JP2013182077A - Photosensitive resin composition, method for producing cured film using the same, cured film, liquid crystal display device and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition excellent in sensitivity, a residual film rate and a dielectric constant.SOLUTION: The photosensitive resin composition comprises: (A) a polymer component including (a1) a repeating unit having a residue of an acid group protected by an acid decomposable group, (a2) a repeating unit having a group selected from an oxiranyl group, oxetanyl group or -NH-CH-OR (where R represents an alkyl group having 1 to 20 carbon atoms), and (a3) a repeating unit having a carboxyl group at a side chain end and having 4 or more atoms in a divalent connecting group that connects the polymer main chain and the carboxyl group, in the same polymer or in different polymers; (B) a photo-acid generator; and (D) a solvent.

Description

  The present invention relates to a photosensitive resin composition, a method for forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device. More specifically, a positive photosensitive resin composition suitable for forming a flattening film, a protective film, and an interlayer insulating film of electronic components such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state imaging device, and the same The present invention relates to a method for forming a cured film using the above.

  In an electronic component such as a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, solid-state imaging element, etc., an interlayer insulation is generally used to insulate between wirings arranged in layers. A membrane is provided. As the material for forming the interlayer insulating film, a photosensitive resin composition is widely used because a material having a small number of steps for obtaining a required pattern shape and sufficient flatness is preferable.

Specifically, as a photosensitive resin composition, a composition containing a resin having an acetal structure and / or a ketal structure and an epoxy structure and a photoacid generator (Patent Document 1) is known. However, since the composition cannot be developed without post exposure bake (PEB), its application range is limited. Further, the composition described in Patent Document 1 is excellent in heat resistance and development margin, but has low sensitivity and a problem in residual film properties.
Also, a composition comprising a repeating unit having a group that decomposes by the action of an acid to generate an alkali-soluble group, a resin having a repeating unit having a functional group that crosslinks between resins by heating, and a photoacid generator (Patent Document) 2) is known. However, since the composition is premised on use in a double patterning method, its application range is limited. In addition, the composition described in Patent Document 2 has problems in residual film properties and relative dielectric constant.
Further, a polymer (Patent Document 3) containing a resin containing a structural unit having a lactone skeleton or a naphthalene skeleton is known. The polymer described in Patent Document 3 cannot exhibit high sensitivity unless an ArF laser is used.

JP 2004-264623 A JP 2009-288343 A JP 2008-95087 A

  The object of the present invention is to solve the above-described problems, and an object of the present invention is to provide a positive photosensitive resin composition excellent in sensitivity, residual film ratio, and relative dielectric constant.

（式（ｉｖ）中、ｚは０〜５の整数を表す。）
［２］ 前記（Ａ）重合体成分が、前記繰り返し単位（ａ２）、および前記繰り返し単位（ａ３）を含む重合体を有する［１］の感光性樹脂組成物。
［３］ 前記（Ａ）重合体成分が、前記繰り返し単位（ａ１）、前記繰り返し単位（ａ２）、および前記繰り返し単位（ａ３）を含む重合体を有する［１］または［２］の感光性樹脂組成物。
［４］ 化学増幅ポジ型感光性樹脂組成物である［１］〜［３］のいずれかの感光性樹脂組成物。
［５］ 前記繰り返し単位（ａ３）が、一般式（i）〜(iii)で表される繰り返し単位を１種以上含む［１］〜［４］のいずれかの感光性樹脂組成物。

（一般式（i）〜（iii）中、Ｒ¹は、水素原子又はメチル基を表し、Ｌは原子数が４以上の２価の連結基を表し、Ｒ²は、ハロゲン原子、水酸基または炭素数１〜３のアルキル基を表し、ｎは、０〜４の整数を表す。）
［６］ 前記繰り返し単位（ａ１）が、一般式（Ａ２’）で表される繰り返し単位である［１］〜［５］のいずれかの感光性樹脂組成物。

（一般式（Ａ２’）中、Ｒ¹およびＲ²は、それぞれ、水素原子、アルキル基またはアリール基を表し、少なくともＲ¹およびＲ²のいずれか一方がアルキル基またはアリール基であり、Ｒ³は、アルキル基またはアリール基を表し、Ｒ¹またはＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子またはメチル基を表し、Ｘは単結合またはアリーレン基を表す。）
［７］ 前記繰り返し単位（ａ２）が、一般式（２）で表される繰り返し単位である［１］〜［６］のいずれかの感光性樹脂組成物。

（一般式（２）中、Ｒ¹は水素原子またはメチル基を表し、Ｒ²は炭素数１〜２０のアルキル基を表す。）
［８］ 前記繰り返し単位（ａ２）が、オキシラニル基および／またはオキセタニル基を有する繰り返し単位である［１］〜［７］のいずれかの感光性樹脂組成物。
［９］ （１）［１］〜［８］のいずれかの感光性樹脂組成物を基板上に適用する工程、
（２）適用された感光性樹脂組成物から溶剤を除去する工程、
（３）活性放射線で露光する工程、
（４）水性現像液で現像する工程、および、
（５）熱硬化するポストベークする工程、を含むことを特徴とする硬化膜の製造方法。
［１０］ 前記現像工程後、ポストベーク工程前に、全面露光する工程を含む、［９］の硬化膜の形成方法。
［１１］ ［１］〜［８］のいずれかの感光性樹脂組成物を硬化してなる硬化膜。
［１２］ 層間絶縁膜である、［１１］の硬化膜。
［１３］ ［１１］又は［１２］の硬化膜を有する、液晶表示装置または有機ＥＬ表示装置。 As a result of intensive studies by the inventors of the present invention based on the above problems, the use of a polymer having a repeating unit of a long-chain carboxylic acid in combination with two specific types of polymers improves the mobility of acid groups and the glass of the film. It was found that a significant improvement in sensitivity and a remaining film ratio, which are considered to be caused by a decrease in the transition point (Tg), were observed, and the above problems could be solved.
The means for solving the problem is the means [1] below, preferably the means [2] to [13] below.
[1] (A) (a1) a repeating unit having a residue in which an acid group is protected with an acid-decomposable group, (a2) an oxiranyl group, an oxetanyl group, or —NH—CH ₂ —OR (where R is 1 carbon atom) A repeating unit having a crosslinkable group selected from (an alkyl group of ˜20), and (a3) an atom of a divalent linking group having a carboxyl group at the end of the side chain and linking the polymer main chain and the carboxyl group A polymer component containing 4 or more repeating units in the same or different polymers,
(B) a photoacid generator, and (D) a solvent,
Containing
The divalent linking group includes —CR ¹ ₂ — (R ¹ represents a hydrogen atom or a methyl group), —O—, —O—SO ₂ —, —O—C (O) —, —C (O ) —O—, —S—, —C (O) —, an optionally substituted amino group, an optionally substituted phenylene group, or the following structure (iv) A photosensitive resin composition, which is a group arbitrarily combined.

(In the formula (iv), z represents an integer of 0 to 5.)
[2] The photosensitive resin composition according to [1], wherein the polymer component (A) has a polymer containing the repeating unit (a2) and the repeating unit (a3).
[3] The photosensitive resin according to [1] or [2], wherein the polymer component (A) has a polymer containing the repeating unit (a1), the repeating unit (a2), and the repeating unit (a3). Composition.
[4] The photosensitive resin composition according to any one of [1] to [3], which is a chemically amplified positive photosensitive resin composition.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the repeating unit (a3) includes one or more repeating units represented by general formulas (i) to (iii).

(In the general formulas (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group, or a carbon atom. Represents an alkyl group of 1 to 3, and n represents an integer of 0 to 4.)
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the repeating unit (a1) is a repeating unit represented by the general formula (A2 ′).

(In the general formula (A2 '), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, either one of at least R ¹ and R ² is an alkyl group or an aryl group, R ³ Represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or Represents an arylene group.)
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the repeating unit (a2) is a repeating unit represented by the general formula (2).

(In general formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms.)
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the repeating unit (a2) is a repeating unit having an oxiranyl group and / or an oxetanyl group.
[9] (1) A step of applying the photosensitive resin composition according to any one of [1] to [8] on a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer, and
(5) A method for producing a cured film comprising a step of post-baking to be thermally cured.
[10] The method for forming a cured film according to [9], including a step of exposing the entire surface after the developing step and before the post-baking step.
[11] A cured film obtained by curing the photosensitive resin composition according to any one of [1] to [8].
[12] The cured film according to [11], which is an interlayer insulating film.
[13] A liquid crystal display device or organic EL display device having the cured film of [11] or [12].

  According to the present invention, it is possible to provide a positive photosensitive resin composition excellent in sensitivity, a remaining film ratio, and a relative dielectric constant, a pattern manufacturing method, an organic EL display device, a liquid crystal display manufacturing method, and a cured film. it can.

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

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

[Photosensitive resin composition]
The photosensitive resin composition of the present invention is
(A) (a1) a repeating unit having a residue in which an acid group is protected with an acid-decomposable group, (a2) an oxiranyl group, an oxetanyl group, or —NH—CH ₂ —OR (where R is a carbon number of 1 to 20) A repeating unit having a group selected from (which is an alkyl group), and (a3) a carboxyl group at the end of the side chain, and the divalent linking group connecting the polymer main chain and the carboxyl group has 4 or more A polymer component containing repeating units in the same or different polymers,
It contains (B) a photoacid generator, and (D) a solvent.

The component (A) is
(1): an embodiment formed by copolymerizing the repeating unit (a1), the repeating unit (a2), and the repeating unit (a3),
(2): A copolymer of the repeating unit (a1) and the repeating unit (a3), an embodiment of a copolymer of the repeating unit (a2) and the repeating unit (a3),
(3): an embodiment of a polymer containing the repeating unit (a1), a polymer containing the repeating unit (a2), and a polymer containing the repeating unit (a3),
(4): a copolymer of the repeating unit (a1) and the repeating unit (a3), an embodiment of a polymer containing the repeating unit (a2),
(5): copolymer of repeating unit (a2) and repeating unit (a3), polymer embodiment containing repeating unit (a1), and (6): repeating unit (a1) and repeating unit (a2) Examples of the copolymer and a polymer including the repeating unit (a3) are included.
Among these embodiments, the embodiments (1), (3) to (4), and (6) are preferable.
The component (A) may contain a plurality of these embodiments, and may further contain other repeating units (a4).

  Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated.

<(A) component>
The photosensitive resin composition of the present invention (hereinafter also referred to as the photosensitive composition of the present invention or the composition of the present invention) includes, as component (A), a repeating unit (a1), a repeating unit (a2), and a repeating unit. (A3) is contained in the same or different polymer.
In addition to the repeating units (a1) to (a3), the component (A) may contain other constituent (repeating) units (a4).

[Repeating unit (a1)]
When the component (A) has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
In the present invention, “residue in which an acid group is protected with an acid-decomposable group” means a residue in which a carboxyl group is protected with an acetal, a residue in which an acid group is protected with a ketal, and an acid group is a tertiary alkyl group Or a residue in which the acid group is protected with a tertiary alkyl carbonate group.
Preferred examples of the acid group include a carboxyl group and a phenolic hydroxyl group.
Specific examples of the residue in which the acid group is protected with an acid-decomposable group include, for example, an ester structure of a group represented by the formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group. And a tertiary alkyl functional group such as a t-butyl ester group and a t-butyl carbonate group.

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

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

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

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

<<<< acid-decomposable group that can be used for the structural unit (a1-1) >>>>
Examples of the acid-decomposable group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group include acid decomposition in a positive resist for KrF and a positive resist for ArF. A well-known thing can be used as a sex group, and it does not specifically limit. Conventionally, as an acid-decomposable group, a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as a tetrahydropyranyl group) or a group that is relatively difficult to be decomposed by an acid (for example, a tert-butyl ester group, a tert-butyl ester group, -Tert-butyl functional groups such as butyl carbonate groups) are known.
Among these acid-decomposable groups, the basic physical properties of the resist, in particular, a structural unit having a protected carboxyl group in which the carboxyl group is protected with an acetal or ketal, or a protected carboxyl group in which the carboxyl group is protected with a ketal It is preferable from the viewpoints of sensitivity, pattern shape, formability of contact holes, and storage stability of the photosensitive resin composition. Furthermore, among the acid-decomposable groups, the carboxyl group is more preferably a protected carboxyl group protected by an acetal or ketal represented by the following general formula (a1-1) from the viewpoint of sensitivity. When the carboxyl group is a protected carboxyl group protected by an acetal or ketal represented by the following general formula (a1-1), the entire protected carboxyl group is — (C═O) —O—CR ^101. The structure is R ¹⁰² (OR ¹⁰³ ).

（式（ａ１−１）中、Ｒ¹⁰¹およびＲ¹⁰²は、それぞれ独立に水素原子またはアルキル基を表し、但し、Ｒ¹⁰¹とＲ¹⁰²とが共に水素原子の場合を除く。Ｒ¹⁰³は、アルキル基を表す。Ｒ¹⁰¹またはＲ¹⁰²と、Ｒ¹⁰³とが連結して環状エーテルを形成してもよい。）

(In formula (a1-1), R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms. R ¹⁰³ is an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.)

In the general formula (a1-1), R ^{101 to} R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched, or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

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

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

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

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

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

In the general formula (a1-1), it is preferable that any one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

  As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-1), a commercially available one may be used, or it may be synthesized by a known method. Things can also be used. For example, as shown below, it can be synthesized by reacting (meth) acrylic acid with vinyl ether in the presence of an acid catalyst. This reaction may be performed at the monomer stage, or may be performed after forming a polymer.

In the above scheme, R ¹¹¹ represents a hydrogen atom or an alkyl group, and the alkyl group is the same as the alkyl group represented by R ^{101 to} R ¹⁰³ in the general formula (a1-1). R ¹¹¹ is preferably a hydrogen atom or a methyl group.
R ¹¹² and R ¹¹³ are the same as R ¹⁰² in the general formula (a1-1) as —CH (R ¹¹² ) (R ¹¹³ ), and R ¹¹⁴ is the same as R ¹⁰¹ in the general formula (a-1). R ¹¹⁵ is synonymous with R ¹⁰³ in the general formula (a1-1), and preferred ranges thereof are also the same.
In the above synthesis, (meth) acrylic acid may be previously copolymerized with other monomers and then reacted with vinyl ether in the presence of an acid catalyst.

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

(Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group; )
When R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferred.

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

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

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

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

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

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

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

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

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

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

Examples of the radical polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected with an acetal or ketal include, for example, 1-alkoxyalkyl protected form of hydroxystyrene, hydroxy Tetrahydropyranyl protected form of styrene, 1-alkoxyalkyl protected form of α-methyl-hydroxystyrene, tetrahydropyranyl protected form of α-methyl-hydroxystyrene, 1-alkoxyalkyl protected form of 4-hydroxyphenyl methacrylate, 4- Tetrahydropyranyl protected form of hydroxyphenyl methacrylate, 1-alkoxyalkyl protected form of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ) Tetrahydropyranyl protected form of ester, 1-alkoxyalkyl protected form of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, tetrahydropyranyl protected form of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 1-alkoxyalkyl protected form of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, tetrahydropyranyl protected form of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyl) 1-alkoxyalkyl protected form of oxy-2-hydroxypropyl) ester, tetrahydropyranyl protected form of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, and the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

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

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

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

<<< Preferred Aspect of Structural Unit (a1) >>>
From the viewpoint of sensitivity, the content of the structural unit (a1) in the structural unit constituting the component (A) is preferably 1 to 95 mol%, more preferably 10 to 80 mol%, based on the polymer as a whole. -70 mol% is further more preferable, and 20-50 mol% is especially preferable. In particular, the acid-decomposable group that can be used for the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected with an acetal, or a protected carboxyl group in which the carboxyl group is protected with a ketal. In some cases, the content of the structural unit (a1) in the structural unit constituting the polymer including the structural unit (a1) is more preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol%.

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

[Repeating unit (a2)]
The repeating unit (a2) is usually incorporated into the resin as a structural unit having a crosslinkable group selected from an oxiranyl group, an oxetanyl group, or —NH—CH ₂ —OR (R is an alkyl group having 1 to 20 carbon atoms). It is. The structural unit having a crosslinkable group is preferably a structural unit derived from a compound having a cyclic ether group, more preferably a structural unit derived from a compound having an oxiranyl group and / or an oxetane group, (3) to (5 The repeating unit consisting of a radically polymerizable monomer represented by any one of These compounds can be used alone or in combination of two or more. Moreover, the repeating unit represented by following General formula (2) may be sufficient.

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

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

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

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

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

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

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

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

As the structural unit (a2-2) having —NH—CH ₂ —O—R, a structural unit having a group represented by the following general formula (2) is preferable.

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

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

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

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

[Repeating unit (a3)]
The photosensitive composition of the present invention is a monomer having a carboxyl group at the end of the side chain and having a divalent linking group having 4 or more atoms constituting the group connecting the polymer main chain and the carboxyl group at the side chain end. The unit (a3) is contained, and the divalent linking group is —CR ¹ ₂ — (R ¹ represents a hydrogen atom or a methyl group), —O—, —O—SO ₂ —, —O—C (O )-, -C (O) -O-, -S-, -C (O)-, an amino group optionally having substituent (s), a phenylene group optionally having substituent (s), or It is a group selected from the structure of (iv) and arbitrarily combined.

  L is a divalent linking group having 4 or more atoms connecting the polymer main chain and the carboxyl group, and the number of atoms is preferably 6 or more and 20 or less, more preferably 8 or more and 12 or less. preferable.

As the divalent linking group (L) having 4 or more atoms, —CR ¹ ₂ — (R ¹ represents a hydrogen atom or a methyl group), —O—, —O—SO ₂ —, —O—C (O)-, -C (O) -O-, -S-, -C (O)-, an amino group which may have a substituent, a phenylene group which may have a substituent, or A group selected from the following structure (iv) and arbitrarily combined.

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

The amino group is preferably an amino group having 0 to 50 carbon atoms, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N-sulfonylamino group, N, N-dialkyl. Examples include an amino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenyla Group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino Group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenyl Amino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) Amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, - dimethyl morpholino group, and a carbazolyl group. Among these, —NH ₂ , N, N-diphenylamino group and carbazole group are preferable.

  Examples of the phenylene group include an o-phenylene group, an m-phenylene group, and a p-phenylene group. Among these, an o-phenylene group and a p-phenylene group are preferable.

  Examples of the substituent that the amino group and phenylene group may have include a halogen atom, an aryl group, and an alkoxy group.

  In the present specification, the number of atoms of the divalent linking group refers to the number of atoms having the smaller number of atoms constituting the main chain connecting the polymer main chain and the carboxyl group. For example, the following exemplary compound (a3-1) has 8 atoms, (a3-2) has 8 atoms (the number of atoms constituting the main chain connecting the polymer main chain and the carboxyl group is 8) The number of atoms is 8 because the number of atoms with the smaller number of atoms constituting the main chain connecting the polymer main chain and the carboxyl group is defined as the number of atoms. (A3-20) has 8 atoms (the number in the following formula means the number of atoms).

The component (a3) preferably contains one or more repeating units represented by the following general formulas (i) to (iii).

(In formulas (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, and L represents a divalent linking group having 4 or more atoms. In general formula (iii), R ² represents Represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 0 to 4.)

  Examples of L are preferably selected from the following group of linking groups. In the following linking groups, “*” represents a linking site with a polymer main chain and a carboxyl group.

In general formula (iii), R < ² > is a halogen atom, a hydroxyl group, or a C1-C3 alkyl group, and a chlorine atom, a bromine atom, a hydroxyl group, or a methyl group is preferable.
n is an integer of 0 to 4, and 0 is preferable.

The repeating units represented by the general formulas (i) to (iii) are preferably repeating units represented by the following general formulas (i ′) to (iii ′).

（式（ｉ’）〜（ｉｉｉ’）中、Ｒ¹は、式（ｉ）〜（ｉｉｉ）のＲ¹と同義であり、Ｌ¹は、炭素数が１〜４のアルキレン基を表す。）

(In formulas (i ′) to (iii ′), R ¹ has the same meaning as R ^{1 in} formulas (i) to (iii), and L ¹ represents an alkylene group having 1 to 4 carbon atoms.)

L ¹ represents an alkylene group having 1 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms.

Specific examples of the repeating unit (a3) include the following structures, but the present invention is not limited to the following structures.

Among the specific examples, (a3-1) to (a3-15) are preferable, and (a3-1) to (a3-3), (a3-5), (a3-7), and (a3-9) Is more preferable, and (a3-2) is more preferable.

  In the structural unit constituting the component (A), the content of the repeating unit (a3) is preferably 0.1 to 50 mol%, more preferably 0.1 to 45 mol% of the structural units of all resin components, 5.0 to 35 mol% is more preferable. When the content is 0.1 mol% or more, the effects of high sensitivity and a high residual film ratio are obtained, and when it is 45 mol% or less, it is preferable in terms of improving developability.

  It is preferable that the weight average molecular weight (Mw) of the polymer which has a repeating unit (a3) is the range of 3000-300000, More preferably, it is 4000-100000, More preferably, it is 8000-50000. By setting it to 3000 or more, the effect of improving the remaining film ratio is obtained, and by setting it to 300000 or less, the effect of high sensitivity is obtained. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

[Repeating unit (a4)]
In addition to the repeating units (a1) to (a3), the component (A) may include a polymer having a repeating unit (a4) derived from another monomer. Further, the repeating unit (a4) may also be copolymerized. Other monomers include hydrogenated hydroxystyrene; halogen, alkoxy or alkyl-substituted hydroxystyrene; styrene; halogen, alkoxy, acyloxy or alkyl-substituted styrene; maleic anhydride; acrylic acid derivative; methacrylic acid derivative; N-substituted maleimide and the like. It can be mentioned, but is not limited to these.

  In the structural unit constituting the component (A), the content of the structural unit (a4) is preferably 0.01 to 50 mol%, more preferably 0.01 to 33 mol%, and still more preferably 5 to 23 mol%. .

  In the present invention, among the repeating units constituting the component (A), the repeating unit having 3 or less “L” atoms in the repeating units represented by the general formulas (i) to (iii) is 3 It is preferable that it is below mol%, and it is more preferable not to contain substantially. “Substantially free” means, for example, that the effect of the present invention is not affected.

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

<< Amount of (A) >>
The photosensitive resin composition of the present invention preferably contains 30% by weight or more of the component (A), more preferably 40% by weight or more, and still more preferably 50% by weight or more. By setting it as such a range, a structural unit (a2) will exist uniformly in a composition, and the effect of this invention will be exhibited more effectively. The upper limit is not particularly defined and may be 100% by weight.

<< (A) Component Production Method >>
Various methods for synthesizing the component (A) are also known. For example, the component (A) is used to form at least the structural units represented by the above (a1) and (a2). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction. Moreover, it is also preferable that (A) component has a carboxy group at the terminal.

[Method for synthesizing resin having carboxyl group at terminal]
The resin having a carboxyl group at the terminal can be produced by copolymerizing the corresponding monomer by radical polymerization, anion polymerization, group transfer polymerization (GTP) or the like. Although the manufacturing method of resin which has a carboxyl group at the terminal of this invention is not specifically limited, For example, Unexamined-Japanese-Patent No. 2005-122035 gazette The (a)-(h) method of paragraph 00099-0117 description can be mentioned. Of these, the methods i and b are preferred.
(A) As a method of using a polymerization initiator having a carboxyl group, a polymerization initiator having a carboxyl group is used as an initiator at the time of polymerization.
As the polymerization initiator having a carboxyl group, it is widely used. Examples thereof include VA-057 (manufactured by Wako Pure Chemical Industries, Ltd.) and V-501 (manufactured by Wako Pure Chemical Industries, Ltd.).

The polymerization initiator is preferably 0.05 to 10 mol%, more preferably 0.1 to 5 mol%, based on 100 mol of the polymerizable monomer.
The reaction temperature for the copolymerization reaction is preferably 50 to 100 ° C, and more preferably 60 to 100 ° C.

(B) In the method using a chain transfer agent having a carboxyl group at the time of polymerization, a thiol compound having at least one carboxyl group is used in combination at the time of polymerization. Examples of thiol compounds having at least one carboxyl group include the following.

The chain transfer agent is preferably blended at a ratio of 1/100 to 2/3 mole, more preferably 1/20 to 1/3 mole relative to the initiator amount.
Although the molecular weight is adjusted by the sum of the initiator amount and the chain transfer agent, it is preferably 0.05 to 10 mol%, more preferably 0.1 to 5 mol%, based on the total moles of all monomers. The reaction temperature for the copolymerization reaction is preferably 50 to 100 ° C, and more preferably 60 to 95 ° C.

<(B) Photoacid generator>
The photosensitive resin composition of the present invention contains a photoacid generator (B). The photoacid generator used in the present invention is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm and generates an acid, but its chemical structure is not particularly limited. . Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, 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. These photoacid generators can be used singly or in combination of two or more.

Specific examples of these include the following.
As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s -Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methyl) Butylphenyl) ethenyl] - bis (4,6-trichloromethyl) -s-triazine or 2- (4-methoxynaphthyl) - bis (4,6-trichloromethyl) -s-triazine and the like;

  Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl, 4- (2′-hydroxy-1 '-Tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodonium hexafluoroantimonate, phenyl, 4- (2'-hydroxy-1'-tetradeca) Oxy) phenyliodonium-p-toluenesulfonate and the like;

  Examples of triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoro. Lomethanesulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, etc .;

  As quaternary ammonium salts, tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyl Dimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate and the like;

Examples of the diazomethane derivative include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and the like;
Examples of imide sulfonate derivatives include trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-enedicarboximide, succinimide trifluoromethyl sulfonate, phthalimide trifluoromethyl sulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxy- 5-norbornene-2,3-dicarboximidopropane sulfonate and the like;
The compound shown below as an oxime sulfonate compound.

  Preferred examples of the oxime sulfonate compound, that is, the compound having an oxime sulfonate residue include compounds containing an oxime sulfonate residue represented by the formula (b1).

（式（ｂ１）中、Ｒ⁵は、アルキル基またはアリール基を表す。）

(In the formula (b1), R ⁵ represents an alkyl group or an aryl group.)

Any group may be substituted, and the alkyl group in R ⁵ may be linear, branched or cyclic. Acceptable substituents are described below.
As the alkyl group for R ^5, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group represented by R ⁵ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^5, 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 ⁵ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

  The compound containing the oxime sulfonate residue represented by the formula (b1) is an oxime sulfonate compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5). Is preferred.

（式（ＯＳ−３）〜式（ＯＳ−５）中、Ｒ¹はアルキル基、アリール基またはヘテロアリール基を表し、Ｒ²はそれぞれ独立に、水素原子、アルキル基、アリール基またはハロゲン原子を表し、Ｒ⁶はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基またはアルコキシスルホニル基を表し、ＸはＯまたはＳを表し、ｎは１または２を表し、ｍは０〜６の整数を表す。）

(In Formula (OS-3) to Formula (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and R ² independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. R ⁶ represents each independently a halogen atom, alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group or alkoxysulfonyl group, X represents O or S, n represents 1 or 2, m Represents an integer of 0 to 6.)

In the formulas (OS-3) to (OS-5), the alkyl group, aryl group, or heteroaryl group in R ¹ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group for R ¹ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyl group in R ¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

Examples of the alkyl group in R ¹ 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 can be mentioned.

In the formulas (OS-3) to (OS-5), the aryl group for R ¹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the aryl group in R ¹ 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 aryloxycarbonyl group, and an aminocarbonyl group. , A sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

Examples of the aryl group in R ¹ include a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, and a p-phenoxyphenyl group.

Further, the formula (OS-3) ~ (OS -5), as the heteroaryl group in R ^1, heteroaryl group having a total carbon number of 4-30 which may have a substituent is preferable.
Examples of the substituent that the heteroaryl group in R ¹ 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 aryloxycarbonyl group, and an aminocarbonyl. Group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group.

In the formulas (OS-3) to (OS-5), at least one of the heteroaryl groups in R ¹ may be a heteroaromatic ring. For example, a heteroaromatic ring and a benzene ring are condensed. May be.
The heteroaryl group in R ¹ may have a substituent, the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring And a group in which one hydrogen atom is removed from the ring selected from the above.

In the formulas (OS-3) to (OS-5), R ² is 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), it is preferable that one or two of R ² present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably 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 ² may have a substituent.
Examples of the substituent that the alkyl group or aryl group in R ² may have include the same groups as the substituent that the alkyl group or aryl group in R ¹ may have.

The alkyl group for R ² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and an alkyl group having 1 to 6 carbon atoms which may have a substituent. It is more preferable.
Examples of the alkyl group in R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, and chloromethyl group. , A bromomethyl group, a methoxymethyl group, and a benzyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group are preferable. , A 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 preferable.

The aryl group for R ² is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
Specifically, the aryl group in R ² is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
Examples of the halogen atom for R ² 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 represents O or S, and is preferably O.
In formulas (OS-3) to (OS-5), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
In the formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is 2 is preferred.

In the formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group in R ⁶ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group for R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyl group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

Examples of the alkyl group in R ⁶ 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, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl and benzyl are preferred.

In the formulas (OS-3) to (OS-5), the alkyloxy group for R ⁶ is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyloxy group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. It is done.

The alkyloxy group for R ⁶ is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group.
In the formulas (OS-3) to (OS-5), examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group. It is done.
In the formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group for R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

  In the formulas (OS-3) to (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. It is particularly preferred.

  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、Ｒ¹はアルキル基、アリール基またはヘテロアリール基を表し、Ｒ⁷は、水素原子または臭素原子を表し、Ｒ⁸は水素原子、炭素数１〜８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基またはクロロフェニル基を表し、Ｒ⁹は水素原子、ハロゲン原子、メチル基またはメトキシ基を表し、Ｒ¹⁰は水素原子またはメチル基を表す。）

(In formulas (OS-6) to (OS-11), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom, 1 to 8 represents an alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group; ¹⁰ represents a hydrogen atom or a methyl group.)

R ¹ in the formulas (OS-6) to (OS-11) has the same meaning as R ¹ in the formulas (OS-3) to (OS-5), and preferred embodiments thereof are also the same.
R ⁷ in formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ⁸ in the formulas (OS-6) to (OS-11) is 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 chlorophenyl. Represents a group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Is more preferable, and a methyl group is particularly preferable.
R ⁹ in formula (OS-8) and formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ¹⁰ in formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
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.

  The compound containing the oxime sulfonate residue represented by the formula (b1) is also preferably a compound represented by the formula (OS-1).

（式（ＯＳ−１）中、Ｒ¹は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基、または、ヘテロアリール基を表す。Ｒ²は、アルキル基、または、アリール基を表す。）

(In the formula (OS-1), R ¹ 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 a hetero group. Represents an aryl group, and R ² represents an alkyl group or an aryl group.)

X is -O -, - S -, - NH -, - NR 5 -, - CH 2 -, - CR 6 H-, or, -CR ⁶ R ⁷ - represents, R ⁵ to R ⁷ is an alkyl group, Or an aryl group is represented.
R ^{21 to} R ²⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group, Or an aryl group is represented. Two of R ^{21 to} R ²⁴ may be bonded to each other to form a ring.
R ^{21 to} R ²⁴ are preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R ^{21 to} R ²⁴ are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R ^{21 to} R ²⁴ 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 said formula (OS-2), R < ¹ >, R < ² >, R < ²¹ > -R < ²⁴ > is synonymous with each in formula (OS-1), and its preferable example is also the same.
Among these, an embodiment in which R ¹ 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 ¹ 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, 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 the oxime sulfonate residue represented by the formula (b1) may be an oxime sulfonate compound represented by the following formula (b2).

（式（ｂ２）中、Ｒ⁵は、アルキル基またはアリール基を表し、Ｘは、アルキル基、アルコキシ基、または、ハロゲン原子を表し、ｍは、０〜３の整数を表し、ｍが２または３であるとき、複数のＸは同一でも異なっていてもよい。）

(In the formula (b2), R ⁵ represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m represents an integer of 0 to 3, and m represents 2 or When X is 3, the plurality of X may be the same or different.)

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m is preferably 0 or 1.
In the formula (b2), m is 1, X is a methyl group, the substitution position of X is an ortho position, R ⁵ 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.

  The compound containing an oxime sulfonate residue represented by the formula (b1) may be an oxime sulfonate compound represented by the formula (b3).

（式（ｂ３）中、Ｒ⁵は式（ｂ１）におけるＲ⁵と同義であり、Ｘ’は、ハロゲン原子、水酸基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、シアノ基またはニトロ基を表し、Ｌは０〜５の整数を表す。）

(In the formula (b3), R ⁵ has the same meaning as R ⁵ in the formula (b1), X 'is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and L represents an integer of 0 to 5.)

R ⁵ in 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 preferred, and an n-octyl group is particularly preferred.
X ′ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As L, 0-2 are preferable, and 0-1 are particularly preferable.

  Specific examples of the compound represented by the formula (b3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) benzyl. Cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- [(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl Acetonitrile, α-[(4-toluene Sulfo) -4-methoxyphenyl] can be mentioned acetonitrile.

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

  In the photosensitive resin composition of the present invention, the photoacid generator (B) is preferably used in an amount of 0.1 to 10 parts by weight, and 0.5 to 10 parts by weight, based on 100 parts by weight of the resin component. It is more preferable.

<(C) component>
The photosensitive resin composition of the present invention preferably contains (C) a polymer (polymer) having at least a crosslinking group.
The component (C) is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
The component (C) preferably contains 50 mol% or more, and 90 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units in the polymer. More preferred is a polymer consisting only of structural units derived from (meth) acrylic acid and / or its ester.
The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”. “(Meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.

The component (C) may further contain (c1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group. When the component (C) contains (c1), the sensitivity is improved, and when (c2) is contained, the permanent film characteristics are improved. Moreover, it is preferable that the component (C) does not substantially contain a structural unit having —NH—CH ₂ —O—R (R is an alkyl group). By setting it as such a structure, it exists in the tendency for the effect of this invention to be exhibited more effectively. Here, “substantially not contained” means that it is not added at a level that affects the effects of the present invention, for example, 3 mol% or less, further 1 mol% or less of the previous constituent unit of the component (C). And so on.
As (c1) of the component (C), the same group as the above-mentioned << (a1) structural unit having a residue in which an acid group is protected with an acid-decomposable group >> can be used. From the viewpoint of sensitivity, the content of the structural unit (c1) in the structural units constituting the copolymer (C) is preferably 0 to 95 mol%, more preferably 5 to 90 mol% from the viewpoint of sensitivity. 20 to 70 mol% is particularly preferable.
As (c2) of the component (C), the same group as the above << (a3) structural unit having a crosslinking group >> can be used. The preferred embodiment is also the same. From the viewpoint of sensitivity, the content of the structural unit (c2) in the structural units constituting the copolymer (C) is preferably 0 to 95 mol%, more preferably 5 to 90 mol% from the viewpoint of sensitivity. 30 to 70 mol% is particularly preferable.
The component (C) may have another structural unit (c3) excluding (c1), (c2) and (a2). There is no restriction | limiting in particular as a monomer used as another structural unit (c3). The same groups as those described above for [Repeating unit (a3)] and << (a4) Other structural units >> can be preferably used. The preferred embodiment is also the same. The preferable range is also the same.

<< Molecular weight of component (C) >>
(C) The molecular weight of a component is a polystyrene conversion weight average molecular weight, Preferably it is 1,000-200,000, More preferably, it is the range of 2,000-50,000. Various characteristics are favorable within the range of the above numerical values. The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

<< Method for producing molecular weight of component (C) >>
Various methods for synthesizing the component (C) are also known. For example, the radical polymerizability used to form the structural units represented by the above (c1) and (c2). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
As with the component (A), it is also preferable to have a carboxy group at the terminal.

As an example of the component (C), methacrylic acid-3,4-epoxycyclohexylmethyl / acrylic acid / hydroxystyrene / methyl methacrylate copolymer (30/40/15/15 in molar ratio, Mw 7000)
Glycidyl methacrylate / methacrylic acid / styrene / dicyclopentanyl methacrylate copolymer (70/10/10/10 in molar ratio, Mw 15000)
p-Vinylbenzylglycidyl ether / (3-ethyl-3-oxetanyl) methyl methacrylate / maleic acid / cyclohexyl methacrylate copolymer (molar ratio 25/25/30/20, Mw 27000)
1-Ethoxyethyl methacrylate / methacrylic acid / methacrylic acid (3-ethyloxetane-3-yl) methyl / 2-hydroxyethyl methacrylate / methyl methacrylate copolymer (38/7/35/15/5, Mw 35000) ,
1-cyclohexyloxyethyl methacrylate / methacrylic acid / methoxypolyethylene glycol methacrylate (Blemmer PME-400, NOF Co., Ltd. copolymer (70/10/10, Mw 45000)
(3-Ethyl-3-oxetanyl) methyl acrylate / methacrylic acid / N-phenylmaleimide copolymer (molar ratio 30/30 /, Mw 57000)
Can be mentioned.

  The content of the component (C) is preferably 0 to 80% by weight, more preferably 8 to 70% by weight, still more preferably 30 to 65% by weight, and particularly preferably 30 to 50% by weight of the total polymer component. preferable. (C) When 2 or more types of components are included, the total amount becomes the said range.

<Ratio of each structural unit to all polymer components>
In the photosensitive resin composition of the present invention, 99% by weight or more of the polymer component is preferably the component (A) or the component (C).
Moreover, in this invention, it is preferable that the ratio of a structural unit (a2) in all the polymer components is 1-50 mol%, It is more preferable that it is 10-50 mol%, 15-50 mol% More preferably. Moreover, in this invention, it is preferable that the ratio of a crosslinking group in all the polymer components is 1-40 mol%, It is more preferable that it is 10-35 mol%, It is 15-30 mol% Is more preferable.
In particular, in the present invention, 10 mol% or more of all polymer components contained in the positive photosensitive composition is a structural unit (a2) having —NH—CH ₂ —O—R (R is an alkyl group), It is preferable that 20 mol% or more of all polymer components are crosslinkable groups.
Furthermore, in this invention, it is preferable that the ratio of the total amount of a crosslinkable group and a structural unit (a2) in all the polymer components is 10-70 mol%, and it is more preferable that it is 40-60 mol%. preferable. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.

<(D) Solvent>
The photosensitive resin composition of the present invention usually contains (D) a solvent. It is preferable that the photosensitive resin composition of this invention is prepared as a solution which melt | dissolved the essential component, the preferable component, and arbitrary components in (D) solvent.
As the solvent (D) used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like.

As the (D) solvent used in the photosensitive resin composition of the present invention, for example,
(D-1) Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
(D-2) Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether;
(D-3) Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate;
(D-4) Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
(D-5) Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;

(D-6) Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
(D-7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;
(D-8) Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate;
(D-9) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether; (co) dipropylene glycol dimethyl ether, dipropylene Dipropylene glycol dialkyl ethers such as glycol diethyl ether and dipropylene glycol ethyl methyl ether;

(D-10) Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate;
(D-11) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate;
(D-12) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate Aliphatic carboxylic acid esters such as isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate;
(D-13) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3- Other esters such as methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
(D-14) Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;

(D-15) Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
(D-16) Lactones such as γ-butyrolactone can be exemplified.
In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, and a combination of propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers. More preferably.

  The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight and more preferably 100 to 2,000 parts by weight per 100 parts by weight of the resin component. Preferably, it is 150-1500 weight part.

  In addition to the above components, the positive photosensitive resin composition of the present invention includes a crosslinking agent, an adhesion improver, a basic compound, a surfactant, a plasticizer, a thermal radical generator, an antioxidant, and Known additives such as a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic suspending agent can be added.

<(E) Adhesion improver>
The photosensitive resin composition of the present invention may contain (E) an adhesion improver. The (E) adhesion improver that can be used in the photosensitive resin composition of the present invention includes an inorganic substance that serves as a substrate, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a metal such as gold, copper, and aluminum. It is a compound that improves adhesion to an insulating film. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the (E) adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent 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 (E) adhesion improving agent in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin component.

<(G) Basic compound>
The photosensitive resin composition of the present invention may contain (G) a basic compound. (G) 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.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7 -Undecene and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. It is preferable to use two kinds of heterocyclic amines in combination.

  The content of the basic compound (G) in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, and 0.005 to 0.2 part by weight with respect to 100 parts by weight of the resin component. More preferably, it is a part.

<(H) Surfactant>
The photosensitive resin composition of the present invention may contain (H) a surfactant. (H) As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Made by Co., Ltd.), Asahi Guard, Surflon (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA), and the like.
In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula (1), and is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.

（式（１）中、Ｒ¹およびＲ³はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴は水素原子または炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐおよびｑは重合比を表す重量百分率であり、ｐは１０重量％以上８０重量％以下の数値を表し、ｑは２０重量％以上９０重量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｎは１以上１０以下の整数を表す。）

(In the 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 carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, and p is a numerical value of 10% to 80% by weight. Q represents a numerical value of 20 wt% or more and 90 wt% or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.)

The L is preferably a branched alkylene group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. More preferred is an alkyl group of 3. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by weight.

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

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the (H) surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, and preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin component. More preferred is 0.01 to 1 part by weight.

<(I) Plasticizer>
The photosensitive resin composition of the present invention may contain (I) a plasticizer. Examples of (I) plasticizers include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The addition amount of the (I) plasticizer in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, and preferably 1 to 10 parts by weight with respect to 100 parts by weight of the resin component. More preferred.

<(J) Thermal radical generator>
The photosensitive resin composition of the present invention may contain (J) a thermal radical generator, and contains an ethylenically unsaturated compound such as the aforementioned compound having at least one ethylenically unsaturated double bond. When it does, it is preferable to contain (J) 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. (J) A thermal radical generator may be used individually by 1 type, and can also use 2 or more types together.
The amount of the (J) thermal radical generator added to the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight when the polymer (A) is 100 parts by weight from the viewpoint of improving film properties. 0.1 to 20 parts by weight is more preferable, and 0.5 to 10 parts by weight is most preferable.

<(K) Antioxidant>
The photosensitive resin composition of the present invention may contain (K) an antioxidant. (K) As an antioxidant, a well-known antioxidant can be contained. (K) By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, 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.

(K) The content of the antioxidant is preferably 0.1 to 6% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 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 can be improved.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

<(L) Crosslinking agent>
It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent (L) as needed. Examples of the crosslinking agent (L) include a compound having two or more epoxy 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. Can be added. By adding the crosslinking agent (L), the cured film can be made stronger. The following can be added as a crosslinking agent.

<Compound having two or more epoxy groups in the molecule>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.
These are available as commercial products. For example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1051, EPICLON1051 DIC Co., Ltd.), etc., as bisphenol F type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Corporation) )), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.), etc. As the enol novolac type epoxy resin, JER152, JER154, JER157S65, JER157S70 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC) (Corporation) etc., as cresol novolac type epoxy resins, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (Above, manufactured by DIC Corporation), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.), etc., as an aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP- 4085S, EP-4088S (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, manufactured by Daicel Chemical Industries, Ltd.), etc. Can be mentioned. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation) and the like can be mentioned. These can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, phenol novolak type epoxy resin, and cresol novolak type epoxy resin are preferable. In particular, bisphenol A type epoxy resin, phenol novolac type epoxy resin, and aliphatic epoxy resin are preferable.

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

  The addition amount of the compound having an epoxy group or oxetanyl group to the photosensitive resin composition is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, when the total amount of the resin components is 100 parts by weight.

<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 crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferable crosslinkable compounds, 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 0.05 to 50 parts by weight with respect to 100 parts by weight of the resin component. Preferably, it is 0.5 to 10 parts by weight. 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 the monofunctional (meth) acrylate 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 tri- 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 proportion 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 weight or less, based on 100 parts by weight of the resin component, and 30 parts by weight. 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 a thermal radical generator (J).

  The positive photosensitive resin composition of the present invention contains at least the photoacid generator (B) in a range of 0.1% by mass to 10% by mass in terms of mass, based on the total solid content, and a resin ( It is preferable that A) is contained in the range of 40 mass% to 95 mass% in total. Furthermore, the resin (A) is included in the range of 40% by mass to 95% by mass in total with respect to the total solid content, the photoacid generator (B) is included in the range of 0.1% by mass to 10% by mass, and More preferably, the crosslinking agent (D) is contained in the range of 3 to 40% by mass.

<Sensitizer>
The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with the photoacid generator (B). The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.

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

(Method for forming cured film)
Next, the formation method of the cured film of this invention is demonstrated.
The method for forming a cured film of the present invention includes the following steps (1) to (5).
(1) Step of applying the photosensitive resin composition of the present invention on a substrate (2) Step of removing a solvent from the applied photosensitive resin composition (3) Step of exposing with actinic rays (4) Aqueous developer (5) Thermal curing process (post-baking process)
Each step will be described below in order.

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

If a step of irradiating the entire surface with actinic rays is added before the heating step, the crosslinking reaction can be promoted by an acid generated by the irradiation of actinic rays.
Next, a method for forming a cured film using the positive photosensitive resin composition of the present invention will be specifically described.
In the solvent removing step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry film on the substrate.

In the exposing step (3), the obtained coating film is irradiated with an actinic ray having a wavelength of 300 nm to 450 nm. In this step, (B) the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the component (A) is hydrolyzed to produce a carboxy group or a phenolic hydroxyl group. When the obtained film is irradiated with actinic rays, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid dissociable group in the structural unit represented by the general formula (A2 ′) contained in the resin (A) is dissociated by a hydrolysis reaction, and a carboxyl group is generated. Next, by developing using an alkaline developer, an exposed portion containing a resin having a carboxyl group that is easily dissolved in the alkaline developer is removed, and a positive image is formed.
The reaction formula of this hydrolysis reaction is shown below.

  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 or a phenolic hydroxyl group from an acid-decomposable group.

The acid-decomposable group in the monomer unit represented by the formula (1) in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to a carboxy group or a phenolic hydroxyl group. Therefore, a positive image can be formed by development without necessarily performing PEB.
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), a copolymer having a liberated carboxy group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxy group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
In the post-baking step of (5), the obtained positive image is heated, whereby the acid-decomposable group in the monomer unit (a1) is thermally decomposed to generate a carboxy group or a phenolic hydroxyl group, and the monomer unit (a2 ), 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.
When a step of irradiating the entire surface with actinic rays, preferably ultraviolet rays, is added before the post-baking step, the crosslinking reaction can be promoted by an acid generated by actinic ray irradiation.
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>
Various components are mixed in a predetermined ratio and in an arbitrary method, and dissolved by stirring to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which each component is 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.

<Application process and 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 decompression 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. The application 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. Manufacturing with a large substrate is preferable because of high productivity. Here, the large substrate means a substrate having a side of 1 m or more on each side.

  In addition, (2) the heating condition of the solvent removal step is a range in which the acid-decomposable group is decomposed in the monomer unit (a1) in the resin component in the unexposed area and the resin component is not soluble in the alkali developer. Although it differs depending on the type and mixing ratio of each component, it is preferably about 80 to 130 ° C. for 30 to 120 seconds.

<Exposure process and development process (pattern formation method)>
In the exposure step, the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. After the exposure step, heat treatment (PEB) is performed as necessary, and then in the development step, the exposed area is removed using an alkaline developer to form an image pattern.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used, and g-line (436 nm), i-line (365 nm), h-line (405 nm). Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.

  The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the development 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.

<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 the resin component, to generate a carboxy group or a phenolic hydroxyl group, and to react with the crosslinkable group to crosslink, thereby heat resistance. It is possible to form a protective film and an interlayer insulating film having excellent properties and hardness. 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 is formed is re-exposed with actinic rays and then post-baked (re-exposure / post-bake) to generate an acid from the component (B) present in the unexposed portion, thereby crosslinking. It is preferable to function as a catalyst that accelerates the process.
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 .

With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
The organic EL display device or liquid crystal display device of the present invention is not particularly limited except that it has a flattening film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and has various structures. Various known organic EL display devices and liquid crystal display devices can be used.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, but can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.

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

  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.

Specific examples of the TFT (Thin-Film Transistor) included in the organic EL display device and the liquid crystal display device of the present invention include amorphous silicon-TFT, silicon low-temperature polysilicon TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, the liquid crystal display device that can be taken by the liquid crystal display device of the present invention includes a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, and an OCB. (Optical Compensated Bend) method and the like.
Specific examples of the alignment method of the liquid crystal alignment film that can be taken by the liquid crystal display device of the present invention include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.

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

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

(A3-1) to (a3-3), (a3-5) to (a3-7), (a3-9), (a3-10), (a3-14), (a3-16) The following compounds

<Synthesis of Polymer C-2>
Diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Co., Ltd., Hisolv EDM, 36 g) was added to a three-necked flask as a solvent, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. Glycidyl methacrylate 34.7 g (244 mmol), methyl methacrylate 1.63 g (16.3 mmol), light acrylate HO-a-HH (manufactured by Kyoeisha, 7.04 g, 26.06 mmol), styrene 4.07 g (39.08 mmol) The mixed solution was heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, a mixed solution of radical polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 3.64 g) and diethylene glycol ethyl methyl ether (35.6 g) was added dropwise over 2.5 hours. did. After completion of the dropwise addition, reaction was carried out at 70 ° C. for 5 hours to obtain a diethylene glycol ethyl methyl ether solution of binder a-1 (solid content concentration: 40% by weight). The obtained binder C-2 had a weight average molecular weight of 9,000.

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

<Synthesis of Polymer A-1>
Diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Industry, Hisolv EDM, 43 g) was placed in a three-necked flask, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. In the solution, as monomer components, 1-ethoxyethyl methacrylate (MAEVE, 20.61 g), n-butoxymethylacrylamide (NBMA, manufactured by Tokyo Chemical Industry, 14.58 g), light acrylate HO-a-HH (Kyoeisha) 19.81 g), styrene (St, manufactured by Wako Pure Chemical Industries, 3.39 g), and dimethyl 2,2′-azobis (2-methylpropionate) (V-601, Wako Pure) as a polymerization initiator. Yakuhin Kogyo Co., Ltd., 6.00 g, 8 mol% with respect to the monomer) and diethylene glycol ethyl methyl ether (Toho Chemical Industries, Hisolv EDM, 43 g) were dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours. V-601 (1.5 g, 2 mol% with respect to the monomer) was further added to the solution, and the mixture was further stirred for 2 hours to complete the reaction. Thereby, binder A-1 was obtained. The weight average molecular weight was 16000.
Monomer type etc. were changed as shown in the following table | surface, and polymer A-2-24, A'-1-5, and C-1, C-3-5 were synthesize | combined similarly.

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

[Examples 2-36, Comparative Examples 1-5]
It adjusted similarly to Example 1 except having changed each compound used in Example 1 into the compound of Tables 4-7.

The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
B-1: PAG-103 (manufactured by BASF)

B-2: PAI-101 (Ciba Specialty Chemicals)
B-3: Structure shown below (synthesis examples will be described later)
B-4: Structure shown below (synthesis examples will be described later)

<Synthesis of B-3>
The compound (α- (methylsulfonyloxyimino) -2-phenylacetonitrile) shown as B-3 was synthesized as follows.
[Synthesis of α- (hydroxyimino) -2-phenylacetonitrile]
5.85 g of phenylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with 50 ml of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), placed in an ice bath, and the reaction solution was cooled to 5 ° C. or lower. Next, 11.6 g of SM-28 (sodium methoxide 28% methanol solution, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was allowed to react with stirring for 30 minutes in an ice bath. Next, 7.03 g of isopentyl nitrite (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while maintaining the internal temperature at 20 ° C. or less, and the reaction solution was reacted at room temperature for 1 hour after the completion of the addition. The obtained reaction solution was poured into 150 mL of water in which 1 g of sodium hydroxide was dissolved to completely dissolve it, and then 100 ml of ethyl acetate was added and separated to obtain about 180 ml of an aqueous layer having a target product. Further, 100 ml of ethyl acetate was added again, the aqueous layer was acidified with concentrated hydrochloric acid to pH 3 or lower, and the product was extracted and concentrated. When the obtained crude crystals were washed with hexane, 4.6 g of α- (hydroxyimino) -2-phenylacetonitrile was obtained in a yield of 63%.

[Synthesis of α- (methylsulfonyloxyimino) -2-phenylacetonitrile (Compound B-3)]
11.5 g of α- (hydroxyimino) -2-phenylacetonitrile was dissolved in 100 ml of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), placed in an ice bath, and the reaction solution was cooled to 5 ° C. or lower. Next, 9.9 g of methanesulfonyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, then 9.55 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise while maintaining the internal temperature at 20 ° C. or lower, and the mixture was stirred for 1 hour in an ice bath. Reacted.
The obtained reaction solution was dropped into 500 mL of water and stirred at room temperature for 1 hour. When the obtained powdery precipitate was filtered and dried, 16 g of α- (methylsulfonyloxyimino) -2-phenylacetonitrile (Compound B-5) was obtained with a yield of 90%. The H-NMR spectrum of this compound showed that the product was a mixture of oxime structural isomers (syn / anti), and the abundance ratio was syn: anti = 25/75.

<Synthesis of B-4>
Α- (p-Toluenesulfonyloxyimino) phenylacetonitrile (Compound B-4) was synthesized according to the method described in paragraph No. [0108] of JP-T-2002-528451.

B-5: Structure shown below (synthesis examples will be described later)
B-6: Structure shown below (synthesis examples will be described later)
B-7: Structure shown below (Synthesis examples will be described later)
B-8: Structure shown below (synthesis examples will be described later)

<Synthesis of B-5>
1-1. Synthesis of Synthetic Intermediate B-5A 2-Aminobenzenethiol: 31.3 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in toluene: 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C.). . Next, 40.6 g of phenylacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour and then at 100 ° C. for 2 hours to cause a reaction. 500 mL of water was added to the resulting reaction solution to dissolve the precipitated salt, the toluene oil was extracted, and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B-5A.

1-2. Synthesis of B-5 2.25 g of the synthetic intermediate B-5A obtained as described above was mixed with tetrahydrofuran (10 mL) (manufactured by Wako Pure Chemical Industries, Ltd.), and then placed in an ice bath and the reaction solution was placed at 5 ° C. Cooled to: Next, tetramethylammonium hydroxide: 4.37 g (25% by mass methanol solution, manufactured by Alfa Acer) was added dropwise to the reaction solution, and the mixture was stirred for 0.5 hour in an ice bath for reaction. Furthermore, 7.03 g of isopentyl nitrite: was dropped while maintaining the internal temperature at 20 ° C. or lower, and after completion of the dropping, the reaction solution was warmed to room temperature and stirred for 1 hour.
Subsequently, after cooling the reaction liquid to 5 ° C. or lower, p-toluenesulfonyl chloride (1.9 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirred for 1 hour while maintaining 10 ° C. or lower. Thereafter, 80 mL of water was added and stirred at 0 ° C. for 1 hour. After filtration of the resulting precipitate, 60 mL of isopropyl alcohol (IPA) was added, heated to 50 ° C., stirred for 1 hour, filtered while hot, and dried to obtain B-5 (the aforementioned structure). 8 g was obtained.
¹ H-NMR spectrum (300 MHz, deuterated DMSO ((D ₃ C) ₂ S═O)) of the obtained B-5 is δ = 8.2 to 8.17 (m, 1H), 8.03 to It was 8.00 (m, 1H), 7.95 to 7.9 (m, 2H), 7.6 to 7.45 (m, 9H), 2.45 (s, 3H).
From the above ¹ H-NMR measurement results, it is estimated that the obtained B-5 is a single geometric isomer.

<Synthesis of B-6>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, then reslurried with methanol (20 mL), filtered and dried to obtain 2.3 g of B-6 (the above-mentioned structure).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-6 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

<Synthesis of B-7>
2-Naphthol (20 g) is dissolved in N, N-dimethylacetamide (150 mL), potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g) are added and reacted at 100 ° C. for 2 hours. It was. To the reaction solution are added water (300 mL) and ethyl acetate (200 mL), and the mixture is separated. The organic layer is concentrated, and then a 48 mass% aqueous sodium hydroxide solution (23 g), ethanol (50 mL), and water (50 mL) are added. The reaction was performed for 2 hours. The reaction solution was poured into 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid, and then 30 g of polyphosphoric acid was added and reacted at 170 ° C. for 30 minutes. The reaction solution was poured into water (300 mL), and ethyl acetate (300 mL) was added for liquid separation, and the organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).
Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to a suspension of the resulting ketone compound (10.0 g) and methanol (100 mL) for 24 hours. Heated to reflux. After standing to cool, water (150 mL) and ethyl acetate (150 mL) were added for liquid separation, and the organic layer was separated four times with 80 mL of water, concentrated and purified by silica gel column chromatography to obtain an oxime compound (5.8 g). Got.
The obtained oxime (3.1 g) was sulfonated in the same manner as B-6 to obtain 3.2 g of B-7 (the aforementioned structure).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-7 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.5 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (dd, 1H) , 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt, 1H), 1.4 to 1.2 (m, 8H), 0.8 (t, 3H) there were.

<Synthesis of B-8>
B-8 (the aforementioned structure) was synthesized in the same manner as B-6, except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in B-6.
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-8 is δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.7-7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d.1H), 5.6 (q, 1H), 1.7 (D, 3H).

B-9: TPS-1000 (manufactured by Midori Chemical)

  NQD: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfone Condensate of acid chloride (2.0 mol)

E-1: DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Chemical Industries)

E-2: NBCA (Kurokinkasei Co., Ltd.)

F-1: JER157S65 (trade name, phenol novolac type epoxy resin, manufactured by Japan Epoxy Resins Co., Ltd.)
F-2: Nikarac MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)
F-3: EX-111 (Nagase ChemteX Corporation)
F-4: EX-212L (Nagase ChemteX Corporation)
F-5: Kayalad DPHA (Nippon Kayaku Co., Ltd.)

G-1: KBM-403 (trade name, 3-glycidoxypropyltrimethoxysilane, structure shown below, manufactured by Shin-Etsu Chemical Co., Ltd.)

G-2: KBE-403 (trade name, 3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-3: KBE-1003 (trade name, vinyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-4: KBM-502 (trade name, 3-methacryloxypropyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-5: KBM-5103 (trade name, 3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-6: KBM-803 (trade name, 3-mercaptopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-7: KBM-903 (trade name, 3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
H-1: 1,5-diazabicyclo [4.3.0] -5-nonene H-2: triphenylimidazole

H-3: The following structure

I-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula

  I-2: Silicone surfactant SH-8400 (Toray Dow Corning Silicone)

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

<Evaluation of sensitivity>
Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) and then pre-baked on a hot plate at 95 ° C. for 140 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 4.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive composition layer was developed with an alkali developer (0.4 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
By these operations, the optimum i-line exposure (Eopt) when resolving 9 μm line and space at 1: 1 was defined as sensitivity. The evaluation criteria are as follows. 3-5 is a level which is satisfactory practically.
5: Less than 40 mJ / cm ² 4: 40 mJ / cm ² or more and less than 60 mJ / cm ² 3: 60 mJ / cm ² or more and less than 80 mJ / cm ² 2: 80 mJ / cm ² or more and less than 150 mJ / cm ² 1: 150 mJ / cm ² or more

<Evaluation of remaining film ratio>
The film thickness of the unexposed area after development is measured, and the ratio to the film thickness after coating (the film thickness of the unexposed area after development ÷ film thickness after coating × 100 (%)) is obtained to determine the remaining film thickness during development. The film rate was evaluated according to the following criteria.
5: 98% or more 4: 95% or more and less than 98% 3: 90% or more and less than 95% 2: 80% or more and less than 90% 1: less than 80%

<Evaluation of relative dielectric constant>
A photosensitive resin composition solution having a film thickness of 3.0 μm is coated on a bare wafer (N type low resistance) (manufactured by SUMCO) by slit coating and then pre-baked on a hot plate at 90 ° C. for 2 minutes. A physical layer was formed. The obtained photosensitive resin composition was exposed to a cumulative irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² ) with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon, The substrate was heated in an oven at 220 ° C. for 1 hour to obtain a cured film.
With respect to this cured film, the relative dielectric constant was measured at a measurement frequency of 1 MHz using CVmap92A (manufactured by Four Dimensions Inc.) and evaluated according to the following criteria. When this value is small, it can be said that the relative dielectric constant of the cured film is good.
5: Less than 3.5 4: 3.5 or more and less than 3.7 3: 3.7 or more and less than 3.9 2: 3.9 or more and less than 4.2 1: 4.2 or more

  As shown in the table, the photosensitive resin composition of the example contains the repeating unit (a3), so that the photosensitive resin composition layer becomes soft. For this reason, it becomes easy to dissolve in the developer, and exhibits excellent sensitivity, excellent residual film rate, and excellent relative dielectric constant regardless of the substrate and the exposure machine, and also in the shape of the formed pattern. I found it excellent. On the other hand, it turns out that the comparative example which does not contain a repeating unit (a3) is inferior in a sensitivity, a residual film property, and a dielectric constant compared with an Example.

[Example 100]
In Example 100, Example 1 was used except that the photosensitive resin composition of Example 24 was used and the substrate was changed from a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) to a 6-inch silicon wafer. When the sensitivity, the remaining film property, and the relative dielectric constant were evaluated in the same manner as for the photosensitive resin composition, the evaluations were all 5.

[Example 101]
For the solid component similar to Example 100, a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol ethyl methyl ether / 1,3-butylene glycol diacetate = 60/37/3 (weight ratio) was used, and the viscosity was 35 mPa · s. The evaluation was performed in the same manner as in Example 100 except that all the coatings were spin-coated. When the sensitivity, the remaining film property, and the relative dielectric constant were evaluated in the same manner as performed for the photosensitive resin composition of Example 1, the evaluations were all 5.

[Example 102]
Except that the photosensitive resin composition of Example 100 was used, and the exposure machine was changed from a Canon-made PLA-501F exposure machine to a Nikon-made FX-803M (gh-Line stepper). When the sensitivity, the remaining film property, and the relative dielectric constant were evaluated in the same manner as performed for the photosensitive resin composition of Example 1, the evaluations were all 5.

[Example 103]
Example 1 except that the photosensitive resin composition of Example 100 was used, and the exposure machine was changed from a PLA-501F exposure machine manufactured by Canon Inc. to a 355 nm laser exposure machine and subjected to 355 nm laser exposure. The sensitivity was evaluated in the same manner as that performed on the photosensitive resin composition.
As the 355 nm laser exposure machine, “AEGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR. The evaluation was 5. Moreover, when the residual film property and the relative dielectric constant were evaluated in the same manner as performed for the photosensitive resin composition of Example 1, the evaluations were all 5.

[Example 104]
The photosensitive resin composition of Example 1 was used except that the photosensitive resin composition of Example 100 was used and the exposure machine was changed from a Canon-made PLA-501F exposure machine to a UV-LED light source exposure machine. When the sensitivity was evaluated in the same manner as that for the test, the evaluation was 5. Moreover, when the residual film property and the relative dielectric constant were evaluated in the same manner as performed for the photosensitive resin composition of Example 1, the evaluations were all 5.

[Example 200]
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 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 16 on the substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. After irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. 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 at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition of Example 100 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

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

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

[Example 201]
In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 201 was obtained.
That is, using the photosensitive resin composition of Example 100, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarization film 4 of the organic EL display device in Example 200.

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

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter

Claims (13)

(A) (a1) a repeating unit having a residue in which an acid group is protected with an acid-decomposable group, (a2) an oxiranyl group, an oxetanyl group, or —NH—CH ₂ —OR (where R is a carbon number of 1 to 20) A repeating unit having a crosslinkable group selected from (which is an alkyl group), and (a3) the number of atoms of the divalent linking group having a carboxyl group at the end of the side chain and linking the polymer main chain and the carboxyl group is 4 A polymer component containing the above repeating unit in the same or different polymer,
(B) a photoacid generator, and (D) a solvent,
Containing
The divalent linking group includes —CR ¹ ₂ — (R ¹ represents a hydrogen atom or a methyl group), —O—, —O—SO ₂ —, —O—C (O) —, —C (O ) —O—, —S—, —C (O) —, an optionally substituted amino group, an optionally substituted phenylene group, or the following structure (iv) A photosensitive resin composition, which is a group arbitrarily combined.

The photosensitive resin composition according to claim 1, wherein the polymer component (A) has a polymer containing the repeating unit (a2) and the repeating unit (a3). The photosensitive resin composition according to claim 1 or 2, wherein the (A) polymer component has a polymer containing the repeating unit (a1), the repeating unit (a2), and the repeating unit (a3). The photosensitive resin composition according to claim 1, which is a chemically amplified positive photosensitive resin composition. The photosensitive resin composition of any one of Claims 1-4 in which the said repeating unit (a3) contains 1 or more types of repeating units represented by general formula (i)-(iii).

(In the general formulas (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group, or a carbon atom. Represents an alkyl group of 1 to 3, and n represents an integer of 0 to 4.) The photosensitive resin composition according to claim 1, wherein the repeating unit (a1) is a repeating unit represented by the general formula (A2 ′).

(In the general formula (A2 '), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, either one of at least R ¹ and R ² is an alkyl group or an aryl group, R ³ Represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or Represents an arylene group.) The said repeating unit (a2) is a repeating unit represented by General formula (2), The photosensitive resin composition of any one of Claims 1-6.

(In general formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms.) The photosensitive resin composition according to claim 1, wherein the repeating unit (a2) is a repeating unit having an oxiranyl group and / or an oxetanyl group. (1) The process of applying the photosensitive resin composition of any one of Claims 1-8 on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer, and
(5) A method for producing a cured film comprising a step of post-baking to be thermally cured. The method for forming a cured film according to claim 9, comprising a step of exposing the entire surface after the developing step and before the post-baking step. The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-8. The cured film according to claim 11, which is an interlayer insulating film. A liquid crystal display device or an organic EL display device having the cured film according to claim 11.

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