JP7332076B1 - Photosensitive resin composition for insulating film formation - Google Patents

Abstract

An insulating film comprising a polymer of at least one of polyimide, polyamic acid, and polyamic acid ester, and a solvent, wherein the polymer has a photopolymerizable group, an aromatic group, and an alkyl group having 5 or more carbon atoms. A photosensitive resin composition for forming.

Description

The present invention provides a photosensitive resin composition for forming an insulating film, an insulating film obtained from the composition, a photosensitive resist film using the composition, a method for producing a substrate with a cured relief pattern, and a semiconductor having a cured relief pattern. Regarding the device.

BACKGROUND ART Conventionally, polyimide resins, which have excellent heat resistance, electrical properties and mechanical properties, have been used as insulating materials for electronic parts, passivation films, surface protective films, interlayer insulating films, etc. for semiconductor devices. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern film by thermal imidization treatment by applying, exposing, developing, and curing the precursor. be able to. Such a photosensitive polyimide precursor has the feature of enabling a significant process reduction compared to conventional non-photosensitive polyimide resins.

Patent Literature 1 and Patent Literature 2 propose a photosensitive resin composition containing polyamic acid or polyimide using a diamine having a (meth)acryloyloxy group.
In addition, increasing the film thickness and modulus of elasticity of the passivation film, surface protection film, interlayer insulating film, etc. of the semiconductor device increases the stress, causing the warpage of the semiconductor wafer to increase, resulting in problems during transportation and wafer fixing. may occur. Therefore, development of a polyimide resin with low residual stress is desired. As a method for reducing the residual stress of the polyimide resin, for example, a method of making the polyimide molecular chain into a rigid skeleton in order to bring the thermal expansion coefficient of the polyimide close to the thermal expansion coefficient of the silicon wafer (for example, Patent Document 3). .

JP-A-2000-347404 Japanese translation of PCT publication No. 2012-516927 JP-A-5-295115

2. Description of the Related Art In recent years, in semiconductor devices, the frequency of electrical signals has been increasing due to the need to transmit and process large amounts of information at high speed. Since high-frequency electrical signals are easily attenuated, it is necessary to reduce transmission loss. Therefore, insulating films used in semiconductor devices are required to have a low dielectric loss tangent.

Further, when forming a cured relief pattern, development is performed using a developing solution, and generally an alkaline aqueous solution developing solution or an organic solvent developing solution is used. The photosensitive resin used to obtain the hardened relief pattern is divided into two types: the positive type, in which the photosensitive resin in the exposed areas is dissolved in the developer by exposure and development, leaving the photosensitive resin in the unexposed areas, and the photosensitive resin in the unexposed areas. is dissolved in the developer and the photosensitive resin in the exposed areas remains. In particular, the negative type is inferior to the positive type in resolution, but is easy to form a thick film or a film, and is excellent in reliability. On the other hand, in the case of a negative photosensitive resin containing polyimide, there is a problem that the development time in organic solvent development is long. In addition, when a negative photosensitive resin is used to increase the thickness of the film, it is desirable that the residual stress is low in order to reduce the warpage of the semiconductor wafer.

Accordingly, there is a demand for a photosensitive resin composition for forming an insulating film which has a low dielectric loss tangent in the resulting insulating film, a short development time in organic solvent development, and a low residual stress.
However, the photosensitive resin compositions described in Patent Documents 1 to 3 do not satisfy all of these properties.

In view of the above circumstances, an object of the present invention is to provide a photosensitive resin composition for forming an insulating film having a low dielectric loss tangent in the obtained insulating film, a short development time in organic solvent development, and low residual stress, and the composition. The object of the present invention is to provide an insulating film obtained from , a photosensitive resist film using the composition, a method for producing a substrate with a cured relief pattern, and a semiconductor device having a cured relief pattern.

The inventors of the present invention have made intensive studies to achieve the above problems, and found that the resulting insulating film has a low dielectric loss tangent by containing a specific polymer in the photosensitive resin composition for forming an insulating film. The inventors have found that a photosensitive resin composition for forming an insulating film having a short development time in organic solvent development and a low residual stress can be obtained, thereby completing the present invention.

［式（１－ａ）中、Ａｒ_１は４価の有機基を表す。
式（１－ｂ）中、Ｘは炭素原子数５以上のアルキル基を有する２価の芳香族基を表す。
式（１－ｃ）中、Ｙは光重合性基を有する２価の芳香族基を表す。］

［式（２）中、Ａｒ_２は４価の有機基を表す。］

［式（３－ａ）中、Ａｒ_３は４価の有機基を表し、Ｌ_１、及びＬ_２はそれぞれ独立して光重合性基を有する１価の有機基を表す。
式（３－ｂ）中、Ａｒ_４は４価の有機基を表し、Ｒ_１、及びＲ_２はそれぞれ独立して１価の有機基を表す。］
［３］ 前記式（１－ｂ）中、Ｘが下記式（Ｖ－１）～（Ｖ－６）のいずれかで表される２価の有機基を表す［２］に記載の絶縁膜形成用感光性樹脂組成物。
（式（Ｖ－１）中、Ｘ^ｖ１は、－Ｏ－、－ＣＨ_２－Ｏ－、－ＣＨ_２－ＯＣＯ－、－ＣＯＯ－、又は－ＯＣＯ－を表す。Ｒ^ｖ１は、炭素原子数５～２０のアルキル基を表す。
式（Ｖ－２）～（Ｖ－５）中、Ｘ^ｖ２～Ｘ^ｖ５は、それぞれ独立に、－（ＣＨ_２）_ａ－（ａは１～１５の整数である。）、－ＣＯＮＨ－、－ＮＨＣＯ－、－ＣＯＮ（ＣＨ_３）－、－ＮＨ－、－Ｏ－、－ＣＨ_２－Ｏ－、－ＣＨ_２－ＯＣＯ－、－ＣＯＯ－、又は－ＯＣＯ－を表す。Ｒ^ｖ２～Ｒ^ｖ５は、それぞれ独立に、炭素原子数５～２０のアルキル基を表す。
式（Ｖ－６）中、Ｘ_ａは、単結合、－Ｏ－、－ＮＨ－、－Ｏ－（ＣＨ_２）_ｍ－Ｏ－（ｍは１～６の整数を表す。）、－Ｃ（ＣＨ_３）_２－、－ＣＯ－、－（ＣＨ_２）_ｍ－（ｍは１～６の整数を表す。）、－ＳＯ_２－、－Ｏ－Ｃ（ＣＨ_３）_２－、－ＣＯ－（ＣＨ_２）_ｍ－（ｍは１～６の整数を表す。）、－ＮＨ－（ＣＨ_２）_ｍ－（ｍは１～６の整数を表す。）、－ＳＯ_２－（ＣＨ_２）_ｍ－（ｍは１～６の整数を表す。）、－ＣＯＮＨ－（ＣＨ_２）_ｍ－（ｍは１～６の整数を表す。）、－ＣＯＮＨ－（ＣＨ_２）_ｍ－ＮＨＣＯ－（ｍは１～６の整数を表す。）、－ＣＯＯ－（ＣＨ_２）_ｍ－ＯＣＯ－（ｍは１～６の整数を表す。）、－ＣＯＮＨ－、－ＮＨ－（ＣＨ_２）_ｍ－ＮＨ－（ｍは１～６の整数を表す。）、又は－ＳＯ_２－（ＣＨ_２）_ｍ－ＳＯ_２－（ｍは１～６の整数を表す。）を表す。Ｘ^ｐ１及びＸ^ｐ２は、それぞれ独立に、－（ＣＨ_２）_ａ－（ａは１～１５の整数である。）、－ＣＯＮＨ－、－ＮＨＣＯ－、－ＣＯＮ（ＣＨ_３）－、－ＮＨ－、－Ｏ－、－ＣＨ_２－Ｏ－、－ＣＨ_２－ＯＣＯ－、－ＣＯＯ－、又は－ＯＣＯ－を表す。Ｒ^１ａ及びＲ^１ｂは、それぞれ独立に、炭素原子数５～２０のアルキル基を表す。ｋ１及びｋ２は、それぞれ独立に、０～２の整数を表す。
式（Ｖ－１）～（Ｖ－６）中、＊は結合手を表す。）
［４］ 前記式（１－ｃ）中、Ｙが下記式（９－ａ）で表される２価の有機基を表し、
前記式（３－ａ）中、Ｌ_１及びＬ_２がそれぞれ独立して下記式（９－ｂ）で表される１価の有機基を表す、
［２］又は［３］に記載の絶縁膜形成用感光性樹脂組成物。

［式（９－ａ）中、Ｖ_１は直接結合、エーテル結合、エステル結合、アミド結合、ウレタン結合、又はウレア結合を表し、Ｗ_１は酸素原子又はＮＨ基を表し、Ｒ_１５は直接結合、又は水酸基で置換されていてもよい炭素原子数２～６のアルキレン基を表し、Ｒ_１６は水素原子又はメチル基を表し、＊は結合手を表す。］

［式（９－ｂ）中、Ｗ_２は酸素原子又はＮＨ基を表し、Ｒ_１７は直接結合、又は水酸基で置換されていてもよい炭素原子数２～６のアルキレン基を表し、Ｒ_１８は水素原子又はメチル基を表し、＊は結合手を表す。］
［５］ 前記式（９－ａ）におけるＶ_１がエステル結合を表し、さらにＷ_１が酸素原子を表す［４］に記載の絶縁膜形成用感光性樹脂組成物。
［６］ 前記式（９－ａ）におけるＲ_１５が１，２－エチレン基を表す［４］又は［５］に記載の絶縁膜形成用感光性樹脂組成物。
［７］ さらに光ラジカル重合開始剤を含む［１］から［６］のいずれかに記載の絶縁膜形成用感光性樹脂組成物。
［８］ さらに架橋性化合物を含む［１］から［７］のいずれかに記載の絶縁膜形成用感光性樹脂組成物。
［９］ ネガ型感光性樹脂組成物である［１］から［８］のいずれかに記載の絶縁膜形成用感光性樹脂組成物。
［１０］ ［１］から［９］のいずれかに記載の絶縁膜形成用感光性樹脂組成物の塗布膜の焼成物である絶縁膜。
［１１］ 基材フィルムと、［１］から［９］のいずれかに記載の絶縁膜形成用感光性樹脂組成物から形成される感光性樹脂層と、カバーフィルムとを有する感光性レジストフィルム。
［１２］ （１）［１］から［９］のいずれかに記載の絶縁膜形成用感光性樹脂組成物を基板上に塗布して、感光性樹脂層を該基板上に形成する工程と、
（２）該感光性樹脂層を露光する工程と、
（３）該露光後の感光性樹脂層を現像して、レリーフパターンを形成する工程と、
（４）該レリーフパターンを加熱処理して、硬化レリーフパターンを形成する工程と、
を含む、硬化レリーフパターン付き基板の製造方法。
［１３］ 前記現像に用いられる現像液が有機溶媒である［１２］に記載の硬化レリーフパターン付き基板の製造方法。
［１４］ ［１２］又は［１３］に記載の方法により製造された硬化レリーフパターン付き基板。
［１５］ 半導体素子と該半導体素子の上部又は下部に設けられた硬化膜とを備える半導体装置であって、該硬化膜は［１］から［９］のいずれかに記載の絶縁膜形成用感光性樹脂組成物から形成される硬化レリーフパターンである半導体装置。[1] Containing at least one polymer of polyimide, polyamic acid, and polyamic acid ester, and a solvent,
The polymer has a photopolymerizable group, an aromatic group and an alkyl group having 5 or more carbon atoms,
A photosensitive resin composition for forming an insulating film.
[2] The polyimide is the following polyimide (1),
The polyamic acid is the following polyamic acid (2),
The polyamic acid ester is the following polyamic acid ester (3),
The photosensitive resin composition for forming an insulating film according to [1].
Polyimide (1): A polyimide having structural units represented by the following formulas (1-a), (1-b) and (1-c) below.
Polyamic acid (2): Polyamic acid having structural units represented by the following formula (2), the following formula (1-b), and the following formula (1-c).
Polyamic acid ester (3): at least one of the following polyamic acid esters (3a) to (3b).
Polyamic acid ester (3a): Polyamic acid ester having structural units represented by the following formula (3-a) and the following formula (1-b).
Polyamic acid ester (3b): Polyamic acid ester having structural units represented by the following formula (3-b), the following formula (1-b), and the following formula (1-c).

[In formula (1-a), Ar ₁ represents a tetravalent organic group.
In formula (1-b), X represents a divalent aromatic group having an alkyl group with 5 or more carbon atoms.
In formula (1-c), Y represents a divalent aromatic group having a photopolymerizable group. ]

[In formula (2), Ar ₂ represents a tetravalent organic group. ]

[In formula (3-a), Ar ₃ represents a tetravalent organic group, and L ₁ and L ₂ each independently represent a monovalent organic group having a photopolymerizable group.
In formula (3-b), Ar ₄ represents a tetravalent organic group, and R ₁ and R ₂ each independently represent a monovalent organic group. ]
[3] Insulating film formation according to [2], wherein X in the formula (1-b) represents a divalent organic group represented by any one of the following formulas (V-1) to (V-6) Photosensitive resin composition for
(In formula (V-1), X ^v1 represents -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-. ^{R v1} has 5 carbon atoms. represents an alkyl group of ∼20.
In formulas (V-2) to (V-5), X ^v2 to X ^v5 are each independently -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, - represents NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO- or -OCO-; R ^v2 to R ^v5 each independently represent an alkyl group having 5 to 20 carbon atoms.
In formula (V-6), X _a is a single bond, —O—, —NH—, —O—(CH ₂ ) _m —O— (m represents an integer of 1 to 6), —C( CH ₃ ) ₂ -, -CO-, -(CH ₂ ) _m - (m represents an integer of 1 to 6), -SO ₂ -, -OC(CH ₃ ) ₂ -, -CO-( CH ₂ ) _m — (m represents an integer of 1 to 6), —NH—(CH ₂ ) _m — (m represents an integer of 1 to 6), —SO ₂ —(CH ₂ ) _m — (m represents an integer of 1 to 6), —CONH—(CH ₂ ) _m — (m represents an integer of 1 to 6), —CONH—(CH ₂ ) _m —NHCO— (m is 1 represents an integer of ~6.), -COO-(CH ₂ ) _m -OCO- (m represents an integer of 1 to 6.), -CONH-, -NH-(CH ₂ ) _m -NH-(m represents an integer of 1 to 6), or -SO ₂ -(CH ₂ ) _m -SO ₂ - (m represents an integer of 1 to 6). X ^p1 and X ^p2 each independently represent -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH- , -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-. R ^1a and R ^1b each independently represent an alkyl group having 5 to 20 carbon atoms. k1 and k2 each independently represent an integer of 0 to 2;
In formulas (V-1) to (V-6), * represents a bond. )
[4] In the formula (1-c), Y represents a divalent organic group represented by the following formula (9-a),
In the above formula (3-a), L ₁ and L ₂ each independently represent a monovalent organic group represented by the following formula (9-b),
The photosensitive resin composition for forming an insulating film according to [2] or [3].

[In formula (9-a), V ₁ represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond, W ₁ represents an oxygen atom or an NH group, R ₁₅ represents a direct bond, or represents an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, R ₁₆ represents a hydrogen atom or a methyl group, and * represents a bond. ]

[In the formula (9-b), W ₂ represents an oxygen atom or an NH group, R ₁₇ represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, and R ₁₈ represents represents a hydrogen atom or a methyl group, and * represents a bond. ]
[5] The photosensitive resin composition for forming an insulating film according to [4], wherein V ₁ in formula (9-a) represents an ester bond and W ₁ represents an oxygen atom.
[6] The photosensitive resin composition for forming an insulating film according to [4] or [5], wherein R ₁₅ in formula (9-a) represents a 1,2-ethylene group.
[7] The photosensitive resin composition for forming an insulating film according to any one of [1] to [6], further comprising a photoradical polymerization initiator.
[8] The photosensitive resin composition for forming an insulating film according to any one of [1] to [7], further comprising a crosslinkable compound.
[9] The photosensitive resin composition for forming an insulating film according to any one of [1] to [8], which is a negative photosensitive resin composition.
[10] An insulating film which is a baked product of a coating film of the photosensitive resin composition for forming an insulating film according to any one of [1] to [9].
[11] A photosensitive resist film comprising a substrate film, a photosensitive resin layer formed from the photosensitive resin composition for forming an insulating film according to any one of [1] to [9], and a cover film.
[12] (1) A step of applying the photosensitive resin composition for forming an insulating film according to any one of [1] to [9] onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) heat-treating the relief pattern to form a cured relief pattern;
A method of manufacturing a cured relief patterned substrate, comprising:
[13] The method for producing a cured relief patterned substrate according to [12], wherein the developer used for the development is an organic solvent.
[14] A substrate with a cured relief pattern produced by the method of [12] or [13].
[15] A semiconductor device comprising a semiconductor element and a cured film provided above or below the semiconductor element, wherein the cured film is the photosensitive material for forming an insulating film according to any one of [1] to [9]. A semiconductor device, which is a cured relief pattern formed from a flexible resin composition.

According to the present invention, a photosensitive resin composition for forming an insulating film having a low dielectric loss tangent in the resulting insulating film, a short development time in organic solvent development, and low residual stress, and an insulating film obtained from the composition. , a photosensitive resist film using the composition, a method for producing a substrate with a cured relief pattern, and a semiconductor device having a cured relief pattern are obtained.

(Photosensitive resin composition for insulating film formation)
The photosensitive resin composition for forming an insulating film of the present invention contains at least a polymer and a solvent, and further contains other components as necessary.

<Polymer>
The polymer is at least one of polyimide, polyamic acid, and polyamic acid ester. Hereinafter, the polymer may be referred to as "specific polymer".
Certain polymers have photopolymerizable groups.
Certain polymers have aromatic groups.
Certain polymers have alkyl groups of 5 or more carbon atoms.

The present inventors consider the reason why the effect of the present invention is exhibited by the photosensitive resin composition for forming an insulating film of the present invention is as follows.
Photosensitivity is imparted to the resin composition containing the specific polymer by the specific polymer having a photopolymerizable group.
When the specific polymer has an alkyl group having 5 or more carbon atoms and an aromatic group, the dielectric loss tangent of the insulating film is lowered.
When the specific polymer has an alkyl group having 5 or more carbon atoms and an aromatic group, development time in organic solvent development can be shortened.
Residual stress can be reduced by having a specific polymer having an alkyl group having 5 or more carbon atoms.

As the polyimide, the following polyimide (1) is preferable.
As the polyamic acid, the following polyamic acid (2) is preferable.
As the polyamic acid ester, the following polyamic acid ester (3) is preferable.
Polyimide (1) is a polyimide having structural units represented by the following formulas (1-a), (1-b) and (1-c) below.
The polyamic acid (2) is a polyamic acid having structural units represented by the following formula (2), the following formula (1-b), and the following formula (1-c).
Polyamic acid ester (3) is at least one of the following polyamic acid esters (3a) to (3b).
The polyamic acid ester (3a) is a polyamic acid ester having structural units represented by the following formula (3-a) and the following formula (1-b).
The polyamic acid ester (3b) is a polyamic acid ester having structural units represented by the following formulas (3-b), (1-b) and (1-c) below.

［式（１－ａ）中、Ａｒ_１は４価の有機基を表す。
式（１－ｂ）中、Ｘは炭素原子数５以上のアルキル基を有する２価の芳香族基を表す。
式（１－ｃ）中、Ｙは光重合性基を有する２価の芳香族基を表す。］

[In formula (1-a), Ar ₁ represents a tetravalent organic group.
In formula (1-b), X represents a divalent aromatic group having an alkyl group with 5 or more carbon atoms.
In formula (1-c), Y represents a divalent aromatic group having a photopolymerizable group. ]

［式（２）中、Ａｒ_２は４価の有機基を表す。］

[In formula (2), Ar ₂ represents a tetravalent organic group. ]

［式（３－ａ）中、Ａｒ_３は４価の有機基を表し、Ｌ_１、及びＬ_２はそれぞれ独立して光重合性基を有する１価の有機基を表す。
式（３－ｂ）中、Ａｒ_４は４価の有機基を表し、Ｒ_１、及びＲ_２はそれぞれ独立して１価の有機基を表す。］

[In formula (3-a), Ar ₃ represents a tetravalent organic group, and L ₁ and L ₂ each independently represent a monovalent organic group having a photopolymerizable group.
In formula (3-b), Ar ₄ represents a tetravalent organic group, and R ₁ and R ₂ each independently represent a monovalent organic group. ]

<<Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ >>
Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent a tetravalent organic group.
Although the tetravalent organic group is not particularly limited, a tetravalent organic group having two or more aromatic rings is preferable because the dielectric loss tangent of the insulating film is further lowered.

The number of aromatic rings possessed by the tetravalent organic group having two or more aromatic rings is not particularly limited as long as it is two or more, and may be, for example, four or more. The upper limit of the number of aromatic rings is not particularly limited, but may be, for example, 8 or less, or 6 or less.

Regarding how to count aromatic rings in "two or more aromatic rings", polycyclic aromatic rings formed by condensing two or more aromatic rings such as naphthalene ring and anthracene ring are counted as one aromatic ring. . Therefore, a naphthalene ring is counted as one aromatic ring. On the other hand, a biphenyl ring is not a fused ring and counts as two aromatic rings. A perylene ring is regarded as a structure formed by bonding two naphthalene rings and counted as two aromatic rings.
Aromatic rings include aromatic hydrocarbon rings, aromatic heterocycles, and the like.

［式（４）中、Ｘ_１及びＸ_２はそれぞれ独立に直接結合、エーテル結合（－Ｏ－）、エステル結合（－ＣＯＯ－）、アミド結合（－ＮＨＣＯ－）、ウレタン結合（－ＮＨＣＯＯ－）、ウレア結合（－ＮＨＣＯＮＨ－）、チオエーテル結合（－Ｓ－）又はスルホニル結合（－ＳＯ_２－）を表す。
Ｒ_ａ１及びＲ_ａ２はそれぞれ独立に置換されていてもよい炭素原子数１～６のアルキル基を表す。
Ｚ_１は下記式（５－ａ）、下記式（５－ｂ）、下記式（５－ｃ）又は下記式（５－ｄ）で表される２価の有機基を表す。
ｎ１及びｎ２はそれぞれ独立に０～３の整数を表す。
Ｒ_ａ１が複数の場合、複数のＲ_ａ１は同じでもよいし異なっていてもよい。Ｒ_ａ２が複数の場合、複数のＲ_ａ２は同じでもよいし異なっていてもよい。
＊は結合手を表す。］Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ preferably represent a tetravalent organic group represented by the following formula (4) from the viewpoint of suitably obtaining the effects of the present invention.

[In the formula (4), X ₁ and X ₂ are each independently a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-) , represents a urea bond (-NHCONH-), a thioether bond (-S-) or a sulfonyl bond (-SO ₂ -).
R _a1 and R _a2 each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms.
Z ₁ represents a divalent organic group represented by the following formula (5-a), (5-b), (5-c) or (5-d) below.
n1 and n2 each independently represent an integer of 0 to 3;
When there are multiple R _{a1 s} , the multiple R _a1s may be the same or different. When R _a2 is plural, the plural R _a2 may be the same or different.
* represents a bond. ]

Examples of optionally substituted alkyl groups having 1 to 6 carbon atoms in R _a1 and R _a2 in formula (4) include alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. In the present specification, alkyl groups and alkylene groups may be linear, branched, or cyclic, unless otherwise specified for their structure. may be a combination of two or more of
Examples of substituents on the optionally substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, nitro group, nitroso group, oxo group, thioxy group, alkoxy group having 1 to 6 carbon atoms, and the like.
The "1 to 6 carbon atoms" of the "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkyl group" excluding substituents. Also, the number of substituents is not particularly limited.

［式（５－ａ）中、Ｒ_３は炭素原子数１～６のアルキル基、炭素原子数２～６のアルケニル基又は炭素原子数１～６のアルコキシ基を表し、ｍ_１は０～４の整数を表す。ｍ_１が２以上の時、Ｒ_３は同じであってもよいし、異なっていてもよい。
式（５－ｂ）中、Ｚ_２は直接結合、又は下記式（６－ａ）若しくは下記式（６－ｂ）で表される２価の有機基を表し、Ｒ_４及びＲ_５はそれぞれ独立して炭素原子数１～６のアルキル基、炭素原子数２～６のアルケニル基又は炭素原子数１～６のアルコキシ基を表し、ｍ_２及びｍ_３はそれぞれ独立して０～４の整数を表す。ｍ_２が２以上の時、Ｒ_４は同じであってもよいし、異なっていてもよい。ｍ_３が２以上の時、Ｒ_５は同じであってもよいし、異なっていてもよい。
式（５－ｃ）中、Ｒ_６は炭素原子数１～６のアルキル基、炭素原子数２～６のアルケニル基又は炭素原子数１～６のアルコキシ基を表し、ｍ_４は０～６の整数を表す。ｍ_４が２以上の時、Ｒ_６は同じであってもよいし、異なっていてもよい。
式（５－ｄ）中、Ｚ_３は直接結合、又は下記式（６－ａ）若しくは下記式（６－ｂ）で表される２価の有機基を表す。
＊は結合手を表す。］

[In the formula (5-a), R ₃ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and m ₁ represents 0 to 4 represents an integer of When _m1 is 2 or more, _R3 may be the same or different.
In formula (5-b), Z ₂ represents a direct bond or a divalent organic group represented by formula (6-a) or (6-b) below, and R ₄ and R ₅ are each independent represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and m ₂ and m ₃ are each independently an integer of 0 to 4. represent. When _m2 is 2 or more, _R4 may be the same or different. When _m3 is 2 or more, _R5 may be the same or different.
In formula (5-c), R ₆ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and m ₄ represents 0 to 6 represents an integer. When _m4 is 2 or more, _R6 may be the same or different.
In formula (5-d), Z ₃ represents a direct bond or a divalent organic group represented by formula (6-a) or (6-b) below.
* represents a bond. ]

［式（６－ａ）中、Ｒ_７、及びＲ_８はそれぞれ独立に水素原子、又はハロゲン原子で置換されていてもよい炭素原子数１～６のアルキル基を表す。
式（６－ｂ）中、Ｒ_９、及びＲ_１０はそれぞれ独立に置換されていてもよい炭素原子数１～６のアルキレン基又は置換されていてもよい炭素原子数６～１２のアリーレン基を表す。
＊は結合手を表す。］

[In formula (6-a), R ₇ and R ₈ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom.
In formula (6-b), R ₉ and R ₁₀ are each independently an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 12 carbon atoms. represent.
* represents a bond. ]

Z ₁ preferably represents a divalent organic group represented by formula (5-b) from the viewpoint of favorably obtaining the effects of the present invention.
From the viewpoint of favorably obtaining the effects of the present invention, in formula (5-b), Z ₂ preferably represents a direct bond.
From the viewpoint of favorably obtaining the effects of the present invention, in formula (5-b), R ₄ and R ₅ preferably represent a methyl group.

Examples of alkyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms for R ₇ and R ₈ include alkyl groups having 1 to 6 carbon atoms and halogenated alkyl groups having 1 to 6 carbon atoms. etc.
Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.
Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include fluorine atom, chlorine atom, bromine atom and iodine atom.
A halogenated alkyl group having 1 to 6 carbon atoms may be partially or completely halogenated.

Examples of substituents on the optionally substituted alkylene group having 1 to 6 carbon atoms in R ₉ and R ₁₀ include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, sulfo group, amino group, nitro group, nitroso group, oxo group, thioxy group, alkoxy group having 1 to 6 carbon atoms, and the like.
Examples of optionally substituted alkylene groups having 1 to 6 carbon atoms include alkylene groups having 1 to 6 carbon atoms and halogenated alkylene groups having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include methylene group, ethylene group, propylene group and butylene group.
The "1 to 6 carbon atoms" of the "optionally substituted alkylene group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkylene group" excluding substituents. Also, the number of substituents is not particularly limited.

Examples of substituents on the optionally substituted arylene group having 6 to 10 carbon atoms in R ₉ and R ₁₀ include a halogen atom, an optionally halogenated alkyl group having 1 to 6 carbon atoms, halogen and an alkoxy group having 1 to 6 carbon atoms which may be substituted. Halogenation may be partially or wholly.
The arylene group includes, for example, a phenylene group and a naphthylene group.
The "6 to 10 carbon atoms" of the "optionally substituted arylene group having 6 to 10 carbon atoms" refers to the number of carbon atoms in the "arylene group" excluding substituents. Also, the number of substituents is not particularly limited.

式中、＊は結合手を表す。Examples of the divalent organic group represented by formula (6-a) include divalent organic groups represented by the following formulas.

In the formula, * represents a bond.

式中、Ｒ_３１～Ｒ_３３はそれぞれ独立にハロゲン原子、ハロゲン原子で置換されていてもよい炭素原子数１～６のアルキル基、又はハロゲン原子で置換されていてもよい炭素原子数１～６のアルコキシ基を表す。ｎ３１は、０～５の整数を表す。ｎ３２及びｎ３３はそれぞれ独立に０～４の整数を表す。Ｒ_３１が複数の場合、複数のＲ_３１は同じでもよいし異なっていてもよい。Ｒ_３２が複数の場合、複数のＲ_３２は同じでもよいし異なっていてもよい。Ｒ_３３が複数の場合、複数のＲ_３３は同じでもよいし異なっていてもよい。＊は結合手を表す。Examples of the divalent organic group represented by formula (6-b) include divalent organic groups represented by the following formulas.

In the formula, R ₃₁ to R ₃₃ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an optionally substituted halogen atom and having 1 to 6 carbon atoms. represents an alkoxy group. n31 represents an integer of 0-5. n32 and n33 each independently represent an integer of 0 to 4; When R ₃₁ is plural, the plural R ₃₁ may be the same or different. When R ₃₂ is plural, the plural R ₃₂ may be the same or different. When R ₃₃ is plural, the plural R ₃₃ may be the same or different. * represents a bond.

Specific examples of alkyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms for R ₃₁ to R ₃₃ include alkyl groups having 1 to 6 carbon atoms and halogen having 1 to 6 carbon atoms. alkyl group.
Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.
Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include fluorine atom, chlorine atom, bromine atom and iodine atom. A halogenated alkyl group having 1 to 6 carbon atoms may be partially or completely halogenated.
Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R ₃₁ to R ₃₃ are an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom. based on.

式中、＊は結合手を表す。Examples of tetravalent organic groups having two or more aromatic rings include tetravalent organic groups represented by the following formulae.

In the formula, * represents a bond.

<<X>>
X represents a divalent aromatic group having an alkyl group with 5 or more carbon atoms. The alkyl group having 5 or more carbon atoms may be directly bonded to the aromatic ring of the divalent aromatic group, or may be bonded via another linking group.
The number of carbon atoms in the alkyl group is not particularly limited as long as it is 5 or more, and may be, for example, 40 or less, 35 or less, or 30 or less.
The number of carbon atoms in the alkyl group is preferably 8 or more and 40 or less, more preferably 10 or more and 35 or less, and particularly preferably 12 or more and 30 or less.
The alkyl group may be linear, branched, cyclic, or a combination of two or more thereof.

X preferably represents a divalent aromatic group represented by any one of formulas (V-1) to (V-6) from the viewpoint of suitably obtaining the effects of the present invention.
(In formula (V-1), X ^v1 represents -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-. ^{R v1} has 5 carbon atoms. represents an alkyl group of ∼20.
In formulas (V-2) to (V-5), X ^v2 to X ^v5 are each independently -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, - represents NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO- or -OCO-; R ^v2 to R ^v5 each independently represent an alkyl group having 5 to 20 carbon atoms.
In formula (V-6), X _a is a single bond, —O—, —NH—, —O—(CH ₂ ) _m —O— (m represents an integer of 1 to 6), —C( CH ₃ ) ₂ -, -CO-, -(CH ₂ ) _m - (m represents an integer of 1 to 6), -SO ₂ -, -OC(CH ₃ ) ₂ -, -CO-( CH ₂ ) _m — (m represents an integer of 1 to 6), —NH—(CH ₂ ) _m — (m represents an integer of 1 to 6), —SO ₂ —(CH ₂ ) _m — (m represents an integer of 1 to 6), —CONH—(CH ₂ ) _m — (m represents an integer of 1 to 6), —CONH—(CH ₂ ) _m —NHCO— (m is 1 represents an integer of ~6.), -COO-(CH ₂ ) _m -OCO- (m represents an integer of 1 to 6.), -CONH-, -NH-(CH ₂ ) _m -NH-(m represents an integer of 1 to 6), or -SO ₂ -(CH ₂ ) _m -SO ₂ - (m represents an integer of 1 to 6). X ^p1 and X ^p2 each independently represent -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH- , -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-. R ^1a and R ^1b each independently represent an alkyl group having 5 to 20 carbon atoms. k1 and k2 each independently represent an integer of 0 to 2;
In formulas (V-1) to (V-6), * represents a bond. )

X ^v1 to X ^v5 preferably represent -O-.
X ^p1 and X ^p2 preferably represent —CH ₂ —O—.
_Xa preferably represents a single bond.

<<Y>>
Y represents a divalent aromatic group having a photopolymerizable group.
Photopolymerizable groups include, for example, radically polymerizable groups, cationic polymerizable groups, and anionically polymerizable groups. Among these, a radically polymerizable group is preferred.
Examples of radically polymerizable groups include acryloyl groups, methacryloyl groups, propenyl ether groups, vinyl ether groups, and vinyl groups.

Examples of the aromatic ring in the divalent aromatic group having a photopolymerizable group include benzene ring, naphthalene ring and anthracene ring.

A divalent aromatic group having a photopolymerizable group is, for example, a residue obtained by removing two amino groups from an aromatic diamine compound having a photopolymerizable group.

［式（９－ａ）中、Ｖ_１は直接結合、エーテル結合（－Ｏ－）、エステル結合（－ＣＯＯ－）、アミド結合（－ＮＨＣＯ－）、ウレタン結合（－ＮＨＣＯＯ－）、又はウレア結合（－ＮＨＣＯＮＨ－）を表し、Ｗ_１は酸素原子又はＮＨ基を表し、Ｒ_１５は直接結合、又は水酸基で置換されていてもよい炭素原子数２～６のアルキレン基を表し、Ｒ_１６は水素原子又はメチル基を表し、＊は結合手を表す。］As the divalent aromatic group having a photopolymerizable group, a divalent organic group represented by the following formula (9-a) is preferred.

[In the formula (9-a), V ₁ is a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), or a urea bond (-NHCONH-), W ₁ represents an oxygen atom or an NH group, R ₁₅ represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, and R ₁₆ represents hydrogen represents an atom or a methyl group, and * represents a bond. ]

The two bonds in formula (9-a) are, for example, bonds that bond to a nitrogen atom.

In the present specification, the alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group includes, for example, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1, 3-propylene group, 1,4-butylene group, 1,2-butylene group, 2,3-butylene group, 1,2-pentylene group, 2,4-pentylene group, 1,2-hexylene group, 1, 2-cyclopropylene group, 1,2-cyclobutylene group, 1,3-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, at least part of these hydrogen atoms are hydroxyl groups and an alkylene group substituted with (eg, 2-hydroxy-1,3-propylene group).

V ₁ preferably represents an ester bond (--COO--).
_W1 preferably represents an oxygen atom.
R ₁₅ preferably represents a 1,2-ethylene group.

式中、＊は結合手を表す。２つの結合手は、例えば、光重合性基を有する置換基に対してメタ位に位置する。Examples of the divalent organic group represented by formula (9-a) include divalent organic groups represented by the following formulas.

In the formula, * represents a bond. The two bonds are, for example, positioned meta to the substituent having a photopolymerizable group.

<<L ₁ and L ₂ >>
L ₁ and L ₂ each independently represent a monovalent organic group having a photopolymerizable group.
Photopolymerizable groups include, for example, radically polymerizable groups, cationic polymerizable groups, and anionically polymerizable groups. Among these, a radically polymerizable group is preferred.
Examples of radically polymerizable groups include acryloyl groups, methacryloyl groups, propenyl ether groups, vinyl ether groups, and vinyl groups.

［式（９－ｂ）中、Ｗ_２は酸素原子又はＮＨ基を表し、Ｒ_１７は直接結合、又は水酸基で置換されていてもよい炭素原子数２～６のアルキレン基を表し、Ｒ_１８は水素原子又はメチル基を表し、＊は結合手を表す。］As the monovalent organic group having a photopolymerizable group, a monovalent organic group represented by the following formula (9-b) is preferable.

[In the formula (9-b), W ₂ represents an oxygen atom or an NH group, R ₁₇ represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, and R ₁₈ represents represents a hydrogen atom or a methyl group, and * represents a bond. ]

_W2 preferably represents an oxygen atom.
R ₁₇ preferably represents a 1,2-ethylene group.

<<R ₁ and R ₂ >>
R ₁ and R ₂ each independently represent a monovalent organic group.
Monovalent organic groups include, for example, alkyl groups having 1 to 30 carbon atoms.
Examples of alkyl groups having 1 to 30 carbon atoms include straight-chain alkyl groups, branched-chain alkyl groups and alicyclic alkyl groups.
Linear alkyl groups having 1 to 30 carbon atoms include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group (amyl group), hexyl group, heptyl group, octyl group, nonyl group and decyl group. , undecyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecyl group, icosyl group (arachyl group), henicosyl group, docosyl group (behenyl group), tricosyl group, tetracosyl group (lignoceryl group), pentacosyl group, hexacosyl group, heptacosyl group and the like.
Branched alkyl groups having 1 to 30 carbon atoms include, for example, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group and isohexyl. group, neohexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2-ethylpentyl group, heptane-3-yl group, heptane-4-yl group, 4-methylhexan-2-yl group, 3-methylhexan-3-yl group, 2,3-dimethylpentan-2-yl group, 2,4-dimethylpentane-2- yl group, 4,4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2-yl group, 6-methyloctyl group, 3 , 5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptan-3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctan-4-yl group, 9-methyldecyl group, undecane-5-yl group, 3-ethylnonane-3- yl group, 5-ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexan-4-yl group, 10-methylundecyl group, 11-methyldodecyl group, tridecane-6-yl group , tridecane-7-yl group, 7-ethylundecane-2-yl group, 3-ethylundecane-3-yl group, 5-ethylundecane-5-yl group, 12-methyltridecyl group, 13-methyltetradecyl group, pentadecane-7-yl group, pentadecane-8-yl group, 14-methylpentadecyl group, 15-methylhexadecyl group, heptadecan-8-yl group, heptadecan-9-yl group, 3,13-dimethylpentadecane -7-yl group, 2,2,4,8,10,10-hexamethylundecane-5-yl group, 16-methylheptadecyl group, 17-methyloctadecyl group, nonadecan-9-yl group, nonadecan-10 -yl group, 2,6,10,14-tetramethylpentadecan-7-yl group, 18-methylnonadecyl group, 19-methylicosyl group, henicosan-10-yl group, 20-methylhenicosyl group, 21-methyldocosyl group , tricosan-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacosan-12-yl group, pentacosan-13-yl group, 2,22-dimethyltricosan-11-yl group, 3,21-dimethyltricosan-11-yl group, 9,15-dimethyltricosan-11-yl group, 24-methylpentacosyl group, 25-methylhexacosyl group, heptacosan-13-yl group, etc. mentioned.
Examples of alicyclic alkyl groups having 1 to 30 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, 1,6-dimethylcyclohexyl and menthyl groups. , cycloheptyl group, cyclooctyl group, bicyclo[2.2.1]heptan-2-yl group, bornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclo[5.2.1.0 ^{2 ,6} ]decan-4-yl group, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl group, cyclododecyl group and the like.

［式（３－ｃ）中、Ａｒ_５は４価の有機基を表し、Ｌ_３、及びＬ_４はそれぞれ独立して光重合性基を有する１価の有機基を表す。］Polyamic acid ester (3) may be the following polyamic acid ester (3c).
Polyamic acid ester (3c): Polyamic acid ester having structural units represented by the above formula (3-b), the following formula (3-c), and the above formula (1-b). However, in formula (3-b), the tetravalent organic group in Ar ₄ represents a tetravalent organic group having two or more aromatic rings.

[In formula (3-c), Ar ₅ represents a tetravalent organic group, and L ₃ and L ₄ each independently represent a monovalent organic group having a photopolymerizable group. ]

Examples of the monovalent organic group having a photopolymerizable group in L ₃ and L ₄ include the monovalent organic groups having a photopolymerizable group exemplified in the description of L ₁ and L ₂ .

式中、＊は結合手を表す。<< Ar ₅ >>
Ar ₅ represents a tetravalent organic group.
The tetravalent organic group is not particularly limited, but includes, for example, a tetravalent organic group other than a tetravalent organic group having two or more aromatic rings. Examples of such tetravalent organic groups include tetravalent organic groups represented by the following formulas.

In the formula, * represents a bond.

<<Other tetravalent organic groups>>
A specific polymer may have a tetravalent organic group other than the tetravalent organic groups exemplified so far.

<<Other divalent organic groups>>
A specific polymer may have divalent organic groups other than X and Y. As such a divalent organic group, for example, a divalent organic group having three or more aromatic rings is preferable in terms of obtaining a lower dielectric loss tangent in the resulting insulating film. A divalent organic group having three or more aromatic rings is, for example, a residue obtained by removing two amino groups from an aromatic diamine compound having three or more aromatic rings.

The number of aromatic rings in the divalent organic group having 3 or more aromatic rings is not particularly limited as long as it is 3 or more. For example, it may be 4 or more. The upper limit of the number of aromatic rings is not particularly limited, but may be, for example, 8 or less, or 6 or less.

［式（１３）中、Ｘ_２１及びＸ_２２はそれぞれ独立に直接結合、エーテル結合（－Ｏ－）、エステル結合（－ＣＯＯ－）、アミド結合（－ＮＨＣＯ－）、ウレタン結合（－ＮＨＣＯＯ－）、ウレア結合（－ＮＨＣＯＮＨ－）、チオエーテル結合（－Ｓ－）又はスルホニル結合（－ＳＯ_２－）を表す。
Ｒ_２１及びＲ_２２はそれぞれ独立に置換されていてもよい炭素原子数１～６のアルキル基を表す。
Ｙ_２０は上記式（５－ａ）、上記式（５－ｂ）又は上記式（５－ｃ）で表される２価の有機基を表す。
ｎ２１及びｎ２２はそれぞれ独立に０～４の整数を表す。
Ｒ_２１が複数の場合、複数のＲ_２１は同じでもよいし異なっていてもよい。Ｒ_２２が複数の場合、複数のＲ_２２は同じでもよいし異なっていてもよい。
＊は結合手を表す。］Although the divalent organic group having three or more aromatic rings is not particularly limited, it is preferably a divalent organic group represented by the following formula (13).

[In the formula (13), X ₂₁ and X ₂₂ are each independently a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-) , represents a urea bond (-NHCONH-), a thioether bond (-S-) or a sulfonyl bond (-SO ₂ -).
R ₂₁ and R ₂₂ each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms.
Y ₂₀ represents a divalent organic group represented by formula (5-a), formula (5-b) or formula (5-c) above.
n21 and n22 each independently represent an integer of 0 to 4;
When R ₂₁ is plural, the plural R ₂₁ may be the same or different. When R ₂₂ is plural, the plural R ₂₂ may be the same or different.
* represents a bond. ]

The optionally substituted alkyl group having 1 to 6 carbon atoms in R ₂₁ and R ₂₂ in formula (13) includes, for example, an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. In the present specification, alkyl groups and alkylene groups may be linear, branched, or cyclic, unless otherwise specified for their structure. may be a combination of two or more of
Examples of substituents on the optionally substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, nitro group, nitroso group, oxo group, thioxy group, alkoxy group having 1 to 6 carbon atoms, and the like.
The "1 to 6 carbon atoms" of the "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkyl group" excluding substituents. Also, the number of substituents is not particularly limited.

式中、＊は結合手を表す。Examples of divalent organic groups having three or more aromatic rings include divalent organic groups represented by the following formulas.

In the formula, * represents a bond.

式中、＊は結合手を表す。Other divalent organic groups include, for example, divalent organic groups represented by the following formulas. These divalent organic groups are, for example, residues obtained by removing two amino groups from diamine.

In the formula, * represents a bond.

Polyimide is, for example, an imidized polyamic acid that is a reaction product of a diamine component and a tetracarboxylic acid derivative.
The imidization rate of polyimide need not be 100%. The imidization rate of polyimide may be, for example, 90% or more, 95% or more, or 98% or more.

Polyamic acids are, for example, reaction products of diamine components and tetracarboxylic acid derivatives.
Polyamic acid esters are, for example, reaction products of diamine components and tetracarboxylic acid diesters.

Here, the tetracarboxylic acid derivatives include tetracarboxylic acids, tetracarboxylic acid diesters, tetracarboxylic acid dihalides, tetracarboxylic acid dianhydrides, and the like.

Tetracarboxylic acid derivatives preferably include tetracarboxylic acid derivatives having two or more aromatic rings.
The tetravalent organic groups represented by Ar ₁ in formula (1-a), Ar ₂ in formula (2), Ar ₃ in formula (3-a), and Ar ₄ in formula (3-b) are For example, it is preferably a residue obtained by removing a carboxyl group, a carboxylic acid ester group, or a carboxylic acid dianhydride group from a tetracarboxylic acid derivative having two or more aromatic rings.

［式（４－Ｚ）中、Ｘ_１及びＸ_２はそれぞれ独立に直接結合、エーテル結合（－Ｏ－）、エステル結合（－ＣＯＯ－）、アミド結合（－ＮＨＣＯ－）、ウレタン結合（－ＮＨＣＯＯ－）、ウレア結合（－ＮＨＣＯＮＨ－）、チオエーテル結合（－Ｓ－）又はスルホニル結合（－ＳＯ_２－）を表す。
Ｒ_ａ１及びＲ_ａ２はそれぞれ独立に置換されていてもよい炭素原子数１～６のアルキル基を表す。
Ｚ_１は上記式（５－ａ）、上記式（５－ｂ）、上記式（５－ｃ）又は上記式（５－ｄ）で表される２価の有機基を表す。
ｎ１及びｎ２はそれぞれ独立に０～３の整数を表す。
Ｒ_ａ１が複数の場合、複数のＲ_ａ１は同じでもよいし異なっていてもよい。Ｒ_ａ２が複数の場合、複数のＲ_ａ２は同じでもよいし異なっていてもよい。］As the tetracarboxylic acid derivative having two or more aromatic rings, a tetracarboxylic dianhydride represented by the following formula (4-Z) is preferable.

[In the formula (4-Z), X ₁ and X ₂ are each independently a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO -), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO ₂ -).
R _a1 and R _a2 each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms.
Z ₁ represents a divalent organic group represented by formula (5-a), formula (5-b), formula (5-c) or formula (5-d).
n1 and n2 each independently represent an integer of 0 to 3;
When there are multiple R _{a1 s} , the multiple R _a1s may be the same or different. When R _a2 is plural, the plural R _a2 may be the same or different. ]

The diamine component preferably contains an aromatic diamine compound having an alkyl group with 5 or more carbon atoms.
The diamine component preferably contains an aromatic diamine compound having a photopolymerizable group.
The divalent aromatic group having an alkyl group having 5 or more carbon atoms, which is X in the formula (1-b), is, for example, two amino groups from an aromatic diamine compound having an alkyl group having 5 or more carbon atoms. is the residue excluding
The divalent aromatic group having a photopolymerizable group, which is Y in formula (1-c), is, for example, a residue obtained by removing two amino groups from an aromatic diamine compound having a photopolymerizable group.

（式（Ｖ－１ａ）中、Ｘ^ｖ１は、－Ｏ－、－ＣＨ_２－Ｏ－、－ＣＨ_２－ＯＣＯ－、－ＣＯＯ－、又は－ＯＣＯ－を表す。Ｒ^ｖ１は、炭素原子数５～２０のアルキル基を表す。
式（Ｖ－２ａ）～（Ｖ－５ａ）中、Ｘ^ｖ２～Ｘ^ｖ５は、それぞれ独立に、－（ＣＨ_２）_ａ－（ａは１～１５の整数である。）、－ＣＯＮＨ－、－ＮＨＣＯ－、－ＣＯＮ（ＣＨ_３）－、－ＮＨ－、－Ｏ－、－ＣＨ_２－Ｏ－、－ＣＨ_２－ＯＣＯ－、－ＣＯＯ－、又は－ＯＣＯ－を表す。Ｒ^ｖ２～Ｒ^ｖ５は、それぞれ独立に、炭素原子数５～２０のアルキル基を表す。
式（Ｖ－６ａ）中、Ｘ_ａは、単結合、－Ｏ－、－ＮＨ－、－Ｏ－（ＣＨ_２）_ｍ－Ｏ－（ｍは１～６の整数を表す。）、－Ｃ（ＣＨ_３）_２－、－ＣＯ－、－（ＣＨ_２）_ｍ－（ｍは１～６の整数を表す。）、－ＳＯ_２－、－Ｏ－Ｃ（ＣＨ_３）_２－、－ＣＯ－（ＣＨ_２）_ｍ－（ｍは１～６の整数を表す。）、－ＮＨ－（ＣＨ_２）_ｍ－（ｍは１～６の整数を表す。）、－ＳＯ_２－（ＣＨ_２）_ｍ－（ｍは１～６の整数を表す。）、－ＣＯＮＨ－（ＣＨ_２）_ｍ－（ｍは１～６の整数を表す。）、－ＣＯＮＨ－（ＣＨ_２）_ｍ－ＮＨＣＯ－（ｍは１～６の整数を表す。）、－ＣＯＯ－（ＣＨ_２）_ｍ－ＯＣＯ－（ｍは１～６の整数を表す。）、－ＣＯＮＨ－、－ＮＨ－（ＣＨ_２）_ｍ－ＮＨ－（ｍは１～６の整数を表す。）、又は－ＳＯ_２－（ＣＨ_２）_ｍ－ＳＯ_２－（ｍは１～６の整数を表す。）を表す。Ｘ^ｐ１及びＸ^ｐ２は、それぞれ独立に、－（ＣＨ_２）_ａ－（ａは１～１５の整数である。）、－ＣＯＮＨ－、－ＮＨＣＯ－、－ＣＯＮ（ＣＨ_３）－、－ＮＨ－、－Ｏ－、－ＣＨ_２－Ｏ－、－ＣＨ_２－ＯＣＯ－、－ＣＯＯ－、又は－ＯＣＯ－を表す。Ｒ^１ａ及びＲ^１ｂは、それぞれ独立に、炭素原子数５～２０のアルキル基を表す。ｋ１及びｋ２は、それぞれ独立に、０～２の整数を表す。）As the aromatic diamine compound having an alkyl group having 5 or more carbon atoms, diamine compounds represented by the following formulas (V-1a) to (V-6a) are preferred.

(In formula (V-1a), X ^v1 represents -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-. ^{R v1} has 5 carbon atoms. represents an alkyl group of ∼20.
In formulas (V-2a) to (V-5a), X ^v2 to X ^v5 are each independently -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, - represents NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO- or -OCO-; R ^v2 to R ^v5 each independently represent an alkyl group having 5 to 20 carbon atoms.
In formula (V-6a), X _a is a single bond, —O—, —NH—, —O—(CH ₂ ) _m —O— (m represents an integer of 1 to 6), —C( CH ₃ ) ₂ -, -CO-, -(CH ₂ ) _m - (m represents an integer of 1 to 6), -SO ₂ -, -OC(CH ₃ ) ₂ -, -CO-( CH ₂ ) _m — (m represents an integer of 1 to 6), —NH—(CH ₂ ) _m — (m represents an integer of 1 to 6), —SO ₂ —(CH ₂ ) _m — (m represents an integer of 1 to 6), —CONH—(CH ₂ ) _m — (m represents an integer of 1 to 6), —CONH—(CH ₂ ) _m —NHCO— (m is 1 represents an integer of ~6.), -COO-(CH ₂ ) _m -OCO- (m represents an integer of 1 to 6.), -CONH-, -NH-(CH ₂ ) _m -NH-(m represents an integer of 1 to 6), or -SO ₂ -(CH ₂ ) _m -SO ₂ - (m represents an integer of 1 to 6). X ^p1 and X ^p2 each independently represent -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH- , -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-. R ^1a and R ^1b each independently represent an alkyl group having 5 to 20 carbon atoms. k1 and k2 each independently represent an integer of 0 to 2; )

Specific examples of the aromatic diamine compound having an alkyl group with 5 or more carbon atoms are shown below.

（式（９－Ａ）中のＶ_１、Ｗ_１、Ｒ_１５、及びＲ_１６は、式（９－ａ）中のＶ_１、Ｗ_１、Ｒ_１５、及びＲ_１６とそれぞれ同義である。）As the aromatic diamine compound having a photopolymerizable group, an aromatic diamine compound represented by the following formula (9-A) is preferable.

(V ₁ , W ₁ , R ₁₅ and R ₁₆ in formula (9-A) are synonymous with V ₁ , W ₁ , R ₁₅ and R ₁₆ in formula (9-a) respectively.)

The ratio of the aromatic tetracarboxylic acid derivative having two or more aromatic rings to the total tetracarboxylic acid derivative constituting the polyimide is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is 20 mol %. ~100 mol % is preferable, and 40 mol % to 100 mol % is more preferable.
The ratio of the aromatic tetracarboxylic acid derivative having two or more aromatic rings to the total tetracarboxylic acid derivative constituting the polyamic acid is not particularly limited, but from the viewpoint of suitably obtaining the effect of the present invention, it is 20 mol. % to 100 mol %, more preferably 40 mol % to 100 mol %.
The ratio of the aromatic tetracarboxylic acid derivative having two or more aromatic rings to the total tetracarboxylic acid derivative constituting the polyamic acid ester is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, 20 mol % to 100 mol % is preferred, and 40 mol % to 100 mol % is more preferred.

The ratio of the aromatic diamine compound having an alkyl group having 5 or more carbon atoms to the total diamine component constituting the polyimide is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is 5 mol % to 80 mol. %, more preferably 10 mol % to 70 mol %, particularly preferably 15 mol % to 65 mol %.
The ratio of the aromatic diamine compound having an alkyl group having 5 or more carbon atoms to the total diamine component constituting the polyamic acid is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is 5 mol % to 80 mol %. mol % is preferred, 10 mol % to 70 mol % is more preferred, and 15 mol % to 65 mol % is particularly preferred.
The ratio of the aromatic diamine compound having an alkyl group having 5 or more carbon atoms to the total diamine component constituting the polyamic acid ester is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is 5 mol % to 5 mol %. 80 mol % is preferred, 10 mol % to 70 mol % is more preferred, and 15 mol % to 65 mol % is particularly preferred.

The ratio of the aromatic diamine compound having a photopolymerizable group to the total diamine component constituting the polyimide is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is preferably 10 mol% to 90 mol%, and 15 mol. % to 75 mol % is more preferred, and 20 mol % to 60 mol % is particularly preferred.
The ratio of the aromatic diamine compound having a photopolymerizable group to the total diamine component constituting the polyamic acid is not particularly limited, but is preferably 10 mol % to 90 mol % from the viewpoint of obtaining sufficient photosensitivity. mol % to 75 mol % is more preferred, and 20 mol % to 60 mol % is particularly preferred.
The ratio of the aromatic diamine compound having a photopolymerizable group to the total diamine component constituting the polyamic acid ester is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is preferably 10 mol% to 90 mol%, 15 mol % to 75 mol % is more preferred, and 20 mol % to 60 mol % is particularly preferred.

The molar ratio (A:B ) is not particularly limited, but is preferably 3:1 to 0.3:1, more preferably 2:1 to 0.5:1, and particularly preferably 1.5:1 to 0.5:1.

The total molar ratio of the aromatic diamine compound having a photopolymerizable group and the aromatic diamine compound having an alkyl group having 5 or more carbon atoms with respect to all the diamine components constituting the polyimide, polyamic acid, and polyamic acid ester is Although not particularly limited, it is preferably 30 mol % or more, more preferably 40 mol % or more, and particularly preferably 50 mol % or more from the viewpoint of suitably obtaining the effects of the present invention. The upper limit of the total molar ratio is not particularly limited, but the total molar ratio may be 100 mol % or less, or may be 90 mol % or less.

The ratio of the aromatic diamine compound having three or more aromatic rings to the total diamine component constituting the polyamic acid is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is 5 mol % to 60 mol. %, more preferably 10 mol % to 55 mol %, particularly preferably 15 mol % to 50 mol %.

The weight average molecular weight of the specific polymer is not particularly limited, but the weight average molecular weight measured in terms of polyethylene oxide by gel permeation chromatography (hereinafter abbreviated as GPC in this specification) is 5,000 to 5,000. 100,000 is preferred, 7,000 to 50,000 is more preferred, 10,000 to 50,000 is even more preferred, and 10,000 to 40,000 is particularly preferred.

<<Method for producing a specific polymer>>
The method for producing the specific polymer is not particularly limited, and includes, for example, a known method in which a diamine component and a tetracarboxylic acid derivative are reacted to obtain polyamic acid, polyamic acid ester, or polyimide. Polyamic acids, polyamic acid esters and polyimides can be synthesized by known methods such as those described in WO2013/157586.

A polyamic acid or a polyamic acid ester is produced, for example, by reacting (condensation polymerization) a diamine component and a tetracarboxylic acid derivative in a solvent.

（式［Ｄ－１］中、Ｄ^１は炭素原子数１～３のアルキル基を示し、式［Ｄ－２］中、Ｄ^２は炭素原子数１～３のアルキル基を示し、式［Ｄ－３］中、Ｄ^３は炭素原子数１～４のアルキル基を表す。）Specific examples of the above solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyric acid amide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone. Further, when the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] Any of the indicated solvents can be used.

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms; in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms; -3], D ³ represents an alkyl group having 1 to 4 carbon atoms.)

These solvents may be used alone or in combination. Furthermore, even a solvent that does not dissolve the polyamic acid or the polyamic acid ester may be used by being mixed with the above solvent within the range that the polyamic acid or the polyamic acid ester does not precipitate.

When the diamine component and the tetracarboxylic acid derivative are reacted in a solvent, the reaction can be carried out at any concentration, preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. is. The initial stage of the reaction can be carried out at a high concentration, and then the solvent can be added.
In the reaction, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid derivative is preferably 0.8 to 1.2. As is the case with ordinary polycondensation reactions, the closer this molar ratio is to 1.0, the greater the molecular weight of the polyamic acid or polyamic acid ester produced.

When reacting the diamine component and the tetracarboxylic acid derivative, a thermal polymerization inhibitor may be added to the reaction system in order to avoid polymerization of the photopolymerizable group.
Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, and glycol ether. diaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-( N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt and the like.
The amount of the thermal polymerization inhibitor used is not particularly limited.

Polyimide is obtained by dehydrating and ring-closing the polyamic acid obtained by the above reaction.
Methods for obtaining polyimide include thermal imidization in which the polyamic acid solution obtained by the above reaction is heated as it is, and chemical imidization in which a catalyst is added to the polyamic acid solution. The temperature for thermal imidization in a solution is 100° C. to 400° C., preferably 120° C. to 250° C. It is preferable to perform the imidization reaction while removing water produced by the imidization reaction from the system.

The chemical imidization is carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution obtained by the reaction and stirring at -20°C to 250°C, preferably 0°C to 180°C. can be done. The amount of the basic catalyst is 0.1 to 30 times the moles of the amic acid groups, preferably 0.2 to 20 times the moles, and the amount of the acid anhydride is 1 to 50 times the moles of the amic acid groups. times, preferably 1.5- to 30-fold. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, triethylamine is preferred because polyisoimide as a by-product is less likely to form. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferable because purification after completion of the reaction is facilitated. The rate of imidization by chemical imidization (ratio of repeating units to be ring-closed to all repeating units of the polyimide precursor, also referred to as rate of ring closure) can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time. can.

In the case of recovering the produced imidized product from the imidization reaction solution, the reaction solution may be poured into a solvent to precipitate. Solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by putting it into a solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure.

Certain polymers may be end-capped. A method for terminal blocking is not particularly limited, and for example, a conventionally known method using a monoamine or an acid anhydride can be used.

（式［Ｄ－１］中、Ｄ^１は炭素原子数１～３のアルキル基を示し、式［Ｄ－２］中、Ｄ^２は炭素原子数１～３のアルキル基を示し、式［Ｄ－３］中、Ｄ^３は炭素原子数１～４のアルキル基を表す。）<Solvent>
As the solvent contained in the photosensitive resin composition for forming an insulating film, it is preferable to use an organic solvent from the viewpoint of solubility with respect to a specific polymer. Specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyric acid amide , dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol Monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl 2-hydroxyisobutyrate, ethyl lactate or the following formulas [D-1] to [D-3] ], and these can be used alone or in combination of two or more.

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms; in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms; -3], D ³ represents an alkyl group having 1 to 4 carbon atoms.)

The solvent is in the range of, for example, 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass, with respect to 100 parts by mass of the specific polymer, depending on the desired coating thickness and viscosity of the photosensitive resin composition for forming an insulating film. parts to 1000 parts by mass.

<Other ingredients>
In an embodiment, the insulating film-forming photosensitive resin composition may further contain components other than the specific polymer and solvent. Other components include, for example, photoradical polymerization initiators (also referred to as “photoradical initiators”), crosslinkable compounds (also referred to as “crosslinkers”), thermosetting agents, other resin components, fillers, and sensitizers. , adhesion promoters, thermal polymerization inhibitors, azole compounds, hindered phenol compounds, and the like.

<<Photo radical polymerization initiator>>
The photoradical polymerization initiator is not particularly limited as long as it is a compound that absorbs the light source used for photocuring. benzoyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexene Hydroperoxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4- Bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2′,5,5′-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone , 3,3′,4,4′-tetra(tert-amylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3′-bis(tert- butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxyisophthalate and other organic peroxides; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloro quinones such as anthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone; benzoin derivatives such as benzoin methyl ether, benzoin ethyl ether, α-methylbenzoin, and α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenyl Ethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy- 2-methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}-phenyl]-2-methyl-propan-1-one , phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one and other alkylphenone compounds; bis(2,4 Acylphosphine oxide compounds such as ,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; ]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone and other oxime ester compounds mentioned. From the viewpoint of i-ray curability, oxime ester compounds are particularly preferred.

Radical photopolymerization initiators are commercially available, for example, IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, OXE03, OXE04, 250, 1173, MBF, TPO, 4265, TPO (manufactured by BASF), KAYACURE [registered trademark] DETX-S, MBP, DMBI, EPA, OA (Nippon Kayaku Co., Ltd.), VICURE-10, 55 (manufactured by STAUFFER Co. LTD), ESACURE KIP150, TZT, 1001, KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, Triazine B (Japan SiberHegner Co., Ltd.), Adeka Optomer N-1717, N-1414, N -1606, ADEKA Arkles N-1919T, ADEKA NCI-831E, ADEKA NCI-930, and ADEKA NCI-730 (manufactured by ADEKA Corporation).
These radical photopolymerization initiators may be used alone or in combination of two or more.

The content of the photoradical polymerization initiator is not particularly limited, but is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the specific polymer, and from the viewpoint of photosensitivity characteristics, 0.5 parts by mass to 15 parts by mass. Parts by mass are more preferred. When 0.1 parts by mass or more of the photoradical polymerization initiator is contained with respect to 100 parts by mass of the specific polymer, the photosensitivity of the photosensitive resin composition for forming an insulating film tends to be improved, while 20 parts by mass When it is contained below, the thick film curability of the insulating film-forming photosensitive resin composition is likely to be improved.

<<crosslinkable compound>>
In the embodiment, in order to improve the resolution of the relief pattern, the photosensitive resin composition for forming an insulating film may optionally contain a monomer having a photoradical polymerizable unsaturated bond (crosslinkable compound). can.
As such a crosslinkable compound, a compound containing a polymerizable group that undergoes a radical polymerization reaction with a photoradical polymerization initiator is preferable, and examples thereof include (meth)acrylic compounds and maleimide compounds, but are not particularly limited to the following. do not have. (Meth)acrylic compounds include diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol or polyethylene glycol mono- or di(meth)acrylate, propylene glycol or polypropylene glycol mono- or di(meth)acrylate. , mono-, di- or tri(meth)acrylate of glycerol, di(meth)acrylate of 1,4-butanediol, di(meth)acrylate of 1,6-hexanediol, di(meth)acrylate of 1,9-nonanediol Acrylates, di(meth)acrylate of 1,10-decanediol, di(meth)acrylate of neopentyl glycol, cyclohexane di(meth)acrylate, di(meth)acrylate of cyclohexanedimethanol, di(meth)acrylate of tricyclodecanedimethanol meth)acrylate, dioxane glycol di(meth)acrylate, bisphenol A mono- or di(meth)acrylate, bisphenol F di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, benzene trimethacrylate, 9, 9-bis[4-(2-hydroxyethoxy)phenyl]fluorene di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, isobornyl (meth)acrylate, acrylamide and its derivatives, methacryl Amide and derivatives thereof, trimethylolpropane tri(meth)acrylate, glycerol di- or tri-(meth)acrylate, pentaerythritol di-, tri-, or tetra-(meth)acrylate, and ethylene oxide or propylene oxide adducts of these compounds, etc. 2-isocyanatoethyl (meth)acrylate or isocyanate-containing (meth)acrylate, and methyl ethyl ketone oxime, ε-caprolactam, γ-caprolactam, 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n- Compounds added with blocking agents such as butanol and 1-methoxy-2-propanol can be mentioned. Examples of maleimide compounds include 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,4-phenylenebismaleimide, N,N'-1,3-phenylenedimaleimide, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(2-maleimidoethyl)disulfide, 2, 2-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,6'-bismaleimido-(2,2,4-trimethyl)hexane and the like can be mentioned. Commercially available maleimide compounds include BMI-689, BMI-1500, BMI-1700, and BMI-3000 (manufactured by Designer Molecules Inc.). In addition, these compounds may be used individually or may be used in combination of 2 or more types. Moreover, in this specification, (meth)acrylate means acrylate and methacrylate.

The content of the crosslinkable compound is not particularly limited, but is preferably 1 part by mass to 100 parts by mass, more preferably 1 part by mass to 50 parts by mass, relative to 100 parts by mass of the specific polymer.

<<Heat curing agent>>
Examples of heat curing agents include hexamethoxymethylmelamine, tetramethoxymethylglycoluril, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis ( butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea and 1, 1,3,3-tetrakis(methoxymethyl)urea and the like.
The content of the thermosetting agent in the insulating film-forming photosensitive resin composition is not particularly limited.

<<Filler>>
Examples of fillers include inorganic fillers, and specific examples include sols of silica, aluminum nitride, boron nitride, zirconia, alumina, and the like.
The content of the filler in the insulating film-forming photosensitive resin composition is not particularly limited.

<<Other resin components>>
In an embodiment, the insulating film-forming photosensitive resin composition may further contain a resin component other than the specific polymer. Examples of resin components that can be contained in the insulating film-forming photosensitive resin composition include polyimides other than specific polymers, polyoxazoles, polyoxazole precursors, phenolic resins, polyamides, epoxy resins, siloxane resins, acrylic resins, and polyoxazole precursors. Resin etc. are mentioned.
The content of these resin components is not particularly limited, but is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the specific polymer.

<<Sensitizer>>
In the embodiment, the photosensitive resin composition for forming an insulating film may optionally contain a sensitizer in order to improve photosensitivity.
Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal)acetone, 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3 -acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Coumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercapto benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl) ) naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene and the like.
These can be used alone or in multiple combinations.

Although the content of the sensitizer is not particularly limited, it is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the specific polymer.

<<Adhesion Aid>>
In the embodiment, in order to improve the adhesion between the film formed using the insulating film-forming photosensitive resin composition and the substrate, an adhesion aid is optionally added to the insulating film-forming photosensitive resin composition. can be compounded.
Examples of adhesion promoters include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, 3-(meth)acryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3 -diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3′-bis(N-[3-triethoxysilyl]propylamide)-4,4′ -dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyl Examples include silane coupling agents such as trimethoxysilane, and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

Among these adhesion aids, the silane coupling agent is more preferable from the point of adhesion.

The content of the adhesion promoter is not particularly limited, but is preferably in the range of 0.5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the specific polymer.

<<Thermal polymerization inhibitor>>
In the embodiment, in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition for forming an insulating film during storage in a solution containing a solvent, a thermal polymerization inhibitor may be arbitrarily blended. can be done.
Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, and glycol ether. diaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-( N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt and the like are used.

The content of the thermal polymerization inhibitor is not particularly limited, but is preferably in the range of 0.005 parts by mass to 12 parts by mass with respect to 100 parts by mass of the specific polymer.

<<Azole compound>>
For example, when a substrate made of copper or a copper alloy is used, an azole compound can optionally be added to the photosensitive resin composition for forming an insulating film in order to suppress discoloration of the substrate.
Azole compounds include, for example, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl -5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, Hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3, 5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl -2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, Hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5- methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like. Particularly preferred are 4-carboxy-1H-benzotriazole and 5-carboxy-1H-benzotriazole.
Moreover, these azole compounds may be used either singly or as a mixture of two or more.

The content of the azole compound is not particularly limited, but it is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the specific polymer, and from the viewpoint of photosensitivity characteristics, 0.5 to 5 parts by mass. Parts by mass are more preferred. When the content of the azole compound with respect to 100 parts by mass of the specific polymer is 0.1 parts by mass or more, when the photosensitive resin composition for forming an insulating film is formed on copper or a copper alloy, copper or Discoloration of the copper alloy surface is suppressed, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

<<Hindered phenol compound>>
In embodiments, a hindered phenol compound can optionally be blended into the insulating film-forming photosensitive resin composition in order to suppress discoloration on copper.
Hindered phenol compounds include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3 -t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2 -thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydro cinnamamide), 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 2,2′-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5- Trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6- dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethyl benzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2 ,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3 -hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl -3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl -5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4 -t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t -butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t -Butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like, but are not limited thereto. not something.
Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione is particularly preferred.

The content of the hindered phenol compound is not particularly limited, but it is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the specific polymer, and 0.5 parts by mass from the viewpoint of photosensitivity characteristics. More preferably, it is up to 10 parts by mass. When the content of the hindered phenol compound with respect to 100 parts by mass of the specific polymer is 0.1 parts by mass or more, for example, when the photosensitive resin composition for forming an insulating film is formed on copper or a copper alloy, copper Alternatively, discoloration and corrosion of the copper alloy can be prevented, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

The insulating film-forming photosensitive resin composition can be suitably used as a negative-type insulating film-forming photosensitive resin composition for producing a cured relief pattern, which will be described later.

(insulating film)
The insulating film of the present invention is a baked product of a coating film of the photosensitive resin composition for forming an insulating film of the present invention.
As the coating method, a method conventionally used for coating a photosensitive resin composition for forming an insulating film, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a spray coater. A method such as spray coating can be used.
As a baking method for obtaining a baked product, various methods can be selected such as, for example, using a hot plate, using an oven, and using a heating oven in which a temperature program can be set. Firing can be performed, for example, at 130° C. to 250° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.
Although the thickness of the insulating film is not particularly limited, it is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm.

(Photosensitive resist film)
The photosensitive resin composition for forming an insulating film of the present invention can be used for a photosensitive resist film (so-called dry film resist).
The photosensitive resist film has a base film, a photosensitive resin layer (photosensitive resin film) formed from the insulating film-forming photosensitive resin composition of the present invention, and a cover film.
Usually, a photosensitive resin layer and a cover film are laminated in this order on a base film.

A photosensitive resist film is produced, for example, by coating a base film with a photosensitive resin composition for forming an insulating film, drying it to form a photosensitive resin layer, and then laminating a cover film on the photosensitive resin layer. It can be manufactured by
As the coating method, a method conventionally used for coating a photosensitive resin composition for forming an insulating film, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a spray coater. A method such as spray coating can be used.
The drying method includes, for example, conditions of 20° C. to 200° C. for 1 minute to 1 hour.
The thickness of the resulting photosensitive resin layer is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm.

A known base film can be used, and for example, a thermoplastic resin film or the like is used. Examples of the thermoplastic resin include polyester such as polyethylene terephthalate. The thickness of the base film is preferably 2 μm to 150 μm.
A known cover film can be used, for example, a polyethylene film, a polypropylene film, or the like. As the cover film, it is preferable to use a film having a weaker adhesion to the photosensitive resin layer than the base film. The thickness of the cover film is preferably 2 μm to 150 μm, more preferably 2 μm to 100 μm, particularly preferably 5 μm to 50 μm.
The base film and the cover film may be made of the same film material, or may be made of different films.

(Manufacturing method of substrate with cured relief pattern)
The method for producing a cured relief patterned substrate of the present invention comprises:
(1) a step of applying the photosensitive resin composition for forming an insulating film according to the present invention onto a substrate to form a photosensitive resin layer (photosensitive resin film) on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) heat-treating the relief pattern to form a cured relief pattern.

Each step will be described below.

(1) A step of applying the photosensitive resin composition for forming an insulating film according to the present invention onto a substrate to form a photosensitive resin layer on the substrate. A resin composition is applied onto a substrate and, if necessary, dried to form a photosensitive resin layer. As the coating method, a method conventionally used for coating a photosensitive resin composition for forming an insulating film, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a spray coater. A method such as spray coating can be used.

If necessary, the coating film made of the photosensitive resin composition for forming an insulating film can be dried. Examples of drying methods include air drying, heat drying using an oven or hot plate, and vacuum drying. be done. Specifically, when air drying or heat drying is performed, drying can be performed at 20° C. to 200° C. for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on the substrate.

(2) Step of exposing the photosensitive resin layer In this step, the photosensitive resin layer formed in the above step (1) is exposed using an exposure device such as a contact aligner, mirror projection, stepper, or the like, using a photomask or a patterned photomask. It is exposed to an ultraviolet light source or the like through a reticle or directly.
Light sources used for exposure include, for example, g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser. The exposure amount is desirably 25 mJ/cm ² to 2000 mJ/cm ² .

After that, for the purpose of improving photosensitivity, if necessary, post-exposure baking (PEB) and/or pre-development baking may be performed at any combination of temperature and time. The range of baking conditions is preferably 50° C. to 200° C. and a time of 10 seconds to 600 seconds. However, it is not limited to this range.

(3) Step of developing the exposed photosensitive resin layer to form a relief pattern In this step, the unexposed portion of the exposed photosensitive resin layer is removed by development. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of conventionally known photoresist developing methods such as a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, and the like can be used. method can be selected and used. After development, rinsing may be performed for the purpose of removing the developer. Furthermore, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking may be performed at any combination of temperature and time, if necessary.
Organic solvents are preferred as the developer used for development. Examples of organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α- Acetyl-γ-butyrolactone and the like are preferred. Moreover, two or more kinds of each solvent can be used, for example, several kinds can be used in combination.
As the rinsing liquid used for rinsing, an organic solvent that is miscible with the developer and has low solubility in the insulating film-forming photosensitive resin composition is preferable. Preferred examples of the rinse solution include methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, and xylene. Moreover, two or more kinds of each solvent can be used, for example, several kinds can be used in combination.

(4) Step of Heating Relief Pattern to Form Hardened Relief Pattern In this step, the relief pattern obtained by the development is heated and converted into a hardened relief pattern. As the heat-curing method, various methods can be selected, for example, using a hot plate, using an oven, or using a heating oven capable of setting a temperature program. Heating can be performed, for example, at 130° C. to 250° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.

The thickness of the cured relief pattern is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm.

(semiconductor device)
Embodiments also provide a semiconductor device comprising a semiconductor element and a cured film provided over or under the semiconductor element. A cured film is a cured relief pattern formed from the photosensitive resin composition for forming an insulating film of the present invention. The cured relief pattern can be obtained, for example, by steps (1) to (4) in the method for producing a substrate with a cured relief pattern described above.
The present invention can also be applied to a method of manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-described method of manufacturing a substrate with a cured relief pattern as part of the steps. The semiconductor device of the present invention forms a cured relief pattern as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, a protective film for a semiconductor device having a bump structure, or the like. It can be manufactured by combining with a manufacturing method of a semiconductor device.

(Display device)
In an embodiment, there is provided a display device comprising a display element and a cured film provided on top of the display element, wherein the cured film is the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween. For example, the cured film includes a surface protective film, an insulating film, and a flattening film for TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, projections for MVA (Multi-domain Vertical Alignment) type liquid crystal display devices, and A partition wall for an organic EL (Electro-Luminescence) element cathode can be mentioned.

The photosensitive resin composition for forming an insulating film of the present invention can be applied not only to the above semiconductor devices, but also to interlayer insulating films of multilayer circuits, cover coats of flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like. is also useful for

EXAMPLES Next, the content of the present invention will be specifically described with reference to Examples, but the present invention is not limited to these.

The compounds shown in the Synthesis Examples and Comparative Synthesis Examples are shown below.
BEM-S: 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (manufactured by Samsung Chemical Industries Co., Ltd.)

BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane

HFBAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane

APC-14: 4-tetradecyloxy-1,3-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

APC-16: 4-hexadecyloxy-1,3-phenylenediamine (manufactured by Wakayama Seika Kogyo Co., Ltd.)

DAB-C18: 4-octadecyloxy-1,3-phenylenediamine (manufactured by Wakayama Seika Kogyo Co., Ltd.)

BPADA: 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride

TMPBP-TME: 2,2′,3,3′,5,5′-hexamethyl-[1,1′-biphenyl]-4,4′-diylbis(1,3-dioxo-1,3-dihydroisobenzofuran -5-carboxylate) (manufactured by Honshu Chemical Industry Co., Ltd.)

6FDA: 4,4'-[perfluoro(propane-2,2-diyl)] phthalic anhydride (manufactured by Daikin Industries, Ltd.)

The weight-average molecular weight (Mw) shown in the synthesis examples below is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). For measurement, a GPC apparatus (HLC-8320GPC (manufactured by Tosoh Corporation)) is used, and the measurement conditions are as follows.
Column: Shodex (registered trademark) KD-805 / Shodex (registered trademark) KD-803 (manufactured by Showa Denko Co., Ltd.)
・Column temperature: 50°C
・Flow rate: 1 mL/min ・Eluent: N,N-dimethylformamide (DMF), lithium bromide monohydrate (30 mM)/phosphoric acid (30 mM)/tetrahydrofuran (1%)
・Standard sample: polyethylene oxide

The chemical imidization rates shown in the synthesis examples below are the results of measurement by a nuclear magnetic resonance spectrometer (hereinafter abbreviated as NMR in this specification). For the measurement, an NMR apparatus (JNM-ECA500) (manufactured by JEOL Ltd.) was used under the following measurement conditions.
・Measurement temperature: room temperature ・Measurement solvent: deuterated tetrahydrofuran (THF-d8)
In addition, the chemical imidization rate is based on the proton derived from the structure that does not change before and after imidization, and the peak integrated value of this proton and the proton derived from the NH group of the amic acid appearing around 9.5 ppm to 11.0 ppm. It was calculated by the following formula using the peak integrated value.
Chemical imidization rate (%) = (1-α x/y) x 100
In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is one NH group proton of the amic acid in the case of polyamic acid (imidization rate is 0%). is the number ratio of reference protons to

<Synthesis Example 1> Synthesis of polyimide (P-1) BEM-S 5.50 g (20.81 mmol), DAB-C18 14.56 g (38.65 mmol), and N-ethyl-2-pyrrolidone 211 in a 4-necked flask 0.43 g was added and dissolved by stirring at room temperature under air. Furthermore, 14.86 g (28.54 mmol) of BPADA, 18.39 g (29.73 mmol) of TMPBP-TME, and 90.61 g of N-ethyl-2-pyrrolidone were added to the flask and stirred at 50°C for 20 hours. A polyamic acid solution was obtained. Next, 177.65 g of N-ethyl-2-pyrrolidone, 18.21 g of acetic anhydride, and 3.01 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. Next, 532.95 g of N-ethyl-2-pyrrolidone was added and dropped into methanol, and the resulting precipitate was filtered and dried at 60° C. under reduced pressure to obtain polyimide powder. The weight average molecular weight (Mw) by GPC was 25,770, and the chemical imidization rate by NMR (THF-d8) was 99%.

<Synthesis Example 2> Synthesis of polyimide (P-2) BEM-S 5.10 g (19.30 mmol), DAB-C18 10.38 g (27.57 mmol), HFBAPP 4.29 g (8.27 mmol) in a 4-necked flask and 200.71 g of N-ethyl-2-pyrrolidone were added and dissolved by stirring at room temperature under air. Furthermore, 13.78 g (26.47 mmol) of BPADA, 17.05 g (27.57 mmol) of TMPBP-TME, and 86.02 g of N-ethyl-2-pyrrolidone were added to the flask and stirred at 50°C for 20 hours. A polyamic acid solution was obtained. Next, 168.65 g of N-ethyl-2-pyrrolidone, 16.89 g of acetic anhydride, and 2.79 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. Next, 505.95 g of N-ethyl-2-pyrrolidone was added and dropped into methanol, and the resulting precipitate was filtered and dried at 60° C. under reduced pressure to obtain polyimide powder. The weight average molecular weight (Mw) by GPC was 32,863, and the chemical imidization rate by NMR (THF-d8) was 99%.

<Synthesis Example 3> Synthesis of polyimide (P-3) BEM-S 5.40 g (20.43 mmol), DAB-C18 14.29 g (37.95 mmol), and N-ethyl-2-pyrrolidone 200 in a 4-necked flask 0.02 g was added and dissolved by stirring at room temperature under air. Furthermore, BPADA 8.51 g (16.35 mmol), TMPBP-TME 14.45 g (23.35 mmol), 6FDA 7.78 g (17.51 mmol) and N-ethyl-2-pyrrolidone 85.72 g were added into the flask, A polyamic acid solution was obtained by stirring at 50° C. for 20 hours. Next, 168.10 g of N-ethyl-2-pyrrolidone, 17.88 g of acetic anhydride, and 2.95 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. Next, 504.30 g of N-ethyl-2-pyrrolidone was added and added dropwise to methanol. The resulting precipitate was filtered and dried at 60° C. under reduced pressure to obtain polyimide powder. The weight average molecular weight (Mw) by GPC was 28,569, and the chemical imidization rate by NMR (THF-d8) was 99%.

<Synthesis Example 4> Synthesis of polyimide (P-4) BEM-S 5.50 g (20.81 mmol), APC-14 12.39 g (38.65 mmol), and N-ethyl-2-pyrrolidone 195 in a four-necked flask .12 g was added and dissolved by stirring at room temperature under air. Furthermore, BPADA 7.92 g (17.84 mmol), TMPBP-TME 14.71 g (23.78 mmol), 6FDA 8.67 g (16.65 mmol) and N-ethyl-2-pyrrolidone 83.62 g were added into the flask, A polyamic acid solution was obtained by stirring at 50° C. for 20 hours. Next, 163.97 g of N-ethyl-2-pyrrolidone, 18.21 g of acetic anhydride, and 3.01 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. Next, 491.91 g of N-ethyl-2-pyrrolidone was added and dropped into methanol, and the resulting precipitate was filtered and dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) by GPC was 32,929, and the chemical imidization rate by NMR (THF-d8) was 99%.

<Synthesis Example 5> Synthesis of polyimide (P-5) BEM-S 5.50 g (20.81 mmol), APC-16 13.47 g (38.65 mmol), and N-ethyl-2-pyrrolidone 199 in a 4-necked flask 0.43 g was added and dissolved by stirring at room temperature under air. Furthermore, BPADA 7.92 g (17.84 mmol), TMPBP-TME 14.71 g (23.78 mmol), 6FDA 8.67 g (16.65 mmol) and N-ethyl-2-pyrrolidone 85.47 g were added into the flask, A polyamic acid solution was obtained by stirring at 50° C. for 20 hours. Next, 167.58 g of N-ethyl-2-pyrrolidone, 18.21 g of acetic anhydride, and 3.01 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. Next, 502.76 g of N-ethyl-2-pyrrolidone was added and dropped into methanol, and the resulting precipitate was filtered and dried at 60° C. under reduced pressure to obtain polyimide powder. The weight average molecular weight (Mw) by GPC was 30,568, and the chemical imidization rate by NMR (THF-d8) was 99%.

<Synthesis Example 6> Synthesis of polyimide (P-6) BEM-S 7.05 g (26.68 mmol), BAPP 4.38 g (10.67 mmol), DAB-C18 6.03 g (16.01 mmol) in a 4-necked flask , and 98.95 g of N-ethyl-2-pyrrolidone were added and dissolved by stirring at room temperature under air. Furthermore, BPADA 7.22 g (13.87 mmol), TMPBP-TME 13.20 g (21.35 mmol), 6FDA 7.11 g (16.01 mmol) and N-ethyl-2-pyrrolidone 156.05 g were added into the flask, A polyamic acid solution was obtained by stirring at 50° C. for 19 hours. Next, 150.00 g of N-ethyl-2-pyrrolidone, 16.34 g of acetic anhydride, and 2.79 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to dilute the reaction solution, and this diluted solution was dropped into methanol. The resulting precipitate was filtered, washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The weight average molecular weight (Mw) by GPC was 22,930, and the chemical imidization rate by NMR (THF-d8) was 98%.

<Synthesis Example 7> Synthesis of polyimide (P-7) BEM-S 6.96 g (26.34 mmol), BAPP 4.32 g (10.53 mmol), DAB-C18 5.95 g (15.80 mmol) in a 4-necked flask , and 97.67 g of N-ethyl-2-pyrrolidone were added and dissolved by stirring at room temperature under air. Furthermore, BPADA 7.40 g (14.22 mmol), TMPBP-TME 13.03 g (21.07 mmol), 6FDA 7.02 g (15.80 mmol), maleic anhydride 0.31 g (3.16 mmol) and N-ethyl- 157.33 g of 2-pyrrolidone was added to the flask and stirred at 50° C. for 19 hours to obtain a polyamic acid solution. Next, 150.00 g of N-ethyl-2-pyrrolidone, 16.13 g of acetic anhydride, and 2.66 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to dilute the reaction solution, and this diluted solution was dropped into methanol. The resulting precipitate was filtered, washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The weight average molecular weight (Mw) by GPC was 22,959, and the chemical imidization rate by NMR (THF-d8) was 100%.

<Synthesis Example 8> Synthesis of polyimide (P-8) BEM-S 6.95 g (26.31 mmol), BAPP 4.32 g (10.52 mmol), DAB-C18 5.95 g (15.79 mmol) in a 4-necked flask , and 97.57 g of N-ethyl-2-pyrrolidone were added and dissolved by stirring at room temperature under air. Furthermore, BPADA 7.39 g (14.21 mmol), TMPBP-TME 13.02 g (21.05 mmol), 6FDA 7.01 g (15.79 mmol), itaconic anhydride 0.35 g (3.16 mmol) and N-ethyl 157.43 g of -2-pyrrolidone was added to the flask and stirred at 50° C. for 19 hours to obtain a polyamic acid solution. Next, 150.00 g of N-ethyl-2-pyrrolidone, 16.12 g of acetic anhydride, and 2.66 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to dilute the reaction solution, and this diluted solution was dropped into methanol. The resulting precipitate was filtered, washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The weight average molecular weight (Mw) by GPC was 26,102, and the chemical imidization rate by NMR (THF-d8) was 100%.

<Synthesis Example 9> Synthesis of polyimide (P-9) BEM-S 6.93 g (26.21 mmol), BAPP 4.30 g (10.49 mmol), DAB-C18 5.92 g (15.73 mmol) in a 4-necked flask , and 97.22 g of N-ethyl-2-pyrrolidone were added and dissolved by stirring at room temperature under air. Furthermore, BPADA 7.37 g (14.16 mmol), TMPBP-TME 12.97 g (20.97 mmol), 6FDA 6.99 g (15.73 mmol), 5-norbornene-2,3-dicarboxylic anhydride 0.52 g ( 3.15 mmol) and 157.78 g of N-ethyl-2-pyrrolidone were added into the flask and stirred at 50° C. for 19 hours to obtain a polyamic acid solution. Next, 150.00 g of N-ethyl-2-pyrrolidone, 16.06 g of acetic anhydride, and 2.65 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to dilute the reaction solution, and this diluted solution was dropped into methanol. The resulting precipitate was filtered, washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The weight average molecular weight (Mw) by GPC was 26,096, and the chemical imidization rate by NMR (THF-d8) was 99%.

<Synthesis Example 10> Synthesis of polyimide (P-10) BEM-S 6.80 g (25.72 mmol), BAPP 4.22 g (10.29 mmol), DAB-C18 5.81 g (15.43 mmol) in a 4-necked flask , and 95.37 g of N-ethyl-2-pyrrolidone were added and dissolved by stirring at room temperature under air. Furthermore, 21.32 g (34.46 mmol) of TMPBP-TME, 6.85 g (15.43 mmol) of 6FDA and 159.63 g of N-ethyl-2-pyrrolidone were added to the flask and stirred at 50° C. for 22 hours to obtain polyamic. An acid solution was obtained. Next, 150.00 g of N-ethyl-2-pyrrolidone, 15.75 g of acetic anhydride, and 2.60 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to dilute the reaction solution, and this diluted solution was dropped into methanol. The resulting precipitate was filtered, washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The weight average molecular weight (Mw) by GPC was 33,309, and the chemical imidization rate by NMR (THF-d8) was 99%.

<Synthesis Example 11> Synthesis of polyimide (P-11) BEM-S 6.75 g (25.54 mmol), BAPP 4.19 g (10.22 mmol), DAB-C18 5.77 g (15.33 mmol) in a 4-necked flask , and 94.73 g of N-ethyl-2-pyrrolidone were added and dissolved by stirring at room temperature under air. Furthermore, TMPBP-TME 21.17 g (34.23 mmol), 6FDA 6.81 g (15.33 mmol), maleic anhydride 0.30 g (3.07 mmol) and N-ethyl-2-pyrrolidone 160.27 g were placed in the flask. The polyamic acid solution was obtained by adding and stirring at 50 degreeC for 19 hours. Next, 150.00 g of N-ethyl-2-pyrrolidone, 15.65 g of acetic anhydride, and 2.58 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to dilute the reaction solution, and this diluted solution was dropped into methanol. The resulting precipitate was filtered, washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The weight average molecular weight (Mw) by GPC was 29,575, and the chemical imidization rate by NMR (THF-d8) was 100%.

<Synthesis Example 12> Synthesis of polyimide (P-12) BEM-S 10.09 g (38.18 mmol), DAB-C18 6.16 g (16.36 mmol), and N-ethyl-2-pyrrolidone 92 in a 4-necked flask 0.09 g was added and dissolved by stirring at room temperature under air. Furthermore, BPADA 7.66 g (14.73 mmol), TMPBP-TME 13.49 g (21.82 mmol), 6FDA 7.27 g (16.36 mmol), maleic anhydride 0.32 g (3.27 mmol) and N-ethyl- 162.91 g of 2-pyrrolidone was added to the flask and stirred at 50° C. for 19 hours to obtain a polyamic acid solution. Next, 150.00 g of N-ethyl-2-pyrrolidone, 16.70 g of acetic anhydride, and 2.76 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to dilute the reaction solution, and this diluted solution was dropped into methanol. The resulting precipitate was filtered, washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The weight average molecular weight (Mw) by GPC was 22,161, and the chemical imidization rate by NMR (THF-d8) was 100%.

<Synthesis Example 13> Synthesis of polyimide (P-13) BEM-S 8.43 g (38.18 mmol), BAPP 5.46 g (13.30 mmol), DAB-C18 3.01 g (7.98 mmol) in a 4-necked flask , and 95.76 g of N-ethyl-2-pyrrolidone were added and dissolved by stirring at room temperature under air. Furthermore, 6.92 g (13.30 mmol) of BPADA, 16.45 g (26.60 mmol) of TMPBP-TME, 4.73 g (10.64 mmol) of 6FDA and 159.24 g of N-ethyl-2-pyrrolidone were added into the flask, A polyamic acid solution was obtained by stirring at 50° C. for 19 hours. Next, 150.00 g of N-ethyl-2-pyrrolidone, 16.29 g of acetic anhydride, and 2.69 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to dilute the reaction solution, and this diluted solution was dropped into methanol. The resulting precipitate was filtered, washed with methanol, and dried under reduced pressure at 60° C. to obtain a polyimide powder. The weight average molecular weight (Mw) by GPC was 23,237, and the chemical imidization rate by NMR (THF-d8) was 98%.

<Comparative Synthesis Example 1> Synthesis of polyimide (P-14) 2.81 g (10.62 mmol) of BEM-S, 10.23 g (19.72 mmol) of HFBAPP, and N-ethyl-2-pyrrolidone were placed in a four-necked flask. 15 g was added and dissolved by stirring at room temperature under air. Furthermore, 7.58 g (14.57 mmol) of BPADA, 9.39 g (15.17 mmol) of TMPBP-TME, and 73.85 g of N-ethyl-2-pyrrolidone were added to the flask and stirred at room temperature for 39 hours to obtain polyamic. An acid solution was obtained. Next, 100.00 g of N-ethyl-2-pyrrolidone, 9.29 g of acetic anhydride, and 1.54 g of triethylamine were added to the flask and stirred at 60° C. for 3 hours for chemical imidization. 128.57 g of N-ethyl-2-pyrrolidone was added to dilute the reaction solution, and this diluted solution was dropped into methanol. The resulting precipitate was washed with methanol and dried under reduced pressure at 60° C. to obtain a polyimide powder. The weight average molecular weight (Mw) by GPC was 44,173, and the chemical imidization rate by NMR (THF-d8) was 99%.

The compounds shown in Examples and Comparative Examples are shown below.
・ NK ester A-DOD-N: 1,10-decanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
· BMI-689: a maleimide compound represented by the formula (manufactured by Designer Molecules Inc.)

· CaA-BTZ: 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK)
· CBT-SG: a mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole (manufactured by Johoku Chemical Industry Co., Ltd.)
· KBM-5103: 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Example 1>
Polyimide obtained in Synthesis Example 1 (P-1) 5.81 g, NK ester A-DOD-N 0.58 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0.12 g as a photoradical initiator, CaA-BTZ 0 .17 g, KBM-5103 0.11 g, N-ethyl-2-pyrrolidone 3.96 g, and cyclopentanone 9.24 g are mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm. , a negative photosensitive resin composition for forming an insulating film was prepared.

<Example 2>
Polyimide obtained in Synthesis Example 2 (P-2) 5.32 g, NK ester A-DOD-N 0.80 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0.21 g as a photoradical initiator, CaA-BTZ 0 .16 g, KBM-5103 0.11 g, N-ethyl-2-pyrrolidone 7.02 g, γ-butyrolactone 9.36 g, and cyclohexanone 7.02 g were mixed and dissolved, and then a polypropylene filter with a pore size of 5 μm was used. A negative photosensitive resin composition for forming an insulating film was prepared by filtering the mixture.

<Example 3>
Polyimide obtained in Synthesis Example 2 (P-2) 7.66 g, NK ester A-DOD-N 1.15 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0.31 g as a photoradical initiator, CaA-BTZ 0 .23 g, KBM-5103 0.15 g, N-ethyl-2-pyrrolidone 12.15 g, γ-butyrolactone 16.20 g, and cyclohexanone 12.15 g were mixed and dissolved, and then a polypropylene filter with a pore size of 5 μm was used. A negative photosensitive resin composition for forming an insulating film was prepared by filtering the mixture.

<Example 4>
Polyimide obtained in Synthesis Example 3 (P-3) 7.02 g, NK ester A-DOD-N 1.05 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0.28 g as a photoradical initiator, CaA-BTZ 0 .21 g, KBM-5103 0.14 g, N-ethyl-2-pyrrolidone 6.39 g, γ-butyrolactone 8.52 g, and cyclohexanone 6.39 g were mixed and dissolved, and then a polypropylene filter with a pore size of 5 μm was used. A negative photosensitive resin composition for forming an insulating film was prepared by filtering the mixture.

<Example 5>
Polyimide obtained in Synthesis Example 3 (P-3) 10.08 g, NK ester A-DOD-N 1.51 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0.40 g as a photoradical initiator, CaA-BTZ 0 .30 g, KBM-5103 0.20 g, N-ethyl-2-pyrrolidone 11.25 g, γ-butyrolactone 15.00 g, and cyclohexanone 11.25 g were mixed and dissolved, and then a polypropylene filter with a pore size of 5 μm was used. A negative photosensitive resin composition for forming an insulating film was prepared by filtering the mixture.

<Example 6>
Polyimide (P-4) 8.06 g obtained in Synthesis Example 4, NK ester A-DOD-N 1.21 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0.32 g as a photoradical initiator, CaA-BTZ 0 .24 g, KBM-5103 0.16 g, N-ethyl-2-pyrrolidone 9.00 g, γ-butyrolactone 12.00 g, and cyclohexanone 9.00 g were mixed and dissolved, and then a polypropylene filter with a pore size of 5 μm was used. A negative photosensitive resin composition for forming an insulating film was prepared by filtering the mixture.

<Example 7>
Polyimide obtained in Synthesis Example 5 (P-5) 8.06 g, NK ester A-DOD-N 1.21 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0.32 g as a photoradical initiator, CaA-BTZ 0 .24 g, KBM-5103 0.16 g, N-ethyl-2-pyrrolidone 9.00 g, γ-butyrolactone 12.00 g, and cyclohexanone 9.00 g were mixed and dissolved, and then a polypropylene filter with a pore size of 5 μm was used. A negative photosensitive resin composition for forming an insulating film was prepared by filtering the mixture.

<Example 8>
Polyimide obtained in Synthesis Example 6 (P-6) 8.82 g, NK ester A-DOD-N 1.32 g and BMI-689 0.88 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0 as a photoradical initiator .26 g, 0.13 g of CBT-SG, 0.18 g of KBM-5103, 8.52 g of N-ethyl-2-pyrrolidone, 11.36 g of γ-butyrolactone, and 8.52 g of cyclohexanone were mixed and dissolved. A negative photosensitive resin composition for forming an insulating film was prepared by filtering using a 5 μm polypropylene filter.

<Example 9>
Polyimide (P-7) 8.82 g obtained in Synthesis Example 7, NK ester A-DOD-N 1.32 g and BMI-689 0.88 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0 as a photoradical initiator .26 g, 0.13 g of CBT-SG, 0.18 g of KBM-5103, 8.52 g of N-ethyl-2-pyrrolidone, 11.36 g of γ-butyrolactone, and 8.52 g of cyclohexanone were mixed and dissolved. A negative photosensitive resin composition for forming an insulating film was prepared by filtering using a 5 μm polypropylene filter.

<Example 10>
Polyimide (P-7) 8.56 g obtained in Synthesis Example 7, NK ester A-DOD-N 1.28 g and BMI-689 0.86 g as a cross-linking agent, Adeka Arcles NCI-9300 as a photoradical initiator .09 g, IRGACURE® 819 0.51 g, CBT-SG 0.13 g, KBM-5103 0.17 g, N-ethyl-2-pyrrolidone 8.52 g, γ-butyrolactone 11.36 g, and cyclohexanone 8.52 g. were mixed and dissolved, and filtered through a polypropylene filter having a pore size of 5 μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 11>
Polyimide (P-8) 8.82 g obtained in Synthesis Example 8, NK ester A-DOD-N 1.32 g and BMI-689 0.88 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0 as a photoradical initiator .26 g, 0.13 g of CBT-SG, 0.18 g of KBM-5103, 8.52 g of N-ethyl-2-pyrrolidone, 11.36 g of γ-butyrolactone, and 8.52 g of cyclohexanone were mixed and dissolved. A negative photosensitive resin composition for forming an insulating film was prepared by filtering using a 5 μm polypropylene filter.

<Example 12>
Polyimide obtained in Synthesis Example 9 (P-9) 8.82 g, NK ester A-DOD-N 1.32 g and BMI-689 0.88 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0 as a photoradical initiator .26 g, CBT-SG 0.13 g, KBM-5103 0.18 g, N-ethyl-2-pyrrolidone 8.52 g, γ-butyrolactone 11.36 g, and cyclohexanone 8.52 g were mixed and dissolved, and then the pore size was determined. A negative photosensitive resin composition for forming an insulating film was prepared by filtering using a 5 μm polypropylene filter.

<Example 13>
Polyimide (P-10) 9.23 g obtained in Synthesis Example 10, NK ester A-DOD-N 1.38 g and BMI-689 0.92 g as a cross-linking agent, Adeka Arcles NCI-9300 as a photoradical initiator 0.09 g and IRGACURE® 819 0.55 g, CBT-SG 0.14 g, KBM-5103 0.18 g, N-ethyl-2-pyrrolidone 11.25 g, γ-butyrolactone 15.00 g, and cyclohexanone 11.25 g. was mixed and dissolved, and filtered using a polypropylene filter having a pore size of 5 μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 14>
7.97 g of the polyimide (P-11) obtained in Synthesis Example 11, NK ester A-DOD-N 1.20 g and BMI-689 0.80 g as a cross-linking agent, and Adeka Arcles NCI-9300 as a photoradical initiator .08 g and IRGACURE® 819 0.48 g, CBT-SG 0.12 g, KBM-5103 0.16 g, N-ethyl-2-pyrrolidone 8.76 g, γ-butyrolactone 11.68 g, and cyclohexanone 8.76 g. were mixed and dissolved, and filtered through a polypropylene filter having a pore size of 5 μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 15>
Polyimide (P-12) 8.56 g obtained in Synthesis Example 12, NK ester A-DOD-N 1.28 g and BMI-689 0.86 g as a cross-linking agent, Adeka Arcles NCI-9300 as a photoradical initiator 0.09 g and IRGACURE® 819 0.51 g, CBT-SG 0.13 g, KBM-5103 0.17 g, N-ethyl-2-pyrrolidone 8.52 g, γ-butyrolactone 11.36 g, and cyclohexanone 8.52 g. were mixed and dissolved, and filtered through a polypropylene filter having a pore size of 5 μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 16>
10.70 g of the polyimide (P-13) obtained in Synthesis Example 13, NK ester A-DOD-N 1.61 g and BMI-689 1.07 g as a cross-linking agent, and Adeka Arcles NCI-9300 as a photoradical initiator .11 g and IRGACURE® 819 0.64 g, CBT-SG 0.16 g, KBM-5103 0.21 g, N-ethyl-2-pyrrolidone 10.65 g, γ-butyrolactone 14.20 g, and cyclohexanone 10.65 g. was mixed and dissolved, and filtered using a polypropylene filter having a pore size of 5 μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Comparative Example 1>
Polyimide obtained in Comparative Synthesis Example 1 (P-14) 10.00 g, NK ester A-DOD-N 1.50 g as a cross-linking agent, IRGACURE [registered trademark] OXE01 0.40 g as a photoradical initiator, CaA-BTZ After mixing and dissolving 0.30 g, KBM-5103 0.20 g, N-ethyl-2-pyrrolidone 12.45 g, γ-butyrolactone 16.61 g, and cyclopentanone 12.45 g, polypropylene with a pore size of 5 μm A negative photosensitive resin composition for forming an insulating film was prepared by filtering using a filter.

<Comparative Example 2>
4.32 g of N-ethyl-2-pyrrolidone, 5.76 g of γ-butyrolactone, and 4.32 g of cyclopentanone were mixed with 32.89 g of the negative photosensitive resin composition for forming an insulating film obtained in Comparative Example 1. and diluted.

[Evaluation of electrical characteristics]
4-inch silicon coated with an aluminum foil having a thickness of 20 μm with the negative photosensitive resin composition for forming an insulating film prepared in Examples 1, 2, 4, 6 to 16 and Comparative Example 1 A photosensitive resin film having a thickness of about 25 μm was formed on the aluminum foil by spin coating on the wafer and baking on a hot plate at 115° C. for 270 seconds. Using an i-line aligner (PLA-501, manufactured by Canon Inc.) on the resulting photosensitive resin film, the entire surface of the wafer was exposed to light at 500 mJ/cm ² , and then placed in a high-temperature clean oven (CLH-21CD(V). -S, Koyo Thermo Systems Co., Ltd.) was used to bake in a nitrogen atmosphere at 230° C. for 2 hours. Furthermore, the film was obtained by immersing the baked aluminum foil in 6N hydrochloric acid to dissolve the aluminum foil. The dielectric loss tangent of the obtained film at 60 GHz was measured using a split cylinder resonator. The dielectric loss tangent measurement conditions are as follows.
・Measurement method: Split cylinder resonator ・Vector network analyzer: FieldFox N9926A (manufactured by Keysight Technologies Inc.)
・Resonator: CR-760 (manufactured by EM Lab Co., Ltd.)
・Measurement frequency: about 60 GHz
Table 1 shows the measurement results of the dielectric loss tangent of the film at 60 GHz.

表１の結果から、実施例１、実施例２、実施例４、実施例６乃至実施例１６の絶縁膜形成用ネガ型感光性樹脂組成物から得られたフィルムは、比較例１の絶縁膜形成用ネガ型感光性樹脂組成物から得られたフィルムよりも６０ＧＨｚにおける誘電正接が低い値を示した。

From the results in Table 1, the films obtained from the negative photosensitive resin compositions for forming an insulating film of Examples 1, 2, 4, and 6 to 16 are the insulating films of Comparative Example 1. It exhibited a lower dielectric loss tangent value at 60 GHz than the film obtained from the negative photosensitive resin composition for formation.

[Photosensitivity evaluation]
The negative photosensitive resin composition for forming an insulating film prepared in Example 3, Examples 5 to 16, and Comparative Example 2 was applied onto an 8-inch silicon wafer using a spin coater (CLEAN TRACK ACT-8, Tokyo Electron Ltd.). ), and then baked at 115° C. for 270 seconds to form a photosensitive resin film having a thickness of about 6.5 μm on the wafer. An i-line stepper (NSR-2205i12D, manufactured by Nikon Corporation) was used to form a 7 mm square exposure pattern (exposure amount: 300 mJ/cm ² ) on the resulting photosensitive resin film. After exposure, using an automatic developing device (AD-1200, manufactured by Mikasa Co., Ltd.), spray development was carried out with cyclopentanone as a developer, and propylene glycol monomethyl ether acetate (PGMEA) as a rinse was spray rinsed. The development time with cyclopentanone was the time until the unexposed area (0 mJ/cm ² ) was completely developed, and the rinse time with PGMEA was 10 seconds. The film thickness immediately after film formation and the film thickness after development in unexposed and exposed areas (300 mJ/cm ² ) were measured using an interferometric film thickness meter (Lambda Ace VM-2110, manufactured by SCREEN Co., Ltd.). , the ratio of the film thickness left undeveloped in the exposed area (remaining film ratio (%)) was calculated by the following formula.
Remaining film thickness (%) = [(film thickness of unexposed portion) or (film thickness of exposed portion)]/(film thickness immediately after film formation) x 100
In other words, if the residual film ratio is 80%, it means that 80% of the film thickness immediately after film formation remains without being developed. Table 2 shows the measurement results of the development time and post-development residual film ratio.

From the results in Table 2, the negative photosensitive resin compositions for forming an insulating film of Example 3, Examples 5 to 16, and Comparative Example 2 were all developed in the unexposed areas of the photosensitive resin film after development. , the photosensitive resin film in the exposed portion was hardly developed. Furthermore, the photosensitive resin film obtained from the negative photosensitive resin composition for forming an insulating film of Comparative Example 2 was obtained from the negative photosensitive resin composition for forming an insulating film of Example 3 and Examples 5 to 16. The development time with cyclopentanone was longer than that of the photosensitive resin film obtained from . That is, the photosensitive resin films obtained from the negative photosensitive resin compositions for forming insulating films of Examples 3 and 5 to 16 have high solubility in the developer, and the development time required for the development process is shortened. It is also effective in reducing the amount of developer used.

[Evaluation of residual stress]
The negative photosensitive resin composition for forming an insulating film prepared in Example 3, Example 5, and Comparative Example 2 was applied to a new 8-inch silicon wafer having a thickness of 724 μm using a spin coater (CLEAN TRACK ACT-8, A photosensitive resin film having a thickness of about 6.5 .mu.m was formed on the wafer by applying the coating solution using a Tokyo Electron Co., Ltd.) and then baking at 115.degree. C. for 270 seconds.
Next, the entire surface was exposed at 500 mJ/cm ² using an i-line stepper (NSR-2205i12D, manufactured by Nikon Corporation). Then, using a high-temperature clean oven (CLH-21CD(V)-S, Koyo Thermo Systems Co., Ltd.), the film was baked in a nitrogen atmosphere at 230° C. for 2 hours to obtain a cured polyimide film. The residual stress of the resulting polyimide film was measured at room temperature using a thin film stress measurement device (FLX-3300-T: manufactured by KLA-Tencor Co., Ltd.).
Table 3 shows the results of measuring the residual stress. A measured value of 25 MPa or less was defined as "good", and a value of 30 MPa or more was defined as "poor".

From the results in Table 3, the cured polyimide films obtained from the negative photosensitive resin compositions for forming an insulating film of Examples 3 and 5 were obtained from the negative photosensitive resin composition for forming an insulating film of Comparative Example 2. Since the residual stress is smaller than that of the obtained polyimide cured film, the silicon wafer is less likely to warp, and problems are less likely to occur during transportation and wafer fixing.

That is, the negative photosensitive resin compositions for forming an insulating film of Examples 1 to 16 not only allow formation of a relief pattern in a short development time, but also have a low dielectric loss tangent and a low residual stress. It can be suitably used for the production of electronic materials that require excellent electrical properties.

Claims (12)

Containing polyimide , a photoradical polymerization initiator, and a solvent,
The polyimide has a photopolymerizable group, an aromatic group and an alkyl group having 5 or more carbon atoms,
A photosensitive resin composition for forming an insulating film ,
The polyimide is the following polyimide (1),
A photosensitive resin composition for forming an insulating film.
Polyimide (1): A polyimide having structural units represented by the following formulas (1-a), (1-b) and (1-c) below.

[In formula (1-a), Ar ₁ represents a tetravalent organic group.
In formula (1-b), X represents a divalent aromatic group having an alkyl group with 5 or more carbon atoms.
In formula (1-c), Y represents a divalent organic group represented by formula (9-a) below. ]

[In formula (9-a), V ₁ represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond, W ₁ represents an oxygen atom or an NH group, R ₁₅ represents a direct bond, or represents an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, R ₁₆ represents a hydrogen atom or a methyl group, and * represents a bond. ] The photosensitive material for forming an insulating film according to claim 1 , wherein X in the formula (1-b) represents a divalent organic group represented by any one of the following formulas (V-1) to (V-6). Resin composition.
(In formula (V-1), X ^v1 represents -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-. ^{R v1} has 5 carbon atoms. represents an alkyl group of ∼20.
In formulas (V-2) to (V-5), X ^v2 to X ^v5 are each independently -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, - represents NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO- or -OCO-; R ^v2 to R ^v5 each independently represent an alkyl group having 5 to 20 carbon atoms.
In formula (V-6), X _a is a single bond, —O—, —NH—, —O—(CH ₂ ) _m —O— (m represents an integer of 1 to 6), —C( CH ₃ ) ₂ -, -CO-, -(CH ₂ ) _m - (m represents an integer of 1 to 6), -SO ₂ -, -OC(CH ₃ ) ₂ -, -CO-( CH ₂ ) _m — (m represents an integer of 1 to 6), —NH—(CH ₂ ) _m — (m represents an integer of 1 to 6), —SO ₂ —(CH ₂ ) _m — (m represents an integer of 1 to 6), —CONH—(CH ₂ ) _m — (m represents an integer of 1 to 6), —CONH—(CH ₂ ) _m —NHCO— (m is 1 represents an integer of ~6.), -COO-(CH ₂ ) _m -OCO- (m represents an integer of 1 to 6.), -CONH-, -NH-(CH ₂ ) _m -NH-(m represents an integer of 1 to 6), or -SO ₂ -(CH ₂ ) _m -SO ₂ - (m represents an integer of 1 to 6). X ^p1 and X ^p2 each independently represent -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH- , -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-. R ^1a and R ^1b each independently represent an alkyl group having 5 to 20 carbon atoms. k1 and k2 each independently represent an integer of 0 to 2;
In formulas (V-1) to (V-6), * represents a bond. ) 2. The photosensitive resin composition for forming an insulating film according to claim 1, wherein V ₁ in the formula (9-a) represents an ester bond and W ₁ represents an oxygen atom. 2. The photosensitive resin composition for forming an insulating film according to claim 1 , wherein R ₁₅ in the formula (9-a) represents a 1,2-ethylene group. 2. The photosensitive resin composition for forming an insulating film according to claim 1, further comprising a crosslinkable compound. 2. The photosensitive resin composition for forming an insulating film according to claim 1, which is a negative photosensitive resin composition. An insulating film, which is a baked product of a coating film of the photosensitive resin composition for forming an insulating film according to any one of claims 1 to 6 . A photosensitive resist film comprising a substrate film, a photosensitive resin layer formed from the photosensitive resin composition for forming an insulating film according to any one of claims 1 to 6 , and a cover film. (1) a step of applying the photosensitive resin composition for forming an insulating film according to any one of claims 1 to 6 onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) heat-treating the relief pattern to form a cured relief pattern;
A method of manufacturing a cured relief patterned substrate, comprising: 10. The method for producing a cured relief patterned substrate according to claim 9 , wherein the developer used for the development is an organic solvent. A cured relief patterned substrate manufactured by the method of claim 9 . A semiconductor device comprising a semiconductor element and a cured film provided above or below the semiconductor element, wherein the cured film is formed from the photosensitive resin composition for forming an insulating film according to any one of claims 1 to 6 . A semiconductor device that is a cured relief pattern formed.