TWI798592B - Negative photosensitive resin composition and method for producing cured embossed pattern - Google Patents

Abstract

{式(1)中，A₁ 為選自由氫原子、羥基、及胺基所組成之群中之基，A₂ 為碳數1～20之二價有機基}。The present invention provides a negative-type photosensitive resin combination capable of obtaining higher imidization rate and chemical resistance during low-temperature curing, and thus having higher copper adhesion and less outgassing in the heating step after thermal curing and a method for producing a hardened relief pattern using the negative photosensitive resin composition. The negative photosensitive resin composition of the present invention includes (A) a polyimide precursor, (B) an imide compound represented by the following general formula (1), and (C) a photopolymerization initiator

{In the formula (1), A ₁ is a group selected from a hydrogen atom, a hydroxyl group, and an amino group, and A ₂ is a divalent organic group having 1 to 20 carbon atoms}.

Description

Negative photosensitive resin composition and method for producing cured embossed pattern

The invention relates to a negative-type photosensitive resin composition and a method for manufacturing a cured embossed pattern.

Previously, polyimide resins and polybenzoxazole resins with excellent heat resistance, electrical properties and mechanical properties were used as insulating materials for electronic parts, passivation films, surface protection films, and interlayer insulating films of semiconductor devices. , Phenolic resin, etc. Among these resins, a heat-resistant emboss can be easily formed by providing a photosensitive resin composition in the form of a thermal imidization treatment by applying, exposing, developing, and curing the composition. Convex pattern coating. Compared with the previous non-photosensitive materials, this photosensitive resin composition has the feature of greatly reducing the number of steps.

On the other hand, in recent years, the mounting method (package structure) of the semiconductor device on the printed wiring board is also changing from the viewpoint of increasing the bulk density and computing function, and reducing the chip size. From the previous installation method using metal pins and lead-tin eutectic soldering, it has gradually changed to BGA (Ball Grid Array, Ball Grid Array), CSP (Chip Size Package, Chip Size Package), which can achieve higher density installation etc. use a structure in which the polyimide film is in direct contact with the solder bump. Furthermore, a structure in which FO (fan-out) equals to the surface of a semiconductor chip has a plurality of redistribution layers whose area is larger than that of the semiconductor chip has also been proposed.

Furthermore, when materials such as polyimide, polybenzoxazole, or phenolic resin are used for the rewiring layer of the package structure described above, a metal wiring layer forming step is required after patterning the resin layer. The metal wiring layer is usually formed by plasma etching the surface of the resin layer to roughen the surface, and then forming a metal layer as a seed layer of the plating film with a thickness of 1 μm or less by sputtering, and then, using the The metal layer serves as an electrode, and a metal wiring layer is formed by electroplating. At this time, generally, titanium (Ti) is used as the metal to be the seed layer, and copper (Cu) is used as the metal of the rewiring layer formed by electroplating. However, the conventional photosensitive resin composition had a problem that the resin and copper peeled off due to insufficient adhesion between the resin and copper.

As means for solving the above-mentioned problems, a method of providing a polyimide exhibiting good adhesion to copper by introducing an unsaturated heterocyclic group or the like into the terminal of the polyimide has been disclosed (see Patent Document 1). [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 6-106678

[Problem to be solved by the invention]

However, the polyimide described in Patent Document 1 has a problem that heating at 250° C. to 400° C. is required for thermosetting. Due to the diversification of packaging structures, the resin used for the rewiring layer is required to be hardened at low temperature. However, if the curing temperature is lowered, the imidization rate and chemical resistance of the polyimide precursor will decrease, and then there will be a problem of outgassing in other heating steps after thermal curing.

Therefore, the object of the present invention is to provide a negative resin capable of obtaining high imidization rate and chemical resistance in low-temperature hardening, high copper adhesion, and less outgassing in the heating step after thermal hardening. A negative photosensitive resin composition and a method for producing a hardened relief pattern using the negative photosensitive resin composition. [Technical means to solve the problem]

{式(1)中，A₁ 為選自由氫原子、羥基、及胺基所組成之群中之基，A₂ 為碳數1～20之二價有機基}；及 (C)光聚合起始劑。 [2] 如項目1所記載之負型感光性樹脂組合物，其中以上述通式(1)表示之(B)醯亞胺化合物之A₁ 為羥基或胺基之任一者。 [3] 如項目1所記載之負型感光性樹脂組合物，其中以上述通式(1)表示之(B)醯亞胺化合物之A₁ 為羥基。 [4] 如項目1～3中任一項所記載之負型感光性樹脂組合物，其中上述(B)醯亞胺化合物係以下述通式(2)表示 [化2]

{式(2)中，A₁ 為選自由氫原子、羥基、及胺基所組成之群中之基，A₃ 為選自由硝基、羥基、及一價有機基所組成之群中之基，b為0～4之整數，於b為2以上之情形時，複數個A₃ 亦可共同形成環結構}。 [5] 如項目1～4中任一項所記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有以下述通式(3)表示之結構單元之聚醯亞胺前驅物 [化3]

{式中，X₁ 為4價有機基，Y₁ 為2價有機基，n₁ 為2～150之整數，並且R₁ 及R₂ 分別獨立地為氫原子、或1價有機基，R₁ 及R₂ 之至少一者為以下述通式(4)表示之1價有機基 [化4]

(式中，L₁ 、L₂ 及L₃ 分別獨立地為氫原子或碳數1～3之1價有機基，並且m₁ 為2～10之整數)}。 [6] 如項目5所記載之負型感光性樹脂組合物，其中上述X₁ 包含以下述通式表示之4價有機基 [化5]

{式中，R6為選自由氟原子、C₁ ～C₁₀ 之烴基、及C₁ ～C₁₀ 之含氟烴基所組成之群中之1價基，m為選自0～3之整數}。 [7] 如項目5所記載之負型感光性樹脂組合物，其中上述X₁ 包含以下述通式表示之4價有機基 [化6]

{式中，R6為選自由氟原子、C₁ ～C₁₀ 之烴基、及C₁ ～C₁₀ 之含氟烴基所組成之群中之1價基，m為選自0～3之整數}。 [8] 如項目5所記載之負型感光性樹脂組合物，其中上述Y₁ 包含以下述通式表示之2價有機基 [化7]

{式中，R6為選自由氟原子、C₁ ～C₁₀ 之烴基、及C₁ ～C₁₀ 之含氟烴基所組成之群中之1價基，並且n為選自0～4之整數}。 [9] 如項目5所記載之負型感光性樹脂組合物，其中上述Y₁ 包含以下述通式表示之2價有機基 [化8]

{式中，R6為選自由氟原子、C₁ ～C₁₀ 之烴基、及C₁ ～C₁₀ 之含氟烴基所組成之群中之1價基，並且n為選自0～4之整數}。 [10] 如項目1～9中任一項所記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有以下述通式(5)表示之結構單元之聚醯亞胺前驅物 [化9]

{式中，R₁ 、R₂ 、及n₁ 為上述所定義者}。 [11] 如項目1～10中任一項所記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有以下述通式(6)表示之結構單元之聚醯亞胺前驅物 [化10]

{式中，R₁ 、R₂ 、及n₁ 為上述所定義者}。 [12] 如項目1～11中任一項所記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有以下述通式(7)表示之結構單元之聚醯亞胺前驅物 [化11]

{式中，R₁ 、R₂ 、及n₁ 為上述所定義者}。 [13] 如項目1～12中任一項所記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含：以下述通式(5) [化12]

{式中，R₁ 、R₂ 、及n₁ 為上述所定義者} 表示之結構單元；及 以下述通式(6)： [化13]

{式中，R₁ 、R₂ 、及n₁ 為上述所定義者；其中，式(5)中之R₁ 、R₂ 、及n₁ 與式(6)中之R₁ 、R₂ 、及n₁ 分別獨立選擇} 表示之結構單元。 [14] 如項目1～13中任一項所記載之負型感光性樹脂組合物，其包含： 100質量份之上述(A)聚醯亞胺前驅物； 以上述(A)聚醯亞胺前驅物100質量份為基準為0.1～30質量份之上述(B)醯亞胺化合物；及 以上述(A)聚醯亞胺前驅物100質量份為基準為0.1～20質量份之上述(C)光聚合起始劑。 [15] 如項目1～14中任一項所記載之負型感光性樹脂組合物，其進而包含以(A)聚醯亞胺前驅物100質量份為基準為0.1～30質量份之(D)熱鹼產生劑。 [16] 如項目1～15中任一項所記載之負型感光性樹脂組合物，其中上述負型感光性樹脂組合物為用於形成絕緣構件之負型感光性樹脂組合物。 [17] 如項目1～16中任一項所記載之負型感光性樹脂組合物，其中上述負型感光性樹脂組合物為用於形成層間絕緣膜之負型感光性樹脂組合物。 [18] 一種硬化浮凸圖案之製造方法，其包括以下步驟： (1)將如項目1～17中任一項所記載之負型感光性樹脂組合物塗佈於基板上，於上述基板上形成感光性樹脂層； (2)對上述感光性樹脂層進行曝光； (3)對曝光後之上述感光性樹脂層進行顯影，形成浮凸圖案；及 (4)對上述浮凸圖案進行加熱處理，形成硬化浮凸圖案。 [19] 如項目18所記載之硬化浮凸圖案之製造方法，其中上述加熱處理為200℃以下之加熱處理。 [20] 如項目19所記載之硬化浮凸圖案之製造方法，其中上述加熱處理為180℃以下之加熱處理。 [21] 一種聚醯亞胺之製造方法，其包括使如項目1～17中任一項所記載之負型感光性樹脂組合物硬化。 [發明之效果]The inventors of the present invention found that the above-mentioned problems can be solved by combining a specific photosensitive resin and an imide compound, and completed the present invention. That is, the present invention is as follows. [1] A negative photosensitive resin composition comprising: (A) a polyimide precursor; (B) an imide compound represented by the following general formula (1) [Chem. 1]

{In formula (1), A ₁ is a group selected from a hydrogen atom, a hydroxyl group, and an amine group, and A ₂ is a divalent organic group with 1 to 20 carbon atoms}; and (C) photopolymerization starter. [2] The negative photosensitive resin composition as described in item 1, wherein A 1 of the (B) imide compound represented by the above general formula ( ₁ ) is any one of a hydroxyl group or an amino group. [3] The negative photosensitive resin composition as described in Item 1, wherein A ₁ of the (B) imide compound represented by the above general formula (1) is a hydroxyl group. [4] The negative photosensitive resin composition as described in any one of Items 1 to 3, wherein the above-mentioned (B) imide compound is represented by the following general formula (2) [Chem. 2]

{In the formula (2), _A1 is a group selected from a hydrogen atom, a hydroxyl group, and an amino group, and _A3 is a group selected from a nitro group, a hydroxyl group, and a monovalent organic group. , b is an integer from 0 to 4, and when b is 2 or more, a plurality of A ₃ may also jointly form a ring structure}. [5] The negative-type photosensitive resin composition as described in any one of items 1 to 4, wherein the polyimide precursor (A) includes a polyimide having a structural unit represented by the following general formula (3) Imine Precursor [Chem. 3]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are independently a hydrogen atom or a monovalent organic group, R ₁ and at least one of _R2 is a monovalent organic group represented by the following general formula (4) [Chem. 4]

(wherein, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbons, and m ₁ is an integer of 2 to 10)}. [6] The negative-type photosensitive resin composition as described in Item 5, wherein the above-mentioned X ₁ contains a tetravalent organic group represented by the following general formula [Chem. 5]

{wherein, R6 is a monovalent group selected from the group consisting of a fluorine atom, a C ₁ to C ₁₀ hydrocarbon group, and a C ₁ to C ₁₀ fluorine-containing hydrocarbon group, and m is an integer selected from 0 to 3}. [7] The negative-type photosensitive resin composition as described in item 5, wherein the above-mentioned X ₁ contains a tetravalent organic group represented by the following general formula [Chem. 6]

{wherein, R6 is a monovalent group selected from the group consisting of a fluorine atom, a C ₁ to C ₁₀ hydrocarbon group, and a C ₁ to C ₁₀ fluorine-containing hydrocarbon group, and m is an integer selected from 0 to 3}. [8] The negative-type photosensitive resin composition as described in item 5, wherein said Y ₁ contains a divalent organic group represented by the following general formula [Chem. 7]

{wherein, R6 is a monovalent group selected from the group consisting of fluorine atoms, C ₁ to C ₁₀ hydrocarbon groups, and C ₁ to C ₁₀ fluorine-containing hydrocarbon groups, and n is an integer selected from 0 to 4} . [9] The negative-type photosensitive resin composition as described in item 5, wherein said Y ₁ contains a divalent organic group represented by the following general formula [Chem. 8]

{wherein, R6 is a monovalent group selected from the group consisting of fluorine atoms, C ₁ to C ₁₀ hydrocarbon groups, and C ₁ to C ₁₀ fluorine-containing hydrocarbon groups, and n is an integer selected from 0 to 4} . [10] The negative photosensitive resin composition as described in any one of items 1 to 9, wherein the polyimide precursor (A) includes a polyamide having a structural unit represented by the following general formula (5) Imine precursor [Chemical 9]

{wherein, R ₁ , R ₂ , and n ₁ are defined above}. [11] The negative photosensitive resin composition as described in any one of items 1 to 10, wherein the polyimide precursor (A) includes a polyamide having a structural unit represented by the following general formula (6): Imine precursor [Chem. 10]

{wherein, R ₁ , R ₂ , and n ₁ are defined above}. [12] The negative-type photosensitive resin composition as described in any one of items 1 to 11, wherein the polyimide precursor (A) includes a polyimide having a structural unit represented by the following general formula (7): Imine precursor [Chem. 11]

{wherein, R ₁ , R ₂ , and n ₁ are defined above}. [13] The negative photosensitive resin composition as described in any one of Items 1 to 12, wherein the above-mentioned (A) polyimide precursor comprises: the following general formula (5) [Chem. 12]

{wherein, R ₁ , R ₂ , and n ₁ are as defined above} the structural unit represented by the following general formula (6): [Chem. 13]

{wherein, R ₁ , R ₂ , and n ₁ are as defined above; wherein, R ₁ , R ₂ , and n ₁ in formula (5) and R ₁ , R ₂ , and n ₁ independently select the structural unit represented by }. [14] The negative-type photosensitive resin composition as described in any one of items 1 to 13, comprising: 100 parts by mass of the above-mentioned (A) polyimide precursor; 0.1 to 30 parts by mass of the above-mentioned (B) imide compound based on 100 parts by mass of the precursor; and 0.1 to 20 parts by mass of the above-mentioned (C) ) photopolymerization initiator. [15] The negative photosensitive resin composition as described in any one of Items 1 to 14, further comprising 0.1 to 30 parts by mass of (D) based on 100 parts by mass of the polyimide precursor (A) ) heat base generator. [16] The negative photosensitive resin composition according to any one of items 1 to 15, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an insulating member. [17] The negative photosensitive resin composition according to any one of items 1 to 16, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an interlayer insulating film. [18] A method for producing a hardened relief pattern, comprising the following steps: (1) Applying the negative-type photosensitive resin composition described in any one of items 1 to 17 on a substrate, Forming a photosensitive resin layer; (2) exposing the above-mentioned photosensitive resin layer; (3) developing the above-mentioned photosensitive resin layer after exposure to form a relief pattern; and (4) carrying out heat treatment to the above-mentioned relief pattern , forming a hardened relief pattern. [19] The method for producing a cured relief pattern according to item 18, wherein the heat treatment is heat treatment at 200° C. or lower. [20] The method for producing a cured relief pattern according to item 19, wherein the heat treatment is heat treatment at 180° C. or lower. [21] A method for producing polyimide, comprising curing the negative photosensitive resin composition described in any one of items 1 to 17. [Effect of Invention]

According to the present invention, it is possible to provide a photosensitive resin composition capable of obtaining higher imidization rate and chemical resistance, and further copper adhesion, and less outgassing in the heating step after thermosetting, And a method for producing a hardened relief pattern using the photosensitive resin composition.

Hereinafter, an embodiment of the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. In addition, this invention is not limited to the following this embodiment, Various changes can be implemented within the range of the summary. In addition, when the structures represented by the same symbol in a general formula throughout this specification exist in plural in a molecule, they may be mutually identical or mutually different.

{式(1)中，A₁ 為選自由氫原子、羥基、及胺基所組成之群中之基，A₂ 為碳數1～20之二價有機基}； (C)光聚合起始劑。<Negative Photosensitive Resin Composition> The negative photosensitive resin composition of the present embodiment includes: (A) a polyimide precursor; (B) an imide compound represented by the following general formula (1) [Chem 14]

{In the formula (1), A ₁ is a group selected from a hydrogen atom, a hydroxyl group, and an amino group, and A ₂ is a divalent organic group with 1 to 20 carbon atoms}; (C) photopolymerization initiation agent.

From the viewpoint of obtaining higher chemical resistance, the negative photosensitive resin composition preferably comprises 100 mass parts of (A) polyimide precursor, with (A) 100 mass parts of polyimide precursor Parts are based on 0.1-30 parts by mass of (B) an imide compound, and 0.1-20 parts by mass of (C) photopolymerization initiator based on 100 parts by mass of (A) polyimide precursor.

(A) Polyimide precursor The (A) polyimide precursor in this embodiment is a resin component included in the negative photosensitive resin composition, and is converted into polyimide by performing a heating cyclization treatment. (A) The structure of the polyimide precursor is not limited as long as it is a resin that can be used in the negative photosensitive resin composition, but it is preferably non-alkali-soluble. Higher chemical resistance can be obtained by making the polyimide precursor non-alkali soluble. The so-called polyimide precursor is non-alkali-soluble, and can be defined as follows. Using a coating developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), spin-coat a solution obtained by dissolving 30% by mass of a polyimide precursor in γ-butyrolactone on a wafer, and use a heating plate Pre-bake at 110°C for 180 seconds to form a coating film about 5 μm thick. Use 2.38% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution to carry out immersion development on the coating film for 60 seconds, wash with water spin spray for 10 seconds, and measure the film thickness of the coating film. Based on the film thickness of the coating film before and after development, the film thickness reduction rate (1 nm/sec) in the above-mentioned development step was calculated. If the film thickness reduction rate is 1 nm/sec or less, the polyimide precursor can be said to be non-alkali-soluble.

{式中，X₂ 為4價有機基，Y₂ 為2價有機基，n₁ 為2～150之整數，並且R₁ 及R₂ 分別獨立地為氫原子、或1價有機基，R₁ 及R₂ 之至少一者為以下述通式(4)表示之1價有機基 [化16]

(式中，L₁ 、L₂ 及L₃ 分別獨立地為氫原子或碳數1～3之1價有機基，並且m₁ 為2～10之整數)} 通式(3)中之R₁ 及R₂ 為氫原子之比率以R₁ 及R₂ 整體之莫耳數為基準較佳為10%以下，更佳為5%以下，進而較佳為1%以下。又，通式(3)中之R₁ 及R₂ 為以上述通式(4)表示之1價有機基之比率以R₁ 及R₂ 整體之莫耳數為基準較佳為70%以上，更佳為80%以上，進而較佳為90%以上。就感光特性及保存穩定性之觀點而言，氫原子之比率、及通式(4)之有機基之比率較佳為處於上述範圍。The polyimide precursor is preferably polyamide having a structure represented by the following general formula (3). [chemical 15]

{In the formula, X ₂ is a tetravalent organic group, Y ₂ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are independently a hydrogen atom or a monovalent organic group, R ₁ and at least one of _R2 is a monovalent organic group represented by the following general formula (4) [Chem. 16]

(In the formula, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or a monovalent organic group with 1 to 3 carbons, and m ₁ is an integer of 2 to 10)} R ₁ in the general formula (3) And the ratio of R ₂ being a hydrogen atom is preferably 10% or less, more preferably 5% or less, and still more preferably 1% or less, based on the total molar number of R ₁ and R ₂ . Also, the ratio of R ₁ and R ₂ in the general formula (3) to the monovalent organic group represented by the above general formula (4) is preferably 70% or more based on the molar number of R ₁ and R ₂ as a whole, More preferably, it is 80% or more, More preferably, it is 90% or more. From the viewpoint of photosensitivity and storage stability, the ratio of hydrogen atoms and the ratio of organic groups of the general formula (4) are preferably within the above-mentioned ranges.

_n1 in the general formula (3) is not limited as long as it is an integer of 2 to 150, and is preferably an integer of 3 to 100 from the viewpoint of the photosensitive properties and mechanical properties of the negative photosensitive resin composition, and more preferably Preferably it is an integer of 5-70.

{式中，R6為選自由氫原子、氟原子、C₁ ～C₁₀ 之烴基、及C₁ ～C₁₀ 之含氟烴基所組成之群中之1價基，l為選自0～2之整數，m為選自0～3之整數，並且n為選自0～4之整數}，但並不限定於其等。又，X₁ 之結構可為一種亦可為兩種以上之組合。就兼具耐熱性與感光特性之方面而言，尤其較佳為具有上述式(20)所表示之結構之X₁ 基。In terms of both heat resistance and photosensitive properties, in the general formula (3), the tetravalent organic group represented by X ₁ is preferably an organic group with 6 to 40 carbon atoms, more preferably -COOR ₁ group and - An aromatic group or an alicyclic aliphatic group in which the COOR ₂ group and the -CONH- group are adjacent to each other. As the tetravalent organic group represented by _X1 , specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, a group having a structure represented by the following general formula (20) [Chemical 17]

{In the formula, R6 is a monovalent group selected from the group consisting of hydrogen atom, fluorine atom, _C1 ～ _C10 hydrocarbon group, and _C1 ～ _C10 fluorine-containing hydrocarbon group, l is selected from 0～2 integer, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4}, but not limited thereto. In addition, the structure of _X1 may be one type or a combination of two or more types. In terms of both heat resistance and photosensitivity, the X ₁ group having the structure represented by the above formula (20) is particularly preferred.

{式中，R6為選自由氟原子、C₁ ～C₁₀ 之烴基、及C₁ ～C₁₀ 之含氟烴基所組成之群中之1價基，m為選自0～3之整數}。Among the structures represented by the above formula (20), the following formula is particularly preferred as the X _group from the viewpoint of the imidization rate at low temperature heating, outgassing properties, copper adhesion, and chemical resistance Structure of Representation[Chem.18]

{wherein, R6 is a monovalent group selected from the group consisting of a fluorine atom, a C ₁ to C ₁₀ hydrocarbon group, and a C ₁ to C ₁₀ fluorine-containing hydrocarbon group, and m is an integer selected from 0 to 3}.

{式中，R6為選自由氫原子、氟原子、C₁ ～C₁₀ 之烴基、及C₁ ～C₁₀ 之含氟烴基所組成之群中之1價基，並且n為選自0～4之整數}，但並不限定於其等。又，Y₁ 之結構可為一種亦可為兩種以上之組合。就兼具耐熱性與感光特性之方面而言，尤其較佳為具有以上述式(21)表示之結構之Y₁ 基。In terms of both heat resistance and photosensitivity, in the above general formula (3), the divalent organic group represented by Y ₁ is preferably an aromatic group with 6 to 40 carbon atoms, for example, the following formula (21) Structure represented by [Chem. 19]

{wherein, R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C ₁ to C ₁₀ hydrocarbon group, and a C ₁ to C ₁₀ fluorine-containing hydrocarbon group, and n is selected from 0 to 4 Integers}, but not limited to them. Also, the structure of _Y1 may be one type or a combination of two or more types. In terms of both heat resistance and photosensitivity, the Y ₁ group having the structure represented by the above formula (21) is particularly preferable.

{式中，R6為選自由氟原子、C₁ ～C₁₀ 之烴基、及C₁ ～C₁₀ 之含氟烴基所組成之群中之1價基，並且n為選自0～4之整數}。Among the structures represented by the above formula (21), the following formula is particularly preferable as the _Y1 group from the viewpoint of the imidization ratio when heated at low temperature, outgassing property, copper adhesion, and chemical resistance Structure of Representation [Chem.20]

{wherein, R6 is a monovalent group selected from the group consisting of fluorine atoms, C ₁ to C ₁₀ hydrocarbon groups, and C ₁ to C ₁₀ fluorine-containing hydrocarbon groups, and n is an integer selected from 0 to 4} .

L ₁ in the above general formula (4) is preferably a hydrogen atom or a methyl group, and L ₂ and L ₃ are preferably hydrogen atoms from the viewpoint of photosensitive properties. In addition, m ₁ is an integer of 2 to 10 from the viewpoint of photosensitivity, preferably an integer of 2 to 4.

{式中，R₁ 、R₂ 、及n₁ 為上述所定義者}。In one embodiment, the (A) polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (5) [Chem. 21]

{wherein, R ₁ , R ₂ , and n ₁ are defined above}.

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 (4). (A) Polyimide precursor By containing the polyimide precursor represented by General formula (5), especially chemical resistance becomes high. Moreover, it is also preferable from the viewpoint of the imidization rate at the time of low-temperature heating, an outgassing property, and copper adhesiveness.

{式中，R₁ 、R₂ 、及n₁ 為上述所定義者}。In one embodiment, the (A) polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (6) [Chem. 22]

{wherein, R ₁ , R ₂ , and n ₁ are defined above}.

In the general formula (6), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the above general formula (4). (A) When a polyimide precursor contains both the structural unit represented by General formula (5) and the structural unit represented by General formula (6), especially chemical resistance tends to become high. For example, the polyimide precursor (A) may comprise a copolymer of a structural unit represented by the general formula (5) and a structural unit represented by the general formula (6), or may be a polyimide represented by the general formula (5). A mixture of a polyimide precursor and a polyimide precursor represented by general formula (6). Moreover, it is also preferable from the viewpoint of the imidization rate at the time of low-temperature heating, an outgassing property, and copper adhesiveness.

{式中，R₁ 、R₂ 、及n₁ 為上述所定義者}。In one embodiment, the (A) polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (7) [Chem. 23]

{wherein, R ₁ , R ₂ , and n ₁ are defined above}.

In the general formula (7), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the above general formula (4). (A) The polyimide precursor contains both the structural unit represented by the general formula (5) and the structural unit represented by the general formula (7), and the effect of resolution is further enhanced tendency. For example, the polyimide precursor (A) may comprise a copolymer of a structural unit represented by the general formula (5) and a structural unit represented by the general formula (7), or may be a polyimide represented by the general formula (5). A mixture of a polyimide precursor and a polyimide precursor represented by general formula (7). Moreover, it is also preferable from the viewpoint of the imidization rate at the time of low-temperature heating, outgassing property, copper adhesiveness, and chemical resistance.

(A) The preparation method of the polyimide precursor (A) the polyimide precursor system firstly makes the tetracarboxylic dianhydride containing the above-mentioned 4-valent organic group _X1 and the alcohol with the photopolymerizable unsaturated double bond Classes, and any alcohols that do not have unsaturated double bonds react to prepare partially esterified tetracarboxylic acids (hereinafter also referred to as acid/ester bodies). Thereafter, (A) a polyimide precursor is obtained by subjecting partially esterified tetracarboxylic acid and diamines containing the above-mentioned divalent organic group _Y to polycondensation amides.

(Preparation of Acid/Ester Body) In this embodiment, tetracarboxylic dianhydrides that are preferably used to prepare (A) polyimide precursors containing quaternary organic groups X ₁ include the above-mentioned general In addition to tetracarboxylic dianhydride represented by formula (20), for example, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone- 3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl-3,3',4,4'- Tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis (3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferably pyromellitic dianhydride, diphenyl ether-3,3',4, 4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but is not limited to such. Moreover, these can be used individually of course, and can also mix and use 2 or more types.

In this embodiment, alcohols having a photopolymerizable unsaturated double bond that are preferably used in the preparation of the polyimide precursor (A) include, for example, 2-acryloxyethanol, 1-propylene Acyloxy-3-propanol, 2-acrylamide ethanol, hydroxymethyl 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-tert-butoxypropyl acrylate, acrylic acid 2-Hydroxy-3-cyclohexyloxypropyl ester, 2-methacryloxyethanol, 1-methacryloxy-3-propanol, 2-methacrylamide ethanol, hydroxymethylethylene ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-methacrylate -Phenoxypropyl, 2-Hydroxy-3-butoxypropyl methacrylate, 2-Hydroxy-3-tert-butoxypropyl methacrylate, 2-Hydroxy-3-cyclohexyl methacrylate Oxypropyl Etc.

It is also possible to mix a part of alcohols with photopolymerizable unsaturated double bonds such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tertiary butanol, 1-pentanol, and 2-pentanol. Alcohol, 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, benzyl alcohol and other alcohols without unsaturated double bonds are used.

Also, a non-photosensitive polyimide precursor prepared only from the above-mentioned alcohols not having an unsaturated double bond may be mixed with a photosensitive polyimide precursor to be used as a polyimide precursor. From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

The above-mentioned preferred tetracarboxylic dianhydride and the above-mentioned alcohols are mixed in the presence of a basic catalyst such as pyridine, in a solvent as described later, at a temperature of 20-50° C. for 4-10 hours, and then mixed for 4-10 hours. The esterification reaction of acid anhydride can obtain the desired acid/ester body.

(Preparation of polyimide precursor) Under cooling in an ice bath, add an appropriate dehydration condensing agent, such as dicyclohexylcarbodiimide, to the above acid/ester body (typically, a solution in the solvent mentioned later) , 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxybis(1,2,3-benzotriazole), N,N'- Disuccinimidyl carbonate and the like are mixed, and the acid/ester body is made into a polyanhydride, and the diamines containing the divalent organic group _Y1 preferably used in this embodiment are added dropwise thereto. What is separately dissolved or dispersed in a solvent is subjected to amide polycondensation, whereby the target polyimide precursor can be obtained. Alternatively, after chlorinating the acid part of the above-mentioned acid/ester body using thionyl chloride or the like, it is reacted with a diamine compound in the presence of a base such as pyridine, whereby the target polyimide precursor can be obtained thing.

As the diamines containing the divalent organic group _Y that are preferably used in this embodiment, in addition to the diamines having the structure represented by the above general formula (21), for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether Thioethers, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide Diphenylene, 3,3'-diaminodiphenylene, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl , 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenyl Methane, 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]pyridine, bis[4-( 3-aminophenoxy)phenyl]pyridine, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4 -(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1, 3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4 -aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)benzene base]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, di-o-toluidinium, 9,9-bis(4-aminophenyl) terpene, and others Part of the hydrogen atom on the benzene ring is replaced by methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobis Benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-bis Methyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'- Diaminobiphenyl, mixtures thereof, etc., are not limited thereto.

After the amide polycondensation reaction is completed, if necessary, filter and separate the water-absorbing by-products of the dehydration condensing agent coexisting in the reaction solution, and then add water, aliphatic lower alcohol, or a mixture thereof, and other poor solvents into the obtained polymer component , to separate out the polymer components, and then repeatedly perform redissolution, reprecipitation, etc., thereby purifying the polymer, vacuum drying, and isolating the target polyimide precursor. In order to improve the degree of purification, the polymer solution can also be passed through a column filled with anion and/or cation exchange resins swollen with organic solvents to remove ionic impurities.

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

{式(1)中，A₁ 為選自由氫原子、羥基、及胺基所組成之群中之基，A₂ 為碳數1～20之二價有機基}。(B) Acyl imide compound The (B) imide compound in this embodiment is an imide compound represented by the following general formula (1) [Chem. 24]

{In the formula (1), A ₁ is a group selected from a hydrogen atom, a hydroxyl group, and an amino group, and A ₂ is a divalent organic group having 1 to 20 carbon atoms}.

{式(22)中，A₁ 為上述所定義者}。Examples of imide compounds include compounds having a structure represented by the following general formula (22) [Chem. 25]

{In formula (22), A ₁ is defined above}.

As the imide compound, more specifically, N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxy-1,8-naphthalimide, N,N '-Dihydroxypyromellitic imide, N-hydroxy-4-nitrophthalimide, N-aminophthalimide, phthalimide, N,N '-Dihydroxy-1,2,3,4-cyclobutanetetraformyldiimide, glutarimide, 3-ethyl-3-methylglutarimide, hexahydrophthalimide imide, maleimide, 1,4,5,8-naphthalene tetracarboxamide diimide, 1,8-naphthalene dicarboxamide, 3-nitrophthaloimide, 5 -northene-2,3-dicarboximide, pyromellitic diimide, 3,3-tetramethyleneglutarimide, cis 1,2,3,6-tetrahydro Phthalimide, N,N'-dihydroxy-1,2,3,4-cyclobutanetetraformyldiimide, N-hydroxy-5-northene-2,3-dicarboxy imide, etc., but not limited thereto.

The negative photosensitive resin composition of this embodiment improves the imidization rate, chemical resistance, and copper adhesiveness by containing the said imide compound, and furthermore, it becomes difficult to generate|occur|produce outgassing. The reason for considering the increase in the imidization rate is that by making the imide compound exist around the imide precursor, the interaction between the imide rings after cyclization becomes stable, thus making the cyclization reaction The activation energy decreases, but is not bound by this theory. In addition, it is considered that the reason for obtaining good chemical resistance is that by coordinating a low-molecular imide compound to a site where the interaction between polyimide molecules is insufficient, the interaction between the imide rings occurs, Thereby inhibiting the infiltration of liquid medicine. The same is true for copper adhesion. It is believed that low-molecular imide compounds enter the micro-voids where polyimide molecules fail to interact with copper, and promote the interaction between copper and polyimide. As a result, the copper of the resin Improved adhesion. The reason for the decrease in the outgassing property after thermosetting is not clear, but it is considered that the main reason is that by promoting the cyclization of the polyimide precursor, the detachment components accompanying the cyclization are volatilized during the thermosetting process.

Regarding the imide compound, A ₁ in the above general formula (1) is preferably either a hydroxyl group or an amino group, more preferably a hydroxyl group. The negative photosensitive resin composition added with the imide compound in which A ₁ is a hydroxyl group exhibits better chemical resistance.

{式(2)中，A₁ 為選自由氫原子、羥基、及胺基所組成之群中之基，A₃ 為選自由硝基、羥基、及一價有機基所組成之群中之基，b為0～4之整數，於b為2以上之情形時，複數個A₃ 亦可共同形成環結構}。From the viewpoint of chemical resistance and copper adhesion, the imide compound is preferably an imide compound represented by the following general formula (2): [Chem. 26]

{In the formula (2), _A1 is a group selected from a hydrogen atom, a hydroxyl group, and an amino group, and _A3 is a group selected from a nitro group, a hydroxyl group, and a monovalent organic group. , b is an integer from 0 to 4, and when b is 2 or more, a plurality of A ₃ may also jointly form a ring structure}.

It is considered that the interaction between the imide compound and the polyimide is further strengthened by having the structure of the general formula (2), and the chemical resistance and copper adhesion are further improved. When the imide compound represented by the general formula (2) has a monovalent organic group in A ₃ , the monovalent organic group preferably has 1 to 10 carbon atoms from the viewpoint of solubility in a solvent. On the other hand, b of the imide compound represented by the general formula (2) is preferably 0 from the viewpoint of chemical resistance. Also, from the viewpoint of chemical resistance, A ₁ is preferably a hydroxyl group. The above-mentioned imide compound may be a single molecule or a combination of plural compounds.

It is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of (A) polyimide precursors, and, as for an imide compound, it is more preferable that it is 1-15 mass parts. By setting the imide compound to 0.1 to 30 parts by mass relative to 100 parts by mass of the polyimide precursor (A), high imidization rate and chemical resistance in low temperature curing can be obtained A negative-type photosensitive resin composition with high copper adhesion and less outgassing during the heating step after thermosetting.

、2-甲基-9-氧硫

、2-異丙基-9-氧硫

、二乙基-9-氧硫

等9-氧硫

衍生物；苯偶醯、苯偶醯二甲基縮酮、苯偶醯-β-甲氧基乙基縮醛等苯偶醯衍生物；安息香、安息香甲醚等安息香衍生物；1-苯基-1,2-丁二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰乙氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰苯甲醯基)肟、1,3-二苯基丙三酮-2-(鄰乙氧基羰基)肟、1-苯基-3-乙氧基丙三酮-2-(鄰苯甲醯基)肟等肟類；N-苯基甘胺酸等N-芳基甘胺酸類；過氧化苯甲醯等過氧化物類；芳香族聯咪唑類；二茂鈦類；α-(正辛磺醯氧基亞胺基)-4-甲氧基苯乙腈等光酸產生劑類等；但並不限定於其等。上述光聚合起始劑中，尤其就感光度之方面而言，更佳為肟類。(C) Photopolymerization initiator The (C) photopolymerization initiator used in this embodiment is demonstrated. As a photopolymerization initiator, preferably a photoradical polymerization initiator, preferably benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyl Benzophenone derivatives such as diphenyl ketone, dibenzyl ketone, and fennelone; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylbenzene Acetophenone derivatives such as ketones; 9-oxosulfur

, 2-methyl-9-oxosulfur

, 2-isopropyl-9-oxosulfur

, Diethyl-9-oxosulfur

9-oxosulfur

Derivatives; benzoyl derivatives such as benzoyl, benzoyl dimethyl ketal, and benzoyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl -1,2-Butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1 ,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropane Triketone-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime and other oximes; N-phenylglycine, etc. N-aryl glycines; peroxides such as benzoyl peroxide; aromatic biimidazoles; titanocenes; α-(n-octylsulfonyloxyimino)-4-methoxybenzene Photoacid generators, such as acetonitrile, etc.; However, it is not limited to these. Among the above-mentioned photopolymerization initiators, oximes are more preferable in terms of sensitivity.

(C) The compounding quantity of a photoinitiator is preferably 0.1-20 mass parts with respect to (A) 100 mass parts of polyimide precursors, More preferably, it is 1-8 mass parts. The above compounding amount is preferably at least 0.1 parts by mass from the viewpoint of sensitivity or patternability, and preferably at most 20 parts by mass from the viewpoint of physical properties of the photosensitive resin layer after the negative photosensitive resin composition is cured. .

(D) Thermal base generator The negative photosensitive resin composition of this embodiment may contain (D) base generator. The term "base generator" refers to a compound that generates a base by heating. The imidization of the photosensitive resin composition can be further promoted by containing a thermal base generator.

The type of the thermal base generator is not particularly limited, and examples thereof include an amine compound protected by a tert-butoxycarbonyl group, or a thermal base generator disclosed in International Publication No. 2017/038598. However, it is not limited thereto, and a known thermal base generator can also be used.

Examples of amine compounds protected by tert-butoxycarbonyl include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, and 4-amine -1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino- 2-Methyl-1-butanol, Valerinol, 3-Amino-1,2-Propanediol, 2-Amino-1,3-Propanediol, Tyramide, Benzoolamine, 2-Amino-1 -Phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N -Methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl ] Benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4- (3-Hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinyl)- 2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine) , 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether , 1,11-diamino-3,6,9-trioxa-undecane, or the amine group of amino acids and their derivatives protected by 3-butoxycarbonyl, but not limited to etc.

(D) The compounding quantity of a thermal base generator is preferably 0.1-30 mass parts with respect to (A) 100 mass parts of polyimide precursors, More preferably, it is 1-20 mass parts. The above compounding amount is preferably at least 0.1 parts by mass from the viewpoint of the imidization promoting effect, and preferably at most 20 parts by mass from the viewpoint of the physical properties of the photosensitive resin layer after the negative photosensitive resin composition is cured. .

The negative photosensitive resin composition of this embodiment may contain components other than said (A)-(D) component further. Components other than components (A) to (D) are not limited, and examples include solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, adhesive additives, sensitizers, and photopolymerizable unsaturated monomers , thermal polymerization inhibitors, etc.

solvent Examples of solvents include amides, sulfides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. For example, N-methyl-2- Pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl Ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether ethyl Ester, propylene glycol monomethyl ether, benzyl alcohol, phenylethylene glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, thioline, dichloromethane, 1,2-dichloro Ethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. Among them, from the viewpoint of the solubility of the resin, the stability of the resin composition, and the adhesiveness to the substrate, N-methyl-2-pyrrolidone, dimethylsulfene, and tetramethylurea are preferred. , butyl acetate, ethyl lactate, gamma-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenylethylene glycol, and tetrahydrofurfuryl alcohol.

Among such solvents, those that completely dissolve the resulting polymer are particularly preferred, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide Amide, dimethyl sulfide, tetramethyl urea, γ-butyrolactone, etc.

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

Nitrogen-containing heterocyclic compounds When using the photosensitive resin composition of this embodiment to form a cured film on a substrate containing copper or copper alloy, in order to suppress discoloration on copper, the negative photosensitive resin composition may optionally contain a nitrogen-containing heterocyclic compound . Examples of nitrogen-containing heterocyclic compounds include azole compounds, purine derivatives, and the like.

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-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-benzene Base-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-di Methylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5- Methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'- Trioctylphenyl)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 preferable ones include toluenetriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. In addition, these azole compounds may be used alone or in 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-methyl Adenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2 -Hydroxyethyl)adenine, Guanoxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine Purine, 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-azaxanthine Xanthine and its derivatives.

When the photosensitive resin composition contains the above-mentioned azole compound or purine derivative, the compounding amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A). From the point of view, it is more preferably 0.5 to 5 parts by mass. When the compounding amount of the azole compound is 0.1 parts by mass or more with respect to 100 parts by mass of the polyimide precursor (A), when the photosensitive resin composition of this embodiment is formed on copper or copper alloy , can suppress the discoloration of copper or copper alloy surface, on the other hand, in the case of 20 parts by mass or less, the sensitivity is excellent.

Hindered phenolic compound Also, the negative photosensitive resin composition may optionally contain a hindered phenol compound in order to suppress discoloration on the copper surface. Examples of hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, 3-(3,5-di-tert-butyl -4-Hydroxyphenyl) propionate octadecyl, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate, 4,4'-methylenebis( 2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl -6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol -bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene bis[3-(3,5-di-tertiary Butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-phenylacrylamide), 2,2'- Methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetra[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], Tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2, 6-Dimethyl-4-isopropylbenzyl)-1,3,5-tris(4)-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4 -tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3 ,5-Tri(4-Second-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)- Triketone, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris-2,4, 6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5- Tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1, 3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-tris Methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl -3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri (4-tert-Butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione , 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6 -(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3 ,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)- 1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-di Methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl group-3-hydroxy-2-methylbenzyl)-1,3,5-trione-2,4,6-(1H,3H,5H)-trione, etc., but not limited thereto. Among them, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4 , 6-(1H,3H,5H)-trione, etc.

The compounding quantity of a hindered phenol compound is preferably 0.1-20 mass parts with respect to 100 mass parts of (A) polyimide precursors, More preferably, it is 0.5-10 mass parts from a viewpoint of a sensitivity characteristic. When the compounded amount of the hindered phenol compound is 0.1 parts by mass or more with respect to 100 parts by mass of the (A) polyimide precursor, when forming the photosensitive resin composition of this embodiment on copper or copper alloy, for example , can prevent discoloration and corrosion of copper or copper alloy, and on the other hand, when it is 20 parts by mass or less, the sensitivity is excellent.

Organic titanium compound The negative photosensitive resin composition of this embodiment may contain an organic titanium compound. By containing an organotitanium compound, it becomes possible to form the photosensitive resin layer excellent in chemical resistance even when it hardens|cures at low temperature.

Usable organic titanium compounds include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown in the following I) to VII): I) Titanium chelate compounds: Among them, titanium chelate compounds having two or more alkoxy groups are more preferred in terms of the storage stability and good pattern of the negative photosensitive resin composition. Specific examples are bis(triethanolamine) titanium diisopropoxide, bis(2,4-glutarate) titanium di-n-butoxide, bis(2,4-glutarate) titanium diisopropoxide, bis(tetramethyl pimelic acid) titanium diisopropoxide, bis (ethyl acetyl acetate) titanium diisopropoxide, etc. II) Titanium tetraalkoxide compound: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetrakis(2-ethylhexyloxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium tetramethoxypropoxide, titanium tetramethylphenolate, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearate, tetrakis[bis{2,2-(allyloxymethyl) base) butanol}] titanium, etc. III) Titanocene compounds: such as (pentamethylcyclopentadienyl)titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl ) titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Titanium monoalkoxide compounds: for example, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, and the like. V) Titanium oxy compounds: for example, titanium oxybis(glutarate), titanium oxybis(tetramethylpimelate), titanium oxyphthalocyanine, and the like. VI) Titanium tetraacetylpyruvate compound: for example, titanium tetraacetylpyruvate and the like. VII) Titanate coupling agent: for example, isopropyl tris(dodecylbenzenesulfonyl) titanate and the like.

Among them, from the viewpoint of exerting better chemical resistance, the organotitanium compound is preferably selected from the group consisting of the above-mentioned I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds At least one compound of the group. Especially preferred are bis(ethyl acetylacetate) titanium diisopropoxide, tetra(n-butoxide) titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6- Difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

When compounding an organic titanium compound, the compounding quantity is preferably 0.05-10 mass parts with respect to 100 mass parts of (A) polyimide precursors, More preferably, it is 0.1-2 mass parts. When the compounding amount is 0.05 parts by mass or more, favorable heat resistance and chemical resistance are exhibited, and on the other hand, when it is 10 parts by mass or less, storage stability is excellent.

Adjuvant In order to improve the adhesiveness of the film formed using the negative photosensitive resin composition of this embodiment and a substrate, the negative photosensitive resin composition may optionally contain an adhesive auxiliary agent. Examples of adhesive additives include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidyloxy Propylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyl Trimethoxysilane, Dimethoxymethyl-3-piperidylpropylsilane, Diethoxy-3-glycidyloxypropylmethylsilane, N-(3-diethoxymethyl silylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalimide, benzophenone-3,3'-bis(N-[3 -triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2 ,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureido Silane coupling agents such as propyltriethoxysilane and 3-(trialkoxysilyl)propyl succinic anhydride; and aluminum tris(ethylacetylacetate), aluminum tris(acetylpyruvate), acetoacetate Aluminum-based adhesive additives such as diisopropyl ethyl aluminate, etc.

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

Examples of the silane coupling agent include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, Chisso Co., Ltd.: trade name Sila-Ace S810), 3-mercaptopropyl triethyl Oxysilane (manufactured by Azmax Co., Ltd.: brand name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS1375, product made by Azmax Co., Ltd.: brand name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.0), 3-Mercaptopropyldiethoxymethoxysilane, 3-Mercaptopropylethoxydimethoxysilane, 3-Mercaptopropyltripropoxysilane, 3-Mercaptopropyldiethoxypropoxy 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-Mercaptoethyldiethoxymethoxysilane, 2-Mercaptoethylethoxydimethoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethyltrimethoxysilane Propoxysilane, 2-Mercaptoethylethoxydipropoxysilane, 2-Mercaptoethyldimethoxypropoxysilane, 2-Mercaptoethylmethoxydipropoxysilane, 4-Mercapto Butyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea (Shin-Etsu Chemical Co., Ltd. Manufactured by the company: trade name LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl) Urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropyl Oxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxy Dimethoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethyl Oxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea , N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3- (m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0) , p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), 2-(trimethyl Oxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl) Pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-tert-butyl carbamate, (3-glycidyloxypropyl) tri Ethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-tertiary butoxysilane tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane) ), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethane, Ethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide ether, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-tert-butoxydiethoxysilane, diisobutoxyaluminumoxytriethoxysilane, phenyl Silanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutyl Phenylsilanediol, tertiary butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane , ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylsilanol Phenyl silanol, ethyl n-propyl phenyl silanol, ethyl isopropyl phenyl silanol, n-butyl ethyl phenyl silanol, isobutyl ethyl phenyl silanol, tertiary butyl ethyl silanol phenyl silanol, methyl diphenyl silanol, ethyl diphenyl silanol, n-propyl diphenyl silanol, isopropyl diphenyl silanol, n-butyl diphenyl silanol, iso Butyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, etc., but not limited thereto. These may be used individually or in combination of plural types.

As the silane coupling agent, from the viewpoint of storage stability, among the above-mentioned silane coupling agents, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, and diphenylsilane are preferred. Diol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydiphenylmethylsilane, triphenylsilanol, and a silane coupling agent having a structure represented by the following formula. [chem 27]

As a compounding quantity at the time of using a silane coupling agent, Preferably it is 0.01-20 mass parts with respect to 100 mass parts of (A) polyimide precursors.

Sensitizer In order to increase the sensitivity, the negative photosensitive resin composition of this embodiment may optionally contain a sensitizer. Examples of the sensitizer include Michelerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopenta Alkane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4 ,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamoindanone, p-dimethylaminoidene Benzylindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylamine phenylvinylene) isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3 ,3'-Carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin Soybean, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-𠰌linylbenzophenone, dimethylamino Isoamyl benzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminobenzene Vinyl)benzoxazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2- (p-Dimethylaminobenzyl)styrene, etc. These can be used individually or in combination of 2-5 types, for example.

When the photosensitive resin composition contains a sensitizer for increasing the sensitivity, the compounding quantity is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the (A) polyimide precursor.

Photopolymerizable unsaturated monomer In order to improve the resolution of the relief pattern, the negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following, and examples include: diethylene glycol dimethacrylate, Mono- or di-acrylates and methacrylates of ethylene glycol or polyethylene glycol such as tetraethylene glycol dimethacrylate; mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol; mono-, Di- or triacrylates and methacrylates; cyclohexane diacrylate and cyclohexane dimethacrylate; diacrylate and dimethacrylate of 1,4-butanediol; 1,6-hexane Diacrylates and dimethacrylates of diols; diacrylates and dimethacrylates of neopentyl glycol; mono- or diacrylates and methacrylates of bisphenol A; benzenetrimethacrylates; Isomethacrylate and isomethacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; Di- or tri-acrylate and methacrylate of glycerol; di-, tri-, or tetra-acrylate and methacrylate of pentaerythritol; and compounds such as ethylene oxide or propylene oxide adducts of these compounds.

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

thermal polymerization inhibitor In addition, in order to improve the stability of the viscosity and sensitivity of the negative photosensitive resin composition when it is stored in the state of a solution containing a solvent, the negative photosensitive resin composition of this embodiment may optionally contain a thermal polymerization inhibitor. agent. As thermal polymerization inhibitors, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenanthylamine, 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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc.

<Manufacturing method of hardened relief pattern and semiconductor device> The manufacturing method of the cured embossed pattern of the present embodiment includes the following steps: (1) coating the negative photosensitive resin composition of the above-mentioned present embodiment on a substrate to form a resin layer on the above-mentioned substrate; exposing the resin layer; (3) developing the exposed resin layer to form a relief pattern; (4) performing heat treatment on the relief pattern to form a hardened relief pattern.

(1) Resin layer forming step In this step, the negative photosensitive resin composition of this embodiment is applied on the base material, and if necessary, it is dried thereafter to form a resin layer. As the coating method, a coating method previously used for photosensitive resin compositions can be used, for example, a spin coater, a bar coater, a knife coater, a curtain coater, a screen coater, etc. A method of coating with a printing machine, etc., a method of spray coating with a sprayer, etc.

The coating film containing the photosensitive resin composition may be dried as needed. As a drying method, methods such as air drying, heat drying with an oven or a hot plate, and vacuum drying can be used. Specifically, when air-drying or heat-drying is performed, it can be dried at 20° C. to 150° C. for 1 minute to 1 hour. As above, a photosensitive resin layer can be formed on the substrate.

(2) Exposure steps In this step, use exposure devices such as contact aligners, mirror projection exposure machines, steppers, etc., to separate the patterned photomask or reticle, or directly by ultraviolet light sources, etc., to the resin formed above. layer for exposure.

Thereafter, post-exposure baking (PEB) and/or pre-development baking may be performed at any combination of temperature and time as required for the purpose of increasing photosensitivity. The range of baking conditions is preferably a temperature of 40° C. to 120° C. and a time of 10 seconds to 240 seconds. However, it is not limited to this range as long as the properties of the photosensitive resin composition of this embodiment are not hindered.

(3) Embossed 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 photosensitive resin layer after exposure (irradiation), any method can be selected from conventionally known photoresist developing methods, such as rotary spray method, dipping method, dipping method with ultrasonic treatment, etc. The method used. Moreover, after image development, for the purpose of adjusting the shape of an embossed pattern, etc., post-image development baking may be implemented in arbitrary combinations of temperature and time as needed.

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

(4) Hardened relief pattern forming step In this step, heat treatment is performed on the relief pattern obtained by the above-mentioned development to volatilize the photosensitive component, and to imide the (A) polyimide precursor, thereby converting it into a polyimide-containing Hardened embossed pattern. As the method of heat treatment, for example, various methods such as those using a hot plate, those using an oven, and those using a temperature-increasing oven that can be programmed for temperature control can be selected. The heat treatment can be performed, for example, at 160° C. to 350° C. for 30 minutes to 5 hours. The temperature of the heat treatment is preferably below 200°C, more preferably below 180°C. As the atmosphere gas at the time of heating and hardening, air may be used, and inert gases such as nitrogen gas and argon gas may also be used.

{通式(8)中，X¹ 及Y¹ 與通式(3)中之X¹ 及Y¹ 相同。出於相同之理由，通式(3)中之較佳之X¹ 、Y¹ 於通式(8)之聚醯亞胺中亦較佳。重複單元數m並無特別限定，可為2～150之整數}。<Polyimide> The polyimide of this embodiment can be manufactured by hardening the negative photosensitive resin composition. 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). [chem 28]

{In general formula (8), ^X1 and ^Y1 are the same as ^X1 and ^Y1 in general formula (3). For the same reason, the preferred X ¹ and Y ¹ in the general formula (3) are also preferred in the polyimide of the general formula (8). The number m of repeating units is not particularly limited, and may be an integer of 2 to 150}.

＜Semiconductor Devices＞ In this embodiment, there is also provided a semiconductor device having a hardened relief pattern obtained by the above-mentioned method of manufacturing a hardened relief pattern. Therefore, it is possible to provide a semiconductor device having: a base material as a semiconductor element; and a hardened relief pattern of polyimide formed on the base material by the above-mentioned hardened relief pattern manufacturing method. Also, it can be applied to a method of manufacturing a semiconductor device that uses a semiconductor element as a base material and includes the method of manufacturing a hardened relief pattern of the present embodiment described above as part of the steps. A semiconductor device can be formed as a surface protection film, an interlayer insulating film, an insulating film for rewiring, a protective film for flip chip devices, or a semiconductor device by forming the hardened relief pattern formed by the method for manufacturing a hardened relief pattern according to this embodiment. The protective film and the like of semiconductor devices with a bump structure are manufactured in combination with known semiconductor device manufacturing methods.

＜Display device＞ In this embodiment, there is provided a display device including 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 hardened relief pattern may be laminated directly in contact with the display element, or may be laminated with other layers interposed therebetween. For example, as the cured film, TFT (Thin-Film Transistor, thin film transistor) liquid crystal display element and color filter element surface protection film, insulating film, and planarization film, MVA (Multi-Domain Vertical Alignment, Projections for multi-domain vertical alignment) type liquid crystal display devices, and partition walls for cathodes of organic EL (Electroluminescence, electroluminescence) elements.

The negative photosensitive resin composition of this embodiment is preferably a negative photosensitive resin composition for forming an insulating member or for forming an interlayer insulating film. The negative photosensitive resin composition of this embodiment can be used not only in the above-mentioned semiconductor devices, but also in interlayer insulating films of multilayer circuits, surface coatings of flexible copper foil boards, solder resist films, and liquid crystal alignment films, etc. use. [Example]

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

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

(2) The production of hardened embossed patterns on Cu uses a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Company), on a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625 ± 25 μm), 200 nm thick Ti and 400 nm thick Cu were sequentially sputtered. Then, using a coating developer (D-Spin60A type, manufactured by SOKUDO Corporation), the photosensitive resin composition prepared by the method described later is spin-coated on the wafer, and prebaked with a heating plate at 110° C. for 180 Seconds, a coating film about 15 μm thick is formed. Using a photomask with a test pattern, the coating film was irradiated with energy of 1000 mJ/cm ² by Prisma GHI (manufactured by Ultratech). Next, use cyclopentanone as the developing solution, and use a coating developer (D-Spin60A type, manufactured by SOKUDO Company) to spray and develop the coating film by multiplying the time when the unexposed part completely dissolves and disappears by 1.4, and use propylene glycol methyl Ether acetate was subjected to a 10 second spin spray wash, whereby a relief pattern on Cu was obtained. Using a temperature-programmed curing furnace (VF-2000, manufactured by Koyo Lindberg), under a nitrogen atmosphere and at the temperature listed in Table 1, the wafer with the embossed pattern formed on Cu was heated for 2 hours. Processing whereby a hardened relief pattern comprising a resin about 8-10 [mu]m thick on Cu is obtained.

(3) Determination of imidization rate ATR-FTIR (Attenuated Total Reflectance-Fourier Transform Infrared Spectrometry, Attenuated Total Reflectance-Fourier Transform Infrared Spectrometry) measuring device (Nicolet Continuum, manufactured by Thermo Fisher Scientific Co., Ltd.) The above-mentioned hardened embossed pattern resin portion was measured, and the value obtained by dividing the peak intensity at 1380 cm ^-1 by the peak intensity at 1500 cm ^-1 was used as the imidization index, and the ratio of the film of each example and comparative example was calculated. The value obtained by dividing the imidization index by the imidization index of a film obtained by curing the corresponding resin composition at 350° C. was used as the imidization rate. The imidization rate was evaluated based on the following criteria. "Excellent": The imidization rate is above 80% "Good": The imidization rate is above 60% - less than 80% "Acceptable": The imidization rate is above 40% - less than 60% " Not allowed": The imidization rate is less than 40%

(4) Gas release evaluation In the same manner as the hardened embossed pattern above, apply the photosensitive resin composition prepared by the method described later on a 6-inch silicon wafer pre-sputtered with Al, and after pre-baking, use a heating program type curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co.), under a nitrogen atmosphere and at the temperature listed in Table 1, heat treatment was carried out for 2 hours, thereby obtaining a resin containing about 10 μm thick on Al. Hardened embossed pattern. Use a wafer dicing machine (manufactured by Disco, model name DAD-2H/6T) to cut the resin film into a width of 3.0 mm, dip it in 10% hydrochloric acid aqueous solution and peel it off from the silicon wafer to make a short film sample. After leaving the film sample at 23°C and 55%RH (Relative Humidity, relative humidity) for more than 24 hours, use a thermogravimetric measuring device (manufactured by Shimadzu Corporation, TGA-50) to measure the temperature at 10°C/min from room temperature. When the temperature was raised, the weight of the film at 150° C. was regarded as 100%, and the temperature at which the weight decreased by 5% (5% weight loss temperature) was measured. The outgassing properties were evaluated based on the following criteria. "Excellent": 5% weight reduction temperature is above 300°C "Good": 5% weight loss temperature is above 280°C and below 300°C "Yes": 5% weight reduction temperature is above 260°C and below 280°C "No": 5% weight reduction temperature does not reach 260°C

(5) Evaluation of copper adhesion In the same manner as the above hardened embossed pattern, the photosensitive resin composition prepared by the method described later was coated on a 6-inch silicon wafer sputtered with Ti and Cu in advance, and after pre-baking, Using a temperature-programmed curing furnace (VF-2000, manufactured by Koyo Lindberg), under a nitrogen atmosphere and at the temperature listed in Table 1, heat treatment was carried out for 2 hours, thereby obtaining a layer containing about 10 μm thick on Cu. Resin hardened embossed pattern. According to the cross-cut method of JIS K 5600-5-6 standard, the adhesive properties of the heat-treated film between the copper substrate and the cured resin coating film were evaluated based on the following criteria. "Excellent": The number of grids of the cured resin coating film on the substrate is 100 "Good": The number of grids of the cured resin coating film on the substrate is 70 to 99 "Yes": The number of grids of the cured resin coating film on the substrate is 40 to 69 "Not allowed": The number of grids of the cured resin coating film on the substrate is less than 40

(6) Chemical resistance evaluation Dip the embossed pattern produced by the method (2) above into a resist release film {manufactured by ATMI, product name ST-44, the main components are 2-(2-aminoethoxy)ethanol, 1-cyclo Hexyl-2-pyrrolidone} was heated to 50°C for 5 minutes, washed with running water for 30 minutes, and air-dried. Thereafter, the surface of the film was visually observed with an optical microscope, and the chemical resistance was evaluated by the presence or absence of damage caused by the chemical solution such as cracks, and the change rate of the film thickness after the chemical solution treatment. Chemical resistance was evaluated based on the following criteria. "Excellent": no cracks, etc., and the film thickness change rate is less than 5% based on the film thickness before dipping in the chemical solution "Good": no cracks, etc., and the film thickness change rate is more than 5% and less than 10% based on the film thickness before dipping in the chemical solution "Acceptable": no cracks, etc., and the film thickness change rate is more than 10% and less than 15% based on the film thickness before dipping in the chemical solution "Not allowed": Cracks, etc., or film thickness change rate is more than 15% based on the film thickness before dipping in the chemical solution

Production Example 1: (A) Synthesis of Polyimide Precursor A-1 Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a 2 L separable flask, put 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and γ-butyl 400 mL of the ester was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction ended, the reaction mixture was allowed to cool to room temperature for 16 hours.

Next, under cooling in an ice bath, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, and then stirred. What suspends 93.0 g of 4,4'- diamino diphenyl ether (ODA) in 350 mL of γ-butyrolactone was added over 60 minutes. Furthermore, after stirring at room temperature for 2 hours, 30 mL of ethanol was added and stirred for 1 hour, and then, 400 mL of γ-butyrolactone was added. The precipitate generated from the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing a crude polymer. The resulting crude polymer was separated by filtration, and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, the obtained precipitate was separated by filtration, and vacuum-dried to obtain a powdery polymer (polyimide precursor A-1) . The molecular weight of the polyimide precursor A-1 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000. Polyimide precursor A-1 is non-alkali soluble.

Manufacturing example 2: (A) Synthesis of polyimide precursor A-2 In addition to using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1 , was reacted in the same manner as the method described in Production Example 1 above to obtain a polymer (polyimide precursor A-2). The molecular weight of the polyimide precursor A-2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000. Polyimide precursor A-2 is non-alkali soluble.

Production Example 3: (A) Synthesis of Polyimide Precursor A-3 Except that 50.2 g of p-phenylenediamine was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (ODA) in Production Example 1, the reaction was carried out in the same manner as described in Production Example 1 above to obtain Polymer (polyimide precursor A-3). The molecular weight of the polyimide precursor A-3 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 19,000. Polyimide precursor A-3 is non-alkali-soluble.

Production Example 4: (D) Synthesis of Thermal Alkali Generator D-1 100 g of diethylene glycol bis(3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol were added to a 1 L eggplant-shaped flask, and mixed with a stirrer to form a homogeneous solution. Cool to below 5°C with ice water. 215 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 120 g of ethanol was added dropwise thereto through a dropping funnel. At this time, the dropwise addition was performed while adjusting the dropping rate so that the temperature of the reaction liquid was kept at 50° C. or lower. After 2 hours from the end of the dropwise addition, the reaction liquid was concentrated under reduced pressure at 50° C. for 3 hours, whereby the target compound D-1 was obtained.

<Example 1> A negative photosensitive resin composition was prepared by the following method using polyimide precursor A-1, and the prepared composition was evaluated. A-1 as (A) polyimide precursor: 100 g, B-1 as (B) imide compound: 5 g, and 1-phenyl as (C) photopolymerization initiator -1,2-propanedione-2-(o-ethoxycarbonyl)-oxime (hereinafter referred to as PDO, equivalent to photosensitizer C-1): 3 g dissolved in γ-butyrolactone (hereinafter referred to as GBL) : 100 g. The viscosity of the solution was adjusted to about 40 poises by further adding a small amount of GBL to prepare a negative photosensitive resin composition. The composition was evaluated as described above. The results are shown in Table 1.

<Examples 2 to 17, Comparative Examples 1 to 3> Except having prepared with the compounding ratio shown in Table 1, the negative photosensitive resin composition similar to Example 1 was prepared, and the evaluation similar to Example 1 was performed. The results are shown in Tables 1 and 2. (B) Amide compounds B-1 to B-7, (C) Photopolymerization initiator C-1, and (D) Thermal base generators D-1 and D-2 described in Tables 1 and 2 respectively as described below.

B-1: N-hydroxyphthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) B-2: N-hydroxysuccinimide (manufactured by Tokyo Chemical Industry Co., Ltd.) B-3: N-Hydroxy-1,8-naphthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) B-4: N,N'-dihydroxypyromellitic acid imide (manufactured by Tokyo Chemical Industry Co., Ltd.) B-5: N-hydroxy-4-nitrophthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) B-6: N-Aminophthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) B-7: Phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) C-1: 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime D-1: The compound described in Production Example 4 D-2: 1-(tert-butoxycarbonyl)-4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 (A) Polyimide precursor Alpha-1 100 100 100 100 100 100 100 50 Alpha-2 100 50 Alpha-3 100 (B) Amide compound B-1 5 5 5 5 B-2 5 B-3 5 B-4 5 B-5 5 B-6 5 B-7 5 (C) Photopolymerization initiator C-1 3 3 3 3 3 3 3 3 3 3 (D) Thermal base generator D-1 D-2 Curing temperature (°C) 170 170 170 170 170 170 170 170 170 170 Imidization rate good good good good good good Can Can Can good Outgassing Evaluation excellent good good good good Can Can good good excellent Copper adhesion evaluation good Can good good good good Can good good excellent Chemical Resistance Evaluation excellent good excellent excellent excellent Can Can good good excellent (unit: g)

[Table 2] Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Comparative example 1 Comparative example 2 Comparative example 3 (A) Polyimide precursor A-1 100 100 100 100 100 100 100 100 100 100 A-2 A-3 (B) Amide compound B-1 5 5 1 15 5 5 5 B-2 B-3 B-4 B-5 B-6 B-7 (C) Photopolymerization initiator C-1 3 3 3 3 1 10 3 3 3 3 (D) Thermal base generator D-1 20 20 D-2 1 Curing temperature (°C) 170 170 170 170 170 170 200 170 200 170 Imidization rate excellent excellent good good good good excellent can't Can good Outgassing Evaluation excellent good good good excellent good excellent can't good good Copper adhesion evaluation good good good good good good excellent can't can't can't Chemical Resistance Evaluation excellent excellent good excellent excellent excellent excellent can't good can't (unit: g)

It can be clearly seen from Tables 1 and 2 that the negative photosensitive resin composition of Example 1 was "good" in the evaluation of imidization rate, "excellent" in the evaluation of outgassing property, and "excellent" in the evaluation of copper adhesion. "Good" in the middle, and "Excellent" in the evaluation of chemical resistance. Similarly, the negative photosensitive resin compositions of Examples 2 to 17 were all "acceptable" or higher in the imidization rate, outgassing evaluation, copper adhesion evaluation, and chemical resistance evaluation. In particular, Example 1 using A-1 as the precursor of (A) polyimide exhibited excellent chemical resistance. Also, when 5 parts by mass of B-1 was added as the (B) imide compound based on 100 parts by mass of the polymer, particularly excellent chemical resistance and outgassing reduction effects were obtained. In addition, when (D) thermal base generators D-1 and D-2 were added, a particularly excellent imidization rate was exhibited. On the other hand, Comparative Example 1 in which (B) imide compound was not added was "impossible" in all evaluations, and even Comparative Example 2 in which the curing temperature was raised from 170°C to 200°C failed in the evaluation of copper adhesion. as "not allowed". In addition, in Comparative Example 3, in which only (D) thermal base generator D-1 was added without adding (B) imide compound, although the imidization rate was "good", it was not good in the evaluation of copper adhesion and chemical resistance. The evaluation is "impossible". [Industrial availability]

By using the photosensitive resin composition of the present invention, it is possible to obtain a hardened embossed product with high imidization rate and chemical resistance, high copper adhesion, and less outgassing in the heating step after thermal hardening. Convex pattern. The present invention can be preferably utilized in the field of photosensitive materials used in the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (20)

A negative photosensitive resin composition comprising: (A) a polyimide precursor; (B) an imide compound represented by the following general formula (1)

{In the formula (1), A ₁ is a hydrogen atom, and A ₂ is a divalent organic group with 1 to 20 carbon atoms}; and (C) a photopolymerization initiator, represented by the above general formula (1) (B) _A of the imide compound has a ring structure directly bonded to the C atom of the NCO structure in the above general formula (1), {wherein, the imide compound is excluded from the maleimide represented by the following formula

(In the formula, _R3 is a single bond, a hydrogen atom or an organic group with a valence of 1 to 3, _R4 and _R5 are independently a hydrogen atom, an alkyl group with 1 to 10 carbons, and a cycloalkane with 3 to 10 carbons group, aryl group, alkoxy group or halogen atom, and m is an integer of 1 or more)}. The negative photosensitive resin composition according to Claim 1, wherein A ₂ of the (B) imide compound represented by the above general formula (1) has an aromatic ring. Such as the negative photosensitive resin composition of claim 2, wherein the above-mentioned (B) imide compound is represented by the following general formula (2)

{In the formula (2), A ₁ is a hydrogen atom, A ₃ is a group selected from the group consisting of nitro, hydroxyl, and monovalent organic groups, b is an integer from 0 to 4, and in the case where b is 2 or more When, a plurality of A ₃ can also jointly form a ring structure}. The negative photosensitive resin composition according to any one of Claims 1 to 3, wherein the (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (3)

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are independently a hydrogen atom or a monovalent organic group, R ₁ and at least one _of R is a monovalent organic group represented by the following general formula (4):

(wherein, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or a monovalent organic group with 1 to 3 carbons, and m ₁ is an integer of 2 to 10)}. Such as the negative photosensitive resin composition of claim 4, wherein the above-mentioned _X1 comprises a tetravalent organic group represented by the following general formula

{wherein, R6 is a monovalent group selected from the group consisting of fluorine atoms, C ₁ ~C ₁₀ hydrocarbon groups, and C ₁ ~C ₁₀ fluorine-containing hydrocarbon groups, m is an integer selected from 0~3}. Such as the negative photosensitive resin composition of claim 4, wherein the above-mentioned _X1 comprises a tetravalent organic group represented by the following general formula

{wherein, R6 is a monovalent group selected from the group consisting of fluorine atoms, C ₁ ~C ₁₀ hydrocarbon groups, and C ₁ ~C ₁₀ fluorine-containing hydrocarbon groups, m is an integer selected from 0~3}. Such as the negative photosensitive resin composition of claim 4, wherein said Y ₁ comprises a divalent organic group represented by the following general formula

{In the formula, R6 is a monovalent group selected from the group consisting of fluorine atoms, C ₁ ~C ₁₀ hydrocarbon groups, and C ₁ ~C ₁₀ fluorine-containing hydrocarbon groups, and n is an integer selected from 0~4} . Such as the negative photosensitive resin composition of claim 4, wherein said Y ₁ comprises a divalent organic group represented by the following general formula

{In the formula, R6 is a monovalent group selected from the group consisting of fluorine atoms, C ₁ ~C ₁₀ hydrocarbon groups, and C ₁ ~C ₁₀ fluorine-containing hydrocarbon groups, and n is an integer selected from 0~4} . The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the above-mentioned (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (5)

{wherein, R ₁ , R ₂ , and n ₁ are defined above}. The negative photosensitive resin composition according to any one of Claims 1 to 3, wherein the above-mentioned (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (6) [chemical 10]

{wherein, R ₁ , R ₂ , and n ₁ are defined above}. The negative photosensitive resin composition according to any one of Claims 1 to 3, wherein the above-mentioned (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (7)

{wherein, R ₁ , R ₂ , and n ₁ are defined above}. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the above-mentioned (A) polyimide precursor comprises: with the following general formula (5):

{wherein, R ₁ , R ₂ , and n ₁ are as defined above} a structural unit represented by the following general formula (6): [Chem. 13]

{wherein, R ₁ , R ₂ , and n ₁ are as defined above; wherein, R ₁ , R ₂ , and n ₁ in formula (5) and R ₁ , R ₂ , and n _{and 1} independently select the structural unit represented by }. The negative photosensitive resin composition according to any one of claims 1 to 3, which comprises: 100 parts by mass of the above-mentioned (A) polyimide precursor; Parts are based on 0.1 to 30 parts by mass of the above-mentioned (B) imide compound; starter. The negative-type photosensitive resin composition according to any one of claims 1 to 3, which further comprises 0.1 to 30 parts by mass of (D) thermal alkali generator based on 100 parts by mass of (A) polyimide precursor agent. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an insulating member. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the negative photosensitive resin composition is a negative photosensitive resin composition for forming an interlayer insulating film. A method of manufacturing a hardened embossed pattern, comprising the following steps: (1) Coating the negative photosensitive resin composition according to any one of Claims 1 to 16 on the substrate, forming a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the above-mentioned photosensitive resin layer after exposure to form a relief pattern; and (4) performing heat treatment on the above-mentioned relief pattern to form a hardened relief pattern. The method of manufacturing a hardened relief pattern according to claim 17, wherein the above-mentioned heat treatment is a heat treatment at a temperature below 200°C. The method of manufacturing a hardened relief pattern according to claim 18, wherein the above-mentioned heat treatment is a heat treatment at a temperature below 180°C. A method for producing polyimide, comprising curing the negative photosensitive resin composition according to any one of claims 1 to 16.