Photosensitive resin composition and use thereof

Abstract

This invention provides a photosensitive resin composition and its application. The photosensitive resin composition comprises a photosensitive polyimide precursor (A) and a photoinitiator (B). The photoinitiator (B) comprises a combination of a fluorene oxime ester photoinitiator (B1) and other photoinitiators (B2) according to the following formula. The other photoinitiators (B2) comprise a ketoxime ester photoinitiator (B2-1) or an aminoketone photoinitiator (B2-2). This invention uses a relatively high-sensitivity photoinitiator (B1) to match other types of photoinitiators (B2), which can effectively widen the lithography window and improve the residual film yield, resulting in a significant improvement in lithography pattern and lithography effect.

Description

Technical Field

[0001] This invention belongs to the field of photocurable materials technology, specifically, it relates to a photosensitive resin composition and its application, and more particularly to a photosensitive resin composition with excellent exposure performance and its application. Background Technology

[0002] Photosensitive polyimide (PSPI) is a class of high-performance polymers with excellent comprehensive properties. Depending on the application, polyimide must meet complex performance requirements, such as high temperature stability, low dielectric constant, low stress accumulation, mechanical stability, high elongation at break and flexibility, excellent adhesion, good planarization properties, low water absorption and chemical resistance, etc. Photolithography effect is its basic property, and good photolithography effect is the primary condition for a good photosensitive polyimide composition. Therefore, widening the photolithography window of photosensitive polyimide composition and improving the residual film yield are of great significance for its application. Summary of the Invention

[0003] To address the shortcomings of existing technologies, the present invention aims to provide a photosensitive resin composition and its applications. The present invention employs a relatively high-sensitivity photoinitiator (B1) matched with other lower-sensitivity photoinitiators (B2), which effectively widens the photolithography window and improves the residual film yield, significantly enhancing the photolithography pattern and photolithography effect.

[0004] To achieve this objective, the present invention adopts the following technical solution:

[0005] On one hand, the present invention provides a photosensitive resin composition comprising a photosensitive polyimide precursor (A) and a photoinitiator (B);

[0006] The photoinitiator (B) comprises a combination of a fluorene oxime ester photoinitiator (B1) and other photoinitiators (B2) of the following formula, wherein the other photoinitiator (B2) comprises a ketooxime ester photoinitiator (B2-1) or an aminoketone photoinitiator (B2-2):

[0007]

[0008] In general formula (B1), R7 and R8 independently represent any one of C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl or C4-C20 alkylcycloalkyl or C7-C20 aryl, or at least one hydrogen atom in the above groups is substituted by one or a combination of at least two of halogen, nitro, carboxyl, sulfonic acid, cyano or alkoxy.

[0009] R9 is any one of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl, C4-C20 alkylcycloalkyl, C3-C20 olefin or C3-C20 polyolefin.

[0010] Where R 10 It represents any one of hydrogen, nitro, cyano, or C1-C20 alkoxy, or any one of C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl or C4-C20 alkylcycloalkyl, furanoyl, thiophenoyl, benzoyl, or substituted benzoyl, wherein the substituent in the substituted benzoyl is selected from at least one of C1-C20 straight-chain alkyl, C1-C20 branched-chain alkyl, phenyl, or halogen.

[0011] In general formula (B2-1), R 11 R 12 Each of the above groups independently represents any one of C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl or C4-C20 alkylcycloalkyl or C7-C20 aryl, or at least one hydrogen atom in the above groups is substituted by one or a combination of at least two of halogen, nitro, carboxyl, sulfonic acid, cyano or alkoxy.

[0012] R13 independently represents any one of hydrogen, nitro, carboxyl, sulfonic acid, cyano, methylthio, or C1-C10 alkoxy, or any one of C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl or C4-C20 alkylcycloalkyl, furanoyl, thiophenoyl, benzoyl, or substituted benzoyl, wherein the substituent in the substituted benzoyl is at least one of C1-C20 straight-chain alkyl, C1-C20 branched-chain alkyl, phenyl, or halogen;

[0013] In general formula (B2-2), R 14 It represents any one of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl, C4-C20 alkylcycloalkyl, C1-C20 alkoxy, C4-C20 alkylepoxyalkyl, C3-C20 olefin or C3-C20 polyolefin;

[0014] Where R 15It represents any one of hydrogen, nitro, carboxyl, sulfonic acid, cyano, C1-C10 alkoxy, or any one of C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl, C4-C20 alkylcycloalkyl, furanoyl, thiophenecarboxyl, benzoyl or substituted benzoyl, wherein the substituent of the substituted benzoyl is at least one of C1-C20 straight-chain alkyl, C1-C20 branched alkyl, phenyl or halogen.

[0015] Preferably, R7 is hydrogen, methyl, ethyl, propyl, butyl, or... The wavy line represents the connection site of the functional group.

[0016] Preferably, R8 is methyl, ethyl, propyl, The wavy line represents the connection site of the functional group.

[0017] Preferably, R9 is hydrogen, methyl, ethyl, propyl, n-butyl, or allyl.

[0018] Preferably, R 10 For hydrogen, nitro, The wavy line represents the connection site of the functional group.

[0019] Preferably, R 11 Methyl, methoxy, ethoxy, C3-C10 alkoxy, or The wavy line represents the connection site of the functional group.

[0020] Preferably, R 12 Methyl, ethyl, vinyl, The wavy line represents the connection site of the functional group.

[0021] Preferably, R 13 It is hydrogen, methyl, ethyl or methoxy, methylthio or The wavy line represents the connection site of the functional group.

[0022] Preferably, R 14 It can be hydrogen, methyl, ethyl, propyl, n-butyl, allyl, or The wavy line represents the connection site of the functional group.

[0023] Preferably, R 15 For hydrogen, nitro, The wavy line represents the connection site of the functional group.

[0024] Preferably, the fluorene oxime ester-containing photoinitiator (B1) may be any one of the following compounds, including but not limited to:

[0025]

[0026]

[0027] Preferably, the ketooxime ester photoinitiator (B2-1) may be any one of the following compounds, including but not limited to:

[0028]

[0029] Preferably, the aminoketone photoinitiator may be any one of the following compounds, including but not limited to:

[0030]

[0031] Preferably, the content of the fluorenoxime ester-containing photoinitiator (B1) is 0.1-6.0% of the weight of the photosensitive polyimide precursor (A), for example, 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, or 6%; and the content of the other photoinitiator (B2) is 0.1-12% of the weight of the photosensitive polyimide precursor (A), for example, 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 5%, 8%, 10%, or 12%.

[0032] Preferably, the content of the fluorenoxime ester-containing photoinitiator (B1) is 0.3-5.0% of the weight of the photosensitive polyimide precursor (A); and the content of other photoinitiators (B2) is 0.5-8.0% of the weight of the photosensitive polyimide precursor (A).

[0033] Preferably, the weight ratio of the fluorenoxime ester photoinitiator (B1) to other photoinitiators (B2) is 1:0.2-1:30, for example, 1:0.2, 1:0.5, 1:1, 1:2, 1:5, 1:8, 1:10, 1:12, 1:14, 1:15, 1:17, 1:18, 1:19, 1:20, 1:22, 1:25, 1:26, 1:27, 1:28, 1:29 or 1:30, and more preferably 1:0.5-1:20.

[0034] Preferably, the photosensitive polyimide precursor (A) has a structural unit of the following structural formula (1):

[0035]

[0036] In general formula (1), n ​​is an integer from 3 to 100 (e.g., 3, 4, 5, 8, 10, 13, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100), and R1 and R2 independently represent a hydrogen atom or the general formula structure (a).

[0037]

[0038] In structure (a), A1, A2, and A3 each independently represent a hydrogen atom, or any one of a C1-C10 alkyl group, a C4-C10 alkylcycloalkyl group, a C4-C10 cycloalkylalkyl group, a phenyl group, or a substituted phenyl group; n1 is an integer from 2 to 10 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0039] In general formula (1), X is a tetravalent organic group, preferably a combination of one or at least two structures in (2):

[0040]

[0041] R3 can represent an ether bond (-O-), a thioether bond (-S-), or an alkyl chain. It can also represent phenyl or phenyl-substituted groups (phenyl ether or phenyl thioether groups), for example, phenyl groups with ether bonds -O- or thioether bonds -S-, preferably the following structure (3).

[0042]

[0043] In general formula (1), Y is a divalent organic group, preferably a combination of one or more of (4).

[0044]

[0045] Among them, R4 and R5 are hydrogen, alkyl, heteroatoms (O, N, S, etc.) or trifluoromethyl, and R6 is carbonyl, sulfone, sulfoxide, oxygen or sulfur, etc.

[0046] Furthermore, the molar ratio of X and Y in the photosensitive polyimide precursor (A) ranges from 1.5 to 0.5:1, for example, 1.5:1, 1.3:1, 1.1:1, 1:1, 0.8:1, 0.7:1, 0.6:1 or 0.5:1, preferably 1.0 to 0.7.

[0047] Preferably, the weight-average molecular weight of the photosensitive polyimide precursor is 5,000-100,000 (using polystyrene as a standard, tested by gel chromatography), for example 5,000, 8,000, 10,000, 30,000, 50,000, 80,000 or 100,000.

[0048] Preferably, the photosensitive resin composition further includes a sensitizer (C) that can effectively improve the photolithography window.

[0049] Preferably, the sensitizer (C) can be any one or a combination of at least two of the following: aminobenzophenone series sensitizers, phenyldiolamine series sensitizers, coumarin series sensitizers, or acridine series compounds.

[0050] Preferably, the sensitizer (C) is selected from any one or a combination of at least two of the following compounds:

[0051]

[0052]

[0053] Preferably, the photosensitive resin composition further includes a photocrosslinker (D).

[0054] Preferably, the photocrosslinking agent is any one or at least a combination of two acrylate compounds.

[0055] Preferably, the acrylate compound is a bifunctional acrylate compound with the general structural formula shown in (9):

[0056]

[0057] Where R 16 It is hydrogen or C1-C5 alkyl; R 17 for etc.; or substituents on the above groups in which any hydrogen is replaced (substituents are OH, C1-C5 alkyl, phenyl, phenyl substituents, etc.), R 17 The terminal O is connected to the carbonyl group in the general formula (9), R 17 The terminal methylene group is attached to an oxygen in the general formula (9), where m is an integer from 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10).

[0058] Preferably, the difunctional acrylate may be selected from: polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, alkyl diacrylate, hydroxyl-containing alkyl diacrylate, hexanediol diacrylate or nonanediol diacrylate, etc., preferably polyethylene glycol dimethacrylate or polyethylene glycol diacrylate.

[0059] Preferably, the structural formulas of other polyfunctional acrylates are shown in (10), (11), and (12):

[0060]

[0061] In general formulas (10), (11), and (12), Z1 is hydrogen, a C1-C20 straight-chain alkyl group, or a C1-C20 branched alkyl group; Z2 is selected from C1-C20 straight-chain alkyleneoxy groups or C1-C20 branched alkyleneoxy groups; Z3 is selected from hydrogen, hydroxyl group, C1-C20 straight-chain alkyl group, C1-C20 branched alkyl group, C1-C20 straight-chain alkoxy group, or C1-C20 branched alkoxy group; and Z4 is selected from hydrogen, C1-C5 straight-chain alkyl group, C1-C5 branched alkyl group, or... n2 is any integer from 0 to 20 (e.g., 0, 2, 5, 8, 10, 12, 14, 15, 18, or 20).

[0062] Preferably, the multifunctional acrylate may be selected from trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol acrylate, and (13-EO) dipentaerythritol hexamethacrylate.

[0063] Preferably, the photosensitive resin composition further includes a thermal crosslinking agent (E).

[0064] Preferably, the thermal crosslinking agent (E) contains Group, wherein R 18 Indicates hydrogen, C1-C 20 Straight-chain alkyl, C3-C 20 cycloalkyl, C4-C 20 cycloalkyl or C4-C 20 Any one of alkyl, cycloalkyl, phenyl, or phenyl substituents.

[0065] Preferably, the thermal crosslinking agent (E) is selected from:

[0066]

[0067] Any one or at least two of them.

[0068] Preferably, the amount of the thermal crosslinking agent (E) added is 0.5-10% of the mass of the photosensitive polyimide precursor, for example, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0069] Furthermore, the photosensitive resin composition further includes an organic solvent (F).

[0070] Preferably, the organic solvent is one or a combination of at least two of the following: amides, lactones, sulfoxides, ketones, ethers, halogenated hydrocarbons, hydrocarbons, and tetramethylurea solvent.

[0071] Preferably, the organic solvent may include, but is not limited to, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, or ethyl lactate.

[0072] Preferably, the amount of organic solvent added is 50 to 1000 parts by weight relative to 100 parts by weight of (A) photosensitive polyimide precursor, for example, 50 parts by weight, 100 parts by weight, 300 parts by weight, 500 parts by weight, 800 parts by weight, 900 parts by weight or 1000 parts by weight.

[0073] On the other hand, the present invention provides a photoresist film layer, which is prepared from the photosensitive resin composition described above.

[0074] The photoresist film layer is obtained by mixing the components of the photosensitive resin composition as described above, filtering the completely dissolved composition, and coating it onto a substrate to obtain a thin film.

[0075] Preferably, the photoresist film is any one of an interlayer insulating film, a cover film, or a surface protective film.

[0076] On the other hand, the present invention provides a method for manufacturing a photoresist cured pattern, wherein the method comprises coating a resin composition as described above onto a substrate to obtain a thin film, subjecting it to light irradiation and development to obtain a photosensitive resin pattern, and then heat-treating to obtain a cured pattern.

[0077] On the other hand, the present invention provides an electronic component comprising the photoresist film as described above.

[0078] Compared with the prior art, the present invention has the following beneficial effects:

[0079] The photosensitive resin composition of the present invention can effectively widen the exposure window and improve the residual film rate, optimize the photolithography pattern, greatly improve the photolithography effect, and is very beneficial to the subsequent application of the photosensitive resin composition. Detailed Implementation

[0080] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0081] The beneficial effects of this application will be further illustrated below with reference to embodiments and comparative examples.

[0082] The list of substances in the embodiments is shown in Table 1 below.

[0083] Table 1

[0084]

[0085]

[0086] Example 1

[0087] In a 500ml reactor, 200g of organic solvent F (200g of N-methyl-2-pyrrolidone), photoinitiator B ((B1-1): 0.3g, (B2-1): 8g), 2.0g of sensitizer C ((C-1): 2g), 10g of photocrosslinking agent D (polyethylene glycol diacrylate), 1.0g of thermal crosslinking agent E, and 100g of polyimide resin precursor A1 were added sequentially. The mixture was stirred and dissolved under dry nitrogen at 23℃±2℃ in the yellow light region until it was completely dissolved into a homogeneous system. The dissolved solution was then filtered through a 0.2μm filter membrane to obtain a photosensitive polyimide resin composition.

[0088] Example 2

[0089] The photoinitiator B1-1 was changed from 0.3g to 0.5g, and the rest was the same as in Example 1.

[0090] Example 3

[0091] The photoinitiator was changed to (B1-1: 2.5g; B2-1: 5g), and the rest was the same as in Example 1.

[0092] Example 4

[0093] The photoinitiator was changed to (B1-1: 5.0g; B2-1: 1.0g), and the rest was the same as in Example 1.

[0094] Example 5

[0095] Remove sensitizer C-1, otherwise the same as in Example 3.

[0096] Example 6

[0097] Replace B2-1 with B2-2 in the photoinitiator, otherwise the same as in Example 1.

[0098] Example 7

[0099] Replace B2-1 with B2-2 in the photoinitiator, otherwise the same as in Example 2.

[0100] Example 8

[0101] The photoinitiator B2-1 was replaced with B2-2, and everything else was the same as in Example 3.

[0102] Example 9

[0103] The photoinitiator B2-1 was replaced with B2-2, and everything else remained the same as in Example 4.

[0104] Example 10

[0105] Replace B2-1 with B2-2 in the photoinitiator, otherwise the same as in Example 5.

[0106] Example 11

[0107] The sensitizer C-1 (2.0g) was replaced with sensitizer C-2 (5.0g), and everything else was the same as in Example 1.

[0108] Example 12

[0109] The sensitizer C-1 (2.0g) was replaced with sensitizer C-2 (5.0g), and the rest was the same as in Example 2.

[0110] Example 13

[0111] The sensitizer C-1 (2.0g) was replaced with sensitizer C-2 (5.0g), and the rest was the same as in Example 3.

[0112] Example 14

[0113] The sensitizer C-1 (2.0g) was replaced with sensitizer C-2 (5.0g), and the rest was the same as in Example 4.

[0114] Example 15

[0115] The sensitizer C-1 (2.0g) was replaced with sensitizer C-3 (5.0g), and the rest was the same as in Example 1.

[0116] Example 16

[0117] The sensitizer C-1 (2.0g) was replaced with sensitizer C-3 (5.0g), and the rest was the same as in Example 4.

[0118] Example 17

[0119] The sensitizer C-1 (2.0g) was replaced with sensitizer C-2 (5.0g), and the rest was the same as in Example 6.

[0120] Example 18

[0121] The sensitizer C-1 (2.0g) was replaced with sensitizer C-2 (5.0g), and the rest was the same as in Example 9.

[0122] Example 19

[0123] Replace B1-1 with B1-2 in the photoinitiator, otherwise the same as in Example 1.

[0124] Example 20

[0125] Replace B1-1 with B1-2 in the photoinitiator, otherwise the same as in Example 2.

[0126] Example 21

[0127] Replace B1-1 with B1-2 in the photoinitiator, otherwise the same as in Example 3.

[0128] Example 22

[0129] Replace B1-1 with B1-2 in the photoinitiator, otherwise the same as in Example 4.

[0130] Example 23

[0131] Replace B1-1 with B1-2 in the photoinitiator, otherwise the same as in Example 5.

[0132] Example 24

[0133] The sensitizer C-1 (2.0g) was replaced with sensitizer C-2 (5.0g), and the rest was the same as in Example 19.

[0134] Example 25

[0135] The sensitizer C-1 (2.0g) was replaced with sensitizer C-2 (5.0g), and the rest was the same as in Example 22.

[0136] Example 26

[0137] Replace sensitizer C-2 with sensitizer C-3, otherwise the same as in Example 24.

[0138] Example 27

[0139] Replace sensitizer C-2 with sensitizer C-3, otherwise the same as in Example 25.

[0140] Example 28

[0141] Replace B2-1 with B2-2 in the photoinitiator, otherwise the same as in Example 19.

[0142] Example 29

[0143] Replace B2-1 with B2-2 in the photoinitiator, otherwise the same as in Example 22.

[0144] Example 30

[0145] Replace B2-1 with B2-2 in the photoinitiator, otherwise the same as in Example 23.

[0146] Example 31

[0147] Replace B1-2 with B1-3 in the photoinitiator, otherwise the same as in Example 19.

[0148] Example 32

[0149] Replace B1-2 with B1-3 in the photoinitiator, otherwise the same as in Example 22.

[0150] Example 33

[0151] Replace B1-2 with B1-3 in the photoinitiator, otherwise the same as in Example 23.

[0152] Example 34

[0153] Replace B2-1 with B2-2 in the photoinitiator, otherwise the same as in Example 31.

[0154] Example 35

[0155] Replace B2-1 with B2-2 in the photoinitiator, otherwise the same as in Example 32.

[0156] Example 36

[0157] Replace B2-1 with B2-2 in the photoinitiator, otherwise the same as in Example 33.

[0158] Comparative Example 1

[0159] The photoinitiator was changed to (B1-1:0.1g; B2-1:10g), and the rest was the same as in Example 1.

[0160] Comparative Example 2

[0161] The photoinitiator was changed to (B1-1:6g; B2-1:1g), and the rest was the same as in Example 5.

[0162] Comparative Example 3

[0163] The photoinitiator was changed to (B1-1:7.5g), and everything else was the same as in Example 5.

[0164] Comparative Example 4

[0165] The photoinitiator was changed to (B2-1:7.5g), and everything else was the same as in Example 5.

[0166] Comparative Example 5

[0167] The photoinitiator was changed to (B2-2: 7.5g), and everything else was the same as in Example 8.

[0168] Comparative Example 6

[0169] The photoinitiator was changed to (B1-1: 7.5g), and everything else was the same as in Example 8.

[0170] Comparative Example 7

[0171] The photoinitiator was changed to (B1-1: 0.3g, B2-1: 10g), and the rest was the same as in Example 3.

[0172] Comparative Example 8

[0173] The sensitizer C-2 (5.0 g) was added, and the rest was the same as in Comparative Example 3.

[0174] Comparative Example 9

[0175] The photoinitiator was changed to (B1-2: 7.5g), and everything else was the same as in Comparative Example 1.

[0176] Comparative Example 10

[0177] The photoinitiator was changed to (B1-3: 7.5g), and the sensitizer C-3 (5.0g) was added. Other aspects were the same as in Comparative Example 3.

[0178] The photolithographic windows of the photosensitive polyimide resin compositions of the examples and comparative examples were evaluated using the following evaluation method: The photosensitive polyimide resin compositions of the examples and comparative examples were placed in a clean room at 23±2℃ and 50±10%RH, and spin-coating, pre-baking, photolithography, development, and post-baking were performed under the same conditions. The film thickness was measured during the process. After post-baking, the window was checked using OM and the cross-sectional images were observed under SEM to confirm the photolithographic windows.

[0179] Performance evaluation:

[0180] Test method for photosensitive resin composition on silicon surface photolithography window: The photosensitive polyimide resin composition was coated onto the surface of an 8-inch silicon wafer using a fully automated coating and developing machine (3000 rpm, 30 s), followed by pre-baking (110℃, 180 s). After pre-baking, full exposure was performed using a stepper exposure machine (Dose: 600 mJ / cm²). 2 (Focus: -15μm to +15μm) and then continue to develop using a fully automatic coating and developing machine (90s). After baking and cooling, the wafer is inspected by OM (15μm round hole) to confirm that there are no shrinkage cavities, no residual glue, no undercut, and no footing breakage in the normal development window. Then, the normal window range is inspected by cross section (SEM or FIB) to confirm that the cross section pattern and angle are normal, and the photolithography window range is further determined.

[0181] The test results are shown in Tables 1-5.

[0182] Table 1

[0183]

[0184]

[0185] Table 2

[0186]

[0187] Table 3

[0188]

[0189]

[0190] Table 4

[0191]

[0192] Table 5

[0193]

[0194]

[0195] Remark:

[0196] 1. Residual film rate (GHI line @ 500mJ / cm) 2 (Developing film thickness - flexible baking film thickness) / flexible baking film thickness * 100%, residual film rate > 90% ◎ (excellent), 86~90% ◇ (good), < 86% X (poor).

[0197] 2. GHI line lithography window: △ lithography window > 600mj / cm 2 ◎(Excellent), 400~600mj / cm 2 ◇(Good), <400mj / cm 2 X (Poor).

[0198] 3. I-line lithography window: Δ lithography window > 400 mJ / cm 2 ◎(Excellent), 300~400mj / cm 2 ◇(Good), <300mj / cm 2 X (Poor).

[0199] 4. The above ◎ (excellent) and ◇ (good) are usable; X (poor) is unusable.

[0200] As can be seen from the table above, the photolithographic windows of the comparative example photosensitive polyimide resin compositions are all relatively narrow, and the residual film rates of comparative examples 1 and 6 are also very low. However, the examples using a combination of high and low sensitivity photoinitiators within a certain proportion range show improved photolithographic windows and residual film rates, achieving excellent results.

[0201] The applicant declares that the present invention is illustrated by the above embodiments to demonstrate the photosensitive resin composition and its application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises a photosensitive polyimide precursor (A) and a photoinitiator (B); The photoinitiator (B) comprises a combination of a fluorene oxime ester photoinitiator (B1) and other photoinitiators (B2) of the following formula, wherein the other photoinitiator (B2) comprises a ketooxime ester photoinitiator (B2-1) or an aminoketone photoinitiator (B2-2): In general formula (B1), R7 and R8 independently represent any one of C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl or C4-C20 alkylcycloalkyl or C7-C20 aryl, or at least one hydrogen atom in the above groups is substituted by one or a combination of at least two of halogen, nitro, carboxyl, sulfonic acid, cyano or alkoxy. R9 is any one of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl, C4-C20 alkylcycloalkyl, C3-C20 olefin or C3-C20 polyolefin. Where R 10 It represents any one of hydrogen, nitro, cyano, or C1-C20 alkoxy, or any one of C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl or C4-C20 alkylcycloalkyl, furanoyl, thiophenoyl, benzoyl, or substituted benzoyl, wherein the substituent in the substituted benzoyl is selected from at least one of C1-C20 straight-chain alkyl, C1-C20 branched-chain alkyl, phenyl, or halogen. In general formula (B2-1), R 11 R 12 Each of the above groups independently represents any one of C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl or C4-C20 alkylcycloalkyl or C7-C20 aryl, or at least one hydrogen atom in the above groups is substituted by one or a combination of at least two of halogen, nitro, carboxyl, sulfonic acid, cyano or alkoxy. Where R 13 Independently represented by any one of hydrogen, nitro, carboxyl, sulfonic acid, cyano, methylthio, or C1-C10 alkoxy, or any one of C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl or C4-C20 alkylcycloalkyl, furanoyl, thiophenoyl, benzoyl, or substituted benzoyl, wherein the substituent in the substituted benzoyl is at least one of C1-C20 straight-chain alkyl, C1-C20 branched-chain alkyl, phenyl, or halogen; In general formula (B2-2), R 14 It represents any one of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl, C4-C20 alkylcycloalkyl, C1-C20 alkoxy, C4-C20 alkylepoxyalkyl, C3-C20 olefin or C3-C20 polyolefin; Where R 15 It represents any one of hydrogen, nitro, carboxyl, sulfonic acid, cyano, C1-C10 alkoxy, or any one of C1-C20 alkyl, C3-C20 cycloalkyl, C4-C20 cycloalkylalkyl, C4-C20 alkylcycloalkyl, furanoyl, thiophenecarboxyl, benzoyl or substituted benzoyl, wherein the substituent of the substituted benzoyl is at least one of C1-C20 straight-chain alkyl, C1-C20 branched alkyl, phenyl or halogen.

2. The photosensitive resin composition according to claim 1, characterized in that, R7 represents hydrogen, methyl, ethyl, propyl, butyl, The wavy line represents the connection site of the functional group; Preferably, R8 is methyl, ethyl, propyl, The wavy line represents the connection site of the functional group; Preferably, R9 is hydrogen, methyl, ethyl, propyl, n-butyl, or allyl; Preferably, R 10 For hydrogen, nitro, The wavy line represents the connection site of the functional group; Preferably, R 11 It is methyl, methoxy, ethoxy, C3-C10 alkoxy or The wavy line represents the connection site of the functional group; Preferably, R 12 Methyl, ethyl, vinyl, The wavy line represents the connection site of the functional group; Preferably, R 13 It is hydrogen, methyl, ethyl or methoxy, methylthio or The wavy line represents the connection site of the functional group; Preferably, R 14 It can be hydrogen, methyl, ethyl, propyl, n-butyl, allyl, or The wavy line represents the connection site of the functional group; Preferably, R 15 For hydrogen, nitro, The wavy line represents the connection site of the functional group.

3. The photosensitive resin composition according to claim 1 or 2, characterized in that, The fluorene oxime ester-containing photoinitiator (B1) is any one of the following compounds: Preferably, the ketooxime ester photoinitiator (B2-1) is any one of the following compounds: Preferably, the aminoketone photoinitiator (B2-2) is any one of the following compounds:

4. The photosensitive resin composition according to any one of claims 1-3, characterized in that, The content of the fluorenoxime ester-containing photoinitiator (B1) is 0.1-6.0% of the weight of the photosensitive polyimide precursor (A), and the content of the other photoinitiator (B2) is 0.1-12% of the weight of the photosensitive polyimide precursor (A). Preferably, the content of the fluorenoxime ester-containing photoinitiator (B1) is 0.3-5.0% of the weight of the photosensitive polyimide precursor (A); and the content of other photoinitiators (B2) is 0.5-8.0% of the weight of the photosensitive polyimide precursor (A).

5. The photosensitive resin composition according to any one of claims 1-4, characterized in that, The weight ratio of the fluorenoxime ester-containing photoinitiator (B1) to other photoinitiators (B2) is 1:0.2-1:20, preferably 1:0.5-1:

10.

6. The photosensitive resin composition according to any one of claims 1-5, characterized in that, The photosensitive polyimide precursor (A) has structural units of the following structural formula (1): In general formula (1), X is a tetravalent organic group, Y is a divalent organic group, n is an integer from 3 to 100, and R1 and R2 independently represent hydrogen atoms or the general formula structure (a). In structure (a), A1, A2, and A3 independently represent a hydrogen atom, or any one of C1-C10 alkyl, C4-C10 alkylcycloalkyl, C4-C10 cycloalkylalkyl, phenyl, or substituted phenyl; n1 is an integer from 2 to 10; Preferably, X in general formula (1) is a combination of one or at least two structures in (2): R3 is an ether bond (-O-), a thioether bond (-S-), or an alkyl chain. Alternatively, it may be a phenyl, phenyl ether, or phenyl sulfide group, preferably the following structure (3). Preferably, Y in general formula (1) is one or a combination of at least two of (4): Among them, R4 and R5 are hydrogen, alkyl, heteroatom or trifluoromethyl, and R6 is carbonyl, sulfone, sulfoxide, oxygen or sulfur; Preferably, the weight-average molecular weight of the photosensitive polyimide precursor is 5,000-100,000.

7. The photosensitive resin composition according to any one of claims 1-6, characterized in that, The photosensitive resin composition further includes a sensitizer (C); Preferably, the sensitizer (C) can be any one or a combination of at least two of the following: aminobenzophenone series sensitizers, phenyldiolamine series sensitizers, coumarin series sensitizers, or acridine series compounds; Preferably, the sensitizer (C) is selected from any one or a combination of at least two of the following compounds: Preferably, the photosensitive resin composition further includes a photocrosslinking agent (D); Preferably, the photocrosslinking agent is any one or a combination of at least two of polyfunctional acrylate compounds; Preferably, the difunctional acrylate may be selected from: polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, alkyl diacrylate, hydroxyl-containing alkyl diacrylate, hexanediol diacrylate or nonanediol diacrylate, etc., preferably polyethylene glycol dimethacrylate or polyethylene glycol diacrylate; Preferably, the multifunctional acrylate may be selected from trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol acrylate and (13-EO) dipentaerythritol hexamethacrylate. Preferably, the photosensitive resin composition further includes a thermal crosslinking agent (E); Preferably, the thermal crosslinking agent (E) contains Group, wherein R 18 Indicates hydrogen, C1-C 20 Straight-chain alkyl, C3-C 20 cycloalkyl, C4-C 20 cycloalkyl or C4-C 20 Any one of alkyl, cycloalkyl, phenyl, or phenyl substituents; Preferably, the thermal crosslinking agent (E) is selected from: Any one or at least two of them; Preferably, the amount of thermal crosslinking agent (E) added is 0.5-10% of the mass of the photosensitive polyimide precursor; Furthermore, the photosensitive resin composition further includes an organic solvent (F); Preferably, the organic solvent is one or a combination of at least two of the following: amides, lactones, sulfoxides, ketones, ethers, halogenated hydrocarbons, hydrocarbons, and tetramethylurea solvent. Preferably, the organic solvent may include, but is not limited to, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, or ethyl lactate; Preferably, the amount of organic solvent added is 50 to 1000 parts by weight relative to 100 parts by weight of (A) photosensitive polyimide precursor.

8. A photoresist film, characterized in that, The photoresist film is prepared from the photosensitive resin composition as described in any one of claims 1-7; Preferably, the photoresist film is any one of an interlayer insulating film, a cover film, or a surface protective film.

9. A method for manufacturing photoresist cured patterns, characterized in that, The method involves coating the resin composition as described in any one of claims 1-7 onto a substrate to obtain a thin film, subjecting it to light irradiation and development to obtain a photosensitive resin pattern, and then heat-treating it to obtain a cured pattern.

10. An electronic component, characterized in that, The electronic component includes the photoresist film as described in claim 8.

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