Photosensitive composition, method for preparing pattern, cured product, and electronic component

Abstract

The present disclosure relates to the technical field of photosensitive dielectric materials, and in particular relates to a photosensitive composition, a method for preparing a pattern, a cured product, and an electronic component. The photosensitive composition includes: component (a), a graft polymer, which is selected from a compound represented by the following structural formula (I), wherein Ar1 is selected from a tetravalent organic group, Ar2 is selected from a divalent organic group, and R' is selected from any one of an alkyl, an alkoxy, a cycloalkyl and an aryl; m+n=5-200, n / (m+n)=0.05-1, k=2-10, and x=0.5-10; component (b), a photoacid generator; component (c), a thermal cross-linking agent, which is a cross-linking agent containing CH2OR", wherein R'' is selected from hydrogen or a monovalent organic group; and component (d), a basic compound. The photosensitive composition has a good sensitivity and a good resolution ratio, the capability to copy fine patterns, a low warping stress after low-temperature curing, and a high chemical stability and cohesiveness.

Description

Photosensitive compositions, methods for preparing patterns, cured products, and electronic components

[0001] Cross-reference to related applications

[0002] This application claims priority to Chinese Patent Application No. 2024115975031, filed on November 11, 2024, entitled "Photosensitive Composition, Method for Preparing Patterns, Cured Product and Electronic Components", the entire contents of which are incorporated herein by reference. Technical Field

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

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

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

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

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

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

[0009] The purpose of this disclosure is to provide photosensitive compositions, methods for preparing patterns, cured products, and electronic components. The photosensitive compositions provided in the embodiments of this disclosure exhibit excellent sensitivity, resolution, and the ability to reproduce fine patterns, and after low-temperature curing, they have low warpage stress, high chemical stability, and good adhesion.

[0010] This disclosure is implemented as follows:

[0011] In a first aspect, this disclosure provides a photosensitizing composition comprising component (a) a grafted polymer selected from compounds of Formula 1 below:

[0012] Wherein, Ar1 is selected from a tetravalent organic group, Ar2 is selected from a divalent organic group, R′ is selected from any one of alkyl, alkoxy, cycloalkyl and aromatic groups; m+n=5~200, n / (m+n)=0.05~1, k=2~10, x=0.5-10;

[0013] Component (b) Photoacid-producing agent;

[0014] Component (c) Thermal crosslinking agent: It is a crosslinking agent containing CH2OR″, where R″ is selected from hydrogen or a monovalent organic group;

[0015] Component (d) is an alkaline compound.

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

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

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

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

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

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

[0022] This disclosure has the following beneficial effects: the portion of the photosensitive composition provided in this disclosure that is 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, thus enabling the effective reproduction of fine patterns. Furthermore, this photosensitive composition exhibits excellent sensitivity, high resolution, and after low-temperature curing (180-200℃), it possesses low warpage stress, high adhesion, and good chemical resistance. Attached Figure Description

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

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

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

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

[0027] Component (a) grafted polymer; component (b) photoacid-producing agent; component (c) thermal crosslinking agent; component (d) basic compound.

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

[0029] Specifically, component (a) is a grafted polymer, which, from the viewpoint of processability and heat resistance, preferably has a polyimide-based backbone and a limited number of poly(p-hydroxystyrene)-based grafted backbones.

[0030] Furthermore, component (a) is more preferably a graft copolymer of polyimide-poly(p-hydroxystyrene), specifically a polymer of the structural unit shown in Formula 1 below:

[0031] Where m+n is the number of repeating structural units in component (a), m+n = 5 to 200, for example, any value between 5 and 200, such as 5, 10, 15, 20, 25, 35, 40, 50, 70, 75, 80, 85, 95, 100, 110, 120, 135, 150, 160, 175, 180, 185, 190, 195, and 200. When m+n is less than 5, the viscosity of the composition is too low, making it unsuitable for use as a thick film; when m+n is greater than 200, the composition becomes too viscous, affecting coating. n / (m+n) = 0.05 to 1, for example, any value between 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 and 0.05-1.

[0032] The solubility of this composition in alkaline aqueous solutions originates from the phenolic hydroxyl groups, therefore it is preferable to include a certain proportion or higher of these structures. More preferably, k = 2 to 10, for example, 2, 4, 6, 8, 10, and any value between 2 and 10. Excessively large k units can lead to a decrease in film toughness. More preferably, x = 0.5 to 10, for example, 0.5, 1, 3, 5, 7, 9, 10, and any value between 0.5 and 10. Excessively small x units can lead to a significant loss in film thickness during development. Therefore, by adjusting the amount of grafting of p-hydroxystyrene and the amount of acetalization of the phenolic hydroxyl groups, a photosensitive grafted composition with a suitable dissolution rate can be obtained.

[0033] Furthermore, Ar1 is selected from tetravalent organic groups, for example, Ar1 is selected from any one of the tetravalent organic groups shown in Formula 2 below each time it appears:

[0034] Among them, R1-R8 are all monovalent organic groups, and X is a divalent group.

[0035] Specifically, R1-R8 are each independently selected from hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl groups; preferably, R1-R8 are each independently selected from hydrogen, fluorine atom, bromine atom, iodine atom, methyl, ethyl, n-propyl, tert-butyl, isobutyl and trifluoromethyl.

[0036] X is selected from any one of oxygen atom, C1-C5 substituted or unsubstituted alkylene, sulfur atom, sulfone group and carbonyl group, and X is selected from any one of oxygen atom, methylene, ethylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 and C(CF3)2.

[0037] Specifically, in Formula 1, Ar1 is a tetravalent organic group, generally a residue from a tetracarboxylic dianhydride or its derivative forming an amide ester structure with a diamine. It is preferably a tetravalent aromatic group, and more preferably a tetracarboxylic dianhydride or its derivative residue having the following structure, where all four binding sites are located on the aromatic ring. Examples of such tetracarboxylic dianhydrides include: pyromellitic dianhydride, 3,3',4,4' biphenyltetracarboxylic dianhydride, 2,3,3',4' biphenyltetracarboxylic dianhydride, 2,2',3,3' biphenyltetracarboxylic dianhydride, 3,3',4,4' benzophenone tetracarboxylic dianhydride, 2,2',3,3' benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride. 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, Aromatic tetracarboxylic anhydrides such as 9,9-bis{4(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 2,3,5,6-pyridinetetracarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic anhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; aliphatic tetracarboxylic anhydrides such as butanetetracarboxylic anhydride; and 1,2,3,4-cyclopentanetetracarboxylic anhydride. These can be used alone or in combination of two or more.

[0038] Furthermore, Ar2 is selected from divalent organic groups, for example, Ar2 is selected from any one of the divalent organic groups shown in Formula 3 each time it appears:

[0039] Among them, R9-R 20 All are monovalent organic groups, and Y is a divalent group.

[0040] Specifically, R9-R 20 Each is independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl groups; preferably, R9-R 20 Each is independently selected from any one of hydrogen, fluorine, bromine, iodine, methyl, ethyl, n-propyl, tert-butyl, isobutyl, and trifluoromethyl.

[0041] Y is selected from any one of oxygen atom, C1-C5 substituted or unsubstituted alkylene, sulfur atom, sulfone group and carbonyl group; Y is selected from any one of oxygen atom, methylene, ethylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 and C(CF3)2.

[0042] Furthermore, in Formula 1, Ar2 is a divalent organic group, generally a residue derived from an amino acid that forms an amide structure with a diamine. It is preferably a divalent aromatic group, and more preferably an amino acid residue with the following structure, where both binding sites are located on the aromatic ring. Examples of such amino acids include p-aminobenzoic acid, m-aminobenzoic acid, and o-aminobenzoic acid. They can be used individually or in combination of two or more.

[0043] In addition, to improve adhesion to the substrate, the Ar2 part can be copolymerized with a certain proportion of aliphatic groups with siloxane structures, provided that the heat resistance is not compromised. Preferred options include 1-10% molar of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc.

[0044] The terminal groups of the aromatic polyamide shown in Formula 1 are either carboxylic acids or amines, depending on the input ratio of Ar1 and Ar2. Depending on the requirements, one or two end-capping agents can react with the polymer ends to make one or both ends each a saturated aliphatic group, an unsaturated aliphatic group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a mercapto group, etc. In this case, the end-capping rate is preferably 30-100%.

[0045] It should be noted that: (1) the above R1-R 20 The halogens mentioned are not limited to F, but can also be bromine and chlorine, etc.

[0046] (2) The above R1-R 20 The C1-C5 substituted or unsubstituted alkyl groups mentioned can be C1-C3 substituted or unsubstituted alkyl groups, such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, tert-butyl and other unsubstituted alkyl groups, or trifluoromethyl, trifluoroethyl, difluoromethyl, trichloromethyl and other substituted alkyl groups.

[0047] (3) The above R1-R 20 The C1-C5 substituted or unsubstituted alkylene mentioned can be C1-C3 unsubstituted alkylene, such as methylene, ethylene, propylene, etc., or C1-C3 substituted alkylene, such as halogen (fluorine, bromine, chlorine) substituted methylene, halogen substituted ethylene, etc.

[0048] R′ is selected from any one of alkyl, alkoxy, cycloalkyl, and aromatic groups, including but not limited to ethyl, propyl, butyl, cyclohexyl, and phenyl.

[0049] Regarding the molecular weight of component (a), it is preferably 3,000-200,000, more preferably 5,000-100,000, based on weight-average molecular weight. The molecular weight here is a value determined by gel permeation chromatography and converted from a standard polystyrene standard curve.

[0050] In the embodiments of this disclosure, the graft polymer having the structural unit shown in Formula 1 is generally first prepared by polycondensation of dianhydride and diamine to obtain a polyamic acid polymer, then chemically imidized to obtain a polyimide polymer, and then chloromethylated and xanthate-esterified to obtain a macromolecular initiator, and then grafted to obtain a polyimide-g-poly(p-hydroxystyrene) graft copolymer, and finally acetalized with a vinyl ether compound to obtain the graft copolymer described in this disclosure.

[0051] Specifically, the first step involves preparing polyamic acid by reacting diamine with dianhydride, followed by chemical imidization to prepare polyimide. The second step involves chloromethylating and xanthate-esterifying the polyimide to obtain a macromolecular initiator. The third step involves grafting p-hydroxystyrene onto the macromole prepared in the second step via RAFT polymerization to prepare a grafted polymer. The fourth step involves acetalizing the grafted copolymer with a vinyl ether compound to obtain the grafted copolymer described in this disclosure. The conditions and operations of the above steps are well known to those skilled in the art, and will not be detailed in the embodiments of this disclosure.

[0052] The photoacid-producing agent in component (b) is a compound that produces acid upon irradiation with active light or radiation. Examples include any one or a combination of two or more of diaryliodomonium salts, triarylsulfonium salts, imide sulfonate derivatives, and oxime sulfonate compounds. Considering thermal stability and photosensitivity, component (b) is preferably a triarylsulfonium salt, more preferably in combination with a sensitizer.

[0053] Examples of sulfonate anions contained in the triarylsulfonate salts in the photosensitizing compositions of this disclosure include aryl sulfonate anions, alkyl sulfonate anions, etc., which are substituted with fluorine atoms or organic groups having fluorine atoms.

[0054] Specifically, the triarylsulfonium salt may be selected from any one or two or more of the following specific examples, but the triarylsulfonium salts provided in the embodiments of this disclosure are not limited to the following specific examples or combinations thereof.

[0055] Furthermore, examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenyliodonium trifluoroacetate, phenyl, 4-(2'-hydroxy-.1'-tetradecyloxy)phenyliodonium trifluoromethanesulfonate, etc.

[0056] Imide sulfonate derivatives include, but are not limited to, trifluoromethanesulfonyloxybicyclo[2.2.1]hept-5-terminated dicarboxylidene imide, succinimide trifluoromethanesulfonate, phthalimide p-toluenesulfonate, phthalimide trifluoromethanesulfonate, and N-hydroxynaphthalimide methanesulfonate, examples of which include N-hydroxy-5-norbornene-2,3-dicarboxylidene propanesulfonate.

[0057] Among compounds that generate acid upon irradiation by active light or radiation, oxime compounds are preferred, and oxime sulfonate compounds are more preferred, from the viewpoints of sensitivity, resolution, dielectric constant, and dimensional stability. As oxime sulfonate compounds, i.e. compounds having oxime sulfonate residues, compounds having oxime sulfonate residues as shown in the following formula are preferably exemplified.

[0058] In the photosensitive resin composition provided in the embodiments of this disclosure, the content of component (b) is 1-5 parts by weight, based on 100 parts by weight of component (a), for example, any value between 1 and 5 parts by weight, such as 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, and 5 parts by weight.

[0059] The photoacid-producing agents provided in this disclosure can be used alone or in combination of two or more. When using two or more in combination, it is preferable to combine compounds that produce two or more organic acids with different total atomic numbers excluding hydrogen atoms.

[0060] The photosensitive composition provided in this disclosure, for the purpose of easily obtaining a cured film, further contains (c) a thermal crosslinking agent, which is a crosslinking agent having a -CH2OR″ (R″ is a hydrogen atom or a monovalent organic group) group. This crosslinking agent reacts with the polymer (a) as component (a) to crosslink during the heat treatment process following coating, exposure, and development of the photosensitive polymer composition of this disclosure, or is a compound that self-polymerizes during the heat treatment process. Furthermore, the crosslinking agent has an affinity for alkaline aqueous solutions, thereby increasing the dissolution rate in alkaline aqueous solutions.

[0061] In this embodiment, component (c) is a crosslinking agent having a -CH2OR″ group (R″ being a hydrogen atom or a monovalent organic group). It is permissible for the compound to have one or more of this group, but preferably two or more. Component (c) is selected from compounds shown in Formula 4-2-1 or 4-2-2 below.

[0062] In Equation 4-2-1, R 21 Each is independently a hydrogen atom or a monovalent organic group, R 22Each can be an independent hydrogen atom or a monovalent organic group, or they can combine with each other to form a ring structure that can have substituents.

[0063] The following formula 4-2-1-1 represents a specific example of the compound shown in formula 4-2-1, which can be used alone or in combination with two or more of these compounds.

[0064] Among them, R 25 It is an alkyl group having 1-20 carbon atoms, preferably an alkyl group having 1-6 carbon atoms, R 26 It is an alkyl group with 1-10 carbon atoms.

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

[0066] In Equation 4-2-2, R 23 Selected from hydrogen atoms or monovalent organic groups, R 23 Preferably, it is hydrogen-based, alkyl-based, or alkenyl-based. The alkyl- or alkenyl-based group preferably has 1-20 carbon atoms. 24 Selected from monovalent organic groups, R 24 Preferably, it is an alkyl, alkenyl, alkoxyalkyl, or hydroxymethyl group, with a preferred number of carbon atoms of 1-20. n is an integer from 1 to 4, and X is selected from single bonds or organic groups with 1-4 valences. Examples include alkyl groups with 1-10 carbon atoms, alkylene groups with 2-10 carbon atoms (e.g., ethylene), aryl groups with 6-30 carbon atoms (e.g., phenylene), or groups obtained by replacing some or all of these hydroxyl hydrogen atoms with halogen atoms such as fluorine atoms. These groups may further include phenyl, sulfone, carbonyl, ether bonds, thioether bonds, amide bonds, etc. a is an integer from 1 to 4, b is an integer from 0 to 3, and when a is 2, 3, or 4, R 23 Whether the values ​​are the same or different, when b is 2 or 3, R 24 Same or different.

[0067] The purity of the compound shown in Formula 4-2 above is preferably 75% or higher, more preferably 85% or higher. When the purity is 85% or higher, it exhibits excellent storage stability and allows for sufficient cross-linking reaction of the polyimide composition. Furthermore, since unreacted groups that become water-absorbing groups can be reduced, the water absorption of the polyimide composition can be decreased. Methods for obtaining a high-purity thermal cross-linking agent include recrystallization and distillation. The purity of the thermal cross-linking agent can be determined using liquid chromatography.

[0068] Relative to 100 parts by weight of polyimide in component (a), the content of the thermal crosslinking agent in component (c) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more. If it is 5 parts by weight or more, the crosslinking density of the cured film is increased, resulting in high chemical resistance and low curing warpage. Furthermore, if it is 10 parts by weight or more, the chemical resistance is even higher, the low curing warpage is even better, and higher mechanical properties can be obtained. Additionally, considering the storage stability and mechanical strength of the composition, it is preferably 30 parts by weight or less.

[0069] Furthermore, the content of c is 5-30 parts, for example, any value between 5, 7, 8, 10, 15, 20, 25, 30 parts, etc.

[0070] The photosensitizing composition of this disclosure further includes component (d) containing a basic compound to reduce changes in performance over time from exposure to heating. Preferably, the basic compound is a compound having the structure shown in Formula 5.

[0071] Wherein, A, Y, and Q can be one of alkyl, alkoxy, and cyclic alkyl groups, respectively. Examples include, but are not limited to, ethyl, ethoxy, ethylethoxy, and cyclohexyl groups. Formula 5-1 below represents a specific example of the compound shown in Formula 5, and this component can use two or more of these compounds alone or in combination.

[0072] In the photosensitive composition provided in the embodiments of this disclosure, the content of component (d) is 0.001-2 parts by weight, based on 100 parts by weight of component (a), for example, any value between 0.001-2 parts by weight, such as 0.001 parts by weight, 0.01 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, and 2 parts by weight.

[0073] In the embodiments of this disclosure, the preferred ratio of photoacid-generating agent to basic compound is an acid-generating agent / basic compound (molar ratio) of 2.5 to 300. That is, from the viewpoint of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the reduction in resolution caused by the thickening of the relief pattern after heat treatment over time, it is preferably 300 or less. The acid-generating agent / basic compound (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0074] The photosensitizing composition provided in this embodiment further contains (e) a silane coupling agent, generally an organosilane compound, such as: γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-ureidopropyltriethoxysilane. Silane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate-propyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, triethoxysilylpropylethyl carbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.

[0075] When an organosilane compound is included, the adhesion between the cured photosensitive polyimide composition and the substrate can be improved. When an organosilane compound is included, the content of the organosilane compound relative to 100 parts by weight of component (a) is more preferably 0.5-15 parts by weight, and even more preferably 0.5-10 parts by weight. For example, any value between 0.5 and 15 parts, such as 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 1 part, 11 parts, 12 parts, 13 parts, 14 parts, and 15 parts.

[0076] The polyimide composition disclosed herein further comprises (f) a solvent, preferably an organic solvent. Examples include ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. Specific examples include polar solvents such as γ-butyrolactone, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl sulfoxide, hexamethylphosphoric triamine, dimethylimidazolinone, tetraethylurea, tetramethylurea, ethyl lactate, 3-methoxy-N,N-dimethylpropaneamide, and N-acetyl-ε-caprolactam. Other ingredients that can be used include: acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, 1-methoxy-2-propanol, 1-methoxy-2-acetoxypropane, propylene glycol 1-monomethyl ether 2-acetate, etc. Component (f) can be used alone or in combination with two or more.

[0077] When component (f) is included, the amount of component (e) is preferably 50-1000 parts by mass relative to 100 parts by mass of component (a), more preferably 100-200 parts by mass. For example, any value between 50 and 1000 parts, such as 50, 60, 70, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, and 1000 parts.

[0078] This disclosure may further include (g) a leveling agent, which may be a surfactant, thereby improving the coatability with the substrate. Examples of surfactants include fluorinated surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name, manufactured by DIC Co., Ltd.), and Surflon (trade name, manufactured by Asahi Glass Co., Ltd.); organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), Polyflow, Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and BYK (trade name, manufactured by BYK-Chemie GmbH); and acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

[0079] In the case of component (f), the content of component (g) is 100-1000 ppm relative to 100 parts by mass of component (a), for example, any value between 100-1000 ppm such as 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm and 1000 ppm.

[0080] Furthermore, a method for preparing the photosensitive composition provided in the embodiments of this disclosure will be described. For example, a photosensitive composition can be obtained by uniformly mixing the above-described components (a)-(d) and components (e)-(g) as needed. Examples of dissolution methods include stirring and heating. When heating, it is preferable to set the heating temperature within a range that does not damage the properties of the polyimide composition, typically room temperature to 80°C. Furthermore, the order in which the components are dissolved is not particularly limited; for example, methods include dissolving compounds with low solubility sequentially starting with those that are less soluble. Additionally, for components such as surfactants and certain adhesion modifiers that are prone to generating bubbles during stirring and dissolution, poor dissolution of other components due to bubble generation can be prevented by adding them last after the other components have been dissolved.

[0081] The resulting photosensitive polyimide composition is preferably filtered to remove impurities and particles. The filter pore size is 0.5-0.02 μm, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, etc., but not limited to these. The filter material includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., with polyethylene and nylon being preferred. When the photosensitive polyimide composition contains inorganic particles, a filter with a pore size larger than the particle size of these inorganic particles is preferred.

[0082] Furthermore, the cured material provided in this disclosure can be obtained by curing the above-described photosensitive composition. The cured material of this disclosure can be used as a patterned cured film or as a patternless cured film.

[0083] A method for manufacturing a patterned cured film or a method for preparing a pattern includes, for example, a step of coating a substrate with the above-mentioned photosensitive composition and drying it to form a photosensitive polyimide film (film formation step); a step of exposing the photosensitive polyimide film (exposure step); a step of diffusing the photosensitive composition with acid (post-exposure baking 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). A method for manufacturing a patternless cured film includes, for example, the above-mentioned film formation step and heating step. An exposure step may also be further included.

[0084] In the film-forming process, the above-mentioned photosensitive composition is coated onto a metal substrate such as Cu, a glass substrate, a semiconductor, a metal oxide insulator (e.g., TiO2, SiO2), or a supporting substrate such as silicon nitride, for example, by dip-coating, spraying, screen printing, or spin coating. From an operational point of view, the coated positive photosensitive polyimide composition can also be dried by heating (e.g., 90-150°C, 1-5 minutes) using a hot plate or oven. The supporting substrate can also be cleaned with acetic acid or the like before coating. The thickness of the resulting photosensitive polyimide film is preferably 5-20 μm.

[0085] In the exposure process, for example, the photosensitive polyimide film formed on the substrate is irradiated with the aforementioned active light through a mask. From the viewpoint of the transparency of component (a), irradiation with i-rays can be appropriately used.

[0086] In the developing process, for example, the exposed portion of the photosensitive polyimide film after the exposure process is removed with a developing solution, thereby patterning the photosensitive polyimide film. As the developing solution, in the case of an alkaline-soluble photosensitive composition, suitable alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (TMAH) can be used. The alkalinity of these aqueous solutions is preferably set to 0.1-10% by mass. Furthermore, alcohols or surfactants can also be added to the above-mentioned developing solution. They can be formulated in a range preferably 0.01-10 parts by mass, more preferably 0.1-5 parts by mass, relative to 100 parts by mass of the developing solution. The patterned photosensitive polyimide film is referred to as a patterned polyimide film.

[0087] In the heating process, the photosensitive composition can be cured by heating the patterned polyimide film or the photosensitive polyimide film. Specifically, the film obtained by curing the patterned polyimide film is called a pattern-cured film. The heating temperature is preferably 150-250°C, more preferably less than or equal to 230°C, more preferably greater than or equal to 170°C, and even more preferably 180-200°C. The heating time is preferably 20 minutes to 6 hours, more preferably 30 minutes to 3 hours. Multi-stage heating can also be performed. The heat treatment can be carried out using ovens such as quartz tube furnaces, hot plates, rapid thermal annealing furnaces, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces. Alternatively, either atmospheric or inactive atmospheres such as nitrogen can be selected, but nitrogen is preferred as it prevents oxidation of the pattern.

[0088] The cured material disclosed herein can be used as an interlayer insulating film or a surface protective film, etc.

[0089] The interlayer insulating film and surface protective film disclosed herein can be used in electronic components, etc., and the electronic components disclosed herein can be used in semiconductor devices, etc. The semiconductor devices can be used in various electronic devices, etc. A schematic diagram of the semiconductor packaging structure disclosed herein is shown in Figure 1.

[0090] Therefore, it exhibits excellent rust prevention and adhesion effects on the supporting substrate (especially copper substrate and copper alloy substrate), and can suppress discoloration of the cured film and the supporting substrate (especially copper substrate and copper alloy substrate).

[0091] Examples of semiconductor devices include wafer-level chip-scale package (WLCSP) and fan-out wafer-level package (FOWLP). Furthermore, the interlayer insulating film and surface protective film disclosed herein can be used in circuit forming substrates, which can be used in hard disk drive suspensions, flexible wiring boards, etc.

[0092] The compounds provided in this disclosure have the following abbreviations corresponding to their substances:

[0093] ODA: 4,4-Diaminodiphenyl ether; SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane; ODPA: 4,4'-oxybisphthalic anhydride; Py: pyridine; Et2A: acetic anhydride; PhA: phthalic anhydride; NMP: N-methyl-2-pyrrolidone; TMAH: tetramethylammonium hydroxide; CMM: chloromethyl methyl ether; SnCl4: tin tetrachloride; AIBN: azobisisobutyronitrile; 4-HS: p-hydroxystyrene; EVE: vinyl ethyl ether; PTST: pyridine p-toluenesulfonic acid; St: styrene; 6FAP: 3,3-diamino-4,4-dihydroxydiphenyl-hexafluoropropane.

[0094] The molecular weight, grafting amount, and grafting rate of component (a) synthesized in the following synthetic example of this disclosure are tested. The specific test methods are as follows:

[0095] (1) Determination of molecular weight

[0096] The number-average molecular weight was determined using gel permeation chromatography (GPC) under the following conditions, converted from standard polystyrene. The determination was performed using a solution of 1 mL relative to 0.5 mg A and solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)].

[0097] Measurement apparatus: Detector: Hitachi, Ltd. L4000UV; Pump: Hitachi, Ltd. L6000

[0098] C-R4A Chromatopac manufactured by Shimadzu Corporation.

[0099] Measurement conditions: Gelpack GL-S300MDT-5 × 2 columns; eluent: THF / DMF = 1 / 1 (volume ratio), LiBr (0.03mol / L), H3PO4 (0.06mol / L); flow rate: 1.0mL / min; detector: UV 270nm.

[0100] (2) Determination of grafting rate n / (m+n)

[0101] Measurement equipment: Bruker BioSpin AV400M.

[0102] Magnetic field strength: 400MHz; reference material: tetramethylsilane (TMS); solvent: dimethyl sulfoxide (DMSO).

[0103] (3) Determination of grafting amount k

[0104] Measurement equipment: Bruker BioSpin AV400M

[0105] Magnetic field strength: 400MHz; reference material: tetramethylsilane (TMS); solvent: dimethyl sulfoxide (DMSO).

[0106] The features and performance of this disclosure will be further described in detail below with reference to embodiments.

[0107] Synthesis example 1

[0108] This disclosure provides a method for preparing grafted polymer A1, comprising:

[0109] Under a dry nitrogen stream, 20.02 g (0.1 mol) of ODA was dissolved in 200 g of NMP, and the resulting solution was then cooled to -10 °C. Subsequently, 26.37 g (0.085 mol) of ODPA was slowly added to the solution, ensuring the temperature of the reaction solution did not exceed 0 °C, and stirring was continued for 3 hours. Then, 4.44 g (0.03 mol) of PhA was added, and stirring was continued at room temperature for 2 hours to obtain a polyamic acid solution.

[0110] 39.55 g of Py and 30.6 g of Et2A were added to a polyamic acid solution, and the mixture was heated to 120 °C and reacted for 12 h. After the reaction was complete, the solution was poured into 2 L of deionized water to precipitate the polyimide resin. The precipitate was washed with water and dried under vacuum at 80 °C to obtain the polyimide resin, the structural formula of which is shown below:

[0111] 5g of dried polyimide resin was dissolved in 30mL of dichloroethane, and 80μL of SnCl4 was added. The mixture was heated to 70℃, and 3mL of CMM was slowly added dropwise to the system. The mixture was stirred for 5 hours. After the reaction was complete, the solution was poured into 300mL of methanol to precipitate the resin. The precipitate was washed and dried at 80℃ for 12 hours to obtain chloromethylated polyimide resin, the structural formula of which is shown below:

[0112] 1 g of dried chloromethylated polyimide resin was dissolved in 20 mL of NMP. After dissolution, 0.1 g of potassium ethyl xanthate was added, and the reaction was carried out at room temperature for 24 h. After the reaction was completed, the solution was poured into 200 mL of deionized water to precipitate the resin, and then dried at 80 °C for 12 h to obtain the macromolecular initiator, the structural formula of which is shown below:

[0113] 1 g of dried macromolecular initiator was dissolved in 20 mL of NMP. After dissolution, the temperature was raised to 65 °C, and 3 g of 4-HS was added dropwise, followed by 0.01 g of AIBN. RAFT polymerization was then carried out, and the reaction was continued for 2 h. After the reaction was completed, the solution was cooled to room temperature, poured into 200 mL of deionized water to precipitate, washed repeatedly with ethanol, and dried at 80 °C for 12 h to obtain polyimide-g-poly(p-hydroxystyrene) graft copolymer A1, with the following structural formula, molecular weight 39000, n / (m+n) = 40%, k = 3.5.

[0114] Synthesis example 2

[0115] This disclosure provides a method for preparing grafted polymer A2, comprising:

[0116] 1 g of dried polyimide-g-poly(p-hydroxystyrene) was dissolved in 20 mL of NMP. After dissolution, the temperature was raised to 35 °C, and 2 g of EVE and 0.1 g of PTST were added. The reaction was continued for 5 h. After the reaction was completed, the solution was cooled to room temperature, poured into 200 mL of deionized water to precipitate, washed repeatedly with ethanol, and dried at 80 °C for 12 h to obtain graft copolymer A2, whose structural formula is shown below: molecular weight 39050, n / (m+n)=40%, k=3.5, x=2.5.

[0117] Synthesis example 3

[0118] This disclosure provides a method for preparing grafted polymer A3, comprising:

[0119] 192g methanol, 172.32g 4-HS, 19.53g St, and 15g AIBN were added sequentially to a four-necked flask and stirred until dissolved and clear. The air in the reaction vessel was purged with nitrogen under vacuum, and the temperature was raised to 75°C. The reaction was allowed to proceed for 18 hours, after which the reaction was stopped. A prepared sodium methoxide (0.4g) solution was slowly added to the reaction system, and the reaction was allowed to proceed for 6 hours. The mixture was then extracted 2-3 times with n-heptane at a 1:1 mass ratio to remove unreacted monomers and initiators. PGMEA was used to replace the methanol in the reaction solution to obtain a PGMEA solution of the desired concentration. PHS resin A3 was obtained, with the following structural formula: the ratio of p-hydroxystyrene to styrene repeating units is 80 / 20, i.e., m = 20 and n = 80.

[0120] Synthesis example 4

[0121] This disclosure provides a method for preparing grafted polymer A4, comprising:

[0122] Under a dry nitrogen stream, 36.63 g (0.1 mol) of 6FAP was dissolved in 200 g of NMP, and the resulting solution was then cooled to -10 °C. Subsequently, 26.37 g (0.085 mol) of ODPA was slowly added to the solution, ensuring the temperature of the reaction solution did not exceed 0 °C, and stirring was continued for 3 hours. Then, 4.44 g (0.03 mol) of PhA was added, and stirring was continued at room temperature for 2 hours to obtain a polyamic acid solution.

[0123] 39.55 g of Py and 30.6 g of Et2A were added to a polyamic acid solution, and the temperature was raised to 120 °C. The reaction was continued for 12 h. After the reaction was completed, the solution was poured into 2 L of deionized water to precipitate the resin. The precipitate was washed with water and dried under vacuum at 80 °C to obtain polyimide resin A4, the structural formula of which is shown below.

[0124] Examples 1-15 and Comparative Examples 1-3

[0125] The photosensitive compositions of Examples 1-15 and Comparative Examples 1-3 were prepared according to the ingredients and proportions shown in Tables 1-3. The amounts in Tables 1-3 are the parts by mass of each component relative to 100 parts by mass of component (a).

[0126] The selection of components (b) to (f) used in Tables 1-3 is as follows:

[0127] Component (b): Photoacid-producing agent

[0128] Component (c): Thermal crosslinking agent

[0129] Component (d): Alkaline compound

[0130] DIA: 2,6-Diisopropylaniline

[0131] PEA:N-Phenylonamine

[0132] Component (e): γ-Ureapropyltriethoxysilane

[0133] Component (f): Solvent

[0134] f1: GBL (γ-butyrolactone)

[0135] f2: EL (ethyl lactate)

[0136] Table 1. Components of the Photosensitive Composition

[0137] Table 2. Components of the Photosensitive Composition

[0138] Table 3. Components of the Photosensitive Composition

[0139] The performance of the photosensitive compositions prepared in Examples 1-15 and Comparative Examples 1-3 was evaluated using the following methods:

[0140] (1) Preparation of developing film

[0141] The photosensitive compositions (varnishes) prepared in Examples 1-15 and Comparative Examples 1-3 were spin-coated onto 8-inch silicon wafers. Then, a 6 μm thick pre-baked film was prepared by heat treatment (pre-baking) at 120°C for 3 minutes using a hot plate (Tokyo Electron Ltd., Mark-7 coating and developing apparatus). An i-line stepper (Nikon Corporation, NSR-2005i9C) was used at 50–400 mJ / cm². 2 Exposure, 10mJ / cm 2 The pre-baked film is exposed through a step-by-step process. After exposure, for the photosensitive polyimide composition, it is baked after exposure at 100°C for 1 minute. After exposure and baking, the photosensitive polyimide composition is developed for 90 seconds using a 2.38 wt% tetramethylammonium (TMAH) aqueous solution (Mitsubishi Gas Chemical Co., Ltd., ELM-D), and then rinsed with pure water to obtain the developed film.

[0142] (2) Evaluation of film thickness loss

[0143] For the film thickness after pre-baking and development, a Filmtris F50 film thickness measuring device with a refractive index of 1.63 was used for measurement. Film thickness loss <0.2 μm was considered A, film thickness loss between 0.2 and 1 μm was considered B, film thickness loss between 1 and 2 μm was considered C, and film thickness loss >2 μm was considered D. The results are shown in Table 4.

[0144] (3) Determination of warpage

[0145] A varnish was applied using a spin-coating and developing apparatus (ACT-8) and pre-baked to a film thickness of 10 μm after 3 minutes at 120°C. Then, an inert oven was used to heat the film to 200°C at a rate of 3.5°C / min under conditions of oxygen concentration below 20 ppm, and the film was heat-treated at 200°C for 1 hour. The wafer was removed when the temperature dropped below 50°C, and the cured film was measured using a pressure device (FLX2908, KLA Tencor). The results showed that pressure above 35 MPa was considered insufficient (D), pressure between 30 MPa and 35 MPa was considered good (C), pressure between 20 MPa and 30 MPa was considered better (B), and pressure below 20 MPa was considered best (A). The results are shown in Table 4.

[0146] (4) Sensitivity evaluation

[0147] After exposure and development, the exposure amount (called the optimal exposure Eop) that forms a 20μm line and gap pattern (1L / 1S) with a 1:1 width is used as the sensitivity. If Eth is 200mJ / cm²... 2 The following values ​​can be considered high sensitivity. More preferably, 150 mJ / cm². 2 The results are shown in Table 4.

[0148] (5) Evaluation of chemical resistance

[0149] The coating was applied to the cured material using a pipette. The cured material was then placed in a nitrogen oven at 200°C and maintained for 60 minutes. Afterward, the cured material was transferred from the heating plate and cooled to room temperature. The cooled cured material was cleaned with NMP at 45°C and then immersed for 1 hour before the film thickness was measured.

[0150] The film thickness change rate (%) was calculated based on the change in film thickness. A positive value indicates film expansion, while a negative value indicates film dissolution. The results are shown in Table 4.

[0151] (6) Adhesion evaluation

[0152] Using the above-described method for manufacturing cured material, a cured material is manufactured on a Cu substrate. The resulting cured material is then divided into 100 small pieces by using a crosscut guide (manufactured by COAT-TECH Co., Ltd.) and a shearing blade to cut 10×10 checkerboard-like grooves.

[0153] An adhesive tape (manufactured by 3M Japan Co., Ltd.) was applied to the cured material, and then the adhesive tape was peeled off. The adhesion was evaluated as follows, based on the number of small pieces of cured material peeled off from the substrate when the adhesive tape was peeled off.

[0154] A: The number of remaining grid cells is 100-80.

[0155] B: The number of remaining cells is less than 80.

[0156] The results are shown in Table 4.

[0157] (7) Evaluation of elongation at break

[0158] A varnish was applied using a spin-coating and developing apparatus (ACT-8) and pre-baked to a film thickness of 10 μm after 3 minutes at 120°C. Then, an inert oven was used to heat the film to 200°C at a rate of 3.5°C / min under conditions of oxygen concentration below 20 ppm, and the film was heat-treated at 200°C for 1 hour. The wafer was removed when the temperature dropped below 50°C, the film was peeled off, and the wafer was cut into 4 mm × 8 mm strips. Tensile testing was performed using a DAGE4000.

[0159] The results showed that cases with an elongation at break of 30% or more were considered excellent (A), 20-30% were considered good (B), 10-20% were considered poor (C), and <10% were considered very poor (D). See Table 4 for the results.

[0160] Table 4 Test Results

[0161] As shown in Table 4, the photosensitive compositions provided in Examples 1-15 of this disclosure all exhibit high sensitivity, excellent low warpage stress, and excellent chemical resistance. Compared with the examples, Comparative Example 1 lacks contrast and has a significant loss in film thickness during development; Comparative Example 2 has poor toughness and low sensitivity; while Comparative Example 3 has high warpage stress, poor sensitivity, and poor chemical stability.

[0162] The above description is merely a preferred embodiment of this disclosure and is not intended to limit this disclosure. Various modifications and variations can be made to this disclosure by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this disclosure should be included within the scope of protection of this disclosure. Industrial applicability

[0163] The photosensitive composition disclosed herein is readily soluble in alkaline aqueous solutions when exposed to ultraviolet light, while the portion not exposed to ultraviolet light is insoluble in alkaline aqueous solutions, thereby effectively replicating fine patterns. This photosensitive composition exhibits excellent sensitivity, high resolution, and low warpage stress, high adhesion, and good chemical resistance after low-temperature curing (180-200℃), making it suitable for industrial production.

Claims

1. A photosensitizing composition, characterized in that, It includes component (a) a graft polymer selected from compounds shown in Formula 1 below: Wherein, Ar1 is selected from a tetravalent organic group, Ar2 is selected from a divalent organic group, R′ is selected from any one of alkyl, alkoxy, cycloalkyl and aromatic groups; m+n=5~200, n / (m+n)=0.05~1, k=2~10, x=0.5-10; Component (b) Photoacid-producing agent; Component (c) Thermal crosslinking agent: It is a crosslinking agent containing CH2OR″, where R″ is selected from hydrogen or a monovalent organic group; Component (d) is an alkaline compound.

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

3. The photosensitive composition according to claim 1 or 2, characterized in that, R1-R8 are each independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl groups.

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

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

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

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

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

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

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

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

12. The photosensitive composition according to any one of claims 1-11, characterized in that, The component (b) is a compound that produces acid when exposed to 365 nm light.

13. The photosensitive composition according to claim 12, characterized in that, The component (b) is a triarylsulfonium salt.

14. The photosensitizing composition according to claim 12 or 13, characterized in that, The sulfonate anion contained in the triarylsulfonate is a fluorine-containing sulfate anion.

15. The photosensitive composition according to any one of claims 1-14, characterized in that, The component (c) is selected from the compounds shown in Formula 4-2-1 and / or Formula 4-2-2. In Equation 4-2-1, R 21 Each is independently a hydrogen atom or a monovalent organic group, R 22 Each can be an independent hydrogen atom or a monovalent organic group, or they can combine with each other to form a ring structure that can have substituents; In Equation 4-2-2, R 23 Selected from hydrogen atoms or monovalent organic groups, R 24 X is selected from monovalent organic groups, n is an integer from 1 to 4, and X is selected from single bonds or 1-4 valent organic groups; a is an integer from 1 to 4, b is an integer from 0 to 3, and when a is 2, 3, or 4, R 23 Same or different, R24 is the same or different when b is 2 or 3.

16. The photosensitive composition according to any one of claims 1-15, characterized in that, Component c is selected from any one of the compounds shown in the following structural formulas: Among them, R 25 It is an alkyl group with 1-20 carbon atoms, R 26 It is an alkyl group with 1-10 carbon atoms.

17. The photosensitizing composition according to claim 16, characterized in that, R 25 It is an alkyl group with 1-6 carbon atoms.

18. The photosensitive composition according to any one of claims 1-17, characterized in that, Component (d) is selected from the compounds shown in the following structural formulas: A, Y, and Q are each independently selected from one of alkyl, alkoxy, and cyclic alkyl groups.

19. The photosensitive composition according to any one of claims 1-18, characterized in that, The component (d) is selected from any one of the compounds shown in the following structural formulas:

20. The photosensitive composition according to any one of claims 1-19, characterized in that, Based on 100 parts by weight of component (a), the content of component (b) is 1-5 parts by weight, the content of component (c) is 5 parts by weight or more, and the content of component (d) is 0.001-2 parts by weight.

21. The photosensitizing composition according to claim 20, characterized in that, Ingredient (c) 10 or more.

22. The photosensitive composition according to claim 20 or 21, characterized in that, Component (c) is 5-30 parts by weight.

23. The photosensitive composition according to any one of claims 20-22, characterized in that, The molar ratio of component (b) to component (d) is 2.5-300.

24. The photosensitive composition according to claims 20-23, characterized in that, The molar ratio of component (b) to component (d) is 7.0-150.

25. The photosensitive composition according to any one of claims 1-24, characterized in that, The photosensitive composition further contains any one or a combination of at least two of the following: a silane coupling agent, a solvent, and a leveling agent.

26. The photosensitive composition according to claim 25, characterized in that, Based on 100 parts by weight of component (a), the content of the silane coupling agent is 0.5-15 parts by weight, the content of the solvent is 50-1000 parts by weight, and the content of the leveling agent is 100-1000 ppm.

27. A method for preparing a graphic, characterized in that, It comprises coating the photosensitive composition of any one of claims 1-26 onto a support substrate.

28. The preparation method according to claim 27, characterized in that, Also includes: After coating, the process involves drying, exposure, development, and heat treatment in sequence.

29. The preparation method according to claim 28, characterized in that, The light source used in the exposure process is i-ray.

30. A cured product, characterized in that, The cured product is formed by curing the photosensitive composition according to any one of claims 1-26.

31. The cured product according to claim 30, characterized in that, The cured material includes a surface protective film or an interlayer insulating film.

32. An electronic component, characterized in that, The electronic component has the cured material as described in claim 30 or 31.

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