Photosensitive resin composition, photoetching patterned film and application thereof

Abstract

The invention provides a photosensitive resin composition, a photoetched patterned film and application of the photoetched patterned film. The photosensitive resin composition is prepared from the following components in parts by mass: 10 to 95 parts of benzocyclobutene grafted butadiene polymer, 5 to 90 parts of component containing active C = C double bonds and 0.001 to 10 parts of photoinitiator. By compounding the benzocyclobutene grafted butadiene polymer and the component containing the active C = C double bond, the photocuring reaction can be carried out in the presence of the photoinitiator, the photocuring efficiency is high, a photoetched pattern can be obtained through exposure, development and thermocuring, the photolithography sensitivity and fineness are high, the curing process is simple, and the cost is low. The formed photoetching patterned film has sufficiently low dielectric constant Dk and low dielectric loss angle tangent Df, is excellent in dielectric property, high in glass-transition temperature, excellent in heat resistance, heat and humidity resistance and reliability and high in modulus, and sufficiently meets the performance requirements of high-frequency and high-speed circuit substrates.

Description

Technical Field

[0001] The present invention belongs to the technical field of communication circuit materials, and particularly relates to a photosensitive resin composition, a lithographic patterning film and their applications. Background Art

[0002] The circuit board material industry is located in the upstream of the electronic industry chain and is the foundation for the development of the industry. The quality of circuit board materials directly affects the performance of integrated circuits and electronic products. With the development of computers, electronic information communication devices towards high performance, high functionality, miniaturization, large information capacity, high frequency and high density, higher requirements are put forward for the performance of circuit boards in terms of fine wiring, high speed, reliability and stability. There is a need for dielectric materials with lower dielectric loss factors to meet the performance requirements of accommodating more metal wirings in a narrower space.

[0003] Ultraviolet (UV) curing is a low-cost and environmentally friendly polymer material curing technology that can cure to form a three-dimensional crosslinked network in a short time. Since the mid-20th century, UV curing technology has made great progress and has been widely used in many fields. The core of UV curing is photoresist. During the manufacturing process of circuit boards, a photochemical reaction occurs in the exposed area of the photoresist, resulting in a solubility difference between the exposed area and the non-exposed area in the developer. The resulting lithographic pattern can be used as the dielectric insulation layer of the circuit board.

[0004] At present, the materials of the UV-curable dielectric insulating layer are mainly acrylate resin systems. For example, CN115368609A discloses a preparation method of a UV-curable PCB dry film for lithography of copper clad laminates, including the following steps: reacting a hydroxyacrylate monomer, an acrylate monomer, an initiator and a relative molecular mass control agent to obtain an acrylate resin oligomer; mixing the acrylate resin oligomer, a photo-reactive monomer composition, a first photoinitiator, a second photoinitiator and an auxiliary agent uniformly to obtain a photosensitive resin solution; coating the photosensitive resin solution on PET, irradiating with light at 273 nm, and winding to obtain a PCB photosensitive dry film. CN109868005A discloses a photo-thermal dual-curable solder resist ink, and the formula includes: 100 parts by mass of an acrylate compound having a carboxyl group, 0.5-30 parts by mass of an organosilicon elastomer, 0.5-20 parts by mass of a blocking agent, 0.1-30 parts by mass of an epoxy resin-acrylate copolymer, 5-30 parts by mass of an epoxy resin, 0.5-5 parts by mass of a photoinitiator, 1-5 parts by mass of a pigment, 0.1-5 parts by mass of an additive and an organic solvent for dissolving the above components; the use steps include: coating, exposure and development, and curing to obtain a printed circuit board; the solder resist ink coating has good adhesion, toughness and flexibility, etc., and is suitable for the roll-to-roll process of FPC circuit boards. However, the glass transition temperature of the acrylate resin system is relatively low, and the formed film has insufficient heat resistance, making it difficult to meet the high heat resistance requirements in the processing of circuit boards; moreover, its dielectric loss is relatively high, which is not conducive to the preparation of high-frequency circuit boards.

[0005] Benzocyclobutene is a thermosetting material that has attracted much attention in recent years. It has excellent heat resistance, mechanical properties, extremely low dielectric loss and dielectric constant, and is expected to be used as a new generation of high-performance electronic materials in the high-end microelectronics field. Benzocyclobutene is a volatile liquid and is generally prepared into derivatives for use. The DOW Chemical Company has developed a series of silicon-oxygen-containing dibenzocyclobutenes, such as CYCLOTENE 4000 Series photosensitive resins, which show good comprehensive properties. However, due to the presence of a silicon-oxygen structure in the structure, they have a relatively high dielectric constant and dielectric loss, sacrificing the original dielectric advantage of benzocyclobutene and limiting its application in the high-frequency field. CN115826359A discloses a preparation method of a fully hydrocarbon low dielectric loss photosensitive resin for lithographic patterning, which uses 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene monomer, 1-(4-vinylphenyl)-2-(4-benzocyclobutenyl)ethylene polymer, a photoinitiating system and an organic solvent to prepare a photosensitive solution, and then prepares a photosensitive film and performs lithographic patterning; although the dielectric loss of this photosensitive resin is relatively low, the lithographic fineness and sensitivity are insufficient, and the curing process of the film is very cumbersome and harsh, requiring high-temperature treatment for more than 10 h to complete curing, and the processing and preparation cost is high, making it difficult to industrialize.

[0006] Therefore, it is an urgent problem to be solved in this field to develop a photosensitive resin material with low dielectric loss, good heat resistance and lithography sensitivity, and easy to prepare to meet the application requirements of high-frequency and high-speed circuit substrates. Summary of the Invention

[0007] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a photosensitive resin composition, a lithographic patterning film and its application. By the mutual compounding of a benzocyclobutene-grafted butadienyl polymer, a component containing an active C═C double bond, and a photoinitiator, the photosensitive resin composition can meet the requirements of lithographic patterning, obtain a lithographic pattern with high sensitivity and high fineness, and the lithographic patterning film has low dielectric loss and excellent heat resistance.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] In the first aspect, the present invention provides a photosensitive resin composition, which includes the following components in parts by mass:

[0010] Benzocyclobutene-grafted butadienyl polymer 10 - 95 parts

[0011] Component containing active C═C double bond 5 - 90 parts

[0012] Photoinitiator 0.001 - 10 parts.

[0013] In the photosensitive resin composition provided by the present invention, the benzocyclobutene-grafted butadienyl polymer is a fully hydrocarbon resin, with a benzocyclobutyl structure in the side chain, having a low dielectric constant Dk and a low dielectric loss tangent Df, small polarity, and low water absorption; at the same time, the molecular structure contains reactive alkenyl groups (alkenyl groups from the butadienyl polymer, alkenyl groups formed by the ring-opening of benzocyclobutene) and multiple benzocyclobutene functional groups, which can be cured to obtain better dielectric properties and higher crosslinking density, with a high glass transition temperature and excellent heat resistance. The benzocyclobutene-grafted butadienyl polymer is compounded with the component containing an active C═C double bond, and can be photocured in the presence of a photoinitiator, with high photocuring efficiency. A lithographic pattern can be obtained through exposure (photocuring), development and thermal curing. The sensitivity and fineness of lithography are high, the curing process is simple, and the formed lithographic patterning film has a sufficiently low dielectric constant Dk and a low dielectric loss tangent Df, excellent dielectric properties, a high glass transition temperature, excellent heat resistance, moisture and heat resistance, and reliability, and a high modulus, fully meeting the performance requirements of high-frequency and high-speed circuit substrates.

[0014] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the purpose and beneficial effects of the present invention can be better achieved.

[0015] In the photosensitive resin composition of the present invention, the mass parts of the benzocyclobutene-grafted butadienyl polymer are 10-95 parts. For example, they can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts or 85 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Preferably, they are 20-80 parts.

[0016] The mass parts of the component containing an active C═C double bond are 5-90 parts. For example, they can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts or 85 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Preferably, they are 20-80 parts.

[0017] The mass parts of the photoinitiator are 0.001-10 parts. For example, they can be 0.005 parts, 0.01 parts, 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Preferably, they are 0.01-5 parts.

[0018] Preferably, the benzocyclobutene-grafted butadienyl polymer contains at least one structural unit A and at least one structural unit B; the structural unit A has the structure shown in Formula I:

[0019]

[0020] In Formula I, R1 is vinylene and / or ethylene.

[0021] The structural unit B has the structure shown in Formula II:

[0022]

[0023] In Formula II, R2 is vinyl, ethyl and / or phenyl.

[0024] Preferably, the molar percentage content of structural unit A in the benzocyclobutene-grafted butadiene-based polymer is ≥5%, for example, it can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is ≥30%, and more preferably 30-60%.

[0025] As a preferred technical solution of the present invention, the benzocyclobutene-grafted butadiene-based polymer contains at least one structural unit A and at least one structural unit B. The side chain of structural unit A contains a benzocyclobutyl structure, and structural unit B is any one or a combination of at least two of a polybutadiene structure, a hydrogenated polybutadiene structure, and a polystyrene structure. Among them, the molar percentage content of structural unit A is preferably 30-60%, so that the benzocyclobutene-grafted butadiene-based polymer contains more benzocyclobutene structures, and the excellent dielectric properties, high heat resistance, and high modulus characteristics of benzocyclobutene are more obvious; if the molar percentage content of structural unit A is too low, the heat resistance of the cured product formed by the photosensitive resin composition and the lithographic patterning film will be reduced, and the modulus and dielectric properties will also be weakened; if the molar percentage content of structural unit A is too high, it will not only bring higher synthesis difficulty (such as increased reaction temperature, extended reaction time, increased catalyst dosage, etc.) and production cost, but also reduce the crosslinking and curing degree of the photosensitive resin composition, affecting the dielectric properties.

[0026] Preferably, the benzocyclobutene-grafted butadiene-based polymer contains structural unit A1 (R1 is a vinylene group), and its structure is The molecular structure contains a reactive vinylene group, which has high crosslinking efficiency in the curing reaction and good elasticity.

[0027] Preferably, the benzocyclobutene-grafted butadiene-based polymer contains structural unit A2 (R2 is an ethylene group), and its structure is Optionally, structural unit A2 can be obtained by hydrogenating structural unit A1; the bridging group between its benzocyclobutene structure and the main chain is a saturated alkyl chain, and it has good dielectric properties.

[0028] Preferably, the molar percentage content of structural unit B in the benzocyclobutene-grafted butadiene-based polymer is 15-90%, for example, it can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0029] As a preferred technical solution of the present invention, the molar percentage content of structural unit A in the benzocyclobutene-grafted butadiene-based polymer is 5-80%, more preferably 30-60%. Thereby, the benzocyclobutene-grafted butadiene-based polymer has excellent dielectric properties, heat resistance, modulus and mechanical properties, as well as high curing crosslinking reaction activity and crosslinking density. If the molar percentage content of structural unit A is too low, the heat resistance and reactivity of the benzocyclobutene-grafted butadiene-based polymer will be reduced; if the molar percentage content of structural unit A is too high, it will not only increase the synthesis difficulty and production cost, but also reduce the flexibility of the benzocyclobutene-grafted butadiene-based polymer.

[0030] Preferably, the benzocyclobutene-grafted butadiene-based polymer contains structural unit B1 (R2 is vinyl), and its structure is The molecular structure contains reactive terminal vinyl groups, which can react with components containing active C=C double bonds and the double bonds after the ring-opening of benzocyclobutene, increasing the crosslinking efficiency in the curing reaction and the crosslinking density after curing.

[0031] Preferably, the benzocyclobutene-grafted butadiene-based polymer contains structural unit B2 (R2 is ethyl), and its structure is Optionally, structural unit B2 can be obtained by hydrogenating structural unit B1. It contains a saturated alkyl structural unit and has low dielectric loss.

[0032] Optionally, structural unit A2 can be obtained by hydrogenating structural unit A1, and structural unit B2 can be obtained by hydrogenating structural unit B1; the introduction of hydrogenated structural unit A2 and / or structural unit B2 helps to further optimize the dielectric properties of the cured product of the photosensitive resin composition and the lithographic patterning film. It should be noted that when R1 of structural unit A in the benzocyclobutene-grafted butadiene-based polymer is vinylidene, R2 of structural unit B can be vinyl or ethyl; similarly, when R1 of structural unit A in the benzocyclobutene-grafted butadiene-based polymer is ethylidene, R2 of structural unit B can be vinyl or ethyl. That is to say, the polybutadiene double bonds in structural unit A and structural unit B in the benzocyclobutene-grafted butadiene-based polymer can be non-hydrogenated, partially hydrogenated, or fully hydrogenated.

[0033] Preferably, the benzocyclobutene resin contains structural unit B3 (R2 is phenyl), and its structure is

[0034] Preferably, the benzocyclobutene-grafted butadiene-based polymer further contains structural unit C, and structural unit C has the structures shown in formula IIIA and / or formula IIIB:

[0035]

[0036] It should be noted that the benzocyclobutene-grafted butadiene-based polymer has a polymer chain segment structure, including at least one (preferably multiple) structural unit A, at least one (preferably multiple) structural unit B, and optionally structural unit C; the present invention does not limit the connection order of the above structural units, and any connection order / connection method feasible in chemistry is within the scope of the present invention.

[0037] Preferably, the number-average molecular weight of the benzocyclobutene-grafted butadiene-based polymer is 1000 - 30000. For example, it can be 2000, 5000, 8000, 10000, 12000, 15000, 18000, 20000, 22000, 25000, or 28000, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0038] Exemplarily, parameters related to molecular weight (such as number-average molecular weight, weight-average molecular weight, etc.) can be measured by the method described in GB / T21863-2008, based on polystyrene calibration, through gel permeation chromatography (GPC).

[0039] Preferably, the component containing an active C═C double bond is a small molecule compound containing an active C═C double bond and / or a resin containing an active C═C double bond.

[0040] Preferably, the group containing an active C═C double bond includes any one or a combination of at least two of vinyl, vinylphenyl, vinylbenzyl, allyl, (meth)acrylate group, (meth)acrylic acid group, and isopropenyl.

[0041] It should be noted that the (meth)acrylate group includes acrylate group and / or methacrylate group; the (meth)acrylic acid group includes acrylic acid group and / or methacrylic acid group.

[0042] In the present invention, the component containing an active C═C double bond can be a small molecule compound and / or a resin (polymer). Exemplarily, it includes, but is not limited to: small molecule compounds and / or resins (polymers) containing any one or a combination of at least two of vinyl, vinylphenyl, vinylbenzyl, allyl, acrylate group, methacrylate group, isopropenyl, acrylic acid group, and methacrylic acid group.

[0043] Preferably, the component containing an active C═C double bond includes any one or a combination of at least two of polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, unsaturated polyphenylene ether, polyfunctional vinyl aromatic polymer, vinyl alicyclic polymer, allyl-containing compound, and polyfunctional vinyl compound.

[0044] In the present invention, the polybutadiene, styrene-butadiene copolymer, and styrene-butadiene-styrene triblock copolymer all contain crosslinkable active C═C double bonds, which can be 1,2-vinyl based on butadiene monomer.

[0045] In the present invention, the styrene-butadiene copolymer can be a styrene-butadiene random copolymer and / or a styrene-butadiene block copolymer.

[0046] Preferably, the unsaturated polyphenylene ether is a polyphenylene ether with active C═C double bonds at the end groups.

[0047] Preferably, the unsaturated polyphenylene ether includes any one or at least two of polyphenylene ethers with vinyl benzyl, vinyl phenyl, acrylate group, or methacrylate group at the end groups.

[0048] Preferably, the polymerization monomers of the polyfunctional vinyl aromatic polymer include a combination of divinyl aromatic compounds and monovinyl aromatic compounds.

[0049] Preferably, the divinyl aromatic compounds include any one or a combination of at least two of divinylbenzene, divinylbiphenyl, divinylnaphthalene, diisopropenylbenzene, diisopropenylnaphthalene, and diisopropenylbiphenyl; the divinyl aromatic compounds listed above include all their isomers.

[0050] Preferably, the monovinyl aromatic compounds include styrene and other monovinyl aromatic compounds except styrene.

[0051] In the present invention, the polyfunctional vinyl aromatic polymer can be obtained through market channels, for example, it can be ODV of Nippon Steel & Sumitomo Metal Corporation in Japan.

[0052] Preferably, the allyl-containing compound includes any one or a combination of at least two of triallyl isocyanurate (TAIC), trimethallyl isocyanate (TMAIC), triallyl cyanurate (TAC), polyallyl isocyanurate, triallyl cyanurate trimer, and diallyl phthalate;

[0053] Preferably, the polyfunctional vinyl compound includes any one or a combination of at least two of divinylbenzene (DVB), 1,2-bis(p-vinylphenyl)ethane (BVPE), and polyfunctional (meth)acrylate.

[0054] Preferably, the number of moles of terminal alkenyl groups in the photosensitive resin composition is n1, and the number of moles of benzocyclobutene groups in the photosensitive resin composition is n2; n1 / (n1 + n2) > 0.5, and n1 / (n1 + n2) can be 0.52, 0.55, 0.58, 0.6, 0.62, 0.65, 0.68, 0.7, 0.72, 0.75, 0.78, 0.8, 0.82, 0.85, 0.88, 0.9, 0.92, 0.95, or 0.97, as well as specific point values between the above point values. For the sake of brevity and limited space, the specific point values included in the scope of the present invention are not exhaustively listed herein.

[0055] Preferably, 0.6 ≤ n1 / (n1 + n2) ≤ 0.95, and more preferably 0.7 ≤ n1 / (n1 + n2) ≤ 0.9.

[0056] In the present invention, the term "terminal alkenyl group" can be understood as * represents the connection site of the group; R X is selected from H, halogen (such as F, Cl, Br, etc.), C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10) straight-chain or branched-chain alkyl group, C3-C10 (such as C3, C4, C5, C6, C7, C8, C9, C10) cycloalkyl group, C2-C10 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10) alkenyl group, C6-C20 (such as C6, C9, C10, C12, C14, C16, C18, etc.) aryl group and its derivatives. The terminal alkenyl group has good reactivity and can react during photocuring and thermal curing to form a crosslinked network in the cured product of the photosensitive resin composition and the lithographic patterning film.

[0057] As a preferred technical solution of the present invention, the number of moles of terminal alkenyl groups in the photosensitive resin composition is n1, and the terminal alkenyl groups are derived from components containing active C═C double bonds, and can also be derived from benzocyclobutene-grafted butadienyl polymers (i.e., structural unit B1 in Formula II where R2 is a vinyl group); the number of moles of benzocyclobutene groups is n2, which is derived from benzocyclobutene-grafted butadienyl polymers. The present invention preferably has n1 / (n1 + n2) > 0.5, so that the molar proportion of terminal alkenyl groups in the active functional groups (terminal alkenyl groups + benzocyclobutene groups) > 50%, which can effectively adjust the degree of photocuring of the photosensitive resin composition, is beneficial to the adjustment of exposure, development, and thermal curing in the preparation of lithographic patterned films, form patterns with high resolution and good line quality, and make the conditions and processes of thermal curing simpler, reduce processing costs, and facilitate industrialization.

[0058] Preferably, the photoinitiator includes any one or a combination of at least two of 2,6-bis(4-azobenzylidene)cyclohexanone, 3,3'-carbonylbis(7-diethylaminocoumarin), benzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), 1-hydroxycyclohexyl phenyl ketone (photoinitiator 184).

[0059] Preferably, the photosensitive resin composition further includes 5 - 300 parts by mass of a filler. For example, the filler can be 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 120 parts, 150 parts, 180 parts, 200 parts, 220 parts, 250 parts or 280 parts, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 5 - 200 parts, and even more preferably 5 - 150 parts.

[0060] Preferably, the filler is an inorganic filler and / or an organic filler, and more preferably an inorganic filler.

[0061] Preferably, the inorganic filler includes any one or a combination of at least two of non-metal oxides, metal oxides, metal hydroxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates, and inorganic phosphorus.

[0062] Preferably, the inorganic filler includes any one or a combination of at least two of silicon dioxide, aluminum hydroxide, aluminum oxide, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, and mica.

[0063] Preferably, the silicon dioxide can be any one or a combination of at least two of fused silica, crystalline silica, spherical silica, and hollow silica.

[0064] Preferably, the organic filler includes any one or a combination of at least two of polyphenylene ether fillers (powder and / or microspheres), polytetrafluoroethylene fillers (powder), polyetheretherketone fillers, polyphenylene sulfide fillers, and polyethersulfone fillers (powder).

[0065] Preferably, the median particle size (D 50 ) of the filler is 0.01 - 50 μm, for example, it can be 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 0.01 - 20 μm, and even more preferably 0.01 - 10 μm.

[0066] Exemplarily, the particle size of the filler is measured by a MS3000 Malvern laser particle size analyzer.

[0067] Preferably, the filler includes surface-treated fillers.

[0068] Preferably, the surface treatment agent for the surface treatment includes any one or a combination of at least two of silane coupling agents, organosilicon oligomers, and titanate coupling agents.

[0069] Preferably, based on 100 parts by mass of the filler to be treated, the mass of the surface treatment agent is 0.1 - 5 parts, for example, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, or 4.5 parts, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 0.5 - 3 parts, and even more preferably 0.75 - 2 parts.

[0070] Preferably, the photosensitive resin composition further includes 1 - 50 parts by mass of a flame retardant. For example, the flame retardant can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, or 45 parts, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0071] Preferably, the flame retardant includes any one or a combination of at least two of halogen-based flame retardants, nitrogen-based flame retardants, phosphorus-based flame retardants, and metal hydroxide flame retardants.

[0072] Preferably, the photosensitive resin composition further comprises a thermoplastic resin, and the mass fraction of the thermoplastic resin is ≤80 parts, for example, it can be 0, 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 or 75 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the specific point values included in the scope of the present invention are not exhaustively listed herein.

[0073] Preferably, the thermoplastic resin comprises a hydrogenated styrene-butadiene block copolymer (SEBS) and / or a thermoplastic polyphenylene ether (thermoplastic PPO).

[0074] Preferably, the hydrogenated styrene-butadiene block copolymer comprises an unmodified SEBS and / or a modified SEBS.

[0075] Preferably, the modified SEBS comprises any one or a combination of at least two of maleic anhydride-modified SEBS, epoxy-modified SEBS, amino-modified SEBS, and carboxyl-modified SEBS.

[0076] Preferably, the photosensitive resin composition further comprises other additives that are motivated to be added in the art, such as a toughening agent and / or a viscosity regulator.

[0077] A solvent can also be added to the photosensitive resin composition, and the addition amount of the solvent is selected by those skilled in the art according to experience and process requirements, so that the photosensitive resin composition reaches a suitable viscosity for facilitating the coating of the photosensitive resin composition and the preparation of the photosensitive film, etc. Subsequently, in the drying (baking) step, the solvent in the photosensitive resin composition will partially or completely volatilize.

[0078] There is no particular limitation on the solvent of the present invention. Generally, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol, or butanol, alcohols such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, or butyl carbitol, and nitrogen-containing compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone can be selected; the solvent can be used alone or in combination of two or more. Ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are preferred.

[0079] The photosensitive resin composition provided by the present invention is prepared by the following method, and the preparation method includes: mixing and dispersing the components in the photosensitive resin composition uniformly to obtain the photosensitive resin composition.

[0080] Preferably, the preparation process of the photosensitive resin composition is carried out under light-shielded conditions.

[0081] In a second aspect, the present invention provides a photosensitive film, and the material of the photosensitive film comprises the photosensitive resin composition as described in the first aspect.

[0082] Preferably, the photosensitive film is prepared by coating the photosensitive resin composition on a substrate and then drying.

[0083] Preferably, the substrate comprises a release material, and by way of example, includes but is not limited to: PET release film, PI release film.

[0084] Preferably, the thickness of the photosensitive film is 5 - 50 μm. For example, it can be 8 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 48 μm, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list all the specific point values included in the range.

[0085] In a third aspect, the present invention provides a lithographically patterned film, and the raw materials for preparing the lithographically patterned film comprise the photosensitive resin composition as described in the first aspect.

[0086] Preferably, the lithographically patterned film is prepared by the following method, which includes: coating the photosensitive resin composition on a substrate and drying to obtain a photosensitive film; subjecting the photosensitive film to exposure, development, and curing to obtain the lithographically patterned film.

[0087] In the present invention, the photosensitive resin composition is coated and dried to form a photosensitive film; the photosensitive film is exposed in the presence of a mask, and the exposed areas undergo photocrosslinking and curing, while the unexposed areas do not undergo curing. As a result, there is a solubility difference between the exposed and unexposed areas in the developer; after developing with the developer, a pattern consistent with the mask is obtained; finally, curing (thermal curing) is carried out to obtain the lithographically patterned film, which has a high crosslink density, a high glass transition temperature, good heat resistance, low dielectric constant and dielectric loss tangent, excellent dielectric properties, and has a high modulus, excellent resistance to humidity and heat, and reliability.

[0088] Preferably, the preparation of the photosensitive film is carried out under light - shielding conditions.

[0089] Preferably, the light source for exposure is an ultraviolet light source, and more preferably a UV - LED point light source.

[0090] Preferably, the wavelength of the ultraviolet light source is 365 nm.

[0091] Preferably, the exposure time is 2 - 10 min, for example, it can be 3 min, 4 min, 5 min, 6 min, 7 min, 8 min or 9 min, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the scope.

[0092] Preferably, the developing solution for development includes any one or a combination of at least two of toluene, xylene, chloroform, n - hexane, cyclohexane, butyl acetate, ethyl acetate, petroleum ether, and is further preferably any one or a combination of at least two of toluene, xylene, cyclohexane.

[0093] Preferably, the development time is 2 - 10 min, for example, it can be 3 min, 4 min, 5 min, 6 min, 7 min, 8 min or 9 min, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the scope.

[0094] Preferably, the curing is thermal curing.

[0095] Preferably, the curing temperature is 180 - 240 °C, for example, it can be 185 °C, 190 °C, 195 °C, 200 °C, 205 °C, 210 °C, 215 °C, 220 °C, 225 °C, 230 °C or 235 °C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the scope.

[0096] Preferably, the curing time is 30 - 300 min, for example, it can be 40 min, 60 min, 80 min, 90 min, 120 min, 150 min, 180 min, 200 min, 220 min, 240 min or 280 min, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the scope.

[0097] In the fourth aspect, the present invention provides a circuit board, which includes at least one of the photosensitive thin film as described in the second aspect and the lithographically patterned thin film as described in the third aspect.

[0098] Compared with the prior art, the present invention has the following beneficial effects:

[0099] (1) In the photosensitive resin composition provided by the present invention, through the compounding of benzocyclobutene-grafted butadiene-based polymer and the component containing active C═C double bond, it can carry out a photocuring reaction in the presence of a photoinitiator, with high photocuring efficiency. A photolithographic pattern can be obtained through exposure, development, and thermal curing. The photolithography has high sensitivity and fineness, the curing process is simple, and the formed photolithographic patterned film has a sufficiently low dielectric constant Dk and a low dielectric loss tangent Df, excellent dielectric properties, a high glass transition temperature, excellent heat resistance, heat and humidity resistance, and reliability, a high modulus, a high peel strength, a low coefficient of thermal expansion, and excellent dimensional stability, fully meeting the performance requirements of high-frequency and high-speed circuit boards.

[0100] (2) Through the component design and optimization of the photosensitive resin composition of the present invention, the photolithography has high sensitivity and fineness, forming a photolithographic pattern with high resolution. The formed copper-clad laminate has Dk≤2.62, Df≤0.0018 at 10 GHz, a glass transition temperature Tg>200 °C, and a peel strength ≥0.35 N / mm, with excellent comprehensive performance. Specific Embodiments

[0101] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0102] In a specific embodiment, the benzocyclobutene-grafted butadiene-based polymer is obtained through the coupling reaction of a butadiene-based polymer and 4-halobenzocyclobutene The butadiene-based polymer includes polybutadiene or styrene-butadiene copolymer, which contains a structural unit of 1,2-polymerization of butadiene Hal is a halogen, for example, it can be Cl, Br, or I.

[0103] In a specific embodiment, the Hal is Br, that is, the raw material is 4-bromobenzocyclobutene

[0104] In a specific embodiment, the coupling reaction is carried out in the presence of a palladium catalytic system.

[0105] In a specific embodiment, the palladium catalytic system includes a palladium catalyst and an organic phosphine ligand.

[0106] In a specific embodiment, the palladium catalyst is palladium acetate, and the organic phosphine ligand is tris(ortho-methylphenyl)phosphine.

[0107] In a specific embodiment, the coupling reaction is carried out in the presence of an acid-binding agent.

[0108] In a specific embodiment, the acid-binding agent includes an organic base, more preferably triethylamine.

[0109] In a specific embodiment, the coupling reaction is carried out in an inert protective atmosphere, and the inert protective atmosphere includes any one of a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere.

[0110] In a specific embodiment, the temperature of the coupling reaction is 60-100 °C, for example, it can be 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, or 95 °C, etc.

[0111] In a specific embodiment, the time of the coupling reaction is 5-36 h, for example, it can be 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 24 h, 28 h, 32 h, or 34 h, etc.

[0112] In a specific embodiment, the preparation of the benzocyclobutene-grafted butadienyl polymer further includes an optional hydrogenation reaction step, and the hydrogenation reaction can be carried out before and / or after the coupling reaction. The hydrogenation reaction can be complete hydrogenation (i.e., all C═C on the main chain and side chains of the benzocyclobutene-grafted butadienyl polymer are hydrogenated, preferably after the coupling reaction) or partial hydrogenation (which can be carried out before or after the coupling reaction). The hydrogenation reaction hydrogenates all or part of the C═C double bonds from the butadienyl polymer (such as polybutadiene and / or styrene-butadiene copolymer) to form a saturated carbon chain (i.e., R1 is an ethylene group, and / or, R2 is an ethyl group); thereby, the dielectric properties of the benzocyclobutene-grafted butadienyl polymer are further optimized.

[0113] The following is a description of the preparation method of the benzocyclobutene-grafted butadienyl polymer in combination with specific preparation examples; among them, the specific information of the hydrocarbon resin involved is as follows:

[0114] B1000, polybutadiene, the molar percentage content of the structural unit formed by 1,2-polymerization of butadiene ( the same below) is 85%, Nippon Soda Co., Ltd.;

[0115] B2000, polybutadiene, the molar percentage content of the structural unit formed by 1,2-polymerization is 88%, Nippon Soda Co., Ltd.;

[0116] B3000, polybutadiene, the molar percentage content of the structural unit formed by 1,2-polymerization is 92%, Nippon Soda Co., Ltd.;

[0117] Ricon 154, polybutadiene, the molar percentage content of the structural unit formed by 1,2-polymerization is 90%, Sartomer Company, USA;

[0118] Ricon 184, a butadiene-styrene copolymer, with the molar percentage content of the structural units formed by 1,2-polymerization being 30%, the molar percentage content of the structural units formed by 1,4-polymerization being 48%, and the molar percentage content of the styrene structural units being 22%, manufactured by Sartomer Company, USA;

[0119] Ricon 100: a butadiene-styrene copolymer, with the molar percentage content of the structural units formed by 1,2-polymerization being 70%, the molar percentage content of the structural units formed by 1,4-polymerization being 8%, and the molar percentage content of the styrene structural units being 22%, manufactured by Sartomer Company, USA.

[0120] Preparation Example 1

[0121] A benzocyclobutene-grafted butadienyl polymer BCB1, and its preparation method is as follows:

[0122] Add 15.15 g of 4-bromobenzocyclobutene (bromo-BCB), 100 g of polybutadiene B1000, 1.46 g of tris(o-methylphenyl)phosphine, 0.669 g of palladium acetate, 50 mL of triethylamine, and 150 mL of acetonitrile into a flask, and stir at 85 °C for 24 h under an argon atmosphere. Cool and rotary evaporate the solvent. Quickly column through neutral alumina, rotary evaporate the solvent to obtain a viscous liquid, dissolve it in toluene, add methanol with a volume four times that of toluene, shake well and let stand, and separate the toluene layer. Then rotary evaporate and concentrate, and dry under vacuum to obtain a colorless viscous liquid, which is BCB1.

[0123] Use a Fourier transform infrared spectrometer (FTIR, IS10 FT-IR, Thermo Fisher) to perform structural characterization on BCB1. The peak at 1473 cm -1 in the infrared spectrum belongs to the characteristic absorption of the benzocyclobutene four-membered ring, indicating that BCB1 contains a benzocyclobutene structure. Thin layer chromatography (TLC) shows that the raw material 4-bromobenzocyclobutene disappears, indicating that the benzocyclobutene structure has been completely grafted onto the polybutadiene.

[0124] Preparation Examples 2 - 6

[0125] A benzocyclobutene-grafted butadienyl polymer is prepared using the materials shown in Table 1. The mass of the butadienyl polymer is 100 g each, and the process parameters not shown in Table 1 are the same as those in Preparation Example 1.

[0126] Table 1

[0127]

[0128]

[0129] In Table 1, "vinyl (%)" represents the molar proportion of vinyl in the benzocyclobutene-grafted butadiene-based polymer, that is, the number of moles of benzocyclobutene groups in the benzocyclobutene-grafted butadiene-based polymer is n A , the number of moles of vinyl is n B , n B / (n A +n B ) is "vinyl (%)".

[0130] In the following specific embodiments of the present invention, the materials involved are as follows:

[0131] 1. Benzocyclobutene-grafted butadiene-based polymer

[0132] BCB1 - BCB6, from Preparation Examples 1 - 6;

[0133] DS5204, benzocyclobutene, Wuhan Disai New Materials;

[0134] DS5202 benzocyclobutene, Wuhan Disai New Materials.

[0135] 2. Components containing active C═C double bonds

[0136] 2.1 Unsaturated polyphenylene ether (PPO)

[0137] MX9000, acrylate-capped PPO, SABIC Corporation, USA;

[0138] OPE-2ST, PPO with vinylphenyl groups at the ends, Mitsubishi Chemical Corporation;

[0139] 2.2 Hydrocarbon resin (CH resin)

[0140] B3000, polybutadiene, Nippon Soda Co., Ltd., Japan;

[0141] Ricon 100, styrene-butadiene resin, Sartomer Company, USA;

[0142] 2.3 Multifunctional vinyl aromatic polymer

[0143] ODV-XET, vinyl aromatic polymer, Nippon Steel Chemical Co., Ltd.;

[0144] LDM-03, vinyl aromatic polymer, Denka Co., Ltd.

[0145] 2.4 Small molecule compounds containing active C═C double bonds

[0146] 1,2-bis(p-vinylphenyl)ethane (BVPE);

[0147] Triallyl isocyanurate (TAIC), Hunan Fangruida.

[0148] 3. Photoinitiator

[0149] Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, TPO, Macklin Reagent;

[0150] IRGACURE 184, BASF, Germany.

[0151] 4. Filler

[0152] HM052BYJ: Spherical silica powder, Jiangsu Huimai;

[0153] 5. Flame retardant

[0154] JH-100, Guangzhou Juhang.

[0155] Examples 1 - 8, Comparative Examples 1 - 3

[0156] A photosensitive resin composition, with specific components shown in Table 2, and the dosage unit of each component is "parts".

[0157] In Table 2, "vinyl molar amount" corresponds to the molar proportion of terminal alkenyl groups in the photosensitive resin composition. That is, taking the number of moles of terminal alkenyl groups in the photosensitive resin composition as n1 and the number of moles of benzocyclobutene groups as n2, n1 / (n1 + n2) is the "vinyl molar amount"; n1 and n2 are calculated based on the feeding amounts of each component.

[0158] A photosensitive film and a lithographically patterned film using the said photosensitive resin composition, the preparation method is as follows:

[0159] (1) Mix each component of the said photosensitive resin composition with toluene according to the formula amount to make a photosensitive glue solution with a solid content of 65%.

[0160] (2) Coating the photosensitive adhesive solution on the PET release film to obtain a photosensitive thin film (with a thickness of 38 μm) in a size of 300 mm × 300 mm. Put it into an oven at 110 °C and bake for 3 min; after the organic solvent has evaporated, use a 365 nm UV LED light source to expose the photosensitive thin film for 240 s. The resin containing double bonds is crosslinked and cured by exposure and is insoluble in the developer, while the unexposed resin is soluble in the developer; develop for 4 min with the developer (cyclohexane) to wash off the uncured resin, obtaining a surface of the adhesive film with a certain roughness. Then chemically deposit copper on this surface, dry the solvent, and then electroplate. The thickness of the electroplated copper is 35 μm. Finally, perform programmed temperature thermal curing on the above copper-plated sample, with a curing temperature of 230 °C and a curing time of 60 min, and then cool down to obtain a copper-plated foil thin film with a high crosslinking density. Make the adhesive film into test PS specimens to test the copper-plating adhesion of PS; etch off the copper plated on the remaining part to make samples for testing Dk, Df, and Tg (DMA) to test the above properties.

[0161] (3) Using a 365 nm UV-LED point light source, expose the photosensitive thin film through a mask for 240 s. The exposed area is crosslinked and cured and is insoluble in the developer, while the unexposed area is soluble in the developer; place the exposed thin film in the developer (cyclohexane) and develop for 4 min to obtain a pattern consistent with the mask; then perform thermal curing on the developed thin film at a temperature of 230 °C for 120 min, and then cool down to obtain a lithographically patterned thin film.

[0162] Perform the following performance tests on the copper-plated foil thin films and lithographically patterned thin films provided in the foregoing examples and comparative examples:

[0163] (1) Resolution of the lithographic pattern: Observe the stereolithographic pattern after development with an optical microscope, and set the smallest size that can observe a smooth pattern edge without scum as the pattern resolution L / S (μm);

[0164] (2) Glass transition temperature Tg: Test with a dynamic mechanical analyzer (DMA) Rheometric RSAIII;

[0165] (3) Dielectric constant Dk and dielectric loss tangent Df: Use the split post dielectric resonator (SPDR) method and measure with a dielectric analyzer (Dielectric Analyzer) HP Agilent E4991A at a frequency of 10 GHz;

[0166] (4) Peel strength PS: Test according to the method in IPC-TM-650 2.4.8C;

[0167] The test results are shown in Table 2.

[0168] Table 2

[0169]

[0170]

[0171]

[0172] Combined with the aforementioned performance test data, it can be seen that the photosensitive resin composition provided by the present invention can meet the requirements of lithographic patterning, has high lithographic sensitivity and fineness, and a simple curing process. Through the design and optimization of the components, the graphic resolution of lithography is 11 - 23 μm, the glass transition temperature Tg of the formed copper clad laminate is 210 - 275 °C, Dk at 10 GHz is 2.3 - 2.62, Df is 0.0010 - 0.0018, and the peel strength is 0.35 - 0.46 N / mm, having excellent dielectric properties, heat resistance and reliability at the same time.

[0173] Compared with Example 1, DS5204 is used in Comparative Example 1, and the vinyl content in the resin composition is low. There is no C=C double bond component in Comparative Example 2. Since the C=C double bond content in Comparative Examples 1 - 2 is low (or there is no double bond), the degree of photocuring is low, the developing effect of the developer cyclohexane is strong, and a lot of the photocured part has been washed away during the developing process, making it impossible to carry out the next operation; the C=C double bond content of the photosensitive resin composition provided in Comparative Example 3 is 46.94%, and the photocuring step is not sufficient to cure the adhesive film sufficiently, resulting in the cured part being eluted during the developing process, leading to poor dielectric properties and a decrease in resolution.

[0174] The applicant declares that the present invention uses the above embodiments to illustrate the photosensitive resin composition, lithographic patterning film and its application of the present invention, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises the following components in parts by mass: 10 - 95 parts of benzocyclobutene-grafted butadienyl polymer 5 - 90 parts of a component containing an active C═C double bond 0.001 - 10 parts of a photoinitiator.

2. The photosensitive resin composition according to claim 1, wherein The benzocyclobutene-grafted butadienyl polymer contains at least one structural unit A and at least one structural unit B; The structural unit A has the structure shown in Formula I: R1 is vinylene and / or ethylene; The structural unit B has the structure shown in Formula II: R2 is vinyl, ethyl and / or phenyl; Preferably, the molar percentage content of the structural unit A in the benzocyclobutene-grafted butadienyl polymer is ≥5%, preferably ≥30%, and more preferably 30 - 60%; Preferably, the benzocyclobutene-grafted butadienyl polymer further contains a structural unit C, and the structural unit C has the structure shown in Formula IIIA and / or Formula IIIB:

3. The photosensitive resin composition according to claim 1 or 2, characterized in that, The number-average molecular weight of the benzocyclobutene-grafted butadienyl polymer is 1000 - 30000.

4. The photosensitive resin composition according to any one of claims 1 to 3, characterized in that, The component containing an active C═C double bond is a small molecule compound containing an active C═C double bond and / or a resin containing an active C═C double bond; Preferably, the group containing an active C═C double bond includes any one or a combination of at least two of vinyl, vinylphenyl, vinylbenzyl, allyl, (meth)acrylate group, (meth)acrylic acid group, and isopropenyl; Preferably, the component containing an active C═C double bond includes any one or a combination of at least two of polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, unsaturated polyphenylene ether, polyfunctional vinyl aromatic polymer, vinyl alicyclic polymer, allyl-containing compound, and polyfunctional vinyl compound; Preferably, the unsaturated polyphenylene ether is a polyphenylene ether with active C═C double bonds at the end groups; Preferably, the allyl-containing compound includes any one or a combination of at least two of triallyl isocyanurate, trimethallyl isocyanate, triallyl cyanurate, triallyl polyisocyanurate, triallyl cyanurate trimer, and diallyl phthalate; Preferably, the polyfunctional vinyl compound includes any one or a combination of at least two of divinylbenzene, 1,2-bis(p-vinylphenyl)ethane, and polyfunctional (meth)acrylate.

5. The photosensitive resin composition according to any one of claims 1-4, characterized in that The number of moles of terminal alkenyl groups in the photosensitive resin composition is n1, and the number of moles of benzocyclobutene groups in the photosensitive resin composition is n2; n1 / (n1 + n2) > 0.5; Preferably, 0.6 ≤ n1 / (n1 + n2) ≤ 0.95, and more preferably 0.7 ≤ n1 / (n1 + n2) ≤ 0.

9.

6. The photosensitive resin composition according to any one of claims 1-5, characterized in that, The photoinitiator includes any one or a combination of at least two of 2,6-bis(4-azobenzylidene)cyclohexanone, 3,3'-carbonylbis(7-diethylaminocoumarin), benzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 1-hydroxycyclohexyl phenyl ketone; Preferably, the photosensitive resin composition further comprises 5 - 300 parts of a filler in parts by mass; Preferably, the filler is an inorganic filler and / or an organic filler, more preferably an inorganic filler; Preferably, the inorganic filler includes any one or a combination of at least two of silica, aluminum hydroxide, alumina, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica; Preferably, the organic filler includes any one or a combination of at least two of polyphenylene ether filler, polytetrafluoroethylene filler, polyetheretherketone filler, polyphenylene sulfide filler, polyethersulfone filler; Preferably, the median particle size of the filler is 0.01 - 50 μm, more preferably 0.01 - 20 μm; Preferably, the photosensitive resin composition further includes 1 - 50 parts by mass of a flame retardant; Preferably, the flame retardant includes any one or a combination of at least two of halogen-based flame retardants, nitrogen-based flame retardants, phosphorus-based flame retardants, metal hydroxide flame retardants; Preferably, the photosensitive resin composition further includes a thermoplastic resin, and the mass parts of the thermoplastic resin ≤ 80 parts; Preferably, the thermoplastic resin includes a hydrogenated styrene-butadiene block copolymer and / or a thermoplastic polyphenylene ether.

7. A photosensitive film, characterized in that, The material of the photosensitive film includes the photosensitive resin composition according to any one of claims 1 - 6; Preferably, the photosensitive film is obtained by coating the photosensitive resin composition on a substrate and drying.

8. A lithographically patterned film, characterized in that, The raw material for preparing the lithographic patterned film includes the photosensitive resin composition according to any one of claims 1 - 6.

9. The lithographically patterned film according to claim 8, wherein The lithographic patterned film is prepared by the following method, which includes: coating the photosensitive resin composition on a substrate and drying to obtain a photosensitive film; the photosensitive film is exposed, developed, and cured to obtain the lithographic patterned film; Preferably, the light source for exposure is an ultraviolet light source; Preferably, the developer for development includes any one or a combination of at least two of toluene, xylene, chloroform, n-hexane, cyclohexane, butyl acetate, ethyl acetate, petroleum ether; Preferably, the temperature for curing is 180 - 240 °C; Preferably, the time for curing is 30 - 300 min.

10. A circuit board, characterized in that, The circuit board includes at least one of the photosensitive film according to claim 7 and the lithographic patterned film according to claim 8 or 9.

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