JP2017194677A - Photosensitive resin composition, method for producing cured relief pattern and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that gives a resin layer having high adhesion with no voids occurring at an interface of a Cu layer in contact with a cured photosensitive resin layer, after a high temperature storage test, and a method of forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern.SOLUTION: A photosensitive resin composition gives a cured film with the occurrence of voids prevented at an interface in contact with a Cu layer, after a high temperature storage test, by containing a cyclic compound having a carbonyl group in a photosensitive resin composition of a specific structure.SELECTED DRAWING: None

Description

  The present invention relates to, for example, an insulating material for an electronic component, and 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 same. And a semiconductor device.

  Conventionally, polyimide resin, polybenzoxazole resin, phenol resin, etc., which have excellent heat resistance, electrical characteristics and mechanical characteristics, are used for insulating materials for electronic parts and passivation films, surface protective films, interlayer insulating films for semiconductor devices, etc. 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 the composition, exposure, development, and thermal imidization treatment by curing. Can be formed. Such a photosensitive polyimide precursor composition has a feature that the process can be significantly shortened as compared with a conventional non-photosensitive polyimide material.

  Incidentally, a semiconductor device (hereinafter, also referred to as “element”) is mounted on a printed circuit board by various methods in accordance with purposes. Conventional devices are generally manufactured by a wire bonding method in which a thin wire is connected from an external terminal (pad) of the device to a lead frame. However, as the speed of the device has increased and the operating frequency has reached GHz, the difference in the wiring length of each terminal in mounting has come to affect the operation of the device. For this reason, when mounting elements for high-end applications, it is necessary to accurately control the length of the mounting wiring, and it has become difficult to satisfy the requirements with wire bonding.

  Therefore, flip chip mounting has been proposed in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is flipped over and mounted directly on a printed circuit board. (For example, refer to Patent Document 1). With this flip-chip mounting, the wiring distance can be controlled accurately, so it is used for high-end devices that handle high-speed signals, or mobile phones due to the small mounting size, and the demand is rapidly expanding. . When materials such as polyimide, polybenzoxazole, and phenol resin are used for flip chip mounting, a metal wiring layer forming step is performed after the pattern of the resin layer is formed. The metal wiring layer is usually formed by plasma etching the resin layer surface to roughen the surface, and then forming a metal layer to be a seed layer for plating with a thickness of 1 μm or less, and then using the metal layer as an electrode. It is formed by electrolytic plating. At this time, in general, Ti is used as a metal to be a seed layer, and Cu is used as a metal of a 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 air is stored at a high temperature of 125 ° C. or higher for 100 hours or more, and a voltage is applied to the wiring while applying a voltage at about 125 ° C. in air. A high-temperature operation test for confirming operation under storage for 100 hours or more, a temperature cycle test in which a low temperature state of about −65 to −40 ° C. and a high temperature state of about 125 to 150 ° C. are cycled in air, 85 High-temperature and high-humidity storage test that is stored in a steam atmosphere at a temperature of 85 ° C or higher and a humidity of 85% or higher, and a high-temperature and high-humidity bias test that is performed while applying voltage to the wiring by constructing wiring. And a solder reflow test in which the solder reflow furnace is passed a plurality of times.

  However, conventionally, in the high temperature storage test among the above reliability tests, there has been a problem that after the test, voids are generated at the interface of the re-wiring Cu layer in contact with the resin layer. When voids are generated at the interface between the Cu layer and the resin layer, the adhesion between the two layers decreases.

JP 2001-338947 A

  The present invention has been devised in view of such a conventional situation, and after a high temperature storage test, no void is generated at the interface between the Cu layer and the cured photosensitive resin layer. An object of the present invention is to provide a photosensitive resin composition from which a resin layer having high adhesion 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. And

  The inventors of the present invention can obtain a photosensitive resin composition that gives a cured film excellent in discoloration suppression even on copper or a copper alloy by incorporating a cyclic compound having a carbonyl group into the photosensitive resin composition. The headline and the present invention were completed. 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 novolak, polyhydroxystyrene and phenol resin 100 parts by mass of at least one resin,
(B) a cyclic compound having two or more carbonyl groups, wherein the carbonyl group is directly bonded to the cyclic structure, and in the case of a monocyclic compound, 1/3 or more of the atoms forming the ring structure are N atoms In the case of a condensed ring compound, at least one compound selected from the group consisting of compounds in which 1/3 or more of the atoms forming the ring structure having the carbonyl group is an N atom is used as the (A) resin. 0.01 to 10 parts by weight based on 100 parts by weight; and
(C) 1 to 50 parts by mass of the photosensitive agent based on 100 parts by mass of the resin (A),
A photosensitive resin composition comprising:
[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), the following general formula (6) ), And a photosensitive resin composition according to [1], which is at least one selected from the group consisting of novolak, polyhydroxystyrene, and a phenol resin containing the following general formula (7).
The following general formula (1) is

{Wherein 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 each independently And a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or the following general formula (2):

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

(Wherein R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group 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 a 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 them. R ₉ is an organic group having at least one radical-polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n ₂ is an integer of 1 to 1000. }
A polyamide having a structure represented by:
The following general formula (5)

{Wherein Y ₃ is a tetravalent organic group having a carbon atom, and Y ₄ , X ₃ and X ₄ are each independently a divalent organic group having 2 or more carbon atoms, 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 arrangement order of n dihydroxy diamide units and n ₄ diamide units including X ₄ and Y ₄ is not limited. }
A polyhydroxyamide which is a polyoxazole precursor having a structure represented by:
The following general formula (6)

{In the formula, X ₅ is a tetravalent to tetravalent organic group, Y ₅ is a divalent to divalent organic group, and R ₁₀ and R ₁₁ are each independently a phenolic hydroxyl group or a sulfonic acid group. or it represents at least one having organic groups a group selected from a thiol group, n ₅ is an integer from 3 to 200, and m ₃ and m ₄ represents an integer of 0. }
A polyimide having a structure represented by:
The following general formula (7) is

{Wherein, 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 a group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, the plurality of R ₁₂ 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, and the following general formula (8):

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

{Wherein R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are substituted with fluorine atoms. 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 a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ is a hydroxyl group, and a plurality of R _{17 s} when n ₆ is an integer of 2 to 4 may be the same or different from each other. Also good. } And the following general formula (10):

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms substituted with fluorine atoms. 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 fluorine atom, or a fluorine atom. A C3-C20 alicyclic group, the following general formula (8):

(Wherein p is an integer of 1 to 10) and the following formula (11):

A divalent group selected from the group consisting of divalent groups represented by the formula: } 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) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a step of forming a cured relief pattern by heat-treating the relief pattern.
[5] The method according to [4], wherein the substrate is made 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, no voids are generated at the interface between the Cu layer and the polyimide layer after the high temperature storage test, and the adhesion is high. A photosensitive resin composition from which a photosensitive resin is obtained, a method for forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern can be provided.

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

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

(A) Resin (A) Resin used for this invention is demonstrated. The resin (A) of the present invention is composed of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and novolak, 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 preferably 80% by mass or more. Moreover, other resin may be included as needed.

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

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

  Photosensitive resins include polyamic acids, polyamic acid esters, polyamic acid salts, polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, and novolaks, phenolic resins containing polyhydroxystyrene, after heat treatment Are excellent in heat resistance and mechanical properties, polyamic acid, polyamic acid ester, polyamic acid salt, polyamide, polyhydroxyamide, polyimide and phenol resin are preferably used. These photosensitive resins can be selected according to the desired application, such as whether to prepare a negative or positive photosensitive resin composition together with the later-described (C) photosensitive agent.

｛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 (A) resin from the viewpoints of heat resistance and photosensitive properties is the general formula (1):

{Wherein 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 each independently , A hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, or the general formula (2):

(Wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group 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. } A monovalent organic group represented by
The following general formula (3):

(Wherein R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group 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 polyimide precursor is converted to polyimide by subjecting it to a cyclization treatment (for example, 200 ° C. or higher). The polyimide precursor is suitable for a negative photosensitive resin composition.

｛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 general formula (1), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably, from the viewpoint of achieving both heat resistance and photosensitive characteristics. , -COOR ₁ group, -COOR ₂ group and -CONH- group are each an aromatic group or an alicyclic aliphatic group in the ortho position. The tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms containing an aromatic ring, and more preferably the following formula (30):

{In the formula, R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorine-containing hydrocarbon group, 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. }
Although the structure represented by these is mentioned, it is not limited to these. The structure of X ₁ may be one type or a combination of two or more types. The X ₁ group having the structure represented by the above formula is particularly preferable in terms of achieving both heat resistance and photosensitive 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 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. Following formula (31):

{In the formula, R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorine-containing hydrocarbon group, and n is an integer selected from 0 to 4. . }
Although the structure represented by these is mentioned, it is not limited to these. The structure of Y ₁ may be one type or a combination of two or more types. The Y ₁ group having the structure represented by the above formula (31) is particularly preferable in terms of achieving 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 a hydrogen atom from the viewpoint of photosensitive properties. 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 properties.

  (A) When using a polyimide precursor as resin, as a system which provides photosensitivity to a photosensitive resin composition, an ester bond type and an ion bond type are mentioned. The former is a method of introducing a photopolymerizable group, that is, a compound having 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 ( In this method, a photopolymerizable group is imparted by bonding an amino group of a (meth) acrylic compound via an ionic bond.

The ester bond-type polyimide precursor is first composed of the tetracarboxylic dianhydride containing the above-described tetravalent organic group X ₁ , an alcohol having a photopolymerizable unsaturated double bond, and optionally having 1 carbon atom. After preparing a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester) by reacting with ˜4 saturated aliphatic alcohols, this and the aforementioned divalent organic group Y _1. It is obtained by amide polycondensation with diamines containing

(Preparation of acid / ester)
In the present invention, a tetracarboxylic dianhydride containing a tetravalent organic group X ₁ which is preferably used for preparing an ester bond type polyimide precursor is a tetracarboxylic acid represented by the general formula (30). In addition to acid dianhydrides, for example, pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride Biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3', 4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3 ', 4 4'-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3 , 3-hexafluoropropane, etc. are preferred Is pyromellitic anhydride, diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride, biphenyl-3,3 ' , 4,4′-tetracarboxylic dianhydride, but is not limited thereto. These may 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 bond type polyimide precursor in the present invention include 2-acryloyloxyethyl alcohol and 1-acryloyloxy. -3-propyl alcohol, 2-acrylamidoethyl 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, Examples include 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

  For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, and the like can be partially mixed and used as the saturated aliphatic alcohol having 1 to 4 carbon atoms.

  In the presence of a basic catalyst such as pyridine, the tetracarboxylic dianhydride suitable for the present invention is dissolved in a solvent as described later at a temperature of 20 to 50 ° C. with stirring for 4 to 10 hours. , By mixing, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester product can be obtained.

(Preparation of polyimide precursor)
An appropriate dehydration condensing agent such as dicyclocarbodiimide (for example, dicyclohexylcarbodiimide), 1-ethoxycarbonyl-2-ethoxy-1 is added to the above acid / ester (typically, a solution in a solvent described later) under ice cooling. , 2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N′-disuccinimidyl carbonate, etc. are added and mixed, and the acid / ester is converted into a polyanhydride. After that, a solution obtained by dissolving or dispersing a diamine containing a divalent organic group Y ₁ suitably used in the present invention in a solvent is added dropwise and subjected to amide polycondensation to obtain a target polyimide. A precursor can be obtained. Alternatively, the acid / ester can be reacted with a diamine compound in the presence of a base such as pyridine after the acid moiety has been acid chlorided using thionyl chloride or the like to obtain the target polyimide precursor. .

Examples of the diamine containing the divalent organic group Y ₁ preferably used in the present invention include a diamine having a structure represented by the 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'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 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-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene, and Those in which a part of hydrogen atoms on these benzene rings are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen or the like, for example, 3,3′-dimethyl-4,4′-diaminobiphenyl 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 2,2′-dimethyl-4,4′-diaminodiphenylmethane, 3,3 ′ -Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-di Tilbenzidine, 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, Examples include, but are not limited to, 2,2′-bis (fluoro) -4,4′-diaminobiphenyl, 4,4′-diaminooctafluorobiphenyl, and mixtures thereof.

  Further, 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 onto the substrate, 1,3- 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-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off if necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, The polymer component is added to precipitate the polymer component, and the polymer is purified by repeating redissolution and reprecipitation operations, followed by vacuum drying to obtain a single target polyimide precursor. Release. In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

On the other hand, the ion-bonded polyimide precursor is typically obtained by reacting tetracarboxylic dianhydride with 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 a tetracarboxylic anhydride 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 a carboxyl group and an 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, dimethylamino Dialkylaminoalkyl acrylates or methacrylates such as butyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, diethylaminobutyl methacrylate, etc. are preferred. Among these, from the viewpoint of photosensitive properties, the alkyl group on the amino group has 1 to 10 carbon atoms and the alkyl chain is C1-C10 dialkylaminoalkyl Acrylate or methacrylate is preferred.

  The compounding amount of the (meth) acrylic compound having an amino group is 1 to 20 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 photosensitivity characteristics. (C) As photosensitizer, (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 (A) resin. Excellent in properties.

  The molecular weight of the ester bond type and the ion bond type polyimide precursor is preferably 8,000 to 150,000, as measured by gel permeation chromatography in terms of polystyrene-reduced weight average molecular weight, and 9,000. 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 developer 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 determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

｛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]
One more example of preferable (A) resin in the photosensitive resin composition of this invention is 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 them. R ₉ is an organic group having at least one radical-polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n ₂ is an integer of 1 to 1000. }
Is a polyamide having a structure represented by This polyamide is suitable for a negative photosensitive resin composition.

｛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), as the group represented by R ₉ , the following general formula (32),

{In the formula, R ₃₂ represents an organic group having at least one radical-polymerizable unsaturated bond group having 2 to 19 carbon atoms. }
It is preferable that it is group represented by these.

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 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):

Is preferably an aromatic group selected from the group represented by formula (II), and more preferably an aromatic group obtained by removing a carboxyl group and an amino group from an 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 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 an aromatic or aliphatic ring which may be substituted. More preferably, it is a cyclic organic group having 1 to 4 carbon atoms, an aliphatic group having no cyclic structure, or a siloxane group. 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 each independently a hydroxyl group, a methyl group (—CH ₃ ), an ethyl group (—C ₂ H ₅ ), a propyl group (—C ₃ H ₇ ) or a butyl group (—C ₄ H ₉ ) is one group selected from the group consisting of, and the propyl group and butyl group include various isomers. }

{In the formula, m ₇ is an integer of 0 to 8, m ₈ and m ₉ are each independently an integer of 0 to 3, and m ₁₀ and m ₁₁ are independently of 0 to ₁₀ respectively. And R ₃₅ and R ₃₆ are a methyl group (—CH ₃ ), an ethyl group (—C ₂ H ₅ ), a propyl group (—C ₃ H ₇ ), a butyl group (—C ₄ H ₉ ) or These isomers. }.

｛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):

{Wherein m ₁₂ is an integer from 2 to 12, m ₁₃ is an integer from 1 to 3, m ₁₄ is an integer from 1 to 20, and R ₃₇ , R ₃₈ , R ₃₉ and R ₄₀ is each independently an alkyl group having 1 to 3 carbon atoms or an optionally substituted phenyl group. } Is preferable.

The polyamide resin of the present invention can be synthesized, for example, as follows.
(Synthesis of sealed phthalate compound)
First, a compound having a trivalent aromatic group X ₂ is selected from the group consisting of phthalic acid substituted with an amino group, isophthalic acid substituted with an amino group, and terephthalic acid substituted with an amino group 1 mol of at least one 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 converted into a radical polymerizable compound described later. A compound modified and sealed with a group containing an unsaturated bond (hereinafter referred to as “phthalic acid compound encapsulated body”) is synthesized. These may be used alone or in combination.

  When the phthalic acid compound is sealed with the radical polymerizable unsaturated bond-containing group, negative photosensitivity (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 particularly preferably a group containing a methacryloyl group or an acryloyl group.

  The above-mentioned sealed phthalic acid compound is obtained by reacting an amino group of a phthalic acid compound with an acid chloride, isocyanate or epoxy compound having at least one radical 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] ethyl chloroformate , 3-[(meth) 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. These may be used alone or in combination, but it is particularly preferable to use methacryloyl chloride and / or 2- (methacryloyloxy) ethyl isocyanate.

  Further, as these phthalic acid compound encapsulated bodies, those in which the phthalic acid compound is 5-aminoisophthalic acid can provide a polyamide having excellent photosensitivity and also excellent film characteristics after heat curing. Is preferable.

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

  Some types of sealants, such as acid chloride, generate hydrogen chloride as a by-product during the sealing reaction. In this case, from the viewpoint of preventing contamination in the subsequent steps, it is preferable to carry out purification as appropriate, such as re-precipitation in water and drying by washing, or removal and reduction of ion components through a column filled with an ion exchange resin. .

(Polyamide synthesis)
By mixing the phthalic acid compound encapsulated body and the diamine compound having a divalent organic group Y ₂ in the presence of a basic catalyst such as pyridine or triethylamine in a solvent as described later, and by amide polycondensation, The polyamide of the present invention can be obtained.

  As the amide polycondensation method, a phthalic acid compound encapsulated body is made into a symmetrical polyacid anhydride using a dehydrating condensing agent and then mixed with a diamine compound, or a phthalic acid compound encapsulated body is acid chloride by a known method. And a method of mixing with a diamine compound after reacting a dicarboxylic acid component and an active esterifying agent in the presence of a dehydrating condensing agent to form an active ester.

  Examples of the dehydrating condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1′-carbonyldioxy-di-1,2,3-benzotriazole, N, N Preferred examples include '-disuccinimidyl carbonate.

  Examples of the chlorinating agent include thionyl chloride.

  As an active esterifying agent, N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, 2-hydroxyimino-2-cyanoacetic acid ethyl, 2-hydroxyimino- Examples include 2-cyanoacetamide.

The diamine compound having an organic group Y ₂ includes 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 can be used in combination as desired.

  Examples of aromatic diamine compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 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'-di Mino diphenylmethane,

  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) pro 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-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene, and some of the hydrogen atoms on these benzene rings Is a diamine compound substituted with one or more groups selected from the group consisting of a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, and a halogen atom.

  Examples of diamine compounds in which hydrogen atoms on the benzene ring are substituted include 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'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro- 4,4′-diaminobiphenyl and the like can be mentioned.

  Aromatic bisaminophenol compounds include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4′-diaminodiphenylsulfone, 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′-di Minodiphenyl 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-methylbenzylidene) -bis (2-aminophenol) 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, 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, norbornane Diamine, 1-cycloheptene-3,7-diamine, , 4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine), 1,4-bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2 4,8,10-tetraoxaspiro- [5,5] -undecane and the like.

  Examples of linear aliphatic diamine compounds 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, or alkylene oxide type diamines such as 2- (2-aminoethoxy) ethylamine, 2,2 ′-(ethylenedioxy) diethylamine, bis [2- (2-aminoethoxy) ethyl] ether, etc. Is mentioned.

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

  After completion of the amide polycondensation reaction, the precipitate derived from the dehydration condensing agent that has precipitated in the reaction solution is filtered off as necessary. Next, a poor polyamide solvent such as water or an aliphatic lower alcohol or a mixture thereof is added to the reaction solution to precipitate the polyamide. Furthermore, the precipitated polyamide is redissolved in a solvent and purified by repeating the reprecipitation precipitation, followed by vacuum drying to isolate the target polyamide. In order to further improve the degree of purification, this polyamide solution may be passed through a column packed with an ion exchange resin to remove ionic impurities.

  The weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”) of polyamide is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. If the weight average molecular weight in terms of polystyrene is 7,000 or more, the basic physical properties of the cured relief pattern are secured. Moreover, if the polystyrene conversion weight average molecular weight is 70,000 or less, the development solubility at the time of forming a relief pattern is ensured.

  Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the eluent for GPC. Moreover, a weight average molecular weight value is calculated | required from the calibration curve created using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

｛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]
Still another example of the preferred resin (A) in the photosensitive resin composition of the present invention is the following general formula (5):

{Wherein Y ₃ is a tetravalent organic group having a carbon atom, preferably a tetravalent organic group having 2 or more carbon atoms, and Y ₄ , X ₃ and X ₄ are each independently And 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₎ is a divalent organic group having 2 or more carbon atoms. )> 0.5, and the order of arrangement of n ₃ dihydroxydiamide units containing X ₃ and Y ₃ and n ₄ diamide units containing X ₄ and Y ₄ is not critical. } Is a polyhydroxyamide (polyoxazole precursor (hereinafter, the polyhydroxyamide represented by the 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 sometimes simply referred to as dihydroxydiamide units), and n ₄ in the general formula (5). May have a number of diamide units (hereinafter sometimes simply referred to as diamide units).

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 preferably 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. Preferably there is.

The dihydroxydiamide unit can be formed by synthesis from a diaminodihydroxy compound having Y ₃ (NH ₂ ) ₂ (OH) ₂ structure (preferably bisaminophenol) and a dicarboxylic acid having X ₃ (COOH) ₂ structure. . Hereinafter, typical embodiments will be described by taking as an example the case where the diaminodihydroxy compound is bisaminophenol. The two groups of amino groups and hydroxy groups of the bisaminophenol are each in the ortho position, and the dihydroxydiamide unit is closed by heating at about 250 to 400 ° C. to form a heat-resistant polyoxazole structure To change. N ₃ in the general formula (5) is 1 or more for the purpose of obtaining photosensitive characteristics and 1000 or less for the purpose of obtaining 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 as necessary. The diamide unit can be formed by synthesis from a diamine having a Y ₄ (NH ₂ ) ₂ structure and a dicarboxylic acid having a X ₄ (COOH) ₂ structure. N ₄ in the general formula (5) is in the range of 0 to 500, and when n ₄ is 500 or less, good photosensitive characteristics can be obtained. n ₄ is more preferably in the range of 0-10. If the ratio of the diamide unit to the dihydroxydiamide unit is too high, the solubility in an alkaline aqueous solution used as a developer is lowered. Therefore, the value of n ₃ / (n ₃ + n ₄ ) in the general formula (5) is 0.5. More than 0.7, 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 the bisaminophenol as the diaminodihydroxy compound having the 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-hydroxy Enyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4′-diamino-3,3′-dihydroxybenzophenone, 3,3′-diamino-4,4′-dihydroxy Benzophenone, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino Examples include -2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols can be used alone or in combination of two or more. The Y ₃ group in the bisaminophenol is represented by the following formula (37):

{Wherein Rs1 and Rs2 each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, or a trifluoromethyl group} This is preferable.

As the diamine having a structure of Y ₄ (NH _{2) 2,} an aromatic diamine, a silicon diamine, and the like. Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 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′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 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-trimethylindane, bis (p-aminophenyl) phosphine 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) diphenylsulfone, 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, phenylindanediamine, 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) diphenylsulfone, 4,4'-diaminobenzanilide, and the like Hydrogen atom of aromatic nucleus of group diamine is chlorine atom, fluorine atom, bromine atom, methyl group, Butoxy group, compounds substituted by at least one group or atom selected from the group consisting of cyano group and a phenyl group.

  Further, as the diamine, silicon diamine can be selected in order to enhance the adhesion with the substrate. Examples of silicon diamines include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldi Examples 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。 In addition, as a preferable dicarboxylic acid having a structure of X ₃ (COOH) ₂ or X ₄ (COOH) ₂ , X ₃ and X ₄ are aliphatic groups or aromatic groups each having a linear, branched or cyclic structure, respectively. What is a group is mentioned. Among these, 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 each represented by the following formula (38):

{Wherein R ₄₁ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO— and —C (CF ₃ ) ₂ —. Represents a valent group. }
Can be preferably selected from the aromatic groups represented by the formula (1), and these are preferable from the viewpoint of photosensitive characteristics.

で表されるものが挙げられる。 The polyoxazole precursor may have a terminal group 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 may be good. Be expected. As a suitable example of such a sealing group, the following formula (39):

The thing represented by is mentioned.

  The polystyrene-reduced weight average molecular weight of the polyoxazole precursor by gel permeation chromatography is preferably 3,000 to 70,000, and 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. Moreover, from a 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 determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

｛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]
One more example of the preferred resin (A) in the photosensitive resin composition of the present invention is the general formula (6):

{Wherein X ₅ is a tetravalent to tetravalent organic group, Y ₅ is a divalent to divalent organic group, and R ₁₀ and R ₁₁ are groups selected from a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. It represents at least one organic group 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 which has the structure represented by these. Here, the resin represented by the general formula (6) is particularly preferable because it does not require a chemical change in the heat treatment step for exhibiting sufficient film characteristics, and is suitable for a treatment at a lower temperature.
X ₅ in the structural unit represented by the general formula (6) is preferably a tetravalent to tetravalent organic group having 4 to 40 carbon atoms, and is compatible with both heat resistance and photosensitive characteristics. More preferably, the organic group has 5 to 40 carbon atoms and contains an aromatic ring or an aliphatic ring.

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

  Suitable tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic 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-Zika Boxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid Anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic 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 dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine Aromatic tetracarboxylic acid such as tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride Dianhydrides, or aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Diphenylsulfone tetracarboxylic dianhydride and the following general formula (40):

{Wherein R ₄₂ represents a group selected from an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ₄₃ and R ₄₄ are the same or different. And a group selected from a hydrogen atom, a hydroxyl group, and a thiol group. } The compound represented by this is mentioned.

  Of these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic 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, Screw (3,4-di Carboxymethyl) 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′-diphenylsulfonetetracarboxylic Acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic dianhydride and The following general formula (41)

{Wherein R ₄₅ represents a group selected from an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ₄₆ and R ₄₇ are the same or different. And a group selected from a hydrogen atom, a hydroxyl group, and a thiol group. } An acid dianhydride having a structure represented by These are used alone or in combination of two or more.

Y _{5 in the} general formula (6) represents a structural component of a diamine, and the diamine represents a divalent to divalent organic group containing an aromatic ring or an aliphatic ring, and in particular has 5 carbon atoms. ~ 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'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 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) pheny } Ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 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 an alkyl group or halogen on these aromatic rings Compounds substituted with atoms, or aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the following general formula (42):

{Wherein R ₄₈ represents a group selected from an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R _{49 to} R ₅₂ are the same or different. And a group selected from a hydrogen atom, a hydroxyl group or a thiol group. } 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。 Among 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):

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

｛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):

{Wherein R ₅₈ represents a group selected from an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ₅₉ and R ₆₀ are the same or different. And a group selected from a hydrogen atom, a hydroxyl group or a thiol group. }
Particularly preferred is a diamine having a structure represented by: These are used alone or in combination of two or more.

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

By controlling the amount of the alkali-soluble group of R ₁₀ and R _11, the dissolution rate with respect to the aqueous alkali solution is changed. Therefore, a photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure as X ₅ and Y ₅ may be copolymerized as long as the heat resistance is not lowered. Specifically, 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.

  For example, the polyimide may be prepared by reacting a tetracarboxylic dianhydride and a diamine compound (partially replaced with a monoamine end-capping agent) at a low temperature. A method of reacting an acid anhydride, a monoacid chloride compound or a monoactive ester compound with an end-capping agent) and a diamine compound, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then a diamine (partially A method of reacting in the presence of a condensing agent with a monoamine end-capping agent, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is converted to an acid chloride to give a diamine (partially) Using a method such as a method of reacting with a monoamine end-capping agent, a polyimide precursor is obtained, which is known. A method of complete imidization using an imidization reaction method, a method of stopping imidization reaction in the middle and introducing a part of imide structure (in this case, polyamideimide), and a completely imidized polymer; By blending the polyimide precursor, it can be synthesized utilizing a method of partially introducing an imide structure.

  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 imidation rate refers to the ratio of imidation present in the entire resin constituting the photosensitive resin composition. When the imidization ratio is less than 15%, the shrinkage amount at the time of thermosetting becomes large, which is not suitable for the production of a thick film.

  The imidization rate can be easily calculated by the following method. First, the infrared absorption spectrum of the polymer is measured, and the presence of an absorption peak (near 1780 cm −1, near 1377 cm −1) of the imide structure due to polyimide is confirmed. Next, the polymer was heat treated at 350 ° C. for 1 hour, the infrared absorption spectrum after the heat treatment was measured, and the peak intensity in the vicinity of 1377 cm −1 was compared with the intensity before the heat treatment, whereby imidization in the polymer before the heat treatment. Calculate the rate.

  The molecular weight of the polyimide is preferably from 3,000 to 200,000, more preferably from 5,000 to 50,000, as measured by polystyrene-reduced 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 developer 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 determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.
Furthermore, in this invention, a phenol resin can also be used conveniently.

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

In this embodiment, the weight average molecular weight of the (A) phenol resin is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000 to 50,000. is there. The weight average molecular weight is preferably 700 or more from the viewpoint of applicability of the reflow treatment to the cured film, and 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 this indication is performed by gel permeation chromatography (GPC), and can be calculated by a calibration curve created 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。 (A) A phenol resin is a novolak, polyhydroxystyrene, following General formula (7) from the viewpoint of the solubility to alkaline aqueous solution, the sensitivity and resolution at the time of forming a resist pattern, and the residual stress of a cured film.

{Wherein, 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 a group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, the plurality of R ₁₂ 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, and the following general formula (8):

(Wherein p is an integer of 1 to 10), and selected from the group consisting of a divalent alkylene oxide group represented by: 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 1 type of phenol resin selected from the phenol resin which has the repeating unit represented by these, and the phenol resin modified | denatured with the compound which has C4-C100 unsaturated hydrocarbon group.

(Novolac)
In the present disclosure, novolak means all polymers obtained by condensing phenols and formaldehyde in the presence of a catalyst. Generally, a novolak can be obtained by condensing less than 1 mol of formaldehyde with respect to 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 include trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like. Specific examples of the novolak include a phenol / formaldehyde condensed novolak resin, a cresol / formaldehyde condensed novolak resin, and a phenol-naphthol / formaldehyde condensed novolak resin.

  The weight average molecular weight of the novolak is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of applicability of the reflow treatment to the cured film, and 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 polymerized unit. Preferable examples of polyhydroxystyrene include polyparavinylphenol. Polyparavinylphenol means all polymers containing paravinylphenol as polymerized units. Accordingly, polymer units other than hydroxystyrene (for example, paravinylphenol) can be used to constitute polyhydroxystyrene (for example, polyparavinylphenol) unless the object of the present invention is contrary. In the polyhydroxystyrene, the ratio of the number of moles of hydroxystyrene units based on the number of moles of all polymerized units is preferably 10 mol% to 99 mol%, more preferably 20 to 97 mol%, still more preferably 30 to 95 mol. %. When the 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 a composition containing a copolymer component described later. This is advantageous from the viewpoint of reflow applicability. The polymerized units other than hydroxystyrene (for example, paravinylphenol) can be any polymerized unit that can be copolymerized with hydroxystyrene (for example, paravinylphenol). Examples of the copolymer component that gives a polymer unit other than hydroxystyrene (for example, paravinylphenol) include, but are not limited to, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, octyl acrylate, and 2-ethoxyethyl. Methacrylate, 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-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Recall diacrylate, glycerol triacrylate, 2,2-di (p-hydroxyphenyl) -propane dimethacrylate, triethylene glycol diacrylate, polyoxyethyl-2--2-di (p-hydroxyphenyl) -propane dimethacrylate, Triethylene glycol dimethacrylate, polyoxypropyltrimethylolpropane triacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1, 2,4-butanetriol trimethacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol Esters of acrylic acid such as methacrylate, 1-phenylethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate and 1,4-benzenediol dimethacrylate; Examples include styrene and substituted styrene such as 2-methylstyrene and vinyltoluene; vinyl ester monomers such as vinyl acrylate and vinyl methacrylate; and o-vinylphenol, m-vinylphenol, and the like.

  Moreover, as a novolak and polyhydroxystyrene demonstrated above, each can be used individually by 1 type or in combination of 2 or more types.

  The weight average molecular weight of polyhydroxystyrene is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of applicability of the reflow treatment to the cured film, and 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 general formula (7))
In this embodiment, the (A) phenol resin is represented by the following general formula (7):

{Wherein, 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 a group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, the plurality of R ₁₂ 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):

(Wherein p is an integer of 1 to 10), and selected from the group consisting of a divalent alkylene oxide group represented by: 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 low temperature as compared with, for example, conventionally used polyimide resin and polybenzoxazole resin, and enables formation of a cured film having good elongation. This is particularly advantageous. The repeating unit present in the phenol resin molecule may be one type or a combination of two or more types.

｛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 general formula (7), R ₁₂ represents a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and cyano from the viewpoint of reactivity when synthesizing the resin according to the general formula (7). A monovalent substituent selected from the group consisting of groups. R ₁₂ is, from the viewpoint of alkali solubility, a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an aromatic group having 6 to 20 carbon atoms, And the following general formula (45):

{Wherein R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, or an alicyclic group 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, 2 having 3 to 20 carbon atoms. A alicyclic group or a divalent aromatic group having 6 to 20 carbon atoms is represented. } Is preferably a monovalent substituent selected from the group consisting of four groups represented by:

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

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

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

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

In the present embodiment, in the general formula (7), b is an integer of 0 to 3, and is preferably 0 or 1 from the viewpoint of alkali solubility and elongation. When b is 2 or 3, the plurality of R ₁₂ may be the same as or different from each other.

  Further, in the present embodiment, in the 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 this embodiment, in the said General formula (7), X is a C2-C10 bivalent which may have an unsaturated bond from a cured relief pattern shape and a viewpoint of the elongation of a cured film. From an aliphatic group, a divalent alicyclic group having 3 to 20 carbon atoms, an alkylene oxide group represented by the general formula (8), and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. A divalent organic group selected from the group consisting of Among these divalent organic groups, X represents the following general formula (9) from the viewpoint of the toughness of the cured film.

{Wherein R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are substituted with fluorine atoms. 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 a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ is a hydroxyl group, and a plurality of R _{17 s} when n ₆ is an integer of 2 to 4 may be the same or different from each other. Also good. } And the following general formula (10):

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms substituted with fluorine atoms. 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 fluorine atom, or a fluorine atom. A C3-C20 alicyclic group, the following general formula (8):

(Wherein p is an integer of 1 to 10) and the following formula (11):

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

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。 Furthermore, the divalent organic group represented by the general formula (10) is represented by the following formula (12) from the viewpoint of good pattern forming properties of the resin composition and good elongation of the cured film after curing.

Is more preferably a divalent organic group represented by the following formula (13):

The divalent organic group represented by the formula is particularly preferred.

  In the structure represented by the general formula (7), X is particularly preferably a structure represented by the formula (12) or (13), and is represented by a structure represented by the formula (12) or (13) in X. 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 elongation. The proportion is preferably 80% by mass or less, and more preferably 70% by mass or less, from the viewpoint of alkali solubility of the composition.

｛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) The structure contained therein is particularly preferable from the viewpoint of alkali solubility of the composition and elongation of the cured film.

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

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

M _{5 in the} general formula (14) and m _{6 in the} general formula (15) represent the total number of each repeating unit in the main chain of the phenol resin. That is, in the (A) phenol resin, 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 each independently an integer 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. is there. m ₅ and m ₆ are each independently preferably 2 or more from the viewpoint of the toughness of the cured film, and 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 toughness of the film after curing, and from the viewpoint of solubility in an aqueous alkali solution, Preferably it is 200 or less, More preferably, it is 175 or less, More preferably, it is 150 or less.

In (A) phenol resin 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, the better the film physical properties 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 film physical properties after curing. More preferably 40/60 or more, particularly preferably 50/50 or more. From the viewpoint of alkali solubility and cured relief pattern shape, it is preferably 90/10 or less, more preferably 80/20 or less, and still more preferably 70 / 30 or less.

The phenol resin having the repeating unit represented by the general formula (7) is typically a phenol compound and a copolymer component (specifically, a compound having an aldehyde group (decomposed as a trioxane to be 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. One or more compounds selected from the group), and more typically a monomer component comprising these can be synthesized by a polymerization reaction. For example, an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, a haloalkyl compound, etc. with respect to phenol and / or a phenol derivative (hereinafter also collectively referred to as “phenol compound”) as shown below (A) a phenol resin can be obtained by polymerizing the copolymer component. In this case, in the general formula (7), the moiety represented by the structure in which the OH group and an arbitrary R ₁₂ group are bonded to the aromatic ring is derived from the phenol compound, and the moiety represented by X is the above-mentioned common group. It comes from the polymerization 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 copolymer component (phenol compound): (copolymer component) is 5 : 1 to 1.01: 1 is preferable, and 2.5: 1 to 1.1: 1 is more preferable.

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

  Examples of the phenol compound that can be used to obtain a phenol resin having a repeating unit represented by the general formula (7) include cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, benzylphenol, Nitrobenzylphenol, cyanobenzylphenol, adamantanephenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N- (hydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- ( Hydroxyphenyl) -5-methyl-5-norbornene-2,3-dicarboximide, trifluoromethylphenol, hydroxybenzoic acid, hydroxy Methyl benzoate, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, resorcinol, xylenol, catechol, methylcatechol, ethylcatechol, hexylcatechol, benzylcatechol, nitro Benzyl catechol, methyl resorcinol, ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, dihydroxy Benzyl benzoate, dihi Roxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, dihydroxybenzonitrile, N- (dihydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (dihydroxyphenyl) -5-methyl-5-norbornene- 2,3-dicarboximide, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1, 2,4-trihydroxybenzene, trihydroxybenzoic acid, methyl trihydroxybenzoate, trihydroxybenzoate 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, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2-carboxyl Examples include aldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde, and the like.

  Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, bicyclohexanone, cyclohexanedione, 3-butyn-2-one, 2-norbornanone, Adamantanone, 2,2-bis (4-oxocyclohexyl) propane, and the like.

  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, libito Arabitol, allitol, 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-norbornene-2,2-dimethanol, 5-norbornene-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 (hydro Cymethyl) cyclohexene, 1,6-bis (hydroxymethyl) adamantane, 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 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 (methoxy) Til) butyric acid, 2,2-bis (methoxymethyl) -5-norbornene, 2,3-bis (methoxymethyl) -5-norbornene, 1,4-bis (methoxymethyl) cyclohexane, 1,4-bis (methoxy) Methyl) cyclohexene, 1,6-bis (methoxymethyl) adamantane, 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) diphenylthio Ether, 4,4′-bis (methoxymethyl) benzophenone, 4-methoxymethylbenzoic acid-4′-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4′-methoxymethylanilide, 4,4′-bis (methoxy) Methyl) 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 dimethyl ether And dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and tetrapropylene glycol dimethyl ether.

  Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol-dimethacrylate, 2,4-hexadien-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-ethylidene-2-norbornene, 5-vinyl-2-norbornene, triallyl cyanurate, diallyl isocyanurate, triisocyanurate Lil, diallyl propyl etc. isocyanuric acid.

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

  (A) A phenol resin can be obtained by condensing the above-described phenolic compound and copolymerization component by dehydration, dehydrohalogenation, or dealcoholization, or by polymerizing while cleaving the unsaturated bond. A catalyst may be used during the polymerization. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1. Examples include '-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex, and the like. 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, Piperazine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, Ammonia, hexamethylenetetramine and the like can be mentioned.

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

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

  In addition, the phenol resin which has a repeating structure represented by General formula (7) is what further polymerized the phenolic compound which is not a raw material of the structure of the said General formula (7) in the range which does not impair the effect of this invention. It may be. The range not impairing the effects of the present invention is, for example, 30% or less of the total number of moles of the phenol compound used as the raw material for the (A) phenol resin.

(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 composed of a compound having phenol or a derivative thereof and an unsaturated hydrocarbon group having 4 to 100 carbon atoms (hereinafter sometimes referred to simply as “unsaturated carbonization”). Reaction product (hereinafter also referred to as “unsaturated hydrocarbon group-modified phenol derivative”) with aldehydes, or a phenol resin and an unsaturated hydrocarbon group. It is a reaction product with the containing compound.

  As the phenol derivative, the same ones 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. Moreover, from the viewpoint of compatibility when the resin composition is used and the 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 still more preferably carbon atoms. 10-60.

  Examples of the unsaturated hydrocarbon group-containing compound include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linoleyl alcohol, oleyl alcohol, unsaturated fatty acid and unsaturated fatty acid ester. Can be mentioned. Suitable unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, eleostearic acid, stearidone Examples include acids, arachidonic acid, eicosapentaenoic acid, sardine acid and docosahexaenoic acid. Among these, vegetable oils that are unsaturated fatty acid esters are particularly preferable from the viewpoints of the degree of elongation of the cured film and the flexibility of the cured film.

  The vegetable oil is usually a non-drying oil containing an ester of glycerin and an unsaturated fatty acid and having an iodine value of 100 or less, a semi-drying oil of more than 100 and less than 130, or a drying oil of 130 or more. Non-drying oils include, for example, olive oil, Asa seed oil, cashew oil, potato oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of the drying oil include paulownia oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, camellia oil and coconut 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 associated with excessive reaction in the reaction of phenol or a derivative thereof or a phenol resin with vegetable oil, and improving yield. On the other hand, it is preferable to use a drying oil from the viewpoint of improving the adhesion, mechanical properties and thermal shock resistance of the resist pattern. Among the drying oils, tung oil, linseed oil, soybean oil, walnut 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 reliably exhibited. These vegetable oils are used alone or in combination of two or more.

  The reaction between phenol or a derivative thereof and an unsaturated hydrocarbon group-containing compound is preferably performed at 50 to 130 ° C. From the viewpoint of reducing the residual stress of the cured film, the reaction ratio between phenol or a derivative thereof and the unsaturated hydrocarbon group-containing compound is 1 to 100 masses of the unsaturated hydrocarbon group-containing compound with respect to 100 parts by mass of phenol or a derivative thereof. Part is preferable, and 5 to 50 parts by mass is more preferable. If 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, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst.

  A phenol resin modified with an unsaturated hydrocarbon group-containing compound is produced by polycondensation of an unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction with an aldehyde. Aldehydes are, 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, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate, pyruvic acid, repric acid, 4-acetylbutyric acid, acetone dicarboxylic acid and 3,3′- Selected from 4,4'-benzophenone tetracarboxylic acid. Further, a formaldehyde precursor such as paraformaldehyde or trioxane may be used. These aldehydes are 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 synthesis conditions for phenol resins can be used. The reaction is preferably performed in the presence of a catalyst such as an acid or a base, and an acid catalyst is more preferably 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 can be used alone or in combination of two or more.

  The above reaction is preferably carried out usually at a reaction temperature of 100 to 120 ° C. Moreover, although reaction time changes with kinds and quantity of a catalyst to be used, it is 1 to 50 hours normally. 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 the unsaturated hydrocarbon group-containing compound. In the reaction, a solvent such as toluene, xylene, or methanol can be used.

  A phenol resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by polycondensing the above unsaturated hydrocarbon group-modified phenol derivative with an aldehyde 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.

  A phenol resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by reacting a phenol resin with an 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 an aldehyde. In this case, as a phenol derivative and aldehydes, the thing similar to the phenol derivative and aldehyde mentioned above can be used, and a phenol resin can be synthesize | combined on the conventionally well-known conditions as mentioned above.

  Specific examples of phenolic resins obtained from phenolic compounds and aldehydes suitable for use in forming phenolic resins modified with unsaturated hydrocarbon group-containing compounds include phenol / formaldehyde novolac resins, cresol / formaldehyde Novolak resins, xylyleneol / formaldehyde novolak resins, resorcinol / formaldehyde novolak resins and phenol-naphthol / formaldehyde novolak resins.

  The unsaturated hydrocarbon group-containing compound to be reacted with the phenol resin may be the same as the unsaturated hydrocarbon group-containing compound described above for the production of the unsaturated hydrocarbon group-modified phenol derivative to be reacted with the aldehyde.

  The reaction between the phenol resin and the unsaturated hydrocarbon group-containing compound is usually preferably performed at 50 to 130 ° C. Moreover, the reaction rate of a phenol resin and an unsaturated hydrocarbon group containing compound is an unsaturated hydrocarbon group containing compound 1 with respect to 100 mass parts of phenol resins from a viewpoint of improving the flexibility of a cured film (resist pattern). It is preferable that it is -100 mass parts, It is more preferable that it is 2-70 mass parts, It is still more preferable that it is 5-50 mass parts. If 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 curing The heat resistance of the film tends to decrease. In the reaction between the phenol resin and the unsaturated hydrocarbon group-containing compound, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst as necessary. In addition, although demonstrated in detail later for reaction, solvents, such as toluene, xylene, methanol, tetrahydrofuran, can be used, for example.

  It is also possible to use an acid-modified phenol resin by reacting a polybasic acid anhydride with the phenolic hydroxyl group remaining in the phenol resin modified by the unsaturated hydrocarbon group-containing compound produced by the above method. it can. By acid-modifying with a polybasic acid anhydride, a carboxy group is introduced and the solubility in an aqueous alkali solution (what is used as a developer) 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 a carboxy group of a polybasic acid having a plurality of carboxy groups. Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Dibasic acid anhydrides such as methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyltetra Carboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride and benzophenone tetra Carboxylic acid aromatic tetracarboxylic acid dianhydride such as dianhydride. You may use these individually by 1 type or in combination of 2 or more types. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably at least one 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, 0.10 to 0.80 mol of polybasic acid anhydride is preferably reacted with 1 mol of phenolic hydroxyl group, more preferably 0.15 to 0.60 mol. More preferably, the reaction is performed at 20 to 0.40 mol. If the 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 area tends to decrease.

  In addition, you may contain a catalyst in the said reaction as needed from a viewpoint of performing reaction rapidly. 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 acid anhydride is preferably 30 to 200 mgKOH / g, more preferably 40 to 170 mgKOH / g, and further preferably 50 to 150 mgKOH / g. . When the acid value is less than 30 mgKOH / g, it tends to require a longer time for alkali development than when the acid value is in the above range, and when it exceeds 200 mgKOH / g, the acid value is in the above range. In comparison with the above, the developer resistance of the unexposed portion tends to be lowered.

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

  As (A) phenol resin of this embodiment, phenol modified with the phenol resin which has a repeating unit represented by the said General formula (7), and the said compound which has a C4-C100 unsaturated hydrocarbon group A mixture of at least one phenol resin selected from 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 (a3) resin and the (a4) resin is (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. 95 to 95/5 is preferable, (a3) / (a4) = 10/90 to 90/10 is more preferable, and (a3) / (a4) = 15/85 to 85/15 is more preferable. preferable. As the novolak and polyhydroxystyrene as the (a4) resin, the same resins as those described in the above section (Novolak) and (polyhydroxystyrene) can be used.

(B) Cyclic compound having a carbonyl group (B) The compound 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 condensed ring compound, 1/3 or more of the atoms to be formed is an N atom, and at least selected from the group consisting of compounds in which 1/3 or more of the atoms forming the ring structure having the carbonyl group are N atoms. One kind of compound.
Classification from ring structure: 5-membered ring compound, 6-membered ring compound, 5-membered ring and 5-membered condensed ring compound, 5-membered ring and 6-membered condensed ring compound, 6-membered ring and 6-membered ring condensed From the viewpoint of migration resistance, it is preferably at least one compound selected from the group consisting of compounds that are ring compounds.
By having two or more carbonyl groups, the area of voids on the copper surface can be reduced. Furthermore, it is preferable to have two or more carbonyl groups from the viewpoints of developability, sensitivity, in-plane uniformity after curing, elongation after reflow, and the like. When the number of carbonyl groups is two or more, the area of voids on the copper surface is remarkably reduced as compared with the case of one carbonyl group. In addition, two or more carbonyl groups are preferable from the viewpoints of developability and sensitivity, in-plane uniformity after curing, elongation after reflow, and the like as compared with the case of one carbonyl group.

  Specific examples of the compound (B) include 5-pyrazolone, 5-pyrazolone, 3-methyl-5-pyrazolone, 1,3-dimethyl-5-pyrazolone, 2-imidazolidinone, 1, 3-Dimethyl-2-imidazolidinone, hydantoin, allantoin, parabanic acid, etc. as a 6-membered ring compound, tetrahydro-2-pyrimidinone, barbituric acid, 1,3-dimethylbarbituric acid, 1,3-dicyclohexylbarbitur Acid, uramil, alloxan, cyanuric acid, isocyanuric acid tris (2-hydroxyethyl), etc. as a condensed ring compound of 5-membered ring and 5-membered ring, glycoluril etc., condensed ring compound of 6-membered ring and 5-membered ring As guanine, isoguanine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) guana , N- (3-ethylphenyl) guanine, hypoxanthine, 8-azahypoxanthine, 7-deazahypoxanthine, xanthine, 1-methylxanthine, 3-methylxanthine, 8-bromo-3-methylxanthine, theobromine , Theophylline, 7- (2-chloroethyl) theophylline, caffeine, uric acid, 8-azaxanthine and the like as 6-membered and 6-membered condensed cyclic compounds, pterin, lumazine, 7,8-dimethylalloxazine, 1 , 4-dihydro-6-methylquinoxaline-2,3-dione, and the like, and mixtures thereof. Among these, it is preferable to use a condensed 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。 Furthermore, the compound (B) has the following general formula (60):

{Wherein Rs3, Rs4 and Rs5 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group optionally substituted with an aromatic group, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group or a carbon number. 1-10 alkyl groups or aromatic groups. }
A compound represented by the following general formula (61):

{Wherein Rs6, Rs7 and Rs8 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group optionally substituted with an aromatic group, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group or a carbon number. 1-10 alkyl groups or aromatic groups. }
A compound represented by the following general formula (62):

{In the formula, Rs9, Rs10, Rs11 and Rs12 are each independently an amino group optionally substituted with a hydrogen atom, a halogen atom, a hydroxyl group or an aromatic group, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group or It is a C1-C10 alkyl group or an aromatic group. }
A compound represented by the following general formula (63):

{Wherein R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently an amino group optionally substituted with a hydrogen atom, a halogen atom, a hydroxyl group or an aromatic group, an alkoxy group having 1 to 6 carbon atoms, A hydroxyalkyl group, an alkyl group having 1 to 10 carbon atoms, or an aromatic group; }
From the viewpoint of migration resistance, at least one compound selected from the group consisting of 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. And derivatives thereof.

(B) The compounding quantity of a compound is 0.01-10 mass parts with respect to 100 mass parts of (A) resin, Preferably it is 0.05-2 mass parts. From the viewpoint of migration resistance, 0.01 parts by mass or more is desirable, and from the viewpoint of solubility, it is preferably less than 10 parts by mass.
These components (B) are considered that the carbonyl group and the nitrogen atom contained in the ring structure change the surface state of copper by coordinating to copper and suppress copper migration during the high-temperature storage test. It is done. In particular, in the case of a condensed ring, a plurality of carbonyl groups and nitrogen atoms act in concert, and thus migration resistance seems to be enhanced.

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

  (C) The compounding quantity in the photosensitive resin composition of a photosensitive agent is 1-50 mass parts with respect to 100 mass parts of (A) resin. The blending amount is 1 part by mass or more from the viewpoint of photosensitivity or patterning property, and is 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 photosensitive agent: photopolymerization initiator and / or photoacid generator]
First, a case where a negative type is desired will be described. In this case, a photopolymerization initiator and / or a photoacid generator is used as the photosensitizer (C), and the photopolymerization initiator is preferably a photoradical polymerization initiator, such as benzophenone and methyl o-benzoylbenzoate. Benzophenone derivatives such as 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Acetophenone derivatives, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal,

  Benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butanedione-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-diphenylpropanetrione- Oximes such as 2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, N-arylglycines such as N-phenylglycine, and benzoyl perchloride Peroxides, aromatic biimidazoles, titanocenes, α- (n-octane Nsu Gandolfo sulfonyl) -4-photoacid generator such as methoxybenzyl cyanide and the like are preferably exemplified, but not limited thereto. Among the above photopolymerization initiators, oximes are more preferable particularly from the viewpoint of photosensitivity.

  In the case of using a photoacid generator as the (C) photosensitizer in the negative photosensitive resin composition, the photoacid generator exhibits acidity upon irradiation with an actinic ray such as ultraviolet rays, and the cross-linking agent described later is added to the component (A) by its action. It has the effect | action which crosslinks with resin which is or polymerizes crosslinking agents. Examples of this photoacid generator include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, Oxime sulfonic acid esters, aromatic N-oxyimide sulfonates, aromatic sulfamides, haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, naphthoquinone diazide-4-sulfonic acid esters, and the like are used. Two or more kinds of such compounds can be used in combination as needed, or can be used in combination with other sensitizers. Among the above photoacid generators, aromatic oxime sulfonates and aromatic N-oxyimide sulfonates are more preferable particularly from the viewpoint 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 preferably 2 to 15 parts by mass from the viewpoint of photosensitivity characteristics. (C) It is excellent in photosensitivity by mix | blending 1 mass part or more of photosensitive agents with respect to 100 mass parts of (A) resin, and is excellent in thick film curability by mix | blending 50 mass parts or less.

  Furthermore, as described above, when the (A) resin represented by the general formula (1) is an ionic bond type, (A) in order to impart a photopolymerizable group to the side chain of the resin via an ionic bond, amino 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 preferred. The alkyl group on the amino group has 1 to 10 carbon atoms. Alkyl chains are preferred dialkylaminoalkyl acrylate or methacrylate having 1 to 10 carbon atoms.

  The compounding amount of the (meth) acrylic compound having an amino group is 1 to 20 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 photosensitivity characteristics. (C) As photosensitizer, (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 (A) resin. Excellent in properties.

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

[(C) Positive photosensitive agent: a compound having a quinonediazide group]
Examples of the compound (C) having a quinonediazide group (hereinafter also referred to as “(C) quinonediazide compound”) include a compound having a 1,2-benzoquinonediazide structure and a compound having a 1,2-naphthoquinonediazide structure, US Pat. No. 2,772,972, US Pat. No. 2,797,213 and US Pat. No. 3,669,658 are known substances. The (C) quinonediazide compound includes 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinonediazide-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 can be obtained by subjecting a naphthoquinone diazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride and subjecting the resulting naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound according to a conventional method. For example, a predetermined amount of a 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, and basic such as triethylamine It can be obtained by reacting in the presence of a catalyst for esterification and washing the resulting product with water and drying.

｛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, (C) the compound having a quinonediazide group is a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a hydroxy compound represented by the following general formulas (70) to (74) and / or 1, 2-Naphthoquinonediazide-5-sulfonic acid ester is preferable from the viewpoints of sensitivity and resolution when forming a resist pattern.
General formula (70) is

{Wherein, 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 each represents 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 of 1 to 5, (r1 + r3) ≦ 5 and (r2 + r4) ≦ 5. }.
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 each independently represent a monovalent organic group having 1 to 30 carbon atoms. 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 0 to 2 And all of r10, r11, r12, and r13 cannot be zero. }.
In addition, the general formula (72) is

{Wherein, r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, and (r14 × r15) L's are each independently a monovalent organic having 1 to 20 carbon atoms. And (r15) T ¹ and (r15) T ² each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. }.
In addition, the general formula (73) is

{Wherein 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: }.
Furthermore, the general formula (74) is

{Wherein, r17, r18, r19 and r20 are each independently an integer of 0 to 2, r17, r18, at least one of r19 and r20 is 1 or 2, X ₂₀ to X ₂₉ is 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 Each independently a single bond, —O—, —S—, —SO—, —SO ₂ —, —CO—, —CO ₂ —, cyclopentylidene, cyclohexylidene, phenylene, and C 1-20 Represents a divalent group selected from the group consisting of divalent organic groups. }.

｛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 each independently the following general formula:

{Wherein, X ₃₀ and X ₃₁ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and at least one monovalent group selected from the group consisting of substituted aryl group, X ₃₂ , X ₃₃ , X ₃₄ and X ₃₅ each independently represent a hydrogen atom or an alkyl group, r 21 is an integer of 1 to 5, and X ₃₆ , X ₃₇ , X ₃₈ and X ₃₉ are each independently Represents a hydrogen atom or an alkyl group. }
It is preferable to be selected from 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

{Wherein, r16 are each independently an integer of 0 to 2, and X ₄₀ each independently represents a monovalent organic group hydrogen atom or a C 1 to 20, X ₄₀ is a plurality When present, the plurality of X ₄₀ may be the same or different from each other, and X ₄₀ is represented by 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、

(Wherein, the r18, is an integer of 0 to 2, X ₄₁ is a hydrogen atom, an alkyl group, and a monovalent organic radical selected from the group consisting of cycloalkyl, and r18 is 2 In some cases, the two X ₄₁ may be the same or different from each other.)
It is preferable that it is a monovalent organic group represented by these. },
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、

{Wherein 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. }.
Further, 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：

{Wherein, r19 are each independently an integer of 0 to 2, X ₄₃ are 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。

(Wherein, r20 is an integer of 0 to 2, X ₄₅ is a hydrogen atom, alkyl group, and the group consisting of cycloalkyl group and, if r20 is 2, two X ₄₅ is X ₄₄ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl having 1 to 20 carbon atoms. Selected from the group consisting of groups. }, And the formulas (78) and (79) are structures as follows.

  As a compound represented by the said General formula (70), the sensitivity when the hydroxy compound represented by following formula (80)-(82) is made into NQD thing is high, and in the photosensitive resin composition. This is preferable because of low precipitation.

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):

Is preferable because it has high sensitivity when it is converted into an NQD compound and has low precipitation 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 converted into NQD compounds, and in the photosensitive resin composition. This is preferable because of low precipitation.
The structures of the formulas (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 general formula (71), Z is not particularly limited as long as it is a tetravalent organic group having 1 to 20 carbon atoms, but from the viewpoint of sensitivity, the following formula:

It is preferable that it is a tetravalent group which has a structure represented by these.

Among the compounds represented by the general formula (71), the hydroxy compounds represented by the following formulas (87) to (90) have high sensitivity when converted into NQD compounds, and in the photosensitive resin composition. This is preferable because of its low precipitation.
The structures of the formulas (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。 As a compound represented by the said General formula (72), following formula (91):

{In formula, r40 is an integer of 0-9 each independently. } Is preferable because the sensitivity when the NQD compound is obtained is high and the precipitation in the photosensitive resin composition is low.

As the compound represented by the general formula (73), the hydroxy compounds represented by the following formulas (92) and (93) have high sensitivity when converted into NQD compounds, and in the photosensitive resin composition. This is preferable because of low precipitation.
The structures of the formulas (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。 Specifically as a compound represented by the said General formula (74), following formula (94):

An NQD product of a polyhydroxy compound represented by the formula is preferred because of its high sensitivity and low precipitation in the photosensitive resin composition.

  (C) When the compound having a quinonediazide group has a 1,2-naphthoquinonediazidosulfonyl group, this group is either a 1,2-naphthoquinonediazide-5-sulfonyl group or a 1,2-naphthoquinonediazide-4-sulfonyl group. There may be. Since the 1,2-naphthoquinonediazide-4-sulfonyl group can absorb the i-line region of a mercury lamp, it is suitable for i-line exposure. On the other hand, the 1,2-naphthoquinonediazide-5-sulfonyl group can absorb even the g-line region of a mercury lamp and is suitable for exposure with g-line.

  In the present embodiment, it is preferable to select one or both of a 1,2-naphthoquinonediazide-4-sulfonic acid ester compound and a 1,2-naphthoquinonediazide-5-sulfonic acid ester compound according to 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 be used, A 2-naphthoquinonediazide-4-sulfonic acid ester compound and a 1,2-naphthoquinonediazide-5-sulfonic acid ester compound may be mixed and used.

  (C) In the compound having a quinonediazide group, the average esterification rate of the naphthoquinonediazidesulfonyl ester of the hydroxy compound is preferably 10% to 100%, more preferably 20% to 100%, from the viewpoint of development contrast. Further 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 cured film properties such as sensitivity and elongation include those represented by the following general formula group.

{Wherein Q is a hydrogen atom or the following group of formulas:

The naphthoquinone diazide sulfonate group represented by any of the above, but not all Q are hydrogen atoms at the same time. } Is represented.

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

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

Is particularly preferred.

  Examples of the onium salt include an iodonium salt, a sulfonium salt, a fosiphonium salt, a phosphonium salt, an ammonium salt, and a diazonium salt. Salts are preferred.

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

  The compounding quantity of these photo-acid generators is 1-50 mass parts with respect to 100 mass parts of (A) resin, and 5-30 mass parts is preferable. (C) If the compounding 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 if it is 50 parts by mass or less, after curing of the photosensitive resin composition. The film has a good tensile elongation and a small amount of development residue (scum) in the exposed area.

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

  In this embodiment, the compounding quantity of the compound which has (C) quinonediazide group in the photosensitive resin composition is 0.1 mass part-70 mass parts with respect to 100 mass parts of (A) resin, Preferably 1 mass part-40 mass parts, More preferably, they are 3 mass parts-30 mass parts, More preferably, they are 5 mass parts-30 mass parts. If this compounding amount is 0.1 parts by mass or more, good sensitivity is obtained, while if 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 component varies depending on whether the negative type using, for example, a polyimide precursor and polyamide, or a positive type using a polyoxazole precursor, a soluble polyimide, or the like as the resin (A).

  The above-described polyimide precursor resin composition and polyamide resin composition, which are negative resin compositions in the present embodiment, and a polyoxazole resin composition, soluble polyimide resin composition, and phenol, 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. For example, N-methyl-2- Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, 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 Use coal dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. be able to. Among them, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene from the viewpoints of resin solubility, resin composition stability, and adhesion to a substrate. Glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

  Among these solvents, those that completely dissolve the produced polymer are preferable. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea And gamma-butyrolactone.

  Solvents suitable for the above phenol 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 this invention, the usage-amount of a solvent becomes like this. Preferably it is 100-1000 mass parts with respect to 100 mass parts of (A) resin, More preferably, it is 120-700 mass parts, More preferably 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 complex such as an azole compound or a purine derivative is used to suppress discoloration on copper. A 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-dimethylben Dil) phenyl] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5 -Methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl -1H-tetrazole, 5-amino-1H-tetra Lumpur, 1-methyl -1H- tetrazole, and the like.

  Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in a mixture of two or more.

  Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, 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) Guanine, N- (3-ethylphenyl) guanine, 2-aza Adenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, it includes 8-aza hypoxanthine or their derivatives.

  In the case where the photosensitive resin composition of the present invention contains the azole compound or the 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). From a viewpoint of 0.5-5 mass parts is more preferable. When the compounding amount of the azole compound with respect to 100 parts by mass of the resin (A) is 0.1 parts by mass or more, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, the surface of the copper or copper alloy On the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent.

  Moreover, in order to suppress discoloration on the copper surface, a hindered phenol compound can be arbitrarily blended. Examples of hindered phenol compounds 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-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphene) ) Propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-) t-butyl-4-hydroxy-hydrocinnamamide), 2,2′-methylene-bis (4-methyl-6-tert-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-tert-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, , 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, , 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, , 3,5-tris (4-tert-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- Droxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-6-ethyl-) 3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl- 5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione,

  1,3,5-tris (4-t-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1, 3,5-tris (4-t-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1, 3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 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 preferred.

  It is preferable that the compounding quantity of a hindered phenol compound is 0.1-20 mass parts with respect to 100 mass parts of (A) resin, and it is more preferable that it is 0.5-10 mass parts from a viewpoint of a photosensitivity characteristic. preferable. When the compounding quantity with respect to 100 mass parts of (A) resin of a hindered phenol compound is 0.1 mass part or more, for example, when forming the photosensitive resin composition of this invention on copper or a copper alloy, copper or Discoloration / corrosion of the copper alloy is prevented, and on the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent.

  You may make the photosensitive resin composition of this invention contain a crosslinking agent. When the relief pattern formed by using the photosensitive resin composition of the present invention is heat-cured, the crosslinking agent (A) can crosslink the resin, or the crosslinking agent itself can form a crosslinked network. Can be. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the photosensitive resin composition.

  Examples of the crosslinking agent include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 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 (Mitsui Cytec Co., Ltd.), Nicalack (registered trademark) MX-270, -280, -290; Nicalack MS-11 Nicalak MW-30, -100, -300, -390, -750 (above, 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- FP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAF-MF (Honshu Chemical) Manufactured by 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 (methoxymethyl) ) Diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethyl benzoate methoxymethyl, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, and the like.

  Also, 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 oxirane compounds -Naphthol 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, trimethylolpropane polyglycidyl ether, 1 , 1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, glycerol triglycidyl Ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (Above product name, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (above product name, Japan) Manufactured by Kayaku Co., Ltd.), Epicoat (registered trademark) 1001, Epicoat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051, Epicoat 1031S, Epicoat 180S65, Epicoat 157H70, YX-315-75 (Product name, Japan Epoxy Resin Co., Ltd.), EHPE3150, Plaxel G402, PUE101, PUE105 (Product name, Daicel Chemical Industries, Ltd.), Epicron (registered trademark) 830, 850, 1050, N-680 N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (above trade name, manufactured by DIC), Denacol (registered trademark) 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), Epolite (registered trademark) 70P, E Examples include Polite 100MF (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

  Further, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, takenate (is an isocyanate group-containing compound) (Registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, ND (trade name, manufactured by Mitsui Chemicals), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402- B80T (trade name, manufactured by Asahi Kasei Chemicals Corporation) and the like.

  Further, 4,4′-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4, which are bismaleimide compounds. '-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4' -Diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI- 3000, BMI-400 , BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.), etc. However, it is not limited to these.

  As a compounding quantity in the case of using a crosslinking agent, it is preferable that it is 0.5-20 mass parts with respect to 100 mass parts of (A) resin, More preferably, it is 2-10 mass parts. When the blending amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are expressed, and 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 an 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. In particular, (B) by including both a cyclic compound having a carbonyl group and an organic titanium compound in the photosensitive resin composition, the cured resin layer is excellent in chemical resistance in addition to substrate adhesion. There is an effect.

  Usable organic titanium compounds include those in which an organic chemical substance is bonded to a titanium atom through a covalent bond or an ionic bond.

Specific examples of organic titanium compounds are shown in the following I) to VII):
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) diisopropoxide, titanium di (n-butoxide) bis (2,4-pentanedionate, titanium diisopropoxide bis (2,4-pentanedionate), titanium diisopropoxide bis ( Tetramethylheptanedionate), titanium diisopropoxide bis (ethylacetoacetate) and the like.

  II) Tetraalkoxytitanium compounds: for example, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , Titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra (n-nonyloxide), titanium tetra (n-propoxide), titanium tetrastearyloxide, titanium tetrakis [bis {2,2- (allyloxymethyl) Butoxide}] and the like.

III) Titanocene compound: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluorophenyl) titanium, bis (η ⁵ − 2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like.

  IV) Monoalkoxytitanium compounds: for example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide, and the like.

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

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

  VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate.

Among them, the organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound. It is preferable from the viewpoint. In particular, titanium diisopropoxide bis (ethyl acetoacetate), titanium tetra (n-butoxide), and bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- ( 1H-pyrrol-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, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the (A) resin. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are expressed, and when it is 10 parts by mass or less, the storage stability is excellent.

  Furthermore, an adhesion assistant can be arbitrarily blended for improving the adhesion between the film formed using the photosensitive resin composition of the present invention and the substrate. Adhesion 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-trie Toxisilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane Silane coupling agents such as 3- (trialkoxysilyl) propyl succinic anhydride, and aluminum-based adhesives such as aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethyl acetoacetate aluminum diisopropylate An auxiliary agent etc. are mentioned.

  Among these adhesion assistants, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the photosensitive resin composition contains an adhesion assistant, the amount of the adhesion assistant 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 Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name: Sila Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation): Trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS1375, manufactured by Azumax Co., Ltd .: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azumax Corporation: product) Name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropyl eth Sidimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercapto Ethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4 -Mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (manufactured by Azmax Co., Ltd .: trade 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-dimethoxypropoxysilylpropyl) urea, N -(3-Methoxydipropoxy Silylpropyl) 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 (manufactured by Azmax Co., Ltd .: trade name SLA0598.0 ), M-aminophenyltrimethoxysilane (Azmax Co., Ltd.) Product name: SLA0599.0), p-aminophenyltrimethoxysilane (Azmax Co., Ltd .: product name SLA0599.1) Aminophenyltrimethoxysilane (Azmax Co., Ltd .: Product name SLA0599.2), 2- ( (Trimethoxysilylethyl) pyridine (manufactured by Azmax Co., Ltd .: trade name SIT83396), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra- n- Toxisilane, 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) ethane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxy Silyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxy Citriethoxysilane, bis (pentadionate) titanium-O, O'-bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropyl Phenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n- Propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenol Lucilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n- Examples include, but are not limited to, propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like. These may be used alone or in combination.

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

  As a compounding quantity in the case of using a silane coupling agent, 0.01-20 mass parts is preferable with respect to 100 mass parts of (A) resin.

  The photosensitive resin composition of this invention may further contain components other than the said component. The preferred component differs depending on whether the negative type using, for example, a polyimide precursor and polyamide, or a positive type using a polyoxazole precursor, a soluble polyimide, a phenol resin, or the like as the resin (A).

  (A) In the case of a negative type using a polyimide precursor or polyamide as a resin, a sensitizer can be arbitrarily blended in order to improve 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) Isonaphthothiazole, 1,3-bis (4 ′ Dimethylaminobenzal) acetone, 1,3-bis (4′-diethylaminobenzal) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxy Carbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 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-dimethylaminostyryl) ) Naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. These can be used alone or in combination of, for example, 2 to 5 kinds.

  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).

  Moreover, in order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be arbitrarily blended. Such a monomer is preferably a (meth) acryl compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following, but includes ethylene glycol or polyethylene such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Mono- or diacrylate and methacrylate of glycol, mono- or diacrylate and methacrylate of propylene glycol or polypropylene glycol, mono-, di- or triacrylate and methacrylate of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylate of 1,4-butanediol and Dimethacrylate, 1,6-hexanediol diacrylate and dimethacrylate, neopentyl glycol diacrylate And dimethacrylate, bisphenol A mono or diacrylate and methacrylate, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropane triacrylate and methacrylate, glycerol di- or Mention may be made of compounds such as triacrylates and methacrylates, di, tri, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

  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 preferable that it is 1-50 mass parts with respect to 100 mass parts of resin.

  Moreover, in the case of the negative type using a polyimide precursor etc. as (A) resin, in order to improve the stability of the viscosity and the photosensitivity of the photosensitive resin composition at the time of storage especially in the state of a solution containing a solvent. A thermal polymerization inhibitor can be optionally blended. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic 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.

  As a compounding quantity of the thermal-polymerization inhibitor in the case of mix | blending with the photosensitive resin composition, the range of 0.005-12 mass parts is preferable with respect to 100 mass parts of (A) resin.

  On the other hand, in the photosensitive resin composition of the present invention, in the case of a 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 as necessary. Dyes, surfactants, thermal acid generators, dissolution accelerators, adhesion aids for improving adhesion to the substrate, and the like can be added.

<Dye, surfactant, adhesion aid>
The additives will be described more specifically. Examples of the dye include methyl violet, crystal violet, and malachite green. Examples of the surfactant include non-ionic surfactants made of polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether or derivatives thereof, such as Fluorard (trade name, manufactured by Sumitomo 3M), Fluorosurfactants such as trade name, Dainippon Ink and Chemicals) or Lumiflon (trade name, manufactured by Asahi Glass), such as KP341 (trade name, manufactured by Shin-Etsu Chemical), DBE (trade name, manufactured by Chisso) ) And granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Examples of the adhesion assistant include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various silane coupling agents.

  As a compounding quantity of said dye and surfactant, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) resin.

In addition, even when the curing temperature is lowered, a thermal acid generator can be arbitrarily blended from the viewpoint of exhibiting good thermal and mechanical properties of the cured product.
The thermal acid generator is preferably blended from the viewpoint of exhibiting good thermal and mechanical properties of the cured product even when the curing temperature is lowered.

  Examples of the thermal acid generator include a salt 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 salts and diphenyliodonium salts; di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts; trialkylsulfonium salts such as trimethylsulfonium salts; Examples thereof include dialkyl monoaryl sulfonium salts such as dimethylphenylsulfonium salt; diarylmonoalkyl iodonium salts such as diphenylmethylsulfonium salt; triarylsulfonium salts and the like.

  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 A dimethylphenylsulfonium salt, a diphenylmethylsulfonium salt of toluenesulfonic acid, and the like are preferable.

  Moreover, as a salt formed from a strong acid and a base, the salt formed from the following strong acids and a base other than the above-mentioned onium salt, for example, a pyridinium salt can also be used. Strong acids include p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, perfluoroalkylsulfonic acid such as nonafluorobutanesulfonic acid, methanesulfonic acid, ethanesulfonic acid And alkylsulfonic acid such as butanesulfonic acid. Examples of the base include pyridine, alkylpyridines such as 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated-N-alkylpyridines.

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

  As a compounding quantity in the case of using a thermal acid generator, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) resin, 0.5-10 mass parts is more preferable, 1-5 mass parts More preferably.

  In the case of a positive photosensitive resin composition, a dissolution accelerator can be used in order to accelerate the removal of the resin that has become unnecessary after the exposure. For example, a compound having a hydroxyl group or a carboxyl group is preferred. Examples of the compound having a hydroxyl group include the ballast agent used in the above-mentioned naphthoquinone diazide compound, paracumylphenol, bisphenols, resorcinol, and linear phenol compounds such as MtrisPC and MtetraPC, TrisP-HAP, TrisP -Non-linear phenolic compounds such as PHBA and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2 to 5 phenol substitutes of diphenylmethane, 1 to 5 phenol substitutes of 3,3-diphenylpropane, A compound obtained by reacting 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane with 5-norbornene-2,3-dicarboxylic anhydride in a molar ratio of 1: 2, bis- ( 3-amino-4-hydroxyphenyl) sulfone and 1,2-cyclo Compounds obtained by reacting xyldicarboxylic anhydride with a molar ratio of 1: 2, N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxy 5-norbornene-2,3-dicarboxylic imide, etc. Can be mentioned. Examples of the compound having a carboxyl group include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2. Examples include-(1-naphthyl) propionic acid, mandelic acid, atrolactic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, itaconic acid, and the like.

  As a compounding quantity in the case of using a solubility promoter, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) resin.

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

  In this embodiment, the resin (A) includes 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 a novolak, polyhydroxystyrene, and a phenol resin containing the general formula (7).

  Further, the photosensitive resin composition includes 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). A divalent organic group selected from the group consisting of a divalent group and a divalent group represented by the general formula (10) is preferable.

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

  (B) The sulfur-containing compound 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) As what can be used as a sulfur-containing compound, as what contains sulfur as one atom which forms a 5-membered ring structure, for example, thiazole, 2-aminothiazole, 2- (4-thiazolyl) benzimidazole 1,3,4-thiadiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,3-thiadiazole, 2,4-thiazolidinedione, benzothiazole, 2-aminobenzothiazole, etc. , Sulfur as one atom forming a 6-membered ring structure, for example, phenothiazine, N-methylphenothiazine, etc., sulfur as a thiocarbonyl group, for example, rhodanine, N-allyl rhodanine, diethyl Thiourea, dibutylthiourea, dicyclohexylthiourea, dipheny Thiourea, 2-thiouracil, 4-thiouracil, 2,4-dithio pyrimidine, 2-thioxanthone, 2-mercapto -4 (3H) - quinazolinone, and the like. Among these, a compound containing a thiourea structure is preferably used.

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

｛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 aspect of the present embodiment, instead of the aforementioned (B) cyclic compound having a carbonyl group, (B) selected from the following general formulas (B-1), (B-2) and (B-3) At least one compound can be used. More specifically,
(A) Polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and at least one selected from the group consisting of novolak, polyhydroxystyrene, and phenol resin 100 parts by mass of resin,
(B)
The following general formula (B-1):

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

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

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

  In this embodiment, the resin (A) includes 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 a novolak, polyhydroxystyrene, and a phenol resin containing the general formula (7).

  Further, the photosensitive resin composition includes 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). A divalent organic group selected from the group consisting of a divalent group and a divalent group represented by the general formula (10) is preferable.

  (B) The compounds represented by the general formulas (B-1), (B-2) and (B-3), preferably the compound represented by (B-1) is a copper atom by a nitrogen atom or an oxygen atom. By interacting with the surface of copper, the surface state 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 having a ureido group, a hydrogen atom, a nitrogen atom, and an oxygen atom. For example, methylurea, ethylurea, butylurea, phenylurea, hydroxyethyl Mention may be made of urea, hydantoic acid, allantoin, citrulline and the like and mixtures thereof.

  (B-2) is a polycondensate of ethylene glycol or a terminal etherified product thereof, such as diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, triethylene glycol, triethylene glycol monoethyl ether, triethylene glycol diethyl. Mention may be made of ether, tetraethylene glycol, tetraethylene glycol dimethyl ether and the like and mixtures thereof.

  Further, (B-3) is an alkoxy polyethylene oxide ester or alkoxyethyl ester of a dicarboxylic acid, such as bis (2-methoxyethyl) adipate, bis (2-butoxyethyl) adipate, bis (2- Ethoxyethyl) and the like and mixtures thereof.

  Among these (B) at least one compound selected from the general formulas (B-1), (B-2) and (B-3), it is preferable to use the general formula (B-1). It is a compound represented by these.

  (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 (A) resin. It is 10-10 mass parts, More preferably, it is 0.05-2 mass parts. 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 this embodiment, instead of the above-mentioned (B) cyclic compound having a carbonyl group, (B) an aromatic amine compound, an aniline derivative represented by the following general formula (I), the following general formula: At least one selected from the group consisting of a triazole derivative represented by (II) and a 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) is an aromatic amine compound having the following general formula (I):

{Ra1 to Ra5 may be the same or different from each other, 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 to 15 carbon atoms. Each of Ra6 to Ra7 may be the same or different from each other, and may be a hydrogen atom or a saturated hydrocarbon group, an unsaturated hydrocarbon group having an integer of 1 to 5 carbon atoms, Or it is an aromatic group. }
Or an aniline derivative represented by the following general formula (II):

{Ra8 to Ra10 may be the same or different from each other, and may be a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic group having an integer of 1 to 15 carbon atoms. Group or amide group. }
Or a triazole derivative represented by the following general formula (III):

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

  In this embodiment, the resin (A) includes 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) is preferably at least one selected from the group consisting of polyimides.

  (B) In an embodiment using an aromatic amine compound, as the photosensitive resin, polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, and polybenzoxazole, among others, heat treatment Since the later 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 a polyimide precursor and polyimide resin are most preferably used.

  (B) By using an aromatic amine compound, it is possible to suppress the generation of voids at the interface between the re-wired Cu layer and the resin layer after the high temperature storage test. The reason for this is not clear, but because the lone pair of aromatic amine compound is coordinated to Cu element on the surface of the Cu layer, the active Cu reaction site is blocked. It is 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。 (B) As an aromatic amine compound, the following general formula (I):

{Ra1 to Ra5 may be the same or different from each other, 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 to 15 carbon atoms. Each of Ra6 to Ra7 may be the same or different from each other, and may be a hydrogen atom or a saturated hydrocarbon group, an unsaturated hydrocarbon group having an integer of 1 to 5 carbon atoms, Or it is an aromatic group. } Is preferably used.

  Examples of the compounds preferably used in the aniline derivatives represented by the general formula (I) include N-phenylbenzylamine, salicylanilide, naphthol AS, 2-acetamidofluorene, oxanilide, N-allylaniline, N-methylaniline. N-ethylaniline, indoline, Nn-butylaniline, 2-anilinoethanol, 4-methoxyacetanilide, acetoacetanilide, 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。 (B) As a triazole derivative, the following general formula (II):

{Ra8 to Ra10 may be the same or different from each other, and may be a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic group having an integer of 1 to 15 carbon atoms. Group or amide group. }
Or a triazole derivative represented by the following general formula (III):

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

  Specific examples 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-triazol-3-yl) benzamide (manufactured by ADEKA, ADK STAB CDA-1), 2- (2H-benzo [d] [1,2 , 3] triazol-2-yl) -4- (2,4,4-trimethylpentan-2-yl) phenol (manufactured by ADEKA, Adeka Stab LA-29), 2- (2′-hydroxy-3 ′), 5'-di-tert-aminophenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzoto Azole is preferably used. Among them, 2-hydroxy-N- (1H-1,2,4-triazol-3-yl) benzamide ((B) -5), 2- (2H-benzo [d] [1,2,3] triazole- 2-yl) -4- (2,4,4-trimethylpentan-2-yl) phenol ((B) -6) is particularly preferably used.

  Specific examples of the triazole derivative represented by the general formula (III) include (4-((1H-1,2,4-triazol-1-ylmethyl) phenyl) methanol, tricyclazole, 1,2,4- 1H-triazole, tripentenol, viteltanol, 4- (1H-1,2,4-triazol-1-yl) benzaldehyde, 4- (1H-1,2,4-triazol-1-yl) benzoic acid, 3 -(1H-1,2,4-triazol-1-ylmethyl) benzoic acid, 4-[(1H-1,2,4-triazol-1-ylmethyl) phenyl] methanol, 3- (1H-1,2, 4-triazol-1-yl) benzaldehyde, 3- (1H-1,2,4-triazol-1-ylmethyl) benzaldehyde, 3- (1H-1,2, -Triazol-1-yl) benzoic acid and 2- (1H-1,2,4-triazol-1-yl) aniline are preferably used, among which (4-((1H-1,2,4-triazole- 1-ylmethyl) phenyl) methanol ((B) -7) is particularly preferably used.

  (B) In the aromatic amine compound, it is preferable that any one of the amine atoms constituting the aniline derivative or the triazole derivative is a secondary amine because of the coordination ability to the Cu element.

  (B) As content of an aromatic amine compound, 0.01-15 mass parts is preferable with respect to 100 mass parts of resin (A), 0.1-10 mass parts is more preferable, 1-8 mass parts More preferably. When the content is higher than the range, storage stability is lowered, which is not preferable. When the content is lower than the range, voids are easily generated between the copper surface and the surface.

<Method for Manufacturing Cured Relief Pattern and Semiconductor Device>
The present invention also includes (1) a step of forming a resin layer on the substrate by applying the above-described photosensitive resin composition of the present invention onto the substrate, and (2) a step of exposing the resin layer. , (3) producing a relief pattern by developing the exposed resin layer, and (4) producing a cured relief pattern by heating the relief pattern to form a cured relief pattern. Provide a method. Hereinafter, typical aspects of each process will be described.

(1) The process of forming a resin layer on this board | substrate by apply | coating the photosensitive resin composition on a board | substrate In this process, the photosensitive resin composition of this invention is apply | coated on a base material, and as needed. Thereafter, the resin layer is formed by drying. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., 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 a drying method, methods such as air drying, heat drying using an oven or a hot plate, vacuum drying, and the like are used. Specifically, when performing air drying or heat drying, 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 directly or directly through a photomask or reticle having a pattern using an exposure apparatus such as a contact aligner, mirror projection, or stepper. Exposure is performed with an ultraviolet light source or the like.

  Thereafter, post-exposure baking (PEB) and / or pre-development baking with any combination of temperature and time may be performed as necessary for the purpose of improving photosensitivity. The range of the baking conditions is that the temperature is 40 to 120 ° C. and the time is preferably 10 seconds to 240 seconds, but this range is not used unless it inhibits the various characteristics 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 or unexposed portion of the exposed photosensitive resin layer is developed and removed. When a negative photosensitive resin composition is used (for example, when (A) a polyimide precursor or polyamide is used as the resin), an unexposed portion is developed and removed, and a positive photosensitive resin composition is used ( For example, when (A) a polyoxazole precursor or a soluble polyimide is used as the resin, the exposed portion is developed and removed. As a developing method, an arbitrary method can be selected and used from conventionally known photoresist developing methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment. Further, after development, for the purpose of adjusting the shape of the relief pattern, post-development baking at any combination of temperature and time may be performed as necessary.

  The developer used for development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent. For example, in the case of a photosensitive resin composition that does not dissolve in an alkaline aqueous solution, good solvents include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, 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 mixing and using a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Also, two or more of each solvent, for example, several types may 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 is one that dissolves and removes the alkaline aqueous solution-soluble polymer, and is typically an alkaline aqueous solution in which an alkaline compound is dissolved. . The alkali compound dissolved in the developer may be either an inorganic alkali compound or an organic alkali compound.

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

  Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine, etc. are mentioned.

  Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, and a resin dissolution inhibitor can be added to the alkaline aqueous solution. . A 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 development is heated to be converted into a cured relief pattern. As a method of heat curing, various methods such as a method using a hot plate, a method using an oven, a method using a temperature rising type oven capable of setting a temperature program can be selected. 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, and 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 above-described method for producing a cured relief pattern of the present invention. The present invention also provides a semiconductor device including a base material that is a semiconductor element and a cured relief pattern of a resin formed on the base material by the above-described cured relief pattern manufacturing method. The present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a cured relief pattern as part of the process. The semiconductor device of the present invention is a semiconductor device having a surface relief film, an interlayer insulation film, a rewiring insulation film, a flip chip device protection film, or a bump structure as a cured relief pattern formed by the above-described cured relief pattern production method. And can be manufactured by combining with a known method for manufacturing a semiconductor device.

The photosensitive resin composition of the present invention is useful not only for application to semiconductor devices as described above, but also for uses such as interlayer insulation for multilayer circuits, cover coating for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. It is.
Moreover, although it divides and demonstrated to the aspect A-the aspect D above, the combination of each aspect is also contained in this invention.

  EXAMPLES 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 properties 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 the gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement is the trade name “Shodex 805M / 806M series” manufactured by Showa Denko KK, and the standard monodisperse polystyrene is selected from 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 a trade name “Shodex RI-930” manufactured by Showa Denko KK.

(2) Creation of cured relief pattern on Cu 200 nm on a 6-inch silicon wafer (Fujimi Electronics Industry Co., Ltd., thickness: 625 ± 25 μm) using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva) Thick Ti and 400 nm thick Cu were sputtered in this order. Subsequently, a photosensitive resin composition prepared by the method described later is spin-coated on this wafer using a coater developer (D-Spin60A type, manufactured by SOKDO Co., Ltd.) and dried to give a coating film having a thickness of 6 to 10 μm. 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 is spray-developed with a coater developer (D-Spin60A type, manufactured by SOKUDO) using cyclopentanone as a developing solution in the case of negative type and 2.38% TMAH in the case of positive type, In the negative type, a relief pattern on Cu was obtained by rinsing with propylene glycol methyl ether acetate, and in the positive type with pure water.

  The wafer having the relief pattern formed on Cu is heat-treated at a temperature described in each example for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg). Thus, 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 A wafer having the cured relief pattern formed on Cu was heated in a temperature-programmed cure furnace (VF-2000, Koyo Lindberg) Made in the air at 150 ° C. for 168 hours. Subsequently, the resin layer on Cu was completely removed by plasma etching using a plasma surface treatment apparatus (EXAM type, manufactured by Shinko Seiki Co., Ltd.). 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 the resin layer has been completely removed is observed with an FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and image analysis software (A Image-kun, manufactured by Asahi Kasei Co., Ltd.) is used to form the Cu surface. The area ratio of voids occupied was calculated.

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

The viscosity was measured at 23 ° C. using a TV-25 viscometer (manufactured by Toki Sangyo).
○: The rate of change in viscosity of the composition after standing (below) 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 after standing)} × 100 / (initial viscosity)

Example A
<Production Example A1> ((A) Synthesis of Polymer A as Polyimide Precursor)
Place 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2 l separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone and stir at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours.

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

  The obtained reaction liquid was added to 3 l of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 l of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 l of water to precipitate a polymer, and the obtained precipitate was filtered off and then dried in vacuum 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.

In addition, the weight average molecular weight of resin obtained by each manufacture example was measured on condition of the following using gel permeation chromatography (GPC), and calculated | required the weight average molecular weight in standard polystyrene conversion.
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 Polyimide Precursor)
Instead of 155.1 g of 4,4′-oxydiphthalic 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 above-mentioned Production Example A1, and Polymer B was obtained. 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 Polyimide Precursor)
Except for using 147.8 g of 2,2′-bistrifluoromethyl-4,4′-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example A1, In the same manner as in the production method A1, the polymer C was obtained. 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 Encapsulated AIPA-MO)
In a separable flask having a volume of 5 l, 5-aminoisophthalic acid {hereinafter abbreviated as AIPA. } 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. A solution obtained by diluting 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone was added dropwise thereto using a dropping funnel, and the mixture was stirred at 50 ° C. for about 2 hours.

  Completion of the reaction (disappearance of 5-aminoisophthalic acid) is described as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, The reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product was crystallized and precipitated, it was filtered, washed with water, and vacuumed 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 obtained AIPA-MO had a low molecular weight GPC purity of about 100%.

(Synthesis of polymer D)
Into a separable flask having a volume of 2 liters, 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 added and mixed, and cooled to 5 ° C. in an ice bath. did. A solution obtained by dissolving and diluting 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) in 125 g of GBL was added dropwise thereto over about 20 minutes under ice-cooling, followed by 4,4′-bis (4-aminophenoxy). ) Biphenyl {Hereinafter referred to as BAPB. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and stirred at room temperature for 5 hours. did. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

  A mixed liquid of 840 g of water and 560 g of isopropanol was added dropwise to the resulting reaction liquid, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was dropped into 5 liters of water to precipitate a polymer, and the resulting precipitate was filtered off and then dried under vacuum 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 Polyoxazole Precursor)
In a separable flask having a volume of 3 l, 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 were added. The mixture was stirred at room temperature (25 ° C.) to obtain a uniform solution. A solution prepared by dissolving 118.0 g of 4,4′-diphenyl ether dicarbonyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise thereto 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 temperature of the reaction solution was 30 ° C. at the maximum.

  Three hours after the completion of the dropping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was allowed to stir at room temperature for 15 hours, and 99% of all amine end groups of the polymer chain were carboxylated. Sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). Thereafter, the reaction solution was dropped into 2 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water, dehydrated and then vacuum dried, and measured by gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (in terms of polystyrene) was obtained.

  After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), this was treated with a cation exchange resin and an anion exchange resin, and the resulting solution was treated with ion exchanged water. Then, the precipitated polymer was separated by filtration, washed with water, and dried under vacuum to obtain a purified polybenzoxazole precursor (Polymer E).

<Production Example A6> ((A) Synthesis of Polymer F as Polyimide)
A condenser tube with a Dean-Stark trap was attached to a glass separable four-necked flask equipped with a Teflon (registered trademark) vertical stirrer. While passing through nitrogen gas, the flask was placed in a silicon oil bath and stirred.

  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) 70.29 g (266 mmol) of -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone and 60 g of toluene were added at 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 Chemical Industry Co., Ltd.) was added, and a silicon bath temperature of 50 ° C. was passed through nitrogen gas. The mixture was heated and stirred at 100 rpm for 8 hours. Thereafter, the silicon bath was heated to 180 ° C. and stirred with heating at 100 rpm for 2 hours. During the reaction, distillates of toluene and water were removed. After completion of the imidization reaction, the temperature was returned to room temperature.

  Thereafter, the reaction solution was dropped into 3 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water and dehydrated, and then measured by gel permeation chromatography (GPC). A crude polyimide (polymer F) having a weight average molecular weight of 23,000 (polystyrene conversion) was obtained.

<Production Example A7> ((A) Synthesis of polymer G as phenol resin)
125.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 4,4′-bis (methoxymethyl) biphenyl (hereinafter “BMMB”) in a separable flask with a Dean-Stark device of 0.5 liter capacity It was also referred to as “.” 121.2 g (0.5 mol), diethyl sulfate 3.9 g (0.025 mol), and diethylene glycol dimethyl ether 140 g were mixed and stirred at 70 ° C. to dissolve the solid matter.

  The mixed solution was heated to 140 ° C. with an oil bath, and 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 atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction dilution is dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water, dehydrated and then vacuum dried to form a co-polymer consisting of methyl 3,5-dihydroxybenzoate / BMMB. A polymer (polymer G) was obtained with a yield of 70%. The weight average molecular weight of this polymer G determined by standard polystyrene conversion by GPC method was 21,000.

<Production Example A8> ((A) Synthesis of polymer H as phenol resin)
A separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, p-toluenesulfone 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 matter.

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

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

  After completion of the reaction, the same treatment as in Production Example A7 was performed 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 standard polystyrene conversion by 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>
A negative photosensitive resin composition was prepared using the polymers A and B by the following method, and the prepared photosensitive resin composition was evaluated. Polymer A50g and B50g (corresponding to (A) resin) as polyimide precursors, 0.2 g of xanthine (corresponding to (B) carbonyl group-containing cyclic compound), 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (described as “PDO” in Table 1) (corresponding to (C) sensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g, N- [3- (triethoxysilyl) propyl] Along with 1.5 g of phthalamic acid, 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 above mixed solvent to obtain a negative photosensitive resin composition.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.2. % Results were obtained.
<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 component (B) was changed to 0.05 g.
About this composition, after curing at 230 ° C. by the above-mentioned method to produce a cured relief pattern on the Cu layer and conducting a high-temperature storage test, the area ratio of voids in the surface of the Cu layer was evaluated, and 6.4 % Results were obtained.
<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 component (B) was changed to 5 g.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 4.9 % Results were obtained.
<Example A4>
In Example A1, 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).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.1. % Results were obtained.
<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 in place of xanthine as the component (B).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.4 % Results were obtained.
<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).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.5. % Results were obtained.
<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).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing a high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 7.3 % Results were obtained.
<Example A8>
A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, and this composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and a high temperature storage test was conducted. After that, the area ratio of voids occupied on the surface of the Cu layer was evaluated, and a result of 4.5% was obtained.
<Example A9>
In Example A1, the polymer A50g and the polymer B50g were changed to the polymer A100g as the (A) resin, and as the component (C), PDO4g 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 the amount was changed to 2.5 g of 2- (O-benzoyloxime)} (Irgacure OXE01 (trade name, manufactured by BASF)).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.1. % Results were obtained.
<Example A10>
In Example A1, (A) the polymer A50g and the polymer B50g as the resin (A), the polymer A100g, the PDO4g as the component (C), 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 dimethyl sulfoxide in the same manner as in Example A1. A negative photosensitive resin composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.2. % Results were obtained.
<Example A11>
In Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that as the resin (A), polymer A50 g and polymer B50 g were changed to polymer C100 g.
The composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids occupied on the surface of the Cu layer was evaluated. % Results were obtained.
<Example A12>
In Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that as the resin (A), polymer A50g and polymer B50g were changed to polymer D100g.
About this composition, after curing at 250 ° C. by the above-mentioned method to produce a cured relief pattern on the Cu layer and conducting a high-temperature storage test, the area ratio of voids in the surface of the Cu layer was evaluated, and 5.0 % Results were obtained.
<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. Polymer E100 g (corresponding to (A) resin), which is a polyoxazole precursor, is represented by the following formula (96):

A photosensitive diazoquinone compound obtained by converting 77% of a phenolic hydroxyl group into naphthoquinonediazide-4-sulfonic acid ester (produced by Toyo Gosei Co., Ltd. (C) corresponds to a photosensitizer) (C1) 20 g, xanthine ((B) Corresponding to a cyclic compound having a carbonyl group) 0.2 g and 3-t-butoxycarbonylaminopropyltriethoxysilane 6 g were dissolved in 100 g of γ-butyrolactone (as a solvent). The viscosity of the resulting solution was adjusted to about 20 poise by further adding a small amount of γ-butyrolactone to obtain a positive photosensitive resin composition.
The composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example A14>
In Example A13, a positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that the polymer E100 g was changed to polymer F100 g as the resin (A).
This composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids occupied on the surface of the Cu layer was evaluated. % Results were obtained.
<Example A15>
In Example A13, a positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that the polymer E100 g was changed to polymer G100 g as the resin (A).
About this composition, it cured at 220 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.3. % Results were obtained.
<Example A16>
In Example A13, a positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that the polymer E100 g was changed to polymer H100 g as the resin (A).
About this composition, it cured at 220 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.2. % Results were obtained.
<Comparative 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 from the composition of Example A1, 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 included.
<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 included.
<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 included.
<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 included.
The results of Examples A1 to 16 and Comparative Examples A1 to A4 are summarized in Table 1.

Example B
<Production Example B1> ((A) Synthesis of Polymer A as Polyimide Precursor)
Place 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2 l separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone and stir at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours.

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

  The obtained reaction liquid was added to 3 l of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 l of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 l of water to precipitate a polymer, and the obtained precipitate was filtered off and then dried in vacuum 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 under the following conditions using gel permeation chromatography (GPC), 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 Polyimide Precursor)
Instead of 155.1 g of 4,4′-oxydiphthalic 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 above-mentioned Production Example B1, to obtain a 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 Polyimide Precursor)
Except for using 147.8 g of 2,2′-bistrifluoromethyl-4,4′-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example B1, The polymer C was obtained by carrying out the reaction in the same manner as described in Production Example B1. 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 Encapsulated AIPA-MO)
In a separable flask having a volume of 5 l, 5-aminoisophthalic acid {hereinafter abbreviated as AIPA. } 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. A solution obtained by diluting 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone was added dropwise thereto using a dropping funnel, and the mixture was stirred at 50 ° C. for about 2 hours.

  Completion of the reaction (disappearance of 5-aminoisophthalic acid) is described as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, The reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product was crystallized and precipitated, it was filtered, washed with water, and vacuumed 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 obtained AIPA-MO had a low molecular weight GPC purity of about 100%.

(Synthesis of polymer D)
Into a separable flask having a volume of 2 liters, 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 added and mixed, and cooled to 5 ° C. in an ice bath. did. A solution obtained by dissolving and diluting 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) in 125 g of GBL was added dropwise thereto over about 20 minutes under ice-cooling, followed by 4,4′-bis (4-aminophenoxy). ) Biphenyl {Hereinafter referred to as BAPB. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and stirred at room temperature for 5 hours. did. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

  A mixed liquid of 840 g of water and 560 g of isopropanol was added dropwise to the resulting reaction liquid, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was dropped into 5 liters of water to precipitate a polymer, and the resulting precipitate was filtered off and then dried under vacuum 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 Polyoxazole Precursor)
In a separable flask having a volume of 3 l, 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 were added. The mixture was stirred at room temperature (25 ° C.) to obtain a uniform solution. A solution prepared by dissolving 118.0 g of 4,4′-diphenyl ether dicarbonyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise thereto 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 temperature of the reaction solution was 30 ° C. at the maximum.

  Three hours after the completion of the dropping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was allowed to stir at room temperature for 15 hours, and 99% of all amine end groups of the polymer chain were carboxylated. Sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). Thereafter, the reaction solution was dropped into 2 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water, dehydrated and then vacuum dried, and measured by gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (in terms of polystyrene) was obtained.

  After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), this was treated with a cation exchange resin and an anion exchange resin, and the resulting solution was treated with ion exchanged water. Then, the precipitated polymer was separated by filtration, washed with water, and dried under vacuum to obtain a purified polybenzoxazole precursor (Polymer E).

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

  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) 70.29 g (266 mmol) of -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone and 60 g of toluene were added at 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 Chemical Industry Co., Ltd.) was added, and a silicon bath temperature of 50 ° C. was passed through nitrogen gas. The mixture was heated and stirred at 100 rpm for 8 hours. Thereafter, the silicon bath was heated to 180 ° C. and stirred with heating at 100 rpm for 2 hours. During the reaction, distillates of toluene and water were removed. After completion of the imidization reaction, the temperature was returned to room temperature.

  Thereafter, the reaction solution was dropped into 3 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water and dehydrated, and then measured by gel permeation chromatography (GPC). A crude polyimide (polymer F) having a weight average molecular weight of 23,000 (polystyrene conversion) was obtained.

<Production Example B7> ((A) Synthesis of polymer G as phenol resin)
125.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 4,4′-bis (methoxymethyl) biphenyl (hereinafter “BMMB”) in a separable flask with a Dean-Stark device of 0.5 liter capacity It was also referred to as “.” 121.2 g (0.5 mol), diethyl sulfate 3.9 g (0.025 mol), and diethylene glycol dimethyl ether 140 g were mixed and stirred at 70 ° C. to dissolve the solid matter.

  The mixed solution was heated to 140 ° C. with an oil bath, and 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 atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction dilution is dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water, dehydrated and then vacuum dried to form a co-polymer consisting of methyl 3,5-dihydroxybenzoate / BMMB. A polymer (polymer G) was obtained with a yield of 70%. The weight average molecular weight of this polymer G determined by standard polystyrene conversion by GPC method was 21,000.

<Production Example B8> ((A) Synthesis of polymer H as phenol resin)
A separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, p-toluenesulfone 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 matter.

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

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

  After completion of the reaction, the same treatment as in Production Example B7 was performed 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 standard polystyrene conversion by 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>
A negative photosensitive resin composition was prepared using the polymers A and B by the following method, and the prepared photosensitive resin composition was evaluated. Polymer A 50 g and B 50 g (corresponding to (A) resin) as polyimide precursors, 0.5 g of dicyclohexylthiourea (corresponding to (B) sulfur-containing compound), 1-phenyl-1,2-propanedione-2- (O -Ethoxycarbonyl) -oxime (described as “PDO” in Table 2) (corresponding to (C) photosensitizer), 4 g of tetraethylene glycol dimethacrylate, N- [3- (triethoxysilyl) propyl] phthalamic acid Along 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 resulting solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to obtain a negative photosensitive resin composition.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.5. % Results were obtained.
<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 component (B) was changed to 0.1 g.
The composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<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 component (B) was changed to 4 g.
The composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated. % Results were obtained.
<Example B4>
In Example B1, 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).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing a high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 7.3 % Results were obtained.
<Example B5>
In Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that rhodanine was used instead of dicyclohexylthiourea as the component (B).
About this composition, after curing at 230 ° C. by the above-mentioned method to produce a cured relief pattern on the Cu layer and conducting a high-temperature storage test, the area ratio of voids in the surface of the Cu layer was evaluated. 7.2 % Results were obtained.
<Example B6>
In Example B1, 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).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing a high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 7.3 % Results were obtained.
<Example B7>
A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, and this composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and a high-temperature storage test was conducted. Then, the area ratio of voids occupied on the surface of the Cu layer was evaluated, and a result of 4.9% was obtained.
<Example B8>
In Example B1, the polymer A50g and the polymer B50g are changed to the polymer A100g as the (A) resin, and as the component (C), PDO4g is 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 (trade name, manufactured by BASF)).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.7 % Results were obtained.
<Example B9>
In Example B1, the polymer A 50 g and the polymer B 50 g are used as the (A) resin, the polymer A 100 g, the PDO 4 g as the component (C), 1,2-octanedione, 1- {4- (phenylthio) -2, -(O-benzoyloxime)} (Irgacure OXE01 (trade name, manufactured by BASF)) was changed to 2.5 g, and the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide in the same manner as in Example B1. A negative photosensitive resin composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.6 % Results were obtained.
<Example B10>
In Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that the polymer A50g and the polymer B50g were changed to the polymer C100g as the (A) resin.
The composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids occupied on the surface of the Cu layer was evaluated. % Results were obtained.
<Example B11>
In Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that the polymer A (50 g) and the polymer B (50 g) were changed to a polymer D (100 g).
This composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<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. Polymer E100 g (corresponding to (A) resin), which is a polyoxazole precursor, is represented by the following formula (96):

The photosensitive diazoquinone compound (Toyo Gosei Co., Ltd. (C) corresponds to a photosensitizer) (C1) 15 g, dicyclohexylthiourea ((B ) Corresponding to 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 resulting solution was adjusted to about 20 poise 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-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example B13>
In the above Example B12, a positive photosensitive resin composition solution was prepared in the same manner as in Example B12 except that the polymer E100 g was changed to the polymer F100 g as the (A) resin.
This composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example B14>
In the above Example B12, a positive photosensitive resin composition solution was prepared in the same manner as in Example B12 except that the polymer E100 g was changed to the polymer G100 g as the resin (A).
About this composition, it cured at 220 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.7 % Results were obtained.
<Example B15>
In Example B12, a positive photosensitive resin composition solution was prepared in the same manner as in Example B12 except that the polymer E100 g was changed to polymer H100 g as the resin (A).
The composition was cured at 220 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<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 included.
<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 included.
<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 included.
The results of Examples B1-15 and Comparative Examples B1-3 are summarized in Table 2.

Example C
<Production Example C1> ((A) Synthesis of Polymer A as Polyimide Precursor)
Place 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2 l separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone and stir at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours.

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

  The obtained reaction liquid was added to 3 l of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 l of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 l of water to precipitate a polymer, and the obtained precipitate was filtered off and then dried in vacuum 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.

In addition, the weight average molecular weight of resin obtained by each manufacture example C was measured on condition of the following using gel permeation chromatography (GPC), and calculated | required the weight average molecular weight in standard polystyrene conversion.
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 Polyimide Precursor)
Instead of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in 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 Polyimide Precursor)
Except for using 147.8 g of 2,2′-bistrifluoromethyl-4,4′-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example C1, In the same manner as in the production method C1, the polymer C was obtained. 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 Encapsulated AIPA-MO)
In a separable flask having a volume of 5 l, 5-aminoisophthalic acid {hereinafter abbreviated as AIPA. } 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. A solution obtained by diluting 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone was added dropwise thereto using a dropping funnel, and the mixture was stirred at 50 ° C. for about 2 hours.

  Completion of the reaction (disappearance of 5-aminoisophthalic acid) is described as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, The reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product was crystallized and precipitated, it was filtered, washed with water, and vacuumed 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 obtained AIPA-MO had a low molecular weight GPC purity of about 100%.

(Synthesis of polymer D)
Into a separable flask having a volume of 2 liters, 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 added and mixed, and cooled to 5 ° C. in an ice bath. did. A solution obtained by dissolving and diluting 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) in 125 g of GBL was added dropwise thereto over about 20 minutes under ice-cooling, followed by 4,4′-bis (4-aminophenoxy). ) Biphenyl {Hereinafter referred to as BAPB. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and stirred at room temperature for 5 hours. did. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

  A mixed liquid of 840 g of water and 560 g of isopropanol was added dropwise to the resulting reaction liquid, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was dropped into 5 liters of water to precipitate a polymer, and the resulting precipitate was filtered off and then dried under vacuum 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 Polyoxazole Precursor)
In a separable flask having a volume of 3 l, 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 were added. The mixture was stirred at room temperature (25 ° C.) to obtain a uniform solution. A solution prepared by dissolving 118.0 g of 4,4′-diphenyl ether dicarbonyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise thereto 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 temperature of the reaction solution was 30 ° C. at the maximum.

  Three hours after the completion of the dropping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was allowed to stir at room temperature for 15 hours, and 99% of all amine end groups of the polymer chain were carboxylated. Sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). Thereafter, the reaction solution was dropped into 2 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water, dehydrated and then vacuum dried, and measured by gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (in terms of polystyrene) was obtained.

  After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), this was treated with a cation exchange resin and an anion exchange resin, and the resulting solution was treated with ion exchanged water. Then, the precipitated polymer was separated by filtration, washed with water, and dried under vacuum to obtain a purified polybenzoxazole precursor (Polymer E).

<Production Example C6> ((A) Synthesis of Polymer F as Polyimide)
A condenser tube with a Dean-Stark trap was attached to a glass separable four-necked flask equipped with a Teflon (registered trademark) vertical stirrer. While passing through nitrogen gas, the flask was placed in a silicon oil bath and stirred.

  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) 70.29 g (266 mmol) of -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone and 60 g of toluene were added at 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 Chemical Industry Co., Ltd.) was added, and a silicon bath temperature of 50 ° C. was passed through nitrogen gas. The mixture was heated and stirred at 100 rpm for 8 hours. Thereafter, the silicon bath was heated to 180 ° C. and stirred with heating at 100 rpm for 2 hours. During the reaction, distillates of toluene and water were removed. After completion of the imidization reaction, the temperature was returned to room temperature.

  Thereafter, the reaction solution was dropped into 3 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water and dehydrated, and then measured by gel permeation chromatography (GPC). A crude polyimide (polymer F) having a weight average molecular weight of 23,000 (polystyrene conversion) was obtained.

<Production Example C7> ((A) Synthesis of Polymer G as Phenol Resin)
125.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 4,4′-bis (methoxymethyl) biphenyl (hereinafter “BMMB”) in a separable flask with a Dean-Stark device of 0.5 liter capacity It was also referred to as “.” 121.2 g (0.5 mol), diethyl sulfate 3.9 g (0.025 mol), and diethylene glycol dimethyl ether 140 g were mixed and stirred at 70 ° C. to dissolve the solid matter.

  The mixed solution was heated to 140 ° C. with an oil bath, and 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 atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction dilution is dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water, dehydrated and then vacuum dried to form a co-polymer consisting of methyl 3,5-dihydroxybenzoate / BMMB. A polymer (polymer G) was obtained with a yield of 70%. The weight average molecular weight of this polymer G determined by standard polystyrene conversion by GPC method was 21,000.

<Production Example C8> ((A) Synthesis of Polymer H as Phenol Resin)
A separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, p-toluenesulfone 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 matter.

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

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

  After completion of the reaction, the same treatment as in Production Example C7 was performed 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 standard polystyrene conversion by 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>
A negative photosensitive resin composition was prepared using the polymers A and B by the following method, and the prepared photosensitive resin composition was evaluated. Polymer A50g and B50g (corresponding to (A) resin) which are polyimide precursors, 1 g of butylurea (corresponding to (B-1) compound), 1-phenyl-1,2-propanedione-2- (O-ethoxy) Carbonyl) -oxime (described as “PDO” in Table 3) (corresponding to (C) photosensitizer), 4 g of tetraethylene glycol dimethacrylate, N- [3- (triethoxysilyl) propyl] phthalamic acid Along 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 resulting solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to obtain a negative photosensitive resin composition.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.5. % Results were obtained.
<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 component (B) was changed to 0.1 g.
This composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<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 component (B) was changed to 5 g.
The composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated. % Results were obtained.
<Example C4>
In Example C1, a negative photosensitive resin composition was used in the same manner as in Example C1, except that tetraethylene glycol (corresponding to the (B-2) compound) was used as the component (B) instead of butylurea. A solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 6.2. % Results were obtained.
<Example C5>
In Example C1, a negative was conducted in the same manner as in Example C1, except that bis (2-methoxyethyl) adipate (corresponding to the (B-3) compound) was used as the component (B) instead of butylurea. Type photosensitive resin composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 6.3 % Results were obtained.
<Example C6>
A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, and this composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and a high-temperature storage test was conducted. Then, the area ratio of voids occupied on the surface of the Cu layer was evaluated, and a result of 4.7% was obtained.
<Example C7>
In Example C1, the polymer A 50 g and the polymer B 50 g are changed to the polymer A 100 g as the (A) resin, and as the component (C), PDO 4 g is 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 the amount was changed to 2.5 g of 2- (O-benzoyloxime)} (Irgacure OXE01 (trade name, manufactured by BASF)).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.4 % Results were obtained.
<Example C8>
In Example C1, (A) the polymer A50g and the polymer B50g as the resin (A), the polymer A100g, the PDO4g as the component (C), 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 dimethyl sulfoxide in the same manner as in Example C1. A negative photosensitive resin composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.5. % Results were obtained.
<Example C9>
In Example C1, a negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that the polymer A (50 g) and the polymer B (50 g) were changed to the polymer C (100 g) as the (A) resin.
The composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids in the surface of the Cu layer was evaluated. % Results were obtained.
<Example C10>
In Example C1, a negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that the polymer A (50 g) and the polymer B (50 g) were changed to a polymer D (100 g).
The composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated. % Results were obtained.
<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. Polymer E100 g (corresponding to (A) resin), which is a polyoxazole precursor, is represented by the following formula (96):

A photosensitive diazoquinone compound obtained by converting 77% of a phenolic hydroxyl group into naphthoquinonediazide-4-sulfonic acid ester (produced by Toyo Gosei Co., Ltd., (C) corresponds to a photosensitive agent) (C1) 15 g, butylurea ((B -1) Corresponding to the compound) 1 g and 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane were dissolved in 100 g of γ-butyrolactone (as a solvent). The viscosity of the resulting solution was adjusted to about 20 poise by further adding a small amount of γ-butyrolactone to obtain a positive photosensitive resin composition.
The composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids in the surface of the Cu layer was evaluated. % Results were obtained.
<Example C12>
In Example C11, a positive photosensitive resin composition solution was prepared in the same manner as in Example C11 except that the polymer E100 g was changed to polymer F100 g as the resin (A).
This composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example C13>
In the above Example C11, a positive photosensitive resin composition solution was prepared in the same manner as in Example C11 except that the polymer E100 g was changed to the polymer G100 g as the resin (A).
About this composition, after curing at 220 ° C. by the above-mentioned method to produce a cured relief pattern on the Cu layer and conducting a high-temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. % Results were obtained.
<Example C14>
In Example C11, a positive photosensitive resin composition solution was prepared in the same manner as in Example C13, except that the polymer E100 g was changed to polymer H100 g as the resin (A).
The composition was cured at 220 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<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 included.
<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 included.
<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 included.

Example D
<Production Example D1> ((A) Synthesis of Polymer (A) -1 as Polyimide Precursor)
Place 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2 l separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone and stir at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours.

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

  The obtained reaction liquid was added to 3 l of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 l of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate was filtered off and dried in vacuum 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.

In addition, the weight average molecular weight of resin obtained by each manufacture example D was measured on condition of the following using gel permeation chromatography (GPC), and calculated | required the weight average molecular weight in standard polystyrene conversion.
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 Polyimide Precursor)
Instead of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in 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 in the method 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 Polyimide Precursor)
Except for using 147.8 g of 2,2′-bistrifluoromethyl-4,4′-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example D1, In the same manner as in the method described in Production Example D1, a polymer (A) -3 was obtained. 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 Encapsulated AIPA-MO)
In a separable flask having a volume of 5 l, 5-aminoisophthalic acid {hereinafter abbreviated as AIPA. } 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. A solution obtained by diluting 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone was added dropwise thereto using a dropping funnel, and the mixture was stirred at 50 ° C. for about 2 hours.

  Completion of the reaction (disappearance of 5-aminoisophthalic acid) is described as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, The reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product was crystallized and precipitated, it was filtered, washed with water, and vacuumed 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 obtained AIPA-MO had a low molecular weight GPC purity of about 100%.

(Synthesis of polymer (A) -4)
Into a separable flask having a volume of 2 liters, 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 added and mixed, and cooled to 5 ° C. in an ice bath. did. A solution obtained by dissolving and diluting 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) in 125 g of GBL was added dropwise thereto over about 20 minutes under ice-cooling, followed by 4,4′-bis (4-aminophenoxy). ) Biphenyl {Hereinafter referred to as BAPB. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and stirred at room temperature for 5 hours. did. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

  A mixed liquid of 840 g of water and 560 g of isopropanol was added dropwise to the resulting reaction liquid, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was dropped into 5 liters of water to precipitate a polymer, and the resulting precipitate was filtered off and dried in vacuo 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> ((A) Synthesis of Polymer (A) -5 as Polyoxazole Precursor)
In a separable flask having a volume of 3 l, 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 were added. The mixture was stirred at room temperature (25 ° C.) to obtain a uniform solution. A solution prepared by dissolving 118.0 g of 4,4′-diphenyl ether dicarbonyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise thereto 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 temperature of the reaction solution was 30 ° C. at the maximum.

  Three hours after the completion of the dropping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was allowed to stir at room temperature for 15 hours, and 99% of all amine end groups of the polymer chain were carboxylated. Sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). Thereafter, the reaction solution was dropped into 2 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water, dehydrated and then vacuum dried, and measured by gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (in terms of polystyrene) was obtained.

  After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), this was treated with a cation exchange resin and an anion exchange resin, and the resulting solution was treated with ion exchanged water. Then, the precipitated polymer was separated by filtration, washed with water, and dried under vacuum to obtain a purified polybenzoxazole precursor (polymer (A) -5).

<Production Example D6> ((A) Synthesis of Polymer (A) -6 as Polyimide)
A condenser tube with a Dean-Stark trap was attached to a glass separable four-necked flask equipped with a Teflon (registered trademark) vertical stirrer. While passing through nitrogen gas, the flask was placed in a silicon oil bath and stirred.

  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) 70.29 g (266 mmol) of -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone and 60 g of toluene were added at 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 Chemical Industry Co., Ltd.) was added, and a silicon bath temperature of 50 ° C. was passed through nitrogen gas. The mixture was heated and stirred at 100 rpm for 8 hours. Thereafter, the silicon bath was heated to 180 ° C. and stirred with heating at 100 rpm for 2 hours. During the reaction, distillates of toluene and water were removed. After completion of the imidization reaction, the temperature was returned to room temperature.

  Thereafter, the reaction solution was dropped into 3 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water and dehydrated, and then measured by gel permeation chromatography (GPC). A crude polyimide (polymer (A) -6) having a weight average molecular weight of 23,000 (polystyrene conversion) 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), N-phenylbenzylamine (manufactured by Tokyo Chemical Industry Co., Ltd., (B) -1 Applicable) 3 g, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (described as “PDO” in Table 4) (corresponding to (C) sensitizer) 4 g, tetraethylene Along with 8 g of glycol dimethacrylate and 1.5 g of N- [3- (triethoxysilyl) propyl] phthalamic acid, 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 above mixed solvent to obtain a negative photosensitive resin composition.
About this composition, after curing at 230 ° C. by the above-mentioned method to produce a cured relief pattern on the Cu layer and conducting a high-temperature storage test, the area ratio of voids occupied on the surface of the Cu layer was evaluated, and 4.5 % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D2>
Negative photosensitive resin in the same manner as in Example D1, except that the component (B) in Example D1 was changed to N, N′-diphenylethane-1,2-diamine (manufactured by Tokyo Chemical Industry Co., Ltd.). A composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 4.2. % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D3>
In Example D1, 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-butylphenyl carbamate (manufactured by Tokyo Chemical Industry Co., Ltd.).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.1. % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D4>
A negative photosensitive resin composition solution in the same manner as in Example D1, except that the component (B) in Example D1 was changed to tert-butyl (3-hydroxyphenyl) carbamate (manufactured by Tokyo Chemical Industry Co., Ltd.). Was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.8 % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D5>
In Example D1, except that the component (B) was changed to 2-hydroxy-N- (1H-1,2,4-triazol-3-yl) benzamide (manufactured by ADEKA Corporation, ADK STAB CDA-1), In the same manner as in Example D1, a negative photosensitive resin composition solution was prepared.
The composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated. % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D6>
In the above Example D1, the component (B) was changed to 2- (2H-benzo [d] [1,2,3] triazol-2-yl) -4- (2,4,4-trimethylpentan-2-yl) A negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that it was changed to phenol (manufactured by ADEKA Corporation, ADK STAB LA-29).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 4.2. % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D7>
In Example D1, except that component (B) was changed to (4-((1H-1,2,4-triazol-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.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, 6.1. % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish 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 the (B) -1 component added was changed to 1 g.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 8.5 % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D9>
In the above Example D1, a negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that the addition amount of the component (B) -1 was changed to 6 g.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 4.9 % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish 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.
About this composition, after curing at 230 ° C. by the above-mentioned method to produce a cured relief pattern on the Cu layer and conducting a high-temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D11>
In Example D1, a negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that the curing temperature was changed from 230 ° C. to 350 ° C.
For this composition, a cured relief pattern was prepared on the Cu layer and subjected to a high-temperature storage test. Then, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 6.1% was obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D12>
In the above Example D1, as the (A) resin, the polymer (A) -1, 50 g and the polymer (A) -2, 50 g are converted into the polymer (A) -1, 100 g, and the component (C) is converted from PDO 1, Example D1 except that 2-octanedione, 1- {4- (phenylthio)-, 2- (O-benzoyloxime)} (Irgacure OXE01 (trade name, manufactured by BASF)) was changed to 2.5 g. In the same manner, a negative photosensitive resin composition solution was prepared.
For this composition, a cured relief pattern was prepared on the Cu layer and subjected to a high temperature storage test, and then the void area ratio in the surface of the Cu layer was evaluated, and a result of 5.8% was obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D13>
A negative photosensitive resin composition solution was prepared in the same manner as in Example D12 except that in Example D12, the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide.
For this composition, a cured relief pattern was prepared on the Cu layer and subjected to a high temperature storage test. Then, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 5.4% was obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D14>
In the above Example D1, as the (A) resin, the polymer (A) -1, 50 g and the polymer (A) -2, 50 g are changed to the polymer (A) -3, 100 g, and the curing temperature is 230 ° C. to 350 ° C. A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that it was changed to.
A cured relief pattern was prepared on the Cu layer for this composition, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 7.2% was obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D15>
In Example D1, Example D1 except that the polymer (A) -1, 50 g and the polymer (A) -2, 50 g were changed to the polymer (A) -4, 100 g as the resin (A). In the same manner, a negative photosensitive resin composition solution was prepared.
A cured relief pattern was prepared on the Cu layer for this composition, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and a result of 4.9% was obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D16>
Using the polymer (A) -5, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Polymer (A) -5 which is a polyoxazole precursor, 100 g (corresponding to (A) resin) is represented by the following formula (96):

A photosensitive diazoquinone compound obtained by converting 77% of a phenolic hydroxyl group into naphthoquinonediazide-4-sulfonic acid ester (produced by Toyo Gosei Co., Ltd., corresponding to the component (C)) (C1) 15 g, γ-butyrolactone (as a solvent) ) Dissolved in 100 g. The viscosity of the resulting solution was adjusted to about 20 poise by further adding a small amount of γ-butyrolactone to obtain a positive photosensitive resin composition.
The composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer, 6.9 % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D17>
In the above Example D16, the positive photosensitive resin composition was the same as Example D12 except that the polymer (A) -5, 100 g was changed to the polymer (A) -6, 100 g as the (A) resin. A solution was prepared.
About this composition, it cured at 250 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 6.0 % Results were obtained. Moreover, the viscosity change rate after the storage stability test of the obtained varnish 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 included. Moreover, the viscosity change rate after the storage stability test of the obtained varnish 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 included. Moreover, the viscosity change rate after the storage stability test of the obtained varnish 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 included. Moreover, the viscosity change rate after the storage stability test of the obtained varnish 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 it did not contain the component (B) of the present invention. Moreover, the viscosity change rate after the storage stability test of the obtained varnish 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 (B) -1 component added was changed to 25 g in the composition of Example D1, and the same evaluation as in Example D1 was made. Was done. The evaluation result was 7.2%. Moreover, the viscosity change rate after the storage stability test of the obtained varnish was 10% or more.
The results of Examples D1-17 and Comparative Examples D1-5 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 the production of electrical / electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (6)

(A) Polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and at least one selected from the group consisting of novolak, polyhydroxystyrene, and phenol resin 100 parts by mass of resin,
(B) a cyclic compound having two or more carbonyl groups, wherein the carbonyl group is directly bonded to the cyclic structure, and in the case of a monocyclic compound, 1/3 or more of the atoms forming the ring structure are N atoms In the case of a condensed ring compound, at least one compound selected from the group consisting of compounds in which 1/3 or more of the atoms forming the ring structure having the carbonyl group is an N atom is used as the (A) resin. 0.01 to 10 parts by weight based on 100 parts by weight; and
(C) 1 to 50 parts by mass of the photosensitive agent based on 100 parts by mass of the resin (A),
A photosensitive resin composition comprising: The (A) resin includes a polyimide precursor including the following general formula (1), a polyamide including the following general formula (4), a polyoxazole precursor including the following general formula (5), and the following general formula (6). The photosensitive resin composition of Claim 1 which is at least 1 type selected from the group which consists of a polyimide resin and a novolak, polyhydroxystyrene, and the phenol resin containing following General formula (7).
The following general formula (1) is

{Wherein 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 each independently And a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or the following general formula (2):

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

(Wherein R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group 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 them. R ₉ is an organic group having at least one radical-polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n ₂ is an integer of 1 to 1000. }
A polyamide having a structure represented by:
The following general formula (5)

{Wherein Y ₃ is a tetravalent organic group having a carbon atom, and Y ₄ , X ₃ and X ₄ are each independently a divalent organic group having 2 or more carbon atoms, 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 arrangement order of n dihydroxy diamide units and n ₄ diamide units including X ₄ and Y ₄ is not limited. }
A polyhydroxyamide which is a polyoxazole precursor having a structure represented by:
The following general formula (6)

{In the formula, X ₅ is a tetravalent to tetravalent organic group, Y ₅ is a divalent to divalent organic group, and R ₁₀ and R ₁₁ are each independently a phenolic hydroxyl group or a sulfonic acid group. or it represents at least one having organic groups a group selected from a thiol group, n ₅ is an integer from 3 to 200, and m ₃ and m ₄ represents an integer of 0. }
A polyimide having a structure represented by:
The following general formula (7) is

{Wherein, 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 a group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, the plurality of R ₁₂ 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, and the following general formula (8):

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

{Wherein R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are substituted with fluorine atoms. 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 a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ is a hydroxyl group, and a plurality of R _{17 s} when n ₆ is an integer of 2 to 4 may be the same or different from each other. Also good. } And the following general formula (10):

{In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms substituted with fluorine atoms. 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 fluorine atom, or a fluorine atom. A C3-C20 alicyclic group, the following general formula (8):

(Wherein p is an integer of 1 to 10) and the following formula (11):

A divalent group selected from the group consisting of divalent groups represented by the formula: } The photosensitive resin composition of Claim 1 or 2 which is a bivalent organic group selected from the group which consists of a bivalent group represented by these. (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) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a step of forming a cured relief pattern by heat-treating the relief pattern.   The method of claim 4, wherein the substrate is formed from copper or a copper alloy.   A semiconductor device comprising a cured relief pattern obtained by the manufacturing method according to claim 4.