JP6968196B2 - Negative photosensitive resin composition and its manufacturing method, and a method for manufacturing a cured relief pattern. - Google Patents

Description

The present invention relates to a negative photosensitive resin composition, a method for producing the same, and a method for producing a cured relief pattern.

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

By the way, a semiconductor device (hereinafter, also referred to as an "element") is mounted on a printed circuit board by various methods according to a purpose. Conventional elements have generally been manufactured by a wire bonding method in which a thin wire is used to connect an external terminal (pad) of the element to a lead frame. However, as the speed of the element increases and the operating frequency reaches GHz, the difference in the wiring length of each terminal in the mounting has come to affect the operation of the element. Therefore, in the mounting of elements for high-end applications, it is necessary to accurately control the length of the mounting wiring, and it is difficult to meet the demand by wire bonding.

Therefore, a flip chip mounting method has been proposed in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on the bumps (electrodes), and then the chip is turned over and mounted directly on a printed circuit board (for example, patent). See Document 1). Since this flip-chip mounting can accurately control the wiring distance, it is used in high-end applications that handle high-speed signals, or in mobile phones due to its small mounting size, and its demand is rapidly expanding. When a material such as polyimide, polybenzoxazole, or phenol resin is used for flip-chip mounting, a metal wiring layer forming step is performed after the pattern of the resin layer is formed. In the metal wiring layer, usually, the surface of the resin layer is plasma-etched to roughen the surface, and then a metal layer to be a seed layer for plating is formed by sputtering with a thickness of 1 μm or less, and then the metal layer is used as an electrode. It is formed by electrolytic plating. At this time, generally, titanium (Ti) is used as the metal to be the seed layer, and copper (Cu) is used as the metal of the rewiring layer formed by electrolytic plating.

Such a metal rewiring layer is required to have high adhesion between the metal layer rewired after the reliability test and the resin layer. As a reliability test, for example, a high temperature storage test in which the product is stored in air at a high temperature of 125 ° C. or higher for 100 hours or more; High-temperature operation test to confirm the operation under storage; a temperature cycle in which a low-temperature state of about -65 ° C to -40 ° C and a high-temperature state of about 125 ° C to 150 ° C are cycled back and forth in air. Test; High-temperature and high-humidity storage test in which the product is stored at a temperature of 85 ° C or higher and in a steam atmosphere with a humidity of 85% or more; Bias test; and a solder reflow test in which a solder reflow furnace at 260 ° C. is passed a plurality of times in air or under nitrogen can be mentioned.

Japanese Unexamined Patent Publication No. 2001-338947

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

Further, in addition to the problem of voids, the demand for miniaturization of the metal rewiring layer (cured relief pattern) is increasing. Therefore, in particular, the photosensitive resin composition used for forming the metal rewiring layer of a semiconductor is required to suppress the generation of voids and to exhibit high resolution. Further, in one embodiment, the metal rewiring layer is required to have high chemical resistance.

The present invention has been devised in view of such conventional circumstances, and a high resolution can be obtained, and after a high temperature storage test, a void is formed at the interface of the Cu layer in contact with the resin layer. One of the objects is to provide a negative photosensitive resin composition (hereinafter, also simply referred to as "photosensitive resin composition" in the present specification) capable of suppressing the generation, and a method for producing the same. It is also one of the objects to provide a method for forming a cured relief pattern using the negative photosensitive resin composition of the present invention. Further, in one embodiment, a negative photosensitive resin composition having high chemical resistance, high resolution, and a high void suppressing effect, a method for producing the same, and a cured relief pattern using the negative photosensitive resin composition. One of the purposes is to provide a forming method.

｛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、又は１価の有機基であり、Ｒ_１及びＲ_２の少なくとも一方は、末端に重合性基を有する１価の有機基である。｝
で表される構造単位を有するポリイミド前駆体を含む、項目１又は２のいずれか一項に記載のネガ型感光性樹脂組成物。
［４］
上記一般式（２）において、Ｒ_１及びＲ_２の少なくとも一方は、下記一般式（３）：

｛式中、Ｌ_１、Ｌ_２及びＬ_３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価の有機基である、項目３に記載のネガ型感光性樹脂組成物。
［５］
上記（Ａ）ポリイミド前駆体が、下記一般式（４）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体を含む、項目３又は４に記載のネガ型感光性樹脂組成物。
［６］
上記（Ａ）ポリイミド前駆体が、下記一般式（５）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体を含む、項目３又は４に記載のネガ型感光性樹脂組成物。
［７］
上記（Ａ）ポリイミド前駆体が、下記一般式（６）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体を含む、項目３又は４に記載のネガ型感光性樹脂組成物。
［８］
上記（Ａ）ポリイミド前駆体が、下記一般式（４）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体と、
下記一般式（５）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものであり、ただし、一般式（５）中のＲ_１、Ｒ_２、及びｎ_１は、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは独立して選択される。｝
で表される構造単位を有するポリイミド前駆体の両方を含む、項目３又は４に記載のネガ型感光性樹脂組成物。
［９］
上記（Ａ）ポリイミド前駆体が、下記一般式（４）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体、と
下記一般式（６）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものであり、ただし、一般式（６）中のＲ_１、Ｒ_２、及びｎ_１は、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは独立して選択される。｝
で表される構造単位を有するポリイミド前駆体の両方を含む、項目３又は４に記載のネガ型感光性樹脂組成物。
［１０］
１００質量部の上記（Ａ）ポリイミド前駆体と、
上記（Ａ）ポリイミド前駆体１００質量部を基準として０．１〜３０質量部の上記（Ｂ）塩基保護化合物と、
上記（Ａ）ポリイミド前駆体１００質量部を基準として０．１〜２０質量部の上記（Ｃ）光重合開始剤と
を含む、項目１〜９のいずれか一項に記載のネガ型感光性樹脂組成物。
［１１］
（Ａ）ポリイミド前駆体；
（Ｄ）酸又は塩基又は熱で脱保護される基で保護された一つ又は複数のアミノ基と、下記一般式（１）：

｛式中Ｚは、水素原子又はメチル基である。また、両端の結合は分子内の他の部分への単結合を表す。｝
で表される一つ又は複数の構造単位を分子内に含む、エーテル化合物；及び
（Ｃ）光重合開始剤
を含む、ネガ型感光性樹脂組成物。
［１２］
上記（Ｄ）エーテル化合物は、分子中に上記一般式（１）で表される構造単位を二つ以上含む、項目１１に記載のネガ型感光性樹脂組成物。
［１３］
上記保護された一つ又は複数のアミノ基は、ｔｅｒｔ−ブトキシカルボニル基で保護されたアミノ基である、項目１１又は１２に記載のネガ型感光性樹脂組成物。
［１４］
上記（Ａ）ポリイミド前駆体が、下記一般式（２）：

｛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、又は１価の有機基であり、Ｒ_１及びＲ_２の少なくとも一方は、末端に重合性基を有する１価の有機基である。｝
で表される構造単位を有するポリイミド前駆体を含む、項目１１〜１３のいずれか一項に記載のネガ型感光性樹脂組成物。
［１５］
上記一般式（２）において、Ｒ_１及びＲ_２の少なくとも一方は、下記一般式（３）：

｛式中、Ｌ_１、Ｌ_２及びＬ_３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価の有機基である、項目１４に記載のネガ型感光性樹脂組成物。
［１６］
上記（Ａ）ポリイミド前駆体が、下記一般式（４）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体を含む、項目１４又は１５に記載のネガ型感光性樹脂組成物。
［１７］
上記（Ａ）ポリイミド前駆体が、下記一般式（５）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体を含む、項目１４又は１５に記載のネガ型感光性樹脂組成物。
［１８］
上記（Ａ）ポリイミド前駆体が、下記一般式（６）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体を含む、項目１４又は１５に記載のネガ型感光性樹脂組成物。
［１９］
上記（Ａ）ポリイミド前駆体が、下記一般式（４）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体と、
下記一般式（５）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものであり、ただし、一般式（５）中のＲ_１、Ｒ_２、及びｎ_１は、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは独立して選択される。｝
で表される構造単位を有するポリイミド前駆体の両方を含む、項目１４又は１５に記載のネガ型感光性樹脂組成物。
［２０］
上記（Ａ）ポリイミド前駆体が、下記一般式（４）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体、と
下記一般式（６）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものであり、ただし、一般式（６）中のＲ_１、Ｒ_２、及びｎ_１は、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは独立して選択される。｝
で表される構造単位を有するポリイミド前駆体の両方を含む、項目１４又は１５に記載のネガ型感光性樹脂組成物。
［２１］
１００質量部の上記（Ａ）ポリイミド前駆体と、
上記（Ａ）ポリイミド前駆体１００質量部を基準として０．１〜３０質量部の上記（Ｄ）エーテル化合物と、
上記（Ａ）ポリイミド前駆体１００質量部を基準として０．１〜２０質量部の上記（Ｃ）光重合開始剤と
を含む、項目１１〜２０のいずれか一項に記載のネガ型感光性樹脂組成物。
［２２］
（Ａ）ポリイミド前駆体；
（Ｅ）酸又は塩基又は熱で脱保護される基で保護された一つ又は複数のアミノ基と、ヒドロキシル基を分子内に少なくとも一つ含むウレタン化合物；及び
（Ｃ）光重合開始剤
を含む、ネガ型感光性樹脂組成物。
［２３］
上記（Ｅ）ウレタン化合物は、脂肪族鎖状若しくは脂環式アミノ基に結合したｔｅｒｔ−ブトキシカルボニル基、ベンジルオキシカルボニル基又は９−フルオレニルメチルオキシカルボニル（Ｆｍｏｃ）基を分子内に少なくとも一つ有する、項目２２に記載のネガ型感光性樹脂組成物。
［２４］
上記（Ｅ）ウレタン化合物の上記保護された一つ又は複数のアミノ基の窒素原子の少なくとも一つが、分子内のヒドロキシル基のγ位若しくはε位にある、項目２２又は２３に記載のネガ型感光性樹脂組成物。
［２５］
上記保護された一つ又は複数のアミノ基は、ｔｅｒｔ−ブトキシカルボニル基で保護されたアミノ基である、項目２２〜２４のいずれか一項に記載のネガ型感光性樹脂組成物。
［２６］
上記（Ａ）ポリイミド前駆体が、下記一般式（２）：

｛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、又は１価の有機基であり、Ｒ_１及びＲ_２の少なくとも一方は、末端に重合性基を有する１価の有機基である。｝
で表される構造単位を有するポリイミド前駆体を含む、項目２２〜２５のいずれか一項に記載のネガ型感光性樹脂組成物。
［２７］
上記一般式（２）において、Ｒ_１及びＲ_２の少なくとも一方は、下記一般式（３）：

｛式中、Ｌ_１、Ｌ_２及びＬ_３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価の有機基である、項目２６に記載のネガ型感光性樹脂組成物。
［２８］
上記（Ａ）ポリイミド前駆体が、下記一般式（４）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体を含む、項目２６又は２７に記載のネガ型感光性樹脂組成物。
［２９］
上記（Ａ）ポリイミド前駆体が、下記一般式（５）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体を含む、項目２６又は２７に記載のネガ型感光性樹脂組成物。
［３０］
上記（Ａ）ポリイミド前駆体が、下記一般式（６）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体を含む、項目２６又は２７に記載のネガ型感光性樹脂組成物。
［３１］
上記（Ａ）ポリイミド前駆体が、下記一般式（４）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体と、
下記一般式（５）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものであり、ただし、一般式（５）中のＲ_１、Ｒ_２、及びｎ_１は、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは独立して選択される。｝
で表される構造単位を有するポリイミド前駆体の両方を含む、項目２６又は２７に記載のネガ型感光性樹脂組成物。
［３２］
上記（Ａ）ポリイミド前駆体が、下記一般式（４）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体、と
下記一般式（６）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記一般式（２）に定義したものであり、ただし、一般式（６）中のＲ_１、Ｒ_２、及びｎ_１は、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは独立して選択される。｝
で表される構造単位を有するポリイミド前駆体の両方を含む、項目２６又は２７に記載のネガ型感光性樹脂組成物。
［３３］
上記（Ｅ）ウレタン化合物が、Ｎα−（ｔｅｒｔ−ブトキシカルボニル）−Ｌ−トリプトファノール、１−（ｔｅｒｔ−ブトキシカルボニル）−４−ヒドロキシピペリジン、又は下記化学式（１）：

で表されるウレタン化合物である、項目２２〜３２のいずれか一項に記載の感光性樹脂組成物。
［３４］
１００質量部の上記（Ａ）ポリイミド前駆体と、
上記（Ａ）ポリイミド前駆体１００質量部を基準として０．１〜３０質量部の上記（Ｅ）ウレタン化合物と、
上記（Ａ）ポリイミド前駆体１００質量部を基準として０．１〜２０質量部の上記（Ｃ）光重合開始剤と
を含む、項目２２〜３３のいずれか一項に記載のネガ型感光性樹脂組成物。
［３５］
項目１〜３４のいずれか一項に記載のネガ型感光性樹脂組成物を硬化するポリイミドの製造方法。
［３６］
（１）項目１〜３４のいずれか一項に記載のネガ型感光性樹脂組成物を基板上に塗布して、感光性樹脂層を上記基板上に形成する工程と、
（２）上記感光性樹脂層を露光する工程と、
（３）露光後の上記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）上記レリーフパターンを加熱処理して、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。The present inventors solve the above-mentioned problems by combining a polyimide precursor and a photopolymerization initiator with a specific compound having an amino group protected by an acid or a base or a group deprotected by heat. We have found that we can do this, and have completed the present invention. Examples of embodiments of the present invention are listed below.
[1]
(A) Polyimide precursor;
(B) It has a plurality of amino groups protected by an acid or a base or a group deprotected by heat, has a molecular weight of 250 to 600, and the above-mentioned protected plurality of amino groups are an aliphatic chain or an alicyclic. A negative photosensitive resin composition comprising a base-protected compound having a formula amino group and a solubility parameter value of 20.0 or more and 24.0 or less; and (C) a photopolymerization initiator.
[2]
The negative photosensitive resin composition according to item 1, wherein the plurality of protected amino groups are amino groups protected by a tert-butoxycarbonyl group.
[3]
The above (A) polyimide precursor is the following general formula (2):

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are independently hydrogen. It is an atomic or monovalent organic group, and _{at least one of R 1} and R ₂ is a monovalent organic group having a polymerizable group at the terminal. }
The negative photosensitive resin composition according to any one of items 1 or 2, which comprises a polyimide precursor having a structural unit represented by.
[4]
In the above general formula (2), _{at least one of R 1} and R ₂ is the following general formula (3):

{In the formula, L ₁ , L ₂ and L ₃ 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. } The negative photosensitive resin composition according to item 3, which is a monovalent organic group represented by.
[5]
The above (A) polyimide precursor is the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to item 3 or 4, which comprises a polyimide precursor having a structural unit represented by.
[6]
The above (A) polyimide precursor is the following general formula (5):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to item 3 or 4, which comprises a polyimide precursor having a structural unit represented by.
[7]
The above (A) polyimide precursor is the following general formula (6):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to item 3 or 4, which comprises a polyimide precursor having a structural unit represented by.
[8]
The above (A) polyimide precursor is the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
A polyimide precursor having a structural unit represented by
The following general formula (5):

{In the formula, R ₁ , R ₂ and n ₁ are defined in the above general formula (2), except that R ₁ , R ₂ and n ₁ in the general formula (5) are general formulas ( 4) Selected independently _{of R 1} , R ₂ , and n _{1 in.} }
The negative photosensitive resin composition according to item 3 or 4, which comprises both polyimide precursors having a structural unit represented by.
[9]
The above (A) polyimide precursor is the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
A polyimide precursor having a structural unit represented by, and the following general formula (6) :.

{In the formula, R ₁ , R ₂ and n ₁ are defined in the above general formula (2), except that R ₁ , R ₂ and n ₁ in the general formula (6) are general formulas ( 4) Selected independently _{of R 1} , R ₂ , and n _{1 in.} }
The negative photosensitive resin composition according to item 3 or 4, which comprises both polyimide precursors having a structural unit represented by.
[10]
With 100 parts by mass of the above (A) polyimide precursor,
With reference to the above (A) 100 parts by mass of the polyimide precursor, 0.1 to 30 parts by mass of the above (B) base-protected compound and
Item 2. The negative photosensitive resin according to any one of Items 1 to 9, which comprises 0.1 to 20 parts by mass of the above (C) photopolymerization initiator based on 100 parts by mass of the above (A) polyimide precursor. Composition.
[11]
(A) Polyimide precursor;
(D) One or more amino groups protected by an acid or a base or a group that is deprotected by heat, and the following general formula (1):

{Z in the formula is a hydrogen atom or a methyl group. Also, the bonds at both ends represent single bonds to other parts of the molecule. }
A negative photosensitive resin composition comprising an ether compound; and (C) a photopolymerization initiator containing one or more structural units represented by.
[12]
The negative photosensitive resin composition according to item 11, wherein the ether compound (D) contains two or more structural units represented by the general formula (1) in the molecule.
[13]
The negative photosensitive resin composition according to item 11 or 12, wherein the protected one or more amino groups are amino groups protected by a tert-butoxycarbonyl group.
[14]
The above (A) polyimide precursor is the following general formula (2):

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are independently hydrogen. It is an atomic or monovalent organic group, and _{at least one of R 1} and R ₂ is a monovalent organic group having a polymerizable group at the terminal. }
The negative photosensitive resin composition according to any one of Items 11 to 13, which comprises a polyimide precursor having a structural unit represented by.
[15]
In the above general formula (2), _{at least one of R 1} and R ₂ is the following general formula (3):

{In the formula, L ₁ , L ₂ and L ₃ 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. } The negative photosensitive resin composition according to item 14, which is a monovalent organic group represented by.
[16]
The above (A) polyimide precursor is the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to item 14 or 15, which comprises a polyimide precursor having a structural unit represented by.
[17]
The above (A) polyimide precursor is the following general formula (5):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to item 14 or 15, which comprises a polyimide precursor having a structural unit represented by.
[18]
The above (A) polyimide precursor is the following general formula (6):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to item 14 or 15, which comprises a polyimide precursor having a structural unit represented by.
[19]
The above (A) polyimide precursor is the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
A polyimide precursor having a structural unit represented by
The following general formula (5):

{In the formula, R ₁ , R ₂ and n ₁ are defined in the above general formula (2), except that R ₁ , R ₂ and n ₁ in the general formula (5) are general formulas ( 4) Selected independently _{of R 1} , R ₂ , and n _{1 in.} }
The negative photosensitive resin composition according to item 14 or 15, which comprises both polyimide precursors having a structural unit represented by.
[20]
The above (A) polyimide precursor is the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
A polyimide precursor having a structural unit represented by, and the following general formula (6) :.

{In the formula, R ₁ , R ₂ and n ₁ are defined in the above general formula (2), except that R ₁ , R ₂ and n ₁ in the general formula (6) are general formulas ( 4) Selected independently _{of R 1} , R ₂ , and n _{1 in.} }
The negative photosensitive resin composition according to item 14 or 15, which comprises both polyimide precursors having a structural unit represented by.
[21]
With 100 parts by mass of the above (A) polyimide precursor,
With reference to 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the above (D) ether compound and
Item 2. The negative photosensitive resin according to any one of Items 11 to 20, which comprises 0.1 to 20 parts by mass of the above (C) photopolymerization initiator with respect to 100 parts by mass of the above (A) polyimide precursor. Composition.
[22]
(A) Polyimide precursor;
(E) A urethane compound containing at least one hydroxyl group in the molecule and one or more amino groups protected by an acid or a base or a group that is deprotected by heat; and (C) a photopolymerization initiator. , Negative photosensitive resin composition.
[23]
The urethane compound (E) has at least one tert-butoxycarbonyl group, benzyloxycarbonyl group or 9-fluorenylmethyloxycarbonyl (Fmoc) group bonded to an aliphatic chain or alicyclic amino group in the molecule. The negative type photosensitive resin composition according to item 22, which has one.
[24]
Item 22 or 23, wherein at least one of the nitrogen atoms of the protected one or more amino groups of the urethane compound (E) is at the γ or ε position of the hydroxyl group in the molecule. Sex resin composition.
[25]
The negative photosensitive resin composition according to any one of items 22 to 24, wherein the protected one or more amino groups are amino groups protected by a tert-butoxycarbonyl group.
[26]
The above (A) polyimide precursor is the following general formula (2):

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are independently hydrogen. It is an atomic or monovalent organic group, and _{at least one of R 1} and R ₂ is a monovalent organic group having a polymerizable group at the terminal. }
The negative photosensitive resin composition according to any one of items 22 to 25, which comprises a polyimide precursor having a structural unit represented by.
[27]
In the above general formula (2), _{at least one of R 1} and R ₂ is the following general formula (3):

{In the formula, L ₁ , L ₂ and L ₃ 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. } The negative photosensitive resin composition according to item 26, which is a monovalent organic group represented by.
[28]
The above (A) polyimide precursor is the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to item 26 or 27, which comprises a polyimide precursor having a structural unit represented by.
[29]
The above (A) polyimide precursor is the following general formula (5):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to item 26 or 27, which comprises a polyimide precursor having a structural unit represented by.
[30]
The above (A) polyimide precursor is the following general formula (6):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to item 26 or 27, which comprises a polyimide precursor having a structural unit represented by.
[31]
The above (A) polyimide precursor is the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
A polyimide precursor having a structural unit represented by
The following general formula (5):

{In the formula, R ₁ , R ₂ and n ₁ are defined in the above general formula (2), except that R ₁ , R ₂ and n ₁ in the general formula (5) are general formulas ( 4) Selected independently _{of R 1} , R ₂ , and n _{1 in.} }
The negative photosensitive resin composition according to item 26 or 27, which comprises both polyimide precursors having a structural unit represented by.
[32]
The above (A) polyimide precursor is the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
A polyimide precursor having a structural unit represented by, and the following general formula (6) :.

{In the formula, R ₁ , R ₂ and n ₁ are defined in the above general formula (2), except that R ₁ , R ₂ and n ₁ in the general formula (6) are general formulas ( 4) Selected independently _{of R 1} , R ₂ , and n _{1 in.} }
The negative photosensitive resin composition according to item 26 or 27, which comprises both polyimide precursors having a structural unit represented by.
[33]
The urethane compound (E) is Nα- (tert-butoxycarbonyl) -L-tryptophanol, 1- (tert-butoxycarbonyl) -4-hydroxypiperidine, or the following chemical formula (1):

The photosensitive resin composition according to any one of items 22 to 32, which is a urethane compound represented by.
[34]
With 100 parts by mass of the above (A) polyimide precursor,
With reference to the above (A) 100 parts by mass of the polyimide precursor, 0.1 to 30 parts by mass of the above (E) urethane compound and
Item 2. The negative photosensitive resin according to any one of Items 22 to 33, which comprises 0.1 to 20 parts by mass of the above (C) photopolymerization initiator based on 100 parts by mass of the above (A) polyimide precursor. Composition.
[35]
A method for producing a polyimide for curing a negative photosensitive resin composition according to any one of items 1 to 34.
[36]
(1) A step of applying the negative photosensitive resin composition according to any one of items 1 to 34 on a substrate to form a photosensitive resin layer on the substrate.
(2) The step of exposing the photosensitive resin layer and
(3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, and
(4) A method for producing a cured relief pattern, which comprises a step of heat-treating the relief pattern to form a cured relief pattern.

According to the present invention, a negative photosensitive resin composition capable of obtaining high resolution and suppressing the generation of voids at the interface of the Cu layer in contact with the resin layer after a high temperature storage test and a method for producing the same are provided. Can be provided. It is possible to provide a method for forming a cured relief pattern using the negative photosensitive resin composition. Further, in one embodiment, a negative photosensitive resin composition having high chemical resistance, high resolution, and a high void suppressing effect, a method for producing the same, and a cured relief pattern using the negative photosensitive resin composition. A forming method can be provided.

Hereinafter, embodiments for carrying out the present invention (hereinafter, abbreviated as “embodiments”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
In addition, throughout the present specification, the structures represented by the same reference numerals in the general formula may be the same or different from each other when a plurality of structures are present in the molecule.

｛式中Ｚは、水素原子又はメチル基である。また、両端の結合は分子内の他の部分への単結合を表す。｝
で表される一つ又は複数の構造単位とを分子内に含む、エーテル化合物；及び
（Ｃ）光重合開始剤を含む。
第三の本実施形態に係るネガ型感光性樹脂組成物は、
（Ａ）ポリイミド前駆体；
（Ｅ）酸又は塩基又は熱で脱保護される基で保護された一つ又は複数のアミノ基と、ヒドロキシル基を分子内に少なくとも一つ含むウレタン化合物；及び
（Ｃ）光重合開始剤を含む。<Negative photosensitive resin composition>
The negative photosensitive resin composition according to the first embodiment is
(A) Polyimide precursor;
(B) It has a plurality of amino groups protected by an acid or a base or a group deprotected by heat, has a molecular weight of 250 to 600, and the above-mentioned protected plurality of amino groups are an aliphatic chain or an alicyclic. It contains a base-protected compound; and (C) a photopolymerization initiator, which is an amino group of the formula and has a solubility parameter value of 20.0 or more and 24.0 or less.
The negative photosensitive resin composition according to the second embodiment is
(A) Polyimide precursor;
(D) One or more amino groups protected by an acid or a base or a group that is deprotected by heat, and the following general formula (1):

{Z in the formula is a hydrogen atom or a methyl group. Also, the bonds at both ends represent single bonds to other parts of the molecule. }
An ether compound comprising one or more structural units represented by (C) in the molecule; and (C) a photopolymerization initiator.
The negative photosensitive resin composition according to the third embodiment is
(A) Polyimide precursor;
(E) A urethane compound containing at least one hydroxyl group in the molecule and one or more amino groups protected by an acid or a base or a group that is deprotected by heat; and (C) a photopolymerization initiator. ..

｛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、又は１価の有機基である。｝(A) Polyimide precursor The (A) polyimide precursor in the first to third embodiments is a resin component contained in a negative photosensitive resin composition, and is converted into polyimide by subjecting it to a heat cyclization treatment. Will be done.
The polyimide precursor is preferably a polyamide having a structure represented by the following general formula (2).

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are independently hydrogen. It is an atomic or monovalent organic group. }

｛式中、Ｌ_１、Ｌ_２及びＬ_３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価の有機基である。At _{least one of R 1} and R ₂ is the following general formula (3) :.

{In the formula, L ₁ , L ₂ and L ₃ 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. } Is a monovalent organic group.

｛式中、Ｒ６は水素原子、フッ素原子、Ｃ_１〜Ｃ_１０の炭化水素基、及びＣ_１〜Ｃ_１０の含フッ素炭化水素基から成る群から選ばれる１価の基であり、ｌは０〜２から選ばれる整数であり、ｍは０〜３から選ばれる整数であり、そしてｎは０〜４から選ばれる整数である。｝
で表される構造を有する基が挙げられるが、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よい。上記式（２０）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。 _{N 1} in the general formula (2) is not limited as long as it is an integer of 2 to 150, but an integer of 3 to 100 is preferable, and an integer of 5 to 70 is preferable from the viewpoint of the photosensitive characteristics and mechanical characteristics of the negative photosensitive resin composition. An integer of is more preferred.
In the general formula (2), the _{tetravalent organic group represented by X 1} is preferably an organic group having 6 to 40 carbon atoms, and more preferably, in terms of achieving both heat resistance and photosensitive characteristics. aromatic group -COOR ₁ group and -COOR ₂ group and -CONH- and groups are in the ortho position to each other, or an alicyclic aliphatic group. As the _{tetravalent organic group represented by X 1} , specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (20):

{Wherein, R6 is a hydrogen atom, a fluorine _atom, a monovalent group selected from the group consisting of a fluorine-containing hydrocarbon group of a hydrocarbon group and a _C 1 _{-C 10,} of C 1 _{-C 10,} l is 0 It is an integer selected from ~ 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4. }
Examples thereof include, but are not limited to, groups having a structure represented by. Further, _{the structure of X 1} may be one kind or a combination of two or more kinds. X ₁ group having the structure represented by the above formula (20) are particularly preferred in that they both the photosensitive characteristic heat resistance.

｛式中、Ｒ６は水素原子、フッ素原子、Ｃ_１〜Ｃ_１０の炭化水素基、及びＣ_１〜Ｃ_１０の含フッ素炭化水素基から成る群から選ばれる１価の基であり、そして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よい。上記式（２１）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 (2), the divalent organic group represented by Y ₁ in that they both heat resistance and sensitivity characteristics, is preferably an aromatic group having 6 to 40 carbon atoms, for example, The following formula (21):

{Wherein, R6 is a hydrogen atom, a fluorine _atom, a monovalent group selected from the group consisting of a fluorine-containing hydrocarbon group of a hydrocarbon group and a _C 1 _{-C 10,} of C 1 _{-C 10,} and n It is an integer selected from 0 to 4. }
The structure represented by is mentioned, but is not limited to these. Further, _{the structure of Y 1} may be one kind or a combination of two or more kinds. _One Y group having a structure represented by the above formula (21) is particularly preferable in terms of achieving both heat resistance and photosensitive characteristics.

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

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体であることが好ましい。
一般式（４）において、Ｒ_１及びＲ_２の少なくともいずれかは、上記一般式（３）で表される１価の有機基であることがより好ましい。（Ａ）ポリイミド前駆体が、一般式（４）で表されるポリイミド前駆体を含むことで、特に解像性の効果が高くなる。In one embodiment, the (A) polyimide precursor is based on the following general formula (4):

{In the equation, R ₁ , R ₂ , and n ₁ are defined in the general equation (2). }
It is preferable that it is a polyimide precursor having a structural unit represented by.
In the general formula (4), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the general formula (3). (A) When the polyimide precursor contains the polyimide precursor represented by the general formula (4), the effect of resolution is particularly enhanced.

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体であることが好ましい。
一般式（５）において、Ｒ_１及びＲ_２の少なくともいずれかは、上記一般式（３）で表される１価の有機基であることがより好ましい。（Ａ）ポリイミド前駆体が、一般式（４）で表されるポリイミド前駆体に加えて、一般式（５）で表されるポリイミド前駆体を含むことにより、特に解像性の効果がさらに高くなる。その場合、一般式（５）中のＲ_１、Ｒ_２、及びｎ_１は、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは独立して選択される。In one embodiment, the (A) polyimide precursor is based on the following general formula (5):

{In the equation, R ₁ , R ₂ , and n ₁ are defined in the general equation (2). }
It is preferable that it is a polyimide precursor having a structural unit represented by.
In the general formula (5), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the general formula (3). (A) Since the polyimide precursor contains the polyimide precursor represented by the general formula (5) in addition to the polyimide precursor represented by the general formula (4), the effect of resolution is particularly high. Become. In that case, the general formula (5) _R 1, _{R 2} in, and _{n 1} is the general formula (4) _R 1, _{R 2} in, and the _{n 1} are independently selected.

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は一般式（２）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体であることが好ましい。
一般式（６）において、Ｒ_１及びＲ_２の少なくともいずれかは、上記一般式（３）で表される１価の有機基であることがより好ましい。（Ａ）ポリイミド前駆体が、一般式（４）で表されるポリイミド前駆体に加えて、一般式（６）で表されるポリイミド前駆体を含むことにより、特に解像性の効果がさらに高くなる。その場合、一般式（６）中のＲ_１、Ｒ_２、及びｎ_１は、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは独立して選択される。In one embodiment, the (A) polyimide precursor is based on the following general formula (6):

{In the equation, R ₁ , R ₂ , and n ₁ are defined in the general equation (2). }
It is preferable that it is a polyimide precursor having a structural unit represented by.
In the general formula (6), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the general formula (3). (A) Since the polyimide precursor contains the polyimide precursor represented by the general formula (6) in addition to the polyimide precursor represented by the general formula (4), the effect of resolution is particularly high. Become. In that case, the general formula (6) _R 1, _{R 2} in, and _{n 1} is the general formula (4) _R 1, _{R 2} in, and the _{n 1} are independently selected.

(A) Method for preparing a polyimide precursor (A) The polyimide precursor is first _{a tetracarboxylic acid dianhydride containing the above-mentioned tetravalent organic group X 1} and alcohols having a photopolymerizable unsaturated double bond. And optionally react with alcohols that do not have an unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester compound), and then this and the above-mentioned 2 and diamines containing valent organic group Y ₁ can be obtained by engagement amide polycondensation.

(Preparation of acid / ester)
_{In the present embodiment, the tetracarboxylic acid dianhydride containing the tetravalent organic group X 1} preferably used for preparing the (A) polyimide precursor is the tetracarboxylic represented by the above general formula (20). Including acid dianhydride, for example, pyromellitic anhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid dianhydride. Biphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylsulfone-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3', 4, 4'-Tetracarboxylic dianhydride, 2,2-bis (3,4-anhydride) propane, 2,2-bis (3,4-anhydride)-1,1,1,3,3 , 3-Hexafluoropropane and the like, preferably pyromellitic anhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid. Dianhydrides, biphenyl-3,3', 4,4'-tetracarboxylic acid dianhydrides can be mentioned, but are not limited thereto. In addition, these can be used alone or in combination of two or more.

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

The alcohols having a photopolymerizable unsaturated double bond include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol and 3-pentanol. , Neopentyl Alcohol, 1-Heptanol, 2-Heptanol, 3-Heptanol, 1-Octanol, 2-Octanol, 3-Octanol, 1-Nonanol, Triethylene Glycol Monomethyl Ether, Triethylene Glycol Monoethyl Ether, Tetraethylene Glycol Monomethyl Alcohols having no unsaturated double bond such as ether, tetraethylene glycol monoethyl ether, and benzyl alcohol can also be partially mixed and used.

Further, as the polyimide precursor, a non-photosensitive polyimide precursor prepared only with alcohols having no unsaturated double bond may be mixed with the photosensitive polyimide precursor and used. From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

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

(Preparation of polyimide precursor)
A suitable dehydration condensing agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, is added to the acid / ester compound (typically a solution in a solvent described later) under ice-cooling. 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, etc. are added and mixed to make an acid / ester compound into a polyacid anhydride. , those diamines containing preferably a divalent organic group Y ₁ used in this embodiment were separately dissolved or dispersed in a solvent is dropped on, by engaged amide polycondensation, to obtain a polyimide precursor of interest Can be done. Alternatively, the acid / ester compound is acid-chlorided with thionyl chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain the desired polyimide precursor. be able to.

The diamines containing divalent organic group Y ₁ used suitably in the present embodiment, including the diamine having a structure represented by the general formula (21), for example, p- phenylenediamine, m- phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl , 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1, , 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] Sulfon, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4-bis (4-aminophenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4-amino) biphenyl Phenoxy) 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-tridin sulfone, 9,9-bis (4-Aminophenyl) fluorene and some of the hydrogen atoms on these benzene rings are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, etc., for example, 3,3'-. Dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-4,4'-diamino Examples thereof include, but are not limited to, biphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

After completion of the amide polycondensation reaction, the water-absorbing by-products of the dehydration condensate coexisting in the reaction solution are filtered out as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added. The polymer is purified by pouring it into the obtained polymer component, precipitating the polymer component, and further repeating the redissolution and reprecipitation precipitation operations to purify the polymer, vacuum dry it, and obtain the desired polyimide precursor. Release. In order to improve the degree of purification, a solution of this polymer may be passed through a column filled with anions and / or cation exchange resins swollen with a suitable organic solvent to remove ionic impurities.

The molecular weight of the (A) polyimide precursor is preferably 8,000 to 150,000, preferably 9,000 to 50,000, as measured by the polystyrene-equivalent weight average molecular weight by gel permeation chromatography. Is more preferable. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developing solution is good, and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from Showa Denko's organic solvent-based standard sample STANDARD SM-105.

(B) Base-protected compound The (B) base-protected compound in the first embodiment has a plurality of amino groups protected by an acid or a base or a group deprotected by heat, and has a molecular weight of 250 to 600. Yes, the protected amino group is an aliphatic chain or alicyclic amino group, and the value of the solubility parameter is 20.0 to 22.0.

(B) The molecular weight of the base-protected compound is 250 to 600. When the molecular weight is 250 or more, the base-protected compound remains in the film even after thermosetting, and the effect of suppressing Cu voids can be exhibited. The molecular weight is preferably 300 or more, more preferably 340 or more. On the other hand, from the viewpoint of obtaining high resolution, the molecular weight is preferably 600 or less, more preferably 550 or less, more preferably 450 or less, and even more preferably 400 or less.

(B) The plurality of protected amino groups of the base-protected compound are aliphatic chain-type or alicyclic amino groups. Since the aliphatic chain-type and alicyclic amino groups have higher nucleophilicity than the aromatic amino groups, it is easy to introduce a protecting group.

(B) The value of the solubility parameter of the base-protected compound shall be 20.0 to 24.0. In the present specification, the "solubility parameter" is a solubility parameter obtained by the calculation method of Hoy. When the solubility parameter is 20.0 or more, the solubility in a solvent is sufficiently high, preferably 20.5 or more, and more preferably 21.0 or more. When the solubility parameter is 24.0 or less, the affinity for the solvent becomes appropriate, the chemical solution does not easily soak into the cured relief pattern during the chemical resistance test, and a cured relief pattern having excellent chemical resistance can be obtained. From the viewpoint of chemical resistance, the value of the solubility parameter is preferably 23.5 or less, more preferably 23.0 or less, still more preferably 22.5 or less, still more preferably 22.0 or less.

Preferable examples of groups that are deprotected by acid or base or heat include, but are not limited to, tert-butoxycarbonyl groups, Fmoc groups. Here, the Fmoc group refers to a 9-fluorenylmethyloxycarbonyl group. More preferably, the one or more amino groups are amino groups protected by a tert-butoxycarbonyl group.

When the amino group is deprotected during heat curing, the basicity of the amino group promotes imide cyclization, so a heat-deprotected group is preferable. Further, from the viewpoint of ease of synthesis of the compound and the viewpoint of resolution, the compound is preferably protected by a tert-butoxycarbonyl group. It is considered that the compound protected by the tert-butoxycarbonyl group exhibits good resolution because the solubility in a developing solution is good and the residue is suppressed.

When the above-mentioned base-protected compound is used, good chemical resistance, resolution, and Cu void suppressing effect can be obtained. Although not bound by theory, the reason why good chemical resistance can be obtained is that the inclusion of a compound having a solubility parameter and a molecular weight in a certain range improves the fluidity of the polyimide resin in the thermosetting process. Is considered to be. As a result, it is considered that the improved fluidity promotes stacking between the imide rings and suppresses the invasion of the chemical solution. Further, although the reason why good resolution can be obtained is unknown, it is considered that the base-protected compound has a solubility parameter in a certain range, which makes it easier to dissolve in a developing solution and suppresses the residue. Be done. In addition, although the reason for the effect of suppressing Cu voids is not clear, having a plurality of nitrogen atoms derived from a protected amino group in the molecule allows them to interact strongly with Cu ions and diffuse Cu. It is considered to suppress and as a result suppress Cu voids.

There is no limitation as long as the number of protected amino groups contained in the molecule of the base-protected compound is 2 or more. From the viewpoint of solubility in a solvent, the compound is preferably a compound in which the amino group of an amine selected from the group consisting of diamine, triamine, and tetraamine is protected. From the viewpoint of coordinating to copper, a compound in which the amino group of the diamine is protected is more preferable. The base-protected compound preferably has at least one protected amino group at each end of the molecule. More preferably, the number of protected amino groups is two, and the base-protected compound preferably has one protected amino group at each end of the molecule.

The base-protected compound preferably does not contain an acidic group such as a carboxyl group, a sulfo group, or a phosphoric acid group. By not containing these acidic groups, damage to copper wiring is reduced. Further, the base-protected compound preferably does not contain an alicyclic structure from the viewpoint of solubility, and preferably does not contain an aromatic group from the viewpoint of chemical resistance. Similarly, from the viewpoint of chemical resistance, it is preferable that it does not contain a hydroxyl group.

Specific examples of the above-mentioned base-protected compound include, but are not limited to, 1,3-di-4-piperidylpropane, 1,4-butanediol (3-aminopropyl) ether, and diethylene glycolbis (3-aminopropyl) ether. , 1,2-bis (2-aminoethoxy) ethane, 2,2-oxybis (ethylamine), 1,3-diaminopropane, m-xylylene diamine, p-xylylene diamine, 1,4-dicyclohexanediamine, Examples thereof include compounds in which an amino group such as 1,4-bis (aminomethyl) cyclohexane and 1,3-bis (aminomethyl) cyclohexane is protected with a tert-butoxycarbonyl group.

The base-protected compound is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. (A) When the base-protected compound is 0.1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyimide precursor, the effect of suppressing Cu voids, improving the resolution and improving the chemical resistance can be obtained. A particularly excellent negative photosensitive resin composition can be obtained.

(C) Photopolymerization Initiator The (C) photopolymerization initiator used in the first to third embodiments will be described. The photopolymerization initiator is preferably a photoradical polymerization initiator, which is a benzophenone derivative such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and fluorenone. Acetophenone derivatives such as 2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, Benzyl derivatives such as benzyl dimethyl ketal and benzyl-β-methoxyethyl acetophenone, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butandion-2- (o-methoxycarbonyl) oxime, 1-phenyl- 1,2-Propandione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2 Oximes such as − (o-benzoyl) oxime, 1,3-diphenylpropanthrion-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrion-2- (o-benzoyl) oxime, N -N-arylglycines such as phenylglycine, peroxides such as benzoylparkloride, aromatic biimidazoles, titanocene, α- (n-octanesluphonyloxyimino) -4-methoxybenzylchanide and the like. Acid generators and the like are preferably mentioned, but are not limited thereto. Among the above-mentioned photopolymerization initiators, oximes are more preferable in terms of photosensitivity.

The blending amount of the (C) photopolymerization initiator is preferably 0.1 part by mass or more and 20 parts by mass, and more preferably 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor. Is. The blending amount is 0.1 part by mass or more from the viewpoint of light sensitivity or patterning property, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

The negative photosensitive resin composition of the present embodiment may further contain components other than the above components (A) to (C). The components other than the components (A) to (C) are not limited, but are limited to a solvent, a nitrogen-containing heterocyclic compound, a hindered phenol compound, an organic titanium compound, an adhesion aid, a sensitizer, a photopolymerizable unsaturated monomer, and the like. Examples include thermal polymerization inhibitors.

｛式中Ｚは、水素原子又はメチル基である。また、両端の結合は分子内の他の部分への単結合を表す。｝で表される構造単位を分子内に含む、エーテル化合物である。
エーテル化合物は、分子内のいずれかの位置に、上記一般式（１）で表される構造単位を少なくとも一つ有していればよく、分子内での該構造単位の配置は限定されない。例えば、エーテル化合物は、分子内に、複数の該構造単位を連続して有していてもよく、該構造単位同士の間に他の構造が介在していてもよい。該構造単位は、エーテル化合物の分子内に規則的に配置されていてもよく、ランダムに配置されていてもよい。(D) Ether compound The (D) ether compound in the second embodiment includes an amino group protected by an acid or a base or a group deprotected by heat, and the following general formula (1):.

{Z in the formula is a hydrogen atom or a methyl group. Also, the bonds at both ends represent single bonds to other parts of the molecule. } Is an ether compound containing a structural unit represented by the above in the molecule.
The ether compound may have at least one structural unit represented by the above general formula (1) at any position in the molecule, and the arrangement of the structural unit in the molecule is not limited. For example, the ether compound may have a plurality of the structural units in succession in the molecule, or other structures may intervene between the structural units. The structural units may be regularly arranged in the molecule of the ether compound or may be randomly arranged.

Examples of the ether compound include 1,4-butanolbis (3-aminopropyl) ether, 1,2-bis (2-aminoethoxy) ethane, 2,2'-oxybis (ethylamine), and 1,14-diamino-. Of 3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis (3-aminopropyl) ether, or 1,11-diamino-3,6,9-trioxaundecane The amino group may be a compound protected with an acid or a base or a group deprotected by heat. Commercially available ether compounds include JEFFAMIN® D-230, D-400, D-2000, D-4000, M-600, M-1000, M-2005, M-2070, T-403, T- The amino groups of 3000, T-5000, HK-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, XTJ-435, or XTJ-436 are removed with acid, base or heat. Examples include, but are not limited to, compounds protected with a protected group.

Preferable examples of groups that are deprotected by acid or base or heat include, but are not limited to, tert-butoxycarbonyl groups, Fmoc groups. Here, the Fmoc group refers to a 9-fluorenylmethyloxycarbonyl group. More preferably, the one or more amino groups are amino groups protected by a tert-butoxycarbonyl group.

When the amino group is deprotected during heat curing, the basicity of the amino group promotes imide cyclization, so a heat-deprotected group is preferable. Further, from the viewpoint of ease of synthesis of the compound and the viewpoint of resolution, the compound is preferably protected by a tert-butoxycarbonyl group. It is considered that the compound protected by the tert-butoxycarbonyl group exhibits good resolution because the solubility in a developing solution is good and the residue is suppressed.

When the above ether compound is used, good chemical resistance, resolution, and Cu void suppressing effect can be obtained. Although not bound by theory, it is thought that the reason why good chemical resistance can be obtained is that the fluidity of the polyimide resin in the thermosetting process is improved by containing a compound having a flexible ether bond. Be done. As a result, it is considered that the improved fluidity promotes stacking between the imide rings and suppresses the invasion of the chemical solution. Further, the reason why good resolution can be obtained is unknown, but it is considered that the structural portion of the general formula (1) is easily dissolved in the developing solution and the residue is suppressed. In addition, although the reason for exhibiting the effect of suppressing Cu voids is not clear, by including a nitrogen atom derived from a protected amino group and an ether group derived from the structure of the above general formula (1) in the same molecule, It is considered that it interacts strongly with Cu ions, suppresses the diffusion of Cu, and as a result suppresses Cu voids.

The number of protected amino groups contained in the molecule of the ether compound is not limited, but the amino of an amine selected from the group consisting of monoamines, diamines, triamines, and tetraamines from the viewpoint of solubility in a solvent. It is preferably a compound in which the group is protected, and more preferably a compound in which the amino group of monoamine or diamine is protected. On the other hand, from the viewpoint of coordinating to copper, a compound in which the amino group of the diamine is protected is particularly preferable. When the number of protected amino groups is two or more, the ether compound has at least one protected amino group at both ends of the molecule containing the structural unit represented by the above general formula (1). Is preferable. More preferably, the number of protected amino groups is two, and the ether compound has one protected amino group at each end of the molecule containing the structural unit represented by the above general formula (1). Is preferable.

Further, the structural unit of the general formula (1) contained in the molecule of the ether compound is preferably two or more. By including two or more structural units of the general formula (1), the resolution is further improved. On the other hand, if there are too many structural units of the general formula (1), swelling occurs in the pattern development process and the resolution is deteriorated. Therefore, the structure of the general formula (1) contained in the molecule. The number of units is preferably 100 or less, more preferably 50 or less, and particularly preferably 30 or less.

When two or more structural units of the general formula (1) are included, Z in the general formula (1) may be the same or different from each other, but it is preferable that they are the same. Further, Z in the general formula (1) is preferably a hydrogen atom from the viewpoint of the effect of suppressing Cu voids. It is considered that the hydrogen atom in the vicinity of the ether group reduces the steric obstacle and improves the coordinating property to Cu.

The ratio (molar ratio) of the total number of protected amino groups contained in the molecule of the ether compound to the total number of structural units of the general formula (1) may be 2: 1 to 2:16. It is preferable, more preferably 2: 1 to 2: 8, and particularly preferably 2: 2 to 2: 6. Within this range, the effect of suppressing Cu voids is enhanced.

The ether compound preferably does not contain an acidic group such as a carboxyl group, a sulfo group or a phosphoric acid group. By not containing these acidic groups, damage to copper wiring is reduced. Further, the ether compound preferably does not contain an alicyclic structure from the viewpoint of solubility, and preferably does not contain an aromatic group from the viewpoint of chemical resistance. Similarly, from the viewpoint of chemical resistance, it is preferable that it does not contain a hydroxyl group.

Specific examples of the ether compound are not limited, but are preferably ether compounds represented by the following chemical formulas.

Depending on the type of the ether compound, it is considered that the protecting group of the amino group may be decomposed in the thermosetting process, but it may or may not be decomposed.

The ether compound is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor. (A) By blending in the range of 0.1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyimide precursor, the effect of suppressing Cu voids, improving the resolution and improving the chemical resistance are particularly effective. An excellent negative photosensitive resin composition can be obtained.

(E) Urethane compound The (E) urethane compound in the third embodiment contains at least one or more amino groups protected by an acid or a base or a group deprotected by heat, and a hydroxyl group in the molecule. Including one.

Preferable examples of groups that are deprotected by acid or base or heat include, but are not limited to, tert-butoxycarbonyl groups, Fmoc groups. Here, the Fmoc group refers to a 9-fluorenylmethyloxycarbonyl group. More preferably, the one or more amino groups are amino groups protected by a tert-butoxycarbonyl group.

When the amino group is deprotected during heat curing, the basicity of the amino group promotes imide cyclization, so a heat-deprotected group is preferable. Further, from the viewpoint of ease of synthesis of the compound and the viewpoint of resolution, the compound is preferably protected by a tert-butoxycarbonyl group. It is considered that the compound protected by the tert-butoxycarbonyl group exhibits good resolution because the solubility in a developing solution is good and the residue is suppressed.

The number of protected amino groups contained in the molecule of the urethane compound is not limited, but is preferably an amine selected from the group consisting of monoamines, diamines, triamines, and tetraamines from the viewpoint of solubility in a solvent. It is preferably a compound in which the amino group of monoamine is protected, more preferably a compound in which the amino group of monoamine or diamine is protected, and even more preferably a compound in which the amino group of monoamine is protected.

｛式中、Ｒ_１０は、ｔｅｒｔ−ブトキシカルボニル基またはベンジルオキシカルボニル基またはＦｍｏｃ基のいずれかであり、Ｒ_１１、Ｒ_１２、及びＲ_１３は、それぞれ独立に、水素原子、ヒドロキシル基、炭素数１〜２０の有機基、又はヒドロキシル基を有する炭素数１〜２０の有機基のいずれかであるが、Ｒ_１１、Ｒ_１２、及びＲ_１３の少なくとも一つは、ヒドロキシル基若しくはヒドロキシル基を有する炭素数１〜２０の有機基のいずれかである。｝
又は下記一般式（ＸＩＩ）：

｛式中、Ｒ_１０はｔｅｒｔ−ブトキシカルボニル基またはベンジルオキシカルボニル基またはＦｍｏｃ基のいずれかであり、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４、Ｒ_１５、及びＲ_１６は、それぞれ独立に、水素原子、ヒドロキシル基、炭素数１〜２０の有機基、又はヒドロキシル基を有する炭素数１〜２０の有機基のいずれかであるが、Ｒ_１１、Ｒ_１２、及びＲ_１３の少なくとも一つは、ヒドロキシル基若しくはヒドロキシル基を有する炭素数１〜２０の有機基のいずれかである。｝
で表すことができる。上記炭素数１〜２０の有機基は、飽和又は不飽和アルキル基、飽和又は不飽和シクロアルキル基、芳香族基等が挙げられる。これらの有機基は、当該有機基中に、炭化水素基以外の窒素原子、酸素原子、硫黄原子等を含む結合又は置換基を含んでよく、これらは、直鎖上でも分岐状でも環状構造を含んでもよい。The urethane compound (E) is preferably a tert-butoxycarbonyl group, a benzyloxycarbonyl group, or 9 bonded to an aliphatic amino group, more particularly to an aliphatic chain or alicyclic amino group. -The aliphatic amino group containing at least one fluorenylmethyloxycarbonyl (Fmoc) group in the molecule and at least one hydroxyl group in the molecule is a linear primary or secondary amino group, or a fat. It refers to an amino group to which an aromatic group or a heterocyclic group is not directly bonded to the nitrogen atom of the cyclic secondary amino group. That is, the urethane compound used in this embodiment has the following general formula (XI) :.

_{{Wherein, R 10} is either tert- butoxycarbonyl group or benzyloxycarbonyl group or Fmoc _group, R _{11, R 12,} and _{R 13} each independently represent a hydrogen atom, a hydroxyl group, the number of carbon atoms Either 1 to 20 organic groups or 1 to 20 carbon atoms having a hydroxyl group, but _{at least one of R 11} , R ₁₂ , and R ₁₃ is a hydroxyl group or a carbon having a hydroxyl group. It is one of the number 1 to 20 organic groups. }
Or the following general formula (XII):

_{{Wherein, R 10} is either tert- butoxycarbonyl group or benzyloxycarbonyl group or Fmoc _{group, R 11, R 12, R} 13, R 14, R 15, and _{R 16} are each independently, It is either a hydrogen atom, a hydroxyl group, an organic group having 1 to 20 carbon atoms, or an organic group having a hydroxyl group and having 1 to 20 carbon atoms, but at least one of _{R 11} , R ₁₂ , and R _{13 is.} It is either a hydroxyl group or an organic group having a hydroxyl group and having 1 to 20 carbon atoms. }
Can be represented by. Examples of the organic group having 1 to 20 carbon atoms include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, and an aromatic group. These organic groups may contain a bond or a substituent containing a nitrogen atom, an oxygen atom, a sulfur atom, etc. other than the hydrocarbon group in the organic group, and these have a cyclic structure, whether linear or branched. It may be included.

In the above formula (XI) or (XII), R ₁₁ , R ₁₂ , R _13, R ₁₄ , R ₁₅ and R ₁₆ are independently hydrogen atoms, hydroxyl groups, and organic groups having 1 to 20 carbon atoms. Or any of the organic groups having a hydroxyl group and having 1 to 20 carbon atoms, but _{at least one of R 11} , R ₁₂ , and R ₁₃ is a hydroxyl group or an organic group having 1 to 20 carbon atoms having a hydroxyl group. Either. Further, any two of R ₁₁ , R ₁₂ , R _13, R ₁₄ , R ₁₅ and R ₁₆ may be bonded to form a cyclic structure, or a hydroxyl group may be contained in the cyclic structure. good.

The bonding or substituents other than the hydrocarbon group in the organic groups of R ₁₁ , R ₁₂ , R _13, R ₁₄ , R ₁₅ and R ₁₆ are not particularly limited as long as the effects of the present invention are not impaired. Ether bond, carbonyl bond, amide bond, urethane bond, urea bond, thiourea bond, azo bond, ester bond, urethane bond, hydroxyl group, amino group, aldehyde group, sulfo group, nitro group, azo group, imino group, nitroso group , Diazo group, ethoxy group, methoxy group, cyano group, heterocyclic group and the like, but from the viewpoint of stability, a heterocyclic group or a hydroxyl group is preferable.

When the above urethane compound is used, good resolution and a Cu void suppressing effect can be obtained. The reason why the resolution is improved is that the photosensitive resin composition contains the compound having the above structure, so that the solubility of the resin composition in the developing solution is improved and the residue is suppressed. it is conceivable that. In addition, it is presumed that having the above structure improves the interaction with Cu, prevents the diffusion of Cu ions, and suppresses Cu voids.

｛式中、Ｒ_１０は、ｔｅｒｔ−ブトキシカルボニル基、ベンジルオキシカルボニル基又はＦｍｏｃ基のいずれかである。）
で表される化合物が挙げられるが、これに限定されるものではない。Examples of the urethane compound include the following general formula (XIII):

{In the formula, R ₁₀ is either a tert-butoxycarbonyl group, a benzyloxycarbonyl group or an Fmoc group. )
Examples thereof include, but are not limited to, the compounds represented by.

The urethane compound (E) is preferably a urethane compound having none of the acidic groups contained in the group consisting of a carboxyl group, a sulfo group and a phosphoric acid group. Since the urethane compound does not have an acidic group, the effect of suppressing Cu voids is particularly high.

The urethane compound (E) is preferably a urethane compound in which at least one of the nitrogen atoms bonded to the tert-butoxycarbonyl group, benzyloxycarbonyl group or Fmoc group is at the γ or ε position of the hydroxyl group in the molecule. When the hydroxyl group in the molecule is at the γ-position or the ε-position with respect to the nitrogen atom, a particularly good Cu void suppressing effect can be obtained. Although the reason is not clear, it is thought that the position of the hydroxyl group with respect to the nitrogen atom makes it more strongly interact with Cu ions, suppresses the diffusion of Cu, and as a result suppresses Cu voids. Be done.

The urethane compound (E) is more preferably a urethane compound containing at least one tert-butoxycarbonyl group bonded to an aliphatic chain or alicyclic amino group in the molecule. Although the reason is unknown, it is considered that the inclusion of the tert-butoxycarbonyl group in the molecule further improves the solubility of the unexposed portion in the developing solution and further improves the resolution. For example, a compound _{wherein R 10} is tert- butoxycarbonyl group of the formula (XIII).

で表されるウレタン化合物であることがより好ましい。上記化合物の場合、解像性とＣｕボイド抑制効果の両方の効果に特に優れる。(E) The urethane compound is Nα- (tert-butoxycarbonyl) -L-tryptophanol, 1- (tert-butoxycarbonyl) -4-hydroxypiperidine, or the following chemical formula (1):

It is more preferable that it is a urethane compound represented by. In the case of the above compound, both the resolution and the effect of suppressing Cu voids are particularly excellent.

Depending on the type of urethane compound, the tert-butoxycarbonyl group, benzyloxycarbonyl group or Fmoc group bonded to the aliphatic amino group may be decomposed in the thermosetting process, but it may be decomposed. May be.

The blending amount of the urethane compound (E) is preferably 0.01 part by mass to 20 parts by mass, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin (A). From the viewpoint of suppressing Cu voids, it is preferably 0.01 parts by mass or more, and from the viewpoint of resolution, it is preferably 20 parts by mass or less. (A) A photosensitive resin composition that is particularly excellent in both the effect of suppressing Cu voids and the effect of improving resolution by blending in the range of 0.01 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin. Obtainable.

In addition to the components (A) to (E) described above, the negative photosensitive resin compositions of the first to third embodiments of the present embodiment include a solvent, a nitrogen-containing heterocyclic compound, a hindered phenol compound, and an organic titanium compound. It may contain other components such as adhesion aids, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors.

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

Among such solvents, those that completely dissolve the produced polymer are preferable, and for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, and tetramethyl Examples thereof include urea and gamma-butyrolactone.

In the photosensitive resin composition of the present embodiment, the amount of the solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. , More preferably in the range of 125-500 parts by mass.

Nitrogen-containing heterocyclic compound When a cured film is formed on a substrate made of copper or a copper alloy using the photosensitive resin composition of the present embodiment, a negative photosensitive resin is used in order to suppress discoloration on copper. The composition may optionally contain a nitrogen-containing heterocyclic compound. Examples of the nitrogen-containing heterocyclic compound include an azole compound and a purine derivative.

Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, and 4-t-butyl-5. -Phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxyphenyl Triazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- Bis (α, α-dimethylbenzyl) phenyl] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2) -Hydroxyphenyl) -benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, hydroxyphenyl Benzotriazole, triltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl- Examples thereof include 1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like.

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

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

When the photosensitive resin composition 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 (A) polyimide precursor, and the light sensitivity characteristics are improved. From the viewpoint, 0.5 to 5 parts by mass is more preferable. When the blending amount of the azole compound (A) with respect to 100 parts by mass of the polyimide precursor is 0.1 part by mass or more, when the photosensitive resin composition of the present embodiment is formed on copper or a copper alloy, copper or Discoloration of the copper alloy surface is suppressed, while the light sensitivity is excellent when the amount is 20 parts by mass or less.

Hindered Phenol Compounds Further, in order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl-4). -Hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4, 4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t) -Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio -Diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrosin) Namamide), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,2'-methylene-bis (4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4- (1-ethylpropyl) -3-hydroxy-2,6- Dimethylbenzyl] -1,3,5-triazine-2,4,6-(1H, 3H, 5H) -trione, 1,3,5-tris [4-triethylmethyl-3-hydroxy-2,6-dimethyl] Benzyl] -1,3 , 5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-Tris (3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3,5 -Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-Tris (4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3 , 5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-Tris (4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2-methyl) Benzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2) , 5-Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5,6-diethyl) -3-Hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3) -Hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy) -2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl) -3-Hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and the like, but are not limited thereto. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H, 3H, 5H) ) -Trione or the like is particularly preferable.

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

Organic Titanium Compound The negative photosensitive resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Examples of the organic titanium compound that can be used include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable because the storage stability of the negative photosensitive resin composition and a good pattern can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanegenate, titanium diisopropoxiside bis (2,4-pentanegeonate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.
III) Titanosen compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetoneate and the like.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, the organic titanium compound is at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound, which exhibits better chemical resistance. It is preferable from the viewpoint. In particular, titanium diisopropoxyside bis (ethylacetacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H)). -Pyrrole-1-yl) Phenyl) Titanium is preferred.

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

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

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

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

で表される構造を有するシランカップリング剤が好ましい。Among the above-mentioned silane coupling agents, the silane coupling agent includes phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, and diethoxy. Diphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the following formula:

A silane coupling agent having a structure represented by is preferable.

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

Sensitizer The negative photosensitive resin composition of the present embodiment may optionally contain a sensitizer in order to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylbinylene) benzothiazole, 2- (p-dimethylaminophenylbinylene) Isonaphthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-Acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylamino) Examples thereof include styryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. These can be used alone or, for example, in a combination of 2 to 5 types.

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

Photopolymerizable unsaturated monomer The negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. As such a monomer, a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is not particularly limited to the following, but ethylene glycol or polyethylene such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Glycol mono or diacrylate and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, glycerol mono, di or triacrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylate and Dimethacrylate, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono or diacrylate and methacrylate of bisphenol A, benzenetrimethacrylate, isobornyl acrylate and methacrylate, acrylamide and the like. Derivatives, methacrylicamides and derivatives thereof, trimethylolpropane triacrylates and methacrylates, di or triacrylates and methacrylates of glycerol, di, tri, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds, etc. Compounds can be mentioned.

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

Thermal Polymerization Inhibitor The negative photosensitive resin composition of the present embodiment is particularly intended to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition during storage in the state of a solution containing a solvent. A thermal polymerization inhibitor may be optionally contained. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6. -Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 (N-ethyl-N-) Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

<Manufacturing method of cured relief pattern and semiconductor device>
In this embodiment, (1) the negative photosensitive resin composition of the present embodiment described above is applied onto a substrate to form a resin layer on the substrate, and (2) the resin layer is exposed. A cured relief pattern including a step of (3) developing the resin layer after exposure to form a relief pattern, and (4) a step of heat-treating the relief pattern to form a cured relief pattern. Provides a manufacturing method for.

(1) Resin layer forming step In this step, the negative photosensitive resin composition of the present embodiment is applied onto a substrate and, if necessary, dried thereafter to form a resin layer. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or a spray coater is used for spray coating. A method or the like can be used.

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

(2) Exposure step In this step, the resin layer formed above is exposed to an exposure device such as a contact aligner, a mirror projection, a stepper, etc., through a photomask or reticle having a pattern, or directly by an ultraviolet light source or the like. To expose.

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

(3) Relief pattern forming step In this step, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of conventionally known photoresist developing methods, for example, a rotary spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, etc. You can select and use the method of. Further, after development, post-development baking may be performed at an arbitrary combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern.

As the developing solution used for development, for example, a good solvent for a negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like are preferable. .. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent by the solubility of the polymer in the negative photosensitive resin composition. Further, two or more kinds of each solvent, for example, several kinds can be used in combination.

(4) Cured relief pattern forming step In this step, the relief pattern obtained by the above development is heated to dilute the photosensitive component, and (A) the polyimide precursor is imidized to form a cured relief made of polyimide. Convert to a pattern. As a method of heat curing, various methods can be selected, for example, a method using a hot plate, a method using an oven, and a method using a temperature-increasing oven in which a temperature program can be set. The heating can be performed, for example, at 170 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas at the time of heat curing, or an inert gas such as nitrogen or argon may be used.

<Semiconductor device>
In the present embodiment, a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern is also provided. Therefore, it is possible to provide a semiconductor device having a base material which is a semiconductor element and a cured relief pattern of polyimide formed on the base material by the above-mentioned cured relief pattern manufacturing method. The present invention can also be applied to a method for manufacturing a semiconductor device, which uses a semiconductor device as a base material and includes the above-mentioned method for manufacturing a cured relief pattern as a part of a process. The semiconductor device of the present embodiment is a semiconductor having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure, in which the cured relief pattern formed by the above-mentioned curing relief pattern manufacturing method is used. It can be manufactured by forming it as a protective film or the like of a device and combining it with a known manufacturing method of a semiconductor device.

<Display device>
In the present embodiment, there is provided a display body device including a display body element and a cured film provided on the upper part of the display body element, wherein the cured film is the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched between them. For example, examples of the cured film include a surface protective film, an insulating film, and a flattening film of a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a partition wall for an organic EL element cathode. ..

The negative photosensitive resin composition of the present embodiment is applied to semiconductor devices as described above, and is also used for interlayer insulation of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like. It is also useful.

Hereinafter, the present embodiment will be specifically described with reference to Examples, but the present embodiment is not limited thereto. In Examples, Comparative Examples, and Production Examples, the physical characteristics of the polymer or negative photosensitive resin composition were measured and evaluated according to the following methods.

<Measurement and evaluation method>
(1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured under the following conditions using a gel permeation chromatography method (standard polystyrene conversion).
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Showa Denko Co., Ltd. Shodex KD-806M Two in series, or
Showa Denko Co., Ltd. Shodex 805M / 806M series standard monodisperse polystyrene: Showa Denko Co., Ltd. Shodex STANDARD SM-105
Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP)
Flow rate: 1 mL / min.

(2) Preparation of cured relief pattern on Cu 200 nm on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a sputtering device (L-440S-FHL type, manufactured by Canon Anerva). Thick Ti and 400 nm thick Cu were sputtered in this order. Subsequently, the photosensitive resin composition prepared by the method described below is spin-coated on this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO), and prebaked at 110 ° C. for 180 seconds on a hot plate. This was done to form a coating film with a thickness of about 7 μm. This coating film was irradiated with energy of 500 mJ / cm2 by Prisma GHI (manufactured by Ultratech) using a mask with a test pattern. Next, this coating film was spray-developed with a coater developer (D-Spin 60A type, manufactured by SOKUDO) using cyclopentanone in the case of a negative type and 2.38% TMAH in the case of a positive type as a developer. A relief pattern on Cu was obtained by rinsing with propylene glycol methyl ether acetate in the case of the negative type and pure water in the case of the positive type.
The wafer having the relief pattern formed on Cu is heat-treated for 2 hours at the temperature shown in Table 1 under a nitrogen atmosphere using a temperature rise program type curing furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.). A cured relief pattern made of a resin having a thickness of about 4 to 5 μm was obtained on Cu.

(3) Evaluation of resolution of cured relief pattern on Cu The cured relief pattern obtained by the above method was observed under an optical microscope, and the size of the minimum aperture pattern was determined. At this time, if the area of the opening of the obtained pattern is ½ or more of the corresponding pattern mask opening area, it is considered to be resolved, and the one having the minimum area among the resolved openings is selected. The length of the corresponding mask opening side was taken as the resolution. Those with a resolution of less than 10 μm were rated as “excellent”, those with a resolution of 10 μm or more and less than 14 μm were rated as “good”, those with a resolution of 14 μm or more and less than 18 μm were rated as “possible”, and those with a resolution of 18 μm or more were rated as “impossible”.

(4) High temperature storage test of the cured relief pattern on Cu and subsequent evaluation of void area The wafer on which the cured relief pattern was formed on Cu was placed in a temperature rise program type cure furnace (VF-2000 type, Using (manufactured by Koyo Lindbergh), the mixture was heated in air at 150 ° C. for 168 hours. Subsequently, using a plasma surface treatment device (EXAM type, manufactured by Shinko Seiki Co., Ltd.), all the resin layers on Cu were removed by plasma etching. The plasma etching conditions are as follows.
Output: 133W
Gas type / flow rate: O2: 40 mL / min + CF4: 1 mL / min Gas pressure: 50 Pa
Mode: Hard mode Etching time: 1800 seconds The Cu surface from which the resin layer has been completely removed is observed by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and image analysis software (A image-kun, manufactured by Asahi Kasei Corporation). Was used to calculate the area of voids on the surface of the Cu layer. When the total area of voids when the photosensitive resin composition described in Comparative Example 5 is evaluated is 100%, those having a total area ratio of voids of less than 50% are "excellent", and 50% or more and less than 75%. Those with 75% or more and less than 100% were judged as "good", those with 100% or more were judged as "impossible".

(5) Chemical resistance evaluation of the cured relief pattern (polyimide coating film) The cured relief pattern formed on Cu is subjected to a resist stripping solution {ATMI, product name ST-44, and the main component is 2- (2-amino). Ethoxy) ethanol, 1-cyclohexyl-2-pyrrolidone} was immersed in a product heated to 50 ° C. for 5 minutes, washed with running water for 1 minute, and air-dried. Then, the surface of the film was visually observed with an optical microscope, and the chemical resistance was evaluated based on the presence or absence of damage due to the chemical solution such as cracks and the rate of change in the film thickness after the chemical solution treatment. As evaluation criteria, those with no cracks and a film thickness change rate of 10% or less based on the film thickness before chemical immersion are "excellent", those with 10 to 15% are "good", and 15 to 20%. Those with cracks or those with a film thickness change rate of more than 20% were regarded as "possible".

<Production example of (A) polyimide precursor>
Production Example 1: (A) Synthesis of Polymer A-1 as a Polyimide Precursor 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was placed in a 2 L volume separable flask, and 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate) was placed. 131.2 g of HEMA) and 400 mL of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of heat generation by the reaction, the reaction mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-oxydianiline (ODA). ) 93.0 g of γ-butyrolactone suspended in 350 mL was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 3 L of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer A-1). When the molecular weight of the polymer (A-1) was measured by gel permeation chromatography (standard polystyrene equivalent), the weight average molecular weight (Mw) was 20,000.

Production Example 2: (A) Synthesis of Polymer A-2 as Polyimide Precursor 3,3', 4,4 instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) of Production Example 1. The reaction was carried out in the same manner as in Production Example 1 described above except that 147.1 g of'-biphenyltetracarboxylic dianhydride (BPDA) was used to obtain a polymer (A-2). When the molecular weight of the polymer (A-2) was measured by gel permeation chromatography (standard polystyrene equivalent), the weight average molecular weight (Mw) was 22,000.

Production Example 3: (A) Synthesis of Polymer A-3 as Polyimide Precursor 50.2 g of p-phenylenediamine was used in place of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1. Except for the above, the 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 equivalent), the weight average molecular weight (Mw) was 19,000.

Production Example 4: (A) Synthesis of Polymer A-4 as Polyimide Precursor (Polybenzoxazole Precursor)
183.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 640.9 g of N, N-dimethylacetamide (DMAc), and 63.3 g of pyridine in a separable flask having a capacity of 3 liters. The mixture was mixed and stirred at room temperature (25 ° C.) to obtain a uniform solution. To this, 118.0 g of 4,4'-diphenyl ether dicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for dropping was 40 minutes, and the reaction liquid temperature was 30 ° C. at the maximum.
3 hours after the completion of the 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 to carboxylate 99% of all amine terminal groups of the polymer chain. It was sealed with a cyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic acid anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, vacuum dried, and measured by gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (polystyrene equivalent) was obtained.
The crude polybenzoxazole precursor obtained above is redissolved in γ-butyrolactone (GBL), treated with a cation exchange resin and an anion exchange resin, and the resulting solution is used in ion exchange water. The precipitated polymer was filtered off, washed with water, and vacuum-dried to obtain a purified polybenzoxazole precursor (polymer A-4).

<Production example of (B) base-protected compound>
Production Example 5: (B) Synthesis of compound B-1 as a base-protected compound In a 1 L-capacity eggplant-shaped flask, 100 g of 1,3-di-4-piperidylpropane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol. Was mixed and stirred with a stirrer to obtain a uniform solution, and the mixture was cooled to 5 ° C. or lower with ice water. To this, 228 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 200 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound B-1. (Molecular weight: 411, Solubility parameter: 20.2)

Production Example 6: (B) Synthesis of compound B-2 as a base-protected compound In a 1 L-capacity eggplant-shaped flask, 100 g of 1,4-butanediol (3-aminopropyl) ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) is added. 100 g of ethanol was added, and the mixture was mixed and stirred with a stirrer to obtain a uniform solution, which was cooled to 5 ° C. or lower with ice water. To this, 234 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 130 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound B-2. (Molecular weight: 405, solubility parameter: 21.2)

Production Example 7: (B) Synthesis of compound B-3 as a base-protected compound 100 g of diethylene glycol bis (3-aminopropyl) ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 100 g of ethanol are added to a 1 L-capacity eggplant-shaped flask. The mixture was mixed and stirred with a stirrer to obtain a uniform solution, and cooled to 5 ° C. or lower with ice water. To this, 215 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 120 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound B-3. (Molecular weight: 421, Solubility parameter: 21.5)

Production Example 8: (B) Synthesis of compound B-4 as a base-protected compound In a 1 L-capacity eggplant-shaped flask, 100 g of 1,2-bis (2-aminoethoxy) ethane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added. 100 g of ethanol was added, and the mixture was mixed and stirred with a stirrer to prepare a uniform solution, and cooled to 5 ° C. or lower with ice water. To this, 319 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 150 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound B-4. (Molecular weight: 348, solubility parameter: 21.9)

Production Example 9: (B) Synthesis of compound B-5 as a base-protected compound 10 g of 2,2'-oxybis (ethylamine) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 10 g of ethanol are placed in a eggplant-shaped flask having a capacity of 250 mL. In addition, the mixture was mixed and stirred with a stirrer to obtain a uniform solution, and cooled to 5 ° C. or lower with ice water. To this, 46 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 40 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound B-5. (Molecular weight: 304, Solubility parameter: 21.9)

Production Example 10: (B) Synthesis of compound B-6 as a base-protected compound To a 250 mL eggplant-shaped flask, 10 g of di-n-octylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 10 g of ethanol are added to stirrer. The mixture was mixed and stirred with a uniform solution, and cooled to 5 ° C. or lower with ice water. To this, 20 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 20 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound B-6. (Molecular weight: 342, solubility parameter: 18.9)

Production Example 11: (B) Synthesis of compound B-7 as a base-protected compound In a eggplant-shaped flask having a capacity of 250 mL, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (Tokyo Chemical Industry Co., Ltd.) (Manufactured) 10 g and 10 g of ethanol were added, mixed and stirred with a stirrer to obtain a uniform solution, and cooled to 5 ° C. or lower with ice water. To this, 12 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 12 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound B-7. (Molecular weight: 611, solubility parameter: 22.0)

<(C) Photopolymerization Initiator>
The (C) photopolymerization initiator used is shown below.
C-1: 1-Phenyl-1,2-Propanedione-2- (O-ethoxycarbonyl) -Oxime C-2: Irgacure OXE01 (manufactured by BASF, trade name)

<Production example of (D) ether compound>
Production Example 12: (D) Synthesis of compound D-1 as an ether compound 100 g of JEFFAMINE (registered trademark) M-600 (manufactured by Huntsman) and 100 g of ethanol are added to an eggplant-shaped flask having a capacity of 1 L, and the mixture is mixed and stirred with a stirrer. The mixture was made into a uniform solution and cooled to 5 ° C. or lower with ice water. To this, 44 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 44 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound D-1.

Production Example 13: (D) Synthesis of compound D-2 as an ether compound 100 g of JEFFAMIN (registered trademark) M-1000 (manufactured by Huntsman) and 100 g of ethanol are added to an eggplant-shaped flask having a capacity of 1 L, and the mixture is mixed and stirred with a stirrer. The mixture was made into a uniform solution and cooled to 5 ° C. or lower with ice water. To this, 26 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 26 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound D-2.

Production Example 14: (D) Synthesis of compound D-3 as an ether compound 100 g of JEFFAMINE (registered trademark) D-400 (distributor: Mitsui Kagaku Fine Co., Ltd.) and 100 g of ethanol are added to a 1 L capacity eggplant-shaped flask. The mixture was mixed and stirred with a stirrer to obtain a uniform solution, and cooled to 5 ° C. or lower with ice water. To this, 110 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 110 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound D-3.

Production Example 15: (D) Synthesis of compound D-4 as an ether compound 100 g of diethylene glycol bis (3-aminopropyl) ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 100 g of ethanol are added to a 1 L capacity eggplant-shaped flask. The mixture was mixed and stirred with a stirrer to obtain a uniform solution, and cooled to 5 ° C. or lower with ice water. To this, 215 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 120 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound D-4.

Production Example 16: (D) Synthesis of compound D-5 as an ether compound In a 1 L capacity eggplant-shaped flask, 100 g of 1,4-butanediol (3-aminopropyl) ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and ethanol. 100 g was added, and the mixture was mixed and stirred with a stirrer to obtain a uniform solution, which was cooled to 5 ° C. or lower with ice water. To this, 234 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 130 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound D-5.

Production Example 17: (D) Synthesis of compound D-6 as an ether compound In a 1 L capacity eggplant-shaped flask, 100 g of 1,2-bis (2-aminoethoxy) ethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol. Was mixed and stirred with a stirrer to obtain a uniform solution, and the mixture was cooled to 5 ° C. or lower with ice water. To this, 319 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 150 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound D-6.

Production Example 18: (D) Synthesis of compound D-7 as an ether compound To an eggplant-shaped flask having a capacity of 250 mL, add 10 g of 2,2'-oxybis (ethylamine) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 g of ethanol. The mixture was mixed and stirred with a stirrer to obtain a uniform solution, and cooled to 5 ° C. or lower with ice water. To this, 46 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 40 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 50 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was concentrated under reduced pressure at 50 ° C. for 3 hours to obtain the desired compound D-7.

<(E) Urethane compound>
The urethane compound (E) used is shown below.
E-1: 1- (tert-butoxycarbonyl) -4-piperidinmethanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-2: 3- (Carboxoxoxyamino) -1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-3: N-[(9H-fluorene-9-ylmethoxy) carbonyl] -D-serine (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-4: 1- (tert-butoxycarbonyl) -4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-5: 40 g of 4-hydroxy-4-phenylpiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 g of ethanol were added to an eggplant-shaped flask having a capacity of 3 L, and the mixture was mixed and stirred to prepare a uniform solution. To this, 54 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 100 g of ethanol was added dropwise by a dropping funnel. At this time, the dropping was performed while adjusting the dropping rate so that the reaction liquid temperature was maintained at 60 ° C. or lower. Two hours after the completion of the dropping, the reaction solution was evaporated under reduced pressure at 50 ° C. to obtain a white solid urethane compound E-5 (compound of the above chemical formula 1).
E-6: Nα- (tert-butoxycarbonyl) -L-tryptophanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-7: N- (tert-butoxycarbonyl) -L-serine (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-8: 1- (tert-butoxycarbonyl) -4-piperidincarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-9: N- (tert-butoxycarbonyl) -4-hydroxyaniline (manufactured by Sigma-Aldrich)
E-10: 2- (2-Aminoethoxy) ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Example 1>
A negative photosensitive resin composition was prepared by the following method using the polymer A-1, and the prepared composition was evaluated. (A) Polymer A-1: 100 g as a polyimide precursor, (B) Compound B-1: 5 g as a base-protected compound, (C) 1-Phenyl-1,2-propanedione-2- (C) as a photopolymerization initiator. O-ethoxycarbonyl) -oxym (hereinafter referred to as PDO, corresponding to the photopolymerization initiator C-1): 3 g was dissolved in γ-butyl lactone (hereinafter referred to as GBL): 150 g. The viscosity of the obtained solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1.

<Examples 2 to 15, Comparative Examples 1 and 2>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the ingredients and compounding ratios were prepared as shown in Tables 1 and 2, and evaluation was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

As is clear from Tables 1 and 2, in the negative photosensitive resin composition of Example 1, the Cu surface void evaluation, the resolution evaluation, and the chemical resistance evaluation were "OK". The negative photosensitive resin compositions of Examples 2 to 15 were all "OK" or higher in all of the Cu surface void evaluation, the resolution evaluation, and the chemical resistance evaluation. In particular, in Example 6 using the polymers A-1 and A-2 as the (A) polyimide precursor, and Example 7 using the polymers A-1 and A-3, particularly excellent Cu surface void evaluation and A resolution evaluation was obtained. Further, as the (B) base-protected compound, when 5 parts by mass of B-2, B-3 or B-4 is added based on 100 parts by mass of the polymer, a particularly excellent effect of suppressing voids on the Cu surface is obtained. Was done. On the other hand, in Comparative Example 1 using B-6 and Comparative Example 2 using B-7, the resolution was "impossible" in the evaluation.

<Example 16>
A negative photosensitive resin composition was prepared by the following method using the polymer A-1, and the prepared composition was evaluated. (A) Polymer A-1: 100 g as a polyimide precursor, (D) Compound D-1: 5 g as an ether compound, (C) 1-Phenyl-1,2-propanedione-2- (O) as a photopolymerization initiator. -Ethoxycarbonyl) -oxime (hereinafter referred to as PDO, corresponding to the photosensitizer C-1): 3 g was dissolved in γ-butyl lactone (hereinafter referred to as GBL): 150 g. The viscosity of the obtained solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 3.

<Examples 17 to 31, Comparative Examples 5 to 7>
A negative photosensitive resin composition was prepared in the same manner as in Example 16 except that the ingredients and compounding ratios were prepared as shown in Table 1, and evaluation was carried out in the same manner as in Example 16. The results are shown in Tables 3 and 4.

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−２に該当）：２０ｇをＧＢＬ１００ｇに溶解した。得られた溶液の粘度を、少量のＧＢＬを更に加えることによって約２０ポイズに調整し、ポジ型感光性樹脂組成物とした。該組成物を、前述の方法に従って評価した。結果を表４に示す。<Comparative Example 3>
A positive photosensitive resin composition was prepared by the following method using the polymer (A-4), and the prepared photosensitive resin composition was evaluated. Polymer A-4: 100 g, which is a polyoxazole precursor as a polymer, D-4: 5 g as a compound, and the following chemical formula (22): as a photosensitive agent.

A photosensitive diazoquinone compound in which 77% of the phenolic hydroxyl group represented by naphthoquinone diazide-4-sulfonic acid esterification (corresponding to C-2, manufactured by Toyo Synthetic Co., Ltd.): 20 g was dissolved in 100 g of GBL. The viscosity of the obtained solution was adjusted to about 20 poise by further adding a small amount of GBL to obtain a positive photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 4.

<Comparative Example 4>
A positive photosensitive resin composition similar to that of Comparative Example 3 was prepared except that the ether compound was prepared using D-5 instead of D-4, and the evaluation was carried out in the same manner as in Comparative Example 3. The results are shown in Table 4.

As is clear from Tables 3 and 4, in the negative photosensitive resin composition of Example 16, the Cu surface void evaluation is “OK”, the resolution evaluation is “Good”, and the chemical resistance evaluation is “OK”. It became. Similarly, all of the negative photosensitive resin compositions of Examples 17 to 31 were "OK" or higher in all of the Cu surface void evaluation, the resolution evaluation, and the chemical resistance evaluation. In particular, in Example 24 in which the polymers A-1 and A-2 were used as the (A) polyimide precursor, and in Example 25 in which the polymers A-1 and A-3 were used, particularly excellent resolution was obtained. Was done. Further, as the (D) ether compound, when 5 parts by mass of D-4, D-5 or D-6 is added based on 100 parts by mass of the polymer, a particularly excellent effect of suppressing voids on the Cu surface can be obtained. rice field. On the other hand, in Comparative Example 5 in which D-9 was used as the ether compound and Comparative Example 6 in which D-10 was used, the Cu surface void area evaluation was “impossible”. Further, in Comparative Example 3 and Comparative Example 4 in which the polymer A-4 which is a polybenzoxazole precursor was used as the polymer, the Cu surface void area evaluation and the chemical resistance evaluation were “impossible”. Then, in Comparative Example 7 containing (D) an ether compound, all the evaluations were "impossible".

<Example 32>
A negative photosensitive resin composition was prepared by the following method using the polymer A-1, and the prepared composition was evaluated. (A) Polymer A-1: 100 g as a resin, (E) 1- (tert-butoxycarbonyl) -4-hydroxypiperidine as a urethane compound (manufactured by Tokyo Kasei Kogyo Co., Ltd., (corresponding to E-4): 5 g, ( C) As a photosensitizer, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (hereinafter referred to as PDO, (corresponding to C-1): 4 g, γ-butyl lactone (hereinafter referred to as PDO)). Then, it was dissolved in GBL): 150 g. The viscosity of the obtained solution was adjusted to about 30 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. The evaluation was performed according to the above method. The results are shown in Table 5.

<Examples 33 to 47, Comparative Examples 8 to 11>
A negative photosensitive resin composition was prepared in the same manner as in Example 32 except that the ingredients and compounding ratios were prepared as shown in Tables 5 and 6, and evaluation was performed in the same manner as in Example 32. The results are shown in Tables 5 and 6.

As is clear from Tables 5 and 6, in the photosensitive resin composition of Example 32, the resolution evaluation was "good", and the void area evaluation of the Cu surface was "best". Similarly, all of the photosensitive resin compositions of Examples 33 to 47 were "OK" or higher in both the resolution evaluation and the void area evaluation of the Cu surface. In particular, in Example 33 using the polymers A-1 and A-2 and Example 34 using the polymers A-1 and A-3 as the resin (A), particularly excellent resolution was obtained. Further, as the urethane compound (E), E-4, E-5, and E-6 are used, and when 5 parts by mass is added based on 100 parts by mass of the polymer, a particularly excellent effect of suppressing voids on the Cu surface is obtained. It was seen. On the other hand, in Comparative Example 8 in which E-8 was used as the urethane compound (E) and Comparative Example 8 in which E-9 was used, the resolution was "possible", but the void area evaluation of the Cu surface was "possible". It became "impossible". Further, in Comparative Example 10 in which E-10 was used as the (E) urethane compound, the evaluation of the void area on the Cu surface was "OK", but the evaluation of the resolution was "impossible". Then, in Comparative Example 11 in which (E) the urethane compound was not used, both the resolution evaluation and the void area evaluation of the Cu surface were "impossible".

By using the negative photosensitive resin composition according to the present embodiment, a cured relief pattern having high resolution can be obtained, and the generation of voids on the Cu surface can be suppressed. The negative photosensitive resin composition of the present embodiment can be suitably used in the field of photosensitive materials useful for manufacturing electric / electronic materials such as semiconductor devices and multilayer wiring substrates.

Claims (12)

(A) Polyimide precursor;
(B) It has a plurality of amino groups protected by an acid or a base or a group deprotected by heat, has a molecular weight of 250 to 600, and the plurality of protected amino groups are an aliphatic chain or an alicyclic. A negative photosensitive resin composition comprising a base-protected compound having a formula amino group and a solubility parameter value of 20.0 or more and 24.0 or less; and (C) a photopolymerization initiator. The negative photosensitive resin composition according to claim 1, wherein the plurality of protected amino groups are amino groups protected by a tert-butoxycarbonyl group. The (A) polyimide precursor has the following general formula (2):

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are independently hydrogen. It is an atomic or monovalent organic group, and _{at least one of R 1} and R ₂ is a monovalent organic group having a polymerizable group at the terminal. }
The negative photosensitive resin composition according to any one of claims 1 or 2, which comprises a polyimide precursor having a structural unit represented by. In the general formula (2), _{at least one of R 1} and R ₂ is the following general formula (3):

{In the formula, L ₁ , L ₂ and L ₃ 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. } The negative photosensitive resin composition according to claim 3, which is a monovalent organic group represented by. The (A) polyimide precursor has the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to claim 3 or 4, which comprises a polyimide precursor having a structural unit represented by. The (A) polyimide precursor has the following general formula (5):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to claim 3 or 4, which comprises a polyimide precursor having a structural unit represented by. The (A) polyimide precursor has the following general formula (6):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
The negative photosensitive resin composition according to claim 3 or 4, which comprises a polyimide precursor having a structural unit represented by. The (A) polyimide precursor has the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
A polyimide precursor having a structural unit represented by
The following general formula (5):

{In the formula, R ₁ , R ₂ and n ₁ are defined in the general formula (2), except that R ₁ , R ₂ and n ₁ in the general formula (5) are the general formula ( 4) Selected independently _{of R 1} , R ₂ , and n _{1 in.} }
The negative photosensitive resin composition according to claim 3 or 4, which comprises both a polyimide precursor having a structural unit represented by. The (A) polyimide precursor has the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are defined in the above general formula (2). }
A polyimide precursor having a structural unit represented by, and the following general formula (6) :.

{In the formula, R ₁ , R ₂ and n ₁ are defined in the general formula (2), except that R ₁ , R ₂ and n ₁ in the general formula (6) are the general formula ( 4) Selected independently _{of R 1} , R ₂ , and n _{1 in.} }
The negative photosensitive resin composition according to claim 3 or 4, which comprises both a polyimide precursor having a structural unit represented by. With 100 parts by mass of the (A) polyimide precursor,
With reference to 100 parts by mass of the (A) polyimide precursor, 0.1 to 30 parts by mass of the (B) base-protected compound and
The negative type photosensitive according to any one of claims 1 to 9, which comprises 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor. Resin composition. The method for producing a polyimide for curing a negative photosensitive resin composition according to any one of claims 1 to 10. (1) A step of applying the negative photosensitive resin composition according to any one of claims 1 to 10 onto a substrate to form a photosensitive resin layer on the substrate.
(2) The step of exposing the photosensitive resin layer and
(3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, and
(4) A method for producing a cured relief pattern, which comprises a step of heat-treating the relief pattern to form a cured relief pattern.