JP7675133B2 - Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device - Google Patents

Description

The present invention relates to a photosensitive resin composition used to form relief patterns, for example, for insulating materials in electronic components, and for passivation films, buffer coat films, interlayer insulating films, and the like in semiconductor devices, a method for forming a cured relief pattern using the same, and a semiconductor device.

Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like, which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic components, and passivation films, surface protective films, and interlayer insulating films for semiconductor devices. Among these polyimide resins, those provided in the form of photosensitive polyimide precursor compositions can easily form heat-resistant relief pattern films by applying the composition, exposing it to light, developing it, and subjecting it to a thermal imidization treatment by curing. Such photosensitive polyimide precursor compositions have the characteristic of enabling a significant reduction in process times compared to conventional non-photosensitive polyimide materials.

Meanwhile, semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards using various methods according to the purpose. Conventional elements were generally produced by wire bonding, which connects the external terminals (pads) of the element to the lead frame with thin wires. However, as elements have become faster and the operating frequencies have reached the GHz range, differences in the wiring length of each terminal during mounting have come to affect the operation of the element. As a result, when mounting elements for high-end applications, it has become necessary to precisely control the length of the mounting wiring, and it has become difficult to meet this requirement using 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 on the rewiring layer, and the chip is then flipped over and mounted directly on a printed circuit board (see, for example, Patent Document 1). This flip-chip mounting allows accurate control of the wiring distance, and is therefore used in high-end devices that handle high-speed signals, and in mobile phones and other devices due to the small mounting size, and demand is rapidly expanding. When materials such as polyimide, polybenzoxazole, and phenolic resin are used for flip-chip mounting, a metal wiring layer formation process is performed after the resin layer pattern is formed. The metal wiring layer is usually formed by roughening the surface of the resin layer by plasma etching, forming a metal layer to a thickness of 1 μm or less by sputtering, which will become a plating seed layer, and then using the metal layer as an electrode, electrolytic plating. In this case, Ti is generally used as the metal that will become the seed layer, and Cu is generally used as the metal for the rewiring layer formed by electrolytic plating.

For such a metal rewiring layer, high adhesion between the rewired metal layer and the resin layer is required after the reliability test. Examples of the reliability tests performed here include a high-temperature storage test in which the device is stored in air at a high temperature of 125°C or higher for 100 hours or more, a high-temperature operation test in which the device is wired and a voltage is applied while storing the device in air at a temperature of about 125°C for 100 hours or more, a temperature cycle test in which the device is cycled between a low-temperature state of about -65 to -40°C and a high-temperature state of about 125 to 150°C in air, a high-temperature, high-humidity storage test in which the device is stored in a water vapor atmosphere at a temperature of 85°C or higher and a humidity of 85% or higher, a high-temperature, high-humidity bias test in which the same test is performed while wiring is applied, and a solder reflow test in which the device is passed through a solder reflow oven at 260°C multiple times in air or nitrogen.

However, in the past, in the case of the high-temperature storage test among the above reliability tests, there was a problem that voids occurred at the interface where the rewired Cu layer contacted the resin layer after the test. When voids occur at the interface between the Cu layer and the resin layer, the adhesion between the two layers decreases.

JP 2001-338947 A

The present invention was devised in consideration of such conventional circumstances, and aims to provide a photosensitive resin composition that produces a resin layer with high adhesion without generating voids at the interface of the Cu layer and the cured photosensitive resin layer after a high temperature storage test, a method for forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern.

The present inventors discovered that by incorporating a cyclic compound having a carbonyl group into a photosensitive resin composition, a photosensitive resin composition can be obtained that gives a cured film that is excellent in preventing discoloration even on copper or copper alloys, and thus completed the present invention. That is, the present invention is as follows.

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

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

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

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

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

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

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

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

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

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

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

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

In the formula, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R1 and _R2 each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or a group represented by 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 from 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms, or a monovalent organic group represented by the following general formula (3):

(wherein R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10), and a polyamic acid, a polyamic acid ester or a polyamic acid salt is a precursor of a polyimide represented by the formula (I),
The following general formula (4)

{In the formula, _X2 is a trivalent organic group having 6 to 15 carbon atoms, _Y2 is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or multiple structures, _R9 is an organic group having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and _n2 is an integer of 1 to 1000.}
A polyamide having a structure represented by
The following general formula (5) is

{In the formula, _Y3 is a tetravalent organic group having a carbon atom, _Y4 , _X3 , and _X4 are each independently a divalent organic group having two or more carbon atoms, _n3 is an integer of 1 to 1000, _n4 is an integer of 0 to 500, _n3 /( _n3 + _n4 )>0.5, and the arrangement order of the _n3 dihydroxydiamide units including X3 and _Y3 and the _n4 diamide units including _{X4 and Y4} is not important.}
is a polyhydroxyamide, which is a polyoxazole precursor having a structure represented by
The following general formula (6) is

{In the formula, _X5 is a 4-14 valent organic group, _Y5 is a 2-12 valent organic group, _R10 and _R11 each independently represent an organic group having at least one group selected from a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, _n5 is an integer from 3 to 200, and _m3 and _m4 are integers from 0 to 10.}
and
The following general formula (7) is

In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, and 1≦(a+b)≦4; R ₁₂ represents a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group; when b is 2 or 3, a plurality of R ₁₂ may be the same or different from each other; X represents 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, or a group represented by the following general formula (8):

(wherein p is an integer of 1 to 10), and a divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula (I) and a divalent organic group having an aromatic ring and having 6 to 12 carbon atoms.
[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 a monovalent aliphatic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms, n ₆ is an integer of 0 to 4, and when n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ is a hydroxyl group, and when n ₆ is an integer of 2 to 4, a plurality of R _17s may be the same or different from each other.}, and a divalent group represented by the following general formula (10):

In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each independently represent a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a monovalent aliphatic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms; W represents a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, or a group represented by 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):

The photosensitive resin composition according to [1] or [2], wherein the divalent organic group is selected from the group consisting of divalent groups represented by the following formula (I):
[4]
(1) A step of 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 to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising: a step of heat-treating the relief pattern to form a cured relief pattern.
[5] The method according to [4], wherein the substrate is formed from copper or a copper alloy.
[6] A semiconductor device comprising a cured relief pattern obtained by the manufacturing method according to [4] or [5].

According to the present invention, by combining a specific photosensitive resin with a specific compound, it is possible to provide a photosensitive resin composition that produces a photosensitive resin with high adhesion and no voids at the interface between the Cu layer and the polyimide layer after a high temperature storage test, a method for forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern.

The present invention will be described in detail below. Throughout this specification, structures represented by the same symbols in general formulas may be the same or different when multiple structures are present in a molecule.

<Photosensitive resin composition>
(Aspect A)
The present invention comprises, as essential components, 100 parts by mass of (A) at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, and polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, as well as novolak, polyhydroxystyrene, and phenolic resin, (B) 0.01 to 10 parts by mass of a cyclic compound having a carbonyl group based on 100 parts by mass of the (A) resin, and (C) 1 to 50 parts by mass of a photosensitizer based on 100 parts by mass of the (A) resin.

Resin (A) The resin (A) used in the present invention will be described. The resin (A) of the present invention is mainly composed of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, novolac, polyhydroxystyrene, and phenolic resin. Here, the main component means that the resin contains 60% by mass or more of the total resin, and preferably 80% by mass or more. In addition, other resins may be contained as necessary.

From the viewpoint of heat resistance and mechanical properties after heat treatment, the weight average molecular weight of these resins is preferably 200 or more, more preferably 5.00 or more, calculated as polystyrene by gel permeation chromatography. The upper limit is preferably 500,000 or less, and when used as a photosensitive resin composition, from the viewpoint of solubility in a developer, it is more preferably 20,000 or less.

In the present invention, the resin (A) is a photosensitive resin in order to form a relief pattern. The photosensitive resin is used together with the photosensitizer (C) described below to form a photosensitive resin composition, and is a resin that causes a phenomenon of dissolving or remaining undissolved in the subsequent development process.

As photosensitive resins, polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and phenolic resins including novolac and polyhydroxystyrene are preferably used, since the resins after heat treatment 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 or positive photosensitive resin composition together with the photosensitizer (C) described below.

｛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 a resin represented by the general formula (1):

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, R ₁ and R ₂ each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, or a group represented by 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 from 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms.)
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), and the polyamic acid, polyamic acid ester or polyamic acid salt is a precursor of a polyimide represented by the formula (I).
The polyimide precursor is converted to a polyimide by heating (for example, at 200° C. or higher) for cyclization. The polyimide precursor is suitable for use in a negative-type photosensitive resin composition.

｛式中、Ｒ２５は水素原子、フッ素原子、Ｃ１～Ｃ１０の炭化水素基、Ｃ１～Ｃ１０の含フッ素炭化水素基から選ばれる１価の基であり、ｌは０～２から選ばれる整数、ｍは０～３から選ばれる整数、ｎは０～４から選ばれる整数である。｝
で表される構造が挙げられるが、これらに限定されるものではない。また、Ｘ₁の構造は１種でも２種以上の組み合わせでも構わない。上記式で表される構造を有するＸ₁基は、耐熱性と感光特性とを両立するという点で特に好ましい。 In the above general formula (1), the tetravalent organic group represented by _X1 is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group in which the _-COOR1 group and the _-COOR2 group are in the ortho position relative to the -CONH- group, or an alicyclic aliphatic group. The tetravalent organic group represented by _X1 is preferably an organic group having 6 to 40 carbon atoms containing an aromatic ring, and more preferably a group represented by the following formula (30):

{In the formula, R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorine-containing hydrocarbon group, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.}
Examples of the structure represented by the formula ( _I) include, but are not limited to, the structure represented by the formula (I). The structure represented by the formula (I) may be one type or a combination of two or more types. The structure represented by the formula ( _I) is particularly preferred in that it provides 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 _Y1 is preferably an aromatic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (31):

{In the formula, R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorine-containing hydrocarbon group, and n is an integer selected from 0 to 4.}
Examples of the structure represented by the formula ( ₃₁ ) include, but are not limited to, the structure represented by the formula (32). The structure represented by the formula (31) may be one type or a combination of two or more types. The structure represented by the formula ( ₃₂ ) is particularly preferred in that it provides both heat resistance and photosensitive properties.

In the above general formula (2), _R3 is preferably a hydrogen atom or a methyl group, and _R4 and _R5 are preferably hydrogen atoms from the viewpoint of photosensitive properties. Also, _m1 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitive properties.

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

The ester bond-type polyimide precursor can be obtained by first reacting a tetracarboxylic dianhydride containing the above-mentioned tetravalent organic group _X1 with an alcohol having a photopolymerizable unsaturated double bond and, optionally, a saturated aliphatic alcohol having 1 to 4 carbon atoms to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid/ester body), and then subjecting this to amide polycondensation with a diamine containing the above-mentioned divalent organic group _Y1 .

(Preparation of Acid/Ester Forms)
In the present invention, the tetracarboxylic dianhydride containing a tetravalent organic group _X1 that is suitably used for preparing an ester bond type polyimide precursor includes the tetracarboxylic dianhydride represented by the above general formula (30), as well as, for example, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, and the like. Examples of suitable dianhydrides include tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and preferably include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited thereto. These may be used alone or in combination of two or more.

In the present invention, examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare an ester-bond type polyimide precursor include 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-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl acrylate. Examples of the methacryloyloxypropyl acrylate include 1-3-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, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

The above alcohols can also be mixed with saturated aliphatic alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

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

(Preparation of polyimide precursor)
The acid/ester (typically a solution in a solvent described below) is mixed with an appropriate dehydration condensation agent, such as dicyclocarbodiimide (e.g., dicyclohexylcarbodiimide), 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate, under ice cooling to convert the acid/ester into a polyacid anhydride, and then a diamine containing a divalent organic group _Y1 preferably used in the present invention, dissolved or dispersed in a separate solvent, is added dropwise to the mixture to carry out amide polycondensation, thereby obtaining the desired polyimide precursor. Alternatively, the acid moiety of the acid/ester is converted into an acid chloride using thionyl chloride or the like, and then the mixture is reacted with a diamine compound in the presence of a base such as pyridine to obtain the desired polyimide precursor.

Diamines containing a divalent organic group _Y1 that are preferably used in the present invention include diamines having the structure represented by the above general formula (31), as well as, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,

1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-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-amino 2,2-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are replaced by methyl groups, ethyl groups, hydroxymethyl groups, methyl groups, ethyl groups, methyl ... those substituted with a ethyl group, a hydroxyethyl group, a halogen, or the like, for example, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, Examples of suitable amines include, but are not limited to, 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 mixtures thereof.

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

After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensation agent coexisting in the reaction solution is filtered off as necessary, and then a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component. The polymer is purified by repeating redissolution and reprecipitation operations, and then vacuum dried to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with anion and/or cation exchange resin swollen with an appropriate 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 _R1 and _R2 in the general formula (1) is a hydroxyl group.

As the tetracarboxylic dianhydride, a tetracarboxylic anhydride having the structure of the above formula (30) is preferred, and as the diamine, a diamine having the structure of the above formula (31) is preferred. 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.

As the (meth)acrylic compound having an amino group, for example, dialkylaminoalkyl acrylates or methacrylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, diethylaminobutyl methacrylate, etc. are preferred, and among them, from the viewpoint of photosensitive properties, 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 these (meth)acrylic compounds having an amino group blended is 1 to 20 parts by weight per 100 parts by weight of the (A) resin, and from the viewpoint of photosensitivity characteristics, 2 to 15 parts by weight is preferable. Blending 1 part by weight or more of a (meth)acrylic compound having an amino group as the (C) photosensitizer per 100 parts by weight of the (A) resin provides excellent photosensitivity, while blending 20 parts by weight or less provides excellent thick-film curing properties.

The molecular weight of the ester-bonded and ion-bonded polyimide precursors is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, when measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good, and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as the developing solvent for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended to select the standard monodisperse polystyrene from Showa Denko KK's organic solvent-based standard sample STANDARD SM-105.

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

{In the formula, _X2 is a trivalent organic group having 6 to 15 carbon atoms, _Y2 is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or a plurality of structures, _R9 is an organic group having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and _n2 is an integer of 1 to 1000.}
The polyamide has a structure represented by the following formula: This polyamide is suitable for use in a negative-type photosensitive resin composition.

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

で表される基の中から選ばれる芳香族基であることが好ましく、そしてアミノ基置換イソフタル酸構造からカルボキシル基及びアミノ基を除いた芳香族基であることがより好ましい。 In the above general formula (4), the trivalent organic group represented by _X2 is preferably a trivalent organic group having 6 to 15 carbon atoms, for example, a trivalent organic group represented by the following formula (33):

and more preferably an aromatic group obtained by removing a carboxyl group and an amino group from an amino-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 _Y2 is preferably an organic group having 6 to 35 carbon atoms, and more preferably a cyclic organic group having 1 to 4 aromatic or aliphatic rings which may be substituted, or an aliphatic group or siloxane group having no cyclic structure. The divalent organic group represented by _Y2 includes the following general formula (I) and the following general formulas (34) and (35):

In the formula, R ₃₃ and R ₃₄ are each independently one group selected from the group consisting of 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 group and the butyl group include various isomers.

{In the formula, _m7 is an integer of 0 to 8, _m8 and _m9 are each independently an integer of 0 to 3, _m10 and _m11 are each independently an integer of 0 to 10, and _R35 and _R36 are a _methyl group ( _-CH3 ), an ethyl _{group (-C2H5 )} , a _propyl group ( _-C3H7 ), a butyl group ( _-C4H9 ) or an isomer thereof.}.

｛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 may be represented by the following general formula (36):

{In the formula, _m12 is an integer of 2 to 12, _m13 is an integer of 1 to 3, _m14 is an integer of 1 to 20, and _R37 , _R38 , _R39 and _R40 each independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group which may be substituted.} is mentioned as a preferred example.

The polyamide resin of the present invention can be synthesized, for example, as follows.
(Synthesis of phthalic acid compound-terminated product)
First, a compound having a trivalent aromatic group _X2 , for example, at least one compound selected from the group consisting of phthalic acid substituted with an amino group, isophthalic acid substituted with an amino group, and terephthalic acid substituted with an amino group (hereinafter referred to as a "phthalic acid compound") is reacted with 1 mole of a compound that reacts with an amino group to synthesize a compound in which the amino group of the phthalic acid compound is modified and blocked with a group containing a radically polymerizable unsaturated bond as described below (hereinafter referred to as a "blocked phthalic acid compound"). These may be used alone or in combination.

By capping a phthalic acid compound with a group containing the above-mentioned radically polymerizable unsaturated bond, it is possible to impart negative photosensitivity (photocurability) to the polyamide resin.

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

The above-mentioned phthalic acid compound-sealed product can be obtained by reacting the amino group of the phthalic acid 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.

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, etc. Suitable isocyanates include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[(meth)acryloyloxymethyl]ethyl isocyanate, 2-[2-(meth)acryloyloxyethoxy]ethyl isocyanate, etc. Suitable epoxy compounds include glycidyl (meth)acrylate, etc. These may be used alone or in combination, but it is particularly preferred to use methacryloyl chloride and/or 2-(methacryloyloxy)ethyl isocyanate.

Furthermore, among these phthalic acid compound-sealed products, those in which the phthalic acid compound is 5-aminoisophthalic acid are preferred, as they have excellent photosensitive properties and can produce polyamides with excellent film properties after heat curing.

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

Some types of sealing agents, such as acid chlorides, produce hydrogen chloride as a by-product during the sealing reaction. In this case, in order to prevent contamination of subsequent processes, it is preferable to purify the product appropriately, such as by reprecipitation in water, rinsing with water and drying, or by passing the product through a column filled with ion exchange resin to remove and reduce ionic components.

(Synthesis of Polyamide)
The polyamide of the present invention can be obtained by mixing the above-mentioned phthalic acid compound-blocked product and a diamine compound having a divalent organic group _Y2 in a solvent as described below in the presence of a basic catalyst such as pyridine or triethylamine, and carrying out amide polycondensation.

Examples of the amide polycondensation method include a method in which a phthalic acid compound-sealed product is converted into a symmetric polyacid anhydride using a dehydrating condensing agent and then mixed with a diamine compound, a method in which a phthalic acid compound-sealed product is converted into an acid chloride by a known method and then mixed with a diamine compound, and a method in which a dicarboxylic acid component is reacted with an active esterifying agent in the presence of a dehydrating condensing agent to convert it into an active ester and then mixed with a diamine compound.

Preferred examples of dehydration condensation agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate.

Chlorinating agents include thionyl chloride.

Examples of active esterification agents include N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, 2-hydroxyimino-2-cyanoethyl acetate, and 2-hydroxyimino-2-cyanoacetic acid amide.

The diamine compound having the organic group _Y2 is preferably at least one diamine compound selected from the group consisting of an aromatic diamine compound, an aromatic bisaminophenol compound, an alicyclic diamine compound, a linear aliphatic diamine compound, and a siloxane diamine compound, and a plurality of diamine compounds may be used in combination as desired.

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-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and diamine compounds in which some of the hydrogen atoms on the benzene ring are substituted with one or more groups selected from the group consisting of methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, and halogen atoms.

Examples of diamine compounds in which the 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, and 3,3'-dichloro-4,4'-diaminobiphenyl.

Aromatic bisaminophenol compounds include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenyl sulfone, 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)hexafluoropropane, nophenyl)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-aminophenol), etc.

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, and 1,3-bis(aminomethyl)cyclohexa amine, 1,4-bis(aminomethyl)cyclohexane, 2-(3-aminocyclopentyl)-2-propylamine, menthene diamine, isophorone diamine, 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, etc.

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

Examples of siloxane diamine compounds include dimethyl (poly)siloxane diamine, such as those manufactured by Shin-Etsu Chemical Co., Ltd. under the trade names PAM-E, KF-8010, and X-22-161A.

After the amide polycondensation reaction is completed, the precipitates derived from the dehydration condensation agent that have precipitated in the reaction solution are filtered off as necessary. Next, a poor solvent for polyamide, such as water or a lower aliphatic alcohol or a mixture thereof, is added to the reaction solution to precipitate the polyamide. The precipitated polyamide is then redissolved in a solvent and purified by repeating the reprecipitation operation, and vacuum dried to isolate the desired polyamide. 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.

The polystyrene-equivalent weight average molecular weight of the polyamide determined 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. Furthermore, if the polystyrene-equivalent weight average molecular weight is 70,000 or less, the development solubility when forming the relief pattern is ensured.

Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the eluent for GPC. The weight-average molecular weight value is determined from a calibration curve created using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from Showa Denko's organic solvent-based standard sample STANDARD SM-105.

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

{wherein _Y3 is a tetravalent organic group having a carbon atom, preferably a tetravalent organic group having two or more carbon atoms, _Y4 , _X3 , and _X4 are each independently a divalent organic group having two or more carbon atoms, _n3 is an integer of 1 to 1000, _n4 is an integer of 0 to 500, _n3 /( _n3 + _n4 )>0.5, and the arrangement order of the _n3 dihydroxydiamide units including _X3 and _Y3 and the _n4 diamide units including _X4 and _Y4 is not important.}.

The polyoxazole precursor is a polymer having _n3 dihydroxydiamide units (hereinafter, sometimes simply referred to as dihydroxydiamide units) in the above general formula (5), and may have _n4 diamide units (hereinafter, sometimes simply referred to as diamide units) in the above general formula (5).

The number of carbon atoms in _X3 is preferably 2 to 40 in order to obtain photosensitive properties, the number of carbon atoms in _X4 is preferably 2 to 40 in order to obtain photosensitive properties, the number of carbon atoms in _Y3 is preferably 2 to 40 in order to obtain photosensitive properties, and the number of carbon atoms in _Y4 is preferably 2 to 40 in order to obtain photosensitive properties.

The dihydroxydiamide unit can be formed by synthesis from a diaminodihydroxy compound (preferably bisaminophenol) having the structure Y ₃ (NH ₂ ) ₂ (OH) ₂ and a dicarboxylic acid having the structure X ₃ (COOH) _2. A typical embodiment will be described below using a case where the diaminodihydroxy compound is bisaminophenol. The two pairs of amino groups and hydroxy groups of the bisaminophenol are in the ortho position relative to each other, and the dihydroxydiamide unit is ring-closed by heating at about 250 to 400°C, and changes to a heat-resistant polyoxazole structure. n ₃ in the general formula (5) is 1 or more for the purpose of obtaining photosensitive properties and 1000 or less for the purpose of obtaining photosensitive properties. n ₃ is preferably in the range of 2 to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 20.

The polyoxazole precursor may have ₄ diamide units condensed therein as necessary. The diamide units can be formed by synthesis from a diamine having a structure of Y ₄ (NH ₂ ) ₂ and a dicarboxylic acid having a structure of X ₄ (COOH) _2. n ₄ in the general formula (5) is in the range of 0 to 500, and good photosensitive characteristics can be obtained when n ₄ is 500 or less. n ₄ is more preferably in the range of 0 to 10. If the ratio of diamide units to dihydroxydiamide units is too high, the solubility in an alkaline aqueous solution used as a developer decreases, so the value of n ₃ /(n ₃ +n ₄ ) in the general formula (5) is more than 0.5, more preferably 0.7 or more, and most preferably 0.8 or more.

｛式中、Ｒｓ１とＲｓ２は、それぞれ独立に、水素原子、メチル基、エチル基、プロピル基、シクロペンチル基、シクロヘキシル基、フェニル基、トリフルオロメチル基を表す｝ で表されるものが、感光特性の点で好ましい。 Examples of bisaminophenols as diaminodihydroxy compounds having the structure Y ₃ (NH ₂ ) ₂ (OH) ₂ include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, 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 ... Examples of the bisaminophenols include 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, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols can be used alone or in combination of two or more. The Y ₃ group in the bisaminophenol is represented by the following formula (37):

In terms of photosensitive properties, those represented by the following formula are preferred: {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}.

Examples of diamines having the structure Y ₄ (NH ₂ ) ₂ include aromatic diamines and silicon diamines. Among these, examples of aromatic diamines include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenyl methane, 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-aminophenyl) 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy]benzophenone, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy]diphenyl sulfone, 4,4'-diaminobiphenyl,

4,4'-diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, o-toluidine sulfone, 2,2-bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl)sulfone, bis(4-aminophenoxyphenyl)sulfide, 1,4-(4-aminophenoxyphenyl)benzene, 1,3-(4-aminophenoxyphenyl)benzene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-di-(3-aminophenoxy)diphenylsulfone, 4,4'-diaminobenzanilide, and the like, as well as compounds in which the hydrogen atoms of the aromatic nuclei of these aromatic diamines are substituted with at least one group or atom selected from the group consisting of chlorine atoms, fluorine atoms, bromine atoms, methyl groups, methoxy groups, cyano groups, and phenyl groups.

As the diamine, a silicon diamine can be selected to enhance 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, 1,4-bis(γ-aminopropyldimethylsilyl)benzene, bis(4-aminobutyl)tetramethyldisiloxane, bis(γ-aminopropyl)tetraphenyldisiloxane, etc.

｛式中、Ｒ₄₁は、－ＣＨ₂－、－Ｏ－、－Ｓ－、－ＳＯ₂－、－ＣＯ－、－ＮＨＣＯ－及び－Ｃ（ＣＦ₃）₂－から成る群から選択される２価の基を表す。｝
で表される芳香族基から好ましく選択でき、これらは感光特性の点で好ましい。 In addition, preferred dicarboxylic acids having the structure _X3 (COOH) ₂ or _X4 (COOH) ₂ include those in which _X3 and _X4 are aliphatic or aromatic groups having a straight chain, branched chain or cyclic structure, respectively. Among them, organic groups having 2 to 40 carbon atoms and which may contain an aromatic or aliphatic ring are preferred, and _X3 and _X4 are each represented by the following formula (38):

{In the formula, R ₄₁ represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, and -C(CF ₃ ) ₂ -.}
These are preferred in terms of photosensitive properties.

で表されるものが挙げられる。 The polyoxazole precursor may have a terminal group blocked with a specific organic group. When a polyoxazole precursor blocked with a blocking group is used, it is expected that the mechanical properties (especially elongation) and the cured relief pattern shape of the coating film after heat curing of the photosensitive resin composition of the present invention will be good. A suitable example of such a blocking group is a polyoxazole precursor represented by the following formula (39):

Examples of the above-mentioned are represented by the following formula:

The polystyrene-equivalent weight average molecular weight of the polyoxazole precursor as determined by gel permeation chromatography is preferably 3,000 to 70,000, more preferably 6,000 to 50,000. From the viewpoint of the physical properties of the cured relief pattern, this weight average molecular weight is preferably 3,000 or more. From the viewpoint of resolution, it is preferably 70,000 or less. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The molecular weight is determined from a calibration curve created using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko KK.

｛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 example of a preferable resin (A) in the photosensitive resin composition of the present invention is a resin represented by the general formula (6):

{In the formula, _X5 is a 4-14 valent organic group, _Y5 is a 2-12 valent organic group, _R10 and _R11 are an organic group having at least one group selected from a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, and may be the same or different, _n5 is an integer from 3 to 200, and _m3 and _m4 are integers from 0 to 10.}
Here, the resin represented by the general formula (6) is particularly preferred in that it does not require chemical change in the heat treatment step in order to develop sufficient film properties, and is therefore suitable for treatment at lower temperatures.
_X5 in the structural unit represented by the above general formula (6) is preferably a tetravalent to tetratetravalent organic group having 4 to 40 carbon atoms, and more preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or an aliphatic ring, from the viewpoint of achieving both heat resistance and photosensitive properties.

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

Suitable tetracarboxylic dianhydrides include pyromellitic dianhydride, 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, dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene 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。 Aromatic tetracarboxylic dianhydrides such as 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, or aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride and 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, and the following general formula (40):

{wherein R ₄₂ represents a group selected from an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ , and R ₄₃ and R ₄₄ may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group or a thiol group.}

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 dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, and compounds represented by 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 may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group or a thiol group.} is preferred. These may be used alone or in combination of two or more.

_Y5 in the above general formula (6) represents a structural component of a diamine, and the diamine represents a divalent to dodecavalent organic group containing an aromatic ring or an aliphatic ring, and among these, an organic group having 5 to 40 carbon atoms is preferable.

Specific examples of diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 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-phenylenediamine, 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'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl,

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

｛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'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 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 compounds represented by the following general formula (43):

In the formula, 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 may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group or a thiol group.
Preferred is a diamine having a structure represented by the following formula:

｛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'-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, and compounds represented by the following general formula (44):

In the formula, 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 may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group or a thiol group.
Particularly preferred are diamines having the structure represented by the following formula: These may be used alone or in combination of two or more kinds.

In the general formula (6), R ₁₀ and R ₁₁ each represent a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. In the present invention, R ₁₀ and R ₁₁ may be a mixture of a phenolic hydroxyl group, a sulfonic acid group, and/or a thiol group.

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

Furthermore, in order to improve adhesion to the substrate, aliphatic groups having a siloxane structure may be copolymerized as X ₅ and Y ₅ within a range that does not decrease heat resistance. Specific examples include those obtained by copolymerizing 1 to 10 mol % of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-amino-phenyl)octamethylpentasiloxane, etc. as a diamine component.

The polyimide can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine compound (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, by reacting a tetracarboxylic dianhydride with a diamine compound (partially substituted with a terminal blocking agent that is an acid anhydride, a monoacid chloride compound, or a monoactive ester compound) at low temperature, by obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, by obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with a diamine (partially substituted with a terminal blocking agent that is a monoamine), or by using a known imidization reaction method to obtain a polyimide precursor, or by stopping the imidization reaction midway and introducing a partial imide structure (in this case, polyamideimide), or by blending a fully imidized polymer with the polyimide precursor to introduce a partial imide structure.

It is preferable that the polyimide has an imidization rate of 15% or more relative to the entire resin constituting the photosensitive resin composition. More preferably, it is 20% or more. Here, the imidization rate refers to the proportion of imidization present in the entire resin constituting the photosensitive resin composition. If the imidization rate is less than 15%, the amount of shrinkage during thermal curing becomes large, making it unsuitable for producing thick films.

The imidization rate can be easily calculated using 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) due to the imide structure resulting from polyimide. Next, the polymer is heat-treated at 350°C for 1 hour, the infrared absorption spectrum after heat treatment is measured, and the imidization rate in the polymer before heat treatment is calculated by comparing the peak intensity near 1377 cm-1 with the intensity before heat treatment.

The molecular weight of the polyimide is preferably 3,000 to 200,000, and more preferably 5,000 to 50,000, when measured as a weight average molecular weight converted into polystyrene by gel permeation chromatography. When the weight average molecular weight is 3,000 or more, the mechanical properties are good, and when it is 50,000 or less, the dispersibility in the developer is good and the resolution performance of the relief pattern is good.

Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko KK.
Furthermore, in the present invention, phenol resins can also be suitably used.

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

In this embodiment, the weight average molecular weight of the (A) phenolic resin is preferably 700 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 50,000. From the viewpoint of the reflow treatment applicability of the cured film, the weight average molecular weight is preferably 700 or more, while from the viewpoint of the alkali solubility of the photosensitive resin composition, it is preferably 100,000 or less.
In the present disclosure, the weight average molecular weight 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。 From the viewpoints of solubility in an alkaline aqueous solution, sensitivity and resolution when forming a resist pattern, and residual stress in a cured film, the (A) phenolic resin may be selected from novolak, polyhydroxystyrene, and compounds represented by the following general formula (7):

In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, and 1≦(a+b)≦4; R ₁₂ represents a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group; when b is 2 or 3, multiple R ₁₂ may be the same or different from each other; X represents 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, or a group represented by the following general formula (8):

(wherein p is an integer of 1 to 10), and a divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the following formula:
and a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms.

(Novolac)
In the present disclosure, novolac refers to any polymer obtained by condensing phenols and formaldehyde in the presence of a catalyst. In general, novolac can be obtained by condensing less than 1 mole of formaldehyde with 1 mole 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 examples of novolak include phenol/formaldehyde condensed novolak resins, cresol/formaldehyde condensed novolak resins, and phenol-naphthol/formaldehyde condensed novolak resins.

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

(Polyhydroxystyrene)
In the present disclosure, polyhydroxystyrene means polymers containing hydroxystyrene as a polymerization unit in general. A preferred example of polyhydroxystyrene is polyparavinylphenol. Polyparavinylphenol means polymers containing paravinylphenol as a polymerization unit in general. Therefore, to constitute polyhydroxystyrene (for example, polyparavinylphenol), polymerization units other than hydroxystyrene (for example, paravinylphenol) can be used as long as it does not go against the purpose of the present invention. In polyhydroxystyrene, the ratio of the number of moles of hydroxystyrene units based on the number of moles of all polymerization units is preferably 10 mol% to 99 mol%, more preferably 20 to 97 mol%, and even more preferably 30 to 95 mol%. When the ratio is 10 mol% or more, it is advantageous from the viewpoint of the alkali solubility of the photosensitive resin composition, and when it is 99 mol% or less, it is advantageous from the viewpoint of the reflow applicability of the cured film obtained by curing the composition containing the copolymerization component described below. The polymerization units other than hydroxystyrene (for example, paravinylphenol) can be any polymerization unit that can be copolymerized with hydroxystyrene (for example, paravinylphenol). Examples of copolymerization components that provide polymerization units other than hydroxystyrene (e.g., paravinylphenol) include, but are not limited to, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, octyl acrylate, 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 ... esters of acrylic acid such as ethylene glycol dimethacrylate, polyoxypropyl trimethylolpropane triacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol trimethacrylate, 1-phenylethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate, and 1,4-benzenediol dimethacrylate; styrene and substituted styrenes such as, for example, 2-methylstyrene and vinyltoluene; vinyl ester monomers such as, for example, vinyl acrylate and vinyl methacrylate; and o-vinylphenol, m-vinylphenol, and the like.

The novolaks and polyhydroxystyrenes described above can each be used alone or in combination of two or more.

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

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

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

In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, and 1≦(a+b)≦4; R ₁₂ represents a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group; when b is 2 or 3, a plurality of R ₁₂ may be the same or different from each other; X represents 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, or a group represented by the following general formula (8):

(wherein p is an integer of 1 to 10), and a divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula: (wherein p is an integer of 1 to 10), and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms.}. Phenol resins having the above repeating units are particularly advantageous in that they can be cured at low temperatures compared to, for example, polyimide resins and polybenzoxazole resins which have been conventionally used, and enable the formation of a cured film having good elongation. The above repeating units present in the phenol resin molecule may be one type or a combination of two or more types.

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

{wherein R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an alicyclic group having 3 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms, and R ₆₄ represents a divalent aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, or a divalent aromatic group having 6 to 20 carbon atoms.}.

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

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

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

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

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

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

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

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

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

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

{wherein R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a monovalent aliphatic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms, n ₆ is an integer of 0 to 4, and when n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or a monovalent organic group having 1 to 12 carbon atoms, at least one R ₁₇ is a hydroxyl group, and when n ₆ is an integer of 2 to 4, a plurality of R _17s may be the same or different from each other.}, and a divalent group represented by the following general formula (10):

In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each independently represent a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a monovalent aliphatic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms; W represents a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, or a group represented by 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):

The divalent organic group X having an aromatic ring with 6 to 12 carbon atoms has preferably 8 to 75 carbon atoms, more preferably 8 to 40 carbon atoms. The structure of the divalent organic group X having an aromatic ring with 6 to 12 carbon atoms is generally different from the structure in which the OH group and any R ₁₂ group are bonded to the aromatic ring in the general formula (7).

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, from the viewpoint of achieving good pattern formability of the resin composition and good elongation of the cured film after curing, the divalent organic group represented by the above general formula (10) is preferably a divalent organic group represented by the following formula (12):

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

It is particularly preferable that the divalent organic group is represented by the following formula:

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

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

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

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

{In the formula, 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 when n ₁₀ is 2, multiple R _22s may be the same or different from each other, and when n ₁₁ is 2 or 3, multiple R _23s may be the same or different from each other.}

_m5 in the general formula (14) and _m6 in the general formula (15) represent the total number of repeating units in the main chain of the phenolic resin. That is, in the (A) phenolic resin, for example, the repeating units in parentheses in the structure represented by the general formula (14) and the repeating units in parentheses in the structure represented by the general formula (15) can be arranged randomly, in blocks, or in a combination thereof. _m5 and _m6 are each independently an integer of 1 to 500, with the lower limit being preferably 2, more preferably 3, and the upper limit being preferably 450, more preferably 400, and even more preferably 350. _m5 and _m6 are each independently preferably 2 or more from the viewpoint of the toughness of the film after curing, and preferably 450 or less from the viewpoint of solubility in an alkaline aqueous solution. The sum of _m5 and _m6 is preferably 2 or more, more preferably 4 or more, and even more preferably 6 or more from the viewpoint of toughness of the cured film, and is preferably 200 or less, more preferably 175 or less, and even more preferably 150 or less from the viewpoint of solubility in an alkaline aqueous solution.

In the (A) phenolic resin having both the structure represented by the general formula (14) and the structure represented by the general formula (15) in the same resin skeleton, the higher the molar ratio of the structure represented by the general formula (14), the better the film properties after curing and the more excellent the heat resistance, while the higher the molar ratio of the structure represented by the general formula (15), the better the alkali solubility and the more excellent the pattern shape after curing. Therefore, the ratio _m5 / _m6 of the structure represented by the general formula (14) to the structure represented by the general formula (15) is preferably 20/80 or more, more preferably 40/60 or more, and particularly preferably 50/50 or more from the viewpoint of the film properties after curing, and is preferably 90/10 or less, more preferably 80/20 or less, and even more preferably 70/30 or less from the viewpoint of the alkali solubility and the shape of the cured relief pattern.

The phenolic resin having a repeating unit represented by the general formula (7) typically contains a phenolic compound and a copolymerization component (specifically, one or more compounds selected from the group consisting of a compound having an aldehyde group (including a compound that decomposes to produce an aldehyde compound, such as trioxane), 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), and more typically can be synthesized by polymerizing a monomer component consisting of these. For example, a phenolic resin (A) can be obtained by polymerizing a copolymerization component such as an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, or a haloalkyl compound with a phenol and/or a phenol derivative (hereinafter collectively referred to as a "phenolic compound") as shown below. In this case, in the 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 phenolic compound, and the portion represented by X is derived from the copolymerization component. From the viewpoint of reaction control and the stability of the obtained (A) phenolic resin and photosensitive resin composition, the molar ratio of the phenolic compound to the copolymerization components is preferably 5:1 to 1.01:1, and 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 even more preferably 2,000 to 50,000. From the viewpoint of the reflow treatment applicability of the cured film, the weight average molecular weight is preferably 700 or more, while from the viewpoint of the alkali solubility of the photosensitive resin composition, it is preferably 100,000 or less.

Examples of phenolic compounds that can be used to obtain a 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-nor Bornene-2,3-dicarboximide, trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, resorcinol, xylenol, catechol, methyl catechol, ethyl catechol, hexyl catechol, benzyl catechol, nitrobenzyl catechol, methyl resorcinol, ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hy 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, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, methyl trihydroxybenzoate, ethyl trihydroxybenzoate, butyl trihydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzonitrile, etc.

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

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, and 2,2-bis(4-oxocyclohexyl)propane.

Examples of the methylol compounds include 2,6-bis(hydroxymethyl)-p-cresol, 2,6-bis(hydroxymethyl)-4-ethylphenol, 2,6-bis(hydroxymethyl)-4-propylphenol, 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-dihydroxydodeca , 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)diphenyl thioether, 4,4'-bis(hydroxymethyl)benzophenone, 4-hydroxymethyl ...'-bis(hydroxymethyl)naphthalene, 2,6'-bis(hydroxymethyl)naphthalene, 1,8-bis(hydroxymethyl)anthracene, 2,2'-bis(hydroxymethyl)diphenyl ether, Examples of the dimethylbenzoate-4'-hydroxymethylphenyl, 4-hydroxymethylbenzoate-4'-hydroxymethylanilide, 4,4'-bis(hydroxymethyl)phenylurea, 4,4'-bis(hydroxymethyl)phenylurethane, 1,8-bis(hydroxymethyl)anthracene, 4,4'-bis(hydroxymethyl)biphenyl, 2,2'-dimethyl-4,4'-bis(hydroxymethyl)biphenyl, 2,2-bis(4-hydroxymethylphenyl)propane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, etc.

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, and 2,6-bis(methoxymethyl)-4-n-butoxyphenol. Phenol, 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) 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)diphenyl thioether, 4,4'-bis(methoxymethyl)benzophenone, 4'-methoxymethylphenyl 4-methoxymethylbenzoate, 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, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, etc.

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

Examples of the haloalkyl compounds include xylylene 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, and tetraethylene glycol bis(chloroethyl)ether.

The phenolic resin (A) can be obtained by condensing the above-mentioned phenolic compound and the copolymerization component by dehydration, dehydrohalogenation, or dealcoholization, or by polymerizing while cleaving the unsaturated bonds, but a catalyst may be used during polymerization. Examples of acidic catalysts include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfate, diethyl sulfate, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride-phenol complex, and boron trifluoride-ether complex. On the other hand, examples of alkaline catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N,N-dimethylaminopyridine, piperidine, piperazine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, ammonia, and hexamethylenetetramine.

The amount of catalyst used to obtain a phenolic resin having a repeating structure represented by general formula (7) is preferably in the range of 0.01 mol % to 100 mol % relative to the total number of moles of copolymerization components (i.e., components other than phenolic compounds), preferably the total number of moles of aldehyde compounds, ketone compounds, methylol compounds, alkoxymethyl compounds, diene compounds, and haloalkyl compounds, 100 mol %.

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

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

(Phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms)
The phenolic resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms is a condensation polymerization product of a reaction product (hereinafter also referred to as an "unsaturated hydrocarbon group-modified phenol derivative") between phenol or a derivative thereof and a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (hereinafter sometimes simply referred to as an "unsaturated hydrocarbon group-containing compound") and an aldehyde, or a reaction product between a phenolic resin and an unsaturated hydrocarbon group-containing compound.

The phenol derivative may be the same as that described above as a raw material for the phenol resin having a repeating unit represented by general formula (7).

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

Examples of compounds containing unsaturated hydrocarbon groups 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. 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, stearidonic acid, 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 and flexibility of the cured film.

The vegetable oil usually contains an ester of glycerin and an unsaturated fatty acid, and is a non-drying oil having an iodine value of 100 or less, a semi-drying oil having an iodine value of more than 100 and less than 130, or a drying oil having an iodine value of 130 or more. Examples of non-drying oils include olive oil, morning glory seed oil, cashew seed oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of drying oils include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, perilla oil, and mustard oil. Processed vegetable oils obtained by processing these vegetable oils may also be used.

Among the above vegetable oils, it is preferable to use non-drying oils from the viewpoint of preventing gelation due to excessive reaction in the reaction between phenol or its derivatives or phenolic resin and vegetable oil and improving yield. On the other hand, it is preferable to use drying oils from the viewpoint of improving the adhesion, mechanical properties and thermal shock resistance of the resist pattern. Among the drying oils, tung oil, linseed oil, soybean oil, walnut oil and safflower oil are preferable, and tung oil and linseed oil are more preferable, because they can more effectively and reliably exert the effects of the present invention. These vegetable oils are used alone 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 to 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 preferably 1 to 100 parts by mass of the unsaturated hydrocarbon group-containing compound per 100 parts by mass of phenol or its derivative, and more preferably 5 to 50 parts by mass. If the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst as necessary.

The unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction is polycondensed with an aldehyde to produce a phenol resin modified with an unsaturated hydrocarbon group-containing compound. The aldehyde is selected from, 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, leplicic acid, 4-acetylbutyric acid, acetonedicarboxylic acid, and 3,3'-4,4'-benzophenonetetracarboxylic acid. Also, precursors of formaldehyde such as paraformaldehyde and trioxane may be used. These aldehydes may be used alone or in combination of two or more.

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

The above reaction is preferably carried out 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 the reaction is completed, 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. Solvents such as toluene, xylene, and methanol can be used for the reaction.

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

A 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 resin used in this case is a polycondensation product of a phenolic compound (i.e., phenol and/or a phenol derivative) and an aldehyde. In this case, the phenolic derivative and the aldehyde can be the same as those described above, and the phenolic resin can be synthesized under the conventionally known conditions as described above.

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

The unsaturated hydrocarbon group-containing compound to be reacted with the phenolic resin can be the same as the unsaturated hydrocarbon group-containing compound described above in relation to the production of the unsaturated hydrocarbon group-modified phenol derivative to be reacted with the aldehydes.

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

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

The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of the carboxy groups of a polybasic acid having multiple carboxy groups. Examples of polybasic acid anhydrides include dibasic acid anhydrides such as phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, and trimellitic anhydride, and aromatic tetrabasic acid dianhydrides such as biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. These may be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably at least one selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern having a better shape can be formed.

The reaction between the phenolic hydroxyl group and the polybasic acid anhydride can be carried out at 50 to 130°C. In this reaction, it is preferable to react 0.10 to 0.80 moles of the polybasic acid anhydride with 1 mole of the phenolic hydroxyl group, more preferably 0.15 to 0.60 moles, and even more preferably 0.20 to 0.40 moles. If the amount of the polybasic acid anhydride is less than 0.10 moles, the developability tends to decrease, and if it exceeds 0.80 moles, the alkali resistance of the unexposed areas tends to decrease.

The above reaction may contain a catalyst as necessary in order to carry out the reaction quickly. Examples of catalysts 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 phenolic resin further modified with a polybasic acid anhydride is preferably 30 to 200 mgKOH/g, more preferably 40 to 170 mgKOH/g, and even more preferably 50 to 150 mgKOH/g. If the acid value is less than 30 mgKOH/g, alkaline development tends to take a longer time than when the acid value is in the above range, and if it exceeds 200 mgKOH/g, the developer resistance of the unexposed areas tends to decrease compared to when the acid value is in the above range.

The molecular weight of the phenolic resin modified with an unsaturated hydrocarbon group-containing compound is preferably a weight average molecular weight of 1,000 to 100,000, more preferably 2,000 to 100,000, taking into consideration the solubility in an alkaline aqueous solution and the balance between the photosensitive characteristics and the physical properties of the cured film.

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

(B) Cyclic Compound Having a Carbonyl Group The compound (B) is at least one compound selected from the group consisting of cyclic compounds having two or more carbonyl groups, the carbonyl group being directly bonded to the cyclic structure, and in the case of a monocyclic compound, at least one third of the atoms forming the cyclic structure are N atoms, and in the case of a condensed ring compound, at least one third of the atoms forming the cyclic structure having the carbonyl group are N atoms.
When classified based on the ring structure, at least one compound selected from the group consisting of a 5-membered ring compound, a 6-membered ring compound, a fused ring compound of 5-membered rings, a fused ring compound of 5-membered rings, a fused ring compound of 5-membered rings, and a fused ring compound of 6-membered rings is preferred from the viewpoint of migration resistance.
By having two or more carbonyl groups, the area of voids on the copper surface can be reduced. Furthermore, from the viewpoints 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. Furthermore, when there are two or more carbonyl groups, it is preferable from the viewpoints of developability, sensitivity, in-plane uniformity after curing, elongation after reflow, etc. compared to when there is one carbonyl group.

Specific examples of (B) compounds include 5-membered ring compounds such as hydantoin, allantoin, and parabanic acid; 6-membered ring compounds such as barbituric acid, 1,3-dimethylbarbituric acid, 1,3-dicyclohexylbarbituric acid, uramil, alloxan, cyanuric acid, and tris(2-hydroxyethyl) isocyanurate; 5-membered ring and 5-membered ring condensed ring compounds such as glycoluril; and 6-membered ring and 5-membered ring condensed ring compounds such as chiral uril. Examples of compounds that can be used include xanthine, 1-methylxanthine, 3-methylxanthine, 8-bromo-3-methylxanthine, theobromine, theophylline, 7-(2-chloroethyl)theophylline, caffeine, uric acid, and 8-azaxanthine, and examples of compounds that can be used as condensed ring compounds of 6-membered rings include lumazine, 7,8-dimethylaloxazine, 1,4-dihydro-6-methylquinoxaline-2,3-dione, and mixtures thereof. Of these, it is preferable to use condensed ring compounds.

｛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) is represented by the following general formula (60):

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

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

{In the formula, Rs9, Rs10, Rs11, and Rs12 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group which may be substituted with an aromatic group, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group, or an alkyl group or aromatic group having 1 to 10 carbon atoms.}
A compound represented by the following general formula (63):

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

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

The amount of the (B) compound is 0.01 to 10 parts by mass, and preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the (A) resin. From the viewpoint of migration resistance, it is desirable to use 0.01 part by mass or more, and from the viewpoint of solubility, it is desirable to use less than 10 parts by mass.
It is believed that the carbonyl groups and nitrogen atoms contained in the ring structure of these components (B) change the surface state of copper by coordinating with copper, thereby suppressing copper migration during high-temperature storage tests. In particular, in the case of condensed rings, it is believed that the concerted action of multiple carbonyl groups and nitrogen atoms enhances migration resistance.

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

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

[(C) Negative Photosensitizer: Photopolymerization Initiator and/or Photoacid Generator]
First, a case where a negative type is desired will be described. In this case, a photopolymerization initiator and/or a photoacid generator is used as the (C) photosensitizer, and the photopolymerization initiator is preferably a photoradical polymerization initiator, and examples of the photopolymerization initiator include benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone and other acetophenone derivatives, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives, benzil, benzil dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives,

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-2- Preferred examples of the photopolymerization initiator include, but are not limited to, oximes such as (o-ethoxycarbonyl)oxime and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, titanocenes, and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Of the above photopolymerization initiators, oximes are more preferred, particularly in terms of photosensitivity.

When a photoacid generator is used as the photosensitizer (C) in a negative photosensitive resin composition, it becomes acidic when irradiated with active light such as ultraviolet light, and by its action, it crosslinks the crosslinking agent described below with the resin, which is the component (A), or polymerizes the crosslinking agents themselves. Examples of this photoacid generator include diaryl sulfonium salts, triaryl sulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, oximesulfonic acid esters, aromatic N-oxyimidosulfonates, aromatic sulfamides, haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and naphthoquinone diazide-4-sulfonic acid esters. Two or more of these compounds can be used in combination as necessary, or in combination with other sensitizers. Among the above photoacid generators, aromatic oximesulfonic acid esters and aromatic N-oxyimidosulfonates are more preferable, especially in terms of photosensitivity.

The amount of these photosensitizers to be blended is 1 to 50 parts by weight per 100 parts by weight of (A) resin, and from the viewpoint of photosensitivity characteristics, 2 to 15 parts by weight is preferable. Blending 1 part by weight or more of (C) photosensitizer per 100 parts by weight of (A) resin provides excellent photosensitivity, while blending 50 parts by weight or less provides excellent thick-film curing properties.

Furthermore, as described above, when the (A) resin represented by the general formula (1) is of the ionic bond type, a (meth)acrylic compound having an amino group is used to impart a photopolymerizable group to the side chain of the (A) resin via an ionic bond. In this case, a (meth)acrylic compound having an amino group is used as the (C) photosensitizer, and as described above, for example, dialkylaminoalkyl acrylates or methacrylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, and diethylaminobutyl methacrylate are preferred, and among them, from the viewpoint of photosensitive properties, 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 these (meth)acrylic compounds having an amino group blended is 1 to 20 parts by weight per 100 parts by weight of the (A) resin, and from the viewpoint of photosensitivity characteristics, 2 to 15 parts by weight is preferable. Blending 1 part by weight or more of a (meth)acrylic compound having an amino group as the (C) photosensitizer per 100 parts by weight of the (A) resin provides excellent photosensitivity, while blending 20 parts by weight or less provides excellent thick-film curing properties.

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

[(C) Positive-type photosensitizer: compound having a quinone diazide group]
Examples of the compound having a quinone diazide group (C) (hereinafter also referred to as "quinone diazide compound (C)") include compounds having a 1,2-benzoquinone diazide structure and compounds having a 1,2-naphthoquinone diazide structure, which are known substances from U.S. Pat. Nos. 2,772,972, 2,797,213, and 3,669,658. The quinone diazide compound (C) is preferably at least one compound selected from the group consisting of 1,2-naphthoquinone diazide-4-sulfonic acid esters of polyhydroxy compounds having a specific structure described in detail below, and 1,2-naphthoquinone diazide-5-sulfonic acid esters of the polyhydroxy compounds (hereinafter also referred to as "NQD compound").

The NQD compound can be obtained by converting a naphthoquinone diazide sulfonic acid compound into a sulfonyl chloride with chlorosulfonic acid or thionyl chloride in a conventional manner, and then subjecting the resulting naphthoquinone diazide sulfonyl chloride to a condensation reaction with a polyhydroxy compound. For example, a predetermined amount of a polyhydroxy compound and 1,2-naphthoquinone diazide-5-sulfonyl chloride or 1,2-naphthoquinone diazide-4-sulfonyl chloride are reacted in a solvent such as dioxane, acetone, or tetrahydrofuran in the presence of a basic catalyst such as triethylamine to perform esterification, and the resulting product is washed with water and dried.

｛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 this embodiment, from the viewpoint of sensitivity and resolution when forming a resist pattern, it is preferable that the compound having a quinonediazide group (C) is a 1,2-naphthoquinonediazide-4-sulfonic acid ester and/or a 1,2-naphthoquinonediazide-5-sulfonic acid ester of a hydroxy compound represented by the following general formulas (70) to (74).
The 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), X ₁₃ and X ₁₄ each independently represent 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 each independently represent an integer of 0 to 5, at least one of r3 and r4 is an integer of 1 to 5, (r1 + r3) ≦ 5, and (r2 + r4) ≦ 5.}
The general formula (71) is

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

{wherein r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, (r14×r15) L's each independently represent a monovalent organic group having 1 to 20 carbon atoms, and (r15) ^T1 's and (r15) ^T2 's each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.}
And, the general formula (73) is

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

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

{wherein r17, r18, r19, and r20 each independently represent an integer of 0 to 2, at least one of r17, r18, r19, and r20 is 1 or 2, X ₂₀ to X ₂₉ each independently represent 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 each independently represent a divalent group selected from the group consisting of a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, -CO ₂ -, cyclopentylidene, cyclohexylidene, phenylene, and a divalent organic group having 1 to 20 carbon atoms.}

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

{In the formula, X ₃₀ and X ₃₁ each independently represent at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and a substituted aryl group; X ₃₂ , 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 represent a hydrogen atom or an alkyl group.}
It is preferable that the divalent organic group is selected from the three divalent organic groups represented by the following formula:

｛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 above general formula (70) include hydroxy compounds represented by the following formulae (75) to (79).
Here, general formula (75) is

In the formula, each r16 is independently an integer of 0 to 2, each X ₄₀ independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and when a plurality of X ₄₀ are present, the plurality of X ₄₀ 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、

(In the formula, 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 when r18 is 2, the two _X41 may be the same or different.)
It is preferable that the alkyl group is a monovalent organic group represented by the following formula:
The general formula (76) is

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

{In the formula, X ₄₂ represents 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.}
Moreover, the general formula (77) is

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

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

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

(wherein r20 is an integer of 0 to 2, X ₄₅ is selected from the group consisting of a hydrogen atom, an alkyl group, and a cycloalkyl group, and when r20 is 2, the two X ₄₅ may be the same or different), and X ₄₄ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.) Formulas (78) and (79) have the following structure.

As the compound represented by the above general formula (70), the hydroxy compounds represented by the following formulas (80) to (82) are preferred because they have high sensitivity when converted into NQDs and low precipitation tendency in the photosensitive resin composition.

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

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

Hydroxy compounds represented by the following formula are preferred because they have high sensitivity when converted into NQDs and low precipitation tendency in the photosensitive resin composition.

As the compound represented by the above general formula (77), the hydroxy compounds represented by the following formulas (84) to (86) are preferred because they have high sensitivity when converted into NQD products and low precipitation tendency in the photosensitive resin composition.
The structures of formulas (84) to (86) are as follows:

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

It is preferable that the aryl group is a tetravalent group having a structure represented by the following formula:

Among the compounds represented by the above general formula (71), the hydroxy compounds represented by the following formulas (87) to (90) are preferred because they have high sensitivity when converted into NQD products and low precipitation tendency in a photosensitive resin composition.
The structures of formulas (87) to (90) are as follows:

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

{wherein each r40 is independently an integer of 0 to 9.} is preferred because it has high sensitivity when converted into an NQD product and low precipitation tendency in a photosensitive resin composition.

As the compound represented by the above general formula (73), the hydroxy compounds represented by the following formulas (92) and (93) are preferred because they have high sensitivity when converted into NQD products and low precipitation tendency in the photosensitive resin composition.
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 compounds represented by the following formula (94):

The NQD product of a polyhydroxy compound represented by the following formula is preferred because it has high sensitivity and low precipitation in a photosensitive resin composition.

(C) When the compound having a quinone diazide group has a 1,2-naphthoquinone diazide sulfonyl group, this group may be either a 1,2-naphthoquinone diazide-5-sulfonyl group or a 1,2-naphthoquinone diazide-4-sulfonyl group. The 1,2-naphthoquinone diazide-4-sulfonyl group can absorb light in the i-line region of a mercury lamp, and is therefore suitable for exposure to i-line. On the other hand, the 1,2-naphthoquinone diazide-5-sulfonyl group can even absorb light in the g-line region of a mercury lamp, and is therefore suitable for exposure to g-line.

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

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

｛式中、Ｑは、水素原子、又は下記式群：

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

In the formula, Q represents a hydrogen atom or a group represented by the following formulae:

However, all of the Q's cannot be hydrogen atoms at the same time.

In this case, 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 as the NQD compound, or a mixture of a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound can be used.

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

Particularly preferred is one represented by the following formula:

The onium salts include iodonium salts, sulfonium salts, phosphinium salts, phosphonium salts, ammonium salts, and diazonium salts, and are preferably onium salts selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, and trialkylsulfonium salts.

The halogen-containing compound may be a haloalkyl group-containing hydrocarbon compound, and trichloromethyltriazine is preferred.

The amount of these photoacid generators is 1 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the (A) resin. If the amount of the photoacid generator as the (C) photosensitizer is 1 part by weight or more, the patterning properties of the photosensitive resin composition are good, and if it is 50 parts by weight or less, the tensile elongation of the film after curing of the photosensitive resin composition is good, and there is little development residue (scum) in the exposed area.

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

In this embodiment, the amount of the compound having a quinone diazide group (C) in the photosensitive resin composition is 0.1 parts by mass to 70 parts by mass, preferably 1 part by mass to 40 parts by mass, more preferably 3 parts by mass to 30 parts by mass, and even more preferably 5 parts by mass to 30 parts by mass, relative to 100 parts by mass of the resin (A). If the amount is 0.1 parts by mass or more, good sensitivity is obtained, while if it is 70 parts by mass or less, the mechanical properties of the cured film are good.

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

The aforementioned polyimide precursor resin composition and polyamide resin composition, which are negative-type resin compositions in this embodiment, and the polyoxazole resin composition, soluble polyimide resin composition, and phenolic resin composition, which are positive-type photosensitive resin compositions, may contain a solvent for dissolving these resins.

Examples of solvents include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, and γ-butyro. Lactone, 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, etc. can be used. Among them, from the viewpoints of the solubility of the resin, the stability of the resin composition, and the adhesion to the substrate, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

Among these solvents, those that completely dissolve the resulting polymer are particularly preferred, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, and gamma-butyrolactone.

Solvents that are more suitable for the above-mentioned 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, gamma-butyrolactone, and N-methyl-2-pyrrolidone.

In the photosensitive resin composition of the present invention, the amount of the solvent used is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 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 (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, an azole compound and a nitrogen-containing heterocyclic compound such as a purine derivative can be optionally blended in order to suppress discoloration on the copper.

Examples of 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, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, triazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.

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

Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminopurine, These include 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-mentioned azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound relative to 100 parts by mass of the (A) resin is 0.1 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, whereas when the blending amount is 20 parts by mass or less, excellent photosensitivity is achieved.

In addition, a hindered phenol compound can be optionally blended to suppress discoloration on the copper surface. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, 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-hydrocinnamamide), 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, etc. are included, but are not limited thereto. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc. are particularly preferred.

The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the hindered phenol compound relative to 100 parts by mass of the (A) resin is 0.1 part by mass or more, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy is prevented, while when the amount is 20 parts by mass or less, excellent photosensitivity is achieved.

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

Examples of crosslinking agents include compounds containing methylol groups and/or alkoxymethyl groups, such as Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174; UFR65, 300; Mycoat 102, 105 (all manufactured by Mitsui Cytec Co., Ltd.), and Nikalac (registered trademark) MX-270, -280. , -290; Nikalak MS-11; Nikalak 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, D Examples include ML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAF-MF (all manufactured by Honshu Chemical Industry Co., Ltd.), benzene dimethanol, 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, and dimethylbis(methoxymethyl)biphenyl.

In addition, oxirane compounds such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol type epoxy resins, trisphenol type epoxy resins, tetraphenol type epoxy resins, phenol-xylylene type epoxy resins, naphthol-xylylene type epoxy resins, phenol-naphthol type epoxy resins, phenol-dicyclopentadiene type epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylol Propane polyglycidyl ether, 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether, glycerol triglycidyl ether, ortho-sec-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 (all trade names, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L , XD-1000, EOCN-4600 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), Epicoat (registered trademark) 1001, Epicoat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051, Epicoat 1031S, Epicoat 180S65, Epicoat 157H70, YX-315-75 (all trade names, manufactured by Japan Epoxy Resins Co., Ltd.), EHPE3150 , Plaxel G402, PUE101, PUE105 (all 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 (all trade names, manufactured by DIC Corporation), 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 (all trade names, manufactured by Nagase ChemteX Corporation), Epolight (registered trademark) 70P, Epolight 100MF (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.), etc.

Other examples of isocyanate group-containing compounds include 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate (registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, ND (all trade names, manufactured by Mitsui Chemicals, Inc.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (all trade names, manufactured by Asahi Kasei Chemicals Corporation), etc.

In addition, the following bismaleimide compounds are available: 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl Examples include sulfone bismaleimide, 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, and BMI-8000 (all trade names, manufactured by Daiwa Kasei Kogyo Co., Ltd.), but are not limited to these as long as they are compounds that undergo thermal crosslinking as described above.

When a crosslinking agent is used, the amount is preferably 0.5 to 20 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the (A) resin. When the amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when the amount is 20 parts by mass or less, excellent storage stability is achieved.

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, by containing both (B) a cyclic compound having a carbonyl group and an organic titanium compound in the photosensitive resin composition, the resin layer after curing has excellent chemical resistance in addition to substrate adhesion.

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

Specific examples of the organotitanium compound are shown below in I) to VII):
I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide good storage stability for the negative photosensitive resin composition and a good pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate, titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.

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

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

IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.

VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, etc.

VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

Among them, from the viewpoint of exhibiting better chemical resistance, it is preferable that the organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η ⁵ -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When an organic titanium compound is added, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the (A) resin. When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, excellent storage stability is exhibited.

Furthermore, an adhesive aid can be optionally blended to improve adhesion between the film formed using the photosensitive resin composition of the present invention and the substrate. Examples of adhesive aids include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl)propane, and benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl)propane. 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-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, and other silane coupling agents; and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

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

Silane coupling agents include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name KBM803, manufactured by Chisso Corporation: product name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: product name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS1375, manufactured by Azmax Corporation: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: product name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: product name SIM6473.0), 3-mercaptopropyl diethoxymethoxysilane, 3-mercaptopropyl ethoxydimethoxysilane, 3-mercaptopropyl tripropoxysilane, 3-mercaptopropyl diethoxypropoxysilane, 3-mercaptopropyl ethoxydipropoxysilane, 3-mercaptopropyl dimethoxypropoxysilane, 3-mercaptopropyl methoxydipropoxysilane, 2-mercaptoethyl trimethoxysilane, 2-mercaptoethyl diethoxymethoxysilane, 2-mercapto triethylethoxydimethoxysilane, 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, manufactured by Azmax Corporation: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: 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-aminophenoxy)propyltrimethoxysilane (trade name: manufactured by Azmax Corporation) SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2), 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: 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(ethoxyethoxy silane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)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(oxy ethyl)-aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilane Examples of the silanol include, but are not limited to, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol. These may be used alone or in combination.

Among the above-mentioned silane coupling agents, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and silane coupling agents represented by the following structures are preferred.

When using a silane coupling agent, the amount is preferably 0.01 to 20 parts by weight per 100 parts by weight of the (A) resin.

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

(A) In the case of a negative type resin using a polyimide precursor or polyamide, a sensitizer can be optionally blended to improve photosensitivity. Examples of such sensitizers 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-dimethylaminocinnamylidene indole, and 1,2-diethylaminobenzal. Non, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone ethyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These can be used alone or in combinations of, for example, 2 to 5 types.

When the photosensitive resin composition contains a sensitizer to improve photosensitivity, the amount of the sensitizer is preferably 0.1 to 25 parts by weight per 100 parts by weight of the (A) resin.

In addition, in order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be optionally blended. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and examples thereof include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, and 1,6-hexane diacrylate and dimethacrylate. Examples of compounds include diacrylates and dimethacrylates of diols, 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, di- or triacrylates and methacrylates of glycerol, di-, tri-, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

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

In the case of a negative type photosensitive resin composition using a polyimide precursor or the like as the (A) resin, a thermal polymerization inhibitor can be optionally blended to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition, particularly when stored in a state of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic 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, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

When blended into a photosensitive resin composition, the amount of the thermal polymerization inhibitor is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of the (A) resin.

On the other hand, in the case of a positive-type photosensitive resin composition of the present invention that uses a polyoxazole precursor or the like as the resin (A), additives that have traditionally been used in photosensitive resin compositions, such as dyes, surfactants, thermal acid generators, dissolution promoters, and adhesion aids for improving adhesion to the substrate, can be added as necessary.

<Dye, surfactant, adhesive agent>
More specifically, examples of the additives include dyes such as methyl violet, crystal violet, and malachite green. Examples of the surfactants include nonionic surfactants made of polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether or derivatives thereof, fluorine-based surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M), Megafac (trade name, manufactured by Dainippon Ink and Chemicals), and Lumiflon (trade name, manufactured by Asahi Glass), and organic siloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), and Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). Examples of the adhesion promoters include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various silane coupling agents.

The amount of the dye and surfactant is preferably 0.1 to 30 parts by weight per 100 parts by weight of the resin (A).

From the viewpoint of achieving good thermal and mechanical properties of the cured product even when the curing temperature is lowered, a thermal acid generator can be optionally blended.
The thermal acid generator is preferably added from the viewpoint of providing a cured product with good thermal and mechanical properties 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 acid by heat, and imidosulfonates.

Examples of onium salts include aryl diazonium salts, diaryliodonium salts such as 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; triarylsulfonium salts, etc.

Among these, di(t-butylphenyl)iodonium salt of paratoluenesulfonic acid, di(t-butylphenyl)iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethylphenylsulfonium salt of trifluoromethanesulfonic acid, diphenylmethylsulfonium salt of trifluoromethanesulfonic acid, di(t-butylphenyl)iodonium salt of nonafluorobutanesulfonic acid, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, dimethylphenylsulfonium salt of benzenesulfonic acid, diphenylmethylsulfonium salt of toluenesulfonic acid, etc. are preferred.

In addition to the above-mentioned onium salts, the salts formed from strong acids and bases may also be pyridinium salts. Examples of strong acids include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid and nonafluorobutanesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid. Examples of bases include pyridine, alkylpyridines such as 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated N-alkylpyridines.

As the imide sulfonate, for example, naphthoyl imide sulfonate, phthalimide sulfonate, etc. 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 amount is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 10 parts by weight, and even more preferably 1 to 5 parts by weight, per 100 parts by weight of the resin (A).

In the case of a positive-type photosensitive resin composition, a dissolution promoter can be used to facilitate the removal of resin that is no longer needed after exposure to light. For example, a compound having a hydroxyl group or a carboxyl group is preferred. Examples of compounds having a hydroxyl group include the ballast agent used in the naphthoquinone diazide compound described above, as well as paracumylphenol, bisphenols, resorcinols, and linear phenolic compounds such as MtrisPC and MtetraPC, non-linear phenolic compounds such as TrisP-HAP, TrisP-PHBA, and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2- to 5-phenol-substituted diphenylmethane, 1- to 5-phenol-substituted 3,3-diphenylpropane, Examples of compounds include a compound obtained by reacting 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane with 5-norbornene-2,3-dicarboxylic anhydride in a molar ratio of 1:2, a compound obtained by reacting bis-(3-amino-4-hydroxyphenyl)sulfone with 1,2-cyclohexyldicarboxylic anhydride in a molar ratio of 1:2, N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxy5-norbornene-2,3-dicarboxylic anhydride, etc. Examples of compounds having a carboxyl group include 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2-(1-naphthyl)propionic acid, mandelic acid, atrolactic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, itaconic acid, etc.

When a dissolution promoter is used, the amount is preferably 0.1 to 30 parts by weight per 100 parts by weight of the (A) resin.

(Aspect B)
In another aspect of this embodiment, a sulfur-containing compound (B) can be used in place of the cyclic compound (B) having a carbonyl group. 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, polybenzoxazole, novolak, polyhydroxystyrene, and phenolic resin,
(B) a sulfur-containing compound in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin; and
(C) a photosensitizer in an amount of 1 to 50 parts by mass based on 100 parts by mass of the (A) resin;
A photosensitive resin composition comprising:

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

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

By incorporating a sulfur-containing compound into the photosensitive resin composition, a photosensitive resin composition can be obtained that gives a cured film in which the generation of voids at the interface 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 the sulfur is preferably contained as an atom forming a ring structure or as a thiocarbonyl group.

(B) Examples of compounds that can be used as sulfur-containing compounds include compounds that contain sulfur as one atom forming a five-membered ring structure, such as thiazole, 2-aminothiazole, 2-(4-thiazolyl)benzimidazole, 1,3,4-thiadiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,3-thiadiazole, 2,4-thiazolidinedione, benzothiazole, and 2-aminobenzothiazole, and compounds that contain sulfur as one atom forming a six-membered ring structure. Examples of compounds containing sulfur as one of the atoms include phenothiazine and N-methylphenothiazine, and examples of compounds containing sulfur as a thiocarbonyl group include rhodanine, N-allylrhodanine, diethylthiourea, dibutylthiourea, dicyclohexylthiourea, diphenylthiourea, 2-thiouracil, 4-thiouracil, 2,4-dithiopyrimidine, 2-thioxanthone, and 2-mercapto-4(3H)-quinazolinone. Of 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, and preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the resin (A). From the viewpoint of migration resistance, it is desirable to add 0.01 parts by mass or more, and from the viewpoint of solubility, it is desirable to add less than 10 parts by mass.
Sulfur-containing compounds, especially thiourea, can coordinate with copper through sulfur atoms, which changes the state of the copper surface and suppresses copper migration during high-temperature storage tests.

｛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 this embodiment, in place of the above-mentioned (B) cyclic compound having a carbonyl group, (B) at least one compound selected from the following general formulae (B-1), (B-2) and (B-3) 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, polybenzoxazole, novolak, polyhydroxystyrene, and phenolic resin,
(B)
The following general formula (B-1):

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

{In the formula, R _q2 and R _q3 each represent an organic group selected from a hydroxyl group, an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and ll represents an integer selected from 1 to 10.}, and
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 or an alkoxy group having 1 to 10 carbon atoms, X _s is a divalent hydrocarbon group having 1 to 10 carbon atoms, and mm and nn are each an integer selected from 1 to 10.} in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin; and
(C) a photosensitizer in an amount of 1 to 50 parts by mass based on 100 parts by mass of the (A) resin;
A photosensitive resin composition comprising:

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

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

(B) Compounds represented by general formulas (B-1), (B-2) and (B-3), preferably (B-1), can change the surface state of copper by interacting with the copper surface through nitrogen atoms or oxygen atoms. As a result, copper migration during high-temperature storage tests is suppressed.

Specific examples of (B-1) include organic compounds formed from carbon atoms, hydrogen atoms, nitrogen atoms, and oxygen atoms having a ureido group, such as methylurea, ethylurea, butylurea, phenylurea, hydroxyethylurea, hydantoic acid, allantoin, citrulline, and mixtures thereof.

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

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

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

The amount of at least one compound selected from (B) general formulae (B-1), (B-2) and (B-3) is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 2 parts by mass, per 100 parts by mass of (A) resin. From the viewpoint of migration resistance, it is desirable to use 0.01 parts by mass or more, and from the viewpoint of solubility, it is desirable to use 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 this embodiment, instead of the above-mentioned (B) cyclic compound having a carbonyl group, (B) an aromatic amine compound can be used which is at least one selected from the group consisting of an aniline derivative represented by the following general formula (I), a triazole derivative represented by the following general formula (II), and a triazole derivative represented by the following general formula (III). 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 each is a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic group, or an amide group having an integer of 1 to 15 carbon atoms, and Ra6 to Ra7 may be the same or different and each is a hydrogen atom, or a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group having an integer of 1 to 5 carbon atoms.}
or an aniline derivative represented by the following general formula (II):

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

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

In this embodiment, the resin (A) is preferably at least one selected from the group consisting of 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 polyimide containing the general formula (6).

(B) In the embodiment using an aromatic amine compound, the photosensitive resin may be polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, or polybenzoxazole. Among them, polyamic acid, polyamic acid ester, polyamic acid salt, polyamide, polyhydroxyamide, or polyimide resin is preferably used, since the resin after heat treatment has excellent heat resistance and mechanical properties, and polyimide precursor or polyimide resin is most preferably used.

(B) By using an aromatic amine compound, it is possible to suppress the occurrence of voids at the interface between the rewired Cu layer and the resin layer after a high-temperature storage test. The reason for this is unclear, but it is thought that the lone electron pair of the aromatic amine compound coordinates with the Cu element on the surface of the Cu layer, blocking the active Cu reaction sites, thereby suppressing the occurrence of voids.

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

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

Examples of compounds that are preferably used among the aniline derivatives represented by general formula (I) include N-phenylbenzylamine, salicylanilide, naphthol AS, 2-acetamidofluorene, oxanilide, N-allylaniline, N-methylaniline, N-ethylaniline, indoline, N-n-butylaniline, 2-anilinoethanol, 4-methoxyacetanilide, acetoacetanilide, 1,2,3,4-tetrahydroquinoline, tert-butylphenylcarbamate, tert-butyl(3-hydroxyphenyl)carbamate, oxanilide, and N,N'-diphenylethane-1,2-diamine. Among these, N-phenylbenzylamine ((B)-1), N,N'-diphenylethane-1,2-diamine ((B)-2), tert-butylphenylcarbamate ((B)-3), and tert-butyl(3-hydroxyphenyl)carbamate ((B)-4) are 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。 The triazole derivative (B) is represented by the following general formula (II):

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

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

Specific examples of the triazole derivative represented by the general formula (II) include benzotriazole, 1-hydroxybenzotriazole, 1-aminobenzotriazole, 5-methyl-1H-benzotriazole, 1H-1,2,3-triazole, 2-hydroxy-N-(1H-1,2,4-triazol-3-yl)benzamide (manufactured by ADEKA CORPORATION, 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 CORPORATION, Adeka STAB LA-29), 2-(2'-hydroxy-3',5'-di-tert-aminophenyl)benzotriazole, and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole. Among these, 2-hydroxy-N-(1H-1,2,4-triazol-3-yl)benzamide ((B)-5) and 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol ((B)-6) are particularly preferably used.

Specific examples of triazole derivatives represented by the general formula (III) include (4-((1H-1,2,4-triazol-1-ylmethyl)phenyl)methanol, tricyclazole, 1,2,4-1H-triazole, triapentenol, 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, and 2-(1H-1,2,4-triazol-1-yl)aniline are preferably used. Among these, (4-((1H-1,2,4-triazol-1-ylmethyl)phenyl)methanol ((B)-7) is particularly preferably used.

(B) In the aromatic amine compound, 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 to 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 even more preferably 1 to 8 parts by mass, per 100 parts by mass of the resin (A). A content higher than this range is not preferred because it reduces storage stability, and a content lower than this range is likely to cause voids to form between the copper surface.

<Method for Producing Cured Relief Pattern and Semiconductor Device>
The present invention also provides a method for producing a cured relief pattern, comprising the steps of: (1) forming a resin layer on a substrate by applying the above-mentioned photosensitive resin composition of the present invention onto the substrate; (2) exposing the resin layer to light; (3) developing the exposed resin layer to form a relief pattern; and (4) subjecting the relief pattern to a heat treatment to form a cured relief pattern. Typical aspects of each step are described below.

(1) 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 then dried as necessary to form a resin layer. As the application method, a method that has been conventionally used for applying a photosensitive resin composition, such as a method of applying with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray application with a spray coater, etc., can be used.

If necessary, the coating film made of the photosensitive resin composition can be dried. Drying methods that can be used include air drying, heat drying in an oven or on a hot plate, and vacuum drying. 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 resin layer In this step, the resin layer formed above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, a mirror projection, or a stepper, either directly or through a photomask or reticle having a pattern.

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

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

As the developer used for development, a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent, is preferable. For example, in the case of a photosensitive resin composition that is not soluble in an alkaline aqueous solution, the good solvent is preferably N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc., and the poor solvent is preferably toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. In addition, two or more types of each solvent, for example, several types, can be used in combination.

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

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

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

If necessary, a suitable 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. In this manner, a relief pattern can be formed.

(4) Step of forming a hardened relief pattern by heat treatment of the relief pattern In this step, the relief pattern obtained by the above development is heated to convert it into a hardened relief pattern. As the heat curing method, various methods can be selected, such as a method using a hot plate, a method using an oven, or a method using a temperature-raising oven in which a temperature program can be set. Heating can be performed, for example, under conditions of 180°C to 400°C for 30 minutes to 5 hours. As the atmospheric gas during heat curing, air may be used, or an inert gas such as nitrogen or argon may also be used.

<Semiconductor Device>
The present invention also provides a semiconductor device comprising a cured relief pattern obtained by the above-mentioned 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 above-mentioned method for producing a cured relief pattern. The present invention is also applicable to a method for producing a semiconductor device which uses a semiconductor element as the substrate and includes the above-mentioned method for producing a cured relief pattern as part of its steps. The semiconductor device of the present invention can be produced by forming the cured relief pattern formed by the above-mentioned method for producing a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure, and combining the method with a known method for producing a semiconductor device.

The photosensitive resin composition of the present invention is useful not only for application to the above-mentioned semiconductor devices, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.
Although the above description is divided into aspects A to D, combinations of the aspects are also included in the present invention.

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.

(1) Weight-average molecular weight The weight-average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene equivalent). The column used in the measurement was a "Shodex 805M/806M series" manufactured by Showa Denko K.K., the standard monodisperse polystyrene was "Shodex STANDARD SM-105" manufactured by Showa Denko K.K., the developing solvent was N-methyl-2-pyrrolidone, and the detector was "Shodex RI-930" manufactured by Showa Denko K.K.

(2) Creation of a cured relief pattern on Cu A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti film and a 400 nm thick Cu film in this order using a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Corporation). Next, a photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), and dried to form a coating film with a thickness of 6 to 10 μm. This coating film was irradiated with energy of 300 mJ/cm ² using a parallel light mask aligner (PLA-501FA type, manufactured by Canon Inc.) using a test pattern mask. Next, this coating film was spray-developed with a coater developer (D-Spin 60A type, manufactured by SOKUDO Co., Ltd.) using cyclopentanone as a developer for a negative type or 2.38% TMAH as a developer for a positive type, and rinsed with propylene glycol methyl ether acetate for a negative type or with pure water for a positive type to obtain a relief pattern on Cu.

The wafer with the relief pattern formed on Cu was heated for 2 hours in a temperature-programmable curing furnace (VF-2000 model, manufactured by Koyo Lindberg) in a nitrogen atmosphere at the temperature specified in each example, to obtain a cured relief pattern made of resin approximately 6 to 7 μm thick on Cu.

(3) High temperature storage test of the cured relief pattern on Cu and subsequent evaluation The wafer on which the cured relief pattern was formed on Cu was heated in air at 150° C. for 168 hours using a temperature-programmable curing furnace (VF-2000 type, manufactured by Koyo Lindberg). Then, the resin layer on Cu was entirely removed by plasma etching using a plasma surface treatment device (EXAM type, manufactured by Shinko Seiki Co., Ltd.). The plasma etching conditions were as follows:
Output: 133W
Gas type and 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 all the resin layers had been removed was observed using an FE-SEM (S-4800 model, Hitachi High-Technologies Corporation), and the area ratio of voids on the surface of the Cu layer was calculated using image analysis software (A-zo-kun, Asahi Kasei Corporation).

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

The viscosity was measured at 23° C. using a TV-25 viscometer (manufactured by Toki Sangyo Co., Ltd.).
A: The viscosity change rate (see below) of the composition after standing is within 10%.
x: The change in viscosity of the composition after standing is more 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 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and left 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 over 40 minutes while stirring, followed by the addition of a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone over 60 minutes while stirring. 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. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer produced was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The crude polymer solution obtained was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (Polymer A). The molecular weight of Polymer A was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.

The weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40°C
Column: Shodex KD-806M, 2 in series Mobile phase: 0.1 mol/l LiBr/NMP
Flow rate: 1ml/min.

<Production Example A2> ((A) Synthesis of Polymer B as Polyimide Precursor)
Except for using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example A1, a reaction was carried out in the same manner as in the above Production Example A1 to obtain Polymer B. The molecular weight of Polymer B was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 22,000.

<Production Example A3> ((A) Synthesis of Polymer C as Polyimide Precursor)
Except for using 147.8 g of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example A1, the reaction was carried out in the same manner as in the above Production Example A1 to obtain Polymer C. The molecular weight of Polymer C was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

<Production Example A4> ((A) Synthesis of Polymer D as Polyamide)
(Synthesis of phthalic acid compound-capped AIPA-MO)
In a 5-liter separable flask, 543.5 g of 5-aminoisophthalic acid (hereinafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone were placed, mixed and stirred, and heated to 50° C. in a water bath. 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise using a dropping funnel, and the mixture was stirred at 50° C. for about 2 hours.

After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography (hereinafter referred to as low molecular weight GPC), the reaction liquid was poured into 15 liters of ion-exchanged water, stirred, and allowed to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered off, washed appropriately with water, and then vacuum dried at 40°C for 48 hours to obtain AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate had reacted. The low molecular weight GPC purity of the obtained AIPA-MO was approximately 100%.

(Synthesis of Polymer D)
In a separable flask with a capacity of 2 L, 100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were charged and mixed, and cooled to 5 ° C. in an ice bath. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was dropped over about 20 minutes under ice cooling, and then 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB.} dissolved in 168 g of NMP was dropped over about 20 minutes, and the mixture was stirred for 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and the mixture was stirred at room temperature for 5 hours. The 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 L of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer (Polymer E). The molecular weight of Polymer D was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 34,700.

<Production Example A5> ((A) Synthesis of Polymer E as Polyoxazole Precursor)
In a 3-liter separable flask, 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 mixed and stirred at room temperature (25°C) to obtain a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyletherdicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20°C. The time required for the dropwise addition was 40 minutes, and the reaction liquid temperature was a maximum of 30°C.

Three hours after the end of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction solution, and the mixture was left to stir at room temperature for 15 hours, after which 99% of all amine end groups on the polymer chain were blocked with carboxycyclohexylamide groups. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). The reaction solution was then dropped into 2 L of water with high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight average molecular weight of 9,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

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

<Production Example A6> ((A) Synthesis of Polymer F as Polyimide)
A separable glass four-neck flask equipped with a Teflon (registered trademark) anchor stirrer and a condenser with a Dean-Stark trap were attached to the flask, which was immersed in a silicone oil bath and stirred while passing nitrogen gas through it.

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

The reaction solution was then added dropwise to 3 L of water under high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polyimide (Polymer F) with a weight average molecular weight of 23,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

<Production Example A7> ((A) Synthesis of Polymer G as Phenolic Resin)
In a 0.5 L separable flask equipped with a Dean-Stark apparatus, 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 121.2 g (0.5 mol) of 4,4'-bis(methoxymethyl)biphenyl (hereinafter also referred to as "BMMB"), 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 in an oil bath, and the generation of methanol from the reaction solution was confirmed. The reaction solution was stirred at 140°C for 2 hours.

The reaction vessel was then cooled in the air, and 100 g of tetrahydrofuran was added to it and stirred. The above reaction dilution was added dropwise to 4 L of water under high speed stirring to disperse and precipitate the resin, which was then recovered, washed with water as appropriate, dehydrated, and vacuum dried to obtain a copolymer (Polymer G) consisting of methyl 3,5-dihydroxybenzoate/BMMB in a yield of 70%. The weight average molecular weight of this Polymer G, calculated as standard polystyrene using the GPC method, was 21,000.

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

The mixed solution was heated to 120°C in an oil bath, and the generation of methanol from the reaction solution was confirmed. 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 a separate container, and the resulting solution was uniformly dissolved. Using a dropping funnel, the solution was added dropwise to the separable flask over one hour, and then stirred for an additional two hours after addition.

After the reaction was completed, the same treatment as in Production Example A7 was carried out to obtain a copolymer (Polymer H) consisting of resorcinol/BMMB/2,6-bis(hydroxymethyl)-p-cresol in a yield of 77%. The weight average molecular weight of this Polymer H, calculated using the GPC method in terms of standard polystyrene, was 9,900.

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

The compound was dissolved in 100 g of γ-butyrolactone (as a solvent) together with 20 g of a photosensitive diazoquinone compound (C1) (manufactured by Toyo Gosei Co., Ltd., corresponding to (C) photosensitizer) in which 77% of phenolic hydroxyl groups have been converted to naphthoquinone diazide-4-sulfonic acid ester, 0.2 g of xanthine (corresponding to (B) cyclic compound having a carbonyl group), and 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane. The viscosity of the obtained solution was adjusted to about 20 poise by further adding a small amount of γ-butyrolactone to obtain a positive photosensitive resin composition.
This composition was cured at 350° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.5%.
<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 replaced with 100 g of Polymer F as the resin (A).
This composition was cured at 250° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.7%.
<Example A15>
A positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of Polymer G was used instead of 100 g of Polymer E as the resin (A) in Example A13.
This composition was cured at 220° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.3%.
<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 replaced with 100 g of Polymer H as the resin (A).
This composition was cured at 220° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.2%.
<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 in the composition of Example A1, and the composition was evaluated in the same manner as in Example A1. 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 composition was evaluated in the same manner as in Example A1. 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 composition was evaluated in the same manner as in Example A10. 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 was carried out as in Example A11. The evaluation result was 14.9% because the compound (B) of the present invention was not included.
The results of Examples A1 to A16 and Comparative Examples A1 to A4 are shown in Table 1.

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 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and left 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 over 40 minutes while stirring, followed by the addition of a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone over 60 minutes while stirring. 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. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer produced was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The crude polymer solution obtained was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (Polymer A). The molecular weight of Polymer A was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.

The weight average molecular weight of the resin obtained in each Production Example B was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40°C
Column: Shodex KD-806M, 2 in series Mobile phase: 0.1 mol/l LiBr/NMP
Flow rate: 1ml/min.

<Production Example B2> ((A) Synthesis of Polymer B as Polyimide Precursor)
Except for using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example B1, a reaction was carried out in the same manner as in the above Production Example B1 to obtain Polymer B. The molecular weight of Polymer B was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 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, the reaction was carried out in the same manner as in the above Production Example B1 to obtain Polymer C. The molecular weight of Polymer C was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

<Production Example B4> ((A) Synthesis of Polymer D as Polyamide)
(Synthesis of phthalic acid compound-capped AIPA-MO)
Into a 5-liter separable flask, 543.5 g of 5-aminoisophthalic acid (hereinafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone were placed, mixed and stirred, and heated to 50° C. in a water bath. 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise using a dropping funnel, and the mixture was stirred at 50° C. for about 2 hours.

After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography (hereinafter referred to as low molecular weight GPC), the reaction liquid was poured into 15 liters of ion-exchanged water, stirred, and allowed to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered off, washed appropriately with water, and then vacuum dried at 40°C for 48 hours to obtain AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate had reacted. The low molecular weight GPC purity of the obtained AIPA-MO was approximately 100%.

(Synthesis of Polymer D)
In a separable flask with a capacity of 2 L, 100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were charged and mixed, and cooled to 5 ° C. in an ice bath. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was dropped over about 20 minutes under ice cooling, and then 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB.} dissolved in 168 g of NMP was dropped over about 20 minutes, and the mixture was stirred for 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and the mixture was stirred at room temperature for 5 hours. The 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 L of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer (Polymer E). The molecular weight of Polymer D was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 34,700.

<Production Example B5> ((A) Synthesis of Polymer E as Polyoxazole Precursor)
In a 3-liter separable flask, 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 mixed and stirred at room temperature (25°C) to obtain a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyletherdicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20°C. The time required for the dropwise addition was 40 minutes, and the reaction liquid temperature was a maximum of 30°C.

Three hours after the end of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction solution, and the mixture was left to stir at room temperature for 15 hours, after which 99% of all amine end groups on the polymer chain were blocked with carboxycyclohexylamide groups. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). The reaction solution was then dropped into 2 L of water with high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight average molecular weight of 9,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

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

<Production Example B6> ((A) Synthesis of Polymer F as Polyimide)
A separable glass four-neck flask equipped with a Teflon (registered trademark) anchor stirrer and a condenser with a Dean-Stark trap were attached to the flask, which was immersed in a silicone oil bath and stirred while passing nitrogen gas through it.

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

The reaction solution was then added dropwise to 3 L of water under high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polyimide (Polymer F) with a weight average molecular weight of 23,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

<Production Example B7> ((A) Synthesis of Polymer G as Phenolic Resin)
In a 0.5 L separable flask equipped with a Dean-Stark apparatus, 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 121.2 g (0.5 mol) of 4,4'-bis(methoxymethyl)biphenyl (hereinafter also referred to as "BMMB"), 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 in an oil bath, and the generation of methanol from the reaction solution was confirmed. The reaction solution was stirred at 140°C for 2 hours.

The reaction vessel was then cooled in the air, and 100 g of tetrahydrofuran was added to it and stirred. The above reaction dilution was added dropwise to 4 L of water under high speed stirring to disperse and precipitate the resin, which was then recovered, washed with water as appropriate, dehydrated, and vacuum dried to obtain a copolymer (Polymer G) consisting of methyl 3,5-dihydroxybenzoate/BMMB in a yield of 70%. The weight average molecular weight of this Polymer G, calculated as standard polystyrene using the GPC method, was 21,000.

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

The mixed solution was heated to 120°C in an oil bath, and the generation of methanol from the reaction solution was confirmed. 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 a separate container, and the resulting solution was uniformly dissolved. Using a dropping funnel, the solution was added dropwise to the separable flask over 1 hour, and then stirred for an additional 2 hours after addition.

After the reaction was completed, the same treatment as in Production Example B7 was carried out to obtain a copolymer (Polymer H) consisting of resorcinol/BMMB/2,6-bis(hydroxymethyl)-p-cresol in a yield of 77%. The weight average molecular weight of this Polymer H, calculated using the GPC method in terms of standard polystyrene, was 9,900.

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

The resulting solution was dissolved in 100 g of γ-butyrolactone (as a solvent) together with 15 g of a photosensitive diazoquinone compound (C1) (manufactured by Toyo Gosei Co., Ltd., corresponding to (C) photosensitizer) in which 77% of phenolic hydroxyl groups have been converted to naphthoquinone diazide-4-sulfonic acid ester, 0.5 g of dicyclohexylthiourea (corresponding to (B) sulfur-containing compound), and 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 obtain 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. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.4%.
<Example B13>
A positive photosensitive resin composition solution was prepared in the same manner as in Example B12, except that 100 g of Polymer F was used instead of 100 g of Polymer E as the resin (A) in Example B12.
This composition was cured at 250° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.5%.
<Example B14>
A positive photosensitive resin composition solution was prepared in the same manner as in Example B12, except that 100 g of Polymer G was used instead of 100 g of Polymer E as the resin (A) in Example B12.
This composition was cured at 220° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.7%.
<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 replaced with 100 g of Polymer H as the resin (A).
This composition was cured at 220° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.6%.
<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 composition was evaluated in the same manner as in Example B1. 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 composition was evaluated in the same manner as in Example B11. 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 composition was evaluated in the same manner as in Example B12. The evaluation result was 14.6% because the compound (B) of the present invention was not included.
The results of Examples B1 to B15 and Comparative Examples B1 to B3 are shown in Table 2.

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 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and left 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 over 40 minutes while stirring, followed by the addition of a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone over 60 minutes while stirring. 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. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer produced was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The crude polymer solution obtained was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (Polymer A). The molecular weight of Polymer A was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.

The weight average molecular weight of the resin obtained in each Production Example C was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40°C
Column: Shodex KD-806M, 2 in series Mobile phase: 0.1 mol/l LiBr/NMP
Flow rate: 1ml/min.

<Production Example C2> ((A) Synthesis of Polymer B as Polyimide Precursor)
Except for using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example C1, a reaction was carried out in the same manner as in the above Production Example C1 to obtain Polymer B. The molecular weight of Polymer B was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 22,000.

<Production Example C3> ((A) Synthesis of Polymer C as Polyimide Precursor)
Except for using 147.8 g of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example C1, the reaction was carried out in the same manner as in the above Production Example C1 to obtain Polymer C. The molecular weight of Polymer C was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

<Production Example C4> ((A) Synthesis of Polymer D as Polyamide)
(Synthesis of phthalic acid compound-capped AIPA-MO)
Into a 5-liter separable flask, 543.5 g of 5-aminoisophthalic acid (hereinafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone were placed, mixed and stirred, and heated to 50° C. in a water bath. 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise using a dropping funnel, and the mixture was stirred at 50° C. for about 2 hours.

After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography (hereinafter referred to as low molecular weight GPC), the reaction liquid was poured into 15 liters of ion-exchanged water, stirred, and allowed to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered off, washed appropriately with water, and then vacuum dried at 40°C for 48 hours to obtain AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate had reacted. The low molecular weight GPC purity of the obtained AIPA-MO was approximately 100%.

(Synthesis of Polymer D)
In a separable flask with a capacity of 2 L, 100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were charged and mixed, and cooled to 5 ° C. in an ice bath. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was dropped over about 20 minutes under ice cooling, and then 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB.} dissolved in 168 g of NMP was dropped over about 20 minutes, and the mixture was stirred for 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and the mixture was stirred at room temperature for 5 hours. The 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 L of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer (Polymer E). The molecular weight of Polymer D was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 34,700.

<Production Example C5> ((A) Synthesis of Polymer E as Polyoxazole Precursor)
In a 3-liter separable flask, 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 mixed and stirred at room temperature (25°C) to obtain a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyletherdicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20°C. The time required for the dropwise addition was 40 minutes, and the reaction liquid temperature was a maximum of 30°C.

Three hours after the end of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction solution, and the mixture was left to stir at room temperature for 15 hours, after which 99% of all amine end groups on the polymer chain were blocked with carboxycyclohexylamide groups. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). The reaction solution was then dropped into 2 L of water with high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight average molecular weight of 9,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

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

<Production Example C6> ((A) Synthesis of Polymer F as Polyimide)
A separable glass four-neck flask equipped with a Teflon (registered trademark) anchor stirrer and a condenser with a Dean-Stark trap were attached to the flask, which was immersed in a silicone oil bath and stirred while passing nitrogen gas through it.

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

The reaction solution was then added dropwise to 3 L of water under high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polyimide (Polymer F) with a weight average molecular weight of 23,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

<Production Example C7> ((A) Synthesis of Polymer G as Phenolic Resin)
In a 0.5 L separable flask equipped with a Dean-Stark apparatus, 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 121.2 g (0.5 mol) of 4,4'-bis(methoxymethyl)biphenyl (hereinafter also referred to as "BMMB"), 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 in an oil bath, and the generation of methanol from the reaction solution was confirmed. The reaction solution was stirred at 140°C for 2 hours.

The reaction vessel was then cooled in the air, and 100 g of tetrahydrofuran was added to it and stirred. The above reaction dilution was added dropwise to 4 L of water under high speed stirring to disperse and precipitate the resin, which was then recovered, washed with water as appropriate, dehydrated, and vacuum dried to obtain a copolymer (Polymer G) consisting of methyl 3,5-dihydroxybenzoate/BMMB in a yield of 70%. The weight average molecular weight of this Polymer G, calculated as standard polystyrene using the GPC method, was 21,000.

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

The mixed solution was heated to 120°C in an oil bath, and the generation of methanol from the reaction solution was confirmed. 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 a separate container, and the resulting solution was uniformly dissolved. Using a dropping funnel, the solution was added dropwise to the separable flask over 1 hour, and then stirred for an additional 2 hours after addition.

After the reaction was completed, the same treatment as in Production Example C7 was carried out to obtain a copolymer (Polymer H) consisting of resorcinol/BMMB/2,6-bis(hydroxymethyl)-p-cresol in a yield of 77%. The weight average molecular weight of this Polymer H, calculated using the GPC method in terms of standard polystyrene, was 9,900.

で表される、フェノール性水酸基の７７％をナフトキノンジアジド－４－スルホン酸エステル化した感光性ジアゾキノン化合物（東洋合成社製、（Ｃ）感光剤に該当）（Ｃ１）１５ｇ、ブチル尿素（（Ｂ－１）化合物に該当）１ｇ、３－ｔ－ブトキシカルボニルアミノプロピルトリエトキシシラン６ｇと共に、γ－ブチロラクトン（溶媒として）１００ｇに溶解した。得られた溶液の粘度を、少量のγ－ブチロラクトンを更に加えることによって約２０ポイズ（ｐｏｉｓｅ）に調整し、ポジ型感光性樹脂組成物とした。
この組成物について、上述の方法により３５０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．６％という結果を得た。
＜実施例Ｃ１２＞
上記実施例Ｃ１１において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＦ１００ｇに変えた以外は、実施例Ｃ１１と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２５０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．９％という結果を得た。
＜実施例Ｃ１３＞
上記実施例Ｃ１１において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＧ１００ｇに変えた以外は、実施例Ｃ１１と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２２０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．５％という結果を得た。
＜実施例Ｃ１４＞
上記実施例Ｃ１１において、（Ａ）樹脂として、ポリマーＥ１００ｇをポリマーＨ１００ｇに変えた以外は、実施例Ｃ１３と同様にしてポジ型感光性樹脂組成物溶液を調製した。
この組成物について、上述の方法により２２０℃キュアしてＣｕ層上に硬化レリーフパターンを作製し、高温保存試験を行なった後、Ｃｕ層の表面に占めるボイドの面積割合を評価し、５．４％という結果を得た。
＜比較例Ｃ１＞
実施例Ｃ１の組成に、ブチル尿素を添加しない他は、実施例Ｃ１と同様にしてネガ型感光性樹脂組成物を調製し、実施例Ｃ１と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１４．３％であった。
＜比較例Ｃ２＞
実施例Ｃ１２の組成に、ブチル尿素を添加しない他は、実施例Ｃ１２と同様にしてポジ型感光性樹脂組成物を調製し、実施例Ｃ１２と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１５．５％であった。
＜比較例Ｃ３＞
実施例Ｃ１３の組成に、ブチル尿素を添加しない他は、実施例Ｃ１３と同様にしてポジ型感光性樹脂組成物を調製し、実施例Ｃ１１と同様の評価を行なった。評価結果は、本発明の（Ｂ）化合物を含まないため１５．７％であった。 <Example C1>
Negative photosensitive resin compositions were prepared using polymers A and B by the following method, and the prepared photosensitive resin compositions were evaluated. 50 g of polymers A and B (corresponding to (A) resin), which are polyimide precursors, were dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate together with 1 g of butyl urea (corresponding to (B-1) compound), 4 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (described as "PDO" in Table 3) (corresponding to (C) photosensitizer), 8 g of tetraethylene glycol dimethacrylate, and 1.5 g of N-[3-(triethoxysilyl)propyl]phthalamic acid. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent, and a negative photosensitive resin composition was obtained.
This composition was cured at 230° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.5%.
<Example C2>
A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that the amount of butylurea added as component (B) was changed to 0.1 g.
This composition was cured at 230° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 6.8%.
<Example C3>
A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that the amount of butylurea added as component (B) was changed to 5 g.
This composition was cured at 230° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 4.8%.
<Example C4>
A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that in Example C1, tetraethylene glycol (corresponding to compound (B-2)) was used instead of butylurea as the component (B).
This composition was cured at 230° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 6.2%.
<Example C5>
A negative type photosensitive resin composition solution was prepared in the same manner as in Example C1, except that in Example C1, bis(2-methoxyethyl) adipate (corresponding to compound (B-3)) was used instead of butylurea as the component (B).
This composition was cured at 230° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 6.3%.
<Example C6>
A negative photosensitive resin composition solution was prepared in the same manner as in Example C1 above, and this composition was cured at 350°C by the method described above to create a cured relief pattern on the Cu layer. After a high-temperature storage test was performed, the area ratio of voids on the surface of the Cu layer was evaluated, resulting in 4.7%.
<Example C7>
A negative type photosensitive resin composition solution was prepared in the same manner as in Example C1, except that in Example C1, 50 g of Polymer A and 50 g of Polymer B were changed to 100 g of Polymer A as the (A) resin, and 4 g of PDO was changed to 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (product name, manufactured by BASF Corporation)) as the (C) component.
This composition was cured at 230° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.4%.
<Example C8>
A negative type photosensitive resin composition solution was prepared in the same manner as in Example C1, except that in Example C1, 50 g of Polymer A and 50 g of Polymer B were replaced with 100 g of Polymer A as the (A) resin, 4 g of PDO was replaced with 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (product name, manufactured by BASF Corporation)) as the (C) component, and further the solvent was replaced with 85 g of γ-butyrolactone and 15 g of dimethylsulfoxide.
This composition was cured at 230° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.5%.
<Example C9>
A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that 50 g of Polymer A and 50 g of Polymer B were replaced with 100 g of Polymer C as the resin (A).
This composition was cured at 350° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 4.7%.
<Example C10>
A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that 50 g of Polymer A and 50 g of Polymer B were replaced with 100 g of Polymer D as the resin (A).
This composition was cured at 250° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.8%.
<Example C11>
A positive-type photosensitive resin composition was prepared using polymer E by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer E (corresponding to resin (A)), which is a polyoxazole precursor, was reacted with a compound represented by the following formula (96):

The resulting solution was dissolved in 100 g of γ-butyrolactone (as a solvent) together with 15 g of a photosensitive diazoquinone compound (C1) (manufactured by Toyo Gosei Co., Ltd., corresponding to photosensitizer (C)) in which 77% of phenolic hydroxyl groups have been converted to naphthoquinone diazide-4-sulfonic acid ester, 1 g of butyl urea (corresponding to compound (B-1)), and 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 obtain 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. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.6%.
<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 replaced with 100 g of Polymer F as the resin (A) in Example C11.
This composition was cured at 250° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.9%.
<Example C13>
A positive photosensitive resin composition solution was prepared in the same manner as in Example C11, except that 100 g of Polymer G was used instead of 100 g of Polymer E as the resin (A) in Example C11.
This composition was cured at 220° C. by the method described above to form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.5%.
<Example C14>
A positive photosensitive resin composition solution was prepared in the same manner as in Example C13, except that in Example C11, 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 form a cured relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, giving a result of 5.4%.
<Comparative Example C1>
A negative photosensitive resin composition was prepared in the same manner as in Example C1, except that butylurea was not added to the composition of Example C1, and the composition was evaluated in the same manner as in Example C1. The evaluation result was 14.3% because the compound (B) of the present invention was not included.
<Comparative Example C2>
A positive photosensitive resin composition was prepared in the same manner as in Example C12, except that butylurea was not added to the composition of Example C12, and the composition was evaluated in the same manner as in Example C12. The evaluation result was 15.5% because the compound (B) of the present invention was not included.
<Comparative Example C3>
A positive photosensitive resin composition was prepared in the same manner as in Example C13, except that butylurea was not added to the composition of Example C13, and the composition was evaluated in the same manner as in Example C11. The evaluation result was 15.7% because the compound (B) of the present invention was not included.

Example D
<Production Example D1> (Synthesis of polymer (A)-1 as polyimide precursor)
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and left 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 over 40 minutes while stirring, followed by the addition of a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone over 60 minutes while stirring. 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. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polymer (A)-1). The molecular weight of polymer (A)-1 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.

The weight average molecular weight of the resin obtained in each Production Example D was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40°C
Column: Shodex KD-806M, 2 in series Mobile phase: 0.1 mol/l LiBr/NMP
Flow rate: 1ml/min.

<Production Example D2> (Synthesis of polymer (A)-2 as polyimide precursor)
Polymer (A)-2 was obtained by carrying out a reaction in the same manner as in Production Example D1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example D1. The molecular weight of polymer (A)-2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 22,000.

<Production Example D3> ((A) Synthesis of polymer (A)-3 as polyimide precursor)
Polymer (A)-3 was obtained by carrying out a reaction in the same manner as in Production Example D1, 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 D1. The molecular weight of Polymer (A)-3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

<Production Example D4> (Synthesis of polymer (A)-4 as polyamide (A))
(Synthesis of phthalic acid compound-capped AIPA-MO)
Into a 5-liter separable flask, 543.5 g of 5-aminoisophthalic acid (hereinafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone were placed, mixed and stirred, and heated to 50° C. in a water bath. 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise using a dropping funnel, and the mixture was stirred at 50° C. for about 2 hours.

After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography (hereinafter referred to as low molecular weight GPC), the reaction liquid was poured into 15 liters of ion-exchanged water, stirred, and allowed to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered off, washed appropriately with water, and then vacuum dried at 40°C for 48 hours to obtain AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate had reacted. The low molecular weight GPC purity of the obtained AIPA-MO was approximately 100%.

(Synthesis of Polymer (A)-4)
In a separable flask with a capacity of 2 L, 100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were charged and mixed, and cooled to 5 ° C. in an ice bath. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was dropped over about 20 minutes under ice cooling, and then 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB.} dissolved in 168 g of NMP was dropped over about 20 minutes, and the mixture was stirred for 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and the mixture was stirred at room temperature for 5 hours. The 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 L of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer (Polymer (A)-4). The molecular weight of Polymer (A)-4 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 34,700.

<Production Example D5> (Synthesis of polymer (A)-5 as polyoxazole precursor (A))
In a 3-liter separable flask, 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 mixed and stirred at room temperature (25°C) to obtain a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyletherdicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20°C. The time required for the dropwise addition was 40 minutes, and the reaction liquid temperature was a maximum of 30°C.

Three hours after the end of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction solution, and the mixture was left to stir at room temperature for 15 hours, after which 99% of all amine end groups on the polymer chain were blocked with carboxycyclohexylamide groups. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). The reaction solution was then dropped into 2 L of water with high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight average molecular weight of 9,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

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

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

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

Then, the reaction solution was added dropwise to 3 L of water under high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polyimide (polymer (A)-6) with a weight average molecular weight of 23,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

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>
Negative photosensitive resin compositions were prepared using polymers (A)-1 and (A)-2 by the following method, and the photosensitive resin compositions were evaluated. 50 g of polymer (A)-1 and 50 g of polymer (A)-2 (corresponding to (A) resin), which are polyimide precursors, were dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate together with 3 g of N-phenylbenzylamine (manufactured by Tokyo Chemical Industry Co., Ltd., corresponding to (B)-1), 4 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (described as "PDO" in Table 4) (corresponding to (C) photosensitizer), 8 g of tetraethylene glycol dimethacrylate, and 1.5 g of N-[3-(triethoxysilyl)propyl]phthalamic acid. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent, to obtain a negative photosensitive resin composition.
This composition was cured at 230°C by the above-mentioned method to form a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 4.5%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D2>
A negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that in Example D1, component (B) was changed to N,N'-diphenylethane-1,2-diamine (manufactured by Tokyo Chemical Industry Co., Ltd.).
This composition was cured at 230°C by the above-mentioned method to form a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 4.2%. In addition, 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 in Example D1, 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 above-mentioned method to form a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and found to be 5.1%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D4>
A negative photosensitive resin composition solution was prepared 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.).
This composition was cured at 230°C by the above-mentioned method to form a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and found to be 5.8%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D5>
A negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that in Example D1, the component (B) was changed to 2-hydroxy-N-(1H-1,2,4-triazol-3-yl)benzamide (manufactured by ADEKA CORPORATION, Adeka STAB CDA-1).
This composition was cured at 230°C by the above-mentioned method to form a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 4.8%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D6>
A negative type photosensitive resin composition solution was prepared in the same manner as in Example D1, except that in Example D1, the component (B) was changed to 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol (manufactured by ADEKA CORPORATION, Adeka STAB LA-29).
This composition was cured at 230°C by the above-mentioned method to form a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 4.2%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D7>
A negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that in Example D1, the component (B) was changed to (4-((1H-1,2,4-triazol-1-yl)methyl)phenyl)methanol (manufactured by Tokyo Chemical Industry Co., Ltd.).
This composition was cured at 230°C by the above-mentioned method to form a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 6.1%. In addition, 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 above, except that the amount of the (B)-1 component added was changed to 1 g.
This composition was cured at 230°C by the above-mentioned method to form a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 8.5%. In addition, 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 above, except that the amount of the (B)-1 component added was changed to 6 g.
This composition was cured at 230°C by the above-mentioned method to form a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and found to be 4.9%. In addition, 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 above, except that the amount of the (B)-1 component added was changed to 10 g.
This composition was cured at 230°C by the above-mentioned method to form a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 5.0%. In addition, 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. in Example D1.
A cured relief pattern was prepared on a Cu layer using this composition, and a high-temperature storage test was performed. The area ratio of the voids on the surface of the Cu layer was evaluated and found to be 6.1%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D12>
A negative type photosensitive resin composition solution was prepared in the same manner as in Example D1, except that in Example D1, 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were replaced with 100 g of polymer (A)-1 as the (A) resin, and 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (BASF Corporation, trade name)) was used as the (C) component instead of PDO.
A cured relief pattern was prepared on a Cu layer using this composition, and a high-temperature storage test was performed. The area ratio of the voids on the surface of the Cu layer was evaluated and found to be 5.8%. 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 in Example D12 was changed to 85 g of γ-butyrolactone and 15 g of dimethylsulfoxide.
A cured relief pattern was prepared on a Cu layer using this composition, and a high-temperature storage test was performed. The area ratio of the voids on the surface of the Cu layer was evaluated and found to be 5.4%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D14>
In the above Example D1, the (A) resin was changed from 50 g of polymer (A)-1 and 50 g of polymer (A)-2 to 100 g of polymer (A)-3, and the curing temperature was changed from 230° C. to 350° C. In the same manner as in Example D1, a negative type photosensitive resin composition solution was prepared.
A cured relief pattern was prepared on a Cu layer using this composition, and a high-temperature storage test was performed. The area ratio of the voids on the surface of the Cu layer was evaluated and found to be 7.2%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D15>
A negative type photosensitive resin composition solution was prepared in the same manner as in Example D1, except that in Example D1, 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were changed to 100 g of polymer (A)-4 as the (A) resin.
A cured relief pattern was prepared on a Cu layer using this composition, and a high-temperature storage test was performed. The area ratio of the voids on the surface of the Cu layer was evaluated and found to be 4.9%. The viscosity change rate of the obtained varnish after the storage stability test was within 10%.
<Example D16>
A positive-type photosensitive resin composition was prepared using polymer (A)-5 by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer (A)-5, which is a polyoxazole precursor (corresponding to resin (A)), was reacted with a compound represented by the following formula (96):

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

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

Claims (7)

(A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid esters, polyamic acid salts, and polyimides,
(B) a sulfur-containing compound in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin; and
(C) a photosensitizer, in an amount of 1 to 50 parts by mass based on 100 parts by mass of the (A) resin;
Including,
The photosensitive resin composition , wherein the sulfur-containing compound (B) contains nitrogen, and the sulfur in the sulfur-containing compound (B) is contained as one atom forming a ring structure. The resin (A) is at least one selected from the group consisting of a polyimide precursor having the following general formula (1) and a polyimide having the following general formula (6),
The following general formula (1) is

In the formula, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R1 and _R2 each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or a group represented by 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 from 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms, or a monovalent organic group represented by the following general formula (3):

(wherein R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10), and a polyamic acid, a polyamic acid ester or a polyamic acid salt which is a polyimide precursor represented by the formula:
The following general formula (6) is

{In the formula, _X5 is a 4-14 valent organic group, _Y5 is a 2-12 valent organic group, _R10 and _R11 each independently represent an organic group having at least one group selected from a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, _n5 is an integer from 3 to 200, and _m3 and _m4 are integers from 0 to 10.}
A polyimide having a structure represented by the formula:
The photosensitive resin composition according to claim 1 . The photosensitive resin composition according to claim 1 or 2, wherein the sulfur-containing compound (B) is at least one selected from the group consisting of thiazole, 2-aminothiazole, 2-(4-thiazolyl)benzimidazole, 1,3,4-thiadiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,3-thiadiazole, 2,4-thiazolidinedione, benzothiazole, 2-aminobenzothiazole, phenothiazine, N-methylphenothiazine, rhodanine, and N-allylrhodanine. An interlayer insulating film formed using the photosensitive resin composition according to any one of claims 1 to 3. (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 to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising: a step of heat-treating the relief pattern to form a cured relief pattern. The method of claim 5, wherein the substrate is formed from copper or a copper alloy. 1. A method for manufacturing a semiconductor device including a cured relief pattern, comprising:
A method for manufacturing a semiconductor device, comprising producing a cured relief pattern by the method according to claim 5 or 6.