JP2011170305A - Positive photosensitive resin composition, method for forming cured film, cured film, organic el display device, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition from which a cured film excellent in suitability to ITO sputtering, hardness and heat-resistant transparency is obtained, and to provide a method for forming a cured film using the same. <P>SOLUTION: The positive photosensitive resin composition includes (A) a resin having a structural unit having an acid-decomposable group which is decomposed by an acid to thereby generate a carboxyl group or a phenolic hydroxyl group, and a structural unit having a functional group which can form a covalent bond upon reaction with a carboxyl group or a phenolic hydroxyl group, and (B) an acid generator represented by formula (1), wherein R<SB>1</SB>to R<SB>5</SB>each independently represent H, alkyl, alkoxy, amino, acyl, halogen, aryl or heteroaryl, adjacent R<SB>1</SB>to R<SB>5</SB>may link together to form a ring; and X<SP>-</SP>represents a conjugated base. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

An organic EL display device, a liquid crystal display device, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
In addition to the properties of the cured film, such as insulation, solvent resistance, heat resistance, hardness, and indium tin oxide (ITO) sputter suitability, the interlayer insulating film in the display device is desired to have high transparency. Yes. For this reason, an attempt has been made to use an acrylic resin having excellent transparency as a film forming component.
Moreover, regarding the light source for sensitizing the photosensitive resin composition, in addition to the direct drawing method by 355 nm laser light exposure, the conventional g, h, and i-line mixed light source, the i-line-cut g and h-line mixed light source, etc. Attempts have been made to form patterns with various light sources.

  As such a photosensitive resin composition, for example, Patent Document 1 discloses (A) (a) an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (b) a radical polymerizable compound having an epoxy group, and (c A photosensitive resin composition having a resin soluble in an alkaline aqueous solution, which is a copolymer of another radical polymerizable compound, and (B) a radiation sensitive acid generating compound has been proposed.

  Patent Document 2 includes (A) a high molecular weight polymer having an acetal structure and / or a ketal structure, and an epoxy structure, and having a polystyrene-equivalent weight average molecular weight of 2,000 or more measured by gel permeation chromatography, In addition, a radiation-sensitive resin composition containing (B) a compound that generates an acid having a pKa of 4.0 or less upon irradiation with radiation has been proposed.

  Patent Document 3 contains (A) a structural unit represented by the following general formula (1) having an acid-dissociable group and a structural unit having a functional group that can react with a carboxyl group to form a covalent bond. And at least a resin that is insoluble or hardly soluble in alkali and becomes alkali-soluble when the acid-dissociable group is dissociated, and (B) a compound that generates an acid upon irradiation with actinic rays or radiation. A positive photosensitive resin composition is described.

In the general formula (1), R ¹ represents a hydrogen atom, a methyl group, a halogen atom or a cyano group. R ² and R ³ each independently represents a hydrogen atom, a linear or branched alkyl group, or a cycloalkyl group. However, at least one of R ² and R ³ represents a linear or branched alkyl group or a cycloalkyl group. R ⁴ represents a linear or branched alkyl group, cycloalkyl group, or aralkyl group which may be substituted. R ² or R ³ and R ⁴ may be linked to form a cyclic ether.

On the other hand, a microlens having a lens diameter of about 3 to 100 μm or an optical system material of an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state image sensor, or the like is defined as an optical system material. An array of microlenses is used.
To form a microlens or a microlens array, a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment and used as a lens as it is, or by using the melt-flowed lens pattern as a mask. A method of transferring a lens shape to a base by etching is known. For the formation of the lens pattern, a radiation sensitive resin composition is widely used (see, for example, Patent Document 4 and Patent Document 5).

JP-A-5-165214 Japanese Patent No. 4207604 JP 2009-98616 A JP-A-6-18702 JP-A-6-136239

  By the way, the element on which the microlens or the microlens array as described above is formed is then applied with a planarizing film and an etching resist film in order to remove various insulating films on the bonding pad which is a wiring forming portion. Exposure and development are performed using a desired mask to remove the etching resist in the bonding pad portion, and then the step is performed to remove the planarizing film and various insulating films by etching to expose the bonding pad portion. Therefore, the microlens or the microlens array needs to have solvent resistance and heat resistance in the flattening film and etching resist coating film forming process and the etching process.

The radiation-sensitive resin composition used to form such a microlens is required to have high sensitivity and good storage stability, and the microlens formed therefrom has a desired radius of curvature. It is required to have high heat resistance and high transmittance.
In addition, in the interlayer insulating film and microlens obtained in this way, when the type of exposure light source and the exposure amount fluctuate from the optimum values in the development process when forming them, the developer is placed between the pattern and the substrate. Since penetration and peeling easily occur, it is necessary to strictly control the exposure amount and the like, and there is a problem in terms of product yield.

  As described above, in forming an interlayer insulating film and a microlens from a radiation-sensitive resin composition, the composition is required to have high sensitivity and good storage stability, as well as an exposure light source and an exposure amount. In addition, the interlayer insulating film formed therefrom is required to have high heat resistance, high solvent resistance, low dielectric constant, high transmittance, etc. On the other hand, when forming a microlens, it is good as a microlens A melt shape (desired radius of curvature), high heat resistance, high solvent resistance, and high transmittance are required, but no radiation-sensitive resin composition satisfying such requirements has been known. It was.

The present invention has been made based on the circumstances as described above, and one object thereof is to have high photosensitivity, and even if the type of exposure light source and the exposure amount fluctuate from the optimum values in the exposure process. A cured film with an exposure margin that can form a good pattern shape and excellent sensitivity, ITO sputtering suitability, hardness, heat-resistant transparency, and solvent resistance when used to form an interlayer insulating film. Is to provide. Another object of the present invention is to provide a photosensitive resin composition capable of forming a microlens having a high transmittance and a good melt shape when used for forming a microlens.
Another object of the present invention is a method for forming a cured film and a microlens that can be used for an interlayer insulating film or the like using the photosensitive resin composition, and a cured film and a microlens formed by the method. Is to provide.

The above-mentioned problems of the present invention have been solved by means described in the following <1>, <8>, <9>, <11> or <12>. It describes below with <2>-<7> and <10> which are preferable embodiments.
<1> (Component A) A structural unit having an acid-decomposable group that decomposes with an acid to form a carboxyl group or a phenolic hydroxyl group, and a functional group that can react with the carboxyl group or the phenolic hydroxyl group to form a covalent bond A positive photosensitive resin composition comprising: a resin having a structural unit; and (Component B) an acid generator represented by the following formula (1):

式中、Ｒ₁〜Ｒ₅はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、アミノ基、アシル基、ハロゲン原子、アリール基、又は、ヘテロアリール基を表し、隣接するＲ₁〜Ｒ₅が互いに連結して環を形成してもよく、Ｘ^-は共役塩基を表し、ＰＦ₆ ^-、ＢＦ₄ ^-、ＳｂＦ₆ ^-、Ｒ₆−ＳＯ₃ ^-、及び、Ｒ₇−ＳＯ₂−Ｎ^-−ＳＯ₂−Ｒ₈（スルホンイミドアニオン）よりなる群から選ばれ、Ｒ₆、Ｒ₇、及びＲ₈はアルキル基又はアリール基を表し、Ｒ₇とＲ₈とが互いに連結して環を形成してもよい。

In the formula, R _{1 to} R ₅ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an acyl group, a halogen atom, an aryl group, or a heteroaryl group, and adjacent R _{1 to} R ₅ are They may be linked to each other to form a ring, and X ⁻ represents a conjugate base, and PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , R ₆ —SO ₃ ⁻ , and R ₇ —SO ₂ —N ⁻ —. Selected from the group consisting of SO ₂ —R ₈ (sulfonimide anion), R ₆ , R ₇ , and R ₈ represent an alkyl group or an aryl group, and R ₇ and R ₈ are linked together to form a ring. May be.

<2> (Component C) The positive photosensitive resin composition according to <1>, further containing a sensitizer, <3> The component C is an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a base A positive photosensitive resin composition according to <2>, selected from the group consisting of a styryl derivative and a distyrylbenzene derivative;
<4> The component A further includes a structural unit derived from at least one compound selected from the group consisting of a styrene derivative, a maleimide derivative, (meth) acrylic acid, and a hydroxyl group-containing (meth) acrylate compound, <1 >-<3> positive photosensitive resin composition of any one of the above,
<5> In any one of <1> to <4>, the acid-decomposable group is a group represented by the formula (Ia), the formula (Ib), the formula (IIa), or the formula (IIb). The positive photosensitive resin composition as described,

（式中、Ｒ¹はそれぞれ独立に、アルキル基又はシクロアルキル基を表し、Ｒ²はそれぞれ独立に、アルキル基を表し、Ｒ³は第三級アルキル基又は２−テトラヒドロピラニル基、２−テトラヒドロフラニル基を表し、Ｒ⁴は第三級アルキル基、ｔｅｒｔ−ブトキシカルボニル基又は２−テトラヒドロピラニル基、２−テトラヒドロフラニル基を表し、Ａｒ¹及びＡｒ²はそれぞれ独立に、二価の芳香族基を表し、波線部分は他の構造との結合箇所を表す。）

(In the formula, each R ¹ independently represents an alkyl group or a cycloalkyl group, each R ² independently represents an alkyl group, R ³ represents a tertiary alkyl group or a 2-tetrahydropyranyl group, 2- Represents a tetrahydrofuranyl group, R ⁴ represents a tertiary alkyl group, a tert-butoxycarbonyl group or a 2-tetrahydropyranyl group, a 2-tetrahydrofuranyl group, and Ar ¹ and Ar ² each independently represents a divalent aromatic group. Represents a group, and the wavy line represents a bond with another structure.)

<6> The positive photosensitive resin composition according to any one of <1> to <5>, wherein the functional group is an epoxy group and / or an oxetanyl group.
<7> The positive photosensitive resin composition according to <6>, wherein the functional group is an oxetanyl group,
<8> (Component D) The positive photosensitive resin composition according to any one of <1> to <7>, further containing a solvent,
<9> (1) An application step of applying the positive photosensitive resin composition according to any one of <1> to <8> onto a substrate, (2) an applied positive photosensitive resin composition A cured film comprising: a solvent removing step for removing the solvent from the substrate; (3) an exposure step for exposing with actinic rays; (4) a developing step for developing with an aqueous developer; and (5) a post-baking step for heat curing. Method,
<10> A cured film formed by the method according to <9>,
<11> The cured film according to <10>, which is an interlayer insulating film,
<12> An organic EL display device comprising the cured film according to <10> or <11>,
<13> A liquid crystal display device comprising the cured film according to <10> or <11>.

  ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition from which the coating property is favorable and the cured film which is excellent in ITO sputtering suitability, hardness, and heat-resistant transparency is obtained, and a cured film formation method using the same are provided. I was able to.

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.

(Positive photosensitive resin composition)
Hereinafter, the positive photosensitive resin composition of the present invention will be described in detail.
The positive photosensitive resin composition of the present invention (hereinafter also simply referred to as “photosensitive resin composition”) has (component A) an acid-decomposable group that decomposes with an acid to generate a carboxyl group or a phenolic hydroxyl group. A resin having a structural unit and a structural unit having a functional group capable of reacting with a carboxyl group or a phenolic hydroxyl group to form a covalent bond, and (Component B) an acid generator represented by the following formula (1); It is characterized by containing.

式中、Ｒ₁〜Ｒ₅はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、アミノ基、アシル基、ハロゲン原子、アリール基、又は、ヘテロアリール基を表し、Ｒ₁〜Ｒ₅の隣接する２つが互いに連結して環を形成してもよく、Ｘ^-は共役塩基を表し、ＰＦ₆ ^-、ＢＦ₄ ^-、ＳｂＦ₆ ^-、Ｒ₆−ＳＯ₃ ^-、及び、Ｒ₇−ＳＯ₂−Ｎ^-−ＳＯ₂−Ｒ₈（スルホンイミドアニオン）よりなる群から選ばれ、Ｒ₆、Ｒ₇、及びＲ₈はアルキル基又はアリール基を表し、Ｒ₇とＲ₈とが互いに連結して環を形成してもよい。

In the formula, R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an acyl group, a halogen atom, an aryl group, or a heteroaryl group, and R _{1 to} R ₅ are adjacent to each other. Two may be linked to each other to form a ring, X ⁻ represents a conjugate base, PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , R ₆ —SO ₃ ⁻ , and R ₇ —SO ₂ —N; ^- is selected from the group consisting of -SO ₂ -R ₈ (sulfonimide anion), R _6, R _7, and R ₈ represents an alkyl group or an aryl group, a ring and R ₇ and R ₈ are mutually It may be formed.

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

(Component A) a structural unit having an acid-decomposable group that decomposes with an acid to produce a carboxyl group or a phenolic hydroxyl group, and a structural unit having a functional group that can react with a carboxyl group or a phenolic hydroxyl group to form a covalent bond; The component A has a functional group capable of reacting with a carboxyl group or a phenolic hydroxyl group to form a covalent bond with a structural unit having an acid-decomposable group that decomposes with an acid to produce a carboxyl group or a phenolic hydroxyl group. A resin having at least a unit.
Component A may have each of the structural units described above alone or in combination of two or more. Component A may have a constituent unit as described later in addition to the constituent units described above.

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

In formula (Ia) and formula (Ib), R ¹ each independently represents an alkyl group or a cycloalkyl group, R ² independently represents an alkyl group, R ³ represents a tertiary alkyl group, 2- Represents a tetrahydropyranyl group or a 2-tetrahydrofuranyl group, R ⁴ represents a tertiary alkyl group, a tert-butoxycarbonyl group, a 2-tetrahydropyranyl group or a 2-tetrahydrofuranyl group, and Ar ¹ and Ar ² each represent Independently, it represents a divalent aromatic group, and a wavy line portion represents a bonding site with another structure.
The alkyl group in R ¹ may be linear or branched.
The number of carbon atoms of the alkyl group in R ¹ is preferably 1-20, more preferably 1-10, and even more preferably 1-7.
Preferred number of carbon atoms of the cycloalkyl group in R ^1, preferably from 3 to 20, more preferably from 3 to 10, and more preferably 5 to 7.
In addition, when these carbon numbers have a substituent, the carbon number of a substituent is also included.

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

In formula (Ia) and formula (Ib), R ² each independently represents an alkyl group.
The alkyl group in R ² may be linear or branched.
The number of carbon atoms of the alkyl group in R ² is preferably 1-20, more preferably 1-10, and even more preferably 1-7.
In addition, when these carbon numbers have a substituent, the carbon number of a substituent is also included.
The alkyl group in R ^2, preferably an alkyl group having 1 to 6 carbon atoms, a methyl group is particularly preferred.

In formula (Ib), Ar ¹ represents a divalent aromatic group and has OCH (OR ¹ ) (R ² ) on the aromatic ring.
The divalent aromatic group in Ar ¹ is not particularly limited, and examples thereof include a phenylene group, a substituted phenylene group, a naphthylene group, and a substituted naphthylene group. A phenylene group or a substituted phenylene group is preferable. A phenylene group is more preferable, and a 1,4-phenylene group is more preferable.
Moreover, the divalent aromatic group in Ar ¹ may have a substituent on the aromatic ring, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, Butyl group, etc.), cycloalkyl group having 3 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxy group, carbon Examples thereof include an alkoxy group of 1 to 10, and these substituents may be further substituted with the above substituents.

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

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

In formula (III), R ⁵ represents an alkyl group or a cycloalkyl group, and a preferred embodiment of R ^{5 is} the same as the preferred embodiment of R ¹ in formula (Ia) and formula (Ib).
In the formula (III), R ⁶ represents a hydrogen atom or a methyl group.
Preferable specific examples of the radical polymerizable monomer used for forming the structural unit represented by the formula (III) include, for example, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl methacrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1-isobutoxyethyl acrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1- ( 2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl methacrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, 1- ( -Cyclohexylethoxy) ethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl methacrylate, 1-benzyloxyethyl acrylate and the like can be mentioned, and particularly preferable ones include 1-ethoxyethyl methacrylate and 1-ethoxyethyl acrylate. These structural units can be used singly or in combination of two or more.

  As the radical polymerizable monomer used for forming the structural unit having an acid-decomposable group, a commercially available one may be used, or one synthesized by a known method may be used. For example, as shown below, it can be synthesized by reacting (meth) acrylic acid with a vinyl ether compound in the presence of an acid catalyst.

Here, R ⁵ and R ⁶ correspond to R ⁵ and R ⁶ in formula (III), respectively.

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

In the formulas (IIa) and (IIb), R ³ represents a tertiary alkyl group, 2-tetrahydropyranyl group, or 2-tetrahydrofuranyl group, R ⁴ represents a tertiary alkyl group, tert-butoxycarbonyl. Represents a group, 2-tetrahydropyranyl group, or 2-tetrahydrofuranyl group, Ar ² represents a divalent aromatic group, and a wavy line portion represents a bonding point with another structure.
The tertiary alkyl group for R ³ and R ⁴ preferably has 4 to 20 carbon atoms, more preferably 4 to 14 carbon atoms, and still more preferably 4 to 8 carbon atoms.
Tertiary alkyl group or 2-tetrahydropyranyl group in R ³ , Tertiary alkyl group in R ⁴ , tert-butoxycarbonyl group, 2-tetrahydropyranyl group, or 2-tetrahydrofuranyl group, divalent in Ar ² Any of these aromatic groups may have a substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms (such as a methyl group, an ethyl group, a propyl group, and a butyl group), and 3 to 3 carbon atoms. 10 cycloalkyl groups, aryl groups having 6 to 10 carbon atoms, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups, hydroxy groups, alkoxy groups having 1 to 10 carbon atoms, and the like. It can be illustrated. These substituents may be further substituted with the above substituents.

The tertiary alkyl group in R ³ and R ⁴ is more preferably at least one selected from the group consisting of groups represented by the following formula (V).
-C (R ⁹ R ¹⁰ R ¹¹ ) (V)
In the formula, R ⁹ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 12 carbon atoms, 3 carbon atoms.
Represents a cycloalkyl group having 12 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and any two of R ⁹ , R ¹⁰ and R ¹¹ are bonded to each other. A ring may be formed together with the carbon atom.

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

R ³ in formula (IIa) is preferably a tertiary alkyl group having 4 to 12 carbon atoms, a 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group, and a third group having 4 to 8 carbon atoms. More preferably, it is a primary alkyl group, 2-tetrahydropyranyl group, or 2-tetrahydrofuranyl group, more preferably t-butyl group, 2-tetrahydropyranyl group, or 2-tetrahydrofuranyl group, t A butyl group or a 2-tetrahydrofuranyl group is particularly preferable.
R ⁴ in formula (IIb) is preferably a tertiary alkyl group having 4 to 12 carbon atoms, a 2-tetrahydropyranyl group, a 2-tetrahydrofuranyl group, or a tert-butoxycarbonyl group. More preferably, it is a 4-12 tertiary alkyl group, a 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group, a t-butyl group, a 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group, It is more preferable that 2-tetrahydropyranyl group or 2-tetrahydrofuranyl group is particularly preferable.
In the formula (IIb), Ar ² represents a divalent aromatic group and has OCH (OR ¹ ) (R ² ) on the aromatic ring.
The preferred embodiment of Ar ² in formula (IIb) is the same as the preferred embodiment of Ar ¹ in formula (IIa).

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

  Among these structures, a particularly preferable structural unit having an acid-decomposable group is a structural unit represented by the following formula (IV).

Represents in Formula (IV), the R ⁷ tertiary alkyl group, 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group, a, R ⁸ represents a hydrogen atom or a methyl group.
In formula (IV), the preferred embodiment of R ^{7 is the same as} the preferred embodiment of R ³ in formula (IIa).
Preferable specific examples of the radical polymerizable monomer used to form the structural unit represented by the formula (IV) include, for example, tert-butyl methacrylate, tert-butyl acrylate, tetrahydro-2H-methacrylate. Pyran-2-yl, tetrahydro-2H-pyran-2-yl acrylate, tetrahydro-2H-furan-2-yl methacrylate, tetrahydro-2H-furan-2-yl acrylate, 2-methyl-2-methacrylate Examples thereof include adamantyl, 2-methyl-2-adamantyl acrylate, 1-methylcyclohexyl methacrylate, 1-methylcyclohexyl acrylate, and tert-butyl methacrylate and tert-butyl acrylate are particularly preferable. These structural units can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit having an acid-decomposable group include the following monomer units.

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

<Constitutional unit having a functional group capable of reacting with a carboxyl group or a phenolic hydroxyl group to form a covalent bond>
Examples of the functional group that can react with a carboxyl group or a phenolic hydroxyl group to form a supply bond include an epoxy group, an oxetanyl group, an acid anhydride group, an acid halide group, and an isocyanate group, and contains such a functional group. It is preferred to synthesize component A using a radical polymerizable monomer. Among these functional groups, an epoxy group and / or an oxetanyl group are preferable.
The structural unit having an epoxy group and / or oxetanyl group is preferably a structural unit having an alicyclic epoxy group and / or oxetanyl group, and more preferably a structural unit having an oxetanyl group.

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

  In the chemical formula relating to the structural unit of component A, the substituents allowed for the alkyl group, cycloalkyl group, aromatic group and the like should be inactive so as not to adversely affect the composition of the present invention or the method for forming a cured film. Any can be used. Specific examples thereof include a lower alkoxy group having 1 to 4 carbon atoms, an acyl group having 2 to 5 carbon atoms, and a chlorine atom.

  Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether Examples include compounds containing an epoxy skeleton That.

Examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, (meth) acrylic acid having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Examples include esters.
Preferred examples of the radical polymerizable monomer include (meth) acrylic acid-1-ethyl-3-oxacyclobutylmethyl.

  Examples of the radical polymerizable monomer used to form a structural unit having an epoxy group and / or an oxetanyl group are a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure. preferable.

  Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and paragraphs 0011 to 0016 of JP 2001-330953 A. (Meth) acrylic acid esters having an oxetanyl group, particularly preferred are (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid (3-ethyloxetane). -3-yl) methyl, most preferred are acrylic acid (3-ethyloxetane-3-yl) methyl and methacrylic acid (3-ethyloxetane-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

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

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

<Other structural units>
The component A may have other structural units other than the structural unit as long as the effects of the present invention are not hindered. Examples of the radical polymerizable monomer that forms other structural units include compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623.
Among these, (meth) acrylic acid esters having an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl acrylate are preferable from the viewpoint of improving electric characteristics.
Component A may have a structural unit derived from at least one compound selected from the group consisting of styrene derivatives, maleimide derivatives, (meth) acrylic acid, and hydroxyl group-containing (meth) acrylate compounds as other structural units. preferable.
As the styrene derivative, styrene, chloromethylstyrene, and acetoxystyrene are preferable.
As the maleimide derivative, N-butylmaleimide and N-cyclohexylmaleimide are preferable.
As the hydroxyl group-containing (meth) acrylate compound, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferable.
0-50 mol% is preferable, as for the content rate of the monomer unit which forms another structural unit in all the monomer units which comprise the component A, 0-45 mol% is more preferable, and 5-40 mol% is especially preferable. By containing in the above ratio, the physical properties of the cured film are improved. The weight average molecular weight of Component A is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. In addition, it is preferable that the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).

Hereinafter, although a preferable thing is illustrated as a component A, this invention is not limited to this.
In addition, it is preferable that the weight average molecular weights of the component A illustrated below are 2,000-50,000.
1-ethoxyethyl methacrylate / tert-butyl methacrylate / glycidyl methacrylate copolymer 1-ethoxyethyl methacrylate / tert-butyl methacrylate / glycidyl methacrylate / methacrylic acid copolymer 1-ethoxyethyl methacrylate / methacrylic acid Tetrahydro-2H-pyran-2-yl / glycidyl methacrylate / methacrylic acid copolymer 1-ethoxyethyl methacrylate / tetrahydro-2H-furan-2-yl methacrylate / glycidyl methacrylate / methacrylic acid copolymer methacrylic acid 1 -Ethoxyethyl / tert-butyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer 1-ethoxyethyl methacrylate / tert-butyl methacrylate / 3,4-epoxycyclohexane methacrylate Silmethyl / methacrylic acid copolymer 1-ethoxyethyl methacrylate / tert-butyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester copolymer 1-ethoxyethyl methacrylate / tert-butyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer 1-ethoxyethyl methacrylate / tert-methacrylic acid Butyl / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / 2-hydroxyethyl methacrylate copolymer 1-ethoxy methacrylate Chillyl / tert-butyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methyl methacrylate copolymer 1-ethoxyethyl methacrylate / tetrahydro-2H methacrylate -Pyran-2-yl / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer 1-ethoxyethyl methacrylate / tetrahydro-2H-furan-2-methacrylate Yl / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer 1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2 methacrylate -Yl / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer 1-ethoxyethyl methacrylate / tetrahydro-2H-furan methacrylate -2-yl / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / 2-hydroxyethyl methacrylate copolymer

1-ethoxyethyl methacrylate / tert-butyl methacrylate / 3,4-epoxycyclohexylmethyl acrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer 1-ethoxyethyl methacrylate / tert-methacrylic acid Butyl / acrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer 1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid (3-Ethyloxetane-3-yl) methyl copolymer 1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid copolymer 1-ethoxyethyl acrylate / tert-butyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester copolymer methacrylic acid 1 -Ethoxyethyl / tert-butyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer 1-ethoxyethyl methacrylate / methacrylic acid 2 -Methyl-2-adamantyl / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer 1-ethoxyethyl methacrylate / 1-methyl methacrylate- 1-cyclohexyl Methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer 1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid (3-ethyloxetane -3-yl) methyl / 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester copolymer 1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-Hydroxybenzoic acid (6-methacryloyloxyhexyl) ester copolymer 1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3 -Methacryloyleo Xylpropyl) ester / methacrylic acid 2-hydroxyethyl copolymer

1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methyl methacrylate copolymer methacrylic acid 1 -Ethoxyethyl / tetrahydro-2H-pyran-2-yl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer Ethoxyethyl / tetrahydro-2H-furan-2-yl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer 1-ethoxy methacrylate Ethyl / meta Tetrahydro-2H-pyran-2-yl acrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer methacryl Acid 1-ethoxyethyl / tetrahydro-2H-furan-2-yl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2- Hydroxyethyl copolymer 1-ethoxyethyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid / 2-hydroxyethyl methacrylate copolymer tetrahydro-2H-furan-2-yl methacrylate / Methacrylic acid (3-ethyl Xetane-3-yl) methyl / methacrylic acid / 2-hydroxyethyl methacrylate copolymer tetrahydro-2H-pyran-2-yl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid / methacrylic acid Acid 2-hydroxyethyl copolymer tetrahydro-2H-furan-2-yl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid / methacrylic acid 2-hydroxyethyl copolymer methacrylate 1- Ethoxyethyl / tert-butyl methacrylate / acrylic acid (3-ethyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer 1-ethoxyethyl methacrylate / tert-methacrylic acid Butyl / acrylic acid (3-d Tyloxetane-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / 2-hydroxyethyl methacrylate copolymer 1- (cyclohexyloxy) ethyl methacrylate / tert-butyl methacrylate / methacrylic acid 3,4-epoxycyclohexylmethyl copolymer 1- (cyclohexyloxy) ethyl methacrylate / tert-butyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / 2-hydroxyethyl methacrylate copolymer 1- (cyclohexyloxy) ethyl methacrylate / tert-butyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl copolymer 1-methacrylic acid 1- Cyclohexyloxy) ethyl / methacrylic acid tert- butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxy propyl) ester / 2-hydroxyethyl methacrylate copolymer

1- (Cyclohexyloxy) ethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2- Hydroxyethyl copolymer 1- (cyclohexyloxy) ethyl methacrylate / tetrahydro-2H-furan-2-yl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / Methacrylic acid 2-hydroxyethyl copolymer 1- (cyclohexyloxy) ethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / methyl (3-ethyloxetane-3-yl) methacrylate / 4 Hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer 1- (cyclohexyloxy) ethyl methacrylate / tetrahydro-2H-furan-2-yl methacrylate / methacrylic acid (3-ethyloxetane -3-yl) methyl-4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester 1-ethoxyethyl ether / 1-ethoxyethyl ether / α-methacrylate of tert-butyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid copolymer 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester 1-Ethoxy of tert-butoxycarbonyl group protected from til-parahydroxystyrene / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid copolymer 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester Protected tert-butyl group of ethyl ether / 4-hydroxyphenyl methacrylate / methacrylic acid (3-ethyloxetane-3-yl) methyl / methacrylic acid copolymer 1-ethoxyethyl methacrylate / styrene / glycidyl methacrylate / methacrylic acid Acid copolymer 1-ethoxyethyl methacrylate / N-cyclohexylmaleimide / glycidyl methacrylate / methacrylic acid copolymer

Component A can be used singly or in combination of two or more.
The content of Component A in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, and preferably 40 to 97% by weight, based on the total solid content of the photosensitive resin composition. More preferably, it is 60 to 95% by weight. When the content is within this range, the pattern formability upon development is good. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
In addition, in the photosensitive resin composition of this invention, you may use together resin other than the component A in the range which does not prevent the effect of this invention. However, the content of the resin other than Component A is preferably smaller than the content of Component A from the viewpoint of developability.

(Component B) Acid generator represented by formula (1) The positive photosensitive resin composition of the present invention contains (Component B) an acid generator (diazonium salt) represented by formula (1).

式中、Ｒ₁〜Ｒ₅はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、アミノ基、アシル基、ハロゲン原子、アリール基、又は、ヘテロアリール基を表し、Ｒ₁〜Ｒ₅の隣接する２つが互いに連結して環を形成してもよく、Ｘ^-は共役塩基を表し、ＰＦ₆ ^-、ＢＦ₄ ^-、ＳｂＦ₆ ^-、Ｒ₆−ＳＯ₃ ^-、及び、Ｒ₇−ＳＯ₂−Ｎ^-−ＳＯ₂−Ｒ₈（スルホンイミドアニオン）よりなる群から選ばれ、Ｒ₆、Ｒ₇、及びＲ₈はアルキル基又はアリール基を表し、Ｒ₇とＲ₈とが互いに連結して環を形成してもよい。

In the formula, R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an acyl group, a halogen atom, an aryl group, or a heteroaryl group, and R _{1 to} R ₅ are adjacent to each other. Two may be linked to each other to form a ring, X ⁻ represents a conjugate base, PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , R ₆ —SO ₃ ⁻ , and R ₇ —SO ₂ —N; ^- is selected from the group consisting of -SO ₂ -R ₈ (sulfonimide anion), R _6, R _7, and R ₈ represents an alkyl group or an aryl group, a ring and R ₇ and R ₈ are mutually It may be formed.

In formula (1), the alkyl group in R _{1 to} R ₅ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms (hereinafter also referred to as “lower alkyl group”). Preferably (for example, methyl group, ethyl group, tert-butyl group), any of them may have a substituent.
In formula (1), as an alkoxy group in R < ₁ > -R < ₅ >, a C1-C10 alkoxy group is preferable, a C1-C4 alkoxy group is more preferable, and all have a substituent. Good.
The amino group in R _{1 to} R ₅ includes a monoalkylamino group and a dialkylamino group in addition to —NH ₂ , and these alkyl groups are preferably lower alkyl groups.
The acyl group in R _{1 to} R ₅ can be an acyl group having 2 to 10 carbon atoms, and includes an alkylcarbonyl group and an arylcarbonyl group.
The halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and is preferably a chlorine atom.

The aryl group for R _{1 to} R ₅ is preferably an aromatic group having 6 to 15 carbon atoms and may have a substituent. Such aromatic groups include phenyl, naphthyl, 4-methoxyphenyl, 4-chlorophenyl, 4-methylphenyl, 4-tertiarybutylphenyl, 4-phenylthiophenyl, 2,4 , 6-trimethylphenyl group, 4-methoxy-1-naphthyl group.
The heteroaryl group in R _{1 to} R ₅ includes O, S or N as a hetero atom, preferably a group having 5 to 15 carbon atoms, and may have a substituent. Examples of such a heteroaryl group include a pyridyl group, a thiophene group, and a thiazole group.
In Formula (1), two adjacent R _{1 to} R ₅ may be linked to each other to form a ring, and when two or more of R _{1 to} R ₅ are alkyl groups, these two or more The alkyl groups are preferably linked to each other to form a ring, and examples of such a ring form include six-membered ring formation by a tetramethylene group.

In Formula (1), X ⁻ represents a conjugate base, and PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , R ₆ —SO ₃ ⁻ , and R ₇ —SO ₂ —N ⁻ —SO ₂ —R ₈ ( R ₆ , R ₇ , and R ₈ may be an alkyl group or an aryl group, and R ₇ and R ₈ may be linked to each other to form a ring.
The alkyl group that R ₆ , R ₇ , and R ₈ can take is preferably a lower alkyl group, and the aryl group is preferably a phenyl group, and any of them may have a substituent. Examples of the ring formed by connecting R ₇ and R ₈ to each other include 6-membered ring formation by a tetramethylene group.

Any of the substituents allowed for the aryl group, alkyl group, and the like in R _{1 to} R ₅ may be any non-active one that does not adversely affect the composition of the present invention or the method for forming a cured film. Specific examples thereof include a lower alkoxy group having 1 to 4 carbon atoms, an acyl group having 2 to 5 carbon atoms, and a chlorine atom.

In the formula (1), the conjugate base represented by X ⁻ is preferably a conjugate base (monoanion) which is an inorganic acid or an organic acid, and is an inorganic acid such as perfluorophosphoric acid or perfluoroboric acid. A conjugate base, a conjugate base of an alkyl sulfonic acid, a conjugate base of an aryl sulfonic acid, or a conjugated base of a bisperfluorosulfonylamide is more preferred, and a conjugate base of an alkyl sulfonic acid or an aryl sulfonic acid is particularly preferred. . As the conjugated base of alkyl sulfonic acid, a conjugated base of 1 to 7 carbon alkyl sulfonic acid or perfluoroalkyl sulfonic acid is preferred, a conjugated base of 1 to 4 carbon atoms is more preferred. Preferable examples include methanesulfonic acid, trifluoromethanesulfonic acid, n-propanesulfonic acid, heptanesulfone, and trifluoromethanesulfonic acid. As the conjugated base of aryl sulfonic acid, a conjugated base having 6 to 10 carbon atoms is more preferable. When expressed in the form of an acid, for example, benzenesulfonic acid, chlorobenzenesulfonic acid, and paratoluenesulfonic acid can be preferably exemplified.

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

式中、Ｙ₁はジアルキルアミノ基、ジアリールアミノ基、アルキルチオ基、又は、アリールチオ基を表し、Ｙ₂はアルコキシ基を表し、Ｒ₆〜Ｒ₈は、それぞれ独立に水素原子、アルキル基又はアルコキシ基を表す。

In the formula, Y ₁ represents a dialkylamino group, a diarylamino group, an alkylthio group, or an arylthio group, Y ₂ represents an alkoxy group, and R _{6 to} R ₈ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group. Represents.

In the formula (2), the above group that Y ₁ may take may further have a substituent. The preferred carbon number range of the above group that Y ₁ can take is 1 to 8 for the alkyl group of the dialkylamino group, 1 to 8 for the alkylthio group, and about the aryl group of the diarylamino group or arylthio group. 6 to 10 and 6 is preferable. The substituent is the same as described above.

The conjugate base represented by X ⁻ in formula (2) has the same meaning as X ⁻ in formula (1), and the preferred range is also the same, and the same specific examples can be exemplified.
Specific examples of component B include the following compounds, but the present invention is not construed as being limited to these specific examples. In the chemical formula, Me represents a methyl group.

(Component C) Sensitizer The positive photosensitive resin composition of the present invention can contain (Component C) a sensitizer as an optional component.
Inclusion of a sensitizer is effective for improving exposure sensitivity, and component B is particularly effective when the exposure light source is a g- or h-line mixed line because the absorption efficiency of visible light is low.
As the sensitizer, anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives, and distyrylbenzene derivatives are preferable.
As anthracene derivatives, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromo Anthracene, 9-chloroanthracene, 9,10-dibromoanthracene, 2-ethylanthracene, and 9,10-dimethoxyanthracene are preferable.
As an acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone and N-ethyl-2-methoxyacridone are preferable.
As the thioxanthone derivative, thioxanthone, diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2-chlorothioxanthone are preferable.
As the coumarin derivative, coumarin-1, coumarin-6H, coumarin-110 and coumarin-102 are preferable.
Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole, and 2- (4-dimethylaminostyryl) naphthothiazole.
Examples of the distyrylbenzene derivative include distyrylbenzene, di (4-methoxystyryl) benzene, and di (3,4,5-trimethoxystyryl) benzene.
Specific examples of the sensitizer include the following. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

  The content of component C in the positive photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight, and preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of component A. More preferred. When the content of component C is 0.1 parts by weight or more, desired sensitivity is easily obtained, and when it is 10 parts by weight or less, the transparency of the coating film is easily secured.

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

  The content of Component D in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, with respect to 100 parts by weight of Component A. More preferably, it is 150 to 1,500 parts by weight.

<Other ingredients>
In the photosensitive resin composition of the present invention, as necessary, (Component E) antioxidant, (Component F) cross-linking agent, (Component G) adhesion improver, and (Component H) are described as optional components as necessary. Basic compounds, (Component I) surfactants, (Component J) plasticizers, and (Component K) thermal radical generators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic Known additives such as suspending agents can be added.

(Component E) Antioxidant The photosensitive resin composition of the present invention preferably contains (Component E) an antioxidant.
Component E can contain a known antioxidant. By adding component E, 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 the heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, a phenolic antioxidant is particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used alone or in combination of two or more.
Examples of commercially available phenolic antioxidants include ADK STAB AO-60 (manufactured by ADEKA Corporation), ADK STAB AO-80 (manufactured by ADEKA Corporation), and Irganox 1098 (manufactured by Ciba Japan Co., Ltd.). It is done.

The content of Component E is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. Particularly preferred is ˜4% by weight. 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.

(Component F) Crosslinking agent The photosensitive resin composition of the present invention preferably contains (Component F) a crosslinking agent.
As a crosslinking agent, for example, 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 are added. be able to. By adding a crosslinking agent, the cured film can be made stronger.

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

  These are available as commercial products. For example, 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 , Manufactured by DIC Corporation), etc., as bisphenol F type epoxy resins, 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, JER157S70 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation) ) Manufactured by EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (or more) , DIC Corporation), EOCN-1020 (Nippon Kayaku Co., Ltd.), etc., as aliphatic epoxy resins, ADEKA RESIN EP-4080S, EP-4085S EP-4088S (above, 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.) and the like. . 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, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolac type epoxy resin. A bisphenol A type epoxy resin is particularly preferable.

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

<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. 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 preferably 0.05 to 50 parts by weight with respect to 100 parts by weight of Component A. 0.5 to 10 parts by weight is more preferable. By adding within this range, preferable alkali solubility during development and excellent solvent resistance of the cured film can be obtained.

<Compound having at least one ethylenically unsaturated double bond>
As the compound having at least one ethylenically unsaturated double bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate is preferably used. be able to.

  Examples of 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, and 30 parts by weight or less with respect to 100 parts by weight of Component A. It is more preferable that By including at least one compound having an ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the insulating film obtained from the photosensitive resin composition of the present invention can be improved. it can. When adding a compound having at least one ethylenically unsaturated double bond, it is preferable to add (Component K) a thermal radical generator.

(Component G) Adhesion improving agent The photosensitive resin composition of the present invention may contain (Component G) an adhesion improving agent.
The adhesion improver that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum, and an insulating film. It is a compound that improves the adhesion. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as an adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known 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.
0.1-20 weight part is preferable with respect to 100 weight part of component A, and, as for content of the component G in the photosensitive resin composition of this invention, 0.5-10 weight part is more preferable.

(Component H) Basic Compound The photosensitive resin composition of the present invention may contain (Component H) a basic compound.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.
Specific examples of the basic compound include the compounds described in paragraphs 0052 to 0056 of JP2009-98616A.

The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. It is preferable to use two kinds of heterocyclic amines in combination.
The content of Component H in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, and preferably 0.005 to 0.2 part by weight with respect to 100 parts by weight of Component A. More preferred.

(Component I) Surfactant The photosensitive resin composition of the present invention may contain (Component I) a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Manufactured by Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.

  In addition, as a surfactant, the structural unit A and the structural unit B represented by the following formula (1) are included, and the 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及びＲ³はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴は水素原子又は炭素数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及びｑは重合比を表す重量百分率であり、ｐは１０重量％以上８０重量％以下の数値を表し、ｑは２０重量％以上９０重量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｎは１以上１０以下の整数を表す。）

(In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, and p is a numerical value of 10% to 80% by weight. Q represents a numerical value of 20 wt% or more and 90 wt% or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.)

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

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The amount of component I added in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight, based on 100 parts by weight of component A. More preferably, it is 01-1 weight part.

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

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

(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) Coating step for applying the positive photosensitive resin composition of the present invention onto a substrate (2) Solvent removal step for removing the solvent from the applied positive photosensitive resin composition (3) Exposure with actinic rays Exposure Step (4) Development Step for Developing with Aqueous Developer (5) Post-Bake Step for Thermal Curing Each step will be described below in order.

In the coating step (1), the positive photosensitive resin composition of the present invention is coated on a substrate to form a wet film containing a solvent.
In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.
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, component B is decomposed and acid is generated. Due to the catalytic action of the generated acid, the acid-decomposable group contained in Component A is hydrolyzed to produce a carboxy group and / or a phenolic hydroxyl group.

In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed as necessary. PEB can promote the formation of a carboxy group from an acid-decomposable group.
The acid-decomposable group in the component A in the present invention has a low activation energy for decomposition by an acid, and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxy group. Therefore, without necessarily performing PEB, A positive image can also be formed by development.
In addition, by performing PEB at a relatively low temperature, hydrolysis of an acid-decomposable group can be promoted without causing a crosslinking reaction. The temperature at which PEB is performed is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 80 ° C. or lower.

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

When a step of irradiating the development pattern with actinic rays, preferably ultraviolet rays, before the post-baking step is added, 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>
For example, the component A to the component C are mixed at a predetermined ratio by an arbitrary method, and dissolved by stirring to prepare a photosensitive resin composition. For example, it is also possible to prepare a resin composition by mixing components A to C in advance in a solution in which each of the components A to C is previously dissolved in a (component D) 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.

<Coating process and solvent removal process>
A desired dry coating film can be formed by applying the resin composition to a predetermined substrate and removing the solvent by reducing pressure and / or heating (pre-baking). As the substrate, for example, in the production of a liquid crystal display element, a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as required, and further a transparent conductive circuit layer can be exemplified. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, the large substrate means a substrate having a side of 1 m or more on each side.

  In addition, (2) the heating conditions in the solvent removal step are ranges in which the acid-decomposable group in component A in the unexposed area is decomposed and component A is not soluble in an alkali developer. Although it depends on the ratio, it is preferably about 80 to 130 ° C. for about 30 to 120 seconds.

<Exposure process>
In the exposure step, the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. After the exposure step, heat treatment (PEB) is performed as necessary.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.
In the case of using a laser, 343 nm and 355 nm are used for a solid (YAG) laser, 351 nm (XeF) is used for an excimer laser, and 375 nm and 405 nm are used for a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoint of stability and cost. The coating can be irradiated with the laser once or a plurality of times.
The energy density per pulse of the laser is preferably 0.1 mJ / cm ² or more and 10,000 mJ / cm ² or less. In order to sufficiently cure the coating film, 0.3 mJ / cm ² or more is more preferable, and 0.5 mJ / cm ² or more is most preferable. cm ² or less is more preferable, and 100 mJ / cm ² or less is most preferable.
The pulse width is preferably 0.1 nsec or more and 30,000 nsec or less. In order to prevent the color coating film from being decomposed due to the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is most preferable. Most preferred is 50 nsec or less.

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

Compared with a mercury lamp, a laser is preferable in that the focus can be easily reduced and a mask for forming a pattern in the exposure process is not necessary and the cost can be reduced.
There are no particular restrictions on the exposure apparatus that can be used in the present invention, but commercially available devices include Calisto (buoy technology), AEGIS (buoy technology), and DF2200G (Dainippon Screen ( Etc.) can be used. Further, devices other than those described above are also 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.

<Development process>
In the development step, the exposed area is removed using a basic developer to form an image pattern. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the developing method may be any of a liquid piling method, a dip method, and the like. After the development, washing with running water is performed for 30 to 90 seconds, and a desired pattern can be formed.

<Post-bake process (crosslinking process)>
For a pattern corresponding to an unexposed area obtained by development, using a heating device such as a hot plate or oven, at a predetermined temperature, for example, 180 to 250 ° C., for a predetermined time, for example, 5-60 minutes on the hot plate, In the case of an oven, heat treatment is performed for 30 to 90 minutes to decompose the acid-decomposable group in component A to generate a carboxy group and / or a phenolic hydroxyl group, which reacts with the functional group in component A. By crosslinking, a protective film and an interlayer insulating film excellent in heat resistance, hardness, etc. can be formed. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.
Prior to the heat treatment, the substrate on which the pattern is formed is re-exposed with actinic rays and then post-baked (re-exposure / post-bake) to generate an acid from component B present in the unexposed portion, thereby performing a crosslinking step. It is preferable to function as a promoting catalyst.
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, It can be used for various uses. For example, in addition to a planarization film and an interlayer insulating film, it can be suitably used for a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, or the like. .

FIG. 1 is a conceptual diagram illustrating an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving 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.

Examples of the present embodiment will be described in detail below, but the present embodiment is not limited to these examples.
(Synthesis example)
<Synthesis of Polymer A-1>
After adding 0.5 parts by weight of phenothiazine to 144.2 parts by weight (2 molar equivalents) of ethyl vinyl ether, and dropping 86.1 parts by weight (1 molar equivalent) of methacrylic acid while cooling the reaction system to 10 ° C. or lower, Stir at room temperature (25 ° C.) for 4 hours. After adding 5.0 parts by weight of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. 5 parts by weight of sodium hydrogen carbonate and 5 parts by weight of sodium sulfate were added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and concentrated under reduced pressure at 40 ° C. or lower. (Bp.) 134.0 parts by weight of 1-ethoxyethyl methacrylate (MAEVE) in a 43 to 45 ° C./7 mmHg fraction was obtained as a colorless oil.

  1-Ethoxyethyl methacrylate (79.1 parts by weight (0.5 molar equivalent)), glycidyl methacrylate (GMA) (71.1 parts by weight (0.5 molar equivalent)) and propylene glycol monomethyl ether acetate ( PGMEA) (125 parts by weight) was heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, a mixed solution of radical polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 10 parts by weight) and PGMEA (100.0 parts by weight) was added dropwise over 2.5 hours. . After completion of the dropwise addition, a PGMEA solution of polymer A-1 (solid content concentration: 40% by weight) was obtained by reacting at 70 ° C. for 4 hours. When the obtained polymer A-1 was measured by gel permeation chromatography (GPC), the weight average molecular weight was 12,000.

<Synthesis of Polymers A-2 to A-10>
The same as the synthesis of polymer A-1, except that the type and amount of monomer used in the synthesis of polymer A-1 and the addition amount of radical polymerization initiator V-65 were changed as described in Table 1. Thus, polymers A-2 to A-10 were respectively synthesized.

In addition, the copolymerization ratio of Table 1 is a molar ratio, and the symbol in Table 1 is as follows.
MAEVE: methacrylate 1-ethoxyethyl MACHVE: methacrylate-1-cyclohexyloxyethyl MATHPE: tetrahydro-2H-pyran-2-yl methacrylate MATHF: tetrahydrofuran-2-yl methacrylate GMA: glycidyl methacrylate PGMEA: propylene glycol monomethyl Ether acetate OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (Osaka Organic Chemical Co., Ltd.)
MAA: methacrylic acid HEMA: methacrylic acid-2-hydroxyethyl St: styrene CHMI: N-cyclohexylmaleimide MACHVE, MATPE, and MATHF are the vinyl ethers of the MAEVE synthesis method, respectively, cyclohexyl vinyl ether, dihydrohydropyran, 2,3- It was changed to dihydrofuran and synthesized.

<Example>
(1) Preparation of photosensitive resin composition solution After mixing the components shown in Table 2 below to obtain a uniform solution, the solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm, The photosensitive resin composition solution of Examples 1-21 and Comparative Examples 1-4 was prepared, respectively.

In Table 2, each compound corresponds to the following abbreviations.
D1: Propylene glycol monomethyl ether acetate (PGMEA)
D2: Diethylene glycol ethyl methyl ether E1: ADK STAB AO-60 (manufactured by ADEKA)
F1: JER-157S70 (polyfunctional novolac type epoxy resin (epoxy equivalent: 200 to 220 g / eq), manufactured by Japan Epoxy Resins Co., Ltd.)
Basic compound 1: 4-dimethylaminopyridine Basic compound 2: 1,5-diazabicyclo [4.3.0] -5-nonene Adhesion improver 1: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Surfactant 1: Megafac R-08 (perfluoroalkyl group-containing nonionic surfactant, manufactured by DIC Corporation)
Surfactant 2: The following

Basic compound 1: 4-dimethylaminopyridine Basic compound 2: 1,5-diazabicyclo [4.3.0] -5-nonene Adhesion improver 1: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)

  In addition, the following compounds were used as sensitizers.

(2) Evaluation of sensitivity <g, h, i-line exposure (exposure source 1)>
A photosensitive resin composition solution was slit-coated on a silicon wafer having a silicon oxide film, 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.
Next, it exposed through the predetermined | prescribed mask using i line | wire stepper (Canon Co., Ltd. product FPA-3000i5 +).
After the exposure, PEB was performed on a hot plate at 80 ° C. for 60 seconds.
Thereafter, the film was developed with a 0.4 wt% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds and rinsed with ultrapure water for 1 minute. By these operations, the optimum exposure amount (Eopt) when resolving 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 .

<G, h line exposure (exposure source 2)>
A photosensitive resin composition solution was slit-coated on a silicon wafer having a silicon oxide film, 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.
Next, an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) was equipped with an i-line cut filter (g, h-line exposure), and exposed through a predetermined mask.
Then, the same operation as g, h, i line exposure was performed.

<355 nm laser exposure (exposure source 3)>
A photosensitive resin composition solution was slit-coated on a silicon wafer having a silicon oxide film, 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.
Next, a predetermined photomask was set through the coating film at an interval of 150 μm, and a laser with a wavelength of 355 nm was irradiated. In addition, the laser apparatus used "AEGIS" by a buoy technology company (wavelength 355nm, pulse width 6nsec), and the exposure amount measured using "PE10B-V2" by OPHIR.
Then, the same operation as g, h, i line exposure was performed.

(3) Evaluation of exposure dose dependency With respect to the above optimum exposure dose (Eopt), (line width when exposed with an exposure amount of Eopt-10%) and line width when exposed with an exposure amount of Eopt + 10% ) And {(Line width when exposed with an exposure amount of Eopt-10%) − (Line width when exposed with an exposure amount of Eopt + 10%)} is less than 1 μm, “1”, The case of 1 μm or more was designated as “2”. In the case of “1”, it can be said that the exposure dose dependency is good.

<Transmissivity>
A solid cured film was obtained in the same manner except that the substrate was changed to glass, pattern exposure was not performed, and the final heat treatment was changed to 210 ° C. for 30 minutes (film thickness: 3 μm).
The transmittance of the cured film was measured at a wavelength of 400 to 800 nm using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). The minimum transmittance is shown in the table. The minimum transmittance is preferably 90% or more, and more preferably 95% or more.

<ITO sputtering suitability>
A solid cured film was obtained in the same manner except that the substrate was changed to glass, pattern exposure was not performed, and the final heat treatment was changed to 220 ° C. for 90 minutes (film thickness: 3 μm). On this cured film, an ITO transparent electrode was formed by sputtering (manufactured by ULVAC, SIH-3030, sputtering temperature 200 ° C.). The surface of the cured film after sputtering was observed with an optical microscope (500 times) and evaluated according to the following criteria.
3: The surface of the cured film is transparent without any wrinkles 2: The surface of the cured film is not wrinkled, but slightly transparent (allowable range)
1: Slight wrinkles are visible on the surface of the cured film (acceptable range)
0: There is wrinkle generation on the surface of the cured film. When wrinkles are observed on the surface of the cured film after the ITO transparent electrode is formed by sputtering, it is preferable because a decrease in linearity during ITO patterning and short circuit easily occur. Absent. Moreover, since the transparency fall of an ITO sputtered film causes the transmittance | permeability fall, it is unpreferable.

<Surface hardness>
A solid cured film was obtained in the same manner except that the substrate was changed to glass, pattern exposure was not performed, and the final heat treatment was changed to 220 ° C. for 90 minutes (film thickness: 3 μm). The cured film was subjected to a surface hardness test by pencil hardness at a load force of 500 g.
The surface of the cured film after the surface hardness test was observed with an optical microscope (50 times), and the highest pencil hardness at which the surface did not scrape was evaluated as the surface hardness of the film.

  From the above examples, it can be seen that the diazonium salt compound exhibits a higher sensitivity than other initiators even when no sensitizing dye is used in combination, and when a sensitizing dye is used in combination, it can achieve both a very high sensitivity and suitability for ITO sputtering. . Further, since a strong acid species can be selected, it can be seen that the acetal structure is highly decomposable by acid, and it can be developed regardless of which component is used for the binder.

<Creation of organic EL display device>
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 to the organic EL element formed between the TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 13 on the substrate, pre-baking (90 ° C. × 2 minutes) on a hot plate, and then applying high pressure from above the mask. After irradiating i-line (365 nm) with 30 mJ / cm ² (illuminance 20 mW / cm ² ) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. for 60 minutes. The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

  Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. The insulating film 8 was formed by using the photosensitive resin composition of Example 7 by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

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

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

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

Claims (13)

(Component A) a structural unit having an acid-decomposable group that decomposes with an acid to produce a carboxyl group or a phenolic hydroxyl group, and a structural unit having a functional group that can react with a carboxyl group or a phenolic hydroxyl group to form a covalent bond And a resin having
(Component B) A positive photosensitive resin composition comprising an acid generator represented by the following formula (1).

In the formula, R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an acyl group, a halogen atom, an aryl group, or a heteroaryl group, and R _{1 to} R ₅ are adjacent to each other. Two may be linked to each other to form a ring, X ⁻ represents a conjugate base, PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , R ₆ —SO ₃ ⁻ , and R ₇ —SO ₂ —N; ^- is selected from the group consisting of -SO ₂ -R ₈ (sulfonimide anion), R _6, R _7, and R ₈ represents an alkyl group or an aryl group, a ring and R ₇ and R ₈ are mutually It may be formed.   The positive photosensitive resin composition according to claim 1, further comprising (Component C) a sensitizer.   The positive photosensitive resin composition according to claim 2, wherein the component C is selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a base styryl derivative, and a distyrylbenzene derivative.   The component A further comprises a structural unit derived from at least one compound selected from the group consisting of a styrene derivative, a maleimide derivative, (meth) acrylic acid, and a hydroxyl group-containing (meth) acrylate compound. The positive photosensitive resin composition according to any one of the above. The positive photosensitive resin according to any one of claims 1 to 4, wherein the acid-decomposable group is a group represented by the formula (Ia), the formula (Ib), the formula (IIa) or the formula (IIb). Resin composition.

(In the formula, each R ¹ independently represents an alkyl group or a cycloalkyl group, each R ² independently represents an alkyl group, and R ³ represents a tertiary alkyl group, a 2-tetrahydropyranyl group, or 2 -Represents a tetrahydrofuranyl group, R ⁴ represents a tertiary alkyl group, a tert-butoxycarbonyl group, a 2-tetrahydropyranyl group, or a 2-tetrahydrofuranyl group, and Ar ¹ and Ar ² each independently represent a divalent group. (The wavy line represents the bonding site with another structure.)   The positive photosensitive resin composition according to any one of claims 1 to 5, wherein the functional group is an epoxy group and / or an oxetanyl group.   The positive photosensitive resin composition according to claim 6, wherein the functional group is an oxetanyl group.   The positive photosensitive resin composition according to claim 1, further comprising (Component D) a solvent. (1) A coating step of coating the positive photosensitive resin composition according to any one of claims 1 to 8 on a substrate,
(2) a solvent removal step of removing the solvent from the applied positive photosensitive resin composition;
(3) an exposure step of exposing with actinic rays;
(4) a development step of developing with an aqueous developer, and
(5) A method for forming a cured film, comprising a post-baking step of thermosetting.   A cured film formed by the method according to claim 9.   The cured film according to claim 10, which is an interlayer insulating film.   An organic EL display device comprising the cured film according to claim 10.   A liquid crystal display device comprising the cured film according to claim 10.

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