JP6947519B2 - Photosensitive resin composition, method for manufacturing cured relief pattern, and semiconductor device - Google Patents

Description

The present invention provides, for example, an insulating material for electronic components, a photosensitive resin composition used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device, and a method for forming a cured relief pattern using the photosensitive resin composition. , And semiconductor devices.

Conventionally, polyimide resins, polybenzoxazole resins, phenol resins, etc., which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic parts, passivation films, surface protective films, interlayer insulating films, etc. for semiconductor devices. It is used. 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 a process can be significantly shortened 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 has increased and the operating frequency has reached 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 chip is flipped over and mounted directly on a printed circuit board. (See, for example, Patent Document 1). 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. .. When a material such as polyimide, polybenzoxazole, or phenol resin is used for flip-chip mounting, a metal wiring layer forming step is performed after the pattern of the resin layer is formed. In the metal wiring layer, usually, the surface of the resin layer is plasma-etched to roughen the surface, and then a metal layer to be a seed layer for plating is formed by sputtering with a thickness of 1 μm or less, and then the metal layer is used as an electrode. It is formed by electrolytic plating. At this time, in general, Ti is used as the metal to be the seed layer, and Cu is used as the metal of the rewiring layer formed by electrolytic plating.

Such a metal rewiring layer is required to have high adhesion between the metal layer rewired after the reliability test and the resin layer. The reliability test performed here includes, for example, a high-temperature storage test in which the product is stored in air at a high temperature of 125 ° C. or higher for 100 hours or longer, and a high-temperature storage test in which the wiring is assembled and a voltage is applied at a temperature of about 125 ° C. in the air. High-temperature operation test to confirm operation under storage for 100 hours or more, temperature cycle test to cycle back and forth between a low-temperature state of about -65 to -40 ° C and a high-temperature state of about 125 to 150 ° C in air, 85 High temperature and high humidity storage test that stores at a temperature of ℃ or higher and in a water vapor atmosphere with a humidity of 85% or higher, high temperature and high humidity bias test in which the same test is performed while applying voltage with wiring, 260 ° C in air or under nitrogen A solder reflow test or the like in which the solder reflow furnace is passed through the solder reflow furnace a plurality of times can be mentioned.

However, conventionally, in the above reliability test, in the case of the high temperature storage test, there is a problem that voids are generated at the interface of the rewired Cu layer in contact with the resin layer after the test. If voids are generated at the interface between the Cu layer and the resin layer, the adhesion between the two is lowered.

Japanese Unexamined Patent Publication No. 2001-338947

The present invention has been devised in view of such conventional circumstances, and no voids are generated at the interface of the Cu layer in contact with the cured photosensitive resin layer after the high temperature storage test. An object of the present invention is to provide a photosensitive resin composition capable of obtaining a resin layer having high adhesion, a method for forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern. And.

The present inventors have stated that by blending a cyclic compound having a carbonyl group in a photosensitive resin composition, a photosensitive resin composition that gives a cured film having excellent discoloration suppression even on copper or a copper alloy can be obtained. We have found and completed the present invention. That is, the present invention is as follows.

｛式中、Ｘ₁は、４価の有機基であり、Ｙ₁は、２価の有機基であり、ｎ₁は、２〜１５０の整数であり、そしてＲ₁及びＲ₂は、それぞれ独立に、水素原子、炭素数１〜３０の飽和脂肪族基、芳香族基、又は下記一般式（２）：

（式中、Ｒ₃、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍ₁は、２〜１０の整数である。）で表される１価の有機基、又は炭素数１〜４の飽和脂肪族基であり、又は、下記一般式（３）：

（式中、Ｒ₆、Ｒ₇及びＲ₈は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍ₂は、２〜１０の整数である。）で表される一価のアンモニウムイオンである。｝、で表されるポリイミドの前駆体であるポリアミド酸、ポリアミド酸エステル又はポリアミド酸塩であり、
下記一般式（４）は

｛式中、Ｘ₂は、炭素数６〜１５の３価の有機基であり、Ｙ₂は、炭素数６〜３５の２価の有機基であり、かつ同一の構造であるか、又は複数の構造を有してよく、Ｒ₉は、炭素数３〜２０のラジカル重合性の不飽和結合基を少なくとも一つ有する有機基であり、そしてｎ₂は、１〜１０００の整数である。｝
で表される構造を有するポリアミドであり、
下記一般式（５）は、

｛式中、Ｙ₃は、炭素原子を有する４価の有機基であり、Ｙ₄、Ｘ₃及びＸ₄は、それぞれ独立に、２個以上の炭素原子を有する２価の有機基であり、ｎ₃は、１〜１０００の整数であり、ｎ₄は、０〜５００の整数であり、ｎ₃／（ｎ₃＋ｎ₄）＞０．５であり、そしてＸ₃及びＹ₃を含むｎ₃個のジヒドロキシジアミド単位並びにＸ₄及びＹ₄を含むｎ₄個のジアミド単位の配列順序は問わない。｝
で表される構造を有するポリオキサゾール前駆体であるポリヒドロキシアミドであり、
下記一般式（６）は、

｛式中、Ｘ₅は、４〜１４価の有機基であり、Ｙ₅は、２〜１２価の有機基であり、Ｒ₁₀及びＲ₁₁は、それぞれ独立に、フェノール性水酸基、スルホン酸基又はチオール基から選ばれる基を少なくとも一つ有する有機基を示し、ｎ₅は、３〜２００の整数であり、そしてｍ₃及びｍ₄は、０〜１０の整数を示す。｝
で表される構造を有するポリイミドであり、並びに、
下記一般式（７）は、

｛式中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ₁₂は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基からなる群から選択される１価の置換基を表し、ｂが２又は３である場合には、複数のＲ₁₂は、互いに同一でも又は異なっていてもよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（８）：

（式中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び炭素数６〜１２の芳香族環を有する２価の有機基からなる群から選択される２価の有機基を表す。｝で表されるフェノール樹脂である。
［３］前記感光性樹脂組成物が、前記一般式（７）で表される繰り返し単位を有するフェノール樹脂を含み、前記一般式（７）中のＸが、下記一般式（９）：

｛式中、Ｒ₁₃、Ｒ₁₄、Ｒ₁₅及びＲ₁₆は、各々独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基であり、ｎ₆は０〜４の整数であって、ｎ₆が１〜４の整数である場合のＲ₁₇は、ハロゲン原子、水酸基、又は炭素数１〜１２の１価の有機基であり、少なくとも１つのＲ₁₇は水酸基であり、ｎ₆が２〜４の整数である場合の複数のＲ₁₇は互いに同一でも又は異なっていてもよい。｝で表される２価の基、及び下記一般式（１０）：

｛式中、Ｒ₁₈、Ｒ₁₉、Ｒ₂₀及びＲ₂₁は、各々独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基を表し、Ｗは、単結合、フッ素原子で置換されていてもよい炭素数１〜１０の脂肪族基、フッ素原子で置換されていてもよい炭素数３〜２０の脂環式基、下記一般式（８）：

（式中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び下記式（１１）：

で表される２価の基からなる群から選択される２価の基である。｝で表される２価の基からなる群から選択される２価の有機基である、[１]又は［２］に記載の感光性樹脂組成物。
［４］
（１）［１］〜［３］のいずれか１つに記載の感光性樹脂組成物を基板上に塗布することによって感光性樹脂層を前記基板上に形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）前記露光後の感光性樹脂層を現像してレリーフパターンを形成する工程と、
（４）前記レリーフパターンを加熱処理することによって硬化レリーフパターンを形成する工程と
を含む、硬化レリーフパターンの製造方法。
［５］前記基板が、銅又は銅合金から形成されている、［４］に記載の方法。
［６］［４］又は［５］に記載の製造方法により得られる硬化レリーフパターンを含む半導体装置。 [1] (A) Selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and novolac, polyhydroxystyrene and phenol resin. 100 parts by mass of at least one type of resin,
(B) A cyclic compound having two or more carbonyl groups, the carbonyl group is directly bonded to the cyclic structure, and in the case of a monocyclic compound, one-third or more of the atoms forming the ring structure are N atoms. In the case of a fused ring compound, at least one compound selected from the group consisting of compounds in which one-third or more of the atoms forming the ring structure having the carbonyl group are N atoms is the resin (A). 0.01 to 10 parts by mass with reference to 100 parts by mass;
(C) 1 to 50 parts by mass of the photosensitizer based on 100 parts by mass of the resin (A).
A photosensitive resin composition containing.
[2] The resin (A) is a polyimide precursor containing the following general formula (1), a polyamide containing the following general formula (4), a polyoxazole precursor containing the following general formula (5), and the following general formula (6). The photosensitive resin composition according to [1], which is at least one selected from the group consisting of a polyimide containing (), and a phenol resin containing novolak, polyhydroxystyrene and the following general formula (7).
The following general formula (1) is

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of _{2 to 150, and R 1} and R 2 are independent of each other. In addition, a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or the following general formula (2):

(In the formula, R ₃ , R ₄ and R ₅ are independently hydrogen atoms or organic groups having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10). It is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms, or the following general formula (3):

(In the formula, R ₆ , R ₇ and R ₈ are independently hydrogen atoms or organic groups having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10). It is a monovalent ammonium ion. }, A polyamic acid, a polyamic acid ester, or a polyamic acid salt, which is a precursor of polyimide represented by.
The following general formula (4) is

{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, and Y ₂ is a divalent organic group having 6 to 35 carbon atoms and has the same structure or a plurality of carbon atoms. R ₉ is an organic group having at least one radically polymerizable unsaturated group having 3 to 20 carbon atoms, and n ₂ is an integer of 1 to 1000. }
It is a polyamide having a structure represented by
The following general formula (5) is

{In the formula, Y ₃ is a tetravalent organic group having a carbon atom, and Y ₄ , X ₃ and X ₄ are divalent organic groups having two or more carbon atoms independently. n ₃ is an integer from 1 to 1000, n ₄ is an integer of _{0~500, n 3 / (n 3} + n 4)> 0.5, and n ₃ containing X ₃ and Y ₃ The sequence order of the dihydroxydiamide units and n _{4 diamide units including X 4} and Y _{4 does not matter.} }
It is a polyhydroxyamide which is a polyoxazole precursor having a structure represented by.
The following general formula (6) is

{Wherein, X ₅ is a 4-14 monovalent organic group, Y ₅ is a 2-12 monovalent organic group, R ₁₀ and R ₁₁ are each independently a phenolic hydroxyl group, a sulfonic acid group Alternatively, it represents an organic group having at least one group selected from thiol groups, n ₅ is an integer of _{3 to} 200, and m 3 and m ₄ are integers of 0 to 10. }
It is a polyimide having a structure represented by, and
The following general formula (7) is

{In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦ (a + b) ≦ 4, and R ₁₂ is a monovalent organic having 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of groups, halogen atoms, nitro groups and cyano groups, where b is 2 or 3, the plurality of R _12s may be the same or different from each other. Well, X is a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, the following general formula (8):

It is selected from the group consisting of a divalent alkylene oxide group represented by (in the formula, p is an integer of 1 to 10) and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. Represents a divalent organic group. } Is a phenol resin.
[3] The photosensitive resin composition contains a phenol resin having a repeating unit represented by the general formula (7), and X in the general formula (7) is the following general formula (9):

{In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently replaced with a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atom with a fluorine atom. has been a becomes a monovalent aliphatic group having 1 to 10 carbon atoms, n ₆ is an integer of 0 to 4, R ₁₇ where n ₆ is an integer of 1 to 4 include a halogen atom, a hydroxyl group Or, it is a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ is a hydroxyl group, and _{a plurality of R 17s when n 6} is an integer of 2 to 4 are the same as or different from each other. May be good. }, And the following general formula (10):

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are each independently replaced with a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atom with a fluorine atom. It represents a monovalent aliphatic group having 1 to 10 carbon atoms, and W is a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, or a fluorine atom. Aliphatic group having 3 to 20 carbon atoms, the following general formula (8):

A divalent alkylene oxide group represented by (in the formula, p is an integer of 1 to 10), and the following formula (11):

It is a divalent group selected from the group consisting of divalent groups represented by. } The photosensitive resin composition according to [1] or [2], which is a divalent organic group selected from the group consisting of divalent groups represented by.
[4]
(1) A step of forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of [1] to [3] on the substrate.
(2) The step of exposing the photosensitive resin layer and
(3) A step of developing the photosensitive resin layer after the exposure to form a relief pattern, and
(4) A method for producing a cured relief pattern, which comprises a step of forming a cured relief pattern by heat-treating the relief pattern.
[5] The method according to [4], wherein the substrate is formed of copper or a copper alloy.
[6] A semiconductor device including a cured relief pattern obtained by the production method according to [4] or [5].

According to the present invention, by combining a specific photosensitive resin and a specific compound, voids are not generated at the interface between the Cu layer and the polyimide layer after a high temperature storage test, and the adhesion is high. It is possible to provide a photosensitive resin composition from which a photosensitive resin can be obtained, a method for forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern.

The present invention will be specifically described below. In addition, throughout the present specification, the structures represented by the same reference numerals in the general formula may be the same as or different from each other when a plurality of structures are present in the molecule.

<Photosensitive resin composition>
(Aspect A)
The present invention comprises the group consisting of (A) polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and novolac, polyhydroxystyrene and phenol resin. At least one selected resin: 100 parts by mass, (B) cyclic compound having a carbonyl group: 0.01 to 10 parts by mass based on (A) 100 parts by mass of resin, (C) photosensitizer: (A) resin 100 1 to 50 parts by mass is an essential component based on the parts by mass.

(A) Resin The (A) resin used in the present invention will be described. The resin (A) of the present invention is a group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and novolac, polyhydroxystyrene and phenol resin. The main component is at least one resin selected from the above. Here, the main component means that these resins are contained in an amount of 60% by mass or more of the total resin, and is preferably contained in an amount of 80% by mass or more. Further, other resins may be contained if necessary.

From the viewpoint of heat resistance after heat treatment and mechanical properties, the weight average molecular weight of these resins is preferably 200 or more, more preferably 5,000 or more in terms of polystyrene by gel permeation chromatography. The upper limit is preferably 500,000 or less, and in the case of a photosensitive resin composition, 20,000 or less is more preferable from the viewpoint of solubility in a developing solution.

In the present invention, the resin (A) is a photosensitive resin in order to form a relief pattern. The photosensitive resin is a resin that is used together with the (C) photosensitive agent described later to form a photosensitive resin composition, which causes a dissolution or undissolution phenomenon in a subsequent development step.

Among the photosensitive resins include polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and phenolic resins containing novolak and polyhydroxystyrene, the resin after heat treatment. Is excellent in heat resistance and mechanical properties, so polyamic acid, polyamic acid ester, polyamic acid salt, polyamide, polyhydroxyamide, polyimide and phenol resin are preferably used. Further, these photosensitive resins can be selected according to a desired application, such as whether to prepare a negative type or positive type photosensitive resin composition together with the (C) photosensitive agent described later.

｛式中、Ｘ₁は、４価の有機基であり、Ｙ₁は、２価の有機基であり、ｎ₁は、２〜１５０の整数であり、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子、炭素数１〜３０の飽和脂肪族基、又は前記一般式（２）：

（式中、Ｒ₃、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍ₁は、２〜１０の整数である。）で表される１価の有機基、又は炭素数１〜４の飽和脂肪族基である。｝で表される一価の有機基；又は、
下記一般式（３）：

（式中、Ｒ₆、Ｒ₇及びＲ₈は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍ₂は、２〜１０の整数である。）で表される一価のアンモニウムイオンである。｝、で表されるポリイミドの前駆体であるポリアミド酸、ポリアミド酸エステル又はポリアミド酸塩である。
ポリイミド前駆体は、加熱（例えば２００℃以上）環化処理を施すことによってポリイミドに変換される。ポリイミド前駆体はネガ型感光性樹脂組成物用として好適である。 [(A) Polyamic acid, polyamic acid ester, polyamic acid salt]
In the photosensitive resin composition of the present invention, one example of the most preferable resin (A) from the viewpoint of heat resistance and photosensitive characteristics is described in the general formula (1):

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of _{2 to 150, and R 1} and R 2 are independent of each other. , A hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, or the general formula (2):

(In the formula, R ₃ , R ₄ and R ₅ are independently hydrogen atoms or organic groups having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10). It is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. } Is a monovalent organic group; or
The following general formula (3):

(In the formula, R ₆ , R ₇ and R ₈ are independently hydrogen atoms or organic groups having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10). It is a monovalent ammonium ion. }, A polyamic acid, a polyamic acid ester, or a polyamic acid salt which is a precursor of polyimide represented by.
The polyimide precursor is converted into polyimide by subjecting it to a cyclization treatment (for example, 200 ° C. or higher). The polyimide precursor is suitable for negative photosensitive resin compositions.

｛式中、Ｒ２５は水素原子、フッ素原子、Ｃ１〜Ｃ１０の炭化水素基、Ｃ１〜Ｃ１０の含フッ素炭化水素基から選ばれる１価の基であり、ｌは０〜２から選ばれる整数、ｍは０〜３から選ばれる整数、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、Ｘ₁の構造は１種でも２種以上の組み合わせでも構わない。上記式で表される構造を有するＸ₁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 each other is in the ortho position. The _{tetravalent organic group represented by X 1} is preferably an organic group having an aromatic ring and having 6 to 40 carbon atoms, and more preferably the following formula (30):

{In the formula, R25 is a monovalent group selected from 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 an integer selected from 0 to 2, m. Is an integer selected from 0 to 3, and n is an integer selected from 0 to 4. }
The structure represented by is mentioned, but is not limited to these. 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 is particularly preferred in that they both heat resistance and sensitivity characteristics.

｛式中、Ｒ２５は水素原子、フッ素原子、Ｃ１〜Ｃ１０の炭化水素基、Ｃ１〜Ｃ１０の含フッ素炭化水素基から選ばれる１価の基であり、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、Ｙ₁の構造は１種でも２種以上の組み合わせでも構わない。上記式（３１）で表される構造を有するＹ₁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 above general formula (1), the _{divalent organic group represented by Y 1} is preferably an aromatic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive characteristics, for example. The following formula (31):

{In the formula, R25 is a monovalent group selected from hydrogen atom, fluorine atom, hydrocarbon group of C1 to C10, and fluorine-containing hydrocarbon group of C1 to C10, and n is an integer selected from 0 to 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 (31) is particularly preferable in that it has both heat resistance and photosensitive characteristics.

_{R 3} in the general formula (2) 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.

When a polyimide precursor is used as the resin (A), examples of the method for imparting photosensitivity to the photosensitive resin composition include an ester bond type and an ionic bond type. The former is a method of introducing a compound having a photopolymerizable group, that is, an olefinic double bond, into the side chain of the polyimide precursor by an ester bond, and the latter has a carboxyl group and an amino group of the polyimide precursor ( Meta) This is a method of imparting a photopolymerizable group by bonding an amino group of an acrylic compound via an ionic bond.

The ester-bonded polyimide precursor first contains the above-mentioned _{tetracarboxylic acid dianhydride containing a tetravalent organic group X 1} , alcohols having a photopolymerizable unsaturated double bond, and optionally 1 carbon number. After reacting with saturated aliphatic alcohols of ~ 4 to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester), this and the above-mentioned divalent organic group Y ₁ It is obtained by amide polycondensation with diamines containing.

(Preparation of acid / ester)
_{In the present invention, the tetracarboxylic acid dianhydride containing a tetravalent organic group X 1} preferably used for preparing an ester-bonded polyimide precursor is the tetracarboxylic represented by the above general formula (30). Including acid dianhydride, for example, pyromellitic 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 hydride, 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, preferably pyromellitic anhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid. Dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic dianhydride can be mentioned, but is not limited thereto. In addition, these can be used alone or in combination of two or more.

Examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used for preparing an ester-bonded polyimide precursor in the present invention include 2-acryloyloxyethyl alcohol and 1-acryloyloxy. -3-propyl alcohol, 2-acrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxy Propyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3- Propyl alcohol, 2-methacrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate , 2-Hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like.

As a saturated fatty alcohol having 1 to 4 carbon atoms, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like can be partially mixed and used with the above alcohols.

The above-mentioned tetracarboxylic acid dianhydride suitable for the present invention and the above-mentioned alcohols are dissolved by stirring in the presence of a basic catalyst such as pyridine in a solvent as described later at a temperature of 20 to 50 ° C. for 4 to 10 hours. By mixing, the esterification reaction of the acid anhydride proceeds, and a desired acid / ester compound can be obtained.

(Preparation of polyimide precursor)
In the acid / ester compound (typically, a solution in a solvent described later) under ice-cooling, a suitable dehydration condensing agent, for example, dicyclocarbodiimide (for example, dicyclohexylcarbodiimide), 1-ethoxycarbonyl-2-ethoxy-1. , 2-Dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-discusin imidazole carbonate, etc. are added and mixed to make the acid / ester form polyacid anhydride. _{Then, a diamine containing a divalent organic group Y 1} preferably used in the present invention is separately dissolved or dispersed in a solvent, and the mixture is added dropwise to the amide polycondensation to cause the desired polyimide. A precursor can be obtained. Alternatively, the desired polyimide precursor can be obtained by reacting the acid / ester compound with a diamine compound in the presence of a base such as pyridine after acid chloride-forming the acid moiety with thionyl chloride or the like. ..

_{Examples of diamines containing a divalent organic group Y 1} preferably used in the present invention include diamines having the structure represented by the above general formula (31), 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'-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 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-amino) Phenoxy) 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-aminophenyl) 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, and some of the hydrogen atoms on these benzene rings are methyl groups. Those substituted with ethyl group, hydroxymethyl group, hydroxyethyl group, halogen, etc., 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, 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-bis (fluoro) -4, 4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc., preferably p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 2,2'-dimethylbenzidine, 2,2'- Bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc., and mixtures thereof. However, it is not limited to this.

Further, in the preparation of the polyimide precursor, 1,3-, for the purpose of improving the adhesion between the resin layer formed on the substrate and various substrates by applying the photosensitive resin composition of the present invention on the substrate. Diaminosiloxanes such as bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane can also be copolymerized.

After completion of the amide 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 mixture thereof is added. The polymer component is added to the obtained polymer component, the polymer component is precipitated, and the polymer is purified and vacuum-dried by repeating the redissolution and reprecipitation precipitation operations to obtain the desired polyimide precursor. Release. 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 an appropriate organic solvent to remove ionic impurities.

On the other hand, the ion-bonded polyimide precursor is typically obtained by reacting a tetracarboxylic acid dianhydride with a diamine. _{In this case, at least one of R 1} and R _{2 in} the general formula (1) is a hydroxyl group.

The tetracarboxylic dianhydride is preferably an anhydride of a tetracarboxylic acid containing the structure of the above formula (30), and the diamine is preferably a diamine containing the structure of the above formula (31). By adding a (meth) acrylic compound having an amino group, which will be described later, to the obtained polyamide precursor, a photopolymerizable group is imparted by an ionic bond between the carboxyl group and the amino group.

Examples of (meth) acrylic compounds having an amino group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, and dimethylamino. Dialkylaminoalkyl acrylates or methacrylates such as butyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, and diethylaminobutyl methacrylate are preferable, and the alkyl group on the amino group has 1 to 10 carbon atoms and the alkyl chain has an alkyl chain from the viewpoint of photosensitive characteristics. Dialkylaminoalkyl acrylates or methacrylates having 1 to 10 carbon atoms are preferable.

The blending amount of these (meth) acrylic compounds having an amino group is 1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), preferably 2 to 15 parts by mass from the viewpoint of light sensitivity characteristics. (C) As a photosensitizer, a (meth) acrylic compound having an amino group is blended in an amount of 1 part by mass or more with respect to 100 parts by mass of the resin (A) to have excellent photosensitivity. Excellent in sex.

The molecular weights of the ester-bonded and ionic-bonded polyimide precursors are preferably 8,000 to 150,000, preferably 9,000, as measured by the polystyrene-equivalent weight average molecular weight by gel permeation chromatography. More preferably, it is ~ 50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developing solution is good, and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average 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.

｛式中、Ｘ₂は、炭素数６〜１５の３価の有機基であり、Ｙ₂は、炭素数６〜３５の２価の有機基であり、かつ同一の構造であるか、又は複数の構造を有してもよく、Ｒ₉は、炭素数３〜２０のラジカル重合性の不飽和結合基を少なくとも一つ有する有機基であり、そしてｎ₂は、１〜１０００の整数である。｝
で表される構造を有するポリアミドである。このポリアミドはネガ型感光性樹脂組成物用として好適である。 [(A) Polyamide]
A further example of the preferred resin (A) in the photosensitive resin composition of the present invention is described in the following general formula (4):

{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, and Y ₂ is a divalent organic group having 6 to 35 carbon atoms and has the same structure or a plurality of carbon atoms. R ₉ is an organic group having at least one radically polymerizable unsaturated group having 3 to 20 carbon atoms, and n ₂ is an integer of 1 to 1000. }
It is a polyamide having a structure represented by. This polyamide is suitable for negative photosensitive resin compositions.

｛式中、Ｒ₃₂は、炭素数２〜１９のラジカル重合性の不飽和結合基を少なくとも一つ有する有機基である。｝
で表される基であることが好ましい。 In the above general formula (4), the _{group represented by R 9} has the following general formula (32), in that both photosensitive characteristics and chemical resistance are compatible.

{In the formula, R ₃₂ is an organic group having at least one radically polymerizable unsaturated bond group having 2 to 19 carbon atoms. }
It is preferably a group represented by.

で表される基の中から選ばれる芳香族基であることが好ましく、そしてアミノ基置換イソフタル酸構造からカルボキシル基及びアミノ基を除いた芳香族基であることがより好ましい。 In the above general formula (4), the _{trivalent organic group represented by X 2} is preferably a trivalent organic group having 6 to 15 carbon atoms, for example, the following formula (33):

It is preferably an aromatic group selected from the groups represented by, and more preferably an aromatic group obtained by removing a carboxyl group and an amino group from the amino group-substituted isophthalic acid structure.

｛式中、Ｒ₃₃及びＲ₃₄は、それぞれ独立に、水酸基、メチル基（−ＣＨ₃）、エチル基（−Ｃ₂Ｈ₅）、プロピル基（−Ｃ₃Ｈ₇）又はブチル基（−Ｃ₄Ｈ₉）から成る群から選ばれる一つの基であり、そして該プロピル基及びブチル基は、各種異性体を含む。｝

｛式中、ｍ₇は、０〜８の整数であり、ｍ₈及びｍ₉は、それぞれ独立に、０〜３の整数であり、ｍ₁₀及びｍ₁₁は、それぞれ独立に、０〜１０の整数であり、そしてＲ₃₅及びＲ₃₆は、メチル基（−ＣＨ₃）、エチル基（−Ｃ₂Ｈ₅）、プロピル基（−Ｃ₃Ｈ₇）、ブチル基（−Ｃ₄Ｈ₉）又はこれらの異性体である。｝が挙げられる。 In the above general formula (4), the _{divalent organic group represented by Y 2} is preferably an organic group having 6 to 35 carbon atoms, and may be substituted with an aromatic ring or an aliphatic ring. It is more preferable that it is a cyclic organic group having 1 to 4 or an aliphatic group or a siloxane group having no cyclic structure. Examples of the _{divalent organic group represented by Y 2} include the following general formula (I) and the following general formulas (34) and (35):

{In the formula, R ₃₃ and R ₃₄ are independently hydroxyl groups, methyl groups (-CH ₃ ), ethyl groups (-C ₂ H ₅ ), propyl groups (-C ₃ H ₇ ) or butyl groups (-C). _It is one group selected from the group consisting of 4H ₉ ), and the propyl group and the butyl group contain various isomers. }

{In the equation, m ₇ is an integer from 0 to 8, m ₈ and m ₉ are independently integers from 0 to 3, and m ₁₀ and m ₁₁ are independently from 0 to 10. It is an integer, and R ₃₅ and R ₃₆ are methyl group (-CH ₃ ), ethyl group (-C ₂ H ₅ ), propyl group (-C ₃ H ₇ ), butyl group (-C ₄ H ₉ ) or These isomers. } Can be mentioned.

｛式中、ｍ₁₂は、２〜１２の整数であり、ｍ₁₃は、１〜３の整数であり、ｍ₁₄は、１〜２０の整数であり、そしてＲ₃₇、Ｒ₃₈、Ｒ₃₉及びＲ₄₀は、それぞれ独立に、炭素数１〜３のアルキル基又は置換されていてもよいフェニル基である。｝が好ましいものとして挙げられる。 Examples of the aliphatic group or siloxane group having no cyclic structure include the following general formula (36):

{In the equation, m ₁₂ is an integer of 2-12, m ₁₃ is an integer of 1-3, m ₁₄ is an integer of 1-20, and R ₃₇ , R ₃₈ , R ₃₉ and R ₄₀ is an alkyl group having 1 to 3 carbon atoms or a optionally substituted phenyl group, respectively. } Is mentioned as a preferable one.

The polyamide resin of the present invention can be synthesized, for example, as follows.
(Synthesis of phthalic acid compound encapsulant)
First, it is selected from the group consisting of compounds having a trivalent aromatic group X ₂ , for example, phthalic acid substituted with an amino group, isophthalic acid substituted with an amino group, and terephthalic acid substituted with an amino group. At least one mol of the compound (hereinafter referred to as "phthalic acid compound") is reacted with 1 mol of a compound that reacts with an amino group, and the amino group of the phthalic acid compound is subjected to radical polymerizable, which will be described later. A compound modified and sealed with a group containing an unsaturated bond (hereinafter referred to as "phthalic acid compound encapsulant") is synthesized. These may be used alone or in combination.

When the phthalic acid compound has a structure in which the phthalic acid compound is sealed with a group containing the radically polymerizable unsaturated bond, negative type photosensitive (photocurability) can be imparted to the polyamide resin.

The group containing a radically polymerizable unsaturated bond is preferably an organic group having a radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and a group containing a methacryloyl group or an acryloyl group is particularly preferable.

In the above-mentioned phthalic acid compound encapsulant, the amino group of the phthalic acid compound is reacted with an acid chloride, isocyanate, epoxy compound or the like having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms. Can be obtained at.

Suitable acid chlorides include (meth) acryloyl chloride, 2-[(meth) acryloyloxy] acetyl chloride, 3-[(meth) acryloyloxy] propionyl chloride, 2-[(meth) acryloyloxy] ethylchloroformate. , 3-[(Meta) acryloyloxypropyl] chloroformate and the like. Suitable isocyanates include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate, 2- [2- (meth) acryloyloxyethoxy] ethyl isocyanate and the like. .. Suitable epoxy compounds include glycidyl (meth) acrylate and the like. These may be used alone or in admixture, but it is particularly preferred to use methacryloyl chloride and / or 2- (methacryloyloxy) ethyl isocyanate.

Further, as these phthalic acid compound encapsulants, those in which the phthalic acid compound is 5-aminoisophthalic acid are excellent in photosensitive characteristics, and at the same time, a polyamide having excellent film characteristics after heat curing can be obtained. Is preferable.

In the sealing reaction, the phthalic acid compound and the sealing agent are stirred in the presence of a basic catalyst such as pyridine or a tin catalyst such as di-n-butyltin dilaurate in a solvent as described later, if necessary. It can be advanced by dissolving and mixing.

Depending on the type of encapsulant, such as acid chloride, hydrogen chloride may be produced as a by-product during the encapsulation reaction. In this case, from the viewpoint of preventing contamination in the subsequent steps, it is preferable to perform appropriate purification such as once re-settling with water and washing and drying, or removing and reducing ionic components through a column filled with an ion exchange resin. ..

(Synthesis of polyamide)
The above phthalic acid compound encapsulant _{and a diamine compound having a divalent organic group Y 2} are mixed in the presence of a basic catalyst such as pyridine or triethylamine in a solvent as described later and amide polycondensed. The polyamide of the present invention can be obtained.

As the amide polycondensation method, a phthalic acid compound encapsulant is made into a symmetric polyacid anhydride using a dehydration condensing agent and then mixed with a diamine compound, or the phthalic acid compound encapsulant is acid chloride by a known method. Examples thereof include a method of mixing with a diamine compound after conversion, a method of reacting a dicarboxylic acid component with an active esterifying agent in the presence of a dehydration condensing agent to form an active ester, and then mixing with a diamine compound.

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. '-Diskosine imidazole carbonate and the like are preferred.

Examples of the chloroagent include thionyl chloride and the like.

Examples of the active esterifying agent include N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acidimide, 2-hydroxyimino-2-cyanoacetate ethyl, and 2-hydroxyimino-. Examples include 2-cyanoacetic acid amide.

The diamine compound having an organic group Y ₂ is at least one diamine selected from the group consisting of an aromatic diamine compound, an aromatic bisaminophenol compound, an alicyclic diamine compound, a linear aliphatic diamine compound, and a siloxane diamine compound. It is preferably a compound, and a plurality of compounds may be used in combination if desired.

Examples of the aromatic diamine compound include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, and the like. 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 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-aminophenyl) 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, and some of the hydrogen atoms on these benzene rings are methyl, ethyl, hydroxymethyl, hydroxyethyl, and halogen atoms. Benzene compounds substituted with one or more groups selected from the group consisting of.

Examples of the diamine compound in which the hydrogen atom on the benzene ring is substituted are 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- Examples thereof include 4,4'-diaminobiphenyl.

Examples of the aromatic bisaminophenol compound include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenylsulfone, and bis-. (3-Amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (3-hydroxy-4-aminophenyl) hexafluoropropane, bis- (3-hydroxy-4-aminophenyl) methane, 2,2-bis- (3-hydroxy-4-aminophenyl) Propane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,5 -Dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis (3-amino-4-hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylene) -bis (2-amino) Phenol) and the like.

Examples of the alicyclic diamine compound include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3,5-diamino-1,1-dimethylcyclohexane, and 1,5. −Diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl-4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2 , 5-Diethylcyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2- (3-aminocyclopentyl) -2-propylamine, mensendiamine, isophoronediamine, norbornan Diamine, 1-cyclohepten-3,7-diamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine), 1,4-bis (3-aminopropyl) piperazine, Examples thereof include 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro- [5,5] -undecane.

Examples of the linear aliphatic diamine compound include 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane. Hydrocarbon-type diamines such as 2- (2-aminoethoxy) ethylamine, 2,2'-(ethylenedioxy) diethylamine, alkylene oxide-type diamines such as bis [2- (2-aminoethoxy) ethyl] ether, etc. Can be mentioned.

Examples of the siloxane diamine compound include dimethyl (poly) siloxane diamine, for example, manufactured by Shin-Etsu Chemical Co., Ltd., trade names PAM-E, KF-8010, X-22-161A and the like.

After the completion of the amide polycondensation reaction, the precipitates derived from the dehydration condensate agent and the like precipitated in the reaction solution are filtered out as necessary. Next, a poor solvent for polyamide such as water or an aliphatic lower alcohol or a mixture thereof is added to the reaction solution to precipitate the polyamide. Further, the precipitated polyamide is redissolved in a solvent, purified by repeating the reprecipitation and precipitation operation, vacuum dried, and the desired polyamide is isolated. In addition, in order to further improve the degree of purification, the solution of this polyamide may be passed through a column packed with an ion exchange resin to remove ionic impurities.

The polystyrene-equivalent weight average molecular weight of the polyamide by gel permeation chromatography (hereinafter referred to as “GPC”) is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. When the polystyrene-equivalent weight average molecular weight is 7,000 or more, the basic physical properties of the cured relief pattern are ensured. Further, when the polystyrene-equivalent weight average molecular weight is 70,000 or less, the develop solubility at the time of forming the relief pattern is ensured.

Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the eluent for GPC. The weight average molecular weight value 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.

｛式中、Ｙ₃は、炭素原子を有する４価の有機基であり、好ましくは２個以上の炭素原子を有する４価の有機基であり、Ｙ₄、Ｘ₃及びＸ₄は、それぞれ独立に、２個以上の炭素原子を有する２価の有機基であり、ｎ₃は、１〜１０００の整数であり、ｎ₄は、０〜５００の整数であり、ｎ₃／（ｎ₃＋ｎ₄）＞０．５であり、そしてＸ₃及びＹ₃を含むｎ₃個のジヒドロキシジアミド単位並びにＸ₄及びＹ₄を含むｎ₄個のジアミド単位の配列順序は問わない。｝で表される構造を有するポリヒドロキシアミド（ポリオキサゾール前駆体（以下、上記一般式（５）で表されるポリヒドロキシアミドを単に「ポリオキサゾール前駆体」という場合がある。））である。 [(A) Polyhydroxyamide]
A further example of the preferred resin (A) in the photosensitive resin composition of the present invention is described in the following general formula (5):

{In the formula, Y ₃ is a tetravalent organic group having a carbon atom, preferably a tetravalent organic group having two or more carbon atoms, and Y ₄ , X ₃ and X ₄ are independent of each other. In addition, it is a divalent organic group having two or more carbon atoms, n ₃ is an integer of 1 to 1000, n ₄ is an integer of 0 to 500, and n ₃ / (n ₃ + n _4). )> 0.5, and the sequence order of n ₃ dihydroxydiamide units _{containing X 3} and Y ₃ and n _{4 diamide units containing X 4} and Y _{4 does not matter.} } Is a polyhydroxyamide having a structure represented by} (polyoxazole precursor (hereinafter, the polyhydroxyamide represented by the above general formula (5) may be simply referred to as “polyoxazole precursor”)).

_{The polyoxazole precursor is a polymer having n 3} dihydroxydiamide units in the general formula (5) (hereinafter, may be simply referred to as dihydroxydiamide units), and n _{4 in the general formula (5).} It may have a number of diamide units (hereinafter, may be simply referred to as a diamide unit).

The number of carbon atoms of _{X 3} is preferably 2 or more and 40 or less for the purpose of obtaining photosensitive characteristics, and the number of carbon atoms of _{X 4 is preferably 2 or more and 40 or less for the purpose of obtaining photosensitive characteristics.} Preferably, the _{number of carbon atoms of Y 3} is 2 or more and 40 or less for the _{purpose of obtaining photosensitive characteristics, and the number of carbon atoms of Y 4} is 2 or more and 40 or less for the purpose of obtaining photosensitive characteristics. It is preferable to have.

The dihydroxydiamide unit can be formed by synthesis from a diaminodihydroxy compound having a structure of _{Y 3} (NH ₂ ) ₂ (OH) ₂ (preferably bisaminophenol) and a dicarboxylic acid having a structure of _{X 3} (COOH) _2. .. Hereinafter, a typical embodiment will be described by taking the case where the diaminodihydroxy compound is bisaminophenol as an example. The two sets of amino groups and hydroxy groups of the bisaminophenol are in ortho positions with each other, and the dihydroxydiamide unit is ring-closed by heating at about 250 to 400 ° C. to form a heat-resistant polyoxazole structure. Changes to. _{N 3} in the general formula (5) is 1 or more for the purpose of obtaining the photosensitive characteristics and 1000 or less for the purpose of obtaining the photosensitive characteristics. n ₃ is preferably in the range of 2 to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 20.

The polyoxazole precursor may be condensed with _{n 4} diamide units, if necessary. The diamide unit can be formed by synthesis from a diamine having a structure of _{Y 4} (NH ₂ ) ₂ and a dicarboxylic acid having a structure of _{X 4} (COOH) _{2. N 4} in the general formula (5) is in the range of 0 to 500, and good photosensitive characteristics can be obtained _{when n 4 is 500 or less.} n ₄ is more preferably in the range of 0 to 10. If the ratio of the diamide unit to the dihydroxydiamide unit is too high, the solubility in the alkaline aqueous solution used as the developer decreases, so _{the value of n 3} / (n ₃ + n ₄ ) in the general formula (5) is 0.5. It is super, more preferably 0.7 or more, and most preferably 0.8 or more.

｛式中、Ｒｓ１とＲｓ２は、それぞれ独立に、水素原子、メチル基、エチル基、プロピル基、シクロペンチル基、シクロヘキシル基、フェニル基、トリフルオロメチル基を表す｝ で表されるものが、感光特性の点で好ましい。 Examples of bisaminophenol as a diaminodihydroxy compound having a structure of Y ₃ (NH ₂ ) ₂ (OH) ₂ include 3,3'-dihydroxybenzidine and 3,3'-diamino-4,4'-dihydroxybiphenyl. , 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-Amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) Propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3 '-Diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene And so on. These bis-aminophenols can be used alone or in combination of two or more. _{The Y 3} groups in the bis-aminophenol include the following formula (37):

{In the formula, Rs1 and Rs2 independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a trifluoromethyl group}. It is preferable in that.

Examples of the diamine having a Y ₄ (NH ₂ ) ₂ structure include aromatic diamines and silicon diamines. Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylene diamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'-diamino. Diphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone, 4,4'-diaminodiphenylketone, 3,4'-diaminodiphenylketone, 2,2'-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-Aminophenoxy) Benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene,

4-Methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, imino-di-p-phenylenediamine, 1, 5-Diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3 3-trimethylindan, bis (p-aminophenyl) phosphenyl oxide, 4,4'-diaminoazobenzene, 4,4'-diaminodiphenylurea, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] Benzophenone, 4,4'-bis (4-aminophenoxy) diphenyl sulfone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4'-bis [4 -(Α, α-dimethyl-4-aminobenzyl) phenoxy] diphenyl sulfone, 4,4'-diaminobiphenyl,

4,4'-Diaminobenzophenone, Phenylindandiamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, o-toluidine sulfone, 2,2 -Bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4) -Aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-di- (3-aminophenoxy) diphenyl sulfone, 4,4'-diaminobenzanilide, etc., and their fragrances. Examples thereof include compounds in which the hydrogen atom of the aromatic nucleus of the group diamine is substituted with at least one group or atom selected from the group consisting of chlorine atom, fluorine atom, bromine atom, methyl group, methoxy group, cyano group and phenyl group. Be done.

Further, as the diamine, silicon diamine can be selected in order to enhance the adhesiveness with the base material. Examples of silicon diamines include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, and bis (γ-aminopropyl) tetramethyldi. Examples thereof include siloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, and bis (γ-aminopropyl) tetraphenyldisiloxane.

｛式中、Ｒ₄₁は、−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−及び−Ｃ（ＣＦ₃）₂−から成る群から選択される２価の基を表す。｝
で表される芳香族基から好ましく選択でき、これらは感光特性の点で好ましい。 Further, as preferable dicarboxylic acids having a structure of _{X 3} (COOH) ₂ or X ₄ (COOH) _{2 , X 3} and X ₄ are aliphatic groups or aromatic acids having a linear, branched chain or cyclic structure, respectively. The basic ones can be mentioned. Among them, an organic group having 2 to 40 carbon atoms which may contain an aromatic ring or an aliphatic ring is preferable, and X ₃ and X ₄ are represented by the following formula (38), respectively.

{Wherein, R _{41 is, -CH 2 -, - O -} , - S -, - SO 2 -, - CO -, - NHCO- and -C (CF _{3) 2} - ₂ is selected from the group consisting of Represents the basis of valuation. }
It can be preferably selected from the aromatic groups represented by, and these are preferable in terms of photosensitive characteristics.

で表されるものが挙げられる。 The polyoxazole precursor may be one in which the terminal group is sealed with a specific organic group. When a polyoxazole precursor sealed with a sealing group is used, the mechanical properties (particularly elongation) and the cured relief pattern shape of the coating film after heat curing of the photosensitive resin composition of the present invention can be improved. Be expected. A suitable example of such a sealing group is the following formula (39):

The one represented by is mentioned.

The polystyrene-equivalent weight average molecular weight of the polyoxazole precursor by gel permeation chromatography is preferably 3,000 to 70,000, more preferably 6,000 to 50,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the cured relief pattern. Further, from the viewpoint of resolution, 70,000 or less is preferable. 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.

｛式中、Ｘ₅は、４〜１４価の有機基、Ｙ₅は、２〜１２価の有機基、Ｒ₁₀及びＲ₁₁は、フェノール性水酸基、スルホン酸基又はチオール基から選ばれる基を少なくとも一つ有する有機基を示し、かつ同一であるか、又は異なっていてよく、ｎ₅は、３〜２００の整数であり、そしてｍ₃及びｍ₄は、０〜１０の整数である。｝
で表される構造を有するポリイミドである。ここで、一般式（６）で表される樹脂は、十分な膜特性を発現する上で熱処理の工程で化学変化を要さないので、より低温での処理に好適である点で特に好ましい。
上記一般式（６）にて示される構造単位中のＸ₅は、炭素数４〜４０の４価〜１４価の有機基であることが好ましく、耐熱性と感光特性とを両立するという点で、芳香族環又は脂肪族環を含有する炭素原子数５〜４０の有機基であることがさらに好ましい。 [(A) Polyimide]
A further example of the preferred resin (A) in the photosensitive resin composition of the present invention is described in the general formula (6):

{Wherein, X ₅ is 4-14 monovalent organic group, Y ₅ is 2-12 monovalent organic group, R ₁₀ and R ₁₁ include a phenolic hydroxyl group, a group selected from a sulfonic acid group or thiol group Indicates an organic group having at least one and may be the same or different, n ₅ is an integer from _{3 to} 200, and m 3 and m ₄ are integers from 0 to 10. }
It is a polyimide having a structure represented by. Here, the resin represented by the general formula (6) is particularly preferable in that it is suitable for treatment at a lower temperature because it does not require a chemical change in the heat treatment step in order to exhibit sufficient film properties.
_{X 5} in the structural unit represented by the general formula (6) is preferably a tetravalent to 14-valent organic group having 4 to 40 carbon atoms, and is compatible with both heat resistance and photosensitive characteristics. It is more preferable that the organic group contains an aromatic ring or an aliphatic ring and has 5 to 40 carbon atoms.

The polyimide represented by the general formula (6) can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, a tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride or the like with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine. can. Polyimide can be obtained by dehydrating and ring-closing polyamic acid, which is one of the polyimide precursors generally obtained by reacting tetracarboxylic acid dianhydride with diamine, by heating or chemical treatment with an acid or a base.

Suitable tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic hydride, 2,3,3', 4'-biphenyltetracarboxylic acid. Dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'- Benzophenone tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1- Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5 6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic acid dianhydride,

｛式中、Ｒ₄₂は、酸素原子、Ｃ（ＣＦ₃）₂、Ｃ（ＣＨ₃）₂又はＳＯ₂から選ばれる基を示し、そしてＲ₄₃及びＲ₄₄は、同一であるか、又は異なっていてもよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝で表される化合物が挙げられる。 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridine Aromatic tetracarboxylic acids such as tetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, etc. Dianhydrides, or aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic acid dianhydrides, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydrides, 3,3', 4,4'. -Diphenylsulfonetetracarboxylic acid dianhydride and the following general formula (40):

{In the formula, R ₄₂ represents a group selected from the oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO _{2 , and R 43} and R ₄₄ are the same or different. It may indicate a group selected from a hydrogen atom, a hydroxyl group or a thiol group. } Can be mentioned.

Of these, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'- Biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride , 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyphenyl) sulfone dianhydride,

｛式中、Ｒ₄₅は、酸素原子、Ｃ（ＣＦ₃）₂、Ｃ（ＣＨ₃）₂又はＳＯ₂から選ばれる基を示し、そしてＲ₄₆及びＲ₄₇は、同一であるか、又は異なっていてもよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝で表される構造の酸二無水物が好ましい。これらは単独で又は２種以上を組み合わせて使用される。 Bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic Acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic hydride and The following general formula (41)

{In the formula, R ₄₅ represents a group selected from oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO _{2 , and R 46} and R ₄₇ are the same or different. It may indicate a group selected from a hydrogen atom, a hydroxyl group or a thiol group. } Is preferable as an acid dianhydride having a structure represented by. These are used alone or in combination of two or more.

_{Y 5} of the above general formula (6) represents a structural component of a diamine, and the diamine represents a 2 to 12-valent organic group containing an aromatic ring or an aliphatic ring, and among them, the number of carbon atoms is 5. -40 organic groups are preferred.

Specific examples of diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylene Diamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- ( 4-Aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diamino Biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl,

｛式中、Ｒ₄₈は、酸素原子、Ｃ（ＣＦ₃）₂、Ｃ（ＣＨ₃）₂又はＳＯ₂から選ばれる基を示し、そしてＲ₄₉〜Ｒ₅₂は、同一であるか、又は異なっていてよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝で表される構造のジアミンなどが挙げられる。 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4 , 4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene or alkyl groups or halogens on these aromatic rings Atomatically substituted compounds, or aliphatic cyclohexyldiamines, methylenebiscyclohexylamines, and the following general formula (42):

{In the formula, R ₄₈ represents a group selected from oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO _{2 , and R 49-} R ₅₂ are the same or different. A group selected from a hydrogen atom, a hydroxyl group or a thiol group is shown. } Can be mentioned, such as a diamine having a structure represented by.

｛式中、Ｒ₅₃は、酸素原子、Ｃ（ＣＦ₃）₂、Ｃ（ＣＨ₃）₂又はＳＯ₂から選ばれる基を示し、そしてＲ₅₄〜Ｒ₅₇は、同一であるか、又は異なっていてよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝
で表される構造のジアミンが好ましい。 Of these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'- Diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, m-phenylenediamine, P-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis (4-Aminophenyl) fluorene and the following general formula (43):

{In the formula, R ₅₃ represents a group selected from oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO _{2 , and R 54 to} R ₅₇ are the same or different. A group selected from a hydrogen atom, a hydroxyl group or a thiol group is shown. }
A diamine having a structure represented by is preferable.

｛式中、Ｒ₅₈は、酸素原子、Ｃ（ＣＦ₃）₂、Ｃ（ＣＨ₃）₂又はＳＯ₂から選ばれる基を示し、そしてＲ₅₉及びＲ₆₀は、同一であるか、又は異なっていてよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝
で表される構造のジアミンが特に好ましい。これらは単独で又は２種以上を組み合わせて使用される。 Of these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'- Diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, and the following general formula (44):

{In the formula, R ₅₈ represents a group selected from oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO _{2 , and R 59} and R ₆₀ are the same or different. A group selected from a hydrogen atom, a hydroxyl group or a thiol group is shown. }
A diamine having a structure represented by is particularly preferable. These are used alone or in combination of two or more.

_{R 10} and R ₁₁ of the general formula (6) represent a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. In the present invention, phenolic hydroxyl groups, sulfonic acid groups and / or thiol groups can be mixed as _{R 10} and R _11.

By controlling the amount of the alkali-soluble groups of R ₁₀ and R _11, the dissolution rate in the alkaline aqueous solution changes. Therefore, a photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment.

Further, in order to improve the adhesiveness to the substrate, aliphatic groups having a siloxane structure as _{X 5} and Y _{5 may be copolymerized as long as the heat resistance is not lowered.} Specific examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

The above-mentioned polyimide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal encapsulant which is monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partially) at a low temperature. A method of reacting a diamine compound with an acid anhydride or a monoacid chloride compound or a terminal encapsulant which is a monoactive ester compound) to obtain a diester by tetracarboxylic acid dianhydride and alcohol, and then diamine (partially). A method of reacting with a monoamine terminal encapsulant) in the presence of a condensing agent, a diester is obtained by tetracarboxylic acid dianhydride and alcohol, and then the remaining dicarboxylic acid is acid chlorided to diamine (partially). A method such as a method of reacting with a terminal-capping agent which is a monoamine) is used to obtain a polyimide precursor, which is completely imidized by a known imidization reaction method, or in the middle of the process. A method of stopping the imidization reaction and introducing a partially imidized structure (in this case, polyamideimide), and further, a partially imidized structure is introduced by blending the completely imidized polymer with its polyimide precursor. It can be synthesized using the method.

The polyimide preferably has a polyimide so that the imidization ratio is 15% or more with respect to the entire resin constituting the photosensitive resin composition. More preferably, it is 20% or more. Here, the imidization ratio refers to the ratio of imidization present in the entire resin constituting the photosensitive resin composition. If the imidization rate is less than 15%, the amount of shrinkage during thermosetting becomes large, which is not suitable for forming a thick film.

The imidization ratio can be easily calculated by the following method. First, the infrared absorption spectrum of the polymer is measured to confirm the presence of absorption peaks (near 1780 cm-1 and around 1377 cm-1) of the imide structure caused by polyimide. Next, the polymer is heat-treated at 350 ° C. for 1 hour, the infrared absorption spectrum after the heat treatment is measured, and the peak intensity near 1377 cm-1 is compared with the intensity before the heat treatment to imidize the polymer before the heat treatment. Calculate the rate.

The molecular weight of the polyimide is preferably 3,000 to 200,000, more preferably 5,000 to 50,000, as measured by the polystyrene-equivalent weight average molecular weight by gel permeation chromatography. When the weight average molecular weight is 3,000 or more, the mechanical properties are good, and when it is 50,000 or less, the dispersibility in the developing solution is good, and the resolution performance of the relief pattern 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.
Further, in the present invention, a phenol resin can also be preferably used.

[(A) Phenol resin]
The phenol resin in the present embodiment means a resin having a repeating unit having a phenolic hydroxyl group. The phenol resin (A) has an advantage that it can be cured at a low temperature (for example, 250 ° C. or lower) because the structural change such that the polyimide precursor is cyclized (imidized) does not occur during thermosetting.

In the present embodiment, the weight average molecular weight of the phenol resin (A) is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000 to 50,000. be. The weight average molecular weight is preferably 700 or more from the viewpoint of reflow treatment applicability of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.
The measurement of the weight average molecular weight in the present disclosure is performed by gel permeation chromatography (GPC), and can be calculated by a calibration curve prepared using standard polystyrene.

｛式中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ₁₂は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基からなる群から選択される１価の置換基を表し、ｂが２又は３である場合には、複数のＲ₁₂は、互いに同一でも又は異なっていてもよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（８）：

（式中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び炭素数６〜１２の芳香族環を有する２価の有機基からなる群から選択される２価の有機基を表す。｝
で表される繰り返し単位を有するフェノール樹脂、及び炭素数４〜１００の不飽和炭化水素基を有する化合物で変性されたフェノール樹脂から選択される少なくとも１種のフェノール樹脂であることが好ましい。 The phenolic resin (A) is novolak, polyhydroxystyrene, or the following general formula (7): from the viewpoints of solubility in an alkaline aqueous solution, sensitivity and resolution when forming a resist pattern, and residual stress of a cured film.

{In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦ (a + b) ≦ 4, and R ₁₂ is a monovalent organic having 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of groups, halogen atoms, nitro groups and cyano groups, where b is 2 or 3, the plurality of R _12s may be the same or different from each other. Well, X is a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, the following general formula (8):

It is selected from the group consisting of a divalent alkylene oxide group represented by (in the formula, p is an integer of 1 to 10) and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. Represents a divalent organic group. }
It is preferable that it is at least one phenol resin selected from a phenol resin having a repeating unit represented by (1) and a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms.

(Novolak)
In the present disclosure, novolak means all polymers obtained by condensing phenols and formaldehyde in the presence of a catalyst. Generally, novolak can be obtained by condensing less than 1 mol of formaldehyde with 1 mol of phenols. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-Xylenol, 2,4-Xylenol, 2,5-Xylenol, 2,6-Xylenol, 3,4-Xylenol, 3,5-Xylenol, 2,3,5-trimethylphenol, 3,4,5- Examples thereof include trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like. Specific examples of the novolak include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin and the like.

The weight average molecular weight of novolak is preferably 700 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of reflow treatment applicability of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

(Polyhydroxystyrene)
In the present disclosure, polyhydroxystyrene means all polymers containing hydroxystyrene as a polymerization unit. Preferred examples of polyhydroxystyrene include polyparavinylphenol. Polyparavinylphenol means all polymers containing paravinylphenol as a polymerization unit. Therefore, a polymerization unit other than hydroxystyrene (for example, paravinylphenol) can be used to form polyhydroxystyrene (for example, polyparavinylphenol) as long as it does not contradict the object of the present invention. In polyhydroxystyrene, the ratio of the number of moles of hydroxystyrene units based on the number of moles of all polymerization units is preferably 10 mol% to 99 mol%, more preferably 20 to 97 mol%, still more preferably 30 to 95 mol. %. When the above ratio is 10 mol% or more, it is advantageous from the viewpoint of alkali solubility of the photosensitive resin composition, and when it is 99 mol% or less, a cured film obtained by curing the composition containing the copolymerization component described later. It is advantageous from the viewpoint of reflow applicability. The polymerization unit other than hydroxystyrene (for example, para-vinylphenol) can be any polymerization unit that can be copolymerized with hydroxystyrene (for example, para-vinylphenol). The copolymerization component that gives a polymerization unit other than hydroxystyrene (for example, paravinylphenol) is not limited, and for example, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, octyl acrylate, and 2-ethoxyethyl. Metaacrylate, t-butyl acrylate, 1,5-pentanediol diacrylate, N, N-diethylaminoethyl acrylate, ethylene glycol diacrylate, 1,3-propanediol diacrylate, decamethylene glycol diacrylate, decamethylene glycol dimethacrylate , 1,4-Cyclohexanediol diacrylate, 2,2-dimethylolpropandiacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, 2,2-di (p-hydroxyphenyl) -propanedimethacrylate, Triethylene glycol diacrylate, polyoxyethyl-2-2-di (p-hydroxyphenyl) -propanedimethacrylate, triethylene glycol dimethacrylate, polyoxypropyltrimethylol propanetriacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate , 1,3-Propanediol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetrioltrimethacrylate, 2,2,4-trimethyl-1,3-pentanedioldi Such as methacrylate, pentaerythritol trimethacrylate, 1-phenylethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylpropantrimethacrylate, 1,5-pentanediol dimethacrylate and 1,4-benzenediol dimethacrylate. Acrylate esters; styrenes and substituted styrenes such as 2-methylstyrene and vinyltoluene; for example vinyl ester monomers such as vinylacrylates and vinylmethacrylates; and o-vinylphenols, m-vinylphenols and the like. Be done.

Further, as the novolak and polyhydroxystyrene described above, one type may be used alone or two or more types may be used in combination, respectively.

The weight average molecular weight of polyhydroxystyrene is preferably 700 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of reflow treatment applicability of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

｛式中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ₁₂は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基からなる群から選択される１価の置換基を表し、ｂが２又は３である場合には、複数のＲ₁₂は、互いに同一でも又は異なっていてよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（８）：

（式中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び炭素数６〜１２の芳香族環を有する２価の有機基からなる群から選択される２価の有機基を表す。｝で表される繰り返し単位を有するフェノール樹脂を含むこともまた好ましい。上記の繰り返し単位を有するフェノール樹脂は、例えば従来使用されてきたポリイミド樹脂及びポリベンゾオキサゾール樹脂と比べて低温での硬化が可能であり、かつ良好な伸度を有する硬化膜の形成を可能にする点で特に有利である。フェノール樹脂分子中に存在する上記繰り返し単位は、１種又は２種以上の組合せであることができる。 (Phenol resin represented by the general formula (7))
In the present embodiment, the phenol resin (A) is based on the following general formula (7):

{In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦ (a + b) ≦ 4, and R ₁₂ is a monovalent organic having 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of groups, halogen atoms, nitro groups and cyano groups, where b is 2 or 3, the plurality of R _12s may be the same or different from each other. , X is a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, the following general formula (8):

It is selected from the group consisting of a divalent alkylene oxide group represented by (in the formula, p is an integer of 1 to 10) and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. Represents a divalent organic group. It is also preferable to include a phenol resin having a repeating unit represented by }. The phenol resin having the above repeating unit can be cured at a lower temperature than, for example, the conventionally used polyimide resin and polybenzoxazole resin, and enables the formation of a cured film having good elongation. It is particularly advantageous in that respect. The repeating unit present in the phenol resin molecule can be one kind or a combination of two or more kinds.

｛式中、Ｒ₆₁、Ｒ₆₂及びＲ₆₃は、各々独立に、水素原子、不飽和結合を有していてもよい炭素数１〜１０の脂肪族基、炭素数３〜２０の脂環式基、又は炭素数６〜２０の芳香族基を表し、そしてＲ₆₄は、不飽和結合を有していてもよい炭素数１〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、又は炭素数６〜２０の２価の芳香族基を表す。｝で表される４つの基からなる群から選択される１価の置換基であることが好ましい。 In the above general formula (7), R ₁₂ is a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group and a cyano from the viewpoint of reactivity when synthesizing the resin according to the general formula (7). It is a monovalent substituent selected from the group consisting of groups. From the viewpoint of alkali solubility, R ₁₂ has a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, and an aromatic group having 6 to 20 carbon atoms. And the following general formula (45):

{In the formula, R ₆₁ , R ₆₂ and R ₆₃ are independently hydrogen atoms, aliphatic groups having 1 to 10 carbon atoms which may have unsaturated bonds, and alicyclic compounds having 3 to 20 carbon atoms. Represents a group, or an aromatic group having 6 to 20 carbon atoms, and R ₆₄ is a divalent aliphatic group having 1 to 10 carbon atoms, which may have an unsaturated bond, and 2 having 3 to 20 carbon atoms. It represents a valent alicyclic group or a divalent aromatic group having 6 to 20 carbon atoms. } Is preferably a monovalent substituent selected from the group consisting of four groups.

In the present embodiment, in the above general formula (7), a is an integer of 1 to 3, but 2 is preferable from the viewpoint of alkali solubility and elongation. When a is 2, the substitution position between the hydroxyl groups may be any of the ortho, meta, and para positions. When a is 3, the substitution positions of the hydroxyl groups may be any of 1,2,3-positions, 1,2,4-positions, 1,3,5-positions, and the like.

In the present embodiment, in the above general formula (7), when a is 1, a phenol resin having a repeating unit represented by the general formula (7) in order to improve alkali solubility (hereinafter, (a1)). A phenol resin (hereinafter, also referred to as (a2) resin) selected from novolak and polyhydroxystyrene can be further mixed with the resin).

The mixing ratio of the resin (a1) and the resin (a2) is preferably in the range of (a1) / (a2) = 10/90 to 90/10 in terms of mass ratio. This mixing ratio is preferably (a1) / (a2) = 10/90 to 90/10, and (a1) / (a2) = 20 from the viewpoint of solubility in an alkaline aqueous solution and elongation of the cured film. It is more preferably / 80 to 80/20, and further preferably (a1) / (a2) = 30/70 to 70/30.

As the novolak and polyhydroxystyrene as the resin (a2), the same resins as those shown in the above (novolak) and (polyhydroxystyrene) sections can be used.

In the present embodiment, in the above general formula (7), b is an integer of 0 to 3, but is preferably 0 or 1 from the viewpoint of alkali solubility and elongation. Further, when b is 2 or 3, the plurality of R _12s may be the same as or different from each other.

Further, in the present embodiment, in the above general formula (7), a and b satisfy the relationship of 1 ≦ (a + b) ≦ 4.

｛式中、Ｒ₁₃、Ｒ₁₄、Ｒ₁₅及びＲ₁₆は、各々独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基であり、ｎ₆は０〜４の整数であって、ｎ₆が１〜４の整数である場合のＲ₁₇は、ハロゲン原子、水酸基、又は炭素数１〜１２の１価の有機基であり、少なくとも１つのＲ₁₇は水酸基であり、ｎ₆が２〜４の整数である場合の複数のＲ₁₇は互いに同一でも又は異なっていてもよい。｝で表される２価の基、及び下記一般式（１０）：

｛式中、Ｒ₁₈、Ｒ₁₉、Ｒ₂₀及びＲ₂₁は、各々独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基を表し、Ｗは、単結合、フッ素原子で置換されていてもよい炭素数１〜１０の脂肪族基、フッ素原子で置換されていてもよい炭素数３〜２０の脂環式基、下記一般式（８）：

（式中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び下記式（１１）：

で表される２価の基からなる群から選択される２価の有機基である。｝で表される２価の基からなる群から選択される２価の有機基であることが好ましい。上記炭素数６〜１２の芳香族環を有する２価の有機基Ｘの炭素数は、好ましくは８〜７５、より好ましくは８〜４０である。なお上記炭素数６〜１２の芳香族環を有する２価の有機基Ｘの構造は、一般的には、上記一般式（７）中、ＯＨ基及び任意のＲ₁₂基が芳香環に結合している構造とは異なる。 In the present embodiment, in the above general formula (7), X is a divalent group having 2 to 10 carbon atoms which may have an unsaturated bond from the viewpoint of the cured relief pattern shape and the elongation of the cured film. From an aliphatic group, a divalent alicyclic group having 3 to 20 carbon atoms, an alkylene oxide group represented by the above general formula (8), and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. It is a divalent organic group selected from the group. Among these divalent organic groups, X is represented by the following general formula (9): from the viewpoint of the toughness of the film after curing.

{In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently replaced with a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atom with a fluorine atom. has been a becomes a monovalent aliphatic group having 1 to 10 carbon atoms, n ₆ is an integer of 0 to 4, R ₁₇ where n ₆ is an integer of 1 to 4 include a halogen atom, a hydroxyl group Or, it is a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ is a hydroxyl group, and _{a plurality of R 17s when n 6} is an integer of 2 to 4 are the same as or different from each other. May be good. }, And the following general formula (10):

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are each independently replaced with a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atom with a fluorine atom. It represents a monovalent aliphatic group having 1 to 10 carbon atoms, and W is a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, or a fluorine atom. Aliphatic group having 3 to 20 carbon atoms, the following general formula (8):

A divalent alkylene oxide group represented by (in the formula, p is an integer of 1 to 10), and the following formula (11):

It is a divalent organic group selected from the group consisting of divalent groups represented by. } Is preferably a divalent organic group selected from the group consisting of divalent groups. The divalent organic group X having an aromatic ring having 6 to 12 carbon atoms has preferably 8 to 75 carbon atoms, more preferably 8 to 40 carbon atoms. Incidentally structure divalent organic radical X having an aromatic ring in the 6 to 12 carbon atoms are generally in the general formula (7), OH group and any R ₁₂ groups are bonded to an aromatic ring It is different from the structure.

で表される２価の有機基であることがより好ましく、さらに下記式（１３）：

で表される２価の有機基であることが特に好ましい。 Further, the divalent organic group represented by the general formula (10) has the following formula (12): from the viewpoint of good pattern forming property of the resin composition and good elongation of the cured film after curing.

It is more preferable that it is a divalent organic group represented by the following formula (13):

It is particularly preferable that it is a divalent organic group represented by.

Among the structures represented by the general formula (7), X is particularly preferably the structure represented by the formula (12) or (13), and is represented by the structure represented by the formula (12) or (13) in X. From the viewpoint of elongation, the proportion of the portion to be formed is preferably 20% by mass or more, and more preferably 30% by mass or more. From the viewpoint of alkali solubility of the composition, the above ratio is preferably 80% by mass or less, and more preferably 70% by mass or less.

｛式中、Ｒ₂₁は炭化水素基及びアルコキシ基からなる群から選択される炭素数１〜１０の１価の基であり、ｎ₇は２又は３であり、ｎ₈は０〜２の整数であり、ｍ₅は１〜５００の整数であり、２≦（ｎ₇＋ｎ₈）≦４であり、ｎ₈が２の場合には、複数のＲ₂₁は互いに同一でも又は異なっていてもよい。｝

｛式中、Ｒ₂₂及びＲ₂₃は各々独立に炭化水素基及びアルコキシ基からなる群から選択される炭素数１〜１０の１価の基であり、ｎ₉は１〜３の整数であり、ｎ₁₀は０〜２の整数であり、ｎ₁₁は０〜３の整数であり、ｍ₆は１〜５００の整数であり、２≦（ｎ₉＋ｎ₁₀）≦４であり、ｎ₁₀が２の場合には、複数のＲ₂₂は互いに同一でも又は異なっていてもよく、ｎ₁₁が２又は３の場合には、複数のＲ₂₃は互いに同一でも又は異なっていてもよい。｝ Further, among the phenol resins having the structure represented by the general formula (7), both the structure represented by the following general formula (14) and the structure represented by the following general formula (15) have the same resin skeleton. The structure contained therein is particularly preferable from the viewpoint of alkali solubility of the composition and elongation of the cured film.

{In the formula, R ₂₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of hydrocarbon groups and alkoxy groups, n ₇ is 2 or 3, and n ₈ is an integer of 0 to 2. , _{M 5} is an integer from 1 to 500, 2 ≦ (n ₇ + n ₈ ) ≦ 4, and when n ₈ is 2, the plurality of R _21s may be the same or different from each other. .. }

{In the formula, R ₂₂ and R ₂₃ are monovalent groups having 1 to 10 carbon atoms independently selected from the group consisting of hydrocarbon groups and alkoxy groups, respectively, and n ₉ is an integer of 1 to 3. n ₁₀ is an integer from 0 to 2, n ₁₁ is an integer from 0 to 3, m ₆ is an integer from 1 to 500, 2 ≦ (n ₉ + n ₁₀ ) ≦ 4, and n ₁₀ is 2. In the case of, the plurality of R _22s may be the same or different from each other, and when n ₁₁ is 2 or 3, the plurality of R _23s may be the same or different from each other. }

_{M 5} of the general formula (14) _{and m 6} of the general formula (15) represent the total number of each repeating unit in the main chain of the phenol resin. That is, in the phenol resin (A), for example, the repeating unit in parentheses in the structure represented by the general formula (14) and the repeating unit in parentheses in the structure represented by the general formula (15) are random. , Blocks or combinations thereof. m ₅ and m ₆ are independently integers of 1 to 500, the lower limit is preferably 2, more preferably 3, and the upper limit is preferably 450, more preferably 400, and even more preferably 350. be. Each of m ₅ and m ₆ is preferably 2 or more independently from the viewpoint of toughness of the film after curing, and is preferably 450 or less from the viewpoint of solubility in an alkaline aqueous solution. The total of m ₅ and m ₆ is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more from the viewpoint of the toughness of the film after curing, and from the viewpoint of solubility in an alkaline aqueous solution, from the viewpoint of solubility in an alkaline aqueous solution. It is preferably 200 or less, more preferably 175 or less, and even more preferably 150 or less.

In the phenol resin (A) having both the structure represented by the general formula (14) and the structure represented by the general formula (15) in the same resin skeleton, the structure represented by the general formula (14). The higher the molar ratio of the above, the better the physical properties of the film after curing and the better the heat resistance. On the other hand, the higher the molar ratio of the structure represented by the general formula (15), the better the alkali solubility. Excellent pattern shape after curing. _{Therefore, the ratio m 5} / m ₆ of the structure represented by the general formula (14) to the structure represented by the general formula (15) is preferably 20/80 or more from the viewpoint of the physical characteristics of the film after curing. It is more preferably 40/60 or more, particularly preferably 50/50 or more, and from the viewpoint of alkali solubility and cured relief pattern shape, it is preferably 90/10 or less, more preferably 80/20 or less, still more preferably 70/50. It is 30 or less.

A phenol resin having a repeating unit represented by the general formula (7) is typically a phenol compound and a copolymerization component (specifically, a compound having an aldehyde group (decomposed like a trioxane) and an aldehyde compound. A compound having a ketone group, a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, and a compound having two haloalkyl groups in the molecule. It can be synthesized by subjecting a monomer component comprising (one or more kinds of compounds selected from the group) and, more typically, these, to a polymerization reaction. For example, aldehyde compounds, ketone compounds, methylol compounds, alkoxymethyl compounds, diene compounds, haloalkyl compounds, etc., with respect to phenols and / or phenol derivatives (hereinafter collectively referred to as "phenolic compounds") as shown below. The phenolic resin (A) can be obtained by polymerizing the copolymerization components of. In this case, in the general formula (7), a portion OH groups and optionally R ₁₂ groups is represented by the structure is bonded to an aromatic ring derived from the phenolic compounds, moieties represented by X above co It will be derived from the polymerized component. From the viewpoint of reaction control and the stability of the obtained (A) phenol resin and photosensitive resin composition, the charged molar ratio of the phenol compound and the above-mentioned copolymer component (phenol compound): (copolymer component) is 5. : 1 to 1.01: 1, more preferably 2.5: 1 to 1.1: 1.

The weight average molecular weight of the phenol resin having the repeating unit represented by the general formula (7) is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000. ~ 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of reflow treatment applicability of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

Examples of the phenolic compound that can be used to obtain a phenolic resin having a repeating unit represented by the general formula (7) include cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, and benzylphenol. Nitrobenzylphenol, cyanobenzylphenol, adamantanphenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N- (hydroxyphenyl) -5-norbornene-2,3-dicarboxyimide, N-( Hydroxyphenyl) -5-methyl-5-norbornene-2,3-dicarboxyimide, trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, Hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, resorcinol, xylenol, catechol, methylcatechol, ethylcatechol, hexylcatechol, benzylcatechol, nitrobenzylcatechol, methylresorcinol, ethylresorcinol, hexylresorcinol, benzylresorcinol, nitrobenzylresorcinol, hydroquinone, Caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, dihydroxybenzonitrile, N -(Dihydroxyphenyl) -5-norbornene-2,3-dicarboxyimide, N- (dihydroxyphenyl) -5-methyl-5-norbornen-2,3-dicarboxyimide, nitrocatechol, fluorocatechol, chlorocatechol, Bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, fluoroglucolcinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, trihydroxybenzoic acid Methyl, trihydroxy cheap Examples thereof include ethyl benzoate, butyl trihydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, and trihydroxybenzonitrile.

Examples of the aldehyde compound include acetaldehyde, propionaldehyde, pivalaldehyde, butylaldehyde, pentanal, hexanal, trioxane, glioxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutylaldehyde, benzaldehyde, glyoxylic acid, and 5-norbornene-2-carboxy. Examples thereof include aldehyde, malondialdehyde, succindialdehyde, glutaaldehyde, salicylaldehyde, naphthoaldehyde, terephthalaldehyde and the like.

Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzylketone, cyclopentanone, cyclohexanone, bicyclohexanone, cyclohexanedione, 3-butin-2-one, 2-norbornanone, and the like. Examples thereof include adamantanone and 2,2-bis (4-oxocyclohexanone) propane.

Examples of the methylol compound include 2,6-bis (hydroxymethyl) -p-cresol, 2,6-bis (hydroxymethyl) -4-ethylphenol, and 2,6-bis (hydroxymethyl) -4-propyl. Phenol, 2,6-bis (hydroxymethyl) -4-n-butylphenol, 2,6-bis (hydroxymethyl) -4-t-butylphenol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, 2, , 6-bis (hydroxymethyl) -4-ethoxyphenol, 2,6-bis (hydroxymethyl) -4-propoxyphenol, 2,6-bis (hydroxymethyl) -4-n-butoxyphenol, 2,6- Bis (hydroxymethyl) -4-t-butoxyphenol, 1,3-bis (hydroxymethyl) urea, libitol, arabitol, alitol, 2,2-bis (hydroxymethyl) butyric acid, 2-benzyloxy-1,3- Propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, monoacetin, 2-methyl-2-nitro-1,3-propanediol, 5-norbornen- 2,2-dimethanol, 5-norbornen-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis (hydroxymethyl) durene , 2-Nitro-p-xylylene glycol, 1,10-dihydroxydecane, 1,12-dihydroxydodecane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexene, 1,6 -Bis (hydroxymethyl) adamantan, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 2,6-bis (hydroxymethyl) -1,4-dimethoxybenzene, 2,3-bis (hydroxymethyl) Naphthalene, 2,6-bis (hydroxymethyl) naphthalene, 1,8-bis (hydroxymethyl) anthracene, 2,2'-bis (hydroxymethyl) diphenyl ether, 4,4'-bis (hydroxymethyl) diphenyl ether, 4, 4'-bis (hydroxymethyl) diphenylthioether, 4,4'-bis (hydroxymethyl) benzophenone, 4-hydroxymethylbenzoic acid-4'-hydroxymethylphenyl, 4-hydroxymethylbenzoic acid-4'-hydroxymethylanilide , 4,4'-bis (hydroxymethyl) phenylurea, 4,4'-bis (hydroxymethyl) phenylurethane, 1,8-bis (hydroxymethyl) anthracene, 4,4'-bis (hydroxymethyl) biphenyl, 2,2'-dimethyl-4,4'-bis (hydroxymethyl) biphenyl, 2,2-bis (4-hydroxymethylphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, di Examples thereof include propylene glycol, tripropylene glycol and tetrapropylene glycol.

Examples of the alkoxymethyl compound include 2,6-bis (methoxymethyl) -p-cresol, 2,6-bis (methoxymethyl) -4-ethylphenol, and 2,6-bis (methoxymethyl) -4-. Propylphenol, 2,6-bis (methoxymethyl) -4-n-butylphenol, 2,6-bis (methoxymethyl) -4-t-butylphenol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 2,6-bis (methoxymethyl) -4-ethoxyphenol, 2,6-bis (methoxymethyl) -4-propoxyphenol, 2,6-bis (methoxymethyl) -4-n-butoxyphenol, 2,6 -Bis (methoxymethyl) -4-t-butoxyphenol, 1,3-bis (methoxymethyl) urea, 2,2-bis (methoxymethyl) butyric acid, 2,2-bis (methoxymethyl) -5-norbornen, 2,3-bis (methoxymethyl) -5-norbornen, 1,4-bis (methoxymethyl) cyclohexane, 1,4-bis (methoxymethyl) cyclohexene, 1,6-bis (methoxymethyl) adamantan, 1,4 -Bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 2,6-bis (methoxymethyl) -1,4-dimethoxybenzene, 2,3-bis (methoxymethyl) naphthalene, 2,6 -Bis (methoxymethyl) naphthalene, 1,8-bis (methoxymethyl) anthracene, 2,2'-bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) diphenyl ether, 4,4'-bis ( Methoxymethyl) diphenylthioether, 4,4'-bis (methoxymethyl) benzophenone, 4-methoxymethylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'-methoxymethylanilide, 4,4' -Bis (methoxymethyl) phenylurea, 4,4'-bis (methoxymethyl) phenylurethane, 1,8-bis (methoxymethyl) anthracene, 4,4'-bis (methoxymethyl) biphenyl, 2,2'- Dimethyl-4,4'-bis (methoxymethyl) biphenyl, 2,2-bis (4-methoxymethylphenyl) propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethylate , Dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether and the like.

Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol-dimethacrate, 2,4-hexadiene-1-ol, and methyl. Cyclohexadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentadiene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2 , 5-Norbornadiene, Tetrahydroindene, 5-Etilidene-2-Norbornene, 5-Vinyl-2-Norbornene, Triallyl cyanurate, Dialyl isocyanurate, Triallyl isocyanurate, Dialylpropyl isocyanurate and the like.

Examples of the haloalkyl compound include xylene chloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, and the like. Examples thereof include bischloromethyl-dimethylbiphenyl, bischloromethylanthracene, ethylene glycol bis (chloroethyl) ether, diethylene glycol bis (chloroethyl) ether, triethylene glycol bis (chloroethyl) ether, and tetraethylene glycol bis (chloroethyl) ether.

The (A) phenol resin can be obtained by condensing the above-mentioned phenol compound and the copolymerization component by dehydration, dehalogenated hydrogen, or dealcoholization, or by polymerizing while cleaving the unsaturated bond. , A catalyst may be used at the time of polymerization. Examples of acidic catalysts include hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, phosphite, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfate, diethylsulfate, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1. ′ -Diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex and the like can be mentioned. On the other hand, examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, and the like. Piperazin, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonen, Examples thereof include ammonia and hexamethylenetetramine.

The amount of the catalyst used to obtain the phenol resin having the repeating structure represented by the general formula (7) is the total number of moles of the copolymerization component (that is, the component other than the phenol compound), preferably the aldehyde compound and the ketone. The total number of moles of the compound, methylol compound, alkoxymethyl compound, diene compound and haloalkyl compound is preferably in the range of 0.01 mol% to 100 mol% with respect to 100 mol%.

In the reaction for synthesizing the phenol resin (A), the reaction temperature is usually preferably 40 ° C. to 250 ° C., more preferably 100 ° C. to 200 ° C., and the reaction time is approximately 1 hour to 10 ° C. It is preferably time. If necessary, a solvent capable of sufficiently dissolving the resin can be used.

The phenol resin having a repeating structure represented by the general formula (7) is obtained by further polymerizing a phenol compound that does not serve as a raw material for the structure of the general formula (7) within a range that does not impair the effects of the present invention. It may be. The range in which the effect of the present invention is not impaired is, for example, 30% or less of the total number of moles of the phenol compound which is the raw material of the phenol resin (A).

(A phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms)
A phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms is a compound having a phenol or a derivative thereof and an unsaturated hydrocarbon group having 4 to 100 carbon atoms (hereinafter, in some cases, simply "unsaturated carbon dioxide". A reaction product with a hydrogen group-containing compound (referred to as "hydrogen group-containing compound") (hereinafter, also referred to as an "unsaturated hydrocarbon group-modified phenol derivative") and a condensed polymerization product of aldehydes, or a phenol resin and an unsaturated hydrocarbon group. It is a reaction product with the contained compound.

As the phenol derivative, the same one as described above can be used as the raw material of the phenol resin having the repeating unit represented by the general formula (7).

The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated groups from the viewpoint of residual stress of the cured film and applicability to reflow treatment. Further, from the viewpoint of compatibility with the resin composition and residual stress of the cured film, the unsaturated hydrocarbon group preferably has 4 to 100 carbon atoms, more preferably 8 to 80 carbon atoms, and even more preferably carbon number. It is 10 to 60.

Examples of the unsaturated hydrocarbon group-containing compound include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybudaziene, linolyl alcohol, oleyl alcohol, unsaturated fatty acids and unsaturated fatty acid esters. Can be mentioned. Suitable unsaturated fatty acids include crotonic acid, myristolenic acid, palmitoleic acid, oleic acid, ellaic acid, vaccenic acid, gadrain acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, eleostearic acid, stearidone. Acids, arachidonic acid, eicosapentaenoic acid, vaccinic acid and docosahexaenoic acid can be mentioned. Among these, vegetable oil, which is an unsaturated fatty acid ester, is particularly preferable from the viewpoint of the elongation of the cured film and the flexibility of the cured film.

Vegetable oils are usually non-drying oils containing esters of glycerin and unsaturated fatty acids and having an iodine value of 100 or less, semi-drying oils of more than 100 and less than 130, or dry oils of 130 or more. Examples of the non-drying oil include olive oil, asaga seed oil, kashu seed oil, sazanka oil, camellia oil, castor oil and peanut oil. Examples of the semi-drying oil include corn oil, cottonseed oil and sesame oil. Examples of the dry oil include tung oil, flaxseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, perilla oil and mustard oil. Moreover, you may use the processed vegetable oil obtained by processing these vegetable oils.

Among the above vegetable oils, it is preferable to use a non-drying oil from the viewpoint of preventing gelation due to excessive progress of the reaction and improving the yield in the reaction of phenol or its derivative or phenol resin with the vegetable oil. On the other hand, it is preferable to use a drying oil from the viewpoint of improving the adhesion of the resist pattern, the mechanical properties and the heat impact resistance. Among the dry oils, tung oil, linseed oil, soybean oil, peach oil and safflower oil are preferable, and tung oil and linseed oil are more preferable, because the effects of the present invention can be more effectively and surely exhibited. These vegetable oils may be used alone or in combination of two or more.

The reaction of phenol or a derivative thereof with an unsaturated hydrocarbon group-containing compound is preferably carried out at 50 to 130 ° C. The reaction ratio of the phenol or its derivative to the unsaturated hydrocarbon group-containing compound is 1 to 100 parts by mass of the unsaturated hydrocarbon group-containing compound with respect to 100 parts by mass of the phenol or its derivative from the viewpoint of reducing the residual stress of the cured film. It is preferably parts, and more preferably 5 to 50 parts by mass. If the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid and the like may be used as a catalyst, if necessary.

By polycondensing the unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction with aldehydes, a phenol resin modified with an unsaturated hydrocarbon group-containing compound is produced. Aldehydes include, for example, formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, glyceraldehyde, glyoxylic acid, methyl glyoxylate, Phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methylformylacetate, 2-formylpropionic acid, methyl2-formylpropionate, pyruvate, repuric acid, 4-acetylbutylic acid, acetonedicarboxylic acid and 3,3'- It is selected from 4,4'-benzophenone tetracarboxylic acid. Further, a formaldehyde precursor such as paraformaldehyde or trioxane may be used. These aldehydes may be used alone or in combination of two or more.

The reaction between the aldehydes and the unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and conventionally known phenol resin synthesis conditions can be used. The reaction is preferably carried out in the presence of a catalyst such as an acid or a base, and more preferably an acid catalyst is used from the viewpoint of the degree of polymerization (molecular weight) of the resin. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid and oxalic acid. These acid catalysts may be used alone or in combination of two or more.

The above reaction is usually preferably carried out at a reaction temperature of 100 to 120 ° C. The reaction time varies depending on the type and amount of the catalyst used, but is usually 1 to 50 hours. After completion of the reaction, the reaction product is dehydrated under reduced pressure at a temperature of 200 ° C. or lower to obtain a phenol resin modified with an unsaturated hydrocarbon group-containing compound. A solvent such as toluene, xylene, and methanol can be used for the reaction.

The phenol resin modified with the unsaturated hydrocarbon group-containing compound can also be obtained by polycondensing the above-mentioned unsaturated hydrocarbon group-modified phenol derivative with aldehydes together with a compound other than phenol such as m-xylene. .. In this case, the charged molar ratio of the compound other than phenol to the compound obtained by reacting the phenol derivative with the unsaturated hydrocarbon group-containing compound is preferably less than 0.5.

The phenol resin modified with the unsaturated hydrocarbon group-containing compound can also be obtained by reacting the phenol resin with the unsaturated hydrocarbon group-containing compound. The phenol resin used in this case is a polycondensation product of a phenol compound (that is, phenol and / or a phenol derivative) and aldehydes. In this case, as the phenol derivative and the aldehydes, the same ones as those of the above-mentioned phenol derivative and the aldehyde can be used, and the phenol resin can be synthesized under the conventionally known conditions as described above.

Specific examples of the phenol resin obtained from the phenol compound and aldehydes, which are suitable for forming a phenol resin modified with an unsaturated hydrocarbon group-containing compound, include phenol / formaldehyde novolak resin and cresol / formaldehyde. Examples thereof include novolak resin, xylylenel / formaldehyde novolak resin, resorcinol / formaldehyde novolak resin and phenol-naphthol / formaldehyde novolak resin.

As the unsaturated hydrocarbon group-containing compound to be reacted with the phenol resin, the same unsaturated hydrocarbon group-containing compound as described above with respect to the production of the unsaturated hydrocarbon group-modified phenol derivative to be reacted with aldehydes can be used.

The reaction between the phenol resin and the unsaturated hydrocarbon group-containing compound is usually preferably carried out at 50 to 130 ° C. Further, the reaction ratio between the phenol resin and the unsaturated hydrocarbon group-containing compound is such that the unsaturated hydrocarbon group-containing compound 1 is based on 100 parts by mass of the phenol resin from the viewpoint of improving the flexibility of the cured film (resist pattern). It is preferably ~ 100 parts by mass, more preferably 2 to 70 parts by mass, and even more preferably 5 to 50 parts by mass. If the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase and the curing tends to occur. The heat resistance of the film tends to decrease. When the phenol resin and the unsaturated hydrocarbon group-containing compound are reacted, p-toluenesulfonic acid, trifluoromethanesulfonic acid and the like may be used as a catalyst, if necessary. As described in detail later, a solvent such as toluene, xylene, methanol, and tetrahydrofuran can be used for the reaction.

It is also possible to use an acid-modified phenol resin by further reacting a polybasic acid anhydride with the phenolic hydroxyl groups remaining in the phenol resin modified by the unsaturated hydrocarbon group-containing compound produced by the above method. can. By acid denaturing with polybasic acid anhydride, a carboxy group is introduced, and the solubility in an alkaline aqueous solution (used as a developing solution) is further improved.

The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of carboxy groups of a polybasic acid having a plurality of carboxy groups. Examples of polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. , Methylhexahydrohydride phthalic acid, Nasicic anhydride, 3,6-endomethylenetetrahydrohydride phthalic acid, methylendomethylenetetrahydrohydride phthalic acid, tetrabromohydride phthalic acid and dibasic acid anhydrides such as trimellitic anhydride, biphenyltetra Carboxic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, pyromellitic anhydride and benzophenone tetracarboxylic acid dianhydride Examples thereof include aromatic tetrabasic acid dianhydrides. These may be used individually by 1 type or in combination of 2 or more type. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern having a better shape can be formed.

The reaction between the phenolic hydroxyl group and the polybasic acid anhydride can be carried out at 50 to 130 ° C. In this reaction, it is preferable to react 0.10 to 0.80 mol of polybasic acid anhydride with 1 mol of the phenolic hydroxyl group, more preferably 0.15 to 0.60 mol, and 0. More preferably, the reaction is carried out in an amount of 20 to 0.40 mol. If the amount of polybasic acid anhydride is less than 0.10 mol, the developability tends to decrease, and if it exceeds 0.80 mol, the alkali resistance of the unexposed portion tends to decrease.

The above reaction may contain a catalyst, if necessary, from the viewpoint of rapidly carrying out the reaction. Examples of the catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine.

The acid value of the phenol resin further modified with polybasic anhydride is preferably 30 to 200 mgKOH / g, more preferably 40 to 170 mgKOH / g, and even more preferably 50 to 150 mgKOH / g. .. When the acid value is less than 30 mgKOH / g, it tends to take a longer time for alkaline development as compared with the case where the acid value is in the above range, and when it exceeds 200 mgKOH / g, the acid value is in the above range. Compared with this, the developer resistance of the unexposed portion tends to decrease.

The molecular weight of the phenol resin modified with the unsaturated hydrocarbon group-containing compound is preferably 1000 to 100,000, preferably 2000 to 100,000, in consideration of the solubility in an alkaline aqueous solution and the balance between the photosensitive characteristics and the physical characteristics of the cured film. Is more preferable.

The phenol resin (A) of the present embodiment includes a phenol resin having a repeating unit represented by the general formula (7) and a phenol modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms. A mixture of at least one phenol resin selected from the resins (hereinafter, also referred to as (a3) resin) and a phenol resin selected from novolak and polyhydroxystyrene (hereinafter, also referred to as (a4) resin) is also preferable. The mixing ratio of the resin (a3) and the resin (a4) is in the range of (a3) / (a4) = 5/95 to 95/5 in terms of mass ratio. This mixing ratio is (a3) / (a4) = 5 / from the viewpoints of solubility in an alkaline aqueous solution, sensitivity and resolution when forming a resist pattern, residual stress of the cured film, and reflow treatment applicability. It is preferably 95 to 95/5, more preferably (a3) / (a4) = 10/90 to 90/10, and further preferably (a3) / (a4) = 15/85 to 85/15. preferable. As the novolak and polyhydroxystyrene as the resin (a4), the same resins as those shown in the above (novolak) and (polyhydroxystyrene) sections can be used.

(B) Cyclic compound having a carbonyl group The compound (B) is a cyclic compound having two or more carbonyl groups, and the carbonyl group is directly bonded to the cyclic structure. In the case of a monocyclic compound, the ring structure is formed. At least one-third or more of the forming atoms are N atoms, and in the case of a fused ring compound, at least one selected from the group consisting of compounds in which one-third or more of the atoms forming the ring structure having the carbonyl group are N atoms. It is a kind of compound.
Classified from the structure of the ring, a 5-membered ring compound, a 6-membered ring compound, a 5-membered ring and a 5-membered ring fused ring compound, a 5-membered ring and a 6-membered ring fused ring compound, and a 6-membered ring and a 6-membered ring fused. From the viewpoint of migration resistance, it is preferable that the compound is at least one selected from the group consisting of compounds which are ring compounds.
By having two or more carbonyl groups, the area of voids on the copper surface can be reduced. Further, from the viewpoints of developability, sensitivity, in-plane uniformity after curing, elongation after reflow, and the like, it is preferable to have two or more carbonyl groups. When there are two or more carbonyl groups, the area of voids on the copper surface is significantly smaller than when there is one carbonyl group. Further, it is preferable that the number of carbonyl groups is two or more from the viewpoints of developability, sensitivity, in-plane uniformity after curing, elongation after reflow, and the like, as compared with the case where one carbonyl group is used.

Specific examples of the compound (B), as a 5-membered ring compound, arsenate Dantoin, allantoin, a parabanic acid, as 6-membered ring compounds, Ba Rubitsuru acid, 1,3-dimethyl barbituric acid, 1,3-dicyclohexyl Barbitulic acid, uramil, aloxanthine, cyanulic acid, tris isocyanurate (2-hydroxyethyl), etc. as a fused ring compound of 5-membered ring and 5-membered ring, glycoluril, etc., condensation of 6-membered ring and 5-membered ring as ring compounds, key trichosanthin, 1-methylxanthine, 3-methylxanthine, 8-bromo-3-methylxanthine, theobromine, theophylline, 7- (2-chloroethyl) theophylline, caffeine, uric acid, 8-azaxanthine, etc. as fused cyclic compounds of the 6-membered ring and 6-membered ring, lumazine, 7,8-dimethyl alloxazine, 1,4-dihydro-6-methyl-2,3-dione, and mixtures thereof be able to. Among these, it is preferable to use a fused ring compound.

｛式中、Ｒｓ３、Ｒｓ４及びＲｓ５はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、芳香族基で置換されていてもよいアミノ基、炭素数１〜６のアルコキシ基、ヒドロキシアルキル基又は炭素数１〜１０のアルキル基若しくは芳香族基である。｝
で表される化合物、下記一般式（６１）：

｛式中、Ｒｓ６、Ｒｓ７及びＲｓ８はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、芳香族基で置換されていてもよいアミノ基、炭素数１〜６のアルコキシ基、ヒドロキシアルキル基又は炭素数１〜１０のアルキル基若しくは芳香族基である。｝
で表される化合物、下記一般式（６２）：

｛式中、Ｒｓ９、Ｒｓ１０、Ｒｓ１１及びＲｓ１２はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、芳香族基で置換されていてもよいアミノ基、炭素数１〜６のアルコキシ基、ヒドロキシアルキル基又は炭素数１〜１０のアルキル基若しくは芳香族基である。｝
で表される化合物、下記一般式（６３）：

｛式中、Ｒ₂₁、Ｒ₂₂、Ｒ₂₃及びＲ₂₄はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、芳香族基で置換されていてもよいアミノ基、炭素数１〜６のアルコキシ基、ヒドロキシアルキル基又は炭素数１〜１０のアルキル基若しくは芳香族基である。｝
で表される化合物から成る群より選ばれる少なくとも１種の化合物であることが、耐マイグレーション性の観点から好ましい。 Further, the compound (B) has the following general formula (60):

{In the formula, Rs3, Rs4 and Rs5 are independently substituted with a hydrogen atom, a halogen atom, a hydroxyl group or an aromatic group, an amino group having 1 to 6 carbon atoms, a hydroxyalkyl group or a carbon number of carbon atoms. It is an alkyl group or an aromatic group of 1 to 10. }
Compound represented by, the following general formula (61):

{In the formula, Rs6, Rs7 and Rs8 are independently substituted with a hydrogen atom, a halogen atom, a hydroxyl group or an aromatic group, an amino group having 1 to 6 carbon atoms, a hydroxyalkyl group or a carbon number of carbon atoms. It is an alkyl group or an aromatic group of 1 to 10. }
Compound represented by, the following general formula (62):

{In the formula, Rs9, Rs10, Rs11 and Rs12 are independently substituted with a hydrogen atom, a halogen atom, a hydroxyl group or an aromatic group, an amino group having 1 to 6 carbon atoms, a hydroxyalkyl group or a hydroxyalkyl group. It is an alkyl group or an aromatic group having 1 to 10 carbon atoms. }
Compound represented by, the following general formula (63):

{In the formula, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are independently substituted with a hydrogen atom, a halogen atom, a hydroxyl group and an aromatic group, an amino group and an alkoxy group having 1 to 6 carbon atoms, respectively. It is a hydroxyalkyl group or an alkyl group or an aromatic group having 1 to 10 carbon atoms. }
From the viewpoint of migration resistance, it is preferable that the compound is at least one selected from the group consisting of the compounds represented by.

Specific examples of the compounds represented by the general formulas (70) to (73) include xanthine, 1-methylxanthine, 3-methylxanthine, theobromine, theophylline, caffeine, uric acid, 8-azaxanthine, and lumazine. Etc. and derivatives thereof.

The blending amount of the compound (B) is 0.01 to 10 parts by mass, preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the resin (A). From the viewpoint of migration resistance, 0.01 parts by mass or more is desirable, and from the viewpoint of solubility, less than 10 parts by mass is desirable.
It is considered that these (B) components change the surface state of copper by coordinating the carbonyl group and nitrogen atoms contained in the ring structure with copper, and suppress the migration of copper during the high temperature storage test. Be done. In particular, in the case of a fused ring, it is considered that the migration resistance is enhanced by the concerted action of a plurality of carbonyl groups and nitrogen atoms.

(C) Photosensitizer The (C) photosensitizer used in the present invention will be described. The photosensitive agent (C) is a negative type in which the photosensitive resin composition of the present invention mainly uses, for example, a polyimide precursor and / or polyamide as the resin (A), or, for example, mainly polyoxazole as the resin (A). It depends on whether it is a positive type using at least one of a precursor, a soluble polyimide and a phenol resin, and the like.

The blending amount of the (C) photosensitive agent in the photosensitive resin composition is 1 to 50 parts by mass with respect to 100 parts by mass of the (A) resin. The blending amount is 1 part by mass or more from the viewpoint of light sensitivity or patterning property, and 50 parts by mass or less from the viewpoint of the curability of the photosensitive resin composition or the physical properties of the photosensitive resin layer after curing.

[(C) Negative emulsion: photopolymerization initiator and / or photoacid generator]
First, a case where a negative type is desired will be described. In this case, (C) a photopolymerization initiator and / or a photoacid generator is used as the photosensitizer, and a photoradical polymerization initiator is preferably used as the photopolymerization initiator, and benzophenone and methyl o-benzoylbenzoate are used. , 4-Benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, benzophenone derivatives such as fluorenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone and the like. Acetophenone derivatives, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl derivatives such as benzyl, benzyldimethylketal, benzyl-β-methoxyethylacetal,

Benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butandion-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-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- Oximes such as 2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanthrion-2- (o-benzoyl) oxime, N-arylglycines such as N-phenylglycine, benzoyl perchloride and the like. Preference is given to photoacid generators such as peroxides, aromatic biimidazoles, titanocenes, α- (n-octanesulfonyloxyimino) -4-methoxybenzylocyanide, but the like. It's not a thing. Among the above-mentioned photopolymerization initiators, oximes are more preferable in terms of photosensitivity.

When a photoacid generator is used as the (C) photosensitizer in the negative-type photosensitive resin composition, it becomes acidic when irradiated with active light such as ultraviolet rays, and the cross-linking agent described later is added to the component (A) by the action. It has the effect of cross-linking with the resin, or polymerizing the cross-linking agents with each other. Examples of this photoacid generator include diarylsulfonium salt, triarylsulfonium salt, dialkylphenacylsulfonium salt, diaryliodonium salt, aryldiazonium salt, aromatic tetracarboxylic acid ester, aromatic sulfonic acid ester, nitrobenzyl ester, Oxym sulfonic acid esters, aromatic N-oxyimide sulphonates, aromatic sulfamides, haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, naphthoquinone diazide-4-sulfonic acid esters and the like are used. Such compounds can be used in combination of two or more kinds, if necessary, or in combination with other sensitizers. Among the above photoacid generators, aromatic oxime sulfonic acid ester and aromatic N-oxyimide sulfonate are more preferable in terms of photosensitivity.

The blending amount of these photosensitizers is 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A), and 2 to 15 parts by mass is preferable from the viewpoint of light sensitivity characteristics. When the (C) photosensitizer is blended in an amount of 1 part by mass or more with respect to 100 parts by mass of the resin (A), the photosensitivity is excellent, and when the photosensitizer is blended in an amount of 50 parts by mass or less, the thick film curability is excellent.

Further, as described above, when the resin (A) represented by the general formula (1) is an ionic bond type, an amino is used to impart a photopolymerizable group to the side chain of the resin (A) via an ionic bond. A (meth) acrylic compound having a group is used. In this case, a (meth) acrylic compound having an amino group is used as the (C) photosensitizer, and as described above, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylamino. Dialkylaminoalkyl acrylates or methacrylates such as propyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, diethylaminobutyl methacrylate, etc. are preferable, and among them, from the viewpoint of photosensitive characteristics. Therefore, dialkylaminoalkyl acrylates or methacrylates in which the alkyl group on the amino group has 1 to 10 carbon atoms and the alkyl chain has 1 to 10 carbon atoms are preferable.

The blending amount of these (meth) acrylic compounds having an amino group is 1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), preferably 2 to 15 parts by mass from the viewpoint of light sensitivity characteristics. (C) As a photosensitizer, a (meth) acrylic compound having an amino group is blended in an amount of 1 part by mass or more with respect to 100 parts by mass of the resin (A) to have excellent photosensitivity. Excellent in sex.

Next, a case where a positive type is desired will be described. In this case, (C) a photoacid generator is used as the photosensitizer, and specifically, a diazoquinone compound, an onium salt, a halogen-containing compound, or the like can be used, but from the viewpoint of solvent solubility and storage stability. , A compound having a diazoquinone structure is preferable.

[(C) Positive photosensitizer: compound having a quinonediazide group]
Examples of the compound having a quinone diazide group (hereinafter, also referred to as “(C) quinone diazide compound”) include a compound having a 1,2-benzoquinone diazide structure and a compound having a 1,2-naphthoquinone diazido structure. It is a substance known from US Pat. No. 2,772,972, US Pat. No. 2,797,213, US Pat. No. 3,669,658, and the like. The (C) quinone diazide compound is a 1,2-naphthoquinone diazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and a 1,2-naphthoquinone diazido-5-sulfone of the polyhydroxy compound. It is preferably at least one compound selected from the group consisting of acid esters (hereinafter, also referred to as “NQD compound”).

The NQD compound is obtained by converting a naphthoquinonediazide sulfonic acid compound into a sulfonyl chloride with chlorsulfonic acid or thionyl chloride according to a conventional method, and subjecting the obtained naphthoquinone diazidosulfonyl chloride to a condensation reaction with a polyhydroxy compound. For example, a predetermined amount of the polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone, or tetrahydrofuran is basic such as triethylamine. It can be obtained by reacting in the presence of a catalyst to carry out esterification, and washing and drying the obtained product with water.

｛式中、Ｘ₁₁及びＸ₁₂は、各々独立に、水素原子又は炭素数１〜６０（好ましくは、炭素数１〜３０）の１価の有機基を表し、Ｘ₁₃及びＸ₁₄は、各々独立に、水素原子又は炭素数１〜６０（好ましくは、炭素数１〜３０）の１価の有機基を表し、ｒ１、ｒ２、ｒ３及びｒ４は、各々独立に、０〜５の整数であり、ｒ３及びｒ４の少なくとも１つは、１〜５の整数であり、（ｒ１＋ｒ３）≦５であり、そして（ｒ２＋ｒ４）≦５である。｝で表される。
一般式（７１）は、

｛式中、Ｚは、炭素数１〜２０の４価の有機基を表し、Ｘ₁₅、Ｘ₁₆、Ｘ₁₇及びＸ₁₈は、各々独立に、炭素数１〜３０の１価の有機基を表し、ｒ６は、０又は１の整数であり、ｒ５、ｒ７、ｒ８及びｒ９は、各々独立に、０〜３の整数であり、ｒ１０、ｒ１１、ｒ１２及びｒ１３は、各々独立に、０〜２の整数であり、そしてｒ１０、ｒ１１、ｒ１２及びｒ１３の全てが０になることはない。｝で表される。
並びに、一般式（７２）は、

｛式中、ｒ１４は、１〜５の整数を表し、ｒ１５は、３〜８の整数を表し、（ｒ１４×ｒ１５）個のＬは、各々独立に、炭素数１〜２０の１価の有機基を表し、（ｒ１５）個のＴ¹及び（ｒ１５）個のＴ²は、各々独立に、水素原子又は炭素数１〜２０の１価の有機基を表す。｝で表される。
並びに、一般式（７３）は、

｛式中、Ａは、脂肪族の３級又は４級炭素を含む２価の有機基を表し、そしてＭは、２価の有機基を表し、好ましくは下記化学式：

で表される３つの基から選択される２価の基を表す。｝で表される。
さらに、一般式（７４）は、

｛式中、ｒ１７、ｒ１８、ｒ１９及びｒ２０は、各々独立に、０〜２の整数であり、ｒ１７、ｒ１８、ｒ１９及びｒ２０の少なくとも１つは、１又は２であり、Ｘ₂₀〜Ｘ₂₉は、各々独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アリル基及びアシル基からなる群から選択される１価の基を表し、そしてＹ₁₀、Ｙ₁₁及びＹ₁₂は、各々独立に、単結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯ₂−、シクロペンチリデン、シクロヘキシリデン、フェニレン、及び炭素数１〜２０の２価の有機基からなる群から選択される２価の基を表す。｝で表される。 In the present embodiment, the compound having a quinonediazide group (C) is a 1,2-naphthoquinonediazide-4-sulfonic acid ester and / or 1, of the hydroxy compounds represented by the following general formulas (70) to (74). A 2-naphthoquinone diazide-5-sulfonic acid ester is preferable from the viewpoint of sensitivity and resolution when forming a resist pattern.
The general formula (70) is

{In the formula, X ₁₁ and X ₁₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably 1 to 30 carbon atoms), and X ₁₃ and X ₁₄ respectively. Independently, it represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably 1 to 30 carbon atoms), and r1, r2, r3 and r4 are each independently an integer of 0 to 5. , R3 and r4 are integers 1 to 5, (r1 + r3) ≤ 5, and (r2 + r4) ≤ 5. } Is represented by.
The general formula (71) is

{In the formula, Z represents a tetravalent organic group having 1 to 20 carbon atoms, and X ₁₅ , X ₁₆ , X ₁₇ and X ₁₈ independently represent a monovalent organic group having 1 to 30 carbon atoms. Represented, r6 is an integer of 0 or 1, r5, r7, r8 and r9 are each independently an integer of 0 to 3, and r10, r11, r12 and r13 are each independently of 0 to 2. Is an integer of, and not all of r10, r11, r12 and r13 are zero. } Is represented by.
In addition, the general formula (72) is

{In the formula, r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, and (r14 × r15) Ls are independently monovalent organics having 1 to 20 carbon atoms. Representing a group, (r15) T ¹ and (r15) T ² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. } Is represented by.
In addition, the general formula (73) is

{In the formula, A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group, preferably the following chemical formula:

Represents a divalent group selected from the three groups represented by. } Is represented by.
Further, the general formula (74) is

{In the formula, r17, r18, r19 and r20 are independently integers of 0 to 2, and at least one of r17, r18, r19 and r20 is 1 or 2, and X _{20 to} X ₂₉ are. , Each independently represents a monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group and an acyl group, and Y ₁₀ , Y ₁₁ and Y ₁₂ are Independently, single-bonded, -O-, -S-, -SO-, -SO _2- , -CO-, _{-CO 2-} , cyclopentylidene, cyclohexylidene, phenylene, and 1 to 20 carbon atoms. Represents a divalent group selected from the group consisting of divalent organic groups. } Is represented by.

｛式中、Ｘ₃₀及びＸ₃₁は、各々独立に、水素原子、アルキル基、アルケニル基、アリール基、及び置換アリール基から成る群から選択される少なくとも１つの１価の基を表し、Ｘ₃₂、Ｘ₃₃、Ｘ₃₄及びＸ₃₅は、各々独立に、水素原子又はアルキル基を表し、ｒ２１は、１〜５の整数であり、そしてＸ₃₆、Ｘ₃₇、Ｘ₃₈及びＸ₃₉は、各々独立に、水素原子又はアルキル基を表す。｝
で表される３つの２価の有機基から選択されることが好ましい。 In a further embodiment, in the above general formula (74), Y _{10 to Y 12} are independently represented by the following general formula:

{In the formula, X ₃₀ and X ₃₁ each independently represent at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and a substituted aryl group, and X _32. , X ₃₃ , X ₃₄ and X ₃₅ each independently represent a hydrogen atom or an alkyl group, r21 is an integer from 1 to 5, and X ₃₆ , X ₃₇ , X ₃₈ and X ₃₉ are independent, respectively. Represents a hydrogen atom or an alkyl group. }
It is preferably selected from the three divalent organic groups represented by.

｛式中、ｒ１６は、各々独立に、０〜２の整数であり、そしてＸ₄₀は、各々独立に、水素原子又は炭素数１〜２０の１価の有機基を表し、Ｘ₄₀が複数で存在する場合には複数のＸ₄₀は、互いに同一でも又は異なっていてもよく、そしてＸ₄₀は、下記一般式： Examples of the compound represented by the general formula (70) include hydroxy compounds represented by the following formulas (75) to (79).
Here, the general formula (75) is

{In the formula, r16 is each independently an integer of 0 to 2, and X ₄₀ is each independently representing a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and X ₄₀ is plural. _{Multiple X 40s} , if present, may be the same or different from each other, and X _40s are the following general formula:

（式中、ｒ１８は、０〜２の整数であり、Ｘ₄₁は、水素原子、アルキル基、及びシクロアルキル基からなる群から選択される１価の有機基を表し、そしてｒ１８が２である場合には、２つのＸ₄₁は、互いに同一でも又は異なっていてもよい。）
で表される１価の有機基であることが好ましい。｝であり、
一般式（７６）は、

(In the formula, r18 is an integer from 0 to 2, X ₄₁ represents a monovalent organic group selected from the group consisting of hydrogen atoms, alkyl groups, and cycloalkyl groups, and r18 is 2. In some cases, the two X _41s may be the same or different from each other.)
It is preferably a monovalent organic group represented by. } And
The general formula (76) is

｛式中、Ｘ₄₂は、水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基及び炭素数１〜２０のシクロアルキル基からなる群から選択される１価の有機基を表す。｝で表される。
また、一般式（７７）は、

{In the formula, X ₄₂ is a monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and a cycloalkyl group having 1 to 20 carbon atoms. Represents. } Is represented by.
In addition, the general formula (77) is

｛式中、ｒ１９は、各々独立に、０〜２の整数であり、Ｘ₄₃は、各々独立に、水素原子又は下記一般式：

{In the formula, r19 is each independently an integer of 0 to 2, and X ₄₃ is each independently a hydrogen atom or the following general formula:

（式中、ｒ２０は、０〜２の整数であり、Ｘ₄₅は、水素原子、アルキル基及びシクロアルキル基からなる群から選択され、そしてｒ２０が２である場合には、２つのＸ₄₅は、互いに同一でも又は異なっていてもよい。）で表される１価の有機基を表し、そしてＸ₄₄は、水素原子、炭素数１〜２０のアルキル基、及び炭素数１〜２０のシクロアルキル基からなる群から選択される。｝であり、式（７８）及び（７９）は、下記のごとく構造である。

(In the equation, r20 is an integer from 0 to 2, X ₄₅ is selected from the group consisting of hydrogen atom, alkyl group and cycloalkyl group, and if r20 is 2, the two X ₄₅ are , Which may be the same or different from each other), and X ₄₄ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms. Selected from the group consisting of groups. }, And equations (78) and (79) have the following structure.

As the compound represented by the general formula (70), the hydroxy compounds represented by the following formulas (80) to (82) have high sensitivity when formed into an NQD compound, and are contained in the photosensitive resin composition. It is preferable because it has low precipitation property.

The structures of the formulas (80) to (82) are as follows.

で表されるヒドロキシ化合物が、ＮＱＤ化物としたときの感度が高く、かつ感光性樹脂組成物中での析出性が低いことから好ましい。 Examples of the compound represented by the general formula (76) include the following formula (83):

The hydroxy compound represented by (1) is preferable because it has high sensitivity when formed into an NQD compound and has low precipitation property in the photosensitive resin composition.

As the compound represented by the general formula (77), the hydroxy compounds represented by the following formulas (84) to (86) have high sensitivity when formed into an NQD compound, and are used in the photosensitive resin composition. It is preferable because it has low precipitation property.
The structures of equations (84) to (86) are as follows.

で表される構造を有する４価の基であることが好ましい。 In the above general formula (71), Z may be a tetravalent organic group having 1 to 20 carbon atoms and is not particularly limited, but from the viewpoint of sensitivity, the following formula:

It is preferably a tetravalent group having a structure represented by.

Among the compounds represented by the general formula (71), the hydroxy compounds represented by the following formulas (87) to (90) have high sensitivity when formed into an NQD compound, and in the photosensitive resin composition. Is preferable because of its low precipitation property.
The structures of equations (87) to (90) are as follows.

｛式中、ｒ４０は、各々独立に、０〜９の整数である。｝で表されるヒドロキシ化合物が、ＮＱＤ化物としたときの感度が高く、かつ感光性樹脂組成物中での析出性が低いことから好ましい。 Examples of the compound represented by the general formula (72) include the following formula (91):

{In the formula, r40 is an integer from 0 to 9 independently. } Is preferable because the hydroxy compound represented by} has high sensitivity when formed into an NQD compound and low precipitation property in the photosensitive resin composition.

As the compound represented by the general formula (73), the hydroxy compounds represented by the following formulas (92) and (93) have high sensitivity when formed into an NQD compound, and are used in the photosensitive resin composition. It is preferable because it has low precipitation property.
The structures of equations (92) and (93) are as follows.

で表されるポリヒドロキシ化合物のＮＱＤ化物が、感度が高く、かつ感光性樹脂組成物中での析出性が低いことから好ましい。 Specific examples of the compound represented by the general formula (74) include the following formula (94):

The NQD compound of the polyhydroxy compound represented by is preferable because it has high sensitivity and low precipitation property in the photosensitive resin composition.

(C) When the compound having a quinone diazide group has a 1,2-naphthoquinone diazidosulfonyl group, this group is either a 1,2-naphthoquinone diazide-5-sulfonyl group or a 1,2-naphthoquinone diazido-4-sulfonyl group. There may be. The 1,2-naphthoquinonediazide-4-sulfonyl group is suitable for i-ray exposure because it can absorb the i-line region of a mercury lamp. On the other hand, the 1,2-naphthoquinonediazide-5-sulfonyl group is suitable for g-line exposure because it can absorb even the g-line region of a mercury lamp.

In the present embodiment, it is preferable to select one or both of the 1,2-naphthoquinonediazide-4-sulfonic acid ester compound and the 1,2-naphthoquinonediazide-5-sulfonic acid ester compound depending on the wavelength to be exposed. Further, a 1,2-naphthoquinonediazide sulfonic acid ester compound having a 1,2-naphthoquinonediazide-4-sulfonyl group and a 1,2-naphthoquinonediazide-5-sulfonyl group in the same molecule can also be used. A 2-naphthoquinone diazide-4-sulfonic acid ester compound and a 1,2-naphthoquinone diazide-5-sulfonic acid ester compound can also be mixed and used.

(C) In the compound having a quinone diazide group, the average esterification rate of the naphthoquinone diazidosulfonyl ester of the hydroxy compound is preferably 10% to 100%, preferably 20% to 100%, from the viewpoint of development contrast. More preferred.

｛式中、Ｑは、水素原子、又は下記式群：

のいずれかで表されるナフトキノンジアジドスルホン酸エステル基であるが、全てのＱが同時に水素原子であることはない。｝で表されるものが挙げられる。 Examples of preferable NQD compounds from the viewpoint of the physical characteristics of the cured film such as sensitivity and elongation include those represented by the following general formula group.

{In the formula, Q is a hydrogen atom, or the following formula group:

Although it is a naphthoquinone diazide sulfonic acid ester group represented by any of the above, not all Qs are hydrogen atoms at the same time. } Can be mentioned.

In this case, as the NQD compound, a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group in the same molecule can also be used, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazide. It can also be used in combination with a sulfonyl ester compound.

で表されるものが特に好ましい。 Among the naphthoquinonediazide sulfonic acid ester groups described in paragraph [0196] above, the following general formula (95):

Those represented by are particularly preferable.

Examples of the onium salt include iodonium salt, sulfonium salt, hosiphonium salt, phosphonium salt, ammonium salt, diazonium salt and the like, and onium selected from the group consisting of diaryliodonium salt, triarylsulfonium salt and trialkylsulfonium salt. Salt is preferred.

Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferable.

The blending amount of these photoacid generators is 1 to 50 parts by mass, preferably 5 to 30 parts by mass, based on 100 parts by mass of the resin (A). (C) When the blending amount of the photoacid generator as a photosensitive agent is 1 part by mass or more, the patterning property by the photosensitive resin composition is good, and when it is 50 parts by mass or less, after curing of the photosensitive resin composition. The tensile elongation of the film is good, and the undeveloped residue (scum) in the exposed area is small.

The NQD compound may be used alone or in combination of two or more.

In the present embodiment, the amount of the compound having the (C) quinonediazide group in the photosensitive resin composition is 0.1 part by mass to 70 parts by mass, preferably 0.1 part by mass to 70 parts by mass with respect to 100 parts by mass of the (A) resin. It is 1 part by mass to 40 parts by mass, more preferably 3 parts by mass to 30 parts by mass, and further preferably 5 parts by mass to 30 parts by mass. When this compounding amount is 0.1 parts by mass or more, good sensitivity can be obtained, while when it is 70 parts by mass or less, the mechanical properties of the cured film are good.

The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (C). The preferred components thereof differ depending on whether the resin (A) is a negative type using, for example, a polyimide precursor and a polyamide, or a positive type using a polyoxazole precursor, a soluble polyimide, or the like.

The above-mentioned polyimide precursor resin composition and polyamide resin composition which are negative resin compositions in the present embodiment, and polyoxazole resin compositions, soluble polyimide resin compositions and phenols which are positive photosensitive resin compositions. The resin composition can contain a solvent for dissolving these resins.

Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols and the like, and examples thereof include N-methyl-2-. Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone, methylethylketone, methylisobutylketone, cyclopentanone, cyclohexanone, methylacetate, ethyl acetate, butylacetate, diethyl oxalate, Ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1 , 2-Dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylen and the like can be used. Among them, N-methyl-2-pyrrolidone, dimethylsulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene from the viewpoint of resin solubility, stability of resin composition, and adhesion to substrate. Glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

Among such solvents, those that completely dissolve the produced polymer are preferable, and for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, and tetramethylurea are preferable. , Gamma-butyrolactone and the like.

Suitable solvents for the phenolic resin include bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, and cyclopentanone. , Toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone and the like.

In the photosensitive resin composition of the present invention, the amount of the solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and further preferably 120 parts by mass with respect to 100 parts by mass of the resin (A). Is in the range of 125 to 500 parts by mass.

The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (C).
For example, when a cured film is formed on a substrate made of copper or a copper alloy using the photosensitive resin composition of the present invention, a nitrogen-containing heterocycle such as an azole compound and a purine derivative is used to suppress discoloration on copper. The ring compound can be arbitrarily blended.

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, hydroxyphenyl Triazole, 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, hydroxyphenyl Bentriazole, triltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl- Examples thereof include 1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like.

Particularly preferred include triltriazole, 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.

Specific examples of the purine derivative include purine, adenine, guanine, hypoxanthin, xanthin, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-Methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-aminoadenine, 6-Amino-8-phenyl-9H-Purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) Examples thereof include guanine, N- (3-ethylphenyl) guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthin, 8-azahipoxanthin and derivatives thereof.

When the photosensitive resin composition of the present invention contains the azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and the light sensitivity characteristics. From the viewpoint of the above, 0.5 to 5 parts by mass is more preferable. When the blending amount of the azole compound (A) with respect to 100 parts by mass of the resin is 0.1 parts by mass or more, the surface of the copper or copper alloy is formed when the photosensitive resin composition of the present invention is formed on copper or a copper alloy. On the other hand, when it is 20 parts by mass or less, the light sensitivity is excellent.

In addition, a hindered phenol compound can be optionally blended in order to suppress discoloration on the copper surface. 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), triethylene glycol-bis [3- (3-t) -Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio -Diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrosin) Namamide), 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-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -Trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6-( 1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4 , 6- (1H, 3H, 5H) -trion,

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, etc. However, it is not limited to this. 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 and the like are particularly preferable.

The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and more preferably 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics. preferable. When the blending amount of the hindered phenol compound (A) with respect to 100 parts by mass of the resin is 0.1 parts by mass or more, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, copper or Discoloration and corrosion of the copper alloy are prevented, while when the amount is 20 parts by mass or less, the light sensitivity is excellent.

The photosensitive resin composition of the present invention may contain a cross-linking agent. The cross-linking agent is a cross-linking agent capable of cross-linking the resin (A) or forming a cross-linking network by itself when the relief pattern formed by using the photosensitive resin composition of the present invention is heat-cured. Can be. The cross-linking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the photosensitive resin composition.

Examples of the cross-linking agent include Cymel® 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141 and 272, which are compounds containing a methylol group and / or an alkoxymethyl group. , 202, 1156, 1158, 1123, 1170, 1174; UFR65, 300; My Coat 102, 105 (all manufactured by Mitsui Cytec Co., Ltd.), Nicarac (registered trademark) MX-270, 280, -290; Nicarac MS-11. Nicarac MW-30, -100, -300, -390, -750 (all manufactured by Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP , DML-PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP , TMOM-BPA, TML-BPAF-MF (manufactured by Honshu Kagaku Kogyo Co., Ltd.), benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) ) Benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis ( Examples thereof include methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, and dimethylbis (methoxymethyl) biphenyl.

In addition, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol which are oxylan compounds. -Naftor type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylpropanpolyglucidyl ether, 1 , 1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, glycerol triglycidyl ether, orthosecondary butylphenylglycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl Ether, Polyethylene Glycoglycidyl Ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020 , NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (trade name, manufactured by Nippon Kayaku Co., Ltd.), Epicoat (registered trademark) 1001, Epicoat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051, Epicoat 1031S, Epicoat 180S65, Epicoat 157H70, YX-315-75 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EHPE3150, Praxel G402, PUE101, PUE105 (trade name, manufactured by Daicel Chemical Industry Co., Ltd.), Epicron (Registered Trademarks) 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (trade name, manufactured by DIC), Denacol (Registered Trademarks) EX-201, EX-251, EX-203, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX- 614B, EX-711, EX-731, EX-810, EX-911, EM-150 (trade name, manufactured by Nagase ChemteX Corporation), Epoxy (registered trademark) 70P , Epolite 100MF (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

In addition, isocyanate group-containing compounds such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and takenate ( Registered trademarks) 500, 600, Cosmonate (registered trademark) NBDI, ND (trademark above, manufactured by Mitsui Chemicals, Inc.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402- B80T (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like can be mentioned.

In addition, bismaleimide compounds such as 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4 '-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4' -Diphenylsulphonbismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy) benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI- 3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and the like can be mentioned. The compound is not limited to these.

When the cross-linking agent is used, the blending amount is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the resin (A). When the blending amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 20 parts by mass or less, the storage stability is excellent.

The photosensitive resin composition of the present invention 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. Further, in particular, by incorporating both the cyclic compound having a carbonyl group (B) and the organic titanium compound in the photosensitive resin composition, the resin layer after curing is said to have excellent chemical resistance in addition to substrate adhesiveness. It works.

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) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable because it provides storage stability and a good pattern of the negative photosensitive resin composition, and a specific example is titanium bis. (Triethanolamine) Diisopropoxiside, Titanium di (n-butoxide) bis (2,4-pentanionate, Titanium diisopropoxyside bis (2,4-pentanionate), Titanium diisopropoxyside bis (2,4-pentanionate) Tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.

II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxide), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide. , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.

III) titanocene compound: For example, 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-pyrrole-1-yl) phenyl) titanium and the like.

IV) Monoalkoxytitanium compound: For example, titanium tris (dioctyl phosphate) isopropoxyside, titanium tris (dodecylbenzene sulfonate) isopropoxide, and the like.

V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.

VI) Titanium tetraacetylacetone compound: For example, titanium tetraacetylacetone.

VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, when the organic titanium compound is at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound, better chemical resistance is exhibited. It is preferable from the viewpoint. 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 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the resin (A). 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.

Further, an adhesive aid can be optionally blended in order to improve the adhesiveness between the film formed by using the photosensitive resin composition of the present invention and the base material. Adhesive aids include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide , N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzene-1, 4-Bis (N- [3-triethoxysilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propylsuccinic hydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyl Silane coupling agents such as trimethoxysilane, 3-ureidopropyltriethoxysilane, 3- (trialkoxysilyl) propylsuccinic acid anhydride, and aluminum tris (ethylacetacetate), aluminumtris (acetylacetonate), ethyl. Examples thereof include aluminum-based adhesive aids such as acetoacetate aluminum diisopropylate.

Among these adhesive aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the photosensitive resin composition contains an adhesive aid, the blending amount of the adhesive aid is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the resin (A).

As the silane coupling agent, 3-mercaptopropyltrimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd .: trade name KBM803, manufactured by Chisso Co., Ltd .: trade name Sila Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Asmax Co., Ltd .: Product name SIM6475.0), 3-Mercaptopropylmethyldimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd .: product name LS1375, manufactured by Asmax Co., Ltd .: product name SIM6474.0), Mercaptomethyltrimethoxysilane (manufactured by Asmax Co., Ltd .: product) Name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by ASMAX Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3 − Mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane , 2-Mercaptoethylethoxydimethoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethylethoxydipropoxysilane, 2-Mercaptoethyldimethoxypropoxysilane, 2-Mercaptoethylmethoxydipropoxysilane , 4-Mercaptobutyltrimethoxysilane, 4-Mercaptobutyltriethoxysilane, 4-Mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: trade name LS3610, ASMAX stock) Company: Product name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (Azmax Co., Ltd .: Product name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- ( 3-ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N-( 3-Dimethoxypropoxysilylpropyl) urea, N -(3-Methoxydipropoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-Tripropoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-Trimethoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (Azmax Co., Ltd.) Manufactured by: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.1) Aminophenyl Trimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.2), 2- (trimethoxysilylethyl) pyridine (manufactured by Azmax Co., Ltd .: trade name SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (Dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetra Ethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n) -Propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxysilane), bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) Ethan, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] Tetrasulfide, di-t-butoxydiase Toxisilane, di-i-butoxyaluminoxytriethoxysilane, bis (pentazionate) titanium-O, O'-bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol , N-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p- Trillsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyl Examples thereof include, but are not limited to, diphenylsilanol and triphenylsilanol. These may be used alone or in combination of two or more.

Among the above-mentioned silane coupling agents, the silane coupling agent includes phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, and diethoxy from the viewpoint of storage stability. Diphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and a silane coupling agent represented by the following structure are preferable.

When a silane coupling agent is used, the blending amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin (A).

The photosensitive resin composition of the present invention may further contain components other than the above components. The preferred components thereof differ depending on whether the resin (A) is a negative type using, for example, a polyimide precursor and a polyamide, or a positive type using a polyoxazole precursor, a soluble polyimide, a phenol resin, or the like.

In the case of the negative type using a polyimide precursor or polyamide as the resin (A), a sensitizer can be optionally added in order to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaphthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocumine), 3-Acetyl-7-Dimethylaminokumarin, 3-ethoxycarbonyl-7-Dimethylaminokumarin, 3-Benzyloxycarbonyl-7-Dimethylaminokumarin, 3-methoxycarbonyl-7-diethylaminokumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylamino) Examples thereof include styryl) naphtho (1,2-d) thiazole and 2- (p-dimethylaminobenzoyl) styrene. These can be used alone or, for example, in a combination of 2 to 5 types.

When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the blending amount is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the resin (A).

Further, in order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be optionally blended. 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 or polyethylene such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Glycol mono or diacrylate and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, glycerol mono, di or triacrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, diacrylate and 1,4-butanediol diacrylate 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, methacrylicamides and derivatives thereof, trimethylolpropane triacrylates and methacrylates, di or triacrylates and methacrylates of glycerol, di, tri, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds, etc. Compounds can be mentioned.

When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the blending amount of the monomer having a photopolymerizable unsaturated bond is ( A) It is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin.

Further, in the case of the negative type using a polyimide precursor or the like as the resin (A), in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition during storage in the state of a solution containing a solvent. A thermal polymerization inhibitor can be arbitrarily blended. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, 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 amount of the thermal polymerization inhibitor blended in the photosensitive resin composition is preferably in the range of 0.005 to 12 parts by mass with respect to 100 parts by mass of the resin (A).

On the other hand, in the photosensitive resin composition of the present invention, in the case of the positive type using a polyoxazole precursor or the like as the resin (A), it has been conventionally used as an additive for the photosensitive resin composition, if necessary. Dyes, surfactants, thermal acid generators, dissolution accelerators, adhesion aids for enhancing adhesion to the substrate, and the like can be added.

<Dyes, surfactants, adhesive aids>
More specifically, the dyes include, for example, methyl violet, crystal violet, malachite green and the like. Examples of the surfactant include nonionic surfactants composed of polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether or derivatives thereof, such as Florard (trade name, manufactured by Sumitomo 3M), Megafuck (trade name, manufactured by Sumitomo 3M). Fluorosurfactants such as product name, Dainippon Ink and Chemicals (manufactured by Dainippon Ink and Chemicals) or Lumiflon (trade name, manufactured by Asahi Glass), such as KP341 (trade name, manufactured by Shinetsu Chemicals), DBE (trade name, manufactured by Chisso). ), Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and other organic siloxane surfactants. Examples of the adhesion aid include alkylimidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinylmethyl ether, t-butyl novolac, epoxy silane, epoxy polymer and the like, and various silane coupling agents.

The blending amount of the dye and the surfactant is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin (A).

Further, even when the curing temperature is lowered, a thermoacid generator can be arbitrarily blended from the viewpoint of exhibiting good thermophysical and mechanical properties of the cured product.
The thermoacid generator is preferably blended from the viewpoint of exhibiting good thermophysical and mechanical properties of the cured product even when the curing temperature is lowered.

Examples of the thermoacid generator include salts formed from a strong acid such as an onium salt having a function of generating an acid by heat and a base, and imide sulfonate.

Examples of the onium salt include diaryliodonium salts such as aryldiazonium salt and diphenyliodonium salt; di (alkylaryl) iodonium salt such as di (t-butylphenyl) iodonium salt; and trialkylsulfonium salt such as trimethylsulfonium salt; Dialkyl monoaryl sulfonium salts such as dimethylphenyl sulfonium salt; diaryl monoalkyl iodonium salt such as diphenyl methyl sulfonium salt; triaryl sulfonium salt and the like can be mentioned.

Among these, di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid, di (t-butylphenyl) iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethyl of trifluoromethanesulfonic acid Phenylsulfonium salt, diphenylmethylsulfonium salt of trifluoromethanesulfonic acid, di (t-butylphenyl) iodonium salt of nonafluorobutanesulfonic acid, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, benzenesulfonic acid Didimethylphenyl sulfonium salt, diphenylmethyl sulfonium salt of toluene sulfonic acid and the like are preferable.

Further, as the salt formed from the strong acid and the base, in addition to the above-mentioned onium salt, the following salt formed from the strong acid and the base, for example, a pyridinium salt can also be used. Strong acids include p-toluene sulfonic acid, aryl sulfonic acid such as benzene sulfonic acid, camphor sulfonic acid, trifluoromethane sulfonic acid, perfluoroalkyl sulfonic acid such as nonafluorobutane sulfonic acid, methane sulfonic acid, ethane sulfonic acid. , Alkyl sulfonic acid such as butane sulfonic acid and the like. Examples of the base include pyridine, alkylpyridine such as 2,4,6-trimethylpyridine, N-alkylpyridine such as 2-chloro-N-methylpyridine, halogenated-N-alkylpyridine and the like.

As the imide sulfonate, for example, naphthoylimide sulfonate, phthalimide sulfonate and the like can be used, but the compound is not limited as long as it is a compound that generates an acid by heat.

When a thermoacid generator is used, the blending amount is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and 1 to 5 parts by mass with respect to 100 parts by mass of the resin (A). Is more preferable.

In the case of a positive photosensitive resin composition, a dissolution accelerator can be used to accelerate the removal of the resin that is no longer needed after the exposure. For example, a compound having a hydroxyl group or a carboxyl group is preferable. Examples of compounds having a hydroxyl group include ballast agents used in the above-mentioned naphthoquinone diazide compounds, paracumylphenols, bisphenols, resorcinols, linear phenol compounds such as MtrisPC and MterraPC, TrisP-HAP, and TrisP. Non-linear phenol compounds such as −PHBA and TrisP-PA (all manufactured by Honshu Kagaku Kogyo Co., Ltd.), 2 to 5 phenol substitutions of diphenylmethane, 1 to 5 phenol substitutions of 3,3-diphenylpropane, Bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, a compound obtained by reacting 5-norbornene-2,3-dicarboxylic acid anhydride with a molar ratio of 1: 2. Compounds obtained by reacting 3-amino-4-hydroxyphenyl) sulfone with 1,2-cyclohexyldicarboxylic acid anhydride at a molar ratio of 1: 2, N-hydroxysuccinimide, N-hydroxyphthalateimide, N. -Hydroxy5-norbornene-2,3-dicarboxylic acid imide and the like can be mentioned. Examples of compounds having a carboxyl group include 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2. − (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, itaconic acid and the like can be mentioned.

When a dissolution accelerator is used, the blending amount is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin (A).

(Aspect B)
In another aspect of this embodiment, (B) a sulfur-containing compound can be used instead of the above-mentioned (B) cyclic compound having a carbonyl group. More specifically
(A) At least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and novolak, polyhydroxystyrene and phenol resin. 100 parts by mass of resin,
0.01 to 10 parts by mass of the sulfur-containing compound (B) based on 100 parts by mass of the resin (A);
(C) 1 to 50 parts by mass of the photosensitizer based on 100 parts by mass of the resin (A).
A photosensitive resin composition containing the above is provided.

In this embodiment, the resin (A) is a polyimide precursor containing the general formula (1), a polyamide containing the general formula (4), a polyoxazole precursor containing the general formula (5), and the general formula (6). ), And at least one selected from the group consisting of novolak, polyhydroxystyrene and a phenol resin containing the general formula (7).

Further, the photosensitive resin composition contains a phenol resin having a repeating unit represented by the general formula (7), and X in the general formula (7) is represented by the general formula (9) 2. It is preferably a divalent organic group selected from the group consisting of a valent group and a divalent group represented by the general formula (10).

By blending the sulfur-containing compound in the photosensitive resin composition, a photosensitive resin composition that gives a cured film in which void generation at the interface in contact with the Cu layer is suppressed after a high-temperature storage test can be obtained.

The sulfur-containing compound (B) is an organic compound having sulfur, preferably sulfur and nitrogen, and sulfur is preferably contained as one atom or thiocarbonyl group forming a ring structure.

(B) Those that can be used as sulfur-containing compounds include, for example, thiazole, 2-aminothiazole, 2- (4-thiazolyl) benzimidazole as those containing sulfur as one atom forming a 5-membered ring structure. , 1,3,4-Thiazylazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,3-thiadiazole, 2,4-thiazolidinedione, benzothiazole, 2-aminobenzothiazole, etc. , Sulfur is contained as one atom forming a 6-membered ring structure, for example, phenothiazine, N-methylphenothiazine, etc. Thiourea, dibutylthiourea, dicyclohexylthiourea, diphenylthiourea, 2-thiouracil, 4-thiouracil, 2,4-dithiopyrimidine, 2-thioxanthone, 2-mercapto-4 (3H) -quinazolinone and the like can be mentioned. Of these, compounds containing a thiourea structure are preferably used.

The blending amount of the sulfur-containing compound (B) is 0.01 to 10 parts by mass, preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the resin (A). From the viewpoint of migration resistance, 0.01 parts by mass or more is desirable, and from the viewpoint of solubility, less than 10 parts by mass is desirable.
Sulfur-containing compounds, especially thiourea, can be coordinated to copper by sulfur atoms. As a result, the state of the copper surface changes, and the migration of copper during the high temperature storage test is suppressed.

｛式中、Ｒ_q1は炭素原子、水素原子、窒素原子、酸素原子から形成される、炭素数１〜１０の有機基で表される。｝、
下記一般式（Ｂ−２）：

｛式中、Ｒ_q2、Ｒ_q3は、それぞれ水酸基、炭素数１〜１０のアルキル基もしくはアルコキシ基から選ばれる有機基、ｌｌは１〜１０から選ばれる整数で表される。｝、及び、
下記一般式（Ｂ−３）：

｛式中、Ｒ_q4、Ｒ_q5は、それぞれ水酸基、炭素数１〜１０のアルキル基もしくはアルコキシ基から選ばれる有機基、Ｘ_Sは炭素数１〜１０の２価の炭化水素基、ｍｍ、ｎｎはそれぞれ１〜１０から選ばれる整数で表される。｝から選ばれる少なくとも１種の化合物を、前記（Ａ）樹脂１００質量部を基準として０．０１〜１０質量部；並びに、
（Ｃ）感光剤を前記（Ａ）樹脂１００質量部を基準として１〜５０質量部、
を含む感光性樹脂組成物が提供される。 (Aspect C)
In another embodiment of the present embodiment, instead of the above-mentioned (B) cyclic compound having a carbonyl group, (B) is selected from the following general formulas (B-1), (B-2) and (B-3). At least one compound can be used. More specifically
(A) At least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and novolak, polyhydroxystyrene and phenol resin. 100 parts by mass of resin,
(B)
The following general formula (B-1):

{In the formula, R _q1 is represented by an organic group having 1 to 10 carbon atoms formed from a carbon atom, a hydrogen atom, a nitrogen atom, and an oxygen atom. },
The following general formula (B-2):

{In the formula, R _q2 and R _q3 are represented by a hydroxyl group, an organic group selected from an alkyl group having 1 to 10 carbon atoms or an alkoxy group, respectively, and ll is represented by an integer selected from 1 to 10. },as well as,
The following general formula (B-3):

{Wherein, R _q4, R _q5 are each hydroxyl, an organic group selected from alkyl group or alkoxy group having 1 to 10 carbon atoms, X _S is a divalent hydrocarbon group having 1 to 10 carbon atoms, mm, nn Is represented by an integer selected from 1 to 10, respectively. }, 0.01 to 10 parts by mass of at least one compound selected from the above (A) based on 100 parts by mass of the resin;
(C) 1 to 50 parts by mass of the photosensitizer based on 100 parts by mass of the resin (A).
A photosensitive resin composition containing the above is provided.

In this embodiment, the resin (A) is a polyimide precursor containing the general formula (1), a polyamide containing the general formula (4), a polyoxazole precursor containing the general formula (5), and the general formula (6). ), And at least one selected from the group consisting of novolak, polyhydroxystyrene and a phenol resin containing the general formula (7).

Further, the photosensitive resin composition contains a phenol resin having a repeating unit represented by the general formula (7), and X in the general formula (7) is represented by the general formula (9) 2. It is preferably a divalent organic group selected from the group consisting of a valent group and a divalent group represented by the general formula (10).

(B) The compound represented by the general formulas (B-1), (B-2) and (B-3), preferably the compound represented by (B-1), is copper by a nitrogen atom or an oxygen atom. By interacting with the surface of copper, the surface condition of copper can be changed. Therefore, copper migration during the high temperature storage test is suppressed.

As a specific example, (B-1) is an organic compound formed from a carbon atom, a hydrogen atom, a nitrogen atom, and an oxygen atom having a ureido group, and for example, methyl urea, ethyl urea, butyl urea, phenyl urea, and hydroxyethyl. Examples thereof include urea, hydantoic acid, allantin, citrulin and the like and mixtures thereof.

(B-2) is a polycondensate of ethylene glycol or a terminal etherified product thereof, for example, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, triethylene glycol, triethylene glycol monoethyl ether, triethylene glycol diethyl. Examples thereof include ether, tetraethylene glycol, tetraethylene glycol dimethyl ether and the like, and mixtures thereof.

Further, (B-3) is an ester of an alkoxypolyethylene oxide of a dicarboxylic acid or an alkoxyethyl ester, for example, bis adipate (2-methoxyethyl), bis adipate (2-butoxyethyl), bis sebacate (2-). Ethoxyethyl) and the like and mixtures thereof can be mentioned.

Of these (B) at least one compound selected from the general formulas (B-1), (B-2) and (B-3), the general formula (B-1) can be preferably used. It is a compound represented by.

(B) The blending amount of at least one compound selected from the general formulas (B-1), (B-2) and (B-3) is preferably 0.01 with respect to 100 parts by mass of the resin (A). It is 10 parts by mass, more preferably 0.05 to 2 parts by mass. From the viewpoint of migration resistance, 0.01 parts by mass or more is desirable, and from the viewpoint of solubility, 10 parts by mass or less is desirable.

｛Ｒａ１〜Ｒａ５はそれぞれ同じであってもよく、異なっていてもよく、水素原子かヒドロキシル基、もしくは炭素数が１以上１５以下の整数である飽和炭化水素基、不飽和炭化水素基、芳香族基もしくはアミド基であり、Ｒａ６〜Ｒａ７はそれぞれ同じであってもよく、異なっていてもよく、水素原子あるいは炭素数が１以上５以下の整数である飽和炭化水素基、不飽和炭化水素基、もしくは芳香族基である。｝
で表わされるアニリン誘導体、もしくは下記一般式（ＩＩ）：

｛Ｒａ８〜Ｒａ１０はそれぞれ同じであってもよく、異なっていてもよく、水素原子かヒドロキシル基、もしくは炭素数が１以上１５以下の整数である飽和炭化水素基、不飽和炭化水素基、芳香族基もしくはアミド基である。｝
で表わされるトリアゾール誘導体、もしくは下記一般式（ＩＩＩ）：

｛Ｒ１１〜Ｒ１３はそれぞれ同じであってもよく、異なっていてもよく、水素原子かヒドロキシル基、もしくは炭素数が１以上１５以下の整数である飽和炭化水素基、不飽和炭化水素基、芳香族基もしくはアミド基である。｝
で表わされるトリアゾール誘導体の少なくともいずれか１種類を前記（Ａ）樹脂１００質量部を基準として０．０１〜１５質量部、並びに
（Ｃ）感光剤を前記（Ａ）樹脂１００質量部を基準として１〜５０質量部、
を含む感光性樹脂組成物が提供される。 (Aspect D)
In another aspect of the present embodiment, the aniline derivative represented by the following general formula (I), which is (B) an aromatic amine compound instead of the above-mentioned (B) cyclic compound having a carbonyl group, is described below. At least one selected from the group consisting of the triazole derivative represented by (II) and the triazole derivative represented by the following general formula (III) can be used. More specifically
(A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, and polybenzoxazole.
(B) It is an aromatic amine compound and has the following general formula (I):

{Ra1 to Ra5 may be the same or different, and may be a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic having an integer of 1 or more and 15 or less carbon atoms. It is a group or an amide group, and Ra6 to Ra7 may be the same or different, respectively, and a hydrogen atom or an unsaturated hydrocarbon group having an integer of 1 or more and 5 or less carbon atoms, an unsaturated hydrocarbon group, Or it is an aromatic group. }
Aniline derivative represented by, or the following general formula (II):

{Ra8 to Ra10 may be the same or different, and may be a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group having an integer of 1 or more and 15 or less carbon atoms. It is a group or an amide group. }
Triazole derivative represented by, or the following general formula (III):

{R11 to R13 may be the same or different, and may be a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic having an integer of 1 or more and 15 or less carbon atoms. It is a group or an amide group. }
At least one of the triazole derivatives represented by (A) is 0.01 to 15 parts by mass based on 100 parts by mass of the resin (A), and (C) the photosensitizer is 1 by mass based on 100 parts by mass of the resin (A). ~ 50 parts by mass,
A photosensitive resin composition containing the above is provided.

In this aspect, the resin (A) is a polyimide precursor containing the general formula (1), a polyamide containing the general formula (4), a polyoxazole precursor containing the general formula (5), and the general formula ( It is preferably at least one selected from the group consisting of polyimides containing 6).

(B) In the embodiment in which the aromatic amine compound is used, the photosensitive resin includes polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, and polybenzoxazole, among which heat treatment is performed. Since the latter resin is excellent in heat resistance and mechanical properties, polyamic acid, polyamic acid ester, polyamic acid salt, polyamide, polyhydroxyamide, and polyimide resin are preferably used, and polyimide precursor and polyimide resin are most preferably used.

By using the (B) aromatic amine compound, it is possible to suppress the generation of voids at the interface between the rewired Cu layer and the resin layer after the high temperature storage test. The reason for this is not clear, but it is thought that the lone electron pair of the aromatic amine compound coordinates with the Cu element on the surface of the Cu layer to block the active Cu reaction site, thus suppressing the generation of voids. Be done.

｛Ｒａ１〜Ｒａ５はそれぞれ同じであってもよく、異なっていてもよく、水素原子かヒドロキシル基、もしくは炭素数が１以上１５以下の整数である飽和炭化水素基、不飽和炭化水素基、芳香族基もしくはアミド基であり、Ｒａ６〜Ｒａ７はそれぞれ同じであってもよく、異なっていてもよく、水素原子あるいは炭素数が１以上５以下の整数である飽和炭化水素基、不飽和炭化水素基、もしくは芳香族基である。｝で表わされるアニリン誘導体が好ましく用いられる。 The aromatic amine compound (B) includes the following general formula (I):

{Ra1 to Ra5 may be the same or different, and may be a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic having an integer of 1 or more and 15 or less carbon atoms. It is a group or an amide group, and Ra6 to Ra7 may be the same or different, respectively, and a hydrogen atom or an unsaturated hydrocarbon group having an integer of 1 or more and 5 or less carbon atoms, an unsaturated hydrocarbon group, Or it is an aromatic group. } Is preferably used.

Examples of compounds preferably used among the aniline derivatives represented by the general formula (I) include N-phenylbenzylamine, salicylanilide, naphthol AS, 2-acetamidofluorene, oxanilide, N-allylaniline, and N-methylaniline. , N-ethylaniline, indolin, Nn-butylaniline, 2-anilinoethanol, 4-methoxyacetanilide, acetanilide, 1,2,3,4-tetrahydroquinoline, tert-butylphenylcarbamate, tert-butyl ( 3-Hydroxyphenyl) carbamate, oxanilide, N, N'-diphenylethane-1,2-diamine and the like are preferably used. Among them, N-phenylbenzylamine ((B) -1), N, N'-diphenylethane-1,2-diamine ((B) -2), tert-butylphenylcarbamate ((B) -3), tert. -Butyl (3-hydroxyphenyl) carbamate ((B) -4) is particularly preferably used.

｛Ｒａ８〜Ｒａ１０はそれぞれ同じであってもよく、異なっていてもよく、水素原子かヒドロキシル基、もしくは炭素数が１以上１５以下の整数である飽和炭化水素基、不飽和炭化水素基、芳香族基もしくはアミド基である。｝
で表わされるトリアゾール誘導体、もしくは下記一般式（ＩＩＩ）：

｛Ｒａ１１〜Ｒａ１３はそれぞれ同じであってもよく、異なっていてもよく、水素原子かヒドロキシル基、もしくは炭素数が１以上１５以下の整数である飽和炭化水素基、不飽和炭化水素基、芳香族基もしくはアミド基である。｝
で表わされるトリアゾール誘導体が好ましく用いられる。 As the (B) triazole derivative, the following general formula (II):

{Ra8 to Ra10 may be the same or different, and may be a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group having an integer of 1 or more and 15 or less carbon atoms. It is a group or an amide group. }
Triazole derivative represented by, or the following general formula (III):

{Ra11 to Ra13 may be the same or different, and may be a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic having an integer of 1 or more and 15 or less carbon atoms. It is a group or an amide group. }
The triazole derivative represented by is preferably used.

Specific examples of the compound of the triazole derivative represented by the general formula (II) include benzotriazole, 1-hydroxybenzotriazole, 1-aminobenzotriazole, 5-methyl-1H-benzotriazole, 1H-1,2,3. -Triazole, 2-hydroxy-N- (1H-1,2,4-triazole-3-yl) benzamide (manufactured by ADEKA Co., Ltd., Adecastab CDA-1), 2- (2H-benzo [d] [1,2 , 3] Triazole-2-yl) -4- (2,4,4-trimethylpentan-2-yl) phenol (manufactured by ADEKA Co., Ltd., Adecastab LA-29), 2- (2'-hydroxy-3', 5'-di-tert-aminophenyl) benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole are preferably used. Among them, 2-hydroxy-N- (1H-1,2,4-triazole-3-yl) benzamide ((B) -5), 2- (2H-benzo [d] [1,2,3] triazole- 2-Il) -4- (2,4,4-trimethylpentan-2-yl) phenol ((B) -6) is particularly preferably used.

Specific examples of the compound of the triazole derivative represented by the general formula (III) include (4-((1H-1,2,4-triazole-1-ylmethyl) phenyl) methanol, tricyclazole, 1,2,4- 1H-triazole, triapentenol, bitertanol, 4- (1H-1,2,4-triazole-1-yl) benzaldehyde, 4- (1H-1,2,4-triazole-1-yl) benzoic acid, 3 -(1H-1,2,4-triazole-1-ylmethyl) benzoic acid, 4-[(1H-1,2,4-triazole-1-ylmethyl) phenyl] methanol, 3- (1H-1,2, 4-Triazole-1-yl) benzaldehyde, 3- (1H-1,2,4-triazole-1-ylmethyl) benzaldehyde, 3- (1H-1,2,4-triazole-1-yl) benzoic acid, 2 -(1H-1,2,4-triazole-1-yl) aniline is preferably used. Among them, (4-((1H-1,2,4-triazole-1-ylmethyl) phenyl) methanol ((B)) -7) is particularly preferably used.

In the aromatic amine compound (B), it is preferable that either the aniline derivative or the amine atom constituting the triazole derivative is a secondary amine because of its ability to coordinate with the Cu element.

The content of the aromatic amine compound (B) is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and 1 to 8 parts by mass with respect to 100 parts by mass of the resin (A). Is more preferable. If the content is larger than the range, the storage stability is lowered, which is not preferable. If the content is lower than the range, voids are likely to be generated between the copper surface and the copper surface.

<Manufacturing method of cured relief pattern and semiconductor device>
Further, the present invention includes (1) a step of forming a resin layer on the substrate by applying the above-mentioned photosensitive resin composition of the present invention on the substrate, and (2) a step of exposing the resin layer. , (3) A step of developing the resin layer after the exposure to form a relief pattern, and (4) a step of forming a cured relief pattern by heat-treating the relief pattern to produce a cured relief pattern. Provide a method. Hereinafter, typical embodiments of each step will be described.

(1) Step of forming a resin layer on the substrate by applying the photosensitive resin composition on the substrate In this step, the photosensitive resin composition of the present invention is applied on the substrate, and if necessary. Then, it is dried to form a 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 the like, 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. As the drying method, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying are used. Specifically, when air-drying or heat-drying is performed, drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. As described above, the resin layer can be formed on the substrate.

(2) Step of exposing the resin layer In this step, the resin layer formed above is exposed to a photomask or reticle having a pattern using an exposure device such as a contact aligner, a mirror projection, or a stepper, or directly. Expose with an ultraviolet light source or the like.

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

(3) Step of developing the exposed resin layer to form a relief pattern In this step, the exposed portion or the unexposed portion of the photosensitive resin layer after exposure is developed and removed. When a negative type photosensitive resin composition is used (for example, when a polyimide precursor or a polyamide is used as the resin (A)), the unexposed portion is developed and removed, and a positive type photosensitive resin composition is used (for example, when a positive type photosensitive resin composition is used. For example, (A) when a polyoxazole precursor or a soluble polyimide is used as the resin), the exposed portion is developed and removed. As the developing method, any method can be selected and used from conventionally known photoresist developing methods such as a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment. 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, a good solvent for the photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. For example, in the case of a photosensitive resin composition that does not dissolve in an alkaline aqueous solution, examples of good solvents include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α. -Acetyl-γ-butyrolactone and the like are preferable, and as the poor solvent, 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 photosensitive resin composition. Further, two or more kinds of each solvent, for example, several kinds can be used in combination.

On the other hand, in the case of a photosensitive resin composition that dissolves in an alkaline aqueous solution, the developer used for development dissolves and removes an alkaline aqueous solution-soluble polymer, and is typically an alkaline aqueous solution in which an alkaline compound is dissolved. .. The alkaline compound dissolved in the developing solution may be either an inorganic alkaline compound or an organic alkaline compound.

Examples of the inorganic alkaline compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, and potassium silicate. , Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia and the like.

Examples of the organic alkaline compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, and di. Examples thereof include -n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine and the like.

Further, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol or ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor and the like can be added to the alkaline aqueous solution. .. The relief pattern can be formed as described above.

(4) Step of forming a cured relief pattern by heat-treating the relief pattern In this step, the relief pattern obtained by the above development is heated to be converted into a cured relief pattern. As a method of heat curing, various methods such as a hot plate method, an oven method, and a temperature rise type oven in which a temperature program can be set can be selected. The heating can be performed, for example, at 180 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.

<Semiconductor device>
The present invention also provides a semiconductor device including a cured relief pattern obtained by the method for producing a cured relief pattern of the present invention described above. The present invention also provides a semiconductor device including a base material which is a semiconductor element and a cured relief pattern of a resin formed on the base material by the above-mentioned cured relief pattern manufacturing method. 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.

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 coating of flexible copper-clad plates, solder resist films, and liquid crystal alignment films. Is.
In addition, although the above description has been divided into aspects A to D, combinations of each aspect are also included in the present invention.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention 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.

(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 was the trade name "Shodex 805M / 806M series" manufactured by Showa Denko KK, and the standard monodisperse polystyrene was the trade 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) Creation of a 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 rotationally applied onto this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO), and dried to obtain a coating film having a thickness of 6 to 10 μm. Was formed. This coating film was irradiated with energy ^{of 300 mJ / cm 2} by a parallel light mask aligner (PLA-501FA type, manufactured by Canon Inc.) using a mask with a test pattern. Next, this coating film was spray-developed by a coater developer (D-Spin 60A type, manufactured by SOKUDO) using cyclopentanone as a developing solution in the case of a negative type and 2.38% TMAH in the case of a positive type. A relief pattern on Cu was obtained by rinsing with propylene glycol methyl ether acetate in the case of the negative type and pure water in the case of the positive type.

A wafer having the relief pattern formed on Cu is heat-treated for 2 hours at the temperature described in each example under a nitrogen atmosphere using a heating program type curing furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.). As a result, a cured relief pattern made of a resin having a thickness of about 6 to 7 μm was obtained on Cu.

(3) High temperature storage test of cured relief pattern on Cu and subsequent evaluation Wafers having the cured relief pattern formed on Cu are heated in a temperature-raising programmed curing furnace (VF-2000 type, Koyo Lindbergh). Was heated in air at 150 ° C. for 168 hours. Subsequently, using a plasma surface treatment device (EXAM type, manufactured by Shinko Seiki Co., Ltd.), all the resin layers on Cu were removed by plasma etching. The plasma etching conditions are as follows.
Output: 133W
Gas type / flow rate: O ₂ : 40 ml / min + CF ₄ : 1 ml / min Gas pressure: 50 Pa
Mode: Hard mode Etching time: 1800 seconds

The Cu surface from which all the resin layer has been removed is observed by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and image analysis software (A image-kun, manufactured by Asahi Kasei Corporation) is used on the surface of the Cu layer. The area ratio of voids to occupy was calculated.

(4) Evaluation of varnish storage stability The photosensitive resin compositions obtained in Examples and Comparative Examples were left to stand in an atmosphere of 23 ° C. and 50% Rh for 3 weeks, and the change in viscosity was observed.

The viscosity was measured at 23 ° C. using a TV-25 type viscometer (manufactured by Toki Sangyo Co., Ltd.).
◯: The viscosity change rate (below) of the composition after being left to stand is within 10%.
X: The rate of change in viscosity of the composition after standing is greater than 10%.
Viscosity change rate (%) = {(initial viscosity)-absolute value of (viscosity after standing)} x 100 / (initial viscosity)

Example A
<Production Example A1> ((A) Synthesis of polymer A as a polyimide precursor)
Place 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) in a 2 liter volume separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and stir at room temperature. , 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.

Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether (DADPE). A suspension of 93.0 g 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 composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer A). When the molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

The weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was determined.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l LiBr / NMP
Flow rate: 1 ml / min.

<Production Example A2> ((A) Synthesis of polymer B as a polyimide precursor)
In place of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) of Production Example A1, 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used. Except for the above, the reaction was carried out in the same manner as in the method described in Production Example A1 to obtain polymer B. When the molecular weight of the polymer B was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Production Example A3> ((A) Synthesis of polymer C as a polyimide precursor)
As described above, except that 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) 147.8 g was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) of Production Example A1. The reaction was carried out in the same manner as described in Production Example A1 of the above to obtain polymer C. When the molecular weight of the polymer C was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

<Production Example A4> ((A) Synthesis of Polymer D as Polyamide)
(Synthesis of phthalic acid compound encapsulant AIPA-MO)
5-Aminoisophthalic acid {hereinafter abbreviated as AIPA in a separable flask with a capacity of 5 liters. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50 ° C. in a water bath. To this, 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise with a dropping funnel, and the mixture was stirred as it was at 50 ° C. for about 2 hours.

Completion of the reaction (disappearance of 5-aminoisophthalic acid) is referred to as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, Add this reaction solution to 15 liters of ion-exchanged water, stir, allow to stand, wait for the crystallization and precipitation of the reaction product, separate by filtration, wash with water as appropriate, and vacuum at 40 ° C. for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate acted was obtained. The low molecular weight GPC purity of the obtained AIPA-MO was about 100%.

(Synthesis of Polymer D)
100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were put into a separable flask having a capacity of 2 liters, mixed, and cooled to 5 ° C. in an ice bath. bottom. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was added dropwise over about 20 minutes under ice-cooling, followed by 4,4'-bis (4-aminophenoxy). ) Biphenyl {Hereafter, it is referred to as BABP. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, and the mixture was stirred in an ice bath for 3 hours while maintaining the temperature below 5 ° C., and then removed from the ice bath and stirred at room temperature for 5 hours. bottom. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

A mixed solution of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was added dropwise to 5 liters of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer E). When the molecular weight of the polymer D was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 34,700.

<Production Example A5> ((A) Synthesis of polymer E as a polyoxazole precursor)
183.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 640.9 g of N, N-dimethylacetamide (DMAc), and 63.3 g of pyridine in a separable flask having a capacity of 3 liters. The mixture was mixed and stirred at room temperature (25 ° C.) to prepare a uniform solution. To this, 118.0 g of 4,4'-diphenyl ether dicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for dropping was 40 minutes, and the reaction liquid temperature was 30 ° C. at the maximum.

3 hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was left to stir for 15 hours at room temperature to carboxy 99% of all amine terminal groups of the polymer chain. It was sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic acid anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, vacuum dried, and measured by gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (polystyrene equivalent) was obtained.

The crude polybenzoxazole precursor obtained above is redissolved in γ-butyrolactone (GBL), treated with a cation exchange resin and an anion exchange resin, and the resulting solution is treated in ion exchange water. The precipitated polymer was filtered, washed with water, and vacuum-dried to obtain a purified polybenzoxazole precursor (polymer E).

<Production Example A6> ((A) Synthesis of polymer F as polyimide)
A cooling tube with a Dean-Stark trap was attached to a glass separable four-necked flask equipped with a Teflon (registered trademark) anchor-shaped stirrer. The flask was placed in a silicon oil bath and stirred while passing nitrogen gas.

2,2-bis (3-amino-4-hydroxyphenyl) propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5- (2,5-dioxotetrahydro-3-furanyl) Add 70.29 g (266 mmol) of -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone, and 60 g of toluene to room temperature. After stirring at 100 rpm for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and the silicon bath temperature was 50 ° C. while passing nitrogen gas. The mixture was heated and stirred at 100 rpm for 8 hours. Then, the silicon bath temperature was heated to 180 ° C., and the mixture was heated and stirred at 100 rpm for 2 hours. Toluene and water distillate were removed during the reaction. After the imidization reaction was completed, the temperature was returned to room temperature.

After that, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, vacuum dried, and measured by gel permeation chromatography (GPC). A crude polyimide (polymer F) having a weight average molecular weight of 23,000 (in terms of polystyrene) was obtained.

<Production Example A7> ((A) Synthesis of polymer G as phenol resin)
128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 4,4'-bis (methoxymethyl) biphenyl (hereinafter "BMMB") in a separable frassco with a capacity of 0.5 liter Dean-Stark apparatus. 121.2 g (0.5 mol), 3.9 g (0.025 mol) of diethyl sulfate, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70 ° C. to dissolve the solid substance.

The mixed solution was heated to 140 ° C. in an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 140 ° C. for 2 hours.

Next, the reaction vessel was cooled in the air, and 100 g of tetrahydrofuran was separately added thereto and stirred. The above reaction diluent was added dropwise to 4 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, washed with water as appropriate, dehydrated, and then vacuum-dried. A polymer (polymer G) was obtained in a yield of 70%. The weight average molecular weight of this polymer G determined by the standard polystyrene conversion of the GPC method was 21,000.

<Production Example A8> ((A) Synthesis of polymer H as phenol resin)
A separable flask with a capacity of 1.0 L with a Dean-Stark apparatus was replaced with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, and p-toluenesulfon. 3.81 g (0.02 mol) of acid and 116 g of propylene glycol monomethyl ether (hereinafter, also referred to as PGME) were mixed and stirred at 50 ° C. to dissolve the solid substance.

The mixed solution was heated to 120 ° C. in an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 120 ° C. for 3 hours.

Next, 24.9 g (0.150 mol) of 2,6-bis (hydroxymethyl) -p-cresol and 249 g of PGME were mixed and stirred in another container, and the uniformly dissolved solution was prepared using a dropping funnel. The mixture was added dropwise to the bull flask in 1 hour, and the mixture was further stirred for 2 hours after the addition.

After completion of the reaction, the same treatment as in Production Example A7 was carried out to obtain a copolymer (polymer H) composed of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol in a yield of 77%. The weight average molecular weight of this polymer H determined by the standard polystyrene conversion of the GPC method was 9,900.

で表される、フェノール性水酸基の７７％をナフトキノンジアジド−４−スルホン酸エステル化した感光性ジアゾキノン化合物（東洋合成社製、（Ｃ）感光剤に該当）（Ｃ１）２０ｇ、キサンチン（（Ｂ）カルボニル基を有する環状化合物に該当）０．２ｇ、３−ｔ−ブトキシカルボニルアミノプロピルトリエトキシシラン６ｇと共に、γ−ブチロラクトン（溶媒として）１００ｇに溶解した。得られた溶液の粘度を、少量のγ−ブチロラクトンを更に加えることによって約２０ポイズ（ｐｏｉｓｅ）に調整し、ポジ型感光性樹脂組成物とした。
この組成物について、上述の方法により３５０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．５％という結果を得た。
＜実施例Ａ１４＞
上記実施例Ａ１３において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＦ１００ｇに変えた以外は、実施例Ａ１３と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２５０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．７％という結果を得た。
＜実施例Ａ１５＞
上記実施例Ａ１３において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＧ１００ｇに変えた以外は、実施例Ａ１３と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２２０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．３％という結果を得た。
＜実施例Ａ１６＞
上記実施例Ａ１３において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＨ１００ｇに変えた以外は、実施例Ａ１３と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２２０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．２％という結果を得た。
＜比較例Ａ１＞
実施例Ａ１の組成から、キサンチン０．２ｇに代えてベンゾトリアゾール０．２ｇを添加した他は、実施例Ａ１と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ａ１と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１５．２％であった。
＜比較例Ａ２＞
実施例Ａ１の組成に、キサンチンを添加しない他は、実施例Ａ１と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ａ１と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１４．３％であった。
＜比較例Ａ３＞
実施例Ａ１０の組成に、キサンチンを添加しない他は、実施例Ａ１０と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ａ１０と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１５．７％であった。
＜比較例Ａ４＞
実施例Ａ１１の組成に、キサンチンを添加しない他は、実施例Ａ１１と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ａ１１と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１４．９％であった。
これら実施例Ａ１〜１６、比較例Ａ１〜４の結果を表１にまとめて示す。 <Example A1>
Negative photosensitive resin compositions were prepared using the polymers A and B by the following methods, and the prepared photosensitive resin compositions were evaluated. Polyimide precursors A50g and B50g (corresponding to (A) resin), xanthin (corresponding to (B) cyclic compound having a carbonyl group) 0.2g, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxym (denoted as "PDO" in Table 1) (corresponding to (C) photosensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g, N- [3- (triethoxysilyl) propyl] It was dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate together with 1.5 g of phthalamic acid. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to obtain a negative photosensitive resin composition.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.2. I got the result of%.
<Example A2>
In Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that the amount of xanthine added as the component (B) was changed to 0.05 g.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 6.4. I got the result of%.
<Example A3>
In Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that the amount of xanthine added as the component (B) was changed to 5 g.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 4.9. I got the result of%.
<Example A4>
A negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that 8-azaxanthine was used instead of xanthine as the component (B) in Example A1.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.1. I got the result of%.
<Example A5>
In Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that uric acid was used instead of xanthine as the component (B).
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.4. I got the result of%.
<Example A6>
In Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that lumazine was used instead of xanthine as the component (B).
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.5. I got the result of%.
<Example A7>
In Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that barbituric acid was used instead of xanthine as the component (B).
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 7.3. I got the result of%.
<Example A8>
A negative photosensitive resin composition solution is prepared in the same manner as in Example A1 above, and this composition is cured at 350 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and a high temperature storage test is performed. After that, the area ratio of voids to the surface of the Cu layer was evaluated, and a result of 4.5% was obtained.
<Example A9>
In Example A1, 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer A as the resin (A), and 4 g of PDO as the component (C) was changed to 1,2-octanedione, 1- {4- (phenylthio)-, A negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that it was changed to 2.5 g of 2- (O-benzoyloxime)} (Irgacure OXE01 (manufactured by BASF, trade name)).
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.1. I got the result of%.
<Example A10>
In Example A1, 50 g of polymer A and 50 g of polymer B as the resin (A), 4 g of PDO as the component (C) in 100 g of the polymer A, 1,2-octanedione, 1- {4- (phenylthio) −2. -(O-benzoyloxime)} (Irgacure OXE01 (manufactured by BASF, trade name)) was changed to 2.5 g, and the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethisulfoxide in the same manner as in Example A1. A negative photosensitive resin composition solution was prepared.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.2. I got the result of%.
<Example A11>
In Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer C as the resin (A).
This composition was cured at 350 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 4.9. I got the result of%.
<Example A12>
In Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer D as the resin (A).
This composition was cured at 250 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.0. I got the result of%.
<Example A13>
A positive photosensitive resin composition was prepared using the polymer E by the following method, and the prepared photosensitive resin composition was evaluated. A polymer E 100 g (corresponding to the resin (A)), which is a polyoxazole precursor, is subjected to the following formula (96):

Photosensitive diazoquinone compound in which 77% of phenolic hydroxyl groups represented by naphthoquinone diazide-4-sulfonic acid esterification (manufactured by Toyo Synthetic Co., Ltd., corresponds to (C) photosensitizer) (C1) 20 g, xanthin ((B)) It was dissolved in 100 g of γ-butyrolactone (as a solvent) together with 0.2 g (corresponding to a cyclic compound having a carbonyl group) and 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane. The viscosity of the obtained solution was adjusted to about 20 poises by further adding a small amount of γ-butyrolactone to obtain a positive photosensitive resin composition.
This composition was cured at 350 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.5. I got the result of%.
<Example A14>
In Example A13, a positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of polymer E was changed to 100 g of polymer F as the resin (A).
This composition was cured at 250 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.7. I got the result of%.
<Example A15>
In Example A13, a positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of polymer E was changed to 100 g of polymer G as the resin (A).
This composition was cured at 220 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.3. I got the result of%.
<Example A16>
In Example A13, a positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of polymer E was changed to 100 g of polymer H as the resin (A).
This composition was cured at 220 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.2. I got the result of%.
<Comparative example A1>
From the composition of Example A1, a negative photosensitive resin composition was prepared in the same manner as in Example A1 except that 0.2 g of benzotriazole was added instead of 0.2 g of xanthine, and the same evaluation as in Example A1 was made. Was done. The evaluation result was 15.2% because the compound (B) of the present invention was not contained.
<Comparative example A2>
A negative photosensitive resin composition was prepared in the same manner as in Example A1 except that xanthine was not added to the composition of Example A1, and the same evaluation as in Example A1 was performed. The evaluation result was 14.3% because the compound (B) of the present invention was not contained.
<Comparative example A3>
A negative photosensitive resin composition was prepared in the same manner as in Example A10 except that xanthine was not added to the composition of Example A10, and the same evaluation as in Example A10 was performed. The evaluation result was 15.7% because the compound (B) of the present invention was not contained.
<Comparative example A4>
A negative photosensitive resin composition was prepared in the same manner as in Example A11 except that xanthine was not added to the composition of Example A11, and the same evaluation as in Example A11 was performed. The evaluation result was 14.9% because the compound (B) of the present invention was not contained.
The results of Examples A1 to 16 and Comparative Examples A1 to 4 are summarized in Table 1.

Example B
<Production Example B1> ((A) Synthesis of polymer A as a polyimide precursor)
Place 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) in a 2 liter volume separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and stir at room temperature. , 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.

Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether (DADPE). A suspension of 93.0 g 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 composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer A). When the molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

The weight average molecular weight of the resin obtained in each Production Example B was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was determined.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l LiBr / NMP
Flow rate: 1 ml / min.

<Production Example B2> ((A) Synthesis of polymer B as a polyimide precursor)
In place of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) of Production Example B1, 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used. Except for the above, the reaction was carried out in the same manner as in the method described in Production Example B1 to obtain polymer B. When the molecular weight of the polymer B was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Production Example B3> ((A) Synthesis of polymer C as a polyimide precursor)
As described above, except that 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) 147.8 g was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) of Production Example B1. The reaction was carried out in the same manner as described in Production Example B1 of the above to obtain polymer C. When the molecular weight of the polymer C was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

<Production Example B4> ((A) Synthesis of Polymer D as Polyamide)
(Synthesis of phthalic acid compound encapsulant AIPA-MO)
5-Aminoisophthalic acid {hereinafter abbreviated as AIPA in a separable flask with a capacity of 5 liters. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50 ° C. in a water bath. To this, 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise with a dropping funnel, and the mixture was stirred as it was at 50 ° C. for about 2 hours.

Completion of the reaction (disappearance of 5-aminoisophthalic acid) is referred to as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, Add this reaction solution to 15 liters of ion-exchanged water, stir, allow to stand, wait for the crystallization and precipitation of the reaction product, separate by filtration, wash with water as appropriate, and vacuum at 40 ° C. for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate acted was obtained. The low molecular weight GPC purity of the obtained AIPA-MO was about 100%.

(Synthesis of Polymer D)
100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were put into a separable flask having a capacity of 2 liters, mixed, and cooled to 5 ° C. in an ice bath. bottom. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was added dropwise over about 20 minutes under ice-cooling, followed by 4,4'-bis (4-aminophenoxy). ) Biphenyl {Hereafter, it is referred to as BABP. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, and the mixture was stirred in an ice bath for 3 hours while maintaining the temperature below 5 ° C., and then removed from the ice bath and stirred at room temperature for 5 hours. bottom. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

A mixed solution of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was added dropwise to 5 liters of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer E). When the molecular weight of the polymer D was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 34,700.

<Production Example B5> ((A) Synthesis of polymer E as a polyoxazole precursor)
183.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 640.9 g of N, N-dimethylacetamide (DMAc), and 63.3 g of pyridine in a separable flask having a capacity of 3 liters. The mixture was mixed and stirred at room temperature (25 ° C.) to prepare a uniform solution. To this, 118.0 g of 4,4'-diphenyl ether dicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for dropping was 40 minutes, and the reaction liquid temperature was 30 ° C. at the maximum.

3 hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was left to stir for 15 hours at room temperature to carboxy 99% of all amine terminal groups of the polymer chain. It was sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic acid anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, vacuum dried, and measured by gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (polystyrene equivalent) was obtained.

The crude polybenzoxazole precursor obtained above is redissolved in γ-butyrolactone (GBL), treated with a cation exchange resin and an anion exchange resin, and the resulting solution is treated in ion exchange water. The precipitated polymer was filtered, washed with water, and vacuum-dried to obtain a purified polybenzoxazole precursor (polymer E).

<Production Example B6> ((A) Synthesis of Polymer F as Polyimide)
A cooling tube with a Dean-Stark trap was attached to a glass separable four-necked flask equipped with a Teflon (registered trademark) anchor-shaped stirrer. The flask was placed in a silicon oil bath and stirred while passing nitrogen gas.

2,2-bis (3-amino-4-hydroxyphenyl) propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5- (2,5-dioxotetrahydro-3-furanyl) Add 70.29 g (266 mmol) of -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone, and 60 g of toluene to room temperature. After stirring at 100 rpm for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and the silicon bath temperature was 50 ° C. while passing nitrogen gas. The mixture was heated and stirred at 100 rpm for 8 hours. Then, the silicon bath temperature was heated to 180 ° C., and the mixture was heated and stirred at 100 rpm for 2 hours. Toluene and water distillate were removed during the reaction. After the imidization reaction was completed, the temperature was returned to room temperature.

After that, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, vacuum dried, and measured by gel permeation chromatography (GPC). A crude polyimide (polymer F) having a weight average molecular weight of 23,000 (in terms of polystyrene) was obtained.

<Production Example B7> ((A) Synthesis of polymer G as phenol resin)
128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 4,4'-bis (methoxymethyl) biphenyl (hereinafter "BMMB") in a separable frassco with a capacity of 0.5 liter Dean-Stark apparatus. 121.2 g (0.5 mol), 3.9 g (0.025 mol) of diethyl sulfate, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70 ° C. to dissolve the solid substance.

The mixed solution was heated to 140 ° C. in an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 140 ° C. for 2 hours.

Next, the reaction vessel was cooled in the air, and 100 g of tetrahydrofuran was separately added thereto and stirred. The above reaction diluent was added dropwise to 4 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, washed with water as appropriate, dehydrated, and then vacuum-dried. A polymer (polymer G) was obtained in a yield of 70%. The weight average molecular weight of this polymer G determined by the standard polystyrene conversion of the GPC method was 21,000.

<Production Example B8> ((A) Synthesis of Polymer H as Phenol Resin)
A separable flask with a capacity of 1.0 L with a Dean-Stark apparatus was replaced with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, and p-toluenesulfon. 3.81 g (0.02 mol) of acid and 116 g of propylene glycol monomethyl ether (hereinafter, also referred to as PGME) were mixed and stirred at 50 ° C. to dissolve the solid substance.

The mixed solution was heated to 120 ° C. in an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 120 ° C. for 3 hours.

Next, 24.9 g (0.150 mol) of 2,6-bis (hydroxymethyl) -p-cresol and 249 g of PGME were mixed and stirred in another container, and the uniformly dissolved solution was prepared using a dropping funnel. The mixture was added dropwise to the bull flask in 1 hour, and the mixture was further stirred for 2 hours after the addition.

After completion of the reaction, the same treatment as in Production Example B7 was carried out to obtain a copolymer (polymer H) composed of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol in a yield of 77%. The weight average molecular weight of this polymer H determined by the standard polystyrene conversion of the GPC method was 9,900.

で表される、フェノール性水酸基の７７％をナフトキノンジアジド−４−スルホン酸エステル化した感光性ジアゾキノン化合物（東洋合成社製、（Ｃ）感光剤に該当）（Ｃ１）１５ｇ、ジシクロヘキシルチオウレア（（Ｂ）含イオウ化合物に該当）０．５ｇ、３−ｔ−ブトキシカルボニルアミノプロピルトリエトキシシラン６ｇと共に、γ−ブチロラクトン（溶媒として）１００ｇに溶解した。得られた溶液の粘度を、少量のγ−ブチロラクトンを更に加えることによって約２０ポイズ（ｐｏｉｓｅ）に調整し、ポジ型感光性樹脂組成物とした。
この組成物について、上述の方法により３５０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．４％という結果を得た。
＜実施例Ｂ１３＞
上記実施例Ｂ１２において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＦ１００ｇに変えた以外は、実施例Ｂ１２と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２５０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．５％という結果を得た。
＜実施例Ｂ１４＞
上記実施例Ｂ１２において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＧ１００ｇに変えた以外は、実施例Ｂ１２と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２２０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．７％という結果を得た。
＜実施例Ｂ１５＞
上記実施例Ｂ１２において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＨ１００ｇに変えた以外は、実施例Ｂ１２と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２２０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．６％という結果を得た。
＜比較例Ｂ１＞
実施例Ｂ１の組成に、ジシクロヘキシルチオウレアを添加しない他は、実施例Ｂ１と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ｂ１と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１４．３％であった。
＜比較例Ｂ２＞
実施例Ｂ１１の組成に、ジシクロヘキシルチオウレアを添加しない他は、実施例Ｂ１１と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ｂ１１と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１５．５％であった。
＜比較例Ｂ３＞
実施例Ｂ１２の組成に、ジシクロヘキシルチオウレアを添加しない他は、実施例Ｂ１２と同様にしてポジ型感光性樹脂組成物を調製し、実施例Ｂ１２と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１４．６％であった。
これら実施例Ｂ１〜１５、比較例Ｂ１〜３の結果を表２にまとめて示す。 <Example B1>
Negative photosensitive resin compositions were prepared using the polymers A and B by the following methods, and the prepared photosensitive resin compositions were evaluated. Polymers A50g and B50g (corresponding to (A) resin) which are polyimide precursors, dicyclohexylthiourea (corresponding to (B) sulfur-containing compound) 0.5g, 1-phenyl-1,2-propanedione-2- (O) -Ethoxycarbonyl) -oxym (denoted as "PDO" in Table 2) (corresponding to (C) photosensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g, N- [3- (triethoxysilyl) propyl] phthalamic acid Together with 1.5 g, it was dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to obtain a negative photosensitive resin composition.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.5. I got the result of%.
<Example B2>
In Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that the amount of dicyclohexylthiourea added as the component (B) was changed to 0.1 g.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 6.9. I got the result of%.
<Example B3>
In Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that the amount of dicyclohexylthiourea added as the component (B) was changed to 4 g.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 4.8. I got the result of%.
<Example B4>
A negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that benzothiazole was used instead of dicyclohexylthiourea as the component (B) in Example B1.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 7.3. I got the result of%.
<Example B5>
In Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that loadanine was used instead of dicyclohexylthiourea as the component (B).
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 7.2. I got the result of%.
<Example B6>
A negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that 2-thioxanthone was used instead of dicyclohexylthiourea as the component (B) in Example B1.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 7.3. I got the result of%.
<Example B7>
A negative photosensitive resin composition solution is prepared in the same manner as in Example B1 above, and this composition is cured at 350 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and a high temperature storage test is performed. After that, the area ratio of voids to the surface of the Cu layer was evaluated, and a result of 4.9% was obtained.
<Example B8>
In Example B1, 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer A as the resin (A), and 4 g of PDO as the component (C) was changed to 1,2-octanedione, 1- {4- (phenylthio)-, A negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that it was changed to 2.5 g of 2- (O-benzoyloxime)} (Irgacure OXE01 (manufactured by BASF, trade name)).
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.7. I got the result of%.
<Example B9>
In Example B1, 50 g of polymer A and 50 g of polymer B as the resin (A), 4 g of PDO as the component (C) in 100 g of the polymer A, 1,2-octanedione, 1- {4- (phenylthio) −2. -(O-benzoyloxime)} (Irgacure OXE01 (manufactured by BASF, trade name)) was changed to 2.5 g, and the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethisulfoxide in the same manner as in Example B1. A negative photosensitive resin composition solution was prepared.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.6. I got the result of%.
<Example B10>
In Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that 50 g of the polymer A and 50 g of the polymer B were changed to 100 g of the polymer C as the resin (A).
This composition was cured at 350 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 4.9. I got the result of%.
<Example B11>
In Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that 50 g of the polymer A and 50 g of the polymer B were changed to 100 g of the polymer D as the resin (A).
This composition was cured at 250 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.3. I got the result of%.
<Example B12>
A positive photosensitive resin composition was prepared using the polymer E by the following method, and the prepared photosensitive resin composition was evaluated. A polymer E 100 g (corresponding to the resin (A)), which is a polyoxazole precursor, is subjected to the following formula (96):

A photosensitive diazoquinone compound in which 77% of phenolic hydroxyl groups are esterified with naphthoquinone diazide-4-sulfonic acid (manufactured by Toyo Synthetic Co., Ltd., corresponding to (C) photosensitizer) (C1) 15 g, dicyclohexylthiourea ((B) ) Corresponding to the sulfur-containing compound) 0.5 g and 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane were dissolved in 100 g of γ-butyrolactone (as a solvent). The viscosity of the obtained solution was adjusted to about 20 poises by further adding a small amount of γ-butyrolactone to obtain a positive photosensitive resin composition.
This composition was cured at 350 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.4. I got the result of%.
<Example B13>
In Example B12, a positive photosensitive resin composition solution was prepared in the same manner as in Example B12, except that 100 g of polymer E was changed to 100 g of polymer F as the resin (A).
This composition was cured at 250 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.5. I got the result of%.
<Example B14>
In Example B12, a positive photosensitive resin composition solution was prepared in the same manner as in Example B12, except that 100 g of polymer E was changed to 100 g of polymer G as the resin (A).
This composition was cured at 220 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.7. I got the result of%.
<Example B15>
In Example B12, a positive photosensitive resin composition solution was prepared in the same manner as in Example B12, except that 100 g of polymer E was changed to 100 g of polymer H as the resin (A).
This composition was cured at 220 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.6. I got the result of%.
<Comparative example B1>
A negative photosensitive resin composition was prepared in the same manner as in Example B1 except that dicyclohexylthiourea was not added to the composition of Example B1, and the same evaluation as in Example B1 was performed. The evaluation result was 14.3% because the compound (B) of the present invention was not contained.
<Comparative example B2>
A negative photosensitive resin composition was prepared in the same manner as in Example B11 except that dicyclohexylthiourea was not added to the composition of Example B11, and the same evaluation as in Example B11 was performed. The evaluation result was 15.5% because the compound (B) of the present invention was not contained.
<Comparative example B3>
A positive photosensitive resin composition was prepared in the same manner as in Example B12 except that dicyclohexylthiourea was not added to the composition of Example B12, and the same evaluation as in Example B12 was performed. The evaluation result was 14.6% because the compound (B) of the present invention was not contained.
The results of Examples B1 to 15 and Comparative Examples B1 to 3 are summarized in Table 2.

Example C
<Production Example C1> ((A) Synthesis of polymer A as a polyimide precursor)
Place 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) in a 2 liter volume separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and stir at room temperature. , 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.

Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether (DADPE). A suspension of 93.0 g 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 composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer A). When the molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

The weight average molecular weight of the resin obtained in each Production Example C was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was determined.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l LiBr / NMP
Flow rate: 1 ml / min.

<Production Example C2> ((A) Synthesis of polymer B as a polyimide precursor)
In place of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) of Production Example C1, 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used. Except for the above, the reaction was carried out in the same manner as in the method described in Production Example C1 to obtain polymer B. When the molecular weight of the polymer B was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Production Example C3> ((A) Synthesis of polymer C as a polyimide precursor)
As described above, except that 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) 147.8 g was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) of Production Example C1. The reaction was carried out in the same manner as described in Production Example C1 of the above to obtain polymer C. When the molecular weight of the polymer C was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

<Production Example C4> ((A) Synthesis of polymer D as polyamide)
(Synthesis of phthalic acid compound encapsulant AIPA-MO)
5-Aminoisophthalic acid {hereinafter abbreviated as AIPA in a separable flask with a capacity of 5 liters. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50 ° C. in a water bath. To this, 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise with a dropping funnel, and the mixture was stirred as it was at 50 ° C. for about 2 hours.

Completion of the reaction (disappearance of 5-aminoisophthalic acid) is referred to as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, Add this reaction solution to 15 liters of ion-exchanged water, stir, allow to stand, wait for the crystallization and precipitation of the reaction product, separate by filtration, wash with water as appropriate, and vacuum at 40 ° C. for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate acted was obtained. The low molecular weight GPC purity of the obtained AIPA-MO was about 100%.

(Synthesis of Polymer D)
100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were put into a separable flask having a capacity of 2 liters, mixed, and cooled to 5 ° C. in an ice bath. bottom. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was added dropwise over about 20 minutes under ice-cooling, followed by 4,4'-bis (4-aminophenoxy). ) Biphenyl {Hereafter, it is referred to as BABP. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, and the mixture was stirred in an ice bath for 3 hours while maintaining the temperature below 5 ° C., and then removed from the ice bath and stirred at room temperature for 5 hours. bottom. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

A mixed solution of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was added dropwise to 5 liters of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer E). When the molecular weight of the polymer D was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 34,700.

<Production Example C5> ((A) Synthesis of polymer E as a polyoxazole precursor)
183.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 640.9 g of N, N-dimethylacetamide (DMAc), and 63.3 g of pyridine in a separable flask having a capacity of 3 liters. The mixture was mixed and stirred at room temperature (25 ° C.) to prepare a uniform solution. To this, 118.0 g of 4,4'-diphenyl ether dicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for dropping was 40 minutes, and the reaction liquid temperature was 30 ° C. at the maximum.

3 hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was left to stir for 15 hours at room temperature to carboxy 99% of all amine terminal groups of the polymer chain. It was sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic acid anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, vacuum dried, and measured by gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (polystyrene equivalent) was obtained.

The crude polybenzoxazole precursor obtained above is redissolved in γ-butyrolactone (GBL), treated with a cation exchange resin and an anion exchange resin, and the resulting solution is treated in ion exchange water. The precipitated polymer was filtered, washed with water, and vacuum-dried to obtain a purified polybenzoxazole precursor (polymer E).

<Production Example C6> ((A) Synthesis of polymer F as polyimide)
A cooling tube with a Dean-Stark trap was attached to a glass separable four-necked flask equipped with a Teflon (registered trademark) anchor-shaped stirrer. The flask was placed in a silicon oil bath and stirred while passing nitrogen gas.

2,2-bis (3-amino-4-hydroxyphenyl) propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5- (2,5-dioxotetrahydro-3-furanyl) Add 70.29 g (266 mmol) of -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone, and 60 g of toluene to room temperature. After stirring at 100 rpm for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and the silicon bath temperature was 50 ° C. while passing nitrogen gas. The mixture was heated and stirred at 100 rpm for 8 hours. Then, the silicon bath temperature was heated to 180 ° C., and the mixture was heated and stirred at 100 rpm for 2 hours. Toluene and water distillate were removed during the reaction. After the imidization reaction was completed, the temperature was returned to room temperature.

After that, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, vacuum dried, and measured by gel permeation chromatography (GPC). A crude polyimide (polymer F) having a weight average molecular weight of 23,000 (in terms of polystyrene) was obtained.

<Production Example C7> ((A) Synthesis of polymer G as phenol resin)
128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 4,4'-bis (methoxymethyl) biphenyl (hereinafter "BMMB") in a separable frassco with a capacity of 0.5 liter Dean-Stark apparatus. 121.2 g (0.5 mol), 3.9 g (0.025 mol) of diethyl sulfate, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70 ° C. to dissolve the solid substance.

The mixed solution was heated to 140 ° C. in an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 140 ° C. for 2 hours.

Next, the reaction vessel was cooled in the air, and 100 g of tetrahydrofuran was separately added thereto and stirred. The above reaction diluent was added dropwise to 4 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, washed with water as appropriate, dehydrated, and then vacuum-dried. A polymer (polymer G) was obtained in a yield of 70%. The weight average molecular weight of this polymer G determined by the standard polystyrene conversion of the GPC method was 21,000.

<Production Example C8> ((A) Synthesis of polymer H as phenol resin)
A separable flask with a capacity of 1.0 L with a Dean-Stark apparatus was replaced with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, and p-toluenesulfon. 3.81 g (0.02 mol) of acid and 116 g of propylene glycol monomethyl ether (hereinafter, also referred to as PGME) were mixed and stirred at 50 ° C. to dissolve the solid substance.

The mixed solution was heated to 120 ° C. in an oil bath, and the generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 120 ° C. for 3 hours.

Next, 24.9 g (0.150 mol) of 2,6-bis (hydroxymethyl) -p-cresol and 249 g of PGME were mixed and stirred in another container, and the uniformly dissolved solution was prepared using a dropping funnel. The mixture was added dropwise to the bull flask in 1 hour, and the mixture was further stirred for 2 hours after the addition.

After completion of the reaction, the same treatment as in Production Example C7 was carried out to obtain a copolymer (polymer H) composed of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol in a yield of 77%. The weight average molecular weight of this polymer H determined by the standard polystyrene conversion of the GPC method was 9,900.

で表される、フェノール性水酸基の７７％をナフトキノンジアジド−４−スルホン酸エステル化した感光性ジアゾキノン化合物（東洋合成社製、（Ｃ）感光剤に該当）（Ｃ１）１５ｇ、ブチル尿素（（Ｂ−１）化合物に該当）１ｇ、３−ｔ−ブトキシカルボニルアミノプロピルトリエトキシシラン６ｇと共に、γ−ブチロラクトン（溶媒として）１００ｇに溶解した。得られた溶液の粘度を、少量のγ−ブチロラクトンを更に加えることによって約２０ポイズ（ｐｏｉｓｅ）に調整し、ポジ型感光性樹脂組成物とした。
この組成物について、上述の方法により３５０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．６％という結果を得た。
＜実施例Ｃ１２＞
上記実施例Ｃ１１において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＦ１００ｇに変えた以外は、実施例Ｃ１１と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２５０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．９％という結果を得た。
＜実施例Ｃ１３＞
上記実施例Ｃ１１において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＧ１００ｇに変えた以外は、実施例Ｃ１１と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２２０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．５％という結果を得た。
＜実施例Ｃ１４＞
上記実施例Ｃ１１において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＨ１００ｇに変えた以外は、実施例Ｃ１３と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２２０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．４％という結果を得た。
＜比較例Ｃ１＞
実施例Ｃ１の組成に、ブチル尿素を添加しない他は、実施例Ｃ１と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ｃ１と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１４．３％であった。
＜比較例Ｃ２＞
実施例Ｃ１２の組成に、ブチル尿素を添加しない他は、実施例Ｃ１２と同様にしてポジ型感光性樹脂組成物を調製し、実施例Ｃ１２と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１５．５％であった。
＜比較例Ｃ３＞
実施例Ｃ１３の組成に、ブチル尿素を添加しない他は、実施例Ｃ１３と同様にしてポジ型感光性樹脂組成物を調製し、実施例Ｃ１１と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１５．７％であった。 <Example C1>
Negative photosensitive resin compositions were prepared using the polymers A and B by the following methods, and the prepared photosensitive resin compositions were evaluated. Polymers A50g and B50g (corresponding to (A) resin) which are polyimide precursors, 1g of butylurea (corresponding to (B-1) compound), 1-phenyl-1,2-propanedione-2- (O-ethoxy) Carbonyl) -oxime (denoted as "PDO" in Table 3) (corresponding to (C) photosensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g, N- [3- (triethoxysilyl) propyl] phthalamic acid 1. Together with 5 g, it was dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to obtain a negative photosensitive resin composition.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.5. I got the result of%.
<Example C2>
In Example C1, a negative photosensitive resin composition solution was prepared in the same manner as in Example C1 except that the amount of butylurea added as the component (B) was changed to 0.1 g.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 6.8. I got the result of%.
<Example C3>
In Example C1, a negative photosensitive resin composition solution was prepared in the same manner as in Example C1 except that the amount of butylurea added as the component (B) was changed to 5 g.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 4.8. I got the result of%.
<Example C4>
Negative photosensitive resin composition in the same manner as in Example C1 except that tetraethylene glycol (corresponding to the compound (B-2)) was used instead of butylurea as the component (B) in Example C1. The solution was prepared.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 6.2. I got the result of%.
<Example C5>
In Example C1, the negative was the same as in Example C1 except that bis (2-methoxyethyl) adipate (corresponding to the (B-3) compound) was used instead of butylurea as the component (B). A type photosensitive resin composition solution was prepared.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 6.3. I got the result of%.
<Example C6>
A negative photosensitive resin composition solution is prepared in the same manner as in Example C1 above, and this composition is cured at 350 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and a high temperature storage test is performed. After that, the area ratio of the voids to the surface of the Cu layer was evaluated, and a result of 4.7% was obtained.
<Example C7>
In Example C1, 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer A as the resin (A), and 4 g of PDO as the component (C) was changed to 1,2-octanedione, 1- {4- (phenylthio)-, A negative photosensitive resin composition solution was prepared in the same manner as in Example C1 except that it was changed to 2.5 g of 2- (O-benzoyloxime)} (Irgacure OXE01 (manufactured by BASF, trade name)).
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.4. I got the result of%.
<Example C8>
In Example C1, 50 g of polymer A and 50 g of polymer B as the resin (A), 4 g of PDO as the component (C) in 100 g of the polymer A, 1,2-octanedione, 1- {4- (phenylthio) −2. -(O-benzoyloxime)} (Irgacure OXE01 (manufactured by BASF, trade name)) was changed to 2.5 g, and the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethisulfoxide in the same manner as in Example C1. A negative photosensitive resin composition solution was prepared.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.5. I got the result of%.
<Example C9>
In Example C1, a negative photosensitive resin composition solution was prepared in the same manner as in Example C1 except that 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer C as the resin (A).
This composition was cured at 350 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 4.7. I got the result of%.
<Example C10>
In Example C1, a negative photosensitive resin composition solution was prepared in the same manner as in Example C1 except that 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer D as the resin (A).
This composition was cured at 250 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.8. I got the result of%.
<Example C11>
A positive photosensitive resin composition was prepared using the polymer E by the following method, and the prepared photosensitive resin composition was evaluated. A polymer E 100 g (corresponding to the resin (A)), which is a polyoxazole precursor, is subjected to the following formula (96):

Photosensitive diazoquinone compound in which 77% of phenolic hydroxyl groups represented by naphthoquinone diazide-4-sulfonic acid esterification (manufactured by Toyo Synthetic Co., Ltd., corresponds to (C) photosensitizer) (C1) 15 g, butylurea ((B) -1) Corresponding to the compound) It was dissolved in 100 g of γ-butyrolactone (as a solvent) together with 1 g and 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane. The viscosity of the obtained solution was adjusted to about 20 poises by further adding a small amount of γ-butyrolactone to obtain a positive photosensitive resin composition.
This composition was cured at 350 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.6. I got the result of%.
<Example C12>
In Example C11, a positive photosensitive resin composition solution was prepared in the same manner as in Example C11 except that 100 g of polymer E was changed to 100 g of polymer F as the resin (A).
This composition was cured at 250 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.9. I got the result of%.
<Example C13>
In Example C11, a positive photosensitive resin composition solution was prepared in the same manner as in Example C11 except that 100 g of polymer E was changed to 100 g of polymer G as the resin (A).
This composition was cured at 220 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.5. I got the result of%.
<Example C14>
In Example C11, a positive photosensitive resin composition solution was prepared in the same manner as in Example C13, except that 100 g of polymer E was changed to 100 g of polymer H as the resin (A).
This composition was cured at 220 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.4. I got the result of%.
<Comparative example C1>
A negative photosensitive resin composition was prepared in the same manner as in Example C1 except that butylurea was not added to the composition of Example C1, and the same evaluation as in Example C1 was performed. The evaluation result was 14.3% because the compound (B) of the present invention was not contained.
<Comparative example C2>
A positive photosensitive resin composition was prepared in the same manner as in Example C12 except that butylurea was not added to the composition of Example C12, and the same evaluation as in Example C12 was performed. The evaluation result was 15.5% because the compound (B) of the present invention was not contained.
<Comparative example C3>
A positive photosensitive resin composition was prepared in the same manner as in Example C13 except that butylurea was not added to the composition of Example C13, and the same evaluation as in Example C11 was performed. The evaluation result was 15.7% because the compound (B) of the present invention was not contained.

Example D
<Production Example D1> ((A) Synthesis of polymer (A) -1 as a polyimide precursor)
Place 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) in a 2 liter volume separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and stir at room temperature. , 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.

Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether (DADPE). A suspension of 93.0 g 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 composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer (A) -1). When the molecular weight of the polymer (A) -1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

The weight average molecular weight of the resin obtained in each Production Example D was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was determined.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l LiBr / NMP
Flow rate: 1 ml / min.

<Production Example D2> ((A) Synthesis of polymer (A) -2 as a polyimide precursor)
In place of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) of Production Example D1, 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used. Except for the above, the reaction was carried out in the same manner as described in Production Example D1 to obtain polymer (A) -2. When the molecular weight of the polymer (A) -2 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Production Example D3> ((A) Synthesis of polymer (A) -3 as a polyimide precursor)
As described above, except that 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) 147.8 g was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) of Production Example D1. The reaction was carried out in the same manner as described in Production Example D1 to obtain polymer (A) -3. When the molecular weight of the polymer (A) -3 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

<Production Example D4> ((A) Synthesis of polymer (A) -4 as polyamide)
(Synthesis of phthalic acid compound encapsulant AIPA-MO)
5-Aminoisophthalic acid {hereinafter abbreviated as AIPA in a separable flask with a capacity of 5 liters. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50 ° C. in a water bath. To this, 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise with a dropping funnel, and the mixture was stirred as it was at 50 ° C. for about 2 hours.

Completion of the reaction (disappearance of 5-aminoisophthalic acid) is referred to as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, Add this reaction solution to 15 liters of ion-exchanged water, stir, allow to stand, wait for the crystallization and precipitation of the reaction product, separate by filtration, wash with water as appropriate, and vacuum at 40 ° C. for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate acted was obtained. The low molecular weight GPC purity of the obtained AIPA-MO was about 100%.

(Synthesis of Polymer (A) -4)
100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were put into a separable flask having a capacity of 2 liters, mixed, and cooled to 5 ° C. in an ice bath. bottom. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was added dropwise over about 20 minutes under ice-cooling, followed by 4,4'-bis (4-aminophenoxy). ) Biphenyl {Hereafter, it is referred to as BABP. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, and the mixture was stirred in an ice bath for 3 hours while maintaining the temperature below 5 ° C., and then removed from the ice bath and stirred at room temperature for 5 hours. bottom. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

A mixed solution of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was added dropwise to 5 liters of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer (A) -4). When the molecular weight of the polymer (A) -4 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 34,700.

<Production Example D5> (Synthesis of polymer (A) -5 as (A) polyoxazole precursor)
183.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 640.9 g of N, N-dimethylacetamide (DMAc), and 63.3 g of pyridine in a separable flask having a capacity of 3 liters. The mixture was mixed and stirred at room temperature (25 ° C.) to prepare a uniform solution. To this, 118.0 g of 4,4'-diphenyl ether dicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for dropping was 40 minutes, and the reaction liquid temperature was 30 ° C. at the maximum.

3 hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was left to stir for 15 hours at room temperature to carboxy 99% of all amine terminal groups of the polymer chain. It was sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic acid anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, vacuum dried, and measured by gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (polystyrene equivalent) was obtained.

The crude polybenzoxazole precursor obtained above is redissolved in γ-butyrolactone (GBL), treated with a cation exchange resin and an anion exchange resin, and the resulting solution is treated in ion exchange water. The precipitated polymer was filtered, washed with water, and vacuum-dried to obtain a purified polybenzoxazole precursor (polymer (A) -5).

<Production Example D6> ((A) Synthesis of polymer (A) -6 as polyimide)
A cooling tube with a Dean-Stark trap was attached to a glass separable four-necked flask equipped with a Teflon (registered trademark) anchor-shaped stirrer. The flask was placed in a silicon oil bath and stirred while passing nitrogen gas.

2,2-bis (3-amino-4-hydroxyphenyl) propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5- (2,5-dioxotetrahydro-3-furanyl) Add 70.29 g (266 mmol) of -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone, and 60 g of toluene to room temperature. After stirring at 100 rpm for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and the silicon bath temperature was 50 ° C. while passing nitrogen gas. The mixture was heated and stirred at 100 rpm for 8 hours. Then, the silicon bath temperature was heated to 180 ° C., and the mixture was heated and stirred at 100 rpm for 2 hours. Toluene and water distillate were removed during the reaction. After the imidization reaction was completed, the temperature was returned to room temperature.

After that, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, vacuum dried, and measured by gel permeation chromatography (GPC). A crude polyimide (polymer (A) -6) having a weight average molecular weight of 23,000 (in terms of polystyrene) was obtained.

で表される、フェノール性水酸基の７７％をナフトキノンジアジド−４−スルホン酸エステル化した感光性ジアゾキノン化合物（東洋合成社製、（Ｃ）成分に該当）（Ｃ１）１５ｇ、γ−ブチロラクトン（溶媒として）１００ｇに溶解した。得られた溶液の粘度を、少量のγ−ブチロラクトンを更に加えることによって約２０ポイズ（ｐｏｉｓｅ）に調整し、ポジ型感光性樹脂組成物とした。
この組成物について、上述の方法により３５０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、６．９％という結果を得た。また、得られたワニスの保存安定性試験後の粘度変化率は１０％以内であった。
＜実施例Ｄ１７＞
上記実施例Ｄ１６において、（Ａ）樹脂として、ポリマー（Ａ）−５、１００ｇをポリマー（Ａ）−６、１００ｇに変えたこと以外は、実施例Ｄ１２と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２５０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、６．０％という結果を得た。また、得られたワニスの保存安定性試験後の粘度変化率は１０％以内であった。
＜比較例Ｄ１＞
実施例Ｄ１の組成に、（Ｂ）−１成分を添加しない他は、実施例Ｄ１と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ｄ１と同様の評価を行なった。評価結果は、本発明の（Ｂ）成分を含まないため１５．２％であった。また、得られたワニスの保存安定性試験後の粘度変化率は１０％以内であった。
＜比較例Ｄ２＞
実施例Ｄ１５の組成に、（Ｂ）−１成分を添加しない他は、実施例Ｄ１５と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ｄ１５と同様の評価を行なった。評価結果は、本発明の（Ｂ）成分を含まないため１４．３％であった。また、得られたワニスの保存安定性試験後の粘度変化率は１０％以内であった。
＜比較例Ｄ３＞
実施例Ｄ１３の組成に、（Ｂ）−１成分を添加しない他は、実施例Ｄ１３と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ｄ１３と同様の評価を行なった。評価結果は、本発明の（Ｂ）成分を含まないため１５．７％であった。また、得られたワニスの保存安定性試験後の粘度変化率は１０％以内であった。
＜比較例Ｄ４＞
実施例Ｄ１７の組成に、（Ｂ）−１成分を添加しない他は、実施例Ｄ１７と同様にしてポジ型感光性樹脂組成物を調製し、実施例Ｄ１７と同様の評価を行なった。評価結果は、本発明の（Ｂ）成分を含まないため１６．３％であった。また、得られたワニスの保存安定性試験後の粘度変化率は１０％以内であった。
＜比較例Ｄ５＞
実施例Ｄ１の組成に、（Ｂ）−１成分の添加量を２５ｇに変更したこと以外は、実施例Ｄ１と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ｄ１と同様の評価を行なった。評価結果は、７．２％であった。また、得られたワニスの保存安定性試験後の粘度変化率は１０％以上であった。
これら実施例Ｄ１〜１７、比較例Ｄ１〜５の結果を表４にまとめて示す。 <Example D1>
A negative photosensitive resin composition was prepared by the following method using the polymers (A) -1 and (A) -2, and the photosensitive resin composition was evaluated. 50 g of polymer (A) -1, which is a polyimide precursor, and 50 g of (A) -2 (corresponding to (A) resin) were added to N-phenylbenzylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd., (B) -1. Applicable) 3 g, 1-Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxym (referred to as "PDO" in Table 4) ((C) Corresponding to photosensitizer) 4 g, tetraethylene It was dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate together with 8 g of glycol dimethacrylate and 1.5 g of N- [3- (triethoxysilyl) propyl] phthalamic acid. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to obtain a negative photosensitive resin composition.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 4.5. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D2>
Negative photosensitive resin in the same manner as in Example D1 except that the component (B) was changed to N, N'-diphenylethane-1,2-diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) in Example D1. A composition solution was prepared.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 4.2. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D3>
A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the component (B) was changed to tert-butylphenylcarbamate (manufactured by Tokyo Chemical Industry Co., Ltd.) in Example D1.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.1. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D4>
Negative photosensitive resin composition solution in the same manner as in Example D1 except that the component (B) was changed to tert-butyl (3-hydroxyphenyl) carbamate (manufactured by Tokyo Chemical Industry Co., Ltd.) in Example D1. Was prepared.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.8. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D5>
Except for changing the component (B) to 2-hydroxy-N- (1H-1,2,4-triazole-3-yl) benzamide (manufactured by ADEKA Corporation, ADEKA STAB CDA-1) in Example D1 above. A negative photosensitive resin composition solution was prepared in the same manner as in Example D1.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 4.8. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D6>
In Example D1 above, the component (B) is 2- (2H-benzo [d] [1,2,3] triazole-2-yl) -4- (2,4,4-trimethylpentane-2-yl). A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the solution was changed to phenol (Adeka Stub LA-29 manufactured by ADEKA Corporation).
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 4.2. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D7>
In Example D1 above, except that the component (B) was changed to (4-((1H-1,2,4-triazole-1-yl) methyl) phenyl) methanol (manufactured by Tokyo Chemical Industry Co., Ltd.). A negative photosensitive resin composition solution was prepared in the same manner as in Example D1.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 6.1. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D8>
In Example D1, a negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the amount of component (B) -1 added was changed to 1 g.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 8.5. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D9>
In Example D1, a negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the amount of component (B) -1 added was changed to 6 g.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 4.9. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D10>
In Example D1, a negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the amount of component (B) -1 added was changed to 10 g.
This composition was cured at 230 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 5.0. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D11>
A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the cure temperature was changed from 230 ° C. to 350 ° C. in Example D1.
A cured relief pattern was prepared on the Cu layer for this composition, and after conducting a high-temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated, and a result of 6.1% was obtained. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D12>
In Example D1, the polymer (A) -1,50 g and the polymer (A) -2,50 g as the resin (A), the polymer (A) -1,100 g, and the component (C) from PDO 1, Except for changing to 2.5 g of 2-octanedione, 1- {4- (phenylthio)-, 2- (O-benzoyloxime)} (Irgacure OXE01 (manufactured by BASF, trade name)), with Example D1. A negative photosensitive resin composition solution was prepared in the same manner.
A cured relief pattern was prepared on the Cu layer for this composition, and after conducting a high-temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated, and a result of 5.8% was obtained. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D13>
A negative photosensitive resin composition solution was prepared in the same manner as in Example D12, except that the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide in Example D12.
A cured relief pattern was prepared on the Cu layer for this composition, and after conducting a high-temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated, and a result of 5.4% was obtained. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D14>
In Example D1, the polymer (A) -1,50 g and the polymer (A) -2,50 g were changed to the polymer (A) -3,100 g as the resin (A), and the cure temperature was changed from 230 ° C. to 350 ° C. A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the solution was changed to.
A cured relief pattern was prepared on the Cu layer for this composition, and after conducting a high-temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated, and a result of 7.2% was obtained. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D15>
In Example D1, the resin (A) is different from that of Example D1 except that the polymer (A) -1,50 g and the polymer (A) -2,50 g are changed to the polymer (A) -4,100 g. A negative photosensitive resin composition solution was prepared in the same manner.
A cured relief pattern was prepared on the Cu layer for this composition, and after conducting a high-temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated, and a result of 4.9% was obtained. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D16>
A positive photosensitive resin composition was prepared using the polymer (A) -5 by the following method, and the prepared photosensitive resin composition was evaluated. A polymer (A) -5, 100 g (corresponding to the resin (A)), which is a polyoxazole precursor, is applied to the following formula (96):

Photosensitive diazoquinone compound in which 77% of phenolic hydroxyl groups represented by naphthoquinone diazide-4-sulfonic acid esterification (manufactured by Toyo Synthetic Co., Ltd., corresponding to component (C)) (C1) 15 g, γ-butyrolactone (as a solvent) ) Dissolved in 100 g. The viscosity of the obtained solution was adjusted to about 20 poises by further adding a small amount of γ-butyrolactone to obtain a positive photosensitive resin composition.
This composition was cured at 350 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 6.9. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D17>
In Example D16, the positive photosensitive resin composition is the same as in Example D12, except that the polymer (A) -5, 100 g is changed to the polymer (A) -6, 100 g as the resin (A). The solution was prepared.
This composition was cured at 250 ° C. by the above method to prepare a cured relief pattern on the Cu layer, and after conducting a high temperature storage test, the area ratio of voids to the surface of the Cu layer was evaluated and 6.0. I got the result of%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Comparative example D1>
A negative photosensitive resin composition was prepared in the same manner as in Example D1 except that the component (B) -1 was not added to the composition of Example D1, and the same evaluation as in Example D1 was performed. The evaluation result was 15.2% because the component (B) of the present invention was not contained. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Comparative example D2>
A negative photosensitive resin composition was prepared in the same manner as in Example D15 except that the component (B) -1 was not added to the composition of Example D15, and the same evaluation as in Example D15 was performed. The evaluation result was 14.3% because the component (B) of the present invention was not contained. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Comparative example D3>
A negative photosensitive resin composition was prepared in the same manner as in Example D13 except that the component (B) -1 was not added to the composition of Example D13, and the same evaluation as in Example D13 was performed. The evaluation result was 15.7% because the component (B) of the present invention was not contained. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Comparative example D4>
A positive photosensitive resin composition was prepared in the same manner as in Example D17 except that the component (B) -1 was not added to the composition of Example D17, and the same evaluation as in Example D17 was performed. The evaluation result was 16.3% because the component (B) of the present invention was not contained. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Comparative example D5>
A negative photosensitive resin composition was prepared in the same manner as in Example D1 except that the amount of the component (B) -1 added to the composition of Example D1 was changed to 25 g, and the same evaluation as in Example D1 was made. Was done. The evaluation result was 7.2%. The viscosity change rate of the obtained varnish after the storage stability test was 10% or more.
The results of Examples D1 to 17 and Comparative Examples D1 to 5 are summarized in Table 4.

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

Claims (6)

(A) At least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and novolak, polyhydroxystyrene and phenol resin. 100 parts by mass of resin,
(B) 0.01 to 10 parts by mass of the cyclic compound having two or more carbonyl groups, based on 100 parts by mass of the resin (A);
(C) 1 to 50 parts by mass of the photosensitizer based on 100 parts by mass of the resin (A).
Including
And the carbon atom of the carbonyl group to form a ring-like structure, the cyclic compound is 5-membered ring compound, 6-membered ring compounds, fused ring compounds of the 5-membered ring and a 5-membered ring, 5-membered ring and 6-membered It is at least one selected from the group consisting of a fused ring compound with a ring and a fused ring compound with a 6-membered ring and a 6-membered ring.
The 5-membered ring compound is at least one selected from the group consisting of hydantoin, allantoin, and paravanic acid.
The 6-membered ring compound is selected from the group consisting of barbitulic acid, 1,3-dimethylbarbitulic acid, 1,3-dicyclohexylbarbituric acid, uramil, alloxan, cyanuric acid, and trisisocyanurate (2-hydroxyethyl). Is at least one kind of
The fused ring compound of the 5-membered ring and the 5-membered ring is glycoluril.
The condensed ring compound of the 5-membered ring and the 6-membered ring is 8-bromo-3-methylxanthine, theobromine, 7- (2-chloroethyl) theophylline, caffeine, and the following general formula (60):

{In the formula, Rs3, Rs4 and Rs5 are independently substituted with a hydrogen atom, a halogen atom, a hydroxyl group or an aromatic group, an amino group having 1 to 6 carbon atoms, a hydroxyalkyl group or a carbon number of carbon atoms. It is an alkyl group or an aromatic group of 1 to 10. }
Compound represented by, the following general formula (61):

{In the formula, Rs6, Rs7 and Rs8 are independently substituted with a hydrogen atom, a halogen atom, a hydroxyl group or an aromatic group, an amino group having 1 to 6 carbon atoms, a hydroxyalkyl group or a carbon number of carbon atoms. It is an alkyl group or an aromatic group of 1 to 10. }
The compound represented by, and the following general formula (62):

{In the formula, Rs9, Rs10, Rs11 and Rs12 are independently substituted with a hydrogen atom, a halogen atom, a hydroxyl group or an aromatic group, an amino group having 1 to 6 carbon atoms, a hydroxyalkyl group or a hydroxyalkyl group. It is an alkyl group or an aromatic group having 1 to 10 carbon atoms. }
At least one selected from the group consisting of compounds represented by
The condensed ring compound of the 6-membered ring and the 6-membered ring includes 7,8-dimethylaloxazine, 1,4-dihydro-6-methylquinoxaline-2,3-dione, and the following general formula (63):

{In the formula, Rs13, Rs14, Rs15 and Rs16 are independently substituted with a hydrogen atom, a halogen atom, a hydroxyl group or an aromatic group, an amino group having 1 to 6 carbon atoms, a hydroxyalkyl group or a hydroxyalkyl group. It is an alkyl group or an aromatic group having 1 to 10 carbon atoms. }
At least one selected from the group consisting of compounds represented by ,
Photosensitive resin composition. The resin (A) contains a polyimide precursor containing the following general formula (1), a polyamide containing the following general formula (4), a polyoxazole precursor containing the following general formula (5), and the following general formula (6). The photosensitive resin composition according to claim 1, which is at least one selected from the group consisting of polyimide, novolak, polyhydroxystyrene, and a phenol resin containing the following general formula (7).
The following general formula (1) is

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of _{2 to 150, and R 1} and R 2 are independent of each other. In addition, a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or the following general formula (2):

(In the formula, R ₃ , R ₄ and R ₅ are independently hydrogen atoms or organic groups having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10). It is a monovalent organic group or a saturated aliphatic group having 1 to 4 carbon atoms, or the following general formula (3):

(In the formula, R ₆ , R ₇ and R ₈ are independently hydrogen atoms or organic groups having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10). It is a monovalent ammonium ion. }, A polyamic acid, a polyamic acid ester, or a polyamic acid salt, which is a polyimide precursor represented by.
The following general formula (4) is

{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, and Y ₂ is a divalent organic group having 6 to 35 carbon atoms and has the same structure or a plurality of carbon atoms. R ₉ is an organic group having at least one radically polymerizable unsaturated group having 3 to 20 carbon atoms, and n ₂ is an integer of 1 to 1000. }
It is a polyamide having a structure represented by
The following general formula (5) is

{In the formula, Y ₃ is a tetravalent organic group having a carbon atom, and Y ₄ , X ₃ and X ₄ are divalent organic groups having two or more carbon atoms independently. n ₃ is an integer from 1 to 1000, n ₄ is an integer of _{0~500, n 3 / (n 3} + n 4)> 0.5, and n ₃ containing X ₃ and Y ₃ The sequence order of the dihydroxydiamide units and n _{4 diamide units including X 4} and Y _{4 does not matter.} }
It is a polyhydroxyamide which is a polyoxazole precursor having a structure represented by.
The following general formula (6) is

{Wherein, X ₅ is a 4-14 monovalent organic group, Y ₅ is a 2-12 monovalent organic group, R ₁₀ and R ₁₁ are each independently a phenolic hydroxyl group, a sulfonic acid group Alternatively, it represents an organic group having at least one group selected from thiol groups, n ₅ is an integer of _{3 to} 200, and m 3 and m ₄ are integers of 0 to 10. }
It is a polyimide having a structure represented by, and
The following general formula (7) is

{In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦ (a + b) ≦ 4, and R ₁₂ is a monovalent organic having 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of groups, halogen atoms, nitro groups and cyano groups, where b is 2 or 3, the plurality of R _12s may be the same or different from each other. Well, X is a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, the following general formula (8):

It is selected from the group consisting of a divalent alkylene oxide group represented by (in the formula, p is an integer of 1 to 10) and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. Represents a divalent organic group. } Is a phenol resin. The photosensitive resin composition contains a phenol resin having a repeating unit represented by the general formula (7), and X in the general formula (7) is the following general formula (9):

{In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently replaced with a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atom with a fluorine atom. has been a becomes a monovalent aliphatic group having 1 to 10 carbon atoms, n ₆ is an integer of 0 to 4, R ₁₇ where n ₆ is an integer of 1 to 4 include a halogen atom, a hydroxyl group Or, it is a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ is a hydroxyl group, and _{a plurality of R 17s when n 6} is an integer of 2 to 4 are the same as or different from each other. May be good. }, And the following general formula (10):

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are each independently replaced with a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atom with a fluorine atom. It represents a monovalent aliphatic group having 1 to 10 carbon atoms, and W is a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, or a fluorine atom. Aliphatic group having 3 to 20 carbon atoms, the following general formula (8):

A divalent alkylene oxide group represented by (in the formula, p is an integer of 1 to 10), and the following formula (11):

It is a divalent group selected from the group consisting of divalent groups represented by. } The photosensitive resin composition according to claim 2 , which is a divalent organic group selected from the group consisting of divalent groups represented by. (1) A step of forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of claims 1 to 3 on the substrate.
(2) The step of exposing the photosensitive resin layer and
(3) A step of developing the photosensitive resin layer after the exposure to form a relief pattern, and
(4) A method for producing a cured relief pattern, which comprises a step of forming a cured relief pattern by heat-treating the relief pattern. The method of claim 4 , wherein the substrate is made of copper or a copper alloy. A semiconductor device including a cured relief pattern obtained by the manufacturing method according to claim 4 or 5.