Photosensitive resin composition, dry film for solder resist, photosensitive laminate, solder resist pattern, and semiconductor package substrate

Abstract

The application provides a photosensitive resin composition, a solder resist dry film, a photosensitive laminated body, a solder resist pattern and a semiconductor package carrier, and relates to the technical field of polymer materials. The photosensitive resin composition comprises, in terms of mass fraction, 100-120 parts of an alkali-soluble resin, 5-25 parts of a photopolymerization monomer, 1-7 parts of a photoinitiator, 10-30 parts of an epoxy resin, 3-15 parts of an epoxy-based glass polymer prepolymer, and 1-5 parts of a curing agent and its accelerator. By limiting the mass fraction of specific components, the heat resistance, hardness, scratch resistance, acid and alkali resistance, solvent resistance, cold and hot impact resistance, developing performance and other performances of the photosensitive resin composition are ensured, the thermal expansion coefficient is reduced, cracking, warping and wrinkling and other problems are avoided, and thus the fine and high-density requirements of the IC carrier are met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular material, in particular to a photosensitive resin composition, a dry solder resist film, a photosensitive laminated body, a solder resist pattern and a semiconductor package carrier. BACKGROUND

[0002] In a printed circuit board used in electronic equipment and the like, in order to prevent the conductor of the circuit from being corroded by being exposed and to prevent solder from being attached to an unnecessary position to cause short circuit, a solder resist layer is generally provided on the area of the substrate on which the circuit pattern is formed except for the connection hole, and a photosensitive resin composition is widely used as the solder resist layer material.

[0003] With the development of miniaturization of electronic products, related components also tend to be miniaturized, precise, high-density and high-integration, and semiconductor package (IC) carriers have gradually attracted widespread attention. Compared with traditional printed circuit boards (PCBs), IC carriers also have more stringent performance requirements for photosensitive resin compositions, including heat resistance, thermal expansion coefficient, hardness, scratch resistance, acid and alkali resistance, solvent resistance, cold and hot impact resistance and the like. Among them, good heat resistance, hardness, acid and alkali resistance, solvent resistance and the like, that is, the photosensitive resin composition needs to have a rigid structure, that is, the photosensitive resin composition has a high glass transition temperature (Tg), but at the same time, it also leads to a high thermal expansion coefficient. If the thermal expansion coefficient is high, the photosensitive resin composition is prone to wrinkling and warping during light and heat curing due to shrinkage. In addition, since the subsequent processing adopts a chemical gold plating process, the photosensitive resin composition is also required to have excellent resistance to gold plating (that is, corrosion resistance at high temperature) to avoid the loss of product appearance and performance due to blistering, discoloration or peeling of the photosensitive resin composition, and the demand for fine and high density also requires the photosensitive resin composition to have good developing performance.

[0004] Currently, most methods improve heat resistance by grafting rigid segments onto components of photosensitive resin compositions. For example, patent document CN116768728A discloses a method for preparing high-performance photosensitive solder resist ink using naphthalene-type chain extender modified epoxy resin. This method utilizes a difunctional acid chain extender to extend the chain of a small molecule naphthalene-type epoxy compound, and then reacts it sequentially with an acrylic modifier and an unsaturated anhydride. Although this invention produces a novel photocurable solder resist ink with high glass transition temperature, toughness, low dielectric constant, and resistance to DC voltage breakdown, the patent does not provide a specific coefficient of thermal expansion. Furthermore, based on the structure of the epoxy compound, it is foreseeable that the photosensitive resin composition has a high coefficient of thermal expansion, making it unsuitable for use in IC substrates. Alternatively, the coefficient of thermal expansion can be reduced by introducing inorganic fillers into the photosensitive resin composition. For example, patent document CN108350107B discloses a photocurable and thermocurable resin composition and a solder resist dry film. This reduces the coefficient of thermal expansion by introducing sheet-like inorganic fillers with a modulus of 90 GPa to 120 GPa into the composition system. However, this requires high-quality inorganic fillers, with a whiteness requirement of over 90%, and particle sizes close to nanometers, increasing costs. Nanoscale inorganic fillers are difficult to disperse in photosensitive resin systems, easily leading to uneven dispersion and incompatibility, which also affects subsequent development performance. Some techniques improve dispersion by modifying the inorganic fillers or adding dispersants, but this increases costs. Alternatively, the coefficient of thermal expansion can be reduced by introducing flexible segments into the alkali-soluble resin or thermocurable resin in the photosensitive resin composition, improving wrinkling and warping issues. For example, patent document CN115793389A discloses a solder resist dry film with a low coefficient of thermal expansion and its application. It uses a highly elastic polymer to reduce the coefficient of thermal expansion to improve the cracking phenomenon under high temperature stress. However, the content of photosensitive acrylate in this patent is low and the content of thermosetting epoxy resin is high. Although it can reduce the coefficient of thermal expansion while ensuring heat resistance, it will lead to a decrease in development performance and cannot meet the fine requirements of IC substrate.

[0005] In summary, while chemical modification methods can improve heat resistance by grafting rigid segments onto components of photosensitive resin compositions, the addition of rigid segments affects the coefficient of thermal expansion. This leads to a decrease in intermolecular spacing and a reduction in volume during photocuring and thermal curing. Rapid polymerization rates and incomplete double bond conversion can cause localized stress concentration in the photosensitive resin, resulting in cracking, warping, and wrinkling, thus affecting the final product's performance and appearance. Introducing flexible segments into components of the photosensitive resin composition can reduce the coefficient of thermal expansion and improve wrinkling and warping, but this results in some loss of heat resistance and other properties. Adding inorganic fillers to reduce the coefficient of thermal expansion is simple and low-cost, but it can lead to uneven dispersion and incompatibility, affecting subsequent development performance. Although some techniques avoid uneven dispersion and incompatibility by modifying inorganic fillers, this increases costs.

[0006] Therefore, how to simultaneously improve the heat resistance, coefficient of thermal expansion, and development performance of photosensitive resin compositions to meet the requirements of fineness and high density in IC substrates is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0007] The main objective of this invention is to provide a photosensitive resin composition, a solder resist dry film, a photosensitive laminate, a solder resist pattern, and a semiconductor packaging substrate, in order to solve the technical problem in the prior art that it is difficult to simultaneously improve the heat resistance, coefficient of thermal expansion, and development performance of the photosensitive resin composition, thereby meeting the requirements of fineness and high density of IC substrates.

[0008] To achieve the above objectives, according to a first aspect of the present invention, a photosensitive resin composition is provided, comprising, by weight parts: 100-120 parts of alkali-soluble resin, 5-25 parts of photopolymerizable monomer, 1-7 parts of photoinitiator, 10-30 parts of epoxy resin, 3-15 parts of epoxy-based glass polymer prepolymer, and 1-5 parts of curing agent and its accelerator.

[0009] Further, based on mass parts, the epoxy-based glass polymer prepolymer comprises 5 to 10 parts; and / or, the epoxy-based glass polymer prepolymer is a prepolymer with a dynamic cross-linked network structure formed by the reaction of glycidyl group compound and carboxylic acid compound, and has an intramolecular hydrogen bond structure formed by the association of β-hydroxyl and ester groups as shown in Formula 1.

[0010]

[0011] Further, the glycidyl compound has a cyclic structure comprising at least four atoms, and the glycidyl compound also comprises at least two epoxy groups; preferably, the glycidyl compound is selected from at least one of bisphenol A diglycidyl ether, magnolol glycidyl ether, resorcinol diglycidyl ether, bisphenol F diglycidyl ether, cashew phenol glycidyl ether, diglycidyl terephthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, triglycidyl isocyanurate, diglycidyl 1,2-cyclohexanedicarboxylate, and diglycidyl 4-cyclohexene-1,2-dicarboxylic acid.

[0012] Furthermore, the carboxylic acid compound contains at least two carboxyl groups, and at least one of the carboxyl groups has a hydroxyl group adjacent to it; preferably, the carboxylic acid compound is selected from at least one of 2-hydroxysuccinic acid and 2,3-hydroxysuccinic acid.

[0013] Further, the mass ratio of epoxy resin to epoxy-based glass polymer prepolymer is (1-5):1; and / or, the epoxy resin is 15-25 parts by mass; and / or, the epoxy resin contains at least two functional groups and has a cyclic structure; preferably, the epoxy resin 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, phenolic epoxy resin, alicyclic epoxy resin, hydantoin epoxy resin, and imide epoxy resin.

[0014] Further, the alkali-soluble resin is an epoxy acrylate resin containing carboxyl groups; preferably, the alkali-soluble resin is an epoxy acrylate resin containing carboxyl groups and having a rigid chemical structure; preferably, the alkali-soluble resin includes epoxy acrylate resins containing polycyclic ring structures on the main chain or side chain; preferably, the alkali-soluble resin is selected from at least one of bisphenol A type epoxy acrylate resin, alicyclic epoxy acrylate resin, and phenolic epoxy acrylate resin.

[0015] Further, the photopolymerizable monomer comprises 7 to 15 parts by weight; and / or, the photopolymerizable monomer includes monofunctional acrylates and polyfunctional acrylates; preferably, the monofunctional acrylate has a cyclic structure; more preferably, the monofunctional acrylate is selected from at least one of tetrahydrofuran acrylate, 2-phenoxyethyl acrylate, cycloaliphatic acrylate, (4) ethoxylated nonylphenol acrylate, isobornyl acrylate, trimethylolpropane formal acrylate, alkyloxyphenol acrylate, alkyloxytetrahydrofuran acrylate, and alkyloxynonylphenol acrylate; preferably, the polyfunctional acrylate comprises acrylates with a functionality of 2 to 6. The acrylate is further preferably selected from at least one of pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol acrylate, trimethylolpropane acrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, (3) ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, (3) propoxylated trimethylolpropane triacrylate, and (6) ethoxylated trimethylolpropane triacrylate; preferably, the mass ratio of monofunctional acrylate to polyfunctional acrylate is (0.3-0.5):1.

[0016] Further, by weight, the photoinitiator comprises 2-4 parts, and the curing agent and its accelerator comprise 1-3 parts; and / or, the photoinitiator includes a free radical photoinitiator and / or a cationic photoinitiator; preferably, the free radical photoinitiator is selected from 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-isopropylthioxanthanone, 1-hydroxycyclohexylphenyl ketone, benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, tetramethylmithiophene, tetraethylmithiophene, 2-chlorothioxanthanone, 1-chloro-4-propoxythiophene. Anthrone, 2,4-diethylthioxanthrone, benzoin dimethyl ether, 2-hydroxy-methylphenylpropane-1-one, ethyl 4-(N,N-dimethylamino)benzoate, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone; the cationic photoinitiator is selected from at least one of triphenylthionium hexafluorophosphate, 4-phenylthionium diphenylthionium salt, 4-dodecyloxyphenyl diphenylthionium hexafluoroantimonate, bis[(4-diphenylthionium)phenyl]sulfide-bis-hexafluorophosphate, 4-phenylthionium diphenylthionium salt, (4-hydroxyphenyl)methyl(benzyl)hexafluorophosphate, 4-acetoxyphenyl dimethylthionium hexafluoroantimonate, diphenyl The curing agent comprises at least one of iodine-6-monophosphate; and / or, the curing agent comprises at least one of amine curing agents, boramine salt curing agents, boramine complex curing agents, acid anhydride curing agents, linear phenolic resin curing agents, polyester resin curing agents, polysulfide rubber curing agents, and imidazole curing agents; and / or, the accelerator comprises at least one of electrophilic accelerators, nucleophilic accelerators, and metal carboxylate accelerators; preferably, the curing agent is selected from 2-methylimidazole, 2-ethylimidazole, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl disulfide, 3-aminobenzylamine, m-phenylenediamine, 3-amino-5-mercapto-1,2,4-triazole, 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole, and 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole. At least one of the following: 4-triazole, 1,3-bis(2,4,6-trimethylphenyl)chloroimidazolium, 1-triphenylmethylimidazolium, 4-imidazol-1-phenylpropanone, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethylimidazolium, 1-allylimidazolium, 2,4,5-triphenylimidazolium, melamine, melamine phosphate, melamine phosphate, trichloromelamine, hexamethoxymelamine, 1,8-diazabicyclo[5,4,0]dodec-7-ene, 4-cyanobenzylamine, 4,4'-diaminodiphenyl sulfone, 1-ethyl-3-methylimidazolium dicyandiamide, 1-butyl-3-methylimidazolium dicyandiamide, adipate dihydrazide, sebacate dihydrazide, and triphenylphosphine.

[0017] According to a second aspect of the present invention, a solder resist dry film is provided, which is obtained by mixing and drying the above-mentioned photosensitive resin composition.

[0018] According to a third aspect of the present invention, a photosensitive laminate is provided, comprising a support layer, a photosensitive layer and a protective layer stacked thereon, wherein the photosensitive layer is the aforementioned solder resist dry film.

[0019] According to a fourth aspect of the present invention, a solder resist pattern is provided, which is formed by sequentially exposing, developing and curing the aforementioned solder resist dry film.

[0020] According to a fifth aspect of the present invention, a semiconductor packaging substrate is provided, comprising a solder resist pattern, wherein the solder resist pattern is obtained by mixing and curing a photosensitive resin composition of the first aspect, or the solder resist pattern is the solder resist pattern described in the fourth aspect.

[0021] The implementation of this invention has at least the following beneficial effects:

[0022] The photosensitive resin composition provided by this invention, through the synergistic interaction between its components, on the one hand, introduces epoxy-based glass polymer prepolymers that interact with other components, resulting in a three-dimensional cross-linked network with dynamic covalent bonds. Under external stimuli (e.g., light, heat) during curing processes (e.g., photocuring, thermocuring), these dynamic covalent bonds can exchange, leading to a rearrangement of the topology of the three-dimensional cross-linked structure. This means that covalent bond breaking and recombination occur within the photosensitive resin composition system, increasing intermolecular distances and chain segment mobility, thereby releasing local stress and reducing the coefficient of thermal expansion. This process avoids cracking, wrinkling, and warping caused by volume shrinkage and stress concentration. Simultaneously, the dynamic covalent bond exchange reaction only changes the crosslinking points without reducing their number, thus preventing loss of crosslinking degree and density. This ensures the photosensitive resin composition's heat resistance, hardness, scratch resistance, acid and alkali resistance, solvent resistance, and resistance to thermal shock. Furthermore, the epoxy-based glass polymer prepolymer, acting as a thermosetting component, only requires a small mass fraction to maximize its performance, guaranteeing good alkaline developability and high resolution. In this way, by limiting the mass fraction of specific components and ensuring their interaction, the photosensitive resin composition maintains its heat resistance, hardness, scratch resistance, acid and alkali resistance, solvent resistance, thermal shock resistance, and developability while reducing the coefficient of thermal expansion, preventing cracking, warping, and wrinkling. This allows it to meet the demands of refined and high-density IC substrates. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0024] As described in the background section, existing technologies suffer from difficulties in simultaneously improving the heat resistance, coefficient of thermal expansion, and developing performance of photosensitive resin compositions. To address these technical problems, a first aspect of the present invention provides a photosensitive resin composition comprising, by weight parts: 100-120 parts of an alkali-soluble resin, 5-25 parts of a photopolymerizable monomer, 1-7 parts of a photoinitiator, 10-30 parts of an epoxy resin, 3-15 parts of an epoxy-based glass polymer prepolymer, and 1-5 parts of a curing agent and its accelerator.

[0025] The photosensitive resin composition of the present invention can be used as a solder resist material on a semiconductor package (IC) substrate. In specific implementation, the components need to be mixed and then cured to achieve the formation of a solder resist pattern.

[0026] In this invention, epoxy-based glass polymer prepolymers refer to glass-like polymer materials containing epoxy groups. Specifically, by introducing epoxy-based glass polymer prepolymers to interact with other components and form dynamic covalent bonds, the three-dimensional cross-linked network formed by the composition system possesses dynamic covalent bonds. These dynamic covalent bonds can undergo exchange reactions under external stimuli (e.g., light, heat) during curing treatments (e.g., photocuring, thermocuring), resulting in a rearrangement of the topological structure of the three-dimensional cross-linked network. Specifically, epoxy-based glass polymer prepolymers can generate dynamic covalent bonds through interactions with other components (e.g., alkali-soluble resins, epoxy resins, curing agents, etc.), and in photosensitive resins… During the curing process of the composition, a dynamic covalent bond exchange reaction occurs. The breaking and recombination of covalent bonds increases the intermolecular distance and improves the chain segment mobility, thereby releasing local stress and reducing the coefficient of thermal expansion. This avoids cracking, wrinkling, and warping caused by volume shrinkage and stress concentration. At the same time, the dynamic covalent bond exchange reaction only changes the crosslinking points without reducing the number of crosslinking points, thus avoiding the loss of crosslinking degree and crosslinking density. This ensures the heat resistance, hardness, scratch resistance, acid and alkali resistance, solvent resistance, and thermal shock resistance of the photosensitive resin composition.

[0027] Furthermore, the epoxy-based glass polymer prepolymer, acting as a thermosetting component in the composition system, achieves maximum performance with a relatively small mass fraction, ensuring excellent alkali developability and high resolution of the photosensitive resin composition. Thus, by limiting the mass fraction of specific components, the components work synergistically to guarantee the photosensitive resin composition's heat resistance, hardness, scratch resistance, acid and alkali resistance, solvent resistance, thermal shock resistance, and developability, while also reducing the coefficient of thermal expansion and preventing cracking, warping, and wrinkling. This allows it to meet the requirements of precision and high density in IC substrate manufacturing.

[0028] In this invention, the dynamic covalent bond can be an ester structure. Specifically, the epoxy groups in the epoxy-based glass polymer prepolymer and / or the epoxy groups in the epoxy resin can react with the carboxylic acid groups of the alkali-soluble resin and / or the anhydride groups of the curing agent to form an ester structure. At this time, the ester structure acts as a dynamic covalent bond and undergoes an ester exchange reaction during the curing process. That is, the dynamic covalent bond exchange reaction during the curing process is based on the dynamic exchange between the ester group and the hydroxyl group. In this way, not only can the performance of the dynamic covalent bond be maximized, but the operation is also simple and easy to implement, which helps to reduce costs.

[0029] In some preferred embodiments, the epoxy-based glass polymer prepolymer is 5 to 10 parts by weight.

[0030] In some embodiments, the epoxy-based glass polymer prepolymer is a prepolymer with a dynamic cross-linked network structure formed by reacting a glycidyl group compound with a carboxylic acid compound, and has an intramolecular hydrogen bond structure formed by the association of β-hydroxyl and ester groups as shown in Formula 1.

[0031]

[0032] Thus, epoxy-based glass polymer prepolymers contain intramolecular hydrogen-bonded six-membered ring structures. Compared to intermolecular hydrogen bonds, intramolecular hydrogen-bonded six-membered ring structures are stronger and have closer interaction distances, giving epoxy-based glass polymer prepolymers containing intramolecular hydrogen-bonded six-membered ring structures excellent rigidity. Consequently, the photosensitive resin composition exhibits good heat resistance, hardness, scratch resistance, acid and alkali resistance, solvent resistance, and resistance to thermal shock.

[0033] This invention does not limit the specific preparation parameters of epoxy-based glass polymer prepolymers, which can be obtained using conventional methods in the art. For example, a glycidyl compound and a carboxylic acid compound are mixed at a certain molar ratio and reacted at a certain reaction temperature. After the reaction is complete, the reaction product is washed with deionized water, dried with anhydrous sodium sulfate, and finally dried in a vacuum oven to obtain the epoxy-based glass polymer prepolymer. In some embodiments, the molar ratio of glycidyl compound to carboxylic acid compound is (2-5):1, the reaction time is 0.5-1.5 h, the reaction temperature is 80-120 °C, the drying temperature is 50-70 °C, and the drying time is 10-14 h. By limiting the specific types and amounts of reactants, it is helpful to obtain epoxy-based glass polymer prepolymers that meet the above requirements. In addition, by limiting the reaction conditions, it is helpful to control the molecular weight and degree of polymerization of the prepolymer within a suitable range.

[0034] In some embodiments, the glycidyl group compound has a cyclic structure comprising at least four atoms, and further comprises at least two epoxy groups. This cyclic structure enhances the rigidity of the epoxy-based glass polymer prepolymer, further improving the heat resistance, hardness, scratch resistance, acid and alkali resistance, solvent resistance, and thermal shock resistance of the photosensitive resin composition. Furthermore, since the epoxy groups in the epoxy-based glass polymer prepolymer mainly originate from the glycidyl group compound, limiting the number of epoxy groups in the glycidyl group compound essentially limits the number of epoxy groups in the epoxy-based glass polymer prepolymer, which helps to provide more epoxy groups for the reaction to achieve the formation of the ester structure, i.e., ensuring sufficient dynamic covalent bond formation, thereby reducing the coefficient of thermal expansion.

[0035] In some preferred embodiments, the glycidyl compound is selected from at least one of bisphenol A diglycidyl ether, resorcinol diglycidyl ether, bisphenol F diglycidyl ether, magnolol glycidyl ether, cashew phenol glycidyl ether, diglycidyl terephthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, triglycidyl isocyanurate, diglycidyl 1,2-cyclohexanedicarboxylate, and diglycidyl 4-cyclohexene-1,2-dicarboxylic acid.

[0036] In some embodiments, the carboxylic acid compound contains at least two carboxyl groups, and at least one carboxyl group has a hydroxyl group adjacent to it. This facilitates the preparation of epoxy-based glass polymer prepolymers with the structure of Formula 1, i.e., forming an intramolecular hydrogen-bonded six-membered ring structure, thereby improving the heat resistance, developing properties, and reducing the coefficient of thermal expansion of the photosensitive resin composition. Furthermore, the multiple epoxy groups in the glycidyl compound can interact with the multiple carboxyl groups in the carboxylic acid compound, increasing the number of crosslinking points in the crosslinking reaction and generating a network crosslinked polymer with a high crosslinking density.

[0037] Specifically, in some preferred embodiments, the carboxylic acid compound is selected from at least one of 2-hydroxysuccinic acid and 2,3-hydroxysuccinic acid.

[0038] In some embodiments, the mass ratio of epoxy resin to epoxy-based glass polymer prepolymer is (1–5):1, for example, a range of 1:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 5:1, or any two of these. By limiting the mass ratio of epoxy resin to epoxy-based glass polymer prepolymer within the above range, it is advantageous to further balance reducing the coefficient of thermal expansion and ensuring heat resistance.

[0039] In some preferred embodiments, the epoxy resin comprises 15 to 25 parts by weight. Further limiting the weight of the epoxy resin helps to further improve the overall performance of the photosensitive resin composition.

[0040] In some embodiments, the epoxy resin contains at least two functional groups and has a cyclic structure. Specifically, in some preferred embodiments, the epoxy resin 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, phenolic epoxy resin, alicyclic epoxy resin, hydantoin epoxy resin, and imide epoxy resin. For example, epoxy resins preferably derived from DIC Japan may include naphthalene ring type multifunctional epoxy resins HP-4710, HP-4032D, HP-9500, HP-6000, HP-7241, HP-7250, HP-6000L, HP-5000, HP-4770, EXA-9900, or dicyclopentadiene type multifunctional epoxy resins HP-7200H, HP-7200HHH, or bisphenol A or bisphenol F type epoxy resins EXA-830CRP, EXA-830LVP, EXA-835LV, EXA-850CRP, or phenolic epoxy resin N-730A, or at least one of NC-3000, NC-3000H, XD-1000 derived from Huayao Chemical (Wuxi) Co., Ltd.

[0041] In some embodiments, the alkali-soluble resin is an epoxy acrylate resin containing carboxyl groups; preferably, the alkali-soluble resin is an epoxy acrylate resin containing carboxyl groups and having a rigid chemical structure; more preferably, the alkali-soluble resin includes epoxy acrylate resins containing polycyclic ring structures on the main chain or side chains. By limiting the type of alkali-soluble resin to be selected from the above range, it is helpful to further improve the photosensitivity and developability of the photosensitive resin composition.

[0042] Specifically, the alkali-soluble resin can be selected from at least one of bisphenol A type epoxy acrylate resin, alicyclic epoxy acrylate resin, and phenolic epoxy acrylate resin. Preferably, the alkali-soluble resin is an epoxy acrylate resin derived from Nippon Kayaku, and can be models such as R-115W, R-190W, KEA-11, EAM-2160W, EAM-5060W, EAM-5080W, CCR-1159HW, CCR-1169HW, CCR-1171HW, CCR-1173HW, CCR-4959HW, CCR-4969HW, and WH-205; or it can be HC166, B325, L1057M, Q857, or Q612 derived from Mitsui Chemicals. Q850, QC300G, Q890; or anhydride-modified o-cresol acetal epoxy acrylate resin from Shanghai Showa, such as PR300CP, PR3000, PR400, etc., or bisphenol A epoxy-modified acrylic resin (PRV series); or GF-105, GF-104HM, GF-106R, GF-105F-1, GF-105GM, GF-108, GF-159, GF-130, GF-148, GF-211LX, GF-068, etc. from Guangzhou Starli.

[0043] In some embodiments, the photopolymerizable monomer is 7 to 15 parts by weight. Specifically, the photopolymerizable monomer includes monofunctional acrylates and polyfunctional acrylates. That is, the photopolymerizable monomer is a blend of monofunctional acrylates and polyfunctional acrylates, specifically a blend of at least one monofunctional acrylate and at least two polyfunctional acrylates.

[0044] In this invention, the monofunctional acrylate has a cyclic structure; more preferably, the monofunctional acrylate is selected from at least one of tetrahydrofuran acrylate, 2-phenoxyethyl acrylate, cycloaliphatic acrylate, (4) ethoxylated nonylphenol acrylate, isobornyl acrylate, trimethylolpropane formal acrylate, alkyloxyphenol acrylate, alkyloxytetrahydrofuran acrylate, and alkyloxynonylphenol acrylate; preferably, the polyfunctional acrylate includes acrylates with a functionality of 2 to 6; Preferably, the multifunctional acrylate is selected from at least one of pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol acrylate, trimethylolpropane acrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, (3) ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, (3) propionyl methoxylated trimethylolpropane triacrylate, and (6) ethoxylated trimethylolpropane triacrylate.

[0045] Preferably, the mass ratio of monofunctional acrylate to polyfunctional acrylate is (0.3 to 0.5):1, for example, 0.3:1, 0.4:1, 0.5:1 or any combination thereof.

[0046] In some embodiments, the photoinitiator comprises 2 to 4 parts by weight, and the curing agent and its accelerator comprise 1 to 3 parts by weight; and / or, the photoinitiator includes a free radical photoinitiator and / or a cationic photoinitiator; preferably, the free radical photoinitiator is selected from 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-isopropylthioxanthanone, 1-hydroxycyclohexylphenyl ketone, benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, tetramethylmithionone, tetraethylmithionone, 2-chlorothioxanthanone, 1-chloro-4-propoxy The photoinitiator is selected from at least one of the following: 2,4-diethylthionone, benzoin dimethyl ether, 2-hydroxy-methylphenylpropane-1-one, ethyl 4-(N,N-dimethylamino)benzoate, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone; the cationic photoinitiator is selected from triphenylthionium hexafluorophosphate, 4-phenylthionium diphenylthionium salt, 4-dodecyloxyphenyl diphenylthionium hexafluoroantimonate, bis[(4-diphenylthionium)phenyl]sulfide-bis-hexafluorophosphate, 4-phenylthionium diphenylthionium salt, (4-hydroxyphenyl)methyl(benzyl)hexafluorophosphate, and 4-acetoxyphenyl dimethylthionium hexafluoroantimonate. At least one of diphenyliodonium hexafluorophosphate; and / or, the curing agent includes at least one of amine curing agents, boramine salt curing agents, boramine complex curing agents, acid anhydride curing agents, linear phenolic resin curing agents, polyester resin curing agents, polysulfide rubber curing agents, and imidazole curing agents; and / or, the accelerator includes at least one of electrophilic accelerators, nucleophilic accelerators, and metal carboxylate accelerators; preferably, the curing agent is selected from 2-methylimidazole, 2-ethylimidazole, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl disulfide, 3-aminobenzylamine, m-phenylenediamine, 3-amino-5-mercapto-1,2,4-triazole, and 4-amino-3-hydrazino-5-mercapto-1,2 At least one of the following: 4-triazole, 1,3-bis(2,4,6-trimethylphenyl)chloroimidazolium, 1-triphenylmethylimidazolium, 4-imidazol-1-phenylpropanone, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethylimidazolium, 1-allylimidazolium, 2,4,5-triphenylimidazolium, melamine, melamine phosphate, melamine phosphate, trichloromelamine, hexamethyl melamine, 1,8-diazabicyclo[5,4,0]dodec-7-ene, 4-cyanobenzylamine, 4,4'-diaminodiphenyl sulfone, 1-ethyl-3-methylimidazolium dicyandiamide, 1-butyl-3-methylimidazolium dicyandiamide, adipate dihydrazide, sebacate dihydrazide, and triphenylphosphine.

[0047] In some embodiments, the photosensitive resin composition further comprises, by weight parts, 15-40 parts of filler, 2-10 parts of additives, and 30 parts of solvent; preferably, the filler is 20-35 parts; preferably, the additives are 2-7 parts; and / or, the additives include colorants, defoamers, antioxidants, and leveling agents; preferably, the filler is an inorganic filler; more preferably, the inorganic filler is selected from at least one of silica, titanium dioxide, barium sulfate, calcium carbonate, aluminum hydroxide, kaolin, talc, titanium dioxide, aluminum oxide, silicon nitride, and aluminum nitride; preferably, the colorant is at least one of pigments, dyes, and colorants. More preferably, the colorant is selected from at least one of carbon black, indigo blue, indigo green, toluidine red, chrome yellow, and titanium dioxide; preferably, the defoamer is selected from at least one of emulsion-type polysiloxane, polyether-modified organosilicon, higher alcohols, and polyethers; preferably, the antioxidant is selected from at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol, catechol, or 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanate; preferably, the leveling agent is selected from at least one of modified polysiloxane and long-chain resin.

[0048] The addition of solvent helps to promote thorough mixing among the components of the photosensitive resin composition. The solvent can be of a type commonly used in the art, preferably γ-butyrolactone.

[0049] In a second aspect, the present invention provides a solder resist dry film, which is obtained by mixing and drying the aforementioned photosensitive resin composition. The solder resist dry film formed from the aforementioned photosensitive resin composition exhibits excellent heat resistance, developability, and a low coefficient of thermal expansion, and is less prone to cracking, warping, and wrinkling. Furthermore, the film formed from the aforementioned photosensitive resin composition also possesses excellent hardness, hardness, acid resistance, alkali resistance, and solvent resistance, while also exhibiting good alkali developability and high resolution. This makes the solder resist dry film made from the aforementioned photosensitive resin composition suitable for the packaging field, meeting the requirements for precision and high density in semiconductor packaging substrates, facilitating the formation of specific solder resist patterns, and ensuring the performance and appearance of the final product.

[0050] A third aspect of the present invention provides a photosensitive laminate, comprising a support layer, a photosensitive layer and a protective layer stacked together, wherein the photosensitive layer is the aforementioned solder resist dry film.

[0051] In a specific implementation of this invention, the above-mentioned photosensitive resin composition can be mixed and directly coated onto a support layer. After drying, a photosensitive layer is formed. Then, a protective layer is laminated onto the photosensitive layer to obtain a photosensitive layer stack. The protective layer serves to protect the photosensitive layer and prevent its performance from deteriorating. In practical use, the protective layer can be removed to allow the photosensitive layer to adhere to the element to be processed, and the support layer can be removed to cover the surface of the element to be processed. The element to be processed can be a conventional electronic component in the art.

[0052] In a fourth aspect, the present invention provides a solder resist pattern formed by sequentially exposing, developing, and curing the aforementioned solder resist dry film. In a specific embodiment of the present invention, the solder resist dry film is applied to the element to be processed, and then sequentially exposed, developed, and cured to obtain the corresponding solder resist pattern. Because the solder resist dry film formed by the aforementioned photosensitive resin composition has excellent heat resistance, developability, and a low coefficient of thermal expansion, the solder resist pattern is more complete and less prone to cracking, wrinkling, and warping. Furthermore, the solder resist dry film formed by the aforementioned photosensitive resin composition also exhibits excellent hardness, hardness, acid resistance, alkali resistance, and solvent resistance, while also possessing good alkali developability and high resolution, ensuring the strength, stability, and resistance to peeling of the solder resist pattern.

[0053] A fifth aspect of the present invention provides a semiconductor packaging substrate, characterized in that it includes a solder resist pattern, which is obtained by mixing and curing a photosensitive resin composition of the first aspect, or the solder resist pattern is a solder resist pattern of the fourth aspect.

[0054] Because it contains the above-mentioned photosensitive resin composition, the solder mask pattern has excellent heat resistance, development performance and low coefficient of thermal expansion, and is not prone to cracking, warping and wrinkling. In addition, it also has excellent hardness, hardness, acid resistance, alkali resistance and solvent resistance, which can meet the requirements of precision and high density of semiconductor packaging substrates, and ensure the performance and appearance of semiconductor packaging substrates.

[0055] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0056] Example 1

[0057] I. Preparation of epoxy-based glass polymer prepolymer A-1

[0058] 13.4 g (0.1 mol) of 2-hydroxysuccinic acid was added to a three-necked flask, and 136 g (0.4 mol) of bisphenol A diglycidyl ether was added to the flask. The mixture was reacted at 110 °C for 1 h. After the reaction was completed, the product was washed with deionized water, dried with anhydrous sodium sulfate, and finally dried in a vacuum oven at 60 °C for 12 h to obtain epoxy-based glass polymer prepolymer A-1.

[0059] II. Preparation of Solder Resist Dry Film

[0060] By mass, alkali-soluble resin, inorganic filler, epoxy-based glass polymer prepolymer, and additives are added to a solvent and mixed evenly. The mixture is then ground in a sand mill until the particle size is <10μm. Subsequently, photopolymerizable monomer, photoinitiator, epoxy resin, and curing agent are added sequentially and mixed thoroughly to obtain a photosensitive resin composition. The photosensitive resin composition is then evenly coated onto a PET support film using a coating machine and placed in an 85℃ oven for 30 minutes to obtain a solder resist dry film with a thickness of 25μm.

[0061] The specific information for each of the above components is as follows:

[0062] The alkali-soluble resin is an acid anhydride-modified o-cresol aldehyde epoxy acrylic resin, with a mass fraction of 110 parts.

[0063] The photopolymerizable monomers are 3 parts by mass of isobornyl acrylate and 7 parts by mass of pentaerythritol tetraacrylate.

[0064] The photoinitiator is 1 part by weight of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 1 part by weight of 1-hydroxycyclohexylphenyl ketone, and 1 part by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone.

[0065] The inorganic filler consists of 20 parts by mass of barium sulfate and 12 parts by mass of silicon dioxide;

[0066] The epoxy resin is 20 parts by weight of bisphenol A type epoxy resin;

[0067] The mass fraction of epoxy-based glass polymer prepolymer A-1 is 6 parts;

[0068] The curing agent is 1 part by weight of 4,4'-diaminodiphenyl sulfone, 0.5 parts by weight of 2-ethyl-4-methylimidazolium and 0.5 parts by weight of 3-amino-5-mercapto-1,2,4-triazole;

[0069] The additives are 1.5 parts by weight of carbon black, 1 part by weight of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.5 parts by weight of leveling agent polyether modified polydimethylsiloxane, and 0.5 parts by weight of defoamer octamethylcyclotetrasiloxane.

[0070] The solvent is 30 parts by mass of γ-butyrolactone.

[0071] Example 2

[0072] The difference from Example 1 is that 2-hydroxysuccinic acid (13.4 g, 0.1 mol) was replaced with 2,3-dihydroxysuccinic acid (15 g, 0.1 mol) when preparing the epoxy-based glass polymer prepolymer, while other conditions remained unchanged, to obtain the epoxy-based glass polymer prepolymer A-2 of this example;

[0073] In preparing the solder resist dry film, epoxy-based glass polymer prepolymer A-1 was replaced with epoxy-based glass polymer prepolymer A-2 in this embodiment to obtain the solder resist dry film of this embodiment.

[0074] Example 3

[0075] The difference from Example 1 is that when preparing the epoxy-based glass polymer prepolymer, bisphenol A diglycidyl ether (136g, 0.4mol) was replaced with magnolol glycidyl ether (152g, 0.4mol), while other conditions remained unchanged, to obtain the epoxy-based glass polymer prepolymer A-3 of this example;

[0076] The synthesis of magnolol glycidyl ether includes the following steps: magnolol (106.4 g, 0.4 mol), epichlorohydrin (148 g, 1.6 mol), and tetrabutylammonium bromide (7.6 g, 3%) are added sequentially to a three-necked round-bottom flask and stirred at 80 °C for 3 h. Then, 50% sodium hydroxide (32 g, 0.8 mol) is added dropwise to the reactor using a constant-pressure dropping funnel. The mixture is stirred at room temperature for 5 h. After the reaction is complete, the filtrate is poured into a separatory funnel, washed with deionized water, dried with anhydrous sodium sulfate, and finally placed in a vacuum oven at 80 °C for 12 h to obtain magnolol glycidyl ether.

[0077] In preparing the solder resist dry film, epoxy-based glass polymer prepolymer A-1 was replaced with epoxy-based glass polymer prepolymer A-3 of this embodiment to obtain the solder resist dry film of this embodiment.

[0078] Example 4

[0079] The difference from Example 1 is that 2-hydroxysuccinic acid (13.4 g, 0.1 mol) was replaced with succinic acid (11.8 g, 0.3 mol) when preparing the epoxy-based glass polymer prepolymer, while other conditions remained unchanged, to obtain the epoxy-based glass polymer prepolymer B-1 of this example;

[0080] In preparing the solder resist dry film, epoxy-based glass polymer prepolymer A-1 is replaced with epoxy-based glass polymer prepolymer B-1 in this embodiment to obtain the solder resist dry film of this embodiment.

[0081] Example 5

[0082] The difference from Example 1 is that when preparing the epoxy-based glass polymer prepolymer, bisphenol A diglycidyl ether (136g, 0.4mol) was replaced with polyethylene glycol diglycidyl ether (52g, 0.4mol), while other conditions remained unchanged, to obtain the epoxy-based glass polymer prepolymer B-2 of this example;

[0083] In preparing the solder resist dry film, epoxy-based glass polymer prepolymer A-1 was replaced with epoxy-based glass polymer prepolymer B-2 in this embodiment to obtain the solder resist dry film of this embodiment.

[0084] Example 6

[0085] The difference from Example 1 is that the epoxy resin has a mass fraction of 23 parts and the epoxy-based glass polymer prepolymer has a mass fraction of 5 parts.

[0086] Example 7

[0087] The difference from Example 1 is that the epoxy resin has a mass fraction of 17 parts and the epoxy-based glass polymer prepolymer has a mass fraction of 9 parts.

[0088] Example 8

[0089] The difference from Example 1 is that the mass fraction of the alkali-soluble resin is 100 parts.

[0090] Example 9

[0091] The difference from Example 1 is that the mass fraction of the alkali-soluble resin is 120 parts.

[0092] Example 10

[0093] The difference from Example 1 is that the photopolymerization monomers are 1 part by mass of isobornyl acrylate and 4 parts by mass of pentaerythritol tetraacrylate.

[0094] Example 11

[0095] The difference from Example 1 is that the photopolymerization monomers are 2 parts by weight of isobornyl acrylate (manufacturer: Sartoma, trade name: SR506EGNS) and 5 parts by weight of pentaerythritol tetraacrylate (manufacturer: Sartoma, trade name: SR295NS).

[0096] Example 12

[0097] The difference from Example 1 is that the photopolymerization monomers are 5 parts by mass of isobornyl acrylate and 10 parts by mass of pentaerythritol tetraacrylate.

[0098] Example 13

[0099] The difference from Example 1 is that the photopolymerization monomers are 10 parts by mass of isobornyl acrylate and 15 parts by mass of pentaerythritol tetraacrylate.

[0100] Example 14

[0101] The difference from Example 1 is that the photoinitiator is 1 part of 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

[0102] Example 15

[0103] The difference from Example 1 is that the photoinitiator is 1 part of 2,4,6-trimethylbenzoyl diphenylphosphine oxide and 1 part of 1-hydroxycyclohexylphenyl ketone.

[0104] Example 16

[0105] The difference from Example 1 is that the photoinitiator is 2 parts of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 1 part of 1-hydroxycyclohexylphenyl ketone, and 1 part of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone.

[0106] Example 17

[0107] The difference from Example 1 is that the photoinitiator is 2 parts of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2 parts of 1-hydroxycyclohexylphenyl ketone, and 3 parts of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone.

[0108] Example 18

[0109] The difference from Example 1 is that the epoxy resin is in parts by weight of 10.

[0110] Example 19

[0111] The difference from Example 1 is that the epoxy resin is in the form of 30 parts by weight.

[0112] Example 20

[0113] The difference from Example 1 is that the epoxy glass polymer prepolymer has a mass fraction of 3 parts.

[0114] Example 21

[0115] The difference from Example 1 is that the epoxy glass polymer prepolymer has a mass fraction of 10 parts.

[0116] Example 22

[0117] The difference from Example 1 is that the mass fraction of the epoxy glass polymer prepolymer is 15 parts.

[0118] Example 23

[0119] The difference from Example 1 is that the curing agent is 1 part of 4,4'-diaminodiphenyl sulfone.

[0120] Example 24

[0121] The difference from Example 1 is that the curing agent is 1 part of 4,4'-diaminodiphenyl sulfone, 1 part of 2-ethyl-4-methylimidazolium and 1 part of 3-amino-5-mercapto-1,2,4-triazole.

[0122] Example 25

[0123] The difference from Example 1 is that the curing agent is 2 parts of 4,4'-diaminodiphenyl sulfone, 2 parts of 2-ethyl-4-methylimidazolium and 1 part of 3-amino-5-mercapto-1,2,4-triazole.

[0124] Example 26

[0125] The difference from Example 1 is that no inorganic filler is added to the photosensitive resin composition.

[0126] Example 27

[0127] The difference from Example 1 is that the inorganic filler is 10 parts barium sulfate and 5 parts silicon dioxide.

[0128] Example 28

[0129] The difference from Example 1 is that the inorganic filler is 20 parts barium sulfate and 20 parts silicon dioxide.

[0130] Example 29

[0131] The difference from Example 1 is that no additives are added to the photosensitive resin composition.

[0132] Example 30

[0133] The difference from Example 1 is that the additives are 0.5 parts carbon black, 0.5 parts pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.5 parts leveling agent polyether-modified polydimethylsiloxane, and 0.5 parts defoamer octamethylcyclotetrasiloxane.

[0134] Example 31

[0135] The difference from Example 1 is that the additives are 2.5 parts carbon black, 2.5 parts pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2.5 parts leveling agent polyether-modified polydimethylsiloxane, and 2.5 parts defoamer octamethylcyclotetrasiloxane.

[0136] Comparative Example 1

[0137] The difference from Example 1 is that no epoxy-based glass polymer prepolymer is added to the photosensitive resin composition.

[0138] Comparative Example 2

[0139] The difference from Example 1 is that the mass fraction of the epoxy-based glass polymer prepolymer is 2 parts.

[0140] Comparative Example 3

[0141] The difference from Example 1 is that the mass fraction of the epoxy-based glass polymer prepolymer is 20 parts.

[0142] Comparative Example 4

[0143] The difference from Example 1 is that no epoxy resin is added to the photosensitive resin composition.

[0144] Comparative Example 5

[0145] The difference from Example 1 is that the epoxy resin is in parts by weight of 5.

[0146] Comparative Example 6

[0147] The difference from Example 1 is that the epoxy resin is in parts by weight of 10.

[0148] Comparative Example 7

[0149] The difference from Example 1 is that the mass fraction of the alkali-soluble resin is 90 parts.

[0150] Comparative Example 8

[0151] The difference from Example 1 is that the mass fraction of the alkali-soluble resin is 130 parts.

[0152] Test case

[0153] (1) Sensitivity test

[0154] The above-mentioned solder resist dry film was applied to a commercial copper-clad laminate using a vacuum laminator. The vacuum section had a pressure of 6 kgf, a vacuum time of 20 s, a pressing time of 30 s, and a temperature of 65°C. The leveling section had a pressure of 6 kgf, a leveling time of 50 s, and a temperature of 85°C. After application, the film was exposed and developed on an ST21 exposure scale. The lowest energy at which the film was not developed and was fully exposed on ST8 was recorded as the sensitivity energy of the formulation.

[0155] (2) L / S (line width and line spacing), lateral erosion and minimum window opening test

[0156] The aforementioned solder resist dry film was applied to a commercial copper-clad laminate using a vacuum laminator. The vacuum section had a pressure of 6 kgf, a vacuum time of 20 s, a pressing time of 30 s, and a temperature of 65°C. The leveling section had a pressure of 6 kgf, a leveling time of 50 s, and a temperature of 85°C. After application, the film was exposed to a standard test mask at an energy sensitivity of ST8 / 21. After thermal curing, the line width / span (L / S) and side etching were observed under a metallographic microscope via cross-sections. The minimum window size could be directly observed under a metallographic microscope. The optimal L / S and minimum window size were defined as those that completely reproduced the image with line width, line spacing, and window diameter within ±5% of the standard mask film. The size of the side etching was then measured and recorded, and it was observed whether the side etching was within ±5% of the standard mask film. The test results were graded as follows: Grade 1: error within ±5%; Grade 2: error between ±5% and ±10%; Grade 3: error beyond ±10%.

[0157] (3) Surface smoothness test after thermosetting

[0158] The aforementioned solder resist dry film was applied to a commercial copper-clad laminate using a vacuum laminator. The vacuum section had a pressure of 6 kgf, a vacuum time of 20 s, a pressing time of 30 s, and a temperature of 65°C. The leveling section had a pressure of 6 kgf, a leveling time of 50 s, and a temperature of 85°C. After application, the copper-clad laminate with the solder resist dry film was exposed under a high-pressure mercury lamp exposure machine. After peeling off the PET support film, it was exposed with appropriate energy. After exposure, it was left at room temperature for 30 minutes, then developed with an alkaline developer (1 wt% sodium carbonate aqueous solution) at 30°C for 30 s. After development, it was rinsed with water for 30 s to remove residual developer from the surface of the solder resist dry film. The copper-clad laminate with the solder resist dry film was then post-cured in an oven at 150°C for 1 hour. The solder resist dry film on the copper-clad laminate was observed under a microscope to check for cracking, wrinkling, and warping. The test results are graded as follows: Grade 1: The surface is flat, without wrinkles, cracks, or warping; Grade 2: The surface shows wrinkles, cracks, and warping.

[0159] (4) Tests of Tg (glass transition temperature) and CTE (coefficient of thermal expansion).

[0160] The aforementioned solder resist dry film was applied to a commercial copper-clad laminate using a vacuum laminator. The vacuum section had a pressure of 6 kgf, a vacuum time of 20 s, a pressing time of 30 s, and a temperature of 65°C. The leveling section had a pressure of 6 kgf, a leveling time of 50 s, and a temperature of 85°C. After application, the entire board was exposed using ST8 / 21 sensitivity energy. After exposure, the board was left at room temperature for 30 min, then developed in an alkaline developer (1 wt% sodium carbonate aqueous solution) at 30°C for 30 s. After development, the board was rinsed with water for 30 s to remove residual developer from the solder resist dry film surface. The copper-clad laminate with the solder resist dry film was then post-cured in an oven at 150°C for 1 h. The laminate was then cut into 5 mm wide and 25 mm long pieces, and the PET support film was peeled off to obtain a cured product of the photosensitive resin composition for evaluating the coefficient of thermal expansion. The coefficient of thermal expansion under tensile conditions was measured using a TMA device (TMAQ400, Shenzhen SANTAK Technology). The tensile load was 0.1 N, the span (distance between clamps) was 15 mm, and the heating rate was 10 °C / min. First, the sample was mounted on the apparatus and heated from room temperature (25 °C) to 160 °C, then left to stand for 15 min. Next, it was cooled to -60 °C and then heated again from -60 °C to 250 °C at a rate of 10 °C / min for measurement. The inflection point observed in the range of 25 °C to 200 °C was marked as Tg, and the temperature at this point was recorded. CTE uses the slope of the tangent line of the curve obtained at temperatures below Tg. The test results were graded as follows: Grade 1: less than 50 ppm / ℃; Grade 2: 50–60 ppm / ℃; Grade 3: 60–70 ppm / ℃; Grade 4: more than 70 ppm / ℃.

[0161] (5) HAST test

[0162] The aforementioned solder resist dry film was applied to a commercial copper-clad laminate using a vacuum laminator. The vacuum section had a pressure of 6 kgf, a vacuum time of 20 s, a pressing time of 30 s, and a temperature of 65°C. The leveling section had a pressure of 6 kgf, a leveling time of 50 s, and a temperature of 85°C. After application, the entire board was exposed using ST8 / 21 sensitivity energy. After exposure, the board was left at room temperature for 30 min and then developed with an alkaline developer (1 wt% sodium carbonate aqueous solution) at 30°C for 30 s. After development, the board was rinsed with water for 30 s to remove residual developer from the solder resist dry film surface. The copper-clad laminate with the solder resist dry film was then post-cured in an oven at 150°C for 1 h to obtain the HAST-treated test sample. The resistivity of the dry film product before and after HAST treatment was measured using a resistivity meter. The test samples were then transferred to a HAST chamber (PC-422R8D, Hirayama Manufacturing Co., Ltd.) and placed at 121℃ and 100% humidity for 120 hours. The resistivity after HAST treatment was then measured again, and the presence of bubbles or peeling was observed. The resistivity changes before and after HAST were compared. The test results were graded as follows: Grade 1: No bubbles or peeling, or resistivity change within ±10%; Grade 2: No bubbles or peeling, or resistivity change within ±30%; Grade 3: Small amount of bubbling, peeling, or even detachment of the dry film; Grade 4: Large number of bubbles or detachment, or resistivity change >50%.

[0163] (6) Acid resistance test

[0164] Test samples prepared using the same method as in the HAST test were immersed in a 10 vol% H2SO4 aqueous solution at 30°C for 30 min, then rinsed with water and dried. A peel test was then performed using 3M tape. Acid resistance was evaluated according to the following standards. The test results were graded as follows: Grade 1: No blistering, peeling, or even detachment of the dry film; Grade 2: Minor blistering, no peeling, and no detachment of the dry film; Grade 3: Minor blistering, peeling, or even detachment of the dry film; Grade 4: Significant detachment of the dry film.

[0165] (7) Alkali resistance test

[0166] Test samples were prepared using the same preparation method as in the HAST test. At 30°C, the samples were immersed in a 10 vol% NaOH aqueous solution for 30 minutes, then rinsed with water and dried. A peel test was then performed using 3M tape. Alkali resistance was evaluated according to the following standards. The test results were graded as follows: Grade 1: No blistering, peeling, or even detachment of the dry film; Grade 2: Minor blistering, no peeling, and no detachment of the dry film; Grade 3: Minor blistering, peeling, or even detachment of the dry film; Grade 4: Significant detachment of the dry film.

[0167] (8) Solvent resistance test

[0168] Test samples were prepared using the same preparation method as in the HAST test. The samples were immersed in propylene glycol methyl ether acetate solvent at 30°C for 30 minutes, then removed and dried. A peel test was performed using 3M tape, and solvent resistance was evaluated according to the following standards. The test results were graded as follows: Grade 1: No blistering, peeling, or even detachment of the dry film; Grade 2: Minor blistering, no peeling, and no detachment of the dry film; Grade 3: Minor blistering, peeling, or even detachment of the dry film; Grade 4: Significant detachment of the dry film.

[0169] (9) Heat resistance test

[0170] Refer to IPC-TM650.2.6.8 standard. Immerse the solder mask dry film in rosin flux for 30 seconds, then vertically immerse it in a solder bath at 288°C for 10 seconds, repeating 3 times. Observe whether blistering, discoloration, or floating occurs on the surface, and observe whether the dry film peels off using 3M tape. Evaluate the changes in appearance based on the following criteria. The test results are graded as follows: Grade 1: No blistering, peeling, or even peeling of the dry film; Grade 2: A small amount of blistering, no peeling, and no peeling of the dry film; Grade 3: A small amount of blistering, peeling, or even peeling of the dry film; Grade 4: A large amount of peeling of the dry film.

[0171] (10) Hardness test

[0172] The test samples were prepared according to the same preparation method as in the HAST test, and hardness tests were conducted using pencils of different hardnesses, in accordance with the GB / T 6739-2006 standard for "Determination of Hardness of Paints and Varnishes by Pencil Method".

[0173] The component ratios of the solder resist dry film in the examples and comparative examples can be referred to in Table 1, with the unit being parts by mass; the solder resist dry films obtained in the examples and comparative examples were subjected to the above-mentioned performance tests, and the performance test results are shown in Tables 2 and 3.

[0174] Table 1

[0175]

[0176]

[0177]

[0178] Table 2

[0179]

[0180]

[0181] Table 3

[0182]

[0183]

[0184] As can be seen from the test results of the above embodiments and comparative examples, the photosensitive resin composition provided by the present invention can effectively reduce the CTE of the solder resist dry film, while significantly improving its heat resistance, hardness, HAST, acid resistance, alkali resistance, and solvent resistance, thus meeting the requirements of IC substrates. It also exhibits good alkali developability and high resolution. Furthermore, the addition of epoxy-based glass polymer prepolymers can prevent cracking, warping, and wrinkling of the solder resist dry film after photocuring and heat curing, resulting in superior overall performance.

[0185] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A photosensitive resin composition, characterized in that, The photosensitive resin composition, by weight, comprises: 100-120 parts of alkali-soluble resin, 5-25 parts of photopolymerizable monomer, 1-7 parts of photoinitiator, 10-30 parts of epoxy resin, 3-15 parts of epoxy-based glass polymer prepolymer, and 1-5 parts of curing agent and its accelerator; the epoxy-based glass polymer prepolymer is a prepolymer with a dynamic cross-linked network structure formed by the reaction of glycidyl group compound and carboxylic acid compound, and has an intramolecular hydrogen bond structure formed by the association of β-hydroxyl and ester groups as shown in Formula 1: Formula 1.

2. The photosensitive resin composition according to claim 1, characterized in that, The epoxy-based glass polymer prepolymer comprises 5 to 10 parts by weight.

3. The photosensitive resin composition according to claim 1, characterized in that, The glycidyl compound has a cyclic structure containing at least four atoms, and the glycidyl compound also contains at least two epoxy groups.

4. The photosensitive resin composition according to claim 1, characterized in that, The glycidyl compound is selected from at least one of bisphenol A diglycidyl ether, magnolol diglycidyl ether, resorcinol diglycidyl ether, bisphenol F diglycidyl ether, cashew phenol diglycidyl ether, diglycidyl terephthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, triglycidyl isocyanurate, diglycidyl 1,2-cyclohexanedicarboxylate, and diglycidyl 4-cyclohexene-1,2-dicarboxylic acid.

5. The photosensitive resin composition according to any one of claims 1 to 4, characterized in that, The carboxylic acid compound contains at least two carboxyl groups, and at least one of the carboxyl groups has a hydroxyl group adjacent to it.

6. The photosensitive resin composition according to any one of claims 1 to 4, characterized in that, The carboxylic acid compound is selected from at least one of 2-hydroxysuccinic acid and 2,3-hydroxysuccinic acid.

7. The photosensitive resin composition according to any one of claims 1 to 4, characterized in that, The mass ratio of the epoxy resin to the epoxy-based glass polymer prepolymer is (1~5):1; and / or, The epoxy resin is 15-25 parts by weight; and / or, The epoxy resin 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, phenolic epoxy resin, alicyclic epoxy resin, hydantoin epoxy resin, and imide epoxy resin.

8. The photosensitive resin composition according to any one of claims 1 to 4, characterized in that, The alkali-soluble resin is selected from at least one of bisphenol A type epoxy acrylate resin, alicyclic epoxy acrylate resin, and phenolic epoxy acrylate resin; and / or, The photopolymerizable monomer is 7-15 parts by weight; and / or, The photopolymerizable monomers include monofunctional acrylates and polyfunctional acrylates. The monofunctional acrylates are selected from at least one of tetrahydrofuran acrylate, 2-phenoxyethyl acrylate, cycloaliphatic acrylate, (4) ethoxylated nonylphenol acrylate, isobornyl acrylate, trimethylolpropane formal acrylate, alkyl oxidized phenol acrylate, alkyl oxidized tetrahydrofuran acrylate, and alkyl oxidized nonylphenol acrylate. The polyfunctional acrylates are selected from pentaerythritol tetraacrylate and dipentaerythritol pentaacrylate. At least one of the following: (1) pentaerythritol tetraacrylate, (2) pentaerythritol tetraacrylate, (3) trimethylolpropane triacrylate, (4) trimethylolpropane triacrylate, (5) pentaerythritol triacrylate, (6) trimethylolpropane triacrylate; the mass ratio of the monofunctional acrylate to the polyfunctional acrylate is (0.3~0.5):1; and / or, The photoinitiator comprises 2-4 parts by weight, and the curing agent and its accelerator comprise 1-3 parts; and / or, The photoinitiator includes a free radical photoinitiator and / or a cationic photoinitiator; the free radical photoinitiator is selected from 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-isopropylthioxanthonone, 1-hydroxycyclohexylphenyl ketone, benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, tetramethylmithionone, tetraethylmithionone, 2-chlorothioxanthonone, 1-chloro-4-propoxythioxanthonone, 2,4-diethylthioxanthonone, benzoin dimethyl ether, and 2-hydroxy-methylbenzene. The photoinitiator is selected from at least one of methylpropane-1-one, ethyl 4-(N,N-dimethylamino)benzoate, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone; the cationic photoinitiator is selected from at least one of triphenylthionium hexafluorophosphate, 4-phenylthionium diphenylthionium salt, 4-dodecyloxyphenyl diphenylthionium hexafluoroantimonate, bis[(4-diphenylthionium)phenyl]sulfide-bis-hexafluorophosphate, 4-phenylthionium diphenylthionium salt, (4-hydroxyphenyl)methyl(benzyl)hexafluorophosphate, 4-acetoxyphenyl dimethylthionium hexafluoroantimonate, and diphenyliodonium hexafluorophosphate; and / or, The accelerator includes at least one of electrophilic accelerators, nucleophilic accelerators, and metal carboxylate accelerators; and / or, The curing agent is selected from 2-methylimidazole, 2-ethylimidazole, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl disulfide, 3-aminobenzylamine, m-phenylenediamine, 3-amino-5-mercapto-1,2,4-triazole, 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole, 1,3-bis(2,4,6-trimethylphenyl)chloroimidazole, 1-triphenylmethylimidazole, 4-imidazole-1-phenylpropanone, 1-ethyl-3-methylimidazole tetrafluoroborate, 1 At least one of the following: ethylimidazole, 1-allylimidazole, 2,4,5-triphenylimidazole, melamine, melamine phosphate, melamine phosphate, trichloromelamine, hexamethyl melamine, 1,8-diazabicyclo[5,4,0]dodec-7-ene, 4-cyanobenzylamine, 4,4'-diaminodiphenyl sulfone, 1-ethyl-3-methylimidazolium dicyandiamide, 1-butyl-3-methylimidazolium dicyandiamide, adipate dihydrazide, sebacate dihydrazide, and triphenylphosphine.

9. A solder resist dry film, characterized in that, The solder resist dry film is obtained by mixing and drying the photosensitive resin composition according to any one of claims 1 to 8.

10. A photosensitive laminate, characterized in that, It includes a support layer, a photosensitive layer and a protective layer stacked together, wherein the photosensitive layer is the solder resist dry film as described in claim 9.

11. A solder resist pattern, characterized in that, The solder resist pattern is formed by sequentially exposing, developing and curing the solder resist dry film as described in claim 9.

12. A semiconductor packaging substrate, characterized in that, The solder resist pattern is obtained by mixing and curing the photosensitive resin composition according to any one of claims 1 to 8, or the solder resist pattern is the solder resist pattern according to claim 11.

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