Photosensitive polyimide composition, manufacturing method for patterns, structure, component, and device

Abstract

Disclosed in the present application are a photosensitive polyimide composition, a manufacturing method for patterns, a structure, a component, and a device. The composition is made of the following raw materials in parts by weight: 100 parts of a block polymer which can be dissolved in an alkaline aqueous solution; 5-30 parts of a thermal crosslinking agent which is selected from a crosslinking agent containing an epoxy group and a crosslinking agent containing -CH2OR; 0.5-5 parts of a photoacid generator; and 0.5-10 parts of a silane coupling agent. The photosensitive polyimide composition provided in the present application has excellent alkali solubility, can duplicate fine patterns, has low warping stress after low-temperature curing, and has high chemical stability and cohesiveness.

Description

Photosensitive polyimide compositions, methods for manufacturing patterns, structures, components, and equipment Technical Field

[0001] This application belongs to the field of new materials technology, and specifically relates to a photosensitive polyimide composition, a method for manufacturing patterns, a structure, components and equipment. Background Technology

[0002] As semiconductor packaging density gradually increases, PSPI materials are also gradually developing towards low-temperature curing, high sensitivity, high resolution, and low warpage stress.

[0003] WO2018225676A1 discloses a method of lowering the glass transition temperature of PI polymers and supplementing it with a hot alkali generating agent. This method can achieve low-temperature curing at 200-230°C to obtain negative PSPI cured products with excellent adhesion. However, this method cannot meet the requirements of high sensitivity, high resolution and low warpage stress.

[0004] CN102575139A discloses a method of using chemically imidized PI polymers with phenolic hydroxyl or carboxyl groups, supplemented with a suitable crosslinking agent, which can achieve low-temperature curing at 200-230°C and obtain positive PSPI cured products with excellent chemical resistance. However, this method has extremely limited improvement on chemical resistance, and the sensitivity of such compositions is generally low.

[0005] WO2008026406A1 discloses a method of using polymers with phenolic hydroxyl groups, such as poly(p-hydroxystyrene) or phenolic resin, supplemented with crosslinking agents and toughened with rubber particles, to obtain a composition that cures at a low temperature of 200°C, has fast sensitivity and high resolution, and low warpage stress. However, the cured product obtained in this way has poor mechanical properties and limited improvement in toughness, which may lead to abnormal reliability issues.

[0006] The information disclosed in this background section is intended only to enhance the understanding of the overall background of this application and should not be construed as an admission or in any way implying that the information constitutes prior art known to those skilled in the art. Summary of the Invention

[0007] This application provides a photosensitive polyimide composition, a method for manufacturing patterns, a structure, a component, and an apparatus. The photosensitive polyimide composition has excellent alkali solubility and can reproduce fine patterns. After low-temperature curing, it has low warpage stress, high chemical stability, and good adhesion.

[0008] In a first aspect, embodiments of this application provide a photosensitive polyimide composition, the raw materials of which comprise the following components, in parts by weight:

[0009] 100 parts of a block polymer, soluble in an alkaline aqueous solution, with the structural formula: Where R is Ar1 is selected from tetrasubstituted organic groups, Ar2 is selected from disubstituted organic groups; m+n=5~200, n / (m+n)=0.05~1, and k=2~10;

[0010] 5-30 parts of thermal crosslinking agent, selected from crosslinking agents containing epoxy groups or crosslinking agents containing -CH2OR;

[0011] Photo-acid-producing agent, 0.5-5 parts, with the following structural formula: Wherein, R' is selected from hydrogen, alkyl groups having 1-4 carbon atoms, or alkoxy groups having 1-4 carbon atoms, X is selected from halogens, and Y is oxygen or sulfur;

[0012] 0.5-10 parts of silane coupling agent.

[0013] In one or more embodiments of this application, the tetrasubstituted organic group of Ar1 is selected from: R1-R8 are all monosubstituted organic groups, and X1 is a disubstituted group.

[0014] In one or more embodiments of this application, the monosubstituted organic groups of R1-R8 are each independently selected from: hydrogen, halogen, C1-C5 substituted alkyl (substitution here refers to being monosubstituted or polysubstituted by other non-alkyl groups, the same below) and C1-C5 unsubstituted alkyl.

[0015] In one or more embodiments of this application, the monosubstituted organic groups of R1-R8 are selected from hydrogen, fluorine, methyl and trifluoromethyl.

[0016] In one or more embodiments of this application, the disubstituted group of X1 is selected from: oxygen, C1-C5 substituted or unsubstituted alkylene groups, sulfur, sulfone, and carbonyl.

[0017] In one or more embodiments of this application, the disubstituted group of X1 is selected from: oxygen, methylene, sulfur, sulfone, carbonyl, -C(CH3)2- and -C(CF3)2-.

[0018] In one or more embodiments of this application, the disubstituted organic group of Ar2 is selected from:

[0019] Among them, R9-R 20 All are monosubstituted organic groups, and Y is a disubstituted group.

[0020] In one or more embodiments of this application, R9-R 20Each of the monosubstituted groups is independently selected from: hydrogen, halogen, C1-C5 substituted alkyl and C1-C5 unsubstituted alkyl.

[0021] In one or more embodiments of this application, R9-R 20 The monosubstituted groups are each independently selected from hydrogen, fluorine, methyl and trifluoromethyl.

[0022] In one or more embodiments of this application, the disubstituted group of Y is selected from: oxygen, C1-C5 substituted alkylene, C1-C5 unsubstituted alkylene, sulfur, sulfone, and carbonyl.

[0023] In one or more embodiments of this application, the disubstituted group of Y is selected from: oxygen, methylene, sulfur, sulfone, carbonyl, -C(CH3)2- and -C(CF3)2-.

[0024] In one or more embodiments of this application, the thermal crosslinking agent is selected from compounds represented by any of the following formulas:

[0025] Wherein, U is selected from disubstituted organic groups containing alicyclic or aromatic rings; R 21 Independently selected from: hydrogen, monosubstituted organic groups, R 22 Selected from hydrogen, monosubstituted organic groups, or ring structures with substituents; R 23 Selected from hydrogen or a monosubstituted organic group; R 24 X2 is selected from monosubstituted organic groups, where n is an integer from 1 to 4; X2 is selected from monosubstituted, disubstituted, trisubstituted, or tetrasubstituted organic groups; a is an integer from 1 to 4, and b is an integer from 0 to 3. Preferably, 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.

[0026] In one or more embodiments of this application, 100-200 parts solvent and / or 100-1000 ppm leveling agent are also included.

[0027] Secondly, embodiments of this application provide a method for manufacturing a pattern. The method for manufacturing a pattern is as follows: coating the photosensitive polyimide composition described in the first aspect onto a support substrate, and then drying, exposing, developing, and heating to obtain the pattern.

[0028] In one or more embodiments of this application, the light source used for exposure is an i-ray (i-line light source).

[0029] Thirdly, embodiments of this application provide a photocurable structure, which is obtained by the pattern manufacturing method described in the second aspect. Here, the pattern includes planar structures (such as surface protective films or interlayer insulating films) or patterned structures (such as embossed structures, patterns, etc.).

[0030] Fourthly, embodiments of this application provide an electronic component comprising a body and a photocurable structure as described in the third aspect formed on the body.

[0031] Fifthly, embodiments of this application provide an apparatus comprising a body and electronic components disposed on the body as described in the fourth aspect.

[0032] Compared with the prior art, the photosensitive polyimide composition, pattern manufacturing method, structure, component and equipment described in this application have a portion that is easily soluble in alkaline aqueous solution when exposed to ultraviolet light, while the portion that is not exposed to ultraviolet light is insoluble in alkaline aqueous solution, thus enabling the effective reproduction of fine patterns; moreover, the photosensitive polyimide composition has excellent alkali solubility, high resolution, and low warpage stress, high adhesion and good chemical resistance after low temperature curing (180-200℃). Attached Figure Description

[0033] Figure 1 is a schematic diagram of a semiconductor packaging structure implemented according to an embodiment of this application. Detailed Implementation

[0034] The specific embodiments of this application are described in detail below, but it should be understood that the scope of protection of this application is not limited to the specific embodiments.

[0035] Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprises" shall be understood to include the stated elements or components without excluding other elements or other components.

[0036] This application provides a photosensitive polyimide composition comprising the following components:

[0037] (a) Block polymers soluble in alkaline aqueous solutions; (b) thermal crosslinking agents; (c) photoacid-generating agents; and (d) silane coupling agents.

[0038] The photosensitive polyimide composition exhibits insoluble portions in alkaline aqueous solutions when exposed to ultraviolet light, while the portions not exposed to ultraviolet light are soluble in alkaline aqueous solutions, thus enabling the effective reproduction of fine patterns. The photosensitive polyimide composition described in this application promotes the reaction between the crosslinking agent and the resin through acid generation, increasing the dissolution rate ratio (dissolution contrast) of the exposed and unexposed portions of the pattern relative to the alkaline developer, thereby providing excellent sensitivity and resolution. Furthermore, the photosensitive polyimide composition exhibits low warpage stress, excellent chemical resistance, and superior adhesion after high-temperature curing.

[0039] First, the following explanation is given regarding a standard for the solubility of component (a) in an alkaline aqueous solution. When component (a) is dissolved alone or together with other components in any solvent to obtain a photosensitive composition, and the resulting photosensitive composition is spin-coated onto a substrate such as a silicon wafer to form a coating film approximately 5 μm thick, and the coating film is immersed in an aqueous solution of tetramethylammonium hydroxide at 20-25°C, and dissolves to form a homogeneous solution, the component (a) used is considered soluble in the alkaline aqueous solution.

[0040] The aforementioned alkaline aqueous solutions refer to tetramethylammonium hydroxide aqueous solutions, metal hydroxide aqueous solutions, or organic amine aqueous solutions, etc.

[0041] Regarding the grafted polymer that is soluble in an alkaline aqueous solution as component (a), from the viewpoint of processability and heat resistance, its main chain backbone is preferably a polyimide-based polymer, and its grafted chain backbone is preferably a poly(p-hydroxystyrene)-based polymer.

[0042] 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:

[0043] Wherein, Ar1 is selected from tetrasubstituted organic groups, and Ar2 is selected from disubstituted organic groups; m+n=5-200, for example, 5, 10, 15, 20, 25, 35, 40, 50, 70, 75, 80, 85, 95, 100, 110, 120, 135, 150, 160, 175, 180, 185, 190, 195, 200, and any value between 5 and 200. n / (m+n)=0.05-1, for example, 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, 1, and any value between 0.05 and 1.

[0044] Furthermore, Ar1, each time it appears, is selected from any one of the tetrasubstituted organic groups shown in Formula 2 below, either identically or differently:

[0045] Among them, R1-R8 are all monosubstituted organic groups, and X1 is a disubstituted group.

[0046] Specifically, R1-R8 are each independently selected from hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl groups; preferably, R1-R8 are each independently selected from hydrogen, fluorine, methyl and trifluoromethyl groups.

[0047] X1 is selected from any one of oxygen, C1-C5 substituted or unsubstituted alkylene, sulfur, sulfone, and carbonyl, and X1 is selected from any one of oxygen, methylene, sulfur, sulfone, carbonyl, -C(CH3)2-, and -C(CF3)2-.

[0048] Specifically, in Formula 1, Ar1 is a tetrasubstituted organic group, generally a residue from a tetracarboxylic dianhydride or its derivative forming an amide ester structure with a diamine. It is preferably a tetrasubstituted aromatic group, preferably a tetracarboxylic dianhydride or its derivative residue having the following structure, where all four binding sites are located on the aromatic ring. The tetracarboxylic dianhydride can be, for example, 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, 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, 9,9 Aromatic tetracarboxylic dianhydrides such as bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, or aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. These can be used alone or in combination of two or more.

[0049] Furthermore, Ar2, each time it appears, is selected from any one of the disubstituted organic groups shown in Formulas 3-1 to 3-12, either identically or differently:

[0050] Among them, R9-R 20 All are monosubstituted organic groups, and Y is a disubstituted group;

[0051] Specifically, R9-R 20 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 any one of hydrogen, fluorine, methyl, and trifluoromethyl.

[0052] Y is selected from any one of the following: an oxygen group with two substitution positions, a C1-C5 substituted or unsubstituted alkylene group, a sulfur group, a sulfone group, and a carbonyl group; more preferably, Y is selected from any one of the following: an oxygen group with two substitution positions, a methylene group, a sulfur group, a sulfone group, a carbonyl group, -C(CH3)2-, and -C(CF3)2-.

[0053] Further, in Formula 1, Ar2 is a disubstituted organic group, generally a residue derived from an amino acid that forms an amide structure with an amino acid and a diamine. It is preferably a disubstituted aromatic group, and more preferably an amino acid residue having the following structure, with both binding sites located on the aromatic ring. The amino acid can be, for example, p-aminobenzoic acid, m-aminobenzoic acid, or o-aminobenzoic acid. The amino acid can be used alone or in combination with two or more.

[0054] 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. Preferably, 1-10 mol% of bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane are used.

[0055] 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 be selected to react with the polymer ends, thereby making 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%.

[0056] It should be noted that: (1) the above R1-R 20 The halogens mentioned are not limited to fluorine, but can also be bromine and chlorine, etc.

[0057] (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 unsubstituted alkyl groups like methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl or tert-butyl, or substituted alkyl groups like trifluoromethyl, trifluoroethyl, difluoromethyl or trichloromethyl.

[0058] (3) The above R1-R 20The C1-C5 substituted or unsubstituted alkylene mentioned can be C1-C3 unsubstituted alkylene, such as methylene, ethylene or propylene, or C1-C3 substituted alkylene, such as halogen (fluorine, bromine, chlorine) substituted methylene or halogen substituted ethylene.

[0059] The polymer's solubility in alkaline aqueous solutions originates from phenolic hydroxyl groups, therefore it is preferable to contain a certain proportion or higher of these structures; more preferably, k = 2 to 10. Excessively large k units can lead to a certain loss of film thickness in the exposed area, resulting in ineffective pattern replication. By adjusting the amount of p-hydroxystyrene grafted, the polymer's dissolution rate in alkaline aqueous solutions changes, thus enabling the acquisition of a photosensitive grafted composition with a suitable dissolution rate.

[0060] Furthermore, the polymer m+n represents the number of repeating structural units in component (a), with a value between 5 and 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; while when m+n is greater than 200, the composition becomes too viscous, affecting coating.

[0061] When each of the structures represented by Formula 1 contains 10% or more fluorine by weight, it exhibits an appropriate degree of water resistance at the interface of the film during development with an alkaline aqueous solution, preventing penetration at the interface. However, when the fluorine content exceeds 20% by weight, the solubility in the alkaline aqueous solution decreases. Therefore, the fluorine content is preferably 10-20% by weight.

[0062] 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 determined by gel permeation chromatography and is a value obtained by conversion from a standard polystyrene standard curve.

[0063] In the embodiments of this application, 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.

[0064] Specifically, the first step is to prepare polyamic acid by reacting diamine with dianhydride, and then prepare polyimide by chemical imidization; the second step is to obtain a macromolecular initiator by chloromethylation and xanthate esterification of the polyimide; the third step is to graft p-hydroxystyrene onto the macromolecular initiator prepared in the second step by RAFT polymerization to prepare a grafted polymer.

[0065] For the purpose of easily obtaining a cured film, the photosensitive polyimide composition provided in this application embodiment may contain component (b) a thermal crosslinking agent, wherein component (b1) is a crosslinking agent having an epoxy group, and component (b2) is a crosslinking agent having a -CH2OR group (R is hydrogen or a monosubstituted organic group). During the heat treatment process following coating, exposure, and development of the photosensitive polymer composition of this application, it reacts with the polymer (a) as component (b1) for crosslinking, or it self-polymerizes to form a compound during the heat treatment process. Furthermore, the crosslinking agent (b2) has an affinity for alkaline aqueous solutions, thereby increasing its dissolution rate in alkaline aqueous solutions.

[0066] In this application, component (b1) is a crosslinking agent having an epoxy group in its structure, wherein component (b1) is selected from the compounds shown in Formula 4-1 below:

[0067] The following are specific examples of compounds represented by Formula 4-1: 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 (the above are trade names manufactured by Dainippon Ink and Chemicals, Inc.), Rikaresin (registered trademark) BPO-20E, Rikaresin BEO-60E (the above are trade names manufactured by Shin Nippon Rikka), EP-4003S or EP-4000S (the above are trade names manufactured by ADEKA), etc. They can be used alone or in combination of two or more. In addition, this ingredient can be used alone or in combination with two or more of these compounds.

[0068] In this application, component (b2) is a crosslinking agent having a -CH2OR group (R is hydrogen or a monosubstituted organic group) in its structure. The compound may have one or more of this group, but preferably two or more. Component (b2) is selected from compounds shown in Formula 4-2-1 or 4-2-2 below.

[0069] In Equation 4-2-1, R 21 Each of the organic groups is independently hydrogen or monosubstituted, R 22Organic groups that are individually hydrogen or monosubstituted can also combine with each other to form ring structures that can have substituents.

[0070] In Equation 4-2-2, R 23 Selected from hydrogen or a monosubstituted organic group, R 24 X is selected from monosubstituted organic groups, where n is an integer from 1 to 4, and X is selected from monosubstituted to tetrasubstituted 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] Furthermore, in Formula 4-2-2, the organic groups that are monosubstituted to tetrasubstituted for X can include alkyl groups with 1-10 carbon atoms, alkylene groups with 2-10 carbon atoms (e.g., ethylene), arylene groups with 6-30 carbon atoms (e.g., phenylene), or groups obtained by replacing some or all of these hydroxyl hydrogens with halogens such as fluorine. These groups may further include phenyl, sulfone, carbonyl, ether, thioether, or amide bonds, 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.

[0075] The purity of the compound shown in Formula 4-2 is preferably 75% or higher, more preferably 85% or higher. When the purity of the compound shown in Formula 4-2 is 85% or higher, it exhibits excellent storage stability and can fully undergo the crosslinking 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 crosslinking agent include, for example, recrystallization or distillation. The purity of the thermal crosslinking agent can be determined using liquid chromatography.

[0076] Relative to 100 parts by weight of polyimide in component (a), the content of the thermal crosslinking agent in component (b) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more. If the content of the thermal crosslinking agent 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 the content of the thermal crosslinking agent is 10 parts by weight or more, the chemical resistance is even higher, the low curing warpage is better, and higher mechanical properties can be obtained. Additionally, considering the storage stability and mechanical strength of the composition, the content of the thermal crosslinking agent is preferably 30 parts by weight or less.

[0077] Furthermore, the content of b1 is 5-15 parts by weight, such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts, and any value between 5 and 15 parts; the content of b2 is 0.1-15 parts, such as 0.1, 0.5, 1, 2, 5, 7, 8, 10, 13, 14, 15 parts, and any value between 0.1 and 15 parts.

[0078] In this application, component (c) photoacid generator refers to a compound that generates acid upon exposure to radiation or the like. Under the action of this acid, the functional groups of the crosslinking agent react with the alkali-soluble resin, and the crosslinking agent is selected from the compounds shown in Formula 5 below:

[0079] In this formula, R' represents hydrogen, an alkyl group with 1-4 carbon atoms, or an alkoxy group with 1-4 carbon atoms, X represents halogen, and Y represents oxygen or sulfur. The triazine derivative shown in Formula 5 exhibits broad absorption in the gamma-ray, h-ray, and i-ray regions, and compared with other general radiation-sensitive acid-producing agents with a triazine skeleton, it has higher acid-producing efficiency and higher residual film rate.

[0080] In Formula 5, R represents hydrogen, an alkyl group having 1-4 carbon atoms, or an alkoxy group having 1-4 carbon atoms; X represents a halogen; and Y represents oxygen or sulfur. Examples of alkyl groups having 1-4 carbon atoms in R in Formula 5 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl. Furthermore, alkoxy groups having 1 to 4 carbon atoms, including methyloxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, or sec-butoxy, can be used as examples. Additionally, R is preferably hydrogen or an alkyl group having 1-4 carbon atoms, hydrogen, methyl, or ethyl.

[0081] In Formula 5 above, X, representing a halogen, is preferably fluorine, chlorine, bromine, or iodine, and more preferably chlorine. Specific triazine derivatives represented by Formula 5 include 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine or 2,4-bis(trichloromethyl)-6-p-methoxystyryl-S-triazine, etc.

[0082] The content of the photoacid generator in component (c) is preferably 0.5-5 parts, more preferably 1-3 parts, relative to 100 parts by weight of component (a) of polyimide, for example, any value between 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, and 1-3 parts. When the content of the photoacid generator is within the above range, higher sensitivity can be achieved.

[0083] The polyimide composition of this application further comprises component (d) a silane coupling agent, which is generally an organosilane compound, such as: γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-ureidopropyltriethoxysilane 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, or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.

[0084] When the polyimide composition contains an organosilane compound, it can improve the adhesion of the photosensitive polyimide composition to the substrate after curing. When containing an organosilane compound, the content of the organosilane compound is preferably 0.5-15 parts by weight, more preferably 0.5-10 parts by weight, relative to 100 parts by weight of component (a). Examples include 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, 15 parts, and any value between 0.5 and 15 parts.

[0085] The polyimide composition of this application further contains component (e) solvent, which is preferably an organic solvent, such as ketones, esters, lactones, ethers, halogenated hydrocarbons, or hydrocarbons, specifically 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-caprolactone. Polar solvents such as amines; other solvents 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, or propylene glycol 1-monomethyl ether 2-acetate, etc. Component (e) can be used alone or in combination with two or more.

[0086] 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, 60, 70, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900 and 50-1000 parts.

[0087] This application may further include component (f) a leveling agent, which may be a surfactant, thereby improving the coatability with the substrate. The surfactant may be, for example, a fluorinated surfactant such as Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name, manufactured by DIC Co., Ltd.), or Surflon (trade name, manufactured by Asahi Glass Co., Ltd.); an organosiloxane surfactant 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.), or BYK (trade name, manufactured by BYK-Chemie GmbH); or an acrylic polymer surfactant such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

[0088] Next, a method for manufacturing the photosensitive polyimide composition provided in the embodiments of this application will be described. For example, by uniformly mixing the above-mentioned components (a)-(d) and components (e)-(f) as needed, a photosensitive polyimide composition can be obtained. Dissolution methods may include, for example, 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, a method of dissolving compounds with low solubility can be used, starting with compounds with low solubility. In addition, 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.

[0089] The resulting photosensitive polyimide composition is preferably filtered using a filter 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, or 0.02 μm, but not limited to these. The filter material includes polypropylene (PP), polyethylene (PE), nylon (NY), or polytetrafluoroethylene (PTFE), preferably polyethylene or nylon. When the photosensitive polyimide composition contains inorganic particles, a filter with a pore size larger than the particle size of these inorganic particles is preferably used.

[0090] The cured product provided in this application embodiment can be obtained by curing the above-described positive photosensitive polyimide composition. The cured product of this application can be used as a patterned cured film or as a patternless cured film.

[0091] A method for manufacturing a patterned cured film includes, for example, a step of coating a substrate with the above-described positive photosensitive polyimide composition and drying it to form a photosensitive polyimide film (film formation step); a step of exposing the photosensitive polyimide film (exposure step); a step of developing the exposed photosensitive polyimide film using an alkaline aqueous solution to form a patterned polyimide film (development step); and a step of heating the patterned polyimide film (heating step). A method for manufacturing a patternless cured film includes, for example, the above-described film formation step and heating step, and may further include an exposure step.

[0092] In the film-forming process, the above-mentioned positive photosensitive polyimide composition is coated onto a metal substrate (e.g., Cu), glass substrate, semiconductor, metal oxide insulator (e.g., TiO2, SiO2), or silicon nitride support substrate by methods such as dip coating, spray coating, screen printing, or spin coating. From an operational point of view, the coated positive photosensitive polyimide composition can also be dried by heating (e.g., 90-150°C, 1-5 minutes) with a hot plate or oven; or the support substrate can be cleaned with acetic acid or the like before coating. The thickness of the resulting photosensitive polyimide film is preferably 5-20 μm.

[0093] 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.

[0094] 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. In the case of an alkali-soluble photosensitive polyimide composition, the developing solution can be, for example, an aqueous alkaline solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, or tetramethylammonium hydroxide (TMAH). The alkali concentration of these aqueous solutions is preferably set to 0.1-10% by mass. Furthermore, alcohols or surfactants can also be added to the aforementioned developing solution; preferably, 0.01-10 parts by mass of alcohol or surfactant, more preferably 0.1-5 parts by mass, per 100 parts by mass of the developing solution. The patterned photosensitive polyimide film is referred to as a patterned polyimide film.

[0095] In the heating process, heating the patterned polyimide film or photosensitive polyimide film can cure the photosensitive polyimide composition. 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. The heating process can also be multi-stage heating. The heat treatment can be performed using, for example, a quartz tube furnace, a hot plate, a rapid thermal annealing furnace, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace. Furthermore, it can be performed in the atmosphere or in an inactive atmosphere such as nitrogen, but oxidation of the pattern can be prevented when performed in an inactive atmosphere such as nitrogen; therefore, an inactive atmosphere such as nitrogen is preferred.

[0096] The cured product of this application can be used as an interlayer insulating film or a surface protective film, etc.

[0097] The interlayer insulating film and surface protective film of this application can be used in electronic components, etc., and the electronic components of this application can be used in semiconductor devices, etc. The semiconductor devices can be used in various electronic devices, etc., and a schematic diagram of the semiconductor packaging structure of this application is shown in Figure 1.

[0098] 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).

[0099] The aforementioned semiconductor device can be, for example, a wafer-level chip-scale package (WLCSP) or a fan-out wafer-level package (FOWLP). Furthermore, the interlayer insulating film and surface protective film of this application can also be used as a circuit forming substrate, which can be used for hard disk drive suspensions and flexible wiring boards, etc.

[0100] The features and performance of this application will be further described in detail below with reference to the embodiments.

[0101] ODA: 4,4-Diaminodiphenyl ether;

[0102] SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane;

[0103] ODPA: 4,4'-O-diphthalic anhydride;

[0104] Py: Pyridine;

[0105] Et2A: Acetic anhydride;

[0106] PhA: Phthalic anhydride;

[0107] NMP: N-methyl-2-pyrrolidone;

[0108] TMAH: Tetramethylammonium hydroxide;

[0109] CMM: Chloromethyl methyl ether;

[0110] SnCl4: Tin tetrachloride;

[0111] AIBN: Azobisisobutyronitrile;

[0112] 4-HS: p-hydroxystyrene;

[0113] St: Styrene;

[0114] 6FAP: 3,3-Diamino-4,4-Dihydroxydiphenyl-hexafluoropropane.

[0115] Synthesis example 1

[0116] 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.

[0117] 39.55 g of Py and 30.6 g of Et2A were added to a polyamic acid solution, and the mixture was heated to 120 °C and reacted 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.

[0118] 5g of dried polyimide resin was dissolved in 30mL of dichloroethane, and 80μL of SnCl4 was added. The mixture was heated to 70℃, and 3mL of CMM was slowly added dropwise to the system. The mixture was stirred for 5h. After the reaction was complete, the solution was poured into 300mL of methanol to precipitate the resin. The precipitate was washed and dried at 80℃ for 12h to obtain chloromethylated polyimide resin.

[0119] 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.

[0120] 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.

[0121] The specific testing method is as follows:

[0122] (1) Determination of molecular weight

[0123] The weight-average molecular weight was determined by gel permeation chromatography (GPC) under the following conditions using standard polystyrene. The weight-average molecular weight of polymer A was 39,000. The determination was performed using a solution of 1 mL of solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1:1 (volume ratio)] relative to 0.5 mg of A.

[0124] Measurement device: L4000UV detector manufactured by Hitachi, Ltd.;

[0125] Pump: L6000 manufactured by Hitachi Manufacturing Co., Ltd.;

[0126] C-R4A Chromatopac manufactured by Shimadzu Corporation;

[0127] Determination conditions: Gelpack GL-S300MDT-5 × 2 columns;

[0128] Eluent: THF / DMF = 1 / 1 (volume ratio), LiBr (0.03 mol / L), H3PO4 (0.06 mol / L);

[0129] Flow rate: 1.0 mL / min, detector: UV 270 nm;

[0130] (2) Determination of grafting rate n / (m+n)

[0131] In addition, NMR measurements were performed under the following conditions, and the grafting rate of A1 was calculated to be 40%.

[0132] Measurement equipment: Bruker BioSpin AV400M;

[0133] Magnetic field strength: 400MHz;

[0134] Reference material: Tetramethylsilane (TMS);

[0135] Solvent: Dimethyl sulfoxide (DMSO).

[0136] (3) Determination of grafting amount k

[0137] Under the following conditions, NMR measurements were performed, and the grafting amount k of A1 was calculated to be 3.5.

[0138] Measurement equipment: Bruker BioSpin AV400M;

[0139] Magnetic field strength: 400MHz;

[0140] Reference material: Tetramethylsilane (TMS);

[0141] Solvent: Dimethyl sulfoxide (DMSO).

[0142] Synthesis example 2

[0143] 192g methanol, 172.32g 4-HS, 19.53g St, and 15g AIBN were added sequentially to a four-necked flask and stirred until dissolved and clear. The air in the reaction vessel was purged with nitrogen under vacuum, and the temperature was raised to 75°C. The reaction was allowed to proceed for 18 hours, after which the reaction was stopped. A prepared sodium methoxide (0.4g) solution was slowly added to the reaction system, and the reaction was allowed to proceed for 6 hours. The mixture was then extracted 2-3 times with n-heptane at a 1:1 mass ratio to remove unreacted monomers and initiators. PGMEA was used to replace the methanol in the reaction solution to obtain a PGMEA solution of the desired concentration. PHS resin A2 was obtained, with a ratio of 80:20 between p-hydroxystyrene and styrene repeating units.

[0144] Synthesis example 3

[0145] 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.

[0146] 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, washed with water, and dried under vacuum at 80 °C to obtain polyimide resin A3.

[0147] Examples 1-10 and Comparative Examples 1-2

[0148] The photosensitive polyimide compositions of Examples 1-5 and Comparative Example 1 were prepared according to the ingredients and proportions shown in Tables 1-2. The proportions in Table 1 are the parts by mass of each component relative to 100 parts by mass of component (a).

[0149] The ingredients used are described below.

[0150] Component (b): Thermal crosslinking agent

[0151] Component (c): Photosensitizer

[0152] Component (d): Silane coupling agent: γ-ureapropyltriethoxysilane

[0153] Component (e): Solvent

[0154] e1: GBL (γ-butyrolactone)

[0155] e2: EL (ethyl lactate)

[0156] Table 1

[0157] Table 2

[0158] The performance of the photosensitive polyimide compositions prepared in the examples and comparative examples was evaluated using the following methods:

[0159] (1) Preparation of developing film

[0160] The photosensitive polyimide compositions (varnish) prepared in the examples and comparative examples were spin-coated onto an 8-inch silicon wafer. Then, a 6 μm thick pre-baked film was prepared by heat treatment (pre-baking) at 120°C for 3 minutes using a hot plate (Tokyo Electron Ltd., Mark-7 coating and developing apparatus). An i-line stepper (Nikon Corporation, NSR-2005i9C) was used at 50-400 mJ / cm². 2 Exposure, 10mJ / cm 2 The pre-baked film is exposed by the stepping process. After exposure, the photosensitive polyimide composition is exposed at 100°C for 1 minute and then baked. 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.

[0161] (2) Methods for measuring film thickness

[0162] 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.

[0163] (3) Determination of warpage

[0164] A varnish was applied using a spin-coating and developing apparatus ACT-8, followed by pre-baking. After pre-baking at 120°C for 3 minutes, the film thickness was 10 μm. Then, using an inert oven, the temperature was increased to 200°C at a rate of 3.5°C / min under conditions of oxygen concentration below 20 ppm, and 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 (manufactured by KLATencor). 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).

[0165] (4) Evaluation of alkali solubility and minimum development time

[0166] The photosensitive compositions (varnish) prepared in the examples and comparative examples were spin-coated onto an 8-inch silicon wafer. Then, a 10 μm thick prebaked film was prepared by heat treatment (prebaking) at 120°C for 3 minutes using a hot plate (Tokyo Electron Ltd., using a Mark-7 coating and developing apparatus). The film was developed using a 2.38 wt% tetramethylammonium (TMAH) aqueous solution, and the minimum development time was recorded after the film was completely dissolved. The results are shown in Table 3.

[0167] (5) Evaluation of chemical resistance

[0168] 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 then cleaned with NMP at 45°C and immersed for 1 hour before the film thickness was measured.

[0169] 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.

[0170] (6) Adhesion evaluation

[0171] 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.

[0172] An adhesive tape (manufactured by 3M Japan Co., Ltd.) was applied to the cured material and then 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 removed.

[0173] A: The number of remaining grid cells is 100-80;

[0174] B: The number of remaining cells is less than 80.

[0175] The results are shown in Table 3.

[0176] (7) Evaluation of elongation at break

[0177] 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.

[0178] The results showed that cases with an elongation at break of more than 30% were considered excellent (A), cases with 20-30% were considered good (B), cases with 10-20% were considered poor (C), and cases with <10% were considered very poor (D).

[0179] Table 3

[0180] As can be seen from Table 3, the photosensitive polyimide compositions provided in Examples 1-10 of this application all exhibit strong alkali solubility, excellent low warpage stress, and excellent chemical resistance. Compared with the examples, Comparative Example 1 has poorer toughness and slightly lower alkali solubility; while Comparative Example 2 has high warpage stress, poorer alkali solubility, poorer adhesion to the substrate, and poorer chemical stability.

[0181] The foregoing description of specific exemplary embodiments of this application is for illustrative and explanatory purposes. These descriptions are not intended to limit this application to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of this application and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of this application, as well as various different choices and variations. The scope of this application is intended to be defined by the claims and their equivalents.

Claims

1. A photosensitive polyimide composition, wherein the raw materials comprise the following components, in parts by weight: a block polymer 100 parts, which is soluble in aqueous alkaline solution, having the structure wherein R is Ar1 is selected from tetrasubstituted organic groups, and Ar2 is selected from disubstituted organic groups; m+n=5-200, n / (m+n)=0.05-1, and k=2-10; 5-30 parts of thermal crosslinking agent, selected from crosslinking agents containing epoxy groups or crosslinking agents containing -CH2OR; a photoacid generator in an amount of 0.5 to 5 parts, which has a structural formula of Wherein, R' is selected from hydrogen, alkyl groups having 1-4 carbon atoms, or alkoxy groups having 1-4 carbon atoms, X is selected from halogens, and Y is oxygen or sulfur; 0.5-10 parts of silane coupling agent.

2. The photosensitive polyimide composition according to claim 1, wherein The tetrasubstituted organic groups of Ar1 are selected from: R1-R8 are all monosubstituted organic groups, and X1 is a disubstituted group.

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

4. The photosensitive polyimide composition according to claim 3, wherein The monosubstituted organic groups of R1-R8 are selected from any one of hydrogen, fluorine, methyl and trifluoromethyl.

5. The photosensitive polyimide composition according to claim 2, wherein The disubstituted group of X1 is selected from any one of oxygen, C1-C5 substituted or unsubstituted alkylene groups, sulfur, sulfone, and carbonyl.

6. The photosensitive polyimide composition according to claim 5, wherein The disubstituted group of X1 is selected from any one of oxygen, methylene, sulfur, sulfone, carbonyl, -C(CH3)2- and -C(CF3)2-.

7. The photosensitive polyimide composition according to claim 1, wherein the disubstituted organic group of Ar2 is selected from: wherein R9-R 20 are each monosubstituted organic radicals and Y is a disubstituted radical.

8. The photosensitive polyimide composition according to claim 7, wherein R9-R 20 each of said monosubstituted groups is independently selected from any one of: hydrogen, halogen, C1-C5 substituted alkyl, and C1-C5 unsubstituted alkyl.

9. The photosensitive polyimide composition according to claim 8, wherein R9-R 20 each of said monosubstituting groups is independently selected from any one of: hydrogen, fluorine, methyl and trifluoromethyl.

10. The photosensitive polyimide composition according to claim 7, wherein The disubstituted group of Y is selected from any one of oxygen, C1-C5 substituted alkylene, C1-C5 unsubstituted alkylene, sulfur, sulfone, and carbonyl.

11. The photosensitive polyimide composition according to claim 10, wherein The disubstituted group of Y is selected from any one of oxygen, methylene, sulfur, sulfone, carbonyl, -C(CH3)2- and -C(CF3)2-.

12. The photosensitive polyimide composition according to claim 1, wherein The thermal crosslinking agent is selected from a compound represented by any of the following formulae: Wherein, U is selected from disubstituted organic groups containing alicyclic or aromatic rings; R 21 Independently selected from: hydrogen or a monosubstituted organic group, R 22 Selected from hydrogen, monosubstituted organic groups, or ring structures with substituents; R 23 Selected from hydrogen, monosubstituted organic groups; R 24 X2 is selected from monosubstituted organic groups, where n is an integer from 1 to 4; X2 is selected from monosubstituted organic groups, disubstituted organic groups, trisubstituted organic groups, or tetrasubstituted organic groups; a is an integer from 1 to 4, and b is an integer from 0 to 3.

13. The photosensitive polyimide composition according to any one of claims 1 to 12, wherein It also includes 100-200 parts solvent and / or 100-1000 ppm leveling agent.

14. A method for manufacturing a pattern, comprising coating a support substrate with the photosensitive polyimide composition as described in any one of claims 1-13, and subjecting it to drying, exposure, development, and heat treatment.

15. The method of manufacturing a pattern according to claim 14, wherein The light source used for the exposure is i-rays.

16. A photocurable structure obtained by the method of manufacturing the pattern as described in claim 14 or 15.

17. An electronic component comprising a body and a photocurable structure as described in claim 16 formed thereon.

18. An apparatus comprising a body and electronic components disposed on the body as described in claim 17.

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