JP7674451B2 - Negative photosensitive resin composition and method for producing same - Google Patents

Description

The present invention relates to a negative-type photosensitive resin composition and a method for producing the same.

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

Meanwhile, semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards using various methods depending on the purpose. Conventional elements were generally produced using a wire bonding method in which thin wires connect the external terminals (pads) of the element to the lead frame. However, today, as elements have become faster and the operating frequencies have reached the GHz range, differences in the wiring length of each terminal during mounting have come to affect the operation of the element. As a result, when mounting elements for high-end applications, it has become necessary to precisely control the length of the mounting wiring, and it has become difficult to meet this requirement using wire bonding.

Therefore, flip-chip mounting has been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on the rewiring layer, and the chip is then flipped over and mounted directly on a printed circuit board (see, for example, Patent Document 1). This flip-chip mounting allows accurate control of the wiring distance, and is therefore used in high-end devices that handle high-speed signals, and in mobile phones and other devices due to the small mounting size, and demand is rapidly expanding. When materials such as polyimide, polybenzoxazole, and phenolic resin are used for flip-chip mounting, a metal wiring layer formation process is performed after the resin layer pattern is formed. The metal wiring layer is usually formed by plasma etching the surface of the resin layer to roughen the surface, forming a metal layer to a thickness of 1 μm or less by sputtering, which will become a plating seed layer, and then using the metal layer as an electrode, electrolytic plating. In this case, titanium (Ti) is generally used as the metal that will become the seed layer, and copper (Cu) is generally used as the metal for the rewiring layer formed by electrolytic plating.

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

JP 2001-338947 A

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

In addition to the problem of voids, metal redistribution layers are required to be chemically resistant, and there is also a growing demand for finer patterns. For this reason, photosensitive resin compositions used in particular to form semiconductor redistribution layers are required to suppress the occurrence of voids, while also exhibiting high chemical resistance and resolution.

The present invention has been devised in view of such conventional circumstances, and has as its object to provide a negative type photosensitive resin composition (hereinafter, also simply referred to as "photosensitive resin composition" in this specification) that can obtain high chemical resistance and resolution and can suppress the generation of voids at the interface where the Cu layer contacts the resin layer after a high temperature storage test. Another object is to provide a method for forming a cured relief pattern using the negative type photosensitive resin composition of the present invention.
In addition, fan-out type semiconductor packages have been attracting attention in recent years. In fan-out type semiconductor packages, a chip sealing body larger than the chip size of the semiconductor chip is formed by covering the semiconductor chip with an encapsulant. Furthermore, a redistribution layer is formed that extends to the area of the semiconductor chip and the encapsulant. The redistribution layer is formed with a thin film thickness. Furthermore, since the redistribution layer can be formed up to the area of the encapsulant, the number of external connection terminals can be increased.

｛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、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、［１］又は［２］に記載のネガ型感光性樹脂組成物。
［４］
前記一般式（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、［３］に記載のネガ型感光性樹脂組成物。
［５］
前記一般式（２）において、Ｘ_１が、下記一般式（２０ａ）：

で表される構造を含む、［３］又は［４］に記載のネガ型感光性樹脂組成物。
［６］
前記一般式（２）において、Ｘ_１が、下記一般式（２０ｂ）：

で表される構造を含む、［３］又は［４］に記載のネガ型感光性樹脂組成物。
［７］
前記一般式（２）において、Ｙ_１が、下記一般式（２１ｂ）：

で表される構造を含む、［３］～［６］のいずれか一項に記載のネガ型感光性樹脂組成物。
［８］
前記（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、［３］又は［４］に記載のネガ型感光性樹脂組成物。
［９］
前記（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、［３］又は［４］に記載のネガ型感光性樹脂組成物。
［１０］
前記（Ａ）ポリイミド前駆体が、下記一般式（４）及び（５）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は、それぞれ、上記に定義したものであり、一般式（５）中のＲ_１、Ｒ_２、及びｎ_１とは同じであるか、又は異なってよい。｝

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は、それぞれ、上記に定義したものであり、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは同じであるか、又は異なってよい。｝
で表される構造単位を同時に含む、［３］～［９］のいずれか一項に記載のネガ型感光性樹脂組成物。
［１１］
前記（Ａ）ポリイミド前駆体が、前記一般式（４）と（５）で表される構造単位の共重合体である、［１０］に記載のネガ型感光性樹脂組成物。
［１２］
１００質量部の前記（Ａ）ポリイミド前駆体と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～３０質量部の前記（Ｂ）活性エステル化剤と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～２０質量部の前記（Ｃ）光重合開始剤と
を含む、［１］～［１１］のいずれか一項に記載のネガ型感光性樹脂組成物。
［１３］
［１］～［１２］のいずれか一項に記載のネガ型感光性樹脂組成物をポリイミドに変換する工程を含むポリイミドの製造方法。
［１４］
（１）［１］～［１２］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、感光性樹脂層を前記基板上に形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）露光後の前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）前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。
［１５］
（Ａ）ポリイミド前駆体；
（Ｂ）熱硬化剤；及び
（Ｃ）光重合開始剤
を含む、ネガ型感光性樹脂組成物。
［１６］
前記（Ｂ）熱硬化剤が、ベンゾオキサジン、エポキシ樹脂、及びオキセタン樹脂から成る群から選択される少なくとも１種である、［１５］に記載のネガ型感光性樹脂組成物。
［１７］
前記（Ｂ）熱硬化剤が、ベンゾオキサジンである、［１５］又は［１６］に記載のネガ型感光性樹脂組成物。
［１８］
前記（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、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、［１５］～［１７］のいずれか一項に記載のネガ型感光性樹脂組成物。
［１９］
前記一般式（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、［１８］に記載のネガ型感光性樹脂組成物。
［２０］
前記一般式（２）において、Ｘ_１が、下記一般式（２０ａ）：

で表される構造を含む、［１８］又は［１９］に記載のネガ型感光性樹脂組成物。
［２１］
前記一般式（２）において、Ｘ_１が、下記一般式（２０ｂ）：

で表される構造を含む、［１８］又は［１９］に記載のネガ型感光性樹脂組成物。
［２２］
前記一般式（２）において、Ｙ_１が、下記一般式（２１ｂ）：

で表される構造を含む、［１８］～［２１］のいずれか一項に記載のネガ型感光性樹脂組成物。
［２３］
前記（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、［１８］又は［１９］に記載のネガ型感光性樹脂組成物。
［２４］
前記（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、［１８］又は［１９］に記載のネガ型感光性樹脂組成物。
［２５］
前記（Ａ）ポリイミド前駆体が、下記一般式（４）及び（５）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は、それぞれ、上記に定義したものであり、一般式（５）中のＲ_１、Ｒ_２、及びｎ_１とは同じであるか、又は異なってよい。｝

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は、それぞれ、上記に定義したものであり、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは同じであるか、又は異なってよい。｝
で表される構造単位を同時に含む、［１８］～［２４］のいずれか一項に記載のネガ型感光性樹脂組成物。
［２６］
前記（Ａ）ポリイミド前駆体が、前記一般式（４）と（５）で表される構造単位の共重合体である、［２５］に記載のネガ型感光性樹脂組成物。
［２７］
１００質量部の前記（Ａ）ポリイミド前駆体と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～３０質量部の前記（Ｂ）熱硬化剤と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～２０質量部の前記（Ｃ）光重合開始剤と
を含む、［１５］～［２６］のいずれか一項に記載のネガ型感光性樹脂組成物。
［２８］
［１５］～［２７］のいずれか一項に記載のネガ型感光性樹脂組成物をポリイミドに変換する工程を含むポリイミドの製造方法。
［２９］
（１）［１５］～［２７］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、感光性樹脂層を前記基板上に形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）露光後の前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）前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。
［３０］
（Ａ）ポリイミド前駆体；
（Ｂ）下記一般式（Ｂ－１）：

｛式中、Ｒａ及びＲｂは、それぞれ独立に、ヘテロ原子を含んでもよい炭素数１～１０の１価の有機基であり、Ｒｃは、それぞれ独立に、ヘテロ原子を含んでもよい１価の有機基であり、かつｍは、０～５の整数を表す。｝
で表される３級アミン化合物、及びグアニジン化合物から成る群から選択される少なくとも１種；及び
（Ｃ）光重合開始剤；
を含むネガ型感光性樹脂組成物。
［３１］
前記一般式（Ｂ－１）において、Ｒａ及びＲｂが、メチル基、エチル基、ｎ－プロピル基、及びイソプロピル基から成る群から選択される少なくとも１種である、［３０］に記載のネガ型感光性樹脂組成物。
［３２］
前記グアニジン化合物が、下記一般式（Ｂ－２）：

｛式中、Ｒｄは、水素原子、又はヘテロ原子を含んでもよい炭素数１～１０の１価の有機基を表す。｝
で表される化合物である、［３０］に記載のネガ型感光性樹脂組成物。
［３３］
前記（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、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、［３０］～［３２］のいずれか一項に記載のネガ型感光性樹脂組成物。
［３４］
前記一般式（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、［３３］に記載のネガ型感光性樹脂組成物。
［３５］
前記一般式（２）において、Ｘ_１が、下記一般式（２０ａ）：

で表される構造を含む、［３３］又は［３４］に記載のネガ型感光性樹脂組成物。
［３６］
前記一般式（２）において、Ｘ_１が、下記一般式（２０ｂ）：

で表される構造を含む、［３３］又は［３４］に記載のネガ型感光性樹脂組成物。
［３７］
前記一般式（２）において、Ｙ_１が、下記一般式（２１ｂ）：

で表される構造を含む、［３３］～［３６］のいずれか一項に記載のネガ型感光性樹脂組成物。
［３８］
前記（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、［３３］又は［３４］に記載のネガ型感光性樹脂組成物。
［３９］
前記（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、［３３］又は［３４］に記載のネガ型感光性樹脂組成物。
［４０］
前記（Ａ）ポリイミド前駆体が、下記一般式（４）及び（５）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は、それぞれ、上記に定義したものであり、一般式（５）中のＲ_１、Ｒ_２、及びｎ_１とは同じであるか、又は異なってよい。｝

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は、それぞれ、上記に定義したものであり、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは同じであるか、又は異なってよい。｝
で表される構造単位を同時に含む、［３３］～［３９］のいずれか一項に記載のネガ型感光性樹脂組成物。
［４１］
前記（Ａ）ポリイミド前駆体が、前記一般式（４）と（５）で表される構造単位の共重合体である、［４０］に記載のネガ型感光性樹脂組成物。
［４２］
１００質量部の前記（Ａ）ポリイミド前駆体と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～３０質量部の前記（Ｂ）３級アミン化合物及び／又はグアニジン化合物と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～２０質量部の前記（Ｃ）光重合開始剤と
を含む、［３０］～［４１］のいずれか一項に記載のネガ型感光性樹脂組成物。
［４３］
［３０］～［４２］のいずれか一項に記載のネガ型感光性樹脂組成物をポリイミドに変換する工程を含むポリイミドの製造方法。
［４４］
（１）［３０］～［４２］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、感光性樹脂層を前記基板上に形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）露光後の前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）前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。
［４５］
以下の成分：
（Ａ）ポリイミド前駆体；
（Ｂ－１）構造中にフェノール性水酸基またはカルボキシル基を２個以上有する酸性化合物；及び
（Ｃ）光重合開始剤
を含む、ネガ型感光性樹脂組成物。
［４６］
前記（Ｂ－１）酸性化合物が、没食子酸メチル、メチレンジサリチル酸、ｏ－クマル酸、フタル酸から成る群から選択される少なくとも１種の酸性化合物である、［４５］に記載のネガ型感光性樹脂組成物。
［４７］
前記（Ｂ－１）酸性化合物が、メチレンジサリチル酸又はｏ－クマル酸である、［４５］又は［４６］に記載のネガ型感光性樹脂組成物。
［４８］
以下の成分：
（Ａ）ポリイミド前駆体；
（Ｂ－２）構造中にフェノール性水酸基またはカルボキシル基より選ばれる基を１個有し、かつ－ＮＨ－ＣＯ－Ａ_１、または－ＣＯ－ＮＨ_２より選ばれる基を１個以上有する酸性化合物（Ａ_１は炭素数１～４の有機基である）；及び
（Ｃ）光重合開始剤
を含む、ネガ型感光性樹脂組成物。
［４９］
前記（Ｂ－２）酸性化合物が、下記一般式（１）：

｛式（１）中、Ａ_２は水酸基、またはカルボキシル基であり、Ａ_３は－ＮＨ－ＣＯ－Ａ_１、または－ＣＯ－ＮＨ_２より選ばれる基であり、Ａ_１は炭素数１～４の有機基であり、Ａ_４は１価の基であり、ｍ_２は１または２であり、ｍ_３は０～４の整数である。｝で表される、［４８］に記載のネガ型感光性樹脂組成物。
［５０］
前記（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、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、［４５］～［４９］のいずれか一項に記載のネガ型感光性樹脂組成物。
［５１］
前記一般式（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、［５０］に記載のネガ型感光性樹脂組成物。
［５２］
前記一般式（２）において、Ｘ_１が、下記一般式（２０ａ）：

で表される構造を含む、［５０］又は［５１］に記載のネガ型感光性樹脂組成物。
［５３］
前記一般式（２）において、Ｘ_１が、下記一般式（２０ｂ）：

で表される構造を含む、［５０］又は［５１］に記載のネガ型感光性樹脂組成物。
［５４］
前記一般式（２）において、Ｙ_１が、下記一般式（２１ｂ）：

又は一般式（７）：

（式中、Ｒ_９～Ｒ_１２は、水素原子又は炭素数１～４の１価の脂肪族基であり、互いに異なっていても、同一であってもよい。）
で表される構造を含む、［５０］～［５３］のいずれか一項に記載のネガ型感光性樹脂組成物。
［５５］
前記（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、［５０］又は［５１］に記載のネガ型感光性樹脂組成物。
［５６］
前記（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、［５０］又は［５１］に記載のネガ型感光性樹脂組成物。
［５７］
前記（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、それぞれ、上記に定義したものであり、一般式（５）中のＲ_１、Ｒ_２、及びｎ_１とは同じであるか、又は異なってよい。｝
及び下記一般式（５）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は、それぞれ、上記に定義したものであり、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは同じであるか、又は異なってよい。｝
で表される構造単位を同時に含む、［５０］～［５６］のいずれか一項に記載のネガ型感光性樹脂組成物。
［５８］
前記（Ａ）ポリイミド前駆体が、前記一般式（４）と（５）で表される構造単位の共重合体である、［５７］に記載のネガ型感光性樹脂組成物。
［５９］
１００質量部の前記（Ａ）ポリイミド前駆体と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～３０質量部の前記（Ｂ－１）酸性化合物と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～２０質量部の前記（Ｃ）光重合開始剤と、
を含む、［４５］～［４７］のいずれか一項に記載のネガ型感光性樹脂組成物。
［６０］
１００質量部の前記（Ａ）ポリイミド前駆体と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～３０質量部の前記（Ｂ－２）酸性化合物）と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～２０質量部の前記（Ｃ）光重合開始剤と、
を含む、［４８］又は［４９］に記載のネガ型感光性樹脂組成物。
［６１］
［４５］～［６０］のいずれか一項に記載のネガ型感光性樹脂組成物をポリイミドに変換する工程を含むポリイミドの製造方法。
［６２］
（１）［４５］～［６０］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、感光性樹脂層を前記基板上に形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）露光後の前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）前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。
［６３］
（Ａ）ポリイミド前駆体；
（Ｂ）ビウレット化合物、カルバゾール化合物、インドール化合物、ヒダントイン化合物、ウラシル誘導体及びバルビツール酸化合物から成る群から選択される少なくとも１種の含窒素化合物；及び
（Ｃ）光重合開始剤
を含む、ネガ型感光性樹脂組成物。
［６４］
前記（Ｂ）含窒素化合物が、ビウレット化合物、カルバゾール化合物、及びインドール化合物から成る群から選択される少なくとも１種である、［６３］に記載のネガ型感光性樹脂組成物。
［６５］
前記（Ｂ）含窒素化合物が、ビウレット化合物である、［６３］又は［６４］に記載のネガ型感光性樹脂組成物。
［６６］
前記（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、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、［６３］～［６５］のいずれか一項に記載のネガ型感光性樹脂組成物。
［６７］
前記一般式（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、［６６］に記載のネガ型感光性樹脂組成物。
［６８］
前記一般式（２）において、Ｘ_１が、下記一般式（２０ａ）：

で表される構造を含む、［６６］又は［６７］に記載のネガ型感光性樹脂組成物。
［６９］
前記一般式（２）において、Ｘ_１が、下記一般式（２０ｂ）：

で表される構造を含む、［６６］又は［６７］に記載のネガ型感光性樹脂組成物。
［７０］
前記一般式（２）において、Ｙ_１が、下記一般式（２１ｂ）：

で表される構造を含む、［６６］～［６９］のいずれか一項に記載のネガ型感光性樹脂組成物。
［７１］
前記（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、［６６］又は［６７］に記載のネガ型感光性樹脂組成物。
［７２］
前記（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、［６６］又は［６７］に記載のネガ型感光性樹脂組成物。
［７３］
前記（Ａ）ポリイミド前駆体が、下記一般式（４）及び（５）：

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は、それぞれ、上記に定義したものであり、一般式（５）中のＲ_１、Ｒ_２、及びｎ_１とは同じであるか、又は異なってよい。｝

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は、それぞれ、上記に定義したものであり、一般式（４）中のＲ_１、Ｒ_２、及びｎ_１とは同じであるか、又は異なってよい。｝
で表される構造単位を同時に含む、［６６］～［７２］のいずれか一項に記載のネガ型感光性樹脂組成物。
［７４］
前記（Ａ）ポリイミド前駆体が、前記一般式（４）と（５）で表される構造単位の共重合体である、［７３］に記載のネガ型感光性樹脂組成物。
［７５］
１００質量部の前記（Ａ）ポリイミド前駆体と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～３０質量部の前記（Ｂ）含窒素化合物と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～２０質量部の前記（Ｃ）光重合開始剤と、
を含む、［６３］～［７４］のいずれか一項に記載のネガ型感光性樹脂組成物。
［７６］
［６３］～［７５］のいずれか一項に記載のネガ型感光性樹脂組成物をポリイミドに変換する工程を含むポリイミドの製造方法。
［７７］
（１）［６３］～［７５］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、感光性樹脂層を前記基板上に形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）露光後の前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）前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 have found that the above problems can be solved by combining a specific photosensitive resin with a specific compound (for example, (B1) an active esterifying agent, (B2) a heat curing agent, (B3) a tertiary amine compound and/or a guanidine compound, (B4) an acidic compound, or (B5) a nitrogen-containing compound), and a photopolymerization initiator, and have completed the present invention. That is, the present invention is as follows.
[1]
(A) a polyimide precursor;
(B) an active esterifying agent; and (C) a photopolymerization initiator.
[2]
The (B) active esterifying agent is at least one selected from the group consisting of bis(pentafluorophenyl)carbonate, bis(4-nitrophenyl)carbonate, di(N-sucrinimidyl)carbonate, pentafluorophenol, 1-hydroxy-7-azabenzotriazole, and 4-nitrophenyl trifluoroacetate. [1]
2. The negative type photosensitive resin composition according to claim 1 .
[3]
The polyimide precursor (A) is represented by the following general formula (2):

In the formula, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of _R1 and _R2 is a monovalent organic group.
The negative type photosensitive resin composition according to [1] or [2], comprising a polyimide precursor having a structural unit represented by the following formula:
[4]
In the general formula (2), at least one of R ₁ and R ₂ is represented by the following general formula (3):

{wherein L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.}. The negative type photosensitive resin composition according to [3],
[5]
In the general formula (2), X ₁ is represented by the following general formula (20a):

The negative type photosensitive resin composition according to [3] or [4], comprising a structure represented by the following formula:
[6]
In the general formula (2), X ₁ is represented by the following general formula (20b):

The negative type photosensitive resin composition according to [3] or [4], comprising a structure represented by the following formula:
[7]
In the general formula (2), Y ₁ is represented by the following general formula (21b):

The negative type photosensitive resin composition according to any one of [3] to [6], comprising a structure represented by:
[8]
The polyimide precursor (A) is represented by the following general formula (4):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to [3] or [4], comprising a polyimide precursor having a structural unit represented by the following formula:
[9]
The polyimide precursor (A) is represented by the following general formula (5):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to [3] or [4], comprising a polyimide precursor having a structural unit represented by the following formula:
[10]
The polyimide precursor (A) is represented by the following general formulas (4) and (5):

{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (5).}

{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (4).}
The negative type photosensitive resin composition according to any one of [3] to [9], further comprising a structural unit represented by the following formula:
[11]
The negative type photosensitive resin composition according to [10], wherein the polyimide precursor (A) is a copolymer of structural units represented by the general formulas (4) and (5).
[12]
100 parts by mass of the polyimide precursor (A);
0.1 to 30 parts by mass of the (B) active esterifying agent based on 100 parts by mass of the (A) polyimide precursor;
The negative type photosensitive resin composition according to any one of [1] to [11], comprising: 0.1 to 20 parts by mass of the photopolymerization initiator (C) based on 100 parts by mass of the polyimide precursor (A).
[13]
A method for producing a polyimide, comprising a step of converting the negative type photosensitive resin composition according to any one of [1] to [12] into a polyimide.
[14]
(1) A step of applying the negative type photosensitive resin composition according to any one of items [1] to [12] onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of heat-treating the relief pattern to form a cured relief pattern.
[15]
(A) a polyimide precursor;
(B) a heat curing agent; and (C) a photopolymerization initiator.
[16]
The negative type photosensitive resin composition according to [15], wherein the (B) heat curing agent is at least one selected from the group consisting of benzoxazine, epoxy resin, and oxetane resin.
[17]
The negative type photosensitive resin composition according to [15] or [16], wherein the (B) heat curing agent is benzoxazine.
[18]
The polyimide precursor (A) is represented by the following general formula (2):

In the formula, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of _R1 and _R2 is a monovalent organic group.
The negative type photosensitive resin composition according to any one of [15] to [17], comprising a polyimide precursor having a structural unit represented by the following formula:
[19]
In the general formula (2), at least one of R ₁ and R ₂ is represented by the following general formula (3):

{wherein L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.}. The negative photosensitive resin composition according to [18],
[20]
In the general formula (2), X ₁ is represented by the following general formula (20a):

The negative type photosensitive resin composition according to [18] or [19], comprising a structure represented by the following formula:
[21]
In the general formula (2), X ₁ is represented by the following general formula (20b):

The negative type photosensitive resin composition according to [18] or [19], comprising a structure represented by the following formula:
[22]
In the general formula (2), Y ₁ is represented by the following general formula (21b):

The negative type photosensitive resin composition according to any one of [18] to [21], comprising a structure represented by:
[23]
The polyimide precursor (A) is represented by the following general formula (4):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to [18] or [19], comprising a polyimide precursor having a structural unit represented by the following formula:
[24]
The polyimide precursor (A) is represented by the following general formula (5):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to [18] or [19], comprising a polyimide precursor having a structural unit represented by the following formula:
[25]
The polyimide precursor (A) is represented by the following general formulas (4) and (5):

{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (5).}

{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (4).}
The negative type photosensitive resin composition according to any one of [18] to [24], further comprising a structural unit represented by the following formula:
[26]
The negative type photosensitive resin composition according to [25], wherein the polyimide precursor (A) is a copolymer of structural units represented by the general formulas (4) and (5).
[27]
100 parts by mass of the polyimide precursor (A);
0.1 to 30 parts by mass of the (B) heat curing agent based on 100 parts by mass of the (A) polyimide precursor;
and 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the (A) polyimide precursor.
[28]
A method for producing a polyimide, comprising a step of converting the negative type photosensitive resin composition according to any one of [15] to [27] into a polyimide.
[29]
(1) A step of applying the negative type photosensitive resin composition according to any one of items [15] to [27] onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of heat-treating the relief pattern to form a cured relief pattern.
[30]
(A) a polyimide precursor;
(B) The following general formula (B-1):

In the formula, Ra and Rb are each independently a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom, Rc are each independently a monovalent organic group which may contain a heteroatom, and m is an integer of 0 to 5.
and (C) at least one selected from the group consisting of a tertiary amine compound represented by the following formula (I) and a guanidine compound; and (C) a photopolymerization initiator;
A negative type photosensitive resin composition comprising:
[31]
In the general formula (B-1), Ra and Rb are at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
[32]
The guanidine compound is represented by the following general formula (B-2):

In the formula, Rd represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom.
The negative type photosensitive resin composition according to [30], wherein the compound is represented by the formula:
[33]
The polyimide precursor (A) is represented by the following general formula (2):

In the formula, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of _R1 and _R2 is a monovalent organic group.
The negative type photosensitive resin composition according to any one of [30] to [32], comprising a polyimide precursor having a structural unit represented by the following formula:
[34]
In the general formula (2), at least one of R ₁ and R ₂ is represented by the following general formula (3):

In the formula, L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.
The negative type photosensitive resin composition according to [33], wherein the monovalent organic group is represented by the following formula:
[35]
In the general formula (2), X ₁ is represented by the following general formula (20a):

The negative type photosensitive resin composition according to [33] or [34], comprising a structure represented by the following formula:
[36]
In the general formula (2), X ₁ is represented by the following general formula (20b):

The negative type photosensitive resin composition according to [33] or [34], comprising a structure represented by the following formula:
[37]
In the general formula (2), Y ₁ is represented by the following general formula (21b):

The negative type photosensitive resin composition according to any one of [33] to [36], comprising a structure represented by:
[38]
The polyimide precursor (A) is represented by the following general formula (4):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to [33] or [34], comprising a polyimide precursor having a structural unit represented by the following formula:
[39]
The polyimide precursor (A) is represented by the following general formula (5):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to [33] or [34], comprising a polyimide precursor having a structural unit represented by the following formula:
[40]
The polyimide precursor (A) is represented by the following general formulas (4) and (5):

{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (5).}

{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (4).}
The negative type photosensitive resin composition according to any one of [33] to [39], further comprising a structural unit represented by the following formula:
[41]
The negative type photosensitive resin composition according to [40], wherein the polyimide precursor (A) is a copolymer of structural units represented by the general formulas (4) and (5).
[42]
100 parts by mass of the polyimide precursor (A);
0.1 to 30 parts by mass of the (B) tertiary amine compound and/or guanidine compound based on 100 parts by mass of the (A) polyimide precursor;
The negative type photosensitive resin composition according to any one of [30] to [41], comprising: 0.1 to 20 parts by mass of the photopolymerization initiator (C) based on 100 parts by mass of the polyimide precursor (A).
[43]
A method for producing a polyimide, comprising a step of converting the negative type photosensitive resin composition according to any one of [30] to [42] into a polyimide.
[44]
(1) A step of applying the negative type photosensitive resin composition according to any one of items [30] to [42] onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of: heat-treating the relief pattern to form a cured relief pattern.
[45]
Ingredients below:
(A) a polyimide precursor;
A negative photosensitive resin composition comprising: (B-1) an acidic compound having two or more phenolic hydroxyl groups or carboxyl groups in its structure; and (C) a photopolymerization initiator.
[46]
The negative type photosensitive resin composition according to [45], wherein the (B-1) acidic compound is at least one acidic compound selected from the group consisting of methyl gallate, methylenedisalicylic acid, o-coumaric acid, and phthalic acid.
[47]
The negative type photosensitive resin composition according to [45] or [46], wherein the acidic compound (B-1) is methylenedisalicylic acid or o-coumaric acid.
[48]
Ingredients below:
(A) a polyimide precursor;
A negative type photosensitive resin composition comprising: (B-2) an acidic compound having in its structure one group selected from a phenolic hydroxyl group or a carboxyl group, and one or more groups selected from -NH-CO- _A1 or -CO- _NH2 ( _A1 is an organic group having 1 to 4 carbon atoms); and (C) a photopolymerization initiator.
[49]
The (B-2) acidic compound is represented by the following general formula (1):

The negative photosensitive resin _composition according to [48], represented by the formula (1), {A ₂ is a hydroxyl group or a carboxyl group, A ₃ is a group selected from -NH-CO-A ₁ or -CO-NH ₂ , A ₁ is an organic group having 1 to 4 carbon atoms, A 4 is a monovalent group, m ₂ is 1 or 2, and m ₃ is an integer of 0 to 4.}.
[50]
The polyimide precursor (A) is represented by the following general formula (2):

In the formula, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of _R1 and _R2 is a monovalent organic group.
The negative type photosensitive resin composition according to any one of [45] to [49], comprising a polyimide precursor having a structural unit represented by the following formula:
[51]
In the general formula (2), at least one of R ₁ and R ₂ is represented by the following general formula (3):

In the formula, L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.
The negative type photosensitive resin composition according to [50], wherein the monovalent organic group is represented by the following formula:
[52]
In the general formula (2), X ₁ is represented by the following general formula (20a):

The negative type photosensitive resin composition according to [50] or [51], comprising a structure represented by the following formula:
[53]
In the general formula (2), X ₁ is represented by the following general formula (20b):

The negative type photosensitive resin composition according to [50] or [51], comprising a structure represented by the following formula:
[54]
In the general formula (2), Y ₁ is represented by the following general formula (21b):

Or general formula (7):

(In the formula, R ₉ to R ₁₂ are hydrogen atoms or monovalent aliphatic groups having 1 to 4 carbon atoms, and may be different from each other or the same.)
The negative type photosensitive resin composition according to any one of [50] to [53], comprising a structure represented by:
[55]
The polyimide precursor (A) is represented by the following general formula (4):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to [50] or [51], comprising a polyimide precursor having a structural unit represented by the following formula:
[56]
The polyimide precursor (A) is represented by the following general formula (5):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to [50] or [51], comprising a polyimide precursor having a structural unit represented by the following formula:
[57]
The polyimide precursor (A) is represented by the following general formula (4):

{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (5).}
and the following general formula (5):

{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (4).}
[57] The negative type photosensitive resin composition according to any one of [50] to [56], further comprising a structural unit represented by the following formula:
[58]
The negative type photosensitive resin composition according to [57], wherein the polyimide precursor (A) is a copolymer of structural units represented by the general formulas (4) and (5).
[59]
100 parts by mass of the polyimide precursor (A);
0.1 to 30 parts by mass of the acidic compound (B-1) based on 100 parts by mass of the polyimide precursor (A);
0.1 to 20 parts by mass of the photopolymerization initiator (C) based on 100 parts by mass of the polyimide precursor (A);
The negative type photosensitive resin composition according to any one of [45] to [47],
[60]
100 parts by mass of the polyimide precursor (A);
(B-2) the acidic compound, in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the (A) polyimide precursor;
0.1 to 20 parts by mass of the photopolymerization initiator (C) based on 100 parts by mass of the polyimide precursor (A);
The negative type photosensitive resin composition according to [48] or [49],
[61]
A method for producing a polyimide, comprising a step of converting the negative type photosensitive resin composition according to any one of [45] to [60] into a polyimide.
[62]
(1) A step of applying the negative type photosensitive resin composition according to any one of items [45] to [60] onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of heat-treating the relief pattern to form a cured relief pattern.
[63]
(A) a polyimide precursor;
(B) at least one nitrogen-containing compound selected from the group consisting of a biuret compound, a carbazole compound, an indole compound, a hydantoin compound, a uracil derivative, and a barbituric acid compound; and (C) a photopolymerization initiator.
[64]
The negative type photosensitive resin composition according to [63], wherein the nitrogen-containing compound (B) is at least one selected from the group consisting of a biuret compound, a carbazole compound, and an indole compound.
[65]
The negative photosensitive resin composition according to [63] or [64], wherein the nitrogen-containing compound (B) is a biuret compound.
[66]
The polyimide precursor (A) is represented by the following general formula (2):

In the formula, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of _R1 and _R2 is a monovalent organic group.
The negative type photosensitive resin composition according to any one of [63] to [65], comprising a polyimide precursor having a structural unit represented by the following formula:
[67]
In the general formula (2), at least one of R ₁ and R ₂ is represented by the following general formula (3):

In the formula, L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.
The negative type photosensitive resin composition according to [66], wherein the monovalent organic group is represented by the following formula:
[68]
In the general formula (2), X ₁ is represented by the following general formula (20a):

The negative type photosensitive resin composition according to [66] or [67], comprising a structure represented by the following formula:
[69]
In the general formula (2), X ₁ is represented by the following general formula (20b):

The negative type photosensitive resin composition according to [66] or [67], comprising a structure represented by the following formula:
[70]
In the general formula (2), Y ₁ is represented by the following general formula (21b):

The negative type photosensitive resin composition according to any one of [66] to [69], comprising a structure represented by:
[71]
The polyimide precursor (A) is represented by the following general formula (4):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to [66] or [67], comprising a polyimide precursor having a structural unit represented by the following formula:
[72]
The polyimide precursor (A) is represented by the following general formula (5):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to [66] or [67], comprising a polyimide precursor having a structural unit represented by the following formula:
[73]
The polyimide precursor (A) is represented by the following general formulas (4) and (5):

{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (5).}

{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (4).}
The negative type photosensitive resin composition according to any one of items [66] to [72], further comprising a structural unit represented by the following formula:
[74]
The negative type photosensitive resin composition according to [73], wherein the polyimide precursor (A) is a copolymer of structural units represented by the general formulas (4) and (5).
[75]
100 parts by mass of the polyimide precursor (A);
0.1 to 30 parts by mass of the nitrogen-containing compound (B) based on 100 parts by mass of the polyimide precursor (A);
0.1 to 20 parts by mass of the photopolymerization initiator (C) based on 100 parts by mass of the polyimide precursor (A);
The negative type photosensitive resin composition according to any one of [63] to [74],
[76]
A method for producing a polyimide, comprising a step of converting the negative type photosensitive resin composition according to any one of [63] to [75] into a polyimide.
[77]
(1) A step of applying the negative type photosensitive resin composition according to any one of items [63] to [75] onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of heat-treating the relief pattern to form a cured relief pattern.

The present invention provides a negative-type photosensitive resin composition that provides high chemical resistance and resolution and suppresses the generation of voids at the interface of the Cu layer and the resin layer after a high temperature storage test, and also provides a method for forming a cured relief pattern using the negative-type photosensitive resin composition.

Hereinafter, a detailed description will be given of an embodiment of the present invention (hereinafter, abbreviated as "embodiment"). Note that the present invention is not limited to the following embodiment, and various modifications can be made within the scope of the present invention.
Throughout this specification, when a plurality of structures represented by the same symbol in a general formula are present in a molecule, they may be the same or different.

[First aspect]
A first aspect of this embodiment will be described.
<Negative Photosensitive Resin Composition>
The negative photosensitive resin composition according to this embodiment is
(A) a polyimide precursor;
(B1) an active esterifying agent; and (C) a photopolymerization initiator.

From the viewpoint of obtaining high resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of (A) polyimide precursor, 0.1 to 30 parts by mass of (B1) active esterification agent based on 100 parts by mass of (A) polyimide precursor, and 0.1 to 20 parts by mass of (C) photopolymerization initiator based on 100 parts by mass of (A) polyimide precursor.

｛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。｝
で表される構造を有するポリアミドであることが好ましい。 (A) Polyimide Precursor (A) in the present embodiment is a resin component contained in the negative photosensitive resin composition, and is converted into a polyimide by subjecting it to a heat cyclization treatment.
The polyimide precursor is represented by the following general formula (2):

In the formula, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group.
It is preferable that the polyamide has a structure represented by the following formula:

｛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 preferably represented by 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.}

｛式中、Ｒ６は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、及び炭素数１～１０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観点から好ましい。
Ｘ_１基としては、上記式（２０）で表される構造のなかでも、下記式（２０Ａ）又は（２０Ｂ）：

で表される構造は、耐薬品性、解像度、及び高温保存試験後のボイド抑制の観点から、より好ましく、下記式（２０ａ）又は（２０ｂ）：

で表される構造が特に好ましい。 In the general formula (2), _n1 is not limited as long as it is an integer from 2 to 150. From the viewpoint of the photosensitive properties and mechanical properties of the negative photosensitive resin composition, n1 is preferably an integer from 3 to 100, and more preferably an integer from 5 to 70.
In the general formula (2), the tetravalent organic group represented by _X1 is preferably an organic group having 6 to 40 carbon atoms, more preferably an aromatic group in which the _-COOR1 group, the _-COOR2 group, and the -CONH- group are in the ortho position relative to each other, or an alicyclic aliphatic group, from the viewpoint of achieving both heat resistance and photosensitive properties. Specific examples of the tetravalent organic group represented by _X1 include organic groups having 6 to 40 carbon atoms containing an aromatic ring, such as those represented by the following general formula (20):

{In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.}
Examples of the structure represented by the formula (20) include, but are not limited to, a group having a structure represented by the formula ( ₂₀ ). The structure represented by the formula (20) may be a _single type or a combination of two or more types. ...
As the _X1 group, among the structures represented by the above formula (20), the following formula (20A) or (20B):

The structure represented by the following formula (20a) or (20b):

The structure represented by the following formula is particularly preferred.

｛式中、Ｒ６は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、及び炭素数１～１０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観点で好ましい。
Ｙ_１基としては、上記式（２１）で表される構造のなかでも、下記式（２１Ａ）又は（２１Ｂ）：

で表される構造は、耐薬品性、解像度、及び高温保存試験後のボイド抑制の観点から好ましく、下記式（２１ｂ）又は下記式（７）：

（式中、Ｒ_９～Ｒ_１２は、水素原子又は炭素数１～４の１価の脂肪族基であり、互いに異なっていても、同一であってもよい。）
で表される構造が特に好ましい。 In the above general formula (2), the divalent organic group represented by _Y1 is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (21):

{In the formula, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.}
Examples of the structure represented by the formula ( ₂₁ ) include, but are not limited to, the structure represented by the formula (21). The structure represented by the formula ( ₂₁ ) is preferable from the viewpoint of achieving both heat resistance and photosensitive properties.
As the _Y1 group, among the structures represented by the above formula (21), those represented by the following formula (21A) or (21B):

The structure represented by the following formula (21b) or the following formula (7):

(In the formula, R ₉ to R ₁₂ are hydrogen atoms or monovalent aliphatic groups having 1 to 4 carbon atoms, and may be different from each other or the same.)
The structure represented by the following formula is particularly preferred.

In the above general formula (3), _L1 is preferably a hydrogen atom or a methyl group, and _L2 and _L3 are preferably hydrogen atoms from the viewpoint of photosensitive properties. Also, _m1 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitive properties.

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記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の少なくとも一方は、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 polyimide precursor (A) is represented by the following general formula (4):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
It is preferable that the polyimide precursor has a structural unit represented by the following formula:
In the general formula (4), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the above general formula (3). When the polyimide precursor (A) contains the polyimide precursor represented by the general formula (4), the effect of particularly improving the resolution is enhanced.

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記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の少なくとも一方は、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。
これらの中で、（Ａ）ポリイミド前駆体は、上記一般式（４）と（５）で表される構造単位を同時に含むか、又は、上記一般式（４）と（５）で表される構造単位の共重合体であることが、耐薬品性、解像度、及び高温保存試験後のボイド抑制の観点から特に好ましい。（Ａ）ポリイミド前駆体が一般式（４）と（５）で表される構造単位の共重合体である場合には、一方の式中のＲ_１、Ｒ_２、及びｎ_１が、それぞれ、他方の式中のＲ_１、Ｒ_２、及びｎ_１とは同じであるか、又は異なってよい。 In one embodiment, the polyimide precursor (A) is represented by the following general formula (5):

{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
It is preferable that the polyimide precursor has a structural unit represented by the following formula:
In the general formula (5), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the above general formula (3). When the polyimide precursor (A) contains a polyimide precursor represented by general formula (5) in addition to the polyimide precursor represented by general formula (4), the effect of particularly improving the resolution is further improved.
Among these, it is particularly preferred from the viewpoints of chemical resistance, resolution, and void suppression after a high-temperature storage test that the polyimide precursor (A) simultaneously contains structural units represented by the above general formulas (4) and (5), or is a copolymer of structural units represented by the above general formulas (4) and (5). When the polyimide precursor (A) is a copolymer of structural units represented by general formulas (4) and (5), R ₁ , R ₂ , and n ₁ in one formula may be the same as or different from R ₁ , R ₂ , and n ₁ in the other formula, respectively.

(A) Method for Preparing Polyimide Precursor (A) The polyimide precursor can be obtained by first reacting a tetracarboxylic dianhydride containing a tetravalent organic group _X1 in the above-mentioned general formula (2) with an alcohol having a photopolymerizable unsaturated double bond and, optionally, an alcohol having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid/ester body), and then subjecting this to amide polycondensation with a diamine containing a divalent organic group _Y1 in the above-mentioned general formula (2).

(Preparation of Acid/Ester Forms)
In this embodiment, the tetracarboxylic dianhydride containing a tetravalent organic group _X1 that is suitably used for preparing the polyimide precursor (A) includes the tetracarboxylic dianhydride represented by the above general formula (20), as well as, for example, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, and the like. Examples of suitable dianhydrides include tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and preferably include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited thereto. These may be used alone or in combination of two or more.

In this embodiment, examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare the polyimide precursor (A) include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl acrylate. 1-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc. can be mentioned.

The above-mentioned photopolymerizable alcohols having an unsaturated double bond can also be mixed with alcohols not having an unsaturated double bond, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 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 ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

In addition, a non-photosensitive polyimide precursor prepared only from alcohols not having the above-mentioned unsaturated double bonds may be used as the polyimide precursor by mixing it with the photosensitive polyimide precursor. From the viewpoint of resolution, it is preferable that the non-photosensitive polyimide precursor is 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

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

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

Diamines containing a divalent organic group _Y1 that are preferably used in this embodiment include diamines having a structure represented by the above general formula (21), as well as, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diamino biphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bi Bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone , 9,9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, or the like, such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof, but are not limited thereto.

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

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

(B1) Active Esterification Agent The (B1) active esterification agent in this embodiment is not limited as long as it is a compound capable of converting a carboxylic acid or a carboxylic acid ester into a highly active ester compound. Specific examples of the active esterification agent include bis(pentafluorophenyl)carbonate, bis(4-nitrophenyl)carbonate, di(N-sucrinimidyl)carbonate, pentafluorophenol, 4-nitrophenyl trifluoroacetate, and 1-hydroxy-7-azabenzotriazole.
Among these, 1-hydroxy-7-azabenzotriazole and pentafluorophenol are preferred from the viewpoint of suppressing Cu voids.
By using the above-mentioned active esterification agent, good chemical resistance, resolution, and Cu void suppression effect can be obtained. Without being bound by theory, it is believed that the reason why good chemical resistance can be obtained is that by using the active esterification agent, imidization proceeds at a lower temperature during heating, which makes it easier for polyimide packing to proceed, thereby improving chemical resistance.
In addition, although the reason why good resolution can be obtained is unclear, it is believed that the active esterification agent before heating is easily dissolved in the developer during development by blending with the polyimide precursor, and residues are suppressed. In addition, although the reason why the Cu void suppression effect is exhibited is unclear, it is believed that the active esterification agent generates polar functional groups (hydroxyl groups, etc.) during heating, and these hydroxyl groups strongly interact with Cu ions, suppressing the diffusion of Cu and, as a result, suppressing Cu voids.

The amount of the active esterification agent in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A). By blending the active esterification agent in the range of 0.1 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A), it is possible to obtain a negative photosensitive resin composition that is particularly excellent in the effects of suppressing Cu voids, improving resolution, and improving chemical resistance.

(C) Photopolymerization Initiator The (C) photopolymerization initiator used in this embodiment will be described. The photopolymerization initiator is preferably a photoradical polymerization initiator, and examples of the photopolymerization initiator include benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone and other acetophenone derivatives, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives, benzyl derivatives, benzil, benzil dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives, benzoin, benzoin methyl ether and other benzoin derivatives, 1-phenyl-1,2-butanedione-2-(o-methoxy Preferred examples of the photopolymerization initiator include, but are not limited to, oximes such as 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, titanocenes, and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among the above photopolymerization initiators, oximes are more preferred, particularly from the viewpoint of photosensitivity.

The amount of the photopolymerization initiator (C) in the negative photosensitive resin composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A). The amount is 0.1 parts by mass or more from the viewpoint of photosensitivity 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 type 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) include, but are not 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, a thermal polymerization inhibitor, and the like.
Among these, the nitrogen-containing heterocyclic compound as an optional component is a compound other than the "nitrogen-containing compound" explained in the fifth embodiment described later.

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

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

In the photosensitive resin composition of this embodiment, the amount of the solvent used is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 100 parts by mass of the polyimide precursor (A).

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

Examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, triazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.

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

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

When the photosensitive resin composition contains the azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound relative to 100 parts by mass of the polyimide precursor (A) is 0.1 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition of this embodiment is formed on copper or a copper alloy, while when the blending amount is 20 parts by mass or less, excellent photosensitivity is achieved.

Hindered Phenol Compounds 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, 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-diethylene bis[3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], Tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydro 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4, 6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3 -hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5- triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, Examples of the hydroxyl group include, but are not limited to, 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, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. 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 is particularly preferred.

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

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

Organotitanium compounds that can be used include those in which an organic chemical is bonded to a titanium atom via a covalent or ionic bond.
Specific examples of the organotitanium compound are shown below in I) to VII):
I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide good storage stability for the negative photosensitive resin composition and a good pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate, titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc.
II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like.
III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.
IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.
VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.
VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

Among them, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance, and titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

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

Adhesion aid In order to improve the adhesion between a film formed using the negative photosensitive resin composition of the present embodiment and a substrate, the negative photosensitive resin composition may optionally contain an adhesion aid. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl)propane, and the like. silane coupling agents such as benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

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

Silane coupling agents include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name KBM803, manufactured by Chisso Corporation: product name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: product name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS1375, manufactured by Azmax Corporation: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: product name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: product name SIM6473.0), 3-mercaptopropyl diethoxymethoxysilane, 3-mercaptopropyl ethoxydimethoxysilane, 3-mercaptopropyl tripropoxysilane, 3-mercaptopropyl diethoxypropoxysilane, 3-mercaptopropyl ethoxydipropoxysilane, 3-mercaptopropyl dimethoxypropoxysilane, 3-mercaptopropyl methoxydipropoxysilane, 2-mercaptoethyl trimethoxysilane, 2-mercaptoethyl diethoxymethoxysilane, 2-mercapto triethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl) Urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (trade name: manufactured by Azmax Corporation) SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2), 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane), tetra tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenyl p-tolylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, Examples of the phenylsilanol include, but are not limited to, phenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol. These may be used alone or in combination.

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, from the viewpoint of storage stability, preferred silane coupling agents include phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and compounds represented by the following formula:

A silane coupling agent having a structure represented by the following formula is preferred.

When a silane coupling agent is used, the amount of the silane coupling agent in the photosensitive resin composition is preferably 0.01 to 20 parts by weight per 100 parts by weight of the polyimide precursor (A).

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

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

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 examples thereof include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylates and dimethacrylates of 1,4-butanediol, and 1,6-hexane diacrylate and dimethacrylate. Examples of such compounds include diacrylates and dimethacrylates of diols, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylates and methacrylates of glycerol, di-, tri-, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

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

Thermal Polymerization Inhibitor The negative photosensitive resin composition of the present embodiment may optionally contain a thermal polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition during storage, particularly in the form of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

<Method for Producing Cured Relief Pattern and Semiconductor Device>
The present invention also provides a method for producing a cured relief pattern, comprising the steps of: (1) applying the negative type photosensitive resin composition of the present embodiment described above onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern.

(1) Photosensitive resin layer forming step In this step, the negative photosensitive resin composition of the present invention is applied onto a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method that has been conventionally used for applying a photosensitive resin composition, such as a method of applying with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray application with a spray coater, etc., can be used.

If necessary, the coating film containing the photosensitive resin composition can be dried. Drying methods that can be used include air drying, heat drying in an oven or on a hot plate, and vacuum drying. Specifically, when air drying or heat drying is performed, drying can be performed under conditions of 20°C to 140°C for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on the substrate.

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

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

(3) Relief Pattern Forming Step In this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a developing method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from conventionally known photoresist developing methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern.

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

(4) Cured Relief Pattern Formation Step In this step, the relief pattern obtained by the above development is heated to disperse the photosensitive component and imidize the polyimide precursor (A), thereby converting it into a cured relief pattern made of polyimide. As a method for heat curing, various methods can be selected, such as a method using a hot plate, a method using an oven, or a method using a temperature-elevating oven that can be set to a temperature program. Heating can be performed, for example, under conditions of 170°C to 400°C for 30 minutes to 5 hours. As the atmospheric gas during heat curing, air may be used, or an inert gas such as nitrogen or argon may be used.

｛式中、Ｘ^１及びＹ^１は、一般式（２）中のＸ_１及びＹ_１と同じであり、ｍは正の整数である。｝
一般式（２）中の好ましいＸ_１とＹ_１は、同じ理由により、一般式（８）のポリイミドにおいても好ましい。一般式（８）の繰り返し単位数ｍは、正の整数であればよく、特に限定は無いが、２～１５０の整数、又は３～１４０の整数であってもよい。
また、上記で説明されたネガ型感光性樹脂組成物をポリイミドに変換する工程を含むポリイミドの製造方法も本発明の一態様である。 <Polyimide>
The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula (8).

{In the formula, ^X1 and ^Y1 are the same as _X1 and _Y1 in general formula (2), and m is a positive integer.}
For the same reason, the preferred _X1 and _Y1 in the general formula (2) are also preferred in the polyimide of the general formula (8). The number m of repeating units in the general formula (8) is not particularly limited as long as it is a positive integer, but may be an integer of 2 to 150 or an integer of 3 to 140.
Another aspect of the present invention is a method for producing a polyimide, which includes a step of converting the above-described negative photosensitive resin composition into a polyimide.

<Semiconductor Device>
In this embodiment, a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern is also provided. Thus, a semiconductor device can be provided having a substrate that is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-mentioned method for producing a cured relief pattern. The present invention can also be applied to a method for producing a semiconductor device that uses a semiconductor element as the substrate and includes the above-mentioned method for producing a cured relief pattern as part of the process. The semiconductor device of the present invention can be produced by forming the cured relief pattern formed by the above-mentioned method for producing a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure, and combining the method with a known method for producing a semiconductor device.

<Display device>
In this embodiment, a display device is provided that includes a display element and a cured film provided on the upper portion of the display element, and 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 therebetween. For example, the cured film may be a surface protection film, an insulating film, and a planarizing film for a thin film transistor (TFT) liquid crystal display element and a color filter element, a protrusion for a multi-domain vertical alignment (MVA) type liquid crystal display device, and a partition wall for a cathode of an organic electroluminescence (EL) element.

In addition to being applicable to the semiconductor devices described above, the negative-type photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

[Second Aspect]
A second aspect of the present embodiment will be described.
<Negative Photosensitive Resin Composition>
The negative photosensitive resin composition according to this embodiment is
(A) a polyimide precursor;
(B2) a heat curing agent; and (C) a photopolymerization initiator.

From the viewpoint of obtaining high resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of (A) polyimide precursor, 0.1 to 30 parts by mass of (B2) heat curing agent based on 100 parts by mass of (A) polyimide precursor, and 0.1 to 20 parts by mass of (C) photopolymerization initiator based on 100 parts by mass of (A) polyimide precursor.

(A) Polyimide Precursor In this embodiment, the polyimide precursor (A) may be the one shown in the first aspect.

エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ナフタレンエポキシ樹脂などの芳香族エポキシ樹脂、３’，４’－エポキシシクロヘキシルメチル ３，４－エポキシシクロヘキサンカルボキシレート、ε－カプロラクトン変性３’，４’－エポキシシクロヘキシルメチル ３，４－エポキシシクロヘキサンカルボキシレートなどの脂環式エポキシ樹脂などが挙げられる。脂環式エポキシ樹脂としては、下記一般式（１２）：
なども挙げられる。
オキセタン樹脂としては、例えば、３－アリロキシオキセタン、３－オキセタニルｐトルエンスルホネートなどが挙げられる。 (B2) Heat Curing Agent The (B2) heat curing agent in the present embodiment is not limited as long as it is a compound that can be cured by heating. Among them, from the viewpoint of adhesion to the sealing material, benzoxazine, epoxy resin, and oxetane resin are preferable, and benzoxazine is more preferable.
Examples of benzoxazine include structures represented by the following general formula (10) or (11).

Examples of the epoxy resin include aromatic epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and naphthalene epoxy resin, and alicyclic epoxy resins such as 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. Examples of the alicyclic epoxy resin include those represented by the following general formula (12):
Other examples include:
Examples of the oxetane resin include 3-allyloxyoxetane and 3-oxetanyl p-toluenesulfonate.

By using the above-mentioned heat curing agent, good chemical resistance, resolution, and Cu void suppression effect can be obtained. Without being bound by theory, it is believed that the reason why good chemical resistance can be obtained is that the penetration of chemicals is suppressed by forming a high-order network after thermal crosslinking, thereby improving chemical resistance.
In addition, although the reason why good resolution can be obtained is unclear, it is believed that the heat curing agent before heat curing is easily dissolved in the developer during development by blending with the polyimide precursor, and residue is suppressed. In addition, although the reason why the Cu void suppression effect is exhibited is unclear, it is believed that the heat curing agent generates hydroxyl groups and the like by heating, and these hydroxyl groups strongly interact with Cu ions, suppressing the diffusion of Cu and, as a result, suppressing Cu voids.

The amount of the heat curing agent in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A). By blending in the range of 0.1 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A), it is possible to obtain a negative photosensitive resin composition that is particularly excellent in the effects of suppressing Cu voids, improving resolution, and improving chemical resistance.

(C) Photopolymerization Initiator In this embodiment, the photopolymerization initiator (C) may be the same as that shown in the first aspect.

Other Components In this embodiment, the other components, such as the solvent, the nitrogen-containing heterocyclic compound, the hindered phenol compound, the organic titanium compound, the adhesion aid, the sensitizer, the photopolymerizable unsaturated monomer, and the thermal polymerization inhibitor, can be those shown in the first aspect.

<Method for Producing Cured Relief Pattern and Semiconductor Device>
In this embodiment, the same method for producing a cured relief pattern and the semiconductor device as those shown in the first embodiment can be applied.

<Polyimide>
In this embodiment, the polyimide may be the same as that shown in the first embodiment.

<Semiconductor Device>
In this embodiment, the same semiconductor device as that shown in the first aspect can be applied.

<Display Device>
In this embodiment, the same display device as that shown in the first aspect can be applied.

The negative-type photosensitive resin composition according to this embodiment, like the negative-type photosensitive resin composition shown in the first embodiment, is useful not only for application to semiconductor devices as described above, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. The preferred configurations, numerical ranges, or steps shown in the first embodiment can also be treated as preferred configurations, numerical ranges, or steps in this embodiment.

｛式中、Ｒａ及びＲｂは、それぞれ独立に、ヘテロ原子を含んでもよい炭素数１～１０の１価の有機基であり、Ｒｃは、それぞれ独立に、ヘテロ原子を含んでもよい１価の有機基であり、かつｍは、０～５の整数を表す。｝
で表される３級アミン化合物及び／又はグアニジン化合物；並びに
（Ｃ）光重合開始剤；
を含む。 [Third Aspect]
A third aspect of the present embodiment will be described.
<Negative Photosensitive Resin Composition>
The negative photosensitive resin composition according to this embodiment is
(A) a polyimide precursor;
(B3) The following general formula (B-1):

{In the formula, Ra and Rb are each independently a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom, Rc are each independently a monovalent organic group which may contain a heteroatom, and m is an integer of 0 to 5.}
and (C) a photopolymerization initiator;
Includes.

From the viewpoint of obtaining high resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of (A) polyimide precursor, 0.1 to 30 parts by mass of (B3) the above-mentioned tertiary amine compound and/or guanidine compound based on 100 parts by mass of (A) polyimide precursor, and 0.1 to 20 parts by mass of (C) photopolymerization initiator based on 100 parts by mass of (A) polyimide precursor.

(A) Polyimide Precursor In this embodiment, the polyimide precursor (A) may be the one shown in the first aspect.

｛式中、Ｒａ及びＲｂは、それぞれ独立にヘテロ原子を含んでもよい炭素数１～１０の１価の有機基であり、Ｒｃは、それぞれ独立にヘテロ原子を含んでもよい１価の有機基であり、かつｍは、０～５の整数を表す。｝
で表される３級アミン化合物である。
一般式（Ｂ－１）において、Ｒａ及びＲｂは、ヘテロ原子を含んでもよい炭素数１～１０の有機基であれば限定されないが、耐熱性の観点からメチル基、エチル基、ｎ－プロピル基、及びイソプロピル基から成る群から選ばれる少なくとも１つが好ましく、解像性の観点から、メチル基及び／又はエチル基がより好ましい。
Ｒｃは、ヘテロ原子を含んでもよい１価の有機基であれば限定されない。この中で、耐熱性の観点から、炭素数１～１０の１価の有機基が好ましい。
このような一般式（Ｂ－１）で表される３級アミン化合物として、例えば、４－ヒドロキシメチル―Ｎ，Ｎ－ジメチルアニリン、ビス［４－（ジメチルアミノ）フェニル］メタンなどが挙げられる。 (B3) Tertiary amine compound and/or guanidine compound (B3) in this embodiment is a tertiary amine compound represented by the following general formula (B-1):

In the formula, Ra and Rb each independently represent a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom, Rc each independently represent a monovalent organic group which may contain a heteroatom, and m represents an integer of 0 to 5.
It is a tertiary amine compound represented by the formula:
In general formula (B-1), Ra and Rb are not limited as long as they are an organic group having 1 to 10 carbon atoms which may contain a heteroatom. From the viewpoint of heat resistance, at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group is preferable, and from the viewpoint of resolution, a methyl group and/or an ethyl group is more preferable.
Rc is not limited as long as it is a monovalent organic group which may contain a heteroatom. Among these, from the viewpoint of heat resistance, a monovalent organic group having 1 to 10 carbon atoms is preferred.
Examples of the tertiary amine compound represented by the general formula (B-1) include 4-hydroxymethyl-N,N-dimethylaniline, bis[4-(dimethylamino)phenyl]methane, and the like.

｛式中、Ｒｄは、水素原子、またはヘテロ原子を含んでもよい炭素数１～１０の１価の有機基を表す。｝
で表される構造であることが好ましい。
一般式（Ｂ－２）において、Ｒｄは、水素原子、又はヘテロ原子を含んでもよい炭素数１～１０の有機基であれば限定されない。その中で、Ｒｄとしては、解像性の観点から、炭素数１～５の有機基が好ましい。
このようなグアニジン化合物として、例えば、アグマチンスルフェート、ジシアンジアミド、アルギニン（例えば、Ｄ－（－）－アルギニン）、１－（ｔ－ブトキシカルボニル）グアニジンなどが挙げられる。 The guanidine compound in the present embodiment is not limited as long as it has a guanidine structure. Among these, from the viewpoint of storage stability of the resin composition, the guanidine compound represented by the following general formula (B-2):

In the formula, Rd represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom.
It is preferable that the structure is represented by the following formula:
In general formula (B-2), Rd is not limited as long as it is a hydrogen atom or an organic group having 1 to 10 carbon atoms which may contain a heteroatom. Among these, Rd is preferably an organic group having 1 to 5 carbon atoms from the viewpoint of resolution.
Examples of such guanidine compounds include agmatine sulfate, dicyandiamide, arginine (eg, D-(-)-arginine), 1-(t-butoxycarbonyl)guanidine, and the like.

By using the above-mentioned tertiary amine compound and/or guanidine compound, good chemical resistance and resolution, and Cu void suppression effect can be obtained. Without being bound by theory, it is believed that the reason why good chemical resistance can be obtained is that nitrogen atoms and polyimide resin form a high-order network after heat curing, which suppresses the penetration of chemical solutions and improves chemical resistance.
In addition, although the reason why good resolution can be obtained is unclear, it is believed that the above-mentioned tertiary amine compound and/or guanidine compound before heat curing is easily dissolved in the developer during development by blending with the polyimide precursor, and residues are suppressed. In addition, although the reason why the Cu void suppression effect is shown is unclear, it is believed that the nitrogen atoms of the above-mentioned compound strongly interact with Cu ions, suppressing the diffusion of Cu and, as a result, suppressing Cu voids.

The amount of the tertiary amine compound or guanidine compound in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A). By blending in the range of 0.1 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A), it is possible to obtain a negative photosensitive resin composition that is particularly excellent in the effects of suppressing Cu voids, improving resolution, and improving chemical resistance.

(C) Photopolymerization Initiator In this embodiment, the photopolymerization initiator (C) may be the same as that shown in the first aspect.

Other Components In this embodiment, the other components, such as the solvent, the nitrogen-containing heterocyclic compound, the hindered phenol compound, the organic titanium compound, the adhesion aid, the sensitizer, the photopolymerizable unsaturated monomer, and the thermal polymerization inhibitor, can be those shown in the first aspect.

<Method for Producing Cured Relief Pattern and Semiconductor Device>
In this embodiment, the same method for producing a cured relief pattern and the semiconductor device as those shown in the first embodiment can be applied.

<Polyimide>
In this embodiment, the polyimide may be the same as that shown in the first embodiment.

<Semiconductor Device>
In this embodiment, the same semiconductor device as that shown in the first aspect can be applied.

<Display Device>
In this embodiment, the same display device as that shown in the first aspect can be applied.

The negative-type photosensitive resin composition according to this embodiment, like the negative-type photosensitive resin composition shown in the first embodiment, is useful not only for application to semiconductor devices as described above, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. The preferred configurations, numerical ranges, or steps shown in the first embodiment can also be treated as preferred configurations, numerical ranges, or steps in this embodiment.

[Fourth aspect]
A fourth aspect of the present embodiment will be described.
<Negative Photosensitive Resin Composition>
The negative photosensitive resin composition according to this embodiment is
(A) a polyimide precursor;
(B4) an acidic compound; and (C) a photopolymerization initiator.
Examples of the acidic compound (B4) include (B-3) an acidic compound having two or more phenolic hydroxyl groups or carboxyl groups in the structure, and (B-4) an acidic compound having one group selected from a phenolic hydroxyl group or a carboxyl group and one or more groups selected from -NH-CO- _A1 or -CO- _NH2 ( _A1 is an organic group having 1 to 4 carbon atoms).

From the viewpoint of obtaining high resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of (A) polyimide precursor, 0.1 to 30 parts by mass of (B4) acidic compound based on 100 parts by mass of (A) polyimide precursor, and 0.1 to 20 parts by mass of (C) photopolymerization initiator based on 100 parts by mass of (A) polyimide precursor.

(A) Polyimide Precursor In this embodiment, the polyimide precursor (A) may be the one shown in the first aspect.

(B4) Acidic compound (B-3)
The acidic compound (B-3) in this embodiment is an acidic compound having two or more phenolic hydroxyl groups or carboxyl groups in the structure. The acidic compound according to this embodiment may have two or more carboxyl groups in the structure, may have two or more phenolic hydroxyl groups, or may have both a carboxyl group and a phenolic hydroxyl group. Among these, from the viewpoints of developability and suppression of Cu voids, a compound having both a carboxyl group and a phenolic hydroxyl group is preferred.

Examples of compounds having two or more carboxyl groups according to this embodiment include phthalic acid, pyromellitic acid, 2,3-naphthalenedicarboxylic acid, trimellitic acid, benzenepentacarboxylic acid, 4-methylphthalic acid, 4-trifluoromethylphthalic acid, 4-methoxyphthalic acid, 1,3,5-tribenzenecarboxylic acid, isophthalic acid, 5-methylisophthalic acid, terephthalic acid, 1,4-naphthaleneterephthalic acid, 2,5-dimethylterephthalic acid, and 3,4-pyridinedicarboxylic acid. Among these compounds, phthalic acid, isophthalic acid, and terephthalic acid are preferred from the viewpoint of chemical resistance.

Examples of compounds having two or more phenolic hydroxyl groups according to this embodiment include catechol, pyrogallol, 2,3-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, 1,2,4-trihydroxybenzene, hexahydroxybenzene, 4-methylcatechol, 3-methoxycatechol, methyl gallate, 5-methylpyrogallol, 2,3,4-trihydroxybenzaldehyde, resorcinol, 1,3-dihydroxynaphthalene, 5-methoxyresorcinol, 2,4-dihydroxybenzamide, and 3,5-dihydroxybenzamide. Among these compounds, methyl gallate, 1,2,4-trihydroxybenzene, 2,4-dihydroxybenzamide, and 3,5-dihydroxybenzamide are preferred from the viewpoint of chemical resistance.

Examples of compounds having both a phenolic hydroxyl group and a carboxyl group according to this embodiment include methylenedisalicylic acid, o-coumaric acid, 2-hydroxybenzoic acid, 4-methylsalicylic acid, 4-hydroxyisophthalic acid, 4-hydroxyphthalic acid, and 5-hydroxyisophthalic acid. Among these, methylenedisalicylic acid and o-coumaric acid are preferred from the standpoint of chemical resistance.

(B-4)
In another embodiment, the acidic compound (B-4) is an acidic compound having one group selected from a phenolic hydroxyl group or a carboxyl group in the structure, and one or more groups selected from -NH-CO-A ₁ or -CO-NH ₂ (A ₁ is an organic group having 1 to 4 carbon atoms).

｛式（１）中、Ａ_２は水酸基、またはカルボキシル基であり、Ａ_３は－ＮＨ－ＣＯ－Ａ_１、または－ＣＯ－ＮＨ_２より選ばれる基であり、Ａ_１は炭素数１～４の有機基であり、Ａ_４は１価の基であり、ｍ_２は１または２であり、ｍ_３は０～４の整数である。｝
で表される構造を有する化合物であることが好ましい。 From the viewpoint of chemical resistance, the acidic compound (B-4) is represented by the following general formula (1):

{In formula (1), A ₂ is a hydroxyl group or a carboxyl group, A ₃ is a group selected from -NH-CO-A ₁ or -CO-NH ₂ , A ₁ is an organic group having 1 to 4 carbon atoms, A ₄ is a monovalent group, m ₂ is 1 or 2, and m ₃ is an integer of 0 to 4.}
It is preferable that the compound has a structure represented by the following formula:

_A1 is an organic group having 1 to 4 carbon atoms, and from the viewpoint of chemical resistance, is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
_A2 is a hydroxyl group or a carboxyl group, and is preferably a carboxyl group from the viewpoint of sensitivity.
A ₃ is a group selected from --NH--CO--A ₁ or --CO--NH ₂ , with --NH--CO--A ₁ being more preferred from the standpoint of chemical resistance.
_A4 is a monovalent group, preferably a monovalent organic group, and more preferably an alkyl group having 1 to 4 carbon atoms.
_m2 is 1 or 2, and is more preferably 1.
_m3 is an integer of 0 to 4, and is more preferably 0 or 1.

Examples of acidic compounds having one group selected from a phenolic hydroxyl group or a carboxyl group and having one or more -NH-CO-A ₁ in the structure according to this embodiment include 2-acetamidobenzoic acid, 3-acetamidobenzoic acid, 4-acetamidobenzoic acid, 5-acetamido-2-aminobenzoic acid, 2-acetamido-5-bromobenzoic acid, 2-(acetoacetamido)benzoic acid, 2-acetamido-6-nitrobenzoic acid, 2-acetamidophenol, 3-acetamidophenol, 4-acetamidophenol, and 2-acetamido-4-methylphenol. Among these compounds, from the viewpoint of chemical resistance, 2-acetamidobenzoic acid, 3-acetamidobenzoic acid, 4-acetamidobenzoic acid, 2-acetamidophenol, 3-acetamidophenol, and 4-acetamidophenol are preferred, and from the viewpoint of sensitivity, 2-acetamidobenzoic acid, 3-acetamidobenzoic acid, and 4-acetamidobenzoic acid are more preferred.

Examples of the acidic compound having one group selected from a phenolic hydroxyl group or a carboxyl group and one or more -CO- _NH2 in the structure according to this embodiment include phthalamic acid, terephthalamic acid, 2-hydroxybenzamide, 2-hydroxy-4-methoxybenzamide, 4-hydroxybenzamide, 5-acetyl-2-hydroxybenzamide, 5-chloro-2-hydroxybenzamide, and 3-hydroxybenzamide. Among these compounds, phthalamic acid, terephthalamic acid, 2-hydroxybenzamide, 3-hydroxybenzamide, and 4-hydroxybenzamide are preferred from the viewpoint of chemical resistance.

By using the above (B4) acidic compound, good chemical resistance and resolution, as well as a Cu void suppression effect can be obtained. Although not bound by theory, it is believed that the reason why good chemical resistance can be obtained is that after heat curing, the compound interacts with the polyimide portion through hydrogen bonds and the like, forming a high-order network, which suppresses the penetration of chemical solutions and improves chemical resistance. In addition, the reason why good resolution can be obtained is unclear, but it is thought that this is because the acidic compound before heat curing is easily dissolved in the developer during development by being mixed with the polyimide precursor, and residues are suppressed. In addition, the reason why the Cu void suppression effect is shown is unclear, but it is thought that the carboxyl group, phenolic hydroxyl group, and/or amide group in the acidic compound strongly interact with Cu ions, suppressing the diffusion of Cu and, as a result, suppressing Cu voids.

The amount of the acidic compound in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A). By blending the acidic compound in the range of 0.1 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A), it is possible to obtain a negative photosensitive resin composition that is particularly excellent in the effects of suppressing Cu voids, improving resolution, and improving chemical resistance.

(C) Photopolymerization Initiator In this embodiment, the photopolymerization initiator (C) may be the same as that shown in the first aspect.

Other Components In this embodiment, the other components, such as the solvent, the nitrogen-containing heterocyclic compound, the hindered phenol compound, the organic titanium compound, the adhesion aid, the sensitizer, the photopolymerizable unsaturated monomer, and the thermal polymerization inhibitor, can be those shown in the first aspect.

<Method for Producing Cured Relief Pattern and Semiconductor Device>
In this embodiment, the same method for producing a cured relief pattern and the semiconductor device as those shown in the first embodiment can be applied.

<Polyimide>
In this embodiment, the polyimide may be the same as that shown in the first embodiment.

<Semiconductor Device>
In this embodiment, the same semiconductor device as that shown in the first aspect can be applied.

<Display Device>
In this embodiment, the same display device as that shown in the first aspect can be applied.

The negative-type photosensitive resin composition according to this embodiment, like the negative-type photosensitive resin composition shown in the first embodiment, is useful not only for application to semiconductor devices as described above, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. The preferred configurations, numerical ranges, or steps shown in the first embodiment can also be treated as preferred configurations, numerical ranges, or steps in this embodiment.

[Fifth aspect]
A fifth aspect of the present embodiment will be described.
<Negative Photosensitive Resin Composition>
The negative photosensitive resin composition according to this embodiment is
(A) a polyimide precursor;
(B5) at least one nitrogen-containing compound selected from the group consisting of biuret, carbazole, indole, hydantoin, uracil derivatives, and barbituric acid; and (C) a photopolymerization initiator.

From the viewpoint of obtaining high resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of (A) polyimide precursor, 0.1 to 30 parts by mass of (B5) at least one nitrogen-containing compound selected from the group consisting of biuret, carbazole, indole, hydantoin, uracil derivatives, and barbituric acid, based on 100 parts by mass of (A) polyimide precursor, and 0.1 to 20 parts by mass of (C) photopolymerization initiator, based on 100 parts by mass of (A) polyimide precursor.

(A) Polyimide Precursor In this embodiment, the polyimide precursor (A) may be the one shown in the first aspect.

(B5) Nitrogen-Containing Compound (B5) in this embodiment is selected from a biuret compound, a carbazole compound, an indole compound, a hydantoin compound, a uracil derivative, and a barbituric acid compound.
The biuret compound according to this embodiment is not limited as long as it has a biuret structure (R-NH-CO-NR'-CO-NH-R''). R, R', and R'' are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
Among these, the following structure (biuret) in which R, R', and R'' are all hydrogen atoms is preferred.

The carbazole compound according to this embodiment is not limited as long as it has a carbazole structure. Examples of such compounds include carbazole, 3,6-diaminocarbazole, 3,6-dimethylcarbazole, 3-methyl-9H-carbazole, 3-phenyl-9H-carbazole, 3-t-butyl-9H-carbazole, 3,6-diethynylcarbazole, and 2-methoxycarbazole. Among these, carbazole and 3,6-diaminocarbazole are preferred from the viewpoint of chemical resistance.

The indole compound according to this embodiment is not limited as long as it has an indole structure. Examples of such compounds include indole, 6-aminoindole, 5-aminoindole, 4-aminoindole, 5-methylindole, 7-methylindole, indole-5-carboxaldehyde, 5-hydroxyindole, 5-nitroindole, methylindole-5-carboxylate, 6-methoxyindole, and 3-acetylindole. Among these, indole, 6-aminoindole, 5-aminoindole, and 4-aminoindole are preferred from the viewpoint of chemical resistance.

The hydantoin compound according to this embodiment is not limited as long as it has a hydantoin structure. Examples of such compounds include hydantoin, 5,5-dimethylhydantoin, 5-methylhydantoin, 5-ethylhydantoin, 5-phenylhydantoin, and 5-(4-hydroxyphenyl)hydantoin. Among these, hydantoin, 5-methylhydantoin, and 5-(4-hydroxyphenyl)hydantoin are preferred from the viewpoint of chemical resistance.

The uracil derivative according to this embodiment is not limited as long as it is uracil, its tautomer, or a derivative thereof. Examples of such compounds include uracil (also known as pyrimidine-2,4(1H,3H)-dione), hydroxypyrimidinone, 2,4-dihydroxypyrimidine, nucleosides derived from uracil (such as uridine), methyl-substituted 5-position (thymine), fluorouracil, and uridylic acid. Of these, uracil is preferred from the standpoint of chemical resistance.

The barbituric acid compound according to this embodiment is not limited as long as it has a barbituric acid structure. Examples of such compounds include violuric acid, barbituric acid, uramil, allobarbital, and cyclobarbital. Among these, violuric acid and barbituric acid are preferred from the viewpoint of chemical resistance.

The nitrogen-containing compound can provide good chemical resistance and resolution, as well as a Cu void suppression effect. Without being bound by theory, it is believed that the reason why good chemical resistance can be obtained is that after thermal curing, the compound interacts with the polyimide portion to form a high-order network, which suppresses the penetration of chemicals and improves chemical resistance.
In addition, although the reason why good resolution can be obtained is unclear, it is believed that the nitrogen-containing compound before heat curing is easily dissolved in the developer during development by blending with the polyimide precursor, and residue is suppressed. In addition, although the reason why the Cu void suppression effect is exhibited is unclear, it is believed that the nitrogen-containing compound generates urea derivatives and the like by heating, and this functional group strongly interacts with Cu ions, suppressing the diffusion of Cu and, as a result, suppressing Cu voids.
From the viewpoints explained above, the nitrogen-containing compound (B5) is more preferably a biuret compound, a carbazole compound, or an indole compound, and even more preferably a biuret compound.

The amount of the nitrogen-containing compound in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, and more preferably 1 part by mass or more and 15 parts by mass or less, per 100 parts by mass of the polyimide precursor (A). By blending the nitrogen-containing compound in the range of 0.1 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the polyimide precursor (A), it is possible to obtain a negative photosensitive resin composition that is particularly excellent in the effects of suppressing Cu voids, improving resolution, and improving chemical resistance.

(C) Photopolymerization Initiator In this embodiment, the photopolymerization initiator (C) may be the same as that shown in the first aspect.

Other Components In this embodiment, the other components, such as the solvent, the nitrogen-containing heterocyclic compound, the hindered phenol compound, the organic titanium compound, the adhesion aid, the sensitizer, the photopolymerizable unsaturated monomer, and the thermal polymerization inhibitor, can be those shown in the first aspect.
However, as described above, the nitrogen-containing heterocyclic compound as the other component is a compound other than the nitrogen-containing compound (B5) in this embodiment.

<Method for Producing Cured Relief Pattern and Semiconductor Device>
In this embodiment, the same method for producing a cured relief pattern and the semiconductor device as those shown in the first embodiment can be applied.

<Polyimide>
In this embodiment, the polyimide may be the same as that shown in the first embodiment.

<Semiconductor Device>
In this embodiment, the same semiconductor device as that shown in the first aspect can be applied.

<Display Device>
In this embodiment, the same display device as that shown in the first aspect can be applied.

The negative-type photosensitive resin composition according to this embodiment, like the negative-type photosensitive resin composition shown in the first embodiment, is useful not only for application to semiconductor devices as described above, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. The preferred configurations, numerical ranges, or steps shown in the first embodiment can also be treated as preferred configurations, numerical ranges, or steps in this embodiment.

[Combination of each aspect]
According to each of the above-mentioned aspects, it is possible to provide a negative type photosensitive resin composition which has high chemical resistance and resolution and suppresses the generation of voids at the interface where the Cu layer contacts the resin layer after a high temperature storage test, and also to provide a method for forming a cured relief pattern using the negative type photosensitive resin composition.
The above-mentioned embodiments can be used in combination with each other. That is, the active esterifying agent (B1), the heat curing agent (B2), the tertiary amine compound and/or the guanidine compound (B3), the acidic compound (B4), and the nitrogen-containing compound (B5) can be used in combination with each other.
When the above-mentioned embodiments are combined with each other, the total mass of the (B1) active esterifying agent, (B2) heat curing agent, (B3) tertiary amine compound and/or guanidine compound, (B4) acidic compound, and (B5) nitrogen-containing compound in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the (A) polyimide precursor. By blending in the range of 0.1 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the (A) polyimide precursor, a negative photosensitive resin composition that is particularly excellent in the effects of suppressing Cu voids, improving resolution, and improving chemical resistance can be obtained.

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

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

(2) Preparation of a cured relief pattern on Cu On a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm), 200 nm thick Ti and 400 nm thick Cu were sputtered in this order using a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Corporation). Next, a photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO Co., Ltd.), and prebaked on a hot plate at 110° C. for 180 seconds to form a coating film with a thickness of about 7 μm. This coating film was irradiated with energy of 500 mJ/cm ² using a test pattern mask with Prisma GHI (manufactured by Ultratech Co., Ltd.). The coating was then spray-developed with a coater developer (D-Spin 60A type, manufactured by Sokudo Co., Ltd.) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu.
The wafer on which the relief pattern was formed on Cu was subjected to a heat treatment in a temperature-ramp programmable curing furnace (VF-2000 type, manufactured by Koyo Lindberg) in a nitrogen atmosphere at the curing temperature shown in Table 1 for 2 hours, thereby obtaining a cured relief pattern made of resin having a thickness of about 4 to 5 μm on Cu.

(3) Resolution evaluation of the cured relief pattern on Cu The cured relief pattern obtained by the above method was observed under an optical microscope to determine the size of the minimum opening pattern. At this time, if the area of the opening of the obtained pattern was 1/2 or more of the corresponding pattern mask opening area, it was considered to be resolved, and the length of the mask opening side corresponding to the resolved opening having the smallest area was taken as the resolution. Resolutions less than 10 μm were rated as "excellent," those between 10 μm and 14 μm as "good," those between 14 μm and 18 μm as "fair," and those over 18 μm as "poor."

(4) High temperature storage test of the cured relief pattern on Cu and subsequent void area evaluation The wafer on which the cured relief pattern was formed on Cu was heated in air at 150° C. for 168 hours using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg). Then, the resin layer on Cu was entirely removed by plasma etching using a plasma surface treatment device (EXAM type, manufactured by Shinko Seiki Co., Ltd.). The plasma etching conditions were as follows:
Output: 133W
Gas type and flow rate: _O2 : 40 mL/min + _CF4 : 1 mL/min Gas pressure: 50 Pa
Mode: Hard mode Etching time: 1800 seconds

The Cu surface from which the resin layer had been completely removed was observed with an FE-SEM (S-4800 model, Hitachi High-Technologies Corporation), and the area of voids on the surface of the Cu layer was calculated using image analysis software (Azo-kun, Asahi Kasei Corporation). When the total area of voids in the evaluation of the photosensitive resin composition described in Comparative Example 1 was taken as 100%, those with a total void area ratio of less than 50% were judged as "excellent", those between 50% and 75% as "good", those between 75% and 100% as "passable", and those over 100% as "unacceptable".

(5) Evaluation of Chemical Resistance of Cured Relief Pattern (Polyimide Coating Film) The cured relief pattern formed on Cu was immersed in a resist stripper {manufactured by ATMI, product name ST-44, main components: 2-(2-aminoethoxy)ethanol and 1-cyclohexyl-2-pyrrolidone} heated to 50°C for 5 minutes, washed with running water for 1 minute, and air-dried. Thereafter, the film surface was visually observed with an optical microscope, and the chemical resistance was evaluated based on the presence or absence of damage caused by the chemical solution, such as cracks, and/or the rate of change in film thickness after chemical treatment. As evaluation criteria, those without damage such as cracks and with a film thickness change rate of 10% or less based on the film thickness before chemical immersion were rated as "excellent", those with a film thickness change rate of more than 10% and less than 15% were rated as "good", those with a film thickness change rate of more than 15% and less than 20% were rated as "passable", and those with cracks or a film thickness change rate of more than 20% were rated as "unacceptable".

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

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

Production Example 3: (A) Synthesis of Polymer A-3 as Polyimide Precursor Polymer (A-3) was obtained by carrying out a reaction in the same manner as in the above Production Example 1, except that 50.2 g of p-phenylenediamine was used instead of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1. The molecular weight of polymer (A-3) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 19,000.

<Example 1-1>
A negative photosensitive resin composition was prepared using polymer A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of polymer A-1 as a polyimide precursor, (B1) 5 g of compound B-11 as an active esterification agent, and (C) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photosensitizer C-1) as a photopolymerization initiator were dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL). 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 above-mentioned method. The results are shown in Table 1.

<Examples 1-2 to 1-10, Comparative Example 1>
Negative photosensitive resin compositions were prepared in the same manner as in Example 1-1, except that they were prepared with the components and blending ratios shown in Table 1, and evaluations were carried out in the same manner as in Example 1-1. The results are shown in Table 1. The compounds (B-11 to B-15) and photosensitizer (C-1) shown in Table 1 are as follows.

B-11: 1-hydroxy-7-azabenzotriazole B-12: Pentafluorophenol B-13: Bis(pentafluorophenyl)carbonate B-14: Bis(4-nitrophenyl)carbonate B-15: 4-nitrophenyl trifluoroacetate C-1: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime

The second aspect will now be described.
Among these, the <Measurement and Evaluation Methods> and Production Examples 1 to 3 are the same as those described above.

<Example 2-1>
A negative photosensitive resin composition was prepared using polymer A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of polymer A-1 as a polyimide precursor, (B2) 8 g of compound B-21 as a heat curing agent, and (C) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photosensitizer C-1) as a photopolymerization initiator were dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL). 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 above-mentioned method. The results are shown in Table 2.

<Examples 2-2 to 2-11, Comparative Example 1>
Negative photosensitive resin compositions were prepared in the same manner as in Example 2-1, except that they were prepared with the components and blending ratios shown in Table 2, and were evaluated in the same manner as above. The results are shown in Table 2. The compounds (B-21 to B-26) and photosensitizer (C-1) shown in Table 2 are as follows.

Ｂ－２２：下記一般式（１１）で表されるベンゾオキサジン
Ｂ－２３：ビスフェノールＡ型エポキシ樹脂（ＬＸ－０１、ダイソー社製）
Ｂ－２４：ビスフェノールＦ型エポキシ樹脂（ＹＬ９８３Ｕ、ジャパンエポキシレジン社製）
Ｂ－２５：下記一般式（１２）で表される化合物
Ｂ－２６：３－アリロキシオキセタン
Ｃ－１：１－フェニル－１，２－プロパンジオン－２－（Ｏ－エトキシカルボニル）－オキシム B-21: Benzoxazine represented by the following general formula (10):

B-22: Benzoxazine represented by the following general formula (11):
B-23: Bisphenol A type epoxy resin (LX-01, manufactured by Daiso Co., Ltd.)
B-24: Bisphenol F type epoxy resin (YL983U, manufactured by Japan Epoxy Resins Co., Ltd.)
B-25: A compound represented by the following general formula (12):
B-26: 3-aryloxyoxetane C-1: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime

The third aspect will now be described.
Among these, the <Measurement and Evaluation Methods> and Production Examples 1 to 3 are the same as those described above.

<Example 3-1>
A negative photosensitive resin composition was prepared using polymer A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of polymer A-1 as a polyimide precursor, (B3) 8 g of compound B-31 as a tertiary amine compound and/or guanidine compound, and (C) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photosensitizer C-1) as a photopolymerization initiator were dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL). 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 above-mentioned method. The results are shown in Table 3.

<Examples 3-2 to 3-8, Comparative Example 1>
Negative photosensitive resin compositions were prepared in the same manner as in Example 3-1, except that they were prepared with the components and blending ratios shown in Table 3, and were evaluated in the same manner as above. The results are shown in Table 3. The compounds (B-31 to B-34) and photosensitizer (C-1) shown in Table 3 are as follows.

B-31: 4-hydroxymethyl-N,N-dimethylaniline B-32: bis[4-(dimethylamino)phenyl]methane B-33: dicyandiamide B-34: D-(-)-arginine C-1: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime

The fourth aspect will now be described.
Among these, the <Measurement and Evaluation Methods> and Production Examples 1 to 3 are the same as those described above.

<Example 4-1>
A negative photosensitive resin composition was prepared using polymer A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of polymer A-1 as a polyimide precursor, (B4) 8 g of compound B-41 as an acidic compound, and (C) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photosensitizer C-1) as a photopolymerization initiator were dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL). 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 above-mentioned method. The results are shown in Table 4.

<Examples 4-2 to 4-10, Comparative Example 1>
Negative photosensitive resin compositions were prepared in the same manner as in Example 4-1, except that they were prepared with the components and blending ratios shown in Table 4, and were evaluated in the same manner as above. The results are shown in Table 4. The compounds (B-41 to B-46) and photosensitizer (C-1) shown in Table 4 are as follows.

B-41: Methyl gallate B-42: Methylenedisalicylic acid B-43: o-Coumaric acid B-44: Phthalic acid B-45: 4-acetamidobenzoic acid B-46: 3-hydroxybenzamide C-1: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime

The fifth aspect will now be described.
Among these, the <Measurement and Evaluation Methods> and Production Examples 1 to 3 are the same as those described above.

<Example 5-1>
A negative photosensitive resin composition was prepared using polymer A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of polymer A-1 as a polyimide precursor, (B5) 8 g of compound B-51 as a nitrogen-containing compound, and (C) 3 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (corresponding to photosensitizer C-1) as a photopolymerization initiator were dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL). 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 above-mentioned method. The results are shown in Table 5.

<Examples 5-2 to 5-12, Comparative Example 1>
Negative photosensitive resin compositions were prepared in the same manner as in Example 5-1, except that they were prepared with the components and blending ratios shown in Table 5, and were evaluated in the same manner as above. The results are shown in Table 5. The compounds (B-51 to B-57) and photosensitizer (C-1) shown in Table 5 are as follows.

B-51: Biuret B-52: 3,6-diaminocarbazole B-53: 5-aminoindole B-54: Hydantoin B-55: Barbituric acid B-56: Violuric acid B-57: Uracil C-1: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime

By using the photosensitive resin composition of the present invention, a cured relief pattern with high chemical resistance and resolution can be obtained, and the occurrence of voids on the Cu surface can be suppressed. The present invention can be suitably used in the field of photosensitive materials that are useful for manufacturing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (11)

(A) a polyimide precursor;
A negative type photosensitive resin composition comprising: (B) an active esterifying agent; and (C) a photopolymerization initiator,
The polyimide precursor (A) is represented by the following general formula (2):
In the formula, _X1 is a tetravalent organic group, Y1 _is a divalent organic group, n1 _is an integer from 2 to 150, and R1 _and R2 _are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 _and R2 _is a monovalent organic group.
The polyimide precursor has a structural unit represented by
In the general formula (2), at least one of R ₁ and R ₂ is represented by the following general formula (3):
{wherein L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.}
The (B) active esterifying agent is at least one selected from the group consisting of bis(pentafluorophenyl)carbonate, bis(4-nitrophenyl)carbonate, di(N-sucrinimidyl)carbonate, pentafluorophenol, 1-hydroxy-7-azabenzotriazole, and 4-nitrophenyl trifluoroacetate.
A negative photosensitive resin composition . In the general formula (2), X ₁ is represented by the following general formula (20a):
The negative type photosensitive resin composition according to claim 1 , comprising a structure represented by the following formula: In the general formula (2), X ₁ is represented by the following general formula (20b):
The negative type photosensitive resin composition according to claim 1 , comprising a structure represented by the following formula: In the general formula (2), Y ₁ is represented by the following general formula (21b):
The negative type photosensitive resin composition according to claim 1 , comprising a structure represented by the following formula: The polyimide precursor (A) is represented by the following general formula (4):
{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to claim 1 , comprising a polyimide precursor having a structural unit represented by the following formula: The polyimide precursor (A) is represented by the following general formula (5):
{wherein R ₁ , R ₂ , and n ₁ are as defined above.}
The negative type photosensitive resin composition according to claim 1 , comprising a polyimide precursor having a structural unit represented by the following formula: The polyimide precursor (A) is represented by the following general formulas (4) and (5):
{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (5).}
{In the formula, R ₁ , R ₂ , and n ₁ are each as defined above, and may be the same as or different from R ₁ , R ₂ , and n ₁ in general formula (4).}
The negative type photosensitive resin composition according to claim 1 , further comprising a structural unit represented by the following formula: 8. The negative type photosensitive resin composition according to claim 7 , wherein the polyimide precursor (A) is a copolymer of structural units represented by the general formulas (4) and (5). 100 parts by mass of the polyimide precursor (A);
0.1 to 30 parts by mass of the (B) active esterifying agent based on 100 parts by mass of the (A) polyimide precursor;
3. The negative type photosensitive resin composition according to claim 1, further comprising 0.1 to 20 parts by mass of the photopolymerization initiator (C) based on 100 parts by mass of the polyimide precursor (A). A method for producing a polyimide comprising a step of converting the negative photosensitive resin composition according to claim 1 or 2 into a polyimide. (1) applying the negative type photosensitive resin composition according to claim 1 or 2 onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of heat-treating the relief pattern to form a cured relief pattern.