JP2021196482A - Photosensitive resin composition containing low dielectric loss tangent agent - Google Patents

Abstract

To provide a photosensitive resin composition which exhibits a low dielectric loss tangent, is excellent in storage stability, and enables formation of a cured relief pattern with high resolution, a method for producing polyimide and a method for producing a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern.SOLUTION: A photosensitive resin composition contains 100 pts.mass of (A) a polyimide precursor, 0.1-10 pts.mass of (B) a photosensitive agent, 1-50 pts.mass of (C) a low dielectric loss tangent agent, and 50-300 pts.mass of (D) a solvent, in which (C) the low dielectric loss tangent agent has a molecular weight of 100-3,500.SELECTED DRAWING: None

Description

INDUSTRIAL APPLICABILITY The present invention is a negative photosensitive resin composition containing a low-dielectric directing agent, for example, an insulating material for electronic parts, and a negative photosensitive film used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device. The present invention relates to a method for producing a polyimide using the sex resin composition, a method for producing a cured relief pattern, and a semiconductor device.

Conventionally, a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties has been used as an insulating material for electronic components, a passivation film for a semiconductor device, a surface protective film, an interlayer insulating film, and the like. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor composition can easily form a heat-resistant relief pattern film by applying, exposing, developing, and thermally imidizing the composition. Can be formed. Such a photosensitive polyimide precursor composition has a feature that it enables a significant process shortening as compared with a conventional non-photosensitive polyimide material.

By the way, a semiconductor device (hereinafter, also referred to as an "element") is mounted on a printed circuit board by various methods according to a purpose. Conventional elements have generally been manufactured by a wire bonding method in which a thin wire is used to connect an external terminal (pad) of the element to a lead frame. However, as the speed of the element increases and the operating frequency reaches GHz, the difference in the wiring length of each terminal in the mounting has come to affect the operation of the element. Therefore, in the mounting of elements for high-end applications, it is necessary to accurately control the length of the mounting wiring, and it is difficult to meet the demand by wire bonding.

Therefore, a flip chip mounting method has been proposed in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on the bumps (electrodes), and then the chips are flipped over and mounted directly on a printed circuit board. .. Since this flip-chip mounting can accurately control the wiring distance, it is used in high-end applications that handle high-speed signals, or in mobile phones due to its small mounting size, and demand is rapidly expanding. .. More recently, the wafers that have been pre-processed are diced to produce individual chips, the individual chips are reconstructed on the support, sealed with mold resin, and the support is peeled off to form a rewiring layer. A semiconductor chip mounting technique called a fan-out wafer level package (FOWLP) has been proposed (for example, Patent Document 1). The fan-out wafer level package has the advantages that the height of the package can be reduced, and high-speed transmission or cost can be reduced.

Japanese Unexamined Patent Publication No. 2005-167191

In recent years, there is an urgent need to develop a package for the 5th generation mobile communication system (5G), which is a new communication standard. By using the millimeter wave (10 Gz to 80 GHz) frequency band in 5G, it is possible to increase the capacity at high speed, reduce the signal delay, and connect a large number of terminals at the same time, which was not possible with conventional communication. On the other hand, it is known that the dielectric loss tangent (tan δ) of the insulating material is high in the high frequency region such as millimeter waves, and transmission loss occurs. An antenna-in package (AiP) in which an FEM) and an antenna are integrated has been developed. However, the dielectric loss tangent of an insulating material has a large effect on transmission loss, and a material having a low dielectric loss tangent is required.

Therefore, the present invention relates to a photosensitive resin composition that exhibits low dielectric loss tangent, has excellent storage stability, and can form a cured relief pattern with high resolution, a method for producing polyimide using the photosensitive resin composition, and a cured relief. It is an object of the present invention to provide a method for manufacturing a pattern and a semiconductor device having the cured relief pattern.

｛式中、Ｒ_１及びＲ_４及びＲ_５は、それぞれ独立に、水素原子またはメチル基またはｔ−ブチル基であり、Ｒ_２及びＲ_３は、それぞれ独立に、水素原子、またはヒドロキシ基、または炭素数１〜３０の有機基であり、Ｚは、硫黄、リン、酸素、及び窒素から成る群から少なくとも１つ選ばれるヘテロ原子を含有する炭素数７〜８０の有機基、またはカルボニル基を含有する炭素数２〜１５の有機基である。｝
で表される構造を有する、項目１に記載の感光性樹脂組成物。
［３］
前記（Ｃ）低誘電正接化剤が、下記式（ＩＩ）：

｛式中、Ｒ_１及びＲ_４及びＲ_５及びＲ_６及びＲ_７及びＲ_１０は、それぞれ独立に、水素原子またはメチル基またはｔ−ブチル基であり、Ｒ_２及びＲ_３及びＲ_８及びＲ_９は、それぞれ独立に、水素原子、またはヒドロキシ基、または炭素数１〜３０の有機基であり、Ｚは、硫黄、リン、酸素、及び窒素から成る群から少なくとも１つ選ばれるヘテロ原子を含有する炭素数１〜５０の２価の有機基、または炭素数１〜７５の２価の有機基である。｝
で表される構造を有する、項目１又は２に記載の感光性樹脂組成物。
［４］
前記（Ｃ）低誘電正接化剤が、下記式（ＩＩＩ）：

｛式中、Ｒ_１及びＲ_４及びＲ_５及びＲ_６及びＲ_９及びＲ_１０及びＲ_１１及びＲ_１２及びＲ_１５は、それぞれ独立に、水素原子またはメチル基またはｔ−ブチル基であり、Ｒ_２及びＲ_３及びＲ_８及びＲ_７及びＲ_１３及びＲ_１４は、それぞれ独立に、水素原子またはヒドロキシ基または炭素数１〜３０の有機基であり、Ｚは、硫黄、リン、酸素、及び窒素から成る群から少なくとも１つ選ばれるヘテロ原子を含有する炭素数１〜５０の３価の有機基、または炭素数１〜５０の３価の有機基である。｝
で表される構造を有する、項目１又は２に記載の感光性樹脂組成物。
［５］
前記Ｚが、硫黄、リン、酸素、及び窒素から成る群から少なくとも１つ選ばれるヘテロ原子を有する、項目２〜４のいずれか１項に記載の感光性樹脂組成物。
［６］
（Ｃ）低誘電正接化剤が、下記式：

｛式中、Ｚは、カルボニル基を含有する炭素数２〜１５の有機基である。｝
中の少なくとも１種で表される構造を有する、項目１又は２に記載の感光性樹脂組成物。
［７］
前記（Ｃ）低誘電正接化剤が、下記式（ＩＶ）：

｛式中、Ｒ_１及びＲ_４及びＲ_５及びＲ_６及びＲ_７及びＲ_１０及びＲ_１１及びＲ_１２及びＲ_１５及びＲ_１６及びＲ_１９及びＲ_２０は、それぞれ独立に、水素原子またはメチル基またはｔ−ブチル基であり、Ｒ_２及びＲ_３及びＲ_８及びＲ_９及びＲ_１３及びＲ_１４及びＲ_１７及びＲ_１８は、それぞれ独立に、水素原子またはヒドロキシ基または炭素数１〜５０の有機基であり、Ｚは、硫黄、リン、酸素、及び窒素から成る群から少なくとも１つ選ばれるヘテロ原子を含有する炭素数１〜５０の４価の有機基、または炭素数１〜５０の４価の有機基である。｝
で表される構造を有する、項目１又は２に記載の感光性樹脂組成物。
［８］
前記（Ａ）ポリイミド前駆体が、下記一般式（１）：

｛式（１）中、Ｘ_１は、炭素数６〜４０の４価の有機基であり、Ｙ_１は、炭素数６〜４０の２価の有機基であり、ｎ_１は、２〜１５０の整数であり、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、又は炭素数１〜４０の１価の有機基である。ただし、Ｒ_１及びＲ_２の少なくとも一方は、下記一般式（２）：

（式（２）中、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜３の１価の有機基であり、そしてｍ_１は、２〜１０の整数である。）
で表される基である。｝
で表される、項目１〜７のいずれか１項に記載の感光性樹脂組成物。
［９］
前記Ｙ_１が、下記式（Ｙ１）：

｛式中、Ｒｚは、それぞれ独立に、ハロゲン原子を含んでもよい炭素数１〜１０の１価の有機基を表し、ａは０〜４の整数を表し、Ａは酸素原子または硫黄原子であり、そしてＢは下記式：

中の１種である。｝
で表される、項目８に記載の感光性樹脂組成物。
［１０］
前記Ｙ_１が、下記式：

または下記式：

または下記式：

で表される構造である、項目９に記載の感光性樹脂組成物。
［１１］
前記Ｘ_１が、下記式（Ｘ１）：

｛式中、Ｒｙは、それぞれ独立に、ハロゲン原子を含んでもよい炭素数１〜１０の１価の有機基を表し、ａは０〜４の整数を表し、Ｃは酸素原子または硫黄原子であり、そしてＤは下記式：

中の１種である。｝
で表される、項目８〜１０のいずれか１項に記載の感光性樹脂組成物。
［１２］
前記Ｘ_１が、下記式：

または下記式：

で表される構造である、項目１１に記載の感光性樹脂組成物。
［１３］
前記（Ｂ）感光剤が、光ラジカル重合開始剤である、項目１〜１２のいずれか１項に記載の感光性樹脂組成物。
［１４］
ネガ型感光性樹脂組成物である、項目１〜１３のいずれか１項に記載の感光性樹脂組成物。
［１５］
ポリイミド前駆体：１００質量部、感光剤：０．１〜１０質量部、及び溶剤：５０〜３００質量部を含む感光性樹脂組成物から得られる硬化膜の製造方法であって、該硬化膜が下記数式（ｉ）：
０．００１＜（ｔａｎδ_４０−ｔａｎδ_１０）／ｔａｎδ_１０＜０．２ （ｉ）
｛式中、ｔａｎδ_４０は摂動方式スプリットシリンダ共振器法による周波数４０ＧＨｚでの誘電正接を示し、ｔａｎδ_１０は摂動方式スプリットシリンダ共振器法による周波数１０ＧＨｚの誘電正接を示す｝を満たす、硬化膜の製造方法。
［１６］
ポリイミド前駆体：１００質量部、感光剤：０．１〜１０質量部、及び溶剤：５０〜３００質量部を含む感光性樹脂組成物から得られる硬化膜の製造方法であって、該硬化膜が下記数式（ｉｉ）：
０．００１＜（ｔａｎδ_６０−ｔａｎδ_１０）／ｔａｎδ_１０＜０．２９ （ｉｉ）
｛式中、ｔａｎδ_６０は摂動方式スプリットシリンダ共振器法による周波数６０ＧＨｚでの誘電正接を示し、ｔａｎδ_１０は摂動方式スプリットシリンダ共振器法による周波数１０ＧＨｚの誘電正接を示す｝を満たす、硬化膜の製造方法。
［１７］
ポリイミド前駆体：１００質量部、感光剤：０．１〜１０質量部、及び溶剤：５０〜３００質量部を含む感光性樹脂組成物から得られる硬化膜の製造方法であって、該硬化膜が下記数式（ｉ）および（ｉｉ）：
０．００１＜（ｔａｎδ_４０−ｔａｎδ_１０）／ｔａｎδ_１０＜０．２ （ｉ）
０．００１＜（ｔａｎδ_６０−ｔａｎδ_１０）／ｔａｎδ_１０＜０．２９ （ｉｉ）
｛式中、ｔａｎδ_４０は摂動方式スプリットシリンダ共振器法による周波数４０ＧＨｚでの誘電正接を示し、ｔａｎδ_１０は摂動方式スプリットシリンダ共振器法による周波数１０ＧＨｚの誘電正接を示し、ｔａｎδ_６０は摂動方式スプリットシリンダ共振器法による周波数６０ＧＨｚでの誘電正接を示す｝を満たす、硬化膜の製造方法。
［１８］
前記感光性樹脂組成物に含まれる前記感光剤が、光ラジカル重合開始剤である、項目１５〜１７のいずれか１項に記載の硬化膜の製造方法。
［１９］
前記感光性樹脂組成物がネガ型感光性樹脂組成物である、項目１５〜１８のいずれか１項に記載の硬化膜の製造方法。
［２０］
前記感光性樹脂組成物が、低誘電正接化剤を含む、項目１５〜１９のいずれか１項に記載の硬化膜の製造方法。 The present inventors have found that the above object can be achieved by combining a polyimide precursor and a low dielectric loss tangent agent, and have completed the present invention. That is, the present invention is as follows.
[1]
(A) Polyimide precursor: 100 parts by mass,
(B) Photosensitizer: 0.1 to 10 parts by mass,
A photosensitive resin composition containing (C) a low dielectric loss tangent agent: 1 to 50 parts by mass and (D) a solvent: 50 to 300 parts by mass, wherein the (C) low dielectric loss tangent agent has a molecular weight of 100. A photosensitive resin composition of ~ 3,500.
[2]
The (C) low dielectric loss tangent agent has the following formula (I).

{In the formula, R ₁ and R ₄ and R ₅ are each independently a hydrogen atom or a methyl group or a t-butyl group, and R ₂ and R ₃ are independently a hydrogen atom or a hydroxy group or a hydroxy group, respectively. It is an organic group having 1 to 30 carbon atoms, and Z contains an organic group having 7 to 80 carbon atoms or a carbonyl group containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen and nitrogen. It is an organic group having 2 to 15 carbon atoms. }
The photosensitive resin composition according to item 1, which has a structure represented by.
[3]
The low dielectric loss tangent agent (C) has the following formula (II):

{In the formula, R ₁ and R ₄ and R ₅ and R ₆ and R ₇ and R ₁₀ are independently hydrogen atoms or methyl groups or t-butyl groups, and are R ₂ and R ₃ and R ₈ and R, respectively. ₉ is an independent hydrogen atom, or a hydroxy group, or an organic group having 1 to 30 carbon atoms, and Z contains at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen. It is a divalent organic group having 1 to 50 carbon atoms or a divalent organic group having 1 to 75 carbon atoms. }
The photosensitive resin composition according to item 1 or 2, which has a structure represented by.
[4]
The low dielectric loss tangent agent (C) is based on the following formula (III):

{In the formula, R ₁ and R ₄ and R ₅ and R ₆ and R ₉ and R ₁₀ and R ₁₁ and R ₁₂ and R ₁₅ are independently hydrogen atoms or methyl groups or t-butyl groups, respectively, and R ₂ and R ₃ and R ₈ and R ₇ and R ₁₃ and R ₁₄ are independently hydrogen atoms or hydroxy groups or organic groups having 1 to 30 carbon atoms, and Z is sulfur, phosphorus, oxygen, and nitrogen. It is a trivalent organic group having 1 to 50 carbon atoms or a trivalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of. }
The photosensitive resin composition according to item 1 or 2, which has a structure represented by.
[5]
Item 6. The photosensitive resin composition according to any one of Items 2 to 4, wherein Z has a heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen.
[6]
(C) The low dielectric loss tangent agent has the following formula:

{In the formula, Z is an organic group having 2 to 15 carbon atoms and containing a carbonyl group. }
The photosensitive resin composition according to item 1 or 2, which has a structure represented by at least one of the above.
[7]
The low dielectric loss tangent agent (C) has the following formula (IV):

{In the formula, R ₁ and R ₄ and R ₅ and R ₆ and R ₇ and R ₁₀ and R ₁₁ and R ₁₂ and R ₁₅ and R ₁₆ and R ₁₉ and R ₂₀ are independently hydrogen atoms or methyl groups, respectively. or a t- butyl group, _{R 2} and _{R 3} and _{R 8} and _{R 9} and _{R 13} and _{R 14} and _{R 17} and _{R 18} are independently an organic hydrogen atom or a hydroxy group, or 1 to 50 carbon atoms A group, where Z is a tetravalent organic group having 1 to 50 carbon atoms or a tetravalent group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen and nitrogen. It is an organic group of. }
The photosensitive resin composition according to item 1 or 2, which has a structure represented by.
[8]
The (A) polyimide precursor has the following general formula (1):

{In formula (1), X ₁ is a tetravalent organic group _{having 6 to 40 carbon atoms, Y 1} is a divalent organic group having 6 to 40 carbon atoms, and n ₁ is 2 to 150. R ₁ and R ₂ are independently hydrogen atoms or monovalent organic groups having 1 to 40 carbon atoms. However, _{at least one of R 1} and R ₂ has the following general formula (2) :.

(In formula (2), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10. .)
It is a group represented by. }
The photosensitive resin composition according to any one of items 1 to 7, which is represented by.
[9]
The Y ₁ is the following formula (Y1):

{In the formula, Rz independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, and A is an oxygen atom or a sulfur atom. , And B is the following formula:

It is one of them. }
The photosensitive resin composition according to item 8, which is represented by.
[10]
The Y ₁ is the following formula:

Or the following formula:

Or the following formula:

The photosensitive resin composition according to item 9, which has a structure represented by.
[11]
The X ₁ is the following formula (X1):

{In the formula, Ry independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, and C is an oxygen atom or a sulfur atom. , And D is the following formula:

It is one of them. }
The photosensitive resin composition according to any one of items 8 to 10 represented by.
[12]
The X ₁ is the following formula:

Or the following formula:

The photosensitive resin composition according to item 11, which has a structure represented by.
[13]
Item 2. The photosensitive resin composition according to any one of Items 1 to 12, wherein the (B) photosensitive agent is a photoradical polymerization initiator.
[14]
The photosensitive resin composition according to any one of items 1 to 13, which is a negative type photosensitive resin composition.
[15]
A method for producing a cured film obtained from a photosensitive resin composition containing a polyimide precursor: 100 parts by mass, a photosensitive agent: 0.1 to 10 parts by mass, and a solvent: 50 to 300 parts by mass. The following formula (i):
0.001 <(tanδ _40- tanδ ₁₀ ) / tanδ ₁₀ <0.2 (i)
{In the equation, tan δ ₄₀ indicates a dielectric loss tangent at a frequency of 40 GHz by the _{perturbation split cylinder resonator method, and tan δ 10} indicates a dielectric loss tangent at a frequency of 10 GHz by the perturbation split cylinder resonator method}. Method.
[16]
A method for producing a cured film obtained from a photosensitive resin composition containing a polyimide precursor: 100 parts by mass, a photosensitive agent: 0.1 to 10 parts by mass, and a solvent: 50 to 300 parts by mass. The following formula (ii):
0.001 <(tanδ _60- tanδ ₁₀ ) / tanδ ₁₀ <0.29 (ii)
{In the equation, tan δ ₆₀ indicates a dielectric loss tangent at a frequency of 60 GHz by the _{perturbation split cylinder resonator method, and tan δ 10} indicates a dielectric loss tangent at a frequency of 10 GHz by the perturbation split cylinder resonator method}. Method.
[17]
A method for producing a cured film obtained from a photosensitive resin composition containing a polyimide precursor: 100 parts by mass, a photosensitive agent: 0.1 to 10 parts by mass, and a solvent: 50 to 300 parts by mass. The following formulas (i) and (ii):
0.001 <(tanδ _40- tanδ ₁₀ ) / tanδ ₁₀ <0.2 (i)
0.001 <(tanδ _60- tanδ ₁₀ ) / tanδ ₁₀ <0.29 (ii)
{In the equation, tan δ ₄₀ indicates the dielectric loss tangent at a frequency of 40 GHz by the _{perturbation split cylinder resonator method, tan δ 10 indicates the dielectric loss tangent at a frequency of 10 GHz by the perturbation split cylinder resonator method, and tan δ 60} indicates the dielectric loss tangent at a frequency of 10 GHz by the perturbation method split cylinder resonator method. A method for producing a cured film, which satisfies the dielectric loss tangent at a frequency of 60 GHz by the resonator method.
[18]
The method for producing a cured film according to any one of items 15 to 17, wherein the photosensitive agent contained in the photosensitive resin composition is a photoradical polymerization initiator.
[19]
The method for producing a cured film according to any one of Items 15 to 18, wherein the photosensitive resin composition is a negative photosensitive resin composition.
[20]
The method for producing a cured film according to any one of Items 15 to 19, wherein the photosensitive resin composition contains a low dielectric loss tangent agent.

According to the present invention, it is possible to provide a photosensitive resin composition having good storage stability and low dielectric loss tangent while maintaining the resolution of the formed relief pattern. In one embodiment, the dielectric loss tangent can be reduced by reducing the polarity of the cured film. Further, in one embodiment, by mixing the resins with good compatibility, the resin can be stored without phase separation, and the resolution at the time of forming the relief pattern can be maintained.

Hereinafter, embodiments for carrying out the present invention (hereinafter, abbreviated as “embodiments”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof. Throughout the present specification, when a plurality of structures represented by the same reference numeral in the general formula are present in a molecule, they are independently selected unless otherwise specified, and may be the same or different from each other. Further, the structures represented by the common reference numerals in different general formulas are also independently selected unless otherwise specified, and may be the same or different from each other.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment contains (A) a polyimide precursor, (B) a photosensitive agent, (C) a low dielectric loss tangent agent, and (D) a solvent. If desired, the photosensitive resin composition comprises other components. Each component will be described below in order.

The photosensitive resin composition may be either a negative type or a positive type depending on the desired use, and is preferably a negative type from the viewpoint of the physical properties of the (A) polyimide precursor described later.

｛式（１）中、Ｘ_１は、炭素数６〜４０の４価の有機基であり、Ｙ_１は、炭素数６〜４０の２価の有機基であり、ｎ_１は、２〜１５０の整数であり、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、又は炭素数１〜４０の１価の有機基である。ただし、Ｒ_１及びＲ_２の少なくとも一方は、下記一般式（２）：

（式（２）中、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜３の１価の有機基であり、そしてｍ_１は、２〜１０の整数である。）
で表される基である。｝
で表される構造単位を有することが好ましく、上記一般式（１）で表される構造単位を有するポリアミドであることがより好ましい。 (A) Polyimide precursor In this embodiment, the (A) polyimide precursor is a resin component contained in the photosensitive resin composition, and has the following general formula (1):

{In formula (1), X ₁ is a tetravalent organic group _{having 6 to 40 carbon atoms, Y 1} is a divalent organic group having 6 to 40 carbon atoms, and n ₁ is 2 to 150. R ₁ and R ₂ are independently hydrogen atoms or monovalent organic groups having 1 to 40 carbon atoms. However, _{at least one of R 1} and R ₂ has the following general formula (2) :.

(In formula (2), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10. .)
It is a group represented by. }
It is preferable to have a structural unit represented by, and it is more preferable to use a polyamide having a structural unit represented by the above general formula (1).

(A) The ratio of the monovalent organic group represented by the general formula (2) to all _{of R 1} and R ₂ of the precursor represented by the general formula (1) contained in the polyimide precursor is From the viewpoint of high resolution, 50 mol% to 100 mol% is preferable, and further, from the viewpoint of high chemical resistance and sensitivity, 75 mol% to 100 mol% is more preferable.

_{For n 1} in the general formula (1), an integer of 3 to 100 is preferable, and an integer of 5 to 70 is more preferable, from the viewpoint of the photosensitive characteristics and the mechanical characteristics of the photosensitive resin composition.

｛式（２０）中、Ｒ６は水素原子、フッ素原子、Ｃ１〜Ｃ１０の炭化水素基、及びＣ１〜Ｃ１０の含フッ素炭化水素基から成る群から選ばれる１価の基であり、ｌは０〜２から選ばれる整数であり、ｍは０〜３から選ばれる整数であり、そしてｎは０〜４から選ばれる整数である。｝
で表される構造を有する基が挙げられるが、これらに限定されるものではない。また、Ｘ_１の構造は１種でも２種以上の組み合わせでもよい。上記式（２０）で表される構造を有するＸ_１基は、耐熱性と感光特性とを両立するという点で特に好ましい。 In the above general formula (1), the _{tetravalent organic group represented by X 1} is preferably an organic group having 6 to 40 carbon atoms, and more preferably, in terms of achieving both heat resistance and photosensitive characteristics. , -COOR ₁ group and -COOR ₂ group and -CONH- group are aromatic groups or alicyclic aliphatic groups in which the ortho positions are mutually exclusive. As the _{tetravalent organic group represented by X 1} , specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (20):

{In formula (20), R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group of C1 to C10, and a fluorine-containing hydrocarbon group of C1 to C10, and l is 0 to 0. 2 is an integer chosen from 2, m is an integer chosen from 0 to 3, and n is an integer chosen from 0 to 4. }
Examples thereof include, but are not limited to, groups having a structure represented by. Further, _{the structure of X 1} may be one kind or a combination of two or more kinds. X ₁ group having the structure represented by the above formula (20) are particularly preferred in that they both the photosensitive characteristic heat resistance.

｛式中、Ｒｙは、それぞれ独立に、ハロゲン原子を含んでもよい炭素数１〜１０の１価の有機基を表し、ａは０〜４の整数を表し、Ｃは酸素原子または硫黄原子であり、そしてＤは下記式：

中の１種である。｝
で表されることが好ましく、下記式：

または下記式：

で表される構造であることがより好ましい。 Further, in the above general formula (1), the _{tetravalent organic group represented by X 1} has the following formula from the viewpoints of storage stability, relief pattern resolution, low dielectric loss tangent, low polarity, compatibility between resins, and the like. (X1):

{In the formula, Ry independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, and C is an oxygen atom or a sulfur atom. , And D is the following formula:

It is one of them. }
It is preferably expressed by the following formula:

Or the following formula:

It is more preferable that the structure is represented by.

｛式（２１）中、Ｒ６は水素原子、フッ素原子、Ｃ１〜Ｃ１０の炭化水素基、及びＣ１〜Ｃ１０の含フッ素炭化水素基から成る群から選ばれる１価の基であり、そしてｎは０〜４から選ばれる整数である。｝
で表される構造が挙げられるが、これらに限定されるものではない。また、Ｙ_１の構造は１種でも２種以上の組み合わせでもよい。上記式（２１）で表される構造を有するＹ_１基は、耐熱性及び感光特性を両立するという点で特に好ましい。 In the general formula (1), the divalent organic group represented by Y ₁ in that they both heat resistance and sensitivity characteristics, is preferably an aromatic group having 6 to 40 carbon atoms, for example, The following formula (21):

{In formula (21), R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group of C1 to C10, and a fluorine-containing hydrocarbon group of C1 to C10, and n is 0. It is an integer selected from ~ 4. }
The structure represented by is mentioned, but is not limited to these. Further, _{the structure of Y 1} may be one kind or a combination of two or more kinds. _One Y group having a structure represented by the above formula (21) is particularly preferable in terms of achieving both heat resistance and photosensitive characteristics.

で表される構造は、低温加熱時のイミド化率、脱ガス性、銅密着性、及び耐薬品性の観点から好ましく、さらに下式：

で表される構造は、低誘電正接の観点から好ましい。 The Y ₁ group, among other structure represented by the above formula (21), the following equation:

The structure represented by is preferable from the viewpoint of imidization rate at low temperature heating, degassing property, copper adhesion, and chemical resistance.

The structure represented by is preferable from the viewpoint of low dielectric loss tangent.

｛式中、Ｒｚは、それぞれ独立に、ハロゲン原子を含んでもよい炭素数１〜１０の１価の有機基を表し、ａは０〜４の整数を表し、Ａは酸素原子または硫黄原子であり、そしてＢは下記式：

中の１種である。｝
で表されることが好ましく、下記式：

または下記式：

または下記式：

で表される構造であることがより好ましい。 Further, in the above general formula (1), the divalent organic group represented by Y ₁ is the storage stability, the relief pattern resolution, low dielectric loss tangent, in view of low polarity, such as the compatibility between the resins, the following formula (Y1):

{In the formula, Rz independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, and A is an oxygen atom or a sulfur atom. , And B is the following formula:

It is one of them. }
It is preferably expressed by the following formula:

Or the following formula:

Or the following formula:

It is more preferable that the structure is represented by.

In the general formula (2), R ₃ is preferably a hydrogen atom or a methyl group, and R ₄ and R ₅ are preferably hydrogen atoms from the viewpoint of photosensitive characteristics. Further, m ₁ is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitive characteristics.

(A) a polyimide precursor containing a structure represented by the general formula (1) in the preparation method embodiment of the polyimide precursor, for example, a tetravalent organic group X ₁ of the above-mentioned carbon number 6 to 40 Tetracarboxylic acid dianhydride, (a) alcohols having a structure in which a monovalent organic group represented by the above general formula (2) and a hydroxyl group are bonded, and optionally (b) the above general formula (2). To prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester form) by reacting with an alcohol having a structure other than the group represented by the above; subsequently, the obtained acid is obtained. and / esters, obtainable by a method comprising the the polycondensation of a diamine containing organic group Y ₁ of the divalent aforementioned carbon atoms 6-40.

(Preparation of acid / ester)
In the present embodiment, the tetracarboxylic acid dianhydride containing tetravalent organic group _{X 1} 6 to 40 carbon atoms, for example, pyromellitic acid anhydride, diphenyl ether-3,3 ', 4,4'-tetracarboxylic Acid dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylsulfone-3,3' , 4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3', 4,4'-tetracarboxylic acid dianhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2, 2-Bis (3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropane and the like can be mentioned. In addition, these can be used individually by 1 type or by mixing 2 or more types.

(B) Examples of alcohols having a structure other than the group represented by the general formula (2) include aliphatic alcohols having 5 to 30 carbon atoms or aromatic alcohols having 6 to 30 carbon atoms, for example, 1-pen. Tanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, Examples thereof include triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

The content of the organic group of the general formula (2) in the polyimide precursor is preferably 50 mol% or more with respect to all the contents of _{R 1} , R ₂ , R ₆ and R _7. When the content of the organic group of the general formula (2) exceeds 50 mol%, desired photosensitive characteristics can be obtained, which is preferable.
The content of the organic group of the general formula (2) in the photosensitive resin composition is preferably 75 mol% or more with _{respect to all the contents of R 1} , R ₂ , R ₆ and R _7.

By dissolving and mixing the above-mentioned tetracarboxylic acid dianhydride and the above-mentioned alcohols (a) in a reaction solvent in the presence of a basic catalyst such as pyridine, a half-esterification reaction of the acid dianhydride can be carried out. It can proceed to obtain the desired acid / ester form. As the reaction conditions, it is preferable to stir at a reaction temperature of 20 to 50 ° C. for 4 to 10 hours.

As the reaction solvent, those that dissolve the acid / ester and the polyimide precursor which is a polycondensation product of the acid / ester and diamines are preferable. The reaction solvent is, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gamma butyrolactone, ketones, esters, lactones, ethers, etc. Halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, Examples thereof include 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene and xylene. These may be used alone or in combination of two or more, if necessary.

(Preparation of polyimide precursor)
The acid / ester compound (typically the solution in the reaction solvent) is mixed with a known dehydration condensing agent under ice-cooling to make the acid / ester compound into a polyacid anhydride, and then the acid / ester compound has a carbon number of carbon atoms. A polyimide precursor can be obtained by dropping and adding a diamine containing 6 to 40 divalent organic groups Y ₁ separately dissolved or dispersed in a solvent and subjecting it to polycondensation. Examples of the dehydration condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'. -Disscin imidyl carbonate and the like can be mentioned.

The diamines containing organic group _{Y 1} of the divalent 6 to 40 carbon atoms, for example, p- phenylenediamine, m- phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3 '-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3 , 3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4, 4-bis (4-aminophenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] Ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-amino) Phenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] Hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-trizine sulfone, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis {3-methyl- 4- (4-Aminophenoxy) phenyl} propane and some of the hydrogen atoms on these benzene rings are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen or the like, for example, 3 , 3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-4,4' -Diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof are also mentioned. However, diamines are not limited to these.

In order to improve the adhesion between the photosensitive resin layer formed on the substrate and various substrates by applying the photosensitive resin composition of the present embodiment on the substrate, (A) at the time of preparing the polyimide precursor. , 1,3-Bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetraphenyldisiloxane and other diaminosiloxanes can also be copolymerized.

After the completion of the polycondensation reaction, the water-absorbing by-products of the dehydration condensate coexisting in the reaction solution are filtered out as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixed solution thereof is added. , May be added to the reaction solution to precipitate the polymer component. Further, the polymer may be purified by repeating the above-mentioned redissolution and reprecipitation operations. Then, the polymer can be vacuum dried to isolate the polyimide precursor. In order to improve the degree of purification, a solution of this polymer may be passed through a column filled with anions and / or cation exchange resins swollen with a suitable organic solvent to remove ionic impurities.

(A) The molecular weight of the polyimide precursor is preferably 8,000 to 150,000, preferably 9,000 to 50,000 when measured by the polystyrene-equivalent weight average molecular weight by gel permeation chromatography. Is more preferable, and 18,000 to 40,000 is particularly preferable. When the weight average molecular weight is 8,000 or more, it is preferable because the mechanical properties are good, while when it is 150,000 or less, the dispersibility in the developing solution and the resolution performance of the relief pattern are good. It is preferable because it is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from Showa Denko's organic solvent-based standard sample STANDARD SM-105.

(B) Photosensitizer The photosensitive resin composition of the present embodiment contains a photosensitive agent. In one embodiment, the photosensitizer may be a photopolymerization initiator. The photopolymerization initiator is preferable because it promotes the curing of the relief pattern by light irradiation. The photopolymerization initiator is preferably a photoradical polymerization initiator, which is a benzophenone derivative such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and fluorenone. Acetophenone derivatives such as 2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, Benzyl derivatives such as benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butandion-2- (o-methoxycarbonyl) oxime, 1-phenyl- 1,2-Propandione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2 -(O-Benzoyl) oxime, 1,3-diphenylpropanthrion-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrion-2- (o-benzoyl) oxime and other oximes, N -N-arylglycines such as phenylglycine, peroxides such as benzoylparkloride, aromatic biimidazoles, titanocene, α- (n-octanesluphonyloxyimino) -4-methoxybenzylchanide and the like. Acid generators and the like are preferably mentioned, but are not limited thereto. Among the above-mentioned photopolymerization initiators, oximes are more preferable in terms of photosensitivity.

The blending amount of the photopolymerization initiator is preferably 0.1 part by mass or more and 10 parts by mass, and more preferably 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor. The blending amount is preferably 0.1 part by mass or more from the viewpoint of light sensitivity or patterning property, and preferably 10 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

(C) Low Dielectric Dissipation Agent The photosensitive resin composition of the present embodiment contains a low dielectric loss tangent agent. (C) The low dielectric loss tangent agent is used as an additive in the resin composition, and (C) the dielectric loss tangent at 40 GHz of the cured film obtained from the composition of the low dielectric loss tangent agent and the resin is (C). C) It is a compound characterized by giving a value 5 to 80% lower than the dielectric loss tangent of a resin composition containing no dielectric loss tangent agent.

The molecular weight of the low dielectric loss tangent agent is preferably 5,000 or less, more preferably 3,500 or less from the viewpoint of solubility, and preferably 100 or more from the viewpoint of low dielectric loss tangent.

(C) The structure of the low dielectric loss tangent agent is not limited as long as it reduces the dielectric loss tangent, but a substituted benzene structure is preferable from the viewpoint of the thermophysical properties of the cured film. The substituent structure in the substituted benzene structure is not limited, but is limited to an alkyl group, an ester group, an ether group, a phenyl group, a hydroxy group, a ketone group, a carboxy group, a peroxide group, an amino group, an imino group, an imide group, an amide group and an isocyanate group. Examples thereof include a group, a sulfo group, an epoxy group, a fluoro group, a nitro group, a thiol group, a phosphonyl group, an isocyanul group and the like, and from the viewpoint of low dielectric positive tangent, an alkyl group, an ester group, an ether group, an amide group and a phenyl group are preferable. , And a phosphonyl group. Above all, it is more preferable to have an alkyl group from the viewpoint of low dielectric loss tangent.

｛式中、Ｒ_１及びＲ_４及びＲ_５は、それぞれ独立に、水素原子またはメチル基またはｔ−ブチル基であり、Ｒ_２及びＲ_３は、それぞれ独立に、水素原子、またはヒドロキシ基、または炭素数１〜３０の有機基であり、Ｚは、硫黄、リン、酸素、及び窒素から成る群から少なくとも１つ選ばれるヘテロ原子を含有する炭素数７〜８０の有機基、またはカルボニル基を含有する炭素数２〜１５の有機基である。｝
で表される構造を有する化合物が好ましい。 (C) The low dielectric loss tangent agent may have one, two or more, or three or more benzene structures in the same molecule. When there is one benzene structure, the following formula (I)

{In the formula, R ₁ and R ₄ and R ₅ are each independently a hydrogen atom or a methyl group or a t-butyl group, and R ₂ and R ₃ are independently a hydrogen atom or a hydroxy group or a hydroxy group, respectively. It is an organic group having 1 to 30 carbon atoms, and Z contains an organic group having 7 to 80 carbon atoms or a carbonyl group containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen and nitrogen. It is an organic group having 2 to 15 carbon atoms. }
A compound having a structure represented by is preferable.

｛式中、Ｚは、カルボニル基を含有する炭素数２〜１５の有機基である。｝
中の少なくとも１種で表される構造を有することがより好ましい。 When there is one benzene structure, (C) the low dielectric loss tangent agent contains a carbonyl group and has 2 carbon atoms from the viewpoints of storage stability, relief pattern resolution, low dielectric loss tangent, low polarity, compatibility between resins, and the like. It is preferable to have an organic group of ~ 15 and a benzene ring which may have a substituent, and the following formula:

{In the formula, Z is an organic group having 2 to 15 carbon atoms and containing a carbonyl group. }
It is more preferable to have a structure represented by at least one of them.

More specifically, examples of the (C) low dielectric loss tangent agent having one benzene structure include, but are not limited to, the following compound group:

｛式中、Ｒ_１及びＲ_４及びＲ_５及びＲ_６及びＲ_７及びＲ_１０は、それぞれ独立に、水素原子またはメチル基またはｔ−ブチル基であり、Ｒ_２及びＲ_３及びＲ_８及びＲ_９は、それぞれ独立に、水素原子、またはヒドロキシ基、または炭素数１〜３０の有機基であり、Ｚは、硫黄、リン、酸素、及び窒素から成る群から少なくとも１つ選ばれるヘテロ原子を含有する炭素数１〜５０の２価の有機基、または炭素数１〜７５の２価の有機基である。｝
で表される構造が好ましい。 (C) When there are two benzene structures in the same molecule of the low dielectric loss tangent agent, the following formula (II):

{In the formula, R ₁ and R ₄ and R ₅ and R ₆ and R ₇ and R ₁₀ are independently hydrogen atoms or methyl groups or t-butyl groups, and are R ₂ and R ₃ and R ₈ and R, respectively. ₉ is an independent hydrogen atom, or a hydroxy group, or an organic group having 1 to 30 carbon atoms, and Z contains at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen. It is a divalent organic group having 1 to 50 carbon atoms or a divalent organic group having 1 to 75 carbon atoms. }
The structure represented by is preferable.

More specifically, examples of the (C) low dielectric loss tangent agent having two benzene structures include, but are not limited to, the following compounds:

｛式中、Ｒ_１及びＲ_４及びＲ_５及びＲ_６及びＲ_９及びＲ_１０及びＲ_１１及びＲ_１２及びＲ_１５は、それぞれ独立に、水素原子またはメチル基またはｔ−ブチル基であり、Ｒ_２及びＲ_３及びＲ_８及びＲ_７及びＲ_１３及びＲ_１４は、それぞれ独立に、水素原子またはヒドロキシ基または炭素数１〜３０の有機基であり、Ｚは、硫黄、リン、酸素、及び窒素から成る群から少なくとも１つ選ばれるヘテロ原子を含有する炭素数１〜５０の３価の有機基、または炭素数１〜５０の３価の有機基である。｝
で表される構造を有することが好ましい。 (C) When there are three benzene structures in the same molecule of the low dielectric loss tangent agent, the following formula (III):

{In the formula, R ₁ and R ₄ and R ₅ and R ₆ and R ₉ and R ₁₀ and R ₁₁ and R ₁₂ and R ₁₅ are independently hydrogen atoms or methyl groups or t-butyl groups, respectively, and R ₂ and R ₃ and R ₈ and R ₇ and R ₁₃ and R ₁₄ are independently hydrogen atoms or hydroxy groups or organic groups having 1 to 30 carbon atoms, and Z is sulfur, phosphorus, oxygen, and nitrogen. It is a trivalent organic group having 1 to 50 carbon atoms or a trivalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of. }
It is preferable to have a structure represented by.

More specifically, examples of the (C) low dielectric loss tangent agent having three benzene structures include, but are not limited to, the following compounds:

｛式中、Ｒ_１及びＲ_４及びＲ_５及びＲ_６及びＲ_７及びＲ_１０及びＲ_１１及びＲ_１２及びＲ_１５及びＲ_１６及びＲ_１９及びＲ_２０は、それぞれ独立に、水素原子またはメチル基またはｔ−ブチル基であり、Ｒ_２及びＲ_３及びＲ_８及びＲ_９及びＲ_１３及びＲ_１４及びＲ_１７及びＲ_１８は、それぞれ独立に、水素原子またはヒドロキシ基または炭素数１〜５０の有機基であり、Ｚは、硫黄、リン、酸素、窒素から少なくとも１つ以上選ばれるヘテロ原子を含有する炭素数１〜５０の４価の有機基、または炭素数１〜５０の４価の有機基である。）、又は下記一般式（Ｖ）：

｛式中、Ｒ_１及びＲ_２及びＲ_４及びＲ_５及びＲ_６及びＲ_７及びＲ_９及びＲ_１０及びＲ_１１及びＲ_１２及びＲ_１４及びＲ_１５は、それぞれ独立に、水素原子またはメチル基またはｔ−ブチル基であり、Ｒ_３及びＲ_８及びＲ_１３は、それぞれ独立に、水素原子または炭素数１〜１０の有機基であり、Ｘは、酸素原子を含んでもよい炭素数１〜５の有機基であり、Ｚは、水素原子、または硫黄、リン、酸素、窒素から少なくとも１つ以上選ばれるヘテロ原子を含有する３価の有機基、または炭素数１〜５０の３価の有機基である。｝、又は下記一般式（ＶＩ）：

｛式中、Ｒ_１及びＲ_３及びＲ_４及びＲ_５及びＲ_６及びＲ_８及びＲ_９及びＲ_１０及びＲ_１１及びＲ_１２及びＲ_１３及びＲ_１５は、それぞれ独立に、水素原子またはメチル基またはｔ−ブチル基であり、Ｒ_２及びＲ_７及びＲ_１４は、それぞれ独立に、水素原子または炭素数１〜１０の有機基であり、Ｘは、酸素原子を含んでもよい炭素数１〜５の有機基であり、Ｚは、水素原子、または硫黄、リン、酸素、窒素から少なくとも１つ以上選ばれるヘテロ原子を含有する３価の有機基、または炭素数１〜５０の３価の有機基である。｝、又は下記一般式（ＶＩＩ）：

｛式中、Ｒ_１及びＲ_２及びＲ_４及びＲ_５及びＲ_６及びＲ_７及びＲ_９及びＲ_１０は、それぞれ独立に、水素原子またはメチル基またはｔ−ブチル基であり、Ｒ_３及びＲ_８は、それぞれ独立に、水素原子またはヒドロキシ基または炭素数１〜３０の有機基であり、Ｒ_４及びＲ_７及びＲ_１２は、それぞれ独立に、水素原子または炭素数１〜１０の有機基であり、Ｘは、酸素原子を含んでもよい炭素数１〜５の有機基であり、Ｚは、水素原子、または硫黄、リン、酸素、窒素から少なくとも１つ以上選ばれるヘテロ原子を含有する２価の有機基、または炭素数１〜５０の２価の有機基である。｝であることが好ましい。 (C) When there are four or more benzene structures in the same molecule of the low dielectric loss tangent agent, the following general formula (IV):

{In the formula, R ₁ and R ₄ and R ₅ and R ₆ and R ₇ and R ₁₀ and R ₁₁ and R ₁₂ and R ₁₅ and R ₁₆ and R ₁₉ and R ₂₀ are independently hydrogen atoms or methyl groups, respectively. or a t- butyl group, _{R 2} and _{R 3} and _{R 8} and _{R 9} and _{R 13} and _{R 14} and _{R 17} and _{R 18} are independently an organic hydrogen atom or a hydroxy group, or 1 to 50 carbon atoms A group, where Z is a tetravalent organic group having 1 to 50 carbon atoms or a tetravalent organic group having 1 to 50 carbon atoms containing at least one hetero atom selected from sulfur, phosphorus, oxygen and nitrogen. Is. ) Or the following general formula (V):

{In the formula, R ₁ and R ₂ and R ₄ and R ₅ and R ₆ and R ₇ and R ₉ and R ₁₀ and R ₁₁ and R ₁₂ and R ₁₄ and R ₁₅ are independently hydrogen atoms or methyl groups, respectively. Alternatively, it is a t-butyl group, R ₃ and R ₈ and R ₁₃ are independently hydrogen atoms or organic groups having 1 to 10 carbon atoms, and X is an organic group having 1 to 5 carbon atoms which may contain an oxygen atom. Z is a trivalent organic group containing a hydrogen atom or a hetero atom selected from at least one of sulfur, phosphorus, oxygen and nitrogen, or a trivalent organic group having 1 to 50 carbon atoms. Is. } Or the following general formula (VI):

{In the formula, R ₁ and R ₃ and R ₄ and R ₅ and R ₆ and R ₈ and R ₉ and R ₁₀ and R ₁₁ and R ₁₂ and R ₁₃ and R ₁₅ are independently hydrogen atoms or methyl groups, respectively. Alternatively, it is a t-butyl group, R ₂ and R ₇ and R ₁₄ are independently hydrogen atoms or organic groups having 1 to 10 carbon atoms, and X is an organic group having 1 to 5 carbon atoms which may contain an oxygen atom. Z is a trivalent organic group containing a hydrogen atom or a hetero atom selected from at least one of sulfur, phosphorus, oxygen and nitrogen, or a trivalent organic group having 1 to 50 carbon atoms. Is. } Or the following general formula (VII):

{In the formula, R ₁ and R ₂ and R ₄ and R ₅ and R ₆ and R ₇ and R ₉ and R ₁₀ are independently hydrogen atoms or methyl groups or t-butyl groups, respectively, and R ₃ and R. ₈ is an independent hydrogen atom or a hydroxy group or an organic group having 1 to 30 carbon atoms, and R ₄ and R ₇ and R ₁₂ are independently an organic group having a hydrogen atom or 1 to 10 carbon atoms. Yes, X is an organic group having 1 to 5 carbon atoms which may contain an oxygen atom, and Z is a hydrogen atom or a divalent group containing at least one heteroatom selected from sulfur, phosphorus, oxygen and nitrogen. Or a divalent organic group having 1 to 50 carbon atoms. } Is preferable.

(C) When there are four or more benzene structures in the same molecule of the low dielectric loss tangent agent, the following compound groups can be mentioned, but the present invention is not limited to these:

(C) The low dielectric loss tangent agent can be obtained, for example, as a reaction product of a phenol compound and an acid chloride compound, although the synthesis method is not limited. Preferably, a solution obtained by adding and mixing a basic catalyst and a solvent to a phenol compound may be obtained, and an acid chloride compound may be added to the solution and reacted to produce (C) a low dielectric loss tangent agent. .. The reaction is not particularly limited as long as the peak derived from the reaction residual disappears by liquid chromatography. For example, the reaction temperature is -10 ° C to 0 ° C after adding an acid chloride and then heated to 30 ° C. It may be kept constant at −10 ° C. to 0 ° C. After synthesis, the basic catalyst was removed through a column packed with a cation exchange resin, diluted with a solvent, purified by separating with a basic solution and water, and the solvent was distilled off with an evaporator. C) A low dielectric directing agent can be obtained. The cation exchange resin is not particularly limited, but a weakly acidic ion exchange resin may be used. Examples of the solvent used for the liquid separation include, but are not limited to, toluene, ethyl acetate, diethyl ether, dichloromethane, benzene, hexane and the like.

(C) Examples of the phenol compound used in the synthesis reaction of the low dielectric loss tangent agent include, but are not limited to, the structures represented by the following general formulas:

(C) The acid crylodo compound used in the synthesis reaction of the dielectric loss tangent agent includes, but is not limited to, a structure represented by the following general formula:

The blending amount of the low dielectric normal contact agent is preferably 0.1 part by mass or more and 100 parts by mass or less, and more preferably 1 part by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor. Yes, more preferably 2 parts by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 32 parts by mass or less. The blending amount is preferably 0.1 part by mass or more from the viewpoint of reducing the dielectric loss tangent of the cured film, and preferably 32 parts by mass or less from the viewpoint of light sensitivity or patterning property.

By containing the above-mentioned low dielectric loss tangent agent, the photosensitive resin composition of the present embodiment has low dielectric loss tangent in the high frequency region (10 to 80 GHz) while maintaining resolution and storage stability, and is frequency-dependent. It is possible to provide a resin film having low properties. Although not bound by theory, the reason why the dielectric loss tangent decreases is that (C) the dipole moment of the low dielectric loss tangent agent itself is small, so the presence of polar functional groups such as imide groups and amide groups occupies the entire film. It is thought that this is to reduce the ratio. Further, although not bound by theory, it is considered that the reason why the frequency dependence is low is that the polarity of the entire film is lowered, so that the water absorption rate at the time of film formation is lowered. Further, although not bound by theory, the reason for maintaining the resolution and storage stability is that the polyimide precursors having a molecular weight of 100 to 3,500 and having different polarities are also phase-separated in the resin composition and the cured film. It is thought that this is because they are mixed without any problem.

(D) Solvent The photosensitive resin composition of the present embodiment contains a solvent. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the (A) polyimide precursor. Specific examples of the solvent include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, and γ. -Butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, 2-octanone, etc. may be mentioned, and these may be used alone or in combination of two or more. Can be used in combination.

The solvent is, for example, 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, depending on the desired coating film thickness and viscosity of the photosensitive resin composition. It can be used in the range of 100 parts by mass to 860 parts by mass, more preferably 100 parts by mass to 860 parts by mass.

From the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing alcohols is preferable. Alcohols that can be preferably used are typically alcohols that have an alcoholic hydroxyl group in the molecule and do not have an olefin-based double bond, and specific examples thereof include methyl alcohol, ethyl alcohol, and n-. Alkyl alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol; lactic acid esters such as ethyl lactate; propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol Propropylene glycol monoalkyl ethers such as -1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- (n-propyl) ether; ethylene glycol methyl ether , Monoalcohols such as ethylene glycol ethyl ether and ethylene glycol-n-propyl ether; 2-hydroxyisobutyric acid esters; dialcohols such as ethylene glycol and propylene glycol. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferable, and in particular, ethyl lactate, propylene glycol-1-methyl ether, and propylene glycol-1-ethyl ether, And propylene glycol-1- (n-propyl) ether are more preferred.

When the solvent contains an alcohol having no olefin-based double bond, the content of the alcohol having no olefin-based double bond in the total solvent is 5% by mass to 50% based on the mass of the total solvent. It is preferably by mass%, more preferably 10% by mass to 30% by mass. When the content of the alcohol having no olefin-based double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is good, while when it is 50% by mass or less, (A) polyimide. It is preferable because the solubility of the precursor is improved.

In one embodiment, in order to improve the resolution of the relief pattern, the photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond. As such a monomer, a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is not particularly limited to the following, but ethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Or polyethylene glycol mono or diacrylate and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, glycerol mono, di or triacrylate and methacrylate, cyclohexanediacrylate and dimethacrylate, 1,4-butanediol di. Acrylate and dimethacrylate, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono or diacrylate and methacrylate of bisphenol A, benzenetrimethacrylate, isobornyl acrylate and methacrylate, acrylamide. And its derivatives, methacrylicamide and its derivatives, trimethylolpropane triacrylates and methacrylates, di or triacrylates and methacrylates of glycerol, di, tri, or tetraacrylates and methacrylates of pentaerythritol, and the addition of ethylene oxide or propylene oxide of these compounds. Examples of compounds such as substances can be mentioned.

The blending amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

In one embodiment, the photosensitive resin composition may optionally contain an adhesion aid in order to improve the adhesiveness between the film formed using the photosensitive resin composition and the substrate. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane. 3-methacryloxypropyl dimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) ) Succinimide, N- [3- (triethoxysilyl) propyl] phthalamide acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzene- Silanes such as 1,4-bis (N- [3-triethoxysilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propylsuccinic hydride, N-phenylaminopropyltrimethoxysilane Examples thereof include a coupling agent and an aluminum-based adhesive aid such as aluminumtris (ethylacetacetate), aluminumtris (acetylacetonate), and ethylacetacetate aluminum diisopropylate.

Among these adhesive aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. The blending amount of the adhesive aid 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 (A) polyimide precursor.

In one embodiment, the photosensitive resin composition may optionally contain a thermal polymerization inhibitor in order to improve the viscosity and photosensitivity stability of the photosensitive resin composition, especially when stored in a solvent-containing solution. Can include. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, 4-methoxyphenol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, and glycol ether. Diamine tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 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 blending amount of the thermal polymerization inhibitor is preferably in the range of 0.005 part by mass to 12 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

For example, when a substrate made of copper or a copper alloy is used, the photosensitive resin composition may optionally contain an azole compound in order to suppress discoloration of the substrate. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole and 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, triltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5- Examples thereof include methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Further, these azole compounds may be used alone or in a mixture of two or more kinds.

The blending amount of the azole compound is preferably 0.1 part by mass to 20 parts by mass, and 0.5 part by mass to 5 parts by mass from the viewpoint of light sensitivity characteristics with respect to 100 parts by mass of the (A) polyimide precursor. It is more preferable to have. When the blending amount of the azole compound (A) with respect to 100 parts by mass of the polyimide precursor is 0.1 part by mass or more, when the photosensitive resin composition is formed on the copper or the copper alloy, the copper or the copper alloy is formed. When the discoloration of the surface is suppressed, while the amount is 20 parts by mass or less, the light sensitivity is excellent, which is preferable.

In this embodiment, the photosensitive resin composition can contain a hindered phenol compound in order to suppress discoloration on copper. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and 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), triethyleneglycol-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-- Dimethylbenzyl] -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-trimethylbenzyl) -1 , 3,5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethyl) Benzyl) -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. .. 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 blending amount of the hindered phenol compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and 0.5 parts by mass to 10 parts by mass from the viewpoint of light sensitivity characteristics. It is more preferable that it is a part. Copper or copper when the blending amount of the hindered phenol compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy. Discoloration and corrosion of the alloy are prevented, while when the amount is 20 parts by mass or less, the light sensitivity is excellent, which is preferable.

In one embodiment, the photosensitive resin composition may contain an organic titanium compound. By containing the organic titanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature of about 250 ° C.

Examples of the organic titanium compound that can be used include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

Specific examples of the organic titanium compound are shown in I) to VII) below:
I) As the titanium chelate compound, a titanium chelate having two or more alkoxy groups is more preferable because the storage stability of the photosensitive resin composition and a good pattern can be obtained. Specific examples of the titanium chelate compound include titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanegenate), and titanium diisopropoxiside bis (2,4). -Pentane dionate), titanium diisopropoxyside bis (tetramethylheptangionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.

II) Examples of the tetraalkoxytitanium compound include titanium tetra (n-butokiside), titanium tetraethoxide, titanium tetra (2-ethylhexoxyside), titanium tetraisobutoxide, titanium tetraisopropoxyside, and titanium tetra. Metoxaside, Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Nonirokiside), Titanium Tetra (n-Propoxide), Titanium Tetrasteer Lloyxide, Titanium Tetrakiss [Bis {2,2- (Aryloxy) Methyl) butoxide}] and the like.

The III) titanocene compounds such as pentamethylcyclopentadienyltitanium tri methoxide, bis (eta ^{5-2,4-cyclopentadiene-1-yl)} bis (2,6-difluorophenyl) titanium, bis (eta ⁵ -2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3-(1H-pyrrol-1-yl) phenyl) titanium, and the like.

IV) Examples of the monoalkoxytitanium compound include titaniumtris (dioctylphosphate) isopropoxyside and titaniumtris (dodecylbenzenesulfonate) isopropoxyside.

V) Examples of the titanium oxide compound include titanium oxide bis (pentangionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.

VI) Examples of the titanium tetraacetylacetonate compound include titaniumtetraacetylacetonate and the like.

Examples of the VII) titanate coupling agent include isopropyltridodecylbenzenesulfonyl titanate and the like.

Among the above I) to VII), the organic titanium compound is more preferably at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound. It is preferable from the viewpoint of achieving good chemical resistance. In particular, titanium di isopropoxide bis (ethylacetoacetate), titanium tetra (n- butoxide), and bis (eta ^{5-2,4-cyclopentadiene-1-yl)} bis (2,6-difluoro-3- ( 1H-pyrrole-1-yl) phenyl) titanium is preferred.

When the organic titanium compound is blended, the blending amount is preferably 0.05 parts by mass to 10 parts by mass, and preferably 0.1 parts by mass to 2 parts by mass with respect to 100 parts by mass of the resin (A). More preferred. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, storage stability is excellent, which is preferable.

｛一般式（１１）中、Ｘ^１及びＹ^１は、一般式（１）中のＸ_１及びＹ_１と同じであり、ｍは正の整数である。｝
一般式（１）中の好ましいＸ_１とＹ_１は、同じ理由により、一般式（１１）のポリイミドにおいても好ましい。一般式（１１）の繰り返し単位数ｍは、特に限定は無いが、２〜１５０の整数であってもよい。
本発明によれば、上記で説明された感光性樹脂組成物をポリイミドに変換する工程を含む、ポリイミドの製造方法も提供することができる。 [Polyimide]
The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is preferably represented by the following general formula (11).

{In the general formula (11), ^{X 1} and ^{Y 1} in formula (1) is the same as _{X 1} and _{Y 1} in, m is a positive integer. }
_{The preferred X 1} and Y ₁ in the general formula (1) are also preferable in the polyimide of the general formula (11) for the same reason. The number of repeating units m in the general formula (11) is not particularly limited, but may be an integer of 2 to 150.
INDUSTRIAL APPLICABILITY According to the present invention, it is also possible to provide a method for producing polyimide, which comprises a step of converting the photosensitive resin composition described above into polyimide.

[Cured film and its manufacturing method]
In another embodiment of the present invention, a cured film obtained from the photosensitive resin composition described above and a method for producing the cured film are provided, and the cured film is the following mathematical formula (i) and / or (ii) :.
0.001 <(tanδ _40- tanδ ₁₀ ) / tanδ ₁₀ <0.2 (i)
{In the equation, tan δ ₄₀ indicates the dielectric loss tangent at a frequency of 40 GHz by the _{perturbation split cylinder resonator method, and tan δ 10} indicates the dielectric loss tangent at a frequency of 10 GHz by the perturbation split cylinder resonator method}.
0.001 <(tanδ _60- tanδ ₁₀ ) / tanδ ₁₀ <0.29 (ii)
{In the equation, tan δ ₆₀ indicates the dielectric loss tangent at a frequency of 60 GHz by the _{perturbation split cylinder resonator method, and tan δ 10} indicates the dielectric loss tangent at a frequency of 10 GHz by the perturbation split cylinder resonator method}.
Satisfy the relationship represented by.

When the above formulas (1) and / or (ii) are satisfied, the polarity of the cured film can be reduced to reduce the dielectric loss tangent, and the resins can be mixed with each other with good compatibility without phase separation. It can be stored in and tends to maintain the resolution at the time of relief pattern formation. From this point of view, the cured film is
0.002 <(tanδ _40- tanδ ₁₀ ) / tanδ ₁₀ <0.1909; and / or 0.002 <(tanδ _60- tanδ ₁₀ ) / tanδ ₁₀ <0.2789
It is preferable to satisfy. The dielectric loss tangent can be measured by the perturbation type split cylinder resonator method shown in Examples described later.

The photosensitive resin composition used in the method for producing a cured film has a polyimide precursor: 100 parts by mass and a photosensitive agent: 0.1 to 10 parts by mass from the viewpoint of satisfying the above formulas (1) and / or (ii). Parts and solvent: It is preferable to contain 50 to 300 parts by mass, it is more preferable to contain a photoradical polymerization initiator as a photosensitive agent and / or a low dielectric direct contact agent, and the photosensitive resin composition is a negative type. Is more preferable.

The specific steps in the method for producing a cured film can be performed according to the steps (1) to (4) of the method for producing a cured relief pattern, which will be described later.

[Curing relief pattern]
According to the present invention, it is possible to provide a cured relief pattern using the photosensitive resin composition described above, and a method for producing the same. In one embodiment, the method for producing the cured relief pattern is described in the following steps (1) to (4):
(1) A step of applying the photosensitive resin composition according to the present embodiment on a substrate to form a photosensitive resin layer on the substrate.
(2) A step of exposing the photosensitive resin layer,
(3) The method includes a step of developing the photosensitive resin layer after the exposure to form a relief pattern, and (4) a step of heat-treating the relief pattern to form a cured relief pattern.

Hereinafter, each step will be described.
(1) Step of applying the photosensitive resin composition of the present embodiment on a substrate to form a photosensitive resin layer on the substrate In this step, the photosensitive resin composition according to the present embodiment is applied on a substrate. And, if necessary, dried afterwards to form a photosensitive resin layer. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or a spray coater, or spray coating with a spray coater. A method or the like can be used.

If necessary, the coating film made of the photosensitive resin composition can be dried, and as the drying method, for example, air drying, heat drying using an oven or a hot plate, vacuum drying and the like are used. Further, it is desirable that the coating film is dried under conditions that do not cause imidization of the (A) polyimide precursor in the photosensitive resin composition. Specifically, when air-drying or heat-drying, the drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. As a result, the 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 to a photomask having a pattern using an exposure device such as a contact aligner, a mirror projection, and a stepper. Alternatively, it is exposed through a reticle or directly with an ultraviolet light source or the like.

After that, post-exposure bake (PEB) and / or pre-development bake may be applied at any combination of temperature and time, if necessary, for the purpose of improving light sensitivity and the like. The range of the baking conditions is preferably 40 ° C. to 120 ° C. and preferably 10 seconds to 240 seconds, but as long as it does not interfere with the properties of the negative photosensitive resin composition. Not limited to this range.

(3) Step of developing the photosensitive resin layer after exposure to form a relief pattern In this step, when the photosensitive resin composition is a negative type, the photosensitive resin layer after exposure is unexposed. The part is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of conventionally known photoresist developing methods, for example, a rotary spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, etc. You can select and use the method of. Further, after development, post-development baking may be performed at an arbitrary combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern. As the developing solution used for development, for example, a good solvent for a negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like are preferable. .. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent by the solubility of the polymer in the negative photosensitive resin composition. Further, two or more kinds of each solvent, for example, several kinds can be used in combination.

(4) Step of heat-treating the relief pattern to form a cured relief pattern In this step, the relief pattern obtained by the above development is heated to disperse the photosensitive component, and (A) the polyimide precursor is used. By imidization, it is converted into a cured relief pattern made of polyimide. As a method of heat curing, various methods can be selected, for example, a method using a hot plate, a method using an oven, and a method using a temperature-increasing oven in which a temperature program can be set. The heating can be performed, for example, at 150 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas at the time of heat curing, or an inert gas such as nitrogen or argon may be used.

[Semiconductor device]
The photosensitive resin composition of the present embodiment can also provide a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern. Therefore, it is possible to provide a semiconductor device having a base material which is a semiconductor element and a cured relief pattern of polyimide formed on the base material by the above-mentioned cured relief pattern manufacturing method. Further, the present invention can also be applied to a method for manufacturing a semiconductor device, which uses a semiconductor element as a base material and includes the above-mentioned method for manufacturing a cured relief pattern as a part of a process. The semiconductor device of the present invention is a semiconductor device having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure of a cured relief pattern formed by the above-mentioned cured relief pattern manufacturing method. It can be manufactured by forming it as a protective film or the like and combining it with a known manufacturing method of a semiconductor device.

[Display device]
The photosensitive resin composition of the present embodiment is a display body device including a display body element and a cured film provided on the display body element, and the cured film is a display body having the above-mentioned cured relief pattern. Equipment can also be provided. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched between them. For example, examples of the cured film include a surface protective film, an insulating film, and a flattening film of a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a partition wall for an organic EL element cathode. ..

The photosensitive resin composition of the present invention is useful not only for applications to semiconductor devices as described above, but also for applications such as interlayer insulation of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. Is.

Hereinafter, the present embodiment will be specifically described with reference to Examples, but the present embodiment is not limited thereto. In Examples, Comparative Examples, and Production Examples, the physical characteristics of the photosensitive resin composition were measured and evaluated according to the following methods.

[Measurement and evaluation method]
(1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured by a gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement is the brand name "Shodex 805M / 806M series" manufactured by Showa Denko KK, and the standard monodisperse polystyrene is the brand name "Shodex STANDARD SM-105" manufactured by Showa Denko KK. The developing solvent was N-methyl-2-pyrrolidone, and the detector used was the brand name "Shodex RI-930" manufactured by Showa Denko KK.

(2) Esterification rate The progress of the reaction between the phenol compound and the acid chloride was measured by the gel permeation chromatography method. The column used for the measurement is the brand name "Shodex 802/801/801 series" manufactured by Showa Denko KK, the developing solvent is tetrahydrofuran, and the detector is the brand name "Shodex RI-" manufactured by Showa Denko KK. 930 ”was used. The reaction was completed when the integral ratio of the peaks derived from the acid chloride became 1% or less of the total peak integral ratio.

(3) Resolution of cured relief pattern on Cu 200 nm on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a sputtering device (L-440S-FHL type, manufactured by Canon Anerva). Thick Ti and 400 nm thick Cu were sputtered in this order. Subsequently, the photosensitive resin composition prepared by the method described later is spin-coated on this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO), and dried to form a coating film having a thickness of 10 μm. did. This coating film was irradiated with energy ^{of 250 mJ / cm 2} by Prisma GHI (manufactured by Ultratech) equipped with an i-line filter using a mask with a test pattern. Next, this coating film was spray-developed with a coater developer (D-Spin 60A type, manufactured by SOKUDO) using cyclopentanone as a developing solution, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. Obtained.
A wafer having the relief pattern formed on Cu is heat-treated at 230 ° C. for 2 hours in a nitrogen atmosphere using a temperature rise program type curing furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.) on Cu. A cured relief pattern made of a resin having a thickness of about 6 to 7 μm was obtained.
The prepared relief pattern was observed under an optical microscope to determine the size of the minimum aperture pattern. At this time, if the area of the opening of the obtained pattern is ½ or more of the corresponding pattern mask opening area, it is considered to be resolved, and the one having the minimum area among the resolved openings is selected. The length of the corresponding mask opening side was taken as the resolution.
"Excellent": The size of the minimum opening pattern is less than 10 μm "Good": The size of the minimum opening pattern is 10 μm or more and less than 14 μm “Yes”: The size of the minimum opening pattern is 14 μm or more and less than 18 μm “No”: The size of the minimum opening pattern is 18 μm or more

(4) Evaluation of storage stability After preparing the photosensitive resin composition, the state after stirring at room temperature (23.0 ° C. ± 0.5 ° C., relative humidity 50% ± 10%) for 3 days was evaluated. As a result of the evaluation, the one in which the whole was mixed was regarded as "good", and the one in which phase separation occurred in the resin composition was regarded as "poor".

(5) Permittivity and dielectric loss tangent measurement 100 nm thick on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a sputter device (L-440S-FHL type, manufactured by Canon Anerva). Aluminum (Al) was sputtered to prepare a sputtered Al wafer substrate.
The negative photosensitive resin composition is spin-coated on the above-mentioned sputtered Al wafer substrate using a spin coating device (D-spin 60A type, manufactured by SOKUDO), and heated and dried at 110 ° C. for 180 seconds to form a spin coating film. Made. ^{After that, the entire surface was exposed with a ghi line having an exposure amount of 600 mJ / cm 2} using an aligner (PLA-501F, manufactured by Canon), and a nitrogen atmosphere was used using a vertical curing furnace (manufactured by Koyo Lindbergh, model name VF-2000B). Below, heat curing treatment was performed at 230 ° C. for 2 hours to prepare a cured film. The film thickness of the cured film was measured by the method described later. This cured film is cut into a length of 80 mm, a width of 60 mm, or a length of 40 mm and a width of 30 mm using a dicing saw (manufactured by DISCO, model name DAD-2H / 6T), and immersed in a 10% hydrochloric acid aqueous solution from above a silicon wafer. It was peeled off and used as a film sample.

Relative permittivity and dielectric loss tangent at 10, 28, 40, and 60 GHz were calculated for the film sample by the resonator perturbation method. The details of the measurement method are as follows.
(Measuring method)
Perturbation method split cylinder resonator method (device configuration)
Network analyzer: PNA Network analyzer E5224B
(Manufactured by Agilent technologies)
Split cylinder resonator: CR-710 (manufactured by Kanto Electronics Application Development Co., Ltd., measurement frequency: approx. 10 GHz), CR-728 (manufactured by Kanto Electronics Application Development Co., Ltd., measurement frequency: approx. 28 GHz), CR-740 (manufactured by Kanto Electronics Application Development Co., Ltd.) Manufactured by, measurement frequency: approx. 40 GHz), CR-760 (manufactured by Kanto Denshi Applied Development Co., Ltd., measurement frequency: approx. 60 GHz)

(6) Film thickness measurement 100 nm thick aluminum (Al) on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a sputtering device (L-440S-FHL type, manufactured by Canon Anerva). ) Was sputtered to prepare a sputtered Al wafer substrate.
The negative photosensitive resin composition is spin-coated on the above-mentioned sputtered Al wafer substrate using a spin coating device (D-spin 60A type, manufactured by SOKUDO), and heated and dried at 110 ° C. for 180 seconds to form a spin coating film. Made. ^{After that, the entire surface was exposed with a ghi line having an exposure amount of 600 mJ / cm 2} using an aligner (PLA-501F, manufactured by Canon), and a nitrogen atmosphere was used using a vertical curing furnace (manufactured by Koyo Lindbergh, model name VF-2000B). Below, heat curing treatment was performed at 230 ° C. for 2 hours to prepare a cured film. The film thickness of the cured film was measured using a step meter (P-15, manufactured by KLA-Tenchore).

<Production Example 1> ((A) Synthesis of polyimide precursor (polymer A-1))
Place 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) in a 2 liter volume separable flask, add 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and stir at room temperature. While doing so, 79.1 g of pyridine was added to obtain a reaction mixture. After the exotherm by the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.

Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-oxydianiline. A suspension of 93.0 g of (ODA) suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate consisting of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was ^{purified using an anion exchange resin (“Amberlist TM} 15” manufactured by Organo Corporation) to obtain a polymer solution. The obtained polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer A-1.
The weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 22,000.

<Production Example 2> (Synthesis of polyimide precursor (polymer A-2))
The same method as described in Production Example 1 except that 2,2-bis {4- (4-aminophenoxy) phenyl} propane (BAPP) 175.9 g was used in place of 93.0 g of ODA in Production Example 1. The reaction was carried out to obtain polymer A-2.
The weight average molecular weight (Mw) of this polymer A-2 was measured and found to be 24,000.

<Production Example 3> (Synthesis of polyimide precursor (polymer A-3))
In Production Example 1, the reaction is carried out in the same manner as in Production Example 1 except that 169.9 g of bis {4- (4-aminophenoxy) phenyl} ketone is used instead of 93.0 g of ODA. Obtained polymer A-3.
The weight average molecular weight (Mw) of this polymer A-3 was measured and found to be 21,000.

<Production Example 4> (Synthesis of polyimide precursor (polymer A-4))
In Production Example 1, 260.2 g of 4,4'-(4,4'-isopropyridendiphenoxy) acid dianhydride was used instead of 155.1 g of ODPA, and 175.9 g of BAPP was used instead of 93.0 g of ODA. Polymer A-4 was obtained by carrying out the reaction in the same manner as in Production Example 1 except for the above.
The weight average molecular weight (Mw) of this polymer A-4 was measured and found to be 29,000.

<Production Example 5> (Synthesis of polyimide precursor (polymer A-5))
In Production Example 2, 260.2 g of 4,4'-(4,4'-isopropyridene diphenoxy) acid dianhydride was replaced with ODA 93.0 g instead of ODPA 155.1 g, and bis {4-( Polymer A-5 was obtained by carrying out the reaction in the same manner as in Production Example 1 except that 169.9 g of 4-aminophenoxy) phenyl} ketone was used.
The weight average molecular weight (Mw) of this polymer A-5 was measured and found to be 28,000.

<Production Example 6> (Synthesis of polyimide precursor (polymer A-6))
In Production Example 1, instead of 155.1 g of ODPA, 130.1 g of ODPA 77.6 g, 4,4'-(4,4'-isopropyridendiphenoxy) acid dianhydride was replaced with 93.0 g of ODA, and BAPP175. Polymer A-6 was obtained by carrying out the reaction in the same manner as described in Production Example 1 except that 9.9 g was used. The weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 24,000.

<Production Example 7> (Synthesis of polyimide precursor (polymer A-7))
In Production Example 1, 130.1 g of BPDA73.6 g, 4,4'-(4,4'-isopropyridendiphenoxy) acid dianhydride was replaced with ODA93.0 g, and BAPP175 was replaced with ODPA155.1 g. Polymer A-7 was obtained by carrying out the reaction in the same manner as in Production Example 1 except that 9.9 g was used.
The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 24,000.

<Production Example 8> (Synthesis of polyimide precursor (polymer A-8))
Described in Production Example 1 except that 2,2-bis {3-methyl-4- (4-aminophenoxy) phenyl} propane (MBAPP) 219.3 g was used in place of 93.0 g of ODA in Production Example 1. The reaction was carried out in the same manner as in the above method to obtain Polymer A-8.
The weight average molecular weight (Mw) of this polymer A-8 was measured and found to be 25,000.

<Production Example 9> (Synthesis of low dielectric loss tangent agent C-1)
38.3 g of ADEKA STAB AO-40 (manufactured by ADEKA) was placed in a 1 L separable flask under a nitrogen atmosphere, and 383 g of toluene and 60.7 g of triethylamine (TEA) were added and dissolved at room temperature. Next, 29.6 g of 3,3-dimethylbutyryl chloride was added under ice-cooling, and after confirming that the temperature rise was not observed, the mixture was heated to 30 ° C. and reacted for 1 hour. After confirming the completion of the reaction by GPC, the obtained reaction solution was purified using an ^{anion exchange resin (“Amberlist TM 15” manufactured by Organo Corporation).} 300 mL of ethyl acetate was added to the purified reaction solution, and the mixture was transferred to a separatory funnel, purified 3 times with saturated aqueous sodium hydrogen carbonate solution and 10 times with water. The solvent was distilled off from the obtained organic layer with an evaporator to obtain a low dielectric loss tangent agent C-1 containing the following compound as a main component.

<Production Example 10> (Synthesis of low dielectric loss tangent agent C-2)
The following compounds were obtained by carrying out the reaction in the same manner as in Production Example 9 except that 74.1 g of AO-80 (manufactured by ADEKA) was used instead of 38.3 g of ADEKA STUB AO-40 (ADEKA). A low dielectric loss tangent agent C-2 as a main component was obtained.

<Production Example 11> (Synthesis of low dielectric loss tangent agent C-3)
54.5 g of ADEKA STUB AO-30 (manufactured by ADEKA) was placed in a 1 L separable flask under a nitrogen atmosphere, and 545 g of toluene and 91.1 g of triethylamine (TEA) were added and dissolved at room temperature. Next, 44.4 g of 3,3-dimethylbutyryl chloride was added under ice-cooling, and after confirming that the temperature rise was not observed, the mixture was heated to 30 ° C. and reacted for 1 hour. After confirming the completion of the reaction by GPC, the obtained reaction solution was purified using an ^{anion exchange resin (“Amberlist TM 15” manufactured by Organo Corporation).} 300 mL of ethyl acetate was added to the purified reaction solution, and the mixture was transferred to a separatory funnel, purified 3 times with saturated aqueous sodium hydrogen carbonate solution and 10 times with water. The solvent was distilled off from the obtained organic layer with an evaporator to obtain a low dielectric loss tangent agent C-3 containing the following compound as a main component.

<Production Example 12> (Synthesis of low dielectric loss tangent agent C-4)
By carrying out the reaction in the same manner as in Production Example 11 except that 54.5 g of ADEKA STUB AO-30 (manufactured by ADEKA) was replaced with 69.9 g of cyanox1790, the following compound was used as a main component. A low dielectric loss tangent agent C-4 was obtained.

<Production Example 13> (Synthesis of low dielectric loss tangent agent C-5)
Production Example except that cyanox1790 69.9 g was used in place of 54.5 g of ADEKA STUB AO-30 (manufactured by ADEKA) and 49.0 g of heptanoyle chloride was used in place of 3,3-dimethylbutyryl chloride 44.4 g. By carrying out the reaction in the same manner as in the method described in No. 11, a low dielectric loss tangent agent C-5 containing the following compound as a main component was obtained.

<Production Example 14> (Synthesis of low dielectric loss tangent agent C-6)
Production Example 11 except that cyanox1790 69.9 g was used in place of 54.5 g of ADEKA STUB AO-30 (manufactured by ADEKA) and 34.5 g of methacryloyl chloride was used in place of 3,3-dimethylbutyryl chloride 44.4 g. By carrying out the reaction in the same manner as in the above method, a low dielectric loss tangent agent C-6 containing the following compound as a main component was obtained.

<Production Example 15> (Synthesis of low dielectric loss tangent agent C-7)
Production Example 11 except that cyanox1790 69.9 g was used in place of 54.5 g of ADEKA STUB AO-30 (manufactured by ADEKA) and 46.4 g of benzoyl chloride was used in place of 3,3-dimethylbutyryl chloride 44.4 g. By carrying out the reaction in the same manner as in the above method, a low dielectric loss tangent agent C-7 containing the following compound as a main component was obtained.

<Production Example 16> (Synthesis of low dielectric loss tangent agent C-8)
4,4', 4'', 4'''-[(1-methylethylidene) -1-iriden] Tetrakis [2-methylphenol] (manufactured by Honshu Chemical Industry Co., Ltd.) 63.3 g, 1 L in a nitrogen atmosphere It was placed in a separable flask, 63.3 g of toluene and 121.4 g of triethylamine (TEA) were added and dissolved at room temperature. Next, 44.4 g of 3,3-dimethylbutyryl chloride was added under ice-cooling, and after confirming that the temperature rise was not observed, the mixture was heated to 30 ° C. and reacted for 1 hour. After confirming the completion of the reaction by GPC, the obtained reaction solution was purified using an ^{anion exchange resin (“Amberlist TM 15” manufactured by Organo Corporation).} 300 mL of ethyl acetate was added to the purified reaction solution, and the mixture was transferred to a separatory funnel, purified 3 times with saturated aqueous sodium hydrogen carbonate solution and 10 times with water. The solvent was distilled off from the obtained organic layer with an evaporator to obtain a low dielectric loss tangent agent C-8 containing the following compound as a main component.

(C) As the low dielectric loss tangent agent, the following compounds were used as they were.
C-9: SR-3000 (manufactured by Daihachi Kagaku)
C-10: PX-200 (manufactured by Daihachi Kagaku)

The following compounds were used in Examples and Comparative Examples.
Photopolymerization Initiator B-1: PBG-304 (manufactured by Joshu Strong Electronics Co., Ltd.)
Photopolymerization Initiator B-2: PBG-305 (manufactured by Joshu Strong Electronics Co., Ltd.)
Photopolymerization Initiator B-3: PBG-3057 (manufactured by Joshu Strong Electronics Co., Ltd.)
Solvent D-1: γ-Butyrolactone Solvent D-2: Dimethyl sulfoxide (DMSO)
Solvent D-3: N-methyl-2-pyrrolidone Polymer E-1: Polystyrene (weight average molecular weight: 20,000)

<Example 1>
As the component (A), 100 g of the polymer A-1 and the photopolymerization initiator B-1 (5 g) as the component (B), and (C) γ-butyrolactone (200 g) as the low dielectric loss tangent agent (200 g). ) To prepare a photosensitive resin composition solution.
This composition was evaluated by the method described above. The evaluation results are shown in Table 1.

<Examples 2 to 24, Comparative Examples 1 to 3>
The evaluation was carried out in the same manner as in Example 1 except that the resin composition solutions were prepared in the proportions shown in Tables 1 and 2. The evaluation results are shown in Tables 1 and 2.

As is clear from Tables 1 and 2, the dielectric loss tangent of the example showed a lower value than that of the comparative example 1 regardless of the measurement frequency. Further, in Comparative Example 2, the polyimide resin and polystyrene were phase-separated, and the developed pattern was opened at 40 μm or more. In Comparative Example 3, (C) the low dielectric loss tangent agent was phase-separated from the polyimide resin, and the developed pattern was opened at 30 μm or more.

In Tables 1 and 2, the values of the dielectric loss tangents obtained at 40 GHz and 10 GHz of Examples 1 to 24 are calculated by the following formula (i):
x = (tanδ _{40 − tanδ 10} ) / tanδ ₁₀ (i)
(Here, tan δ ₄₀ indicates a dielectric loss tangent at a frequency of 40 GHz according to the _{perturbation split cylinder resonator method, and tan δ 10} indicates a dielectric loss tangent at a frequency of 10 GHz according to the perturbation split cylinder resonator method). The values were 0.14 to 0.19, and Comparative Example 1 was 0.25. As is clear from the results of Examples 1 and 24, the same results were obtained when cured films having different film thicknesses were used.
In Tables 1 and 2, the values of the dielectric loss tangent obtained at 60 GHz and 10 GHz of the cured film formed into 10 μm of Examples 1 to 23 are calculated by the following mathematical formula (ii):
x = (tanδ _{60 -tanδ 10} ) / tanδ ₁₀ (ii)
(Here, tan δ ₆₀ indicates a dielectric loss tangent at a frequency of 60 GHz according to the _{perturbation split cylinder resonator method, and tan δ 10} indicates a dielectric loss tangent at a frequency of 10 GHz according to the perturbation split cylinder resonator method). The value was 0.25 to 0.28, and Comparative Example 1 was 0.34. As is clear from the results of Examples 1 and 24, the same results were obtained when cured films having different film thicknesses were used.

Although the embodiments of the present invention have been described above, the present invention is not limited to this, and can be appropriately changed without departing from the spirit of the invention.

The photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for manufacturing electric / electronic materials such as semiconductor devices and multilayer wiring substrates.

Claims (20)

(A) Polyimide precursor: 100 parts by mass,
(B) Photosensitizer: 0.1 to 10 parts by mass,
A photosensitive resin composition containing (C) a low dielectric loss tangent agent: 1 to 50 parts by mass and (D) a solvent: 50 to 300 parts by mass, wherein the (C) low dielectric loss tangent agent has a molecular weight of 100. A photosensitive resin composition of ~ 3,500. The (C) low dielectric loss tangent agent has the following formula (I).

{In the formula, R ₁ and R ₄ and R ₅ are each independently a hydrogen atom or a methyl group or a t-butyl group, and R ₂ and R ₃ are independently a hydrogen atom or a hydroxy group or a hydroxy group, respectively. It is an organic group having 1 to 30 carbon atoms, and Z contains an organic group having 7 to 80 carbon atoms or a carbonyl group containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen and nitrogen. It is an organic group having 2 to 15 carbon atoms. }
The photosensitive resin composition according to claim 1, which has a structure represented by. The low dielectric loss tangent agent (C) has the following formula (II):

{In the formula, R ₁ and R ₄ and R ₅ and R ₆ and R ₇ and R ₁₀ are independently hydrogen atoms or methyl groups or t-butyl groups, and are R ₂ and R ₃ and R ₈ and R, respectively. ₉ is an independent hydrogen atom, or a hydroxy group, or an organic group having 1 to 30 carbon atoms, and Z contains at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen. It is a divalent organic group having 1 to 50 carbon atoms or a divalent organic group having 1 to 75 carbon atoms. }
The photosensitive resin composition according to claim 1 or 2, which has a structure represented by. The low dielectric loss tangent agent (C) is based on the following formula (III):

{In the formula, R ₁ and R ₄ and R ₅ and R ₆ and R ₉ and R ₁₀ and R ₁₁ and R ₁₂ and R ₁₅ are independently hydrogen atoms or methyl groups or t-butyl groups, respectively, and R ₂ and R ₃ and R ₈ and R ₇ and R ₁₃ and R ₁₄ are independently hydrogen atoms or hydroxy groups or organic groups having 1 to 30 carbon atoms, and Z is sulfur, phosphorus, oxygen, and nitrogen. It is a trivalent organic group having 1 to 50 carbon atoms or a trivalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of. }
The photosensitive resin composition according to claim 1 or 2, which has a structure represented by. The photosensitive resin composition according to any one of claims 2 to 4, wherein Z has a heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen. (C) The low dielectric loss tangent agent has the following formula:

{In the formula, Z is an organic group having 2 to 15 carbon atoms and containing a carbonyl group. }
The photosensitive resin composition according to claim 1 or 2, which has a structure represented by at least one of the above. The low dielectric loss tangent agent (C) has the following formula (IV):

{In the formula, R ₁ and R ₄ and R ₅ and R ₆ and R ₇ and R ₁₀ and R ₁₁ and R ₁₂ and R ₁₅ and R ₁₆ and R ₁₉ and R ₂₀ are independently hydrogen atoms or methyl groups, respectively. or a t- butyl group, _{R 2} and _{R 3} and _{R 8} and _{R 9} and _{R 13} and _{R 14} and _{R 17} and _{R 18} are independently an organic hydrogen atom or a hydroxy group, or 1 to 50 carbon atoms A group, where Z is a tetravalent organic group having 1 to 50 carbon atoms or a tetravalent group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen and nitrogen. It is an organic group of. }
The photosensitive resin composition according to claim 1 or 2, which has a structure represented by. The (A) polyimide precursor has the following general formula (1):

{In formula (1), X ₁ is a tetravalent organic group _{having 6 to 40 carbon atoms, Y 1} is a divalent organic group having 6 to 40 carbon atoms, and n ₁ is 2 to 150. R ₁ and R ₂ are independently hydrogen atoms or monovalent organic groups having 1 to 40 carbon atoms. However, _{at least one of R 1} and R ₂ has the following general formula (2) :.

(In formula (2), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10. .)
It is a group represented by. }
The photosensitive resin composition according to any one of claims 1 to 7, which is represented by. The Y ₁ is the following formula (Y1):

{In the formula, Rz independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, and A is an oxygen atom or a sulfur atom. , And B is the following formula:

It is one of them. }
The photosensitive resin composition according to claim 8. The Y ₁ is the following formula:

Or the following formula:

Or the following formula:

The photosensitive resin composition according to claim 9, which has a structure represented by. The X ₁ is the following formula (X1):

{In the formula, Ry independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom, a represents an integer of 0 to 4, and C is an oxygen atom or a sulfur atom. , And D is the following formula:

It is one of them. }
The photosensitive resin composition according to any one of claims 8 to 10. The X ₁ is the following formula:

Or the following formula:

The photosensitive resin composition according to claim 11, which has a structure represented by. The photosensitive resin composition according to any one of claims 1 to 12, wherein the (B) photosensitive agent is a photoradical polymerization initiator. The photosensitive resin composition according to any one of claims 1 to 13, which is a negative photosensitive resin composition. A method for producing a cured film obtained from a photosensitive resin composition containing a polyimide precursor: 100 parts by mass, a photosensitive agent: 0.1 to 10 parts by mass, and a solvent: 50 to 300 parts by mass. The following formula (i):
0.001 <(tanδ _40- tanδ ₁₀ ) / tanδ ₁₀ <0.2 (i)
{In the equation, tan δ ₄₀ indicates a dielectric loss tangent at a frequency of 40 GHz by the _{perturbation split cylinder resonator method, and tan δ 10} indicates a dielectric loss tangent at a frequency of 10 GHz by the perturbation split cylinder resonator method}. Method. A method for producing a cured film obtained from a photosensitive resin composition containing a polyimide precursor: 100 parts by mass, a photosensitive agent: 0.1 to 10 parts by mass, and a solvent: 50 to 300 parts by mass. The following formula (ii):
0.001 <(tanδ _60- tanδ ₁₀ ) / tanδ ₁₀ <0.29 (ii)
{In the equation, tan δ ₆₀ indicates a dielectric loss tangent at a frequency of 60 GHz by the _{perturbation split cylinder resonator method, and tan δ 10} indicates a dielectric loss tangent at a frequency of 10 GHz by the perturbation split cylinder resonator method}. Method. A method for producing a cured film obtained from a photosensitive resin composition containing a polyimide precursor: 100 parts by mass, a photosensitive agent: 0.1 to 10 parts by mass, and a solvent: 50 to 300 parts by mass. The following formulas (i) and (ii):
0.001 <(tanδ _40- tanδ ₁₀ ) / tanδ ₁₀ <0.2 (i)
0.001 <(tanδ _60- tanδ ₁₀ ) / tanδ ₁₀ <0.29 (ii)
{In the equation, tan δ ₄₀ indicates the dielectric loss tangent at a frequency of 40 GHz by the _{perturbation split cylinder resonator method, tan δ 10 indicates the dielectric loss tangent at a frequency of 10 GHz by the perturbation split cylinder resonator method, and tan δ 60} indicates the dielectric loss tangent at a frequency of 10 GHz by the perturbation method split cylinder resonator method. A method for producing a cured film, which satisfies the dielectric loss tangent at a frequency of 60 GHz by the resonator method. The method for producing a cured film according to any one of claims 15 to 17, wherein the photosensitive agent contained in the photosensitive resin composition is a photoradical polymerization initiator. The method for producing a cured film according to any one of claims 15 to 18, wherein the photosensitive resin composition is a negative photosensitive resin composition. The method for producing a cured film according to any one of claims 15 to 19, wherein the photosensitive resin composition contains a low dielectric loss tangent agent.