TW202000739A - Photosensitive resin composition, method for manufacturing curable relief pattern, and semiconductor device - Google Patents

Abstract

Provided are: a photosensitive resin composition with which good resolution is exhibited even when displacement occurs in the focus depth, good resolution is exhibited regardless of the base material, and good chemical resistance is achieved; a method for forming a curable relief pattern using the photosensitive resin composition; and a semiconductor device having the curable relief pattern. The photosensitive resin composition is characterized by containing the following components: (A) a polyimide precursor in which the i-ray absorbance of a 0.1 wt% N-methylpyrrolidone solution is 0.1-0.6; and (B) a photopolymerization initiator having a carbazole structure.

Description

Photosensitive resin composition, method for manufacturing hardened relief pattern, and semiconductor device

The present invention relates to, for example, an insulating material for electronic parts and a photosensitive resin composition used for forming a relief pattern such as a passivation film, a buffer coating film, an interlayer insulating film in a semiconductor device, and a cured relief pattern using the same Manufacturing method and semiconductor device.

Previously, polyimide resins with excellent heat resistance, electrical properties, and mechanical properties have been used in insulating materials for electronic parts, passivation films, surface protection films, interlayer insulating films, etc. of semiconductor devices. Among the polyimide resins, the provider in the form of a photosensitive polyimide precursor composition can easily use the thermal imidization treatment of coating, exposure, development and curing of the composition, using the composition A heat-resistant embossed pattern film is formed. Compared with the previous non-photosensitive polyimide material, this photosensitive polyimide precursor composition has the feature that it can greatly shorten the steps.

In addition, the semiconductor device (hereinafter, also referred to as "element") is mounted on the printed circuit board by various methods depending on the purpose. The previous device is usually manufactured by a wire bonding method that uses thinner metal wires to connect from the external terminals (pads) of the device to the lead frame. However, due to the high-speed development of components and the operating frequency reaching GHz, the difference in the wiring length of each terminal in the installation affects the operation of the component. Therefore, in the installation of high-end components, there is a need to correctly control the length of the installation wiring, and it is difficult to meet this requirement by wire bonding.

Therefore, the industry proposes flip chip mounting as follows: a redistribution layer is formed on the surface of a semiconductor wafer, and bumps (electrodes) are formed thereon, then the wafer is flipped over (flip) and directly mounted on a printed board. In this flip chip installation, since the wiring distance can be accurately controlled, the demand for high-end components for processing high-speed signals, or for mobile phones due to the small installation size, is rapidly expanding. Furthermore, recently, the industry has proposed to cut the pre-completed wafer to manufacture a single wafer, reconstruct the single wafer on the support and seal it with mold resin, after peeling the support to form a redistribution layer is called Fan-out wafer level packaging (FOWLP) semiconductor chip mounting technology (for example, Patent Document 2). In fan-out wafer-level packaging, there is an advantage that the package can be made highly thin, and high-speed transmission or low cost can be performed. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-167191

[Problems to be solved by the invention]

However, in recent years, due to the diversification of packaging and mounting technologies, the diversification of support types, and the multi-layering of rewiring layers, the following problems arise when the photosensitive resin composition is exposed: the focus depth shifts and the resolution is large Deterioration, or the resolution obtained by the base material is obviously different. Therefore, there is a problem that a signal delay occurs due to a disconnection in the redistribution layer due to deterioration of the resolution, or a decrease in productivity. In addition, when the rewiring layer is laminated, when the desired resolution cannot be obtained, the layer is peeled off with a chemical solution and the layer is laminated again. However, due to the chemical solution, the film in the lower layer is damaged and the film thickness is increased. Reduce the problem.

The object of the present invention is to provide a photosensitive resin that exhibits good resolution even when the focus depth is shifted, does not depend on the base substrate and exhibits good resolution, and exhibits good chemical resistance A composition; a method of forming a hardened relief pattern using the photosensitive resin composition and a semiconductor device having the hardened relief pattern. [Technical means to solve the problem]

(式中，Ra表示碳數1～10之一價有機基，Rb表示碳數1～20之有機基，Rc表示碳數1～10之有機基，Rd表示碳數1～10之有機基)。 [4] 如[3]中所記載之感光性樹脂組合物，其中上述(B)光聚合起始劑含有通式(B)中之Rc為碳數3～10之飽和脂環結構。 [5] 如[1]至[4]中任一項所記載之感光性樹脂組合物，其中上述(A)成分係包含下述通式(A1)所表示之結構之聚醯亞胺前驅物： [化2]

{式中，X為四價有機基，Y為二價有機基，R₁ 及R₂ 分別獨立地為氫原子、下述通式(R1)： [化3]

(通式(R1)中，R₃ 、R₄ 及R₅ 分別獨立地為氫原子或碳數1～3之有機基，p為選自2～10中之整數)所表示之一價有機基、或碳數1～4之飽和脂肪族基；其中，R₁ 及R₂ 之兩者不會同時為氫原子}。 [6] 如[5]中所記載之感光性樹脂組合物，其中上述X包含下述結構： [化4]

。 [7] 如[5]中所記載之感光性樹脂組合物，其中上述X包含下述結構： [化5]

。 [8] 如[5]至[7]中任一項所記載之感光性樹脂組合物，其中上述Y包含下述結構： [化6]

。 [9] 如[5]至[7]中任一項所記載之感光性樹脂組合物，其中上述Y包含下述結構： [化7]

。 [10] 如[5]中所記載之感光性樹脂組合物，其中上述X包含下述結構： [化8]

， 上述Y包含下述結構： [化9]

。 [11] 如[1]至[10]中任一項所記載之感光性樹脂組合物，其進而含有(C)聚合抑制劑。 [12] 如[11]中所記載之感光性樹脂組合物，其中上述(C)聚合抑制劑係選自含有芳香族性羥基之化合物、亞硝基化合物、N-氧化物化合物、醌化合物、N-氧基化合物、及酚噻𠯤化合物中之至少1種。 [13] 如[11]或[12]中所記載之感光性樹脂組合物，其中上述(C)聚合抑制劑係含有芳香族性羥基之化合物。 [14] 如[1]至[13]中任一項所記載之感光性樹脂組合物，其進而包含(D)含有2個以上醇性羥基之化合物。 [15] 如[14]中所記載之感光性樹脂組合物，其中上述(D)含有2個以上醇性羥基之化合物係選自由醛糖、酮糖、吡喃糖、呋喃糖、及醛糖醇所組成之群中之至少1種。 [16] 如[11]至[15]中任一項所記載之感光性樹脂組合物，其中(B)成分及(C)成分之合計含量相對於上述(A)成分100質量份為0.1～20質量份。 [17] 如[1]至[16]中任一項所記載之感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物之上述0.1 wt%溶液之i線吸光度為0.18～0.5。 [18] 如[1]至[17]中任一項所記載之感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物之上述0.1 wt%溶液之i線吸光度為0.18～0.4。 [19] 如[1]至[18]中任一項所記載之感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物之上述0.1 wt%溶液之i線吸光度為0.18～0.3。 [20] 如[1]至[19]中任一項所記載之感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物之上述0.1 wt%溶液之i線吸光度為0.18～0.2。 [21] 如[1]至[20]中任一項所記載之感光性樹脂組合物，其中於將上述(A)聚醯亞胺前驅物之上述0.1 wt%上述溶液之i線吸光度設為DA， 將上述(B)光聚合起始劑之0.001 wt% N-甲基吡咯啶酮溶液之i線吸光度設為DB時， 上述DA與DB之和(DA＋DB)為0.25～0.90。 [22] 一種聚醯亞胺之製造方法，其包括使如[1]至[21]中任一項所記載之感光性樹脂組合物硬化。 [23] 一種硬化浮凸圖案之製造方法，其特徵在於包括以下之步驟： (1)塗佈步驟，其將如[1]至[21]中任一項所記載之感光性樹脂組合物塗佈於基板上，而於該基板上形成感光性樹脂層； (2)曝光步驟，其對該感光性樹脂層曝光； (3)顯影步驟，其將該曝光後之感光性樹脂層顯影而形成浮凸圖案；及 (4)加熱步驟，其藉由對該浮凸圖案進行加熱處理而形成硬化浮凸圖案。 [24] 一種半導體裝置，其特徵在於：其係具有藉由如[23]中所記載之製造方法所獲得之硬化浮凸圖案而成。 [25] 一種感光性樹脂組合物，其特徵在於含有以下之成分： (A)聚醯亞胺前驅物，其係由下述通式(A1)表示： [化10]

{式中，X為四價有機基，Y為二價有機基，R₁ 及R₂ 分別獨立地為氫原子、下述通式(R1)： [化11]

(通式(R1)中，R₃ 、R₄ 及R₅ 分別獨立地為氫原子或碳數1～3之有機基，p為選自2～10中之整數)所表示之一價有機基、或碳數1～4之飽和脂肪族基。其中，R₁ 及R₂ 之兩者不會同時為氫原子}； (B)光聚合起始劑，其係由下述通式(B)表示： [化12]

{(式中，Ra表示碳數1～10之一價有機基，Rb表示碳數1～20之有機基，Rc表示碳數1～10之有機基，Rd表示碳數1～10之有機基)} 或(B1)表示： [化13]

{式中，Re表示碳數1～20之一價有機基，Rf表示碳數1～10之有機基}； (D)含有2個以上醇性羥基之化合物；及 (E)選自由γ-丁內酯、二甲基亞碸、四氫呋喃甲醇、乙醯乙酸乙酯、琥珀酸二甲酯、丙二酸二甲酯、N,N-二甲基乙醯乙醯胺、ε-己內酯、及1,3-二甲基-2-咪唑啶酮、3-甲氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺所組成之群中之至少1種溶劑。 [26] 如[25]中所記載之感光性樹脂組合物，其包含(E)選自上述群中之至少2種溶劑。 [27] 如[25]或[26]中所記載之感光性樹脂組合物，其中上述Y包含下述結構： [化14]

或下述結構： [化15]

{式中，A表示碳數1～6之可包含鹵素原子之有機基}。 [28] 一種聚醯亞胺之製造方法，其包括使如[25]至[27]中任一項所記載之感光性樹脂組合物硬化。 [29] 一種硬化浮凸圖案之製造方法，其特徵在於包括以下之步驟： (1)塗佈步驟，其將如[25]至[27]中任一項所記載之感光性樹脂組合物塗佈於基板上，而於該基板上形成感光性樹脂層； (2)曝光步驟，其對該感光性樹脂層曝光； (3)顯影步驟，其將該曝光後之感光性樹脂層顯影而形成浮凸圖案；及 (4)加熱步驟，其藉由對該浮凸圖案進行加熱處理而形成硬化浮凸圖案。 [30] 一種半導體裝置，其特徵在於：其係具有藉由如[29]中所記載之製造方法所獲得之硬化浮凸圖案而成。 [發明之效果]The inventors of the present invention have found that by combining a specific polyimide precursor and a specific initiator, the above object is achieved, and the present invention is completed. That is, the present invention is as follows. [1] A photosensitive resin composition characterized by containing the following components: (A) A polyimide precursor with an i-line absorbance of 0.1 to 0.6% N-methylpyrrolidone solution of 0.1 to 0.6; and ( B) A photopolymerization initiator with a carbazole structure. [2] The photosensitive resin composition as described in [1], wherein the i-line absorbance of the 0.1 wt% solution of the (A) polyimide precursor is 0.18 to 0.6. [3] The photosensitive resin composition as described in [1] or [2], wherein the (B) photopolymerization initiator has a structure represented by the following general formula (B):

(In the formula, Ra represents a C 1-10 monovalent organic group, Rb represents a C 1-20 organic group, Rc represents a C 1-10 organic group, Rd represents a C 1-10 organic group) . [4] The photosensitive resin composition as described in [3], wherein the (B) photopolymerization initiator contains a saturated alicyclic structure in which Rc in the general formula (B) is 3 to 10 carbon atoms. [5] The photosensitive resin composition as described in any one of [1] to [4], wherein the component (A) is a polyimide precursor containing a structure represented by the following general formula (A1) : [Chem 2]

{In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are each independently a hydrogen atom, and the following general formula (R1): [Chem 3]

(In the general formula (R1), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10) , Or a saturated aliphatic group having 1 to 4 carbon atoms; wherein, both of R ₁ and R ₂ will not be hydrogen atoms at the same time}. [6] The photosensitive resin composition as described in [5], wherein the above X includes the following structure:

. [7] The photosensitive resin composition as described in [5], wherein the above X includes the following structure:

. [8] The photosensitive resin composition as described in any one of [5] to [7], wherein the above Y contains the following structure:

. [9] The photosensitive resin composition as described in any one of [5] to [7], wherein the above Y contains the following structure:

. [10] The photosensitive resin composition as described in [5], wherein the above X contains the following structure:

, The above Y contains the following structure: [Chem 9]

. [11] The photosensitive resin composition as described in any one of [1] to [10], which further contains (C) a polymerization inhibitor. [12] The photosensitive resin composition as described in [11], wherein the (C) polymerization inhibitor is selected from compounds containing aromatic hydroxyl groups, nitroso compounds, N-oxide compounds, quinone compounds, At least one of N-oxyl compound and phenol thiol compound. [13] The photosensitive resin composition as described in [11] or [12], wherein the (C) polymerization inhibitor is a compound containing an aromatic hydroxyl group. [14] The photosensitive resin composition as described in any one of [1] to [13], which further contains (D) a compound containing two or more alcoholic hydroxyl groups. [15] The photosensitive resin composition as described in [14], wherein the compound (D) containing two or more alcoholic hydroxyl groups is selected from the group consisting of aldose, ketose, pyranose, furanose, and aldose At least one kind of alcohol. [16] The photosensitive resin composition as described in any one of [11] to [15], wherein the total content of the (B) component and (C) component is 0.1 to 100 parts by mass of the (A) component 20 parts by mass. [17] The photosensitive resin composition according to any one of [1] to [16], wherein the i-line absorbance of the 0.1 wt% solution of the (A) polyimide precursor is 0.18 to 0.5. [18] The photosensitive resin composition as described in any one of [1] to [17], wherein the i-line absorbance of the 0.1 wt% solution of the (A) polyimide precursor is 0.18 to 0.4. [19] The photosensitive resin composition according to any one of [1] to [18], wherein the i-line absorbance of the 0.1 wt% solution of the (A) polyimide precursor is 0.18 to 0.3. [20] The photosensitive resin composition as described in any one of [1] to [19], wherein the i-line absorbance of the 0.1 wt% solution of the (A) polyimide precursor is 0.18 to 0.2. [21] The photosensitive resin composition as described in any one of [1] to [20], wherein the i-line absorbance of the above 0.1 wt% solution of the (A) polyimide precursor is set to DA, when the i-line absorbance of the 0.001 wt% N-methylpyrrolidone solution of the (B) photopolymerization initiator is set to DB, the sum of the DA and DB (DA+DB) is 0.25 to 0.90. [22] A method for producing polyimide, which comprises curing the photosensitive resin composition as described in any one of [1] to [21]. [23] A method for manufacturing a hardened relief pattern, characterized by comprising the following steps: (1) a coating step, which coats the photosensitive resin composition as described in any one of [1] to [21] Laid on the substrate and forming a photosensitive resin layer on the substrate; (2) exposure step, which exposes the photosensitive resin layer; (3) development step, which develops the exposed photosensitive resin layer to form A relief pattern; and (4) a heating step, which forms a hardened relief pattern by subjecting the relief pattern to heat treatment. [24] A semiconductor device characterized by having a hardened relief pattern obtained by the manufacturing method described in [23]. [25] A photosensitive resin composition characterized by containing the following components: (A) Polyimide precursor, which is represented by the following general formula (A1):

{In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are each independently a hydrogen atom, and the following general formula (R1): [Chem 11]

(In the general formula (R1), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10) , Or a saturated aliphatic group having 1 to 4 carbon atoms. Among them, both R ₁ and R ₂ will not be hydrogen atoms simultaneously; (B) Photopolymerization initiator, which is represented by the following general formula (B):

{(In the formula, Ra represents a C 1-10 monovalent organic group, Rb represents a C 1-20 organic group, Rc represents a C 1-10 organic group, Rd represents a C 1-10 organic group )} or (B1) means: [Chem 13]

{In the formula, Re represents a monovalent organic group having 1 to 20 carbon atoms, and Rf represents an organic group having 1 to 10 carbon atoms}; (D) a compound containing two or more alcoholic hydroxyl groups; and (E) selected from γ- Butyrolactone, dimethyl sulfoxide, tetrahydrofuran methanol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, N,N-dimethyl acetoacetamide, ε-caprolactone , And 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide At least one solvent in the group. [26] The photosensitive resin composition as described in [25], which contains (E) at least two solvents selected from the above group. [27] The photosensitive resin composition as described in [25] or [26], wherein the above Y contains the following structure:

Or the following structure: [Chem 15]

{In the formula, A represents an organic group having 1 to 6 carbon atoms which may contain a halogen atom}. [28] A method for producing polyimide, which comprises curing the photosensitive resin composition as described in any one of [25] to [27]. [29] A method for manufacturing a hardened relief pattern, characterized by comprising the following steps: (1) a coating step, which coats the photosensitive resin composition as described in any one of [25] to [27] Laid on the substrate and forming a photosensitive resin layer on the substrate; (2) exposure step, which exposes the photosensitive resin layer; (3) development step, which develops the exposed photosensitive resin layer A relief pattern; and (4) a heating step, which forms a hardened relief pattern by subjecting the relief pattern to a heat treatment. [30] A semiconductor device characterized by having a hardened relief pattern obtained by the manufacturing method described in [29]. [Effect of invention]

According to the present invention, it is possible to provide a photosensitivity that exhibits good resolution even when shifted in the depth of focus, does not depend on the base material, and exhibits good chemical resistance A resin composition; a method of forming a cured relief pattern using the photosensitive resin composition and a semiconductor device having the cured relief pattern.

The present embodiment will be specifically described below. In addition, according to the present specification, when the structures represented by the same symbol in the general formula exist in the case where a plurality of molecules exist in the molecule, they may be the same or different from each other.

<Photosensitive resin composition> The first aspect of this embodiment will be described. The photosensitive resin composition of the first aspect of the present invention contains (A) a polyimide precursor having an i-line absorbance of 0.1 to 0.6 wt% N-methylpyrrolidone solution of 0.1 to 0.6, and (B) has a Photopolymerization initiator of azole structure. In addition, the photosensitive resin composition of the present invention may further contain (C) a polymerization inhibitor in addition to the above components. In addition, the photosensitive resin composition of the present invention may further contain (D) a compound containing two or more alcoholic hydroxyl groups. According to such a photosensitive resin composition, a cured relief pattern having good focus margin, good resolution, and improved chemical resistance can be obtained.

[(A) Polyimide precursor] The (A) polyimide precursor of this embodiment will be described. The i-line absorbance of the 0.1 wt% N-methylpyrrolidone solution of (A) polyimide precursor of this embodiment is 0.1 to 0.6, as long as it can be hardened by the action of (B) photopolymerization initiator The relief pattern is not limited. Here, as a method for measuring absorbance, the polyimide precursor can be dissolved in N-methylpyrrolidone at a concentration of 0.1 wt%, and a 1 cm quartz cell is used, using a conventional spectrophotometer. Determination. As long as the i-line absorbance of the 0.1 wt% solution of (A) polyimide precursor of the present embodiment is 0.1 to 0.6, it is not particularly limited, and from the viewpoint of the coating property of the inorganic film, it is preferably 0.18 to 0.6. Furthermore, from the viewpoint of developability when the film thickness is increased, it is preferably 0.18 to 0.5, and more preferably 0.18 to 0.4. The i-line absorbance can be 0.18 to 0.3 or 0.18 to 0.2.

From the viewpoint of the heat resistance and mechanical properties of the film obtained after the heat treatment, (A) the weight average molecular weight of the polyimide precursor is preferably calculated as a polystyrene conversion value by gel permeation chromatography 1,000 or more. More preferably, it is more than 5,000. The upper limit is preferably 100,000 or less. From the viewpoint of the solubility of the developer, the weight average molecular weight is more preferably 50,000 or less.

{式中，X為四價有機基，Y為二價有機基，R₁ 及R₂ 分別獨立地為氫原子、下述通式(R1)： [化17]

(式中，R₃ 、R₄ 及R₅ 分別獨立地為氫原子或碳數1～3之有機基，p為選自2～10中之整數)所表示之一價有機基、或碳數1～4之飽和脂肪族基；其中，R₁ 及R₂ 之兩者不會同時為氫原子}所表示之結構之酯型之聚醯亞胺前驅物。In the resin composition of this embodiment, from the viewpoint of heat resistance and photosensitivity, one of the best (A) polyimide precursors includes the following general formula (A1):

{In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are each independently a hydrogen atom, and the following general formula (R1): [Chem. 17]

(In the formula, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10) Saturated aliphatic group of 1 to 4; wherein, both of R ₁ and R ₂ will not be the ester polyimide precursor of the structure represented by hydrogen atom}.

In the above general formula (A1), the tetravalent organic group represented by X is preferably an organic group having 6 to 40 carbon atoms, and more preferably, one of the -COOR ₁ group and the -CONH- group is bonded to the same An aromatic ring, and the tetravalent aromatic group or the alicyclic aliphatic group in which the two are adjacent to each other. In the former case, the aromatic ring bonded to the -COOR ₁ group and the aromatic ring bonded to the -COOR ₂ group may be the same aromatic ring or different aromatic rings. The aromatic ring in this context is preferably a benzene ring.

所表示之結構，但並不限定於其等。又，X之結構可為1種亦可為2種以上之組合。As the tetravalent organic group represented by X, more preferably, the following formulas are given: [Chem 18]

The structure shown is not limited to it. In addition, the structure of X may be one type or a combination of two or more types.

或下述結構： [化20]

。 藉由聚醯亞胺前驅物具有此種結構，耐熱性及感光性提高，於所獲得之硬化浮凸圖案中，可提高聚焦裕度及耐化學品性。Especially in the photosensitive resin composition of the present invention, in the above general formula (A1), as the tetravalent organic group represented by X, it is particularly preferable to include the following structure:

Or the following structure: [Chem 20]

. Since the polyimide precursor has such a structure, heat resistance and photosensitivity are improved, and in the obtained hardened relief pattern, focus margin and chemical resistance can be improved.

In the above general formula (A1), the divalent organic group represented by Y is preferably an aromatic group having 6 to 40 carbon atoms, and examples thereof include the following formulas:

{上述式中，A為甲基(-CH₃ )、乙基(-C₂ H₅ )、丙基(-C₃ H₇ )、或丁基(-C₄ H₉ )}所表示之結構，但並不限定於其等；又，Y之結構可為1種亦可為2種以上之組合。[化22]

{In the above formula, A is a structure represented by methyl (-CH ₃ ), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ), or butyl (-C ₄ H ₉ )} , But not limited to the same; and the structure of Y may be one kind or a combination of two or more kinds.

R ₃ in the general formula (R1) is preferably a hydrogen atom or a methyl group, and from the viewpoint of photosensitive characteristics, R ₄ and R _{5 are} preferably hydrogen atoms, respectively. From the viewpoint of photosensitive characteristics, p is preferably an integer of 2 or more and 10 or less, and more preferably an integer of 2 or more and 4 or less.

或下述結構： [化24]

。 藉由使聚醯亞胺前驅物具有此種結構，耐熱性及感光性提高，而所獲得之硬化浮凸圖案可提高聚焦裕度及耐化學品性。Especially in the photosensitive resin composition of the present invention, regarding the polyimide precursor, in the general formula (A1), the divalent organic group represented by Y particularly preferably includes the following structure:

Or the following structure: [Chem 24]

. By making the polyimide precursor have such a structure, heat resistance and photosensitivity are improved, and the obtained hardened relief pattern can improve focus margin and chemical resistance.

， Y包含下述結構： [化26]

。 藉由使聚醯亞胺前驅物具有此種結構，耐熱性及感光性進而提高，而所獲得之硬化浮凸圖案可進一步提高聚焦裕度及耐化學品性。In the photosensitive resin composition of the present invention, in the above general formula (A1), it is preferable that X includes the following structure:

, Y contains the following structure: [Chem 26]

. By making the polyimide precursor have such a structure, heat resistance and photosensitivity are further improved, and the obtained hardened relief pattern can further improve focus margin and chemical resistance.

[(A) Preparation method of polyimide precursor] The ester bond type polyimide precursor, for example, first reacts a tetracarboxylic dianhydride having a desired tetravalent organic group X with an alcohol having a photopolymerizable group (such as an unsaturated double bond), and Preparation of partially esterified tetracarboxylic acid (hereinafter, also referred to as acid/ester body). Thereafter, it can be obtained by subjecting the acid/ester body to polyamine condensation polymerization of diamines having a divalent organic group Y. It is also possible to use saturated aliphatic alcohols together with the above-mentioned alcohols having a photopolymerizable group arbitrarily.

(Preparation of acid/ester body) In the present invention, as a tetracarboxylic dianhydride having a tetravalent organic group X that can be suitably used for preparing an ester-bonded polyimide precursor, 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, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2, 2-bis(3,4-phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., But it is not limited to it. Of course, they can be used singly or in combination of two or more.

In the present invention, examples of alcohols having a photopolymerizable group that can be suitably used for preparing ester-bonded polyimide precursors include, for example, 2-propenyloxyethanol and 1-propenyloxy -3-propanol, 2-acrylamide ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butyl acrylate Oxypropyl ester, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-third butoxypropyl acrylate, 2-hydroxy acrylate -3-cyclohexyloxypropyl ester, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacryloylaminoethanol, methacrylic acid 2-hydroxy- 3-methoxypropyl ester, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxy methacrylate Propyl ester, 2-hydroxy-3-tributyloxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc.

As the saturated aliphatic alcohol that can be used arbitrarily with the above-mentioned alcohol having a photopolymerizable group, a saturated aliphatic alcohol having 1 to 4 carbon atoms is preferred. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, and third butanol.

The tetracarboxylic dianhydride suitable for the present invention and the alcohol described above are preferably stirred and mixed in the presence of a basic catalyst such as pyridine and preferably in an appropriate reaction solvent at a temperature of 20 to 50°C. From 4 to 10 hours, the esterification reaction of the acid anhydride proceeds to obtain the desired acid/ester body.

As the reaction solvent, it is preferable to completely dissolve the tetracarboxylic dianhydride and alcohols of the raw materials and the acid/ester body as the product. More preferably, it is a solvent which also completely dissolves the polyimide precursor, which is the polycondensation product of the amide polycondensate of the acid/ester body and the diamine. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, ketones , Esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. As a specific example of it, Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate;

Examples of lactones include γ-butyrolactone and the like; Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran; Examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, and o-dichlorobenzene; Examples of the hydrocarbons include hexane, heptane, benzene, toluene, and xylene. They can be used alone or in combination of two or more as needed.

(Preparation of Polyimide Precursor) To the acid/ester body (typically in the state of a solution dissolved in the reaction solvent), it is preferable to add an appropriate dehydrating condensing agent under ice bath cooling to mix the acid/ester body into a polyanhydride. Then, those obtained by dissolving or dispersing diamines having a divalent organic group Y in a solvent, which can be suitably used in the present invention, are added dropwise thereto, and the two are subjected to amide polycondensation, whereby the target polymerization can be obtained Precursor of amide imine. The diamine siloxanes can also be used in combination with the above-mentioned diamines having a divalent organic group Y. Examples of the dehydrating condensation agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, and 1,1-carbonyldioxy- Di-1,2,3-benzotriazole, N,N'-dibutanediimide carbonate, etc. The polyanhydride as an intermediate can be obtained in the above manner.

In the present invention, examples of diamines having a divalent organic group Y that can be suitably used in the reaction with the polyanhydride obtained in the above manner include, for example, p-phenylenediamine, m-phenylenediamine, and 4, 4-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4' -Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3, 3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-di Aminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,

1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[ 4-(4-aminophenoxy)phenyl] lanthanum, bis[4-(3-aminophenoxy)phenyl] lanthanum, 4,4-bis(4-aminophenoxy)biphenyl , 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)benzene Group] ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2 ,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl ) Propane, 2,2-bis(4-(4-aminophenoxy)phenyl) hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-bi Toluidine, 9,9-bis(4-aminophenyl) stilbene, etc.; and some of the hydrogen atoms on the benzene ring are substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen Atom, etc.; And its mixture.

Specific examples of the above-mentioned substitutes include, for example, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl Benzene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-di Methoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, etc.; and mixtures thereof. The diamines are not limited to the above examples.

In order to improve the adhesion between the coating film formed using the photosensitive resin composition of the present invention and various substrates, in the preparation of (A) photosensitive polyimide precursors, the diaminosiloxanes are Diamines containing divalent organic group Y are used together. Specific examples of such diaminosiloxanes include, for example, 1,3-bis(3-aminopropyl)tetramethyldisilaxane, 1,3-bis(3-aminopropyl) Group) Tetraphenyl disilaxane and so on.

After the amide polycondensation reaction is completed, after filtering and separating the water-absorbing secondary organisms of the dehydrating condensing agent coexisting in the reaction solution as necessary, an appropriate poor solvent (for example, water, aliphatic lower alcohol) is added to the solution containing the polymer component , Its mixed solution, etc.), the polymer composition is analyzed, and then the operation of re-dissolving and re-precipitation precipitation operation is repeated as necessary to purify the polymer, followed by vacuum drying, thereby making the target polyimide precursor Things separate. In order to improve the fineness system, the polymer solution can be used to remove ionic impurities by using a suitable organic solvent to swell and fill the anion and/or cation exchange resin.

The weight average molecular weight of the ester-bonded polyimide precursor is calculated from the polystyrene conversion value by gel permeation chromatography from the viewpoint of the heat resistance and mechanical properties of the film obtained after heat treatment , Preferably 1,000 or more. More preferably, it is more than 5,000. The upper limit is preferably 100,000 or less. From the viewpoint of the solubility of the developer, the weight average molecular weight is more preferably 50,000 or less. As a developing solvent for gel permeation chromatography, tetrahydrofuran or N-methyl-2-pyrrolidone is recommended. The molecular weight is determined using a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to choose from the organic solvent series standard sample STANDARD SM-105 manufactured by Showa Denko.

(式中，Ra表示碳數1～10之一價有機基，Rb表示碳數1～20之有機基，Rc表示碳數1～10之有機基，Rd表示碳數1～10之有機基) Ra只要為碳數1～10之一價有機基，則並無特別限定，就耐熱性之觀點而言，較佳為碳數1～5之烷基，更佳為甲基、乙基、丙基。 Rb只要為碳數1～20之有機基，則並無特別限定，就解像度之觀點而言，較佳為碳數6～20之芳香族基、源自碳數5～20之雜環化合物之一價有機基。 Rc只要為碳數1～10之有機基，則並無限定。其中，就解像性之觀點而言，更佳為含有碳數3～10之飽和脂環結構之一價有機基。 Rd只要為碳數1～10之有機基，則並無限定。其中，就解像性之觀點而言，較佳為碳數1～3之有機基，更佳為甲基、乙基、丙基。[(B) Photopolymerization Initiator] Next, the component (B) of this embodiment will be described. The component (B) of this embodiment is a photopolymerization initiator having a carbazole structure. If the (B) photopolymerization initiator has a carbazole structure, it is not particularly limited, and more preferably has an oxime structure. More specifically, (B) the photopolymerization initiator is more preferably a structure represented by the following general formula (B). [化27]

(In the formula, Ra represents a C 1-10 monovalent organic group, Rb represents a C 1-20 organic group, Rc represents a C 1-10 organic group, Rd represents a C 1-10 organic group) Ra is not particularly limited as long as it is a monovalent organic group having 1 to 10 carbon atoms. From the viewpoint of heat resistance, alkyl groups having 1 to 5 carbon atoms are preferred, and methyl, ethyl, and propylene are more preferred. base. Rb is not particularly limited as long as it is an organic group having 1 to 20 carbon atoms. From the viewpoint of resolution, an aromatic group having 6 to 20 carbon atoms and a heterocyclic compound derived from 5 to 20 carbon atoms are preferred. Monovalent organic radical. Rc is not limited as long as it is an organic group having 1 to 10 carbon atoms. Among them, from the viewpoint of resolution, it is more preferably a monovalent organic group containing a saturated alicyclic structure having 3 to 10 carbon atoms. Rd is not limited as long as it is an organic group having 1 to 10 carbon atoms. Among them, from the viewpoint of resolution, an organic group having 1 to 3 carbon atoms is preferred, and a methyl group, an ethyl group, and a propyl group are more preferred.

About the (A) 0.1 wt% N-methylpyrrolidone solution of this embodiment, the polyimide precursor having an i-line absorbance of 0.1 to 0.6 and (B) the photopolymerization represented by the general formula (B) above The starting agent has excellent focusing margin, shows good resolution without depending on the base material, and the reason for showing good chemical resistance is not clear, but the inventors of the present invention considered as follows. In general, the transmittance of the polyimide precursor with a 0.1 wt% solution having an i-line absorbance of 0.1 to 0.6 is high, especially when the base substrate is a metal such as copper or aluminum, and the resolution deteriorates due to reflected light As a result, by selecting a specific initiator, good resolution can be obtained without depending on the base substrate. In addition, it is considered that the chemical resistance can be improved by increasing the imidate ratio of the heterocyclic tertiary amine portion of the starter of the present embodiment during thermal curing.

In the present embodiment, the (B) 0.001 wt% N-methylpyrrolidone solution of the photopolymerization initiator has an i-line absorbance of preferably 0.01 to 0.5 from the viewpoint of the coverage of the inorganic film. Furthermore, from the viewpoint of developability when the film thickness is increased, it is preferably 0.01 to 0.2. The i-line absorbance is preferably 0.02 to 0.2, and more preferably 0.03 to 0.15.

Especially in the photosensitive resin composition of this embodiment, it is preferable to set the i-line absorbance of the (A) polyimide precursor 0.1 wt% N-methylpyrrolidone solution to DA, and set (B ) When the i-line absorbance of the 0.001 wt% N-methylpyrrolidone solution of the photopolymerization initiator is set to DB, the sum of DA and DB (DA + DB) is 0.25 to 0.90. With this, the photosensitive resin composition can optimally absorb the i-line, and the focus margin can be further improved.

[(C) Polymerization inhibitor] In this embodiment, a polymerization inhibitor can be added. By adding a polymerization inhibitor, in particular, good resolution can be obtained without depending on the base substrate. As the polymerization inhibitor of the present embodiment, there may be exemplified compounds containing aromatic hydroxyl groups, nitroso compounds, N-oxide compounds, quinone compounds, N-oxy compounds, and phenol thiol compounds. Examples of compounds containing aromatic hydroxyl groups include 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetra[3-(3,5-di-tert-butyl -4-hydroxyphenyl) propionate], thiodiethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3-(3,5 -Di-tert-butyl-4-hydroxyphenyl)octadecyl propionate, N,N′-hexane-1,6-diylbis[3-(3,5-di-tert-butyl- (4-hydroxyphenyl)propionamide], 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene- 2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) o-cresol, ethylidene bis (ethylene oxide) bis [3- (5- tertiary butyl- 4-hydroxy-m-tolyl) propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tri( 3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl Yl-4-(4,6-bis(octylthio)-1,3,5-tris-2-ylamino)phenol, catechol, tert-butyl catechol, 4,4 ',4''-(1-Methylpropyl-3-ylidene)tris(6-third butyl m-cresol), 6,6'-di-third butyl-4,4'-butylene M-cresol, 3,9-bis[2-[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro[5,5]undecane, hydroquinone, methylhydroquinone, tert-butyl hydroquinone, di-tert-butyl hydroquinone Phenol, pyrogallol, 4,4-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butyl) Phenol), phenol resins and cresol resins.

As the nitroso compound, there can be exemplified: nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1-nitroso Nitro-2-naphthol, 2-nitroso-1-naphthol, 4-nitroso-diphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonic acid, N-nitroso Pyrrolidine, N-third butyl-N-nitrosoaniline, N-nitrosodimethylamine, N-nitrosodiethylamine, 1-nitrosopiperidine, 4-nitroso Radicals, N-nitroso-N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, N-nitrosophenylhydroxylamine Cerium (III) salt and aluminum salt of N-nitrosophenylhydroxylamine, 2,4,6-tri-tert-butyl-nitrosobenzene, N-nitrosodiphenylamine.

As the N-oxide compound, there can be exemplified: phenyl third butyl nitrone, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide, 5,5-dimethyl-1 -Pyrroline-N-oxide, 4-methyl pyroline-N-oxide, pyridine-N-oxide, 4-nitropyridine-N-oxide, 3-hydroxypyridine-N-oxide, pyridine Formic acid-N-oxide, nicotinic acid-N-oxide, and isonicotinic acid-N-oxide.

As the quinone compound, there can be exemplified: p-benzoquinone, p-quinone, methyl p-benzoquinone, 2,6-dimethyl-1,4-benzoquinone, tetramethyl-1,4-benzoquinone, 2-th Tributyl p-benzoquinone, 2,5-di-tertiary butyl-1,4-benzoquinone, 2,6-di-tertiary-1,4-benzoquinone, rebaudioquinone, 2,5-di-tertiary Amylbenzoquinone, 2-bromo-1,4-benzoquinone, 2,5-dibromo-1,4-benzoquinone, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro -1,4-benzoquinone, 2-bromo-5-methyl-1,4-benzoquinone, tetrafluoro-1,4-benzoquinone, tetrabromo-1,4-benzoquinone, 2-chloro-5- Methyl-1,4-benzoquinone, tetrachloro-1,4-benzoquinone, methoxy-1,4-benzoquinone, 2,5-dihydroxy-1,4-benzoquinone, 2,5-bis Methoxy-1,4-benzoquinone, 2,6-dimethoxy-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, tetrahydroxy -1,4-benzoquinone, 2,5-diphenyl-1,4-benzoquinone, 1,4-naphthoquinone, 1,4-anthraquinone, 2-methyl-1,4-naphthoquinone, 5 ,8-dihydroxy-1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 5-hydroxy-2-methyl-1,4-naphthoquinone , 1-nitroanthraquinone, anthraquinone, 1-aminoanthraquinone, 1,2-benzoanthraquinone, 1,4-diaminoanthraquinone, 2,3-dimethylanthraquinone, 2-ethyl Anthraquinone, 2-methylanthraquinone, 5,12-thick tetrabenzoquinone.

As the N-oxyl compound, there can be exemplified: 2,2,6,6-tetramethylpiperidine-1-oxy, 4-cyano-2,2,6,6-tetramethylpiperidine-1- Oxy, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxy, 4-carboxy-2,2,6,6-tetramethylpiperidine-1-oxy, 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxy, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxy, 4- Methacryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxy, piperidine-1-oxy radical, 4-oxo-2,2,6,6-tetra Methylpiperidine-1-oxy radical, 4-acetamide-2,2,6,6-tetramethylpiperidine-1-oxy radical, 4-cis-butenediimide-2 , 2,6,6-Tetramethylpiperidine-1-oxy radical and 4-phosphonooxy-2,2,6,6-Tetramethylpiperidine-1-oxy radical, pyrrolidine -1-oxy radical compounds, 3-carboxy PROXYL radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine-1-oxy radical).

As the phenol thiol compound, there can be exemplified: phenol thiol, 10-methylphenol thiol, 2-methylthiophenol thiol, 2-chlorophenol thiol, 2-ethylthiophenol thiol, 2-( Trifluoromethyl) phenol thiophene, 2-methoxyphenol thiophene 𠯤.

From the viewpoint of the development residual film rate and the resolution, it is preferably a compound containing an aromatic hydroxyl group and a nitroso compound, and particularly preferably a compound containing an aromatic hydroxyl group. The compound containing an aromatic hydroxyl group is preferably 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, and particularly preferably 4-methoxyphenol.

Further, in the photosensitive resin composition of the present invention, the total content of (B) photopolymerization initiator and (C) polymerization inhibitor is preferably 100 parts by mass of the (A) polyimide precursor component. 0.1 to 20 parts by mass.

[(D) Compounds containing more than two alcoholic hydroxyl groups] In addition to the components (A) to (C), the photosensitive resin composition of the present invention may further contain (D) a compound containing two or more alcoholic hydroxyl groups. The second aspect of the compound containing two or more alcoholic hydroxyl groups is not limited as long as it has two or more alcoholic hydroxyl groups in the molecular structure. Examples of such compounds include glycerin, 1,2,3-butanetriol, 1,3,5-pentanetriol, and 1,2,6-hexanetriol. Moreover, aldose, ketose, pyranose, furanose, alditol, etc. can be illustrated. Specifically, it is preferably at least 1 selected from the group consisting of xylitol ((2R,3R,4S)-pentane-1,2,3,4,5-pentanol), and D-glucose Species. By adding these compounds, when combined with the above-mentioned photopolymerization initiator, the adhesiveness with the mold resin used in the fan-out structure tends to be good.

[(E)Other ingredients] The photosensitive resin composition of the present invention may further contain components other than the aforementioned components (A) to (D). The photosensitive resin composition of the present invention is typically used as a varnish-like liquid photosensitive resin composition by dissolving the above-mentioned components and optional components further used as necessary in a solvent. Therefore, as (E) other components, in addition to solvents, for example, resins other than the above-mentioned (A) photosensitive polyimide precursors, sensitizers, crosslinking agents, and photopolymerizable unsaturated Bond monomers, adhesion aids, azole compounds, hindered phenol compounds, etc. As the above-mentioned crosslinking agent, any compound having a plurality of functional groups in the molecule can be mentioned. Here, as the functional group, for example, an acrylic group, a methacryl group, an epoxy group, a methylol group, an allyl group, a vinyl group, a maleimide group, and the like can be mentioned.

Examples of the solvent include polar organic solvents and alcohols. As the solvent, it is preferable to use a polar organic solvent in terms of solubility in the (A) photosensitive polyimide precursor. Specifically, for example, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide Amine, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl 2-imidazolidinone, N-cyclohexyl-2-pyrrolidone and the like can be used alone or in combination of two or more.

As the solvent in the present invention, from the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing alcohols is preferred. The alcohol which can be suitably used is typically an alcohol having an alcoholic hydroxyl group in the molecule and having no olefinic double bond. Specific examples include alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and third butanol; Lactate esters such as ethyl lactate;

Propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-(n-propyl) ether, propylene glycol-2-(n-propyl) ether, etc. Alkyl ethers; Monools such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol n-propyl ether; 2-hydroxyisobutyrate; Glycols such as ethylene glycol and propylene glycol. Among them, lactates, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate and ethanol are preferred, and ethyl lactate, propylene glycol-1-methyl ether and propylene glycol-1-ethyl ether are particularly preferred And propylene glycol-1-(n-propyl) ether.

The above-mentioned solvent may be in the range of 30 to 1500 parts by mass, preferably 100 to 100 parts by mass of the (A) polyimide precursor according to the required coating film thickness and viscosity of the photosensitive resin composition Use within 1,000 parts by mass. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in all solvents is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the above content of the alcohol having no olefinic double bond is 5 mass% or more, the storage stability of the photosensitive resin composition becomes good, and when it is 50 mass% or less, (A) polyacrylic acid The solubility of the amine precursor becomes good.

The photosensitive resin composition of this embodiment may further contain a resin component other than the (A) polyimide precursor. Examples of the resin component that can be contained include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, silicone resin, acrylic resin, and the like. The blending amount of these resin components is preferably in the range of 0.01 to 20 parts by mass relative to (A) 100 parts by mass of the polyimide precursor.

In order to improve photosensitivity, a sensitizer may be arbitrarily added to the photosensitive resin composition of this embodiment. Examples of the sensitizer include: Michelerone, 4,4′-bis(diethylamino)benzophenone, and 2,5-bis(4′-diethylaminobenzylidene) ) Cyclopentane, 2,6-bis(4'-diethylaminobenzylidene) cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methyl Cyclohexanone, 4,4'-bis(dimethylamino) chalcone, 4,4'-bis(diethylamino) chalcone, p-dimethylaminobenzylidene di Indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylethylene) Group) benzothiazole, 2-(p-dimethylaminophenyl vinylidene) isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis( 4'-diethylaminobenzylidene) acetone,

3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetoxy-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethyl Aminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7 -Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinyldiphenyl Methone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho (1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzylanilide, N-methylacetanilide, 3', 4 '-Dimethylacetanilide etc. These can be used alone or in combination of 2 to 5 kinds, for example.

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

In order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be arbitrarily blended into the resin composition of the present invention. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction using a photopolymerization initiator is preferred. It is not limited to the following, and it can be specifically exemplified by mono- or di(meth)acrylic acid of ethylene glycol or polyethylene glycol represented by diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. ester; Mono- or di(meth)acrylate of propylene glycol or polypropylene glycol; Glycerin mono-, di- or tri-(meth)acrylate; Cyclohexane di(meth)acrylate; 1,4-Butanediol diacrylate and dimethacrylate, 1,6-Hexanediol di(meth)acrylate;

Neopentyl glycol bis (meth)acrylate; Mono- or di(meth)acrylate of bisphenol A; Benzene trimethacrylate; (Meth)acrylic acid isobutyl ester; Acrylamide and its derivatives; Methacrylamide and its derivatives; Trimethylolpropane tri(meth)acrylate; Glycerin bis or tri(meth)acrylate; Pentaerythritol bis, tri, or tetra (meth) acrylate; And compounds such as ethylene oxide or propylene oxide adducts of these compounds.

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

In order to improve the adhesion between the film formed by the photosensitive resin composition of the present embodiment and the substrate, an adhesion aid may be arbitrarily added to the photosensitive resin composition. Examples of the adhesion auxiliary agent include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-glycidol Oxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxycarbonyl Propylpropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxy Methylsilylpropyl)butanediimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3'-bis(N -[3-Triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide) )-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane and other silane coupling agents and tris(ethyl acetate ethyl acetate) ) Aluminum-based adhesives such as aluminum, tris(acetone) aluminum, acetoacetate, ethyl aluminum diisopropyl acetate, etc.

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

When the substrate using the resin composition of the present embodiment uses, for example, a substrate containing copper or a copper alloy, in order to suppress discoloration of the copper surface, an azole compound can be arbitrarily formulated. 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- Phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-bis Ethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α -Dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl- 5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-third-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5 '-Third octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole , 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5- Amino group-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred is one or more kinds selected from tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. One kind of these azole compounds may be used, or a mixture of two or more kinds may be used.

In the case where the photosensitive resin composition of the present embodiment contains the azole compound, the formulation amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyimide precursor, from the viewpoint of light sensitivity characteristics In particular, it is more preferably 0.5 to 5 parts by mass. When the formulation amount of the azole compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, when the photosensitive resin composition of this embodiment is formed on copper or a copper alloy, To suppress the discoloration of the surface of copper or copper alloy, on the other hand, when it is 10 parts by mass or less, the excellent light sensitivity of the photosensitive resin composition is maintained.

In order to suppress the discoloration of the copper surface, the above-mentioned azole compound may be substituted, or a hindered phenol compound may be arbitrarily formulated together with the above-mentioned azole compound. Examples of the hindered phenol compound include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, and 3-(3,5-di-tert-butyl Octadecyl-4-hydroxyphenyl) propionate, 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-hexanedi Alcohol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylidene bis[3-(3,5-di-di Tributyl-4-hydroxyphenyl) propionate],

N,N' hexamethylene bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionamide), 2,2'-methylene-bis(4-methyl-6-third Butylphenol), 2,2'-methylene-bis(4-ethyl-6-third-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4- (Hydroxyphenyl) propionate], tri-(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-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-tris(4-second butyl-3- Hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 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-trimethylbenzyl)-1,3,5-tris 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethyl Benzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl- 3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris (4-third 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)- Triketone, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H ,3H,5H)-trione, 1,3,5-tris(4-third-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris- 2,4,6-(1H,3H,5H)-trione, etc., but not limited to this. Among others, particularly preferred is 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 amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyimide precursor, and more preferably 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics. When the formulation amount of the hindered phenol compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy To prevent discoloration and corrosion of copper or copper alloys, on the other hand, in the case of 20 parts by mass or less, the excellent light sensitivity of the photosensitive resin composition is maintained.

From the viewpoint of the coverage of the inorganic film, the i-line absorbance of the 0.1 wt% N-methylpyrrolidone solution of the photosensitive resin composition of the present embodiment is preferably 0.01 to 1.2. Furthermore, from the viewpoint of developability when the film thickness is increased, it is preferably 0.01 to 1.0. The absorbance of the i-line can be 0.1 to 0.9 or 0.2 to 0.8.

{通式(2)中，X¹ 及Y¹ 與通式(A1)中之X及Y相同；通式(A1)中之較佳之X、Y因相同之原因，於通式(2)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}<Manufacturing method of polyimide and polyimide> Furthermore, the present invention also provides a method of manufacturing polyimide. The method for producing polyimide in the present invention includes the operation of hardening the photosensitive resin composition. The structure of the polyimide formed by the photosensitive resin composition (polyimide precursor composition) is represented by the following general formula (2). [Chem 28]

{In the general formula (2), X ¹ and Y ¹ are the same as X and Y in the general formula (A1); the preferred X and Y in the general formula (A1) are for the same reason, in the general formula (2) Polyimide is also preferred; the number of repeating units m is not particularly limited, and may be an integer from 2 to 150}

<Manufacturing method of hardened relief pattern> In addition, the present invention also provides a method for manufacturing a hardened relief pattern. The method for manufacturing a hardened relief pattern in the present invention is characterized by passing the following steps in the order described below, for example: (1) A coating step, which coats the above-mentioned photosensitive resin composition of the present invention on a substrate and forms a photosensitive resin layer on the substrate; (2) An exposure step, which exposes the photosensitive resin layer; (3) A development step, which develops the exposed photosensitive resin layer to form a relief pattern; and (4) A heating step of forming a hardened relief pattern by subjecting the relief pattern to heat treatment. In the following, typical aspects of each step will be described.

(1) Coating step In this step, the photosensitive resin composition of the present invention is coated on a substrate, and then dried as necessary to form a photosensitive resin layer. As the substrate, for example, a metal substrate containing silicon, aluminum, copper, copper alloy, etc. can be used; Resin substrates such as epoxy resin, polyimide, and polybenzoxazole; A substrate with a metal circuit formed on the resin substrate; A plurality of metals, or a substrate in which metal and resin are laminated in multiple layers. As a coating method, a method conventionally used for coating of a photosensitive resin composition can be used, for example, using a spin coater, a bar coater, a blade coater, a curtain coater, screen printing The method of coating with a machine, etc., the method of spray coating with a spray coater, etc.

If necessary, the photosensitive resin composition film may be dried. As the drying method, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying can be used. In addition, the drying of the coating film is preferably carried out under conditions that do not cause the imidization of the (A) polyimide precursor (polyamide) in the photosensitive resin composition. Specifically, in the case of air-drying or heat-drying, drying can be performed at 20°C to 140°C under the conditions of 1 minute to 1 hour. According to the above, a photosensitive resin layer can be formed on the substrate.

(2) Exposure steps In this step, the photosensitive resin layer formed as described above is exposed. As the exposure device, for example, an exposure device such as a contact exposure machine, a mirror projection exposure machine, a stepper and the like can be used. The exposure can be carried out via a patterned photomask or a reduced-magnification photomask or directly. The light used for exposure is, for example, an ultraviolet light source.

After exposure, in order to improve light sensitivity, etc., post-exposure baking (PEB) and/or pre-development baking at any combination of temperature and time may be performed as necessary. Regarding the range of baking conditions, the temperature is preferably 40 to 120° C., and the time is preferably 10 seconds to 240 seconds, but as long as the characteristics of the photosensitive resin composition of this embodiment are not hindered, it is not limited to this range. .

(3) Development steps In this step, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), a previously known developing method of photoresist can be selected and used. For example, the rotary spray method, the liquid coating method, the immersion method with ultrasonic treatment, and the like. After development, for the purpose of adjusting the shape of the relief pattern, post-development baking at any combination of temperature and time may be performed as necessary. The temperature of baking after development can be set to 80 to 130° C., and the time can be set to 0.5 to 10 minutes, for example.

As the developer used in development, a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent is preferred. As a good solvent, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ- Butyrolactone, α-acetyl-γ-butyrolactone, etc., as poor solvents, preferably toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. . When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the negative photosensitive resin composition. In addition, each solvent may be used in combination of two or more kinds, for example, a combination of several kinds.

(4) Heating step In this step, the relief pattern obtained by the above development is heated to dilute the photosensitive component, and (A) the polyimide precursor is imidized into a hardened polyimide. Embossed pattern. As a method of heat hardening, various methods such as those using a heating plate, those using an oven, and those using a temperature-increasing oven with a programmable temperature program can be selected. The heating can be performed at 160°C to 400°C for 30 minutes to 5 hours, for example. As the atmosphere gas during heat curing, air may be used, and inert gas such as nitrogen and argon may also be used. The hardened relief pattern can be manufactured in the above manner.

<Semiconductor device> Furthermore, the present invention provides a semiconductor device having a hardened relief pattern obtained by the above-described method of manufacturing a hardened relief pattern of the present invention. The semiconductor device may be, for example, a semiconductor device having a base material as a semiconductor element and a hardened relief pattern formed on the base material by the above-mentioned hardened relief pattern manufacturing method. For example, the semiconductor device may use a semiconductor element as a base material, and may be manufactured by a method including the above-described method for manufacturing the hardened relief pattern as part of the steps. The semiconductor device of the present invention can be formed by forming the hardened relief pattern formed by the above-mentioned hardened relief pattern manufacturing method as, for example, a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or having The protective film and the like of the bump-structured semiconductor device are manufactured in combination with a well-known semiconductor device manufacturing method.

The photosensitive resin composition of the present invention is useful for applications such as interlayer insulation of multilayer circuits, coatings of flexible copper foils, solder resist films, and liquid crystal alignment films in addition to the semiconductor devices described above.

The second aspect of this embodiment will be described. The photosensitive resin composition of the second aspect contains: (A1) a polyimide precursor, (B) a photopolymerization initiator of a specific structure, (D) a compound containing two or more alcoholic hydroxyl groups, and ( E) selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofuran methanol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, N,N-dimethyl acetoacetamide , Ε-caprolactone, and 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-di At least one solvent in the group consisting of methyl acrylamide. More preferably, it contains (E) at least 2 solvents. According to such a photosensitive resin composition, a cured relief pattern with improved adhesion and durability of the sealing material can be obtained. This is explained below.

{式中，X為四價有機基，Y為二價有機基，R₁ 及R₂ 分別獨立地為氫原子、下述通式(R1) [化30]

(通式(R1)中，R₃ 、R₄ 及R₅ 分別獨立地為氫原子或碳數1～3之有機基，p為選自2～10中之整數)所表示之一價有機基、或碳數1～4之飽和脂肪族基；其中，R₁ 及R₂ 之兩者不會同時為氫原子} 其中，作為較佳之聚醯亞胺前驅物，可例示與第一態樣同樣者。[(A1) Polyimide precursor] The polyimide precursor of the second aspect is not limited if it includes the structure represented by the following general formula (A1). [Chem 29]

{In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are each independently a hydrogen atom, and the following general formula (R1) [Chem 30]

(In the general formula (R1), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10) , Or a saturated aliphatic group having 1 to 4 carbon atoms; wherein, both of R ₁ and R ₂ are not simultaneously hydrogen atoms} where, as a preferred precursor of polyimide, the same as the first aspect can be exemplified By.

或下述結構： [化32]

{式中，A表示碳數1～6之可包含鹵素原子之有機基} 所表示之結構。 A只要為可含有碳數1～6之鹵素原子之有機基，則並無限定。作為此種取代基，可例示：甲基、乙基、丙基等烷基、三氟甲基等含氟原子之烷基等。Among them, it is particularly preferable that Y contains the following structure: [Chem 31]

Or the following structure: [Chem 32]

{In the formula, A represents an organic group having 1 to 6 carbon atoms which may contain a halogen atom} A is not limited as long as it is an organic group that can contain a halogen atom having 1 to 6 carbon atoms. Examples of such substituents include alkyl groups such as methyl, ethyl, and propyl groups, and alkyl groups containing fluorine atoms such as trifluoromethyl groups.

{式中，Ra、Rb、Rc、Rd係如上所述} [化34]

{式中，Re表示碳數1～20之一價有機基，Rf表示碳數1～10之一價有機基} Ra只要為碳數1～10之一價有機基，則並無特別限定，就耐熱性之觀點而言，較佳為碳數1～5之烷基，更佳為甲基、乙基、丙基。 Rb只要為碳數1～20之有機基，則並無特別限定，就解像度之觀點而言，較佳為碳數6～20之芳香族基、源自碳數5～20之雜環化合物之一價有機基。 Rc只要為碳數1～10之有機基，則並無限定。其中，就解像性之觀點而言，更佳為含有碳數3～10之飽和脂環結構之一價有機基。 Rd只要為碳數1～10之有機基，則並無限定。其中，就解像性之觀點而言，較佳為碳數1～3之有機基，更佳為甲基、乙基、丙基。 Re只要為碳數1～20之一價有機基，則並無限定。其中，就耐化學品性之觀點而言，較佳為包含飽和烴基。 Rf只要為碳數1～10之有機基，則並無限定。其中，就解像性之觀點而言，較佳為碳數1～3之有機基，更佳為甲基、乙基、丙基。[(B) Photopolymerization initiator] The second aspect (B) photopolymerization initiator is not particularly limited as long as it has a structure having an oxime structure and further contains heteroatoms, and includes the following general formula (B) Or the structure represented by (B1). [化33]

{In the formula, Ra, Rb, Rc, Rd are as described above} [Chem 34]

{In the formula, Re represents a C 1-20 monovalent organic group, Rf represents a C 1-10 monovalent organic group} Ra is not particularly limited as long as it is a C 1-10 monovalent organic group, From the viewpoint of heat resistance, alkyl groups having 1 to 5 carbon atoms are preferred, and methyl, ethyl, and propyl groups are more preferred. Rb is not particularly limited as long as it is an organic group having 1 to 20 carbon atoms. From the viewpoint of resolution, an aromatic group having 6 to 20 carbon atoms and a heterocyclic compound derived from 5 to 20 carbon atoms are preferred. Monovalent organic radical. Rc is not limited as long as it is an organic group having 1 to 10 carbon atoms. Among them, from the viewpoint of resolution, it is more preferably a monovalent organic group containing a saturated alicyclic structure having 3 to 10 carbon atoms. Rd is not limited as long as it is an organic group having 1 to 10 carbon atoms. Among them, from the viewpoint of resolution, an organic group having 1 to 3 carbon atoms is preferred, and a methyl group, an ethyl group, and a propyl group are more preferred. Re is not limited as long as it is a monovalent organic group having 1 to 20 carbon atoms. Among them, from the viewpoint of chemical resistance, it is preferable to include a saturated hydrocarbon group. Rf is not limited as long as it is an organic group having 1 to 10 carbon atoms. Among them, from the viewpoint of resolution, an organic group having 1 to 3 carbon atoms is preferred, and a methyl group, an ethyl group, and a propyl group are more preferred.

(D) Compounds containing more than two alcoholic hydroxyl groups The second aspect of the compound containing two or more alcoholic hydroxyl groups is not limited as long as it has two or more alcoholic hydroxyl groups in the molecular structure. Examples of such compounds include 1,2,3-butanetriol, 1,3,5-pentanetriol, and 1,2,6-hexanetriol. If (D) compounds containing more than two alcoholic hydroxyl groups are polyalcohol compounds such as aldose, ketose, pyranose, furanose, alditol, etc., especially under high temperature environment, the oxidation of copper or copper alloy is also suppressed, Maintain tightness. It is believed that the reason is that it has a primary hydroxyl group and a large number of secondary hydroxyl groups, and these compounds are not modified at high temperatures. Specific examples of aldose include erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, Galactose, talose, etc. In addition, among the aldoses, compounds that can be converted into a pyranose structure or a furanose structure by intramolecular hemiacetal reaction can be obtained in the same manner as aldose even if they are used in a pyranose or furanose structure. Of effect. Specific examples of pyranose include allopyranose, altropyranose, glucopyranose, mannopyranose, and gulopyranose. , Idopyranose (Idopyranose), Galactopyranose (Galactopyranose), Talopyranose (Talopyranose) and so on. Specific examples of furanose include ribofuranose, arabinofuranose, xylofuranose, Lyxofuranose and the like. Specific examples of ketose include erythrulose, xylulose, ribulose, alloxanose, fructose, sorbose, tagatose, sedum heptulose, and coriose. Specific examples of alditol include glycerin, erythritol, threitol, ribitol, arabitol, xylitol, allitol, glucose alcohol, mannitol, iditol, galactose Alcohol, talitol, etc. Among them, in particular, alditols have primary hydroxyl groups at both ends, so the effects of the present invention can be obtained remarkably. By adding these compounds, when combined with the above-mentioned photopolymerization initiator, the adhesiveness with the mold resin used in the fan-out structure tends to be good.

By adding the second aspect of the present compound, the reason why the adhesion with the mold resin becomes good is not clear, but the inventors of the present invention considered as follows. Molding resin usually uses epoxy resin, etc. It is believed that the remaining epoxy group interacts with the hydroxyl group, and then the remaining nitrogen atom or sulfur atom interacts with other hydroxyl groups after the free radical of the photopolymerization initiator of the above structure is generated. Function, thereby improving adhesion. The solvent in the second aspect is selected from γ-butyrolactone, dimethyl sulfoxide, tetrahydrofuran methanol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, N,N-dimethyl Acetylacetamide, ε-caprolactone, and 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy- At least one of N,N-dimethylpropylamide. By using these solvents, the coverage of the inorganic film tends to be good, so it is preferable.

In the photosensitive resin composition of the second aspect, the components other than the above, the content of each component, and the like can be configured in the same manner as the photosensitive resin composition of the first aspect. The photosensitive resin composition of the second aspect can be used to produce a cured relief pattern in the same manner as the method of the first aspect described above. Furthermore, it is possible to provide a semiconductor device having the obtained hardened relief pattern. [Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited thereto. The physical properties of the photosensitive resin compositions in Examples, Comparative Examples and Production Examples were measured and evaluated according to the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) of each photosensitive resin is measured by gel permeation chromatography (standard polystyrene conversion). The column used in the measurement is the brand name Shodex 805M/806M connected in series by Showa Denko. The standard monodisperse polystyrene is Shodex STANDARD SM-105 made by Showa Denko Co., Ltd. The developing solvent is N-methyl-2 -Pyrrolidone, the detector uses Shodex RI-930 manufactured by Showa Denko.

(2) Absorbance measurement (A) The absorbance of the polyimide precursor is prepared with a 0.1 wt% NMP (N-methyl-2-pyrrolidone, N-methylpyrrolidone) solution, filled into a 1 cm quartz cell, and manufactured by Shimadzu Corporation The UV-1800 device was measured at a scanning speed of medium speed and a sampling interval of 0.5 nm. Here, in the case of mixing the polymers described in the two examples and comparative examples, the absorbance of the mixed polymer mixed in each weight ratio was measured.

(3) Focus margin evaluation On a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm), use a sputtering device (L-440S-FHL type, manufactured by Canon Anelva) to sequentially deposit 200 nm thick Ti , 400 nm thick Cu, and prepare to sputter Cu wafer substrate. The photosensitive resin composition was spin-coated on the above-mentioned sputtering Cu wafer substrate using a spin coating device (D-spin60A type, manufactured by SOKUDO), and heated and dried at 110°C for 180 seconds to produce a film thickness of 17 μm± 0.2 μm spin coating film.

For the spin-coated film, a reduced-exposure mask with a test pattern having a circular pattern with a mask size of 6 μm in diameter was used, and exposure was performed using an equal-magnification projection exposure apparatus PrismaGHI S/N5503 (manufactured by Ultratech). At this time, for each exposure amount, the focus was shifted by 4 μm toward the bottom of the film for exposure using the surface of the spin-coated film as a reference. Then, using cyclopentanone, the coating film formed on the sputtered Cu wafer was spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Co., Ltd.), and rinsed with propylene glycol methyl ether acetate to obtain Polyurethane round punching concave relief pattern. Furthermore, the development time of spray development is defined as a time that is 1.4 times the minimum time for development of the resin composition of the unexposed portion in the above 17 μm spin-coated film.

Can the opening of the circular punching concave relief pattern with a mask size of 15 μm obtained in the above be judged that the patterns that meet the following criteria (I) and (II) are qualified, and will form a qualified pattern The thickness of the focus margin is recorded in the results. (I) The area of the pattern opening is at least 1/2 of the area of the corresponding pattern mask opening. (II) The pattern cross-section is not crimped, undercut, swelling or bridging is not generated.

(4) Resolution evaluation: Sputtered on a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm) using a sputtering device (L-440S-FHL type, manufactured by Canon Anelva) 0.1 μm thick Al, and ready to sputter Al wafer substrate. Similarly, on a 6-inch wafer, an epoxy-based sealing material (R4000 series, manufactured by Nagase Chemtex) was applied to a thickness of approximately 150 microns, and was thermally cured at 130°C. On a sputtered Cu wafer substrate, a sputtered Al substrate, and an epoxy sealing material coated substrate, 17 μm±0.2 μm was fabricated on each substrate by the same method as the above (3) focus margin evaluation Spin the film. On this spin-coated film, use a reduced-exposure reticle with a test pattern with a circular pattern with a mask size of 12 μm in diameter and 100 μm in diameter, using an equal-magnification projection exposure device PrismaGHI S/N5503 (manufactured by Ultratech), from 200 mJ/cm ^{2 is} increased by 50 mJ/cm ² to 800 mJ/cm ² for exposure. For the sputtered Cu wafer substrate and the sputtered Al substrate, the possibility of opening is evaluated according to the judgment criteria of (3) above. The substrate coated with epoxy sealing material will be evaluated as qualified if there is no undercut in the residual pattern of 100 μm. Among all the sputtering Cu wafer substrates, sputtering Al substrates, and epoxy sealing material-coated substrates, the acceptable exposure amount was set as the exposure amount, and the range was calculated.

(5) Evaluation of chemical resistance Using a temperature-programmed curing furnace (VF-2000, manufactured by Japan, Koyo Lindberg), under a nitrogen atmosphere, the pattern obtained in the above is heat-treated at 200°C for 2 hours, thereby obtaining about 11 μm thick polyimide hardened relief pattern. For the relief pattern, the chemicals (DMSO (Dimethylsulfoxide, dimethyl sulfoxide): 70% by weight, 2-aminoethanol: 25% by weight, TMAH (Tetramethylammonium Hydroxide, tetramethylammonium hydroxide): 5 weight %) After immersion at 50°C for 5 minutes, the film thickness was measured using a Tencor P-15 step difference meter (manufactured by KLA Tencor), and compared with before the chemical treatment to calculate the dissolution rate (nm/ min).

(6) Evaluation of inorganic film coverage On a 6-inch silicon wafer, coating, exposure, development, and heat hardening were performed by the above method, thereby producing a test pattern with a film thickness of 5 μm and a via size of 7 μm. On this test pattern, 0.4 μm thick Ti was sputtered using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva) to obtain a sputtered Ti-coated polyimide hardened relief pattern. The appearance after immersing this pattern in the chemical used in the above-mentioned chemical resistance evaluation at 65°C for 30 minutes was observed. The coating of Ti was sufficient, and those who had no change in appearance were evaluated as ◎, those with visible peeling or bulging of 10% or less of the whole were rated as ○, those with 30% or less were rated as △, and those with more than 30% were rated as × .

(7) Sealing material deterioration test The R4000 series manufactured by Nagase Chemtex was prepared as an epoxy-based sealing material. Then, on the polysilicon wafer subjected to aluminum sputtering, the sealing material was spin-coated so as to have a thickness of about 150 microns, and was thermally cured at 130°C to harden the epoxy-based sealing material. On the above epoxy-based cured film, the photosensitive resin composition prepared in each example and each comparative example was applied so that the final film thickness became 10 μm. With respect to the applied photosensitive resin composition, the entire surface was exposed to the exposure conditions of 300 mJ/cm ² for Examples 9 to 16 and Comparative Example 4. Thereafter, it was thermally cured at 200° C. for 2 hours to produce a cured film of the first layer with a thickness of 10 μm.

On the cured film of the first layer, apply the photosensitive resin composition used in the formation of the cured film of the first layer, and expose the entire surface under the same conditions as the production of the cured film of the first layer. The second layer of cured film with a thickness of 10 microns is produced by thermal curing.

Using a FIB device (manufactured by Nippon Electronics Co., Ltd., JIB-4000), after cutting the cross section of the test piece after forming the cured film of the second layer, the presence or absence of pores in the epoxy resin portion was confirmed, and the degree of deterioration was evaluated. Those with no porosity were evaluated as ○, and those with no porosity were evaluated as ×.

(8) Adhesion test with sealing material The pin was erected on the sample prepared in the sealing material deterioration test, and the adhesion test was performed using a coiling tester (Quad Group, Sebastian 5 type). That is, the adhesion between the epoxy-based sealing material and the cured relief pattern produced using the photosensitive resin compositions produced in the Examples and Comparative Examples was tested. Evaluation: Adhesive strength 70 MPa or more 50 MPa or more and less than -70 MPa tight contact ○ Above 30 MPa and less than -50 MPa Less than 30 MPa tight relay×

<Production Example 1> ((A) Synthesis of Polyimide Precursor (Polymer A-1)) 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was added to a separable flask with a capacity of 2 liters, 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolene were added The ester was 400 ml, and while stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the heat generated by the reaction was completed, it was left to cool to room temperature, and then allowed to stand for 16 hours.

Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes. With stirring, a suspension prepared by suspending 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) 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 produced in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to 3 liters of ethanol to produce a precipitate containing crude polymer. The resulting crude polymer was filtered and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered and vacuum dried to obtain a powdery polymer A-1. The weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 20,000. The i-line absorbance of the 0.1 wt% solution of the polymer was 0.18.

<Production Example 2> (Synthesis of Polyimide Precursor (Polymer A-2)) In the above Production Example 1, 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 15,5.1 g of 4,4'-oxydiphthalic dianhydride. The reaction described in Example 1 was carried out in the same manner to obtain polymer A-2. The weight average molecular weight (Mw) of this polymer A-2 was measured and found to be 22,000. The i-line absorbance of the 0.1 wt% solution of the polymer is 1.2.

<Production Example 3> Mix 20.0 g of ODPA (dried at 140°C for 12 hours), 18.6 g of HEMA, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl ether, It was stirred at a temperature of 60°C for 18 hours to produce diesters of ODPA and HEMA. Then, after the obtained diester was chlorinated with SOCl ₂ , then, to the reaction mixture was added dropwise DADPE 11.08 g in 100 mL of N-methylpyrrolidone at 20 to 23° C. for 20 minutes. Solution. Then, the reaction mixture was stirred at room temperature for 1 night. Then, 5 L of water was added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was filtered and removed, and stirred again in 4 L of water for 30 minutes and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45°C for 3 days to obtain polymer A-3. The i-line absorbance of the 0.1 wt% solution of the polymer was 0.09.

<Production Example 4> In the above Production Example 1, 4,4'-diamino-2,2'-dimethylbiphenyl (90.98 g) was used instead of DADPE, and the synthesis was carried out in the same manner as in Production Example 1, except that Thus, polymer A-4 was obtained.

<Production Example 5> In the above Production Example 1, it was assumed that fumaric anhydride (229.2 g) was substituted for ODPA, and 2,2′-bis(trifluoromethyl)benzidine (148.51 g) was substituted for DADPE. 1 Synthesize in the same way to obtain polymer A-5.

Photopolymerization initiator B1: ethyl ketone 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetamide)( Brand name: IRGACURE OXE-02 (hereinafter, only expressed as "OXE-02"), manufactured by Ciba Japan) Photopolymerization initiator B2: 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]acetone-1-(O- Acetyl oxime) (trade name: PBG-304, manufactured by Changzhou Qiangli Electronics Co., Ltd.) Photopolymerization initiator B3: 3-cyclopentylacetone-1-(6-2-methylthiophene-9-ethylcarbazol-3-yl)-1-oxime acetate (trade name: PBG-314 , Manufactured by Changzhou Qiangli Electronics Co., Ltd.) Photopolymerization initiator B4: 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzyl oxime) (trade name: (PBG-305, manufactured by Changzhou Qiangli Electronics Co., Ltd.) Photopolymerization initiator B5: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime Polymerization inhibitor C1: 4-methoxyphenol Polymerization inhibitor C2: 2-nitroso-1-naphthol Compounds containing more than 2 alcoholic hydroxyl groups D1: Xylitol D2: D-glucose Solvent E1: γ-butyrolactone Solvent E2: dimethyl sulfoxide

<Example 1> Dissolve 100 g of polymer A-1 as component (A), starter B1 (4 g) as component (B), and 14 g of tetraethylene glycol dimethacrylate (M4G) as other components in In a mixed solvent (weight ratio 75:25) containing γ-butyrolactone and DMSO, the amount of solvent was adjusted so that the viscosity became about 35 poises, thereby preparing a photosensitive resin composition solution. The composition was evaluated by the above method. The evaluation results are shown in Table 1.

<Examples 2 to 8, Comparative Examples 1 to 3> Except having prepared the resin composition solution at the ratio described in Table 1, it evaluated by the method similar to Example 1 except having used. The evaluation results are shown in Table 1.

[Table 1]

It is clear from Table 1 that in the examples satisfying the conditions of the first aspect of the present invention, good results were obtained regarding the focus margin, resolution, and chemical resistance, but in the comparative examples, they were not obtained Full results.

<Examples 9 to 16, Comparative Example 4> A resin composition solution was prepared at the ratio described in Table 2 and evaluated by the above method. The evaluation results are shown in Table 2.

[Table 2]

It is clear from Table 2 that in the examples satisfying the conditions of the second aspect of the present invention, both the sealing material deterioration test and the adhesion test to the sealing material obtained good results, but in the comparative examples, they were not obtained Full results.

The embodiment of the present invention has been described above, but the present invention is not limited to this, and can be appropriately modified within the scope not departing from the gist of the invention. [Industry availability]

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

Claims (30)

A photosensitive resin composition characterized by containing the following components: (A) A polyimide precursor with an i-line absorbance of 0.1 wt% N-methylpyrrolidone solution of 0.1 to 0.6; and (B) A photopolymerization initiator having a carbazole structure. The photosensitive resin composition according to claim 1, wherein the i-line absorbance of the 0.1 wt% solution of the (A) polyimide precursor is 0.18 to 0.6. The photosensitive resin composition according to claim 1 or 2, wherein the above (B) photopolymerization initiator has a structure represented by the following general formula (B): [Chem. 1]

(In the formula, Ra represents a C 1-10 monovalent organic group, Rb represents a C 1-20 organic group, Rc represents a C 1-10 organic group, Rd represents a C 1-10 organic group) . The photosensitive resin composition according to claim 3, wherein the (B) photopolymerization initiator contains a saturated alicyclic structure in which Rc in the general formula (B) has 3 to 10 carbon atoms. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (A) component is a polyimide precursor containing the structure represented by the following general formula (A1): [Chem 2]

{In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are each independently a hydrogen atom, and the following general formula (R1): [Chem 3]

(In the general formula (R1), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10) , Or a saturated aliphatic group having 1 to 4 carbon atoms; wherein, both of R ₁ and R ₂ will not be hydrogen atoms at the same time}. The photosensitive resin composition according to claim 5, wherein the above X contains the following structure: [化4]

. The photosensitive resin composition according to claim 5, wherein the above X contains the following structure: [化5]

. The photosensitive resin composition according to any one of claims 5 to 7, wherein the above Y contains the following structure:

. The photosensitive resin composition according to any one of claims 5 to 7, wherein the above Y contains the following structure: [化7]

. The photosensitive resin composition according to claim 5, wherein the above X contains the following structure:

, The above Y contains the following structure: [Chem 9]

. The photosensitive resin composition according to any one of claims 1 to 10, which further contains (C) a polymerization inhibitor. The photosensitive resin composition according to claim 11, wherein the above (C) polymerization inhibitor is selected from compounds containing aromatic hydroxyl groups, nitroso compounds, N-oxide compounds, quinone compounds, N-oxy compounds, And at least one of the phenol thiol compounds. The photosensitive resin composition according to claim 11 or 12, wherein the (C) polymerization inhibitor is a compound containing an aromatic hydroxyl group. The photosensitive resin composition according to any one of claims 1 to 13, which further contains (D) a compound containing two or more alcoholic hydroxyl groups. The photosensitive resin composition according to claim 14, wherein the compound (D) containing more than two alcoholic hydroxyl groups is selected from the group consisting of aldose, ketose, pyranose, furanose, and alditol At least one of them. The photosensitive resin composition according to any one of claims 11 to 15, wherein the total content of the (B) component and (C) component is 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) component. The photosensitive resin composition according to any one of claims 1 to 16, wherein the i-line absorbance of the above 0.1 wt% solution of the (A) polyimide precursor is 0.18 to 0.5. The photosensitive resin composition according to any one of claims 1 to 17, wherein the i-line absorbance of the 0.1 wt% solution of the (A) polyimide precursor is 0.18 to 0.4. The photosensitive resin composition according to any one of claims 1 to 18, wherein the above-mentioned 0.1 wt% solution of the (A) polyimide precursor has an i-line absorbance of 0.18 to 0.3. The photosensitive resin composition according to any one of claims 1 to 19, wherein the i-line absorbance of the above-mentioned 0.1 wt% solution of the (A) polyimide precursor is 0.18 to 0.2. The photosensitive resin composition according to any one of claims 1 to 20, wherein the i-line absorbance of the above 0.1 wt% solution of the (A) polyimide precursor is DA, When the i-line absorbance of the 0.001 wt% N-methylpyrrolidone solution of the above (B) photopolymerization initiator is set to DB, The sum of the aforementioned DA and DB (DA+DB) is 0.25 to 0.90. A method for producing polyimide, which comprises curing the photosensitive resin composition according to any one of claims 1 to 21. A method for manufacturing a hardened relief pattern is characterized by the following steps: (1) A coating step, which coats the photosensitive resin composition according to any one of claims 1 to 21 on a substrate, and forms a photosensitive resin layer on the substrate; (2) An exposure step, which exposes the photosensitive resin layer; (3) A development step, which develops the exposed photosensitive resin layer to form a relief pattern; and (4) A heating step of forming a hardened relief pattern by subjecting the relief pattern to heat treatment. A semiconductor device characterized by having a hardened relief pattern obtained by the manufacturing method according to claim 23. A photosensitive resin composition characterized by containing the following components: (A) Polyimide precursor, which is represented by the following general formula (A1):

{In the formula, X is a tetravalent organic group, Y is a divalent organic group, R ₁ and R ₂ are each independently a hydrogen atom, and the following general formula (R1): [Chem 11]

(In the general formula (R1), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer selected from 2 to 10) , Or a saturated aliphatic group having 1 to 4 carbon atoms; wherein, both of R ₁ and R ₂ are not simultaneously hydrogen atoms}; (B) a photopolymerization initiator, which is represented by the following general formula (B) Means: [化12]

{(In the formula, Ra represents a C 1-10 monovalent organic group, Rb represents a C 1-20 organic group, Rc represents a C 1-10 organic group, Rd represents a C 1-10 organic group )} or (B1) means: [Chem 13]

{In the formula, Re represents a monovalent organic group having 1 to 20 carbon atoms, and Rf represents an organic group having 1 to 10 carbon atoms}; (D) a compound containing two or more alcoholic hydroxyl groups; and (E) selected from γ- Butyrolactone, dimethyl sulfoxide, tetrahydrofuran methanol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, N,N-dimethyl acetoacetamide, ε-caprolactone , And 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide At least one solvent in the group. The photosensitive resin composition according to claim 25, which comprises (E) at least two solvents selected from the above group. The photosensitive resin composition according to claim 25 or 26, wherein the above Y contains the following structure:

Or the following structure: [Chem 15]

{In the formula, A represents an organic group having 1 to 6 carbon atoms which may contain a halogen atom}. A method for producing polyimide, which comprises hardening the photosensitive resin composition according to any one of claims 25 to 27. A method for manufacturing a hardened relief pattern is characterized by the following steps: (1) A coating step, which applies the photosensitive resin composition according to any one of claims 25 to 27 on a substrate, and forms a photosensitive resin layer on the substrate; (2) An exposure step, which exposes the photosensitive resin layer; (3) A development step, which develops the exposed photosensitive resin layer to form a relief pattern; and (4) A heating step of forming a hardened relief pattern by subjecting the relief pattern to heat treatment. A semiconductor device characterized by having a hardened relief pattern obtained by the manufacturing method of claim 29.