JP2012133211A - Positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition with an excellent swelling ratio.SOLUTION: The positive photosensitive resin composition contains resins (A) and a radiation-sensitive acid generator (B). At least one of the resins (A) contains a crosslinkable group as well as a structural unit (A1) having an acid group protected by an acid-dissociable group, represented by the specified general formula (1).

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, a composition containing a resin containing a structural unit derived from hydroxyvinylnaphthalene and a photoacid generator (Patent Document 2), or a composition containing a resin containing a structural unit derived from hydroxybiphenylene and a photoacid generator (Patent Document 3). )It has been known. However, these compositions have a problem with the swelling rate.

JP 2004-264623 A JP 2007-254495 A JP 2005-8769 A

  The object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a positive photosensitive resin composition having an excellent swelling rate.

（式（１）中、Ａｒはアリーレン基、Ｒ¹は水素原子またはアルキル基を表し、Ｌ¹は２価の連結基を表し、Ｒ²、Ｒ³およびＲ⁴は、それぞれ、水素原子、アルキル基またはシクロアルキル基を表す。Ｒ²とＲ⁴またはＲ³とＲ⁴は、それぞれ、互いに結合して、環構造を形成していてもよい。）
（２）前記樹脂（Ａ）の少なくとも１種が、一般式（１）で表される、酸解離性基により保護された酸基を有する構造単位（Ａ１）を含み、かつ、側鎖に架橋性基（Ａ２）を有する、（１）に記載のポジ型感光性樹脂組成物。
（３）前記樹脂（Ａ）の少なくとも１種が、さらに、酸基（Ａ３）を含む、（１）または（２）に記載のポジ型感光性樹脂組成物。
（４）一般式（１）のＡｒがフェニレン基である、（１）〜（３）のいずれか１項に記載のポジ型感光性樹脂組成物。
（５）一般式（１）のＬ¹が−Ｏ−、−ＣＨ₂−、−Ｓ−、−ＮＨ−、−ＳＯ₂−及びこれらの組み合わせからなる基である、（１）〜（４）のいずれか１項に記載のポジ型感光性樹脂組成物。
（６）架橋性基（Ａ２）が環状エーテル基である、（１）〜（５）のいずれか１項に記載のポジ型感光性樹脂組成物。
（７）架橋性基（Ａ２）がエポキシ基および／またはオキセタン基である、（１）〜（６）のいずれか１項に記載のポジ型感光性樹脂組成物。
（８）感放射線酸発生剤（Ｂ）が、オキシムスルホネート基を有する化合物である、（１）〜（７）のいずれか１項に記載のポジ型感光性樹脂組成物。
（９）前記（Ａ３）酸基が、カルボン酸である（３）〜（８）のいずれか１項に記載のポジ型感光性樹脂組成物。
（１０）前記（Ａ３）酸基が、主鎖構造がスチレン骨格を含む構造単位に含まれている、（３）〜（９）のいずれか１項に記載のポジ型感光性樹脂組成物。
（１１）（１）（１）〜（１０）のいずれか１項に記載の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、及び、
（５）熱硬化する工程、を含む
硬化膜の形成方法。
（１２）前記現像する工程後、熱硬化する工程前に、全面露光する工程を含む、（１１）に記載の硬化膜の形成方法。
（１３）前記露光する工程後に、加熱処理を行わずに、前記現像工程を行う、（１１）または（１２）に記載の硬化膜の形成方法。
（１４）（１）〜（１０）のいずれか１項に記載のポジ型感光性樹脂組成物を基板上に適用し、光および／または熱によって硬化させた硬化膜。
（１５）（１１）〜（１３）のいずれか１項に記載の形成方法により形成された硬化膜。
（１６）層間絶縁膜である（１４）または（１５）に記載の硬化膜。
（１７）（１４）〜（１６）のいずれか１項に記載の硬化膜を具備する液晶表示装置または有機ＥＬ表示装置。
（１８）一般式（１）で表される、酸解離性基により保護された酸基を有する繰返し単位（Ａ１）を含み、かつ、側鎖に架橋性基（Ａ２）とカルボン酸である酸基（Ａ３）を有する樹脂。
一般式（１）

（式（１）中、Ａｒはアリーレン基、Ｒ¹は水素原子またはアルキル基を表し、Ｌ¹は２価の連結基を表し、Ｒ²、Ｒ³およびＲ⁴は、それぞれ、水素原子、アルキル基またはシクロアルキル基を表す。Ｒ²とＲ⁴またはＲ³とＲ⁴は、それぞれ、互いに結合して、環構造を形成していてもよい。） Under such circumstances, as a result of intensive studies by the inventor of the present application, by adopting a resin having a structural unit having a specific styrene skeleton and a crosslinkable group as a resin component, a positive type having an excellent swelling rate The inventors have found that a photosensitive resin composition can be provided, and have completed the present invention.
(1) A positive photosensitive resin composition comprising one or more resins (A) and a radiation-sensitive acid generator (B), wherein at least one of the resins (A) is represented by the general formula (1) And a photosensitive unit containing a structural unit (A1) having an acid group protected by an acid-dissociable group, and the resin composition satisfies the following (1) and / or (2): Resin composition.
(1) The resin (A) containing the structural unit (A1) having an acid group protected by an acid dissociable group represented by the general formula (1) has a crosslinkable group (A2) in the side chain.
(2) Furthermore, the resin which has a crosslinkable group (A2) in a side chain is included.
General formula (1)

(In the formula (1), Ar represents an arylene group, R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a divalent linking group, and R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group, respectively. And R ² and R ⁴ or R ³ and R ⁴ may be bonded to each other to form a ring structure.
(2) At least one kind of the resin (A) includes the structural unit (A1) represented by the general formula (1) and having an acid group protected by an acid dissociable group, and is crosslinked to a side chain. The positive photosensitive resin composition according to (1), which has a functional group (A2).
(3) The positive photosensitive resin composition according to (1) or (2), wherein at least one of the resins (A) further contains an acid group (A3).
(4) The positive photosensitive resin composition according to any one of (1) to (3), wherein Ar in the general formula (1) is a phenylene group.
(5) L ^{1 in the} general formula (1) is a group consisting of —O—, —CH ₂ —, —S—, —NH—, —SO ₂ — and combinations thereof (1) to (4) The positive photosensitive resin composition according to any one of the above.
(6) The positive photosensitive resin composition according to any one of (1) to (5), wherein the crosslinkable group (A2) is a cyclic ether group.
(7) The positive photosensitive resin composition according to any one of (1) to (6), wherein the crosslinkable group (A2) is an epoxy group and / or an oxetane group.
(8) The positive photosensitive resin composition according to any one of (1) to (7), wherein the radiation-sensitive acid generator (B) is a compound having an oxime sulfonate group.
(9) The positive photosensitive resin composition according to any one of (3) to (8), wherein the (A3) acid group is a carboxylic acid.
(10) The positive photosensitive resin composition according to any one of (3) to (9), wherein the (A3) acid group is contained in a structural unit having a main chain structure containing a styrene skeleton.
(11) (1) A step of applying the photosensitive resin composition according to any one of (1) to (10) 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) developing with an aqueous developer, and
(5) A method of forming a cured film including a step of thermosetting.
(12) The method for forming a cured film according to (11), including a step of exposing the entire surface after the step of developing and before the step of thermosetting.
(13) The method for forming a cured film according to (11) or (12), wherein the developing step is performed without performing a heat treatment after the exposing step.
(14) A cured film obtained by applying the positive photosensitive resin composition according to any one of (1) to (10) onto a substrate and curing it by light and / or heat.
(15) A cured film formed by the formation method according to any one of (11) to (13).
(16) The cured film according to (14) or (15), which is an interlayer insulating film.
(17) A liquid crystal display device or an organic EL display device comprising the cured film according to any one of (14) to (16).
(18) An acid represented by the general formula (1), which includes a repeating unit (A1) having an acid group protected by an acid dissociable group, and which is a crosslinkable group (A2) and a carboxylic acid in the side chain Resin having a group (A3).
General formula (1)

(In the formula (1), Ar represents an arylene group, R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a divalent linking group, and R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group, respectively. And R ² and R ⁴ or R ³ and R ⁴ may be bonded to each other to form a ring structure.

  According to the present invention, a positive photosensitive resin composition having an excellent swelling rate can be obtained.

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. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
The organic EL element in the present invention refers to an 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.

The positive photosensitive resin composition used in the present invention contains one or more resins (A) and a radiation-sensitive acid generator (B), and at least one of the resins (A) is represented by the general formula (1). And a structural unit (A1) having an acid group protected by an acid-dissociable group, and satisfying the following (1) or (2).
(1) The resin (A) containing the structural unit (A1) having an acid group protected by an acid dissociable group represented by the general formula (1) has a crosslinkable group (A2) in the side chain ( 2) Further, the resin contains a crosslinkable group (A2) in the side chain. That is, the crosslinkable group (A2) is an acid group protected by an acid dissociable group represented by the general formula (1). It may be contained in the same resin as the structural unit (A1) it has, or may be contained in another resin.
Here, the acid dissociable group represents a functional group capable of dissociating in the presence of an acid.

  The resin (A) used in the present invention includes a structural unit (A1) having an acid group protected by an acid dissociable group, at least one of which is represented by the general formula (1), and at least one of which is A crosslinkable group (A2) is included. In addition to these, the resin (A) preferably further contains an acid group (A3). Further, other structural units may be included. In the present invention, these groups and structural units may be contained only in one kind of resin, or may be contained in any one kind or two or more kinds of two or more kinds of resins. Hereinafter, embodiments of the resin used in the present invention are shown below. However, it goes without saying that the resin used in the present invention is not limited to these.

(Embodiment 1)
The aspect in which the resin containing the structural unit (A1) having an acid group protected by an acid dissociable group represented by the general formula (1) further contains a crosslinkable group (A2).
(Embodiment 2)
The aspect containing resin containing the structural unit (A1) which has the acid group protected by the acid dissociable group represented by General formula (1), and crosslinkable group (A2).
(Embodiment 3)
The aspect in which the resin containing the structural unit (A1) having an acid group protected by an acid dissociable group represented by the general formula (1) further contains a crosslinkable group (A2) and an acid (A3).
(Embodiment 4)
In the first to third embodiments, the resin further includes another structural unit.
(Embodiment 5)
In the first to fourth embodiments, the structural unit (A1) further includes another resin, and the other resin has an acid group protected by an acid-dissociable group, represented by the general formula (1). ), At least one kind of a crosslinkable group (A2) and an acid (A3).
(Embodiment 6)
Embodiments 1 to 4 further include another resin, and the other resin includes at least a crosslinkable group (A2).
(Embodiment 7)
In the embodiment 5 or 6, the other resin further includes another structural unit.
(Embodiment 8)
In the said Embodiment 7, the aspect in which another structural unit contains an acid group.

（式（１）中、Ａｒはアリーレン基、Ｒ¹は水素原子またはアルキル基を表し、Ｌ¹は２価の連結基を表し、Ｒ²、Ｒ³およびＲ⁴は、それぞれ、水素原子、アルキル基またはシクロアルキル基を表す。Ｒ²とＲ⁴またはＲ³とＲ⁴は、それぞれ、互いに結合して、環構造を形成していてもよい。） (A1) Structural unit represented by general formula (1), which has an acid group protected by an acid dissociable group, general formula (1)

(In the formula (1), Ar represents an arylene group, R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a divalent linking group, and R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group, respectively. And R ² and R ⁴ or R ³ and R ⁴ may be bonded to each other to form a ring structure.

In general formula (1), R ¹ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. In the case of a hydrogen atom, the copolymerizability increases, and the swelling rate, the unexposed portion remaining film rate, and the heat-resistant transparency are more easily exhibited.
R ² , R ³ and R ⁴ are preferably a water atom or a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. . R ² and R ⁴ or R ³ and R ⁴ may be bonded to each other to form a ring structure, and in this case, a 5-membered ring or a 6-membered ring is preferable.
L ¹ is preferably a group consisting of —O—, —CH ₂ —, —S—, —NH—, —SO ₂ — and combinations thereof. L ¹ preferably has —CH ₂ — as essential, or a group consisting of only —CH ₂ — or at least one of —O—, —S—, —NH— and —SO ₂ —. A combination is more preferable, and a portion corresponding to L ¹ in the example of the repeating unit represented by the general formula (1) described later is particularly preferable.
Ar is preferably a phenylene group or a naphthalene group, and more preferably a phenylene group.

一般式（１）で表される構成単位を形成するために用いられるラジカル重合性単量体は、市販のものを用いてもよいし、公知の方法で合成したものを用いることもできる。例えば、下記に示すようにビニル安息香酸を酸触媒の存在下でビニルエーテルと反応させることにより合成することができる。

Although the preferable example of a structural unit represented by General formula (1) below is illustrated below, it cannot be overemphasized that this invention is not limited to these.

As the radical polymerizable monomer used for forming the structural unit represented by the general formula (1), a commercially available one may be used, or one synthesized by a known method may be used. For example, as shown below, vinyl benzoic acid can be synthesized by reacting with vinyl ether in the presence of an acid catalyst.

Here, Ar, L ^1, R ^1, R ³ and R ⁴ correspond Ar, to L ^1, R ^1, R ³ and R ⁴ in the general formula (1), R ¹³ and R ^14, -CH (R ¹³ ) (R ¹⁴ ) corresponds to R ² in the general formula (1).
The photosensitive composition of the present invention is applied on a substrate and dried to form a coating film, exposed to light using an actinic ray through a mask, developed using an alkaline developer to form a pattern, necessary The cured film is formed through a process including a step of exposing the entire surface in accordance with the above and a step of heat-treating the obtained pattern, and the structural unit represented by the general formula (1) in the step of the entire surface exposure or heat treatment The acid dissociable group (—C (R ² ) (R ³ ) OR ⁴ ) is dissociated from the resin to form a carboxyl group in the side chain of the resin.
That is, the resin (A) containing the structural unit represented by the general formula (1) is a resin that is insoluble in alkali or hardly soluble in alkali and becomes alkali-soluble when the acid-dissociable group is dissociated.

  The crosslinkable group contained in the resin (A) component of the present invention forms a covalent bond by heat treatment with the carboxyl group generated in the side chain of the resin (A), and crosslinks to form a good cured film. Will form.

  The content of the structural unit represented by the general formula (1) is preferably 5 to 90 mol%, more preferably 10 to 60 mol% of the structural units of all resin components.

Crosslinkable group (A2)
As such a crosslinkable group, for example, a cyclic ether group is preferable, and an epoxy group, an oxetane group and the like can be mentioned, and an epoxy group is particularly preferable.

The crosslinkable group is usually incorporated into the resin as a structural unit having a crosslinkable group. 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 epoxy group and / oxetane group, and the following general formulas (3) to ( The structural unit consisting of the radically polymerizable monomer represented by any one of 5) is more preferable. These compounds can be used alone or in combination of two or more. The molecular weight of the radical polymerizable monomer represented by any one of the general formulas (3) to (5) is preferably 100 to 500, and more preferably 120 to 200.

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 epoxy group include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl acrylate, 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-Vini Vinyl benzyl glycidyl ethers such as 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; Is mentioned. 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 the 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 above-described specific examples of the radical polymerizable monomer containing an epoxy group, wherein the epoxy group is an oxetanyl 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.

  5-80 mol% of the structural unit of all the resin components is preferable, as for the content rate of the structural unit which has a crosslinkable group, 10-70 mol% is more preferable, and 15-60 mol% is further more preferable.

(A3) Acid group The alkali-soluble resin used in the present invention preferably contains an acid group. By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the resin as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the resin, alkali solubility tends to increase.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. .

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

In the resin (A), if necessary, other than the structural unit (A1) represented by the general formula (1), the structural unit having a crosslinkable group (A2), and the structural unit having an acid group (A3) The structural units can be copolymerized. Such structural units include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, α-methyl-acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, Ethyl vinyl benzoate, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, tert-acrylate -Butyl, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate , Benzyl methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, acrylonitrile and the like, and may be used alone or in combination of two or more.
In the present invention, (meth) acrylic resins and styrene resins are particularly preferable.

The total content of these other structural units is preferably 85 mol% or less, more preferably 60 mol% or less in the total repeating units constituting the resin (A).
The molecular weight of the resin (A) is a polystyrene-equivalent weight average molecular weight, and is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000.

  Various methods for synthesizing the resin (A) are known. To give an example, at least one radical polymerizable monomer used to form the structural unit represented by the general formula (1) is given. A radical polymerizable monomer mixture containing a radical polymerizable monomer used to form a monomer and a structural unit having a crosslinkable group is synthesized by polymerizing in an organic solvent using a radical polymerization initiator. be able to.

Radiation sensitive acid generator (B)
The photosensitive resin composition of this invention contains a radiation sensitive acid generator (B). The radiation-sensitive acid 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. Absent. Further, a radiation-sensitive acid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with the sensitizer. It can be preferably used in combination. The radiation-sensitive acid generator used in the present invention is preferably a radiation-sensitive acid generator that generates an acid having a pKa of 4 or less, and more preferably a radiation-sensitive acid generator that generates an acid having a pKa of 3 or less.

  Examples of the radiation-sensitive acid 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 radiation-sensitive acid 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 preferable.

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, R ¹ in formula (OS-1) and formula (OS-2) is a cyano group, or
An embodiment that is an aryl group is more preferable, and an embodiment that is represented by the formula (OS-2) and in which R ¹ is a cyano group, 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 radiation sensitive acid generator (B).

  In the photosensitive resin composition of the present invention, the radiation-sensitive acid 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. More preferably.

Cross-linking agent (C)
It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent (C) as needed. Examples of the crosslinking agent (C) 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 (C), 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, 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 radiation-sensitive acid generator (B) in a range of 0.1% by mass to 10% by mass with respect to the total solid content, and is a resin. It is preferable to contain (A) in the range of 40% by mass to 95% by mass in total. Furthermore, the resin (A) is included in the total amount in the range of 40% to 95% by mass, the radiation-sensitive acid generator (B) is included in the range of 0.1% to 10% by mass, and the total solid content. More preferably, the crosslinking agent (C) is contained in the range of 3 to 40% by mass.

(D) Solvent The photosensitive resin composition of the present invention usually contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which essential components, preferred components, and optional components are dissolved in the solvent (D).
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 Solvents such as benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, 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 an adhesion improver, a basic compound, a surfactant, a plasticizer, a thermal radical generator, an antioxidant, and a thermal acid generator. Known additives such as an agent, an ultraviolet absorber, a thickener, and an organic or inorganic suspending agent can be added.

(E) Adhesion improving agent The photosensitive resin composition of the present invention may contain (E) an adhesion improving agent. 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 this invention may contain the (G) 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), Mega Fuck (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 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 with respect to the coated surface. More preferred is an alkyl group of 3. The sum of p and q (p + 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 (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, such as a compound having at least one ethylenically unsaturated double bond as described above. When it contains an ethylenically unsaturated compound, 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 becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

<Sensitizer>
The photosensitive resin composition of the present invention preferably contains a sensitizer in order to accelerate its decomposition in combination with the radiation-sensitive acid 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 application 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 removal step (1), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry film on the substrate.

In the exposure step (3), the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less. 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 copolymer (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 (1) 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 (a1-1) 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 phenol. Since a positive hydroxyl group is generated, 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 to thermally decompose the acid-decomposable group in the monomer unit (a1) to produce a carboxy group or a phenolic hydroxyl group, and the monomer unit (a2) A cured film can be formed by crosslinking with the crosslinking group. 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 ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.

  The 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.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Synthesis Example 1—Synthesis Example of Monomer Constructing Structural Unit Representing General Formula (1) and having Acid Group Protected by Acid Dissociable Group>
M-1: Synthesis of 4- (4-vinylphenyl) sulfonylbutanoic acid 1-1: ethyl 4- (4-bromophenyl) sulfonylbutyrate Sodium ethoxide in ethanol solution of 4-bromomercaptophenol (18.0 g) (10.2 g) and ethyl 4-bromobutyrate were added, and the mixture was stirred at room temperature for 16 hours. The reaction mixture was concentrated and acidified with dilute hydrochloric acid. Extracted with ethyl acetate, dried over anhydrous sodium sulfate and concentrated. Hexane and ethyl acetate were added to the residue to form a slurry, and then insoluble matters were removed by filtration. The filtrate was concentrated and the residue was dissolved in ethyl acetate (1000 mL), cooled in a water bath and mCPBA (50 g) was added. The reaction mixture was washed with saturated aqueous sodium carbonate solution and dried over sodium sulfate. After concentration, crystals are precipitated by adding hexane in an ice bath. Filtration and drying gave ethyl 4- (4-bromophenyl) sulfonylbutyrate (21.5 g, yield: 64%).

1-2: Synthesis of ethyl 4- (4-vinylphenyl) sulfonylbutyrate Ethyl 4- (4-bromophenyl) sulfonylbutyrate (17.8 g), dichlorobis (triphenylphosphine) palladium (II) under argon atmosphere (0.9 g), lithium chloride (19.2 g) and tributylvinyltin (18.3 mL) were added to a mixture of N, N-dimethylformamide (DMF, 500 mL). After reacting at 90 ° C. for 1 hour, the reaction mixture was cooled and added to an ice-water bath. The mixture was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. After concentration, the residue was purified by column chromatography to obtain a pale yellow liquid (12.1 g, yield: 71%).

Synthesis of 4- (4-vinylphenyl) sulfonylbutanoic acid Ethyl 4- (4-vinylphenyl) sulfonylbutyrate (13.4 g) was dissolved in methanol (10 mL), and 2N aqueous sodium hydroxide solution (40 mL) was added. The reaction mixture was stirred at room temperature for 3 hours. When concentrated, dissolved by adding water and acidified with 3N hydrochloric acid, crystals were obtained. After filtration and washing with water, the mixture was dissolved in a mixed solvent of ethyl acetate and tetrahydrofuran (THF) and dried over anhydrous sodium sulfate. The residue was crystallized from ethyl acetate, filtered and dried to obtain 4- (4-vinylphenyl) sulfonylbutanoic acid M-1 (8.2 g, yield: 68%).

Synthesis of S-19 4- (4-vinylphenyl) sulfonylbutanoic acid M-1 (8.9 g, 0.035 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was cooled to 15 ° C., and camphorsulfonic acid ( 0.16 g, 0.0007 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added. 2-dihydropyran (2.45 g, 0.035 mol, 1.0 equivalent, Wako Pure Chemical Industries, Ltd.) was added dropwise to the solution. After stirring for 1 hour, a saturated aqueous sodium hydrogen carbonate solution (15 mL) was added, and the mixture was extracted with ethyl acetate (30 mL), dried over magnesium sulfate, the insoluble material was filtered, and the filtrate was concentrated under reduced pressure at 40 ° C. or lower to obtain S-19 ( 5.6 g, yield: 49%) was obtained as a colorless oil.

Synthesis of B-7 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. And reacted for 2 hours. 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 50% by weight hydroxylamine aqueous solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (18 mL), and the mixture was heated to reflux for 10 hours. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain B-8 (2.3 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-8 has δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

Synthesis of B-8 2-Naphthol (20 g) was dissolved in N, N-dimethylacetamide (150 mL), and potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g) were added to the mixture at 100 ° C. For 2 hours. 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 48 wt% 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 A-1, and B-9 (3.2 g) was obtained.
The B-9 ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) 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) It was.

Synthesis of B-9 B-10 was synthesized in the same manner as B-8, except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in B-8.
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).

According to the synthesis example of S-19, S-6, S-7, S-12, S-14, S-19, S-25, S-29, and S-34 were also synthesized.

<Synthesis Example 2: Synthesis of Resin>
Synthesis of A-1 High Solve EDM (41.8 g, manufactured by Toho Chemical Industry Co., Ltd.) was placed in a three-necked flask, and the temperature was raised to 70 ° C. in a nitrogen atmosphere. S-19 (19.46 g), methacrylic acid (MAA, 3.44 g, manufactured by Wako Pure Chemical Industries), glycidyl methacrylate (GMA, 7.69 g, manufactured by Wako Pure Chemical Industries), hydroxyethyl methacrylate (HEMA) were added to the solution. 5.21 g, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2,4-dimethylvaleronitrile (V-65, 2.34 g, 5 mol% based on monomer, manufactured by Wako Pure Chemical Industries)) The reaction was completed by stirring for 4 hours after completion of the dropwise addition, whereby Resin A-1 was obtained.

  The following resins were synthesized in the same manner as in the synthesis of Resin A-1, except that each monomer type and the amount used thereof were changed to those shown in the following table.

In the above table, MAEVE represents 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries), StCO ₂ EVE represents 4-vinylphenylcarboxylic acid 1-ethoxyethyl ester, and StCO ₂ CHVE represents 4-vinylphenylcarboxylic. Acid 1-cyclohexyl ethyl ester, StCO ₂ H is styrene carboxylic acid, M-1 is 4- (4-vinylphenyl) sulfonylbutanoic acid, AA is acrylic acid (manufactured by Wako Pure Chemical Industries), ITA is itaconic acid (manufactured by Wako Pure Chemical Industries), PHS is 4-hydroxystyrene, OXE-30 is 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry), NBMA is N-butoxymethylacrylamide (manufactured by Wako Pure Chemical Industries), GAA is glycidyl acrylate (manufactured by Wako Pure Chemical Industries) , M100 represents 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Chemical Industries, Ltd.), and A400 represents 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd.) as OXE-10. Is 3-ethyl-3-oxetanylmethyl acrylate (manufactured by Osaka Organic Chemical Industry), BzMA is benzyl methacrylate (manufactured by Wako Pure Chemical Industries), and DCPM is dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical). ), St is styrene (Wako Pure Chemical Industries), CHMI is N-cyclohexylmaleimide (Wako Pure Chemical Industries), and V-601 is 2,2-azobis (2-methylpropionic acid). Dimethyl (made by Wako Pure Chemical Industries) is shown respectively.

<Adjustment of photosensitive resin composition of Examples and Comparative Examples>
The components shown below were mixed and adjusted with methyl ethyl diglycol (MEDG) so that the solid content concentration was 20% by weight. Filtration was performed using a 0.2 μm polytetrafluoroethylene filter to prepare a positive photosensitive resin composition.

Details of various components used in the above table are as follows.
(Acid generator)
B1: CGI1397 (manufactured by BASF)
B2: CGI1325 (manufactured by BASF)
B3: CGI725 (the following structure, manufactured by BASF)
B4: CGI725 (the following structure, manufactured by BASF)
B5: PAI-1001 (structure shown below, manufactured by Midori Chemical Co., Ltd.)
B6: PAI-101 (the following structure, manufactured by Midori Chemical Co., Ltd.)
B7: Compound having the following structure (synthetic product)
B8: Compound having the following structure (synthetic product)
B9: Compound having the following structure (synthetic product)

(solvent)
C1: Propylene glycol monomethyl ether acetate C2: Diethylene glycol ethyl methyl ether

(Antioxidant)
D1: ADK STAB AO-60 (the following structure, manufactured by ADEKA Corporation)

(Crosslinking agent)
E1: JER-157S70 (polyfunctional novolac type epoxy resin (epoxy equivalent: 200 to 220 g / eq), manufactured by Japan Epoxy Resins Co., Ltd.)
F3: KBM-403 (the following structure, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Surfactant)
H1: Megafax R-08 (perfluoroalkyl group-containing nonionic surfactant, manufactured by DIC Corporation)

(Basic compound)
G1: 4-dimethylaminopyridine G2: 1,5-diazabicyclo [4.3.0] -5-nonene

(Adhesive)
F3: KBM-403 (the following structure, manufactured by Shin-Etsu Chemical Co., Ltd.)
(Sensitizer)
I1: DBA (9,10-dibutoxyanthracene, the following structure, manufactured by Kawasaki Chemical Industry Co., Ltd.)
I2: DEA (9,10-diethoxyanthracene, the following structure, manufactured by Kawasaki Chemical Industry Co., Ltd.)

<Evaluation>
The obtained composition was evaluated as follows.

<Sensitivity>
The sensitivity was obtained by slit-coating the photosensitive resin compositions of Examples and Comparative Examples on a silicon wafer having a silicon oxide film. Then, it prebaked on a hot plate at 95 ° C. for 90 seconds to form a coating film having a thickness of 3 μm.
Next, it exposed through the predetermined | prescribed mask using i line | wire stepper (The Canon Corporation make, FPA-3000i5 +). After the exposure, the resist film was developed with a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 80 seconds and rinsed with ultrapure water for 1 minute. By these operations, the optimum exposure amount when resolving a 10 μm line and space at 1: 1 was defined as sensitivity. It can be said that the sensitivity is high when the exposure dose is lower than 100 mJ / cm ² .
Evaluation was made according to the following criteria.
A: Less than 20 mJ / cm ² B: 20 mJ / cm ² or more and 50 mJ / cm ² or less C: More than 50 mJ / cm ²

<Unexposed film ratio>
The film thickness of the unexposed area after development of the coating film formed in the same manner as the sensitivity evaluation was measured with a stylus type film thickness meter, and the ratio of the remaining film thickness to the initial film thickness measured in the same manner was determined as the remaining film. Rated as a rate. That is, unexposed portion residual film ratio = film thickness after development (unexposed portion) ÷ film thickness before development (unexposed portion) × 100 (unit: 100%). An unexposed portion residual film ratio of 85% or more is in a practical range, which can be said to be favorable.

<Transparency and heat-resistant transparency>
Transparency and heat-resistant transparency were evaluated by slitting the photosensitive resin composition solution on a glass substrate (Corning 1737, manufactured by Corning), prebaking on a hot plate at 95 ° C. for 90 seconds, and a film thickness of 3 μm. The coating film was formed. The obtained coating film is exposed to a cumulative irradiation amount of 200 mJ / cm ² (illuminance: 20 mW / cm ² ) using a PLA-501F manufactured by Canon Inc., an exposure machine (super high pressure mercury lamp), and then The substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film.
The light transmittance of the glass substrate with the cured film thus obtained was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer (150-20 type double beam, manufactured by Hitachi, Ltd.). The evaluation of the transmittance of 400 nm at that time was set as the evaluation of transparency.
The glass substrate with the cured film was further heated at 230 ° C. for 2 hours in an oven, and then the light transmittance was measured in the same manner to evaluate heat-resistant transparency.
If the value of transparency and heat-resistant transparency is 90% or more, it can be said that transparency and heat-resistant transparency are good.

<Evaluation of solvent swelling ratio>
A photosensitive resin composition solution was slit-coated on a glass substrate (Corning 1737, manufactured by Corning) and then pre-baked on a hot plate at 95 ° C. for 90 seconds to form a coating film having a thickness of 3 μm. The obtained coating film was exposed to a cumulative exposure of 200 mJ / cm ² (illuminance: 20 mW / cm ² ) with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon, This substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film.
The cured film was immersed in a solution of monoethanolamine / dimethyl sulfoxide (DMSO) = 70/30 for 6 minutes, the film thickness immediately after the immersion was measured, and the swelling ratio was compared with the film thickness before immersion. Calculated.
Swell ratio (%) = film thickness after immersion (μm) / film thickness before immersion (μm) × 100
When this value is 103% or less, the solvent swelling ratio of the cured film is low and it can be said that the value is good.

<Dry etching resistance (DE resistance)>
After each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thickness, manufactured by Corning), the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to obtain a film thickness of 3. A 0 μm photosensitive resin composition layer was formed.
The obtained photosensitive resin composition layer is made by Canon Inc., PLA-501F exposure machine (ultra-high pressure mercury lamp), and the integrated dose becomes 100 mJ / cm ² (illuminance: 20 mW / cm ² , i-line). Then, this substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film. The cured film was dry-etched using a dry etching apparatus (CDE-80N, manufactured by Shibaura Mechatronics Co., Ltd.) under the following conditions, the film thickness before and after the treatment was measured, and the amount of film reduction by dry etching was calculated. The evaluation criteria are as follows. A to C are practical ranges, and D is not practical.
Etching gas: CF ₄ 50 ml / min
O ₂ 10ml / min Output: 400mW
Etching time: 90 seconds A: Less than 0.2 μm B: 0.2 μm or more and less than 0.4 μm C: 0.4 μm or more and less than 0.8 μm D: 0.8 μm or more

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

The above results are summarized in the following table.

  As is apparent from the above table, by using a resin represented by the general formula (1) having a structural unit having an acid group protected by an acid dissociable group and having a crosslinkable group in the side chain It became possible to reduce the swelling rate. Furthermore, it has become possible to achieve high dry etching resistance by having a structural unit having a styrene skeleton.

(Example 111)
Using the photosensitive resin composition of Example 11, the same evaluation as in Example 11 was performed using a UV-LED light source exposure machine in place of the ultrahigh pressure mercury lamp. As a result, the same result as in Example 11 was obtained.

(Example 112)
Similar to the sensitivity evaluation performed on the photosensitive resin composition of Example 11, except that the photosensitive resin composition of Example 11 was used and the substrate was changed from a silicon wafer to a glass substrate, the sensitivity and the sensitivity were improved. Was evaluated. As a result, the same result as in Example 11 was obtained.

(Example 113)
Example 11 was used except that the photosensitive resin composition of Example 11 was used, and the exposure machine was changed from an exposure machine manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The sensitivity was evaluated in the same manner as the sensitivity evaluation performed on the photosensitive resin composition. As a result, the same result as in Example 11 was obtained.

(Example 114)
The photosensitive resin composition of Example 11 was used except that the photosensitive resin composition of Example 11 was used and the exposure machine was changed from an exposure machine manufactured by Canon Inc. to a 355 nm laser exposure machine and 355 nm laser exposure was performed. Sensitivity and evaluation were performed in the same manner as the sensitivity evaluation performed on the composition. As a result, the same result as in Example 11 was obtained.
As the 355 nm laser exposure machine, “EGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR.

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

(Example 115)
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 flattening layer 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 18 on the substrate, pre-baking (90 ° C. × 2 minutes) on a hot plate, 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 using a resist stripping solution (mixed solution of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. For the insulating film, the photosensitive resin composition of Example 6 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process can be prevented.

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

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

(Example 116)
An organic EL device was produced in the same manner except that the photosensitive resin composition of Example 11 was replaced with the photosensitive resin composition of Example 1 in Example 115. It was found that the organic EL display device had good display characteristics and high reliability.

(Example 117)
An organic EL device was produced in the same manner as in Example 115 except that the photosensitive resin composition of Example 11 was replaced with the photosensitive resin composition of Example 24. It was found that the organic EL display device had good display characteristics and high reliability.

(Example 118)
In the active matrix liquid crystal display device described in FIG. 1 and FIG. 2 of Japanese Patent No. 332003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 118 was obtained.
That is, using the photosensitive resin composition of Example 11, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 115 above.

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

(Example 119)
A liquid crystal display device was produced in the same manner as in Example 118 except that the photosensitive resin composition of Example 11 was replaced with the photosensitive resin composition of Example 1. It was found that the liquid crystal display device had good display characteristics and high reliability.

(Example 120)
A liquid crystal display device was prepared in the same manner as in Example 118 except that the photosensitive resin composition of Example 11 was replaced with the photosensitive resin composition of Example 25. It was found that the liquid crystal display device had 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 (18)

A positive photosensitive resin composition comprising one or more resins (A) and a radiation-sensitive acid generator (B), wherein at least one of the resins (A) is represented by the general formula (1). A positive photosensitive resin composition comprising a structural unit (A1) having an acid group protected by an acid-dissociable group and satisfying the following (1) and / or (2) .
(1) The resin (A) containing the structural unit (A1) having an acid group protected by an acid dissociable group represented by the general formula (1) has a crosslinkable group (A2) in the side chain.
(2) Furthermore, the resin which has a crosslinkable group (A2) in a side chain is included.
General formula (1)

(In the formula (1), Ar represents an arylene group, R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a divalent linking group, and R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group, respectively. And R ² and R ⁴ or R ³ and R ⁴ may be bonded to each other to form a ring structure. At least one of the resins (A) includes a structural unit (A1) having an acid group protected by an acid-dissociable group, represented by the general formula (1), and has a crosslinkable group ( The positive photosensitive resin composition of Claim 1 which has A2). The positive photosensitive resin composition according to claim 1, wherein at least one of the resins (A) further contains an acid group (A3). The positive photosensitive resin composition of any one of Claims 1-3 whose Ar of General formula (1) is a phenylene group. L ¹ in the general formula (1) is _{-O -, - CH 2 -,} - S -, - NH -, - SO 2 - and a group comprising a combination thereof, any one of claims 1-4 The positive photosensitive resin composition described in 1. The positive photosensitive resin composition of any one of Claims 1-5 whose crosslinkable group (A2) is a cyclic ether group. The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the crosslinkable group (A2) is an epoxy group and / or an oxetane group. The positive photosensitive resin composition according to any one of claims 1 to 7, wherein the radiation-sensitive acid generator (B) is a compound having an oxime sulfonate group. The positive photosensitive resin composition according to claim 3, wherein the (A3) acid group is a carboxylic acid. The positive photosensitive resin composition according to any one of claims 3 to 9, wherein the (A3) acid group is contained in a structural unit having a main chain structure containing a styrene skeleton. (1) The process of applying the photosensitive resin composition of any one of Claims 1-10 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) developing with an aqueous developer, and
(5) A method of forming a cured film including a step of thermosetting. The method for forming a cured film according to claim 11, comprising a step of exposing the entire surface after the step of developing and before the step of thermosetting. The method for forming a cured film according to claim 11 or 12, wherein the developing step is performed without performing a heat treatment after the exposing step. The cured film which applied the positive photosensitive resin composition of any one of Claims 1-10 on a board | substrate, and was hardened | cured with light and / or heat. The cured film formed by the formation method of any one of Claims 11-13. The cured film according to claim 14, which is an interlayer insulating film. The liquid crystal display device or organic electroluminescence display which comprises the cured film of any one of Claims 14-16. An acid group (A3) containing a repeating unit (A1) having an acid group protected by an acid-dissociable group represented by the general formula (1) and having a crosslinkable group (A2) and a carboxylic acid in the side chain ).
General formula (1)

(In the formula (1), Ar represents an arylene group, R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a divalent linking group, and R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group, respectively. And R ² and R ⁴ or R ³ and R ⁴ may be bonded to each other to form a ring structure.

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