JP2017198977A - Photosensitive resin composition and manufacturing method of cured relief pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of obtaining a resin layer of high adhesion, without causing a void at a boundary face of a Cu layer abutting on the cured photosensitive resin layer after a high temperature storage test, and also to provide a formation method of a cured relief pattern using the photosensitive resin composition.SOLUTION: In a photosensitive resin composition, a photosensitive resin and a specific plasticizer are combined to achieve a photosensitive resin of high adhesion, without causing a void at a boundary face of a Cu layer and a resin layer after a high temperature storage test. A cured relief pattern uses the photosensitive resin composition.SELECTED DRAWING: None

Description

  The present invention relates to, for example, an insulating material for an electronic component, and a photosensitive resin composition used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device, and formation of a cured relief pattern using the same. It is about the method.

  Conventionally, polyimide resin, polybenzoxazole resin, phenol resin, etc., which have excellent heat resistance, electrical characteristics and mechanical characteristics, are used for insulating materials for electronic parts and passivation films, surface protective films, interlayer insulating films for semiconductor devices, etc. It is used. Among these resins, those provided in the form of a photosensitive resin composition easily form a heat-resistant relief pattern film by applying the composition, exposure, development, and thermal imidization treatment by curing. be able to. Such a photosensitive resin composition has a feature that enables a significant reduction in the process compared to conventional non-photosensitive materials.

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

  Therefore, flip chip mounting has been proposed in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is flipped over and mounted directly on a printed circuit board. (For example, refer to Patent Document 1). With this flip-chip mounting, the wiring distance can be controlled accurately, so it is used for high-end devices that handle high-speed signals, or mobile phones due to the small mounting size, and the demand is rapidly expanding. . When materials such as polyimide, polybenzoxazole, and phenol resin are used for flip chip mounting, a metal wiring layer forming step is performed after the pattern of the resin layer is formed. The metal wiring layer is usually formed by plasma etching the resin layer surface to roughen the surface, and then forming a metal layer to be a seed layer for plating with a thickness of 1 μm or less, and then using the metal layer as an electrode. It is formed by electrolytic plating. At this time, in general, Ti is used as a metal to be a seed layer, and Cu is used as a metal of a rewiring layer formed by electrolytic plating.

  Such a metal rewiring layer is required to have high adhesion between the metal layer rewired after the reliability test and the resin layer. The reliability test performed here includes, for example, a high-temperature storage test in which air is stored at a high temperature of 125 ° C. or higher for 100 hours or more, and a voltage is applied to the wiring while applying a voltage at about 125 ° C. in air. A high-temperature operation test for confirming operation under storage for 100 hours or more, a temperature cycle test in which a low temperature state of about −65 to −40 ° C. and a high temperature state of about 125 to 150 ° C. are cycled in air, 85 High-temperature and high-humidity storage test that is stored in a steam atmosphere at a temperature of 85 ° C or higher and a humidity of 85% or higher, and a high-temperature and high-humidity bias test that is performed while applying voltage to the wiring by constructing wiring. And a solder reflow test in which the solder reflow furnace is passed a plurality of times.

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

JP 2001-338947 A

  The present invention has been devised in view of such a conventional situation, and after a high temperature storage test, no void is generated at the interface of the Cu layer in contact with the resin layer, and the adhesiveness is high. It aims at providing the photosensitive resin composition from which the resin layer is obtained, the formation method of the hardening relief pattern using this photosensitive resin composition, and the semiconductor device which has this hardening relief pattern.

  By combining a specific photosensitive resin and a specific plasticizer, the present inventors have no high void storage at the interface between the Cu layer and the resin layer after the high temperature storage test, and the adhesion The present inventors have found that a photosensitive resin composition that gives a cured film from which a high resin layer can be obtained is obtained, and the present invention has been completed. That is, the present invention is as follows.

｛式中、Ｘ_１は、４価の有機基であり、Ｙ_１は、２価の有機基であり、ｎ_１は、２〜１５０の整数であり、そしてＲ_１及びＲ_２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、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍ_１は、２〜１０の整数である。）で表される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、Ｒ_７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、Ｘ_２は、炭素数６〜１５の３価の有機基であり、Ｙ_２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、Ｒ_９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ｎ_２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、Ｙ_３は、炭素原子を有する４価の有機基であり、Ｙ_４、Ｘ_３及びＸ_４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、ｎ_３は、１〜１０００の整数であり、ｎ_４は、０〜５００の整数であり、ｎ_３／（ｎ_３＋ｎ_４）＞０．５であり、そしてＸ_３及びＹ_３を含むｎ_３個のジヒドロキシジアミド単位並びにＸ_４及びＹ_４を含むｎ_４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、並びに、
下記一般式（６）は、

｛式中、Ｘ_５は、４〜１４価の有機基であり、Ｙ_５は、２〜１２価の有機基であり、Ｒ_１０及びＲ_１１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、ｎ_５は、３〜２００の整数であり、そしてｍ_３及びｍ_４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、Ｒ_１２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Ｒ₁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]前記一般式（７）中のＸが、下記一般式（９）：

｛式中、Ｒ_１３、Ｒ_１４、Ｒ_１５及びＲ_１６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、ｎ_６は０〜４の整数であって、ｎ_６が１〜４の整数である場合のＲ_１７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Ｒ₆は水酸基であり、ｎ_６が２〜４の整数である場合の複数のＲ_１７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、Ｒ_１８、Ｒ_１９、Ｒ_２０及びＲ_２１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]前記（Ｂ）可塑剤が下記一般式（７）：

｛式中、Ｘは炭素数が１以上１５以下の飽和炭化水素もしくは不飽和炭化水素もしくは芳香族炭化水素を含む構造であって、ｎは１〜４の整数であって、ｎが２以上の場合、Ｒはそれぞれ同一でも異なっていてもよく、炭素数が２以上１５以下の飽和炭化水素もしくは不飽和炭化水素もしくは芳香族炭化水素である。｝で表され、
下記一般式（８）：

｛式中、ｍは１〜４の整数であって、ｍが２以上の場合、Ｒはそれぞれ同一でも異なっていてもよく、炭素数が２以上１５以下の飽和炭化水素もしくは不飽和炭化水素もしくは芳香族炭化水素で表される。｝で表され、及び
下記一般式（９）：

｛式中、Ｙは炭素数が１以上１０以下の飽和炭化水素もしくは不飽和炭化水素もしくは芳香族炭化水素を含む構造であって、Ｒはそれぞれ同一でも異なっていてもよく、炭素数が２以上１５以下の飽和炭化水素もしくは不飽和炭化水素もしくは芳香族炭化水素で表される。｝からなる群から選択される少なくとも一種である、[１]に記載の感光性樹脂組成物。
[５]
（１）[１]〜[４]のいずれか一項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。
[６]前記基板が、銅又は銅合金から形成されている、[５]に記載の方法。 [1] (A) at least selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, novolac, polyhydroxystyrene, and phenol resin 100 parts by mass of a kind of resin,
(B) 0.1 to 50 parts by mass of the plasticizer based on 100 parts by mass of the resin (A), and
(C) 1 to 50 parts by mass of the photosensitive agent based on 100 parts by mass of the resin (A),
A photosensitive resin composition comprising:
[2] The resin (A) is a polyimide precursor containing the following general formula (1), a polyamide containing the following general formula (4), a polyoxazole precursor containing the following general formula (5), the following general formula (6 ), And a photosensitive resin composition according to [1], which is at least one selected from the group consisting of novolak, polyhydroxystyrene, and a phenol resin containing the following general formula (7).
The following general formula (1) is

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

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

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

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

{Wherein Y ₃ is a tetravalent organic group having a carbon atom, and Y ₄ , X ₃ and X ₄ are each independently a divalent organic group having 2 or more carbon atoms, n ₃ is an integer from 1 to 1000, _{n 4} is an integer of _{0~500, n 3 / (n 3} + n 4)> 0.5, and _{n 3} containing _{X 3} and _{Y 3} The arrangement order of the n ₄ diamide units including X ₄ and Y ₄ is not limited. }
A polyhydroxyamide that is a polyoxazole precursor having a structure represented by:
The following general formula (6)

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

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

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

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

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

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

A divalent group selected from the group consisting of divalent groups represented by the formula: } The photosensitive resin composition according to [1] or [2], which is a divalent organic group selected from the group consisting of divalent groups represented by:
[4] The plasticizer (B) is represented by the following general formula (7):

{Wherein X is a structure containing a saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon having 1 to 15 carbon atoms, n is an integer of 1 to 4, and n is 2 or more In this case, each R may be the same or different and is a saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon having 2 to 15 carbon atoms. },
The following general formula (8):

{In the formula, m is an integer of 1 to 4, and when m is 2 or more, each R may be the same or different and is a saturated or unsaturated hydrocarbon having 2 to 15 carbon atoms, or Represented by aromatic hydrocarbons. } And the following general formula (9):

{Wherein Y is a structure containing a saturated hydrocarbon, an unsaturated hydrocarbon or an aromatic hydrocarbon having 1 to 10 carbon atoms, and R may be the same or different, and each having 2 or more carbon atoms. It is represented by 15 or less saturated hydrocarbon, unsaturated hydrocarbon, or aromatic hydrocarbon. } The photosensitive resin composition according to [1], which is at least one selected from the group consisting of:
[5]
(1) A step of forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of [1] to [4] on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a step of forming a cured relief pattern by heat-treating the relief pattern.
[6] The method according to [5], wherein the substrate is made of copper or a copper alloy.

｛式中、Ｘ_１は、４価の有機基であり、Ｙ_１は、２価の有機基であり、ｎ_１は、２〜１５０の整数であり、そしてＲ_１及びＲ_２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、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍ_１は、２〜１０の整数である。）で表される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、Ｒ_７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、Ｘ_２は、炭素数６〜１５の３価の有機基であり、Ｙ_２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、Ｒ_９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ｎ_２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、Ｙ_３は、炭素原子を有する４価の有機基であり、Ｙ_４、Ｘ_３及びＸ_４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、ｎ_３は、１〜１０００の整数であり、ｎ_４は、０〜５００の整数であり、ｎ_３／（ｎ_３＋ｎ_４）＞０．５であり、そしてＸ_３及びＹ_３を含むｎ_３個のジヒドロキシジアミド単位並びにＸ_４及びＹ_４を含むｎ_４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、Ｘ_５は、４〜１４価の有機基であり、Ｙ_５は、２〜１２価の有機基であり、Ｒ_１０及びＲ_１１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、ｎ_５は、３〜２００の整数であり、そしてｍ_３及びｍ_４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、Ｒ_１２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Ｒ₁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、Ｒ_１３、Ｒ_１４、Ｒ_１５及びＲ_１６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、ｎ_６は０〜４の整数であって、ｎ_６が１〜４の整数である場合のＲ_１７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Ｒ_１７は水酸基であり、ｎ_６が２〜４の整数である場合の複数のＲ_１７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、Ｒ_１８、Ｒ_１９、Ｒ_２０及びＲ_２１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項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。 The present inventors also provide a photosensitive resin composition that gives a cured film in which void generation at the interface contacting the Cu layer is suppressed after a high-temperature storage test by incorporating nanoparticles into the photosensitive resin composition. It was found that can be obtained. The present invention can also be applied to the following modes.
[1]
(A) Polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and at least one selected from the group consisting of novolak, polyhydroxystyrene, and phenol resin 100 parts by mass of resin,
(B-1) 0.01 to 10 parts by mass of nanoparticles based on 100 parts by mass of the resin (A);
(C) 1 to 50 parts by mass of the photosensitive agent based on 100 parts by mass of the resin (A),
A photosensitive resin composition comprising:
[2]
The (A) resin includes a polyimide precursor including the following general formula (1), a polyamide including the following general formula (4), a polyoxazole precursor including the following general formula (5), and the following general formula (6). The photosensitive resin composition of Claim 1 which is at least 1 type selected from the group which consists of a polyimide resin and a novolak, polyhydroxystyrene, and the phenol resin containing following General formula (7).
The following general formula (1) is

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

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

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

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

{Wherein Y ₃ is a tetravalent organic group having a carbon atom, and Y ₄ , X ₃ and X ₄ are each independently a divalent organic group having 2 or more carbon atoms, n ₃ is an integer from 1 to 1000, _{n 4} is an integer of _{0~500, n 3 / (n 3} + n 4)> 0.5, and _{n 3} containing _{X 3} and _{Y 3} The arrangement order of the n ₄ diamide units including X ₄ and Y ₄ is not limited. }
A polyhydroxyamide which is a polyoxazole precursor having a structure represented by:
The following general formula (6)

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

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

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

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

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

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

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

｛式中、Ｘ_１は、４価の有機基であり、Ｙ_１は、２価の有機基であり、ｎ_１は、２〜１５０の整数であり、そしてＲ_１及びＲ_２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、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍ_１は、２〜１０の整数である。）で表される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、Ｒ_７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、Ｘ_２は、炭素数６〜１５の３価の有機基であり、Ｙ_２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、Ｒ_９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ｎ_２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、

で表される構造を有するポリイミドである。
［３］
前記（Ｂ−２）熱架橋剤が、（Ｂ−２−１）メチロール基またはアルコキシアルキル基の少なくとも一方を含有する化合物、（Ｂ−２−２）オキシラン環含有化合物、（Ｂ−２−３）イソシアネート基含有化合物、（Ｂ−２−４）ビスマレイミド基含有化合物、（Ｂ−２−５）アルデヒド基含有化合物、（Ｂ−２−６）オキセタン環含有化合物、（Ｂ−２−７）ベンゾオキサジン環含有化合物、（Ｂ−２−８）オキサゾリン環含有化合物、（Ｂ−２−９）カルボジイミド基含有化合物、（Ｂ−２−１０）アリル化合物、（Ｂ−２−１１）トリアジンチオール化合物、及び(Ｂ−２−１２）金属キレート化合物、からなる群から選ばれる少なくとも１つである、［１］に記載の感光性樹脂組成物。
［４］
前記（Ｂ−２）熱架橋剤が、（Ｂ−２−１)メチロール基またはアルコキシアルキル基の少なくとも一方を含有する化合物である、［１］又は［３］に記載の感光性樹脂組成物。
［５］
前記（Ｂ−２）熱架橋剤が、下記一般式（ＴＳ１）：

｛式中、Ｒｓ１は、水素原子、メチル基、エチル基、n-プロピル基、及びイソプロピル基からなる群より選ばれる一価の基であり、Ｒｓ２は水酸基、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数１〜１０のエステル基、およびウレタン基からなる群より選ばれる基であり、ｍｍ１は１〜５の整数であり、ｍｍ２は０〜４の整数である。ここで、１≦（ｍｍ１＋ｍｍ２）≦５であり、ｎｎ１は１〜４の整数であり、Ｖ_１はｎｎ１＝１のときＣＨ_２ＯＲｓ１であり、ｎｎ１＝２〜４のとき、単結合また２〜４価の有機基である。ＣＨ_２ＯＲｓ１およびＲ_１０が複数存在する場合、これらは互いに同一でも異なっていてもよい｝
で表わされる構造を有する、［１］又は［３］に記載の感光性樹脂組成物。
［６］
（１）［１］〜［５］のいずれか一項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。
［７］
前記基板が、銅又は銅合金から形成されている、［６］に記載の方法。 In addition, the present inventors have combined a photosensitive resin and a specific thermal crosslinking agent to provide a negative photosensitive resin that gives a cured film in which void generation at the interface contacting the Cu layer is suppressed after a high-temperature storage test. It was found that a composition was obtained. The present invention can also be applied to the following modes.
[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,
(B-2) 0.01-50 parts by mass of a thermal crosslinking agent based on 100 parts by mass of the resin (A);
(C) 1 to 50 parts by mass of the photosensitive agent based on 100 parts by mass of the resin (A),
A negative photosensitive resin composition comprising:
[2]
The photosensitive resin according to [1], wherein the resin (A) is at least one selected from the group consisting of a polyimide precursor containing the following general formula (1) and a polyamide containing the following general formula (4). Composition.
The following general formula (1) is

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

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

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

{In the formula, X ₂ is a trivalent organic group having 6 to 15 carbon atoms, and Y ₂ is a divalent organic group having 6 to 35 carbon atoms and has the same structure or a plurality of them. R ₉ is an organic group having at least one radical-polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n ₂ is an integer of 1 to 1000. }
A polyamide having a structure represented by:

It is a polyimide which has the structure represented by these.
[3]
(B-2) the thermal crosslinking agent is (B-2-1) a compound containing at least one of a methylol group or an alkoxyalkyl group, (B-2-2) an oxirane ring-containing compound, (B-2-3) ) Isocyanate group-containing compound, (B-2-4) bismaleimide group-containing compound, (B-2-5) aldehyde group-containing compound, (B-2-6) oxetane ring-containing compound, (B-2-7) Benzoxazine ring-containing compound, (B-2-8) oxazoline ring-containing compound, (B-2-9) carbodiimide group-containing compound, (B-2-10) allyl compound, (B-2-11) triazine thiol compound And (B-2-12) The photosensitive resin composition according to [1], which is at least one selected from the group consisting of metal chelate compounds.
[4]
The photosensitive resin composition according to [1] or [3], wherein the (B-2) thermal crosslinking agent is a compound containing at least one of (B-2-1) a methylol group or an alkoxyalkyl group.
[5]
The (B-2) thermal crosslinking agent has the following general formula (TS1):

{In the formula, Rs1 is a monovalent group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and Rs2 is a hydroxyl group and an alkyl group having 1 to 10 carbon atoms. , A group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a urethane group, mm1 is an integer of 1 to 5, and mm2 is 0 to 4 It is an integer. Here, 1 ≦ (mm1 + mm2) ≦ 5, nn1 is an integer of 1 to 4, V ₁ is CH ₂ ORs1 when nn1 = 1, and a single bond or 2 to 2 when nn1 = 2-4. It is a tetravalent organic group. When there are a plurality of CH ₂ ORs1 and R ₁₀ , these may be the same or different from each other}
The photosensitive resin composition as described in [1] or [3] which has a structure represented by these.
[6]
(1) A step of forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of [1] to [5] on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a step of forming a cured relief pattern by heat-treating the relief pattern.
[7]
The method according to [6], wherein the substrate is formed of copper or a copper alloy.

｛式中、Ｘ_１は、４価の有機基であり、Ｙ_１は、２価の有機基であり、ｎ_１は、２〜１５０の整数であり、そしてＲ_１及びＲ_２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、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍ_１は、２〜１０の整数である。）で表される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、Ｒ_７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、Ｘ_２は、炭素数６〜１５の３価の有機基であり、Ｙ_２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、Ｒ_９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ｎ_２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、Ｙ_３は、炭素原子を有する４価の有機基であり、Ｙ_４、Ｘ_３及びＸ_４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、ｎ_３は、１〜１０００の整数であり、ｎ_４は、０〜５００の整数であり、ｎ_３／（ｎ_３＋ｎ_４）＞０．５であり、そしてＸ_３及びＹ_３を含むｎ_３個のジヒドロキシジアミド単位並びにＸ_４及びＹ_４を含むｎ_４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、
下記一般式（６）は、

｛式中、Ｘ_５は、４〜１４価の有機基であり、Ｙ_５は、２〜１２価の有機基であり、Ｒ_１０及びＲ_１１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、ｎ_５は、３〜２００の整数であり、そしてｍ_３及びｍ_４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、Ｒ_１２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Ｒ₁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］
前記一般式（７）中のＸが、下記一般式（９）：

｛式中、Ｒ_１３、Ｒ_１４、Ｒ_１５及びＲ_１６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、ｎ_６は０〜４の整数であって、ｎ_６が１〜４の整数である場合のＲ_１７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Ｒ₆は水酸基であり、ｎ_６が２〜４の整数である場合の複数のＲ_１７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、Ｒ_１８、Ｒ_１９、Ｒ_２０及びＲ_２１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］
前記（Ｂ−３）フッ素含有疎水性化合物の分子中のフッ素原子の重量割合が３０質量％以上、８０質量％以下である、［１］から［３］のいずれか一項に記載の感光性樹脂組成物。
［５］
前記（Ｂ−３）フッ素含有疎水性化合物が、分子内に不飽和二重結合を少なくとも１つ有する、［１］〜［４］のいずれか一項に記載の感光性樹脂組成物。
［６］
前記（Ｂ−３）フッ素含有疎水性化合物が、パーフルオロ基を有するアクリレートもしくはメタクリレート化合物である［１］〜［５］のいずれか一項に記載の感光性樹脂組成物。
［７］
（１）［１］〜［６］のいずれか一項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。
［８］
前記基板が、銅又は銅合金から形成されている、［７］に記載の方法。 In addition, the present inventors combined a specific photosensitive resin and a specific fluorine-containing hydrophobic compound, thereby generating voids at the interface of the Cu layer in contact with the resin layer after a high temperature storage test. It discovered that the photosensitive resin composition which gives the cured film from which the resin layer with high adhesiveness was obtained without obtaining was obtained. The present invention can also be applied to the following modes.
[1]
(A) 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 phenol resin 100 parts by mass,
(B-3) 0.01 to 50 parts by mass of the fluorine-containing hydrophobic compound based on 100 parts by mass of the (A) resin, and (C) 1 to 4 parts of the photosensitive agent based on 100 parts by mass of the (A) resin. 50 parts by mass,
A photosensitive resin composition comprising:
[2]
The (A) resin includes a polyimide precursor including the following general formula (1), a polyamide including the following general formula (4), a polyoxazole precursor including the following general formula (5), and the following general formula (6). The photosensitive resin composition according to [1], which is at least one selected from the group consisting of polyimide, and novolak, polyhydroxystyrene, and a phenol resin including the following general formula (7).
The following general formula (1) is

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

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

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

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

{Wherein Y ₃ is a tetravalent organic group having a carbon atom, and Y ₄ , X ₃ and X ₄ are each independently a divalent organic group having 2 or more carbon atoms, n ₃ is an integer from 1 to 1000, _{n 4} is an integer of _{0~500, n 3 / (n 3} + n 4)> 0.5, and _{n 3} containing _{X 3} and _{Y 3} The arrangement order of the n ₄ diamide units including X ₄ and Y ₄ is not limited. }
A polyhydroxyamide which is a polyoxazole precursor having a structure represented by:
The following general formula (6)

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

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

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

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

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

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

A divalent group selected from the group consisting of divalent groups represented by the formula: } The photosensitive resin composition as described in [1] or [2] which is a divalent organic group selected from the group consisting of a divalent group represented by:
[4]
The photosensitivity according to any one of [1] to [3], wherein a weight ratio of fluorine atoms in the molecule of the (B-3) fluorine-containing hydrophobic compound is 30% by mass or more and 80% by mass or less. Resin composition.
[5]
The photosensitive resin composition according to any one of [1] to [4], wherein the (B-3) fluorine-containing hydrophobic compound has at least one unsaturated double bond in the molecule.
[6]
The photosensitive resin composition according to any one of [1] to [5], wherein the (B-3) fluorine-containing hydrophobic compound is an acrylate or methacrylate compound having a perfluoro group.
[7]
(1) A step of forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of [1] to [6] on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a step of forming a cured relief pattern by heat-treating the relief pattern.
[8]
The method according to [7], wherein the substrate is formed of copper or a copper alloy.

  According to the present invention, after the high temperature storage test, a photosensitive resin composition in which no void is generated at the interface between the Cu layer and the resin layer and a highly sensitive photosensitive resin is obtained, the photosensitive property A method for forming a cured relief pattern using a resin composition, and a semiconductor device having the cured relief pattern can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. In addition, this embodiment is an illustration for demonstrating this invention, and does not intend limiting this invention. The present invention can be implemented with appropriate modifications within the scope of the gist.
Throughout this specification, structures represented by the same reference numerals in the general formula may be the same as or different from each other when there are a plurality of structures in the molecule.

<Photosensitive resin composition>
In this embodiment, (A) selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, novolak, polyhydroxystyrene, and phenol resin. At least one kind of resin: 100 parts by weight, (B) plasticizer: 0.1 to 50 parts by weight based on 100 parts by weight of the resin (A), (C) photosensitive agent: based on 100 parts by weight of the resin (A) 1 to 50 parts by mass is an essential component.

<Photosensitive resin composition>
Also, another embodiment is (A) from polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and novolak, polyhydroxystyrene and phenolic resin. 100 parts by mass of at least one resin selected from the group consisting of: (B-1) nanoparticles: 0.01 to 10 parts by mass based on 100 parts by mass of (A) resin, (C) photosensitizer: (A) resin 1-50 mass parts is made into an essential component on the basis of 100 mass parts.

<Photosensitive resin composition>
Another embodiment is a negative photosensitive resin composition, wherein (A) at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, and polyamic acid salt: 100 parts by mass, (B- 2) Thermal crosslinking agent: 0.01 to 10 parts by mass based on 100 parts by mass of (A) resin, (C) Photosensitive agent: 1 to 50 parts by mass based on 100 parts by mass of resin as essential components .

<Photosensitive resin composition>
Another embodiment is the group consisting of (A) polyamic acid, polyamic acid ester polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole and novolak, polyhydroxystyrene and phenolic resin. At least one resin selected from 100 parts by mass, (B-3) 0.01 to 50 parts by mass of a fluorine-containing hydrophobic compound based on 100 parts by mass of the resin (A), and (C) a photosensitive agent: (A ) 1 to 50 parts by mass as an essential component based on 100 parts by mass of resin.

(A) Resin (A) Resin used for this invention is demonstrated. The resin (A) of the present invention comprises a group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and novolak, polyhydroxystyrene and phenolic resin. The main component is at least one selected resin. Here, the main component means that these resins are contained in an amount of 60% by mass or more of the total resin, and preferably 80% by mass or more. Moreover, other resin may be included as needed.

  The weight average molecular weight of these resins is preferably 200 or more and more preferably 5,000 or more in terms of polystyrene by gel permeation chromatography from the viewpoint of heat resistance after heat treatment and mechanical properties. It is preferably 1,000 or more, more preferably 1,000 or more. The upper limit is preferably 500,000 or less, and more preferably 20,000 or less from the viewpoint of solubility in a developer when a photosensitive resin composition is used.

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

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

｛式中、Ｘ_１は、４価の有機基であり、Ｙ_１は、２価の有機基であり、ｎ_１は、２〜１５０の整数であり、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、炭素数１〜３０の飽和脂肪族基、又は前記一般式（２）：

（式中、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍ_１は、２〜１０の整数である。）で表される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、Ｒ_７及びＲ₈は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍ₂は、２〜１０の整数である。）で表される一価のアンモニウムイオンである。｝、で表されるポリイミドの前駆体であるポリアミド酸、ポリアミド酸エステル又はポリアミド酸塩である。
ポリイミド前駆体は、加熱（例えば２００℃以上）環化処理を施すことによってポリイミドに変換される。ポリイミド前駆体はネガ型感光性樹脂組成物用として好適である。 [(A) Polyamic acid, polyamic acid ester, polyamic acid salt]
In the photosensitive resin composition of the present invention, one example of the most preferable (A) resin from the viewpoints of heat resistance and photosensitive properties is the general formula (1):

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

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

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

｛式中、Ｒ２５は水素原子、フッ素原子、Ｃ１〜Ｃ１０の炭化水素基、Ｃ１〜Ｃ１０の含フッ素炭化水素基から選ばれる１価の基であり、ｌは０〜２から選ばれる整数、ｍは０〜３から選ばれる整数、ｎは０〜４から選ばれる整数である。｝
で表される構造が挙げられるが、これらに限定されるものではない。また、Ｘ_１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Ｘ_１基は、耐熱性と感光特性とを両立するという点で特に好ましい。 In the general formula (1), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably, from the viewpoint of achieving both heat resistance and photosensitive characteristics. , -COOR ₁ group, -COOR ₂ group and -CONH- group are each an aromatic group or an alicyclic aliphatic group in the ortho position. The tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms containing an aromatic ring, and more preferably the following formula (30):

{In the formula, R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorine-containing hydrocarbon group, and l is an integer selected from 0 to 2, m Is an integer selected from 0 to 3, and n is an integer selected from 0 to 4. }
Although the structure represented by these is mentioned, it is not limited to these. The structure of X ₁ are may be two or more kinds in combination. The X ₁ group having a structure represented by the above formula is particularly preferable in terms of achieving both heat resistance and photosensitive characteristics.

｛式中、Ｒ２５は水素原子、フッ素原子、Ｃ１〜Ｃ１０の炭化水素基、Ｃ１〜Ｃ１０の含フッ素炭化水素基から選ばれる１価の基であり、ｎは０〜４から選ばれる整数である。｝
で表される構造が挙げられるが、これらに限定されるものではない。また、Ｙ_１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Ｙ_１基は、耐熱性及び感光特性を両立するという点で特に好ましい。 In the general formula (1), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive properties. Following formula (31):

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

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

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

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

(Preparation of acid / ester)
In the present invention, a tetracarboxylic dianhydride containing a tetravalent organic group X ₁ which is preferably used for preparing an ester bond type polyimide precursor has a structure represented by the above general formula (30). Including tetracarboxylic dianhydride having, for example, pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic Acid dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylmethane-3,3 ′ , 4,4′-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1, 3,3,3-hexafluoropropaprop Etc., preferably pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl- Although 3,3 ', 4,4'-tetracarboxylic dianhydride can be mentioned, it is not limited to these. These may be used alone or in combination of two or more.

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

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

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

(Preparation of polyimide precursor)
An appropriate dehydration condensation agent such as dicyclocarbodiimide, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2 is added to the acid / ester (typically, a solution in a solvent described later) under ice cooling. -Dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate and the like were added and mixed to make the acid / ester body a polyanhydride Thereafter, a solution obtained by dissolving or dispersing a diamine containing a divalent organic group Y ₁ suitably used in the present invention in a solvent is added dropwise thereto and subjected to amide polycondensation to thereby obtain a target polyimide precursor. Can be obtained. Alternatively, the acid / ester can be reacted with a diamine compound in the presence of a base such as pyridine after the acid moiety has been acid chlorided using thionyl chloride or the like to obtain the target polyimide precursor. .

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

  1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4-bis (4-amino) Phenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2 -Bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2 Bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene, and Those in which a part of hydrogen atoms on these benzene rings are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen or the like, for example, 3,3′-dimethyl-4,4′-diaminobiphenyl 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 2,2′-dimethyl-4,4′-diaminodiphenylmethane, 3,3 ′ -Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-di Tilbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl Etc., preferably p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 2,2′-dimethylbenzidine, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl 2,2′-bis (fluoro) -4,4′-diaminobiphenyl, 4,4′-diaminooctafluorobiphenyl and the like, and mixtures thereof, but are not limited thereto.

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

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

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

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

  Examples of (meth) acrylic compounds having an amino group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylamino Dialkylaminoalkyl acrylates or methacrylates such as butyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, diethylaminobutyl methacrylate, etc. are preferred. Among these, from the viewpoint of photosensitive properties, the alkyl group on the amino group has 1 to 10 carbon atoms and the alkyl chain is C1-C10 dialkylaminoalkyl Acrylate or methacrylate is preferred.

  The compounding amount of the (meth) acrylic compound having an amino group is 1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and 2 to 15 parts by mass is preferable from the viewpoint of photosensitivity characteristics. (C) As photosensitizer, (meth) acrylic compound having an amino group is blended in an amount of 1 part by mass or more with respect to 100 parts by mass of (A) resin. Excellent in properties.

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

｛式中、Ｘ_２は、炭素数６〜１５の３価の有機基であり、Ｙ_２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、Ｒ_９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ｎ_２は、１〜１０００の整数である。｝
で表される構造を有するポリアミドである。このポリアミドはネガ型感光性樹脂組成物用として好適である。 [(A) Polyamide]
One more example of preferable (A) resin in the photosensitive resin composition of this invention is following General formula (4):

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

｛式中、Ｒ_３２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 general formula (4), as the group represented by R ₉ , the following general formula (32),

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

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

Is preferably an aromatic group selected from the group represented by formula (II), and more preferably an aromatic group obtained by removing a carboxyl group and an amino group from an amino group-substituted isophthalic acid structure.

｛式中、Ｒ_３３及びＲ_３４は、それぞれ独立に、水酸基、メチル基（−ＣＨ_３）、エチル基（−Ｃ_２Ｈ_５）、プロピル基（−Ｃ_３Ｈ_７）又はブチル基（−Ｃ_４Ｈ_９）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、ｍ_７は、０〜８の整数であり、ｍ_８及びｍ_９は、それぞれ独立に、０〜３の整数であり、ｍ_１０及びｍ_１１は、それぞれ独立に、０〜１０の整数であり、そしてＲ_３５及びＲ_３６は、メチル基（−ＣＨ_３）、エチル基（−Ｃ_２Ｈ_５）、プロピル基（−Ｃ_３Ｈ_７）、ブチル基（−Ｃ_４Ｈ_９）又はこれらの異性体である。｝が挙げられる。 In the general formula (4), the divalent organic group represented by Y ₂ is preferably an organic group having 6 to 35 carbon atoms, and may be an aromatic or aliphatic ring which may be substituted. More preferably, it is a cyclic organic group having 1 to 4 carbon atoms, an aliphatic group having no cyclic structure, or a siloxane group. Examples of the divalent organic group represented by Y ₂ include the following general formula (I) and the following general formulas (34) and (35):

{In the formula, R ₃₃ and R ₃₄ each independently represent 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 one group selected from the group consisting of ₄ H ₉ ), and the propyl group and butyl group include various isomers. }

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

｛式中、ｍ_１２は、２〜１２の整数であり、ｍ_１３は、１〜３の整数であり、ｍ_１４は、１〜２０の整数であり、そしてＲ_３７、Ｒ_３８、Ｒ_３９及びＲ_４０は、それぞれ独立に、炭素数１〜３のアルキル基又は置換されていてもよいフェニル基である。｝が好ましいものとして挙げられる。 Examples of the aliphatic group or siloxane group having no cyclic structure include the following general formula (36):

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

The polyamide resin of the present invention can be synthesized, for example, as follows.
(Synthesis of sealed phthalate compound)
Firstly, selected compounds having a trivalent aromatic group X _2, for example, phthalic acid substituted by amino groups, isophthalic acid substituted with amino group, and, from the group consisting of terephthalic acid substituted with an amino group 1 mol of at least one compound (hereinafter referred to as “phthalic acid compound”) is reacted with 1 mol of a compound that reacts with an amino group, and the amino group of the phthalic acid compound is converted into a radical polymerizable compound described later. A compound modified and sealed with a group containing an unsaturated bond (hereinafter referred to as “phthalic acid compound encapsulated body”) is synthesized. These may be used alone or in combination.

  When the phthalic acid compound is sealed with the radical polymerizable unsaturated bond-containing group, negative photosensitivity (photocurability) can be imparted to the polyamide resin.

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

  The above-mentioned sealed phthalic acid compound is obtained by reacting an amino group of a phthalic acid compound with an acid chloride, isocyanate or epoxy compound having at least one radical polymerizable unsaturated bond group having 3 to 20 carbon atoms. Can be obtained at

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

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

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

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

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

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

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

  Examples of the chlorinating agent include thionyl chloride.

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

The diamine compound having the organic group Y ₂ is at least one diamine selected from the group consisting of an aromatic diamine compound, an aromatic bisaminophenol compound, an alicyclic diamine compound, a linear aliphatic diamine compound, and a siloxane diamine compound. It is preferable that it is a compound, and it is also possible to use two or more together as desired.

  Examples of aromatic diamine compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'- Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane , 3,4'-di Mino diphenylmethane,

  3,3′-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4 -(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) ) Biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis ( 4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) pro 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene, and some of the hydrogen atoms on these benzene rings Is a diamine compound substituted with one or more groups selected from the group consisting of a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, and a halogen atom.

  Examples of diamine compounds in which hydrogen atoms on the benzene ring are substituted include 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro- 4,4′-diaminobiphenyl and the like can be mentioned.

  Aromatic bisaminophenol compounds include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4′-diaminodiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (3-hydroxy-4-aminophenyl) hexafluoropropane, bis- (3-hydroxy-4-aminophenyl) methane, 2,2-bis- (3-hydroxy-4-aminophenyl) Propane, 3,3′-dihydroxy-4,4′-diaminobenzophenone, 3,3′-dihydroxy-4,4′-di Minodiphenyl ether, 4,4′-dihydroxy-3,3′-diaminodiphenyl ether, 2,5-dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis (3-amino-4- Hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylidene) -bis (2-aminophenol) and the like.

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

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

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

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

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

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

｛式中、Ｙ_３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、Ｙ_４、Ｘ_３及びＸ_４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、ｎ_３は、１〜１０００の整数であり、ｎ_４は、０〜５００の整数であり、ｎ_３／（ｎ_３＋ｎ_４）＞０．５であり、そしてＸ_３及びＹ_３を含むｎ_３個のジヒドロキシジアミド単位並びにＸ_４及びＹ_４を含むｎ_４個のジアミド単位の配列順序は問わない。｝で表される構造を有するポリヒドロキシアミド（ポリオキサゾール前駆体（以下、上記一般式（５）で表されるポリヒドロキシアミドを単に「ポリオキサゾール前駆体」という場合がある。））である。 [(A) Polyhydroxyamide]
Still another example of the preferred resin (A) in the photosensitive resin composition of the present invention is the following general formula (5):

{Wherein Y ₃ is a tetravalent organic group having a carbon atom, preferably a tetravalent organic group having 2 or more carbon atoms, and Y ₄ , X ₃ and X ₄ are each independently And n ₃ is an integer of 1 to 1000, n ₄ is an integer of 0 to 500, and n ₃ / (n ₃ + n ₄ is a divalent organic group having 2 or more carbon atoms. )> 0.5, and the arrangement order of n ₃ dihydroxydiamide units including X ₃ and Y ₃ and n ₄ diamide units including X ₄ and Y ₄ is not limited. } Is a polyhydroxyamide (polyoxazole precursor (hereinafter, the polyhydroxyamide represented by the general formula (5) may be simply referred to as “polyoxazole precursor”)).

The polyoxazole precursor is a polymer having n ₃ dihydroxydiamide units in the general formula (5) (hereinafter sometimes simply referred to as dihydroxydiamide units), and n ₄ in the general formula (5). May have a number of diamide units (hereinafter sometimes simply referred to as diamide units).

The number of carbon atoms of X ₃ is preferably from 40 2 or more in order to obtain a photosensitive properties, carbon atoms X ₄ is not more than 40 more than the purpose of obtaining a sensitometric Preferably, the number of carbon atoms of Y ₃ is preferably 2 or more and 40 or less for the purpose of obtaining photosensitive characteristics, and the number of carbon atoms of Y ₄ is 2 or more and 40 or less for the purpose of obtaining photosensitive characteristics. Preferably there is.

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

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

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

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

_As the diamine having a structure of Y 4 _{(NH 2)} 2, an aromatic diamine, a silicon diamine, and the like. Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene,

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

  4,4′-diaminobenzophenone, phenylindanediamine, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, o-toluidine sulfone, 2,2 -Bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4 -Aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-di- (3-aminophenoxy) diphenylsulfone, 4,4'-diaminobenzanilide, and the like Hydrogen atom of aromatic nucleus of group diamine is chlorine atom, fluorine atom, bromine atom, methyl group, Butoxy group, compounds substituted by at least one group or atom selected from the group consisting of cyano group and a phenyl group.

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

｛式中、Ｒ_４１は、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−及び−Ｃ（ＣＦ_３）_２−から成る群から選択される２価の基を表す。｝
で表される芳香族基から好ましく選択でき、これらは感光特性の点で好ましい。 In addition, as a preferable dicarboxylic acid having a structure of X ₃ (COOH) ₂ or X ₄ (COOH) ₂ , X ₃ and X ₄ are each an aliphatic group or an aromatic group having a linear, branched or cyclic structure. What is a group is mentioned. Among these, an organic group having 2 to 40 carbon atoms which may contain an aromatic ring or an aliphatic ring is preferable, and X ₃ and X ₄ are each represented by the following formula (38):

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

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

The thing represented by is mentioned.

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

｛式中、Ｘ_５は、４〜１４価の有機基、Ｙ_５は、２〜１２価の有機基、Ｒ_１０及びＲ_１１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、ｎ_５は、３〜２００の整数であり、そしてｍ_３及びｍ_４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Ｘ_５は、炭素数４〜４０の４価〜１４価の有機基であることが好ましく、耐熱性と感光特性とを両立するという点で、芳香族環又は脂肪族環を含有する炭素原子数５〜４０の有機基であることがさらに好ましい。 [(A) Polyimide]
One more example of the preferred resin (A) in the photosensitive resin composition of the present invention is the general formula (6):

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

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

  Suitable tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1- Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-Zika Boxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid Anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride,

｛式中、Ｒ_４２は、酸素原子、Ｃ（ＣＦ_３）_２、Ｃ（ＣＨ_３）_２又はＳＯ_２から選ばれる基を示し、そしてＲ_４３及びＲ_４４は、同一であるか、又は異なっていてもよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝で表される化合物が挙げられる。 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine Aromatic tetracarboxylic acid such as tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride Dianhydrides, or aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Diphenylsulfone tetracarboxylic dianhydride and the following general formula (40):

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

  Of these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Screw (3,4-di Carboxymethyl) sulfone dianhydride,

｛式中、Ｒ_４５は、酸素原子、Ｃ（ＣＦ_３）_２、Ｃ（ＣＨ_３）_２又はＳＯ_２から選ばれる基を示し、そしてＲ_４６及びＲ_４７は、同一であるか、又は異なっていてもよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝で表される構造の酸二無水物が好ましい。これらは単独で又は２種以上を組み合わせて使用される。 Bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic Acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic dianhydride and The following general formula (41)

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

Y _{5 in the} general formula (6) represents a structural component of a diamine, and the diamine represents a divalent to divalent organic group containing an aromatic ring or an aliphatic ring, and in particular has 5 carbon atoms. ~ 40 organic groups are preferred.

  Specific examples of diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylene Diamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- ( 4-aminophenoxy) pheny } Ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3 ′ -Dimethyl-4,4'-diaminobiphenyl,

｛式中、Ｒ_４８は、酸素原子、Ｃ（ＣＦ_３）_２、Ｃ（ＣＨ_３）_２又はＳＯ_２から選ばれる基を示し、そしてＲ_４９〜Ｒ_５２は、同一であるか、又は異なっていてよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝で表される構造のジアミンなどが挙げられる。 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4′-diaminobiphenyl, 3,3 ′, 4,4′-tetramethyl-4 , 4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, or an alkyl group or halogen on these aromatic rings Compounds substituted with atoms, or aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the following general formula (42):

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

｛式中、Ｒ_５３は、酸素原子、Ｃ（ＣＦ_３）_２、Ｃ（ＣＨ_３）_２又はＳＯ_２から選ばれる基を示し、そしてＲ_５４〜Ｒ_５７は、同一であるか、又は異なっていてよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝
で表される構造のジアミンが好ましい。 Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'- Diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, m-phenylenediamine, P-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis (4-Aminophenyl) fluorene and the following general formula (43):

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

｛式中、Ｒ_５８は、酸素原子、Ｃ（ＣＦ_３）_２、Ｃ（ＣＨ_３）_２又はＳＯ_２から選ばれる基を示し、そしてＲ_５９及びＲ_６０は、同一であるか、又は異なっていてよく、かつ水素原子、水酸基又はチオール基から選ばれる基を示す。｝
で表される構造のジアミンが特に好ましい。これらは単独で又は２種以上を組み合わせて使用される。 Of these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'- Diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, and the following general formula (44):

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

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

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

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

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

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

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

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

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

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

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

｛式中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ_２６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Ｒ_１２は、互いに同一でも又は異なっていてもよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（８）：

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

{Wherein, a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦ (a + b) ≦ 4, and R ₂₆ is a monovalent organic having 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of a group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R ₁₂ may be the same or different from each other X is a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, and the following general formula (8):

(Wherein p is an integer of 1 to 10), and selected from the group consisting of a divalent alkylene oxide group represented by: and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. Represents a divalent organic group. }
It is preferable that it is at least 1 type of phenol resin selected from the phenol resin which has the repeating unit represented by these, and the phenol resin modified | denatured with the compound which has C4-C100 unsaturated hydrocarbon group.

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

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

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

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

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

｛式中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ_１２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Ｒ_１２は、互いに同一でも又は異なっていてよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（８）：

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

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

(Wherein p is an integer of 1 to 10), and selected from the group consisting of a divalent alkylene oxide group represented by: and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. Represents a divalent organic group. It is also preferable to include a phenol resin having a repeating unit represented by: The phenol resin having the above repeating unit can be cured at a low temperature as compared with, for example, conventionally used polyimide resin and polybenzoxazole resin, and enables formation of a cured film having good elongation. This is particularly advantageous. The repeating unit present in the phenol resin molecule may be one type or a combination of two or more types.

｛式中、Ｒ_６１、Ｒ_６２及びＲ_６３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Ｒ_６４は、不飽和結合を有していてもよい炭素数１〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、又は炭素数６〜２０の２価の芳香族基を表す。｝で表される４つの基からなる群から選択される１価の置換基であることが好ましい。 In the general formula (7), R ₁₂ represents a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and cyano from the viewpoint of reactivity when synthesizing the resin according to the general formula (7). A monovalent substituent selected from the group consisting of groups. R ₁₂ is, from the viewpoint of alkali solubility, a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an aromatic group having 6 to 20 carbon atoms, And the following general formula (45):

{In the formula, R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, or an alicyclic group having 3 to 20 carbon atoms. Represents a group, or an aromatic group having 6 to 20 carbon atoms, and R ₆₄ is a divalent aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, 2 having 3 to 20 carbon atoms. A alicyclic group or a divalent aromatic group having 6 to 20 carbon atoms is represented. } Is preferably a monovalent substituent selected from the group consisting of four groups represented by:

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

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

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

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

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

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

｛式中、Ｒ_１３、Ｒ_１４、Ｒ_１５及びＲ_１６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、ｎ_６は０〜４の整数であって、ｎ_６が１〜４の整数である場合のＲ_１７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Ｒ_１７は水酸基であり、ｎ_６が２〜４の整数である場合の複数のＲ_１７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、Ｒ_１８、Ｒ_１９、Ｒ_２０及びＲ_２１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Ｒ_１２基が芳香環に結合している構造とは異なる。 In this embodiment, in the said General formula (7), X is a C2-C10 bivalent which may have an unsaturated bond from a cured relief pattern shape and a viewpoint of the elongation of a cured film. From an aliphatic group, a divalent alicyclic group having 3 to 20 carbon atoms, an alkylene oxide group represented by the general formula (8), and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. A divalent organic group selected from the group consisting of Among these divalent organic groups, X represents the following general formula (9) from the viewpoint of the toughness of the cured film.

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

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

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

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

で表される２価の有機基であることがより好ましく、さらに下記式（１３）：

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

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

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

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

｛式中、Ｒ_２１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、ｎ_７は２又は３であり、ｎ_８は０〜２の整数であり、ｍ_５は１〜５００の整数であり、２≦（ｎ_７＋ｎ_８）≦４であり、ｎ_８が２の場合には、複数のＲ_２１は互いに同一でも又は異なっていてもよい。｝

｛式中、Ｒ_２２及びＲ_２３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、ｎ_９は１〜３の整数であり、ｎ_１０は０〜２の整数であり、ｎ_１１は０〜３の整数であり、ｍ_６は１〜５００の整数であり、２≦（ｎ_９＋ｎ_１０）≦４であり、ｎ_１０が２の場合には、複数のＲ_２２は互いに同一でも又は異なっていてもよく、ｎ_１１が２又は３の場合には、複数のＲ_２３は互いに同一でも又は異なっていてもよい。｝ Further, among the phenol resins having the structure represented by the general formula (7), both the structure represented by the following general formula (14) and the structure represented by the following general formula (15) The structure contained therein is particularly preferable from the viewpoint of alkali solubility of the composition and elongation of the cured film.

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

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

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

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

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

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

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

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

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

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

  Examples of the alkoxymethyl compound include 2,6-bis (methoxymethyl) -p-cresol, 2,6-bis (methoxymethyl) -4-ethylphenol, and 2,6-bis (methoxymethyl) -4-. Propylphenol, 2,6-bis (methoxymethyl) -4-n-butylphenol, 2,6-bis (methoxymethyl) -4-t-butylphenol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 2,6-bis (methoxymethyl) -4-ethoxyphenol, 2,6-bis (methoxymethyl) -4-propoxyphenol, 2,6-bis (methoxymethyl) -4-n-butoxyphenol, 2,6 -Bis (methoxymethyl) -4-t-butoxyphenol, 1,3-bis (methoxymethyl) urea, 2,2-bis (methoxy) Til) butyric acid, 2,2-bis (methoxymethyl) -5-norbornene, 2,3-bis (methoxymethyl) -5-norbornene, 1,4-bis (methoxymethyl) cyclohexane, 1,4-bis (methoxy) Methyl) cyclohexene, 1,6-bis (methoxymethyl) adamantane, 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 2,6-bis (methoxymethyl) -1,4 -Dimethoxybenzene, 2,3-bis (methoxymethyl) naphthalene, 2,6-bis (methoxymethyl) naphthalene, 1,8-bis (methoxymethyl) anthracene, 2,2'-bis (methoxymethyl) diphenyl ether, 4 , 4′-bis (methoxymethyl) diphenyl ether, 4,4′-bis (methoxymethyl) diphenylthio Ether, 4,4′-bis (methoxymethyl) benzophenone, 4-methoxymethylbenzoic acid-4′-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4′-methoxymethylanilide, 4,4′-bis (methoxy) Methyl) phenylurea, 4,4′-bis (methoxymethyl) phenylurethane, 1,8-bis (methoxymethyl) anthracene, 4,4′-bis (methoxymethyl) biphenyl, 2,2′-dimethyl-4, 4'-bis (methoxymethyl) biphenyl, 2,2-bis (4-methoxymethylphenyl) propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether And dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and tetrapropylene glycol dimethyl ether.

  Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol-dimethacrylate, 2,4-hexadien-1-ol, and methyl. Cyclohexadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentadiene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2 , 5-norbornadiene, tetrahydroindene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, triallyl cyanurate, diallyl isocyanurate, triisocyanurate Lil, diallyl propyl etc. isocyanuric acid.

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

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

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

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

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

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

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

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

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

  The vegetable oil is usually a non-drying oil containing an ester of glycerin and an unsaturated fatty acid and having an iodine value of 100 or less, a semi-drying oil of more than 100 and less than 130, or a drying oil of 130 or more. Non-drying oils include, for example, olive oil, Asa seed oil, cashew oil, potato oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of the drying oil include paulownia oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, camellia oil and coconut oil. Moreover, you may use the processed vegetable oil obtained by processing these vegetable oils.

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

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

  A phenol resin modified with an unsaturated hydrocarbon group-containing compound is produced by polycondensation of an unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction with an aldehyde. Aldehydes are, for example, formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, glyceraldehyde, glyoxylic acid, methyl glyoxylate, Phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate, pyruvic acid, repric acid, 4-acetylbutyric acid, acetone dicarboxylic acid and 3,3′- Selected from 4,4'-benzophenone tetracarboxylic acid. Further, a formaldehyde precursor such as paraformaldehyde or trioxane may be used. These aldehydes are used alone or in combination of two or more.

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

  The above reaction is preferably carried out usually at a reaction temperature of 100 to 120 ° C. Moreover, although reaction time changes with kinds and quantity of a catalyst to be used, it is 1 to 50 hours normally. After completion of the reaction, the reaction product is dehydrated under reduced pressure at a temperature of 200 ° C. or lower to obtain a phenol resin modified with the unsaturated hydrocarbon group-containing compound. In the reaction, a solvent such as toluene, xylene, or methanol can be used.

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

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

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

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

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

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

  The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of a carboxy group of a polybasic acid having a plurality of carboxy groups. Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Dibasic acid anhydrides such as methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyltetra Carboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride and benzophenone tetra Carboxylic acid aromatic tetracarboxylic acid dianhydride such as dianhydride. You may use these individually by 1 type or in combination of 2 or more types. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably at least one selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern having a better shape can be formed.

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

  In addition, you may contain a catalyst in the said reaction as needed from a viewpoint of performing reaction rapidly. Examples of the catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine.

  The acid value of the phenol resin further modified with polybasic acid anhydride is preferably 30 to 200 mgKOH / g, more preferably 40 to 170 mgKOH / g, and further preferably 50 to 150 mgKOH / g. . When the acid value is less than 30 mgKOH / g, it tends to require a longer time for alkali development than when the acid value is in the above range, and when it exceeds 200 mgKOH / g, the acid value is in the above range. In comparison with the above, the developer resistance of the unexposed portion tends to be lowered.

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

As (A) phenol resin of this embodiment, phenol modified with the phenol resin which has a repeating unit represented by the said General formula (7), and the said compound which has a C4-C100 unsaturated hydrocarbon group A mixture of at least one phenol resin selected from resins (hereinafter also referred to as (a3) resin) and a phenol resin selected from novolak and polyhydroxystyrene (hereinafter also referred to as (a4) resin) is also preferable. The mixing ratio of the (a3) resin and the (a4) resin is (a3) / (a4) = 5/95 to 95/5 in terms of mass ratio. This mixing ratio is (a3) / (a4) = 5 / from the viewpoints of solubility in an alkaline aqueous solution, sensitivity and resolution when forming a resist pattern, residual stress of the cured film, and reflow treatment applicability. 95 to 95/5 is preferable, (a3) / (a4) = 10/90 to 90/10 is more preferable, and (a3) / (a4) = 15/85 to 85/15 is more preferable. preferable. As the novolak and polyhydroxystyrene as the (a4) resin, the same resins as those described in the above section (Novolak) and (polyhydroxystyrene) can be used.

(B) Plasticizer (B) The plasticizer in this embodiment is demonstrated in detail below. (B) The plasticizer improves the fluidity of the resin (A) when the relief pattern formed using the photosensitive resin composition of the present embodiment is heat-cured, and (A) the polymer packing of the resin. It is a compound that improves the properties. By improving the packing property, it is possible to suppress the generation of voids during the high-temperature storage test, and it is possible to suppress a decrease in adhesion at the interface between the Cu layer and the resin layer. (B) A plasticizer will not be specifically limited if it corresponds to the said conditions.

｛式中、Ｘは炭素数が１以上１５以下の飽和炭化水素もしくは不飽和炭化水素もしくは芳香族炭化水素を含む構造であって、ｎは１〜４の整数であって、ｎが２以上の場合、Ｒはそれぞれ同一でも異なっていてもよく、炭素数が２以上１５以下の飽和炭化水素もしくは不飽和炭化水素もしくは芳香族炭化水素である。）で表わされる化合物が特に好ましく用いられる。 (B) As a compound which functions as a plasticizer, the following general formula (7):

{Wherein X is a structure containing a saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon having 1 to 15 carbon atoms, n is an integer of 1 to 4, and n is 2 or more In this case, each R may be the same or different and is a saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon having 2 to 15 carbon atoms. ) Is particularly preferably used.

｛式中、ｍは１〜４の整数であって、ｍが２以上の場合、Ｒはそれぞれ同一でも異なっていてもよく、炭素数が２以上１５以下の飽和炭化水素もしくは不飽和炭化水素もしくは芳香族炭化水素で表される。｝で表され、又は、
下記一般式（９）：

｛式中、Ｙは炭素数が１以上１０以下の飽和炭化水素もしくは不飽和炭化水素もしくは芳香族炭化水素を含む構造であって、Ｒはそれぞれ同一でも異なっていてもよく、炭素数が２以上１５以下の飽和炭化水素もしくは不飽和炭化水素もしくは芳香族炭化水素で表される。｝からなる群から選択される少なくとも一種が、本発明の可塑剤として好ましい。 Among them, the following general formula (8):

{In the formula, m is an integer of 1 to 4, and when m is 2 or more, each R may be the same or different and is a saturated or unsaturated hydrocarbon having 2 to 15 carbon atoms, or Represented by aromatic hydrocarbons. }, Or
The following general formula (9):

{Wherein Y is a structure containing a saturated hydrocarbon, an unsaturated hydrocarbon or an aromatic hydrocarbon having 1 to 10 carbon atoms, and R may be the same or different, and each having 2 or more carbon atoms. It is represented by 15 or less saturated hydrocarbon, unsaturated hydrocarbon, or aromatic hydrocarbon. } Is preferable as the plasticizer of the present invention.

  Examples of the plasticizer represented by the general formula (7) include benzoic acid ester, phthalic acid ester, isophthalic acid ester, terephthalic acid ester, trimellitic acid ester, pyromellitic acid ester, and aliphatic acid tetrahydrofurfuryl. . Specific examples of benzoic acid esters include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, heptyl benzoate, normal octyl benzoate, nonyl benzoate, isononyl benzoate, benzoate Isodecyl acid, 2-ethylhexyl benzoate, isodecyl benzoate, butyl benzyl benzoate, cyclopropyl benzoate, cyclobutyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, cycloheptyl benzoate, allyl benzoate, butyl benzyl benzoate And phenyl benzoate. Of these, 2-ethylhexyl benzoate, cyclohexyl benzoate, and phenyl benzoate are particularly preferably used.

  Specific examples of phthalate esters include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, diheptyl phthalate, di-normal octyl phthalate, dinonyl phthalate, diisononyl phthalate Diisodecyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, dicyclopropyl phthalate, dicyclobutyl phthalate, dicyclopentyl phthalate, dicyclohexyl phthalate, dicycloheptyl phthalate, Examples include diallyl phthalate, bisbutylbenzyl phthalate, and diphenyl phthalate. Of these, bis (2-ethylhexyl) phthalate, dicyclohexyl phthalate, and diphenyl phthalate are particularly preferably used.

  Specific examples of isophthalic acid esters include dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, dipentyl isophthalate, diheptyl isophthalate, dinormal octyl isophthalate, dinonyl isophthalate, diisononyl isophthalate , Diisodecyl isophthalate, bis (2-ethylhexyl) isophthalate, diisodecyl isophthalate, butylbenzyl isophthalate, dicyclopropyl isophthalate, dicyclobutyl isophthalate, dicyclopentyl isophthalate, dicyclohexyl isophthalate, dicycloheptyl isophthalate, Examples include diallyl isophthalate, bisbutylbenzyl isophthalate, and diphenyl isophthalate. Of these, bis (2-ethylhexyl) isophthalate, dicyclohexyl isophthalate, and diphenyl isophthalate are particularly preferably used.

  Specific examples of terephthalic acid esters include dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dipentyl terephthalate, diheptyl terephthalate, di-normal octyl terephthalate, dinonyl terephthalate, diisononyl terephthalate , Diisodecyl terephthalate, bis (2-ethylhexyl) terephthalate, diisodecyl terephthalate, butylbenzyl terephthalate, dicyclopropyl terephthalate, dicyclobutyl terephthalate, dicyclopentityl terephthalate, dicyclohexyl terephthalate, dicycloheptyl terephthalate, Examples include diallyl terephthalate, bisbutylbenzyl terephthalate, and diphenyl terephthalate. Among these, bis (2-ethylhexyl) terephthalate, dicyclohexyl terephthalate, and diphenyl terephthalate are particularly preferably used.

  Specific examples of trimellitic acid esters include trimethyl trimellitic acid, triethyl trimellitic acid, tripropyl trimellitic acid, tributyl trimellitic acid, tripentyl trimellitic acid, triheptyl trimellitic acid, and trimellitic acid trimethyl. Normal octyl, trinonyl trimellitic acid, triisononyl trimellitic acid, triisodecyl trimellitic acid, tris (2-ethylhexyl) trimellitic acid, triisodecyl trimellitic acid, trisbutylbenzyl trimellitic acid, tricyclopropyl trimellitic acid, trimellitic acid Tricyclobutyl, Tricyclopentityl trimellitic acid, Tricyclohexyl trimellitic acid, Tricycloheptyl trimellitic acid, Triaryl trimellitic acid, Trisbutyl trimellitic acid Njiru include trimellitic acid triphenyl. Especially, trimellitic acid tris (2-ethylhexyl), trimellitic acid tricyclohexyl, and trimellitic acid triphenyl are used suitably.

  Specific examples of pyromellitic acid ester compounds include tetramethyl pyromellitic acid, tetraethyl pyromellitic acid, tetrapropyl pyromellitic acid, tetrabutyl pyromellitic acid, tetrapentyl pyromellitic acid, tetraheptyl pyromellitic acid, and pyromellitic acid. Tetranormaloctyl acid, tetranonyl pyromellitic acid, tetraisononyl pyromellitic acid, tetraisodecyl pyromellitic acid, tetrakis pyromellitic acid (2-ethylhexyl), tetraisodecyl pyromellitic acid, tetrakisbutylbenzyl pyromellitic acid, pyromellitic Tetracyclopropyl acid, pyromellitic acid tetracyclobutyl, pyromellitic acid tetracyclopentityl, pyromellitic acid tetracyclohexyl, pyromellitic acid tetracycloheptyl, pyromellitic Tetraallyl, pyromellitic acid tetrakis butyl benzyl, pyromellitic acid tetraphenyl. Among these, pyromellitic acid tetrakis (2-ethylhexyl), pyromellitic acid tetracyclohexyl, and pyromellitic acid tetraphenyl are particularly preferably used.

  As the plasticizer represented by the general formula (8), malonic acid ester, succinic acid ester, glutaric acid ester, adipic acid ester, pimelic acid ester, suberic acid ester, azelaic acid ester, sebacic acid ester and the like are preferably used. . Specific examples of malonic acid esters include dimethyl malonate, diethyl malonate, dipropyl malonate, dibutyl malonate, dipentyl malonate, diheptyl malonate, dinormal octyl malonate, dinonyl malonate, malonic acid Diisononyl, diisodecyl malonate, bis (2-ethylhexyl) malonate, diisodecyl malonate, butylbenzyl malonate, dicyclopropyl malonate, dicyclobutyl malonate, dicyclopentyl malonate, dicyclohexyl malonate, dicycloheptyl malonate , Diallyl malonate, bisbutylbenzyl malonate, and diphenyl malonate. Of these, bis (2-ethylhexyl) malonate, dicyclohexyl malonate, and diphenyl malonate are particularly preferably used.

  Specific examples of succinic acid esters include dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dipentyl succinate, diheptyl succinate, dinormal octyl succinate, dinonyl succinate, succinic acid Diisononyl, diisodecyl succinate, bis (2-ethylhexyl) succinate, diisodecyl succinate, butylbenzyl succinate, dicyclopropyl succinate, dicyclobutyl succinate, dicyclopentity succinate, dicyclohexyl succinate, dicycloheptyl succinate , Diallyl succinate, bisbutylbenzyl succinate, diphenyl succinate. Of these, bis (2-ethylhexyl) succinate, dicyclohexyl succinate, and diphenyl succinate are particularly preferably used.

  Specific examples of glutarate esters include dimethyl glutarate, diethyl glutarate, dipropyl glutarate, dibutyl glutarate, dipentyl glutarate, diheptyl glutarate, di-octyl glutarate, dinonyl glutarate, glutaric acid Diisononyl, diisodecyl glutarate, bis (2-ethylhexyl) glutarate, diisodecyl glutarate, butylbenzyl glutarate, dicyclopropyl glutarate, dicyclobutyl glutarate, dicyclopentyl glutarate, dicyclohexyl glutarate, dicycloheptyl glutarate , Diallyl glutarate, bisbutylbenzyl glutarate, and diphenyl glutarate. Of these, bis (2-ethylhexyl) glutarate, dicyclohexyl glutarate, and diphenyl glutarate are particularly preferably used.

  Specific examples of adipic acid esters include dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dipentyl adipate, diheptyl adipate, dinormal octyl adipate, dinonyl adipate, adipic acid Diisononyl, diisodecyl adipate, bis (2-ethylhexyl) adipate, diisodecyl adipate, butylbenzyl adipate, dicyclopropyl adipate, dicyclobutyl adipate, dicyclopentity adipate, dicyclohexyl adipate, dicycloheptyl adipate , Diallyl adipate, bisbutylbenzyl adipate, and diphenyl adipate. Among these, bis (2-ethylhexyl) adipate, dicyclohexyl adipate, and diphenyl adipate are particularly preferably used.

  Specific examples of the pimelic acid ester include dimethyl pimelate, diethyl pimelate, dipropyl pimelate, dibutyl pimelate, dipentyl pimelate, diheptyl pimelate, dinormal octyl pimelate, dinonyl pimelate, pimelic acid. Diisononyl, diisodecyl pimelate, bis (2-ethylhexyl) pimelate, diisodecyl pimelate, butylbenzyl pimelate, dicyclopropyl pimelate, dicyclobutyl pimelate, dicyclopentyl pimelate, dicyclohexyl pimelate, dicycloheptyl pimelate , Diallyl pimelate, bisbutylbenzyl pimelate, and diphenyl pimelate. Among these, bis (2-ethylhexyl) pimelate, dicyclohexyl pimelate, and diphenyl pimelate are particularly preferably used.

  Specific examples of the compounds of the suberic acid ester include dimethyl suberate, diethyl suberate, dipropyl suberate, dibutyl suberate, dipentyl suberate, diheptyl suberate, dinormal octyl suberate, dinonyl suberate, suberic acid Diisononyl, diisodecyl suberate, bis (2-ethylhexyl) suberate, diisodecyl suberate, butylbenzyl suberate, dicyclopropyl suberate, dicyclobutyl suberate, dicyclopentyl suberate, dicyclohexyl suberate, dicycloheptyl suberate , Diallyl suberate, bisbutylbenzyl suberate, and diphenyl suberate. Among these, bis (2-ethylhexyl) suberate, dicyclohexyl suberate, and diphenyl suberate are particularly preferably used.

  Specific examples of azelaic acid esters include dimethyl azelate, diethyl azelate, dipropyl azelate, dibutyl azelate, dipentyl azelate, diheptyl azelate, dinormal octyl azelate, dinonyl azelate, azelaic acid Diisononyl, azelaic acid diisodecyl, azelaic acid bis (2-ethylhexyl), azelaic acid diisodecyl, azelaic acid butylbenzyl, azelaic acid dicyclopropyl, azelaic acid dicyclobutyl, azelaic acid dicyclohexyl, azelaic acid dicycloheptyl , Diallyl azelate, bisbutylbenzyl azelate, diphenyl azelate. Among them, bis (2-ethylhexyl) azelate, dicyclohexyl azelate, and diphenyl azelate are particularly preferably used.

  Specific examples of sebacic acid esters include dimethyl sebacate, diethyl sebacate, dipropyl sebacate, dibutyl sebacate, dipentyl sebacate, diheptyl sebacate, dinormal octyl sebacate, dinonyl sebacate, sebacic acid Diisononyl, diisodecyl sebacate, bis (2-ethylhexyl) sebacate, diisodecyl sebacate, butylbenzyl sebacate, dicyclopropyl sebacate, dicyclobutyl sebacate, dicyclopentity sebacate, dicyclohexyl sebacate, dicycloheptyl sebacate , Diallyl sebacate, bisbutylbenzyl sebacate, and diphenyl sebacate. Of these, bis (2-ethylhexyl) sebacate, dicyclohexyl sebacate, and diphenyl sebacate are particularly preferably used.

  Specific examples of the tetrahydrofurfuryl aliphatic acid include tetrahydrofurfuryl formate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, tetrahydrofurfuryl isobutyrate, tetrahydrofurfuryl valerate, Examples include tetrahydrofurfuryl herbate and tetrahydrofurfuryl caproate. Of these, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, and tetrahydrofurfuryl isobutyrate are particularly preferably used.

  As content of a plasticizer (B), 0.1-50 mass parts is preferable with respect to 100 mass parts of resin (A), 1-40 mass parts is more preferable, and it is 1-30 mass parts. Further preferred. If the content is higher than the range, the glass transition temperature decreases, which is not preferable. If the content is lower than the range, sufficient plasticity cannot be obtained, and voids are easily generated between the copper surface and the surface.

  The role of the plasticizer (B) in the present embodiment is to improve the fluidity of the resin (A) when the relief pattern formed using the photosensitive resin composition of the present embodiment is heated and cured. ) To improve the packing properties of the resin polymer. As a result, a robust cured film can be obtained, generation of voids can be suppressed in a high-temperature storage test, and a decrease in adhesion at the interface between the Cu layer and the resin layer can be suppressed.

In the photosensitive resin composition of the present embodiment, (B-1) nanoparticles, (B-2) a thermal crosslinking agent, and (B-3) instead of or in combination with the above-described (B) plasticizer. Any of the fluorine-containing hydrophobic compounds can be contained.
After a high temperature storage test by combining a photosensitive resin with a specific (B-1) nanoparticle, (B-2) a thermal crosslinking agent, or (B-3) a fluorine-containing hydrophobic compound Provided is a photosensitive resin composition in which a photosensitive resin having high adhesion is obtained without generating voids at the interface between the Cu layer and the resin layer, and a method for forming a cured relief pattern using the photosensitive resin composition can do.

(B-1) Nanoparticles (B-1) The nanoparticles are solid particles at room temperature, and have an average primary particle size of 1 μm or less, preferably 300 nm or less, from the viewpoint of light transmittance. The primary particle size can be determined from SEM observation or laser diffraction. In addition, from the viewpoint of resistance to Cu migration during HTS, plate-like, scaly, needle-like or fibrous particles having an aspect ratio of 5 or more are preferred. (A) From the viewpoint of compatibility with the resin, silane coupling It is preferable that the surface is treated with an agent or the like. Furthermore, from the viewpoint of water resistance, these nanoparticles preferably contain oxides, composite oxides, doped oxides, oxoacids, oxoacid salts, nitrides, carbides or sulfides.

Examples of (B-1) nanoparticles that can be used in the present invention include SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZrO ₂ , HfO ₂ , V ₂ O ₅ , WO ₃ , In ₂ O ₃ , SnO. ₂ , Sb ₂ O ₃ , Nb ₂ O ₅ , MoO ₃ , Fe ₂ O ₃ , CuO, ZnO, CaO, MgO, aerosil, silica alumina, mica, montmorillonite, talc, clay, boehmite, kaolin, (poly) phosphoric acid Zirconium, barium titanate, calcium carbonate, (poly) zirconium tungstate, PZT, glass, aluminum borate, aluminum nitride, titanium nitride, silicon nitride, boron nitride, or a mixture thereof can be given.
By adding nanoparticles, the thermal expansion coefficient of the photosensitive resin can be reduced. Due to the decrease in the thermal expansion coefficient, the thermal expansion of the resin during the high temperature storage test is suppressed, and the migration of copper is suppressed. At this time, as the nanoparticle, a shape having a high aspect ratio is preferable because the thermal expansion coefficient can be lowered with a smaller amount of addition. A shape having a high aspect ratio is more preferable because the number of voids on the copper surface is reduced, and the developability and chemical resistance tend to be good.

The aspect ratio of the nanoparticles is preferably larger than 1, from the viewpoint of the number of voids on the copper surface, developability and chemical resistance, the aspect ratio is preferably 2 or more, more preferably 3 or more, More preferably, it is 4 or more. The aspect ratio is more preferably 5 or more, more preferably 8 or more, more preferably 10 or more, more preferably 12 or more, and more preferably 15 or more, It is especially preferable that it is 20 or more.
The aspect ratio is a value represented by the length of the major axis / length of the minor axis of the nanoparticle. When the nanoparticle is a perfect sphere, the aspect ratio is 1. If the nanoparticle is not a perfect sphere or a perfect ellipsoid, the smallest sphere diameter of the spheres that can contain the nanoparticle completely inside is the major axis of the nanoparticle, and the nanoparticle Among the spheres of a size that can be completely contained in the inside, the diameter of the largest sphere is defined as the minor axis of the nanoparticles.

  (B-1) The compounding quantity of a nanoparticle is 0.1-50 mass parts with respect to 100 mass parts of (A) resin, Preferably it is 0.05-10 mass parts. From the viewpoint of migration resistance, 0.1 part by mass or more is preferable, and from the viewpoint of solubility, it is preferably less than 50 parts by mass.

｛式中、Ｒｓ３は１価の有機基又は水素原子である。｝で表される有機基を分子内に含有している化合物である。
具体的には、下記一般式（ＴＳ１）：

｛式中、Ｒｓ１は、水素原子、メチル基、エチル基、n-プロピル基、及びイソプロピル基からなる群より選ばれる一価の基であり、Ｒｓ２は水酸基、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数１〜１０のエステル基、およびウレタン基からなる群より選ばれる基であり、ｍｍ１は１〜５の整数であり、ｍｍ２は０〜４の整数である。ここで、１≦（ｍｍ１＋ｍｍ２）≦５であり、ｎｎ１は１〜４の整数であり、Ｖ_１はｎｎ１＝１のときＣＨ_２ＯＲｓ１であり、ｎｎ１＝２〜４のとき、単結合また２〜４価の有機基である。ＣＨ_２ＯＲｓ１およびＲ_１０が複数存在する場合、これらは互いに同一でも異なっていてもよい。｝、並びに、
一般式（ＴＳ３）及び（ＴＳ４）：

｛式中、Ｒｓ３及びＲｓ４は、それぞれ独立に、水素原子、及び炭素原子数１〜１０の炭化水素基からなる群から選ばれる１価の有機基である。｝で表され、

｛式中、Ｒｓ５は、それぞれ独立に水素原子、及び炭素原子数１〜１０の炭化水素基からなる群から選ばれる１価の有機基である。｝で表される構造を有するＮ−メチロール化合物及びＮ−アルコキシメチル化合物等が挙げられるが、これらに限定されない。 (B-2) Thermal crosslinking agent (B-2) Thermal crosslinking agent used for this invention is demonstrated. (B-2) The thermal crosslinking agent can be crosslinked with the resin (A) when the relief pattern formed using the photosensitive resin composition of the present embodiment is heat-cured, or the crosslinking agent itself is a crosslinked network. Refers to a compound that forms (B) Although it will not specifically limit if a thermal crosslinking agent corresponds to the said conditions, It is preferable that it is either shown to the following (B-2-1)-(B-2-12).
(B-2-1) Compound containing methylol group and / or alkoxymethyl group The compound containing methylol group and / or alkoxymethyl group is the following general formula (TS2):

{Wherein Rs3 represents a monovalent organic group or a hydrogen atom. } Is a compound containing an organic group represented by
Specifically, the following general formula (TS1):

{In the formula, Rs1 is a monovalent group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and Rs2 is a hydroxyl group and an alkyl group having 1 to 10 carbon atoms. , A group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a urethane group, mm1 is an integer of 1 to 5, and mm2 is 0 to 4 It is an integer. Here, 1 ≦ (mm1 + mm2) ≦ 5, nn1 is an integer of 1 to 4, V ₁ is CH ₂ ORs1 when nn1 = 1, and a single bond or 2 to 2 when nn1 = 2-4. It is a tetravalent organic group. When a plurality of CH ₂ ORs1 and R ₁₀ are present, these may be the same as or different from each other. }, And
General formulas (TS3) and (TS4):

{In the formula, Rs3 and Rs4 are each independently a monovalent organic group selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms. },

{In formula, Rs5 is a monovalent organic group chosen from the group which consists of a hydrogen atom and a C1-C10 hydrocarbon group each independently. } N-methylol compounds and N-alkoxymethyl compounds having a structure represented by

  Preferred specific examples include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65. , 300, My Coat 102, 105 (Mitsui Cytec Co., Ltd.), Nicarak (registered trademark) MX-270, -280, -290, Nicarak MS-11, Nicarak MW-30, -100, -300, -390 -750 (above, manufactured by Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML-PTBP, DML-PCHP, DML-POP, DML -PFP, DML-MBOC, BisCMP-F, DML-BisO -Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAFMF, TM-BIP-A, HMOM-TP-HAP (above, manufactured by Honshu Chemical Industry Co., Ltd.) ), Benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis (hydroxymethyl) biphenyl, Dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether , Bis (methoxymethyl) benzophenone, methoxymethyl benzoate methoxymethyl, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, methylolated body novolak, and the like.

Among these, those having the structure represented by the general formula (12) are more preferable. Specifically, DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML- PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM- BPA, TML-BPAFMF, TM-BIP-A, HMOM-TP-HAP (above, manufactured by Honshu Chemical Industry Co., Ltd.), benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) ) Diphenyl ether, bis (hydride) Xymethyl) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis Examples thereof include methylolated products of (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethylphenyl methoxybenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl and novolak.
Of these, TMOM-BP, TMOM-BPA, TML-BPAFMF, TM-BIP-A, and HMOM-TP-HAP are particularly preferable.

(B-2-2) Oxirane Compound The oxirane (epoxy) compound is not particularly limited as long as it is a compound containing an epoxy group in the molecule. Specifically, a phenol novolac type epoxy resin, a cresol novolac type epoxy Resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, fat Cyclic epoxy resin, chain aliphatic epoxy resin, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglu Cidyl ether, 1,1,2,2-tetra (p-hydroxyphenyl) ethane tetraglycidyl ether, glycerol triglycidyl ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, Diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), GAN, GOT, NC-3000-H, EPPN-501H, EPPN-502H, EOCN-1020, NC-6000, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (trade name, manufactured by Nippon Kayaku Co., Ltd.), Epicort (registered trademark) 1001 , Epi Coat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051, Epicoat 1031S, Epicoat 180S65, Epicoat 157H70, YX-315-75 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EHPE3150, Plaxel G402, PUE101, PUE105 (trade names) Manufactured by Daicel Chemical Industries, Ltd.), Epicron (registered trademark) 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-850CRP, 860 , EXA-4701, EXA-4850-1000 (trade name, manufactured by DIC),
Denacol (registered trademark) EX-201, EX-212L, EX-214L, EX-216L, 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-850L, EX-911, EM-150 (trade names, manufactured by Nagase ChemteX), Epolite (Registered trademark) 70P, 40E, 100E, 100MF, 200E, 400E, 200P, 400P, 1500NP, 80MF, 4000, 3002 (trade name, manufactured by Kyoeisha Chemical), jER (registered trademark) 828, 834, 1001, 1002, 1003 , 1004, 1005, 1007, 1010, 1100
L, 630, ESCN-220L, 220F, 220H, 220HH, 180H65, 1032H60, YX4000H, 152, 157S70, 1031 (manufactured by Mitsubishi Chemical), Adeka Resin (registered trademark) EP-4000s, EP-4003s (manufactured by Adeka), etc. It is done.

  Among these, from the viewpoint of reliability after the HTS test, triglycidyl isocyanurate, epiclone 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA -4850-1000, Denacol EX-201, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-731, Ex-810, EX-911, and EM-150 epoxy compounds are particularly preferred.

(B-2-3) Isocyanate group-containing compound The isocyanate group-containing compound is not particularly limited as long as it is a compound containing an isocyanate group in the molecule. From the viewpoint of reliability after the HTS test, 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 (trade name, manufactured by Mitsui Chemicals) Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (trade name, manufactured by Asahi Kasei Chemicals) and the like are preferable.

(B-2-4) Bismaleimide Compound The bismaleimide compound is not particularly limited as long as it is a compound containing a maleimide group in the molecule. From the viewpoint of reliability after the HTS test, 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'-diphenylsulfone bismaleimide, 1,3-bis (3 -Maleimidophenoxy) benzene, 1,3-bis (4-maleimidophene) Xyl) benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (trade names) , Daiwa Kasei Kogyo Co., Ltd.) and the like are preferable.
(B-2-5) Aldehyde group-containing compound The aldehyde group-containing compound is not particularly limited as long as it contains an aldehyde group in the molecule. From the viewpoint of reliability after the HTS test, formaldehyde and benzaldehyde are used. , Acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde , Furfural, glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde, hexamethylenetetramine, trioxane, malondialdehyde, Nji aldehyde, and the like are preferable.

で表される２価の基を含有する化合物である。
オキセタン環含有化合物としては、オキセタニル基を分子内に含有していれば特に制限されず、１，４−ビス｛［（３−エチル−３−オキセタニル）メトキシ］メチル｝ベンゼン、ビス［１−エチル（３−オキセタニル）］メチルエーテル、４，４’−ビス［（３−エチル−３−オキセタニル）メトキシメチル］ビフェニル、４，４’−ビス（３−エチル−３−オキセタニルメトキシ）ビフェニル、エチレングリコールビス（３−エチル−３−オキセタニルメチル）エーテル、ジエチレングリコールビス（３−エチル−３−オキセタニルメチル）エーテル、ビス（３−エチル−３−オキセタニルメチル）ジフェノエート、トリメチロールプロパントリス（３−エチル−３−オキセタニルメチル）エーテル、ペンタエリスリトールテトラキス（３−エチル−３−オキセタニルメチル）エーテル、３−エチル−３｛［（３−エチルオキセタン―イル）メトキシ］メチル｝オキセタン、東亜合成（株）製の３−エチル−３−ヒドロキシメチルオキセタン（ＯＸＴ−１０１）、２−エチルヘキシシルオキセタン（ＯＸＴ−２１２）、キシリレンビスオキセタン（ＯＸＴ−１２１）、３−エチル−３−｛［（３−エチルオキセタン−３−イル）メトキシ］メチル｝オキセタン（ＯＸＴ−２２１）、ＯＸ−ＳＱ−Ｈ、ＯＸＴ−１９１、ＰＮＯＸ−１００９、ＲＳＯＸ、
以下の：

、宇部興産（株）社のエタナコールＥＨＯ、ＯＸＢＰ、ＯＸＭＡ、ＯＸＩＰＡ、ＨＢＯＸ、ＯＸＴＰ等が挙げられる。
中でも、現像液への溶解性及び得られた硬化膜の伸度の観点から、ＯＸＢＰ、ＯＸＩＰＡ、ＯＸＴ−１２１、及びＯＸＴ−２２１が好ましい。
（Ｂ−２−７）ベンゾオキサジン環含有化合物
ベンゾオキサジン環含有化合物としては、ベンゾオキサジン環を分子内に含有している化合物であれば特に制限されないが、ＨＴＳ試験後の信頼性の観点から、特開２００６−３３５６７１号公報に開示されている化合物、並びにビスフェノールＦ型ベンゾオキサジンＢＦ−ＢＸＺ、ビスフェノールＡ型ベンゾオキサジンＢＡ−ＢＸＺ、ビスフェノールＳ型ベンゾオキサジンＢＳ−ＢＸＺ（商品名、小西化学工業製）等が好ましい。 (B-2-6) Oxetane ring-containing compound The oxetane ring-containing compound is a compound represented by the following formula:

It is a compound containing the bivalent group represented by these.
The oxetane ring-containing compound is not particularly limited as long as it contains an oxetanyl group in the molecule. 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-Oxetanyl)] methyl ether, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3 -Oxetanylmethyl) ether, pentaerythritol tetrakis (3 Ethyl-3-oxetanylmethyl) ether, 3-ethyl-3 {[(3-ethyloxetane-yl) methoxy] methyl} oxetane, 3-ethyl-3-hydroxymethyloxetane (OXT-101) manufactured by Toagosei Co., Ltd. ), 2-ethylhexyl oxetane (OXT-212), xylylenebisoxetane (OXT-121), 3-ethyl-3-{[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (OXT- 221), OX-SQ-H, OXT-191, PNOX-1009, RSOX,
below:

, Etanacol EHO, OXBP, OXMA, OXIPA, HBOX, OXTP, etc. of Ube Industries, Ltd.
Among these, OXBP, OXIPA, OXT-121, and OXT-221 are preferable from the viewpoint of solubility in a developer and elongation of the obtained cured film.
(B-2-7) Benzoxazine ring-containing compound The benzoxazine ring-containing compound is not particularly limited as long as it is a compound containing a benzoxazine ring in the molecule, but from the viewpoint of reliability after the HTS test, Compounds disclosed in JP-A-2006-335671, bisphenol F-type benzoxazine BF-BXZ, bisphenol A-type benzoxazine BA-BXZ, bisphenol S-type benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical Industries) Etc. are preferred.

(B-2-8) Oxazoline ring-containing compound The oxazoline ring-containing compound is not particularly limited as long as it is a compound containing an oxazoline ring in the molecule, and 2-oxazoline, 2-amino-2-oxazoline, 2 , 2′-bis (2-oxazoline), 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3 , 5-tris (4,5-dihydro-2-oxazolyl) benzene, 2,2 '-(2,6-pyridinediyl) bis (4-isopropyl-2-oxazoline), 2,2'-(2,6 -Pyridinediyl) bis (4-phenyl-2-oxazoline), 2-phenyl (2-oxazoline), 4,4-dimethyl-2-oxazoline, 2,2'-isopropylidenebis (4- Enyl-2-oxazoline), 2-ethyl-2-oxazoline, 2,2′-isopropylidenebis (4-t-butyl-2-oxazoline), 2-isopropyl-2-oxazoline, 4-methoxymethyl-2- Methyl-5-phenyl-2-oxazoline, 2-methyl-2-oxazoline, 2,4,4-trimethyl-2-oxazoline, Nippon Shokubai Epocross Series K-1010E, K-2010E, K-1020E, K -2020E, K-1030E, K-2030E, WS-500, WS-700, RPS-1005, RAS-1005 and the like.
From the viewpoint of reliability after the HTS test, for example, 2,2′-bis (2-oxazoline), 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 1,4-bis (4, 5-Dihydro-2-oxazolyl) benzene, 1,3,5-tris (4,5-dihydro-2-oxazolyl) benzene, 2-phenyl (2-oxazoline), Epocross WS-500, and the like are preferable.

｛式中、Ｒｓ６は炭素数１〜１０の有機基であり、ｎｎ２は０〜４の整数である。｝
で表される化合物であることがより好ましく、最も好ましいのは、１，３−ビス（４，５−ジヒドロ−２−オキサゾリル）ベンゼン、及び１，３，５−トリス（４，５−ジヒドロ−２−オキサゾリル）ベンゼンである。
（Ｂ−２−９）カルボジイミド基含有化合物
カルボジイミド基含有化合物としては、カルボジイミド基を分子内に含有する化合物であれば特に限定されないが、ＨＴＳ試験後の信頼性の観点から、ビス（２，６−ジイソプロピルフェニル）カルボジイミド、カルボジライトＳＶ−０２、Ｖ−０１、Ｖ−０２、Ｖ−０３、Ｖ−０４、Ｖ−０５、Ｖ−０７、Ｖ−０９、Ｅ−０１、Ｅ−０２、ＬＡ−１（商品名、日清紡ケミカル社製）等が好ましい。 The oxazoline ring-containing compound is represented by the following general formula (TS5):

{In formula, Rs6 is a C1-C10 organic group, and nn2 is an integer of 0-4. }
And most preferred are 1,3-bis (4,5-dihydro-2-oxazolyl) benzene and 1,3,5-tris (4,5-dihydro- 2-oxazolyl) benzene.
(B-2-9) Carbodiimide group-containing compound The carbodiimide group-containing compound is not particularly limited as long as it is a compound containing a carbodiimide group in the molecule. From the viewpoint of reliability after the HTS test, bis (2,6 -Diisopropylphenyl) carbodiimide, carbodilite SV-02, V-01, V-02, V-03, V-04, V-05, V-07, V-09, E-01, E-02, LA-1 (Trade name, manufactured by Nisshinbo Chemical Co., Ltd.) is preferred.

(B-2-10) Allyl compound The allyl compound is not particularly limited as long as it contains an allyl group in the molecule. Trimethylolpropane trimethacrylate, triallyl 1,3,5-benzenetricarboxylate, trimellitic acid Triallyl, pyromellitic acid tetraallyl ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, NK ester 1G, 2G, 3G 4G, 9G, 14G, NPG, BPE-100, BPE-200, BPE-500, BPE-1400, A-200, A-400, A-600, TMPT, A -TMM-3 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), BANI-M, BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) and the like.

  Among these, from the viewpoint of reliability after the HTS test, vinyl acetate, trimethylolpropane trimethacrylate, triallyl 1,3,5-benzenetricarboxylic acid, triallyl trimellitic acid, pyromellitic acid tetraallyl ester, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, BANIM, and BANI-X are particularly preferred.

(B-2-11) Triazine thiol compound The triazine thiol compound is not particularly limited as long as it contains a thiocyanuric acid group in the molecule. From the viewpoint of reliability after the obtained HTS test, 2, 4, 6- Trithiol-1,3,5-triazine, 2-dimethylamino-4,6-dithiol-1,3,5-triazine, 2-dibutylamino-4,6-dithiol-1,3,5-triazine, 2- Phenylamino-4,6-dithiol-1,3,5-triazine and the like are preferable.

(B-2-12) Metal chelate compound Examples of the metal chelate compound include an aluminum chelate compound, a titanium chelate compound, a zirconium chelate compound, a chromium chelate compound, a magnesium chelate compound, and a nickel chelate compound. From the viewpoint of reliability, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone chromium (III) salt, acetylacetone magnesium (II) salt, acetylacetone nickel (II) salt, acetylacetone zirconium (IV) salt, trifluoro Acetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium (III) salt, trifluoroacetylacetate Seton magnesium (II) salt, trifluoroacetylacetone nickel (II) salt, trifluoroacetylacetone zirconium (IV) salt, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium di-2-ethylhexoxy Bis (2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis (ethyl acetoacetate) and the like are preferable.

Among these compounds, from the viewpoint of reliability after the HTS test, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone zirconium (IV) salt, acetylacetone nickel (II) salt, trifluoroacetylacetone aluminum ( III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone nickel (II) salt, trifluoroacetylacetone zirconium (IV) salt, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium di 2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide) and titanium diisopropoxybis (ethylacetoacetate) are preferred, and adhesion on a silicon wafer From the viewpoint of acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone zirconium (IV) salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone zirconium (IV) salt And titanium diisopropoxybis (acetylacetonate) are preferred.
Among these crosslinking agents described in (B-2-1) to (B-2-12), from the viewpoint of reliability after the HTS test, (B-2-1) methylol group and / or alkoxymethyl group Containing compound, (B-2-2) oxirane compound, (B-2-3) isocyanate group-containing compound, (B-2-4) bismaleimide group-containing compound, (B-2-5) aldehyde group-containing compound, (B-2-6) oxetane ring-containing compound, (B-2-7) benzoxazine ring-containing compound, (B-2-8) oxazoline ring-containing compound, and (B-2-10) allyl compound are preferred, B-2-1) methylol group and / or alkoxymethyl group-containing compound, (B-2-3) isocyanate group-containing compound, (B-2-4) bismaleimide group-containing compound, (B-2-6) oxetane Ring-containing compound (B 2-7) benzoxazine ring-containing compound, (B-2-10) allyl compounds are more preferred, and most preferably (B-2-1) methylol groups and / or alkoxymethyl group-containing compound.

｛式中、Ｒｓ１は、水素原子、メチル基、エチル基、n-プロピル基、及びイソプロピル基からなる群より選ばれる一価の基であり、Ｒｓ２は水酸基、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数１〜１０のエステル基、およびウレタン基からなる群より選ばれる基であり、ｍｍ１は１〜５の整数であり、ｍｍ２は０〜４の整数である。ここで、１≦（ｍｍ１＋ｍｍ２）≦５であり、ｎｎ１は１〜４の整数であり、Ｖ_１はｎｎ１＝１のときＣＨ_２ＯＲｓ１であり、ｎｎ１＝２〜４のとき、単結合また２〜４価の有機基である。ＣＨ_２ＯＲｓ１およびＲ_１０が複数存在する場合、これらは互いに同一でも異なっていてもよい。｝で表されるメチロール化合物及びアルコキシメチル化合物である。
架橋剤を添加することにより、同じキュア温度での樹脂のガラス転移温度を向上させることができる。樹脂のガラス転移温度が上がることにより、銅の樹脂中へのマイグレーションが抑えられる。 These crosslinking agents (B-2) can be used individually by 1 type or in combination of 2 or more types.
Among the above (B-2) cross-linking agents, (B-2-1) methylol group and / or alkoxymethyl group-containing compounds are preferably used in the present invention, and more preferably used are the following general compounds. Formula (12):

{In the formula, Rs1 is a monovalent group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and Rs2 is a hydroxyl group and an alkyl group having 1 to 10 carbon atoms. , A group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a urethane group, mm1 is an integer of 1 to 5, and mm2 is 0 to 4 It is an integer. Here, 1 ≦ (mm1 + mm2) ≦ 5, nn1 is an integer of 1 to 4, V ₁ is CH ₂ ORs1 when nn1 = 1, and a single bond or 2 to 2 when nn1 = 2-4. It is a tetravalent organic group. When a plurality of CH ₂ ORs1 and R ₁₀ are present, these may be the same as or different from each other. } Is a methylol compound and an alkoxymethyl compound.
By adding a crosslinking agent, the glass transition temperature of the resin at the same curing temperature can be improved. By increasing the glass transition temperature of the resin, migration of copper into the resin is suppressed.

  As a compounding quantity of a crosslinking agent (B-2), 0.1-50 mass parts is preferable with respect to 100 mass parts of resin (A), 1-30 mass parts is more preferable, and it is 5-20 mass parts. More preferably.

(B-3) Fluorine-containing hydrophobic compound (B-3) Fluorine-containing hydrophobic compound in this embodiment will be described in detail below. (B) A fluorine-containing hydrophobic compound will not be specifically limited if it is a compound which contains a fluorine atom in a molecule | numerator and has hydrophobicity.

Compounds that can be suitably used as the (B-3) fluorine-containing hydrophobic compound of the present embodiment are fluorinated acid, fluorinated acrylate, fluorinated methacrylate, fluorinated alcohol, fluorinated alkane, fluorinated ester and fluorinated ester. Such as ether.
<Fluorinated acid>
(B-3) Specific compound examples of the fluorinated acid that is a fluorine-containing hydrophobic compound include perfluoropentanoyl fluoride, perfluorohexanoyl fluoride, perfluoroheptanoyl fluoride, and perfluorooctanoyl fluoride. , Perfluorosuccinoyl fluoride, hexafluoroglutaryl fluoride, octafluoroadipoyl fluoride, perfluoromethoxypropionoyl fluoride, perfluorobutoxyethoxyacetyl fluoride, perfluoropolyether diacrylic fluoride ( n = 1), perfluoropolyether diacrylic fluoride (n = 2), perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perful Rhododecanoic acid, perfluorotetradecanoic acid, perfluorohexadecanoic acid, perfluoro-3,5,5-trimethylhexanoic acid, perfluoro-3,7-dimethyloctanoic acid, perfluorosuccinic acid, perfluoroglutaric acid, perfluoro Adipic acid, perfluorosuberic acid, perfluoroazelineic acid, perfluorosebacic acid, perfluorododecanedioic acid, perfluoro-3,6-dioxaheptanoic acid, perfluoro-3,6,9-trioxadecanoic acid, Perfluoro-3,6-dioxadecanoic acid, perfluoro-3,6,9-trioxatridecanoic acid, perfluoro-3,6-dioxaoctane-1,8-dioic acid, perfluoro-3,6 9-trioxaundecane-1,11-dioic acid and the like are preferably used.
<Fluorinated acrylate>
(B-3) As a specific compound example of fluorinated acrylate which is a fluorine-containing hydrophobic compound, 1H, 1H-perfluoro-n-butyl acrylate, 1H, 1H-perfluoro-n-octyl acrylate, 1H, 1H -Perfluoro-n-decyl acrylate, 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diacrylate, 1H, 1H, 8H, 8H-perfluorotetraethylene glycol diacrylate, 1H, 1H, 6H , 6H-perfluorotriethylene glycol diacrylate, 1H, 1H, 4H, 4H-perfluorodiethylene glycol diacrylate, 1H, 1H, 10H, 10H-pentaethylene glycol diacrylate, 1H, 1H, 18H, 18H-nonaethylene glycol Diac Relay Perfluoro-1,6-hexanediol diacrylate, perfluorotetraethylene glycol diacrylate, perfluorotriethylene glycol diacrylate, perfluorodiethylene glycol diacrylate, pentaethylene glycol diacrylate, nonaethylene glycol diacrylate, and the like are preferably used. It is done. Among them, 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diacrylate and 1H, 1H, 8H, 8H-perfluorotetraethylene glycol diacrylate are particularly preferably used. Available as C6DIACRY and product name DA-F4EO.
<Fluorinated methacrylate>
(B-3) As a specific compound example of fluorinated methacrylate which is a fluorine-containing hydrophobic compound, 1H, 1H-perfluoro-n-butyl methacrylate, 1H, 1H-perfluoro-n-octyl methacrylate, 1H, 1H -Perfluoro-n-decyl methacrylate, 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol dimethacrylate, 1H, 1H, 8H, 8H-perfluorotetraethylene glycol dimethacrylate, 1H, 1H, 6H , 6H-perfluorotriethylene glycol dimethacrylate, 1H, 1H, 4H, 4H-perfluorodiethylene glycol dimethacrylate, 1H, 1H, 10H, 10H-pentaethylene glycol dimethacrylate, 1H, 1H, 18H, 18H-nonaethylene glycol Dimethacrylate, perfluoro-1,6-hexanediol dimethacrylate, perfluorotetraethylene glycol dimethacrylate, perfluorotriethylene glycol dimethacrylate, perfluorodiethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, etc. Is preferably used.
<Fluorinated alcohol>
(B-3) As a specific compound example of the fluorinated alcohol which is a fluorine-containing hydrophobic compound, 1H, 1H-perfluoro-1-hexanol, 1H, 1H-perfluoro-1-heptanol, 1H, 1H-per Fluoro-1-octanol, 1H, 1H-perfluoro-1-nonanol, 1H, 1H-perfluoro-1-decanol, 1H, 1H-perfluoro-1-undecanol, 1H, 1H-perfluoro-1-dodecanol, 1H, 1H-perfluoro-1-tetradecanol, 1H, 1H-perfluoro-1-hexadecanol, perfluoro-3,5,5-trimethylhexane-1-ol, perfluoro-3,7-dimethyl Octane-1-ol, 1H, 1H, 4H, 4H-perfluoro-1,4-butanediol, 1H, 1H 5H, 5H-perfluoro-1,5-pentanediol, 1H, 1H, 5H, 5H-perfluoro-1,5-pentanediol, 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol, 1H, 1H, 8H, 8H-perfluoro-1,8-octanediol, 1H, 1H, 9H, 9H-perfluoro-1,9-nonanediol, 1H, 1H, 10H, 10H-perfluoro-1,10 -Decanediol, 1H, 1H, 12H, 12H-perfluoro-1,12-dodecanediol, perfluoro-tert-butanol, fluorinated diethylene glycol monomethyl ether, fluorinated triethylene glycol monomethyl ether, fluorinated diethylene glycol monobutyl ether, fluorine Triethylene glycol monobuty Ether, fluorinated triethylene glycol, and fluorinated tetraethylene glycol are preferably used.
<Fluorinated alkane>
(B-3) Specific examples of the fluorinated alkane that is a fluorine-containing hydrophobic compound include perfluoroheptane, perfluorooctane, perfluorononane, perfluorotridecane, perfluoropentadecane, 1H-perfluoropentane, 1H-perfluorohexane, 1H-perfluoroheptane, 1H-perfluorooctane, 1H-perfluorononane, 1H-perfluorodecane, 1H-perfluoroundecane, 1H-perfluorotridecane, 1H-perfluoropentadecane, 1H -Perfluoro-2,4,4-trimethylpentane, 1H-perfluoro-2,6-dimethylheptane, 1H, 4H-perfluorobutane, 1H, 6H-perfluorohexane 1H, 7H-perfluoroheptane, 1H, 8H-Perful Rookutan, IH, 10H-like perfluoro decane are preferably used.
<Fluorinated ester>
(B-3) Specific examples of the fluorinated ester that is a fluorine-containing hydrophobic compound include methyl perfluoropentanoate, methyl perfluorohexanoate, methyl perfluoroheptanoate, methyl perfluorooctanoate, and perfluorononane. Methyl acid, methyl perfluorodecanoate, methyl perfluoroundecanoate, methyl perfluorododecanoate, methyl perfluorotetradecanoate, methyl perfluorohexadecanoate, dimethyl perfluorosuccinate, dimethyl perfluoroglutarate, perfluoroadipic acid Dimethyl, dimethyl perfluorosuberate, dimethyl perfluoroazelate, dimethyl perfluorosebacate, dimethyl perfluoro-1,12-decanedionate, perfluoro-3,6-dioxaheptane Methyl, perfluoro-3,6,9-trioxadecanoic acid methyl, perfluoro-3,6-dioxadecanoic acid methyl, perfluoro-3,6,9-trioxatridecanoic acid methyl, perfluoro-3,6 -Dioxaoctane-1,8-dioic acid dimethyl, perfluoro-3,6,9-trioxaundecane-1,11-dioic acid dimethyl, etc. are preferably used.
<Fluorinated ether>
(B-3) Specific examples of fluorinated ethers that are fluorine-containing hydrophobic compounds are preferably perfluoro (diethylene glycol dimethyl ether), perfluoro (triethylene glycol dimethyl ether), perfluoro (triethylene glycol dimethyl ether), and the like. Used.

  (B-3) It is preferable that the weight ratio of the fluorine atom in the molecule | numerator of a fluorine-containing hydrophobic compound is 30 to 80 mass%. When the weight ratio of fluorine is lower than the above range, sufficient hydrophobicity cannot be obtained. Further, if there is more fluorine than the above range, the compatibility with the solvent is lowered, and it becomes difficult to obtain a coating film having uniform surface flatness, which is not preferable. A more preferable range of the fluorine content is 35% by mass or more and 75% by mass or less.

  The (B-3) fluorine-containing hydrophobic compound in this embodiment preferably has at least one unsaturated double bond in the molecule. When it has an unsaturated double bond, in the exposure step, a crosslinking reaction proceeds between (B-3) molecules between the fluorine-containing hydrophobic compounds and between (A) molecules with the resin. Thereby, (B-3) the fluorine-containing hydrophobic compound is less likely to volatilize during the heat treatment, and the hydrophobic effect can be sufficiently exhibited. Examples of suitable unsaturated double bonds include acrylates and methacrylates.

  (B-3) As content of a fluorine-containing hydrophobic compound, 0.01-50 mass parts is preferable with respect to 100 mass parts of resin (A), 0.02-30 mass parts is more preferable, and 0.0. More preferably, it is 05-20 mass parts. If the content is higher than the above range, the compatibility with the solvent is lowered, and it becomes difficult to obtain a coating film with uniform surface flatness, which is not preferable. If the content is lower than the above range, the hydrophobic effect is sufficient. Therefore, voids are easily generated between the copper surface and the copper surface.

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

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

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

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

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

  In the case of the negative type, the blending amount of these photosensitizers is 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A), and preferably 2 to 15 parts by mass from the viewpoint of photosensitivity characteristics. (C) It is excellent in photosensitivity by mix | blending 1 mass part or more of photosensitive agents with respect to 100 mass parts of (A) resin, and is excellent in thick film curability by mix | blending 50 mass parts or less.

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

  The compounding amount of the (meth) acrylic compound having an amino group is 1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and 2 to 15 parts by mass is preferable from the viewpoint of photosensitivity characteristics. (C) As photosensitizer, (meth) acrylic compound having an amino group is blended in an amount of 1 part by mass or more with respect to 100 parts by mass of (A) resin. Excellent in properties.

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

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

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

｛式中、Ｘ_１１及びＸ_１２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、Ｘ_１３及びＸ_１４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、Ｘ_１５、Ｘ_１６、Ｘ_１７及びＸ_１８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、Ｘ_２０〜Ｘ_２９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Ｙ_１０、Ｙ_１１及びＹ_１２は、各々独立に、単結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯ₂−、シクロペンチリデン、シクロヘキシリデン、フェニレン、及び炭素数１〜２０の２価の有機基からなる群から選択される２価の基を表す。｝で表される。 In the present embodiment, (C) the compound having a quinonediazide group is a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a hydroxy compound represented by the following general formulas (70) to (74) and / or 1, 2-Naphthoquinonediazide-5-sulfonic acid ester is preferable from the viewpoints of sensitivity and resolution when forming a resist pattern.
General formula (70) is

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

{In the formula, Z represents a tetravalent organic group having 1 to 20 carbon atoms, and X ₁₅ , X ₁₆ , X ₁₇ and X ₁₈ each independently represent a monovalent organic group having 1 to 30 carbon atoms. R6 is an integer of 0 or 1, r5, r7, r8 and r9 are each independently an integer of 0 to 3, and r10, r11, r12 and r13 are each independently 0 to 2 And all of r10, r11, r12, and r13 cannot be zero. }.
In addition, the general formula (72) is

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

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

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

{Wherein, r17, r18, r19 and r20 are each independently an integer of 0 to 2, r17, r18, at least one of r19 and r20 is 1 or _2, X 20 _{to X 29} is Each independently represents a monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group and an acyl group, and Y ₁₀ , Y ₁₁ and Y ₁₂ are Each independently a single bond, —O—, —S—, —SO—, —SO ₂ —, —CO—, —CO ₂ —, cyclopentylidene, cyclohexylidene, phenylene, and C 1-20 Represents a divalent group selected from the group consisting of divalent organic groups. }.

｛式中、Ｘ_３０及びＸ_３１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、Ｘ_３２、Ｘ_３３、Ｘ_３４及びＸ_３５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Ｘ_３６、Ｘ_３７、Ｘ_３８及びＸ_３９は、各々独立に、水素原子又はアルキル基を表す。｝
で表される３つの２価の有機基から選択されることが好ましい。 In a further embodiment, in General Formula (74) above, Y _{10 to} Y ₁₂ are each independently the following General Formula:

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

｛式中、ｒ１６は、各々独立に、０〜２の整数であり、そしてＸ_４０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、Ｘ_４０が複数で存在する場合には複数のＸ_４０は、互いに同一でも又は異なっていてもよく、そしてＸ_４０は、下記一般式： Examples of the compound represented by the general formula (70) include hydroxy compounds represented by the following formulas (75) to (79).
Here, the general formula (75) is

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

（式中、ｒ１８は、０〜２の整数であり、Ｘ_４１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Ｘ_４１は、互いに同一でも又は異なっていてもよい。）
で表される１価の有機基であることが好ましい。｝であり、
一般式（７６）は、

(Wherein, the r18, is an integer of 0 to 2, X ₄₁ is a hydrogen atom, an alkyl group, and a monovalent organic radical selected from the group consisting of cycloalkyl, and r18 is 2 In some cases, the two X ₄₁ may be the same or different from each other.)
It is preferable that it is a monovalent organic group represented by these. },
The general formula (76) is

｛式中、Ｘ_４２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, _X42 is a monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms. Represents. }.
Further, the general formula (77) is

｛式中、ｒ１９は、各々独立に、０〜２の整数であり、Ｘ_４３は、各々独立に、水素原子又は下記一般式：

{Wherein, r19 are each independently an integer of 0 to _{2, X 43} are each independently a hydrogen atom or the following general formula:

（式中、ｒ２０は、０〜２の整数であり、Ｘ_４５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Ｘ_４５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Ｘ_４４は、水素原子、炭素数１〜２０のアルキル基、及び炭素数１〜２０のシクロアルキル基からなる群から選択される。｝であり、式（７８）及び（７９）は、下記のごとく構造である。

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

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

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

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

Is preferable because it has high sensitivity when it is converted into an NQD compound and has low precipitation in the photosensitive resin composition.

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

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

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

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

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

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

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

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

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

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

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

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

｛式中、Ｑは、水素原子、又は下記式群：

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

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

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

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

で表されるものが特に好ましい。 Among the naphthoquinone diazide sulfonic acid ester groups described in paragraph [0243] above, the following general formula (95):

Is particularly preferred.

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

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

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

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

  In this embodiment, the compounding quantity of the compound which has (C) quinonediazide group in the photosensitive resin composition is 0.1 mass part-70 mass parts with respect to 100 mass parts of (A) resin, Preferably 1 mass part-40 mass parts, More preferably, they are 3 mass parts-30 mass parts, More preferably, they are 5 mass parts-30 mass parts. If this compounding amount is 0.1 parts by mass or more, good sensitivity is obtained, while if it is 70 parts by mass or less, the mechanical properties of the cured film are good.

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

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

<Solvent>

  Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, and the like. For example, N-methyl-2- Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, Ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol Use coal dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. be able to. Among them, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene from the viewpoints of resin solubility, resin composition stability, and adhesion to a substrate. Glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

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

  Suitable solvents for the above phenolic resins include bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone. , Toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone and the like, but are not limited thereto.

  In the photosensitive resin composition of this invention, the usage-amount of a solvent becomes like this. Preferably it is 100-1000 mass parts with respect to 100 mass parts of (A) resin, More preferably, it is 120-700 mass parts, More preferably Is in the range of 125 to 500 parts by mass.

  The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (C).

  For example, when a cured film is formed on a substrate made of copper or a copper alloy using the photosensitive resin composition of the present invention, a nitrogen-containing complex such as an azole compound or a purine derivative is used to suppress discoloration on copper. A ring compound can be arbitrarily blended.

  Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, and 4-t-butyl-5. -Phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxyphenyl Triazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- Bis (α, α-dimethylben Dil) phenyl] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5 -Methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl -1H-tetrazole, 5-amino-1H-tetra Lumpur, 1-methyl -1H- tetrazole, and the like.

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

  Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) Guanine, N- (3-ethylphenyl) guanine, 2-aza Adenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, it includes 8-aza hypoxanthine or their derivatives.

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

  Moreover, in order to suppress discoloration on the copper surface, a hindered phenol compound can be arbitrarily blended. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl-4. -Hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4, 4′-thio-bis (3-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphene) ) Propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-) t-butyl-4-hydroxy-hydrocinnamamide), 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis (4-ethyl-6-t) -Butylphenol),

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

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

  1,3,5-tris (4-t-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1, 3,5-tris (4-t-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1, 3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, etc. However, it is not limited to this. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione and the like are particularly preferred.

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

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

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

  Also, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol, which are oxirane compounds -Naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 1 , 1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, glycerol triglycidyl Ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (Above product name, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (above product name, Japan) Manufactured by Kayaku Co., Ltd.), Epicoat (registered trademark) 1001, Epicoat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051, Epicoat 1031S, Epicoat 180S65, Epicoat 157H70, YX-315-75 (Product name, Japan Epoxy Resin Co., Ltd.), EHPE3150, Plaxel G402, PUE101, PUE105 (Product name, Daicel Chemical Industries, Ltd.), Epicron (registered trademark) 830, 850, 1050, N-680 N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (above trade name, manufactured by DIC), Denacol (registered trademark) EX-201, EX-251, EX -203, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-711, EX-731, EX-810 EX-911, EM-150 (trade name, manufactured by Nagase ChemteX), Epolite (registered trademark) 70P, E Examples include Polite 100MF (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

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

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

  As a compounding quantity in the case of using a crosslinking agent, it is preferable that it is 0.5-20 mass parts with respect to 100 mass parts of (A) resin, More preferably, it is 2-10 mass parts. When the blending amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are expressed, and when it is 20 parts by mass or less, the storage stability is excellent.

The photosensitive resin composition of the present invention may contain an organic titanium compound. By containing an organic titanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature of about 250 ° C. In particular, when both the (B) compound and the organic titanium compound are contained in the photosensitive resin composition, the cured resin layer has an effect of being excellent in chemical resistance in addition to the substrate adhesiveness.
In particular, by including both (B-1) nanoparticles and an organic titanium compound in the photosensitive resin composition, the effect that the cured resin layer is excellent in chemical resistance in addition to substrate adhesion is obtained. Play.
In particular, (B-2) the effect that the cured resin layer is excellent in chemical resistance in addition to the substrate adhesiveness by including both the thermal crosslinking agent and the organic titanium compound in the photosensitive resin composition. Play.
In particular, by including both the compound (B-3) and the organic titanium compound in the photosensitive resin composition, the cured resin layer has the effect of being excellent in chemical resistance in addition to substrate adhesion. .

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

Specific examples of organic titanium compounds are shown in the following I) to VII):
I) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable because it provides storage stability and a good pattern of the negative photosensitive resin composition, and a specific example is titanium bis (Triethanolamine) diisopropoxide, titanium di (n-butoxide) bis (2,4-pentanedionate, titanium diisopropoxide bis (2,4-pentanedionate), titanium diisopropoxide bis ( Tetramethylheptanedionate), titanium diisopropoxide bis (ethylacetoacetate) and the like.

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

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

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

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

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

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

Among them, the organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound. It is preferable from the viewpoint. In particular, titanium diisopropoxide bis (ethyl acetoacetate), titanium tetra (n-butoxide), and bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- ( 1H-pyrrol-1-yl) phenyl) titanium is preferred.

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

  Furthermore, an adhesion assistant can be arbitrarily blended for improving the adhesion between the film formed using the photosensitive resin composition of the present invention and the substrate. Adhesion aids include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3′-bis (N- [3-triethoxysilyl] propylamide) -4,4′-dicarboxylic acid, benzene-1, 4-bis (N- [3-trie Toxisilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane Silane coupling agents such as 3- (trialkoxysilyl) propyl succinic anhydride, and aluminum-based adhesives such as aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethyl acetoacetate aluminum diisopropylate An auxiliary agent etc. are mentioned.

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

  As the silane coupling agent, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name: Sila Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation): Trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS1375, manufactured by Azumax Co., Ltd .: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azumax Corporation: product) Name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropyl eth Sidimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercapto Ethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4 -Mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (manufactured by Azmax Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N -(3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N -(3-Methoxydipropoxy Silylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-tripropoxysilylethyl) ) Urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxysilylbutyl) ) Urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0598.0 ), M-aminophenyltrimethoxysilane (Azmax Co., Ltd.) Product name: SLA0599.0), p-aminophenyltrimethoxysilane (Azmax Co., Ltd .: product name SLA0599.1) Aminophenyltrimethoxysilane (Azmax Co., Ltd .: Product name SLA0599.2), 2- ( (Trimethoxysilylethyl) pyridine (manufactured by Azmax Co., Ltd .: trade name SIT83396), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra- n- Toxisilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxysilane), bis ( Trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxy Silyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxy Citriethoxysilane, bis (pentadionate) titanium-O, O'-bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropyl Phenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n- Propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenol Lucilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n- Examples include, but are not limited to, propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like. These may be used alone or in combination.

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

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

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

  (A) In the case of a negative type using a polyimide precursor or polyamide as a resin, a sensitizer can be arbitrarily blended in order to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4′-diethylaminobenzal) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) chalcone, 4,4′-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaphthothiazole, 1,3-bis (4 ′ Dimethylaminobenzal) acetone, 1,3-bis (4′-diethylaminobenzal) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxy Carbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N′-ethylethanolamine N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) ) Naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. These can be used alone or in combination of, for example, 2 to 5 kinds.

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

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

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

  Further, in the case of a negative type using a polyimide precursor or polyamide as the resin (A), the viscosity of the photosensitive resin composition and the stability of photosensitivity during storage in the state of a solution containing a solvent are improved. Therefore, a thermal polymerization inhibitor can be arbitrarily blended. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6 -Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N- Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

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

  On the other hand, in the photosensitive resin composition of the present invention, in the case of a positive type using (A) a polyoxazole precursor, a soluble polyimide, a phenol resin, or the like as the resin, addition of a photosensitive resin composition is conventionally required. Dyes used as agents, surfactants, thermal acid generators, dissolution accelerators, adhesion aids for improving adhesion to the substrate, and the like can be appropriately added.

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

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

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

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

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

  Among these, di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid, di (t-butylphenyl) iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethyl of trifluoromethanesulfonic acid Phenylsulfonium salt, diphenylmethylsulfonium salt of trifluoromethanesulfonic acid, di (t-butylphenyl) iodonium salt of nonafluorobutanesulfonic acid, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, benzenesulfonic acid A dimethylphenylsulfonium salt, a diphenylmethylsulfonium salt of toluenesulfonic acid, and the like are preferable.

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

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

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

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

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

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

(1) The process of forming a resin layer on this board | substrate by apply | coating the photosensitive resin composition on a board | substrate In this process, the photosensitive resin composition of this invention is apply | coated on a base material, and as needed. Thereafter, the resin layer is formed by drying. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., spray coating with a spray coater A method or the like can be used.

  As a method for forming a relief pattern using the photosensitive resin composition of the present invention, the photosensitive resin composition is not only applied to a substrate by coating the photosensitive resin composition on the substrate, but also the photosensitive resin composition. The resin layer may be formed by laminating a photosensitive resin composition layer on a substrate in the form of a film. Further, a film of the photosensitive resin composition according to the present invention may be formed on a supporting substrate, and the supporting substrate may be removed after being laminated when the film is used, or removed before laminating. May be.

  If necessary, the coating film made of the photosensitive resin composition can be dried. As a drying method, methods such as air drying, heat drying using an oven or a hot plate, vacuum drying, and the like are used. Specifically, when performing air drying or heat drying, drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. As described above, the resin layer can be formed on the substrate.

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

  Thereafter, post-exposure baking (PEB) and / or pre-development baking with any combination of temperature and time may be performed as necessary for the purpose of improving photosensitivity. The range of the baking conditions is that the temperature is 40 to 120 ° C. and the time is preferably 10 seconds to 240 seconds, but this range is not used unless it inhibits the various characteristics of the photosensitive resin composition of the present invention. Not limited to.

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

  The developer used for development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent. For example, in the case of a photosensitive resin composition that does not dissolve in an alkaline aqueous solution, good solvents include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α -Acetyl-γ-butyrolactone and the like are preferable, and as the poor solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When mixing and using a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Also, two or more of each solvent, for example, several types may be used in combination.

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

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

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

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

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

<Semiconductor device>
The present invention also provides a semiconductor device including a cured relief pattern obtained by the above-described method for producing a cured relief pattern of the present invention. The present invention also provides a semiconductor device including a base material that is a semiconductor element and a cured relief pattern of a resin formed on the base material by the above-described cured relief pattern manufacturing method. The present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a cured relief pattern as part of the process. The semiconductor device of the present invention is a semiconductor device having a surface relief film, an interlayer insulation film, a rewiring insulation film, a flip chip device protection film, or a bump structure as a cured relief pattern formed by the above-described cured relief pattern production method. And can be manufactured by combining with a known method for manufacturing a semiconductor device.

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

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

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

(2) Creation of cured relief pattern on Cu 200 nm on a 6-inch silicon wafer (Fujimi Electronics Industry Co., Ltd., thickness: 625 ± 25 μm) using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva) Thick Ti and 400 nm thick Cu were sputtered in this order. Subsequently, a photosensitive resin composition prepared by the method described later is spin-coated on this wafer using a coater developer (D-Spin60A type, manufactured by SOKUDO) and dried to form a 10 μm thick coating film. (In the second example, a coating film having a thickness of 6 to 10 μm was formed). This coating film was irradiated with energy of 300 mJ / cm ² by a parallel light mask aligner (PLA-501FA type, manufactured by Canon Inc.) using a mask with a test pattern. Next, this coating film is spray-developed with a coater developer (D-Spin60A type, manufactured by SOKUDO) using cyclopentanone as a developing solution in the case of negative type and 2.38% TMAH in the case of positive type, In the negative type, a relief pattern on Cu was obtained by rinsing with propylene glycol methyl ether acetate, and in the positive type with pure water.

  The wafer having the relief pattern formed on Cu is heat-treated at a temperature described in each example for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg). Thus, a cured relief pattern made of a resin having a thickness of about 6 to 7 μm was obtained on Cu.

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

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

<First embodiment>
As a first example, the following experiment was performed.

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

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

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

In addition, the weight average molecular weight of resin obtained by each manufacture example was measured on condition of the following using gel permeation chromatography (GPC), and calculated | required the weight average molecular weight in standard polystyrene conversion.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l LiBr / NMP
Flow rate: 1 ml / min.

<Production Example 2> ((A) Synthesis of Polymer (A) -2 as Polyimide Precursor)
Instead of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in Production Example 1, 147.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was used. Except for the above, the reaction was carried out in the same manner as in the method described in Production Example 1 to obtain polymer (A) -2. When the molecular weight of the polymer (A) -2 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Production Example 3> ((A) Synthesis of Polymer (A) -3 as Polyimide Precursor)
Except for using 147.8 g of 2,2′-bistrifluoromethyl-4,4′-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example 1, A reaction was carried out in the same manner as in the method described in Production Example 1 to obtain a polymer (A) -3. When the molecular weight of the polymer (A) -3 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

<Production Example 4> (Synthesis of polymer (A) -4 as (A) polyamide)
(Synthesis of Phthalic Acid Compound Encapsulated AIPA-MO)
In a separable flask having a volume of 5 l, 5-aminoisophthalic acid {hereinafter abbreviated as AIPA. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50 ° C. in a water bath. A solution obtained by diluting 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone was added dropwise thereto using a dropping funnel, and the mixture was stirred at 50 ° C. for about 2 hours.

  Completion of the reaction (disappearance of 5-aminoisophthalic acid) is described as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, The reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product was crystallized and precipitated, it was filtered, washed with water, and vacuumed at 40 ° C. for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate acted was obtained. The obtained AIPA-MO had a low molecular weight GPC purity of about 100%.

(Synthesis of polymer (A) -4)
Into a separable flask having a volume of 2 liters, 100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added and mixed, and cooled to 5 ° C. in an ice bath. did. A solution obtained by dissolving and diluting 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) in 125 g of GBL was added dropwise thereto over about 20 minutes under ice-cooling, followed by 4,4′-bis (4-aminophenoxy). ) Biphenyl {Hereinafter referred to as BAPB. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and stirred at room temperature for 5 hours. did. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

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

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

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

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

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

  2,2-bis (3-amino-4-hydroxyphenyl) propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5- (2,5-dioxotetrahydro-3-furanyl) 70.29 g (266 mmol) of -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone and 60 g of toluene were added at room temperature. After stirring at 100 rpm for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and a silicon bath temperature of 50 ° C. was passed through nitrogen gas. The mixture was heated and stirred at 100 rpm for 8 hours. Thereafter, the silicon bath was heated to 180 ° C. and stirred with heating at 100 rpm for 2 hours. During the reaction, distillates of toluene and water were removed. After completion of the imidization reaction, the temperature was returned to room temperature.

  Thereafter, the reaction solution was dropped into 3 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water and dehydrated, and then measured by gel permeation chromatography (GPC). A crude polyimide (polymer (A) -6) having a weight average molecular weight of 23,000 (polystyrene conversion) was obtained.

<Production Example 7> ((A) Synthesis of polymer (A) -8 as phenol resin)
A separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, p-toluenesulfone 3.81 g (0.02 mol) of acid and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred at 50 ° C. to dissolve the solid matter.

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

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

  After completion of the reaction, the same treatment as in Production Example 7 was performed to obtain a copolymer (polymer H) composed of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol in a yield of 77%. The weight average molecular weight of this polymer H determined by standard polystyrene conversion by GPC method was 9,900.

で表される、フェノール性水酸基の７７％をナフトキノンジアジド−４−スルホン酸エステル化した感光性ジアゾキノン化合物（東洋合成社製、（Ｃ）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、５．１％という結果を得た。
＜実施例１８＞
上記実施例１７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１７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、６．２％という結果を得た。
＜実施例１９＞
上記実施例１７において、（Ａ）樹脂として、ポリマー（Ａ）−６、１００ｇをポリマー（Ａ）−７（ノボラック樹脂、ポリスチレン換算重量平均分子量（Ｍｗ）＝１０，６００（旭有機材社製、製品名ＥＰ−４０８０Ｇ）、１００ｇに変えたこと以外は、実施例１７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、５．２％という結果を得た。
＜実施例２０＞
上記実施例１７において、（Ａ）樹脂として、ポリマー（Ａ）−６、１００ｇをポリマー（Ａ）−７（ノボラック樹脂、ポリスチレン換算重量平均分子量（Ｍｗ）＝１０，６００（旭有機材社製、製品名ＥＰ−４０８０Ｇ）、１００ｇに変え、（Ｂ）成分を酪酸テトラヒドロフルフリル（東京化成工業株式会社製）に変えたこと以外は、実施例１７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、５．６％という結果を得た。
＜実施例２１＞
上記実施例１７において、（Ａ）樹脂として、ポリマー（Ａ）−６、１００ｇをポリマー（Ａ）−８、１００ｇに変えたこと以外は、実施例１７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、４．６％という結果を得た。
＜実施例２２＞
上記実施例１７において、（Ａ）樹脂として、ポリマー（Ａ）−６、１００ｇをポリマー（Ａ）−８、１００ｇに変え、（Ｂ）成分を酪酸テトラヒドロフルフリル（東京化成工業株式会社製）に変えたこと以外は、実施例１７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、４．３％という結果を得た。
＜比較例１＞
実施例１の組成に、（Ｂ）−１成分を添加しない他は、実施例１と同様にしてネガ型感光性樹脂組成物を調製し、実施例１と同様の評価を行なった。評価結果は、本発明の（Ｂ）可塑剤を含まないため１５．２％であった。
＜比較例２＞
実施例１６の組成に、（Ｂ）−１成分を添加しない他は、実施例１５と同様にしてネガ型感光性樹脂組成物を調製し、実施例１５と同様の評価を行なった。評価結果は、本発明の（Ｂ）可塑剤を含まないため１４．３％であった。
＜比較例３＞
実施例１４の組成に、（Ｂ）−１成分を添加しない他は、実施例１３と同様にしてネガ型感光性樹脂組成物を調製し、実施例１３と同様の評価を行なった。評価結果は、本発明の（Ｂ）可塑剤を含まないため１５．７％であった。
＜比較例４＞
実施例１８の組成に、（Ｂ）−１成分を添加しない他は、実施例１７と同様にしてポジ型感光性樹脂組成物を調製し、実施例１７と同様の評価を行なった。評価結果は、本発明の（Ｂ）可塑剤を含まないため１６．３％であった。
＜比較例５＞
実施例１の組成に、（Ｂ）−１成分の添加量を０．０５ｇに変更したこと以外は、実施例１と同様にしてネガ型感光性樹脂組成物を調製し、実施例１と同様の評価を行なった。評価結果は、１３．１％であった。
＜比較例６＞
実施例１の組成に、（Ｂ）−１成分の添加量を６０ｇに変更したこと以外は、実施例１と同様にしてネガ型感光性樹脂組成物を調製し、実施例１と同様の評価を行なった。評価結果は、１５．２％であった。
これら実施例１〜２２、比較例１〜６の結果を表１にまとめて示す。

<Example 1>
A negative photosensitive resin composition was prepared by the following method using the polymers (A) -1 and (A) -2, and the photosensitive resin composition was evaluated. 50 g of polymer (A) -1 which is a polyimide precursor and 50 g of (A) -2 (corresponding to (A) resin), dicyclohexyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd., corresponding to (B) -1) 4 g, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (described as “PDO” in Table 1) (corresponding to (C) sensitizer), 4 g, tetraethylene glycol di Along with 8 g of methacrylate and 1.5 g of N- [3- (triethoxysilyl) propyl] phthalamic acid, it was dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the above mixed solvent to obtain a negative photosensitive resin composition.
About this composition, it cured at 230 degreeC by the above-mentioned method, and after producing a hardening relief pattern on Cu layer and performing a high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 4.1. % Results were obtained.
<Example 2>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the component (B) was changed to diphenyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 4.9 % Results were obtained.
<Example 3>
In Example 1 above, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the component (B) was changed to di-2-ethylhexyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.). .
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.2. % Results were obtained.
<Example 4>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that the component (B) was changed to dicyclohexyl trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.).
The composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids in the surface of the Cu layer was evaluated. 4.3 % Results were obtained.
<Example 5>
A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the component (B) was changed to dicyclohexyl pyromellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 4.2. % Results were obtained.
<Example 6>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that the component (B) was changed to dicyclohexyl adipate (manufactured by Tokyo Chemical Industry Co., Ltd.).
About this composition, it cured at 230 degreeC by the above-mentioned method, and after producing a hardening relief pattern on Cu layer and performing a high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.9 % Results were obtained.
<Example 7>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that the component (B) was changed to dicyclohexyl sebacate (manufactured by Tokyo Chemical Industry Co., Ltd.).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.8 % Results were obtained.
<Example 8>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the component (B) was changed to tetrahydrofurfuryl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.).
The composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated. % Results were obtained.
<Example 9>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the addition amount of the component (B) -1 was changed to 2 g.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 7.6 % Results were obtained.
<Example 10>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the addition amount of the component (B) -1 was changed to 8 g.
The composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated. % Results were obtained.
<Example 11>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the addition amount of the component (B) -1 was changed to 16 g.
About this composition, after curing at 230 ° C. by the above-mentioned method to produce a cured relief pattern on the Cu layer and conducting a high-temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. % Results were obtained.
<Example 12>
A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the curing temperature was changed from 230 ° C. to 350 ° C. in Example 1.
For this composition, a cured relief pattern was prepared on the Cu layer and subjected to a high-temperature storage test. Then, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.5% was obtained.
<Example 13>
In Example 1 above, as the (A) resin, the polymer (A) -1, 50 g and the polymer (A) -2, 50 g were converted into the polymer (A) -1, 100 g, and the component (C) was changed from PDO 1, Example 1 with the exception that 2-octanedione, 1- {4- (phenylthio)-, 2- (O-benzoyloxime)} (Irgacure OXE01 (trade name, manufactured by BASF)) was changed to 2.5 g. In the same manner, a negative photosensitive resin composition solution was prepared.
For this composition, a cured relief pattern was prepared on the Cu layer and subjected to a high-temperature storage test. Then, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.3% was obtained.
<Example 14>
A negative photosensitive resin composition solution was prepared in the same manner as in Example 12 except that the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide in Example 12.
For this composition, a cured relief pattern was prepared on the Cu layer and subjected to a high-temperature storage test. Then, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.5% was obtained.
<Example 15>
In Example 1 above, as the (A) resin, the polymer (A) -1, 50 g and the polymer (A) -2, 50 g are changed to the polymer (A) -3, 100 g, and the curing temperature is 230 ° C. to 350 ° C. A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the above was changed.
For this composition, a cured relief pattern was prepared on the Cu layer and subjected to a high-temperature storage test. Then, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.8% was obtained.
<Example 16>
In Example 1 above, as the resin (A), Example 1 except that the polymer (A) -1, 50 g and the polymer (A) -2, 50 g were changed to the polymer (A) -4, 100 g. In the same manner, a negative photosensitive resin composition solution was prepared.
A cured relief pattern was prepared on the Cu layer for this composition, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and a result of 4.9% was obtained.
<Example 17>
Using the polymer (A) -5, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Polymer (A) -5 which is a polyoxazole precursor, 100 g (corresponding to (A) resin) is represented by the following formula (96):

A photosensitive diazoquinone compound obtained by converting 77% of a phenolic hydroxyl group into naphthoquinonediazide-4-sulfonic acid ester (produced by Toyo Gosei Co., Ltd., corresponding to the component (C)) (C1) 15 g, γ-butyrolactone (as a solvent) ) Dissolved in 100 g. The viscosity of the resulting solution was adjusted to about 20 poise by further adding a small amount of γ-butyrolactone to obtain a positive photosensitive resin composition.
This composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example 18>
In Example 17, the positive photosensitive resin composition was the same as Example 17 except that the polymer (A) -5, 100 g was changed to the polymer (A) -6, 100 g as the resin (A). A solution was prepared.
The composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids occupied on the surface of the Cu layer was evaluated. 6.2 % Results were obtained.
<Example 19>
In the said Example 17, as (A) resin, polymer (A) -6 and 100g are polymer (A) -7 (Novolac resin, polystyrene conversion weight average molecular weight (Mw) = 10,600 (made by Asahi Organic Materials Co., Ltd., Product name EP-4080G), a positive photosensitive resin composition solution was prepared in the same manner as in Example 17 except that it was changed to 100 g.
The composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids in the surface of the Cu layer was evaluated. 5.2 % Results were obtained.
<Example 20>
In the said Example 17, as (A) resin, polymer (A) -6 and 100g are polymer (A) -7 (Novolac resin, polystyrene conversion weight average molecular weight (Mw) = 10,600 (made by Asahi Organic Materials Co., Ltd., Product name EP-4080G), positive photosensitive resin composition solution in the same manner as in Example 17 except that component (B) was changed to tetrahydrofurfuryl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.). Was prepared.
The composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example 21>
In Example 17, the positive photosensitive resin composition was the same as Example 17 except that the polymer (A) -6, 100 g was changed to the polymer (A) -8, 100 g as the resin (A). A solution was prepared.
The composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids in the surface of the Cu layer was evaluated. % Results were obtained.
<Example 22>
In Example 17 above, as the (A) resin, the polymer (A) -6, 100 g is changed to the polymer (A) -8, 100 g, and the component (B) is changed to tetrahydrofurfuryl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.). A positive photosensitive resin composition solution was prepared in the same manner as in Example 17 except for the change.
The composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids in the surface of the Cu layer was evaluated. 4.3 % Results were obtained.
<Comparative Example 1>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the component (B) -1 was not added to the composition of Example 1, and the same evaluation as in Example 1 was performed. The evaluation result was 15.2% because (B) the plasticizer of the present invention was not included.
<Comparative example 2>
A negative photosensitive resin composition was prepared in the same manner as in Example 15 except that the component (B) -1 was not added to the composition of Example 16, and the same evaluation as in Example 15 was performed. The evaluation result was 14.3% because the plasticizer (B) of the present invention was not included.
<Comparative Example 3>
A negative photosensitive resin composition was prepared in the same manner as in Example 13 except that the component (B) -1 was not added to the composition of Example 14, and the same evaluation as in Example 13 was performed. The evaluation result was 15.7% because the plasticizer (B) of the present invention was not included.
<Comparative Example 4>
A positive photosensitive resin composition was prepared in the same manner as in Example 17 except that the component (B) -1 was not added to the composition of Example 18, and the same evaluation as in Example 17 was performed. The evaluation result was 16.3% because it did not contain the plasticizer (B) of the present invention.
<Comparative Example 5>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the amount of the component (B) -1 added to the composition of Example 1 was changed to 0.05 g. Was evaluated. The evaluation result was 13.1%.
<Comparative Example 6>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the addition amount of the component (B) -1 was changed to 60 g in the composition of Example 1, and the same evaluation as in Example 1 was made. Was done. The evaluation result was 15.2%.
The results of Examples 1 to 22 and Comparative Examples 1 to 6 are summarized in Table 1.

)
<Second embodiment>
As the second example, the following experiment was performed.

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

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

  The obtained reaction liquid was added to 3 l of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 l of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 l of water to precipitate a polymer, and the obtained precipitate was filtered off and then dried in vacuum to obtain a powdery polymer (polymer A). When the molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

In addition, the weight average molecular weight of resin obtained by each manufacture example was measured on condition of the following using gel permeation chromatography (GPC), and calculated | required the weight average molecular weight in standard polystyrene conversion.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l LiBr / NMP
Flow rate: 1 ml / min.

<Production Example 2> ((A) Synthesis of polymer B as polyimide precursor)
Instead of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in Production Example 1, 147.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was used. Except for the above, the reaction was carried out in the same manner as in the method described in Production Example 1 to obtain polymer B. When the molecular weight of the polymer B was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Production Example 3> ((A) Synthesis of polymer C as polyimide precursor)
Except for using 147.8 g of 2,2′-bistrifluoromethyl-4,4′-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example 1, In the same manner as in the method described in Production Example 1, a polymer C was obtained. When the molecular weight of the polymer C was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

<Production Example 4> ((A) Synthesis of polymer D as polyamide)
(Synthesis of Phthalic Acid Compound Encapsulated AIPA-MO)
In a separable flask having a volume of 5 l, 5-aminoisophthalic acid {hereinafter abbreviated as AIPA. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50 ° C. in a water bath. A solution obtained by diluting 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone was added dropwise thereto using a dropping funnel, and the mixture was stirred at 50 ° C. for about 2 hours.

  Completion of the reaction (disappearance of 5-aminoisophthalic acid) is described as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, The reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product was crystallized and precipitated, it was filtered, washed with water, and vacuumed at 40 ° C. for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate acted was obtained. The obtained AIPA-MO had a low molecular weight GPC purity of about 100%.

(Synthesis of polymer D)
Into a separable flask having a volume of 2 liters, 100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added and mixed, and cooled to 5 ° C. in an ice bath. did. A solution obtained by dissolving and diluting 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) in 125 g of GBL was added dropwise thereto over about 20 minutes under ice-cooling, followed by 4,4′-bis (4-aminophenoxy). ) Biphenyl {Hereinafter referred to as BAPB. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and stirred at room temperature for 5 hours. did. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

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

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

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

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

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

  2,2-bis (3-amino-4-hydroxyphenyl) propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5- (2,5-dioxotetrahydro-3-furanyl) 70.29 g (266 mmol) of -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone and 60 g of toluene were added at room temperature. After stirring at 100 rpm for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and a silicon bath temperature of 50 ° C. was passed through nitrogen gas. The mixture was heated and stirred at 100 rpm for 8 hours. Thereafter, the silicon bath was heated to 180 ° C. and stirred with heating at 100 rpm for 2 hours. During the reaction, distillates of toluene and water were removed. After completion of the imidization reaction, the temperature was returned to room temperature.

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

<Production Example 7> ((A) Synthesis of polymer G as phenol resin)
125.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 4,4′-bis (methoxymethyl) biphenyl (hereinafter “BMMB”) in a separable flask with a Dean-Stark device of 0.5 liter capacity It was also referred to as “.” 121.2 g (0.5 mol), diethyl sulfate 3.9 g (0.025 mol), and diethylene glycol dimethyl ether 140 g were mixed and stirred at 70 ° C. to dissolve the solid matter.

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

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

<Production Example 8> ((A) Synthesis of polymer H as phenol resin)
A separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, p-toluenesulfone 3.81 g (0.02 mol) of acid and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred at 50 ° C. to dissolve the solid matter.

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

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

  After completion of the reaction, the same treatment as in Production Example 7 was performed to obtain a copolymer (polymer H) composed of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol in a yield of 77%. The weight average molecular weight of this polymer H determined by standard polystyrene conversion by GPC method was 9,900.

で表される、フェノール性水酸基の７７％をナフトキノンジアジド−４−スルホン酸エステル化した感光性ジアゾキノン化合物（東洋合成社製、（Ｃ）感光剤に該当）（Ｃ１）１５ｇ、リン酸ジルコニウム（長径１００ｎｍ、厚さ５ｎｍの板状粒子、（Ｂ）ナノ粒子に該当）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、５．７％という結果を得た。
＜実施例１１＞
上記実施例１０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１０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１２＞
上記実施例１０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１０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。
＜実施例１３＞
上記実施例１０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１０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。
＜比較例１＞
実施例１の組成に、リン酸ジルコニウムを添加しない他は、実施例１と同様にしてネガ型感光性樹脂組成物を調製し、実施例１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２＞
実施例８の組成に、リン酸ジルコニウムを添加しない他は、実施例８と同様にしてネガ型感光性樹脂組成物を調製し、実施例１０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。
＜比較例３＞
実施例１０の組成に、リン酸ジルコニウムを添加しない他は、実施例１０と同様にしてポジ型感光性樹脂組成物を調製し、実施例１０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。
これらの結果をまとめて表１に示す。 <Example 1>
A negative photosensitive resin composition was prepared using the polymers A and B by the following method, and the prepared photosensitive resin composition was evaluated. Polymer A 50 g and B 50 g (corresponding to (A) resin) which are polyimide precursors, zirconium phosphate (corresponding to (B-1) nano particles having a major axis of 100 nm, a minor axis of 5 nm and an aspect ratio of 20) 5 g 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (described as “PDO” in Table 1) (corresponding to (C) photosensitizer), 4 g of tetraethylene glycol dimethacrylate 8 g and 1.5 g of N- [3- (triethoxysilyl) propyl] phthalamic acid 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. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the above mixed solvent to obtain a negative photosensitive resin composition.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.5. % Results were obtained.
<Example 2>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the amount of zirconium phosphate added as component (B-1) was changed to 1 g.
The composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example 3>
In Example 1, except that montmorillonite (plate-like particles having a major axis of 100 nm, a minor axis of 10 nm, and an aspect ratio of 10) was used as the component (B-1) instead of zirconium phosphate. A negative photosensitive resin composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.8 % Results were obtained.
<Example 4>
In the above Example 1, as the component (B-1), negative type was used in the same manner as in Example 1 except that 1 g of Aerosil (spherical particle having a particle diameter of 12 nm, aspect ratio 1) was used instead of 5 g of zirconium phosphate. A photosensitive resin composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.4 % Results were obtained.
<Example 5>
A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, and this composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and a high-temperature storage test was conducted. After that, the area ratio of voids occupied on the surface of the Cu layer was evaluated, and a result of 4.5% was obtained.
<Example 6>
In Example 1 above, as the (A) resin, the polymer A 50 g and the polymer B 50 g are changed to the polymer A 100 g, and as the component (C), PDO 4 g is changed to 1,2-octanedione, 1- {4- (phenylthio)-, A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the amount was changed to 2.5 g of 2- (O-benzoyloxime)} (Irgacure OXE01 (trade name, manufactured by BASF)).
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.3. % Results were obtained.
<Example 7>
In Example 1 above, as the (A) resin, the polymer A 50 g and the polymer B 50 g, the polymer A 100 g, the (C) component, PDO 4 g, 1,2-octanedione, 1- {4- (phenylthio) -2, -(O-benzoyloxime)} (Irgacure OXE01 (trade name, manufactured by BASF)) was changed to 2.5 g, and the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide in the same manner as in Example 1. A negative photosensitive resin composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.3. % Results were obtained.
<Example 8>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the polymer A (50 g) and the polymer B (50 g) were changed to the polymer C (100 g) as the (A) resin.
The composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. % Results were obtained.
<Example 9>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the polymer A (50 g) and the polymer B (50 g) were changed to the polymer D (100 g) as the (A) resin.
The composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example 10>
A positive photosensitive resin composition was prepared using the polymer E by the following method, and the prepared photosensitive resin composition was evaluated. Polymer E100 g (corresponding to (A) resin), which is a polyoxazole precursor, is represented by the following formula (96):

A photosensitive diazoquinone compound obtained by converting 77% of a phenolic hydroxyl group into naphthoquinonediazide-4-sulfonic acid ester (produced by Toyo Gosei Co., Ltd., (C) corresponds to a photosensitive agent) (C1) 15 g, zirconium phosphate (long diameter It was dissolved in 100 g of γ-butyrolactone (as a solvent) together with 6 g of plate-like particles having a thickness of 100 nm and a thickness of 5 nm (corresponding to (B) nanoparticles) and 5 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 above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example 11>
In Example 10, a positive photosensitive resin composition solution was prepared in the same manner as in Example 10 except that the polymer E100 g was changed to the polymer F100 g as the (A) resin.
This composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids occupied on the surface of the Cu layer was evaluated. % Results were obtained.
<Example 12>
In Example 10, a positive photosensitive resin composition solution was prepared in the same manner as in Example 10 except that the polymer E100 g was changed to the polymer G100 g as the resin (A).
The composition was cured at 220 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example 13>
In Example 10, a positive photosensitive resin composition solution was prepared in the same manner as in Example 10 except that the polymer E100 g was changed to the polymer H100 g as the (A) resin.
About this composition, after curing at 220 ° C. by the above-mentioned method to produce a cured relief pattern on the Cu layer and conducting a high-temperature storage test, the area ratio of voids occupying the surface of the Cu layer was evaluated. % Results were obtained.
<Comparative Example 1>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that zirconium phosphate was not added to the composition of Example 1, and the same evaluation as in Example 1 was performed. The evaluation result was 14.3% because the compound (B) of the present invention was not included.
<Comparative example 2>
A negative photosensitive resin composition was prepared in the same manner as in Example 8 except that zirconium phosphate was not added to the composition of Example 8, and the same evaluation as in Example 10 was performed. The evaluation result was 14.9% because the compound (B) of the present invention was not included.
<Comparative Example 3>
A positive photosensitive resin composition was prepared in the same manner as in Example 10 except that zirconium phosphate was not added to the composition of Example 10, and the same evaluation as in Example 10 was performed. The evaluation result was 14.6% because the compound (B) of the present invention was not included.
These results are summarized in Table 1.

<Third embodiment>
As the third example, the following experiment was performed.

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

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

  The obtained reaction liquid was added to 3 l of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 l of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 l of water to precipitate a polymer, and the obtained precipitate was filtered off and then dried in vacuum to obtain a powdery polymer (polymer A). When the molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

In addition, the weight average molecular weight of resin obtained by each manufacture example was measured on condition of the following using gel permeation chromatography (GPC), and calculated | required the weight average molecular weight in standard polystyrene conversion.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l LiBr / NMP
Flow rate: 1 ml / min.

<Production Example 2> ((A) Synthesis of polymer B as polyimide precursor)
Instead of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in Production Example 1, 147.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was used. Except for the above, the reaction was carried out in the same manner as in the method described in Production Example 1 to obtain polymer B. When the molecular weight of the polymer B was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Production Example 3> ((A) Synthesis of polymer C as polyimide precursor)
Except for using 147.8 g of 2,2′-bistrifluoromethyl-4,4′-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example 1, In the same manner as in the method described in Production Example 1, a polymer C was obtained. When the molecular weight of the polymer C was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

<Production Example 4> ((A) Synthesis of polymer D as polyamide)
(Synthesis of Phthalic Acid Compound Encapsulated AIPA-MO)
In a separable flask having a volume of 5 l, 5-aminoisophthalic acid {hereinafter abbreviated as AIPA. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50 ° C. in a water bath. A solution obtained by diluting 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone was added dropwise thereto using a dropping funnel, and the mixture was stirred at 50 ° C. for about 2 hours.

  Completion of the reaction (disappearance of 5-aminoisophthalic acid) is described as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, The reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product was crystallized and precipitated, it was filtered, washed with water, and vacuumed at 40 ° C. for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate acted was obtained. The obtained AIPA-MO had a low molecular weight GPC purity of about 100%.

(Synthesis of polymer D)
Into a separable flask having a volume of 2 liters, 100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added and mixed, and cooled to 5 ° C. in an ice bath. did. A solution obtained by dissolving and diluting 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) in 125 g of GBL was added dropwise thereto over about 20 minutes under ice-cooling, followed by 4,4′-bis (4-aminophenoxy). ) Biphenyl {Hereinafter referred to as BAPB. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and stirred at room temperature for 5 hours. did. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

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

<Example 1>
A negative photosensitive resin composition was prepared using the polymers A and B by the following method, and the prepared photosensitive resin composition was evaluated. Polymer A50g and B50g (corresponding to (A) resin) which are polyimide precursors, TMOM-BP (trade name, Honshu Chemical, corresponding to (B-2) thermal crosslinking agent) 10g, 1-phenyl-1,2- Propanedion-2- (O-ethoxycarbonyl) -oxime (described as “PDO” in Table 1) (corresponding to (C) photosensitizer), 4 g of tetraethylene glycol dimethacrylate, N- [3- (tri Along with 1.5 g of ethoxysilyl) propyl] phthalamic acid, it was dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the above mixed solvent to obtain a negative photosensitive resin composition.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.7 % Results were obtained.
<Example 2>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the amount of TMOM-BP added as the component (B-2) was changed to 20 g.
This composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example 3>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the amount of TMOM-BP added as the component (B-2) was changed to 5 g.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 9.3 % Results were obtained.
<Example 4>
In the above Example 1, a negative photosensitive resin was used in the same manner as in Example 1 except that TM-BIP-A (trade name, Honshu Chemical) was used as the component (B-2) instead of TMOM-BP. A composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.2. % Results were obtained.
<Example 5>
In Example 1 above, a negative photosensitive resin was used in the same manner as in Example 1 except that HMOM-TP-HAP (trade name, Honshu Chemical) was used as the component (B-2) instead of TMOM-BP. A composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.8 % Results were obtained.
<Example 6>
In the above Example 1, negative photosensitive resin was used in the same manner as in Example 1 except that Nicarak MW-390 (trade name, Sanwa Chemical) was used as the component (B-2) instead of TMOM-BP. A composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing a high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 10.3 % Results were obtained.
<Example 7>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the polymer A (50 g) and the polymer B (50 g) were changed to the polymer A (100 g) as the (A) resin.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.3. % Results were obtained.
<Example 8>
In Example 1 above, as the (A) resin, the polymer A 50 g and the polymer B 50 g, the polymer A 100 g, the (C) component, PDO 4 g, 1,2-octanedione, 1- {4- (phenylthio) -2, -(O-benzoyloxime)} (Irgacure OXE01 (trade name, manufactured by BASF)) was changed to 2.0 g, and the solvent was further changed to 80 g of γ-butyrolactone and 20 g of dimethylsulfoxide in the same manner as in Example 1. A negative photosensitive resin composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 5.8 % Results were obtained.
<Example 9>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the polymer A (50 g) and the polymer B (50 g) were changed to the polymer C (100 g) as the (A) resin.
About this composition, after curing at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer and conducting a high-temperature storage test, the area ratio of voids in the surface of the Cu layer was evaluated, and 5.0 % Results were obtained.
<Example 10>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the polymer A (50 g) and the polymer B (50 g) were changed to the polymer D (100 g) as the (A) resin.
This composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Comparative Example 1>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that TMOM-BP was not added to the composition of Example 1, and the same evaluation as in Example 1 was performed. The evaluation result was 14.3% because the compound (B) of the present invention was not included.
<Comparative example 2>
A negative photosensitive resin composition was prepared in the same manner as in Example 10 except that TMOM-BP was not added to the composition of Example 10, and the same evaluation as in Example 11 was performed. The evaluation result was 15.5% because the compound (B) of the present invention was not included.
The results of Examples 1 to 10 and Comparative Examples 1 and 2 are summarized in Table 1.

<Fourth embodiment>
As a fourth example, the following experiment was performed.

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

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

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

In addition, the weight average molecular weight of resin obtained by each manufacture example was measured on condition of the following using gel permeation chromatography (GPC), and calculated | required the weight average molecular weight in standard polystyrene conversion.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l LiBr / NMP
Flow rate: 1 ml / min.

<Production Example 2> ((A) Synthesis of Polymer (A) -2 as Polyimide Precursor)
Instead of 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in Production Example 1, 147.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was used. Except for the above, the reaction was carried out in the same manner as in the method described in Production Example 1 to obtain polymer (A) -2. When the molecular weight of the polymer (A) -2 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Production Example 3> ((A) Synthesis of Polymer (A) -3 as Polyimide Precursor)
Except for using 147.8 g of 2,2′-bistrifluoromethyl-4,4′-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4′-diaminodiphenyl ether (DADPE) of Production Example 1, A reaction was carried out in the same manner as in the method described in Production Example 1 to obtain a polymer (A) -3. When the molecular weight of the polymer (A) -3 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

<Production Example 4> (Synthesis of polymer (A) -4 as (A) polyamide)
(Synthesis of Phthalic Acid Compound Encapsulated AIPA-MO)
In a separable flask having a volume of 5 l, 5-aminoisophthalic acid {hereinafter abbreviated as AIPA. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50 ° C. in a water bath. A solution obtained by diluting 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone was added dropwise thereto using a dropping funnel, and the mixture was stirred at 50 ° C. for about 2 hours.

  Completion of the reaction (disappearance of 5-aminoisophthalic acid) is described as low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC. }, The reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand. After the reaction product was crystallized and precipitated, it was filtered, washed with water, and vacuumed at 40 ° C. for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate acted was obtained. The obtained AIPA-MO had a low molecular weight GPC purity of about 100%.

(Synthesis of polymer (A) -4)
Into a separable flask having a volume of 2 liters, 100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added and mixed, and cooled to 5 ° C. in an ice bath. did. A solution obtained by dissolving and diluting 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) in 125 g of GBL was added dropwise thereto over about 20 minutes under ice-cooling, followed by 4,4′-bis (4-aminophenoxy). ) Biphenyl {Hereinafter referred to as BAPB. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and stirred at room temperature for 5 hours. did. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

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

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

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

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

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

  2,2-bis (3-amino-4-hydroxyphenyl) propane (manufactured by Clariant Japan) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5- (2,5-dioxotetrahydro-3-furanyl) 70.29 g (266 mmol) of -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone and 60 g of toluene were added at room temperature. After stirring at 100 rpm for 4 hours, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and a silicon bath temperature of 50 ° C. was passed through nitrogen gas. The mixture was heated and stirred at 100 rpm for 8 hours. Thereafter, the silicon bath was heated to 180 ° C. and stirred with heating at 100 rpm for 2 hours. During the reaction, distillates of toluene and water were removed. After completion of the imidization reaction, the temperature was returned to room temperature.

  Thereafter, the reaction solution was dropped into 3 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water and dehydrated, and then measured by gel permeation chromatography (GPC). A crude polyimide (polymer (A) -6) having a weight average molecular weight of 23,000 (polystyrene conversion) was obtained.

<Production Example 7> ((A) Synthesis of polymer (A) -8 as phenol resin)
A separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, p-toluenesulfone 3.81 g (0.02 mol) of acid and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred at 50 ° C. to dissolve the solid matter.

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

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

  After completion of the reaction, the same treatment as in Production Example 7 was performed to obtain a copolymer (polymer H) composed of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol in a yield of 77%. The weight average molecular weight of this polymer H determined by standard polystyrene conversion by GPC method was 9,900.

で表される、フェノール性水酸基の７７％をナフトキノンジアジド−４−スルホン酸エステル化した感光性ジアゾキノン化合物（東洋合成社製、（Ｃ）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、５．２％という結果を得た。
＜実施例１７＞
上記実施例１６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１１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１８＞
上記実施例１６において、（Ａ）樹脂として、ポリマー（Ａ）−５、１００ｇをポリマー（Ａ）−７、（ノボラック樹脂、ポリスチレン換算重量平均分子量（Ｍｗ）＝１０，６００（旭有機材社製、製品名ＥＰ−４０８０Ｇ）１００ｇに変えたこと以外は、実施例１１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、４．８％という結果を得た。
＜実施例１９＞
上記実施例１６において、（Ａ）樹脂として、ポリマー（Ａ）−５、１００ｇをポリマー（Ａ）−８、１００ｇに変えたこと以外は、実施例１１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、５．１％という結果を得た。
＜比較例１＞
実施例１の組成に、（Ｂ）−１成分を添加しない他は、実施例１と同様にしてネガ型感光性樹脂組成物を調製し、実施例１と同様の評価を行なった。評価結果は、本発明の（Ｂ）フッ素含有疎水性化合物を含まないため１５．２％であった。
＜比較例２＞
実施例１の（Ｂ）−１成分の変わりにテトラエチレングリコールジメタクリレート（下記式（Ｂ−９）で表され、東京化成工業株式会社製）を使用したこと以外は、実施例１と同様にしてネガ型感光性樹脂組成物を調製し、実施例１と同様の評価を行なった。評価結果は、本発明の（Ｂ）フッ素含有疎水性化合物を含まないため１５．５％であった。なお（Ｂ）−９化合物の分子中のフッ素原子の重量割合は０質量％である。
＜比較例３＞
実施例１５の（Ｂ）−１成分の変わりにテトラエチレングリコールジメタクリレート（（Ｂ）−９、東京化成工業株式会社製）を使用したこと以外は、実施例１５と同様にしてネガ型感光性樹脂組成物を調製し、実施例１５と同様の評価を行なった。評価結果は、本発明の（Ｂ）フッ素含有疎水性化合物を含まないため１４．３％であった。
＜比較例４＞
実施例１２の（Ｂ）−１成分の変わりにテトラエチレングリコールジメタクリレート（（Ｂ）−９、東京化成工業株式会社製）を使用したこと以外は、実施例１２と同様にしてネガ型感光性樹脂組成物を調製し、実施例１２と同様の評価を行なった。評価結果は、本発明の（Ｂ）フッ素含有疎水性化合物を含まないため１５．７％であった。
＜比較例５＞
実施例１７の（Ｂ）−１成分の変わりにテトラエチレングリコールジメタクリレート（（Ｂ）−９、東京化成工業株式会社製）を使用したこと以外は、実施例１７と同様にしてポジ型感光性樹脂組成物を調製し、実施例１７と同様の評価を行なった。評価結果は、本発明の（Ｂ）フッ素含有疎水性化合物を含まないため１６．３％であった。 <Example 1>
A negative photosensitive resin composition was prepared by the following method using the polymers (A) -1 and (A) -2, and the photosensitive resin composition was evaluated. 50 g of polymer (A) -1 which is a polyimide precursor and 50 g of (A) -2 (corresponding to (A) resin) were added to 1H, 1H, 8H, 8H-perfluorotetraethylene glycol diacrylate (the following formula ( B-3-1), manufactured by Exfluor, 8 g, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (referred to as “PDO” in Table 1) ( (C) Applicable to photosensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g, N- [3- (triethoxysilyl) propyl] phthalamic acid 1.5 g and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 80 g And 20 g of ethyl lactate were dissolved in a mixed solvent. The viscosity of the obtained solution was adjusted to about 35 poise by further adding a small amount of the above mixed solvent to obtain a negative photosensitive resin composition.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 3.1. % Results were obtained. In addition, (B-3) -1 compound (represents a compound of the following formula (B-3-1). Hereinafter, a compound represented by the following formula (B-3-X) (X is 1 to 9) is represented by (B-3). ) -X.) The weight ratio of fluorine atoms in the molecule is 44% by mass.
<Example 2>
In Example 1, the component (B-3) was changed to 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diacrylate (expressed by the following formula (B-2), manufactured by Exfluor). Except for the change, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 3.3 % Results were obtained. In addition, the weight ratio of the fluorine atom in the molecule | numerator of (B-3) -2 compound is 41 mass%.
<Example 3>
Example 1 except that the component (B-3) in Example 1 was changed to 1H, 1H-perfluoro-n-decyl methacrylate (represented by the following formula (B-3-3), manufactured by Exfluor). In the same manner as in Example 1, a negative photosensitive resin composition solution was prepared.
The composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained. In addition, the weight ratio of the fluorine atom in the molecule | numerator of (B-3) -3 compound is 64 mass%.
<Example 4>
In Example 1 above, the negative component was the same as Example 1 except that the component (B-3) was changed to perfluorodecanoic acid (represented by the following formula (B-3-4), manufactured by Exfluor). Type photosensitive resin composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 6.2. % Results were obtained. In addition, the weight ratio of the fluorine atom in the molecule | numerator of (B-3) -4 compound is 70 mass%.
<Example 5>
Example 1 except that the component (B-3) was changed to 1H, 1H-perfluoro-1-decanol (represented by the following formula (B-3-5), manufactured by Exfluor) in Example 1 above. In the same manner as described above, a negative photosensitive resin composition solution was prepared.
The composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained. In addition, the weight ratio of the fluorine atom in the molecule | numerator of (B-3) -5 compound is 72 mass%.
<Example 6>
In the above Example 1, the negative type is the same as Example 1 except that the component (B-3) is changed to perfluorotridecane (represented by the following formula (B-3-6), manufactured by Exfluor). A photosensitive resin composition solution was prepared.
About this composition, it cured at 230 degreeC by the above-mentioned method, produced a hardening relief pattern on Cu layer, and after performing the high temperature storage test, the area ratio of the void which occupies for the surface of Cu layer was evaluated, and 7.7 % Results were obtained. In addition, the weight ratio of the fluorine atom in the molecule | numerator of (B-3) -6 compound is 77 mass%.
<Example 7>
In the same manner as in Example 1, except that the component (B-3) was changed to methyl perfluorodecanoate (represented by the following formula (B-7), manufactured by Exfluor) in Example 1, the negative photosensitive resin was used. Resin composition solution was prepared.
The composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained. In addition, the weight ratio of the fluorine atom in the molecule | numerator of (B-3) -7 compound is 68 mass%.
<Example 8>
In the above Example 1, the negative type is the same as Example 1 except that the component (B-3) is changed to perfluorotetraglyme (represented by the following formula (B-3-8), manufactured by Exfluor). A photosensitive resin composition solution was prepared.
This composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained. In addition, the weight ratio of the fluorine atom in the molecule | numerator of (B-3) -8 compound is 68 mass%.
<Example 9>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the amount of the (B-3) -1 component added was changed to 2 g.
About this composition, after curing at 230 ° C. by the above-mentioned method to produce a cured relief pattern on the Cu layer and conducting a high-temperature storage test, the area ratio of voids occupied on the surface of the Cu layer was evaluated, and 4.5 % Results were obtained.
<Example 10>
In Example 1, a negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the amount of the (B-3) -1 component added was changed to 20 g.
This composition was cured at 230 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example 11>
A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the curing temperature was changed from 230 ° C. to 350 ° C. in Example 1.
For this composition, a cured relief pattern was prepared on the Cu layer and subjected to a high-temperature storage test. Then, the void area ratio in the surface of the Cu layer was evaluated, and a result of 4.2% was obtained.
<Example 12>
In Example 1 above, as the (A) resin, the polymer (A) -1, 50 g and the polymer (A) -2, 50 g were converted into the polymer (A) -1, 100 g, and the component (C) was changed from PDO 1, Example 1 with the exception that 2-octanedione, 1- {4- (phenylthio)-, 2- (O-benzoyloxime)} (Irgacure OXE01 (trade name, manufactured by BASF)) was changed to 2.5 g. In the same manner, a negative photosensitive resin composition solution was prepared.
For this composition, a cured relief pattern was prepared on the Cu layer and subjected to a high-temperature storage test. Then, the void area ratio on the surface of the Cu layer was evaluated, and a result of 4.6% was obtained.
<Example 13>
A negative photosensitive resin composition solution was prepared in the same manner as in Example 12 except that the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide in Example 12.
For this composition, a cured relief pattern was prepared on the Cu layer and subjected to a high-temperature storage test. Then, the area ratio of voids on the surface of the Cu layer was evaluated, and a result of 4.8% was obtained.
<Example 14>
In Example 1 above, as the (A) resin, the polymer (A) -1, 50 g and the polymer (A) -2, 50 g are changed to the polymer (A) -3, 100 g, and the curing temperature is 230 ° C. to 350 ° C. A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the above was changed.
For this composition, a cured relief pattern was prepared on the Cu layer and subjected to a high-temperature storage test. Then, the void area ratio in the surface of the Cu layer was evaluated, and a result of 4.7% was obtained.
<Example 15>
In Example 1 above, as the (A) resin, the polymer (A) -1, 50 g and the polymer (A) -2, 50 g are changed to the polymer (A) -4, 100 g, and the curing temperature is 230 ° C. to 250 ° C. A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 except that the above was changed.
For this composition, a cured relief pattern was prepared 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 a result of 4.4% was obtained.
<Example 16>
Using the polymer (A) -5, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Polymer (A) -5 which is a polyoxazole precursor, 100 g (corresponding to (A) resin) is represented by the following formula (96):

A photosensitive diazoquinone compound obtained by converting 77% of a phenolic hydroxyl group into naphthoquinonediazide-4-sulfonic acid ester (produced by Toyo Gosei Co., Ltd., corresponding to the component (C)) (C1) 15 g, γ-butyrolactone (as a solvent) ) Dissolved in 100 g. The viscosity of the resulting solution was adjusted to about 20 poise by further adding a small amount of γ-butyrolactone to obtain a positive photosensitive resin composition.
This composition was cured at 350 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example 17>
In the above Example 16, as the resin (A), the positive photosensitive resin composition was the same as Example 11 except that the polymer (A) -5, 100 g was changed to the polymer (A) -6, 100 g. A solution was prepared.
This composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Example 18>
In the said Example 16, as polymer (A) -5, 100 g is polymer (A) -7, (Novolac resin, polystyrene conversion weight average molecular weight (Mw) = 10,600 (made by Asahi Organic Materials Co., Ltd.) , Product name EP-4080G) A positive photosensitive resin composition solution was prepared in the same manner as in Example 11 except that it was changed to 100 g.
This composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, and after a high temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated. % Results were obtained.
<Example 19>
In the above Example 16, as the resin (A), the positive photosensitive resin composition was the same as Example 11 except that the polymer (A) -5, 100 g was changed to the polymer (A) -8, 100 g. A solution was prepared.
This composition was cured at 250 ° C. by the above-described method to produce a cured relief pattern on the Cu layer, subjected to a high-temperature storage test, and then evaluated for the area ratio of voids on the surface of the Cu layer. % Results were obtained.
<Comparative Example 1>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the component (B) -1 was not added to the composition of Example 1, and the same evaluation as in Example 1 was performed. The evaluation result was 15.2% because (B) the fluorine-containing hydrophobic compound of the present invention was not included.
<Comparative example 2>
Instead of the component (B) -1 of Example 1, tetraethylene glycol dimethacrylate (represented by the following formula (B-9), manufactured by Tokyo Chemical Industry Co., Ltd.) was used in the same manner as in Example 1. A negative photosensitive resin composition was prepared and evaluated in the same manner as in Example 1. The evaluation result was 15.5% because (B) the fluorine-containing hydrophobic compound of the present invention was not included. In addition, the weight ratio of the fluorine atom in the molecule | numerator of (B) -9 compound is 0 mass%.
<Comparative Example 3>
Negative photosensitivity in the same manner as in Example 15 except that tetraethylene glycol dimethacrylate ((B) -9, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the component (B) -1 in Example 15. A resin composition was prepared and evaluated in the same manner as in Example 15. The evaluation result was 14.3% because the (B) fluorine-containing hydrophobic compound of the present invention was not included.
<Comparative Example 4>
Negative photosensitivity in the same manner as in Example 12, except that tetraethylene glycol dimethacrylate ((B) -9, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the component (B) -1 in Example 12. A resin composition was prepared and evaluated in the same manner as in Example 12. The evaluation result was 15.7% because (B) the fluorine-containing hydrophobic compound of the present invention was not included.
<Comparative Example 5>
Positive photosensitivity in the same manner as in Example 17 except that tetraethylene glycol dimethacrylate ((B) -9, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the component (B) -1 in Example 17. A resin composition was prepared and evaluated in the same manner as in Example 17. The evaluation result was 16.3% because the (B) fluorine-containing hydrophobic compound of the present invention was not included.

The weight ratios of fluorine atoms in the molecules of the (B) -1 to (B) -9 compounds are summarized in Table 1 below.

Table 2 summarizes the results of Examples 1 to 19 and Comparative Examples 1 to 5.

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

Claims (6)

(A) 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 phenol resin 100 parts by mass,
(B) 0.1 to 50 parts by mass of the plasticizer based on 100 parts by mass of the resin (A), and
(C) 1 to 50 parts by mass of the photosensitive agent based on 100 parts by mass of the resin (A),
A photosensitive resin composition comprising: The (A) resin includes a polyimide precursor including the following general formula (1), a polyamide including the following general formula (4), a polyoxazole precursor including the following general formula (5), and the following general formula (6). The photosensitive resin composition of Claim 1 which is at least 1 type selected from the group which consists of a phenol resin containing a polyimide and novolak, polyhydroxystyrene, and the following general formula (7).
The following general formula (1) is

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

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

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

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

{Wherein Y ₃ is a tetravalent organic group having a carbon atom, and Y ₄ , X ₃ and X ₄ are each independently a divalent organic group having 2 or more carbon atoms, n ₃ is an integer from 1 to 1000, _{n 4} is an integer of _{0~500, n 3 / (n 3} + n 4)> 0.5, and _{n 3} containing _{X 3} and _{Y 3} The arrangement order of the n ₄ diamide units including X ₄ and Y ₄ is not limited. }
A polyhydroxyamide that is a polyoxazole precursor having a structure represented by:
The following general formula (6)

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

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

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

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

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

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

A divalent group selected from the group consisting of divalent groups represented by the formula: } The photosensitive resin composition of Claim 1 or 2 which is a bivalent organic group selected from the group which consists of a bivalent group represented by these. The (B) plasticizer is represented by the following general formula (7):

{Wherein X is a structure containing a saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon having 1 to 15 carbon atoms, n is an integer of 1 to 4, and n is 2 or more In this case, each R may be the same or different and is a saturated hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon having 2 to 15 carbon atoms. },
The following general formula (8):

{In the formula, m is an integer of 1 to 4, and when m is 2 or more, each R may be the same or different and is a saturated or unsaturated hydrocarbon having 2 to 15 carbon atoms, or Represented by aromatic hydrocarbons. } And the following general formula (9):

{Wherein Y is a structure containing a saturated hydrocarbon, an unsaturated hydrocarbon or an aromatic hydrocarbon having 1 to 10 carbon atoms, and R may be the same or different, and each having 2 or more carbon atoms. It is represented by 15 or less saturated hydrocarbon, unsaturated hydrocarbon, or aromatic hydrocarbon. } The photosensitive resin composition of Claim 1 which is at least 1 type selected from the group consisting of. (1) A step of forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of claims 1 to 4 on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a step of forming a cured relief pattern by heat-treating the relief pattern.   The method of claim 5, wherein the substrate is formed from copper or a copper alloy.