Photosensitive polyimide composition, method for producing pattern, cured product, and electronic component

Abstract

The invention relates to the technical field of photosensitive dielectric materials, in particular to a photosensitive polyimide composition, a pattern manufacturing method, a cured product and an electronic component. The photosensitive polyimide composition includes a component (a) which is soluble in an alkaline aqueous solution and is selected from compounds represented by the following structural formula: # imgabs0 # wherein Ar1 is selected from a tetravalent organic group and Ar2 is selected from a divalent organic group; m + n = 5-200, n / (m + n) = 0.05-1, and k = 2-10; (b) a photosensitizer; (c) a thermal crosslinking agent; the cross-linking agent comprises a component (c1) which contains an epoxy group and a component (c2) which contains CH2OR '; and (d) a silane coupling agent. The photosensitive polyimide composition has extremely excellent sensitivity and resolution, can copy fine patterns, has low warping stress after being cured at 200 DEG C, and has high chemical stability and cohesiveness.

Description

Technical Field

[0001] The present invention relates to the technical field of photosensitive dielectric materials, and in particular to a photosensitive polyimide composition, a method for producing a pattern, a cured product and an electronic component. Background Art

[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] There are literature reports on lowering the glass transition temperature of PI polymer and assisting with a thermal alkali generator (WO2018225676A1). This method can achieve low-temperature curing at 200-230 degrees to obtain a negative PSPI cured product with excellent adhesion. However, this method cannot achieve the requirements of high sensitivity, high resolution and low warpage stress.

[0004] Other literature reports the use of chemically imidized PI polymers with phenolic hydroxyl or carboxyl groups, assisted by a suitable crosslinking agent (CN102575139A). This method can achieve low-temperature curing at 200-230°C, and obtain a positive PSPI cured product with excellent chemical resistance. However, this method has limited improvement in chemical resistance, and the sensitivity of this composition is generally low.

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

[0006] In view of this, the present invention is proposed. Summary of the invention

[0007] An object of the present invention is to provide a photosensitive polyimide composition, a method for producing a pattern, a cured product, and an electronic component.

[0008] The present invention is achieved in that:

[0009] In a first aspect, the present invention provides a photosensitive polyimide composition, which includes component (a) a graft polymer soluble in an alkaline aqueous solution, which is selected from the compounds represented by the following structural formula:

[0010]

[0011] wherein Ar1 is selected from a tetravalent organic group, Ar2 is selected from a divalent organic group; m+n=5 to 200, n / (m+n)=0.05 to 1, k=2 to 10;

[0012] Component (b) a photosensitizer;

[0013] Component (c) a thermal crosslinking agent; which includes a component (c1) a crosslinking agent containing an epoxy group and a component (c2) a crosslinking agent containing CH2OR'; R' represents a hydrogen atom or a monovalent organic group;

[0014] Component (d) Silane coupling agent.

[0015] In a second aspect, the present invention provides a method for manufacturing a pattern, comprising coating the photosensitive polyimide composition described in any one of the aforementioned embodiments on a supporting substrate;

[0016] Preferably, the method further comprises: drying, exposure, development and heating treatment in sequence after coating;

[0017] Preferably, the light source used in the exposure process is i-ray.

[0018] In a third aspect, the present invention provides a cured product, wherein the cured product is formed by curing the photosensitive polyimide composition according to any one of the aforementioned embodiments;

[0019] Preferably, the cured product includes a surface protection film or an interlayer insulating film.

[0020] In a fourth aspect, the present invention provides an electronic component, comprising the cured product described in the above embodiment.

[0021] The present invention has the following beneficial effects: the photosensitive polyimide composition formed by selecting specific components has excellent sensitivity and resolution, high chemical stability and adhesion, and low warpage stress after low-temperature curing (180-200°C). At the same time, the part of the photosensitive polyimide composition exposed to ultraviolet light is easily soluble in alkaline aqueous solution, while the part not exposed to ultraviolet light is insoluble in alkaline aqueous solution, so that fine patterns can be effectively replicated. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0023] Figure 1A schematic diagram of a semiconductor packaging structure provided by an embodiment of the present invention. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0025] The embodiment of the present invention provides a photosensitive polyimide composition, which contains the following components:

[0026] (a) a graft polymer soluble in alkaline aqueous solution; (b) a photosensitizer; (c) a thermal crosslinking agent; (d) a silane coupling agent.

[0027] The photosensitive polyimide composition provided by the embodiment of the present invention is easily soluble in alkaline aqueous solution in the part exposed to ultraviolet light, while the part not exposed to ultraviolet light is insoluble in alkaline aqueous solution, so that fine patterns can be effectively replicated. The photosensitive polyimide composition of the present invention increases the dissolution rate ratio (dissolution contrast) of the exposed part of the pattern to the unexposed part relative to the alkaline developer, so that the sensitivity and resolution are excellent. At the same time, the photosensitive polyimide composition has low warping stress after low-temperature curing (180-200°C), and has excellent chemical resistance and adhesion.

[0028] First, a standard for component (a) being soluble in an alkaline aqueous solution is described below. When a photosensitive composition obtained by dissolving component (a) alone or together with other components in any solvent is spin-coated on a substrate such as a silicon wafer to form a coating film having a thickness of about 5 μm, and the coating film is immersed in an aqueous solution of tetramethylammonium hydroxide at 20-25°C and dissolves to form a uniform solution, component (a) is considered to be soluble in an alkaline aqueous solution.

[0029] The alkaline aqueous solution is any one of a tetramethylammonium hydroxide aqueous solution, a metal hydroxide aqueous solution, an organic ammonia aqueous solution, and the like.

[0030] The graft polymer soluble in an alkaline aqueous solution as component (a) is preferably a polyimide polymer in terms of processability and heat resistance, and the graft chain skeleton is preferably a polyhydroxystyrene polymer composed of p-hydroxystyrene.

[0031] Furthermore, component (a) is more preferably a graft copolymer of polyimide-poly(p-hydroxystyrene), a polymer having a structural unit represented by the following formula 1:

[0032]

[0033] In the embodiments of the present invention, m+n represents the number of repeating structural units of component (a), and the value of m+n is 5 to 200. When m+n is less than 5, the viscosity of the composition is too low, resulting in the composition being unable to be used as a thick film, and when m+n is greater than 200, the composition becomes too viscous, affecting coating.

[0034] 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 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 0.05-1.

[0035] The solubility of component (a) in alkaline aqueous solution originates from phenolic hydroxyl groups, so it is preferred to contain a structure of a certain proportion or more. That is, k = 2 to 10. For example, it is any value between 2 and 10, such as 2, 3, 4, 5, 6, 7, 8, 9 and 10. Too large a k unit will cause a certain film thickness loss in the exposed area, resulting in an inability to effectively replicate the pattern. Therefore, by adjusting the grafting amount of para-hydroxystyrene, the dissolution rate of the polymer in the alkaline aqueous solution changes, so that a photosensitive grafted composition with a moderate dissolution rate can be obtained.

[0036] Further, Ar1 is selected from a quaternary organic group, for example, Ar1 is selected from any one of the quaternary organic groups represented by the following formula 2, the same or different each time it appears:

[0037]

[0038] Wherein, R1-R8 are all monovalent organic groups, and X is a divalent group.

[0039] Specifically, R1-R8 are each independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; for example, R1-R8 are each independently selected from any one of but not limited to hydrogen, fluorine atom, methyl and trifluoromethyl.

[0040] X is selected from any one of an oxygen atom, a C1-C5 substituted or unsubstituted alkylene group, a sulfur atom, a sulfone group and a carbonyl group, and X includes but is not limited to any one of an oxygen atom, a methylene group, a sulfur atom, a sulfone group, a carbonyl group, C(CH3)2 and C(CF3)2.

[0041] Specifically, in Formula 1, Ar1 is a tetravalent organic group, generally a residue of tetracarboxylic dianhydride or its derivatives with an amide ester structure formed by tetracarboxylic dianhydride or its derivatives and diamine, preferably a tetravalent aromatic group, preferably a residue of tetracarboxylic dianhydride or its derivatives having the following structure, wherein all four binding sites are present 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'benzophenonetetracarboxylic dianhydride, 2,2',3,3'benzophenonetetracarboxylic 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 dianhydride, 9,,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, Aromatic tetracarboxylic dianhydrides such as 9,9-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, and aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride, etc. These may be used alone or in combination of two or more.

[0042] Further, Ar2 is selected from a divalent organic group, for example, Ar2 is selected from any one of the divalent organic groups shown in Formula 3, the same or different each time it appears:

[0043]

[0044] Among them, R9-R 20 are all monovalent organic groups, and Y is a divalent group.

[0045] Specifically, R9-R 20 Each is independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; preferably, R9-R 20 Each is independently selected from but not limited to any one of hydrogen, fluorine, methyl and trifluoromethyl.

[0046] Y is selected from any one of an oxygen atom, a C1-C5 substituted or unsubstituted alkylene group, a sulfur atom, a sulfone group and a carbonyl group; Y includes but is not limited to any one of an oxygen atom, a methylene group, a sulfur atom, a sulfone group, a carbonyl group, C(CH3)2 and C(CF3)2.

[0047] Furthermore, in Formula 1, Ar2 is a divalent organic group, generally an amide structure formed by an amino acid and a diamine, and is derived from an amino acid residue, preferably a divalent aromatic group, preferably an amino acid residue having the following structure, wherein both binding sites are present on the aromatic ring, and such amino acids include p-aminobenzoic acid, m-aminobenzoic acid, ortho-aminobenzoic acid, etc. They can be used alone or in combination of two or more.

[0048] In addition, in order to improve adhesion to the substrate, as long as the heat resistance is not damaged, the Ar2 part can be selected to copolymerize with a certain proportion of aliphatic groups with a siloxane structure, preferably 1-10 mol% of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc.

[0049] The terminal groups of the aromatic polyamide shown in Formula 1 are carboxylic acid or amine depending on the input ratio of Ar1 and Ar2. As required, one or two end-capping agents may react with the polymer ends to make one or both ends saturated aliphatic groups, unsaturated aliphatic groups, carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups or mercapto groups, etc. In this case, the end-capping rate is preferably 30-100%.

[0050] It should be noted that: (1) the above R1-R 20 The halogen mentioned in is not limited to F, and may also be bromine, chlorine, and the like.

[0051] (2) The above R1-R 20 The C1-C5 substituted or unsubstituted alkyl mentioned in the above may be a C1-C3 substituted or unsubstituted alkyl, for example, it may be an unsubstituted alkyl such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, tert-butyl, or a substituted alkyl such as trifluoromethyl, trifluoroethyl, difluoromethyl, trichloromethyl.

[0052] (3) The above R1-R 20 The C1-C5 substituted or unsubstituted alkylene mentioned in the above may be C1-C3 unsubstituted alkylene, such as methylene, ethylene, propylene and other unsubstituted alkylene, or may be C1-C3 substituted alkylene, such as halogen (fluorine, bromine, chlorine) substituted methylene, halogen substituted ethylene, etc.

[0053] The molecular weight of component (a) is preferably 3000 to 200000, more preferably 5000 to 100000, as a weight average molecular weight. The molecular weight here is a value measured by gel permeation chromatography and converted from a standard polystyrene calibration curve.

[0054] In the embodiments of the present invention, the graft polymer having the structural unit shown in Formula 1 is generally prepared by polycondensation of dianhydride and diamine to obtain a polyamic acid polymer, which is then chemically imidized to obtain a polyimide polymer, which is then chloromethylated and xanthate-esterified to obtain a macromolecular initiator, and then grafted polymerized to obtain a graft copolymer of polyimide-g-poly(p-hydroxystyrene).

[0055] Specifically, in the first step, polyamic acid can be prepared by reacting diamine with dianhydride, and then polyimide can be prepared by chemical imidization. In the second step, the polyimide is chloromethylated and xanthate-esterified to obtain a macroinitiator. In the third step, the macroinitiator prepared in the second step is grafted with p-hydroxystyrene by RAFT polymerization to prepare a grafted polymer. The specific conditions in the above preparation process are all well known to those skilled in the art, and therefore, the embodiments of the present invention will not be described in detail.

[0056] In the present invention, a quinonediazide compound is used as the photosensitizer of component (b), and naphthoquinonediazide-5-sulfonyl and naphthoquinonediazide-4-sulfonyl can be preferably used. In the present invention, naphthoquinonediazide-5-sulfonyl ester compounds using naphthoquinonediazide-4-sulfonyl in the same molecule can be obtained, and naphthoquinonediazide-5-sulfonyl ester compounds and naphthoquinonediazide-4-sulfonyl ester compounds can also be mixed and used.

[0057] Among them, the (b) quinonediazide compound more preferably comprises an ester formed of a phenol compound and naphthoquinonediazide-5-sulfonyl group, whereby high sensitivity can be obtained under i-line exposure.

[0058] The content of the quinonediazide compound (b) is preferably 5-20 parts, more preferably 8-15 parts, for example, any value between 5-20 parts such as 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 16 parts, 18 parts and 20 parts, relative to 100 parts by weight of the polyimide of the component (a). By making the content of the quinonediazide compound within the above range, higher sensitivity can be achieved, and a sensitizer can be added as needed.

[0059] The photosensitive polyimide composition provided by an embodiment of the present invention may contain (c) a thermal crosslinking agent for the purpose of easily obtaining a cured film. Among them, component (c1) is a crosslinking agent having an epoxy group, and component (c2) is a crosslinking agent having a -CH2O′R (R′ is a hydrogen atom or a monovalent organic group) group. In the heat treatment process after coating, exposing and developing the photosensitive polymer composition of the present invention, it reacts with the polymer as component (a) to crosslink, or a compound that polymerizes itself during the heat treatment process. In addition, the crosslinking agent as component (c2) has affinity for alkaline aqueous solutions and can increase the dissolution rate in alkaline aqueous solutions.

[0060] In an embodiment of the present invention, component (c1) is a cross-linking agent having an epoxy group in its structure, specifically, selected from the compound represented by the following formula 4-1,

[0061]

[0062] The following are specific examples of the compound represented by Formula 4-1, for example, including but 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 (above, trade names, manufactured by Dainippon Ink and Chemicals, Inc.), Rikaresin (registered trademark) BPO-20E, Rikaresin BEO-60E (above, trade names, manufactured by Shin Nippon Rika Chemical), EP-4003S and EP-4000S (above, trade names, manufactured by ADEKA), etc.

[0063] It should be noted that the above-mentioned components (c1) can be used alone or in combination of two or more.

[0064] In the present invention, component (c2) is a crosslinking agent having a -CH2OR' (R' is a hydrogen atom or a monovalent organic group) group in its structure. The compound may have at least one -CH2OR' group, but preferably two or more.

[0065] The component (c2) is selected from the compounds represented by the following formula 4-2-1 or 4-2-2.

[0066]

[0067] In formula 4-2-1, R 21 are each independently a hydrogen atom or a monovalent organic group, R 22 Each of them is independently a hydrogen atom or a monovalent organic group, and may be combined with each other to form a ring structure which may have a substituent.

[0068] In formula 4-2-2, R 23 is selected from a hydrogen atom or a monovalent organic group, R 24is selected from a monovalent organic group, n is an integer of 1-4, X is selected from a single bond or a 1-4 valent organic group. a is an integer of 1-4, b is an integer of 0-3, when a is 2, 3 or 4, R 23 Same or different, when b is 2 or 3, R 24 Same or different.

[0069] In formula 4-2-2, as the 1-4 valent organic group of X, there can be listed an alkyl group having 1-10 carbon atoms, an alkylene group having 2-10 carbon atoms (such as ethylene), an arylene group having 6-30 carbon atoms (such as phenylene), or a group obtained by replacing part or all of the hydrogen atoms of these hydroxy groups with halogen atoms such as fluorine atoms, and these groups may further include phenyl, sulfone, carbonyl, ether bond, thioether bond, amide bond, etc. R 23 Preferably, it is hydrogen, alkyl or alkenyl. The number of carbon atoms in the alkyl or alkenyl group is preferably 1 to 20. 24 It is preferably an alkyl group, an alkenyl group, an alkoxyalkyl group or a hydroxymethyl group, and the number of carbon atoms is preferably 1-20.

[0070] Furthermore, the following formula 4-2-1-1 shows specific examples of the compound represented by formula 4-2-1, and these compounds can be used alone or in combination of two or more.

[0071]

[0072] Among them, R 25 is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, R 26 It is an alkyl group having 1 to 10 carbon atoms.

[0073] The following formula 4-2-2-1 shows specific examples of the compound represented by formula 4-2-2. These compounds can be used alone or in combination of two or more.

[0074]

[0075] The purity of the compound represented by the above formula 4-2 is preferably 75% or more, more preferably 85% or more. When the purity is 85% or more, the storage stability is excellent, and the crosslinking reaction of the polyimide composition can be fully carried out. In addition, since the unreacted groups that become water-absorbing groups can be reduced, the water absorption of the polyimide composition can be reduced. As a method for obtaining a high-purity thermal crosslinking agent, recrystallization, distillation, etc. can be cited. The purity of the thermal crosslinking agent can be obtained by liquid chromatography.

[0076] Relative to 100 parts by mass of the polyimide of component (a), the content of the thermal crosslinking agent of component (c) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more. If it is 5 parts by mass or more, the crosslinking density of the cured film is improved, the chemical resistance is high, and there is low curing warpage, and if it is 10 parts by mass or more, the chemical resistance is higher, the low curing warpage is better, and higher mechanical properties can be obtained at the same time. In addition, from the perspective of composition storage stability and mechanical strength, it is preferably less than 30 parts by mass.

[0077] Further, the content of c1 is 5-15 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts and 15 parts, etc., any value between 5-15 parts; the content of c2 is 0.1-15 parts, for example, 0.1 parts, 0.5 parts, 1 parts, 2 parts, 5 parts, 7 parts, 8 parts, 10 parts, 13 parts, 14 parts and 15 parts, etc., any value between 0.1-15 parts.

[0078] The polyimide composition provided in the embodiment of the present invention further contains (d) a silane coupling agent, which is generally an organic silane compound. Examples of the organic silane compound include: γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, γ-glycidyloxypropyl triethoxysilane, γ-glycidyloxypropyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-acryloxypropyl trimethoxysilane, γ-ureidopropyl triethoxysilane, Silane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, triethoxysilylpropylethyl carbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(l,3-dimethylbutylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.

[0079] When an organosilane compound is included, the adhesion between the photosensitive polyimide composition and the substrate after curing can be improved. When an organosilane compound is included, the content of the organosilane compound is 0.5-15 parts by mass, more preferably 0.5-10 parts by mass, relative to 100 parts by mass of component (a). For example, it is any value between 0.5-15 parts such as 0.5 parts, 1 parts, 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.

[0080] The polyimide composition of the present invention further contains (e) a solvent, preferably an organic solvent. For example, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can be used. 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 triamide, dimethylimidazolidinone, tetraethyl urea, tetramethyl urea, ethyl lactate, 3-methoxy-N,N-dimethylpropaneamide and N-acetyl-ε-caprolactam. Other examples 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, and propylene glycol 1-monomethyl ether 2-acetate. Component (e) may be used alone or in combination of two or more.

[0081] When component (e) is included, the amount of component (e) is preferably 50-1000 parts by mass, more preferably 100-200 parts by mass, relative to 100 parts by mass of component (a), for example, 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, and any value between 50 and 1000 parts.

[0082] The present invention may further contain (f) a leveling agent. The leveling agent may be a surfactant, thereby improving the coating property between the substrate and the substrate. Examples of the surfactant include fluorine-based 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.);

[0083] Organic silicone 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); acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0084] The sulfur content of component (f) is 100-1000 ppm relative to 100 parts by mass of component (a), 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.

[0085] Next, the manufacture method of the photosensitive polyimide composition provided by the embodiment of the present invention is described. For example, by uniformly mixing the above-mentioned (a)-(d) components and the (e)-(f) components used as needed, the photosensitive polyimide composition can be obtained. As a dissolving method, stirring and heating can be cited. When heating, it is preferred to set the heating temperature within the range of not destroying the performance of the polyimide composition, usually room temperature-80. In addition, the dissolution order of each component is not particularly limited, for example, including a method of dissolving in sequence from a compound with low solubility. In addition, for components such as surfactants and a part of a close fit improver that are prone to generate bubbles when stirred and dissolved, the poor dissolution of other components caused by the generation of bubbles can be prevented by adding them last after dissolving other components.

[0086] The obtained 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, 0.02 μm, etc., but not limited to this. The material of the filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., preferably polyethylene and nylon. When the photosensitive polyimide composition contains inorganic particles, it is preferred to use a filter with a pore size larger than the particle size of these inorganic particles.

[0087] The embodiment of the present invention provides a cured product, which can be obtained by curing the above-mentioned photosensitive polyimide composition. The cured product of the present invention can be used as a patterned cured film or a non-patterned cured film.

[0088] The method for manufacturing a patterned cured film includes, for example, a process of coating a photosensitive polyimide composition provided by an embodiment of the present invention on a substrate and drying it to form a photosensitive polyimide film (film forming process); a process of exposing the photosensitive polyimide film (exposure process); a process of developing the exposed photosensitive polyimide film with an alkaline aqueous solution to form a patterned polyimide film (development process); and a process of heating the patterned polyimide film (heating process). The method for manufacturing a non-patterned cured film includes, for example, the above-mentioned film forming process and heating process. It may also further include an exposure process.

[0089] In the film forming process, the photosensitive polyimide composition is coated on a metal substrate such as Cu, a glass substrate, a semiconductor, a metal oxide insulator (such as TiO2, SiO2, etc.) or a supporting substrate such as silicon nitride by, for example, dipping, spraying, screen printing, spin coating, etc. From the viewpoint of operability, the coated photosensitive polyimide composition can also be used by drying by heating (for example, 90-150, 1-5 minutes) using a hot plate or an oven, etc. The supporting substrate can also be cleaned with acetic acid, etc. before coating. The film thickness of the obtained photosensitive polyimide film is preferably 5-20 μm.

[0090] In the exposure step, for example, the photosensitive polyimide film formed on the substrate is irradiated with the above-mentioned active light rays through a mask. From the viewpoint of transparency of the component (a), irradiation with i-rays can be preferably used.

[0091] In the developing process, for example, the exposure portion of the photosensitive polyimide film after the exposure process is removed with a developer, so that the photosensitive polyimide film is patterned. As a developer, in the case of an alkali-soluble photosensitive polyimide composition, an alkali aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine or tetramethylammonium hydroxide (TMAH) can be suitably used. The alkali concentration of these aqueous solutions is preferably set to 0.1-10 mass %. Alcohols or surfactants can also be added to the above-mentioned developer and used. They can be respectively coordinated with a range of preferably 0.01-10 mass parts, more preferably 0.1-5 mass parts relative to 100 mass parts of the developer. The photosensitive polyimide film after patterning is referred to as a patterned polyimide film.

[0092] In the heating process, by heating the pattern polyimide film or the photosensitive polyimide film, the photosensitive polyimide composition can be cured. In particular, the film obtained by curing the pattern polyimide film is called a pattern cured film. The heating temperature is preferably 150-250, preferably less than or equal to 230, more preferably greater than or equal to 170, and more preferably 180-200. The heating time is preferably 20 minutes to 6 hours, more preferably 30 minutes to 3 hours. Multi-stage heating can also be performed. Heat treatment can be performed using ovens such as quartz tube furnaces, hot plates, rapid annealing furnaces (rapid thermal anneal), vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces. In addition, any one of the inert atmospheres such as the atmosphere or nitrogen can also be selected, but when carried out under nitrogen, oxidation of the pattern can be prevented, so inert atmospheres such as nitrogen are preferred.

[0093] The cured product of the present invention can be used as an interlayer insulating film, a surface protective film, or the like.

[0094] The interlayer insulating film and surface protection film of the present invention can be used in electronic components, etc. The electronic components provided by the embodiments of the present invention can be used in semiconductor devices, etc. The semiconductor devices can be used in various electronic devices, etc. The semiconductor packaging structure schematic diagram of the present invention is shown in FIG. Figure 1 shown.

[0095] This exhibits excellent rust prevention and adhesion effects on a supporting substrate (particularly a copper substrate or a copper alloy substrate), and can suppress discoloration of the cured film or the supporting substrate (particularly a copper substrate or a copper alloy substrate).

[0096] As the semiconductor device, for example, semiconductor packages such as wafer level chip size package (WLCSP) and fan-out wafer level package (FOWLP) can be cited. In addition, the interlayer insulating film and surface protection film of the present invention can also be used for a circuit forming substrate, and the circuit forming substrate can be used for a hard disk drive suspension, a flexible wiring board, etc.

[0097] The abbreviations of the compounds provided in the embodiments of the present invention are as follows: ODA: 4,4-diaminodiphenyl ether; SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane; ODPA: 4,4'-oxydiphthalic 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.

[0098] The molecular weight, grafting ratio (n / (m+n)) and grafting amount (k) of component (a) are determined as follows:

[0099] (1) Determination of molecular weight

[0100] The number average molecular weight was determined by gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene: The measurement was performed using 1 mL of a solution containing 0.5 mg of A and a solvent of [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)].

[0101] Measuring apparatus: detector: L4000UV manufactured by Hitachi, Ltd.; pump: L6000 manufactured by Hitachi, Ltd.; C-R4A Chromatopac manufactured by Shimadzu Corporation.

[0102] Measurement conditions: Chromatographic columns Gelpack GL-S300MDT-5 × 2 pieces.

[0103] Eluent: THF / DMF=1 / 1 (volume ratio), LiBr (0.03 mol / L), H3PO4 (0.06 mol / L).

[0104] Flow rate: 1.0 mL / min, detector: UV 270 nm.

[0105] (2) Determination of grafting ratio n / (m+n)

[0106] In addition, NMR measurement was performed under the following conditions.

[0107] Measurement equipment: AV400M manufactured by Bruker BioSpin.

[0108] Magnetic field strength: 400MHz.

[0109] Reference substance: tetramethylsilane (TMS).

[0110] Solvent: dimethyl sulfoxide (DMSO).

[0111] (3) Determination of grafting amount k

[0112] NMR measurement was performed under the following conditions.

[0113] Measurement equipment: AV400M manufactured by Bruker BioSpin.

[0114] Magnetic field strength: 400MHz.

[0115] Reference substance: tetramethylsilane (TMS).

[0116] Solvent: dimethyl sulfoxide (DMSO).

[0117] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0118] Synthesis example 1

[0119] This synthesis example provides a method for preparing component (a), comprising:

[0120] 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 cooled to -10°C. Subsequently, 26.37 g (0.085 mol) of ODPA was slowly added thereto so that the temperature of the reaction solution did not exceed 0°C, and stirring was continued for 3 hours, and then 4.44 g (0.03 mol) of PhA was added, and stirring was continued for 2 hours at room temperature to obtain a polyamic acid solution.

[0121] 39.55 g of Py and 30.6 g of Et2A were added to the polyamic acid solution, the temperature was raised to 120°C, and the reaction was continued for 12 hours. After the reaction was completed, the solution was poured into 2 L of deionized water for precipitation, washed with water, and vacuum dried at 80°C to obtain a polyimide resin.

[0122]

[0123] Dissolve 5g of dried polyimide resin in 30mL of dichloroethane, add 80μL SnCl4, heat to 70, slowly drop 3mL of CMM into the system, and stir for 5h. After the reaction is completed, pour the solution into 300mL of methanol for precipitation, wash, and dry at 80 for 12h to obtain chloromethylated polyimide resin.

[0124]

[0125] Dissolve 1g of dried chloromethylated polyimide resin in 20mL NMP. After dissolution, add 0.1g potassium ethyl xanthate and react at room temperature for 24h. After the reaction is completed, pour the solution into 200mL deionized water for precipitation and dry at 80℃ for 12h to obtain a macromolecular initiator.

[0126]

[0127] Dissolve 1g of the dried macromolecular initiator in 20mL of NMP. After dissolution, heat to 65°C, drop 3g of 4-HS, and then add 0.01g of AIBN to carry out RAFT polymerization. Continue the reaction for 2h. After the reaction is completed, cool the solution to room temperature, pour it into 200mL of deionized water for precipitation, wash it with ethanol several times, and dry it at 80°C for 12h to obtain polyimide-g-poly(p-hydroxystyrene) graft copolymer A1.

[0128]

[0129] According to the detection, the number average molecular weight of the polyimide-g-poly(p-hydroxystyrene) graft copolymer A1 is 39,000; the grafting rate is 40%; and the grafting amount k of A1 is 3.5.

[0130] Synthesis example 2-7

[0131] The preparation methods of Synthesis Examples 2-7 refer to Synthesis Example 1, except that some conditions are different, as follows:

[0132] Synthesis Example 2: Compared with Synthesis Example 1, CMM was changed to 2 mL to obtain grafted product A2, whose molecular weight was 38,000, grafting rate was 25%, and k=3.8.

[0133] Synthesis Example 3: Compared with Synthesis Example 1, CMM was changed to 4 mL to obtain grafted product A3, whose molecular weight was 38500, grafting rate was 53%, and k=3.2.

[0134] Synthesis Example 4: Compared with Synthesis Example 1, the RAFT polymerization time was changed to 1.5 h to obtain a grafted product A4 with a molecular weight of 37,800, a grafting rate of 40%, and k=2.5.

[0135] Synthesis Example 5: Compared with Synthesis Example 1, the RAFT polymerization time was changed to 4 h to obtain a grafted product A5, which had a molecular weight of 39,500, a grafting rate of 40%, and k=4.3.

[0136] Synthesis Example 6: Compared with Synthesis Example 1, the RAFT polymerization time was changed to 6 h to obtain a grafted product A6 with a molecular weight of 39,900, a grafting rate of 40%, and k=5.7.

[0137] Synthesis Example 7: Compared with Synthesis Example 1, the RAFT polymerization time was changed to 9 h to obtain a grafted product A7 with a molecular weight of 40,500, a grafting rate of 40%, and k=6.9.

[0138] Synthesis example 8

[0139] This synthesis example provides a method for preparing component (a), comprising:

[0140] Add 192g methanol, 172.32g 4-HS, 19.53g St and 15g AIBN to a four-necked flask in turn, stir and dissolve until clear. Vacuum and replace the air in the reaction vessel with nitrogen, heat to 75, react for 18h, and stop the reaction. Slowly add the prepared sodium methoxide (0.4g) solution to the reaction system, react for 6h, extract 2 to 3 times with n-heptane and reaction liquid in a mass ratio of 1:1, remove the unreacted monomers and initiators in the reaction liquid, replace the methanol in the reaction liquid with PGMEA, obtain the required concentration of PGMEA solution, and obtain PHS resin A8 (see the following structural formula), the ratio of hydroxystyrene to styrene repeating units is 80 / 20, that is, m is 80 and n is 20.

[0141]

[0142] Synthesis example 9

[0143] This synthesis example provides a method for preparing component (a), comprising:

[0144] 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 cooled to -10°C. Subsequently, 26.37 g (0.085 mol) of ODPA was slowly added thereto so that the temperature of the reaction solution did not exceed 0°C, and stirring was continued for 3 hours, and then 4.44 g (0.03 mol) of PhA was added, and stirring was continued for 2 hours at room temperature to obtain a polyamic acid solution.

[0145] 39.55 g of Py and 30.6 g of Et2A were added to the polyamic acid solution, the temperature was raised to 120°C, and the reaction was continued for 12 hours. After the reaction was completed, the solution was poured into 2 L of deionized water for precipitation, washed with water, and vacuum dried at 80°C to obtain polyimide resin A9 (whose structural formula is shown below).

[0146]

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

[0148] The photosensitive polyimide compositions of Examples 1-10 and Comparative Examples 1-2 were prepared according to the components and blending amounts shown in Table 1-2. The blending amounts in Table 1-2 are parts by mass of each component relative to 100 parts by mass of component (a).

[0149] The structural formulas of the components used in Table 1 and Table 2 are as follows:

[0150] Component (b): Photosensitizer

[0151]

[0152] Component (c): thermal crosslinking agent

[0153]

[0154] Component (d): solvent

[0155] d1: GBL (γ-butyrolactone); d2: EL (ethyl lactate).

[0156] Component (e): silane coupling agent; e1: γ-ureapropyltriethoxysilane.

[0157] Table 1 Ingredients

[0158]

[0159]

[0160] Table 2 Ingredients

[0161]

[0162] The performance of the photosensitive polyimide compositions prepared in the above Examples 1-10 and Comparative Examples 1-2 was evaluated as follows:

[0163] (1) Preparation of developing film

[0164] The photosensitive polyimide compositions (varnishes) prepared in Examples 1-10 and Comparative Examples 1-2 were respectively spin-coated on an 8-inch silicon wafer, and then heat-treated (prebaked) at 120°C for 3 minutes using a hot plate (coating and developing device Mark-7 manufactured by Tokyo Electron Ltd.) to prepare a prebaked film with a thickness of 6 μm. An i-line stepper (manufactured by Nikon Corporation, NSR-2005i9C) was used at 50 to 400 mJ / cm 2 Exposure, 10mJ / cm 2 The obtained prebaked film was exposed in steps of . After exposure, for the photosensitive polyimide composition, it was baked after exposure at 100 for 1 minute. After the photosensitive polyimide composition was baked after exposure, it was developed for 90 seconds using a 2.38 wt % tetramethylammonium (TMAH) aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D), and then rinsed with pure water to obtain a developed film.

[0165] (2) Film thickness measurement method

[0166] The film thickness after prebaking and after development was measured using a film thickness measuring device Filmtris F50 at a refractive index of 1.63.

[0167] (3) Determination of warpage

[0168] The varnish was applied by spin coating using a coating and developing device ACT-8 and prebaked so that the film thickness after prebaking at 120°C for 3 minutes was 10 μm. Then, the temperature was raised to 200°C at a rate of 3.5 / min under the condition of an oxygen concentration of less than 20 ppm using an inert oven, and heat-treated at 200°C for 1 hour. When the temperature became less than 50°C, the wafer was taken out and the cured film was measured using a pressure device FLX2908 (manufactured by KLA Tencor). As a result, the case of 35 MPa or more was considered insufficient (D), the case of 30 MPa or more and less than 35 MPa was considered good (C), the case of 20 MPa or more and less than 30 MPa was considered better (B), and the case of less than 20 MPa was considered the best (A). The results are shown in Table 3.

[0169] (4) Sensitivity evaluation

[0170] After exposure and development, the exposure amount (called the optimal exposure amount Eop) that forms a 20μm line and space pattern (1L / 1S) with a width of 1:1 is used as the sensitivity.2 Below 150 mJ / cm2, it can be judged as high sensitivity. More preferably, it is 150 mJ / cm2. 2 The results are shown in Table 3 below.

[0171] (5) Chemical resistance evaluation

[0172] The cured product was coated with a pipette. The coated cured product was placed in a nitrogen oven at 200°C for 60 minutes. Afterwards, the cured product was transferred from the hot plate and cooled to room temperature. The cooled cured product was washed with NMP at 45°C and soaked for 1 hour, and the film thickness was measured.

[0173] The film thickness change rate (%) was calculated from the film thickness change. A positive value means that the film expanded, and a negative value means that the film dissolved. The results are shown in Table 3.

[0174] (6) Adhesion evaluation

[0175] A cured product was produced on a Cu substrate using the above-mentioned method for producing a cured product. The cured product was cut into 10×10 grids using a crosscut guide (manufactured by COAT-TECH Co., Ltd.) with a shear knife, thereby dividing the cured product into 100 small pieces.

[0176] An adhesive tape (manufactured by 3M Japan Ltd.) was attached to the cured product, and then the adhesive tape was peeled off. The adhesiveness was evaluated as follows based on the number of small pieces of the cured product peeled off from the substrate when the adhesive tape was peeled off.

[0177] A: The number of remaining grids is 100 to 80.

[0178] B: The number of remaining grids is less than 80.

[0179] The results are shown in Table 3.

[0180] (7) Evaluation of elongation at break

[0181] The varnish was applied by spin coating using a coating and developing device ACT-8 and prebaked to a film thickness of 10 μm after prebaking at 120°C for 3 minutes. Then, the temperature was raised to 200°C at a rate of 3.5 / min under an oxygen concentration of less than 20 ppm using an inert oven and heat treated at 200°C for 1 hour. When the temperature was less than 50°C, the wafer was taken out, the film was peeled off, and the strips were cut into 4 mm × 8 mm strips, and tensile tests were performed using DAGE4000.

[0182] The results showed that the elongation at break was 30% or more as excellent (A), 20-30% as good (B), 10-20% as poor (C), and <10% as very poor (D).

[0183] Table 3 Test results

[0184] Elongation at break Warping stress Sensitivity Chemical resistance Adhesion Example 1 A A <![CDATA[140mJ / cm 2 ]]> No change A Example 2 A A <![CDATA[120mJ / cm 2 ]]> No change A Example 3 A A <![CDATA[125mJ / cm 2 ]]> No change A Example 4 A A <![CDATA[130mJ / cm 2 ]]> No change A Example 5 A A <![CDATA[175mJ / cm 2 ]]> No change A Example 6 A A <![CDATA[115mJ / cm 2 ]]> No change A Example 7 A A <![CDATA[170mJ / cm 2 ]]> No change A Example 8 A A <![CDATA[120mJ / cm 2 ]]> No change A Example 9 A A <![CDATA[115mJ / cm 2 ]]> No change A Example 10 A A <![CDATA[100mJ / cm 2 ]]> No change A Comparative Example 1 D B <![CDATA[300mJ / cm 2 ]]> Swelling 5% A Comparative Example 2 A C <![CDATA[400mJ / cm 2 ]]> Film minus 20% A

[0185] As can be seen from Table 3, the photosensitive polyimide compositions provided by Examples 1-10 of the present invention all have a small amount of developing film loss, excellent low warpage stress, and excellent chemical resistance. Compared with the examples, the toughness and sensitivity of Comparative Example 1 are poor. Comparative Example 2 has high warpage stress, poor sensitivity, and poor chemical resistance.

[0186] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A photosensitive polyimide composition, characterized in that: The invention comprises component (a) a graft polymer soluble in alkaline aqueous solution, which is selected from the 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 to 200, n / (m+n)=0.05 to 1, k=2 to 10; Component (b) a photosensitizer; Component (c) a thermal crosslinking agent; which includes a component (c1) a crosslinking agent containing an epoxy group and a 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, when it appears each time, is selected from any one of the tetravalent organic groups represented by the following formulae 2-1 to 2-9, either identically or differently: Wherein, R1-R8 are all monovalent organic groups, and X is a divalent group; Preferably, R1-R8 are each independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; Preferably, R1-R8 are each independently selected from any one of hydrogen, fluorine atom, methyl and trifluoromethyl; Preferably, X is selected from any one of an oxygen atom, a C1-C5 substituted or unsubstituted alkylene group, a sulfur atom, a sulfone group and a carbonyl group; Preferably, X is selected from any one of an oxygen atom, a methylene group, a sulfur atom, a sulfone group, a carbonyl group, C(CH3)2 and C(CF3)2; Preferably, Ar2 is selected from any one of the divalent organic groups represented by Formula 3-1 to Formula 3-12, the same or different each time it appears: Among them, R9-R 20 are all monovalent organic groups, and Y is a divalent group; Preferably, R9-R 20 Each is independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; preferably, R9-R 20 Each is independently selected from any one of hydrogen, fluorine, methyl and trifluoromethyl; Preferably, Y is selected from any one of an oxygen atom, a C1-C5 substituted or unsubstituted alkylene group, a sulfur atom, a sulfone group and a carbonyl group; Preferably, Y is selected from any one of an oxygen atom, a methylene group, a sulfur atom, a sulfone group, a carbonyl group, C(CH3)2 and C(CF3)2.

3. The photosensitive polyimide composition according to claim 1, characterized in that The photosensitizer is selected from quinone diazide compounds.

4. The photosensitive polyimide composition according to claim 1, characterized in that The component (c1) is selected from the compound represented by formula 4-1; Component (c2) is selected from the compounds represented by formula 4-2-1 or formula 4-2-2; Wherein, in formula 4-1, U is selected from a divalent organic group containing an alicyclic ring or an aromatic ring; In formula 4-2-1, R 21 are each independently a hydrogen atom or a monovalent organic group, R 22 Each is independently a hydrogen atom or a monovalent organic group, or is combined with each other to form a ring structure which may have a substituent; In formula 4-2-2, R 23 is selected from a hydrogen atom or a monovalent organic group, R 24 is selected from a monovalent organic group, n is an integer of 1-4, X is selected from a single bond or a 1-4 valent organic group; a is an integer of 1-4, b is an integer of 0-3, when a is 2, 3 or 4, R 23 Same or different, when b is 2 or 3, R 24 Same or different; Preferably, component (c2) is selected from any one of the compounds represented by the following structural formulas: Among them, R 25 is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, R 26 is the number of carbon atoms The alkyl group has 1-10 moieties.

5. The photosensitive polyimide composition according to any one of claims 1 to 4, characterized in that: Based on 100 parts by weight of the component (a), the content of the component (b) is 5-20 parts by weight, the content of the component (c) is more than 5 parts by weight, the content of c1 is 5-15 parts by weight, the content of c2 is 0.1-15 parts, and the content of the component (d) is 0.5-15 parts by weight.

6. The photosensitive polyimide composition according to any one of claims 1 to 4, characterized in that: The photosensitive polyimide composition further contains any one or a combination of at least two of a solvent and a leveling agent; Preferably, based on 100 parts by weight of the component (a), the content of the solvent is 50-1000 parts, preferably 100-200 parts by weight. Preferably, the content of the leveling agent is 100-1000 ppm.

7. A method for manufacturing a graphic, characterized in that: The method comprises coating the photosensitive polyimide composition according to any one of claims 1 to 6 on a supporting substrate; Preferably, the method further comprises: drying, exposure, development and heating treatment in sequence after coating; Preferably, the light source used in the exposure process is i-ray.

8. A solidified product, characterized in that: The cured product is formed by curing the photosensitive polyimide composition according to any one of claims 1 to 6; Preferably, the cured product includes a surface protection film or an interlayer insulating film.

9. An electronic component, characterized in that: The electronic component includes the cured product according to claim 8.

10. The electronic component according to claim 9, characterized in that The electronic component includes a semiconductor device.

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