Photosensitive resin composition, preparation method, photosensitive dry film and application

Abstract

The invention discloses a photosensitive resin composition, a preparation method, a photosensitive dry film and application, and relates to the technical field of photosensitive resin. The embodiment of the invention provides a photosensitive resin composition which comprises the following components in parts by mass: 100 parts of photosensitive resin, 0.3-25 parts of a photopolymerization initiator, 10-80 parts of an inorganic filler, 10-30 parts of a photopolymerizable monomer and 0.05-15 parts of a low-dielectric nano filler, wherein the low-dielectric nano filler comprises at least one of fluorinated graphene, fluorinated carbon black, fluorinated graphene quantum dots, fluorinated carbon nanotubes, multi-walled carbon nanotubes, multi-layer graphene oxide, graphene oxide gel and graphitized multi-walled carbon nanotubes. The low-dielectric nano filler is added into the photosensitive resin composition, so that the dielectric constant and dielectric loss of the photosensitive solder resist ink can be effectively reduced.

Description

Technical Field

[0001] The present application relates to the technical field of photosensitive resins, and in particular, to a photosensitive resin composition and a preparation method thereof, a photosensitive dry film and an application thereof. Background Art

[0002] Currently, there are mainly two ideas for reducing the dielectric constant and dielectric loss of solder resist inks. One is to change the main resin. For example, epoxy resin is modified with fluorine-containing groups to endow the epoxy resin itself with the properties of low dielectric constant and low dielectric loss. The other is to introduce low-dielectric nanometer fillers containing pores or fluorinated groups. Commonly used fillers in solder resist inks are silica, barium sulfate, calcium carbonate, silicate, etc. The effects of these traditional fillers in reducing the dielectric constant and dielectric loss are limited. Summary of the Invention

[0003] In view of this, the present application provides a photosensitive resin composition and a preparation method thereof, a photosensitive dry film and an application thereof, aiming to provide a photosensitive resin composition with relatively low dielectric constant and dielectric loss.

[0004] In a first aspect, an embodiment of the present application provides a photosensitive resin composition. Calculated by mass, the photosensitive resin composition includes 100 parts of a photosensitive resin, 0.3 - 25 parts of a photoinitiator, 10 - 80 parts of an inorganic filler, 10 - 30 parts of a photopolymerizable monomer, and 0.05 - 15 parts of a low-dielectric nanometer filler.

[0005] Wherein, the low-dielectric nanometer filler includes at least one of fluorinated graphene, fluorinated carbon black, fluorinated graphene quantum dots, fluorinated carbon nanotubes, multi-walled carbon nanotubes, multi-layer graphene oxide, graphene oxide gel, and graphitized multi-walled carbon nanotubes.

[0006] In some embodiments of the present application, the photosensitive resin composition includes 1 - 10 parts of the low-dielectric nanometer filler.

[0007] And / or, the average diameter of the fluorinated carbon black is 50 nm - 500 nm.

[0008] And / or, the average outer diameter of the fluorinated carbon nanotubes is 10 nm - 30 nm, and the average length of the fluorinated carbon nanotubes is 2 μm - 20 μm.

[0009] And / or, the average lateral size of the fluorinated graphene is 100 nm - 800 nm, and the average thickness of the fluorinated graphene is 0.7 nm - 3 nm.

[0010] And / or, the average outer diameter of the graphitized multi-walled carbon nanotubes is 8 nm - 28 nm, and the average length of the graphitized multi-walled carbon nanotubes is 10 μm - 50 μm.

[0011] And / or, the average outer diameter of the multi-walled carbon nanotubes is 8 nm to 50 nm, and the average length of the multi-walled carbon nanotubes is 10 μm to 30 μm;

[0012] And / or, the average lateral size of the multi-layer graphene oxide is 300 nm to 800 nm, and the average thickness of the multi-layer graphene oxide is 1.4 nm to 4.8 nm;

[0013] And / or, the number of layers of the graphene oxide gel is less than 3, the average thickness of the graphene oxide gel is 0.55 nm to 1.2 nm, and the average lateral size of the graphene oxide gel is 0.5 μm to 3 μm;

[0014] And / or, by mass, the photosensitive resin composition further comprises 15 to 45 parts of a thermosetting component and 0.05 to 20 parts of a thermosetting agent.

[0015] In some embodiments of the present application, the photosensitive resin composition comprises 5 to 10 parts of the low-dielectric nanoscale filler;

[0016] And / or, the inorganic filler includes at least one of barium sulfate, barium titanate, calcium oxide, talc powder, fumed silica, silicon dioxide, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, titanium oxide, mica powder, and kaolin powder;

[0017] And / or, the average particle size of the inorganic filler is 0.001 μm to 100 μm;

[0018] And / or, the photosensitive resin is an alkali-soluble polyfunctional photosensitive epoxy resin.

[0019] In some embodiments of the present application, the acid value of the alkali-soluble polyfunctional photosensitive epoxy resin is 30 mgKOH / g to 200 mg KOH / g;

[0020] And / or, the number-average molecular weight of the alkali-soluble polyfunctional photosensitive epoxy resin is 2000 to 100000.

[0021] In some embodiments of the present application, the thermosetting agent includes any one or more of 3,5-dimethylpiperidine, imidazole, benzimidazole, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, triethylamine, dicyandiamide, melamine, melamine phosphate, melamine phosphite, trichloromelamine, hexamethoxymethylmelamine, 1,8-diazabicyclo[5,4,0]undec-7-ene, 4-cyanobenzylamine, 4,4'-diaminodiphenylsulfone, 1-ethyl-3-methylimidazolium dicyandiamide, 1-butyl-3-methylimidazole dicyandiamide, adipic dihydrazide, sebacic dihydrazide, and triphenylphosphine;

[0022] And / or, the thermosetting component is an epoxy resin.

[0023] In some embodiments of the present application, the photoinitiator includes at least one of photoinitiator 907, oxime ester photoinitiator, acylphosphine oxide photoinitiator, acetophenone photoinitiator, benzoin and its alkyl ether photoinitiators, anthraquinone photoinitiators, thioxanthone photoinitiators, ketal photoinitiators, and benzophenone photoinitiators;

[0024] And / or, the photopolymerizable monomer includes at least one of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)methyl acrylate, (meth)ethyl acrylate, (meth)butyl acrylate, (meth)lauryl acrylate, 1,6-hexanediol di(meth)acrylate, dipropylene glycol / tripropylene glycol di(meth)acrylate, diethylene glycol / triethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, neopentyl glycol diethoxy / dipropoxy di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and polydipentaerythritol hexa(meth)acrylate;

[0025] And / or, the photosensitive resin composition further includes an additive.

[0026] The second aspect of the present application provides a method for preparing a photosensitive resin composition, including the following steps:

[0027] Provide a photosensitive resin, a photoinitiator, a photopolymerizable monomer, an inorganic filler, and a low-dielectric nanocomposite filler according to a preset ratio; wherein, the low-dielectric nanocomposite filler includes at least one of fluorinated graphene, fluorinated carbon black, fluorinated graphene quantum dots, fluorinated carbon nanotubes, multi-walled carbon nanotubes, multi-layer graphene oxide, graphene oxide gel, and graphitized multi-walled carbon nanotubes;

[0028] Mix the photosensitive resin, the photoinitiator, the photopolymerizable monomer, the inorganic filler, and the low-dielectric nanocomposite filler to obtain a photosensitive resin composition.

[0029] In some embodiments of the present application, by mass, the photosensitive resin composition includes 100 parts of a photosensitive resin, 0.3 to 25 parts of a photoinitiator, 10 to 80 parts of an inorganic filler, 10 to 30 parts of a photopolymerizable monomer, and 0.05 to 15 parts of a low-dielectric nanocomposite filler.

[0030] The third aspect of the present application provides a photosensitive dry film, which is prepared from the photosensitive resin composition or the photosensitive resin composition prepared by the method for preparing a photosensitive resin composition.

[0031] The fourth aspect of the present application provides the use of the photosensitive resin composition or the photosensitive dry film described above in semiconductor packaging.

[0032] Beneficial effects:

[0033] In the present application, by adding an appropriate amount of low-dielectric nanoscale fillers to the photosensitive resin composition, the low-dielectric nanoscale fillers include at least one of fluorinated graphene, fluorinated carbon black, fluorinated graphene quantum dots, fluorinated carbon nanotubes, multi-walled carbon nanotubes, multi-layer graphene oxide, graphene oxide gel, and graphitized multi-walled carbon nanotubes. When the photosensitive resin composition in the present application is used as a photosensitive solder resist ink, the dielectric constant and dielectric loss of the photosensitive resin composition can be effectively reduced. The possible reason is that the low-dielectric nanoscale fillers added in the present application have a small size and a large specific surface area. When added to the photosensitive resin composition, it can increase the interface and interfacial polarization between different components in the photosensitive resin composition and its cured product, thereby reducing the dielectric constant and dielectric loss. In addition, the low-dielectric nanoscale fillers added to the photosensitive resin composition can also change the microstructure and electron distribution of the photosensitive resin composition and its cured product, thereby reducing the dielectric constant and dielectric loss of the photosensitive resin composition. Specific embodiments

[0034] The experimental examples described in the present application are only a part of the embodiments of the present application, rather than all embodiments. All other embodiments obtained by those skilled in the art without creative efforts fall within the scope of protection of the present application. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0036] In the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third, etc. are only used as labels, and do not impose numerical requirements or establish an order.

[0037] In the present application, "and / or" describes the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B may represent: A exists alone, A and B exist simultaneously, and B exists alone. Wherein A and B may be singular or plural.

[0038] In this application, "at least one" means one or more, and "a plurality" means two or more. "One or more", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can each represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can each be single or plural.

[0039] The various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be construed as a rigid limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub - ranges and the individual values within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub - ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and the individual numbers within that range, such as 1, 2, 3, 4, 5, and 6, and this applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0040] An IC substrate (also known as a "package substrate") is a key component in electronic packaging. Among them, solder mask ink or solder mask dry film mainly plays a role in insulation protection, that is, preventing short - circuits between wires during soldering and avoiding problems such as insulation deterioration and corrosion caused by external factors such as dust and moisture.

[0041] In the field of high-frequency communication, with the rapid development of 5G communication, the accelerating signal transmission speed and the dramatic increase in information volume make it easy for problems such as delay and crosstalk to occur at the signal receiving end. Low-dielectric and low-loss solder resist inks can reduce the losses and distortions during signal transmission, improve the stability and reliability of signal transmission, and meet the requirements of high-speed communication printed circuit boards (PCBs), such as high-speed backplanes in 5G base stations and data centers. In high-frequency circuits such as satellite communication, radar, and wireless charging, the dielectric properties of traditional solder resist inks will limit the performance of the circuits. Low-dielectric and low-loss solder resist inks can reduce the transmission losses of high-frequency signals, improve the efficiency and performance of the circuits, and contribute to the miniaturization and high performance of equipment. In the consumer electronics field, consumer electronic products such as smartphones, tablets, and laptops are constantly developing towards thinner, lighter, and higher-performance. Low-dielectric and low-loss solder resist inks can be applied to the internal PCBs of them to reduce signal interference, improve the operating speed and stability of electronic devices, and at the same time facilitate a more dense circuit layout, providing support for product miniaturization. In the automotive electronics field, the development of automotive intelligence and electrification has made automotive electronic systems increasingly complex. Low-dielectric and low-loss solder resist inks can be used in PCBs such as automotive autonomous driving systems and in-vehicle communication systems to ensure the accurate transmission of signals in a complex electromagnetic environment, improve the reliability and stability of automotive electronic devices, and ensure driving safety. The aerospace and military fields have extremely high requirements for the performance and reliability of electronic devices. Low-dielectric and low-loss solder resist inks can meet the requirements of aerospace and military electronic devices for high-frequency and high-speed signal transmission, improve the anti-interference ability and stability of the devices in a complex electromagnetic environment, and are of great significance for improving the performance of weaponry.

[0042] At present, there are mainly two ideas for reducing the dielectric constant and dielectric loss of solder resist inks. One is to change the main resin. For example, epoxy resin modified with fluorine-containing groups is used to endow epoxy resin itself with the properties of low dielectric constant and low dielectric loss. The other is to introduce low-dielectric nanoscale fillers containing pores or fluorinated groups. The commonly used fillers in solder resist inks are silica, barium sulfate, calcium carbonate, and silicates, etc. These traditional fillers have limited effects in reducing the dielectric constant and dielectric loss.

[0043] In view of this, the present application provides a photosensitive resin composition. By mass, the photosensitive resin composition includes 100 parts of a photosensitive resin, 0.3 - 25 parts of a photoinitiator, 10 - 80 parts of an inorganic filler, 10 - 30 parts of a photopolymerizable monomer, and 0.05 - 15 parts of a low-dielectric nanoscale filler; wherein, the low-dielectric nanoscale filler includes at least one of fluorinated graphene, fluorinated carbon black, fluorinated graphene quantum dots, fluorinated carbon nanotubes, multi-walled carbon nanotubes, multi-layered graphene oxide, graphene oxide gel, and graphitized multi-walled carbon nanotubes. Exemplarily, the low-dielectric nanoscale filler is selected from at least one of fluorinated graphene, fluorinated carbon black, fluorinated graphene quantum dots, fluorinated carbon nanotubes, multi-walled carbon nanotubes, multi-layered graphene oxide, graphene oxide gel, and graphitized multi-walled carbon nanotubes.

[0044] In the present application, by adding an appropriate amount of a low-dielectric nanoscale filler to the photosensitive resin composition, the low-dielectric nanoscale filler includes at least one of fluorinated graphene, fluorinated carbon black, fluorinated graphene quantum dots, fluorinated carbon nanotubes, multi-walled carbon nanotubes, multi-layered graphene oxide, graphene oxide gel, and graphitized multi-walled carbon nanotubes. When the photosensitive resin composition in the present application is used as a photosensitive solder resist ink, it can effectively reduce the dielectric constant and dielectric loss of the photosensitive resin composition. The possible reason is that the added low-dielectric nanoscale filler in the present application has a small size and a large specific surface area. When added to the photosensitive resin composition, it can increase the interface and interface polarization between different components in the photosensitive resin composition and its cured product, thereby reducing the dielectric constant and dielectric loss. In addition, the added low-dielectric nanoscale filler in the photosensitive resin composition can also change the microstructure and electron distribution of the photosensitive resin composition and its cured product, thereby reducing the dielectric constant and dielectric loss of the photosensitive resin composition.

[0045] It should be noted that the photosensitive resin composition in the present application can be applicable to scenarios requiring a low dielectric constant and low dielectric loss, including but not limited to uses in semiconductor packaging. For example, it can be used as a photosensitive solder resist ink or a protective layer during the preparation of circuit boards, FC-BGA, and FC-CSP substrates.

[0046] In some embodiments of the present application, the number of parts of the low-dielectric nanoscale filler in the photosensitive resin composition can be 0.05 parts, 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, and the range values between any two of the above values. Exemplarily, the photosensitive resin composition includes 1 - 10 parts of the low-dielectric nanoscale filler.

[0047] In some embodiments of the present application, by mass, the photosensitive resin composition further includes 15 - 45 parts of a thermosetting component and 0.05 - 20 parts of a thermosetting agent.

[0048] In some embodiments of the present application, the average diameter of the fluorinated carbon black is 50 nm to 500 nm. The moderate diameter and moderate length of the fluorinated carbon black can provide good dispersibility and enhance the comprehensive performance of the solder resist ink.

[0049] In some embodiments of the present application, the average outer diameter of the fluorinated carbon nanotubes is 10 nm to 30 nm, and the average length of the fluorinated carbon nanotubes is 2 μm to 20 μm. The moderate outer diameter and moderate length of the fluorinated carbon nanotubes can provide good dispersibility and enhance the comprehensive performance of the solder resist ink.

[0050] In some embodiments of the present application, the average lateral size of the fluorinated graphene is 100 nm to 800 nm, and the average thickness of the fluorinated graphene is 0.7 nm to 3 nm. The moderate average lateral size and moderate average thickness of the fluorinated graphene can provide good dispersibility and enhance the comprehensive performance of the solder resist ink.

[0051] In some embodiments of the present application, the average outer diameter of the graphitized multi-walled carbon nanotubes is 8 nm to 28 nm, and the average length of the graphitized multi-walled carbon nanotubes is about 10 to 50 μm. The moderate average outer diameter and moderate average length of the graphitized multi-walled carbon nanotubes can provide good dispersibility and enhance the comprehensive performance of the solder resist ink.

[0052] In some embodiments of the present application, the average outer diameter of the multi-walled carbon nanotubes is 8 nm to 50 nm, and the average length of the multi-walled carbon nanotubes is 10 μm to 30 μm. The moderate outer diameter and moderate length can provide good dispersibility and enhance the comprehensive performance of the solder resist ink. If the outer diameter is too small, it may lead to too large specific surface area of the filler, easy to agglomerate in the matrix and unable to be effectively dispersed. In addition, too small outer diameter may increase surface defects and reduce the conductivity of the carbon nanotubes. If the carbon nanotubes are too long, they may aggregate into bundles and cannot be evenly distributed in the polymer matrix, resulting in poor interfacial bonding between the multi-walled carbon nanotubes and the matrix and reducing the mechanical strength of the material. If the length is too short, it may not be able to effectively form a conductive path or enhancement effect, while too long length may lead to processing difficulties and affect fluidity and uniformity.

[0053] In some embodiments of the present application, the lateral size of the multi-layer graphene oxide is 300 nm to 800 nm, and the thickness of the multi-layer graphene oxide is 1.4 nm to 4.8 nm. Appropriate lateral size and thickness contribute to the uniform dispersion and interfacial bonding of the multi-layer graphene oxide in the ink matrix, enhancing the comprehensive performance of the solder resist ink. When the lateral size is too small, the surface area is relatively large, which may lead to an increase in surface defects and affect the conductivity and mechanical properties of the solder resist ink. When the lateral size is too large, the large flakes are prone to aggregation and accumulation, resulting in poor dispersibility. The reinforcing effect of graphene oxide mainly depends on its number of layers and thickness. Too thin graphene oxide may not have enough conductive paths, thus reducing the electrical properties of the solder resist ink. Excessive thickness will lead to an increase in the interaction force between its layers, making it easy to stack and agglomerate.

[0054] In some embodiments of the present application, the number of layers of the graphene oxide gel is less than 3, the thickness is 0.55 nm to 1.2 nm, and the lateral size is 0.5 μm to 3 μm. Suitable number of layers, thickness and lateral size can enhance the dispersibility and interfacial bonding. Graphene oxide gel with a larger number of layers will increase the viscosity of the material, making its dispersion and uniformity in the solder resist ink worse, increasing the difficulty in the processing process and affecting the forming performance. When the thickness of the graphene oxide gel is too thin, the reinforcing effect between its layers is weak and cannot provide sufficient mechanical strengthening or thermal stability. Excessive thickness may lead to too strong mutual attraction between the flakes, making it easy to agglomerate and stack. When the lateral size is too large, the dispersibility becomes poor and agglomeration is likely to occur. When the lateral size is too small, it may not be able to effectively provide a conductive path, resulting in poor electrical properties of the composite material.

[0055] In some embodiments of the present application, the inorganic filler includes at least one of barium sulfate, barium titanate, calcium oxide, talc powder, fumed silica, silicon dioxide, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, titanium oxide, mica powder and kaolin. Further, the inorganic filler is selected from at least one of barium sulfate, silicon dioxide, aluminum oxide, aluminum hydroxide and calcium carbonate. It can be understood that adding inorganic filler to the photosensitive resin composition in this embodiment can adjust the rheological properties and mechanical properties of the photosensitive resin composition.

[0056] Exemplarily, the inorganic filler includes at least one of barium sulfate, barium titanate, calcium oxide, talc powder, fumed silica, silicon dioxide, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, titanium oxide, mica powder and kaolin. Further, the inorganic filler is selected from at least one of barium sulfate, silicon dioxide, aluminum oxide, aluminum hydroxide and calcium carbonate.

[0057] In some embodiments of the present application, the average particle size of the inorganic filler is 0.001 μm to 100 μm. Further, the average particle size of the inorganic filler is 0.03 μm to 20 μm, and more preferably, the average particle size of the inorganic filler is 0.03 μm to 3 μm. In particular, when further grinding is required in the process of preparing the photosensitive resin composition, the particle size of the inorganic filler can also be in other ranges, and there is no particular limitation thereto.

[0058] In some embodiments of the present application, the photosensitive resin can be a photosensitive resin having photosensitivity obtained by grafting double bonds onto an epoxy resin modified with acrylic acid. Further, the photosensitive resin is an alkali-soluble polyfunctional photosensitive epoxy resin. The specific type of the photosensitive resin is not limited herein.

[0059] Exemplarily, the acid value of the alkali-soluble polyfunctional photosensitive epoxy resin is 30 mg KOH / g to 200 mg KOH / g, and more preferably 40 mg KOH / g to 180 mg KOH / g.

[0060] Exemplarily, the number average molecular weight of the alkali-soluble polyfunctional photosensitive epoxy resin is 2000 to 100000, and more preferably 5000 to 30000.

[0061] In some embodiments of the present application, the preparation method of the alkali-soluble polyfunctional photosensitive epoxy resin includes the following steps:

[0062] S110 Dissolve the polyfunctional epoxy compound in the first organic solvent, and then add an unsaturated monocarboxylic acid for an esterification reaction.

[0063] Specifically, the unsaturated monocarboxylic acid can be added to the first organic solvent in which the polyfunctional epoxy compound is dissolved in a dropwise manner for the esterification reaction.

[0064] Exemplarily, the polyfunctional epoxy compound is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, dimethylxylenol type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, soluble fusible phenolic epoxy resin, cresol soluble epoxy resin, triphenol methane type epoxy resin, N-glycidyl type epoxy resin, isocyanuric acid triglycidyl ester, 2,6-dimethylphenol dimer diglycidyl ether, alicyclic epoxy resin, and xylene type epoxy resin.

[0065] It should be noted that the type of the first organic solvent is not particularly limited, and specifically, at least one of ethers, esters, ketones, aromatic solvents, and petroleum solvents can be listed.

[0066] Further, the ether solvent may be at least one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, etc.

[0067] Further, the ester solvent may be at least one of ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, etc.

[0068] Further, the ketone solvent may be at least one of methyl ethyl ketone, cyclohexanone, isophorone.

[0069] Further, the aromatic solvent may be at least one of toluene, xylene, tetramethylbenzene.

[0070] Further, the petroleum solvent may be at least one of naphtha, oxidized naphtha, solvent naphtha, etc.

[0071] In some embodiments of the present application, the unsaturated monocarboxylic acid is selected from at least one of acrylic acid, acrylic acid dimer, methacrylic acid, β-styrylacrylic acid, β-furylacrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, reaction product of saturated / unsaturated dibasic anhydride and hydroxy-containing (meth)acrylate, reaction product of saturated / unsaturated dibasic acid and unsaturated monoglycidyl compound.

[0072] In some embodiments of the present application, the molar ratio of the polyfunctional epoxide to the unsaturated monocarboxylic acid is 1:0.5 to 1.5.

[0073] In some embodiments of the present application, the reaction is carried out under an inert atmosphere and stirring conditions. The reaction temperature is 80°C to 120°C, and the reaction time is 6h to 24h.

[0074] It should be noted that the specific conditions of the esterification reaction do not belong to the main improvement points of the present application and are not limited herein.

[0075] In step S120, the esterified product obtained in step S110 reacts with a saturated / unsaturated polybasic anhydride to obtain an alkali-soluble photosensitive resin solution.

[0076] In some embodiments of the present application, the saturated / unsaturated polyanhydride refers to a saturated / unsaturated compound having two or more anhydride groups. Exemplarily, the saturated / unsaturated polyanhydride includes, but is not limited to, saturated / unsaturated dianhydrides, trianhydrides, tetracarboxylic dianhydrides, and corresponding anhydride derivatives.

[0077] In some embodiments of the present application, the molar ratio of the polyfunctional compound to the saturated / unsaturated polyanhydride is 1:0.5 to 1.5.

[0078] Exemplarily, dianhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride; polyaromatic carboxylic anhydrides such as trimellitic anhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic dianhydride; and other anhydride derivatives such as 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexenyl-1,2-dicarboxylic anhydride. The above-listed can be used alone or in any mixture; preferably tetrahydrophthalic anhydride.

[0079] It should be noted that tetrahydrophthalic anhydride is used to modify epoxy resin, which can significantly improve the thermal stability, mechanical properties, electrical properties, and chemical stability of the main resin in the solder mask ink. At the same time, it has good processing performance and environmental friendliness. These advantages make it an ideal choice widely used in the modification of the main resin of the solder mask ink.

[0080] S130 Drying the alkali-soluble photosensitive resin solution obtained in step S120 to obtain an alkali-soluble photosensitive resin.

[0081] Exemplarily, the alkali-soluble photosensitive resin is an alkali-soluble polyfunctional photosensitive epoxy resin, and the acid value of the alkali-soluble polyfunctional photosensitive epoxy resin is 30 mg KOH / g to 200 mg KOH / g, further preferably 40 mg KOH / g to 180 mg KOH / g. Exemplarily, the number average molecular weight of the alkali-soluble polyfunctional photosensitive epoxy resin is 2000 to 100000, further preferably 5000 to 30000.

[0082] In some embodiments of the present application, the thermal curing agent includes, but is not limited to, any one or more of 3,5-dimethylpiperidine, imidazole, benzimidazole, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, triethylamine, dicyandiamide, melamine, melamine phosphate, melamine phosphite, trichloromelamine, hexamethoxymethylmelamine, 1,8-diazabicyclo[5,4,0]dodec-7-ene, 4-cyanobenzylamine, 4,4'-diaminodiphenyl sulfone, 1-ethyl-3-methylimidazolium dicyandiamide, 1-butyl-3-methylimidazole dicyandiamide, adipic dihydrazide, sebacic dihydrazide, and triphenylphosphine.

[0083] In some embodiments of the present application, the type of the photoinitiator is not particularly limited. Specifically, photoinitiator 907 can be cited; oxime ester-based photoinitiators such as OXE-1 and OXE-2; acylphosphine oxide-based photoinitiators such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide; acetophenone-based photoinitiators such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; benzoin and its alkyl ether photoinitiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; anthraquinone-based photoinitiators such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone; thioxanthone-based photoinitiators such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketal-based photoinitiators such as acetophenone dimethyl ketal, benzyl dimethyl ketal; benzophenone-based photoinitiators such as benzophenone, 4,4'-bis(diethylamino)benzophenone. The above can be used alone or in any mixture, and preferably an oxime ester-based photoinitiator is used.

[0084] In some embodiments of the present application, the photopolymerizable monomer is selected from at least one of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid lauryl ester, 1,6-hexanediol bis(meth)acrylate, di / triglycerol bis(meth)acrylate, di / triglycol bis(meth)acrylate, ethoxylated bisphenol A bis(meth)acrylate, neopentyl glycol diethoxy / propoxy bis(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and polydipentaerythritol hexa(meth)acrylate.

[0085] In some embodiments of the present application, the thermosetting component can be an epoxy resin. Exemplarily, the thermosetting component is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, dimethylxylenol type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, soluble fusible phenolic epoxy resin, cresol soluble epoxy resin, triphenol methane type epoxy resin, N-glycidyl type epoxy resin, isocyanuric acid triglycidyl ester, 2,6-dimethylphenol dimer diglycidyl ether, alicyclic epoxy resin, and xylene type epoxy resin.

[0086] In some embodiments of the present application, the photosensitive resin composition further includes a pigment. Further, the pigment is selected from at least one of phthalocyanine green, phthalocyanine blue, titanium dioxide, carbon black, and lithopone, and preferably a pigment free of free halogens.

[0087] In some embodiments of the present application, the photosensitive resin composition further includes an additive. Further, the additive is selected from at least one of a curing accelerator, a photoinitiator assistant, a thixotropic thickener, a diluent, a polymerization inhibitor, a tackifier, an antifoaming agent, a leveling agent, a coupling agent, an antioxidant, and a rust inhibitor. Further, the weight parts of the additive are 0.05 to 20 parts.

[0088] A second aspect of the embodiments of the present application further provides a preparation method of a photosensitive resin composition, including the following steps: providing a photosensitive resin, an inorganic filler, and a low-dielectric nanocomposite filler according to a preset ratio, and then mixing the photosensitive resin, the inorganic filler, and the low-dielectric nanocomposite filler to obtain the photosensitive resin composition. The low-dielectric nanocomposite filler includes at least one of fluorinated graphene, fluorinated carbon black, fluorinated graphene quantum dots, fluorinated carbon nanotubes, multi-walled carbon nanotubes, multi-layer graphene oxide, graphene oxide gel, and graphitized multi-walled carbon nanotubes.

[0089] In some embodiments of the present application, the step of mixing the photosensitive resin, the inorganic filler, and the low-dielectric nanocomposite filler includes:

[0090] S210 Dissolve the above alkali-soluble photosensitive resin in a second organic solvent to prepare a colloidal solution.

[0091] It should be noted that the alkali-soluble photosensitive resin has been specifically described above and will not be elaborated here. Exemplarily, the alkali-soluble photosensitive resin is an alkali-soluble multi-functional photosensitive epoxy resin.

[0092] In some embodiments of the present application, the type of the second organic solvent is not particularly limited, and specifically, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, etc. can be listed; esters such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, etc. can be listed; ketones such as methyl ethyl ketone, cyclohexanone, isophorone; aromatic solvents such as toluene, xylene, and pseudocumene; and petroleum solvents such as naphtha, oxidized naphtha, and solvent naphtha, etc. The above-listed solvents can be used alone or in any mixture.

[0093] S220 adds an inorganic filler to the glue solution obtained in the above step S110, and a composite material is obtained after mixing.

[0094] In some embodiments of the present application, the photosensitive resin composition further includes a photoinitiator and a photopolymerizable monomer. Further, the photosensitive resin composition further includes an additive. Further, the additive is selected from at least one of a curing accelerator, a photoinitiation aid, a thixotropic thickener, a diluent, a polymerization inhibitor, a tackifier, an antifoaming agent, a leveling agent, a coupling agent, an antioxidant, and a rust inhibitor. The step of adding the inorganic filler to the glue solution obtained in the above step S110 includes: adding the components in the photosensitive resin composition except for the low-dielectric material to the glue solution and mixing to obtain a composite material.

[0095] S230 adds a low-dielectric filler to the composite material obtained in the above step S220 to obtain the photosensitive resin composition.

[0096] In some embodiments of the present application, in step S220, high-speed stirring is carried out for 2 to 10 h, and then mixing is carried out with a three-roll mill.

[0097] In some embodiments of the present application, in step S230, high-speed stirring is carried out for 2 to 10 h, and then mixing is carried out with a three-roll mill.

[0098] The third aspect of the present application further provides a photosensitive dry film, which is prepared from the above photosensitive resin composition.

[0099] In some embodiments of the present application, the average thickness of the photosensitive dry film is 5 μm to 200 μm. Preferably, the average thickness of the photosensitive dry film is 15 μm to 60 μm, and particularly preferably 20 μm to 50 μm.

[0100] In some embodiments of the present application, the photosensitive dry film further includes a protective film covering the surface of the photosensitive dry film and a carrier film carrying the photosensitive film; the thicknesses of the carrier film and the protective film are preferably 5 μm to 100 μm, and further preferably 10 to 30 μm. The types of the carrier film and the protective film can respectively be polymers such as polyethylene terephthalate, polypropylene, polyethylene, and polyester having heat resistance and solvent resistance.

[0101] The fourth aspect of the embodiments of the present application further provides a method for preparing a photosensitive dry film, including the following steps: coating the above photosensitive resin composition on a carrier film, and laminating a protective film after drying to obtain the photosensitive dry film.

[0102] Exemplarily, coating the above photosensitive resin composition on the carrier film can be carried out by using a known coating device such as a reverse roll coater, an intaglio roll coater, a bevel wheel coater, a curtain coater, or a four-sided coater to coat the photosensitive resin composition on the carrier film.

[0103] Furthermore, the drying can be hot air drying or far-infrared / near-infrared drying. Preferably, the drying temperature is 50°C to 120°C, more preferably 55°C to 90°C. The drying time is 1 minute to 60 minutes, more preferably 2 minutes to 30 minutes.

[0104] Example 1

[0105] (1) Preparation of multifunctional photosensitive resin A

[0106] 100 g of phenol-biphenyl type epoxy resin (SQXN-324 purchased from Shandong Shengquan New Materials Co., Ltd., epoxy equivalent 287.9), 0.3 g of hydroquinone and 140 mL of diethylene glycol monoethyl ether acetate were added to a four-necked round-bottom flask under N2 atmosphere, stirred and heated to 110°C and maintained at this temperature for 1 hour to dissolve all substances; after complete dissolution, the temperature was lowered to 90°C, then 25 g of acrylic acid and 0.7 g of triphenylphosphine were added dropwise, the temperature was controlled at 95°C during the dropwise addition, after the dropwise addition was completed, the temperature was raised to 105°C, and the reaction was carried out at this temperature for 12 hours; during the reaction, the acid value of the reactants was measured, until the acid value reached 0.8 mg KOH / g, the temperature was lowered to 60°C, then 52 g of tetrahydrophthalic anhydride was added, and the reaction was carried out at 90°C for 4 - 12 hours. Finally, a light yellow alkali-soluble multifunctional photosensitive resin A with a solid content of 65% and a solid acid value of 100.6 mg KOH / g was obtained.

[0107] (2) Preparation of photosensitive resin composition

[0108] The alkali-soluble multifunctional photosensitive resin A was dissolved in diethylene glycol monoethyl ether acetate according to a solid content of 65%, mechanically stirred for 2 h, and a photosensitive epoxy resin solution was obtained after filtration;

[0109] 29.25 g of the photosensitive epoxy resin solution, 2.1 g of photoinitiator 907, 3 g of dipentaerythritol hexaacrylate, 16 g of silica (particle size 100 nm - 3 μm), 1 g of barium sulfate (particle size 50 nm - 3 μm), 0.8 g of phthalocyanine green, 0.12 g of melamine, 0.48 g of dicyandiamide, 0.2 g of imidazole, 0.019 g of fluorinated carbon black (diameter of fluorinated carbon black 50 - 100 nm; fluorinated carbon black accounts for 0.1% of the multifunctional photosensitive resin A), 20 g of diethylene glycol monoethyl ether acetate were stirred at a speed of 800 rpm for 2 h under mechanical stirring; after mixing evenly, it was mixed again by a three-roll mill, and finally a photosensitive resin composition was prepared.

[0110] Example 2

[0111] The difference from Example 1 is that: the amount of fluorinated carbon black is increased, and the fluorinated carbon black in the photosensitive resin composition accounts for 1% of the multifunctional photosensitive resin A.

[0112] Example 3

[0113] The difference from Example 1 is that the amount of fluorinated carbon black is increased, and the fluorinated carbon black in the photosensitive resin composition accounts for 5% of the polyfunctional photosensitive resin A.

[0114] Example 4

[0115] The difference from Example 1 is that the amount of fluorinated carbon black is increased, and the fluorinated carbon black in the photosensitive resin composition accounts for 10% of the polyfunctional photosensitive resin A.

[0116] Example 5

[0117] The difference from Example 2 is that the low dielectric nanometer filler in the photosensitive resin composition is fluorinated graphene quantum dots (average diameter 2 - 5nm).

[0118] Example 6

[0119] The difference from Example 2 is that the low dielectric nanometer filler in the photosensitive resin composition is fluorinated graphene (average lateral size 100 - 300nm, average thickness 0.7 - 1nm).

[0120] Example 7

[0121] The difference from Example 2 is that the low dielectric nanometer filler in the photosensitive resin composition is fluorinated carbon nanotubes (average outer diameter 20 - 30nm, average length 2 - 10um).

[0122] Example 8

[0123] The difference from Example 2 is that the low dielectric nanometer filler in the photosensitive resin composition is multi - walled carbon nanotubes (average outer diameter 10 - 20nm, average length 10 - 30um).

[0124] Example 9

[0125] The difference from Example 2 is that the low dielectric nanometer filler in the photosensitive resin composition is multi - layer graphene oxide (average lateral size 300 - 500nm, average thickness 1.5 - 3nm).

[0126] Example 10

[0127] The difference from Example 2 is that the low dielectric nanometer filler in the photosensitive resin composition is graphene oxide gel (average lateral size 0.5 - 2um, average thickness 0.55 - 1nm).

[0128] Example 11

[0129] The difference from Example 2 is that the low-dielectric nanoscale filler in the photosensitive resin composition is graphitized multi-walled carbon nanotubes (average outer diameter: 8 - 15 nm, average length: 10 - 30 μm).

[0130] Comparative Example 1

[0131] The difference from Example 1 is that no fluorinated carbon black is added.

[0132] The photosensitive resin compositions prepared in the examples and comparative examples were coated or spin-coated to prepare a film with a thickness of about 25 μm, soft-baked at 80 °C for 10 minutes, exposed, developed with 1% dilute sodium carbonate solution, and then thermally cured at 170 °C for 1 hour to obtain a cured dry film. Then, the relevant properties were tested, and the results are shown in Table 1.

[0133] Experimental tests:

[0134] The glass transition temperature, Young's modulus, elongation at break, and tensile strength in Table 1 were measured by a dynamic thermomechanical analyzer. The heating rate during the test was 5 °C / min, and the test range was from room temperature to 300 °C. The glass transition temperature in Table 1 was characterized by the abscissa temperature corresponding to the maximum point of the loss tangent value.

[0135] In Table 1, the coefficient of thermal expansion in different temperature ranges was measured by a thermomechanical analyzer. The heating rate during the test was 10 °C / min, and the test range was from room temperature to 270 °C. Among them, α1 is the coefficient of thermal expansion in the temperature range of 30 °C - 60 °C, and α2 is the coefficient of thermal expansion in the temperature range of 200 °C - 230 °C.

[0136] Thermal decomposition temperature (°C) test: The thermal stability of the SR film was tested by a thermogravimetric analyzer. Before the test, the sample to be tested was dried in a vacuum oven at 80 °C for more than 8 h to eliminate the influence of moisture in the sample bar on the accuracy of the results. During the test, 15 - 20 mg of the film sample was loaded into the crucible, and the temperature was raised from room temperature to 600 °C at a heating rate of 10 °C / min. The curve of the sample mass changing with temperature was recorded as the TGA curve, and thus the 5% thermal decomposition temperature (T d,5％ ) of the sample could be obtained.

[0137] Dielectric property test: The dielectric constant and dielectric loss of the SR film at 5 GHz were tested and characterized by a vector network analyzer in the resonant cavity mode. The sample was made into a rectangular film of 5 cm × 10 cm and dried in a vacuum oven at 100 °C for at least 8 h before the test. After the instrument was connected and debugged, a set of air data was measured first to ensure the data was correct. Subsequently, the thickness of the sample film was measured with a thickness gauge and recorded in the program. The sample was placed in the cavity, and the dielectric property data of the sample was tested and recorded. Each group of samples needed to be measured at least 5 times, and the average value was taken after excluding the obvious abnormal data.

[0138] B-HAST Test: A comb-shaped electrode with an L / S ratio of 15 / 15 μm was designed to further analyze the reliability of SR. The temperature was 130 °C, the humidity was 85%, and the bias voltage was 5 V. When the insulation resistance dropped below 10 6 ohms, it was defined as a failure.

[0139] Lithography Performance Test: The lithography performance of the examples was better than that of the comparative examples. When the resolution of the lithography pattern lines or round holes reached 40 μm < resolution < 60 μm, it was judged as excellent; when 60 μm < resolution < 90 μm, it was judged as good; when 90 μm < resolution < 100 μm, it was judged as passing.

[0140] Table 1

[0141]

[0142]

[0143] The differences between Examples 1 to 11 and Comparative Example 1 lie in whether fluorinated carbon black is added to the photosensitive resin composition. The differences between Examples 5 to 11 and Example 2 lie in the different types of low-dielectric nanoscale fillers added. From the test results in Table 1, it can be seen that when fluorinated carbon black is added as a low-dielectric nanoscale filler to the photosensitive resin composition and the fluorinated carbon black accounts for 0.1% to 10% of the mass of the main resin (i.e., the multi-functional photosensitive resin A), on the premise of having little influence on its thermal and mechanical properties, the dielectric constant and dielectric loss of the cured product can be significantly reduced. When the mass ratio of the fluorinated carbon black filler is 0.1% - 1%, the fluorine-containing groups can significantly reduce the polarizability of the photosensitive ink composition, thereby reducing the dielectric constant from 3.78 to 3.08 and the dielectric loss to 0.0198. At the same time, the filler can be well dispersed in the composition system, forming a good interfacial bond with the resin matrix. Therefore, the glass transition temperature and thermal decomposition temperature of Examples 1 and 2 increase, the thermal expansion coefficient decreases, the fracture strength increases, and the lithography performance is excellent. When the content of fluorinated carbon black accounts for 1% - 10% of the main resin, the dielectric constant of the cured product is reduced to about 3, and the dielectric loss is below 0.02, showing outstanding dielectric properties and good lithography performance. However, due to the increase in the filler content, it is easy to agglomerate or introduce defects in the system, resulting in a gradual decrease in its thermal stability, a decrease in the glass transition temperature and thermal decomposition temperature, and a downward trend in mechanical properties. In addition, the results in the table show that other low-dielectric nanoscale fillers such as fluorinated graphene, fluorinated graphene quantum dots, fluorinated carbon nanotubes, multi-walled carbon nanotubes, multi-layer graphene oxide, graphene oxide gel, and graphitized multi-walled carbon nanotubes can also effectively reduce the dielectric constant and dielectric loss of the solder resist ink.

[0144] The above has introduced in detail the technical solutions provided by the embodiments of the present application. Specific examples are used herein to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present application.

Claims

1. A photosensitive resin composition, characterized in that, By mass, the photosensitive resin composition comprises 100 parts of a photosensitive resin, 0.3 to 25 parts of a photoinitiator, 10 to 80 parts of an inorganic filler, 10 to 30 parts of a photopolymerizable monomer, and 0.05 to 15 parts of a low-dielectric nanoscale filler; Among them, the low-dielectric nanoscale filler includes at least one of fluorinated graphene, fluorinated carbon black, fluorinated graphene quantum dots, fluorinated carbon nanotubes, multi-walled carbon nanotubes, multi-layered graphene oxide, graphene oxide gel, and graphitized multi-walled carbon nanotubes.

2. The photosensitive resin composition according to claim 1, wherein The photosensitive resin composition contains 1 to 10 parts of the low-dielectric nanoscale filler; and / or, the average diameter of the fluorinated carbon black is 50 nm to 500 nm; and / or, the average outer diameter of the fluorinated carbon nanotubes is 10 nm to 30 nm, and the average length of the fluorinated carbon nanotubes is 2 μm to 20 μm; and / or, the average lateral size of the fluorinated graphene is 100 nm to 800 nm, and the average thickness of the fluorinated graphene is 0.7 nm to 3 nm; and / or, the average outer diameter of the graphitized multi-walled carbon nanotubes is 8 nm to 28 nm, and the average length of the graphitized multi-walled carbon nanotubes is 10 μm to 50 μm; and / or, the average outer diameter of the multi-walled carbon nanotubes is 8 nm to 50 nm, and the average length of the multi-walled carbon nanotubes is 10 μm to 30 μm; and / or, the average lateral size of the multi-layered graphene oxide is 300 nm to 800 nm, and the average thickness of the multi-layered graphene oxide is 1.4 nm to 4.8 nm; and / or, the number of layers of the graphene oxide gel is less than 3, the average thickness of the graphene oxide gel is 0.55 nm to 1.2 nm, and the average lateral size of the graphene oxide gel is 0.5 μm to 3 μm; and / or, by mass, the photosensitive resin composition further comprises 15 to 45 parts of a thermosetting component and 0.05 to 20 parts of a thermosetting agent.

3. The photosensitive resin composition according to claim 1 or 2, wherein The photosensitive resin composition contains 5 to 10 parts of the low-dielectric nanoscale filler; and / or, the inorganic filler includes at least one of barium sulfate, barium titanate, calcium oxide, talc powder, fumed silica, silicon dioxide, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, titanium oxide, mica powder, and kaolin powder; and / or, the average particle size of the inorganic filler is 0.001 μm to 100 μm; and / or, the photosensitive resin is an alkali-soluble polyfunctional photosensitive epoxy resin.

4. The photosensitive resin composition according to claim 3, wherein The acid value of the alkali-soluble polyfunctional photosensitive epoxy resin is 30 mg KOH / g to 200 mg KOH / g; and / or, the number-average molecular weight of the alkali-soluble polyfunctional photosensitive epoxy resin is 2000 to 100000.

5. The photosensitive resin composition according to claim 2, wherein The thermal curing agent includes any one or more of 3,5-dimethylpiperidine, imidazole, benzimidazole, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, triethylamine, dicyandiamide, melamine, melamine phosphate, melamine phosphite, trichloromelamine, hexamethoxymethylmelamine, 1,8-diazabicyclo[5,4,0]dodec-7-ene, 4-cyanobenzylamine, 4,4'-diaminodiphenyl sulfone, 1-ethyl-3-methylimidazolium dicyandiamide, 1-butyl-3-methylimidazole dicyandiamide, adipic dihydrazide, sebacic dihydrazide, and triphenylphosphine; and / or, the thermosetting component is an epoxy resin.

6. The photosensitive resin composition according to claim 1, wherein The photoinitiator includes at least one of photoinitiator 907, oxime ester-based photoinitiator, acylphosphine oxide-based photoinitiator, acetophenone-based photoinitiator, benzoin and its alkyl ether photoinitiators, anthraquinone-based photoinitiators, thioxanthone-based photoinitiators, ketal-based photoinitiators, and benzophenone-based photoinitiators; and / or, the photopolymerizable monomer includes at least one of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylate methyl, (meth)acrylate ethyl, (meth)acrylate butyl, (meth)acrylate lauryl, 1,6-hexanediol bis(meth)acrylate, di / tripropylene glycol bis(meth)acrylate, di / triethylene glycol bis(meth)acrylate, ethoxylated bisphenol A bis(meth)acrylate, neopentyl glycol diethoxy / propoxy bis(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and polydipentaerythritol hexa(meth)acrylate; and / or, the photosensitive resin composition further includes an additive.

7. A method for preparing a photosensitive resin composition, comprising the following steps: providing a photosensitive resin, a photoinitiator, a photopolymerizable monomer, an inorganic filler, and a low-dielectric nanoscale filler according to a preset ratio; wherein, the low-dielectric nanoscale filler includes at least one of fluorinated graphene, fluorinated carbon black, fluorinated graphene quantum dots, fluorinated carbon nanotubes, multi-walled carbon nanotubes, multi-layer graphene oxide, graphene oxide gel, and graphitized multi-walled carbon nanotubes; mixing the photosensitive resin, the photoinitiator, the photopolymerizable monomer, the inorganic filler, and the low-dielectric nanoscale filler to obtain a photosensitive resin composition.

8. The preparation method according to claim 7, characterized in that, Calculated by mass, the photosensitive resin composition includes 100 parts of photosensitive resin, 0.3 to 25 parts of photoinitiator, 10 to 80 parts of inorganic filler, 10 to 30 parts of photopolymerizable monomer, and 0.05 to 15 parts of low-dielectric nanoscale filler.

9. A photosensitive dry film, characterized in that, The photosensitive dry film is prepared from the photosensitive resin composition according to any one of claims 1 to 6 or the photosensitive resin composition prepared by the method for preparing a photosensitive resin composition according to any one of claims 7 or 8.

10. The photosensitive resin composition according to any one of claims 1 to 6 or the photosensitive dry film according to claim 9 is used for semiconductor packaging.

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