Photosensitive polyamic acid ester resin, photosensitive polyamic acid ester resin solution, preparation method thereof and application

Abstract

The present application discloses a photosensitive polyamic acid ester resin, a photosensitive polyamic acid ester resin solution, and their preparation methods and applications. The structure of the photosensitive polyamic acid ester resin has a regular molecular chain arrangement and a relatively small molecular weight, thus having a low coefficient of thermal expansion. When applied to a photosensitive solder resist ink composition, it can reduce the coefficient of thermal expansion of the cured product of the photosensitive solder resist ink composition, enabling its coefficient of thermal expansion to match that of copper, thereby improving the reliability of electronic components. At the same time, the photosensitive polyamic acid ester resin with this structure has high heat resistance. When applied to a photosensitive solder resist ink composition, it can increase the glass transition temperature and decomposition temperature of the photosensitive solder resist ink composition.

Description

Technical Field

[0001] The present application relates to the field of display technologies, and particularly to a photosensitive polyamide acid ester resin, a photosensitive polyamide acid ester resin solution, and their preparation methods and applications. Background Art

[0002] A photosensitive solder resist ink refers to a layer of polymer material deposited on a printed circuit board (PCB) and an electronic component substrate, also known as a permanent mask resist. In the process of flip-chip mounting semiconductor components on a printed circuit board by soldering, it has the function of preventing solder from adhering to unnecessary parts of the conductor layer of the printed circuit board, and can also prevent corrosion of the conductor layer and maintain electrical insulation between conductor layers. With the high density of the circuit diagram of the printed circuit board, the cured product formed by the photosensitive solder resist ink needs to have higher resolution. At the same time, in semiconductor packaging substrates such as flip-chip ball grid array (FC-BGA) and chip scale package (CSP), the cured product formed by the photosensitive solder resist ink requires higher heat resistance and a thermal expansion coefficient (CTE) more matched with copper circuits to overcome the failure risks brought by its harsh actual working environment. And due to the reflow soldering process at about 260°C during the substrate preparation process, this requires that the photosensitive solder resist ink or the dry film cured product needs to have high heat-resistant soldering performance (high glass transition temperature and thermal decomposition temperature).

[0003] Currently, the most commonly used photosensitive solder resist inks mainly contain a photoinitiator and a photosensitive resin containing carboxyl groups. Among them, the photosensitive resin is generally an acrylic-modified epoxy resin. Although it has good photocurability, developability, and mechanical properties, the heat resistance of its cured film is insufficient, and it is easy to foam or lose oil during soldering, unable to meet the application requirements of demanding electrical circuit boards. At the same time, in order to improve reliability, the cured film formed after curing the photosensitive solder resist ink coating also needs to have a thermal expansion coefficient (CTE) matched with copper to avoid circuit failure during use. Traditional epoxy resin-based solder resist inks are limited in their applications in PCBs and IC substrates due to poor heat resistance, low glass transition temperature, and mismatched CTE with copper. Summary of the Invention

[0004] In view of this, the present application provides a photosensitive polyamide acid ester resin, a photosensitive polyamide acid ester resin solution, and their preparation methods and applications, aiming to improve the problems of poor heat resistance of epoxy resin in existing photosensitive solder resist inks and mismatched thermal expansion coefficient with copper.

[0005] An embodiment of the present application provides a photosensitive polyamide acid ester resin, and the structural formula of the photosensitive polyamide acid ester resin is

[0006]

[0007] Wherein, A is independently selected from at least one of a linear structural group and a group containing a fluorine atom, a nitrogen atom, an oxygen atom, a sulfur atom, a chlorine atom, an iodine atom, or a bromine atom; R2 is independently selected from at least one of a hydroxyl group, a carboxyl group, and a hydrogen atom; R3 is independently selected from at least one of a group containing an unsaturated double bond and a hydrogen atom; and / or

[0008] The number-average molecular weight of the photosensitive polyamic acid ester resin is 2,000 to 100,000.

[0009] Correspondingly, an embodiment of the present application further provides a method for preparing a photosensitive polyamic acid ester resin, including the following steps:

[0010] Provide a diamine, a polar organic solvent, a monoanhydride, and a dianhydride. In an inert gas atmosphere, carry out a capping reaction of the diamine and the monoanhydride in the polar organic solvent, and then add the dianhydride to carry out a polycondensation reaction to obtain a polyamic acid solution;

[0011] Provide a dehydrating agent, mix the dehydrating agent with the polyamic acid solution, and carry out a dehydration reaction to obtain a polyimide solution;

[0012] Provide a compound containing a photosensitive group, mix the compound containing a photosensitive group with the polyimide solution, and carry out an esterification reaction to obtain a photosensitive polyamic acid ester resin.

[0013] Correspondingly, an embodiment of the present application further provides a photosensitive polyamic acid ester resin glue solution, including the above-mentioned photosensitive polyamic acid ester resin, a curing accelerator, and a solvent.

[0014] Correspondingly, an embodiment of the present application further provides a photosensitive solder resist ink composition, including the above-mentioned photosensitive polyamic acid ester resin, or the above-mentioned photosensitive polyamic acid ester resin glue solution.

[0015] Correspondingly, an embodiment of the present application further provides a photosensitive dry film / photosensitive cured film, including the above-mentioned photosensitive polyamic acid ester resin, or prepared from the above-mentioned photosensitive polyamic acid ester resin glue solution, or prepared from the above-mentioned photosensitive solder resist ink composition.

[0016] Correspondingly, an embodiment of the present application further provides an electronic component, including the above-mentioned photosensitive dry film / photosensitive cured film.

[0017] In this application, the photosensitive polyamide acid ester resin of this structure has a regular molecular chain arrangement and a relatively small molecular weight, thus having a low coefficient of thermal expansion. When it is applied to the photosensitive solder resist ink composition, it can reduce the coefficient of thermal expansion of the cured product of the photosensitive solder resist ink composition, making its coefficient of thermal expansion match that of copper, thereby improving the reliability of electronic components. At the same time, the photosensitive polyamide acid ester resin of this structure has high heat resistance. When it is applied to the photosensitive solder resist ink composition, it can increase the glass transition temperature and decomposition temperature of the photosensitive solder resist ink composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0019] Figure 1 is a schematic flow chart of the preparation method of the photosensitive polyamide acid ester resin provided by the embodiment of the present application;

[0020] Figure 2 is a graph of the coefficient of thermal expansion of the photosensitive polyamide acid ester - 1 provided in Embodiment 1 of the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0021] The following will clearly and completely describe the technical solutions in the embodiments of the present application with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, rather than all embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present application. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which this invention belongs. The terms used in the specification of this invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0023] In this application, unless otherwise stated, the orientation terms such as "upper" and "lower" generally refer to the upper and lower directions in the actual use or working state of the device, specifically the drawing directions in the attached drawings; while "inner" and "outer" refer to the outline of the device. Additionally, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc. are only used as labels and do not impose numerical requirements or establish an order.

[0024] In this application, "and / or" describes the association relationship of associated objects and indicates that three relationships can exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, or B exists alone. Here, A and B can be singular or plural.

[0025] In this application, "at least one" means one or more, and "a plurality" means two or more. "One or more kinds", "at least one of the following (items)" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can both represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0026] The various embodiments of this application can exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be construed as a rigid limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub - ranges and individual values within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub - ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and individual numbers within the range, such as 1, 2, 3, 4, 5, and 6, and this applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0027] The technical solution of this application is as follows:

[0028] In a first aspect, an embodiment of this application provides a photosensitive polyamic acid ester resin, and its structural formula is

[0029] ;

[0030] Among them, A is independently selected from at least one of a linear structural group and a group containing a fluorine atom / nitrogen atom / oxygen atom / sulfur atom / chlorine atom / iodine atom / bromine atom, and each R2 is independently selected from at least one of a hydroxyl group, a carboxyl group, and a hydrogen atom; each R3 is independently selected from at least one of a group containing an unsaturated double bond and a hydrogen atom; and / or

[0031] The number-average molecular weight of the photosensitive polyamic acid ester resin is 2,000 to 100,000.

[0032] In this application, the photosensitive polyamic acid ester resin with this structure has a regular molecular chain arrangement and a relatively small molecular weight, so it has a low coefficient of thermal expansion. When it is applied to the photosensitive solder resist ink composition, the coefficient of thermal expansion of the cured product of the photosensitive solder resist ink composition can be reduced, so that its coefficient of thermal expansion can match that of copper, thereby improving the reliability of electronic components; at the same time, the photosensitive polyamic acid ester resin with this structure has high heat resistance. When it is applied to the photosensitive solder resist ink composition, the glass transition temperature and decomposition temperature of the photosensitive solder resist ink composition can be increased; the hydroxyl group and carboxyl group in this structure can provide alkali-soluble effects, and the group containing an unsaturated double bond and H can provide photosensitive characteristics and alkali-soluble effects, so that it has alkali-developable properties. The linear structure refers to a chain-like structure.

[0033] In some embodiments, each A is independently selected from

[0034]

[0035]

[0036]

[0037] .

[0038] In this application, * represents the connection point on group A. The two amino groups connected to group A in the structural formula of the photosensitive polyamic acid ester resin are respectively connected to any two connection points * on group A, and the two R2s connected to group A in the structural formula of the photosensitive polyamic acid ester resin are respectively connected to any two connection points * on group A or replace the hydrogen atoms on group A.

[0039] In some embodiments, the number-average molecular weight of the photosensitive polyamic acid ester resin is 5,000 to 30,000.

[0040] In a second aspect, please refer to Figure 1 , this application embodiment provides a preparation method of a photosensitive polyamic acid ester resin, including the following steps:

[0041] S1. Provide a diamine, a polar organic solvent, a monoanhydride, and a dianhydride. In an inert gas atmosphere, carry out a capping reaction of the diamine and the monoanhydride in the polar organic solvent, and then add the dianhydride to carry out a polycondensation reaction to obtain a polyamic acid solution;

[0042] S2. Provide a dehydrating agent, mix the dehydrating agent with the polyamic acid solution, and carry out a dehydration reaction to obtain a polyimide solution;

[0043] S3. Provide a compound containing a photosensitive group, mix the compound containing the photosensitive group with the polyimide solution, and carry out an esterification reaction to obtain a photosensitive polyamic acid ester resin.

[0044] In the present application, first, the diamine is capped with a monoanhydride to control the molecular weight of the photosensitive polyamic acid ester, making it alkali-soluble. Then, the dianhydride reacts with the diamine and the partially capped diamine through a polycondensation reaction to form a polyamic acid solution. The polyamic acid is then transformed into a polyimide under the action of a dehydrating agent. Finally, through the reaction of the highly reactive imide ring with the compound containing a photosensitive group, a photosensitive group is grafted to obtain a photosensitive polyamic acid ester resin.

[0045] In some embodiments, the molar ratio of the diamine, the monoanhydride, the dianhydride, the dehydrating agent, and the compound containing a photosensitive group is 1:(0.1 - 0.5):(0.75 - 0.95):(1 - 4.5):(2 - 6), for example, it can be 1:0.1:0.75:1:2, 1:0.2:0.8:2:3, 1:0.3:0.85:3:3.5, 1:0.4:0.9:4:4.5, 1:0.5:0.95:4.5:6, etc. Within the said ratio range, the molecular weight of the product can be controlled. If the molecular weight is too small, it is difficult to form a photolithographic pattern by photocuring. If the molecular weight is too large, it is difficult to achieve alkali solubility.

[0046] In the present application, by controlling the dosage of the monoanhydride, the molecular weight of the synthesized photosensitive polyamic acid ester resin can be controlled, thereby the developing performance of the photosensitive solder resist ink composition can be adjusted. The high heat resistance of the photosensitive polyamic acid ester resin can also increase the glass transition temperature and decomposition temperature of the photosensitive solder resist ink composition.

[0047] The solid content of the reaction solution for the polycondensation reaction, the dehydration reaction, and the esterification reaction is 5% - 35%. Within the said solid content range, the molecular weight and morphology of the photosensitive polyamic acid ester resin can be controlled. Too high a solid content will cause gelation, and too low a solid content will result in a smaller molecular weight.

[0048] In step S1,

[0049] In some embodiments, the diamine includes a linear diamine and at least one of a group containing a fluorine atom, a nitrogen atom, an oxygen atom, a sulfur atom, a chlorine atom, an iodine atom, or a bromine atom.

[0050] In this application, through a copolymerization method, a diamine with a linear structure or a group containing a fluorine atom, a nitrogen atom, an oxygen atom, a sulfur atom, a chlorine atom, an iodine atom, or a bromine atom is used. It is easy to form a polyimide with a regular molecular chain arrangement with dianhydride, thereby reducing its coefficient of thermal expansion. Furthermore, a photosensitive polyamic acid ester with a negative CTE can be obtained. When mixed with a photosensitive epoxy resin, the CTE of the cured product of the photosensitive solder resist ink composition can be reduced, enabling its CTE to match that of copper.

[0051] In some embodiments, the diamine includes at least one of a hydroxyl-containing diamine or a carboxyl-containing diamine. In this way, the alkali solubility of the photosensitive polyamic acid ester can be improved.

[0052] In some embodiments, the diamine can be selected from

[0053]

[0054]

[0055]

[0056] and at least one of 2,5-diamino-4,6-dihydroxypyrimidine hydrochloride, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,5-diaminobenzene-1,4-diol dihydrochloride, 3,3-diamino-4,4'-biphenyldiol, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,4-diamino-6-hydroxymethylpteridine, 4,6-diaminoresorcinol dihydrochloride, bis(5-amino-2-hydroxyphenyl)methane hydrochloride, 3,3'-dihydroxybenzidine, and 2,4-diamino-6-hydroxypyrimidine.

[0057] In some embodiments, the monoanhydride includes one or more of dihydro-2,5-furandione, palmitic anhydride, glutaric anhydride, n-decanoic anhydride, maleic anhydride, crotonic anhydride, isobutyric anhydride, methylsuccinic anhydride, chloroacetic anhydride, itaconic anhydride, pentafluoropropionic anhydride, heptafluorobutyric anhydride, phenylsuccinic anhydride, phthalic anhydride, 2,3-dimethylmaleic anhydride, and trimellitic anhydride. In this way, effective end-capping of the molecular chain can be achieved, thereby controlling the molecular weight of the product.

[0058] In some embodiments, the dianhydride includes one or more of pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenylether tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenylsulfone tetracarboxylic dianhydride, 4,4'-phenylenedioxydiphthalic anhydride, hexafluorodiacid anhydride, 1,2-ethylenedi[1,3-dihydro-1,3-dioxoisobenzofuran-5-carboxylate], bisphenol A dianhydride, glycerol bis(dehydromellitate) acetate, 2,3,3',4'-biphenyltetracarboxylic dianhydride, p-phenylene-bis(trimellitate) dianhydride, 9,9-bis(3,4-dicarboxyphenyl) fluorene dianhydride, 4,4'-(ethyne-1,2-diyl) diphthalic anhydride, and diphenyl sulfide dianhydride.

[0059] In some embodiments, the polar organic solvent includes one or more of N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric triamide, and chloroform.

[0060] In step S2,

[0061] In some embodiments, the dehydrating agent includes one or more of an acid anhydride-tertiary amine dehydrating agent, a thionyl chloride-tertiary amine dehydrating agent, and an acetyl chloride-tertiary amine dehydrating agent; the acid anhydride in the acid anhydride-tertiary amine dehydrating agent includes one or more of acetic anhydride, phthalic anhydride, and trifluoroacetic anhydride; the tertiary amine in the acid anhydride-tertiary amine dehydrating agent, the thionyl chloride-tertiary amine dehydrating agent, and the acetyl chloride-tertiary amine dehydrating agent includes one or more of pyridine and triethylamine.

[0062] In some embodiments, the molar ratio of the polyamic acid, the acid anhydride, and the tertiary amine in the dehydrating agent is 1:(4 - 6):(4 - 6), and for example, it can be 1:4:4, 1:4.5:4.5, 1:5:5, 1:5.5:5.5, 1:6:6, etc. Within the range of this molar ratio, the conversion rate of the polyimide can be increased.

[0063] In step S3,

[0064] In some embodiments, the compound containing a photosensitive group includes one or more of 2-hydroxyethyl methacrylate, tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, and N-hydroxymethylacrylamide.

[0065] An embodiment of the present application further provides a photosensitive polyamic acid ester resin glue solution, which includes the above-mentioned photosensitive polyamic acid ester resin, a curing accelerator, and a solvent.

[0066] In the present application, by adding a curing accelerator to the photosensitive polyamic acid ester, the curing temperature of the photosensitive polyamic acid ester resin can be reduced, and the curing temperature can be reduced to 200 °C or even lower, which is beneficial to achieving the same curing conditions for the epoxy system in the photosensitive polyamic acid ester resin and the photosensitive solder resist ink composition.

[0067] In some embodiments, the mass ratio of the curing accelerator to the photosensitive polyamic acid ester resin is (2.5-200):100. Within this mass ratio range, the thermal properties and low-temperature curing properties of the cured film formed by the photosensitive polyamic acid ester resin glue solution can be better. If the amount of the curing agent is too much, the thermal properties of the cured film will decrease due to the difficulty in removing the curing agent. If the amount of the curing agent is too little, the low-temperature curing effect will be poor.

[0068] In some embodiments, the curing accelerator includes at least one of quinoline-based curing accelerators, isoquinoline-based curing accelerators, imidazole-based curing accelerators, and pyridine-based curing accelerators.

[0069] In some embodiments, the curing accelerator includes one or more of ethylenediamine, 3,5-dimethylpiperidine, imidazole, benzimidazole, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, triethylamine, quinoline, 6-aminoquinoline, isoquinoline, 4-methylquinoline, 5,6,7,8-tetrahydroquinoline, 4-chloro-6,7-dihydro-5H-cyclopentadieno[b]pyridine, 4-chloroquinoline, 6-chloroquinoline, 4,5,7-trichloroquinoline, 7-chloroquinoline, 4-chloro-5,6,7,8-tetrahydroquinoline, 9-chloroacridine, and 8-chloroisoquinoline.

[0070] In some embodiments, the curing accelerator includes one or more of 4-chloroquinoline, 6-chloroquinoline, 4,5,7-trichloroquinoline, 7-chloroquinoline, 4-chloro-5,6,7,8-tetrahydroquinoline, 9-chloroacridine, and 8-chloroisoquinoline.

[0071] The embodiment of the present application also provides a method for preparing a photosensitive polyamic acid ester resin solution, including the following steps:

[0072] Provide a curing accelerator, a photosensitive polyamic acid ester resin, and a solvent, and mix them to obtain a photosensitive polyamic acid ester resin solution.

[0073] The embodiment of the present application also provides a photosensitive solder resist ink composition, including the above-mentioned photosensitive polyamic acid ester resin.

[0074] In the present application, by adding a photosensitive polyamic acid ester resin with a negative coefficient of thermal expansion (CTE) that can be cured at low temperature to the photosensitive solder resist ink composition, the glass transition temperature of the composition can be increased from below 170 °C to above 200 °C, and at the same time, the CTE of the composition is reduced to 16 ppm / °C (the CTE of copper is about 16 - 18 ppm / °C), which can well meet the heat resistance requirements of the solder resist ink composition curing film for the soldering process, and can significantly reduce the risk of thermal expansion coefficient mismatch, improve the reliability of the circuit, and has good application prospects in flip chip ball grid array (FCBGA) packaging.

[0075] In some embodiments, the photosensitive solder resist ink composition further includes a photosensitive epoxy resin, a photoinitiator, a photopolymerizable monomer, a thermal curing component, and an inorganic filler.

[0076] In some embodiments, the mass fraction of the photosensitive polyamic acid ester resin in the photosensitive solder resist ink composition is 5% - 60%. Within this range, it can effectively reduce the CTE and improve the thermal properties, while avoiding the problem of poor compatibility between the photosensitive polyamic acid ester resin and the photosensitive epoxy resin due to excessive content of the photosensitive polyamic acid ester resin.

[0077] In some embodiments, the mass ratio of the photosensitive epoxy resin, the photoinitiator, the polymerizable monomer, the thermosetting component, and the inorganic filler is 100: (3 to 25): (10 to 30): (15 to 45): (10 to 80).

[0078] In some embodiments, the molecular chain of the photosensitive epoxy resin contains photosensitive groups and alkali-soluble groups; the photosensitive groups include at least one of carbonyl group, carboxyl group, peroxy group, and carbon-carbon double bond; the alkali-soluble groups include at least one of carboxyl group, acid anhydride, and ester group.

[0079] In some embodiments, the weight-average molecular weight of the photosensitive epoxy resin is 2,000 to 100,000.

[0080] In some embodiments, the weight-average molecular weight of the photosensitive epoxy resin is 5,000 to 30,000.

[0081] In some embodiments, the acid value of the photosensitive epoxy resin is 40 to 200 mg KOH / g.

[0082] In some embodiments, the acid value of the photosensitive epoxy resin is 50 to 180 mg KOH / g.

[0083] In some embodiments, the photosensitive epoxy resin is a bifunctional or trifunctional epoxy resin.

[0084] In some embodiments, the photosensitive epoxy resin includes, but is not limited to, one or more of novolac epoxy resin, bisphenol A novolac epoxy resin, naphthalene epoxy resin, o-cresol novolac epoxy resin, alkylphenol novolac epoxy resin, dicyclopentadiene epoxy resin, glycidylamine epoxy resin, trihydroxybenzene methane epoxy resin, tetraphenylethane epoxy resin, and diglycidyl phthalate resin.

[0085] In some embodiments, the photoinitiator can be selected from one or more of oxime ester-based photoinitiators, acylphosphine oxide-based photoinitiators, acetophenone-based photoinitiators, benzoin and its alkyl ether photoinitiators, anthraquinone-based photoinitiators, thioxanthone-based photoinitiators, ketal-based photoinitiators, and benzophenone-based photoinitiators.

[0086] In some embodiments, the photoinitiator can be selected from oxime ester-based photoinitiators.

[0087] As an example, the acylphosphine oxide-based photoinitiator can be selected from but not limited to 2,4,6-trimethylbenzoyl diphenylphosphine oxide; the acetophenone-based photoinitiator can be selected from but not limited to acetophenone; the benzoin and its alkyl ether-based photoinitiators can be selected from but not limited to benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; the anthraquinone-based photoinitiators can be selected from but not limited to 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone; the thioxanthone-based photoinitiators can be selected from but not limited to 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; the ketal-based photoinitiators can be selected from but not limited to acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; the benzophenone-based photoinitiators can be selected from but not limited to benzophenone, 4,4'-bis(diethylamino)benzophenone.

[0088] In some embodiments, the photopolymerizable monomer can be selected from hydroxy-containing (meth)acrylates, monofunctional (meth)acrylates, 1,6-hexanediol bis(meth)acrylate, dipropylene glycol / tripropylene glycol bis(meth)acrylate, diethylene glycol / triethylene glycol bis(meth)acrylate, ethoxylated bisphenol A bis(meth)acrylate, neopentyl glycol diethoxy / propoxy bis(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polydipentaerythritol hexa(meth)acrylate. The hydroxy-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate. The monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate.

[0089] In some embodiments, the thermosetting component is an epoxy resin.

[0090] In some embodiments, the epoxy resin includes one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, dimethylxylenol type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, soluble fusible phenolic epoxy resin, cresol soluble epoxy resin, triphenol methane type epoxy resin, N-glycidyl type epoxy resin, isocyanuric acid triglycidyl ester, 2,6-dimethylphenol dimer diglycidyl ether, alicyclic epoxy resin, xylene type epoxy resin. Thus, heat resistance can be imparted to the photosensitive solder resist ink composition.

[0091] In some embodiments, the inorganic filler includes one or more of barium sulfate, barium titanate, calcium oxide, talc powder, fumed silica, silicon dioxide, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, titanium oxide, mica powder, and kaolin. Thus, the physical strength of the photosensitive dry film / photosensitive cured film formed by the photosensitive solder resist ink composition can be improved.

[0092] In some embodiments, the photosensitive solder resist ink composition further includes a pigment. Thus, the covering power of the photosensitive solder resist ink composition can be improved.

[0093] In some embodiments, the pigment includes one or more of phthalocyanine green, phthalocyanine blue, titanium dioxide, carbon black, and lithopone.

[0094] In some embodiments, the pigment is a pigment free of free halogens. Thus, the burden on the environment can be reduced.

[0095] In some embodiments, the photosensitive solder resist ink composition further includes additives, and the additives include one or more of an epoxy resin curing accelerator, a photoinitiator assistant, a thixotropic thickener, a diluent, a polymerization inhibitor, a tackifier, an antifoaming agent, a leveling agent, a coupling agent, an antioxidant, and a rust inhibitor.

[0096] The embodiments of the present application further provide a preparation method of a photosensitive solder resist ink composition, including the following steps:

[0097] Providing a curing accelerator, a photosensitive polyamic acid ester resin, and a solvent, and mixing them to obtain a photosensitive polyamic acid ester resin solution;

[0098] Providing a photosensitive epoxy resin and a solvent, and mixing them to obtain a photosensitive epoxy resin solution;

[0099] Providing a photoinitiator, a photopolymerizable monomer, a thermosetting component, and an inorganic filler, and mixing them with the photosensitive polyamic acid ester resin solution and the photosensitive epoxy resin solution to obtain a photosensitive solder resist ink composition.

[0100] In some embodiments, the preparation method of the photosensitive epoxy resin includes the following steps:

[0101] Providing an epoxide, an unsaturated monocarboxylic acid, and a solvent, mixing them, and performing an esterification reaction to obtain an esterified product;

[0102] Providing a polyanhydride, and reacting the esterified product with the polyanhydride to obtain a photosensitive epoxy resin.

[0103] In some embodiments, the unsaturated monocarboxylic acid includes one or more of acrylic acid, acrylic acid dimer, methacrylic acid, β-styrylacrylic acid, β-furylacrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, reaction products of saturated / unsaturated dibasic anhydrides and hydroxyl-containing (meth)acrylate esters, and reaction products of saturated / unsaturated dibasic acids and unsaturated monoglycidyl compounds.

[0104] In some embodiments, the polybasic anhydride includes one or more of dibasic anhydrides, polyaromatic carboxylic anhydrides, and anhydride derivatives.

[0105] As an example, the dibasic anhydride can be selected from maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride; the polyaromatic carboxylic anhydride can be selected from trimellitic anhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic dianhydride; the anhydride derivative can be selected from 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexenyl-1,2-dicarboxylic anhydride.

[0106] In some embodiments, the polybasic anhydride includes one or more of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and succinic anhydride.

[0107] In some embodiments, the solvent includes one or more of ether solvents, ester solvents, ketone solvents, aromatic solvents, and petroleum solvents.

[0108] As an example, the ethers can be selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether; the esters can be selected from ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate; the ketones can be selected from methyl ethyl ketone, cyclohexanone, isophorone; the aromatic solvents can be selected from toluene, xylene, and durene; the petroleum solvents can be selected from naphtha, oxidized naphtha, and solvent naphtha.

[0109] In some embodiments, the photosensitive solder resist ink of the present invention further contains some well-known additives, such as thermal polymerization inhibitors, fine silica, organic bentonite, montmorillonite and other well-known thickeners, silicone-based, fluorine-based, polymer-based defoamers or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, ultraviolet absorbers, sealants, rust inhibitors, diluents, elastomers and other well-known additives.

[0110] The embodiments of the present application also provide a photosensitive dry film, which is prepared by adjusting the above photosensitive solder resist ink composition to a suitable viscosity with an organic solvent, and then coating it onto a base film by methods such as dip coating, flow coating, roll coating, knife coating, screen printing, curtain coating, etc. The types of base films include polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyethylene terephthalate, etc. After drying with hot air, the organic solvent of the composition is volatilized and dried at a temperature of about 60-120°C for 1 to 60 minutes. A protective film is covered as needed to form a photosensitive dry film.

[0111] The embodiments of the present application also provide a photosensitive cured film, which is formed by curing the above photosensitive solder resist ink composition.

[0112] In some embodiments, the thickness of the photosensitive dry film is 10-50 μm.

[0113] The embodiments of the present application also provide an electronic component, which includes the above photosensitive dry film.

[0114] The electronic component includes, but is not limited to, printed circuit boards, FC-BGA substrates, etc.

[0115] The present application will be specifically described below through specific embodiments. The following embodiments are only partial embodiments of the present application and do not limit the present application. The raw materials used in the following embodiments are all commercially available products unless otherwise specified.

[0116] Example 1

[0117] A preparation method of a photosensitive polyamic acid ester resin includes the following steps:

[0118] (1) At room temperature, 60 mmol of 2-(4-aminophenyl)-5-aminobenzimidazole and 30 mmol of 2,4-diamino-6-hydroxypyrimidine are dissolved in 200 g of N-methylpyrrolidone (NMP) solution. Under a nitrogen atmosphere, 27 mmol of phthalic anhydride (PA) is added, and then 100 g of NMP solution is added again for dilution. After PA is completely dissolved, 76.5 mmol of pyromellitic dianhydride is added in two portions and stirred for 12 h to obtain a polyamic acid (PAA) solution;

[0119] (2) Under ice bath conditions, the polyamic acid solution (solid content of 20%) is diluted with 260 g of NMP solution, and then 200 mmol of trifluoroacetic anhydride and 200 mmol of triethylamine are added dropwise to the polyamic acid solution. After the addition is complete, the reaction is carried out for 1.5 h to obtain a polyimide solution;

[0120] (3) Heat the polyimide solution to 50 °C, add 200 mmol of 2-hydroxyethyl methacrylate to the polyimide solution for an esterification reaction. After reacting for 24 h, a photosensitive polyamic acid ester solution is obtained;

[0121] (5) Wash the photosensitive polyamic acid ester solution to obtain photosensitive polyamic acid ester resin-1.

[0122] A method for preparing a photosensitive polyamic acid ester resin adhesive solution, comprising the following steps:

[0123] Dissolve photosensitive polyamic acid ester resin-1 in diethylene glycol monoethyl ether acetate according to a solid content of 65%, and stir for 2 h. Add a curing accelerator 4-chloroquinoline (4-chloroquinoline accounts for 2.5% of the mass of photosensitive polyamic acid ester resin-1), and stir at room temperature for 2 h to obtain photosensitive polyamic acid ester resin adhesive solution A1.

[0124] A method for preparing a photosensitive epoxy resin, comprising the following steps:

[0125] Stir and heat 210 g of o-cresol novolac epoxy resin (SQPN-704M purchased from Shandong Shengquan New Materials Co., Ltd., epoxy equivalent is 210), 0.5 g of hydroquinone and 195 g of diethylene glycol monoethyl ether acetate in an N2 atmosphere to 105 °C, and maintain this temperature for 1 h to dissolve all substances;

[0126] After complete dissolution, cool down to 90 °C, then dropwise add 72 g of acrylic acid and 1 g of triphenylphosphine. During the dropping process, the temperature is controlled at 95 °C. After the dropping is completed, raise the temperature to 105 °C and react at this temperature for 12 h. During the reaction process, measure the acid value of the reactants until the acid value reaches 0.8 mg KOH / g, then cool down to 60 °C, and then add 75 g of tetrahydrophthalic anhydride and react at 90 °C for 6 h to obtain a light yellow alkali-soluble polyfunctional photosensitive epoxy resin (solid content is 65%, and the solid acid value is 95 mg KOH / g).

[0127] A method for preparing a photosensitive solder resist ink composition, comprising the following steps:

[0128] (1) Dissolve the photosensitive epoxy resin in diethylene glycol monoethyl ether acetate according to a solid content of 65%, and stir for 2 h to obtain a photosensitive epoxy resin adhesive solution A2;

[0129] (2) Stir 1.55 g of photosensitive polyamic acid ester resin solution A1 (photosensitive polyamic acid ester resin accounts for 5% of the total mass of the photosensitive solder resist ink composition), 30.23 g of photosensitive epoxy resin solution, 2.1 g of photoinitiator 819, 3 g of dipentaerythritol hexaacrylate, 12 g of bisphenol F type epoxy resin (Nanya 170), 5 g of silica, 10 g of barium sulfate, 0.8 g of phthalocyanine green, 0.4 g of melamine, 0.9 g of dicyandiamide and 20 g of diethylene glycol ethyl ether acetate at 800 rpm for 2 h, and then remix with a three-roll mill to obtain the photosensitive solder resist ink composition.

[0130] Example 2

[0131] This example is basically the same as Example 1, except that 2-(4-aminophenyl)-5-aminobenzimidazole and 2,4-diamino-6-hydroxypyrimidine in Example 1 are replaced with [2,2'-bipyridine]-5,5'-diamine (Compound 15), and pyromellitic dianhydride is replaced with 4,4'-oxybisphthalic anhydride to obtain photosensitive polyamic acid ester resin-2.

[0132] Example 3

[0133] This example is basically the same as Example 1, except that 2-(4-aminophenyl)-5-aminobenzimidazole and 2,4-diamino-6-hydroxypyrimidine in Example 1 are replaced with 2-(4-aminophenyl)-1H-benzo[d]imidazol-5-amine (Compound 38) and benzo[1,2-d:4,5-d']bis(thiazole)-2,6-diamine (Compound 59), and pyromellitic dianhydride is replaced with 3,3',4,4'-biphenyltetracarboxylic dianhydride to obtain photosensitive polyamic acid ester resin-3.

[0134] Example 4

[0135] This example is basically the same as Example 1, except that 2-(4-aminophenyl)-5-aminobenzimidazole and 2,4-diamino-6-hydroxypyrimidine in Example 1 are replaced with [3,3'-bipyridine]-6,6'-diamine (Compound 54) and 4,4'-diaminodiphenyl sulfide, and pyromellitic dianhydride is replaced with hexafluorodiacid anhydride to obtain photosensitive polyamic acid ester resin-4.

[0136] Example 5

[0137] This example is basically the same as Example 1, except that the amount of phthalic anhydride in Example 1 is changed to 9 mmol.

[0138] Example 6

[0139] This example is basically the same as Example 1, except that the amount of phthalic anhydride in Example 1 is changed to 45 mmol.

[0140] Example 7

[0141] This example is basically the same as Example 1, except that the amount of the curing accelerator 4-chloroquinoline in this example accounts for 200% of the mass of the photosensitive polyamic acid ester resin-1.

[0142] Example 8

[0143] This example is basically the same as Example 1, except that the curing accelerator 4-chloroquinoline in this example is changed to benzimidazole.

[0144] Example 9

[0145] This example is basically the same as Example 1, except that the curing accelerator 4-chloroquinoline in this example is changed to isoquinoline.

[0146] Example 10

[0147] This example is basically the same as Example 1, except that the curing accelerator 4-chloroquinoline in this example is changed to imidazole.

[0148] Example 11

[0149] This example is basically the same as Example 1, except that the curing accelerator 4-chloroquinoline in this example is changed to quinoline.

[0150] Example 12

[0151] This example is basically the same as Example 1, except that the curing accelerator 4-chloroquinoline in this example is changed to 3,5-dimethylpiperidine.

[0152] Example 13

[0153] This example is basically the same as Example 9, except that the photosensitive polyamic acid ester resin in this example accounts for 10% of the total mass of the photosensitive solder resist ink composition.

[0154] Example 14

[0155] This example is basically the same as Example 10, except that the photosensitive polyamic acid ester resin in this example accounts for 15% of the total mass of the photosensitive solder resist ink composition, and at the same time, the curing accelerator 4-chloroquinoline is changed to isoquinoline.

[0156] Example 15

[0157] This example is basically the same as Example 11, except that in this example, the photosensitive polyamide acid ester resin accounts for 30% of the total mass of the photosensitive solder resist ink composition, and at the same time, the curing accelerator 4-chloroquinoline is changed to imidazole.

[0158] Example 16

[0159] This example is basically the same as Example 12, except that in this example, the photosensitive polyamide acid ester resin accounts for 50% of the total mass of the photosensitive solder resist ink composition, and at the same time, the curing accelerator 4-chloroquinoline is changed to quinoline.

[0160] Example 17

[0161] This example is basically the same as Example 13, except that in this example, the photosensitive polyamide acid ester resin accounts for 60% of the total mass of the photosensitive solder resist ink composition, and at the same time, the curing accelerator 4-chloroquinoline is changed to 3,5-dimethylpiperidine.

[0162] Comparative Example 1

[0163] This comparative example is basically the same as Example 1, except that in this comparative example, the photosensitive epoxy resin solution in the photosensitive solder resist ink composition is 30.77 g and does not contain photosensitive polyamide acid ester resin.

[0164] Comparative Example 2

[0165] This example is basically the same as Example 1, except that in this example, the amount of the curing accelerator 4-chloroquinoline used accounts for 250% of the mass of the photosensitive polyamide acid ester resin-1.

[0166] Comparative Example 3

[0167] This example is basically the same as Example 1, except that in this example, the photosensitive polyamide acid ester resin accounts for 3% of the total mass of the photosensitive solder resist ink composition.

[0168] Comparative Example 4

[0169] This example is basically the same as Example 1, except that in this example, the photosensitive polyamide acid ester resin accounts for 65% of the total mass of the photosensitive solder resist ink composition.

[0170] The photosensitive solder resist ink compositions in Examples 1-19 and the comparative examples were coated, keeping the thickness at about 25 microns. After soft baking at 80 °C for 10 minutes, they were exposed, then developed with 1% dilute sodium carbonate solution, thermally cured at 170 °C for 1 hour, and then their glass transition temperature, Young's modulus, elongation at break, breaking strength, coefficient of thermal expansion, lithography performance, and development performance were tested. The results are shown in Table 1.

[0171] Among them, the glass transition temperature, Young's modulus, elongation at break, and breaking strength were measured by a dynamic thermomechanical analyzer (DMA850, produced by TA Instruments, USA). The heating rate was 5°C / min, and the test range was from room temperature to 300°C. The glass transition temperature was characterized by the abscissa temperature corresponding to the maximum point of the loss tangent value.

[0172] The coefficient of thermal expansion in different temperature ranges was measured by a thermomechanical analyzer (TMA402, produced by NETZSCH, Germany). The heating rate was 10°C / min, and the test range was from room temperature to 270°C.

[0173] The lithography performance was evaluated by SEM testing to observe the resolution of lines and round holes.

[0174] Lithography performance judgment criteria: When the resolution of the lines or round holes in the lithography pattern reaches 40μm < resolution < 60μm, it is judged as excellent; when 60μm < resolution < 90μm, it is judged as good; when 90μm < resolution < 100μm, it is judged as passing.

[0175] For the development performance, the photosensitive solder mask film after lithography was impregnated with a 0.1M sodium carbonate solution, and the time in seconds to observe a clear pattern was recorded:

[0176] Table 1

[0177]

[0178] As can be seen from Table 1:

[0179] Compared with Comparative Example 1, in the example, by adding the prepared photosensitive polyamic acid ester resin, the glass transition temperature of the photosensitive solder mask ink composition was significantly increased, reaching above 180°C; at the same time, the coefficient of thermal expansion decreased, which could be as low as 16 ppm / °C, reaching a level matching that of copper (about 16 - 18 ppm / °C); moreover, the thermal properties were improved, the lithography performance was better, and the development time was also significantly shortened.

[0180] Figure 2 Figure of the coefficient of thermal expansion of the photosensitive polyamic acid ester resin - 1 obtained in Example 1 after thermal curing at 170°C for 1 hour. From Figure 2 It can be seen that for the cured photosensitive polyamic acid ester resin - 1 on the curve of dimensional change versus temperature, in the range of 50 - 200°C, the coefficient of thermal expansion of the cured photosensitive polyamic acid ester resin - 1 was -15 ppm / K, thus indicating the rationality and feasibility of the negative CTE polyimide ester in this solution.

[0181] The above has introduced in detail the photosensitive polyamic acid ester resin, the photosensitive polyamic acid ester resin solution, and their preparation methods and applications provided by the embodiments of the present application. Specific examples are used herein to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation on the present application.

Claims

1. A photosensitive polyamic acid ester resin, characterized in that: The photosensitive polyamic acid ester resin has the structural formula , wherein R3 is independently selected from at least one of a group containing an unsaturated double bond and a hydrogen atom, and A is and , and when preparing the photosensitive polyamic acid ester resin, the and Corresponding raw material diamine and The molar ratio is 2:1; Or the A is ; Or the A is and , and when preparing the photosensitive polyamic acid ester resin, the and Corresponding raw material diamine and The molar ratio is 2:1; Or the A is and , and when preparing the photosensitive polyamic acid ester resin, the and Corresponding raw material diamine and The molar ratio is 2:1; Where * indicates the connection point on group A ； The photosensitive polyamic acid ester resin has a number average molecular weight of 2,000 to 100,000.

2. The photosensitive polyamic acid ester resin according to claim 1, characterized in that: The photosensitive polyamic acid ester resin has a number average molecular weight of 5000-30000.

3. A method for preparing a photosensitive polyamic acid ester resin, characterized in that: The following steps are involved: Providing a diamine, a polar organic solvent, a monoanhydride and a dianhydride, performing an end-capping reaction on the diamine and the monoanhydride in the polar organic solvent in an inert gas atmosphere, and then adding the dianhydride to perform a condensation reaction to obtain a polyamic acid solution; Providing a dehydrating agent, mixing the dehydrating agent with the polyamic acid solution, performing a dehydration reaction, and obtaining a polyisoimide solution; Providing a compound containing a photosensitive group, mixing the compound containing a photosensitive group with the polyisoimide solution, and performing an esterification reaction to obtain a photosensitive polyamic acid ester resin; The diamine is in a molar ratio of 2:1 and ; Or the diamine is ; Or the diamine is in a molar ratio of 2:1 and ; Or the diamine is in a molar ratio of 2:1 and .

4. The method for preparing the photosensitive polyamic acid ester resin according to claim 3, wherein: The molar ratio of the diamine, the monoanhydride, the dianhydride, the dehydrating agent, and the compound containing the photosensitive group is 1: (0.1-0.5): (0.75-0.95): (1-4.5): (2-6); and / or The solid content of the reaction solution of the polycondensation reaction, the dehydration reaction and the esterification reaction is 5% to 35%; and / or The monoanhydride includes one or more of dihydro-2,5-furandione, palmitic anhydride, glutaric anhydride, decanoic anhydride, maleic anhydride, crotonic anhydride, isobutyric anhydride, methylsuccinic anhydride, chloroacetic anhydride, itaconic anhydride, pentafluoropropionic anhydride, heptafluorobutyric anhydride, phenylsuccinic anhydride, phthalic anhydride, 2,3-dimethylmaleic anhydride, and trimellitic anhydride; and / or The dianhydride includes pyromellitic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride, 4,4'-phenylenedioxydiphthalic anhydride, hexafluoro dianhydride, 1,2-ethylenedi[1,3 -dihydro-1,3-dioxoisobenzofuran-5-carboxylate], bisphenol A dianhydride, glycerol bis(dehydrated trimellitate) acetate, 2,3,3',4'-biphenyltetracarboxylic dianhydride, p-phenylene-bis(triphenylene) dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-(acetylene-1,2-diyl) diphthalic anhydride, diphenyl sulfide dianhydride, one or more thereof; and / or The dehydrating agent includes one or more of anhydride-tertiary amine dehydrating agent, thionyl chloride-tertiary amine dehydrating agent and acetyl chloride-tertiary amine dehydrating agent; the anhydride in the anhydride-tertiary amine dehydrating agent includes one or more of acetic anhydride, phthalic anhydride and trifluoroacetic anhydride; the tertiary amine in the anhydride-tertiary amine dehydrating agent, the thionyl chloride-tertiary amine dehydrating agent and the acetyl chloride-tertiary amine dehydrating agent includes one or more of pyridine and triethylamine; and / or The photosensitive group-containing compound includes hydroxyethyl methacrylate, triethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate. , 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol trialsenate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, N-vinyl pyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide and N-hydroxymethylacrylamide. One or more of the following.

5. The method for preparing the photosensitive polyamic acid ester resin according to claim 3, characterized in that: The molar ratio of the polyamic acid and the anhydride to the tertiary amine in the dehydrating agent is 1:(4-6):(4-6).

6. A photosensitive polyamic acid ester resin glue, characterized in that: The invention comprises a photosensitive polyamic acid ester resin as claimed in claim 1 or 2 or a photosensitive polyamic acid ester resin prepared by the preparation method of the photosensitive polyamic acid ester resin as claimed in any one of claims 3 to 5, a curing accelerator and a solvent, wherein the mass ratio of the curing accelerator to the photosensitive polyamic acid ester resin is (2.5-200):

100.

7. The photosensitive polyamic acid ester resin adhesive according to claim 6, characterized in that: The curing accelerator includes at least one of a quinoline curing accelerator, an isoquinoline curing accelerator, an imidazole curing accelerator and a pyridine curing accelerator.

8. A photosensitive solder resist ink composition, characterized in that: It includes the photosensitive polyamic acid ester resin as described in claim 1 or 2, or the photosensitive polyamic acid ester resin prepared by the preparation method of the photosensitive polyamic acid ester resin as described in any one of claims 3-5, or the photosensitive polyamic acid ester resin glue as described in claim 6 or 7, and the mass fraction of the photosensitive polyamic acid ester resin in the photosensitive solder resist ink composition is 5%-60%.

9. The photosensitive solder resist ink composition according to claim 8, characterized in that: The photosensitive solder resist ink composition further comprises a photosensitive epoxy resin, a photopolymerization initiator, a photopolymerizable monomer, a thermosetting component and an inorganic filler.

10. The photosensitive solder resist ink composition according to claim 9, characterized in that: The mass ratio of the photosensitive epoxy resin to the photopolymerization initiator, the photopolymerizable monomer, the thermosetting component, and the inorganic filler is 100: (3-25): (10-30): (15-45): (10-80); and / or The molecular chain of the photosensitive epoxy resin contains photosensitive groups and alkali-soluble groups; the photosensitive groups include at least one of carbonyl groups, peroxide groups and carbon-carbon double bonds; the alkali-soluble groups include at least one of carboxyl groups, acid anhydrides and ester groups.

11. A photosensitive dry film or a photosensitive cured film, characterized in that: The invention comprises a photosensitive solder resist ink composition as described in any one of claims 8 to 10.

12. An electronic component, characterized in that: The photosensitive dry film or photosensitive cured film according to claim 11 is included.

Images