JP7293299B2 - Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device - Google Patents

Description

The present invention relates to, for example, an insulating material for electronic parts, 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 semiconductor devices.

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

By the way, semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards by various methods according to their purposes. Conventional devices are generally manufactured by a wire bonding method in which thin wires are used to connect external terminals (pads) of the device to lead frames. However, today, when the speed of devices has increased and the operating frequency has reached GHz, the difference in the wiring length of each terminal in mounting affects the operation of the device. Therefore, in 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 this requirement 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, the chip is flipped over, and the chip is directly mounted on a printed circuit board. (See Patent Document 1, for example). Since this flip-chip mounting can accurately control the wiring distance, it has been adopted for high-end devices that handle high-speed signals, and for mobile phones due to its small mounting size, and demand is growing rapidly. . When a material such as polyimide, polybenzoxazole, or phenolic resin is 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 surface of the resin layer to roughen the surface, then forming a metal layer as a seed layer for plating with a thickness of 1 μm or less by sputtering. It is formed by electrolytic plating. At this time, generally, Ti is used as the metal for the seed layer, and Cu is used as the metal for the rewiring layer formed by electrolytic plating.

Such a metal rewiring layer is required to have high adhesion between the metal layer and the resin layer, which are rewired after the reliability test. As a reliability test performed here, for example, a high temperature storage test in which the sample is stored at a high temperature of 125° C. or higher in the air for 100 hours or longer, and a voltage is applied by connecting wires to the temperature of about 125° C. in the air. High temperature operation test to confirm operation under storage for 100 hours or more, temperature cycle test 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 the air, 85 A high-temperature, high-humidity storage test in which the product is stored in a steam atmosphere with a humidity of 85% or higher at a temperature of ℃ or higher, a high-temperature and high-humidity bias test in which the same test is performed while wiring is connected and a voltage is applied, and a temperature of 260℃ in the air or under nitrogen. A solder reflow test in which a solder reflow oven is passed multiple times.

However, conventionally, among the reliability tests described above, in the case of a high-temperature storage test, there has been a problem that voids are generated at the interface between the re-wiring Cu layer and the resin layer after the test. If voids occur at the interface between the Cu layer and the resin layer, the adhesion between the two will be reduced.

JP-A-2001-338947

The present invention has been devised in view of such conventional circumstances, and after a high temperature storage test, the Cu layer does not generate voids at the interface in contact with the cured photosensitive resin layer. , a photosensitive resin composition capable of forming a resin layer with high adhesion, a method for forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern. and

The present inventors have found that by blending a cyclic compound having a carbonyl group in a photosensitive resin composition, a photosensitive resin composition that provides a cured film that is excellent in suppressing discoloration even on copper or copper alloy can be obtained. The discovery led to the completion of the present invention. That is, the present invention is as follows.

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

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

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

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

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

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

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

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

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

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

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

で表される２価の基からなる群から選択される２価の基である。｝で表される２価の基からなる群から選択される２価の有機基である、[１]又は［２］に記載の感光性樹脂組成物。
［４］
（１）［１］～［３］のいずれか１つに記載の感光性樹脂組成物を基板上に塗布することによって感光性樹脂層を前記基板上に形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）前記露光後の感光性樹脂層を現像してレリーフパターンを形成する工程と、
（４）前記レリーフパターンを加熱処理することによって硬化レリーフパターンを形成する工程と
を含む、硬化レリーフパターンの製造方法。
［５］前記基板が、銅又は銅合金から形成されている、［４］に記載の方法。
［６］［４］又は［５］に記載の製造方法により得られる硬化レリーフパターンを含む半導体装置。 [1] (A) selected from the group consisting of polyamic acids, polyamic acid esters, polyamic acid salts, polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, and novolaks, polyhydroxystyrenes and phenolic resins 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, ⅓ or more of the atoms forming the ring structure are N atoms. and in the case of a condensed ring compound, at least one compound selected from the group consisting of compounds in which ⅓ or more of the atoms forming the ring structure having the carbonyl group are N atoms, the (A) resin 0.01 to 10 parts by mass based on 100 parts by mass;
(C) a photosensitive agent of 1 to 50 parts by mass based on 100 parts by mass of the resin (A);
A photosensitive resin composition comprising:
[2] The (A) resin is a polyimide precursor containing the following general formula (1), a polyamide containing the following general formula (4), a polyoxazole precursor containing the following general formula (5), and a general formula (6) ), and at least one selected from the group consisting of novolaks, polyhydroxystyrenes, and phenolic resins containing the following general formula (7), the photosensitive resin composition according to [1].
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 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 or a saturated aliphatic group having 1 to 4 carbon atoms, or 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. }, which is a polyamic acid, a polyamic acid ester, or a polyamic acid salt that 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, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and has the same structure, or a plurality of wherein R ₉ is an organic group having at least one radically polymerizable unsaturated bond group of 3-20 carbon atoms, and n ₂ is an integer of 1-1000. }
A polyamide having a structure represented by
The following general formula (5) is

{wherein Y ₃ is a tetravalent organic group having carbon atoms, 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 from 0 to 500, n ₃ /(n ₃ +n ₄ )>0.5, and n ₃ including X ₃ and Y ₃ The arranging order of the dihydroxy diamide units and n ₄ diamide units including X ₄ and Y ₄ does not matter. }
A polyhydroxyamide that is a polyoxazole precursor having a structure represented by
The following general formula (6) is

{In the formula, X ₅ is a 4- to 14-valent organic group, Y ₅ is a 2- to 12-valent organic group, R ₁₀ and R ₁₁ are each independently a phenolic hydroxyl group and a sulfonic acid group. or an organic group having at least one group selected from thiol groups, n ₅ is an integer of 3-200, and m ₃ and m ₄ are integers of 0-10. }
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 compound having 1 to 20 carbon atoms represents a monovalent substituent selected from the group consisting of groups, halogen atoms, nitro groups and cyano groups, and when b is 2 or 3, a plurality of R ₁₂ may be the same or different from each other Well, X is a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, the following general formula (8):

(Wherein, p is an integer of 1 to 10.) 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. } is a phenol resin represented by.
[3] The photosensitive resin composition contains a phenol resin having a repeating unit represented by the general formula (7), and X in the general formula (7) is 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 some or all of the hydrogen atoms are substituted with fluorine atoms; is a monovalent aliphatic group having 1 to 10 carbon atoms, n ₆ is an integer of 0 to 4, and R ₁₇ when n ₆ is an integer of 1 to 4 is a halogen atom or a hydroxyl group , or a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ is a hydroxyl group, and when n ₆ is an integer of 2 to 4, a plurality of R ₁₇ may be the same or different. good too. } and the following general formula (10):

{wherein 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 some or all of the hydrogen atoms are substituted with fluorine atoms; represents a monovalent aliphatic group having 1 to 10 carbon atoms, W is a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and an alicyclic group having 3 to 20 carbon atoms, the following general formula (8):

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

is a divalent group selected from the group consisting of divalent groups represented by } is a divalent organic group selected from the group consisting of divalent groups represented by [1] or [2].
[4]
(1) forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of [1] to [3] onto the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a hardened relief pattern, comprising the step of forming a hardened 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 comprising a cured relief pattern obtained by the manufacturing method described in [4] or [5].

According to the present invention, by combining a specific photosensitive resin and a specific compound, voids do not occur at the interface between the Cu layer and the polyimide layer after a high temperature storage test, resulting in high adhesion. 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 the present specification, structures represented by the same reference numerals in general formulas may be the same or different when a plurality of structures are present in a molecule.

<Photosensitive resin composition>
(Aspect A)
(A) from the group consisting of polyamic acids, polyamic acid esters and polyamic acid salts, polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, and novolacs, polyhydroxystyrenes and phenolic resins At least one selected resin: 100 parts by mass, (B) a cyclic compound having a carbonyl group: 0.01 to 10 parts by mass based on 100 parts by mass of (A) resin, (C) photosensitive agent: (A) resin 100 The essential component is 1 to 50 parts by mass based on parts by mass.

(A) Resin The resin (A) used in the present invention will be described. The (A) resin of the present invention is a group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and novolac, polyhydroxystyrene and phenolic resins. The main component is at least one selected resin. 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 resins may be included as necessary.

From the viewpoint of heat resistance after heat treatment and mechanical properties, the weight average molecular weight of these resins is preferably 200 or more, more preferably 5,00 or more, in terms of polystyrene by gel permeation chromatography. The upper limit is preferably 500,000 or less, and in the case of a photosensitive resin composition, from the viewpoint of solubility in a developer, 20,000 or less is more preferable.

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

Photosensitive resins include polyamic acid, polyamic acid esters, polyamic acid salts, polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, and phenolic resins including novolacs and polyhydroxystyrenes, and resins after heat treatment. Polyamic acids, polyamic acid esters, polyamic acid salts, polyamides, polyhydroxyamides, polyimides and phenolic resins are preferably used because they have excellent heat resistance and mechanical properties. In addition, these photosensitive resins can be selected according to the desired application, such as whether to prepare a negative-type or positive-type photosensitive resin composition together with the (C) photosensitive agent described later.

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

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

（式中、Ｒ₆、Ｒ₇及びＲ₈は、それぞれ独立に、水素原子又は炭素数１～３の有機基であり、そしてｍ₂は、２～１０の整数である。）で表される一価のアンモニウムイオンである。｝、で表されるポリイミドの前駆体であるポリアミド酸、ポリアミド酸エステル又はポリアミド酸塩である。
ポリイミド前駆体は、加熱（例えば２００℃以上）環化処理を施すことによってポリイミドに変換される。ポリイミド前駆体はネガ型感光性樹脂組成物用として好適である。 [(A) polyamic acid, polyamic acid ester, polyamic acid salt]
In the photosensitive resin composition of the present invention, one example of the most preferable (A) resin from the viewpoint 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; 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 that is a precursor of polyimide represented by.
A polyimide precursor is converted to a polyimide by subjecting it to a heating (for example, 200° C. or higher) cyclization treatment. Polyimide precursors are suitable for negative photosensitive resin compositions.

｛式中、Ｒ２５は水素原子、フッ素原子、Ｃ１～Ｃ１０の炭化水素基、Ｃ１～Ｃ１０の含フッ素炭化水素基から選ばれる１価の基であり、ｌは０～２から選ばれる整数、ｍは０～３から選ばれる整数、ｎは０～４から選ばれる整数である。｝
で表される構造が挙げられるが、これらに限定されるものではない。また、Ｘ₁の構造は１種でも２種以上の組み合わせでも構わない。上記式で表される構造を有するＸ₁基は、耐熱性と感光特性とを両立するという点で特に好ましい。 In the above general formula (1), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably , --COOR ₁ group and --COOR ₂ group and --CONH-- group are aromatic groups or alicyclic aliphatic groups in the ortho position to each other. The tetravalent organic group represented by X ₁ is preferably an aromatic ring-containing organic group having 6 to 40 carbon atoms, more preferably the following formula (30):

{Wherein, R25 is a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group, a monovalent group selected from a C1-C10 fluorine-containing hydrocarbon group, l is an integer selected from 0 to 2, m is an integer selected from 0-3, and n is an integer selected from 0-4. }
Examples include, but are not limited to, structures represented by: Moreover, 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 preferred in terms of achieving both heat resistance and photosensitive properties.

｛式中、Ｒ２５は水素原子、フッ素原子、Ｃ１～Ｃ１０の炭化水素基、Ｃ１～Ｃ１０の含フッ素炭化水素基から選ばれる１価の基であり、ｎは０～４から選ばれる整数である。｝
で表される構造が挙げられるが、これらに限定されるものではない。また、Ｙ₁の構造は１種でも２種以上の組み合わせでも構わない。上記式（３１）で表される構造を有するＹ₁基は、耐熱性及び感光特性を両立するという点で特に好ましい。 In the above general formula (1), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive properties. Formula (31) below:

{Wherein, 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. . }
Examples include, but are not limited to, structures represented by: Moreover, 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 properties.

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

(A) When a polyimide precursor is used as the resin, methods for imparting photosensitivity to the photosensitive resin composition include an ester bond type and an ionic bond type. The former is a method of introducing a compound having a photopolymerizable group, i.e., an olefinic double bond, into the side chain of the polyimide precursor via an ester bond, and the latter is a method of introducing a carboxyl group of the polyimide precursor and an amino group ( In this method, the amino group of the meth)acrylic compound is bonded via an ionic bond to impart a photopolymerizable group.

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

(Preparation of acid/ester form)
In the present invention, the tetracarboxylic dianhydride containing a tetravalent organic group X ₁ , which is suitably used for preparing the ester bond type polyimide precursor, includes the tetracarboxylic acid represented by the general formula (30). Acid dianhydrides such as pyromellitic anhydride, diphenyl ether-3,3′,4,4′-tetracarboxylic dianhydride, benzophenone-3,3′,4,4′-tetracarboxylic dianhydride product, 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 and the like, preferably pyromellitic anhydride, diphenyl ether-3,3′,4,4′-tetracarboxylic dianhydride, benzophenone-3,3′,4,4′-tetracarboxylic acid dianhydride, biphenyl-3,3′,4,4′-tetracarboxylic dianhydride, but not limited thereto. In addition, these may be used alone, or two or more of them may be mixed and used.

In the present invention, alcohols having a photopolymerizable unsaturated double bond that are suitably used for preparing an ester bond type polyimide precursor include, for example, 2-acryloyloxyethyl alcohol, 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-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate , 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like.

A saturated aliphatic alcohol having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc., can be partially mixed with the above alcohols.

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

(Preparation of polyimide precursor)
To the above acid/ester form (typically a solution in a solvent described later), under ice cooling, a suitable dehydration condensation agent such as dicyclocarbodiimide (eg dicyclohexylcarbodiimide), 1-ethoxycarbonyl-2-ethoxy-1 ,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc. are added and mixed to convert the acid/ester into polyanhydride. After that, a diamine containing a divalent organic group Y ₁ preferably used in the present invention is separately dissolved or dispersed in a solvent and added dropwise thereto, and amide polycondensation is performed to obtain the desired polyimide. A precursor can be obtained. Alternatively, the acid/ester compound is reacted with a diamine compound in the presence of a base such as pyridine after the acid moiety is acid chlorided using thionyl chloride or the like, whereby the desired polyimide precursor can be obtained. .

Examples of diamines containing a divalent organic group Y ₁ preferably used in the present invention include diamines having a structure represented by the general formula (31), p-phenylenediamine, m-phenylenediamine, 4 , 4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl , 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 1 , 4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,

1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-amino phenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis (4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2 - bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolysine sulfone, 9,9-bis(4-aminophenyl)fluorene, and some of the hydrogen atoms on their benzene rings are methyl groups, ethyl group, hydroxymethyl group, hydroxyethyl group, those substituted with halogen, etc., such as 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'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'- dichloro-4,4'-diaminobiphenyl, 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4, 4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like, preferably p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 2,2'-dimethylbenzidine, 2,2'- bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like, and mixtures thereof. but not limited to this.

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

After the completion of the amide polycondensation reaction, water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution are optionally filtered off, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is It is added to the obtained polymer component, the polymer component is precipitated, and the polymer is purified by repeating redissolution, reprecipitation, etc., and vacuum drying to obtain the desired polyimide precursor. release. In order to improve the degree of purification, the polymer solution may be passed through a column packed with anion and/or cation exchange resins swollen with a suitable organic solvent to remove ionic impurities.

On the other hand, the ionic bond type polyimide precursor is typically obtained by reacting a tetracarboxylic dianhydride with a diamine. In this case, at least one of R ₁ and R ₂ in the general formula (1) is a hydroxyl group.

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

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

The amount of the (meth)acrylic compound having an amino group is 1 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the resin (A). (C) As a photosensitizer, a (meth)acrylic compound having an amino group is added to 100 parts by mass of the resin (A) by blending 1 part by mass or more to achieve excellent photosensitivity, and by blending 20 parts by mass or less to cure thick films. Excellent in nature.

The molecular weight of the ester bond type and the ion bond type polyimide precursor is preferably 8,000 to 150,000, preferably 9,000, when measured by polystyrene-equivalent weight average molecular weight by gel permeation chromatography. More preferably ~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 a developer is good and the relief pattern resolution performance is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Also, 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 STANDARD SM-105, an organic solvent-based standard sample 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]
Another preferred example of the (A) resin in the photosensitive resin composition of the present invention is represented by the following general formula (4):

{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and has the same structure, or a plurality of wherein R ₉ is an organic group having at least one radically polymerizable unsaturated bond group of 3-20 carbon atoms, and n ₂ is an integer of 1-1,000. }
is a polyamide having a structure represented by This polyamide is suitable for use in negative photosensitive resin compositions.

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

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

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

It is preferably an aromatic group selected from groups represented by the following, 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 above general formula (4), the divalent organic group represented by Y ₂ is preferably an organic group having 6 to 35 carbon atoms, and an optionally substituted aromatic or aliphatic ring. is more preferably a cyclic organic group having 1 to 4 or an aliphatic group or a siloxane group having no cyclic structure. The divalent organic group represented by Y ₂ includes the following general formula (I) and the following general formulas (34) and (35):

{wherein 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 ), and the propyl and butyl groups include various isomers. }

{wherein m ₇ is an integer of 0 to 8, m ₈ and m ₉ are each independently an integer of 0 to 3, m ₁₀ and m ₁₁ are each independently an integer of 0 to 10 is an integer 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 isomers of these. } is mentioned.

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

{wherein m ₁₂ is an integer of 2 to 12, m ₁₃ is an integer of 1 to 3, m ₁₄ is an integer of 1 to 20, and R ₃₇ , R ₃₈ , R ₃₉ and Each R ₄₀ is independently an alkyl group having 1 to 3 carbon atoms or an optionally substituted phenyl group. } are preferred.

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

When a phthalic acid compound is sealed with a group containing a radically polymerizable unsaturated bond, it is possible to impart negative photosensitivity (photocurability) to the polyamide resin.

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

The above-mentioned phthalate compound encapsulant is obtained by reacting the amino group of the phthalate compound with an acid chloride, isocyanate, epoxy compound, or the like having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms. can be obtained with

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 and the like. These may be used alone or in combination, but it is particularly preferred to use methacryloyl chloride and/or 2-(methacryloyloxy)ethyl isocyanate.

Furthermore, as for these phthalic acid compound sealing bodies, those in which the phthalic acid compound is 5-aminoisophthalic acid are excellent in photosensitivity, and at the same time, a polyamide having excellent film properties after heat curing can be obtained. preferred.

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

Depending on the type of sealing agent such as acid chloride, hydrogen chloride may be produced as a by-product in the process of the sealing reaction. In this case, from the viewpoint of preventing contamination in subsequent steps, it is preferable to carry out appropriate purification such as reprecipitation with water, washing with water and drying, or removing and reducing ion components through a column filled with an ion exchange resin. .

(Synthesis of Polyamide)
The above-mentioned phthalic acid compound-blocked product and a diamine compound having a divalent organic group Y ₂ are mixed in the presence of a basic catalyst such as pyridine or triethylamine in a solvent as described below to effect amide polycondensation. A polyamide of the present invention can be obtained.

As the amide polycondensation method, the phthalate compound-capped product is converted to a symmetrical polyacid anhydride using a dehydration condensation agent and then mixed with a diamine compound, or the phthalic compound-capped product is converted to an acid chloride by a known method. and a method of reacting a dicarboxylic acid component and an active esterifying agent in the presence of a dehydration condensing agent to effect active esterification, followed by mixing with a diamine compound.

Dehydration condensation agents include, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1′-carbonyldioxy-di-1,2,3-benzotriazole, N,N '-Disuccinimidyl carbonate and the like are preferred.

Examples of the chlorinating agent include thionyl chloride.

Active esterification agents include N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic imide, 2-hydroxyimino-2-ethyl cyanoacetate, 2-hydroxyimino- 2-cyanoacetamide and the like.

The diamine compound having an organic group _Y2 is at least one diamine selected from the group consisting of aromatic diamine compounds, aromatic bisaminophenol compounds, alicyclic diamine compounds, linear aliphatic diamine compounds, and siloxane diamine compounds. Compounds are preferred, and a plurality of them can be used in combination if desired.

The 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'-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-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy ) biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis( 4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2, 2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene , ortho-tolysine sulfone, 9,9-bis(4-aminophenyl)fluorene, and some of the hydrogen atoms on their benzene rings are methyl, ethyl, hydroxymethyl, hydroxyethyl, and halogen atoms. diamine compounds substituted with one or more groups selected from the group consisting of

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'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro- 4,4'-diaminobiphenyl and the like.

Examples of 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'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,5 -dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane, 4,4-(α-methylbenzylidene)-bis(2-amino phenol) and the like.

Alicyclic diamine compounds 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, menzenediamine, isophoronediamine, norbornane diamine, 1-cycloheptene-3,7-diamine, 4,4′-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.

Linear aliphatic diamine compounds include 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane. or alkylene oxide 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, such as trade names PAM-E, KF-8010 and X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.

After completion of the amide polycondensation reaction, precipitates derived from the dehydration condensing agent deposited in the reaction solution are separated by filtration, if necessary. Next, a poor solvent for polyamide such as water, lower aliphatic alcohol, or a mixture thereof is introduced into the reaction solution to precipitate polyamide. Further, the precipitated polyamide is redissolved in a solvent, purified by repeating the reprecipitation procedure, and vacuum-dried to isolate the target polyamide. In order to further improve the degree of purification, the polyamide solution may be passed through a column filled with an ion exchange resin to remove ionic impurities.

Polystyrene equivalent weight average molecular weight of polyamide measured by gel permeation chromatography (hereinafter referred to as "GPC") is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. If the polystyrene equivalent weight average molecular weight is 7,000 or more, the basic physical properties of the cured relief pattern are ensured. Further, if the polystyrene-equivalent weight average molecular weight is 70,000 or less, development solubility when forming a relief pattern is ensured.

Tetrahydrofuran or N-methyl-2-pyrrolidone are recommended as eluents for GPC. Also, the weight average molecular weight value is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent-based standard sample 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]
Another preferred example of the (A) resin in the photosensitive resin composition of the present invention is represented by the following general formula (5):

{wherein Y ₃ is a tetravalent organic group having carbon atoms, preferably a tetravalent organic group having two or more carbon atoms, and Y ₄ , X ₃ and X ₄ are each independently , a divalent organic group having two or more carbon atoms, n ₃ is an integer of 1 to 1000, n ₄ is an integer of 0 to 500, and n ₃ /(n ₃ +n ₄ )>0.5, and the arrangement order of _n3 dihydroxydiamide units containing _X3 and _Y3 and n4 diamide units _{containing X4 and Y4} is not critical. } (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 (hereinafter sometimes simply referred to as dihydroxydiamide units) in the general formula (5), and n ₄ in the general formula (5) diamide units (hereinafter sometimes simply referred to as diamide units).

The number of carbon atoms in _X3 is preferably 2 or more and 40 or less for the purpose of obtaining photosensitivity, and the number of carbon atoms in _X4 is preferably 2 or more and 40 or less for the purpose of obtaining photosensitivity. The number of carbon atoms in _Y3 is preferably 2 or more and 40 or less for the purpose of obtaining photosensitivity, and the number of carbon atoms in _Y4 is preferably 2 or more and 40 or less for the purpose of obtaining photosensitivity. Preferably.

The dihydroxydiamide unit can be formed by synthesis from a diaminodihydroxy compound (preferably bisaminophenol) having the structure _Y3 ( _NH2 ) ₂ (OH) ₂ and a dicarboxylic acid having the structure _X3 (COOH) ₂ . . A typical embodiment will be described below, taking as an example the case where the diaminodihydroxy compound is bisaminophenol. The two pairs of amino group and hydroxy group of the bisaminophenol are ortho-positioned to each other, and the dihydroxydiamide unit is ring-closed by heating at about 250 to 400° C. to form a heat-resistant polyoxazole structure. change to 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 2-1000, more preferably in the range of 3-50, most preferably in the range of 3-20.

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

｛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 Y ₃ (NH ₂ ) ₂ (OH) ₂ include 3,3'-dihydroxybenzidine and 3,3'-diamino-4,4'-dihydroxybiphenyl. , 4,4′-diamino-3,3′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl) Propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3 '-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene etc. These bisaminophenols can be used alone or in combination of two or more. As the Y ₃ group in the bisaminophenol, the following formula (37):

{wherein Rs1 and Rs2 each independently represent 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} is preferable.

Diamines having a structure of Y ₄ (NH ₂ ) ₂ include aromatic diamines and silicon diamines. Of these, aromatic diamines include, for example, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 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)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis (4-aminophenoxy)benzene, 4-methyl-2,4-bis(4-aminophenyl)-1-pentene,

4-methyl-2,4-bis(4-aminophenyl)-2-pentene, 1,4-bis(α,α-dimethyl-4-aminobenzyl)benzene, imino-di-p-phenylenediamine, 1, 5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis(4-aminophenyl)pentane, 5 (or 6)-amino-1-(4-aminophenyl)-1,3, 3-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]diphenylsulfone, 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, etc., and aromatics thereof A compound in which the hydrogen atom of the aromatic nucleus of the group diamine is substituted by at least one group or atom selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group and a phenyl group. be done.

As the diamine, silicon diamine can be selected in order to improve adhesion to the substrate. Examples of silicon diamines include bis(4-aminophenyl)dimethylsilane, bis(4-aminophenyl)tetramethylsiloxane, bis(4-aminophenyl)tetramethyldisiloxane, bis(γ-aminopropyl)tetramethyldisiloxane. siloxane, 1,4-bis(γ-aminopropyldimethylsilyl)benzene, bis(4-aminobutyl)tetramethyldisiloxane, bis(γ-aminopropyl)tetraphenyldisiloxane and the like.

｛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 preferred dicarboxylic acids having a structure of X ₃ (COOH) ₂ or X ₄ (COOH) ₂ , X ₃ and X ₄ are each an aliphatic group or an aromatic group having a linear, branched or cyclic structure. Those which are groups are mentioned. Among them, an organic group having 2 to 40 carbon atoms which may contain an aromatic ring or an aliphatic ring is preferable, and X ₃ and X ₄ are each represented by the following formula (38):

{wherein R ₄₁ is 2 selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO- and -C(CF ₃ ) ₂ - represents a valence group. }
can be preferably selected from aromatic groups represented by and these are preferred in terms of photosensitive characteristics.

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

Those represented by are mentioned.

The polystyrene equivalent weight average molecular weight of the polyoxazole precursor measured by gel permeation chromatography is preferably 3,000 to 70,000, more preferably 6,000 to 50,000. This weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the cured relief pattern. Moreover, from the viewpoint of resolution, it is preferably 70,000 or less. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Also, the molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent-based standard sample 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]
Another preferred example of the (A) resin in the photosensitive resin composition of the present invention is represented by the general formula (6):

{wherein X ₅ is a tetravalent to 14valent organic group, Y ₅ is a divalent to 12valent organic group, R ₁₀ and R ₁₁ are groups selected from phenolic hydroxyl, sulfonic acid and thiol groups; represents an organic group having at least one and may be the same or different, n ₅ is an integer from 3 to 200, and m ₃ and m ₄ are integers from 0 to 10; }
is a polyimide having a structure represented by Here, the resin represented by the general formula (6) is particularly preferable in that it is suitable for treatment at a lower temperature because it does not require a chemical change in the heat treatment process in order to develop sufficient film properties.
X ₅ in the structural unit represented by the above general formula (6) is preferably a tetravalent to tetravalent organic group having 4 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties. , an aromatic ring- or aliphatic ring-containing organic group having 5 to 40 carbon atoms is more preferable.

The polyimide represented by the general formula (6) can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride, or the like with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine. can. Polyimide is generally obtained by dehydrating and ring-closing polyamic acid, which is one of the polyimide precursors obtained by reacting tetracarboxylic dianhydride and diamine, by heating or chemical treatment with an 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'- 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, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluoric 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}fluoric dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine Aromatic tetracarboxylic acids such as tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and 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′ - diphenylsulfonetetracarboxylic 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 represents a group selected from a hydrogen atom, a hydroxyl group and a thiol group. } is exemplified.

Among 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, bis(3,4-dicarboxyphenyl)sulfone dianhydride,

｛式中、Ｒ₄₅は、酸素原子、Ｃ（ＣＦ₃）₂、Ｃ（ＣＨ₃）₂又はＳＯ₂から選ばれる基を示し、そしてＲ₄₆及びＲ₄₇は、同一であるか、又は異なっていてもよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝で表される構造の酸二無水物が好ましい。これらは単独で又は２種以上を組み合わせて使用される。 Bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluoric dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluoric 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 represents a group selected from a hydrogen atom, a hydroxyl group and a thiol group. } is preferred. These are used alone or in combination of two or more.

Y ₅ in the above general formula (6) represents a structural component of a diamine, and this diamine represents a divalent to 12-valent organic group containing an aromatic ring or an aliphatic ring, especially ~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′-diaminodiphenyl sulfone, 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)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diamino biphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl,

｛式中、Ｒ₄₈は、酸素原子、Ｃ（ＣＦ₃）₂、Ｃ（ＣＨ₃）₂又はＳＯ₂から選ばれる基を示し、そしてＲ₄₉～Ｒ₅₂は、同一であるか、又は異なっていてよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝で表される構造のジアミンなどが挙げられる。 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2′,3,3′-tetramethyl-4,4′-diaminobiphenyl, 3,3′,4,4′-tetramethyl-4 ,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, or an alkyl group or halogen on the aromatic ring thereof Atom-substituted compounds, 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 represents a group selected from a hydrogen atom, a hydroxyl group and a thiol group. } and the like 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′-diaminodiphenyl sulfone, 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 represents a group selected from a hydrogen atom, a hydroxyl group and a thiol group. }
A diamine having a structure represented by is preferred.

｛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。 Among these, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenyl sulfone, 4,4′- diaminodiphenylsulfone, 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 represents a group selected from a hydrogen atom, a hydroxyl group and a thiol group. }
A diamine having a structure represented by is particularly preferred. These are used alone or in combination of two or more.

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

By controlling the amount of alkali-soluble groups of R ₁₀ and R ₁₁ , the dissolution rate in alkaline aqueous solution can be changed, and a photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment.

Furthermore, in order to improve the adhesiveness to the substrate, an aliphatic group having a siloxane structure may be copolymerized as X ₅ and Y ₅ within a range that does not lower the heat resistance. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-amino-phenyl)octamethylpentasiloxane, etc. may be copolymerized in an amount of 1 to 10 mol %.

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

It is preferable that the polyimide has an imidization rate of 15% or more with respect to the entire resin constituting the photosensitive resin composition. More preferably, it is 20% or more. Here, the imidization rate refers to the imidization rate present in the entire resin constituting the photosensitive resin composition. If the imidization rate is less than 15%, the amount of shrinkage during thermosetting will increase, making it unsuitable for producing thick films.

The imidization rate can be easily calculated by the following method. First, the infrared absorption spectrum of the polymer is measured to confirm the presence of absorption peaks (near 1780 cm −1 and 1377 cm −1 ) of the imide structure due to polyimide. 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 near 1377 cm was compared with the intensity before the heat treatment to determine the imidization in the polymer before the heat treatment. Calculate the rate.

The molecular weight of the polyimide is preferably 3,000 to 200,000, more preferably 5,000 to 50,000, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight. 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 a developer is good and the relief pattern resolution performance is good.

Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Also, the molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko KK.
Furthermore, in the present invention, phenolic resins can also be preferably used.

[(A) Phenolic resin]
The phenolic resin in this embodiment means a resin having a repeating unit having a phenolic hydroxyl group. (A) The phenolic resin has the advantage that it can be cured at a low temperature (for example, 250° C. or less) because it does not undergo a structural change such as cyclization (imidization) of the polyimide precursor during thermosetting.

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

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

（式中、ｐは、１～１０の整数である。）で表される２価のアルキレンオキシド基、及び炭素数６～１２の芳香族環を有する２価の有機基からなる群から選択される２価の有機基を表す。｝
で表される繰り返し単位を有するフェノール樹脂、及び炭素数４～１００の不飽和炭化水素基を有する化合物で変性されたフェノール樹脂から選択される少なくとも１種のフェノール樹脂であることが好ましい。 (A) Phenolic resins are novolak, polyhydroxystyrene, and the following general formula (7) from the viewpoint of solubility in an alkaline aqueous solution, sensitivity and resolution when forming a resist pattern, and 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, R ₁₂ is a monovalent organic compound having 1 to 20 carbon atoms represents a monovalent substituent selected from the group consisting of groups, halogen atoms, nitro groups and cyano groups, and when b is 2 or 3, a plurality of R ₁₂ may be the same or different from each other Well, X is a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, the following general formula (8):

(Wherein, p is an integer of 1 to 10.) 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. }
and at least one phenolic resin selected from phenolic resins modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms.

(Novolac)
In the present disclosure, novolac means any polymer obtained by condensing phenols and formaldehyde in the presence of a catalyst. In general, novolaks can be obtained by condensing less than 1 mol of formaldehyde with 1 mol of phenols. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 ,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like. Specific novolacs include, for example, phenol/formaldehyde condensed novolak resins, cresol/formaldehyde condensed novolak resins, phenol-naphthol/formaldehyde condensed novolac resins, and the like.

The weight average molecular weight of 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 reflow treatment applicability of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

(polyhydroxystyrene)
In the present disclosure, polyhydroxystyrene means all polymers containing hydroxystyrene as polymerized units. A preferred example of polyhydroxystyrene is polyparavinylphenol. Polyparavinylphenol means all polymers containing paravinylphenol as polymerized units. Thus, polymerized units other than hydroxystyrene (eg, paravinylphenol) can be used to make up the polyhydroxystyrene (eg, polyparavinylphenol) without departing from the objectives of the present invention. In 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%, and still more preferably 30 to 95 mol. %. When the above ratio is 10 mol% or more, it is advantageous from the viewpoint of alkali solubility of the photosensitive resin composition, and when it is 99 mol% or less, a cured film obtained by curing a composition containing a copolymer component described later. from the point of view of reflow applicability. The polymerized units other than hydroxystyrene (eg paravinylphenol) can be any polymerized units copolymerizable with hydroxystyrene (eg paravinylphenol). Examples of copolymer components that give polymerized units other than hydroxystyrene (eg, 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 glycol 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 methacrylates such as pentaerythritol trimethacrylate, 1-phenylethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate and 1,4-benzenediol dimethacrylate esters of acrylic acid; styrene and substituted styrenes such as 2-methylstyrene and vinyltoluene; vinyl ester monomers such as vinyl acrylate and vinyl methacrylate; and o-vinylphenol, m-vinylphenol, and the like. be done.

Moreover, as the novolak and polyhydroxystyrene described above, each may be used alone or in combination of two or more.

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 reflow treatment applicability of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

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

（式中、ｐは、１～１０の整数である。）で表される２価のアルキレンオキシド基、及び炭素数６～１２の芳香族環を有する２価の有機基からなる群から選択される２価の有機基を表す。｝で表される繰り返し単位を有するフェノール樹脂を含むこともまた好ましい。上記の繰り返し単位を有するフェノール樹脂は、例えば従来使用されてきたポリイミド樹脂及びポリベンゾオキサゾール樹脂と比べて低温での硬化が可能であり、かつ良好な伸度を有する硬化膜の形成を可能にする点で特に有利である。フェノール樹脂分子中に存在する上記繰り返し単位は、１種又は２種以上の組合せであることができる。 (Phenolic resin represented by general formula (7))
In this embodiment, (A) the phenolic resin has 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 compound having 1 to 20 carbon atoms represents a monovalent substituent selected from the group consisting of groups, halogen atoms, nitro groups and cyano groups, and when b is 2 or 3, a 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.) 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 preferred to include a phenolic resin having repeating units represented by }. Phenolic resins having the above repeating units can be cured at lower temperatures than, for example, conventionally used polyimide resins and polybenzoxazole resins, and enable the formation of cured films with good elongation. It is particularly advantageous in terms of The repeating units present in the phenolic resin molecule can be one or a combination of two or more.

｛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 is a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group and a cyano is 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 are each independently a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an alicyclic group having 3 to 20 carbon atoms, 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, a divalent aliphatic group having 3 to 20 carbon atoms, 2 represents a valent alicyclic group or a divalent aromatic group having 6 to 20 carbon atoms. } is preferably a monovalent substituent selected from the group consisting of four groups represented by:

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

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

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

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

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

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

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

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

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

で表される２価の基からなる群から選択される２価の有機基である。｝で表される２価の基からなる群から選択される２価の有機基であることが好ましい。上記炭素数６～１２の芳香族環を有する２価の有機基Ｘの炭素数は、好ましくは８～７５、より好ましくは８～４０である。なお上記炭素数６～１２の芳香族環を有する２価の有機基Ｘの構造は、一般的には、上記一般式（７）中、ＯＨ基及び任意のＲ₁₂基が芳香環に結合している構造とは異なる。 In the present embodiment, in the general formula (7), X is a divalent divalent having 2 to 10 carbon atoms which may have an unsaturated bond from the viewpoint of the cured relief pattern shape and the elongation of the cured film. From an aliphatic group, a divalent alicyclic group having 3 to 20 carbon atoms, an alkylene oxide group represented by the general formula (8), and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms is a divalent organic group selected from the group consisting of; Among these divalent organic groups, from the viewpoint of the toughness of the cured film, X 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 some or all of the hydrogen atoms are substituted with fluorine atoms; is a monovalent aliphatic group having 1 to 10 carbon atoms, n ₆ is an integer of 0 to 4, and R ₁₇ when n ₆ is an integer of 1 to 4 is a halogen atom or a hydroxyl group , or a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ is a hydroxyl group, and when n ₆ is an integer of 2 to 4, a plurality of R ₁₇ may be the same or different. good too. } and the following general formula (10):

{wherein 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 some or all of the hydrogen atoms are substituted with fluorine atoms; represents a monovalent aliphatic group having 1 to 10 carbon atoms, W is a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and an alicyclic group having 3 to 20 carbon atoms, the following general formula (8):

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

is a divalent organic group selected from the group consisting of divalent groups represented by } is preferably a divalent organic group selected from the group consisting of divalent groups represented by }. The number of carbon atoms in the divalent organic group X having an aromatic ring of 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 the OH group and optional R ₁₂ group are bonded to the aromatic ring in the general formula (7). different from the structure

で表される２価の有機基であることがより好ましく、さらに下記式（１３）：

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

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

A divalent organic group represented by 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 represented by the structure represented by the formula (12) or (13) in X From the viewpoint of elongation, the proportion of the portion to be stretched is preferably 20% by mass or more, more preferably 30% by mass or more. From the viewpoint of the alkali solubility of the composition, the above proportion is preferably 80% by mass or less, more preferably 70% by mass or less.

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

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

{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 When n _{11 is 2 or 3, multiple R 23 may} be the same or different. }

m ₅ in the general formula (14) and m ₆ in the general formula (15) represent the total number of repeating units in the main chain of the phenolic resin. That is, in (A) the phenol resin, for example, the repeating unit in the parentheses in the structure represented by the general formula (14) and the repeating unit in the 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, still more preferably 350. be. Each of m ₅ and m ₆ is 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, and still more preferably 6 or more from the viewpoint of the toughness of the cured film. It is preferably 200 or less, more preferably 175 or less, still more preferably 150 or less.

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

A phenolic resin having a repeating unit represented by the general formula (7) typically comprises a phenolic compound and a copolymer component (specifically, a compound having an aldehyde group (such as trioxane, which is decomposed into 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 composed of these can be synthesized by a polymerization reaction. For example, aldehyde compounds, ketone compounds, methylol compounds, alkoxymethyl compounds, diene compounds, haloalkyl compounds, etc., for phenols and/or phenol derivatives (hereinafter collectively referred to as "phenol compounds") as shown below. (A) a phenol resin can be obtained by polymerizing the copolymerization component of (A). In this case, in the above general formula (7), the portion represented by the structure in which the OH group and any R ₁₂ group are bonded to the aromatic ring is derived from the above phenol compound, and the portion represented by X is the above covalent It comes from the polymerization component. From the viewpoint of reaction control and the stability of the obtained (A) phenolic resin and photosensitive resin composition, the charging molar ratio of the phenolic compound and the copolymerization component (phenol compound): (copolymerization component) is 5 :1 to 1.01:1, more preferably 2.5:1 to 1.1:1.

The weight average molecular weight of the phenolic resin having a repeating unit represented by 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 reflow treatment applicability of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

Examples of phenolic compounds that can be used to obtain the phenolic resin having a repeating unit represented by 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, methyl hydroxybenzoate, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, resorcinol, xylenol, catechol, methylcatechol, ethylcatechol, hexylcatechol, benzylcatechol, nitrobenzylcatechol, methylresorcinol, ethylresorcinol, hexylresorcinol, benzylresorcinol, nitrobenzylresorcinol, hydroquinone, Caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, dihydroxybenzonitrile, N -(dihydroxyphenyl)-5-norbornene-2,3-dicarboximide, N-(dihydroxyphenyl)-5-methyl-5-norbornene-2,3-dicarboximide, nitrocatechol, fluorocatechol, chlorocatechol, Bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, broromesorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, trihydroxybenzoic acid methyl, ethyl trihydroxybenzoate, butyl trihydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzonitrile and the like. .

Examples of the aldehyde compound include acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2-carboxy aldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde and the like.

Examples of the ketone compounds 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, 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, ribitol, 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(hydroxymethyl)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'-hydroxymethylphenyl 4-hydroxymethylbenzoate, 4'-hydroxymethylanilide 4-hydroxymethylbenzoate , 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 Propylene glycol, tripropylene glycol, tetrapropylene glycol and the like can be mentioned.

Examples of the alkoxymethyl compounds include 2,6-bis(methoxymethyl)-p-cresol, 2,6-bis(methoxymethyl)-4-ethylphenol, 2,6-bis(methoxymethyl)-4- propylphenol, 2,6-bis(methoxymethyl)-4-n-butylphenol, 2,6-bis(methoxymethyl)-4-t-butylphenol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 2,6-bis(methoxymethyl)-4-ethoxyphenol, 2,6-bis(methoxymethyl)-4-propoxyphenol, 2,6-bis(methoxymethyl)-4-n-butoxyphenol, 2,6 -bis(methoxymethyl)-4-t-butoxyphenol, 1,3-bis(methoxymethyl)urea, 2,2-bis(methoxymethyl)butyric acid, 2,2-bis(methoxymethyl)-5-norbornene, 2,3-bis(methoxymethyl)-5-norbornene, 1,4-bis(methoxymethyl)cyclohexane, 1,4-bis(methoxymethyl)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)diphenylthioether, 4,4'-bis(methoxymethyl)benzophenone, 4-methoxymethylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'-methoxymethylanilide, 4,4' -bis(methoxymethyl)phenylurea, 4,4'-bis(methoxymethyl)phenylurethane, 1,8-bis(methoxymethyl)anthracene, 4,4'-bis(methoxymethyl)biphenyl, 2,2'- Dimethyl-4,4'-bis(methoxymethyl)biphenyl, 2,2-bis(4-methoxymethylphenyl)propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, di Propylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether and the like.

Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol-dimethacrylate, 2,4-hexadien-1-ol, 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, triallyl isocyanurate, diallylpropyl isocyanurate and the like.

Examples of the haloalkyl compounds include xylene dichloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, 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.

The phenolic resin (A) can be obtained by condensing the above phenolic compound and the copolymerization component by dehydration, dehydrohalogenation, or dealcoholization, or by polymerizing while cleaving the unsaturated bond. , a catalyst may be used during the polymerization. Acidic catalysts include, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfuric acid, diethylsulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1 '-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride/phenol complex, boron trifluoride/ether complex and the like. On the other hand, alkaline catalysts include, for example, 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 phenolic 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 phenolic 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 generally 1 hour to 10°C. Time is preferred. If necessary, a solvent capable of sufficiently dissolving the resin can be used.

The phenolic resin having a repeating structure represented by general formula (7) is obtained by further polymerizing a phenolic compound, which is not a raw material for the structure of general formula (7), within a range that does not impair the effects of the present invention. may be The range that does not impair 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 of (A) the phenol resin.

(Phenolic resin modified with a compound having an unsaturated hydrocarbon group with 4 to 100 carbon atoms)
A phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms is a compound having phenol or a derivative thereof and an unsaturated hydrocarbon group having 4 to 100 carbon atoms (hereinafter sometimes simply “unsaturated hydrocarbon group”). Hydrogen group-containing compound".) with a reaction product (hereinafter also referred to as "unsaturated hydrocarbon group-modified phenol derivative") and condensation polymerization products with aldehydes, or phenolic resin and unsaturated hydrocarbon group It is a reaction product with the containing compound.

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

The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated groups from the viewpoint of the residual stress of the cured film and reflow treatment applicability. In addition, from the viewpoint of compatibility and residual stress of a cured film when made into a resin composition, the unsaturated hydrocarbon group preferably has 4 to 100 carbon atoms, more preferably 8 to 80 carbon atoms, and still more preferably has 8 to 80 carbon atoms. 10-60.

Examples of unsaturated hydrocarbon group-containing compounds include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linolyl alcohol, oleyl alcohol, unsaturated fatty acids and unsaturated fatty acid esters. 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. acids, arachidonic acid, eicosapentaenoic acid, sardine acid and docosahexaenoic acid. Among these, vegetable oils, which are unsaturated fatty acid esters, are particularly preferred from the viewpoint of the elongation of the cured film and the flexibility of the cured film.

Vegetable oils usually contain esters of glycerin and unsaturated fatty acids and are non-drying oils with an iodine value of 100 or less, semi-drying oils with an iodine value of more than 100 and less than 130, or drying oils with an iodine value of 130 or more. Non-drying oils include, for example, olive oil, morning glory seed oil, cashew seed oil, turmeric oil, camellia oil, castor oil and peanut oil. Semi-drying oils include, for example, corn oil, cottonseed oil and sesame oil. Drying oils include, for example, tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, perilla oil and mustard oil. Moreover, you may use the processed vegetable oil obtained by processing these vegetable oils.

Among the above vegetable oils, it is preferable to use a non-drying oil in the reaction of phenol or its derivatives or phenolic resin with vegetable oil from the viewpoint of preventing gelation due to excessive progress of the reaction and improving the yield. On the other hand, it is preferable to use a drying oil from the viewpoint of improving the adhesion of the resist pattern, mechanical properties and thermal shock resistance. Among the drying oils, tung oil, linseed oil, soybean oil, walnut oil and safflower oil are preferred, and tung oil and linseed oil are more preferred, since the effects of the present invention can be exhibited more effectively and reliably. These vegetable oils are used singly or in combination of two or more.

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

By polycondensing the unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction and aldehydes, a phenol resin modified with an unsaturated hydrocarbon group-containing compound is produced. Aldehydes include, for example, formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, glyceraldehyde, glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate, pyruvic acid, lepulinic acid, 4-acetylbutyric acid, acetonedicarboxylic acid and 3,3'- selected from 4,4'-benzophenonetetracarboxylic acids; Formaldehyde precursors such as paraformaldehyde and trioxane may also be used. These aldehydes are used individually by 1 type or in combination of 2 or more types.

The reaction between the aldehyde 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 carried out in the presence of a catalyst such as an acid or base, and more preferably an acid catalyst from the viewpoint of the degree of polymerization (molecular weight) of the resin. Acid catalysts include, for example, hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid and oxalic acid. These acid catalysts can be used singly or in combination of two or more.

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

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

A phenolic resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by reacting a phenolic resin with an unsaturated hydrocarbon group-containing compound. The phenolic resins used in this case are polycondensation products of phenolic compounds (ie phenol and/or phenol derivatives) and aldehydes. In this case, the same phenol derivative and aldehyde as described above can be used as the phenol derivative and aldehyde, and the phenol resin can be synthesized under the conventionally known conditions as described above.

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

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

The reaction between the phenolic resin and the unsaturated hydrocarbon group-containing compound is generally preferably carried out at 50-130°C. In addition, from the viewpoint of improving the flexibility of the cured film (resist pattern), the reaction ratio between the phenolic resin and the unsaturated hydrocarbon group-containing compound is 1 part of the unsaturated hydrocarbon group-containing compound per 100 parts by mass of the phenolic resin. It is preferably up to 100 parts by mass, more preferably 2 to 70 parts by mass, even more preferably 5 to 50 parts by mass. 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. If necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst for the reaction between the phenolic resin and the unsaturated hydrocarbon group-containing compound. For the reaction, for example, a solvent such as toluene, xylene, methanol, tetrahydrofuran, etc. can be used, which will be described later in detail.

It is also possible to use an acid-modified phenolic resin by further reacting the phenolic hydroxyl groups remaining in the phenolic resin modified by the unsaturated hydrocarbon group-containing compound produced by the above method with a polybasic acid anhydride. can. Acid modification with a polybasic acid anhydride introduces a carboxy group, further improving the solubility in an alkaline aqueous solution (used as a developer).

The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of the carboxy groups of a polybasic acid having a plurality of carboxy groups. Examples of polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. , methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, dibasic acid anhydrides such as biphenyltetra Carboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride aromatic tetrabasic acid dianhydrides such as 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 one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern having a better shape can be formed.

The reaction between the phenolic hydroxyl group and the polybasic anhydride can be carried out at 50-130°C. In this reaction, it is preferable to react 0.10 to 0.80 mol of polybasic acid anhydride, more preferably 0.15 to 0.60 mol, with respect to 1 mol of phenolic hydroxyl group. It is more preferable to react 0.20 to 0.40 mol. When the polybasic acid anhydride is less than 0.10 mol, the developability tends to be lowered, and when it exceeds 0.80 mol, the alkali resistance of the unexposed area tends to be lowered.

From the viewpoint of speeding up the reaction, the above reaction may contain a catalyst, if necessary. 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 a polybasic acid anhydride is preferably 30 to 200 mgKOH/g, more preferably 40 to 170 mgKOH/g, even more preferably 50 to 150 mgKOH/g. . When the acid value is less than 30 mgKOH/g, alkali development tends to take a longer time than when the acid value is within the above range, and when it exceeds 200 mgKOH/g, the acid value is within the above range. As compared with , the developing solution resistance of the unexposed area tends to decrease.

The molecular weight of the phenolic resin modified with an unsaturated hydrocarbon group-containing compound is preferably 1,000 to 100,000, more preferably 2,000 to 100,000, in terms of weight average molecular weight, considering the solubility in an alkaline aqueous solution and the balance between the photosensitivity and the physical properties of the cured film. is more preferred.

The (A) phenolic resin of the present embodiment includes a phenolic resin having a repeating unit represented by the general formula (7), and a phenol modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms. A mixture of at least one phenolic resin selected from resins (hereinafter also referred to as (a3) resin) and a phenolic resin selected from novolak and polyhydroxystyrene (hereinafter also referred to as (a4) resin) is also preferred. The mixing ratio of the (a3) resin and the (a4) resin is in the range of (a3)/(a4)=5/95 to 95/5 in mass ratio. This mixing ratio is (a3) / (a4) = 5/ 95 to 95/5 is preferable, (a3)/(a4) is more preferably 10/90 to 90/10, and (a3)/(a4) is 15/85 to 85/15. preferable. As the novolak and polyhydroxystyrene as the resin (a4), the same resins as those shown in the above sections of (novolak) and (polyhydroxystyrene) can be used.

(B) a cyclic compound having a carbonyl group The compound (B) is a cyclic compound having two or more carbonyl groups, and the carbonyl group is directly bonded to the cyclic structure. 1/3 or more of the atoms to form are N atoms, and in the case of a condensed ring compound, at least 1/3 or more of the atoms forming the ring structure having the carbonyl group are selected from the group consisting of N atoms. It is a compound.
Classified according to the ring structure, 5-membered ring compound, 6-membered ring compound, 5-membered ring and 5-membered ring condensed ring compound, 5-membered ring and 6-membered ring condensed ring compound, 6-membered ring and 6-membered ring condensed ring compound From the viewpoint of migration resistance, it is preferably at least one compound selected from the group consisting of compounds that are cyclic compounds.
By having two or more carbonyl groups, the area of voids on the copper surface can be reduced. Furthermore, from the viewpoint of developability, sensitivity, in-plane uniformity after curing, elongation after reflow, etc., it is preferable to have two or more carbonyl groups. When there are two or more carbonyl groups, the area of voids on the copper surface is significantly reduced compared to when there is one carbonyl group. Two or more carbonyl groups are preferable from the viewpoint of developability, sensitivity, in-plane uniformity after curing, elongation after reflow, and the like, compared to the case of one carbonyl group.

Specific examples of the (B) compound include five-membered ring compounds such as hydantoin, allantoin, and parabanic acid, and six-membered ring compounds such as barbituric acid, 1,3-dimethylbarbituric acid, and 1,3-dicyclohexylbarbituric acid. Acid, uramil, alloxan, cyanuric acid, tris(2-hydroxyethyl)isocyanurate, etc. as 5-membered and 5-membered condensed ring compounds, glycoluril, etc. as 6-membered and 5-membered condensed ring compounds as xanthine, 1-methylxanthine, 3-methylxanthine, 8-bromo-3-methylxanthine, theobromine, theophylline, 7-(2-chloroethyl)theophylline, caffeine, uric acid, 8-azaxanthin, etc. Examples of condensed cyclic compounds of a ring and a 6-membered ring include lumazine, 7,8-dimethylalloxazine, 1,4-dihydro-6-methylquinoxaline-2,3-dione, 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 1 to 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 1 to 10 alkyl groups or aromatic groups. }
A compound represented by the following general formula (62):

{wherein Rs9, Rs10, Rs11 and Rs12 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 It is an alkyl group having 1 to 10 carbon atoms 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 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, It is a hydroxyalkyl group, an alkyl group having 1 to 10 carbon atoms, or an aromatic group. }
At least one compound selected from the group consisting of compounds represented by is preferable from the viewpoint of migration resistance.

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.

The compounding amount of the compound (B) is 0.01 to 10 parts by mass, preferably 0.05 to 2 parts by mass, per 100 parts by mass of the resin (A). From the viewpoint of migration resistance, it is preferably 0.01 parts by mass or more, and from the viewpoint of solubility, it is preferably less than 10 parts by mass.
These (B) components are thought to suppress the migration of copper during high-temperature storage tests by changing the surface state of copper by coordinating the carbonyl group and the nitrogen atoms contained in the ring structure to copper. be done. Especially in the case of a condensed ring, it is believed that a plurality of carbonyl groups and nitrogen atoms act in concert to enhance the migration resistance.

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

The amount of the (C) photosensitive agent in the photosensitive resin composition is 1 to 50 parts by weight per 100 parts by weight of the (A) resin. The blending amount is 1 part by mass or more from the viewpoint of photosensitivity or patterning properties, 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 cured photosensitive resin layer.

[(C) Negative photosensitive agent: photopolymerization initiator and/or photoacid generator]
First, the case where a negative type is desired will be described. In this case, the photosensitizer (C) is a photopolymerization initiator and/or a photoacid generator, and the photopolymerization initiator is preferably a photoradical polymerization initiator such as benzophenone or methyl o-benzoylbenzoate. , 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, benzophenone derivatives such as fluorenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, etc. acetophenone derivatives, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzyl, benzyl dimethyl ketal, and benzyl-β-methoxyethyl acetal;

benzoin, benzoin derivatives such as 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; Photoacid generators such as peroxides, aromatic biimidazoles, titanocenes, and α-(n-octane sulfonyloxyimino)-4-methoxybenzyl cyanide are preferred, but are limited to these. not a thing Among the above photopolymerization initiators, oximes are more preferable, particularly in terms of photosensitivity.

When a photoacid generator is used as the (C) photosensitive agent in the negative photosensitive resin composition, it exhibits acidity when irradiated with actinic rays such as ultraviolet rays, and the effect causes the crosslinking agent described later to be added as the component (A). It has an action of cross-linking with a resin, or polymerizing cross-linking agents with each other. 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-oximide sulfonates, aromatic sulfamides, haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, naphthoquinonediazide-4-sulfonate esters, and the like are used. Two or more of such compounds may be used in combination, or may be used in combination with other sensitizers, if necessary. Among the above photoacid generators, aromatic oxime sulfonate esters and aromatic N-oximido sulfonates are more preferable, particularly in terms of photosensitivity.

The blending amount of these photosensitizers is 1 to 50 parts by mass, preferably 2 to 15 parts by mass, based on 100 parts by mass of the resin (A). When 1 part by mass or more of the photosensitizer (C) is blended with 100 parts by mass of the resin (A), excellent photosensitivity is obtained, and when 50 parts by mass or less of the photosensitive agent is blended, excellent thick-film curability is obtained.

Furthermore, as described above, when the (A) resin represented by the general formula (1) is an ionic bond type, 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) photosensitive agent, 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, especially from the viewpoint of photosensitive properties. Therefore, dialkylaminoalkyl acrylates or methacrylates in which the alkyl group on the amino group has 1 to 10 carbon atoms and the alkyl chain has 1 to 10 carbon atoms are preferred.

The amount of the (meth)acrylic compound having an amino group is 1 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the resin (A). (C) As a photosensitizer, a (meth)acrylic compound having an amino group is added to 100 parts by mass of the resin (A) by blending 1 part by mass or more to achieve excellent photosensitivity, and by blending 20 parts by mass or less to cure thick films. Excellent in nature.

Next, the case where a positive type is desired will be described. In this case, a photoacid generator is used as the photosensitizer (C), and specifically, a diazoquinone compound, an onium salt, a halogen-containing compound, or the like can be used. , a compound having a diazoquinone structure is preferred.

[(C) Positive photosensitive agent: compound having a quinonediazide group]
(C) Compounds having a quinonediazide group (hereinafter also referred to as "(C) quinonediazide compounds") include compounds having a 1,2-benzoquinonediazide structure and compounds having a 1,2-naphthoquinonediazide structure. It is a known substance from US Pat. No. 2,772,972, US Pat. No. 2,797,213, US Pat. The quinonediazide compound (C) is a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure detailed below, and a 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 converting a naphthoquinonediazide sulfonic acid compound into a sulfonyl chloride with chlorosulfonic acid or thionyl chloride, and subjecting the resulting naphthoquinonediazide sulfonyl chloride to a condensation reaction with 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 is dissolved in a solvent such as dioxane, acetone, or tetrahydrofuran with a basic solvent such as triethylamine. It can be obtained by reacting in the presence of a catalyst to effect esterification, washing the resulting product with water, and drying it.

｛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) a compound having a quinonediazide group is a 1,2-naphthoquinonediazide-4-sulfonate and/or 1,2-naphthoquinonediazide-4-sulfonate of a hydroxy compound represented by the following general formulas (70) to (74). 2-Naphthoquinonediazide-5-sulfonic acid ester is preferable from the viewpoint 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); independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably 1 to 30 carbon atoms), r1, r2, r3 and r4 are each independently an integer of 0 to 5 , r3 and r4 is an integer from 1 to 5, (r1+r3)≦5 and (r2+r4)≦5. }.
General formula (71) is

{wherein Z represents a tetravalent organic group having 1 to 20 carbon atoms, and X ₁₅ , X ₁₆ , X ₁₇ and X ₁₈ each independently represents a monovalent organic group having 1 to 30 carbon atoms; wherein r6 is an integer of 0 or 1, r5, r7, r8 and r9 are each independently an integer of 0 to 3, r10, r11, r12 and r13 are each independently 0 to 2 and r10, r11, r12 and r13 cannot all be zero. }.
And general formula (72) is

{Wherein, r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, (r14 × r15) L are each independently a monovalent organic having 1 to 20 carbon atoms (r15) T ¹ and (r15) T ² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. }.
And 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 represented by the following chemical formula:

represents a divalent group selected from the three groups represented by }.
Furthermore, general formula (74) is

{wherein r17, r18, r19 and r20 are each independently an integer of 0 to 2, at least one of r17, r18, r19 and r20 is 1 or 2, and X ₂₀ to X ₂₉ are , each independently represents a monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group and an acyl group, and Y ₁₀ , Y ₁₁ and Y ₁₂ are 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 general formula (74) above, each of Y ₁₀ to Y ₁₂ is independently represented by the following general formula:

{Wherein, X ₃₀ and X ₃₁ each independently represent at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, _an alkenyl group, an aryl group, and a substituted aryl group; , X ₃₃ , X ₃₄ and X ₃₅ each independently represent a hydrogen atom or an alkyl group, r21 is an integer of 1 to 5, and X ₃₆ , X ₃₇ , X ₃₈ and X ₃₉ each independently represents a hydrogen atom or an alkyl group. }
is preferably 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, each r16 is independently an integer of 0 to 2, and each _{X40 independently} represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; When present, multiple X _40s may be the same or different, 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 r18 is an integer of 0 to 2, _X41 represents a monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group and a cycloalkyl group, and r18 is 2 two X ₄₁ may be the same or different.)
It is preferably a monovalent organic group represented by. } and
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 is each independently an integer of 0 to 2, and X ₄₃ is each independently a hydrogen atom or the following general formula:

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

(wherein r20 is an integer from 0 to 2, X ₄₅ is selected from the group consisting of a hydrogen atom, an alkyl group and a cycloalkyl group, and when r20 is 2, two X ₄₅ are , which may be the same or different), and X ₄₄ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 1 to 20 carbon atoms. selected from the group consisting of: } and formulas (78) and (79) are structures as follows.

As the compound represented by the general formula (70), the hydroxy compounds represented by the following formulas (80) to (82) have high sensitivity when converted into NQD compounds, and can be used in a photosensitive resin composition. It is preferable because of its low sedimentation property.

The structures of formulas (80)-(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。 As the compound represented by the general formula (76), the following formula (83):

The hydroxy compound represented by is preferable because it has high sensitivity when converted into an NQD compound and has low deposition property in the photosensitive resin composition.

As the compound represented by the general formula (77), the hydroxy compounds represented by the following formulas (84) to (86) have high sensitivity when converted into NQD compounds, and can be used in a photosensitive resin composition. It is preferable because of its low sedimentation property.
The structures of formulas (84)-(86) are as follows.

で表される構造を有する４価の基であることが好ましい。 In the above general formula (71), Z 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:

A tetravalent group having a structure represented by is preferred.

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 to NQD compounds, and in the photosensitive resin composition is preferable because of its low precipitation.
The structures of formulas (87)-(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 the compound represented by the general formula (72), the following formula (91):

{Wherein, each r40 is independently an integer of 0 to 9. } is preferable because it has high sensitivity when converted into an NQD compound and has low deposition property in the photosensitive resin composition.

As the compound represented by the general formula (73), the hydroxy compounds represented by the following formulas (92) and (93) have high sensitivity when converted into NQD compounds, and can be used in a photosensitive resin composition. It is preferable because of its low sedimentation property.
The structures of 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。 Specific examples of the compound represented by the general formula (74) include the following formula (94):

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

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

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

In the compound (C) having a quinonediazide group, the average esterification rate of the naphthoquinonediazide sulfonyl ester of the hydroxy compound is preferably 10% to 100%, more preferably 20% to 100%, from the viewpoint of development contrast. More preferred.

｛式中、Ｑは、水素原子、又は下記式群：

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

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

is a naphthoquinonediazide sulfonic acid ester group represented by any one of, but not all Q are hydrogen atoms at the same time. } can be mentioned.

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 A mixture with a sulfonyl ester compound can also be used.

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

is particularly preferred.

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

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

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

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

In the present embodiment, the amount of (C) the compound having a quinonediazide group in the photosensitive resin composition is 0.1 parts by mass to 70 parts by mass with respect to 100 parts by mass of the (A) resin, preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, still more preferably 5 to 30 parts by mass. If the amount is 0.1 parts by mass or more, good sensitivity can be obtained, and if it is 70 parts by mass or less, the mechanical properties of the cured film will be good.

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

The above-described polyimide precursor resin composition and polyamide resin composition, which are negative resin compositions in the present embodiment, and the 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. pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, 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 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 and the like can be used. Among them, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene, from the viewpoint of resin solubility, resin composition stability, and adhesion to substrates. Glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol and tetrahydrofurfuryl alcohol are preferred.

Among such solvents, those capable of completely dissolving the resulting polymer are preferred, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea. , gamma-butyrolactone and the like.

Solvents more suitable for said phenolic resins 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, cyclopentanone. , toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, and the like.

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

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

Azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5 -phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyl triazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5- Bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2 -hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenyl benzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl- 1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like.

Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. Moreover, these azole compounds may be used singly or as 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-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine and derivatives thereof.

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

In addition, a hindered phenol compound can optionally be blended to suppress discoloration on the copper surface. Hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4, 4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t -butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio -diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrosine namamide), 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 2,2′-methylene-bis(4-ethyl-6-t-butylphenol),

pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl -4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2 ,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2 ,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3- hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,

1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1 , 3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3 ,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1 , 3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H) -trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H, 5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-( 1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione,

1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1, 3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1, 3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like are mentioned, but are not limited to these. 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.

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

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

Examples of cross-linking agents include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, and 272, which are compounds containing methylol groups and/or alkoxymethyl groups. , 202, 1156, 1158, 1123, 1170, 1174; UFR65, 300; Mycoat 102, 105 (manufactured by Mitsui Cytec Co., Ltd.), Nikalac (registered trademark) MX-270, -280, -290; Nikalac MS-11 ;Nicalac MW-30, -100, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP , DML-PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMO-PTBT, TMOM-BP , TMOM-BPA, TML-BPAF-MF (manufactured by Honshu Chemical Industry 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, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl and the like.

In addition, phenol novolak type epoxy resin, cresol novolak 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 resins, phenol-dicyclopentadiene-type epoxy resins, cycloaliphatic epoxy resins, aliphatic epoxy resins, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 1 , 1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl 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 (trade names, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020 , NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (trade names, manufactured by Nippon Kayaku Co., Ltd.), Epicot (registered trademark) 1001, Epicot 1007, Epicot 1009, Epicot 5050, Epicot 5051, Epicot 1031S, Epicort 180S65, Epicort 157H70, YX-315-75 (trade names, manufactured by Japan Epoxy Resin Co., Ltd.), EHPE3150, Plaxel G402, PUE101, PUE105 (trade names, manufactured by Daicel Chemical Industries, Ltd.), Epiclon (registered trademark) 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (trade names, 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 names, manufactured by Nagase ChemteX Corporation), Epolite (registered trademark) 70P, Epolite 100MF (trade names, manufactured by Kyoeisha Chemical ) and the like.

In addition, isocyanate group-containing compounds, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bambooate ( Registered trademarks) 500, 600, Cosmonate (registered trademark) NBDI, ND (trade names, manufactured by Mitsui Chemicals, Inc.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402- B80T (trade name above, manufactured by Asahi Kasei Chemicals) and the like.

In addition, bismaleimide compounds such as 4,4'-diphenylmethanebismaleimide, phenylmethanemaleimide, m-phenylenebismaleimide, bisphenol A diphenylether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4 '-Diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4' -diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI- 3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (these are trade names, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and the like. It is not limited to these as long as it is a compound that

When the cross-linking agent is used, the blending amount is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the resin (A). When the amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are exhibited, 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, it is said that by including both (B) a cyclic compound having a carbonyl group and an organic titanium compound in the photosensitive resin composition, the resin layer after curing is excellent in chemical resistance in addition to substrate adhesion. Effective.

Organotitanium compounds that can be used include those in which organic chemicals are attached to titanium atoms through covalent or ionic bonds.

Specific examples of organotitanium compounds are shown below in I) to VII):
I) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable because the storage stability of the negative photosensitive resin composition and a good pattern can be obtained. (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 compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η ⁵ - and 2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

IV) Monoalkoxy titanium compounds: for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide and the like.

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

VI) Titanium tetraacetylacetonate compounds: such as titanium tetraacetylacetonate.

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

Among them, the organotitanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, thereby exhibiting better chemical resistance. From this point of view, it is preferable. In particular, titanium diisopropoxide bis(ethylacetoacetate), 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.

The amount of the organotitanium compound to be blended is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of resin (A). When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, and when the amount is 10 parts by mass or less, the storage stability is excellent.

Furthermore, an adhesion aid can be arbitrarily blended in order to improve 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-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyl Silane coupling agents such as trimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, and aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethyl Examples include aluminum-based adhesion promoters such as acetoacetate aluminum diisopropylate.

Among these adhesion aids, the silane coupling agent is more preferable from the point of adhesion. When the photosensitive resin composition contains an adhesion promoter, the content of the adhesion promoter is preferably in the range of 0.5 to 25 parts by weight per 100 parts by weight of the resin (A).

As the silane coupling agent, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, Chisso Corporation: trade name Sila Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS1375, Azmax Co., Ltd.: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3 -mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane , 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane , 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, Azmax Co., Ltd. company: 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-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl)urea, N-(3 -tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3- Methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-amino phenoxy)propyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0) Manufactured by: trade name SLA0599.1) aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: trade name SIT8396.0), 2- (Triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl) ) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis ( methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxy silyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis [3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, bis(pentadionate)titanium-O,O'-bis(oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenyl Silanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol , tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyl Examples include, but are not limited to, diphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like. These may be used singly or in combination.

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

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

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

(A) In the case of a negative type using a polyimide precursor or polyamide as the resin, a sensitizer may optionally be 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, 2,6-bis(4'-diethylaminobenzal). ) cyclohexanone, 2,6-bis(4′-diethylaminobenzal)-4-methylcyclohexanone, 4,4′-bis(dimethylamino)chalcone, 4,4′-bis(diethylamino)chalcone, p-dimethylamino thinner mylideneindanone, p-dimethylaminobenzylideneindanone, 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-ethoxycarbonyl-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-dimethylamino) styryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene and the like. These can be used singly or in combination, for example of 2 to 5 types.

When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the blending amount is preferably 0.1 to 25 parts by weight per 100 parts by weight 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)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator. Although not particularly limited to the following, ethylene glycol or polyethylene such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate mono- or di- or di-acrylates and methacrylates of glycols, mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or tri-acrylates and methacrylates of glycerol, cyclohexane diacrylates and dimethacrylates, diacrylates of 1,4-butanediol and Dimethacrylates, diacrylates and dimethacrylates of 1,6-hexanediol, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol di- or tri-acrylate and methacrylate, pentaerythritol di-, tri-, or tetra-acrylate and methacrylate, and ethylene oxide or propylene oxide adducts of these compounds, etc. can be mentioned.

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

In addition, in the case of a negative type using a polyimide precursor or the like as the resin (A), in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition during storage in the state of a solution containing a solvent. A thermal polymerization inhibitor can be arbitrarily blended. 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.

The amount of the thermal polymerization inhibitor to be added to the photosensitive resin composition is preferably in the range of 0.005 to 12 parts by weight per 100 parts by weight of the resin (A).

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

<Dyes, surfactants, adhesion aids>
More specifically, examples of dyes include methyl violet, crystal violet, and malachite green. Examples of surfactants include nonionic surfactants composed of polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether, or derivatives thereof, such as Florard (trade name, manufactured by Sumitomo 3M), Megafac ( Fluorinated surfactants such as KP341 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) or Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), etc. ), granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and other organic siloxane surfactants. Adhesion aids include, for example, alkylimidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolak, epoxysilane, epoxy polymer, and various silane coupling agents.

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

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

Examples of thermal acid generators include salts formed from strong acids and bases, such as onium salts that have the function of generating an acid by heat, and imidosulfonates.

Onium salts include, for example, 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; dialkylmonoarylsulfonium salts such as dimethylphenylsulfonium salts; diarylmonoalkyliodonium salts such as diphenylmethylsulfonium salts; and triarylsulfonium salts.

Among these, di(t-butylphenyl)iodonium salt of paratoluenesulfonic acid, di(t-butylphenyl)iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethyl 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 Dimethylphenylsulfonium salts, diphenylmethylsulfonium salts of toluenesulfonic acid, and the like are preferred.

As the salt formed from a strong acid and a base, in addition to the onium salts described above, the following salts formed from a strong acid and a base, such as a pyridinium salt, can also be used. Strong acids include p-toluenesulfonic acid, arylsulfonic acids such as benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, perfluoroalkylsulfonic acids such as nonafluorobutanesulfonic acid, methanesulfonic acid, ethanesulfonic acid. , alkylsulfonic acids such as butanesulfonic acid, and the like. The base includes pyridine, alkylpyridine such as 2,4,6-trimethylpyridine, N-alkylpyridine such as 2-chloro-N-methylpyridine, halogenated-N-alkylpyridine and the like.

As the imidosulfonate, for example, naphthoimidosulfonate, phthalimidosulfonate, or the like can be used, but there is no limitation as long as it is a compound that generates an acid by heat.

When a thermal acid generator is used, the blending amount is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and 1 to 5 parts by mass, based on 100 parts by mass of the resin (A). is more preferable.

In the case of a positive photosensitive resin composition, a dissolution accelerator can be used in order to promote removal of the resin that is no longer needed after exposure. For example, compounds having a hydroxyl group or a carboxyl group are preferred. Examples of compounds having a hydroxyl group include ballast agents used in the naphthoquinone diazide compounds described above, paracumylphenol, bisphenols, resorcinols, linear phenol compounds such as MtrisPC and MtetraPC, TrisP-HAP, and TrisP. -Non-linear phenol compounds such as PHBA and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), diphenylmethane with 2 to 5 phenol substitutions, 3,3-diphenylpropane with 1 to 5 phenol substitutions, bis-( 3-amino-4-hydroxyphenyl)sulfone and 1,2-cyclohexyldicarboxylic anhydride in a molar ratio of 1:2, N-hydroxysuccinimide, N-hydroxyphthalimide, N -hydroxy 5-norbornene-2,3-dicarboxylic acid imide and the like. Examples of compounds having a carboxyl group include 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2 -(1-naphthyl)propionic acid, mandelic acid, atrolactinic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, itaconic acid and the like.

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

(Aspect B)
In another aspect of the present embodiment, (B) a sulfur-containing compound can be used in place of (B) the cyclic compound having a carbonyl group. More specifically,
(A) at least one selected from the group consisting of polyamic acids, polyamic acid esters, polyamic acid salts, polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, and novolacs, polyhydroxystyrenes and phenolic resins 100 parts by mass of resin,
(B) a sulfur-containing compound of 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin;
(C) a photosensitive agent of 1 to 50 parts by mass based on 100 parts by mass of the resin (A);
Provided is a photosensitive resin composition comprising:

In this aspect, the resin (A) is a polyimide precursor containing the general formula (1), a polyamide containing the general formula (4), a polyoxazole precursor containing the general formula (5), and a polyoxazole precursor containing the general formula (6). ), and at least one selected from the group consisting of novolaks, polyhydroxystyrenes, and phenolic resins containing the general formula (7).

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

By blending the sulfur-containing compound into the photosensitive resin composition, it is possible to obtain a photosensitive resin composition that gives a cured film in which the generation of voids at the interface in contact with the Cu layer is suppressed after a high-temperature storage test.

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

(B) Compounds that can be used as sulfur-containing compounds include those containing sulfur as one atom forming a five-membered ring structure, such as thiazole, 2-aminothiazole, and 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 and the like , containing sulfur as one atom forming a six-membered ring structure, such as phenothiazine, N-methylphenothiazine, etc., and containing sulfur as a thiocarbonyl group, such as rhodanine, N-allylrhodanine, diethyl Thiourea, dibutylthiourea, dicyclohexylthiourea, diphenylthiourea, 2-thiouracil, 4-thiouracil, 2,4-dithiopyrimidine, 2-thioxanthone, 2-mercapto-4(3H)-quinazolinone and the like. Among these, compounds containing a thiourea structure are preferably used.

The amount of the sulfur-containing compound (B) is 0.01 to 10 parts by mass, preferably 0.05 to 2 parts by mass, per 100 parts by mass of the resin (A). From the viewpoint of migration resistance, it is preferably 0.01 parts by mass or more, and from the viewpoint of solubility, it is preferably less than 10 parts by mass.
Sulfur-containing compounds, particularly thiourea, can coordinate to copper via a sulfur atom. 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 (B) the cyclic compound having a carbonyl group, (B) selected from the following general formulas (B-1), (B-2) and (B-3) can be used. More specifically,
(A) at least one selected from the group consisting of polyamic acids, polyamic acid esters, polyamic acid salts, polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, and novolacs, polyhydroxystyrenes and phenolic resins 100 parts by mass of resin,
(B)
The following general formula (B-1):

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

{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):

{wherein R _q4 and R _q5 are each an organic group selected from a hydroxyl group, 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 (A) resin;
(C) a photosensitive agent of 1 to 50 parts by mass based on 100 parts by mass of the resin (A);
Provided is a photosensitive resin composition comprising:

In this aspect, the resin (A) is a polyimide precursor containing the general formula (1), a polyamide containing the general formula (4), a polyoxazole precursor containing the general formula (5), and a polyoxazole precursor containing the general formula (6). ), and at least one selected from the group consisting of novolaks, polyhydroxystyrenes, and phenolic resins containing the general formula (7).

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

(B) The compounds represented by general formulas (B-1), (B-2) and (B-3), preferably the compound represented by (B-1), contain copper can change the surface state of copper by interacting with the surface of Therefore, copper migration is suppressed during the high-temperature storage test.

As a specific example, (B-1) is an organic compound formed from a carbon atom, a hydrogen atom, a nitrogen atom and an oxygen atom having a ureido group, such as methylurea, ethylurea, butylurea, phenylurea, hydroxyethyl Urea, hydantoic acid, allantoin, citrulline, etc. and mixtures thereof may be mentioned.

(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. Ethers, tetraethylene glycol, tetraethylene glycol dimethyl ether, etc. and mixtures thereof may be mentioned.

Furthermore, (B-3) is an alkoxypolyethylene oxide ester or alkoxyethyl ester of a dicarboxylic acid, such as bis(2-methoxyethyl) adipate, bis(2-butoxyethyl) adipate, bis(2- ethoxyethyl), etc. and mixtures thereof.

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

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

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

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

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

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

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

{R11 to R13 may be the same or different, and may be a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group having an integer of 1 to 15 carbon atoms, an unsaturated hydrocarbon group, an aromatic or an amide group. }
0.01 to 15 parts by mass based on 100 parts by mass of the (A) resin, and (C) a photosensitive agent of 1 based on 100 parts by mass of the (A) resin. ~50 parts by mass,
Provided is a photosensitive resin composition comprising:

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

(B) In the embodiment using an aromatic amine compound, the photosensitive resin includes polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamidoimide, polyimide, and polybenzoxazole, among which heat treatment Polyamic acids, polyamic acid esters, polyamic acid salts, polyamides, polyhydroxyamides and polyimide resins are preferably used, and polyimide precursors and polyimide resins are most preferably used, since the subsequent resins are excellent in heat resistance and mechanical properties.

(B) By using an aromatic amine compound, it is possible to suppress the generation of voids at the interface between the rewiring Cu layer and the resin layer after the high-temperature storage test. Although the reason for this is not clear, it is believed that the lone electron pair of the aromatic amine compound coordinates with the Cu element on the surface of the Cu layer to block the active Cu reaction site, thereby suppressing the generation of voids. be done.

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

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

Examples of compounds suitably used among the aniline derivatives represented by general formula (I) include N-phenylbenzylamine, salicylanilide, naphthol AS, 2-acetamidofluorene, oxanilide, N-allylaniline, and 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-butylphenyl carbamate ((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) The triazole derivative has the following general formula (II):

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

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

Specific compound 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 Co., Ltd., ADEKA STAB CDA-1), 2-(2H-benzo[d][1,2 , 3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol (manufactured by ADEKA Co., Ltd., Adekastab LA-29), 2-(2′-hydroxy-3′, 5'-di-tert-aminophenyl)benzotriazole and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole are preferably used. Among others, 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 compound 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, bitertanol, 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-1,2,4-triazol-1-yl)benzoic acid, 2 -(1H-1,2,4-triazol-1-yl)aniline is preferably used, especially (4-((1H-1,2,4-triazol-1-ylmethyl)phenyl)methanol ((B) -7) is particularly preferably used.

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

The content of the aromatic amine compound (B) is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and 1 to 8 parts by mass, relative to 100 parts by mass of the resin (A). is more preferable. If the content is more than the range, the storage stability is lowered, and if the content is less than the range, voids are likely to occur with the copper surface.

<Method for producing cured relief pattern and semiconductor device>
Further, the present invention comprises (1) the step of forming a resin layer on a substrate by applying the above-described photosensitive resin composition of the present invention onto the substrate, and (2) the step of exposing the resin layer. (3) developing the exposed resin layer to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern. provide a way. Typical aspects of each step are described below.

(1) A step of forming a resin layer on a substrate by applying a photosensitive resin composition onto the substrate In this step, the photosensitive resin composition of the present invention is applied onto a substrate, and if necessary After that, it is dried to form a resin layer. As the coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray coating with a spray coater. method etc. 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, and vacuum drying are used. Specifically, when air drying or heat drying is performed, drying can be performed at 20° C. to 140° C. for 1 minute to 1 hour. As described above, a 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 using an exposure apparatus such as a contact aligner, mirror projection, stepper, etc., through a photomask or reticle having a pattern, or directly. It is exposed with an ultraviolet light source or the like.

After that, for the purpose of improving photosensitivity, if necessary, post-exposure baking (PEB) and/or pre-development baking may be performed at any combination of temperature and time. The range of baking conditions is preferably 40 to 120° C. and 10 to 240 seconds for time. is not limited to

(3) Step of developing the exposed resin layer to form a relief pattern In this step, the exposed portion or the unexposed portion of the exposed photosensitive resin layer is removed by development. When using a negative photosensitive resin composition (for example, when using a polyimide precursor or polyamide as (A) resin), the unexposed area is removed by development, and when using a positive photosensitive resin composition ( For example, in the case of (A) using a polyoxazole precursor or a soluble polyimide as the resin, the exposed portion is removed by development. As a developing method, any method can be selected and used from conventionally known photoresist developing methods, such as a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, and the like. For the purpose of adjusting the shape of the relief pattern after development, post-development baking may be performed at any combination of temperature and time, if necessary.

A developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a 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 preferred, and poor solvents such as toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate and water are preferred. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. Moreover, two or more kinds of each solvent can be used, for example, several kinds can be used in combination.

On the other hand, in the case of a photosensitive resin composition soluble in an alkaline aqueous solution, the developer used for development 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, and 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, di -n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, triethanolamine, and the like.

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 Heating Relief Pattern to Form Hardened Relief Pattern In this step, the relief pattern obtained by the development is heated to be converted into a hardened relief pattern. As the heat curing method, various methods such as a method using a hot plate, a method using an oven, and a method using a heating 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 for heat curing, or an inert gas such as nitrogen or argon may be used.

<Semiconductor device>
The present invention also provides a semiconductor device including a cured relief pattern obtained by the above-described method for producing a cured relief pattern of the present invention. The present invention also provides a semiconductor device comprising a substrate which is a semiconductor element and a cured relief pattern of a resin formed on the substrate by the method for producing a cured relief pattern described above. The present invention can also be applied to a semiconductor device manufacturing method that uses a semiconductor element as a base material and includes the above-described cured relief pattern manufacturing method as part of the process. The semiconductor device of the present invention is a semiconductor device having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure, in which the cured relief pattern formed by the method for producing a cured relief pattern described above is used. It can be manufactured by forming it as a protective film or the like and combining it 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 applications such as interlayer insulation of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. is.
In addition, although the embodiments A to D have been described above, combinations of the embodiments are also included in the present invention.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these. In Examples, Comparative Examples and Production Examples, the physical properties of the photosensitive resin compositions 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 gel permeation chromatography (converted to standard polystyrene). The column used for the measurement is the trade name "Shodex 805M/806M Series" manufactured by Showa Denko K.K. , the developing solvent was N-methyl-2-pyrrolidone, and the detector used was trade name "Shodex RI-930" manufactured by Showa Denko KK.

(2) Creation of cured relief pattern on Cu On a 6-inch silicon wafer (manufactured by Fujimi Denshi Kogyo Co., Ltd., thickness 625 ± 25 μm), a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Co., Ltd.) is used to make a thickness of 200 nm. 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 the wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO) and dried to form a coating film having a thickness of 6 to 10 μm. formed. Using a mask with a test pattern, 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.). Next, this coating film is spray-developed with a coater developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.) using cyclopentanone in the case of a negative type developer and 2.38% TMAH in the case of a positive type as a developer, A relief pattern on Cu was obtained by rinsing with propylene glycol methyl ether acetate in the case of the negative type and with pure water in the case of the positive type.

The wafer having the relief pattern formed on Cu is heat-treated for 2 hours at the temperature described in each example in a nitrogen atmosphere using a temperature-rising programmable curing furnace (Model VF-2000, manufactured by Koyo Lindbergh Co., Ltd.). Thus, a hardened relief pattern of about 6-7 μm thick resin on Cu was obtained.

(3) High temperature storage test of hardened relief pattern on Cu and subsequent evaluation The wafer on which the hardened relief pattern was formed was placed in a temperature-rising programmable curing furnace (VF-2000 type, Koyo Lindbergh Co., Ltd.). (manufactured) and heated in air at 150° C. for 168 hours. Subsequently, the entire resin layer on the Cu was 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: _O2 : 40 ml/min + _CF4 : 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 by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and image analysis software (Azo-kun, manufactured by Asahi Kasei Corporation) is used to determine the surface of the Cu layer. The area ratio of voids was calculated.

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

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

Example A
<Production Example A1> ((A) Synthesis of polymer A as polyimide precursor)
155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature. 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the end of heat generation due to the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.

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

The resulting reaction mixture was added to 3 liters of ethyl alcohol to form a precipitate consisting of crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 l of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (polymer A). When the molecular weight of polymer A was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 20,000.

The weight average molecular weight of the resin obtained in each production example was measured using gel permeation chromatography (GPC) under the following conditions to determine the weight average molecular weight in terms of standard polystyrene.
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)
147.1 g of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) was used in place of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in Production Example A1. Except for this, the reaction was carried out in the same manner as described in Production Example A1 above to obtain Polymer B. When the molecular weight of polymer B was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 22,000.

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

<Production Example A4> ((A) Synthesis of polymer D as polyamide)
(Synthesis of phthalate compound-encapsulated AIPA-MO)
5-aminoisophthalic acid (hereinafter abbreviated as AIPA) is placed in a 5-liter separable flask. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50° C. in a water bath. To this, 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise from a dropping funnel, and the mixture was stirred at 50° C. for about 2 hours.

Completion of the reaction (disappearance of 5-aminoisophthalic acid) was measured by low-molecular-weight gel permeation chromatography {hereinafter referred to as low-molecular-weight GPC. }, the reaction mixture was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product crystallized and precipitated, the reaction mixture was separated by filtration, washed with water as needed, 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)
100.89 g (0.3 mol) of the resulting AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added to a 2-liter separable flask, mixed, and cooled to 5°C in an ice bath. bottom. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was added dropwise over about 20 minutes under ice cooling, followed by 4,4′-bis(4-aminophenoxy ) Biphenyl {hereinafter referred to as BAPB. } A solution obtained by dissolving 103.16 g (0.28 mol) in 168 g of NMP was added dropwise over about 20 minutes, followed by stirring in an ice bath for 3 hours while maintaining the temperature below 5°C, then removing the ice bath and stirring at room temperature for 5 hours. bottom. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

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

<Production Example A5> ((A) Synthesis of Polymer E as Polyoxazole Precursor)
183.1 g of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 640.9 g of N,N-dimethylacetamide (DMAc), and 63.3 g of pyridine were placed in a 3-liter separable flask. The mixture was mixed and stirred at room temperature (25° C.) to form a uniform solution. A solution obtained by dissolving 118.0 g of 4,4′-diphenyl ether dicarbonyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from the dropping funnel. At this time, the separable flask was cooled in a water bath at 15-20°C. The time required for dropping was 40 minutes, and the maximum temperature of the reaction solution was 30°C.

After 3 hours from the end of dropping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction mixture and left to stir at room temperature for 15 hours to convert 99% of all amine terminal groups on the polymer chain to carboxylate. It was capped with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was collected, appropriately washed with water, dehydrated, and 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 vacuum dried to obtain a purified polybenzoxazole precursor (polymer E).

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

2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan Co., Ltd.) (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 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, and the mixture was stirred at room temperature. After stirring at 100 rpm for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added. The mixture was heated and stirred at 100 rpm for 8 hours. Thereafter, the temperature of the silicon bath was raised to 180° C., and the mixture was heated and stirred at 100 rpm for 2 hours. Toluene and water distillates were removed during the reaction. After completion of the imidization reaction, the temperature was returned to room temperature.

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

<Production Example A7> ((A) Synthesis of polymer G as phenolic resin)
128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 4,4′-bis(methoxymethyl)biphenyl (hereinafter “BMMB 121.2 g (0.5 mol), 3.9 g (0.025 mol) of diethyl sulfate, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70° C. to dissolve the solid 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 reactor was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added and stirred. The reaction dilution solution was dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which was collected, washed with water as appropriate, dehydrated, and vacuum-dried. A polymer (Polymer G) was obtained with a yield of 70%. The weight average molecular weight of this polymer G was 21,000 as determined by standard polystyrene conversion by the GPC method.

<Production Example A8> ((A) Synthesis of polymer H as phenolic resin)
A separable flask with a capacity of 1.0 L equipped with a Dean-Stark apparatus was purged with nitrogen, and then resorcinol 81.3 g (0.738 mol), BMMB 84.8 g (0.35 mol), p-toluenesulfone were added in the separable flask. 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, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)-p-cresol and 249 g of PGME were mixed and stirred in another vessel, and the solution uniformly dissolved was added to the separator using a dropping funnel. The mixture was added dropwise to the Bull flask over 1 hour, and after the dropwise addition, the mixture was further stirred for 2 hours.

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

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 by the following method using the polymers A and B, and the prepared photosensitive resin composition was evaluated. 0.2 g of xanthine (corresponding to (B) a cyclic compound having a carbonyl group), 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl)-oxime (described as “PDO” in Table 1) (corresponding to (C) photosensitive agent) 4 g, tetraethylene glycol dimethacrylate 8 g, N-[3-(triethoxysilyl)propyl] Together with 1.5 g of phthalamic acid, it was dissolved in a mixed solvent 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 prepare a negative photosensitive resin composition.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. We got a result of %.
<Example A2>
A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that the amount of xanthine added as the component (B) was changed to 0.05 g.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 6.4. We got a result of %.
<Example A3>
A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that the amount of xanthine added as the component (B) was changed to 5 g.
This composition was cured at 230° C. by the above-described method to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 4.9. We got a result of %.
<Example A4>
A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that 8-azaxanthin was used as the component (B) instead of xanthine.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. We got a result of %.
<Example A5>
A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that uric acid was used as the component (B) instead of xanthine.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 5.4. We got a result of %.
<Example A6>
A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that lumazine was used as the component (B) instead of xanthine.
This composition was cured at 230° C. by the method described above to form a cured relief pattern on the Cu layer, and subjected to a high-temperature storage test. We got a result of %.
<Example A7>
A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that barbituric acid was used as the component (B) instead of xanthine.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 7.3. We got a result of %.
<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 prepare a cured relief pattern on the Cu layer, and a high temperature storage test was performed. After that, the area ratio of voids occupying the surface of the Cu layer was evaluated, and a result of 4.5% was obtained.
<Example A9>
In Example A1 above, 50 g of polymer A and 50 g of polymer B were replaced with 100 g of polymer A as the resin (A), and 4 g of PDO was used 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 to prepare a negative photosensitive resin composition solution in the same manner as in Example A1.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. We got a result of %.
<Example A10>
In Example A1 above, 50 g of polymer A and 50 g of polymer B were added to 100 g of polymer A as (A) resins, and 4 g of PDO as component (C), 1,2-octanedione, 1-{4-(phenylthio)-, 2 -(O-benzoyloxime)} (Irgacure OXE01 (manufactured by BASF, trade name)) in the same manner as in Example A1, except that the solvent was changed to 2.5 g, and the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethylsulfoxide. A negative photosensitive resin composition solution was prepared.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. We got a result of %.
<Example A11>
A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that 100 g of polymer C was used as the resin (A) in place of 50 g of polymer A and 50 g of polymer B.
This composition was cured at 350° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 4.9. We got a result of %.
<Example A12>
A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that 100 g of polymer D was used as the resin (A) in place of 50 g of polymer A and 50 g of polymer B.
This composition was cured at 250° C. by the method described above to form a cured relief pattern on the Cu layer and subjected to a high-temperature storage test. We got a result of %.
<Example A13>
Using polymer E, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer E (corresponding to (A) resin), which is a polyoxazole precursor, was subjected to the following formula (96):

a photosensitive diazoquinone compound (manufactured by Toyo Gosei Co., Ltd., corresponding to (C) photosensitive agent) (C1) 20 g, xanthine ((B) (corresponding to a cyclic compound having a carbonyl group) was dissolved in 100 g of γ-butyrolactone (as a solvent) together with 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane. The viscosity of the resulting solution was adjusted to about 20 poise by further adding a small amount of γ-butyrolactone to prepare a positive photosensitive resin composition.
This composition was cured at 350° C. by the method described above to prepare a cured relief pattern on the Cu layer and subjected to a high-temperature storage test. We got a result of %.
<Example A14>
A positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of polymer E was changed to 100 g of polymer F as the resin (A).
This composition was cured at 250° C. by the method described above to prepare a cured relief pattern on the Cu layer and subjected to a high-temperature storage test. We got a result of %.
<Example A15>
A positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of Polymer E was changed to 100 g of Polymer G as the resin (A).
This composition was cured at 220° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. We got a result of %.
<Example A16>
A positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of polymer E was changed to 100 g of polymer H as the resin (A).
This composition was cured at 220° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. We got a result of %.
<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 performed. did 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.
Table 1 summarizes the results of Examples A1 to A16 and Comparative Examples A1 to A4.

Example B
<Production Example B1> ((A) Synthesis of polymer A as polyimide precursor)
155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature. 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the end of heat generation due to the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.

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

The resulting reaction mixture was added to 3 liters of ethyl alcohol to form a precipitate consisting of crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 l of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (polymer A). When the molecular weight of polymer A was measured by gel permeation chromatography (converted to standard polystyrene), 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 using gel permeation chromatography (GPC) under the following conditions to determine the weight-average molecular weight in terms of standard polystyrene.
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)
147.1 g of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) was used in place of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in Production Example B1. Except for this, the reaction was carried out in the same manner as described in Production Example B1 above to obtain Polymer B. When the molecular weight of polymer B was measured by gel permeation chromatography (converted to standard polystyrene), 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) in Production Example B1, Polymer C was obtained by reacting in the same manner as described in Production Example B1. When the molecular weight of Polymer C was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 21,000.

<Production Example B4> ((A) Synthesis of polymer D as polyamide)
(Synthesis of phthalate compound-encapsulated AIPA-MO)
5-aminoisophthalic acid (hereinafter abbreviated as AIPA) is placed in a 5-liter separable flask. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50° C. in a water bath. To this, 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise from a dropping funnel, and the mixture was stirred at 50° C. for about 2 hours.

Completion of the reaction (disappearance of 5-aminoisophthalic acid) was measured by 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 crystallized and precipitated, the reaction solution was separated by filtration, washed with water as needed, 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)
100.89 g (0.3 mol) of the resulting AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added to a 2-liter separable flask, mixed, and cooled to 5°C in an ice bath. bottom. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was added dropwise over about 20 minutes under ice cooling, followed by 4,4′-bis(4-aminophenoxy ) Biphenyl {hereinafter referred to as BAPB. } A solution obtained by dissolving 103.16 g (0.28 mol) in 168 g of NMP was added dropwise over about 20 minutes, followed by stirring in an ice bath for 3 hours while maintaining the temperature below 5°C, then removing the ice bath and stirring at room temperature for 5 hours. bottom. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

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

<Production Example B5> ((A) Synthesis of Polymer E as Polyoxazole Precursor)
183.1 g of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 640.9 g of N,N-dimethylacetamide (DMAc), and 63.3 g of pyridine were placed in a 3-liter separable flask. The mixture was mixed and stirred at room temperature (25° C.) to form a homogeneous solution. A solution obtained by dissolving 118.0 g of 4,4′-diphenyl ether dicarbonyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from the dropping funnel. At this time, the separable flask was cooled in a water bath at 15-20°C. The time required for dropping was 40 minutes, and the maximum temperature of the reaction solution was 30°C.

After 3 hours from the end of dropping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction mixture and left to stir at room temperature for 15 hours to convert 99% of all amine terminal groups on the polymer chain to carboxylate. It was capped with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was collected, appropriately washed with water, dehydrated, and 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 vacuum dried to obtain a purified polybenzoxazole precursor (polymer E).

<Production Example B6> ((A) Synthesis of polymer F as polyimide)
A condenser with a Dean-Stark trap was attached to a four-neck glass separable flask equipped with a Teflon (registered trademark) anchor stirrer. The flask was placed in a silicon oil bath and stirred while passing nitrogen gas through it.

2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan Co., Ltd.) (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 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, and the mixture was stirred at room temperature. After stirring at 100 rpm for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added. The mixture was heated and stirred at 100 rpm for 8 hours. Thereafter, the temperature of the silicon bath was raised to 180° C., and the mixture was heated and stirred at 100 rpm for 2 hours. Toluene and water distillates were removed during the reaction. After completion of the imidization reaction, the temperature was returned to room temperature.

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

<Production Example B7> ((A) Synthesis of polymer G as phenolic resin)
128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 4,4′-bis(methoxymethyl)biphenyl (hereinafter “BMMB 121.2 g (0.5 mol), 3.9 g (0.025 mol) of diethyl sulfate, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70° C. to dissolve the solid 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 reactor was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added and stirred. The reaction dilution solution was dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which was collected, washed with water as appropriate, dehydrated, and vacuum-dried. A polymer (Polymer G) was obtained with a yield of 70%. The weight average molecular weight of this polymer G was 21,000 as determined by standard polystyrene conversion by the GPC method.

<Production Example B8> ((A) Synthesis of Polymer H as Phenolic Resin)
A separable flask with a capacity of 1.0 L equipped with a Dean-Stark apparatus was purged with nitrogen, and then resorcinol 81.3 g (0.738 mol), BMMB 84.8 g (0.35 mol), p-toluenesulfone were added in the separable flask. 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, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)-p-cresol and 249 g of PGME were mixed and stirred in another vessel, and the solution uniformly dissolved was added to the separator using a dropping funnel. The mixture was added dropwise to the Bull flask over 1 hour, and after the dropwise addition, the mixture was further stirred for 2 hours.

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

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 by the following method using the polymers A and B, and the prepared photosensitive resin composition was evaluated. 50 g of polymer A and 50 g of B (corresponding to (A) resin), which are polyimide precursors, were mixed with 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) photosensitive agent) 4 g, tetraethylene glycol dimethacrylate 8 g, N-[3-(triethoxysilyl)propyl]phthalamic acid Together with 1.5 g, it was dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. The viscosity of the resulting solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to prepare a negative photosensitive resin composition.
This composition was cured at 230° C. by the method described above to form a cured relief pattern on the Cu layer, and subjected to a high-temperature storage test. We got a result of %.
<Example B2>
A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that the amount of dicyclohexylthiourea added as the component (B) was changed to 0.1 g.
This composition was cured at 230 ° C. by the above-described method to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. We got a result of %.
<Example B3>
A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that the amount of dicyclohexylthiourea added as the component (B) was changed to 4 g.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 4.8. We got a result of %.
<Example B4>
A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that benzothiazole was used as the component (B) instead of dicyclohexylthiourea.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 7.3. We got a result of %.
<Example B5>
A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that rhodanine was used as the component (B) instead of dicyclohexylthiourea.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 7.2. We got a result of %.
<Example B6>
A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that 2-thioxanthone was used as the component (B) instead of dicyclohexylthiourea.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 7.3. We got a result of %.
<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 prepare a cured relief pattern on the Cu layer, and a high temperature storage test was performed. After that, the area ratio of voids occupying the surface of the Cu layer was evaluated, and a result of 4.9% was obtained.
<Example B8>
In Example B1 above, 50 g of polymer A and 50 g of polymer B were replaced with 100 g of polymer A as the resin (A), and 4 g of PDO was used 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 to prepare a negative photosensitive resin composition solution in the same manner as in Example B1.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and subjected to a high temperature storage test. We got a result of %.
<Example B9>
In Example B1 above, 50 g of polymer A and 50 g of polymer B were added to 100 g of polymer A as the (A) resin, and 4 g of PDO as the component (C), 1,2-octanedione, 1-{4-(phenylthio)-, 2 -(O-benzoyloxime)} (Irgacure OXE01 (manufactured by BASF, trade name)) 2.5 g, and the same procedure as in Example B1 except that the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethylsulfoxide. A negative photosensitive resin composition solution was prepared.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 5.6. We got a result of %.
<Example B10>
A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that 100 g of Polymer C was used instead of 50 g of Polymer A and 50 g of Polymer B as the resin (A).
This composition was cured at 350° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 4.9. We got a result of %.
<Example B11>
A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that 100 g of polymer D was used instead of 50 g of polymer A and 50 g of polymer B as the resin (A).
This composition was cured at 250° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. We got a result of %.
<Example B12>
Using polymer E, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer E (corresponding to (A) resin), which is a polyoxazole precursor, was subjected to the following formula (96):

(C1) 15 g, dicyclohexylthiourea ((B ) corresponds to a sulfur-containing compound) 0.5 g was dissolved in 100 g of γ-butyrolactone (as a solvent) together with 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane. The viscosity of the resulting solution was adjusted to about 20 poise by further adding a small amount of γ-butyrolactone to prepare a positive photosensitive resin composition.
This composition was cured at 350° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 5.4. We got a result of %.
<Example B13>
A positive photosensitive resin composition solution was prepared in the same manner as in Example B12, except that 100 g of polymer E was changed to 100 g of polymer F as the resin (A).
This composition was cured at 250° C. by the method described above to prepare a cured relief pattern on the Cu layer and subjected to a high-temperature storage test. We got a result of %.
<Example B14>
A positive photosensitive resin composition solution was prepared in the same manner as in Example B12, except that 100 g of Polymer E was changed to 100 g of Polymer G as the resin (A).
This composition was cured at 220° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 5.7. We got a result of %.
<Example B15>
A positive photosensitive resin composition solution was prepared in the same manner as in Example B12, except that 100 g of polymer E was changed to 100 g of polymer H as the resin (A).
This composition was cured at 220° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 5.6. We got a result of %.
<Comparative Example B1>
A negative photosensitive resin composition was prepared in the same manner as in Example B1 except that dicyclohexylthiourea was not added to the composition of Example B1, and the same evaluation as in Example B1 was performed. The evaluation result was 14.3% because the compound (B) of the present invention was not 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.
Table 2 summarizes the results of Examples B1 to B15 and Comparative Examples B1 to B3.

Example C
<Production Example C1> ((A) Synthesis of polymer A as polyimide precursor)
155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature. 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the end of heat generation due to the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.

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

The resulting reaction mixture was added to 3 liters of ethyl alcohol to form a precipitate consisting of crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 l of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (polymer A). When the molecular weight of polymer A was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 20,000.

The weight average molecular weight of the resin obtained in each Production Example C was measured using gel permeation chromatography (GPC) under the following conditions to determine the weight average molecular weight in terms of standard polystyrene.
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)
147.1 g of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) was used in place of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in Production Example C1. Except for this, the reaction was carried out in the same manner as described in Production Example C1 above to obtain Polymer B. When the molecular weight of polymer B was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 22,000.

<Production Example C3> ((A) Synthesis of Polymer C as Polyimide Precursor)
Except that 147.8 g of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example C1. Polymer C was obtained by reacting in the same manner as described in Production Example C1. When the molecular weight of Polymer C was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 21,000.

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

Completion of the reaction (disappearance of 5-aminoisophthalic acid) was measured by low-molecular-weight gel permeation chromatography {hereinafter referred to as low-molecular-weight GPC. }, the reaction mixture was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product crystallized and precipitated, the reaction mixture was separated by filtration, washed with water as needed, 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)
100.89 g (0.3 mol) of the resulting AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added to a 2-liter separable flask, mixed, and cooled to 5°C in an ice bath. bottom. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was added dropwise over about 20 minutes under ice cooling, followed by 4,4′-bis(4-aminophenoxy ) Biphenyl {hereinafter referred to as BAPB. } A solution obtained by dissolving 103.16 g (0.28 mol) in 168 g of NMP was added dropwise over about 20 minutes, followed by stirring in an ice bath for 3 hours while maintaining the temperature below 5°C, then removing the ice bath and stirring at room temperature for 5 hours. bottom. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

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

<Production Example C5> ((A) Synthesis of Polymer E as Polyoxazole Precursor)
183.1 g of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 640.9 g of N,N-dimethylacetamide (DMAc), and 63.3 g of pyridine were placed in a 3-liter separable flask. The mixture was mixed and stirred at room temperature (25° C.) to form a uniform solution. A solution obtained by dissolving 118.0 g of 4,4′-diphenyl ether dicarbonyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from the dropping funnel. At this time, the separable flask was cooled in a water bath at 15-20°C. The time required for dropping was 40 minutes, and the maximum temperature of the reaction solution was 30°C.

After 3 hours from the end of dropping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction mixture and left to stir at room temperature for 15 hours to convert 99% of all amine terminal groups on the polymer chain to carboxylate. It was capped with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was collected, appropriately washed with water, dehydrated, and 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 vacuum dried to obtain a purified polybenzoxazole precursor (polymer E).

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

2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan Co., Ltd.) (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 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, and the mixture was stirred at room temperature. After stirring at 100 rpm for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added. The mixture was heated and stirred at 100 rpm for 8 hours. Thereafter, the temperature of the silicon bath was raised to 180° C., and the mixture was heated and stirred at 100 rpm for 2 hours. Toluene and water distillates were removed during the reaction. After completion of the imidization reaction, the temperature was returned to room temperature.

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

<Production Example C7> ((A) Synthesis of polymer G as phenolic resin)
128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 4,4′-bis(methoxymethyl)biphenyl (hereinafter “BMMB 121.2 g (0.5 mol), 3.9 g (0.025 mol) of diethyl sulfate, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70° C. to dissolve the solid 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 reactor was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added and stirred. The reaction dilution solution was dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which was collected, washed with water as appropriate, dehydrated, and vacuum-dried. A polymer (Polymer G) was obtained with a yield of 70%. The weight average molecular weight of this polymer G was 21,000 as determined by standard polystyrene conversion by the GPC method.

<Production Example C8> ((A) Synthesis of polymer H as phenolic resin)
A separable flask with a capacity of 1.0 L equipped with a Dean-Stark apparatus was purged with nitrogen, and then resorcinol 81.3 g (0.738 mol), BMMB 84.8 g (0.35 mol), p-toluenesulfone were added in the separable flask. 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, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)-p-cresol and 249 g of PGME were mixed and stirred in another vessel, and the solution uniformly dissolved was added to the separator using a dropping funnel. The mixture was added dropwise to the Bull flask over 1 hour, and after the dropwise addition, the mixture was further stirred for 2 hours.

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

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 by the following method using the polymers A and B, and the prepared photosensitive resin composition was evaluated. 50 g of polymer A and 50 g of B (corresponding to (A) resin) which are polyimide precursors, 1 g of butyl urea (corresponding to (B-1) compound), 1-phenyl-1,2-propanedione-2-(O-ethoxy Carbonyl)-oxime (described as "PDO" in Table 3) (corresponding to (C) photosensitive agent) 4 g, tetraethylene glycol dimethacrylate 8 g, N-[3-(triethoxysilyl)propyl]phthalamic acid1. It was dissolved together with 5 g 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 prepare a negative photosensitive resin composition.
This composition was cured at 230° C. by the method described above to form a cured relief pattern on the Cu layer, and subjected to a high-temperature storage test. We got a result of %.
<Example C2>
A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that the amount of butyl urea added as the component (B) was changed to 0.1 g.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 6.8. We got a result of %.
<Example C3>
A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that the amount of butyl urea added as the component (B) was changed to 5 g.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 4.8. We got a result of %.
<Example C4>
A negative photosensitive resin composition was prepared in the same manner as in Example C1 except that tetraethylene glycol (corresponding to the (B-2) compound) was used instead of butyl urea as the component (B) in Example C1. A solution was prepared.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. We got a result of %.
<Example C5>
In Example C1 above, a negative film was produced in the same manner as in Example C1, except that bis(2-methoxyethyl) adipate (corresponding to the (B-3) compound) was used instead of butyl urea as the component (B). A mold photosensitive resin composition solution was prepared.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. We got a result of %.
<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 prepare a cured relief pattern on the Cu layer, and a high temperature storage test was performed. After that, the area ratio of voids occupying the surface of the Cu layer was evaluated, and a result of 4.7% was obtained.
<Example C7>
In Example C1 above, 50 g of polymer A and 50 g of polymer B were replaced with 100 g of polymer A as the resin (A), and 4 g of PDO was used 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 to prepare a negative photosensitive resin composition solution in the same manner as in Example C1.
This composition was cured at 230° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 5.4. We got a result of %.
<Example C8>
In Example C1 above, 50 g of polymer A and 50 g of polymer B were added to 100 g of polymer A as (A) resins, and 4 g of PDO as 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 dimethylsulfoxide in the same manner as in Example C1. A negative photosensitive resin composition solution was prepared.
This composition was cured at 230° C. by the method described above to form a cured relief pattern on the Cu layer, and subjected to a high-temperature storage test. We got a result of %.
<Example C9>
A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that 100 g of polymer C was used as the resin (A) in place of 50 g of polymer A and 50 g of polymer B.
This composition was cured at 350° C. by the method described above to prepare a cured relief pattern on the Cu layer, and subjected to a high-temperature storage test. We got a result of %.
<Example C10>
A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that 100 g of polymer D was used as the resin (A) in place of 50 g of polymer A and 50 g of polymer B.
This composition was cured at 250° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 5.8. We got a result of %.
<Example C11>
Using polymer E, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer E (corresponding to (A) resin), which is a polyoxazole precursor, was subjected to the following formula (96):

A photosensitive diazoquinone compound (manufactured by Toyo Gosei Co., Ltd., corresponding to (C) photosensitive agent) (C1) 15 g, butyl urea ((B -1) corresponding to the compound) was dissolved in 100 g of γ-butyrolactone (as a solvent) together with 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane. The viscosity of the resulting solution was adjusted to about 20 poise by further adding a small amount of γ-butyrolactone to prepare a positive photosensitive resin composition.
This composition was cured at 350° C. by the method described above to form a cured relief pattern on the Cu layer, and subjected to a high temperature storage test. We got a result of %.
<Example C12>
A positive photosensitive resin composition solution was prepared in the same manner as in Example C11, except that 100 g of Polymer E was changed to 100 g of Polymer F as the resin (A).
This composition was cured at 250° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 5.9. We got a result of %.
<Example C13>
A positive photosensitive resin composition solution was prepared in the same manner as in Example C11, except that 100 g of Polymer E was changed to 100 g of Polymer G as the resin (A).
This composition was cured at 220° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated, and the ratio was 5.5. We got a result of %.
<Example C14>
A positive photosensitive resin composition solution was prepared in the same manner as in Example C13, except that 100 g of Polymer E was changed to 100 g of Polymer H as the resin (A) in Example C11.
This composition was cured at 220° C. by the method described above to prepare a cured relief pattern on the Cu layer, and after performing a high temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. We got a result of %.
<Comparative Example C1>
A negative photosensitive resin composition was prepared in the same manner as in Example C1 except that butyl urea 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 butyl urea 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 butyl urea 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)
155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature. 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the end of heat generation due to the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.

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

The resulting reaction mixture was added to 3 liters of ethyl alcohol to form a precipitate consisting of crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 l of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer. The obtained precipitate was separated by filtration and dried in vacuo to obtain a powdery polymer (Polymer (A)-1). When the molecular weight of polymer (A)-1 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 20,000.

The weight-average molecular weight of the resin obtained in each Production Example D was measured using gel permeation chromatography (GPC) under the following conditions to determine the weight-average molecular weight in terms of standard polystyrene.
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)
147.1 g of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) was used in place of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in Production Example D1. Except for this, the reaction was carried out in the same manner as described in Production Example D1 above to obtain Polymer (A)-2. When the molecular weight of polymer (A)-2 was measured by gel permeation chromatography (converted to standard polystyrene), 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) in Production Example D1, Polymer (A)-3 was obtained by carrying out the reaction in the same manner as in Production Example D1. When the molecular weight of polymer (A)-3 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 21,000.

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

Completion of the reaction (disappearance of 5-aminoisophthalic acid) was measured by low-molecular-weight gel permeation chromatography {hereinafter referred to as low-molecular-weight GPC. }, the reaction mixture was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product crystallized and precipitated, the reaction mixture was separated by filtration, washed with water as needed, 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)
100.89 g (0.3 mol) of the resulting AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added to a 2-liter separable flask, mixed, and cooled to 5°C in an ice bath. bottom. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was added dropwise over about 20 minutes under ice cooling, followed by 4,4′-bis(4-aminophenoxy ) Biphenyl {hereinafter referred to as BAPB. } A solution obtained by dissolving 103.16 g (0.28 mol) in 168 g of NMP was added dropwise over about 20 minutes, followed by stirring in an ice bath for 3 hours while maintaining the temperature below 5°C, then removing the ice bath and stirring at room temperature for 5 hours. bottom. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

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

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

After 3 hours from the end of dropping, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction mixture and left to stir at room temperature for 15 hours to convert 99% of all amine terminal groups on the polymer chain to carboxylate. It was capped with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was collected, appropriately washed with water, dehydrated, and 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 in vacuum to obtain a purified polybenzoxazole precursor (polymer (A)-5).

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

2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan Co., Ltd.) (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 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, and the mixture was stirred at room temperature. After stirring at 100 rpm for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added. The mixture was heated and stirred at 100 rpm for 8 hours. Thereafter, the temperature of the silicon bath was raised to 180° C., and the mixture was heated and stirred at 100 rpm for 2 hours. Toluene and water distillates were removed during the reaction. After completion of the imidization reaction, the temperature was returned to room temperature.

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

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

A photosensitive diazoquinone compound (manufactured by Toyo Gosei Co., Ltd., corresponding to component (C)) (C1) 15 g, γ-butyrolactone (as a solvent ) was 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 prepare a positive photosensitive resin composition.
This composition was cured at 350° C. by the method described above to prepare a cured relief pattern on the Cu layer and subjected to a high-temperature storage test. We got a result of %. Moreover, the viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D17>
A positive photosensitive resin composition was prepared in the same manner as in Example D12, except that in Example D16, Polymer (A)-5, 100 g, was changed to Polymer (A)-6, 100 g as the resin (A). A solution was prepared.
This composition was cured at 250° C. by the method described above to prepare a cured relief pattern on the Cu layer and subjected to a high temperature storage test. We got a result of %. Moreover, the viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Comparative Example D1>
A negative photosensitive resin composition was prepared in the same manner as in Example D1 except that 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 of the obtained varnish after the storage stability test was within 10%.
<Comparative Example D2>
A negative photosensitive resin composition was prepared in the same manner as in Example D15 except that 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 of the obtained varnish after the storage stability test was within 10%.
<Comparative Example D3>
A negative photosensitive resin composition was prepared in the same manner as in Example D13 except that 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 of the obtained varnish after the storage stability test was within 10%.
<Comparative Example D4>
A positive photosensitive resin composition was prepared in the same manner as in Example D17 except that component (B)-1 was not added to the composition of Example D17, and the same evaluation as in Example D17 was performed. The evaluation result was 16.3% because the component (B) of the present invention was not included. Moreover, the viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Comparative Example D5>
A negative photosensitive resin composition was prepared in the same manner as in Example D1 except that the amount of component (B)-1 added to the composition of Example D1 was changed to 25 g, and the same evaluation as in Example D1 was performed. did The evaluation result was 7.2%. Moreover, the viscosity change rate of the obtained varnish after the storage stability test was 10% or more.
Table 4 summarizes the results of Examples D1 to D17 and Comparative Examples D1 to D5.

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

Claims (6)

(A) at least one selected from the group consisting of polyamic acids, polyamic acid esters, polyamic acid salts, polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, and novolacs, polyhydroxystyrenes and phenolic resins 100 parts by mass of resin,
(B) 0.01 to 10 parts by mass of at least one compound selected from the group consisting of methyl urea, ethyl urea and butyl urea based on 100 parts by mass of the (A) resin;
(C) a photosensitive agent of 1 to 50 parts by mass based on 100 parts by mass of the resin (A);
A photosensitive resin composition comprising: The (A) resin includes a polyimide precursor containing the following general formula (1), a polyamide containing the following general formula (4), a polyoxazole precursor containing the following general formula (5), and a following general formula (6). 2. The photosensitive resin composition according to claim 1, which is at least one selected from the group consisting of polyimide, novolac, polyhydroxystyrene, and phenolic resins having 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 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 or a saturated aliphatic group having 1 to 4 carbon atoms, or 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 that 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, Y ₂ is a divalent organic group having 6 to 35 carbon atoms, and has the same structure, or a plurality of wherein R ₉ is an organic group having at least one radically polymerizable unsaturated bond group of 3-20 carbon atoms, and n ₂ is an integer of 1-1000. }
A polyamide having a structure represented by
The following general formula (5) is

{wherein Y ₃ is a tetravalent organic group having carbon atoms, 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 from 0 to 500, n ₃ /(n ₃ +n ₄ )>0.5, and n ₃ including X ₃ and Y ₃ The arranging order of the dihydroxy diamide units and n ₄ diamide units including X ₄ and Y ₄ does not matter. }
A polyhydroxyamide that is a polyoxazole precursor having a structure represented by
The following general formula (6) is

{In the formula, X ₅ is a 4- to 14-valent organic group, Y ₅ is a 2- to 12-valent organic group, R ₁₀ and R ₁₁ are each independently a phenolic hydroxyl group and a sulfonic acid group. or an organic group having at least one group selected from thiol groups, n ₅ is an integer of 3-200, and m ₃ and m ₄ are integers of 0-10. }
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 compound having 1 to 20 carbon atoms represents a monovalent substituent selected from the group consisting of groups, halogen atoms, nitro groups and cyano groups, and when b is 2 or 3, a plurality of R ₁₂ may be the same or different from each other Well, X is a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, the following general formula (8):

(Wherein, p is an integer of 1 to 10.) 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. } is a phenol resin represented by. The photosensitive resin composition contains a phenol resin having a repeating unit represented by the general formula (7), and X in the general formula (7) is represented by the 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 some or all of the hydrogen atoms are substituted with fluorine atoms; is a monovalent aliphatic group having 1 to 10 carbon atoms, n ₆ is an integer of 0 to 4, and R ₁₇ when n ₆ is an integer of 1 to 4 is a halogen atom or a hydroxyl group , or a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ is a hydroxyl group, and when n ₆ is an integer of 2 to 4, a plurality of R ₁₇ may be the same or different. good too. } and the following general formula (10):

{wherein 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 some or all of the hydrogen atoms are substituted with fluorine atoms; represents a monovalent aliphatic group having 1 to 10 carbon atoms, W is a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and an alicyclic group having 3 to 20 carbon atoms, the following general formula (8):

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

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