Photosensitive polyimide composition, cured product and electronic component

Abstract

The present invention relates to the technical field of photosensitive dielectric materials, and in particular, to a photosensitive polyimide composition, a cured product and an electronic component. The photosensitive polyimide composition contains the following components: (a) a block polymer soluble in an alkaline aqueous solution; the block polymer is selected from a compound represented by the following structural formula: #imgabs0# wherein R is selected from one of unsubstituted alkyl groups, Ar1 is selected from a quaternary organic group, Ar2 is selected from a quaternary organic group, and Ar3 is selected from a quaternary organic group; k+m=5-200, m / k=0.01-0.5; (b) a photosensitizer; (c) a thermal crosslinking agent; component (c) includes a crosslinking agent containing an epoxy group as component (C1) and a crosslinking agent containing CH2OR as component (C2); and (d) a silane coupling agent. The photosensitive polyimide composition has excellent sensitivity, resolution and can form fine patterns, and has low warpage stress after curing, high chemical stability and adhesion.

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 cured product and an electronic component. Background Art

[0002] The development of photosensitive polyimide has always used organic solvents such as N-methylpyrrolidone. However, due to environmental awareness in recent years and considering the treatment of waste liquid, it is believed that the use of alkaline aqueous solution development has fewer problems, but the solubility of these photosensitive polyimide materials is very poor and it is difficult to form a pattern. In order to improve the above problems, positive photosensitive polyimide materials that can be used for alkaline aqueous solution development can be used. Specific methods include, for example, a method of introducing 2-nitrobenzyl groups into a polyimide precursor through an ester bond, a method of mixing diazonaphthoquinone into a soluble dihydroxyimide or polybenzoxazole precursor, etc. However, after high-temperature curing, the above-mentioned positive photosensitive polyimide composition has high warping stress and low sensitivity, and therefore cannot be widely used.

[0003] In view of this, the present invention is proposed. Summary of the invention

[0004] The purpose of the present invention is to provide a photosensitive polyimide composition, a cured product and an electronic component. The photosensitive polyimide composition provided by the embodiment of the present invention has excellent sensitivity, resolution and can form fine patterns, and has low warpage stress after curing, high chemical stability and adhesion.

[0005] The present invention is achieved in that:

[0006] In a first aspect, the present invention provides a photosensitive polyimide composition comprising the following components (a), (b), (c) and (d):

[0007] (a) a block polymer soluble in alkaline aqueous solution; which is selected from the compound represented by the following formula 1

[0008]

[0009] Wherein, R is selected from one of the unsubstituted alkyl groups, Ar 1 Selected from 4-valent organic groups, Ar 2 Selected from divalent organic groups, Ar 3 Selected from 4-valent organic groups; k+m=5-200, m / k=0.01-0.5;

[0010] (b) photosensitizer;

[0011] (c) a thermal crosslinking agent; component (c) comprises a component (C1) a crosslinking agent containing an epoxy group and a component (C2) containing CH 2 Cross-linking agent for OR;

[0012] (d) Silane coupling agent.

[0013] In a second aspect, the present invention provides a method for producing a pattern, comprising coating the photosensitive polyimide composition described in any one of the aforementioned embodiments on a supporting substrate, and performing drying, exposure, development and heating processes;

[0014] Preferably, the light source used in the exposure process is i-ray.

[0015] 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;

[0016] Preferably, the cured product includes a surface protection film or an interlayer insulating film.

[0017] In a fourth aspect, the present invention provides an electronic component comprising the cured product according to the above embodiment.

[0018] The present invention has the following beneficial effects: the portion of the photosensitive polyimide composition provided by the embodiment of the present invention that is exposed to ultraviolet light is easily soluble in an alkaline aqueous solution, while the portion that is not exposed to ultraviolet light is insoluble in an alkaline aqueous solution, thereby being able to effectively replicate fine patterns. The photosensitive polyimide composition has excellent sensitivity, high resolution, low warpage stress, high adhesion and good chemical resistance after high temperature curing. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] 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.

[0020] Figure 1 A schematic diagram of a semiconductor packaging structure provided by an embodiment of the present invention. DETAILED DESCRIPTION

[0021] 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.

[0022] The embodiment of the present invention provides a photosensitive polyimide composition, which contains the following components:

[0023] (a) a block polymer soluble in alkaline aqueous solution; (b) a photosensitizer; (c) a thermal crosslinking agent; (d) a silane coupling agent.

[0024] The part of the photosensitive polyimide composition exposed to ultraviolet light is easily soluble in an alkaline aqueous solution, while the part not exposed to ultraviolet light is insoluble in an 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 warpage stress after high-temperature curing, and has excellent chemical resistance and adhesion.

[0025] 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, the component (a) used is soluble in an alkaline aqueous solution.

[0026] The alkaline aqueous solution mentioned above refers to a tetramethylammonium hydroxide aqueous solution, a metal hydroxide aqueous solution, an organic ammonia aqueous solution, or the like.

[0027] The block polymer soluble in an alkaline aqueous solution as component (a) preferably has a main chain skeleton of a polyimide-based or polyoxazole-based polymer, and more preferably an alternating block polymer of the two types of polymers, from the viewpoint of processability and heat resistance.

[0028] From the viewpoint of solubility in an alkaline aqueous solution, the component (a) is preferably a polymer having a plurality of phenolic hydroxyl groups, a plurality of carboxyl groups, or both.

[0029] Furthermore, component (a) is more preferably a block copolymer of polyamide ester-polyhydroxyamide, a polymer having a structural unit represented by the following formula 1, which utilizes the alkali solubility, good photosensitivity and film properties of phenolic hydroxyl groups and part of carboxyl groups:

[0030]

[0031] Wherein, R is selected from one of the unsubstituted alkyl groups, Ar 1 Selected from 4-valent organic groups, Ar 2 Selected from divalent organic groups, Ar 3is selected from a tetravalent organic group; k+m=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, etc., any value between 5 and 200. m / k=0.01-0.5, for example, 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 and 0.5, etc., any value between 0 and 0.5.

[0032] The amide structure containing a hydroxyl group as shown in Formula 1 can be finally converted into an oxazole by curing dehydration ring closure, while the amide ester structure can be converted into an imide by curing dealcoholization ring closure, so that the cured film has excellent chemical resistance and low warpage stress.

[0033] Furthermore, Ar 1 Each occurrence is the same or different and is selected from any one of the tetravalent organic groups represented by the following formula 2:

[0034]

[0035] Among them, R 1 -R 8 are all monovalent organic groups, and X is a divalent group.

[0036] Specifically, R 1 -R 8 Each is independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; preferably, R 1 -R 8 Each is independently selected from any one of hydrogen, a fluorine atom, a methyl group and a trifluoromethyl group.

[0037] 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 is selected from any one of an oxygen atom, a methylene group, a sulfur atom, a sulfone group, a carbonyl group, C(CH 3 ) 2 and C(CF 3 ) 2 Any one of .

[0038] Specifically, in Formula 1, Ar 1The tetravalent organic group is generally a residue of a tetracarboxylic dianhydride or a derivative thereof having an amide ester structure formed by tetracarboxylic dianhydride or a derivative thereof and a diamine. It is preferably a tetravalent aromatic group. It is preferably a residue of a tetracarboxylic dianhydride or a derivative thereof 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)propane 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-bis(3,4-dicarboxyphenyl)fluorene dianhydride, Aromatic tetracarboxylic dianhydrides such as {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.

[0039] Furthermore, Ar 2 Each occurrence is identical or different and is selected from any one of the divalent organic groups represented by Formula 3:

[0040]

[0041] Among them, R 9 -R 20 are all monovalent organic groups, and Y is a divalent group;

[0042] Specifically, R 9 -R 20 Each is independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; preferably, R 9 -R 20 Each is independently selected from any one of hydrogen, a fluorine atom, a methyl group and a trifluoromethyl group.

[0043] 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 is selected from any one of an oxygen atom, a methylene group, a sulfur atom, a sulfone group, a carbonyl group, a C(CH3 ) 2 and C(CF 3 ) 2 Any one of .

[0044] Furthermore, in Formula 1, Ar 2 It is a divalent organic group, generally a residue derived from an amino acid having an amide structure formed by an amino acid and a diamine, 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, o-aminobenzoic acid, etc. These may be used alone or in combination of two or more.

[0045] Furthermore, Ar 3 Each occurrence is identical or different and is selected from any one of the 4-valent organic groups represented by Formula 4:

[0046]

[0047] Among them, R 21 -R 26 All are monovalent organic groups, and Q is a divalent group;

[0048] Preferably, R 21 -R 26 Each is independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; preferably, R 21 -R 26 Each is independently selected from any one of hydrogen, a fluorine atom, a methyl group and a trifluoromethyl group.

[0049] Q 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; Q is selected from any one of an oxygen atom, a methylene group, a sulfur atom, a sulfone group, a carbonyl group, C(CH 3 ) 2 and C(CF 3 ) 2 Any one of .

[0050] Specifically, in Formula 1, Ar 3It is a tetravalent organic group, generally a residue of a dihydroxydiamine having an amide structure formed by the reaction of a hydroxyl-containing diamine and an amino acid, and is preferably a tetravalent aromatic group, and its carbon number is preferably 6-40, and more preferably a tetravalent aromatic group having a carbon number of 6-40. As the above-mentioned tetravalent aromatic group, a residue of a diamine having the following structure is preferred, wherein the four binding sites are all on the aromatic ring, and the two hydroxyl groups are each located at the ortho position to which W is bound. Examples of such diamines include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)1,1,1,3,3,3-hexafluoropropane, and bis(4-amino-3-hydroxyphenyl)1,1,1,3,3,3-hexafluoropropane. The residue of such diamines is not limited to these, and the residues of these compounds may be used alone or in combination of two or more.

[0051] In addition, in order to improve the adhesion to the substrate, as long as the heat resistance is not damaged, Ar 3 A certain proportion of aliphatic groups having a siloxane structure can be selected for copolymerization, preferably 1-10 mol% of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0052] The terminal groups of the aromatic polyamide shown in Formula 1 are 1 ,Ar 2 and Ar 3 The end-capping agent may react with the polymer end to form a saturated aliphatic group, an unsaturated aliphatic group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group or a mercapto group, etc. The end-capping ratio is preferably 30-100%.

[0053] It should be noted that: (1) the above R 1 -R 26 The halogen mentioned in is not limited to F, and may also be bromine, chlorine, and the like.

[0054] (2) The above R 1 -R 26 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.

[0055] (3) The above R 1 -R 26The 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.

[0056] The solubility of the polymer in alkaline aqueous solution is derived from the phenolic hydroxyl group and the carboxyl group, so it is preferred to contain a structure of a certain proportion or more. More preferably, m is an amide unit containing a carboxyl group, and the molar ratio of m and k is m = 1-33 mol%, k = 67-99 mol%. Too large a m 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 amount of alkali-soluble groups of phenolic hydroxyl groups and carboxyl groups, the dissolution rate of the polymer in alkaline aqueous solution changes, so that a photosensitive polyimide composition with a moderate dissolution rate can be obtained.

[0057] Further, the polymer m+k is the number of repeating structural units of component (a), and the value of m+k is 5 to 200. When m+k is less than 5, the viscosity of the composition is too small, resulting in the composition being unable to be used as a thick film, and when m+k is greater than 200, the composition becomes insoluble in an alkaline aqueous solution.

[0058] When the structures represented by Formula 1 each contain fluorine atoms greater than or equal to 10% by weight, during development with an alkaline aqueous solution, an appropriate degree of water resistance is exhibited at the interface of the film to prevent penetration at the interface. However, when the content of fluorine atoms exceeds 20% by weight, the solubility in alkaline aqueous solutions is reduced. Therefore, the fluorine atom content is preferably 10-20% by weight.

[0059] 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.

[0060] In the embodiments of the present invention, the block polymer having the structural unit shown in Formula 1 is generally obtained by first esterifying dianhydride with alcohol and then chlorinating to obtain a diacyl chloride compound, then condensing hydroxy diamine and dianhydride into an oligomer, and then polymerizing with the obtained diacyl chloride compound.

[0061] Specifically, in the first step, a diacid diester can be prepared by reacting an alcohol with a dianhydride, and then a diacyl chloride diester can be prepared by chlorination. In the second step, a hydroxyl-containing diamine compound and a dianhydride can be subjected to a condensation reaction to prepare an amino-terminated polyhydroxyamide oligomer. In the third step, a block polymer can be prepared by a condensation reaction of the diacyl chloride diester prepared in the first step and the amino-terminated polyhydroxyamide.

[0062] In the present invention, naphthoquinonediazide-5-sulfonyl, naphthoquinonediazide-4-sulfonyl, etc. can be preferably used as the quinonediazide compound of component (b). In the present invention, naphthoquinonediazide-5-sulfonyl and naphthoquinonediazide-4-sulfonyl ester compounds can be obtained by using both naphthoquinonediazide-5-sulfonyl and naphthoquinonediazide-4-sulfonyl in the same molecule, and naphthoquinonediazide-5-sulfonyl ester compounds and naphthoquinonediazide-4-sulfonyl ester compounds can be mixed and used.

[0063] Among them, the (b) quinonediazide compound more preferably comprises an ester formed of a phenol compound and naphthoquinonediazide-5-sulfonyl group, thereby achieving high sensitivity under i-line exposure.

[0064] 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.

[0065] The photosensitive polyimide composition provided in the embodiment of the present invention may contain (c) a thermal crosslinking agent for the purpose of easily obtaining a cured film. As component (c1), it is a crosslinking agent having an epoxy group, and as component (c2), it is a crosslinking agent having -CH 2 A crosslinking agent having an OR (R is a hydrogen atom or a monovalent organic group) group, which reacts with the polymer as component (a) to crosslink during the heat treatment step after coating, exposure and development of the photosensitive polymer composition of the present invention, or a compound that polymerizes itself during the heat treatment step. In addition, the crosslinking agent as component (c2) has affinity for alkaline aqueous solutions and can increase the dissolution rate in alkaline aqueous solutions.

[0066] In the present invention, component (c1) is a crosslinking agent having an epoxy group in its structure. Component (c1) is selected from the compounds represented by the following formula 5-1:

[0067]

[0068] The specific examples of the compound shown in the following formula 5-1 include, for example, 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 name, Dainippon Ink and Chemicals, Inc.), Rikaresin (registered trademark) BPO-20E, Rikaresin BEO-60E (above, trade name, New Japan Chemical), EP-4003S, EP-4000S (above, trade name, ADEKA), etc. They can be used alone or in combination of two or more. As this component, these compounds may be used alone or in combination of two or more.

[0069] In the present invention, component (c2) is a compound having -CH 2 A crosslinking agent of an OR (R is a hydrogen atom or a monovalent organic group) group. The compound may have at least one of the group, but preferably has at least two. Component (c2) is selected from the compounds represented by the following formula 5-2.

[0070]

[0071] In formula 5-2, R 29 is selected from a hydrogen atom or a monovalent organic group, R 30 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 29 Same or different, when b is 2 or 3, R 30 Same or different.

[0072] The following formula 5-2-1 shows specific examples of the compound represented by formula 5-2. These compounds may be used alone or in combination of two or more.

[0073]

[0074] In Formula 5-2, 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. 29 Preferably, it is hydrogen, alkyl or alkenyl. The number of carbon atoms in the alkyl or alkenyl group is preferably 1 to 20. 30 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.

[0075] The purity of the compound represented by the above formula 5-2 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 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, Alkane, 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 more preferably 0.5-15 parts by mass, and more preferably 0.5-10 parts by mass relative to 100 parts by mass of component (a). For example, 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, and the leveling agent may be selected from surfactants to improve the coating properties 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.); organic siloxane 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);

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

[0084] Next, the method for producing the photosensitive polyimide composition provided by an 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, a 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 a range that does not destroy the performance of the polyimide composition, usually room temperature-80°C. In addition, the dissolution order of each component is not particularly limited, for example, including a method of dissolving in sequence starting from a compound with low solubility. In addition, for components such as surfactants and a portion of adhesion improvers that are prone to generate bubbles when stirred and dissolved, poor dissolution of other components caused by the generation of bubbles can be prevented by adding them last after dissolving other components.

[0085] 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.

[0086] The cured product provided in the embodiment of the present invention can be obtained by curing the positive photosensitive polyimide composition. The cured product of the present invention can be used as a patterned cured film or a non-patterned cured film.

[0087] The method for manufacturing a patterned cured film comprises, for example, a step of coating the positive photosensitive polyimide composition on a substrate and drying it to form a photosensitive polyimide film (film forming step); a step of exposing the photosensitive polyimide film (exposure step); a step of developing the exposed photosensitive polyimide film with an alkaline aqueous solution to form a patterned polyimide film (development step); and a step of heating the patterned polyimide film (heating step). The method for manufacturing a non-patterned cured film comprises, for example, the above-mentioned film forming step and heating step. It may also further comprise an exposure step.

[0088] In the film forming step, the positive photosensitive polyimide composition is applied to a metal substrate such as Cu, a glass substrate, a semiconductor, a metal oxide insulator (such as TiO 2 、SiO 2 The positive photosensitive polyimide composition may be applied on a supporting substrate such as silicon nitride, etc. From the viewpoint of operability, the applied positive photosensitive polyimide composition may be dried by heating with a hot plate, an oven, etc. (e.g., 90-150° C., 1-5 minutes) and used. The supporting substrate may also be cleaned with acetic acid, etc. before coating. The film thickness of the obtained photosensitive polyimide film is preferably 5-20 μm.

[0089] In the exposure process, for example, the photosensitive polyimide film formed on the substrate is irradiated with the above-mentioned active light through a mask. From the viewpoint of the transparency of the component (a), irradiation with i-rays can be appropriately used. After exposure, post-exposure heating (PEB) can also be performed as needed. The temperature of post-exposure heating is preferably 70°C-140°C, and the time of post-exposure heating is preferably 1 minute-5 minutes.

[0090] 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, tetramethylammonium hydroxide (TMAH) can be suitably used. The alkali concentration of these aqueous solutions is preferably set to 0.1-10 mass %. Furthermore, 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.

[0091] 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 100-500°C, preferably less than or equal to 400°C, more preferably less than or equal to 375°C, and further preferably 300-350°C. The heating time is preferably 20 minutes to 6 hours, more preferably 30 minutes to 3 hours. Multi-stage heating can also be performed. The heat treatment can be performed using, for example, a quartz tube furnace, a hot plate, a rapid annealing furnace (rapid thermal anneal), a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace. Ovens and the like. In addition, any one of the inert atmospheres such as the atmosphere or nitrogen can be selected, but when carried out under nitrogen, oxidation of the pattern can be prevented, so an inert atmosphere such as nitrogen is preferred.

[0092] The cured product of the present invention can be used as an interlayer insulating film, a surface protective film, or the like.

[0093] The interlayer insulating film and the surface protection film of the present invention can be used for electronic components, etc. The electronic components of the present invention can be used for semiconductor devices, etc. The semiconductor devices can be used for various electronic devices, etc. The semiconductor packaging structure schematic diagram of the present invention is as follows Figure 1 shown.

[0094] 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).

[0095] 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.

[0096] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0097] Bis-AP-AF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0098] PNDC: p-Nitrobenzoyl chloride

[0099] SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane

[0100] ODPA: 4,4'-oxydiphthalic anhydride

[0101] MAP: meta-aminophenol

[0102] NMP: N-methyl 2-pyrrolidone

[0103] GBL; γ-butyrolactone

[0104] TMAH: Tetramethylammonium hydroxide

[0105] SOCl 2 :Thionyl chloride

[0106] Synthesis example 1

[0107] This embodiment provides a method for preparing a diamine containing a hydroxyl group, comprising:

[0108] Under a dry nitrogen stream, 18.3 g (0.05 mol) of Bis-AP-AF was dissolved in 100 g of acetone, and the resulting solution was then cooled to -10°C. Subsequently, a 50 g acetone solution of 18.56 g (0.1 mol) of PNDC was added dropwise thereto so that the temperature of the reaction solution did not exceed 0°C. After the addition was completed, the reaction mixture was returned to room temperature, the precipitated white solid was filtered out, and vacuum dried at 50°C.

[0109] 30 g of the solid was added to a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl melting agent, 2 g of 5% palladium carbon was added, hydrogen was introduced into the mixture using a balloon, and reduction reaction was carried out at room temperature. After about 2 hours, it was confirmed that the balloon did not shrink further, and the reaction was terminated. After the reaction was completed, the catalyst was filtered out, and the mixture was concentrated under reduced pressure to obtain diamine compound (I), and the obtained solid was directly used for the reaction.

[0110]

[0111] Diamine compound (I)

[0112] Synthesis example 2

[0113] This embodiment provides a method for synthesizing polymer A, comprising:

[0114] Under a dry nitrogen flow, 28.08 g (0.09 mol) ODPA, 8.3 g (0.18 mol) ethanol, 14.24 g (0.18 mol) pyridine, and 300 g tetrahydrofuran were added and reacted at 60°C for 8 h. The system was then cooled to 0°C, 23.4 g (0.198 mol) SOCl2 was added dropwise, and the reaction was continued for 1 h, and the diacid diacid chloride compound was obtained by distillation.

[0115] Dissolve 54.4g (0.09mol) of diamine (I) in 220g of NMP, add 3.1g (0.01mol) of ODPA and 12g of NMP, and react at 20°C for 3 hours. Then add 2.2g (0.02mol) of MAP and 14.24g (0.198mol) of pyridine. Then cool to -10°C, add the diacyl chloride diester obtained by distillation dropwise, and continue to react at -10°C for 1 hour. After the reaction, put the solution into 5L of water, and collect the polymer solid precipitate by filtration. Dry the polymer solid in a vacuum dryer at 80°C for 72 hours to obtain polymer A. The molecular weight and esterification rate of polymer A were measured, and the molecular weight was 21000 and the esterification degree was 90%.

[0116]

[0117] The specific test method is as follows:

[0118] (1) Determination of molecular weight

[0119] The number average molecular weight was determined by gel permeation chromatography (GPC) under the following conditions using standard polystyrene conversion. The number average molecular weight of polymer A was 39,000. 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)].

[0120] Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.

[0121] Pump: L6000 manufactured by Hitachi Manufacturing Co., Ltd.

[0122] C-R4A Chromatopac manufactured by Shimadzu Corporation

[0123] Measurement conditions: Chromatographic column Gelpack GL-S300MDT-5 × 2

[0124] Eluent: THF / DMF = 1 / 1 (volume ratio), LiBr (0.03 mol / L), H 3 PO 4(0.06mol / L) Flow rate: 1.0mL / min, Detector: UV270nm

[0125] (2) Determination of esterification rate

[0126] In addition, NMR measurement was performed under the following conditions to calculate the esterification rate of A (the esterification rate of the carboxyl groups of ODPA and HEMA was 80 mol% with respect to all the carboxyl groups of the polyamic acid (the remaining 20 mol% were carboxyl groups).

[0127] Measurement equipment: AV400M manufactured by Bruker BioSpin

[0128] Magnetic field strength: 400MHz

[0129] Reference material: Tetramethylsilane (TMS)

[0130] Solvent: dimethyl sulfoxide (DMSO)

[0131] Synthesis example 3

[0132] Compared with Synthesis Example 2, the molar number of the diacid chloride diester was changed to 0.8 mol, and the molar number of ODPA was changed to 0.2 mol, to obtain a polymer C with a molecular weight of 22,000 and an esterification degree of 80%. m / k=2 / 8.

[0133] Synthesis example 4

[0134] Compared with Synthesis Example 2, the molar number of the diacid chloride diester was changed to 0.7 mol, and the molar number of ODPA was changed to 0.3 mol, to obtain a polymer D having a molecular weight of 21,000 and an esterification degree of 70%. m / k=3 / 7.

[0135] Synthesis example 5

[0136] The molar number of the diacid chloride diester was changed to 0.6 mol, and the molar number of ODPA was changed to 0.4 mol, to obtain polymer E, whose molecular weight was 21000 and degree of esterification was 60%. m / k=4 / 6.

[0137] Synthesis example 6

[0138] The molar number of the diacid chloride diester was changed to 1 mol, and the molar number of ODPA was changed to 0 mol to obtain a polymer F having a molecular weight of 22,000 and a degree of esterification of 100%. m / k=0.

[0139]

[0140] Synthesis Example 7

[0141] The molar number of the diacid chloride diester was changed to 0 mol, and the molar number of ODPA was changed to 1 mol to obtain a polymer G having a molecular weight of 20,000 and a degree of esterification of 0%.

[0142]

[0143] Examples 1-10 and Comparative Examples 1-2

[0144] The photosensitive polyimide compositions of Examples 1 to 5 and Comparative Example 1 were prepared according to the components and blending amounts shown in Table 1-2. The blending amounts in Table 1 are parts by mass of each component relative to 100 parts by mass of the component (a).

[0145] The components used are as follows.

[0146] Component (b): Photosensitizer

[0147]

[0148] Component (c): thermal crosslinking agent

[0149]

[0150]

[0151] Component (d): solvent

[0152] d1: GBL (γ-butyrolactone)

[0153] d2: EL (ethyl lactate)

[0154] Component (e): Silane coupling agent

[0155] e1: γ-ureapropyltriethoxysilane

[0156] e2: Vinyltriethoxysilane

[0157] Table 1

[0158]

[0159] Table 2

[0160]

[0161]

[0162] The performance of the photosensitive polyimide compositions prepared in the examples and comparative examples was evaluated as follows:

[0163] (1) Preparation of developing film

[0164] The photosensitive polyimide composition (varnish) prepared in the examples and comparative examples was 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, the photosensitive polyimide composition was exposed at 100° C. for 1 minute and then baked. 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 an optical interference film thickness measuring apparatus LAMBDA ACE STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. at a refractive index of 1.63.

[0167] (3) Calculation of developing film loss

[0168] The loss of the developing film is calculated according to the following formula. Since the film thickness after prebaking is 6 μm, the loss of the developing film is preferably less than 1 μm. The case where the loss of the developing film is less than 1 μm is judged as "A", the case where it is 1-1.5 μm is judged as "B", and the case where it is more than 2 μm is judged as "C".

[0169] The results are shown in Table 3: Development film loss amount (μm) = film thickness after prebaking - film thickness after development.

[0170] (4) Determination of warpage

[0171] 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°C / min under the condition of an oxygen concentration of 20 ppm or less using an inert oven, and heat-treated at 200°C for 1 hour. When the temperature became 50°C or less, 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).

[0172] (5) Sensitivity evaluation

[0173] 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.

[0174] (6) Chemical resistance evaluation

[0175] Apply the solution to the solidified product using a pipette. Place the solidified product after application in a nitrogen oven at 200°C for 60 minutes. Then, transfer the solidified product from the hot plate and cool it to room temperature. Wash the solidified product after cooling with a 25% NaOH aqueous solution, dry it, and measure the film thickness.

[0176] 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.

[0177] (7) Adhesion evaluation

[0178] 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.

[0179] 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.

[0180] A: The number of remaining grids is 100 to 80.

[0181] B: The number of remaining grids is less than 80.

[0182] The results are shown in Table 3.

[0183] Table 3

[0184]

[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 loss of developing film, excellent low warpage stress, and excellent chemical resistance. Compared with the examples, the warpage stress of Comparative Example 1 is higher. However, the developing film loss of Comparative Example 2 is large, the warpage stress is high, and the chemical resistance stability is poor.

[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: Contains the following ingredients (a), (b), (c) and (d): (a) a block polymer soluble in alkaline aqueous solution; which is selected from the compound represented by the following formula 1 Wherein, R is selected from C1-C10 unsubstituted alkyl; Ar1, when it appears each time, is identically or differently selected from any one of the tetravalent organic groups represented by Formula 2-1 to Formula 2-9: R1-R8 are each independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; 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; 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: R9-R 20 Each is independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; Y is selected from any one of oxygen atom, C1-C5 substituted or unsubstituted alkylene, sulfur atom, sulfone group and carbonyl group; Ar3 is selected from any one of the tetravalent organic groups represented by formulae 4-1 to 4-6, the same or different each time it occurs: R 21 -R 26 Each is independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; Q is selected from any one of oxygen atom, C1-C5 substituted or unsubstituted alkylene, sulfur atom, sulfone group and carbonyl group; k+m=5~200, m / k=0.01~0.5; The weight average molecular weight of the block polymer is 3000-200000; (b) photosensitizer; (c) a thermal crosslinking agent; component (c) comprises a component (C1) a crosslinking agent containing an epoxy group and a component (C2) a crosslinking agent containing CH2OR; (d) Silane coupling agent.

2. The photosensitive polyimide composition according to claim 1, characterized in that R is selected from C1-C5 unsubstituted alkyl.

3. The photosensitive polyimide composition according to claim 1, characterized in that R is a C1-C3 unsubstituted alkyl group.

4. The photosensitive polyimide composition according to claim 1, characterized in that R is any one of CH3, CH2CH3 and CH(CH3)2.

5. The photosensitive polyimide composition according to claim 1, characterized in that: R1-R8 are each independently selected from any one of hydrogen, fluorine, methyl and trifluoromethyl; 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.

6. The photosensitive polyimide composition according to claim 1, characterized in that: R9-R 20 Each is independently selected from any one of hydrogen, fluorine, methyl and trifluoromethyl; 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.

7. The photosensitive polyimide composition according to claim 1, characterized in that: R 21 -R 26 Each is independently selected from any one of hydrogen, fluorine, methyl and trifluoromethyl; Q 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.

8. The photosensitive polyimide composition according to claim 1, characterized in that: The weight average molecular weight of the block polymer is 5,000-100,000.

9. The photosensitive polyimide composition according to claim 1, characterized in that: The photosensitizer is a quinone diazide compound.

10. The photosensitive polyimide composition according to claim 1, characterized in that: The component (c) is selected from the compound represented by Formula 5-1 or Formula 5-2, Wherein, in formula 5-1, U is selected from a divalent organic group containing an alicyclic ring or an aromatic ring; In formula 5-2, R 29 is selected from a hydrogen atom or a monovalent organic group, R 30 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 29 Same or different, when b is 2 or 3, R 30 Same or different.

11. The photosensitive polyimide composition according to any one of claims 1 to 10, 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 5-30 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 0.5-10 parts by weight.

12. The photosensitive polyimide composition according to any one of claims 1 to 10, characterized in that: The photosensitive polyimide composition further contains any one of a solvent and a leveling agent or a combination of at least two of them.

13. The photosensitive polyimide composition according to claim 12, characterized in that: Based on 100 parts by weight of the component (a), the content of the solvent is 100-200 parts by weight, and the content of the leveling agent is 100-1000 ppm.

14. A method for manufacturing a graphic, characterized in that: The method comprises the steps of coating the photosensitive polyimide composition according to any one of claims 1 to 10 on a supporting substrate, and performing drying, exposure, development and heating treatment.

15. The method for manufacturing a pattern according to claim 14, characterized in that: The light source used in the exposure process is i-ray.

16. 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 10.

17. The cured product according to claim 16, characterized in that The cured product includes a surface protection film or an interlayer insulating film.

18. An electronic component, characterized in that: The electronic component comprises the cured product according to claim 16.

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