JP5191567B2 - Positive photosensitive resin composition, method for forming cured film, cured film, organic EL display device, and liquid crystal display device - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, a method for forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device.

An organic EL display device, a liquid crystal display device, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
Patent Document 1 contains (A) a structural unit having an acid-dissociable group and a structural unit having a functional group that can react with a carboxyl group to form a covalent bond, and is alkali-insoluble or alkali-insoluble, and A positive photosensitive resin composition comprising at least a resin that becomes alkali-soluble when the acid-dissociable group is dissociated, and a compound that generates acid upon irradiation with actinic rays or radiation. Have been described.

JP 2009-98616 A Japanese Patent No. 2584311 Japanese Patent No. 3929648 Japanese Patent No. 4181760

The applicability of a composition containing a resin having an acid dissociable group as described in Patent Document 1 has been hardly studied.
On the other hand, it is known that the positive photosensitive resin composition has a problem of precipitation of particles during refrigerated storage (see Patent Documents 2 to 4). The composition of the photosensitive resin composition described in this document is based on the premise that it is applied to a small substrate, and is not considered for applicability to a large substrate. However, in the positive-type chemically amplified photosensitive resin composition for large LCDs, compatibility between the applicability of the composition containing a resin having an acid-dissociable group and the precipitation of particles during refrigerated storage is It was difficult from the viewpoint of characteristic changes, and the actual situation was not yet achieved.
The problem to be solved by the present invention is to provide a positive photosensitive resin composition that is excellent in applicability and can prevent precipitation during refrigerated storage.

The present inventors have found that such a composition has a specific effect by using a fluorine-containing surfactant having a specific structure and a surfactant containing a silicon atom having a specific structure in combination. Was completed.
That is, the present invention has the following configuration.

（一般式（１）中、Ｒ¹及びＲ³はそれぞれ独立に水素原子又はメチル基を表し、Ｒ²は炭素数１〜４の直鎖アルキレン基を表し、Ｒ⁴は水素原子又はアルキル基を表し、Ｌは炭素数３〜６のアルキレン基を表し、ｐ及びｑは構成単位Ａと構成単位Ｂとの重合比を表す質量百分率であり、ｐは１０〜８０質量％を表し、ｑは２０〜９０質量％を表し、ｒは１〜１８の整数を表し、ｎは１〜１０の整数を表す。）

（一般式（２）中、Ｒ⁵〜Ｒ¹²はそれぞれ独立に、アミノ基、水酸基、カルボキシル基、グリシジル基、チオール基、炭素数１〜２０の直鎖または環状構造の繰り返し構造も取り得るアルキル基、アルキレン基、アラルキル基およびアルコキシ基を表し、ｍおよびｎはジメチルシロキサン構成単位と変性シロキサン構成単位との重合比を表す質量百分率を表す。）
［２］ 前記一般式（２）における前記Ｒ⁵、Ｒ⁷、Ｒ⁹およびＲ¹¹の少なくとも１つが、ポリプロピレンオキシ基で置換されたポリエチレンオキシ基、無置換のアルキル基、脂環エポキシ基置換のアルキル基、グリシジル基置換のアルキル基およびアラルキル基から選ばれる少なくとも１つである、［１］に記載のポジ型感光性樹脂組成物。
［３］ 前記Ｌが、下記一般式（３）で表される分岐アルキレン基である、［１］または［２］に記載のポジ型感光性樹脂組成物。

（一般式（３）中、Ｒ¹³は炭素数１〜４のアルキル基を表す。）
［４］ 前記Ｒ¹³がエチル基である、［３］に記載のポジ型感光性樹脂組成物。
［５］ 前記成分Ｃが、スチレン誘導体、マレイミド誘導体、（メタ）アクリル酸および水酸基含有（メタ）アクリレート化合物よりなる群から選ばれた少なくとも１つの化合物由来の構成単位をさらに有する、［１］〜［４］のいずれか１項に記載のポジ型感光性樹脂組成物。
［６］ 前記成分Ｃの酸分解性基が、下記一般式（Ia）、一般式（Ib）、一般式（IIa）又は一般式（IIb）で表される基である、［１］〜［５］のいずれか１項に記載のポジ型感光性樹脂組成物。

（一般式（Ia）、一般式（Ib）、一般式（IIa）及び一般式（IIb）中、Ｒ²¹はそれぞれ独立に、アルキル基又はシクロアルキル基を表し、Ｒ²²はそれぞれ独立に、アルキル基を表し、Ｒ²¹とＲ²²とが環を形成してもよく、Ｒ²³は第三級アルキル基を表し、Ｒ²⁴は第三級アルキル基又はｔｅｒｔ−ブトキシカルボニル基を表し、Ａｒ¹及びＡｒ²はそれぞれ独立に、二価の芳香族基を表し、波線部分は他の構造との結合箇所を表す。）
［７］ 前記成分Ｃの官能基として、オキシラニル基およびオキセタニル基の少なくとも一方を含む、［１］〜［６］のいずれか１項に記載のポジ型感光性樹脂組成物。
［８］ 前記成分Ｃの官能基が、オキセタニル基である、［７］に記載のポジ型感光性樹脂組成物。
［９］ 前記成分Ｄが、オキシムスルホネート化合物である、［１］〜［８］のいずれか１項に記載のポジ型感光性樹脂組成物。
［１０］ 前記成分Ｅが、沸点１３０℃以上１６０℃未満の溶剤、沸点１６０℃以上の溶剤、又は、これらの混合物である、［１］〜［９］のいずれか１項に記載のポジ型感光性樹脂組成物。
［１１］（１）［１］〜［１０］のいずれか１項に記載のポジ型感光性樹脂組成物を基板上に適用する適用工程、（２）適用されたポジ型感光性樹脂組成物から溶剤を除去する溶剤除去工程、（３）活性光線により露光する露光工程、（４）水性現像液により現像する現像工程、及び、（５）熱硬化するポストベーク工程、を含む硬化膜の製造方法。
［１２］ ［１１］に記載の方法により製造された、硬化膜。
［１３］ 層間絶縁膜である、［１２］に記載の硬化膜。
［１４］ ［１２］又は［１３］に記載の硬化膜を具備する、有機ＥＬ表示装置または液晶表示装置。 [1] (Component A) A copolymer having a structural unit A and a structural unit B represented by the following general formula (1) and having a weight average molecular weight of 1,000 to 10,000, (Component B) A polymer having a weight average molecular weight of 1,000 to 50,000 represented by the formula (2), (Component C) a structural unit having an acid-decomposable group that decomposes with an acid to form a carboxyl group or a phenolic hydroxyl group. And a resin having a structural unit having a functional group capable of reacting with a carboxyl group or a phenolic hydroxyl group to form a covalent bond, (Component D) a photoacid generator, and (Component E) a solvent, A positive photosensitive resin composition, wherein the content of component A is 0.001 to 1.00% by mass, and the content of component B is 0.001 to 1.00% by mass.

(In General Formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group. L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio of the structural unit A and the structural unit B, p represents 10 to 80% by mass, and q represents 20 -90 mass% is represented, r represents the integer of 1-18, n represents the integer of 1-10.)

(In the general formula (2), R ^{5 to} R ¹² are each independently an amino group, a hydroxyl group, a carboxyl group, a glycidyl group, a thiol group, or an alkyl that can have a linear or cyclic structure having 1 to 20 carbon atoms. A group, an alkylene group, an aralkyl group, and an alkoxy group, and m and n represent a mass percentage that represents a polymerization ratio of a dimethylsiloxane structural unit and a modified siloxane structural unit.)
[2] In the general formula (2), at least one of R ⁵ , R ⁷ , R ⁹ and R ¹¹ is a polyethyleneoxy group substituted with a polypropyleneoxy group, an unsubstituted alkyl group, an alicyclic epoxy group-substituted The positive photosensitive resin composition according to [1], which is at least one selected from an alkyl group, an alkyl group substituted with a glycidyl group, and an aralkyl group.
[3] The positive photosensitive resin composition according to [1] or [2], wherein L is a branched alkylene group represented by the following general formula (3).

(In General Formula (3), R ¹³ represents an alkyl group having 1 to 4 carbon atoms.)
[4] The positive photosensitive resin composition according to [3], wherein R ¹³ is an ethyl group.
[5] The component C further includes a structural unit derived from at least one compound selected from the group consisting of a styrene derivative, a maleimide derivative, (meth) acrylic acid, and a hydroxyl group-containing (meth) acrylate compound. The positive photosensitive resin composition according to any one of [4].
[6] The acid-decomposable group of the component C is a group represented by the following general formula (Ia), general formula (Ib), general formula (IIa), or general formula (IIb): [1] to [ [5] The positive photosensitive resin composition according to any one of [5].

(In the general formula (Ia), the general formula (Ib), the general formula (IIa) and the general formula (IIb), each R ²¹ independently represents an alkyl group or a cycloalkyl group, and each R ²² independently represents an alkyl group. R ²¹ and R ²² may form a ring, R ²³ represents a tertiary alkyl group, R ²⁴ represents a tertiary alkyl group or a tert-butoxycarbonyl group, Ar ¹ and Ar ² independently represents a divalent aromatic group, and the wavy line represents a bonding site with another structure.)
[7] The positive photosensitive resin composition according to any one of [1] to [6], which contains at least one of an oxiranyl group and an oxetanyl group as a functional group of the component C.
[8] The positive photosensitive resin composition according to [7], wherein the functional group of component C is an oxetanyl group.
[9] The positive photosensitive resin composition according to any one of [1] to [8], wherein the component D is an oxime sulfonate compound.
[10] The positive type according to any one of [1] to [9], wherein the component E is 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. Photosensitive resin composition.
[11] (1) An application step of applying the positive photosensitive resin composition according to any one of [1] to [10] on a substrate, (2) an applied positive photosensitive resin composition A cured film comprising: a solvent removal step for removing the solvent from the substrate; (3) an exposure step for exposure with actinic rays; (4) a development step for development with an aqueous developer; and (5) a post-bake step for thermal curing. Method.
[12] A cured film produced by the method according to [11].
[13] The cured film according to [12], which is an interlayer insulating film.
[14] An organic EL display device or a liquid crystal display device comprising the cured film according to [12] or [13].

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in applicability and can provide the positive photosensitive resin composition which can prevent precipitation at the time of refrigerated storage, and the formation method of a cured film using the same.

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

  Hereinafter, the positive photosensitive resin composition of the present invention will be described in detail.

（一般式（１）中、Ｒ¹及びＲ³はそれぞれ独立に水素原子又はメチル基を表し、Ｒ²は炭素数１〜４の直鎖アルキレン基を表し、Ｒ⁴は水素原子又はアルキル基を表し、Ｌは炭素数３〜６のアルキレン基を表し、ｐ及びｑは構成単位Ａと構成単位Ｂとの重合比を表す質量百分率であり、ｐは１０〜８０質量％を表し、ｑは２０〜９０質量％を表し、ｒは１〜１８の整数を表し、ｎは１〜１０の整数を表す。）

（一般式（２）中、Ｒ⁵〜Ｒ¹²はそれぞれ独立に、アミノ基、水酸基、カルボキシル基、グリシジル基、チオール基、炭素数１〜２０の直鎖または環状構造の繰り返し構造も取り得るアルキル基、アルキレン基、アラルキル基およびアルコキシ基を表し、ｍおよびｎはジメチルシロキサン構成単位と変性シロキサン構成単位との重合比を表す質量百分率を表す。）
このような構成により、適用性に優れ、冷蔵保存時の析出が防止できる。
さらに、本発明のポジ型感光性樹脂組成物のより好ましい態様では、さらに画素欠陥が少なく、平面性に優れる硬化膜が得られることが好ましい。
以下、本発明の感光性樹脂組成物について説明する。 [Positive photosensitive resin composition]
The positive photosensitive resin composition of the present invention (hereinafter also simply referred to as “photosensitive resin composition”) includes (Component A) a structural unit A and a structural unit B represented by the following general formula (1). A copolymer having a weight average molecular weight of 1,000 to 10,000, (component B) a polymer having a weight average molecular weight of 1,000 to 50,000 represented by the following general formula (2), (component C) a structural unit having an acid-decomposable group that decomposes with an acid to produce a carboxyl group or a phenolic hydroxyl group, and a structural unit having a functional group that can react with the carboxyl group or the phenolic hydroxyl group to form a covalent bond. A resin having (Component D) a photoacid generator and (Component E) a solvent, the content of Component A is 0.001 to 1.00% by mass, and the content of Component B is 0. 0.001 to 1.00% by mass To.

(In General Formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group. L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio of the structural unit A and the structural unit B, p represents 10 to 80% by mass, and q represents 20 -90 mass% is represented, r represents the integer of 1-18, n represents the integer of 1-10.)

(In the general formula (2), R ^{5 to} R ¹² are each independently an amino group, a hydroxyl group, a carboxyl group, a glycidyl group, a thiol group, or an alkyl that can have a linear or cyclic structure having 1 to 20 carbon atoms. A group, an alkylene group, an aralkyl group, and an alkoxy group, and m and n represent a mass percentage that represents a polymerization ratio of a dimethylsiloxane structural unit and a modified siloxane structural unit.)
With such a configuration, the applicability is excellent and precipitation during refrigerated storage can be prevented.
Furthermore, in a more preferable embodiment of the positive photosensitive resin composition of the present invention, it is preferable that a cured film with fewer pixel defects and excellent flatness can be obtained.
Hereinafter, the photosensitive resin composition of the present invention will be described.

The photosensitive resin composition of the present invention is a positive photosensitive resin composition.
The positive photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).
The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. A 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
On the other hand, the (component D) photoacid generator used in the present invention acts as a catalyst for the deprotection of the acid-protected acid group produced in response to actinic rays. The acid produced by the above action contributes to a number of deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10, and high sensitivity is obtained as a result of so-called chemical amplification. .
Hereinafter, each component shown by these (component A) etc. is also called "component A" etc., respectively.

(Component A)
The photosensitive resin composition of the present invention includes (Component A) a copolymer containing the structural unit A and the structural unit B represented by the following formula (1), and having a weight average molecular weight of 1,000 or more and 10,000 or less. Is 0.001-1.00 mass% with respect to the total mass of the photosensitive resin composition.

In formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group. , L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing the polymerization ratio of the structural unit A and the structural unit B, and p is a numerical value of 10% by mass to 80% by mass. Q represents a numerical value of 20% by mass to 90% by mass, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.
The carbon number of L refers to all the carbon atoms constituting the alkylene group including the branched portion.
L may be a linear alkylene group or a branched alkylene group, but is preferably a branched alkylene group, more preferably an alkylene group represented by the following general formula (3). .

Here, R ¹³ represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the application surface, an alkyl group having 2 carbon atoms, That is, an ethyl group is more preferable.

The p and q are mass percentages representing the polymerization ratio.
p represents a numerical value of 10% by mass or more and 80% by mass or less, and a numerical value of 20% by mass or more and 60% by mass or less is preferable in terms of the balance between hydrophobicity and hydrophilicity.
Moreover, q represents a numerical value of 20% by mass or more and 90% by mass or less, and a numerical value of 40% by mass or more and 80% by mass or less is preferable in terms of a balance between hydrophobicity and hydrophilicity.
The r is preferably a numerical value of 6 or more and 18 or less. The n is preferably an integer from 6 to 10.
R ² is preferably a linear alkylene group having 1 or 2 carbon atoms, that is, a methylene group or an ethylene group, and more preferably an ethylene group.
R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.

Component A may have other structural units other than the structural unit A and the structural unit B. There is no restriction | limiting in particular as another structural unit, The structural unit derived from a well-known ethylenically unsaturated compound can be illustrated suitably.
The total of the content of monomer units forming the structural unit A and the content of monomer units forming the structural unit B in all monomer units constituting the component A is preferably 90 mol% or more.

  Specific examples of component A include A-1 to A-12 shown below, but the present invention is not limited to these.

The weight average molecular weight (Mw) of Component A is 1,000 or more and 10,000 or less, and preferably 1,000 or more and 6,000 or less from the viewpoint of applicability (preferably coatability, the same applies hereinafter). More preferably, it is 1,000 or more and 3,000 or less, and further preferably 1,200 or more and 2,000 or less. In addition, it is preferable that the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by the gel permeation chromatography (GPC) which used the tetrahydrofuran (THF) solvent as the carrier.
There is no restriction | limiting in particular as a preparation method of the component A, It can manufacture by a well-known synthesis method and a polymerization method.

Component A can be used alone or in combination of two or more.
The addition amount of the component A in the photosensitive resin composition of this invention is 0.001-1.00 mass% with respect to the total mass of the photosensitive resin composition, and 0.005-0 from a viewpoint of applicability. It is preferably 20% by mass, more preferably 0.007 to 0.15% by mass. By adding the component A in an amount within the above range, excellent applicability can be obtained. It is particularly effective for slit coating on large substrates. Here, the large substrate refers to a substrate having a size of 1 m × 1 m square to 5 m × 5 m square. Further, by adding the component A in an amount within the above range, excellent developability can be obtained even with a large substrate. Furthermore, it has been surprisingly found that the effect of good liquid crystal specific resistance can be obtained by adding component A in an amount in the above range.

(Component B)
The photosensitive resin composition of the present invention comprises a polymer having a weight average molecular weight of 1,000 to 50,000 represented by the following general formula (2) as component B with respect to the total mass of the photosensitive resin composition. 0.001 to 1.00% by mass. By using such a component B together with the component A which is a fluorinated copolymer, the photosensitive resin composition of the present invention has a synergistic effect, and the solvent solubility at low temperature is remarkably improved and stored at low temperature. Sometimes particle generation can be suppressed.
Component B is represented by the following general formula (2).

In general formula (2), R ^{5 to} R ¹² are each independently an amino group, a hydroxyl group, a carboxyl group, a glycidyl group, a thiol group, or an alkyl group that can also have a linear or cyclic structure having 1 to 20 carbon atoms. Represents an alkylene group, an aralkyl group and an alkoxy group.
R ⁶ , R ⁸ , R ¹⁰ and R ¹² are preferably each independently an alkyl group capable of taking a linear structure having 1 to 20 carbon atoms or a cyclic structure, and linear alkyl having 1 to 20 carbon atoms. It is more preferably a group, particularly preferably a linear alkyl group having 1 to 10 carbon atoms, and particularly preferably a methyl group.
At least one of R ⁵ , R ⁷ , R ⁹ and R ¹¹ is a polyethyleneoxy group (hereinafter also referred to as EO), a polypropyleneoxy group (hereinafter also referred to as PO), or a polyethyleneoxy group substituted with a polypropyleneoxy group. , An alkyl group (which may be further modified with an epoxy group or a glycidyl group), a glycidyl group, an aralkyl group or an epoxy group, a polyethyleneoxy group substituted with a polypropyleneoxy group, an unsubstituted alkyl group ( In this case, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and an alicyclic epoxy group-substituted alkyl group (in this case, the alkyl group has 1 to 30 carbon atoms). And more preferably 1 to 20), an alkyl group substituted with a glycidyl group (in this case, Preferably alkyl groups are C1-30, and more preferably from 1 to 20), it is particularly preferred aralkyl group (having 8 to 20 carbon atoms is at least one selected from the preferred). That is, the polymer represented by the general formula (2) is particularly preferably a polyethylene oxide-modified, polypropylene oxide-modified, glycidyl-modified, alkyl-modified (more optionally glycidyl-modified), or aralkyl-modified polymer. . R ⁵ , R ⁷ , R ⁹ and R ¹¹ may be the same or different.
A preferred combination of R ⁵ , R ⁷ , R ⁹ and R ¹¹ will be described. First, R ⁵ and R ^9, when at least one of R ⁷ and R ¹¹ is a group other than methyl group, the preferable range of R ⁵ and R ⁹ are preferably of the R ^6, R ^8, R ¹⁰ and R ¹² Similar to range. On the other hand, when R ⁷ and R ¹¹ are both methyl groups, R ⁵ and R ⁹ are polyethyleneoxy groups, polypropyleneoxy groups, polyethyleneoxy groups substituted with polypropyleneoxy groups, alkyl groups (further, epoxy groups, glycidyls). A glycidyl group, an aralkyl group, an epoxy group, a polyethyleneoxy group substituted with a polypropyleneoxy group, an unsubstituted alkyl group, an alicyclic epoxy group-substituted alkyl group, It is preferably at least one selected from a glycidyl group-substituted alkyl group and an aralkyl group.
Next, when R ⁷ and R ¹¹ are at least one of R ⁵ and R ⁹ is a group other than a methyl group, the preferred range of R ⁷ and R ¹¹ is that of R ⁶ , R ⁸ , R ¹⁰ and R ¹² . This is the same as the preferred range. On the other hand, when R ⁵ and R ⁹ are both methyl groups, R ⁷ and R ¹¹ are polyethyleneoxy groups, polypropyleneoxy groups, polyethyleneoxy groups substituted with polypropyleneoxy groups, alkyl groups (further, epoxy groups, glycidyls). A glycidyl group, an aralkyl group, an epoxy group, a polyethyleneoxy group substituted with a polypropyleneoxy group, an unsubstituted alkyl group, an alicyclic epoxy group-substituted alkyl group, It is preferably at least one selected from a glycidyl group-substituted alkyl group and an aralkyl group.

When R ⁷ and R ¹¹ are modified, m and n represent a dimethylsiloxane structural unit, a modified siloxane structural unit, and a mass percentage representing a polymerization ratio.
The m is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.
Moreover, n is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.
The number of repeating units of the dimethylsiloxane structure is not particularly limited. However, when the number of repeating units (molecular weight) increases, surface uneven distribution improves, and when the number of repeating units decreases, compatibility with the composition improves. For example, the number of repeating units can be 1 to 20, but the number of units is usually determined in consideration of the molecular weight, the polarity of the substituent and the polarity of the composition. In particular, in the present invention, since component B is used as an additive, it is unevenly distributed on the surface with a small addition amount (assuming low critical micelle concentration and low) on the assumption that it is compatible with the photosensitive resin composition of the present invention. It is desirable to select it by suppressing the increase in viscosity of the composition (surface tension reducing ability) (small molecular weight).
The component B has an HLB value (Hydrophile-Lipophile Balance, hydrophilic / lipophilic balance) of preferably 1 to 15, more preferably 1 to 10, and particularly preferably 1 to 7.
The weight average molecular weight of the polymer represented by the general formula (2) is preferably 1000 to 50,000, more preferably 1000 to 40,000, and particularly preferably 1000 to 35,000. preferable.

The polymer represented by the general formula (2) can be synthesized or commercially obtained. For example, polymers such as Toray Dow Corning and Shin-Etsu Chemical Co., Ltd. can be used as Component B.
The photosensitive resin composition of the present invention preferably contains the polymer represented by the general formula (2) in a range of 0.001 to 1.00% by mass, and 0.005 to 0.5% by mass. It is more preferable to include in the range.

(Component C)
Component C includes a structural unit having an acid-decomposable group that decomposes with an acid to produce a carboxyl group or a phenolic hydroxyl group, and a structural unit having a functional group that can react with a carboxyl group or a phenolic hydroxyl group to form a covalent bond. It is resin which has at least.
Component C may have each of the structural units described above alone or in combination of two or more. In addition, component C may have a structural unit other than the above structural units.
Component C is preferably a resin that is insoluble in alkali and becomes alkali-soluble when the acid-decomposable group is decomposed. Here, the “acid-decomposable group” means a functional group that can be decomposed in the presence of an acid. “Alkali-soluble” refers to 0 at 23 ° C. when a coating (thickness: 3 μm) formed by applying a compound (resin) solution on a substrate and heating at 90 ° C. for 2 minutes is dip-developed. It means that the dissolution rate with respect to a 4 mass% tetramethylammonium hydroxide aqueous solution is 0.01 μm / second or more. On the other hand, “alkali insoluble” means that the dissolution rate is less than 0.01 μm / second.

<C- (1): a structural unit having an acid-decomposable group that decomposes with an acid to generate a carboxyl group or a phenolic hydroxyl group>
The structural unit having an acid-decomposable group (hereinafter also simply referred to as “acid-decomposable group”) that decomposes with an acid contained in Component C to generate a carboxyl group or a phenolic hydroxyl group is decomposed (dissociated) with an acid, A structural unit having the structure represented by formula (Ia) or (IIa) that generates a carboxyl group, or a structure represented by formula (Ib) or (IIb) that decomposes with an acid to form a phenolic hydroxyl group It is preferable to contain the structural unit which has.

First, the structural unit having the structure represented by the formula (Ia) and the formula (Ib) will be described.
In formula (Ia) and formula (Ib), R ²¹ each independently represents an alkyl group or a cycloalkyl group.
The alkyl group for R ²¹ may be linear or branched.
Alkyl group are preferable as the carbon number of the R ^21, preferably 1 to 20 is, more preferably 1 to 10, more preferably 1-7.
Preferred number of carbon atoms of the cycloalkyl group in R ^21, preferably from 3 to 20, more preferably from 3 to 10, more preferably 5-7.
In addition, when these carbon numbers have a substituent, the carbon number of a substituent is also included.

The alkyl group in R ²¹ is, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-pentyl group, neopentyl group, n- A hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. can be mentioned.
Examples of the cycloalkyl group for R ²¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, and the like.
In addition, the alkyl group and cycloalkyl group in R ²¹ may have a substituent.
Examples of the substituent in the alkyl group and the cycloalkyl group include alkyl groups having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.), cycloalkyl groups having 3 to 10 carbon atoms, and 6 to 6 carbon atoms. 10 aryl groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxy group, alkoxy group having 1 to 10 carbon atoms, and the like. It may be further substituted with a substituent.
In addition, the alkyl group or cycloalkyl group in R ²¹ is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms. Is more preferably an alkyl group having 1 to 6, a cycloalkyl group having 3 to 6 carbon atoms, or a benzyl group, more preferably an ethyl group or a cyclohexyl group, and particularly preferably an ethyl group.

In formula (Ia) and formula (Ib), R ²² each independently represents an alkyl group.
The alkyl group for R ²² may be linear or branched.
The preferred carbon number of the alkyl group for R ²² is preferably 1-20, more preferably 1-10, and even more preferably 1-7.
In addition, when these carbon numbers have a substituent, the carbon number of a substituent is also included.
Moreover, as an alkyl group in R < ²² >, a C1-C6 alkyl group is preferable and a methyl group is especially preferable.
R ²¹ and R ²² may form a ring, and a preferred example thereof is preferably a ring formed by a saturated hydrocarbon chain, a 5-membered ring structure, that is, a tetrahydrofuranyl ester structure, or a 6-membered structure. A ring structure, that is, a tetrahydropyranyl ester structure can be mentioned. These ring structures may have a substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.), and 3 to 10 carbon atoms. Cycloalkyl group, aryl group having 6 to 10 carbon atoms, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxy group, alkoxy group having 1 to 10 carbon atoms, etc. it can. These substituents may be further substituted with the above substituents.

In the formula (Ib), Ar ¹ represents a divalent aromatic group and has OCH (OR ²¹ ) (R ²² ) on the aromatic ring.
The divalent aromatic group in Ar ¹ is not particularly limited, and examples thereof include a phenylene group, a substituted phenylene group, a naphthylene group, and a substituted naphthylene group, and a phenylene group or a substituted phenylene group is preferable. A phenylene group is more preferable, and a 1,4-phenylene group is still more preferable.
Moreover, the divalent aromatic group in Ar ¹ may have a substituent on the aromatic ring, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, Butyl group, etc.), cycloalkyl group having 3 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxy group, carbon Examples thereof include an alkoxy group of 1 to 10, and these substituents may be further substituted with the above substituents.

  As the carboxylic acid monomer capable of forming the structural unit having the structure represented by the formula (Ia) by protecting the carboxy group, the structural unit having an acid-decomposable group by protecting the carboxy group Can be used, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-methyl-p-carboxystyrene; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid And the like. Moreover, as a structural unit which has an acid-decomposable group, the monomer unit derived from the carboxylic acid by which these carboxy groups were protected can be mentioned as a preferable thing.

  As a monomer having a phenolic hydroxyl group capable of forming a structural unit having the structure represented by the formula (Ib) by protecting the phenolic hydroxyl group, acid-decomposable by protecting the phenolic hydroxyl group Any structural unit having a group can be used. Examples thereof include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene, and paragraphs 0011 to 0016 of JP-A-2008-40183. Described compounds, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxybenzoic acid and glycidyl acrylate The addition reaction product of can be mentioned as a preferable one. Among these, α-methyl-p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, and 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454 An addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate and an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.

  Among the structural units having an acid-decomposable group having the structure represented by formula (Ia) or formula (Ib), more preferred as the structural unit having an acid-decomposable group is represented by the following formula (III). This is a structural unit.

In formula (III), R ²⁵ represents an alkyl group or a cycloalkyl group, and a preferred embodiment of R ^{25 is} the same as the preferred embodiment of R ²¹ in formula (Ia) and formula (Ib).
In the formula (III), R ²⁶ represents a hydrogen atom or a methyl group.
Preferable specific examples of the radical polymerizable monomer used for forming the structural unit represented by the formula (III) include, for example, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl methacrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1-isobutoxyethyl acrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1- ( 2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl methacrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, 1- ( -Cyclohexylethoxy) ethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl methacrylate, 1-benzyloxyethyl acrylate and the like can be mentioned, and particularly preferable ones include 1-ethoxyethyl methacrylate and 1-ethoxyethyl acrylate. These structural units can be used singly or in combination of two or more.

  As the radically polymerizable monomer used to form the structural unit having an acid-decomposable group having a structure represented by the formula (Ia) or (Ib), a commercially available one may be used. What was synthesize | combined by the method can also be used. For example, as shown below, it can be synthesized by reacting (meth) acrylic acid with a vinyl ether compound in the presence of an acid catalyst.

Here, R ²⁵ and R ²⁶ correspond to R ²⁵ and R ²⁶ in the formula (III), respectively.

  In addition, the structural unit having an acid-decomposable group is obtained by reacting a carboxy group or a phenolic hydroxyl group with a vinyl ether compound after polymerizing a protected carboxy group or a phenolic hydroxyl group-containing monomer with a monomer or a precursor thereof described later. Can also be formed. In addition, the specific example of the preferable monomer unit formed in this way is the same as the monomer unit derived from the preferable specific example of the said radical polymerizable monomer.

（式（ＩＶ）中、Ｒ⁵¹は水素原子又は炭素数１〜４のアルキル基を表し、Ｌ¹はカルボニル基又はフェニレン基を表し、Ｒ⁵²〜Ｒ⁵⁸はそれぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表す。）
また、下記式（IV-1）〜（IV-4）で表される構成単位も好ましい。さらに、酸分解性基を有する構成単位として、下記式（IV-1）又は（IV-2）で表される構成単位が特に好ましく、下記式（IV-1）で表される構成単位がより特に好ましい。 Among the structural units having an acid-decomposable group having a structure represented by formula (Ia) or formula (Ib), a structural unit of the following formula (VI) is also preferred as a structural unit having an acid-decomposable group.

(In formula (IV), R ⁵¹ 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 ^{52 to} R ⁵⁸ each independently represents a hydrogen atom or a carbon number. Represents 1 to 4 alkyl groups.)
In addition, structural units represented by the following formulas (IV-1) to (IV-4) are also preferable. Furthermore, as the structural unit having an acid-decomposable group, a structural unit represented by the following formula (IV-1) or (IV-2) is particularly preferable, and a structural unit represented by the following formula (IV-1) is more preferable. Particularly preferred.

（式（IV-1）〜（IV-4）中、Ｒ²⁷〜Ｒ³⁰はそれぞれ独立に水素原子又はメチル基を表す。）

(Formula (IV-1) ~ (IV -4) in, R ²⁷ to R ³⁰ each independently represent a hydrogen atom or a methyl group.)

  Next, the structural unit which has a structure represented by Formula (IIa) and Formula (IIb) is demonstrated.

前記式（IIa）及び式（IIb）中、Ｒ²³は第三級アルキル基を表し、Ｒ²⁴は第三級アルキル基又はｔｅｒｔ−ブトキシカルボニル基を表し、Ａｒ²は二価の芳香族基を表し、波線部分は他の構造との結合箇所を表す。
Ｒ²³及びＲ²⁴における第三級アルキル基としては、炭素数が４〜２０のものが好ましく、炭素数が４〜１４のものがより好ましく、炭素数が４〜８のものが更に好ましい。
また、式（IIa）におけるＲ²³は、炭素数４〜１２の第三級アルキル基であることが好ましく、炭素数４〜８の第三級アルキル基であることがより好ましく、ｔ−ブチル基であることが更に好ましい。
また、式（IIb）におけるＲ²⁴は、炭素数４〜１２の第三級アルキル基、ｔｅｒｔ−ブトキシカルボニル基であることが好ましく、炭素数４〜１２の第三級アルキル基であることがより好ましく、ｔ−ブチル基であることが更に好ましく、２−テトラヒドロピラニル基が特に好ましい。
式（IIb）中、Ａｒ²は、二価の芳香族基を表し、芳香環上にＯ（Ｒ²⁴）を有している。
式（IIb）におけるＡｒ²の好ましい態様は、前記式（Iｂ）におけるＡｒ¹の好ましい態様と同様である。

In the formulas (IIa) and (IIb), R ²³ represents a tertiary alkyl group, R ²⁴ represents a tertiary alkyl group or a tert-butoxycarbonyl group, and Ar ² represents a divalent aromatic group. The wavy line portion represents a coupling point with another structure.
The tertiary alkyl group for R ²³ and R ²⁴ preferably has 4 to 20 carbon atoms, more preferably has 4 to 14 carbon atoms, and still more preferably has 4 to 8 carbon atoms.
R ²³ in formula (IIa) is preferably a tertiary alkyl group having 4 to 12 carbon atoms, more preferably a tertiary alkyl group having 4 to 8 carbon atoms, and a t-butyl group. More preferably.
R ²⁴ in formula (IIb) is preferably a tertiary alkyl group having 4 to 12 carbon atoms or a tert-butoxycarbonyl group, and more preferably a tertiary alkyl group having 4 to 12 carbon atoms. A t-butyl group is more preferable, and a 2-tetrahydropyranyl group is particularly preferable.
In the formula (IIb), Ar ² represents a divalent aromatic group and has O (R ²⁴ ) on the aromatic ring.
The preferred embodiment of Ar ² in formula (IIb) is the same as the preferred embodiment of Ar ¹ in formula (Ib).

The tertiary alkyl group in R ²³ , the tertiary alkyl group or tert-butoxycarbonyl group in R ^4, and the divalent aromatic group in Ar ² may have a substituent. C1-C10 alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), C3-C10 cycloalkyl group, C6-C10 aryl group, halogen atom (fluorine atom, chlorine atom) , Bromine atom, iodine atom), cyano group, nitro group, hydroxy group, alkoxy group having 1 to 10 carbon atoms, and the like. These substituents may be further substituted with the above substituents.

The tertiary alkyl group for R ²³ and R ²⁴ is more preferably at least one selected from the group consisting of groups represented by the following formula (V).
-C (R ²⁹ R ³⁰ R ³¹ ) (V)
In the formula, R ²⁹ , R ³⁰ and R ³¹ are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 7 to 12 carbon atoms. It represents an aralkyl group, and any two of R ²⁹ , R ³⁰ and R ³¹ may be bonded to each other to form a ring together with the carbon atom to which they are bonded.

The alkyl group having 1 to 12 carbon atoms of R ²⁹ , R ³⁰ and R ³¹ in the formula (V) may be linear or branched, and examples thereof include a methyl group, an ethyl group, n- Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group (2,3-dimethyl- 2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
Examples of the cycloalkyl group having 3 to 12 carbon atoms 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.
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
R ²⁹ , R ³⁰ and R ³¹ can be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , or R ¹⁰ and R ¹¹ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, and an adamantyl group. And a tetrahydropyranyl group.

As the carboxylic acid monomer capable of forming a monomer unit having a structure represented by the formula (IIa) by protecting the carboxy group, a structural unit having an acid-decomposable group by protecting the carboxy group Any of the carboxylic acid monomers described above in the description of the formula (Ia) can be preferably used.
As a monomer having a phenolic hydroxyl group capable of forming a monomer unit having a structure represented by the formula (IIb) by protecting the phenolic hydroxyl group, acid decomposability is achieved by protecting the phenolic hydroxyl group. Any monomer can be used as long as it can be a structural unit having a group. For example, a monomer having a phenolic hydroxyl group described above in the description of formula (Ib) is preferable.

  Among the structural units having the structures represented by the formula (IIa) and the formula (IIb), those particularly preferable as the structural unit having an acid-decomposable group are structural units represented by the following formula (VI). is there.

In the formula (VI), R ³¹ represents a tertiary alkyl group, and R ³² represents a hydrogen atom or a methyl group.
In Formula (VI), a preferred embodiment of R ^{31 is the same as} the preferred embodiment of R ²³ in Formula (IIa).
Preferable specific examples of the radical polymerizable monomer used for forming the structural unit represented by the formula (VI) include, for example, tert-butyl methacrylate, tert-butyl acrylate, 2-methyl methacrylate Examples thereof include 2-adamantyl, 2-methyl-2-adamantyl acrylate, 1-methylcyclohexyl methacrylate and 1-methylcyclohexyl acrylate, and tert-butyl methacrylate and tert-butyl acrylate are particularly preferable. 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 having an acid-decomposable group include the following monomer units.

  The content of the monomer unit forming the structural unit having an acid-decomposable group in all the monomer units constituting Component C is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and more preferably 10 to 40 mol%. Is particularly preferred. A photosensitive resin composition having a high sensitivity and a wide exposure latitude is obtained at the above ratio.

（式中、Ｒ²は炭素数１〜９のアルキル基を示す。）、（メタ）アクリロイル基が例示される。この中でも、オキシラニル基、オキセタニル基、酸無水物基、酸ハライド基、イソシアネート基、下記式（Ａ）で表される基が好ましく、オキシラニル基、オキセタニル基、または式（Ａ）で表される基がより好ましく、オキシシラニル基及びオキセタニル基がさらに好ましい。 <C- (2): a structural unit having a functional group capable of reacting with a carboxyl group or a phenolic hydroxyl group to form a covalent bond>
Examples of the functional group capable of reacting with a carboxyl group or a phenolic hydroxyl group to form a covalent bond include an oxiranyl group, an oxetanyl group, an acid anhydride group, an acid halide group, an isocyanate group, a group represented by the following formula (A),
Formula (A)

(Wherein, R ² represents an alkyl group having 1 to 9 carbon atoms.) Are exemplified (meth) acryloyl groups. Among these, an oxiranyl group, an oxetanyl group, an acid anhydride group, an acid halide group, an isocyanate group, and a group represented by the following formula (A) are preferable, and an oxiranyl group, an oxetanyl group, or a group represented by the formula (A) Are more preferable, and an oxysilanyl group and an oxetanyl group are more preferable.

It is preferable to synthesize Component B using a radically polymerizable monomer containing such a functional group.
The structural unit having an oxiranyl group and / or oxetanyl group is preferably a structural unit having an alicyclic epoxy group and / or oxetanyl group, and more preferably a structural unit having an oxetanyl group.
The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring. Specifically, for example, 3,4-epoxycyclohexyl group, 2,3-epoxycyclohexyl group, 2,3 -An epoxy cyclopentyl group etc. are mentioned preferably.
The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetane-3-yl) methyl group can be preferably exemplified.
The constitutional unit having an oxiranyl group and / or oxetanyl group may have at least one oxiranyl group or oxetanyl group in one constitutional unit, one or more oxiranyl groups and one or more oxetanyl groups, two Although it may have the above oxiranyl group or two or more oxetanyl groups and is not particularly limited, it is preferable to have a total of 1 to 3 oxiranyl groups and / or oxetanyl groups. It is more preferable to have one or two groups in total, and it is even more preferable to have one oxiranyl group or oxetanyl group.

  Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxiranyl 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, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, cycloaliphatic described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Compounds containing an epoxy skeleton It is.

Examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, (meth) acrylic acid having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Examples include esters.
Examples of the radical polymerizable monomer used to form a structural unit having an oxiranyl group and / or an oxetanyl group may be a monomer containing a methacrylic ester structure or a monomer containing an acrylic ester structure. preferable.
Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and paragraphs 0011 to 0016 of JP 2001-330953 A. (Meth) acrylic acid esters having an oxetanyl group, particularly preferred are (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid (3-ethyloxetane). Most preferred are acrylic acid (3-ethyloxetane-3-yl) methyl and methacrylic acid (3-ethyloxetane-3-yl) methyl. 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 having a functional group capable of reacting with a carboxyl group or a phenolic hydroxyl group to form a covalent bond include the following structural unit and the repeating unit represented by the general formula (1).

（式中、Ｒ¹は水素原子またはメチル基を示し、Ｒ²は炭素数１〜９のアルキル基を示す。）
一般式（１）において、Ｒ¹は水素原子またはメチル基を示し、水素原子が好ましい。
Ｒ²は炭素数１〜９のアルキル基を示し、炭素数１〜７のアルキル基が好ましく、炭素数
２〜６のアルキル基がさらに好ましい。アルキル基は、直鎖または分岐のアルキル基のいずれであってもよい。 Repeating unit represented by the following general formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 9 carbon atoms.)
In General formula (1), R < ¹ > shows a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
R ² represents an alkyl group having 1 to 9 carbon atoms, preferably an alkyl group having 1 to 7 carbon atoms, and more preferably an alkyl group having 2 to 6 carbon atoms. The alkyl group may be either a linear or branched alkyl group.

The content of monomer units that form a structural unit having a functional group capable of forming a covalent bond by reacting with a carboxyl group or a phenolic hydroxyl group in all monomer units constituting Component C is preferably 10 to 80 mol%, 15-70 mol% is still more preferable, and 20-65 mol% is especially preferable. By containing in the above ratio, the physical properties of the cured film are improved.
Among these structural units, a structural unit having an oxetanyl group is particularly preferable in terms of excellent storage stability of the photosensitive composition.

<C- (3): Other structural unit>
The component C may have other structural units other than the C- (1) structural unit and the C- (2) structural unit as long as the effects of the present invention are not hindered. The other structural unit is at least one selected from the group consisting of a structural unit having a carboxy group and / or a phenolic hydroxyl group, a styrene derivative, a maleimide derivative, (meth) acrylic acid, and a hydroxyl group-containing (meth) acrylate compound. Preferred examples are structural units derived from one compound. Among them, in the present invention, the component C further has a structural unit derived from at least one compound selected from the group consisting of a styrene derivative, a maleimide derivative, (meth) acrylic acid, and a hydroxyl group-containing (meth) acrylate compound. It is more preferable.

[Structural unit having carboxy group and / or phenolic hydroxyl group]
Component C can contain, as other structural units, structural units having a carboxy group and / or a phenolic hydroxyl group as long as component C is not alkali-soluble. The carboxy group also includes a carboxylic anhydride residue. Examples of the radical polymerizable monomer used to form the structural unit having a carboxy group include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Dicarboxylic acids such as itaconic acid are preferred. Moreover, as a radically polymerizable monomer used in order to form the structural unit which has a carboxylic anhydride residue, maleic anhydride, itaconic anhydride, etc. are preferable, for example. Examples of the radical polymerizable monomer that forms a structural unit having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene, paragraph 0011 of JP2008-40183A. To 0016 are preferred. Among these, (meth) acrylic acid and hydroxystyrenes are more preferable. These structural units can be used individually by 1 type or in combination of 2 or more types.

  As preferred specific examples, the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.

  Since the excellent sensitivity and developability can be obtained, the content of the monomer unit forming the structural unit having a carboxy group and / or a phenolic hydroxyl group in all monomer units constituting the component B is 0 to 20 mol%. Is preferable, and 5 to 15 mol% is more preferable.

Moreover, as a radically polymerizable monomer which forms another structural unit, the compound as described in Paragraph 0021-0024 of Unexamined-Japanese-Patent No. 2004-264623 can be mentioned, for example.
Among these, (meth) acrylic acid esters having an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl acrylate are preferable from the viewpoint of improving electric characteristics.

[Structural unit derived from at least one compound selected from the group consisting of styrene derivatives, maleimide derivatives, (meth) acrylic acid, and hydroxyl group-containing (meth) acrylate compounds]
Component C may have, as other structural units, structural units derived from at least one compound selected from the group consisting of styrene derivatives, maleimide derivatives, (meth) acrylic acid, and hydroxyl group-containing (meth) acrylate compounds. preferable.
As the styrene derivative, styrene, chloromethylstyrene, and acetoxystyrene are preferable.
As the maleimide derivative, N-butylmaleimide and N-cyclohexylmaleimide are preferable.
As the hydroxyl group-containing (meth) acrylate compound, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferable.
0-50 mol% is preferable, as for the content rate of the monomer unit which forms another structural unit in all the monomer units which comprise the component C, 0-45 mol% is more preferable, and 5-40 mol% is especially preferable. By containing in the above ratio, the physical properties of the cured film are improved.

<C- (4): Characteristics of resin of component C>
The weight average molecular weight of Component C is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000.

Hereinafter, preferable examples of the component C are illustrated, but the present invention is not limited thereto.
In addition, it is preferable that the weight average molecular weights of the component C illustrated below are 2,000-50,000.
1-ethoxyethyl methacrylate / tert-butyl methacrylate / glycidyl methacrylate copolymer;
Tetrahydro-2H-furan-2-yl methacrylate / tert-butyl methacrylate / glycidyl methacrylate / methacrylic acid copolymer;
1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / glycidyl methacrylate / methacrylic acid copolymer;
1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer;
1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / 2-hydroxyethyl methacrylate Polymer 1-ethoxyethyl methacrylate / 2-methyl-2-adamantyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer;
1-ethoxyethyl methacrylate / 1-methyl-1-cyclohexyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer;
1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer;
1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2 -Hydroxyethyl copolymer;
1-ethoxyethyl methacrylate / N-cyclohexylmaleimide / glycidyl methacrylate / methacrylic acid copolymer;
1-ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid-2-hydroxyethyl copolymer;
1-Ethoxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / -2-hydroxyethyl methacrylate copolymer.

Component C can be used alone or in combination of two or more.
When two or more types are used in combination, an embodiment in which at least one type is a resin containing a resin containing a structural unit represented by the general formula (1) (hereinafter sometimes referred to as “(C ′) resin”) is preferred. Is done. The structural unit represented by the general formula (1) is preferably contained in a proportion of 1 to 60 mol% of the resin including the structural unit represented by the general formula (1), and in a proportion of 10 to 40 mol%. More preferably it is included.
Moreover, when 2 or more types of resin is included, it is preferable that 10 to 50 weight% of (Component C) is (C ') resin.
(C ') As resin, the resin of the following aspects is illustrated preferably.
(Form 1)
(C ') The aspect in which resin containing the structural unit represented by General formula (1) contains an acid group further.
(Form 2)
(C ′) An embodiment in which the resin further contains a crosslinkable group (preferably any one or more of an oxiranyl group, an oxetanyl group, an acid anhydride group, an acid halide group, an isocyanate group, and a (meth) acrylate group).
(Form 3)
(C ′) the resin is further crosslinked with an acid group and a crosslinkable group (preferably one or more of an oxiranyl group, an oxetanyl group, an acid anhydride group, an acid halide group, an isocyanate group, and a (meth) acrylate group). An embodiment comprising a group.
(Form 4)
(C ′) the resin further includes an acid labile group, a crosslinkable group (preferably one or more of an oxiranyl group, an oxetanyl group, an acid anhydride group, an acid halide group, an isocyanate group, and a (meth) acrylate group. ) An embodiment containing a crosslinking group and an acid group.
(Form 5)
In any one of the above aspects 1 to 4, the (C ′) resin further includes another structural unit.

  The total content of Component C in the photosensitive resin composition of the present invention is preferably 20 to 99% by mass, and 40 to 97% by mass with respect to the total solid content of the photosensitive resin composition. Is more preferable, and it is still more preferable that it is 60-95 mass%. When the content is within this range, the pattern formability upon development is good. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.

  In addition, in the photosensitive resin composition of this invention, you may use together resin other than the component C in the range which does not prevent the effect of this invention. However, the content of the resin other than Component C is preferably smaller than the content of Component A from the viewpoint of developability.

(Component D) Photoacid Generator The photosensitive resin composition of the present invention contains (Component D) a photoacid generator.
As the component D, a known photoacid generator can be used, but a photoacid generator is preferably used.
The photoacid generator used in the present invention is a compound that reacts with an actinic ray having a wavelength of 300 nm or more, more preferably 300 to 450 nm, and generates an acid, but is limited to its chemical structure. is not. Further, for example, even if it is a photoacid generator that is not directly sensitive to actinic rays having a wavelength of 300 nm or more, if it is a compound that reacts with actinic rays having a wavelength of 300 nm or more by using in combination with a sensitizer and generates an acid, It can be preferably used in combination with a sensitizer.
The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, and more preferably a photoacid generator that generates an acid having a pKa of 3 or less.
Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation and sensitivity.
These photoacid generators can be used singly or in combination of two or more.
Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate residue include compounds having an oxime sulfonate residue represented by the following formula (B1).

In the formula (B1), R ⁴¹ represents an alkyl group, an alkoxy group, an aryl group, or a halogen atom.
As the alkyl group for R ^41, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ⁴¹ is a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or cyclo It may be substituted with an alkyl group (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably a bicycloalkyl group).
As the alkoxy group for R ^41, a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is preferable. The alkoxy group may be substituted in the same manner as the alkyl group.
As the aryl group for R ^41, 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 ⁴¹ may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.

  The compound containing the oxime sulfonate residue represented by the formula (B1) is more preferably an oxime sulfonate compound represented by the following formula (B2).

（式（Ｂ２）中、Ｒ⁴²は、式（Ｂ１）におけるＲ⁴¹と同義であり、Ｘは、アルキル基、アルコキシ基又はハロゲン原子を表し、ｍ１は、０〜３の整数を表し、ｍ１が２又は３であるとき、複数のＸは同一でも異なっていてもよい。）

(In formula (B2), R ⁴² has the same meaning as R ⁴¹ in formula (B1), X represents an alkyl group, an alkoxy group or a halogen atom, m1 represents an integer of 0 to 3, and m1 represents When it is 2 or 3, the plurality of X may be the same or different.)

The alkyl group in X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom is preferably a chlorine atom or a fluorine atom.
m1 is preferably 0 or 1.
In formula (B2), m1 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-dimethyl- A compound that is a 2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

  Specific examples of the oxime sulfonate compound include (i) to (vii), which can be used alone or in combination of two or more. Compounds (i) to (vii) can be obtained as commercial products. It can also be used in combination with other types of photoacid generators.

  The compound containing an oxime sulfonate residue represented by the formula (B1) is more preferably an oxime sulfonate compound represented by the following formula (B3).

式（Ｂ３）中、Ｒ⁴³は、ハロゲン原子、水酸基、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、シアノ基又はニトロ基を表し、ｎ１は０〜５の整数を表す。Ｘ¹は、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数１〜５のハロゲン化アルキル基、炭素原子数１〜５のハロゲン化アルコキシ基、Ｗで置換されていてもよいフェニル基、Ｗで置換されていてもよいナフチル基又はＷで置換されていてもよいアントラニル基を表し、Ｗは、ハロゲン原子、シアノ基、ニトロ基、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数１〜５のハロゲン化アルキル基又は炭素原子数１〜５のハロゲン化アルコキシ基を表すものである。
式（Ｂ３）におけるＲ⁴³としては、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−オクチル基、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロ−ｎ−プロピル基、パーフルオロ−ｎ−ブチル基、ｐ−トリル基、４−クロロフェニル基又はペンタフルオロフェニル基が好ましく、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基又はｐ−トリル基であることが特に好ましい。
Ｘ¹で表されるハロゲン原子としては、フッ素原子、塩素原子又は臭素原子が好ましい。
Ｘ¹で表される炭素原子数１〜４のアルキル基としては、メチル基又はエチル基が好ましい。
Ｘ¹で表される炭素原子数１〜４のアルコキシ基としては、メトキシ基又はエトキシ基が好ましい。
ｎ１としては、０〜２の整数が好ましく、０又は１が特に好ましい。

In the formula (B3), R ⁴³ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, and n1 is an integer of 0 to 5 Represents. X ¹ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, 1 to 1 carbon atoms It represents a 10 alkyl group, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.
R ⁴³ in the formula (B3) is methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro A fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and a methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group is particularly preferable. .
The halogen atom represented by X ¹ is preferably a fluorine atom, a chlorine atom or a bromine atom.
The alkyl group having 1 to 4 carbon atoms represented by X ¹ is preferably a methyl group or an ethyl group.
The alkoxy group having 1 to 4 carbon atoms represented by X ¹ is preferably a methoxy group or an ethoxy group.
As n1, an integer of 0 to 2 is preferable, and 0 or 1 is particularly preferable.

As a preferred embodiment of the compound included in the photoacid generator represented by the formula (B3), R ⁴³ represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 4-tolyl group, X ¹ represents a hydrogen atom or a methoxy group, and n1 is 0 or 1.

  Hereinafter, although the especially preferable example of the compound included by the photo-acid generator represented by Formula (II) is shown, this invention is not limited to these.

α- (Methylsulfonyloxyimino) benzyl cyanide (R ⁴³ = methyl group, X ¹ = hydrogen atom)
α- (Ethylsulfonyloxyimino) benzyl cyanide (R ⁴³ = ethyl group, X ¹ = hydrogen atom)
α- (n-propylsulfonyloxyimino) benzyl cyanide (R ⁴³ n-propyl group, X ¹ = hydrogen atom)
α- (n-butylsulfonyloxyimino) benzyl cyanide (R ⁴³ = n-butyl group, X ¹ = hydrogen atom)
α- (4-Toluenesulfonyloxyimino) benzyl cyanide (R ⁴³ = 4-tolyl group, X ¹ = hydrogen atom)
α-[(Methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁴³ methyl group, X ¹ = methoxy group)
α-[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁴³ ethyl group, X ¹ = methoxy group)
α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = n-propyl group, X ¹ = methoxy group)
α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁴³ = n-butyl group, X ¹ = methoxy group)
α-[(4-Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁴³ = 4-tolyl group, X ¹ = methoxy group)

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

In the 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 hetero Represents an aryl group. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ₂ —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ^{105 to} R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ^{121 to} R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring.
R ^{121 to} R ¹²⁴ are preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R ^{121 to} R ¹²⁴ are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R ^{121 to} R ¹²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

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

In the formula (OS-2), R ¹⁰¹ , R ¹⁰² and R ^{121 to} R ¹²⁴ have the same meanings as in the formula (OS-1), and preferred examples thereof are also the same.
Among these, an embodiment in which R ¹⁰¹ in the formula (OS-1) and the formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the formula (OS-2), and R ¹⁰¹ is a cyano group. The embodiment which is a phenyl group or a naphthyl group is most preferable.

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

  Specific examples (exemplary compounds b-1 to b-34) of the compound represented by the formula (OS-1) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto. Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, Ts represents a tosyl group, and Ph represents a phenyl group.

  Among the above compounds, b-9, b-16, b-31, and b-33 are preferable from the viewpoint of achieving both sensitivity and stability.

  The compound containing an oxime sulfonate residue represented by the formula (B1) is an oxime sulfonate compound represented by the formula (OS-3), formula (OS-4) or formula (OS-5). Is preferred.

（式（ＯＳ−３）〜式（ＯＳ−５）中、Ｒ²⁰¹、Ｒ²⁰⁴およびＲ²⁰⁷はそれぞれ独立にアルキル基、アリール基又はヘテロアリール基を表し、Ｒ²⁰²、Ｒ²⁰⁵およびＲ²⁰⁸はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、Ｒ²⁰³、Ｒ²⁰⁶およびＲ²⁰⁹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又はアルコキシスルホニル基を表し、Ｘ²⁰¹〜Ｘ²⁰³はそれぞれ独立にＯ又はＳを表し、ｎ²〜ｎ⁴はそれぞれ独立に１又は２を表し、ｍ²〜ｍ⁴はそれぞれ独立に０〜６の整数を表す。）

(In the formula (OS-3) ~ formula (OS-5), respectively R ^201, R ²⁰⁴ and R ²⁰⁷ are independently an alkyl group, an aryl group or a heteroaryl group, R ^202, R ²⁰⁵ and R ²⁰⁸ each Independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ are each independently a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ^{201 to} X ²⁰³ each independently represents O or S, n ^{2 to} n ⁴ each independently represents 1 or 2, and m ^{2 to} m ⁴ each independently represents an integer of 0 to 6. .)

In the formulas (OS-3) to (OS-5), the alkyl group, aryl group, or heteroaryl group in ^R201 , ^R204, and ^R207 may have a substituent.
The formula (OS-3) ~ (OS -5), it The alkyl group of R ^201, R ²⁰⁴ and R ^207, an alkyl group having a total carbon number of 1 to 30 which may have a substituent Is preferred.

^Examples of the alkyl group for ^R201 , ^R204 and ^R207 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group Ethoxycarbonylethyl group, phenoxycarbonylethyl group, dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, An n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.
Examples of the substituent that the alkyl group in R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, An aminocarbonyl group is mentioned.

In the formulas (OS-3) to (OS-5), the aryl group represented by R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent. .

The aryl group in R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ includes a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, a p-phenoxyphenyl group, p -Methylthiophenyl group, p-phenylthiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, p-dimethylaminocarbonylphenyl group.
Among these, a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.
Examples of the substituent that the aryl group in R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxy group Examples include a carbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

Further, the formula (OS-3) ~ (OS -5), as the heteroaryl group in R ^201, R ²⁰⁴ and R ^207, heteroaryl group having a total carbon number of 4-30 which may have a substituent Is preferred.

In the above formulas (OS-3) to (OS-5), the heteroaryl group in R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ only needs to have at least one heteroaromatic ring, such as a heteroaromatic ring and a benzene ring. And may be condensed.
As the heteroaryl group for R ²⁰¹ , R ²⁰⁴ and R ^207, an optionally substituted thiophene ring, pyrrole ring, thiazole ring, imidazole ring, furan ring, benzothiophene ring, benzothiazole ring, and And a group in which one hydrogen atom is removed from a ring selected from the group consisting of benzimidazole rings.
Examples of the substituent that the heteroaryl group in R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ may have include a halogen atom, alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryl Examples thereof include an oxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

In the formulas (OS-3) to (OS-5), R ²⁰² , R ²⁰⁵ and R ²⁰⁸ are preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. .
In the formulas (OS-3) to (OS-5), one or two of R ²⁰² , R ²⁰⁵ and R ²⁰⁸ present in the compound are each an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
In the formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ²⁰² , R ²⁰⁵ and R ²⁰⁸ may have a substituent.
As the substituent that the alkyl group or aryl group in R ²⁰² , R ^205, and R ²⁰⁸ may have, the substituent that the alkyl group or aryl group in R ²⁰¹ , R ^204, and R ²⁰⁷ may have The same group can be illustrated.

The alkyl group in R ²⁰² , R ²⁰⁵ and R ²⁰⁸ is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.
Specific examples of the alkyl group for R ²⁰² , R ²⁰⁵ and R ²⁰⁸ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t- Butyl group, allyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, perfluorohexyl group, chloromethyl group, bromomethyl group, methoxymethyl group, benzyl group, Examples include phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, phenoxycarbonylethyl group, and dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, chloromethyl group, bromomethyl group, Methoxymethyl group and benzyl group are preferable, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and n-hexyl group are more preferable, and methyl group , An ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are more preferable, and a methyl group is particularly preferable.

The aryl group in R ²⁰² , R ²⁰⁵ and R ²⁰⁸ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
Specific examples of the aryl group in R ²⁰² , R ²⁰⁵ and R ²⁰⁸ include a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, p-phenoxyphenyl group, p- Examples thereof include a methylthiophenyl group, a p-phenylthiophenyl group, a p-ethoxycarbonylphenyl group, a p-phenoxycarbonylphenyl group, and a p-dimethylaminocarbonylphenyl group.
Among these, a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.
Examples of the halogen atom in R ²⁰² , R ²⁰⁵ and R ²⁰⁸ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Among these, a chlorine atom and a bromine atom are preferable.

In the formulas (OS-3) to (OS-5), X ^{201 to} X ²⁰³ each independently represents O or S, and is preferably O.
In the formula (OS-3) ~ (OS -5), ring containing X ²⁰¹ to X ²⁰³ as a ring member is a 5- or 6-membered ring.
The formula (OS-3) ~ (OS -5), n represents 1 or 2, when X ²⁰¹ to X ²⁰³ is O, and preferably n ² ~n ⁴ are each independently 1, also, when X ²⁰¹ to X ²⁰³ is S, it is preferable n ² ~n ⁴ are each independently 2.

In the formulas (OS-3) to (OS-5), R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. . Among them, R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ are preferably each independently an alkyl group or an alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.

^Examples of the alkyl group for R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group Ethoxycarbonylethyl group, phenoxycarbonylethyl group, dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, An n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.
Examples of the substituent that the alkyl group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, An aminocarbonyl group is mentioned.

In formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. It is preferable.

^Examples of the alkyloxy group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ include methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, ethoxyethyloxy group, methylthioethyloxy group, phenyl Examples include a thioethyloxy group, an ethoxycarbonylethyloxy group, a phenoxycarbonylethyloxy group, and a dimethylaminocarbonylethyloxy group.
Among these, a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferable.
Examples of the substituent that the alkyloxy group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, and an aryloxycarbonyl group. And aminocarbonyl group.

In the formulas (OS-3) to (OS-5), the aminosulfonyl group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ includes a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, and a methylphenylaminosulfonyl group. And an aminosulfonyl group.

In the formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group. .

Further, the formula (OS-3) ~ (OS -5), m 2 ~m 4 each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, is 0 or 1 Is more preferable, and 0 is particularly preferable.

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

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

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

R ^{301 to} R ³⁰⁶ in formulas (OS-6) to (OS-11) have the same meanings as R ²⁰¹ , R ²⁰⁴ and R ^{207 in} formulas (OS-3) to (OS-5), and preferred embodiments It is the same.
R ³⁰⁷ in Formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ^{308 to} R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ in formulas (OS-6) to (OS-11) are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a chloromethyl group. Represents a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, and an alkyl group having 1 to 8 carbon atoms. Are more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable.
R ³¹¹ and R ³¹⁴ in formula (OS-8) and formula (OS-9) each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and preferably a hydrogen atom.
R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ in formulas (OS-8) to (OS-11) each independently represent a hydrogen atom or a methyl group, and are preferably hydrogen atoms.
In the oxime sulfonate compound, the oxime steric structure (E, Z) may be either one or a mixture.

  Specific examples of the oxime sulfonate compound represented by the formula (OS-3) to the formula (OS-5) include the following exemplified compounds, but the present invention is not limited thereto.

  In the photosensitive resin composition of the present invention, (Component D) the photoacid generator is preferably contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of (Component C) copolymer. More preferably 5 to 10 parts by weight is contained.

(Component E) Solvent The photosensitive resin composition of the present invention preferably contains (Component E) a solvent.
The photosensitive resin composition of the present invention is preferably prepared as a solution in which components A to D, which are essential components, and optional components described below are dissolved in a (component E) solvent.
As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, butylene glycol monoalkyl ethers, butylene glycol monoalkyl ether acetates, butylene glycol dialkyl ethers, butylene glycol dialkyl ether acetates, diethylene glycol dialkyl ethers, Diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl Ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones and the like. Examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph 0074 of JP-A-2009-258722.
These solvents can be used alone or in combination of two or more.
The solvent that can be used in the present invention is preferably a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates and diethylene glycol. More preferably, dialkyl ethers or esters and butylene glycol alkyl ether acetates are used in combination.

Component E is preferably a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., a solvent having a boiling point of 160 ° C. or more, or a mixture thereof, a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., and a boiling point of 160 ° C. or more and 200 ° C. A solvent having a boiling point of 130 ° C. or lower or a mixture thereof is more preferable, and a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C. and a solvent having a boiling point of 160 ° C. or higher and 200 ° C. or lower is still more preferable.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.

  The content of the (component E) solvent in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by mass, and 100 to 2,000 parts by mass with respect to 100 parts by mass of the component C. Is more preferable, and it is still more preferable that it is 150-1,500 mass parts.

<Other ingredients>
In the photosensitive resin composition of the present invention, as necessary, (Component F) sensitizer, (Component G) antioxidant, (Component H) cross-linking agent, and (Component I) described below as optional components. Adhesion improver, (component J) basic compound, (component K) plasticizer, (component L) thermal radical generator, thermal acid generator, ultraviolet absorber, thickener, and organic or inorganic precipitate Known additives such as inhibitors can be added.

(Component F) Sensitizer The positive photosensitive resin composition of the present invention can contain (Component F) a sensitizer.
The inclusion of a sensitizer is effective for improving exposure sensitivity, and is particularly effective when the exposure light source is a g / h line mixed line.
As the sensitizer, anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives, and distyrylbenzene derivatives are preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-dibromoanthracene, 2-ethylanthracene and 9,10-dimethoxyanthracene are preferred.
As an acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone and N-ethyl-2-methoxyacridone are preferable.
As the thioxanthone derivative, thioxanthone, diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2-chlorothioxanthone are preferable.
As the coumarin derivative, coumarin-1, coumarin-6H, coumarin-110 and coumarin-102 are preferable.
Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole, and 2- (4-dimethylaminostyryl) naphthothiazole.
Examples of the distyrylbenzene derivative include distyrylbenzene, di (4-methoxystyryl) benzene, and di (3,4,5-trimethoxystyryl) benzene.
Among these, an anthracene derivative is preferable, and 9,10-dialkoxyanthracene (an alkoxy group having 1 to 6 carbon atoms) is more preferable.
Specific examples of the sensitizer include the following. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

  The content of the (component F) sensitizer in the positive photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by mass, and 0.5 to 10 parts by mass with respect to 100 parts by mass of the component C. More preferably, it is a part. When the content of (Component F) sensitizer is 0.1 parts by mass or more, desired sensitivity is easily obtained, and when it is 10 parts by mass or less, transparency of the coating film is easily secured.

(Component G) Antioxidant The photosensitive resin composition of the present invention may contain (Component G) an antioxidant. (G) As an antioxidant, a well-known antioxidant can be contained. (G) By adding an antioxidant, coloring of the cured film can be prevented, or a reduction in film thickness due to decomposition can be reduced, and the heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, a phenolic antioxidant is particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used alone or in combination of two or more.

  As a commercial item of a phenolic antioxidant, ADK STAB AO-60, ADK STAB AO-80 (above, the product made from ADEKA), and Irganox 1098 (made by Ciba Japan Co., Ltd.) are mentioned, for example.

(Component G) The content of the antioxidant is preferably 0.1 to 6% by mass and more preferably 0.2 to 5% by mass with respect to the total solid content of the photosensitive resin composition. It is preferably 0.5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used for the photosensitive property of the present invention. You may add to a resin composition.

(Component H) Crosslinking agent The photosensitive resin composition of the present invention preferably contains (Component H) a crosslinking agent.
Examples of the crosslinking agent include a compound having two or more oxiranyl groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, and a compound having at least one ethylenically unsaturated double bond. be able to. By adding a crosslinking agent, the cured film can be made stronger.

<Compound having two or more oxiranyl groups or oxetanyl groups in the molecule>
Specific examples of compounds having two or more oxiranyl groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.
These are available as commercial products. Examples of the bisphenol A type epoxy resin include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resins Co., Ltd.). These can be used alone or in combination of two or more.

Among these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolac type epoxy resin. A bisphenol A type epoxy resin is particularly preferable.
As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, the compound containing an oxetanyl group can be used individually or in mixture with the compound containing an oxiranyl group.
The addition amount of the compound having two or more oxiranyl groups or oxetanyl groups in the molecule to the photosensitive resin composition is preferably 1 to 50 parts by mass when the total amount of component C is 100 parts by mass, and 3 to 30 Part by mass is more preferable.

<Alkoxymethyl group-containing crosslinking agent>
As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of outgas generated, A methoxymethyl group is preferred.
Among these, as the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.
These alkoxymethyl group-containing crosslinking agents are available as commercial products. For example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nicarac MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.
When the alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the addition amount of the alkoxymethyl group-containing crosslinking agent is preferably 0.05 to 50 parts by mass with respect to 100 parts by mass of the component C. 0.5 to 10 parts by mass is more preferable. By adding within this range, preferable alkali solubility during development and excellent solvent resistance of the cured film can be obtained.

<Compound having at least one ethylenically unsaturated double bond>
As the compound having at least one ethylenically unsaturated double bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate is preferably used. be able to.
Examples of monofunctional (meth) acrylates include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate.
Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

These compounds having at least one ethylenically unsaturated double bond are used singly or in combination of two or more.
The use ratio of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by mass or less with respect to 100 parts by mass of the component C, and 30 parts by mass. The following is more preferable. By including at least one compound having an ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the insulating film obtained from the photosensitive resin composition of the present invention can be improved. it can. When adding a compound having at least one ethylenically unsaturated double bond, it is preferable to add (Component L) a thermal radical generator.

(Component I) Adhesion Improving Agent The photosensitive resin composition of the present invention may contain (Component I) an adhesion improving agent.
The adhesion improver that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum, and an insulating film. It is a compound that improves the adhesion. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as an adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known one can be used without any particular limitation.
Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned.
Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.
These can be used alone or in combination of two or more. These are effective in improving the adhesion to the substrate and are also effective in adjusting the taper angle with the substrate.
The content of the (Component I) adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by mass, and 0.5 to 10 parts by mass with respect to 100 parts by mass of (Component C) resin. Is more preferable.

(Component J) Basic Compound The photosensitive resin composition of the present invention may contain (Component J) a basic compound.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.
Specific examples of the basic compound include the compounds described in paragraphs 0052 to 0056 of JP2009-98616A.
The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. Preferably, two kinds of heterocyclic amines are used in combination.
The content of (Component J) in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of (Component C) resin, and 0.005 to 0.2. More preferably, it is part by mass.

(Component K) Plasticizer The photosensitive resin composition of the present invention may contain (Component K) a plasticizer.
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The amount of (component K) plasticizer added in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of (component C) resin, and 1 to 10 parts by mass. It is more preferable that

(Component L) Thermal Radical Generator The photosensitive resin composition of the present invention may contain (Component L) a thermal radical generator, which is a compound having at least one ethylenically unsaturated double bond as described above. When such an ethylenically unsaturated compound is contained, it is preferable to contain (Component L) a thermal radical generator.
As the thermal radical generator in the present invention, a known thermal radical generator can be used.
The thermal radical generator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance may be improved.
Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon Examples thereof include compounds having a halogen bond, azo compounds, and bibenzyl compounds.
A thermal radical generator may be used individually by 1 type, and it is also possible to use 2 or more types together.
In the photosensitive resin composition of the present invention, the amount of (Component L) thermal radical generator added is 0.01 to 50 parts by mass, with 100 parts by mass of (Component C) resin from the viewpoint of improving film properties. Preferably, 0.1-20 mass parts is more preferable, and it is most preferable that it is 0.5-10 mass parts.

[Method for producing cured film]
Next, the manufacturing method of the cured film of this invention is demonstrated.
The manufacturing method of the cured film of this invention is characterized by including the process of the following (1)-(5).
(1) An application step of applying the positive photosensitive resin composition of the present invention to a substrate;
(2) a solvent removal step of removing the solvent from the applied positive photosensitive resin composition;
(3) an exposure step of exposing with actinic rays;
(4) Development step of developing with an aqueous developer;
(5) A post-bake process for thermosetting.
Each step will be described below in order.

In the application step (1), the positive photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
In the solvent removal step (2), it is preferable to remove the solvent from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.
In the exposure step (3), it is preferable to irradiate the obtained coating film with an actinic ray having a wavelength of 300 nm to 450 nm. In this step, (Component D) the photoacid generator is decomposed to generate an acid. Due to the catalytic action of the generated acid, the acid-decomposable group contained in the (Component C) resin is hydrolyzed to produce a carboxy group and / or a phenolic hydroxyl group.

In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed as necessary. PEB can promote the formation of a carboxy group from an acid-decomposable group.
The acid-decomposable group in the component C in the present invention has a low activation energy for decomposition by an acid and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxy group. Therefore, PEB is not necessarily performed. A positive image can also be formed by development.
In addition, by performing PEB at a relatively low temperature, hydrolysis of an acid-decomposable group can be promoted without causing a crosslinking reaction. The temperature at which PEB is performed is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 80 ° C. or lower.

In the developing step (4), it is preferable to develop the polymer having a liberated carboxy group using an alkaline developer. By removing the exposed area, a positive image can be formed.
In the post-baking step of (5), by heating the obtained positive image, the acid-decomposable group in component B is pyrolyzed to generate a carboxy group, and crosslinked with an oxiranyl group and / or oxetanyl group. A cured film can be formed. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 250 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.

It is preferable to add a step of irradiating the developing pattern with actinic rays, preferably ultraviolet rays, before the post-baking step, because the crosslinking reaction can be promoted by the acid generated by the irradiation of actinic rays.
Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

<Method for preparing photosensitive resin composition>
The essential components of component A to component E are mixed at a predetermined ratio and by any method, and dissolved by stirring to prepare a photosensitive resin composition. For example, it is also possible to prepare a resin composition by mixing components A to D in advance with components (component E) previously dissolved in a solvent and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

<(1) Application process and (2) Solvent removal process>
A desired dry coating film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by reducing pressure and / or heating (pre-baking). As the substrate, for example, in the production of a liquid crystal display element, a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as required, and further a transparent conductive circuit layer can be exemplified. Although there is no restriction | limiting in particular as a method of applying the photosensitive resin composition to a board | substrate, Among these, it is preferable to apply | coat a touristic resin composition to a board | substrate in this invention. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, the large substrate means a substrate having a side of 1 m or more on each side.

  In addition, (2) the heating condition in the solvent removal step is a range in which the acid-decomposable group in the resin of component C in the unexposed area is decomposed and the resin of component C is not soluble in the alkaline developer. However, it is preferably about 80 to 130 ° C. for about 30 to 120 seconds.

<(3) Exposure process>
In the exposure step, the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. The actinic ray is not particularly limited as long as exposure is possible, but actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. After the exposure step, heat treatment (PEB) is performed as necessary.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.
In the case of using a laser, 343 nm and 355 nm are used for a solid (YAG) laser, 351 nm (XeF) is used for an excimer laser, and 375 nm and 405 nm are used for a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoint of stability and cost. The coating can be irradiated with the laser once or a plurality of times.
The energy density per pulse of the laser is 0.1 mJ / cm ² or more and 10,000 mJ
/ Cm ² or less is preferable. In order to sufficiently cure the coating film, 0.3 mJ / cm ² or more is more preferable, and 0.5 mJ / cm ² or more is most preferable. To prevent the coating film from being decomposed by an ablation phenomenon, 1,000 mJ / cm ² is preferable. More preferably, it is 10 cm ² or less.
Most preferred is 0 mJ / cm ² or less.
The pulse width is preferably 0.1 nsec or more and 30,000 nsec or less. In order not to decompose the color coating film due to the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is most preferable, and in order to improve the alignment accuracy at the time of scanning exposure, 1,000 nsec or less is more preferable, Most preferred is 50 nsec or less.

Furthermore, the frequency of the laser is preferably 1 to 50,000 Hz, and more preferably 10 to 1,000 Hz. If the frequency of the laser is less than 1 Hz, the exposure processing time increases.
In order to shorten the exposure processing time, 10 Hz or more is more preferable, and 100 Hz or more is most preferable. In order to improve the alignment accuracy at the time of scanning exposure, 10,000 Hz or less is more preferable, and 1,000 Hz or less is most preferable.

Compared with a mercury lamp, a laser is preferable in that the focus can be easily reduced and a mask for forming a pattern in the exposure process is not necessary and the cost can be reduced.
There are no particular restrictions on the exposure apparatus that can be used in the present invention, but commercially available devices include Calisto (buoy technology), AEGIS (buoy technology), and DF2200G (Dainippon Screen ( Etc.) can be used. In addition, devices other than those described above are also preferably used. Irradiation light can also be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as necessary.

<(4) Development process>
In the development step, it is preferable to form an image pattern by removing the exposed area using a basic developer (alkaline developer). Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the developing method may be any of a liquid piling method, a dip method, and the like. After the development, washing with running water is performed for 30 to 90 seconds, and a desired pattern can be formed.

<(5) Post-bake process (crosslinking process)>
For a pattern corresponding to an unexposed area obtained by development, using a heating device such as a hot plate or oven, at a predetermined temperature, for example, 180 to 250 ° C., for a predetermined time, for example, 5-60 minutes on the hot plate, In the case of an oven, heat treatment is performed for 30 to 90 minutes to decompose the acid-decomposable group in component A to generate a carboxy group and / or a phenolic hydroxyl group, which reacts with the functional group in component A. By crosslinking, a protective film and an interlayer insulating film excellent in heat resistance, hardness, etc. can be formed. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.
Prior to the heat treatment, the substrate on which the pattern has been formed is re-exposed with actinic rays and then post-baked (re-exposure / post-bake) so that the acid is removed from the photoacid generator present in the unexposed portion (component D). It is preferable to generate and function as a catalyst for accelerating the crosslinking step.
That is, the method for forming a cured film of the present invention preferably includes a re-exposure step in which re-exposure is performed with actinic rays between the development step and the post-bake step.
The exposure in the re-exposure step may be performed by the same means as in the exposure step. In the re-exposure step, the entire surface of the substrate on which the film is formed by the photosensitive resin composition of the present invention is exposed. It is preferable. A preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm ² .

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

[Organic EL display device, Liquid crystal display device]
The organic EL display device and the liquid crystal display device of the present invention are characterized by including the cured film of the present invention.
The organic EL display device and the liquid crystal display device of the present invention are not particularly limited except for having a protective film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and have various structures. Examples include various known organic EL display devices and liquid crystal display devices.
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 a protective film and an interlayer insulating film, it can be suitably used for a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, or the like.

FIG. 1 is a conceptual diagram illustrating 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 used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving the organic EL element. An EL display device is obtained.

  FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.

  The 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.

<Synthesis of Polymer C-1>
After adding 0.5 parts by mass of phenothiazine to 144.2 parts by mass (2 molar equivalents) of ethyl vinyl ether, and dropping 86.1 parts by mass (1 molar equivalent) of methacrylic acid while cooling the reaction system to 10 ° C. or lower, Stir at room temperature (25 ° C.) for 4 hours. After adding 5.0 parts by mass of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. 5 parts by mass of sodium hydrogen carbonate and 5 parts by mass of sodium sulfate were added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and concentrated under reduced pressure at 40 ° C. or lower. (Bp.) 134.0 parts by mass of 1-ethoxyethyl methacrylate in a 43 to 45 ° C./7 mmHg fraction was obtained as a colorless oil.
1-Ethoxyethyl methacrylate (79.1 parts by mass (0.5 molar equivalent)), glycidyl methacrylate (GMA) (71.1 parts by mass (0.5 molar equivalent)) and propylene glycol monomethyl ether acetate ( PGMEA) (125 parts by mass) was heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, the target molecular weight of the mixed solution of radical polymerization initiator V-65 (2,2′-azobis (2,4-dimethylvaleronitrile), Wako Pure Chemical Industries, Ltd.) and PGMEA was achieved. Was added dropwise over a period of 2.5 hours. After completion of the dropping, the PGMEA solution (solid content concentration: 40% by mass) of polymer C-1 was obtained by reacting at 70 ° C. for 4 hours. The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained polymer C-1 was 12,000.

<Synthesis of Polymers C-2 to C-20>
Polymers C-2 to C-20 were respectively synthesized in the same manner as the synthesis of the polymer C-1, except that each monomer used and the amount used thereof were changed to those shown in the following table. In addition, each copolymerization ratio of Table 2 is described in molar ratio.

In addition, the copolymerization ratio of Table 2 is a molar ratio, and the symbol in Table 2 is as follows.
MAEVE: 1-ethoxyethyl methacrylate MACHVE: 1-cyclohexyloxyethyl methacrylate MATHPE: tetrahydro-2H-pyran-2-yl methacrylate MATHF: tetrahydrofuran-2-yl methacrylate t-BMA: tert-butyl methacrylate GMA : Glycidyl methacrylate OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
MAA: methacrylic acid HEMA: 2-hydroxyethyl methacrylate St: styrene PHSEVE: 4- (1-ethoxyethyloxy) styrene PHStBOC: 4- (t-butoxycarbonyloxy) styrene CHMI: N-cyclohexylmaleimide MACHVE, MATHPE was synthesized by changing the vinyl ether of the MAEVE synthesis method to cyclohexyl vinyl ether and dihydropyran, respectively.
PHSEVE was synthesized by changing methacrylic acid in the MAEVE synthesis method to 4-hydroxystyrene.
PHStBOC was obtained by reacting 4-hydroxystyrene and t-butoxycarboxylic anhydride under basic conditions, followed by extraction and purification by silica gel chromatography.

<Synthesis of MATHF (tetrahydrofuran-2-yl methacrylate)>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated aqueous sodium hydrogen carbonate solution (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 yellow oily residue. Was distilled under reduced pressure to obtain 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oily substance having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg (yield 80%).

(Synthesis of polymer C ′)
Diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Industry, Hisolv EDM, 45 g) was added to a three-necked flask as a solvent, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. In the solution, as a monomer component, methyl methacrylate (MMA, manufactured by Wako Pure Chemical Industries, 3.27 g), 2-tetrahydrofuranyl methacrylate (MATHF, synthetic product, 22.17 g), hydroxyethyl methacrylate (HEMA, Wako Pure) Yakuhin, 6.57 g), 3-ethyl-3-oxetanylmethyl methacrylate (OXE-30, Osaka Organic Chemical Industry, 20.26 g) and n-butoxymethylacrylamide (NBMA, Tokyo Kasei, 9.43 g) In addition, dimethyl 2,2′-azobis (2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, 7.36 g, 8 mol% with respect to the monomer) was dissolved as a polymerization initiator for 2 hours. It was dripped over. After completion of the dropwise addition, the mixture was stirred for 2 hours. V-601 (1.84 g, 2 mol% based on the monomer) was further added to the solution, and the mixture was further stirred for 2 hours to complete the reaction. Thereby, binder C′-1 was obtained. The weight average molecular weight was 12000.
Monomer types and the like were changed as shown in the following table, and C′-2 to C′-4 were synthesized in the same manner as others.

The unit of the monomer component in the above table is shown in mol%. The initiator is shown as mol% when the monomer component is 100 mol%. The solid content concentration is indicated by monomer weight / (monomer weight + solvent weight) × 100 (unit: wt%). The reaction temperature when V-601 was used as an initiator was 90 ° C., and the reaction temperature when V-65 was used was 70 ° C. (the same applies to the following tables).
In the above table, PHS represents p-hydroxystyrene (synthetic product), MAEVE represents 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries), and GMA represents glycidyl methacrylate (manufactured by Wako Pure Chemical Industries). , IBMA represents i-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry), St represents styrene (manufactured by Wako Pure Chemical Industries), and V-65 represents 2,2′-azobis (2,4-dimethylvaleronitrile). ) (Made by Wako Pure Chemical Industries).

<Component A used in Examples>
Component A (A-1 to 12) used in Examples and Component A (A-13) used in Comparative Examples are shown below. These were prepared by known synthesis methods and polymerization methods.

<Component B used in Examples>
Component B (B-1 to B-26) used in Examples and Component B (B-27) used in Comparative Examples are shown below.

  In the table, EO represents a divalent linking group derived from a polyethyleneoxy group, PO represents a divalent linking group derived from a polypropyleneoxy group, and a and b are EO and PO such that each component B satisfies HLB. R represents a hydrogen atom or C = 1-8 alkyl group.

[Examples and Comparative Examples]
(1) Preparation of photosensitive resin composition solution Each component shown in the following table was mixed to make a uniform solution, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm. And the photosensitive resin composition solution of a comparative example was prepared, respectively.

Photoacid generator PAG-1: The oxime sulfonate compound shown below, IRGCURE PAG103 (manufactured by Ciba Specialty Chemicals)
PAG-2: PAI-1001 (manufactured by Midori Chemical Co., Ltd.)
PAG-3: PAI-101 (manufactured by Midori Chemical Co., Ltd.)
PAG-4 to PAG-6: Compounds having the following structures

Solvent E1: Diethylene glycol methyl ethyl ether Solvent E2: Propylene glycol monomethyl ether acetate

  In the table, the “solid content” column represents a value (unit: mass%) of (residual amount / composition amount) × 100 when the composition is evaporated to dryness.

<Evaluation of coatability>
Each of the photosensitive resin composition solutions prepared in each Example and Comparative Example was applied on a 1,500 mm × 1,800 mm Cr vapor-deposited glass substrate (glass is EAGLE2000, Corning) with a coating speed of 100 mm / sec using a slit die. The film was applied so as to have a dry film thickness of 4 μm (wet thickness of 20 μm) under the conditions of a gap of 100 μm and a coating flow rate of 0.5 ml / s, and vacuum-dried in a vacuum drying chamber so that the ultimate vacuum was 0.4 Torr. The dried substrate was dried on a hot plate at 90 ° C. for 120 seconds, and observed in the dark using a Na lamp, a white lamp, and a green lamp. Evaluated by criteria.
[Coating stripe]
○: There is no coating stripe.
Δ: There are slight streaks at the peripheral edge.
X: There are stripes on the entire surface.
[Drying unevenness]
○: Drying unevenness (interference fringes) is not observed at all.
Δ: Slightly observed but within acceptable range.
X: Drying unevenness (interference fringes) exceeding the allowable range is observed.
[Reduced vacuum pin mark]
The contact mark of the pin supporting the substrate in the vacuum drying chamber was determined according to the following criteria.
○: No observation after the vacuum drying pin.
Δ: Slightly observed but within acceptable range.
X: After the vacuum drying pin exceeding the allowable range is observed.

<Evaluation of pixel defects that occur during application>
The number of pixel defects due to repelling on the substrate was counted on the substrate by AOI (color filter defect inspection apparatus manufactured by Takano Co., Ltd.).
○: 10 or less on the entire surface of the substrate.
Δ: 11 to 25 on the entire surface of the substrate.
X: 26 or more on the entire surface of the substrate.

<Surface evaluation after post-baking>
The developed substrate was exposed at 300 mJ / cm ² (illuminance 20 mW / cm ² ) and then post-baked at 230 ° C. for 1 hour in a convection oven, and then the surface state was observed with an optical microscope.
○: The surface is flat and there is no unevenness.
(Triangle | delta): Although there are some unevenness | corrugations, it is in an allowable range.
X: Separation of components was observed, and the entire surface was severely uneven.

<Liquid crystal contamination degree evaluation (liquid crystal resistivity)>
Each of the photosensitive resin composition solutions prepared in each Example and Comparative Example was spin-coated on a 100 mm × 100 mm glass substrate (EAGLE2000, Corning) so as to have a dry film thickness of 4 μm (wet thickness of 20 μm), Vacuum drying was performed in a vacuum drying chamber so that the ultimate vacuum was 0.4 Torr. The dried substrate was dried at 90 ° C. × 120 sec on a hot plate, then exposed at 300 mJ / cm ² and then post-baked at 230 ° C. for 1 hour in a convection oven. After peeling off the completed coating film from the substrate, it was mixed with liquid crystal (MLC-6608 manufactured by Merck), heated at 120 ° C for 5 hours, and then an ultramicro ammeter (Digital Ultra High Resistance / Microcurrent manufactured by ADC Co., Ltd.) The liquid crystal specific resistance was measured using a total of 8340A). Evaluation results were determined as follows.
○: Specific resistance is equivalent to that of a liquid crystal in which nothing is mixed.
Δ: The specific resistance is slightly lower than the liquid crystal in which nothing is mixed, but is within an allowable range.
X: The specific resistance is greatly reduced as compared with a liquid crystal in which nothing is mixed.
In general, the higher the specific resistance of the liquid crystal, the lower the degree of contamination of the liquid crystal and the better the panel reliability.

<Particle>
The amount of particles immediately after production and the amount of particles (unit: months / ml) after 1 week of refrigeration at 4 ° C. were measured by the following methods.
The resist solution passing through the transparent flow path was irradiated with laser, and the number of particles having a size of 0.3 μm or more was counted by measuring the amount of light scattered by the particles (light scattering method).
For the measurement, a liquid particle counter (KS-42A) manufactured by LION was used.

  The results of the above evaluation are shown in the following table.

  From the above table, the composition of the present invention is a positive photosensitive resin composition that is excellent in applicability, can prevent precipitation during refrigerated storage, has a development unevenness and pixel defects, and provides a cured film with excellent flatness. I found out.

(Example 101)
<Production of organic EL display device>
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 to the organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by slit coating the photosensitive resin composition of Example 3 on the substrate, pre-baking (90 ° C. × 2 minutes) on a hot plate, and then applying high pressure from above the mask. After irradiating i-line (365 nm) with 30 mJ / cm ² (illuminance 20 mW / cm ² ) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. for 60 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 using a resist stripping solution (mixed solution of monoethanolamine and dimethyl sulfoxide (DMSO)). 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. The insulating film 8 was formed by the same method as described above using the photosensitive resin composition of Example 3. 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 through the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 102)
Evaluation similar to the said Example 101 was implemented using the UV-LED light source exposure machine instead of the ultrahigh pressure mercury lamp. As a result, the same result as in Example 101 was obtained.

(Example 103)
In Example 103, the procedure was performed on the photosensitive resin composition of Example 101, except that the substrate was changed from the glass substrate 6 (Corning 1737, 0.7 mm thickness (manufactured by Corning)) to a 6-inch silicon wafer. The sensitivity was evaluated in the same manner as the sensitivity evaluation. As a result, the same result as in Example 101 was obtained.

(Example 104)
In Example 104, the photosensitive resin composition of Example 101 was used except that the exposure machine was changed from a Canon-made PLA-501F exposure machine to Nikon Corporation's FX-803M (gh-Line stepper). The sensitivity was evaluated in the same manner as the sensitivity evaluation performed for the above. As a result, the same result as in Example 101 was obtained.

(Example 105)
In Example 105, the photosensitive resin composition of Example 101 was used, and the exposure machine was changed from a Canon-made PLA-501F exposure machine to a 355 nm laser exposure machine, and 355 nm laser exposure was performed. The sensitivity was evaluated in the same manner as the sensitivity evaluation performed on the photosensitive resin composition of Example 2. As a result, the same result as in Example 101 was obtained.
In addition, as a 355 nm laser exposure machine, "EGIS" manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using "PE10B-V2" manufactured by OPHIR.

  As described above, it can be seen that the photosensitive resin compositions of the examples exhibit excellent sensitivity regardless of the substrate and the exposure machine.

  1: TFT (thin film transistor), 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: Transparent ITO electrode, 20: Liquid crystal, 22: Color filter

Claims (14)

(Component A) a copolymer containing the structural unit A and the structural unit B represented by the following general formula (1) and having a weight average molecular weight of 1,000 to 10,000,
(Component B) a polymer having a weight average molecular weight of 1,000 to 50,000 represented by the following general formula (2):
(Component C) a structural unit having an acid-decomposable group that decomposes with an acid to form a carboxyl group or a phenolic hydroxyl group, and a structural unit having a functional group that can react with a carboxyl group or a phenolic hydroxyl group to form a covalent bond A resin having
(Component D) a photoacid generator, and
(Component E) contains a solvent,
The content of component A is 0.001 to 1.00% by mass,
The positive photosensitive resin composition, wherein the content of the component B is 0.001 to 1.00% by mass.

(In General Formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group. L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio of the structural unit A and the structural unit B, p represents 10 to 80% by mass, and q represents 20 -90 mass% is represented, r represents the integer of 1-18, n represents the integer of 1-10.)

(In the general formula (2), R ^{5 to} R ¹² are each independently an amino group, a hydroxyl group, a carboxyl group, a glycidyl group, a thiol group, or an alkyl that can have a linear or cyclic structure having 1 to 20 carbon atoms. A group, an alkylene group, an aralkyl group, and an alkoxy group, and m and n represent a mass percentage that represents a polymerization ratio of a dimethylsiloxane structural unit and a modified siloxane structural unit.) In the general formula (2), at least one of R ⁵ , R ⁷ , R ⁹ and R ¹¹ is a polyethyleneoxy group substituted with a polypropyleneoxy group, an unsubstituted alkyl group, an alicyclic epoxy group-substituted alkyl group, The positive photosensitive resin composition according to claim 1, which is at least one selected from a glycidyl group-substituted alkyl group and an aralkyl group. The positive photosensitive resin composition according to claim 1 or 2, wherein the L in the general formula (1) is a branched alkylene group represented by the following general formula (3).

(In General Formula (3), R ¹³ represents an alkyl group having 1 to 4 carbon atoms.) Wherein a said R ¹³ is an ethyl group in the general formula (3), the positive photosensitive resin composition of claim 3.   The component C further comprises at least one compound-derived structural unit selected from the group consisting of a styrene derivative, a maleimide derivative, a (meth) acrylic acid, and a hydroxyl group-containing (meth) acrylate compound. 2. The positive photosensitive resin composition according to item 1. The acid-decomposable group of component C is a group represented by the following general formula (Ia), general formula (Ib), general formula (IIa) or general formula (IIb). 2. The positive photosensitive resin composition according to item 1.

(In the general formula (Ia), the general formula (Ib), the general formula (IIa) and the general formula (IIb), each R ²¹ independently represents an alkyl group or a cycloalkyl group, and each R ²² independently represents an alkyl group. R ²¹ and R ²² may form a ring, R ²³ represents a tertiary alkyl group, R ²⁴ represents a tertiary alkyl group or a tert-butoxycarbonyl group, Ar ¹ and Ar ² independently represents a divalent aromatic group, and the wavy line represents a bonding site with another structure.)   The positive photosensitive resin composition of any one of Claims 1-6 containing at least one of an oxiranyl group and an oxetanyl group as a functional group of the said component C.   The positive photosensitive resin composition according to claim 7, wherein the functional group is an oxetanyl group.   The positive photosensitive resin composition of any one of Claims 1-8 whose said component D is an oxime sulfonate compound.   The positive photosensitive resin composition according to any one of claims 1 to 9, wherein the component E is 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. . (1) An application step of applying the positive photosensitive resin composition according to any one of claims 1 to 10 on a substrate,
(2) a solvent removal step for removing the solvent from the applied positive photosensitive resin composition;
(3) an exposure step of exposing with actinic rays;
(4) a development step of developing with an aqueous developer, and
(5) A method for producing a cured film comprising a post-bake step of thermosetting.   A cured film produced by the method according to claim 11.   The cured film according to claim 12, which is an interlayer insulating film.   An organic EL display device or a liquid crystal display device comprising the cured film according to claim 12 or 13.

Images