Photosensitive polyimide composition, cured product and electronic component

Abstract

The present invention relates to the technical field of photosensitive dielectric materials, and more specifically, to a photosensitive polyimide composition, a cured product, and an electronic component. A photosensitive polyimide composition having low-temperature crosslinking and low warpage stress contains the following components (a), (b), and (c): (a) a block polymer soluble in an alkaline aqueous solution; (b) a photosensitizer; and (c) a thermal crosslinker, wherein the thermal crosslinker includes a component (c1) a crosslinker containing an epoxy group and a component (c2) a crosslinker containing CH2OR. The photosensitive polyimide composition can simultaneously achieve low-temperature curing, excellent exposure sensitivity, low warpage, low stress, high chemical resistance, and high 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] In recent years, based on the requirements of reducing the heat load on the device and reducing the warpage of the device, a positive photosensitive material that can be cured by firing at a low temperature of 250°C or less (preferably 200°C or less) and has high sensitivity and high resolution is needed. As polyimide compositions that can be cured at low temperatures, photosensitive polyimide compositions using closed-loop polyimide, photoacid generators, and hydroxymethyl-containing thermal crosslinking agents can be cited. However, these compositions have a problem of large warpage due to their high shrinkage during curing.

[0003] In order to achieve low warpage, a water-soluble photosensitive composition is provided, which comprises a multi-component system block copolymer polyimide polyimide, a photosensitizer and water, wherein the multi-component system block copolymer polyimide polyimide contains specific diamine residues and acid dianhydride residues. However, the water-soluble photosensitive composition has poor exposure sensitivity because it uses a material for forming low linear expansion, and further because it contains a large amount of water, its use is limited, and it cannot be used for surface protection films of semiconductor elements, interlayer insulation films, and insulation layers of organic electroluminescent elements.

[0004] It can be seen that the photosensitive polyimide composition in the prior art cannot simultaneously achieve low temperature curing, excellent exposure sensitivity, low warpage, low stress, high chemical resistance and high adhesion.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] 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 can simultaneously achieve low temperature curing, excellent exposure sensitivity, low warpage, low stress, high chemical resistance and high adhesion.

[0007] The present invention is achieved in that:

[0008] In a first aspect, the present invention provides a photosensitive polyimide composition having low temperature crosslinking and low warpage stress, comprising the following components (a), (b) and (c):

[0009] (a) a block polymer soluble in alkaline aqueous solution; the structural formula of which is shown in the following formula 1: Formula 1

[0010] Wherein, k+m=5-200, m / k=0.01-0.5; Ar1 ​​is selected from a tetravalent organic group, Ar2 is selected from a divalent organic group, and Ar3 is selected from a tetravalent organic group.

[0011] (b) photosensitizer;

[0012] (c) A thermal crosslinking agent, wherein the thermal crosslinking agent includes a component (c1) of a crosslinking agent containing an epoxy group and a component (c2) of a crosslinking agent containing CH2OR.

[0013] In a second aspect, the present invention provides a method for manufacturing a pattern, the method comprising coating the low-temperature cross-linking, low warpage stress 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 obtained by curing the photosensitive polyimide composition having low temperature crosslinking and low warpage stress 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 described in the aforementioned embodiment;

[0018] Preferably, the cured product is used as a surface protection film or an interlayer insulating film.

[0019] The present invention has the following beneficial effects: the part 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 part that is not exposed to ultraviolet light is insoluble in an alkaline aqueous solution, thereby being able to effectively replicate fine patterns. In addition, the photosensitive polyimide composition of the present invention has an excellent dissolution rate ratio (contrast) between the unexposed part and the exposed part, and has good resolution, sensitivity, low warpage, low stress and low temperature curing ability, and the film formed after curing has good chemical resistance and adhesion. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] 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.

[0021] Figure 1A schematic diagram of a semiconductor packaging structure provided by an embodiment of the present invention. DETAILED DESCRIPTION

[0022] 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.

[0023] The embodiment of the present invention provides a photosensitive polyimide composition, which contains the following components:

[0024] (a) a block polymer soluble in alkaline aqueous solution; (b) a photosensitizer; (c) a thermal crosslinking agent; (d) a silane coupling agent.

[0025] The photosensitive polyimide composition of the present invention increases the dissolution rate ratio (dissolution contrast) of the exposed portion of the pattern to the unexposed portion relative to the alkaline developer, thereby having excellent sensitivity and resolution. The portion of the photosensitive polyimide composition exposed to ultraviolet light is easily soluble in an alkaline aqueous solution, while the portion not exposed to ultraviolet light is insoluble in an alkaline aqueous solution, thereby being able to effectively replicate fine patterns. At the same time, the photosensitive polyimide composition has the ability to cure at low temperatures, as well as low warpage, low stress, and chemical resistance.

[0026] 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.

[0027] The alkaline aqueous solution mentioned above refers to a tetramethylammonium hydroxide aqueous solution, a metal hydroxide aqueous solution, an organic ammonia aqueous solution, and the like.

[0028] From the viewpoint of solubility in alkaline aqueous solutions, component (a) has a plurality of phenolic hydroxyl groups and a plurality of carboxyl groups.

[0029] The main chain skeleton of the component (a) is an alternating block polymer of polyimide and polyoxazole polymers, so that the photosensitive polyimide composition has better processability and heat resistance.

[0030] Furthermore, component (a) is more preferably a block copolymer of polyimide-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:

[0031]

[0032] wherein 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. Ar1 is selected from a 4-valent organic group, Ar2 is selected from a 2-valent organic group, and Ar3 is selected from a 4-valent organic group;

[0033] The amide structure containing a hydroxyl group as shown in Formula 1 can be finally converted into an oxazole through curing dehydration ring closure, so that the cured film has excellent chemical resistance, heat resistance, adhesion and the like.

[0034] 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.

[0035] 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 alkaline aqueous solutions.

[0036] Furthermore, Ar1 is selected from any one of the tetravalent organic groups represented by the following formula 2, either identically or differently, each time it appears:

[0037]

[0038] Wherein, R1-R8 are all monovalent organic groups, and 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 hydrogen, fluorine atom, methyl and trifluoromethyl; X is a divalent group, preferably, X is selected from any one of oxygen atom, C1-C5 substituted or unsubstituted alkylene, sulfur atom, sulfone group and carbonyl group; for example, X is selected from any one of oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 and C(CF3)2.

[0039] In Formula 1, Ar1 is a tetravalent organic group, which is generally a residue of a tetracarboxylic dianhydride or a derivative thereof having an amide ester structure formed by a tetracarboxylic dianhydride or a derivative thereof and a diamine, and is preferably a tetravalent aromatic group, 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) ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl) ethane dianhydride, bis(3,4-dicarboxyphenyl) methane dianhydride, bis(2,3-dicarboxyphenyl) methane dianhydride, bis(3,4-dicarboxyphenyl) sulfone dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl) fluorene dianhydride, 9,9 - Aromatic tetracarboxylic dianhydrides such as bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0040] Ar2 is selected from any one of the divalent organic groups represented by Formula 3, the same or different each time it appears:

[0041]

[0042] Among them, R9-R 20 are all monovalent organic groups, preferably, R9-R 20 Each is independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; for example, R9-R20 Each is independently selected from any one of hydrogen, fluorine atom, methyl and trifluoromethyl; Y is a divalent group; Y is selected from any one of oxygen atom, C1-C5 substituted or unsubstituted alkylene, sulfur atom, sulfone group and carbonyl group; for example, Y is selected from any one of oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 and C(CF3)2.

[0043] 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, o-aminobenzoic acid, etc. These can be used alone or in combination of two or more.

[0044] Ar3 is selected from any one of the 4-valent organic groups represented by formula 4, the same or different each time it appears:

[0045]

[0046] Among them, R 21 -R 26 They are all monovalent organic groups, each independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl; Q is a divalent group, selected from any one of oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 or C(CF3)2.

[0047] In Formula 1, Ar3 is a tetravalent organic group, generally a residue of a dihydroxy diamine having an amide structure formed by the reaction of a hydroxyl diamine and an amino acid, preferably a tetravalent aromatic group, preferably 6-40 carbon atoms, more preferably a tetravalent aromatic group having 6-40 carbon atoms. 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.

[0048] In addition, in order to improve adhesion to the substrate, as long as the heat resistance is not damaged, the Ar3 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, Ar2 and Ar3. 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 ratio is preferably 30-100%.

[0050] 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.

[0051] It should be noted that: (1) the above R1-R 26 The halogen mentioned in is not limited to F, and may also be bromine, chlorine, and the like.

[0052] (2) The above R1-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.

[0053] (3) The above R1-R 26 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.

[0054] 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.

[0055] In the present invention, the block polymer having the structural unit shown in Formula 1 is generally prepared by first using dianhydride and aminobenzoic acid polymer to imide and then chlorinate to obtain a diacyl chloride compound, and then condensing hydroxy diamine and dianhydride into an oligomer, which is then polymerized with the obtained diacyl chloride compound.

[0056] Specifically, in the first step, a compound having a carboxyl-terminated polyimide structure can be prepared by reacting aminobenzoic acid with dianhydride, and then a compound having a terminal acyl chloride and a polyimide structure can be prepared by chlorination. In the second step, a diamine compound containing a hydroxyl group and 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 terminal acyl chloride compound prepared in the first step and the amino-terminated polyhydroxyamide.

[0057] In the embodiment of the present invention, naphthoquinone diazide-5-sulfonyl and naphthoquinone diazide-4-sulfonyl can be preferably used for the quinone diazide compound. In the embodiment of the present invention, naphthoquinone diazide-5-sulfonyl ester compounds using naphthoquinone diazide-4-sulfonyl in the same molecule can be obtained, and naphthoquinone diazide-5-sulfonyl ester compounds and naphthoquinone diazide-4-sulfonyl ester compounds can also be mixed for use.

[0058] The component (b) quinonediazide compound more preferably comprises an ester formed of a phenol compound and naphthoquinonediazide-5-sulfonyl group, thereby achieving high sensitivity in i-line exposure.

[0059] The content of component (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 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.

[0060] The photosensitive polyimide composition 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 a -CH2OR (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 process after coating, exposure and development of the photosensitive polymer composition of the present invention, or is 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.

[0061] In the present invention, the crosslinking agent having an epoxy group in its structure is used as component (c1). Component (c1) is selected from the compounds represented by the following formula 5-1:

[0062]

[0063] wherein U is selected from a divalent organic group containing an alicyclic ring or an aromatic ring; the following are specific examples of the compound represented by formula 5-1, 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 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, EP-4000S (above, trade names, manufactured by ADEKA), etc. These may be used alone or in combination of two or more. Also, these compounds may be used alone or in combination of two or more as the component.

[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 of the group, but preferably has at least two. Component (c2) is selected from the compounds shown in the following formula 5-2.

[0065]

[0066] Among them, 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.

[0067] Specific examples of the compound represented by Formula 5-2 are shown below. These compounds may be used alone or in combination of two or more.

[0068]

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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, 0.1f 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.

[0073] The photosensitive polyimide composition with low-temperature crosslinking and low warpage stress of the present invention further contains (d) a solvent, preferably an organic solvent. For example, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can be used. Specifically, for example, polar solvents such as γ-butyrolactone, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl sulfoxide, hexamethylphosphoric acid triamide, dimethylimidazolidinone, tetraethyl urea, tetramethyl urea, ethyl lactate, 3-methoxy-N,N-dimethylpropaneamide and N-acetyl-ε-caprolactam can be listed. 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 (d) may be used alone or in combination of two or more.

[0074] When component (d) is included, the amount of component (d) is preferably 50 to 1000 parts by mass, more preferably 100 to 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.

[0075] The polyimide composition of the present invention further contains (e) an alkoxysilane binder, and 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, 3- Mercaptopropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, bis(2-hydroxyethyl)-3-aminopropyl triethoxysilane, triethoxysilylpropyl ethyl carbamate, 3-(triethoxysilyl)propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, 3-triethoxysilyl-N-(l,3-dimethylbutylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.

[0076] 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 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass relative to 100 parts by mass of component (a). For example, it is any value between 0.5 and 15 parts, such as 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 1, 11, 12, 13, 14, and 15.

[0077] The present invention may further contain (f) a leveling agent, and the leveling agent may be a surfactant, so as to improve 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.); 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); acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.); and the like.

[0078] Next, the method for producing a photosensitive polyimide composition with low-temperature crosslinking and low warpage stress provided by an embodiment of the present invention is described. For example, a photosensitive polyimide composition can be obtained by uniformly mixing the above-mentioned (a) to (c) components and the (d) to (f) components used as needed. As dissolving methods, 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 photosensitive polyimide composition, usually room temperature to 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.

[0079] The obtained photosensitive polyimide composition is preferably filtered using a filter to remove impurities and particles. The filter pore size is 0.5 to 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.

[0080] The cured product provided in the embodiment of the present invention can be obtained by curing the above-mentioned photosensitive polyimide composition with low temperature crosslinking and low warpage stress. The cured product of the present invention can be used as a patterned cured film or as a non-patterned cured film.

[0081] The method for manufacturing a patterned cured film comprises, for example, a step of coating the above-mentioned 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.

[0082] In the film forming process, the photosensitive polyimide composition is applied on a metal substrate such as Cu, a glass substrate, a semiconductor, a metal oxide insulator (such as TiO2, SiO2, etc.), a supporting substrate such as silicon nitride, etc., for example, by dipping, spraying, screen printing, spin coating, etc. From the viewpoint of operability, the applied photosensitive polyimide composition can also be used by drying by heating (for example, 90 to 150° C., 1 to 5 minutes) using a hot plate, 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 to 20 μm.

[0083] 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 (a) component, 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 to 140°C, and the time of post-exposure heating is preferably 1 minute to 5 minutes.

[0084] In the developing process, for example, the exposure portion of the photosensitive polyimide film after the exposure process is removed with a developer, thereby patterning the photosensitive polyimide film. 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 to 10% by mass. Furthermore, alcohols or surfactants can also be added to the above-mentioned developer and used. They can be respectively matched in a range of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the developer. The photosensitive polyimide film after patterning is referred to as a patterned polyimide film.

[0085] In the heating process, the photosensitive polyimide composition can be cured by heating the pattern polyimide film or the photosensitive polyimide film. In particular, the film obtained by curing the pattern polyimide film is called a pattern cured film. The heating temperature is preferably 100 to 500 ° C. From the viewpoint of fully preventing the damage to the electronic components caused by heat, it is preferably less than or equal to 250 ° C, more preferably less than or equal to 225 ° C, and further preferably 140 to 210 ° 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 thermal annealing furnace, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace. In addition, any one of the inert atmospheres such as the atmosphere or nitrogen can be selected, but when it is carried out under nitrogen, the oxidation of the pattern can be prevented, so an inert atmosphere such as nitrogen is preferred.

[0086] The cured product of the present invention can be used as an interlayer insulating film, a surface protective film, or the like.

[0087] 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.

[0088] 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).

[0089] 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.

[0090] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0091] The abbreviated names of the compounds, auxiliary agents and solvents in the following examples and comparative examples are as follows.

[0092] Bis-AP-AF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0093] 4-ABA p-aminobenzoic acid

[0094] SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane

[0095] ODPA: 4,4'-oxydiphthalic anhydride

[0096] MAP: meta-aminophenol

[0097] NMP: N-methyl 2-pyrrolidone

[0098] GBL; γ-butyrolactone

[0099] TMAH: Tetramethylammonium hydroxide

[0100] SOCl2: Sulfonyl chloride

[0101] Synthesis example 1

[0102] This embodiment provides a method for preparing a terminal acyl chloride compound containing an imide structure, comprising:

[0103] Under a dry nitrogen stream, 13.71 g (0.1 mol) of 4-ABA was dissolved in 100 g of tetrahydrofuran, and the resulting solution was then cooled to -10°C. Subsequently, 15.51 g (0.05 mol) of ODPA was added, and the mixture was reacted at 0°C for 4 hours. Then 13.09 g (0.11 mol) of SOCl2 was added dropwise thereto, and after the addition was complete, the mixture was reacted at 0°C for 1 hour, and then the solution was concentrated by distillation under reduced pressure to obtain a terminal acyl chloride compound (I) containing an imide structure.

[0104]

[0105] Compounds containing imide structures at terminal acyl chlorides (I)

[0106] Synthesis example 2

[0107] This embodiment provides a method for synthesizing polymer A, comprising:

[0108] Under a dry nitrogen stream, 32.96 g (0.09 mol) of Bis-AP-AF was dissolved in 132 g of NMP, and 6.2 g (0.02 mol) of ODPA and 25 g of NMP were added thereto, and the mixture was reacted at 20°C for 3 hours, followed by the addition of 2.18 g (0.02 mol) of MAP and 12.66 g of pyridine as a capping agent, and then the system was cooled to -10°C, and a solution of 46.8 g (0.08 mol) of compound (I) dissolved in 187 g of NMP was added dropwise, and the mixture was continued to react at -10°C for 1 hour. After the reaction was completed, the solution was put into 4 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80°C for 72 hours to obtain polymer A. The molecular weight of polymer A was measured, and the molecular weight was 22,000.

[0109]

[0110] The molecular weight test method is as follows:

[0111] 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 40,000. 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)].

[0112] Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.

[0113] Pump: L6000 manufactured by Hitachi Manufacturing Co., Ltd.

[0114] C-R4A Chromatopac manufactured by Shimadzu Corporation

[0115] Measurement conditions: Chromatographic column Gelpack GL-S300MDT-5 × 2

[0116] Eluent: THF / DMF=1 / 1 (volume ratio), LiBr (0.03 mol / L), H3PO4 (0.06 mol / L) Flow rate: 1.0 mL / min, Detector: UV270 nm

[0117] Synthesis example 3

[0118] This embodiment provides a method for synthesizing polymer B, which is as follows:

[0119] Under a dry nitrogen stream, 32.96g (0.09mol) Bis-AP-AF was dissolved in 132g NMP, and 7.76g (0.025mol) ODPA and 31g NMP were added thereto, and the mixture was reacted at 20°C for 3 hours. Then, 2.18g (0.02mol) MAP and 11.9g pyridine as end-capping agents were added, and the system was cooled to -10°C, and a solution of 43.88g (0.075mol) compound (I) dissolved in 175g NMP was added dropwise. After the addition was completed, the mixture was reacted at -10°C for 1 hour. After the reaction was completed, the solution was put into 4L water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80°C for 72 hours to obtain polymer B. The molecular weight of polymer B was measured, and the molecular weight was 21000. The structure is the same, m / k=25 / 75.

[0120] Synthesis example 4

[0121] This embodiment provides a method for synthesizing polymer C, which is as follows:

[0122] Under a dry nitrogen stream, 32.96g (0.09mol) Bis-AP-AF was dissolved in 132g NMP, and 10.2g (0.033mol) ODPA and 41g NMP were added thereto, and the mixture was reacted at 20°C for 3 hours. Then, 2.18g (0.02mol) MAP and 10.6g pyridine as end-capping agents were added, and the system was cooled to -10°C, and a solution of 39.2g (0.067mol) compound (I) dissolved in 156g NMP was added dropwise. After the addition was completed, the mixture was reacted at -10°C for 1 hour. After the reaction was completed, the solution was put into 4L water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80°C for 72 hours to obtain polymer C. The molecular weight of polymer C was measured to be 21000. The structure is the same, m / k=33 / 67.

[0123] Synthesis example 5

[0124] This embodiment provides a method for synthesizing polymer D, which is as follows:

[0125] Under a dry nitrogen stream, 32.96 g (0.09 mol) of Bis-AP-AF and 2.18 g (0.02 mol) of MAP as a capping agent were dissolved in 132 g of NMP, and 31.02 g (0.1 mol) of ODPA and 124 g of NMP were added thereto. The mixture was reacted at 20° C. for 3 hours. After the reaction was completed, the solution was put into 4 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80° C. for 72 hours to obtain polymer D. The molecular weight of polymer D was measured and the molecular weight was 23,000.

[0126]

[0127] Examples 1-10 and Comparative Examples 1-2

[0128] The photosensitive resin compositions of Examples 1-10 and Comparative Examples 1-2 were prepared according to the components and blending amounts shown in Table 1. The blending amounts in Table 1-2 are parts by mass of each component relative to 100 parts by mass of component (a).

[0129] The components used are as follows.

[0130] Component (b): Photosensitizer

[0131]

[0132] Component (c): thermal crosslinking agent

[0133]

[0134] Component (d): solvent

[0135] d1: GBL (γ-butyrolactone)

[0136] d2: EL (ethyl lactate)

[0137] Component (e): Silane coupling agent

[0138] e1: γ-ureapropyltriethoxysilane

[0139] e2: Vinyltriethoxysilane

[0140] Table 1

[0141]

[0142]

[0143] Table 2

[0144]

[0145] The performance of the photosensitive resin compositions prepared in the examples and comparative examples was evaluated as follows:

[0146] (1) Preparation of developing film

[0147] The photosensitive resin 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 resin composition was exposed at 100° C. for 1 minute and then baked. After the photosensitive resin 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.

[0148] (2) Film thickness measurement method

[0149] 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.

[0150] (3) Calculation of developing film loss

[0151] 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".

[0152] The results are shown in Table 3: Development film loss amount (μm) = film thickness after prebaking - film thickness after development.

[0153] (4) Determination of warpage

[0154] 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).

[0155] (5) Sensitivity evaluation

[0156] 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.

[0157] (6) Chemical resistance evaluation

[0158] The solidified product was coated with a pipette. The coated solidified product was placed in a nitrogen oven at 200°C for 60 minutes. Then, the solidified product was cooled to room temperature. The cooled solidified product was washed with a 25% NaOH aqueous solution and dried, and the film thickness was measured.

[0159] 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.

[0160] (7) Adhesion evaluation

[0161] 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.

[0162] 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.

[0163] A: The number of remaining grids is 100 to 80.

[0164] B: The number of remaining grids is less than 80.

[0165] The results are shown in Table 3.

[0166] Table 3

[0167]

[0168]

[0169] As can be seen from Table 3, the photosensitive resin 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 warpage stress of Comparative Example 1 is higher. The sensitivity and chemical resistance stability of Comparative Example 2 are poor.

[0170] 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 having low temperature crosslinking and low warpage stress, characterized in that: It contains the following ingredients (a), (b) and (c): (a) a block polymer soluble in alkaline aqueous solution; the structural formula of which is shown in the following formula 1: Wherein, k+m=5-200, m / k=0.01-0.5; Ar1, when it appears each time, is selected identically or differently from any one of the tetravalent organic groups represented by Formula 2: 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 oxygen atom, C1-C5 substituted or unsubstituted alkylene, sulfur atom, sulfone group and carbonyl group; Ar2 is selected from any one of the divalent organic groups represented by Formula 3, 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 4-valent organic groups represented by formula 4, the same or different each time it appears: 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; (b) photosensitizer; (c) A thermal crosslinking agent, wherein the thermal crosslinking agent includes a component (c1) of a crosslinking agent containing an epoxy group and a component (c2) of a crosslinking agent containing CH2OR.

2. The photosensitive polyimide composition with low-temperature crosslinking and low warpage stress 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.

3. The photosensitive polyimide composition with low-temperature crosslinking and low warpage stress 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.

4. The photosensitive polyimide composition with low-temperature crosslinking and low warpage stress 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.

5. The photosensitive polyimide composition with low-temperature crosslinking and low warpage stress according to claim 1, characterized in that: The weight average molecular weight of the component (a) is 3,000-200,000.

6. The photosensitive polyimide composition with low-temperature crosslinking and low warpage stress according to claim 1, characterized in that: The weight average molecular weight of the component (a) is 5,000-100,000.

7. The photosensitive polyimide composition with low-temperature crosslinking and low warpage stress according to claim 1, characterized in that: The component (b) is a quinonediazide compound.

8. The photosensitive polyimide composition with low-temperature crosslinking and low warpage stress according to claim 1, characterized in that: The component (c) is selected from the compound shown in Formula 5, 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.

9. The photosensitive polyimide composition with low-temperature crosslinking and low warpage stress according to any one of claims 1 to 8, 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, wherein the content of c1 is 5-15 parts by weight, and the content of c2 is 0.1-15 parts.

10. The photosensitive polyimide composition with low-temperature crosslinking and low warpage stress according to any one of claims 1 to 8, characterized in that: The invention also includes any one of a solvent, an alkoxysilane binder or a leveling agent, or a combination of at least two of them.

11. The photosensitive polyimide composition with low-temperature crosslinking and low warpage stress according to claim 10, characterized in that: Based on 100 parts by weight of the component (a), the content of the solvent is 100-200 parts by weight, the content of the alkoxysilane binder is 0.5-10 parts by weight, and the content of the leveling agent is 100-1000 ppm.

12. A method for manufacturing a graphic, characterized in that: The manufacturing method comprises the steps of coating the low-temperature crosslinking and low warpage stress photosensitive polyimide composition according to any one of claims 1 to 11 on a supporting substrate, and performing drying, exposure, development and heating treatment.

13. The method for manufacturing a graphic according to claim 12, characterized in that: The light source used in the exposure process is i-ray.

14. A solidified product, characterized in that: The invention is obtained by curing the photosensitive polyimide composition with low-temperature crosslinking and low warpage stress as described in any one of claims 1 to 11.

15. The cured product according to claim 14, characterized in that The cured product includes a surface protection film or an interlayer insulating film.

16. An electronic component, characterized in that: It comprises the cured product according to claim 14.

17. The electronic component according to claim 16, characterized in that The cured product is used as a surface protection film or an interlayer insulating film.

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