Photosensitive polyimide composition, pattern manufacturing method, cured product, and electronic component

Abstract

Disclosed are a photosensitive polyimide composition, a pattern manufacturing method, a cured product, and an electronic component. The photosensitive polyimide composition comprises: component (a): a graft polymer soluble in an alkaline aqueous solution, the graft polymer being selected from compounds represented by the following structural formula: wherein Ar1 is selected from a tetravalent organic group, Ar2 is selected from a divalent organic group, m+n = 5-200, n / (m+n) = 0.05-1, and k = 2-10; component (b): a photosensitizer; component (c): a thermal cross-linking agent comprising component (c1): a cross-linking agent containing an epoxy group, and component (c2): a cross-linking agent containing CH2OR'; and component (d): a silane coupling agent. The photosensitive polyimide composition has extremely excellent sensitivity and resolution, is capable of replicating a fine pattern, and shows low warping stress after cured at 200°C and high chemical stability and adhesiveness.

Description

Photosensitive polyimide compositions, methods for manufacturing patterns, cured products, and electronic components

[0001] Cross-reference to related applications

[0002] This application claims priority to Chinese Patent Application No. 2024115976320, filed on November 11, 2024, entitled "Photosensitive Polyimide Composition, Method for Manufacturing a Pattern, Cured Product and Electronic Component", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to the field of photosensitive dielectric materials technology, and more specifically, to photosensitive polyimide compositions, methods for manufacturing patterns, cured products, and electronic components. Background Technology

[0004] As semiconductor packaging density gradually increases, PSPI materials are also gradually developing towards low-temperature curing, high sensitivity, high resolution, and low warpage stress.

[0005] Literature reports a method of lowering the glass transition temperature of PI polymer and supplementing it with a hot alkali generating agent (WO2018225676A1). This method can achieve low-temperature curing at 200-230℃ and obtain negative PSPI cured products with excellent adhesion. However, this method cannot meet the requirements of high sensitivity, high resolution and low warpage stress.

[0006] Another literature reports the use of chemically imidized PI polymers with phenolic hydroxyl or carboxyl groups, supplemented with a suitable crosslinking agent (CN102575139A). This method can achieve low-temperature curing at 200-230℃, resulting in positive PSPI cured products with excellent chemical resistance. However, this method has very limited improvement in chemical resistance, and the sensitivity of this composition is generally low.

[0007] Another literature reports the use of polymers with phenolic hydroxyl groups, such as poly(p-hydroxystyrene) or phenolic resin, supplemented with crosslinking agents and toughened with rubber particles (WO2008026406A1), to obtain low-temperature curing at 200℃. However, this method produces compositions with faster sensitivity, higher resolution, and lower warpage stress, but the cured products obtained in this way have poor mechanical properties and limited toughness improvement, which may lead to reliability issues.

[0008] In view of this, this disclosure is hereby made. Summary of the Invention

[0009] The purpose of this disclosure is to provide a photosensitive polyimide composition, a method for manufacturing a pattern, a cured product, and an electronic component.

[0010] This disclosure is implemented as follows:

[0011] In a first aspect, this disclosure provides a photosensitive polyimide composition comprising component (a) a graft polymer soluble in an alkaline aqueous solution, selected from compounds shown in the following structural formula:

[0012] Wherein, Ar1 is selected from tetravalent organic groups, and Ar2 is selected from divalent organic groups; m+n=5~200, n / (m+n)=0.05~1, k=2~10;

[0013] Component (b) photosensitizer;

[0014] Component (c) thermal crosslinking agent; which includes component (c1) a crosslinking agent containing an epoxy group and component (c2) a crosslinking agent containing CH2OR′; R′ represents a hydrogen atom or a monovalent organic group;

[0015] Component (d) Silane coupling agent.

[0016] In a second aspect, this disclosure provides a method for manufacturing a pattern, which includes coating a photosensitive polyimide composition as described in any of the foregoing embodiments onto a support substrate.

[0017] Preferably, the process further includes: drying, exposure, development, and heat treatment sequentially after coating;

[0018] Preferably, the light source used in the exposure process is i-ray.

[0019] Thirdly, this disclosure provides a cured product formed by curing the photosensitive polyimide composition described in any one of the foregoing embodiments;

[0020] Preferably, the cured material includes a surface protective film or an interlayer insulating film.

[0021] Fourthly, this disclosure provides an electronic component, the electronic component comprising the cured material described in the foregoing embodiments.

[0022] This disclosure offers the following advantages: By selecting specific components, the resulting photosensitive polyimide composition exhibits excellent sensitivity and resolution, high chemical stability and adhesion, and low warpage stress after low-temperature curing (180-200°C). Furthermore, the portion of the photosensitive polyimide composition exposed to ultraviolet light is readily soluble in alkaline aqueous solutions, while the portion not exposed to ultraviolet light is insoluble in alkaline aqueous solutions, thus enabling the effective reproduction of fine patterns. Attached Figure Description

[0023] To more clearly illustrate the technical solutions of the embodiments of this disclosure, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this disclosure and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0024] Figure 1 is a schematic diagram of a semiconductor packaging structure provided in an embodiment of this disclosure. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of the embodiments of this disclosure clearer, the technical solutions in the embodiments of this disclosure will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0026] This disclosure provides a photosensitive polyimide composition comprising the following components:

[0027] (a) Grafted polymers soluble in alkaline aqueous solutions; (b) Photosensitizers; (c) Thermal crosslinking agents; (d) Silane coupling agents.

[0028] The photosensitive polyimide composition provided in this disclosure is readily soluble in alkaline aqueous solution for the portion exposed to ultraviolet light, while the portion not exposed to ultraviolet light is insoluble in alkaline aqueous solution, thus enabling effective reproduction of fine patterns. The photosensitive polyimide composition of this disclosure achieves excellent sensitivity and resolution by increasing the ratio of the dissolution rate of the exposed to the unexposed portion of the pattern relative to the alkaline developer (dissolution contrast). Furthermore, this photosensitive polyimide composition exhibits low warpage stress, excellent chemical resistance, and good adhesion after low-temperature curing (180-200°C).

[0029] First, the following explanation is given regarding a standard for the solubility of component (a) in an alkaline aqueous solution. A coating film with a thickness of approximately 5 μm is formed by spin-coating a photosensitive composition obtained by dissolving component (a) alone or together with other components in any solvent onto a substrate such as a silicon wafer. If this coating film is immersed in an aqueous solution of tetramethylammonium hydroxide at 20-25°C and dissolves to form a homogeneous solution, then component (a) is considered soluble in the alkaline aqueous solution.

[0030] The aforementioned alkaline aqueous solution refers to any one of tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic ammonia aqueous solution.

[0031] For grafted polymers in which component (a) is soluble in alkaline aqueous solutions, from the viewpoint of processability and heat resistance, the main chain backbone is preferably a polyimide-based polymer, and the grafted chain backbone is preferably a polyhydroxystyrene-based polymer formed from p-hydroxystyrene.

[0032] Further, component (a) is more preferably a graft copolymer of polyimide and poly(p-hydroxystyrene), a polymer having the structural unit shown in Formula 1 below:

[0033] In this embodiment, m+n represents the number of repeating structural units of component (a), and the value of m+n is 5-200. When m+n is less than 5, the viscosity of the composition is too low, making it unsuitable for use as a thick film. When m+n is greater than 200, the composition becomes too viscous, affecting coating.

[0034] m+n = 5 to 200, for example, any value between 5 and 200, such as 5, 10, 15, 20, 25, 35, 40, 50, 70, 75, 80, 85, 95, 100, 110, 120, 135, 150, 160, 175, 180, 185, 190, 195, and 200. n / (m+n) = 0.05 to 1, for example, any value between 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1, and any value between 0.05 and 1.

[0035] The solubility of component (a) in alkaline aqueous solution originates from the phenolic hydroxyl group, therefore it is preferable to contain a certain proportion or higher of this structure. That is, k = 2 to 10. For example, any value between 2 and 10, such as 2, 3, 4, 5, 6, 7, 8, 9, and 10. Excessively large k units will lead to a certain loss of film thickness in the exposed area, resulting in ineffective pattern reproduction. Therefore, by adjusting the amount of p-hydroxystyrene grafted, the dissolution rate of the polymer in alkaline aqueous solution changes, thus obtaining a photosensitive grafted composition with a suitable dissolution rate.

[0036] Furthermore, Ar1 is selected from tetravalent organic groups, for example, Ar1 is selected from any one of the tetravalent organic groups shown in Formula 2 below each time it appears:

[0037] Among them, R1-R8 are all monovalent organic groups, and X is a divalent group.

[0038] Specifically, R1-R8 are each independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl groups; for example, R1-R8 are each independently selected from, but not limited to, any one of hydrogen, fluorine atom, bromine atom, iodine atom, methyl, ethyl, isopropyl, tert-butyl, isobutyl and trifluoromethyl.

[0039] X is selected from any one of oxygen atom, C1-C5 substituted or unsubstituted alkylene group, sulfur atom, sulfone group and carbonyl group, and X includes, but is not limited to, any one of oxygen atom, methylene, ethylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 and C(CF3)2.

[0040] Specifically, in Formula 1, Ar1 is a tetravalent organic group, generally a residue from a tetracarboxylic dianhydride or its derivative forming an amide ester structure with a diamine. It is preferably a tetravalent aromatic group, and more preferably a tetracarboxylic dianhydride or its derivative residue having the following structure, where all four binding sites are located on the aromatic ring. Examples of such tetracarboxylic dianhydrides include: pyromellitic dianhydride, 3,3',4,4' biphenyltetracarboxylic dianhydride, 2,3,3',4' biphenyltetracarboxylic dianhydride, 2,2',3,3' biphenyltetracarboxylic dianhydride, 3,3',4,4' benzophenone tetracarboxylic dianhydride, 2,2',3,3' benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride. 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, Aromatic tetracarboxylic anhydrides such as 9,9-bis{4(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 2,3,5,6-pyridinetetracarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic anhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; aliphatic tetracarboxylic anhydrides such as butanetetracarboxylic anhydride; and 1,2,3,4-cyclopentanetetracarboxylic anhydride. These can be used alone or in combination of two or more.

[0041] Furthermore, Ar2 is selected from divalent organic groups, for example, Ar2 is selected from any one of the divalent organic groups shown in Formula 3 each time it appears:

[0042] Among them, R9-R 20 All are monovalent organic groups, and Y is a divalent group.

[0043] Specifically, R9-R20 Each is independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl groups; preferably, R9-R 20 Each is independently selected from, but not limited to, any one of hydrogen, fluorine, bromine, iodine, methyl, ethyl, isopropyl, tert-butyl, isobutyl and trifluoromethyl.

[0044] Y is selected from any one of oxygen atom, C1-C5 substituted or unsubstituted alkylene group, sulfur atom, sulfone group and carbonyl group; Y includes, but is not limited to, any one of oxygen atom, methylene, ethylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 and C(CF3)2.

[0045] Furthermore, in Formula 1, Ar2 is a divalent organic group, generally a residue derived from an amino acid that forms an amide structure with a diamine. It is preferably a divalent aromatic group, and more preferably an amino acid residue with the following structure, where both binding sites are located on the aromatic ring. Examples of such amino acids include p-aminobenzoic acid, m-aminobenzoic acid, and o-aminobenzoic acid. They can be used individually or in combination of two or more.

[0046] In addition, to improve adhesion to the substrate, the Ar2 part can be copolymerized with a certain proportion of aliphatic groups with siloxane structures, provided that the heat resistance is not compromised. Preferred options include 1-10% molar of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc.

[0047] The terminal groups of the aromatic polyamide shown in Formula 1 are either carboxylic acids or amines, depending on the input ratio of Ar1 and Ar2. Depending on the requirements, one or two end-capping agents can react with the polymer ends to make one or both ends each a saturated aliphatic group, an unsaturated aliphatic group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a mercapto group, etc. In this case, the end-capping rate is preferably 30-100%.

[0048] It should be noted that: (1) the above R1-R 20 The halogens mentioned are not limited to F, but can also be bromine and chlorine, etc.

[0049] (2) The above R1-R 20 The C1-C5 substituted or unsubstituted alkyl groups mentioned can be C1-C3 substituted or unsubstituted alkyl groups, such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, tert-butyl and other unsubstituted alkyl groups, or trifluoromethyl, trifluoroethyl, difluoromethyl, trichloromethyl and other substituted alkyl groups.

[0050] (3) The above R1-R 20The C1-C5 substituted or unsubstituted alkylene mentioned can be C1-C3 unsubstituted alkylene, such as methylene, ethylene, propylene, etc., or C1-C3 substituted alkylene, such as halogen (fluorine, bromine, chlorine) substituted methylene, halogen substituted ethylene, etc.

[0051] Regarding the molecular weight of component (a), it is preferably 3,000-200,000, more preferably 5,000-100,000, based on weight-average molecular weight. The molecular weight here is a value determined by gel permeation chromatography and converted from a standard polystyrene standard curve.

[0052] In the embodiments of this disclosure, the graft polymer having the structural unit shown in Formula 1 is generally first prepared by polyamic acid polymer by polycondensation of dianhydride and diamine, then by chemical imidization to obtain polyimide polymer, and then by chloromethylation and xanthate esterification to obtain macromolecular initiator, and then by graft polymerization to obtain polyimide-g-poly(p-hydroxystyrene) graft copolymer.

[0053] Specifically, the first step involves preparing polyamic acid by reacting diamine with dianhydride, followed by chemical imidization to prepare polyimide. The second step involves chloromethylation and xanthate esterification of the polyimide to obtain a macromolecular initiator. The third step involves grafting p-hydroxystyrene onto the macromole prepared in the second step via RAFT polymerization to prepare a grafted polymer. The specific conditions in the above preparation process are well-known to those skilled in the art; therefore, they will not be described in detail in the embodiments disclosed herein.

[0054] In this disclosure, for component (b) the photosensitizer, a quinone diazide compound is used, preferably diazidonaphthoquinone-5-sulfonyl and diazidonaphthoquinone-4-sulfonyl. In this disclosure, a diazidonaphthoquinone sulfonyl ester compound containing both diazidonaphthoquinone-5-sulfonyl and diazidonaphthoquinone-4-sulfonyl groups in the same molecule can be obtained, or a mixture of diazidonaphthoquinone-5-sulfonyl ester and diazidonaphthoquinone-4-sulfonyl ester compounds can be used.

[0055] (b) The quinone diazide compound preferably comprises an ester formed by a phenol compound and a diazidonaphthoquinone-5-sulfonyl group, thereby achieving high sensitivity under i-line exposure.

[0056] The content of (b) quinone diazide compound relative to 100 parts by weight of (a) component polyimide is preferably 5-20 parts, more preferably 8-15 parts, for example, any value between 5 and 20 parts, such as 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 16 parts, 18 parts, and 20 parts. By setting the content of quinone diazide compound within the above range, higher sensitivity can be achieved, and sensitizers can be added as needed.

[0057] The photosensitive polyimide composition provided in this disclosure, for the purpose of easily obtaining a cured film, may contain (c) a thermal crosslinking agent. Component (c1) is a crosslinking agent having an epoxy group, and component (c2) is a crosslinking agent having a -CH2O′R group (R′ is a hydrogen atom or a monovalent organic group). In the heat treatment step following coating, exposure, and development of the photosensitive polymer composition of this disclosure, it reacts with the polymer as component (a) to crosslink, or it is a compound that self-polymerizes during the heat treatment step. Furthermore, the crosslinking agent as component (c2) has an affinity for alkaline aqueous solutions, thereby increasing the dissolution rate in alkaline aqueous solutions.

[0058] In this embodiment, component (c1) is a crosslinking agent having epoxy groups in its structure, specifically selected from compounds represented by the following formula 4-1.

[0059] Specific examples of the compounds represented by Formula 4-1 below include, but are not limited to, Epiclon (registered trademark) 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon EXA-4710, Epiclon HP-4770, Epiclon EXA-859CRP, Epiclon EXA-4880, Epiclon EXA-4850, Epiclon EXA-4816, Epiclon EXA-4822 (all of the above are trade names manufactured by Dainippon Ink and Chemicals, Inc.), Rikaresin (registered trademark) BPO-20E, Rikaresin BEO-60E (all of the above are trade names manufactured by Shin Nippon Rikka), EP-4003S and EP-4000S (all of the above are trade names manufactured by ADEKA), etc.

[0060] It should be noted that the above-listed ingredients (c1) can be used alone or in combination of two or more.

[0061] In this disclosure, component (c2) is a crosslinking agent having a -CH2OR′ group (R′ is a hydrogen atom or a monovalent organic group) in its structure. This group may have one or more -CH2OR′ groups in the compound, but preferably two or more. Component (c2) is selected from compounds shown in Formula 4-2-1 or 4-2-2 below.

[0062] In Equation 4-2-1, R 21 Each is independently a hydrogen atom or a monovalent organic group, R22 Each can be an independent hydrogen atom or a monovalent organic group, or they can combine with each other to form a ring structure that can have substituents.

[0063] In Equation 4-2-2, R 23 Selected from hydrogen atoms or monovalent organic groups, R 24 X is selected from monovalent organic groups, where n is an integer from 1 to 4, and X is selected from single bonds or 1-4 valent organic groups. a is an integer from 1 to 4, and b is an integer from 0 to 3. When a is 2, 3, or 4, R... 23 Whether the values ​​are the same or different, when b is 2 or 3, R 24 Same or different.

[0064] In Formula 4-2-2, the 1-4 valent organic groups of X can be alkyl groups with 1-10 carbon atoms, alkylene groups with 2-10 carbon atoms (e.g., ethylene), aryl groups with 6-30 carbon atoms (e.g., phenylene), or groups obtained by replacing some or all of these hydroxyl hydrogen atoms with halogen atoms such as fluorine atoms. These groups may further include phenyl, sulfone, carbonyl, ether, thioether, amide, etc. R 23 Preferably, it is hydrogen-based, alkyl-based, or alkenyl-based. The alkyl- or alkenyl-based group preferably has 1-20 carbon atoms. 24 Preferably, it is alkyl, alkenyl, alkoxyalkyl, or hydroxymethyl, and the number of carbon atoms is preferably 1-20.

[0065] Furthermore, the following formula 4-2-1-1 represents a specific example of the compound shown in formula 4-2-1, which can be used alone or in combination with two or more of these compounds.

[0066] Among them, R 25 It is an alkyl group having 1-20 carbon atoms, preferably an alkyl group having 1-6 carbon atoms, R 26 It is an alkyl group with 1-10 carbon atoms.

[0067] The following formula 4-2-2-1 represents a specific example of the compound shown in formula 4-2-2, which can be used alone or in combination with two or more of these compounds.

[0068] The purity of the compound shown in Formula 4-2 above is preferably 75% or higher, more preferably 85% or higher. When the purity is 85% or higher, it exhibits excellent storage stability and allows for sufficient cross-linking reaction of the polyimide composition. Furthermore, since unreacted groups that become water-absorbing groups can be reduced, the water absorption of the polyimide composition can be decreased. Methods for obtaining a high-purity thermal cross-linking agent include recrystallization and distillation. The purity of the thermal cross-linking agent can be determined using liquid chromatography.

[0069] Relative to 100 parts by weight of polyimide in component (a), the content of the thermal crosslinking agent in component (c) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more. If it is 5 parts by weight or more, the crosslinking density of the cured film is increased, resulting in high chemical resistance and low curing warpage. Furthermore, if it is 10 parts by weight or more, the chemical resistance is even higher, the low curing warpage is even better, and higher mechanical properties can be obtained. Additionally, considering the storage stability and mechanical strength of the composition, it is preferably 30 parts by weight or less.

[0070] Furthermore, the content of c1 is 5-15 parts by weight, such as any value between 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 parts; the content of c2 is 0.1-15 parts, such as any value between 0.1 and 15 parts, such as 0.1, 0.5, 1, 2, 5, 7, 8, 10, 13, 14, and 15 parts.

[0071] This disclosure provides a polyimide composition further comprising (d) a silane coupling agent, generally an organosilane compound, such as: γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-ureidopropyltriethoxysilane. Silane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate-propyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, triethoxysilylpropylethyl carbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.

[0072] When an organosilane compound is included, the adhesion between the cured photosensitive polyimide composition and the substrate can be improved. When an organosilane compound is included, the content of the organosilane compound is 0.5-15 parts by weight relative to 100 parts by weight of component (a), more preferably 0.5-10 parts by weight. For example, any value between 0.5 and 15 parts, such as 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 1 part, 11 parts, 12 parts, 13 parts, 14 parts, and 15 parts.

[0073] The polyimide composition disclosed herein further comprises (e) a solvent, preferably an organic solvent. Examples include ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. Specific examples include polar solvents such as γ-butyrolactone, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl sulfoxide, hexamethylphosphoric triamine, dimethylimidazolinone, tetraethylurea, tetramethylurea, ethyl lactate, 3-methoxy-N,N-dimethylpropaneamide, and N-acetyl-ε-caprolactam. Other ingredients that may be used include: acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, 1-methoxy-2-propanol, 1-methoxy-2-acetoxypropane, propylene glycol 1-monomethyl ether 2-acetate, etc. Component (e) may be used alone or in combination with two or more ingredients.

[0074] When component (e) is included, the amount of component (e) is preferably 50-1000 parts by mass relative to 100 parts by mass of component (a), more preferably 100-200 parts by mass. For example, any value between 50 and 1000 parts is used, such as 50 parts, 60 parts, 70 parts, 100 parts, 150 parts, 200 parts, 300 parts, 400 parts, 500 parts, 600 parts, 700 parts, 800 parts, 900 parts, and 1000 parts.

[0075] This disclosure may further include (f) a leveling agent, which may be a surfactant, thereby improving the coatability with the substrate. Examples of surfactants include fluorinated surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name, manufactured by DIC Co., Ltd.), and Surflon (trade name, manufactured by Asahi Glass Co., Ltd.); organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), Polyflow, Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and BYK (trade name, manufactured by BYK-Chemie GmbH); and acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

[0076] Relative to 100 parts by mass of component (a), component (f) contains sulfur in the range of 100-1000 ppm, for example, any value between 100-1000 ppm such as 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm and 1000 ppm.

[0077] Next, a method for manufacturing the photosensitive polyimide composition provided in the embodiments of this disclosure will be described. For example, a photosensitive polyimide composition can be obtained by uniformly mixing the components (a)-(d) and components (e)-(f) as needed. Examples of dissolution methods include stirring and heating. When heating, it is preferable to set the heating temperature within a range that does not damage the properties of the polyimide composition, typically room temperature to 80°C. Furthermore, the order in which the components are dissolved is not particularly limited; for example, methods include dissolving compounds with low solubility sequentially starting with those that are less soluble. Additionally, for components such as surfactants and certain adhesion modifiers that are prone to generating bubbles during stirring and dissolution, poor dissolution of other components due to bubble generation can be prevented by adding them last after the other components have been dissolved.

[0078] The resulting photosensitive polyimide composition is preferably filtered to remove impurities and particles. The filter pore size is 0.5-0.02 μm, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, etc., but not limited to these. The filter material includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., with polyethylene and nylon being preferred. When the photosensitive polyimide composition contains inorganic particles, a filter with a pore size larger than the particle size of these inorganic particles is preferred.

[0079] This disclosure provides a cured product that can be obtained by curing the above-described photosensitive polyimide composition. The cured product can be used as a patterned cured film or as a patternless cured film.

[0080] Methods for manufacturing patterned cured films include, for example, a process of coating a substrate with the photosensitive polyimide composition provided in the embodiments of this disclosure and drying it to form a photosensitive polyimide film (film formation process); a process of exposing the photosensitive polyimide film (exposure process); a process of developing the exposed photosensitive polyimide film using an alkaline aqueous solution to form a patterned polyimide film (development process); and a process of heating the patterned polyimide film (heating process). Methods for manufacturing unpatterned cured films may include, for example, the above-described film formation process and heating process. An exposure process may also be further included.

[0081] In the film-forming process, the above-mentioned photosensitive polyimide composition is coated onto a metal substrate such as Cu, a glass substrate, a semiconductor, a metal oxide insulator (e.g., TiO2, SiO2), or a support substrate such as silicon nitride, for example by dip-coating, spraying, screen printing, or spin coating. From an operational point of view, the coated photosensitive polyimide composition can also be dried by heating (e.g., 90-150°C, 1-5 minutes) using a hot plate or oven. The support substrate can also be cleaned with acetic acid or the like before coating. The thickness of the resulting photosensitive polyimide film is preferably 5-20 μm.

[0082] In the exposure process, for example, the photosensitive polyimide film formed on the substrate is irradiated with the aforementioned active light through a mask. From the viewpoint of the transparency of component (a), irradiation with i-rays can be appropriately used.

[0083] In the developing process, for example, the exposed portion of the photosensitive polyimide film after the exposure process is removed with a developing solution, thereby patterning the photosensitive polyimide film. As the developing solution, in the case of an alkaline-soluble photosensitive polyimide composition, an aqueous alkaline solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, or tetramethylammonium hydroxide (TMAH) can be suitably used. The alkalinity of these aqueous solutions is preferably set to 0.1-10% by mass. Alcohols or surfactants can also be added to the above-mentioned developing solution. They can be formulated in a range of preferably 0.01-10 parts by mass, more preferably 0.1-5 parts by mass, relative to 100 parts by mass of the developing solution. The patterned photosensitive polyimide film is referred to as a patterned polyimide film.

[0084] In the heating process, the photosensitive polyimide composition can be cured by heating the patterned polyimide film or the photosensitive polyimide film. Specifically, the film obtained by curing the patterned polyimide film is called a pattern-cured film. The heating temperature is preferably 150-250°C, more preferably less than or equal to 230°C, more preferably greater than or equal to 170°C, and even more preferably 180-200°C. The heating time is preferably 20 minutes to 6 hours, more preferably 30 minutes to 3 hours. Multi-stage heating can also be performed. The heat treatment can be carried out using ovens such as quartz tube furnaces, hot plates, rapid thermal annealing furnaces, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces. Alternatively, either atmospheric or inactive atmospheres such as nitrogen can be selected, but nitrogen is preferred as it prevents oxidation of the pattern.

[0085] The cured material disclosed herein can be used as an interlayer insulating film or a surface protective film, etc.

[0086] The interlayer insulating film and surface protective film disclosed herein can be used in electronic components, etc. The electronic components provided in the embodiments of this disclosure can be used in semiconductor devices, etc. The semiconductor devices can be used in various electronic devices, etc. A schematic diagram of the semiconductor packaging structure of this disclosure is shown in Figure 1.

[0087] Therefore, it exhibits excellent rust prevention and adhesion effects on the supporting substrate (especially copper substrate and copper alloy substrate), and can suppress discoloration of the cured film and the supporting substrate (especially copper substrate and copper alloy substrate).

[0088] Examples of semiconductor devices include wafer-level chip-scale package (WLCSP) and fan-out wafer-level package (FOWLP). Furthermore, the interlayer insulating film and surface protective film disclosed herein can be used in circuit forming substrates, which can be used in hard disk drive suspensions, flexible wiring boards, etc.

[0089] The compounds provided in this disclosure are abbreviated as follows: ODA: 4,4-diaminodiphenyl ether; SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane; ODPA: 4,4'-oxobisphthalic anhydride; Py: pyridine; Et2A: acetic anhydride; PhA: phthalic anhydride; NMP: N-methyl-2-pyrrolidone; TMAH: tetramethylammonium hydroxide; CMM: chloromethyl methyl ether; SnCl4: tin tetrachloride; AIBN: azobisisobutyronitrile; 4-HS: p-hydroxystyrene; St: styrene; 6FAP: 3,3-diamino-4,4-dihydroxydiphenyl-hexafluoropropane.

[0090] The molecular weight, grafting rate (n / (m+n)), and grafting amount (k) of component (a) were determined as follows:

[0091] (1) Determination of molecular weight

[0092] The number-average molecular weight was determined using gel permeation chromatography (GPC) under the following conditions, converted from standard polystyrene. The determination was performed using a solution of 1 mL relative to 0.5 mg A and solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)].

[0093] Measurement apparatus: Detector: Hitachi, Ltd. L4000UV; Pump: Hitachi, Ltd. L6000; Shimadzu Corporation C-R4A Chromatopac.

[0094] Determination conditions: Gelpack GL-S300MDT-5 × 2 columns.

[0095] Eluent: THF / DMF = 1 / 1 (volume ratio), LiBr (0.03 mol / L), H3PO4 (0.06 mol / L).

[0096] Flow rate: 1.0 mL / min, detector: UV270 nm.

[0097] (2) Determination of grafting rate n / (m+n)

[0098] In addition, NMR measurements were performed under the following conditions.

[0099] Measurement equipment: Bruker BioSpin AV400M.

[0100] Magnetic field strength: 400MHz.

[0101] Reference material: Tetramethylsilane (TMS).

[0102] Solvent: Dimethyl sulfoxide (DMSO).

[0103] (3) Determination of grafting amount k

[0104] NMR measurements were performed under the following conditions.

[0105] Measurement equipment: Bruker BioSpin AV400M.

[0106] Magnetic field strength: 400MHz.

[0107] Reference material: Tetramethylsilane (TMS).

[0108] Solvent: Dimethyl sulfoxide (DMSO).

[0109] The features and performance of this disclosure will be further described in detail below with reference to embodiments.

[0110] Synthesis example 1

[0111] This synthetic example provides a method for preparing component (a), comprising:

[0112] Under a dry nitrogen stream, 20.02 g (0.1 mol) of ODA was dissolved in 200 g of NMP, and the resulting solution was then cooled to -10 °C. Subsequently, 26.37 g (0.085 mol) of ODPA was slowly added to the solution, ensuring the temperature of the reaction solution did not exceed 0 °C, and stirring was continued for 3 hours. Then, 4.44 g (0.03 mol) of PhA was added, and stirring was continued at room temperature for 2 hours to obtain a polyamic acid solution.

[0113] 39.55 g of Py and 30.6 g of Et2A were added to a polyamic acid solution, and the temperature was raised to 120 °C. The reaction was continued for 12 h. After the reaction was completed, the solution was poured into 2 L of deionized water to precipitate the polyimide resin. The precipitate was washed with water and dried under vacuum at 80 °C to obtain the polyimide resin.

[0114] 5g of dried polyimide resin was dissolved in 30mL of dichloroethane, 80μL of SnCl4 was added, the temperature was raised to 70℃, and 3mL of CMM was slowly added dropwise to the system, which was stirred for 5h. After the reaction was completed, the solution was poured into 300mL of methanol to precipitate, washed, and dried at 80℃ for 12h to obtain chloromethylated polyimide resin.

[0115] 1 g of dried chloromethylated polyimide resin was dissolved in 20 mL of NMP. After dissolution, 0.1 g of potassium ethyl xanthate was added, and the reaction was carried out at room temperature for 24 h. After the reaction was completed, the solution was poured into 200 mL of deionized water to precipitate the resin, and then dried at 80 °C for 12 h to obtain the macromolecular initiator.

[0116] 1 g of dried macromolecular initiator was dissolved in 20 mL of NMP. After dissolution, the temperature was raised to 65 °C, and 3 g of 4-HS was added dropwise, followed by 0.01 g of AIBN. RAFT polymerization was then initiated, and the reaction was continued for 2 h. After the reaction was complete, the solution was cooled to room temperature, poured into 200 mL of deionized water to precipitate, washed repeatedly with ethanol, and dried at 80 °C for 12 h to obtain polyimide-g-poly(p-hydroxystyrene) graft copolymer A1.

[0117] According to the test results, the number average molecular weight of polyimide-g-poly(p-hydroxystyrene) graft copolymer A1 is 39,000; the grafting rate is 40%; and the grafting amount of A1 is k = 3.5.

[0118] Synthesis example 2-7

[0119] The preparation methods for Synthetic Examples 2-7 are the same as those for Synthetic Example 1, with the only difference being some of the conditions, as follows:

[0120] Synthesis Example 2: Compared with Synthesis Example 1, CMM was changed to 2 mL to obtain graft A2 with a molecular weight of 38000, a grafting rate of 25%, and k = 3.8.

[0121] Synthesis Example 3: Compared with Synthesis Example 1, CMM was changed to 4 mL to obtain graft A3 with a molecular weight of 38,500, a grafting rate of 53%, and k = 3.2.

[0122] Synthesis Example 4: Compared with Synthesis Example 1, the RAFT polymerization time was changed to 1.5 h to obtain graft A4 with a molecular weight of 37800, a grafting rate of 40%, and k = 2.5.

[0123] Synthesis Example 5: Compared with Synthesis Example 1, the RAFT polymerization time was changed to 4h to obtain graft A5 with a molecular weight of 39500, a grafting rate of 40%, and k = 4.3.

[0124] Synthesis Example 6: Compared with Synthesis Example 1, the RAFT polymerization time was changed to 6h to obtain graft A6 with a molecular weight of 39900, a grafting rate of 40%, and k = 5.7.

[0125] Synthesis Example 7: Compared with Synthesis Example 1, the RAFT polymerization time was changed to 9h to obtain graft A7 with a molecular weight of 40500, a grafting rate of 40%, and k = 6.9.

[0126] Synthesis example 8

[0127] This synthetic example provides a method for preparing component (a), comprising:

[0128] Add 192g methanol, 172.32g 4-HS, 19.53g St, and 15g AIBN sequentially to a four-necked flask, stirring until dissolved and clear. Vacuum the reaction vessel with nitrogen to purge air, heat to 75℃, and react for 18 hours, then stop the reaction. Slowly add a prepared sodium methoxide (0.4g) solution to the reaction system, react for 6 hours, and then extract 2-3 times with n-heptane at a 1:1 mass ratio to remove unreacted monomers and initiators. Replace the methanol in the reaction solution with PGMEA to obtain a PGMEA solution of the desired concentration, yielding PHS resin A8 (see structural formula below). The ratio of p-hydroxystyrene to styrene repeating units is 80 / 20, i.e., m = 80 and n = 20.

[0129] Synthesis example 9

[0130] This synthetic example provides a method for preparing component (a), comprising:

[0131] Under a dry nitrogen stream, 36.63 g (0.1 mol) of 6FAP was dissolved in 200 g of NMP, and the resulting solution was then cooled to -10 °C. Subsequently, 26.37 g (0.085 mol) of ODPA was slowly added to the solution, ensuring the temperature of the reaction solution did not exceed 0 °C, and stirring was continued for 3 hours. Then, 4.44 g (0.03 mol) of PhA was added, and stirring was continued at room temperature for 2 hours to obtain a polyamic acid solution.

[0132] 39.55 g of Py and 30.6 g of Et2A were added to a polyamic acid solution, and the temperature was raised to 120 °C. The reaction was continued for 12 h. After the reaction was completed, the solution was poured into 2 L of deionized water to precipitate the resin. The precipitate was washed with water and dried under vacuum at 80 °C to obtain polyimide resin A9 (its structural formula is shown below).

[0133] Examples 1-10 and Comparative Examples 1-2

[0134] The photosensitive polyimide compositions of Examples 1-10 and Comparative Examples 1-2 were prepared according to the components and proportions shown in Tables 1-2. The proportions in Tables 1-2 are parts by mass relative to 100 parts by mass of component (a).

[0135] The structural formulas of the components used in Tables 1 and 2 are shown below:

[0136] Component (b): Photosensitizer

[0137] Component (c): Thermal crosslinking agent

[0138] Component (d): Solvent

[0139] d1: GBL (γ-butyrolactone); d2: EL (ethyl lactate).

[0140] Component (e): silane coupling agent; e1: γ-ureapropyltriethoxysilane.

[0141] Table 1 Ingredients

[0142] Table 2 Ingredients

[0143] The performance of the photosensitive polyimide compositions prepared in Examples 1-10 and Comparative Examples 1-2 was evaluated using the following methods:

[0144] (1) Preparation of developing film

[0145] The photosensitive polyimide compositions (varnishes) prepared in Examples 1-10 and Comparative Examples 1-2 were spin-coated onto 8-inch silicon wafers, respectively. Then, they were heat-treated (pre-baked) at 120°C for 3 minutes using a hot plate (Tokyo Electron Ltd., Mark-7 coating and developing apparatus) to produce a 6 μm thick pre-baked film. An i-line stepper (Nikon Corporation, NSR-2005i9C) was used at 50–400 mJ / cm². 2 Exposure, 10mJ / cm 2The pre-baked film is exposed through a step-by-step process. After exposure, for the photosensitive polyimide composition, it is baked after exposure at 100°C for 1 minute. After exposure and baking, the photosensitive polyimide composition is developed for 90 seconds using a 2.38 wt% tetramethylammonium (TMAH) aqueous solution (Mitsubishi Gas Chemical Co., Ltd., ELM-D), and then rinsed with pure water to obtain the developed film.

[0146] (2) Methods for measuring film thickness

[0147] For the film thickness after pre-baking and development, a Filmtris F50 film thickness measuring device was used to measure the thickness at a refractive index of 1.63.

[0148] (3) Determination of warpage

[0149] A varnish was applied using a spin-coating and developing apparatus (ACT-8) and pre-baked to a film thickness of 10 μm after 3 minutes at 120°C. Then, an inert oven was used to heat the film to 200°C at a rate of 3.5°C / min under conditions of oxygen concentration below 20 ppm, and the film was heat-treated at 200°C for 1 hour. The wafer was removed when the temperature dropped below 50°C, and the cured film was measured using a pressure device (FLX2908, KLA Tencor). The results showed that pressure above 35 MPa was considered insufficient (D), pressure between 30 MPa and 35 MPa was considered good (C), pressure between 20 MPa and 30 MPa was considered better (B), and pressure below 20 MPa was considered best (A). The results are shown in Table 3.

[0150] (4) Sensitivity evaluation

[0151] After exposure and development, the exposure amount (called the optimal exposure Eop) that forms a 20μm line and gap pattern (1L / 1S) with a 1:1 width is used as the sensitivity. If Eth is 200mJ / cm²... 2 The following values ​​can be considered high sensitivity. More preferably, 150 mJ / cm². 2 The results are shown in Table 3.

[0152] (5) Evaluation of chemical resistance

[0153] The coating was applied to the cured material using a pipette. The cured material was then placed in a nitrogen oven at 200°C and maintained for 60 minutes. Afterward, the cured material was transferred from the heating plate and cooled to room temperature. The cooled cured material was cleaned with NMP at 45°C and then immersed for 1 hour before the film thickness was measured.

[0154] The film thickness change rate (%) was calculated based on the change in film thickness. A positive value indicates film expansion, while a negative value indicates film dissolution. The results are shown in Table 3.

[0155] (6) Adhesion evaluation

[0156] Using the above-described method for manufacturing cured material, a cured material is manufactured on a Cu substrate. The resulting cured material is then divided into 100 small pieces by using a crosscut guide (manufactured by COAT-TECH Co., Ltd.) and a shearing blade to cut 10×10 checkerboard-like grooves.

[0157] An adhesive tape (manufactured by 3M Japan Co., Ltd.) was applied to the cured material, and then the adhesive tape was peeled off. The adhesion was evaluated as follows, based on the number of small pieces of cured material peeled off from the substrate when the adhesive tape was peeled off.

[0158] A: The number of remaining grid cells is 100-80.

[0159] B: The number of remaining cells is less than 80.

[0160] The results are shown in Table 3.

[0161] (7) Evaluation of elongation at break

[0162] A varnish was applied using a spin-coating and developing apparatus (ACT-8) and pre-baked to a film thickness of 10 μm after 3 minutes at 120°C. Then, an inert oven was used to heat the film to 200°C at a rate of 3.5°C / min under conditions of oxygen concentration below 20 ppm, and the film was heat-treated at 200°C for 1 hour. The wafer was removed when the temperature dropped below 50°C, the film was peeled off, and the wafer was cut into 4 mm × 8 mm strips. Tensile testing was performed using a DAGE4000.

[0163] The results showed that cases with an elongation at break of 30% or more were considered excellent (A), 20-30% were considered good (B), 10-20% were considered poor (C), and <10% were considered very poor (D). See Table 3 for the results.

[0164] Table 3 Detection Results

[0165] As can be seen from Table 3, the photosensitive polyimide compositions provided in Examples 1-10 of this disclosure all exhibit low developing film loss, excellent low warpage stress, and excellent chemical resistance. Compared with the examples, Comparative Example 1 has poorer toughness and lower sensitivity. Comparative Example 2, on the other hand, has high warpage stress, poorer sensitivity, and poorer chemical stability.

[0166] The above description is merely a preferred embodiment of this disclosure and is not intended to limit this disclosure. Various modifications and variations can be made to this disclosure by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this disclosure should be included within the scope of protection of this disclosure. Industrial applicability

[0167] The photosensitive polyimide composition disclosed herein has excellent sensitivity and resolution, high chemical stability and adhesion, and low warpage stress after low-temperature curing (180-200℃). Furthermore, the portion of the photosensitive polyimide composition exposed to ultraviolet light is readily soluble in alkaline aqueous solution, while the portion not exposed to ultraviolet light is insoluble in alkaline aqueous solution. Therefore, it can effectively reproduce fine patterns and is suitable for industrial production.

Claims

1. A photosensitive polyimide composition, characterized in that, It includes component (a) a graft polymer soluble in an alkaline aqueous solution, selected from compounds shown in the following structural formula: Wherein, Ar1 is selected from tetravalent organic groups, and Ar2 is selected from divalent organic groups; m+n=5~200, n / (m+n)=0.05~1, k=2~10; Component (b) photosensitizer; Component (c) thermal crosslinking agent; which includes component (c1) a crosslinking agent containing an epoxy group and component (c2) a crosslinking agent containing CH2OR′; R′ represents a hydrogen atom or a monovalent organic group; Component (d) Silane coupling agent.

2. The photosensitive polyimide composition according to claim 1, characterized in that, Ar1 is selected, in each instance, either identically or differently, from any of the four-valent organic groups shown in Formulas 2-1 to 2-9 below: Among them, R1-R8 are all monovalent organic groups, and X is a divalent group.

3. The photosensitive polyimide composition according to claim 2, characterized in that, R1-R8 are each independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl groups.

4. The photosensitive polyimide composition according to claim 2 or 3, characterized in that, R1-R8 are each independently selected from any one of hydrogen, fluorine, methyl, and trifluoromethyl.

5. The photosensitive polyimide composition according to any one of claims 2-4, characterized in that, X is selected from any one of oxygen atom, C1-C5 substituted or unsubstituted alkylene group, sulfur atom, sulfone group and carbonyl group.

6. The photosensitive polyimide composition according to any one of claims 2-5, characterized in that, X is selected from any one of oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 and C(CF3)2.

7. The photosensitive polyimide composition according to any one of claims 1-6, characterized in that, Ar2 is selected, either identically or differently, from any of the divalent organic groups shown in Formulas 3-1 to 3-12: Among them, R9-R 20 All are monovalent organic groups, and Y is a divalent group.

8. The photosensitive polyimide composition according to claim 7, characterized in that, R9-R 20 Each is independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl groups.

9. The photosensitive polyimide composition according to claim 7 or 8, characterized in that, R9-R 20 Each is independently selected from any one of hydrogen, fluorine, methyl, and trifluoromethyl.

10. The photosensitive polyimide composition according to any one of claims 7-9, characterized in that, Y is selected from any one of oxygen atom, C1-C5 substituted or unsubstituted alkylene group, sulfur atom, sulfone group and carbonyl group.

11. The photosensitive polyimide composition according to any one of claims 7-10, characterized in that, Y is selected from any one of oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 and C(CF3)2.

12. The photosensitive polyimide composition according to any one of claims 1-11, characterized in that, The photosensitizer is selected from quinone diazide compounds.

13. The photosensitive polyimide composition according to any one of claims 1-12, characterized in that, The component (c1) is selected from the compounds shown in Formula 4-1; Component (c2) is selected from the compounds shown in Formula 4-2-1 or Formula 4-2-2; In Formula 4-1, U is selected from divalent organic groups containing alicyclic or aromatic rings; In Equation 4-2-1, R 21 Each is independently a hydrogen atom or a monovalent organic group, R 22 Each can be an independent hydrogen atom or a monovalent organic group, or they can combine to form a ring structure that can have substituents; In Equation 4-2-2, R 23 Selected from hydrogen atoms or monovalent organic groups, R 24 X is selected from monovalent organic groups, n is an integer from 1 to 4, and X is selected from single bonds or 1-4 valent organic groups; a is an integer from 1 to 4, b is an integer from 0 to 3, and when a is 2, 3, or 4, R 23 Whether the values ​​are the same or different, when b is 2 or 3, R 24 Same or different.

14. The photosensitive polyimide composition according to claim 13, characterized in that, Component (c2) is selected from any one of the compounds shown in the following structural formulas: Among them, R 25 It is an alkyl group with 1-20 carbon atoms; R 26 It is an alkyl group with 1-10 carbon atoms.

15. The photosensitive polyimide composition according to claim 14, characterized in that, R 25 It is an alkyl group having 1-6 carbon atoms.

16. The photosensitive polyimide composition according to any one of claims 1-15, characterized in that, Based on 100 parts by weight of component (a), the content of component (b) is 5-20 parts by weight, the content of component (c) is 5 parts by weight or more, wherein the content of c1 is 5-15 parts by weight, the content of c2 is 0.1-15 parts by weight, and the content of component (d) is 0.5-15 parts by weight.

17. The photosensitive polyimide composition according to any one of claims 1-16, characterized in that, The photosensitive polyimide composition further comprises any one or a combination of at least two of a solvent and a leveling agent.

18. The photosensitive polyimide composition according to claim 17, characterized in that, The content of the solvent is 50-1000 parts per 100 parts by weight of component (a).

19. The photosensitive polyimide composition according to claim 17 or 18, characterized in that, The content of the solvent is 100-200 parts by weight, based on 100 parts by weight of component (a).

20. The photosensitive polyimide composition according to any one of claims 17-19, characterized in that, The leveling agent content is 100-1000 ppm, based on 100 parts by weight of component (a).

21. A method for manufacturing a graphic, characterized in that, It comprises coating the photosensitive polyimide composition of any one of claims 1-20 onto a support substrate.

22. The manufacturing method according to claim 21, characterized in that, Also includes: After coating, the process involves drying, exposure, development, and heat treatment in sequence.

23. The manufacturing method according to claim 22, characterized in that, The light source used in the exposure process is i-ray.

24. A cured product, characterized in that, The cured product is formed by curing the photosensitive polyimide composition according to any one of claims 1-20.

25. The cured product according to claim 24, characterized in that, The cured material includes a surface protective film or an interlayer insulating film.

26. An electronic component, characterized in that, The electronic component includes the cured material as described in claim 24 or 25.

27. The electronic component according to claim 26, characterized in that, The electronic components include semiconductor devices.

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