (1-1) and / or (1-2), the structural unit (a1-1) and the structural unit (a1-2) are not substantially included, and the other structural unit (a1-3). An embodiment having a polymer having
(Sixth embodiment)
The form which consists of 2 or more combinations of the said 1st-5th embodiment.

In an embodiment having a polymer having other structural unit (a1-3) substantially not including the structural unit (a1-1) and the structural unit (a1-2), the structural unit (a1-1) and / or Alternatively, the total amount of the polymer having the structural unit (a1-2) and the other structural unit (a1-3) substantially not including the structural unit (a1-1) and the structural unit (a1-2). The mass ratio with the total amount of the polymer is preferably 99: 1 to 5:95, more preferably 97: 3 to 30:70, and still more preferably 95: 5 to 50:50.
It is preferable that the photosensitive resin composition of this invention contains a polymer component in the ratio of 70 mass% or more of solid content of the photosensitive resin composition, and 70-99 mass% is more preferable.

<< (A1) Molecular Weight of Polymer Component >>
The molecular weight of the polymer contained in the (A1) polymer component is a polystyrene-equivalent weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the said range. The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
(A1) The weight average molecular weight and dispersity of the polymer contained in the polymer component are defined as polystyrene-converted values by GPC (gel permeation chromatography) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer component are, for example, HLC-8120 (manufactured by Tosoh Corporation) and TSK gel Multipore HXL-M (Tosoh ( 7.8 mm ID × 30.0 cm manufactured by Co., Ltd. can be obtained by using THF (tetrahydrofuran) as an eluent.

<< (A1) Production Method of Polymer Component >>
Various methods are known for producing the polymer component (A1). To name one example, it is used to form at least the structural units represented by (a1-1) and (a1-3). It can synthesize | combine by superposing | polymerizing the composition containing the radically polymerizable monomer obtained using a radical polymerization initiator in an organic solvent. It can also be synthesized by a so-called polymer reaction.
(A1) The polymer component preferably contains 50 mol% or more, more preferably 80 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units. preferable.

<(B1) Photoacid generator>
The photosensitive resin composition of the 1st aspect of this invention contains the photo-acid generator which generate | occur | produces the acid whose pKa is 3 or less. The photoacid generator is preferably one that generates an acid having a pKa of 2 or less. In the present invention, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to. The acid having a pKa of 3 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.

  The photoacid generator is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm and generates an acid, but is not limited to its chemical structure. 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 the sensitizer It can be preferably used in combination.

  Examples of photoacid generators include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. . Among these, onium salt compounds, imide sulfonate compounds, and oxime sulfonate compounds are preferable, and onium salt compounds and oxime sulfonate compounds are particularly preferable. A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.

Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane compounds include compounds described in paragraphs 0083 to 0088 of JP2011-221494A; And compounds described in paragraph numbers 0013 to 0049 of JP-A-2011-105645, and the contents thereof are incorporated in the present specification.
Specific examples of the imide sulfonate compound include the compounds described in paragraphs 0065 to 0075 of WO2011 / 087011, and the contents thereof are incorporated herein.

  Examples of the onium salt compound include diphenyl iodonium salt, triarylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and the like.

  Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium. Butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate Bis (4-t-butylphenyl) iodonium trifluorome Sulphonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid, etc. .

  Examples of the triarylsulfonium salt include triphenylsulfonium tosylate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p- Toluenesulfonate, triphenylsulfonium butyltris (2,6-difluorophenyl) borate and the like can be mentioned.

  Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

  Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like can be mentioned.

  Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenyl. Methylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl Examples include methylsulfonium hexafluorophosphate.

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, and dibenzyl-4-methoxyphenylsulfonium. Hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl- Examples include 4-hydroxyphenylsulfonium hexafluorophosphate.

  Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethyl. Sulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3- Examples include chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-methoxybenzyl). ) Benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane. Sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1 , 2,2-Tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo) [2.2.1] Heptan-2-yl) -1,1, , 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl ) -1,1,2,2-tetrafluoroethanesulfonate and the like.

  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 (B1-1).

一般式（Ｂ１−１）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 (B1-1)

In General Formula (B1-1), R ²¹ represents an alkyl group or an aryl group. Wavy lines represent bonds with other groups.

In general formula (B1-1), 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 of R ²¹ is a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group (such as a 7,7-dimethyl-2-oxonorbornyl group). It may be substituted with a bridged alicyclic 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 the oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-2).

式（Ｂ１−２）中、Ｒ⁴²は、置換されていても良いアルキル基またはアリール基を表し、Ｘは、アルキル基、アルコキシ基、または、ハロゲン原子を表し、ｍ４は、０〜３の整数を表し、ｍ４が２または３であるとき、複数のＸは同一でも異なっていてもよい。 General formula (B1-2)

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

Preferred ranges of R ^42, the same as the preferable range of the R ^21.
The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Moreover, 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 (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-3).

式（Ｂ１−３）中、Ｒ⁴³は式（Ｂ１−２）におけるＲ⁴²と同義であり、Ｘ¹は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、シアノ基またはニトロ基を表し、ｎ４は０〜５の整数を表す。 General formula (B1-3)

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

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

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

上記一般式（ＯＳ−１）中、Ｒ¹⁰¹は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基、または、ヘテロアリール基を表す。Ｒ¹⁰²は、アルキル基、または、アリール基を表す。

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, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is incorporated herein by reference.

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 this invention, as a compound containing the oxime sulfonate structure represented by the said general formula (B1-1), the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-) The oxime sulfonate compound represented by 5) is preferred.

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 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 are 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 Represent.

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

Moreover, the compound containing the oxime sulfonate structure represented by the above general formula (B1-1) is, for example, described in the general formula (OS-6) described in paragraph 0117 of JP2012-163937A. A compound represented by any of (OS-11) is particularly preferred, the contents of which are incorporated herein.
Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. The contents of which are incorporated herein by reference.
Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. The contents of which are incorporated herein by reference. The present invention is not limited to these.

  The compound containing the oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-4).

一般式（Ｂ１−４）中、Ｒ¹は、アルキル基またはアリール基を表し、Ｒ²は、アルキル基、アリール基、またはヘテロアリール基を表す。Ｒ³〜Ｒ⁶は、それぞれ、水素原子、アルキル基、アリール基、ハロゲン原子を表す。但し、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、またはＲ⁵とＲ⁶が結合して脂環または芳香環を形成してもよい。Ｘは、−Ｏ−またはＳ−を表す。 General formula (B1-4)

In General Formula (B1-4), R ¹ represents an alkyl group or an aryl group, and R ² represents an alkyl group, an aryl group, or a heteroaryl group. R ^{3 to} R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. However, R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form an alicyclic ring or aromatic ring. X represents -O- or S-.

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

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

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

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

  Specific examples of the general formula (B1-4) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

  As an imide sulfonate type compound, a naphthalene imide type compound is preferable, the description of international publication WO11 / 087011 pamphlet can be referred to, These content is integrated in this-application specification. In the present invention, a compound represented by the following formula is particularly preferable.

式中、Ｒ¹およびＲ²は、それぞれ、下記一般式（Ａ）で表される基または水素原子を表す。Ｒ³は、ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１〜１８の脂肪族炭化水素基、ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６〜２０のアリール基、ハロゲン原子および／またはアルキルチオ基で置換されてもよい炭素数７〜２０のアリールアルキル基、１０−カンファーイル基または、下記一般式（Ｂ）で表される基を表す。
一般式（Ａ）

一般式（Ａ）中、Ｘ¹は、酸素原子または硫黄原子を表し、Ｙ¹は、単結合または炭素数１〜４のアルキレン基を表し、Ｒ⁴は、炭素数１〜１２の炭化水素基を表し、Ｒ⁵は、炭素数１〜４のアルキレン基を表し、Ｒ⁶は、水素原子、分岐していてもよい炭素数１〜４のアルキル基、炭素数３〜１０の脂環式炭化水素基、複素環基、または水酸基を表す。ｎは、０〜５の整数を表し、ｎが２〜５の場合、複数存在するＲ⁵は同一でも異なってもよい。
一般式（Ｂ）

一般式（Ｂ）中、Ｙ²は、単結合または炭素数１〜４のアルキレン基を表し、Ｒ⁷は、炭素数２〜６のアルキレン基、炭素数２〜６のハロゲン化アルキレン基、炭素数６〜２０のアリーレン基、または炭素数６〜２０のハロゲン化アリーレン基を表し、Ｒ⁸は、単結合、炭素数２〜６のアルキレン基、炭素数２〜６のハロゲン化アルキレン基、炭素数６〜２０のアリーレン基または炭素数６〜２０のハロゲン化アリーレン基を表し、Ｒ⁹は、分岐していてもよい炭素数１〜１８のアルキル基、分岐していてもよい炭素数１〜１８のハロゲン化アルキル基、炭素数６〜２０のアリール基、炭素数６〜２０のハロゲン化アリール基、炭素数７〜２０のアリールアルキル基、または炭素数７〜２０のハロゲン化アリールアルキル基を表す。ａおよびｂはそれぞれ独立に０または１を表し、ａおよびｂの少なくとも一方は１である。

In the formula, R ¹ and R ² each represent a group represented by the following general formula (A) or a hydrogen atom. R ³ represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group, a halogen atom, an alkylthio group, an alkyl group and an acyl. An aryl group having 6 to 20 carbon atoms which may be substituted with any one or more of the groups, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, 10-camphoryl group Or represents the group represented by the following general formula (B).
Formula (A)

In the general formula (A), X ¹ represents an oxygen atom or a sulfur atom, Y ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms. R ⁵ represents an alkylene group having 1 to 4 carbon atoms, R ⁶ represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic carbon atom having 3 to 10 carbon atoms. Represents a hydrogen group, a heterocyclic group, or a hydroxyl group. n represents an integer of 0 to 5, and when n is 2 to 5, a plurality of R ⁵ may be the same or different.
General formula (B)

In general formula (B), Y ² represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ⁷ represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, or carbon. Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R ⁸ represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R ⁹ is an alkyl group having 1 to 18 carbon atoms which may be branched, or 1 to 1 carbon atoms which may be branched. 18 halogenated alkyl groups, aryl groups having 6 to 20 carbon atoms, halogenated aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, or halogenated arylalkyl groups having 7 to 20 carbon atoms. Represent. a and b each independently represents 0 or 1, and at least one of a and b is 1.

  Although the example of the imide sulfonate type compound preferably used by this invention below is shown, it cannot be overemphasized that this invention is not limited to these.

  In the photosensitive resin composition of the present invention, the content of the photoacid generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid component of the photosensitive resin composition. For example, the lower limit is more preferably 0.2 parts by mass or more, and further preferably 0.5 parts by mass or more. For example, the upper limit is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

式（Ｉ）において、Ｒ¹は、水素原子またはｎ価の有機基を表し、Ｒ²〜Ｒ⁵は、それぞれ独立に、水素原子またはアルキル基を表し、ｎは、１以上の整数を表す。 <(C) Compound>
The photosensitive resin composition of the 1st aspect of this invention contains the compound represented by the following general formula (I). Hereinafter, the compound represented by the general formula (I) is also referred to as (C) compound.

In the formula (I), R ¹ represents a hydrogen atom or an n-valent organic group, R ^{2 to} R ⁵ each independently represents a hydrogen atom or an alkyl group, and n represents an integer of 1 or more.

In general formula (I), R ¹ represents a hydrogen atom or an n-valent organic group. Examples of the organic group include an aliphatic group, an aromatic ring group, and a group formed by combining an aliphatic group or an aromatic ring group with a linking group described later. Examples of the linking group include —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, or a linking group in which a plurality of these are linked. . -COO- and -OCO- are preferable. Specific examples of the group formed by combining an aliphatic group or an aromatic ring group and a linking group include an alkoxycarbonyl group and an acyloxy group.
R ¹ is preferably an aromatic ring group. By making R ^{1 an} aromatic ring group, a base having a high boiling point can be easily generated at a lower temperature. By increasing the boiling point of the generated base, it is difficult to volatilize or decompose by heating during post-baking, and display unevenness in an image display device or the like can be improved more effectively.
Examples of when R ¹ is a monovalent aliphatic group include an alkyl group and an alkenyl group.
1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are still more preferable. The alkyl group may be linear, branched or cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group.
2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-10 are still more preferable. The alkenyl group may be linear, branched or cyclic. The alkenyl group may have a substituent or may be unsubstituted. Examples of the alkenyl group include a vinyl group and a (meth) allyl group.
Examples of when R ¹ is a divalent aliphatic group include groups in which one or more hydrogen atoms have been removed from the above monovalent aliphatic group.
The aromatic ring group may be monocyclic or polycyclic. The aromatic ring group may be a heteroaromatic ring group containing a hetero atom. The aromatic ring group may have a substituent or may be unsubstituted. Specific examples of the aromatic ring group include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, Chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran Ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, Antoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring is most preferred.
In the aromatic ring group, a plurality of aromatic rings may be linked via a single bond or a linking group described later. As the linking group, for example, —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group (preferably a straight chain having 1 to 10 carbon atoms or A branched alkylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 10 carbon atoms), or a linking group in which a plurality of these are linked. A group consisting of an alkylene group, —O— and a combination thereof is preferred, and a combination of an alkylene group and —O— is more preferred. The alkylene group and cycloalkylene group may be unsubstituted or may have a substituent. Examples of the substituent include those described later.
Specific examples of the aromatic ring group in which a plurality of aromatic rings are linked through a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropane, triphenylmethane, tetraphenylmethane, diphenoxymethane, di Examples include phenoxyethane.
1-30 are preferable, as for carbon number of an alkoxycarbonyl group, 1-20 are more preferable, and 1-10 are still more preferable. The alkoxycarbonyl group may be linear or branched. The alkoxycarbonyl group may have a substituent or may be unsubstituted.
1-30 are preferable, as for carbon number of an acyloxy group, 1-20 are more preferable, and 1-10 are still more preferable. The acyloxy group may be linear or branched. The acyloxy group may have a substituent or may be unsubstituted.

Examples of the substituent that the organic group represented by R ¹ may have include, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy such as methoxy group, ethoxy group and tert-butoxy group Groups; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, tert-butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; Group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group and other acyl groups; methylsulfanyl group and tert-butylsulfanyl group and other alkylsulfanyl groups; phenylsulfanyl group and p-tolylsulfanyl group and the like Lylsulfanyl group; alkyl group such as methyl group, ethyl group, tert-butyl group and dodecyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group and adamantyl group; phenyl group, p-tolyl group and xylyl group , Cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxyl group; carboxyl group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; Monoalkylamino group; dialkylamino group; arylamino group; diarylamino group thioxy group; carbamoyl group or a combination thereof.

R ^{2 to} R ⁵ each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. A compound in which R ^{2 to} R ⁵ are represented by a hydrogen atom easily generates a base by heating at a lower temperature.
1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, 1-10 are still more preferable, 1-5 are still more preferable, and a methyl group is especially preferable. The alkyl group may be linear or branched, and is preferably linear. The alkyl group may have a substituent and may be unsubstituted, but is preferably unsubstituted.

n represents an integer of 1 or more, preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 or 2. The upper limit of n is the maximum number of substituents that the organic group can take when R ¹ represents an organic group. When R ¹ represents a hydrogen atom, n is 1.

As for the molecular weight of the compound represented by general formula (I), 100-1000 are preferable. The lower limit is more preferably 130 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the structural formula.
The compound represented by the general formula (I) is preferably a compound that generates a base when heated to 120 to 250 ° C., and more preferably a compound that generates a base at 120 to 200 ° C. The base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
The base generated by the compound represented by the general formula (I) is preferably a cyclic amine.
The boiling point of the base generated by the compound represented by formula (I) is preferably 80 ° C. or higher, preferably 100 ° C. or higher, and more preferably 140 ° C. or higher. Further, the molecular weight of the generated base is preferably 80 to 500. The upper limit is more preferably 400 or less. The molecular weight value is a theoretical value obtained from the structural formula.

  Specific examples of the compound represented by the general formula (I) include the following compounds. Needless to say, the present invention is not limited to these examples.

In the photosensitive resin composition of the present invention, the content of the compound (C) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. For example, the lower limit is more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and still more preferably 0.5 parts by mass or more. For example, the upper limit is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.
In the photosensitive resin composition of the present invention, the content of the compound (C) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the polymer component (A1) described above. For example, the lower limit is more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and still more preferably 0.5 parts by mass or more. For example, the upper limit is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.

<(D) Solvent>
The photosensitive resin composition of the first aspect of the present invention contains 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 further optional components described below are dissolved in a solvent. The solvent is preferably a solvent that dissolves essential components and optional components and does not react with each component.
In the present invention, a known solvent can be used as the solvent.
For example, 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 (for example, Diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc.), diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides And lactones Kill. Further, the solvent described in paragraph Nos. 0174 to 0178 of JP2011-221494A and the solvent described in paragraph numbers 0167 to 0168 of JP2012-194290A are also included, and the contents thereof are incorporated in the present specification. .

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.
One type of solvent may be used alone, or two or more types may be used. When two or more are used, for example, it is more preferable to use propylene glycol monoalkyl ether acetates and dialkyl ethers, diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates in combination. .

The solvent 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.

  It is preferable that content of the solvent in the photosensitive resin composition of this invention is 40-95 mass parts with respect to 100 mass parts of all the components in the photosensitive resin composition. The lower limit is more preferably 45 parts by mass or more, and still more preferably 50 parts by mass or more. The upper limit is more preferably 90 parts by mass or less, and still more preferably 80 parts by mass or less. Only one type of solvent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.

<Adhesion improver>
The photosensitive resin composition of the first aspect of the present invention may contain an adhesion improving agent. Examples of the adhesion improving agent include alkoxysilane compounds.
The content of the adhesion improving agent is preferably 0.001 to 15 parts by mass, and more preferably 0.005 to 10 parts by mass with respect to 100 parts by mass of the total solid components of the photosensitive resin composition.
Only one type of adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

一般式（ＳＣ１）中、Ｒ¹およびＲ²は、それぞれ独立してアルキル基またはアリール基を表し、ｎは０〜２の整数を表し、Ｌ¹は単結合または２価の連結基を表し、Ａ¹は、官能基を表す。 As the adhesion improving agent, those represented by the following general formula (SC1) are preferable.
General formula (SC1)

In general formula (SC1), R ¹ and R ² each independently represents an alkyl group or an aryl group, n represents an integer of 0 to 2, L ¹ represents a single bond or a divalent linking group, A ¹ represents a functional group.

R ¹ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms. 1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are more preferable. 6-12 are preferable and, as for carbon number of an aryl group, 6 is more preferable.
R ² is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
n represents an integer of 0 to 2, and 0 or 1 is preferable.
When L ¹ represents a divalent linking group, a group consisting of — (CH ₂ ) _n1 — or a combination of — (CH ₂ ) _n1 — and —O— is preferable. Here, n1 is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.
A ¹ is preferably at least one functional group selected from vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group, amino group, ureido group, mercapto group, sulfide group and isocyanate group, and epoxy group, methacryloxy group A group or an acryloxy group is more preferable.

  Examples of the adhesion improving agent include vinyl silane, epoxy silane, styryl silane, methacryloxy silane, acryloxy silane, amino silane, ureido silane, chloropropyl silane, mercapto silane, polyfluoride silane, isocyanate silane and the like.

  Specific examples of the adhesion improver include, for example, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ- Glycidoxypropyl dialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxy (Cyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane, 3-acryloxypropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide and the like.

  The weight average molecular weight of the adhesion improving agent is preferably 50 to 500, more preferably 100 to 300.

  The adhesion improver includes a structural unit having a partial structure represented by the following general formula (SC2), a vinyl group, an epoxy group, a styryl group, a (meth) acryloyloxy group, an amino group, a ureido group, a mercapto group, and a sulfide. A polymer containing a structural unit having at least one group (X) selected from the group consisting of a group and an isocyanate group can also be used. This polymer has a plurality of each of the respective structural units, and it is usually preferable that each polymer has 5 or more.

一般式（ＳＣ２）中、Ｒ¹およびＲ²はそれぞれ独立に炭素数１〜４のアルキル基を表し、ｎは０〜２の整数を表す。 General formula (SC2)

In General Formula (SC2), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 2.

In the general formula (SC2), R ¹ and R ² each independently represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. is there. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group. R ¹ and R ² preferably represent the same group.
n represents an integer of 0 to 2, an integer of 0 or 1 is preferable, and 0 is more preferable.

  The structural unit having a partial structure represented by the general formula (SC2) is preferably represented by the following general formula (I).

一般式（Ｉ）中、Ｒ¹およびＲ²はそれぞれ独立に炭素数１〜４のアルキル基を表し、ｎは０〜２の整数を表す。Ｒ³は水素原子またはメチル基を表す。Ｌ¹は単結合、または連結部の原子数が１〜６の連結基を表す。 Formula (I)

In the general formula (I), R ¹ and R ² represents an alkyl group having 1 to 4 carbon atoms each independently, n is an integer of 0 to 2. R ³ represents a hydrogen atom or a methyl group. L ¹ represents a single bond or a linking group having 1 to 6 atoms in the linking part.

R ¹ and R ² in the general formula (I) has the same meaning as R ¹ and R ² in the general formula (SC2), and preferred ranges are also the same.
N in general formula (I) is synonymous with n in general formula (SC2), and its preferable range is also the same.
R ³ represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.
L ¹ represents a single bond or a linking group having 1 to 6 atoms in the linking part, preferably a divalent linking group having 2 to 6 atoms in the linking part, and 3 to 6 atoms in the linking part. The divalent linking group is more preferable.

Here, the number of atoms in the linking portion refers to the number of chains connecting the carbon atoms and silicon atoms constituting the main chain in the general formula (I), and the shortest when there are multiple chains due to branching or ringing. The number of atoms that make up the chain. Specifically, as represented by the following formula (A), when L ¹ is a propylene group, the chain connecting the main chain and the silicon atom is three carbon atoms, so the number of atoms of the connecting portion is 3. In addition, when L ¹ is a cyclohexylene group as represented by the following formula (B), there are three cases and five cases where the main chain and the silicon atom are connected to each other. The number of atoms in the connecting portion is 3. Even when the main chain in L ¹ has a carbonyl group as represented by the following formula (C), the number of atoms in the linking portion is 3.

Specific examples of the linking group having 1 to 6 atoms in the linking portion represented by L ¹ include alkylene groups having 1 to 6 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group). Cyclohexylene group), an arylene group having 6 to 10 carbon atoms (for example, a phenylene group or a naphthylene group), and the like. Among these, an alkylene group having 1 to 6 carbon atoms is preferable.

The group (X) is synonymous with A ¹ in the general formula (SC1), and is preferably selected from the group consisting of an epoxy group, a mercapto group, and a (meth) acryloyl group. More preferably, it is a mercapto group. The groups (X) may be different from each other, but the groups (X) are preferably the same.

  The structural unit having at least one group (X) is preferably represented by the following general formula (II).

一般式（ＩＩ）中、Ｒ⁴はそれぞれ独立に水素原子またはメチル基を表す。Ｌ²は単結合、または連結部の原子数が１〜６の連結基を表す。Ｒ⁵は、エポキシ基、メルカプト基、（メタ）アクリロイル基、ビニル基、またはアミノ基を表す。 Formula (II)

In general formula (II), each R ⁴ independently represents a hydrogen atom or a methyl group. L ² represents a single bond or a linking group having 1 to 6 atoms in the linking part. R ⁵ represents an epoxy group, a mercapto group, a (meth) acryloyl group, a vinyl group, or an amino group.

R ⁴ represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.
R ⁵ has the same meaning as A ¹ in formula (SC1), preferably an epoxy group, a mercapto group, or a (meth) acryloyl group, and more preferably an epoxy group or a mercapto group.
L ² has the same meaning as L ¹ in formula (I), and the preferred range is also the same.

  The adhesion improver preferably contains a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II). The structural unit represented by the general formula (I) and the general formula (II) ) Preferably occupies 60 mol% or more of the total structural units of the polymer, and more preferably occupies 80 mol% or more.

  A structural unit having a partial structure represented by the general formula (SC2) (preferably a structural unit represented by the general formula (I)) and a structural unit having at least one group (X) (preferably the general formula (II) 15 to 85:85 to 15 is preferable, and 25 to 75:75 to 25 is more preferable.

  Illustrative compounds are shown below, but it goes without saying that the present invention is not limited thereto. Me represents a methyl group, and Et represents an ethyl group.

  As the polymer type adhesion improver, commercially available products may be used. For example, X-12-981S, X-12-984S, X-12-1154, X-12-1048, X-12-972F (both Shin-Etsu) Silicone) can be used.

<Sensitizer>
The photosensitive resin composition of the first aspect of the present invention may contain a sensitizer. The sensitizer absorbs actinic rays 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. As a result, the photoacid generator undergoes a chemical change and decomposes to generate an acid. For this reason, decomposition | disassembly of a photo-acid generator can be accelerated | stimulated by containing a sensitizer. Examples of preferred sensitizers include compounds that belong to the following compounds and have an absorption wavelength in the wavelength range of 350 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), anthraquinones (eg, anthraquinone), squariums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-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.

  When the photosensitive resin composition of this invention contains a sensitizer, content of a sensitizer is 0.001-100 mass parts with respect to 100 mass parts of all the solid components in the photosensitive resin composition. It is preferable. For example, the lower limit is more preferably 0.1 parts by mass or more, and still more preferably 0.5 parts by mass or more. For example, the lower limit is more preferably 50 parts by mass or less, and still more preferably 20 parts by mass or less. Two or more sensitizers can be used in combination. When two or more sensitizers are used in combination, the total amount is preferably within the above range.

<Crosslinking agent>
The photosensitive resin composition of the first aspect of the present invention may contain a crosslinking agent. By containing a crosslinking agent, a harder cured film can be obtained. In particular, when the polymer component (A) does not contain a polymer containing a structural unit having a crosslinkable group or when the content is small, it is more preferred to contain a crosslinking agent.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat. Examples thereof include compounds having two or more epoxy groups or oxetanyl groups in the molecule, blocked isocyanate compounds, alkoxymethyl group-containing crosslinking agents, compounds having ethylenically unsaturated double bonds, and the like.

<< Compound having two or more epoxy groups or oxetanyl groups in the molecule >>
Examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.
These are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) and the like, commercially available products described in paragraph number 0189 of JP2011-221494A, and the like can be mentioned. In addition, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX -321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941 , EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC -301, DLC-402 (manufactured by Nagase Chemtech), YH-300, YH-301, YH-302, YH-315, YH 324, YH-325 (or Nippon Steel Chemical Co., Ltd.) 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 and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.

As the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.
The compound containing an oxetanyl group may be used alone or in combination with a compound containing an epoxy group.

<< 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 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 a blocked isocyanate group is a group which can produce | generate an isocyanate group by the heating at 90 to 250 degreeC.
The skeleton of the blocked isocyanate compound is not particularly limited, and any skeleton may be used as long as it has two isocyanate groups in one molecule. For example, aliphatic, alicyclic or aromatic polyisocyanate can be mentioned. Specific examples include, 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 (cyclohexane Isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′- Isocyanate compounds such as diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, and prepolymers derived from these compounds Type skeleton compounds. 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 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 an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide compound. Can do. 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 thereof 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 mercaptan compounds include alkyl mercaptans and aryl mercaptans.

  The block isocyanate compound is available as a commercial product. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, MFA-100, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation) ), Death Module BL1100, BL126 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. it can.

<< Other cross-linking agent >>
As other crosslinking agents, alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A, compounds having an ethylenically unsaturated double bond, and the like can also be preferably used. The contents are incorporated herein. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

  When the photosensitive resin composition of this invention has a crosslinking agent, it is preferable that content of a crosslinking agent is 0.01-50 mass parts with respect to a total of 100 mass parts of said (A) polymer component. For example, the lower limit is more preferably 0.1 parts by mass or more, and still more preferably 0.5 parts by mass or more. For example, the upper limit is more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less. If it is this range, the cured film excellent in mechanical strength and solvent resistance will be obtained. Only one type of crosslinking agent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.

<Basic compound>
The photosensitive resin composition according to the first aspect of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified positive resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A-2011-221494, paragraphs 0204 to 0207, and the contents thereof are incorporated in the present specification.

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, tetrapropylammonium hydroxide, benzyltrimethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide. And so on.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

  When the photosensitive resin composition of the present invention has a basic compound, the content of the basic compound is 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid component in the photosensitive resin composition. Is preferable, and it is more preferable that it is 0.005-1 mass part. A basic compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types, it is preferable that the total amount becomes the said range.

<Surfactant>
The photosensitive resin composition of the first aspect of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. As the surfactant, for example, those described in paragraph Nos. 0201 to 0205 of JP2012-88459A and those described in paragraph Nos. 0185 to 0188 of JP2011-215580A can be used. Is incorporated herein by reference.
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. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Mitsubishi Materials Kasei Co., Ltd.), MegaFuck (manufactured by DIC Corporation), F-554 (manufactured by DIC Corporation), Florard Novec FC-4430 (Sumitomo) 3M Co.), Surflon S-242 (AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (OMNOVA Co., Ltd.), SH-8400 (Toray Dow Corning Silicone Co., Ltd.), Footgent FTX-218G (Neos Co., Ltd.), etc. Can be mentioned.
Further, as a surfactant, it is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and using tetrahydrofuran (THF) as a solvent. A copolymer having a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 to 10,000 can be mentioned as a preferred example. The weight average molecular weight (Mw) is more preferably 1,500 to 5,000.

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

In formula (I-1-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom. Alternatively, it 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 10 mass% to 80 mass%. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

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

Formula (I-1-2)

Surfactant can be used individually by 1 type or in mixture of 2 or more types.
When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid components of the photosensitive resin composition. 0.001-10 mass parts is more preferable, and 0.01-3 mass parts is still more preferable.

<Antioxidant>
The photosensitive resin composition according to the first aspect of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, coloring of the cured film can be prevented. Furthermore, there is an advantage that a reduction in film thickness due to decomposition can be reduced and heat-resistant transparency is excellent.
Examples of antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur antioxidants from the viewpoint of coloring the cured film and reducing film thickness Agents are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraph Nos. 0026 to 0031 of JP-A-2005-29515 and the compounds described in paragraph Nos. 0106 to 0116 of JP-A-2011-227106. It is incorporated herein.
Preferred commercially available products include ADK STAB AO-20, ADK STAB AO-60, ADK STAB AO-80, ADK STAB LA-52, ADK STAB LA-81, ADK STAB AO-412S, ADK STAB PEP-36, IRGANOX 1035, IRGANOX 1098, and Tinuvin 144. Can be mentioned.

  When the photosensitive resin composition of this invention has antioxidant, content of antioxidant is 0.1-10 mass parts with respect to 100 mass parts of all the solid components of the photosensitive resin composition. Preferably, it is 0.2-5 mass parts, and it is especially preferable that it is 0.5-4 mass parts. 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.

<Acid multiplication agent>
In the photosensitive resin composition of the first aspect of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent 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.
Specific examples of the acid proliferating agent include the acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.

<Development accelerator>
The photosensitive resin composition according to the first aspect of the present invention can contain a development accelerator.
As the development accelerator, those described in paragraph Nos. 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
When the photosensitive resin composition of the present invention has a development accelerator, the addition amount of the development accelerator is 0 to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoints of sensitivity and residual film ratio. 30 mass parts is preferable, 0.1-20 mass parts is more preferable, and it is most preferable that it is 0.5-10 mass parts.

<Other ingredients>
The photosensitive resin composition according to the first aspect of the present invention may be added with a known addition of a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, an organic or inorganic precipitation inhibitor, if necessary. One or more agents can be added independently.
As these compounds, for example, compounds described in paragraph Nos. 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.
Further, a thermal radical generator described in paragraphs 0120 to 0121 of JP2012-8223A, a nitrogen-containing compound and a thermal acid generator described in WO2011 / 136604A1, can be used, and the contents thereof are described in the present specification. Incorporated into. Moreover, it can also be set as the aspect which does not contain other thermal base generators other than the compound represented by the general formula (I) mentioned above.

[Second embodiment of the present invention]
Next, the 2nd aspect of the photosensitive resin composition of this invention is demonstrated.
The photosensitive resin composition according to the second aspect of the present invention comprises (A2) a polymer component containing a polymer having a structural unit having an acid group, (B2) a quinonediazide compound, and (C) the general formula described above. The compound represented by (I) and (D) a solvent are contained.

<(A2) Polymer component>
(A2) The polymer component includes a polymer having a structural unit (a2-1) having an acid group.
By including the structural unit (a2-1) having an acid group, it is easily dissolved in an alkaline developer. The acid group is usually incorporated into the polymer as a structural unit having an acid group using a monomer capable of forming an acid group.
Acid groups derived from carboxylic acid groups, derived from sulfonamide groups, derived from phosphonic acid groups, derived from sulfonic acid groups, derived from phenolic hydroxyl groups, sulfonamide groups, sulfonylimides Examples include groups derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups. The structural unit having an acid group is preferably a structural unit having a carboxyl group and / or a phenolic hydroxyl group.
The structural unit having an acid group is also preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid and / or an ester thereof. For example, the compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein. Among these, a structural unit derived from at least one selected from p-hydroxystyrene, (meth) acrylic acid, maleic acid and maleic anhydride is preferable.

In the present invention, the (A2) polymer component preferably contains a polymer having a structural unit (a2-2) having a crosslinkable group. According to this aspect, it is easy to form a cured film having excellent surface hardness. Specific examples of the structural unit having a crosslinkable group include those described above for the structural unit (a1-2) of the polymer component (A2), and the preferred range is also the same.
The structural unit (a2-2) may be contained in a polymer having the structural unit (a2-1), or may be a polymer different from the polymer having the structural unit (a2-1). It may be included. That is, in the present invention, the (A2) polymer component preferably satisfies at least one of the following (2-1) and (2-2).
(2-1) (a2-1) a polymer containing a structural unit having an acid group and (a2-2) a structural unit having a crosslinkable group,
(2-2) (a2-1) A polymer having a structural unit having an acid group and (a2-2) a polymer having a structural unit having a crosslinkable group.

<< (a2-3) Other structural units >>
(A2) The polymer component may have a structural unit (a2-3) other than the structural unit (a2-1) and the structural unit (a2-2).
The monomer to be the structural unit (a2-3) is not particularly limited as long as it is an unsaturated compound other than the structural units (a2-1) and (a2-2).
For example, styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatics Examples thereof include compounds, conjugated diene compounds, and other unsaturated compounds. The monomer which becomes a structural unit (a2-3) can be used individually or in combination of 2 or more types.

(A2) Among all the structural units of the polymer component, the structural unit (a2-1) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol%. More preferably, it is contained in an amount of 50 mol%.
(A2) Among all the structural units of the polymer component, the structural unit (a2-2) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol%. More preferably, it is contained in an amount of 40 mol%.
(A2) Among all the structural units of the polymer component, the structural unit (a2-3) is preferably contained in an amount of 1 to 80 mol%, more preferably 5 to 50 mol%, more preferably 8 to More preferably, the content is 30 mol%.
It is preferable that the photosensitive resin composition of the 2nd form of this invention contains (A2) polymer component in the ratio of 70 mass% or more of the total solid of the photosensitive resin composition.

<(B2) Quinonediazide compound>
The photosensitive resin composition of the 2nd form of this invention contains a quinonediazide compound. As the quinonediazide compound, a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with actinic rays can be preferably used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used. As specific examples of these compounds, for example, description of paragraphs 0075 to 0078 of JP2012-088459A can be referred to, and the contents thereof are incorporated in the present specification.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the 1,2-quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphtho. Quinonediazide-4-sulfonic acid amide and the like are also preferably used. Also, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid chloride (3.0 mol), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) Mol)), 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44 mol), etc. It may be used.

  These quinonediazide compounds can be used alone or in combination of two or more. The content of the quinonediazide compound in the photosensitive resin composition of the present invention is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. For example, the lower limit is more preferably 2 parts by mass or more, and still more preferably 10 parts by mass or more. For example, the upper limit is more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less. By setting the content of the quinonediazide compound in the above range, the difference in solubility between the irradiated portion of the actinic ray and the unirradiated portion with respect to the alkaline aqueous solution serving as the developer is large, the patterning performance is improved, and the resistance of the cured film obtained is improved. Good solvent properties.

<(C) Compound>
The photosensitive resin composition of the 2nd aspect of this invention contains (C) compound. (C) As a compound, the (C) compound demonstrated by the photosensitive resin composition of the 2nd aspect mentioned above is mentioned, A preferable range is also the same.
(C) As for content of a compound, 0.01-20 mass parts is preferable with respect to 100 mass parts of total solids of the photosensitive resin composition. For example, the lower limit is more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and still more preferably 0.3 parts by mass or more. For example, the upper limit is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.
Moreover, as for content of (C) compound, 0.01-20 mass parts is preferable with respect to 100 mass parts of (A1) polymer component mentioned above. For example, the lower limit is more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and still more preferably 0.3 parts by mass or more. For example, the upper limit is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.

<(D) Solvent>
The photosensitive resin composition of the 2nd aspect of this invention contains a solvent. As a solvent, the solvent demonstrated by the photosensitive resin composition of the 1st aspect mentioned above is mentioned, A preferable range is also the same.
As for content of a solvent, 40-95 mass parts is preferable with respect to 100 mass parts of all the components in the photosensitive resin composition. The lower limit is more preferably 45 parts by mass or more, and still more preferably 50 parts by mass or more. The upper limit is more preferably 90 parts by mass or less, and still more preferably 85 parts by mass or less. Only one type of solvent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.

<Other ingredients>
The photosensitive resin composition according to the second aspect of the present invention includes, in addition to the above components, a crosslinking agent, a basic compound, a surfactant, an antioxidant, a development as long as the effects of the present invention are not impaired. Known additives such as accelerators, plasticizers, thermal radical generators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors can be added. These components are the same as those in the first embodiment described above, and the preferred ranges are also the same. Each of these components may be used alone or in combination of two or more.

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

<Method for producing cured film>
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 (application | coating process)
(2) Step of removing the solvent from the applied photosensitive resin composition (solvent removal step)
(3) Step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays (exposure step)
(4) Step of developing the exposed photosensitive resin composition with a developer (exposure step)
(5) Step of thermosetting the developed photosensitive resin composition (post-baking step)
Each step will be described below in order.

  In the step (1), it is preferable to apply the photosensitive resin composition of the present invention on a substrate to form a wet film containing a solvent.

In the step (1), before the photosensitive resin composition is applied to the substrate, the substrate may be subjected to cleaning such as alkali cleaning or plasma cleaning. Further, the substrate surface may be treated with hexamethyldisilazane or the like with respect to the cleaned substrate. The method of treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate 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.
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 And the like.
These substrates are rarely used in the above-described form, and a multilayer stacked structure such as a TFT (Thin-Film Transistor) element may be formed depending on the form of the final product.
The method for applying the photosensitive resin composition to 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 may be used. it can.
In the case of the slit coating method, the relative moving speed between the substrate and the slit die is preferably 50 to 120 mm / sec.
The wet film thickness when the photosensitive resin composition is applied is not particularly limited, and can be applied with a film thickness according to the application. For example, 0.5-10 micrometers is preferable.
Before applying the photosensitive resin composition of the present invention to the substrate, it is also possible to apply a so-called prewetting method as described in JP-A-2009-145395.

  In the step (2), the solvent is removed from the wet film formed by applying the photosensitive resin composition by vacuum (vacuum) and / or heating to form a dry 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 step (3), the substrate provided with the dry film is irradiated with actinic rays having a predetermined pattern. In this step, a carboxyl group or a phenolic hydroxyl group is generated in the exposed area, and the solubility in the developer in the exposed area is improved. That is, in an embodiment including a polymer component having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and a photoacid generator, the photoacid generator is decomposed by irradiation with actinic rays. Acid is generated. And the acid-decomposable group contained in a coating-film component is hydrolyzed by the catalytic action of the generated acid, and a carboxyl group or a phenolic hydroxyl group is generated. Moreover, in the aspect containing a quinonediazide compound, a carboxyl group is produced | generated from a quinonediazide compound by irradiation of actinic light.
As the light source of actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used. Actinic rays having a wavelength of 300 nm to 450 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. The exposure amount is preferably 1 to 500 mJ / cm ² .
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, a lens scanner, and a laser exposure can be used. In addition, exposure using a so-called super-resolution technique can be performed. Examples of the super-resolution technique include multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, and an annular illumination method. By using these super-resolution techniques, it is possible to form a higher definition pattern, which is preferable.

In the step (4), the copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using a developer. A positive image is formed by removing an exposed area having a carboxyl group and / or a phenolic hydroxyl group that is easily dissolved in the developer.
The developer used in the development step preferably contains an aqueous solution of a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkyl amines such as dimethyl alcohol; alcohol amines such as dimethyl ethanol amine and triethanol amine; 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] Cycloaliphatic amines such as -5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

In the step (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and crosslinked with a crosslinkable group, a crosslinking agent, etc. A cured film can be formed. Furthermore, it is presumed that a base is generated from the compound represented by the general formula (I), and the acid released in the cured film can be neutralized. For this reason, discoloration, such as a metal, can be suppressed.
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 the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed. 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.

  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 above-described photosensitive resin composition of the present invention. 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 mentioned above.
The cured film of the present invention can be suitably used as an interlayer insulating film. In particular, it can be preferably used as an insulating substrate for metal wiring.
The photosensitive resin composition of the present invention can provide an interlayer insulating film having high transparency even when baked at a high temperature. The interlayer insulation film formed using the photosensitive resin composition of the present invention has high transparency and is useful for applications such as a liquid crystal display device, an organic electroluminescence display device, and a touch panel.

<Liquid crystal display device>
The liquid crystal display device of the present invention has 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 planarizing film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures. 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) disclosed in JP-A-2005-284291 or JP-A-2005-346054 is used. It can be used as an 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 liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is disposed on all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. Corresponding TFT 16 elements 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, white light emitting diodes (LEDs), multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), organic electroluminescence (organic EL), and the like can be given.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, a flexible type can also be used, and it is used as the second interlayer insulating film (48) described in JP 2011-145686 A and the interlayer insulating film (520) described in JP 2009-258758 A. Can do.
Further, even in a static drive type liquid crystal display device, a pattern with high designability can be displayed by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A No. 2001-125086.

<Organic electroluminescence display device>
The organic electroluminescence (organic EL) display device of the present invention has 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 organic materials having various structures. An EL display device and a liquid crystal display device can be given.
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 film 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. be able to.
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 has good sensitivity and excellent pattern adhesiveness during development, it is formed using the photosensitive resin composition of the present invention as a structural member of a MEMS (Micro Electro Mechanical Systems) device. The resist pattern thus formed is used as a partition wall or incorporated as a part of a mechanical drive component. Examples of the MEMS device include parts such as a SAW (Surface Acoustic Wave) filter, a BAW (Bulk Acoustic Wave) filter, a gyro sensor, a micro shutter for display, an image sensor, an electronic paper, an inkjet head, a biochip, and a sealant. It is done. 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). In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.

<Touch panel>
The touch panel of the present invention includes a capacitive input device having the cured film of the present invention. Moreover, the capacitance-type input device has the cured film of the present invention. That is, the touch panel of the present invention has the cured film of the present invention.
The capacitive input device has at least the following elements (1) to (5) on the front plate and the non-contact side of the front plate, and the insulating layer of (4) is the photosensitive resin composition of the present invention. It is preferable that it is a cured film using.
(1) Mask layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) First transparent electrode pattern and electrical And a plurality of second transparent electrode patterns comprising a plurality of pad portions formed extending in a direction crossing the first direction. (4) First transparent electrode pattern and second transparent electrode pattern (5) The first transparent electrode pattern and the second transparent electrode pattern are electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern. Another conductive element In the capacitive input device of the present invention, it is preferable that a transparent protective layer is further provided so as to cover all or a part of the elements (1) to (5). The cured film of the present invention is more preferable. Arbitrariness.

  First, the configuration of the capacitive input device will be described. FIG. 3 is a cross-sectional view illustrating a configuration example of the capacitive input device. In FIG. 3, the capacitive input device 30 includes a front plate 31, a mask layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, and a conductive element 36. And a transparent protective layer 37.

  The front plate 31 is made of a light-transmitting substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. Moreover, in FIG. 3, the side in which each element of the front plate 31 is provided is called a non-contact surface. In the capacitive input device 30, input is performed by bringing a finger or the like into contact with the contact surface of the front plate 31 (the surface opposite to the non-contact surface). Hereinafter, the front plate may be referred to as a “base material”.

A mask layer 32 is provided on the non-contact surface of the front plate 31. The mask layer 32 is a frame-like pattern around the display area formed on the non-contact side of the touch panel front plate, and is formed so as not to show the lead wiring and the like.
As shown in FIG. 4, the capacitance type input device is provided with a mask layer 32 so as to cover a part of the front plate 31 (a region other than the input surface in FIG. 4). Further, the front plate 31 can be provided with an opening 38 in part as shown in FIG. A mechanical switch by pressing can be installed in the opening 38.

As shown in FIG. 5, on the contact surface of the front plate 31, a plurality of first transparent electrode patterns 33 formed with a plurality of pad portions extending in the first direction via the connection portions, A plurality of second transparent electrode patterns 34 each including a plurality of pad portions that are electrically insulated from one transparent electrode pattern 33 and extend in a direction crossing the first direction; An insulating layer 35 that electrically insulates the electrode pattern 33 and the second transparent electrode pattern 34 is formed. The first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 to be described later are, for example, translucent conductive materials such as ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide). It can be made of a metal oxide film. Examples of such metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO ₂ . At this time, the film thickness of each element can be 10 to 200 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced. Moreover, the 1st transparent electrode pattern 33, the 2nd transparent electrode pattern 34, and the electroconductive element 36 mentioned later are manufactured using the photosensitive transfer material which has the photosensitive resin composition using a conductive fiber. You can also In addition, when the first conductive pattern or the like is formed by ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to, and the contents thereof are incorporated in this specification.

  Further, at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 extends over both the non-contact surface of the front plate 31 and the region opposite to the front plate 31 of the mask layer 32. Can be installed. In FIG. 3, a diagram is shown in which the second transparent electrode pattern is placed across both the non-contact surface of the front plate 31 and the surface of the mask layer 32 opposite to the front plate 31. Yes.

  The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. FIG. 5 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern. As shown in FIG. 5, the first transparent electrode pattern 33 is formed such that a pad portion 33a extends in a first direction via a connection portion 33b. The second transparent electrode pattern 34 is electrically insulated by the first transparent electrode pattern 33 and the insulating layer 35 and extends in a direction intersecting the first direction (second direction in FIG. 5). It is constituted by a plurality of pad portions that are formed. Here, when the first transparent electrode pattern 33 is formed, the pad portion 33a and the connection portion 33b may be manufactured integrally, or only the connection portion 33b is manufactured, and the pad portion 33a and the second transparent electrode pattern 33 are formed. The electrode pattern 34 may be integrally formed (patterned). When the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 5, a part of the connection part 33b and a part of the pad part 33a are connected, and an insulating layer is formed. Each layer is formed so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by 35.

  In FIG. 3, a conductive element 36 is provided on the side of the mask layer 32 opposite to the front plate 31. The conductive element 36 is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34, and is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34. Is another element. In FIG. 3, a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.

  Moreover, in FIG. 3, the transparent protective layer 37 is installed so that all of each component may be covered. The transparent protective layer 37 may be configured to cover only a part of each component. The insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.

  Capacitive input devices and touch panels equipped with capacitive input devices are the latest touch panel technology (Techno Times, issued July 6, 2009), supervised by Yuji Mitani, “Touch Panel Technology and The configurations disclosed in “Development” CMC Publishing (2004, 12), “FPD International 2009 Forum T-11 Lecture Textbook”, “Cypress Semiconductor Corporation Application Note AN2292” and the like can be applied.

<Manufacturing method of touch panel>
In the touch panel of the present invention, it is preferable that all or part of the insulating layer is composed of a cured film of the photosensitive resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an ITO electrode, and an insulating layer at least. Preferred examples of the transparent substrate include a glass substrate, a quartz substrate, a transparent resin substrate, and the like.

The touch panel of the present invention can be manufactured, for example, as follows.
That is, the photosensitive resin composition of the present invention is applied by various methods such as an inkjet coating method so as to be in contact with the ITO electrode, and an opening pattern having a predetermined shape is formed on the photosensitive resin composition applied to the ITO electrode. It can be manufactured through Step 2 in which a mask is placed and exposed by irradiation with active energy rays, Step 3 in which the exposed photosensitive resin composition is developed, and Step 4 in which the photosensitive resin composition after development is heated. .

In Step 1, when the photosensitive resin composition is applied so as to be in contact with the ITO electrode, it is sufficient that at least a part of the applied photosensitive resin composition of the present invention is in contact with the ITO electrode.
Step 2 can be performed in the same manner as the exposure step described above, and the preferred embodiment is also the same.
Step 3 can be performed in the same manner as the development step described above, and the preferred embodiment is also the same.
Step 4 can be performed in the same manner as the post-baking step described above, and the preferred embodiment is also the same.
Moreover, as an example of the ITO electrode pattern in the touch panel of this invention, the pattern shown in FIG. 5 mentioned above is mentioned preferably.

  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.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MATHP: tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
StOEVE: 4- (1-ethoxyethyloxy) styrene (synthetic product)
OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
NBMA: n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
AA: Acrylic acid (Wako Pure Chemical Industries, Ltd.)
HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
HS-EDM: Diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Co., Ltd., High Solve EDM)
PGMEA: Methoxypropyl acetate (manufactured by Showa Denko)

<Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.

<Synthesis of StOEVE>
StOEVE was synthesized (using hydroxystyrene and ethyl vinyl ether as raw materials in the same manner as described above).

<Synthesis Example of Polymer A1-1>
HS-EDM (82 parts) was heated and stirred at 90 ° C. under a nitrogen stream. MATHF (43 parts (corresponding to 40.5 mol% in all monomer components)), OXE-30 (48 parts (corresponding to 37.5 mol% in all monomer components)), MAA (6 parts (total Equivalent to 9.5 mol% in the monomer component)), HEMA (11 parts (corresponding to 12.5 mol% in the total monomer component)), radical polymerization initiator V-601 (trade name, Wako Pure Chemical Industries, Ltd.) A mixed solution of Kogyo Co., Ltd. (4.3 parts) and PGMEA (82 parts) was added dropwise over 2 hours, and further reacted at 90 ° C. for 2 hours, whereby a PGMEA solution of polymer A1-1 (solid content) Concentration: 40%).
The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained polymer A1-1 was 15,000.

<Synthesis Example of Polymers A1-2 to A1-12>
Each copolymer was synthesized in the same manner as the synthesis of polymer A1-1, except that each monomer used and the amount used thereof were changed to those shown in the following table.

  In the above table, the numerical values not particularly given in the table are in mol%. The numerical value of the polymerization initiator is mol% when the monomer component is 100 mol%. The solid content concentration is shown as monomer mass / (monomer mass + solvent mass) × 100 (unit mass%). When V-601 was used as the polymerization initiator, the reaction temperature was 90 ° C., and when V-65 was used, the reaction temperature was 70 ° C.

<Synthesis Example of Polymer A2-1>
As monomer components, 12.05 g (35 mol%) of methacrylic acid, 4.17 g (10 mol) of styrene, 13.22 g (15 mol%) of dicyclopentanyl methacrylate, and 22.74 g (40 mol%) of glycidyl methacrylate were used for radical polymerization. Using 2.57 g of azobisisobutyronitrile (AIBN) as an initiator and polymerizing them in 115 g of PGMEA at 70 ° C. for 4 hours, a PGMEA solution of A2-1 (solid content concentration: 30% by mass) was obtained. Obtained.
The styrene conversion weight average molecular weight measured by GPC of the obtained A2-1 was 15,000.

<Synthesis Example of Polymer A2-2>
As monomer components, 12.05 g (35 mol%) of methacrylic acid, 4.17 g (10 mol) of styrene, 13.22 g (15 mol%) of dicyclopentanyl methacrylate, 29.48 g (40 mol%) of 3-ethyl-3oxetanyl methacrylate were used. And azobisisobutyronitrile (AIBN) 2.57 g was used as a radical polymerization initiator, and these were polymerized in 135 g of PGMEA at 70 ° C. for 4 hours to obtain a PGMEA solution of A2-2 (solid content concentration: 30% by mass) was obtained.
The styrene conversion weight average molecular weight measured by GPC of the obtained A2-2 was 13,000.

＜ナフトキノンジアジド＞
Ｂ２−１：下記に示す構造の化合物（ＴＡＳ−２００、東洋合成工業（株）製）

＜（Ｃ）化合物＞
Ｃ−１：Ｎ−フェニルイミノ２酢酸（和光純薬社製）
Ｃ−４：１，２−ビス（２−アミノフェノキシ）エタン−Ｎ，Ｎ，Ｎ’，Ｎ’−４酢酸（東京化成社製）
Ｃ−５：Ｎ−メチルイミノ２酢酸（東京化成社製）
Ｃ−９：Ｎ−ベンジルイミノ２酢酸（東京化成社製）
（比較例の化合物）
Ｒ−１：Ｎ−メチルグリシン（東京化成社製）
Ｒ−２：Ｎ−フェニルグリシン（東京化成社製）
Ｒ−３：Ｎ，Ｎ−ジメチルグリシン（東京化成社製）
Ｒ−４：Ｎ，Ｎ−ジ（２−ヒドロキシエチル）グリシン（東京化成社製）

＜溶剤＞
ＨＳ−ＥＤＭ：ジエチレングリコールメチルエチルエーテル：東邦化学社製
＜増感剤＞
Ｅ−１：９，１０−ジブトキシアントラセン（川崎化成社製）
＜架橋剤＞
Ｆ−１：ＪＥＲ１５７Ｓ６５ （エポキシ架橋剤：ジャパンエポキシレジン社製）
Ｆ−２：ＪＥＲ１７５Ｓ７０（エポキシ架橋剤：ジャパンエポキシレジン社製）
Ｆ−３：ＪＥＲ１００７Ｋ（エポキシ架橋剤：ジャパンエポキシレジン社製）
＜密着改良剤＞
Ｇ−１：γ−グリシドキシプロピルトリアルコキシシラン（ＫＢＭ−４０３:信越化学社製）
＜塩基性化合物＞
Ｈ−１：ＤＢＮ：１，５−ジアザビシクロ［４．３．０］−５−ノネン（東京化成社製）
Ｈ−２：ＴＰＩ：トリフェニルイミダゾール（和光純薬工業社製）
＜界面活性剤＞
Ｉ−１：下記構造式で示されるパーフルオロアルキル基含有ノニオン界面活性剤（Ｆ−５５４，ＤＩＣ製）

<Preparation of photosensitive resin composition>
Each component shown in the following table was mixed to obtain a uniform solution, and then filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to prepare photosensitive resin compositions of various examples and comparative examples.
The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
<Polymer component>
A1-1 to A1-12, A2-1, A2-2: Polymer synthesized according to the above synthesis example <Photoacid generator>
B1-1: Compound having the structure shown below (Synthesis examples will be described later).
B1-2: Compound having the structure shown below (trade name: PAG-103, manufactured by BASF)
B1-3: Compound having the structure shown below (trade name: PAl-101, manufactured by Midori Chemical Co., Ltd.)
B1-4: Compound having the structure shown below (trade name: TPS-1000, manufactured by Midori Chemical Co., Ltd.)
B1-5: Compound having the structure shown below (Synthesis examples will be described later)
In the following formulae, Ts represents a tosyl group (p-toluenesulfonyl group).

<Naphthoquinone diazide>
B2-1: Compound having the structure shown below (TAS-200, manufactured by Toyo Gosei Co., Ltd.)

<(C) Compound>
C-1: N-phenyliminodiacetic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
C-4: 1,2-bis (2-aminophenoxy) ethane-N, N, N ′, N′-4 acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-5: N-methyliminodiacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-9: N-benzyliminodiacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
(Comparative Example Compound)
R-1: N-methylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.)
R-2: N-phenylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.)
R-3: N, N-dimethylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.)
R-4: N, N-di (2-hydroxyethyl) glycine (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Solvent>
HS-EDM: Diethylene glycol methyl ethyl ether: manufactured by Toho Chemical Co., Ltd. <sensitizer>
E-1: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd.)
<Crosslinking agent>
F-1: JER157S65 (epoxy crosslinking agent: manufactured by Japan Epoxy Resin Co., Ltd.)
F-2: JER175S70 (epoxy crosslinking agent: manufactured by Japan Epoxy Resin Co., Ltd.)
F-3: JER1007K (epoxy crosslinking agent: manufactured by Japan Epoxy Resin Co., Ltd.)
<Adhesion improver>
G-1: γ-glycidoxypropyltrialkoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.)
<Basic compound>
H-1: DBN: 1,5-diazabicyclo [4.3.0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)
H-2: TPI: Triphenylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.)
<Surfactant>
I-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)

<Synthesis of B1-1>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. After adding potassium carbonate (19.2 g) to the organic layer and reacting at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added for liquid separation, and the organic layer was concentrated. ), Followed by filtration and drying to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50% by mass hydroxylamine aqueous solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, then reslurried with methanol (20 mL), filtered and dried to obtain a compound of B1-1 (the above structure) (2.3 g).
In addition, the 1H-NMR spectrum (300 MHz, CDCl3) of B-1 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 ( d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2 .4 (s, 3H), 1.7 (d, 3H).

<Synthesis of B1-5>
Under a nitrogen atmosphere, 9.29 g of 4-bromonaphthalic anhydride, 34 g of dimethyl sulfoxide, and 4.14 g of 1,4-diazabicyclo [2.2.2] octane were added to a three-necked flask, and 5.14 g of octanethiol was added to 30. The solution was added dropwise at a temperature of not higher than ° C. and stirred at 40 ° C. for 5 hours. 70 mL of methanol was added to the reaction solution, and the mixture was ice-cooled. After stirring for 30 minutes, the precipitated crystals were collected by filtration and dried to obtain 8.65 g of Intermediate B-1A.
Subsequently, 8.21 g of B-1A, 27.5 g of dimethylformamide, and 2.00 g of hydroxylamine hydrochloride were added to a three-necked flask in a nitrogen atmosphere, and 2.40 g of a 48 wt% aqueous sodium hydroxide solution was added to 30 ° C. The solution was added dropwise below and stirred at room temperature for 2 hours. Distilled water (30 mL) was added to the reaction mixture, and the mixture was cooled with ice. The precipitated crystals were collected by filtration and dried to obtain 8.35 g of intermediate B-1B.
To a three-necked flask, 3.51 g of B-1B, 25 g of dichloromethane and 1.03 g of pyridine were added and stirred, and then 2.96 g of trifluoromethanesulfonic anhydride was added dropwise at 15 to 20 ° C., and the mixture was stirred at 25 ° C. for 3 hours. Stir. Distilled water (20 mL) and dichloromethane (20 g) were added to the reaction mixture and stirred. After separation, the dichloromethane layer was twice with 0.25 wt% aqueous sodium hydroxide solution (30 mL), 5 wt% aqueous hydrochloric acid solution (30 mL) once, and distilled water (40 mL). And washed three times with water. After concentrating the organic layer, 25 g of n-heptane was added and stirred, and the precipitated crystals were collected by filtration and dried to obtain 3.83 g of B1-5.

<Evaluation of photosensitive resin composition>
<Evaluation of sensitivity>
A glass substrate (EAGLE XG, 0.7 mm thickness (manufactured by Corning)) was exposed to hexamethyldisilazane vapor for 30 seconds, and then each photosensitive resin composition was spin-coated. Then, it prebaked on a 90 degreeC / 120 second hotplate, the solvent was volatilized, and the photosensitive resin composition layer with a film thickness of 3.0 micrometers was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (0.4% 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. AC is preferable on the following criteria, and A or B is more preferable.
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

<Evaluation of heat-resistant transparency>
A glass substrate (EAGLE XG, 0.7 mm thickness (manufactured by Corning)) was exposed to hexamethyldisilazane vapor for 30 seconds, and then each photosensitive resin composition was spin-coated. Then, it prebaked on a 90 degreeC / 120 second hotplate, the solvent was volatilized, and the photosensitive resin composition layer with a film thickness of 3.0 micrometers was formed. Subsequently, exposure was performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and this substrate was heated in an oven at 230 ° C./30 minutes. Further, it was heated in an oven at 230 ° C. for 2 hours. The transmittance of this cured film was measured at a wavelength of 400 nm using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). The unit is expressed in%. AC is preferable on the following criteria, and A or B is more preferable.
A: 95% or more B: 90% or more and less than 95% C: 85% or more and less than 90% D: 80% or more and less than 85% E: Less than 80%

<Evaluation of display unevenness (panel reliability)>
A liquid crystal display device using a thin film transistor (TFT) was manufactured by the following method (see FIG. 2). 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 to obtain a liquid crystal display device.
That is, as a pretreatment for improving the wettability of the substrate and the interlayer insulating film 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldisilazane vapor for 30 seconds, and then each photosensitive resin composition is spun. After coating application, pre-baking was performed on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 2 μm was formed. Next, the obtained photosensitive resin composition layer was irradiated with i-line (365 nm) at 25 mJ / cm ² (illuminance 20 mW / cm ² ) using a high-pressure mercury lamp from above the mask, and then developed with an aqueous alkali solution. A pattern was formed, and a heat treatment was performed at 230 ° C. for 60 minutes. The applicability when applying the photosensitive resin composition of the example was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and baking.
The obtained liquid crystal display device was left for 24 hours under forced conditions (temperature 85 ° C./relative humidity 80% RH, LH-113 constant temperature and humidity chamber manufactured by Espec), and the liquid crystal display device was taken out. When a drive voltage was applied to the liquid crystal display device and a gray test signal was input, the gray display was visually observed, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria. AC is preferable on the following criteria, and A or B is more preferable.
A: No unevenness at all (very good)
B: Slight unevenness is observed on the edge of the glass substrate, but there is no problem in the display (good)
C: Slight unevenness on the display, but practical level (normal)
D: Display is uneven (somewhat bad)
E: Strong unevenness in display (very bad)

<Comprehensive evaluation>
Based on the result of each evaluation test, comprehensive evaluation was performed as follows. The overall evaluation is preferably 6 or more, more preferably 7 or more.
Overall evaluation = 10− (number of B in each evaluation test × 1) − (number of C in each evaluation test × 2) − (number of D in each evaluation test × 3) − (number of E in each evaluation test × 4)

As is clear from the above results, the photosensitive resin composition of the present invention had high sensitivity and an excellent effect in improving display unevenness. Furthermore, it was excellent in heat-resistant transparency.
On the other hand, the photosensitive resin composition of the comparative example was inferior in at least one of sensitivity and display unevenness.

<Creation of organic EL display device>
(Example 101)
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 planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiation with i-line (365 nm) at 45 mJ / cm ² (energy intensity 20 mW / cm ² ) using a mercury lamp, development is performed with an alkaline aqueous solution (0.4% TMAH aqueous solution) to form a pattern. Was used to expose the entire surface so that the integrated dose was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and a 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 16 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.

(Examples 102 to 123)
In Example 101, an organic EL display device was produced in the same manner as in Example 101 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Examples 2 to 23. When a drive voltage was applied to the obtained organic EL display device, it was found that the organic EL display device showed good display characteristics and had high reliability.

<Production of touch panel>
(Example 301)
A touch panel was produced by the method described below.
<Formation of first transparent electrode pattern>
<< Formation of transparent electrode layer >>
A front plate of tempered glass (300 mm × 400 mm × 0.7 mm) with a mask layer formed in advance is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5) with a SnO ₂ content of 10% by mass. (Molar ratio)) was used to form an ITO thin film having a thickness of 40 nm by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode layer was formed. A formed front plate was obtained. The surface resistance of the ITO thin film was 80Ω / □.

Next, a commercially available etching resist was applied onto ITO and dried to form an etching resist layer. The distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the etching resist layer is set to 100 μm, pattern exposure is performed at an exposure amount of 50 mJ / cm ² (i-line), and development is performed with a developer. Then, a post-baking treatment at 130 ° C. for 30 minutes was performed to obtain a front plate on which a transparent electrode layer and a photosensitive resin layer pattern for etching were formed.

The front plate on which the transparent electrode layer and the photo-sensitive resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched resist. The exposed transparent electrode layer not covered with the layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern with an etching resist layer pattern.
Next, the front plate with the transparent electrode layer pattern with the etching resist layer pattern is immersed in a dedicated resist stripping solution, the photosensitive resin layer for etching is removed, and the mask layer and the first transparent electrode pattern A front plate formed was obtained.

<< Formation of insulating layer >>
On the front plate on which the mask layer and the first transparent electrode pattern were formed, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm, 90 ° C., 120 seconds) to form a photosensitive resin composition layer. Got. The distance between the surface of the exposure mask (quartz exposure mask having a pattern for insulating layer) and the photosensitive resin composition layer was set to 30 μm, and pattern exposure was performed with the optimum exposure amount obtained by sensitivity evaluation.
Next, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds and rinsed with ultrapure water for 10 seconds. Subsequently, a post-bake treatment at 220 ° C. for 45 minutes was performed to obtain a front plate on which a mask layer, a first transparent electrode pattern, and an insulating layer pattern were formed.

<Formation of second transparent electrode pattern>
<< Formation of transparent electrode layer >>
Similarly to the formation of the first transparent electrode pattern, the front plate formed up to the insulating layer pattern was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa). An ITO thin film having a thickness of 80 nm was formed to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 110Ω / □.
Similarly to the formation of the first transparent electrode pattern, using a commercially available etching resist, the first transparent electrode pattern, an insulating layer pattern formed using the photosensitive resin composition of Example 1, a transparent electrode layer, A front plate on which an etching resist pattern was formed was obtained (post-baking treatment; 130 ° C. for 30 minutes).
Further, etching was performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer was removed to form the mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. A front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was obtained.

<Formation of Conductive Element Different from First and Second Transparent Electrode Pattern>
Similar to the formation of the first and second transparent electrode patterns, the first transparent electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 1, and the second transparent electrode pattern The front plate on which was formed was subjected to DC magnetron sputtering to obtain a front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed.
Insulating layer formed using the first transparent electrode pattern, the photosensitive resin composition of Example 1, using a commercially available etching resist in the same manner as the formation of the first and second transparent electrode patterns. A front plate on which a pattern, a second transparent electrode pattern, and an etching resist pattern were formed was obtained (post-bake treatment; 130 ° C. for 30 minutes).
Further, in the same manner as the formation of the first transparent electrode pattern, etching (30 ° C. for 50 seconds) is performed, and the etching resist layer is removed (45 ° C. for 200 seconds). A front plate on which a conductive element different from the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns formed using the photosensitive resin composition of Example 1 was obtained was obtained.

<Formation of transparent protective layer>
In the same manner as the formation of the insulating layer, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm) on the front plate formed up to the conductive element different from the first and second transparent electrode patterns. , 90 ° C. for 120 seconds) to obtain a photosensitive resin composition film. Furthermore, exposure, development, post-exposure (1,000 mJ / cm ² ), post-bake treatment were performed, and the insulating layer formed using the mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1 Insulating layer (transparent protection) formed using the photosensitive resin composition of Example 1 so as to cover all the conductive elements different from the pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns Layer) was obtained.

<Production of touch panel>
The liquid crystal display element manufactured by the method of Unexamined-Japanese-Patent No. 2009-47936 was bonded to the front plate manufactured previously, and the touchscreen provided with the capacitive input device as a component by the well-known method was produced.

<Evaluation of front plate and touch panel>
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and other conductive elements, while the first transparent electrode pattern and the second transparent electrode pattern Between the electrode patterns, there was insulation, and good display characteristics as a touch panel were obtained. Furthermore, the 1st and 2nd transparent electrode pattern was hard to be visually recognized, and the touch panel excellent in the display characteristic was obtained.

  1: TFT, 2: wiring, 3: insulating film, 4: planarization film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12: backlight Unit, 14, 15: Glass substrate, 16: TFT, 17: Cured film, 18: Contact hole, 19: ITO transparent electrode, 20: Liquid crystal, 22: Color filter, 30: Capacitance type input device, 31: Front Face plate, 32: Mask layer, 33: First transparent electrode pattern, 33a: Pad portion, 33b: Connection portion, 34: Second transparent electrode pattern, 35: Insulating layer, 36: Conductive element, 37: Transparent protection Layer, 38: opening

Claims (18)

A polymer component containing a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group;
a photoacid generator that generates an acid having a pKa of 3 or less;
A compound represented by the following general formula (I):
Solvent,
A photosensitive resin composition comprising:

In the formula (I), R ¹ represents a hydrogen atom or an n-valent organic group, R ^{2 to} R ⁵ each independently represents a hydrogen atom or an alkyl group, and n represents an integer of 1 or more. A polymer component containing a polymer having a structural unit having an acid group;
A quinonediazide compound,
A compound represented by the following general formula (I):
Solvent,
A photosensitive resin composition comprising:

In the formula (I), R ¹ represents a hydrogen atom or an n-valent organic group, R ^{2 to} R ⁵ each independently represents a hydrogen atom or an alkyl group, and n represents an integer of 1 or more. The photosensitive resin composition of Claim 1 or 2 whose R < ¹ > is an aromatic ring group in general formula (I). The photosensitive resin composition of any one of Claims 1-3 whose R < ² > -R < ⁵ > is a hydrogen atom in general formula (I).   The photosensitive resin composition of any one of Claims 1-4 in which the said polymer component contains the polymer which has a structural unit which has a crosslinkable group. The photosensitive resin composition according to claim 1, wherein the polymer component is a polymer component satisfying at least one of the following (1-1) and (1-2);
(1-1) (a1-1) a polymer having a structural unit having an acid group protected by an acid-decomposable group, and (a1-2) a structural unit having a crosslinkable group,
(1-2) (a1-1) A polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a1-2) a polymer having a structural unit having a crosslinkable group. The photosensitive resin composition according to claim 6, wherein the structural unit (a1-1) is a structural unit represented by the following formula (A2 ′);

In formula (A2 ′), R ²¹ and R ²² each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, and R ²³ is: Represents an alkyl group or an aryl group, and R ²¹ or R ²² and R ²³ may combine to form a cyclic ether, R ²⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. Represents. The photosensitive resin according to claim 5, wherein the crosslinkable group is one or more selected from an epoxy group, an oxetanyl group, and a group represented by —NH—CH ₂ —OR. Composition; wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.   The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a chemically amplified positive photosensitive resin composition.   The photosensitive resin composition according to claim 1, wherein the photoacid generator is an oxime sulfonate compound and / or an onium salt compound.   The photosensitive resin composition according to claim 1, wherein the photoacid generator is an oxime sulfonate compound. Applying the photosensitive resin composition according to any one of claims 1 to 11 on a substrate;
Removing the solvent from the applied photosensitive resin composition;
Exposing the photosensitive resin composition from which the solvent has been removed with actinic rays;
Developing the exposed photosensitive resin composition with a developer;
And a step of thermally curing the developed photosensitive resin composition.   The manufacturing method of the cured film of Claim 12 including the process of exposing the developed said photosensitive resin composition after the process to develop and before the process of thermosetting.   The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-11.   The cured film of Claim 14 which is an interlayer insulation film.   A liquid crystal display device comprising the cured film according to claim 14.   An organic electroluminescence display device comprising the cured film according to claim 14.   A touch panel having the cured film according to claim 14.

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