A photosensitive polyimide resin composition and its preparation method and application

Abstract

The present invention discloses a photosensitive polyimide resin composition, a preparation method and application thereof. The composition comprises: a photosensitive polyamic acid ester resin, a low temperature curing accelerator, 100 parts by weight of an alkali-soluble multifunctional photosensitive epoxy resin, 3 to 25 parts by weight of a photopolymerization initiator, 10 to 30 parts by weight of a photopolymerizable monomer, 15 to 45 parts by weight of a thermosetting component and 10 to 80 parts by weight of an inorganic filler; the mass of the photosensitive polyamic acid ester resin is 4.5% to 60% of the total mass of the photosensitive polyamic acid ester resin and the alkali-soluble multifunctional photosensitive epoxy resin; the mass of the low temperature curing accelerator is 0.5% to 3% of the mass of the photosensitive polyamic acid ester resin; the preparation method of the photosensitive polyamic acid ester resin comprises the following steps: reacting dianhydride and diamine, using monoacid anhydride as a capping agent, to obtain polyamic acid; reacting to obtain polyisoimide under the action of a dehydrating agent; and grafting a photosensitive group onto the polyisoimide to obtain a photosensitive polyamic acid ester.

Description

Technical Field

[0001] The invention relates to the technical field of photo-imaging solder resist ink compositions, and in particular to a photosensitive polyimide resin composition and a preparation method and application thereof. Background Art

[0002] Printed circuit boards (PCBs) are important electronic components that serve as electrical connections between electronic components. Usually, electronic components are soldered to the soldering area on the circuit pattern by reflow soldering and other methods, while the circuits on the non-soldering area need to be covered with a layer of photosensitive solder resist ink to avoid being covered by solder. In addition, the photosensitive solder resist ink layer as a protective layer can also prevent the corrosion and disconnection of the circuit, reduce the pollution caused by the dissolution of copper in the weld, and avoid the occurrence of cold solder joints. In addition, the coating also has excellent electrical insulation properties, which can effectively avoid faults such as short circuits between circuits.

[0003] With the development of high-frequency and high-speed communication technology, PCB substrates are increasingly developing in the direction of high precision and refinement, which also puts higher and higher requirements on the performance of the solder mask. Usually, PCB boards used for high-frequency and high-speed communication need to go through a lead-tin soldering process above 260°C, which requires the photosensitive solder mask coating to have a high heat-resistant soldering performance (high glass transition temperature and thermal decomposition temperature). For high-reliability circuit boards, PCB boards usually fail during the TCT (Temperature Cycle Test) process due to the mismatch between the solder mask coating and its CTE, such as peeling, cracking, and even falling off. In order to improve the reliability of the device, the solder mask formed after the solder mask coating is cured also needs to have a thermal expansion coefficient (CTE) that matches the PCB board to avoid failure during use.

[0004] However, the photosensitive solder mask inks that are widely used in the market are mainly photosensitive resin compositions containing photopolymerization initiators and carboxyl groups, and epoxy resins are mostly used as the main resin. Among them, epoxy resins are usually modified with acrylic acid and grafted with double bonds to have photosensitivity. The main resin and photopolymerization initiators, sensitizers, leveling agents and other additives together constitute the solder mask ink composition. Although it has good photocurability, developability, high adhesion and low curing shrinkage, due to its low glass transition temperature (generally lower than 160°C), CTE that does not match copper (generally higher than 30ppm / °C) and low elongation at break (generally lower than 3%), the heat resistance of the cured film is insufficient, it is easy to bubble or oil off during soldering, and it is easy to have failure phenomena such as circuit cracking under a wide range of temperature cycles. It cannot meet the demanding application requirements of electrical circuit boards.

[0005] In the prior art, in order to improve the mechanical and thermal properties of photosensitive solder resist ink, a common practice is to add inorganic fillers such as silica. For example, Chinese invention patent CN110895381A discloses a method of adding silica and vinyl silica to improve the heat resistance, adhesion, and acid resistance of solder resist ink. By adding reactive functional groups on the surface that can react with the resin, the bonding force between the inorganic filler and the resin is improved, cracking of the filler-resin interface is avoided, and TCT resistance is improved. However, due to the amount of inorganic filler added, this method has limitations on improving mechanical and thermal properties. Too high a proportion of inorganic filler usually reduces the leveling performance and photolithography performance of the ink, affects the elongation at break, and introduces a greater risk of interface failure.

[0006] In summary, the photosensitive solder mask ink in the prior art cannot have the properties of high glass transition temperature, high thermal stability, CTE matching with copper, etc., and cannot meet the application requirements of high-frequency, high-speed, and high-reliability PCBs. Summary of the invention

[0007] In view of the deficiencies of the prior art, the present invention provides a photosensitive polyimide resin composition that can be developed with alkali, and a preparation method and application thereof. The present invention controls the molecular weight of the photosensitive polyimide resin by the amount of the end-capping agent, thereby adjusting the developing performance of the composition. At the same time, thanks to the high glass transition temperature and high heat resistance of the synthesized photosensitive polyimide resin, the final composition has good developing performance, high glass transition temperature and high heat resistance. On the other hand, the present invention adds a curing accelerator, so that the photosensitive polyimide can be applied to the curing process commonly used in epoxy resins. At the same time, by regulating the rigidity and flexibility of the polyimide molecular chain, the CTE of the composition is reduced so that it can match the PCB.

[0008] To achieve the above object, the technical solution adopted by the present invention is:

[0009] On the one hand, the present invention provides a photosensitive polyamic acid ester resin composition, comprising: a photosensitive polyamic acid ester resin, a low-temperature curing accelerator, 100 parts by weight of an alkali-soluble multifunctional photosensitive epoxy resin, 3 to 25 parts by weight of a photopolymerization initiator, 10 to 30 parts by weight of a photopolymerizable monomer, 15 to 45 parts by weight of a thermosetting component, and 10 to 80 parts by weight of an inorganic filler; the mass of the photosensitive polyamic acid ester resin is 4.5% to 60% of the total mass of the photosensitive polyamic acid ester resin and the alkali-soluble multifunctional photosensitive epoxy resin; the mass of the low-temperature curing accelerator is 0.5% to 3% of the mass of the photosensitive polyamic acid ester resin;

[0010] The preparation method of the photosensitive polyamic acid ester resin comprises the following steps:

[0011] (1) reacting dianhydride and diamine in a polar organic solvent, and using monoanhydride as a capping agent to obtain polyamic acid (PAA);

[0012] (2) reacting the polyamic acid to form polyisoimide under the action of a dehydrating agent;

[0013] (3) The polyisoimide is subjected to an esterification reaction with a compound containing a photosensitive group, so that the photosensitive group is grafted onto the polyisoimide molecular chain to obtain the photosensitive polyamic acid ester.

[0014] As a preferred embodiment, in step (1), the diamine is a hydroxyl-containing diamine and a hydroxyl-free diamine; the molar ratio of the hydroxyl-containing diamine to the hydroxyl-free diamine is 1.9 to 5:1;

[0015] In the technical solution of the present invention, the type of the hydroxyl-free diamine is not particularly limited, and specific examples include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide. Diphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-amino 4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 9,9-bis(4-aminophenyl)fluorene, etc.; the above can be used alone or in any combination.

[0016] Preferably, the hydroxyl-containing diamine is selected from at least one of 2,5-diamino-4,6-dihydroxypyrimidine hydrochloride, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,5-diaminobenzene-1,4-diphenol dihydrochloride, 3,3-diamino-4,4'-biphenyldiol, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,4-diamino-6-hydroxymethylpteridine, 4,6-diaminoresorcinol dihydrochloride, di(5-amino-2-hydroxyphenyl)methane hydrochloride, 3,3'-dihydroxybenzidine and 2,4-diamino-6-hydroxypyrimidine;

[0017] Preferably, the monoanhydride is selected from at least one 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;

[0018] Preferably, the dianhydride is selected from pyromellitic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride, 4,4'-dioxydiphthalic anhydride, hexafluoro dianhydride , 1,2-ethylenebis[1,3-dihydro-1,3-dioxoisobenzofuran-5-carboxylate], bisphenol A dianhydride, glycerol bis(anhydrotrimellitate) acetate, 2,3,3',4'-biphenyltetracarboxylic dianhydride, p-phenylene-bis(trimellitate) dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-(acetylene-1,2-diyl) diphthalic anhydride and at least one of diphenyl sulfide dianhydride;

[0019] Preferably, the polar organic solvent is selected from at least one of N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric acid triamide and chloroform;

[0020] Preferably, the molar ratio of the dianhydride to the diamine is 0.8 to 1:1;

[0021] Preferably, the molar ratio of the end-capping agent to the diamine is 0.1 to 0.6:1;

[0022] Preferably, the reaction is carried out in an inert atmosphere;

[0023] Preferably, the reaction is carried out under stirring conditions;

[0024] Preferably, the reaction time is 5 to 24 hours;

[0025] In certain specific embodiments, the specific operation of step (1) is: in an inert atmosphere, dissolving a diamine in a polar organic solvent, adding monoanhydride and dianhydride, stirring and reacting to obtain a polyamic acid (PAA) solution.

[0026] As a preferred embodiment, in step (2), the dehydrating agent is selected from at least one of anhydride-tertiary amine dehydrating agent, thionyl chloride-tertiary amine dehydrating agent and acetyl chloride-tertiary amine dehydrating agent;

[0027] Preferably, the acid anhydride is selected from at least one of acetic anhydride, phthalic anhydride and trifluoroacetic anhydride;

[0028] Preferably, the tertiary amine is selected from at least one of pyridine and triethylamine;

[0029] Preferably, the molar ratio of the acid anhydride to the tertiary amine is 1 to 1.2:1;

[0030] Preferably, the molar ratio of the acid anhydride to the diamine in step (1) is 2 to 5:1;

[0031] Preferably, the reaction temperature is ≤10°C;

[0032] Preferably, the reaction time is 0.5 to 4 hours;

[0033] In certain specific embodiments, the specific operation of step (2) is as follows: below 10° C., diluting the polyamic acid glue obtained in step (1) with a polar organic solvent to a solid content of 10%, adding a dehydrating agent dropwise and reacting for 0.5 to 4 hours to obtain the polyisoimide solution.

[0034] As a preferred embodiment, in step (3), the photosensitive group-containing compound is selected from 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- At least one of butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol trialsenoate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, 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;

[0035] Preferably, the molar ratio of the compound containing the photosensitive group to the diamine is 1.5 to 3.5:1;

[0036] Preferably, the temperature of the esterification reaction is 45 to 80°C;

[0037] Preferably, the esterification reaction time is 12 to 36 hours;

[0038] In some specific embodiments, the specific operation of step (3) is: maintaining the temperature of the polyisoimide solution at 45 to 80° C., adding a compound containing a photosensitive group to carry out an esterification reaction, and reacting for 12 to 36 hours to obtain the photosensitive polyamic acid ester solution; slowly adding the photosensitive polyamic acid ester solution dropwise to 10 to 30 times the volume of water, stirring, filtering, and drying to constant weight to obtain the photosensitive polyamic acid ester.

[0039] As a preferred embodiment, the alkali-soluble multifunctional photosensitive epoxy resin is a multifunctional epoxy resin containing a photosensitive group and an alkali-soluble group on the molecular chain; the photosensitive group is selected from at least one of a carbonyl group, a carboxyl group, a peroxide group and a carbon-carbon double bond; the alkali-soluble group is selected from at least one of a carboxyl group, an acid anhydride group and an ester group;

[0040] Preferably, the acid value of the alkali-soluble multifunctional photosensitive epoxy resin is 40 to 200 mg KOH / g, more preferably 50 to 180 mg KOH / g;

[0041] Preferably, the number average molecular weight of the alkali-soluble multifunctional photosensitive epoxy resin is 2000 to 100000, more preferably 5000 to 30000;

[0042] In the technical solution of the present invention, the alkali-soluble multifunctional photosensitive epoxy resin is selected from commonly available difunctional and trifunctional epoxy resins, specifically phenol 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, tetraphenol ethane epoxy resin, diglycidyl phthalate resin and at least one epoxy compound of a condensate of phenols and an aromatic aldehyde having a phenolic hydroxyl group.

[0043] In certain specific embodiments, the method for preparing the alkali-soluble multifunctional photosensitive epoxy resin comprises the following steps: subjecting (a) a multifunctional epoxy compound and (b) an unsaturated monocarboxylic acid to an esterification reaction, and then reacting the obtained ester with (c) a saturated / unsaturated polyacid anhydride;

[0044] Examples of the above-mentioned (b) unsaturated monocarboxylic acid include acrylic acid, acrylic acid dimer, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, reaction products of saturated / unsaturated dibasic acid anhydrides and hydroxyl-containing (meth)acrylates, and reaction products of saturated / unsaturated dibasic acids and unsaturated monoglycidyl compounds. The above-mentioned may be used alone or in any combination.

[0045] Examples of the above-mentioned (c) saturated / unsaturated polybasic acid anhydride include: dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride; polybasic aromatic carboxylic anhydride such as trimellitic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic anhydride; and other acid anhydride derivatives such as 5-(2,5-dioxytetrahydrofuranyl)-3-methyl-3-cyclohexenyl-1,2-dicarboxylic anhydride. The above-mentioned anhydrides may be used alone or in any combination. In view of the characteristics of the cured resin film, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and succinic anhydride are preferred;

[0046] Preferably, the mass ratio of the (a) multifunctional epoxy compound, (b) unsaturated monocarboxylic acid and (c) saturated / unsaturated polyacid anhydride is 2.5-4:0.5-1.1:0.5-1.1.

[0047] In the technical solution of the present invention, the low-temperature curing accelerator is not particularly limited, and any commercial polyimide low-temperature curing agent can be used, and specific examples include 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-cyclopentadien[B] Pyridine, 4-chloroquinoline, 6-chloroquinoline, 4,5,7-trichloroquinoline, 7-chloroquinoline, 4-chloro-5,6,7,8-tetrahydroquinoline, 9-chloroacridine, 8-chloroisoquinoline, etc.; particularly preferred are 4-chloroquinoline, 6-chloroquinoline, 4,5,7-trichloroquinoline, 7-chloroquinoline, 4-chloro-5,6,7,8-tetrahydroquinoline, 9-chloroacridine and 8-chloroisoquinoline, etc. The above-mentioned compounds can be used alone or in any combination.

[0048] In the technical solution of the present invention, the type of the photopolymerization initiator is not particularly limited, and specific examples include photopolymerization initiator 907; oxime ester photopolymerization initiators, such as OXE-1, OXE-2, etc.; acylphosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.; acetophenone photopolymerization initiators, such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc.; benzoin and its alkyl ether photopolymerization initiators, such as benzoin anthraquinone-based photopolymerization initiator, such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, etc.; thioxanthone-based photopolymerization initiator, such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.; ketal-based photopolymerization initiator, such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; benzophenone-based photopolymerization initiator, such as benzophenone, 4,4'-bis-diethylaminobenzophenone, etc. The above can be used alone or in any combination, and are preferably oxime ester-based photopolymerization initiators.

[0049] As a preferred embodiment, the photopolymerizable monomer is selected from at least one of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, neopentyl glycol diethoxy / propoxy di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and polydipentaerythritol hexa(meth)acrylate.

[0050] As a preferred embodiment, the heat curing component is epoxy resin;

[0051] Preferably, the thermosetting component is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, dimethylbenzene epoxy resin, diphenol epoxy resin, alicyclic epoxy resin, soluble novolac epoxy resin, cresol soluble epoxy resin, trisphenol methane epoxy resin, N-glycidyl epoxy resin, triglycidyl isocyanurate, 2,6-dimethylbenzene dimer diglycidyl ether, alicyclic epoxy resin and xylene epoxy resin.

[0052] As a preferred embodiment, the inorganic filler is selected from at least one of barium sulfate, barium titanate, calcium oxide, talc, fumed silica, silica, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, titanium oxide, mica powder and kaolin, preferably at least one of barium sulfate, silica, aluminum oxide, aluminum hydroxide and calcium carbonate;

[0053] Preferably, the particle size of the inorganic filler is 0.001 to 100 μm, preferably 0.05 to 20 μm, and more preferably 0.05 to 3 μm; in particular, when the photosensitive polyamic acid ester resin composition needs to be further ground, the particle size of the inorganic filler may also be in other ranges, and there is no particular limitation on this;

[0054] In the technical scheme of the present invention, a solvent is also included; the type of the solvent is not particularly limited, and specific examples include ethers, such as ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, etc.; esters, such as ethyl acetate, butyl acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, etc. Glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol butyl ether acetate, etc.; ketones, such as butanone, cyclohexanone, isophorone; aromatic solvents, such as toluene, xylene, tetramethylbenzene; and petroleum solvents, such as naphtha, oxidized naphtha, solvent naphtha, etc., the above-mentioned can be used alone or in any combination.

[0055] In certain specific embodiments, the photosensitive polyamic acid ester resin composition further comprises a pigment; the pigment is selected from at least one of phthalocyanine green, phthalocyanine blue, titanium dioxide, carbon black and lithopone, and is preferably a pigment free of free halogen.

[0056] In some specific embodiments, the photosensitive polyamic acid ester resin composition further includes an additive; the additive is selected from at least one of an epoxy resin curing accelerator, a photoinitiator aid, a thixotropic tackifier, a diluent, an inhibitor, a tackifier, a defoamer, a leveling agent, a coupling agent, an antioxidant and a rust inhibitor; in some specific embodiments, the weight portion of the additive is 0.05 to 20 parts.

[0057] In another aspect, the present invention provides a method for preparing the photosensitive polyamic acid ester resin composition, comprising the following steps:

[0058] S1) dissolving a photosensitive polyamic acid ester resin in a solvent to prepare a glue solution, and adding a low-temperature curing accelerator to dissolve it;

[0059] S2) adding the remaining components into the mixed system obtained in step S1) to obtain the photosensitive polyamic acid ester resin composition after mixing.

[0060] In some specific embodiments, in step S2, the mixing is performed by stirring at a speed of 500 to 15,000 rpm for 2 to 10 hours, and then mixing is performed using a three-roll mill.

[0061] In another aspect, the present invention provides a photosensitive polyimide resin composition obtained by imidizing the photosensitive polyamic acid ester resin composition.

[0062] In another aspect, the present invention provides a photosensitive dry film, comprising a photosensitive film obtained by curing the above-mentioned photosensitive polyamic acid ester resin composition;

[0063] Preferably, the thickness of the photosensitive film is 5 to 200 μm, more preferably 15 to 60 μm, and particularly preferably 20 to 50 μm;

[0064] Preferably, the curing is carried out under heating conditions;

[0065] Preferably, the heating temperature is 50 to 120°C, more preferably 55 to 90°C;

[0066] Preferably, the heating time is 1 to 60 minutes, more preferably 2 to 30 minutes;

[0067] In some specific embodiments, the photosensitive dry film further comprises a protective film covering the surface of the photosensitive film and a carrier film carrying the photosensitive film; the thickness of the carrier film and the protective film is preferably 5-100 μm, and more preferably 10-30 μm; the types of the carrier film and the protective film can include heat-resistant and solvent-resistant polymers such as polyethylene terephthalate, polypropylene, polyethylene, and polyester;

[0068] In the technical solution of the present invention, the preparation method of the photosensitive dry film comprises the following steps: coating the photosensitive polyamic acid ester resin on a carrier film using a known coating equipment such as a reverse roll coater, a gravure roll coater, a notch wheel coater, a curtain coater, a four-sided coater, etc., and laminating a protective film after drying.

[0069] Preferably, the drying is hot air drying or far infrared / near infrared drying machine;

[0070] Preferably, the drying temperature is 50 to 120°C, more preferably 55 to 90°C;

[0071] Preferably, the drying time is 1 to 60 minutes, more preferably 2 to 30 minutes.

[0072] On the other hand, the present invention provides the use of the above-mentioned photosensitive polyamic acid ester resin composition and the photosensitive polyimide resin composition in semiconductor packaging, preferably, in the preparation of photosensitive solder resist ink, the preparation of circuit boards, and the preparation of FC-BGA substrates.

[0073] The above technical solution has the following advantages or beneficial effects:

[0074] As PCB substrates develop towards high precision and refinement, the performance requirements for solder mask layers are getting higher and higher. The glass transition temperature of the cured film of the currently common photosensitive solder mask ink coating after curing is low, and the heat resistance is insufficient. It is easy to bubble or lose oil during soldering, and cannot meet the stringent application requirements of electrical circuit boards. At the same time, in order to improve reliability, the solder mask formed by the solder mask coating after curing also needs to have a thermal expansion coefficient (CTE) that matches copper. The present invention successfully increases the glass transition temperature of the composition from below 170°C to 210°C by introducing photosensitive polyamic acid ester and low-temperature curing agent, and at the same time, the CTE of the composition is reduced from 35.5ppm / ℃ to 16.6ppm / ℃ (the CTE of copper is about 17ppm / ℃), which can well meet the needs of soldering process for the heat resistance of the cured film of solder mask ink, and can significantly reduce the risk of mismatching thermal expansion coefficients, improve the reliability of the circuit, and have good application prospects in flip chip ball grid array (FCBGA) packaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0075] Figure 1 It is a curve diagram showing the change of loss tangent value of dry films prepared from the photosensitive polyamic acid ester resin compositions in the examples of the present invention and the comparative examples with temperature. DETAILED DESCRIPTION

[0076] The following embodiments are only some embodiments of the present invention, rather than all embodiments. Therefore, the detailed description in the embodiments of the present invention provided below is not intended to limit the scope of the present invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making creative work belong to the protection scope of the present invention.

[0077] In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are commonly used in the industry. The methods in the following embodiments are all conventional methods in the art unless otherwise specified.

[0078] Preparation Example 1:

[0079] (1) Pretreatment of dianhydride and diamine: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-diaminodiphenyl ether were treated in a vacuum oven at 60°C for 4 h; bisphenol A dianhydride was treated in a vacuum oven at 160°C for 4 h;

[0080] (2) At room temperature, 21.98 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 6.00 g of 4,4'-diaminodiphenyl ether were added to a flask, and then 200 g of N-methylpyrrolidone was added to dissolve; under a nitrogen atmosphere, 4.04 g of phthalic anhydride (PA) was added, and then 100 g of N-methylpyrrolidone was added again to dilute, and after PA was completely dissolved, 40.63 g of bisphenol A dianhydride was added twice and stirred for 12 hours to obtain a polyamic acid solution;

[0081] (3) Under ice bath conditions, the polyamic acid solution was diluted with 260 g of N-methylpyrrolidone, and then 85.07 g of trifluoroacetic anhydride and 40.98 g of triethylamine were added dropwise. After the addition was completed, the reaction was continued for 1.5 h to convert the polyamic acid solution into a polyisoimide solution;

[0082] (4) heating the oil bath to 50° C., adding 26.290 g of hydroxyethyl methacrylate to carry out esterification reaction; after reacting for 24 hours, a photosensitive polyamic acid ester solution was obtained;

[0083] (5) The photosensitive polyamic acid ester solution was slowly added dropwise to 12 L of water and stirred continuously with a mechanical stirring paddle. After the addition was completed, the yellow polyamic acid ester precipitate was collected by suction filtration and dried in a vacuum oven for 36 h to constant weight to obtain a photosensitive polyamic acid ester resin-1.

[0084] Preparation Example 2

[0085] In this preparation example, the preparation method of the photosensitive polyamic acid ester resin is the same as that of Preparation Example 1, except that the diamine "21.98g 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 6.00g 4,4'-diaminodiphenyl ether" in step (2) is replaced by "15.50g 2,2-bis(3-amino-4-hydroxyphenyl)propane, 5.53g 4,4'-diaminobiphenyl", and the dianhydride "40.63g bisphenol A dianhydride" in step (2) is replaced by "23.73g 4,4'-oxydiphthalic anhydride" to prepare photosensitive polyamic acid ester resin-2.

[0086] Preparation Example 3

[0087] In this preparation example, the preparation method of the photosensitive polyamic acid ester resin is the same as that of Preparation Example 1, except that the diamine "21.98g 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 6.00g 4,4'-diaminodiphenyl ether" in step (2) is replaced by "12.97g 3,3'-dihydroxybenzidine, 5.95g 4,4'-diaminodiphenylmethane", and the dianhydride "40.63g bisphenol A dianhydride" in step (2) is replaced by "22.51g 3,3',4,4'-biphenyltetracarboxylic dianhydride" to prepare photosensitive polyamic acid ester resin-3.

[0088] Preparation Example 4

[0089] In this preparation example, the preparation method of the photosensitive polyamic acid ester resin is the same as that of Preparation Example 1, except that the diamine "21.98g 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 6.00g 4,4'-diaminodiphenyl ether" in step (2) is replaced by "2.97g 3,3'-diamino-4,4'-biphenyl diol, 6.49g 4,4'-diaminodiphenyl sulfide", and the dianhydride "40.63g bisphenol A dianhydride" in step (2) is replaced by "33.98g hexafluoro dianhydride" to prepare photosensitive polyamic acid ester resin-4.

[0090] Preparation Example 5

[0091] 210g o-cresol epoxy resin (SQPN-704M purchased from Shandong Shengquan New Materials Co., Ltd., with an epoxy equivalent of 210), 0.5g hydroquinone and 195g diethylene glycol ethyl ether acetate were added to a four-necked round-bottom flask in a N2 atmosphere, stirred and heated to 105°C and maintained at this temperature for 1 hour to dissolve all the substances; after complete dissolution, the temperature was lowered to 90°C, and then 72g acrylic acid and 1g triphenylphosphine were added dropwise, and the temperature was controlled at 95°C during the addition process. After the addition was completed, the temperature was raised to 105°C and reacted at this temperature for 12 hours; during the reaction process, the acid value of the reactant was measured until the acid value was 0.8mg KOH / g, the temperature was lowered to 60°C, and then 75g tetrahydrophthalic anhydride was added, and the reaction was carried out at 90°C for 4 to 8 hours. Finally, a light yellow alkali-soluble multifunctional photosensitive resin A with a solid content of 65% and a solid acid value of 95.2mg KOH / g was obtained.

[0092] Example 1

[0093] Dissolve the photosensitive polyamic acid ester resin-1 and the alkali-soluble multifunctional photosensitive resin A in diethylene glycol ethyl ether acetate at a solid content of 65%, mechanically stir for 2 hours, and filter to obtain a photosensitive polyamic acid ester resin glue and a photosensitive epoxy resin glue;

[0094] Take 1.54g of photosensitive polyamic acid ester glue, add 0.01g of low-temperature curing accelerator 4-chloroquinoline, and stir at room temperature for 2h; add 29.23g of photosensitive epoxy resin glue, 2.1g of photopolymerization initiator 907, 3g of polydipentaerythritol hexaacrylate, 8g of heat-curing epoxy resin YX4000, 5g of silica (particle size of 100nm~3μm), 10g of barium sulfate (particle size of 50nm~3μm), 0.8g of phthalocyanine green, 0.4g of melamine, 0.9g of dicyandiamide, and 20g of diethylene glycol ethyl ether acetate, stir at 800rpm for 2h under mechanical stirring; after mixing evenly, mix again with a three-roll mill to finally prepare a photosensitive polyamic acid ester resin composition.

[0095] In the photosensitive polyamic acid ester resin composition prepared in this embodiment, the photosensitive polyamic acid ester resin-1 accounts for 5% of the total mass of the photosensitive polyamic acid ester resin-1 and the alkali-soluble multifunctional photosensitive resin A.

[0096] Example 2

[0097] In this embodiment, the preparation method of the photosensitive polyamic acid ester resin composition is the same as that of Example 1, except that the ratio of the photosensitive polyamic acid ester resin-1 to the total mass of the photosensitive polyamic acid ester resin-1 and the alkali-soluble multifunctional photosensitive resin A is 10%, and the low-temperature curing accelerator is adjusted to benzimidazole.

[0098] Example 3

[0099] In this embodiment, the preparation method of the photosensitive polyamic acid ester resin composition is the same as that of Example 1, except that the ratio of the photosensitive polyamic acid ester resin-1 to the total mass of the photosensitive polyamic acid ester resin-1 and the alkali-soluble multifunctional photosensitive resin A is 15%, and the low-temperature curing accelerator is adjusted to isoquinoline.

[0100] Example 4

[0101] In this embodiment, the preparation method of the photosensitive polyamic acid ester resin composition is the same as that of Example 1, except that the ratio of the photosensitive polyamic acid ester resin-1 to the total mass of the photosensitive polyamic acid ester resin-1 and the alkali-soluble multifunctional photosensitive resin A is 30%, and the low-temperature curing accelerator is adjusted to imidazole.

[0102] Example 5

[0103] In this embodiment, the preparation method of the photosensitive polyamic acid ester resin composition is the same as that of Example 1, except that the ratio of the photosensitive polyamic acid ester resin-1 to the total mass of the photosensitive polyamic acid ester resin-1 and the alkali-soluble multifunctional photosensitive resin A is 50%, and the low-temperature curing accelerator is adjusted to quinoline.

[0104] Example 6

[0105] In this embodiment, the preparation method of the photosensitive polyamic acid ester resin composition is the same as that of Example 1, except that the ratio of the photosensitive polyamic acid ester resin-1 to the total mass of the photosensitive polyamic acid ester resin-1 and the alkali-soluble multifunctional photosensitive resin A is 60%, and the low-temperature curing accelerator is adjusted to 3,5-dimethylpiperidine.

[0106] Comparative Example 1

[0107] The difference between this comparative example and Example 1 is that the alkali-soluble multifunctional photosensitive resin A in the composition is adjusted to 30.77 g, and the photosensitive polyamic acid ester resin-1 is removed, so that a composition containing only the alkali-soluble multifunctional photosensitive resin A is finally obtained.

[0108] Effect Example

[0109] The compositions in the examples and comparative examples were coated or spin-coated to prepare a film with a thickness of about 25 μm, soft-baked at 80° C. for 10 minutes, exposed, developed with a 1% dilute sodium carbonate solution, and thermally cured at 170° C. for 1 hour to obtain a dry film solid. The relevant properties were then tested. The results are shown in Table 1.

[0110] Table 1

[0111]

[0112]

[0113] The glass transition temperature, Young's modulus, elongation at break and strength at break in Table 1 were measured by a dynamic thermomechanical analyzer (DMA850, manufactured by TA Corporation, USA). The heating rate during the test was 5°C / min, and the test range was from room temperature to 300°C. The test curve is shown in Figure 1 In Table 1, the glass transition temperature is represented by the abscissa temperature corresponding to the maximum value of the loss tangent value.

[0114] In Table 1, the thermal expansion coefficients in different temperature ranges were measured by a thermomechanical analyzer (TMA402, produced by NETZSCH, Germany). The heating rate during the test was 10°C / min, and the test range was from room temperature to 270°C.

[0115] The above results show that the addition of the alkali-soluble photosensitive polyimide resin prepared by the present invention can significantly increase the glass transition temperature of the solder resist ink composition, and the glass transition temperature of the composition can reach above 210°C. At the same time, the thermal expansion coefficient can be reduced to 16.61ppm / °C within a certain addition range, reaching a level matching the thermal expansion coefficient of copper (about 17ppm / °C), and the glass transition temperature can still reach above 180°C. Compared with Comparative Example 1, the thermodynamic properties of the composition prepared in Example 1 are greatly improved. The lithography performance of the embodiment is better than that of the comparative example, wherein the resolution of the lines or holes of the lithography pattern reaches 40μm<resolution<60μm, which is judged as excellent, 60μm<resolution<90μm is judged as good, and 90μm<resolution<100μm is judged as qualified. Compared with Comparative Example 1, the development time is also greatly shortened.

[0116] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A photosensitive polyamic acid ester resin composition, characterized in that: include: Photosensitive polyamic acid ester resin, low temperature curing accelerator, 100 parts by weight of alkali-soluble multifunctional photosensitive epoxy resin, 3 to 25 parts by weight of photopolymerization initiator, 10 to 30 parts by weight of photopolymerizable monomer, 15 to 45 parts by weight of thermosetting component and 10 to 80 parts by weight of inorganic filler; the mass of the photosensitive polyamic acid ester resin is 5% to 50% of the total mass of the photosensitive polyamic acid ester resin and the alkali-soluble multifunctional photosensitive epoxy resin; the mass of the low temperature curing accelerator is 0.5% to 3% of the mass of the photosensitive polyamic acid ester resin; The low temperature curing accelerator is selected from at least one of 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-cyclopenta[B]pyridine, 4-chloroquinoline, 6-chloroquinoline, 4,5,7-trichloroquinoline, 7-chloroquinoline, 4-chloro-5,6,7,8-tetrahydroquinoline, 9-chloroacridine and 8-chloroisoquinoline; The thermosetting component is an epoxy resin; the epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, dixylenol epoxy resin, diphenol epoxy resin, alicyclic epoxy resin, soluble novolac epoxy resin, cresol soluble epoxy resin, trisphenol methane epoxy resin, N-glycidyl epoxy resin, triglycidyl isocyanurate, 2,6-xylenol dimer diglycidyl ether, alicyclic epoxy resin and xylene epoxy resin; The preparation method of the photosensitive polyamic acid ester resin comprises the following steps: (1) reacting dianhydride and diamine in a polar organic solvent, and using monoanhydride as a capping agent to obtain polyamic acid; (2) Under the action of a dehydrating agent, the polyamic acid is reacted to form polyisoimide; (3) subjecting polyisoimide to an esterification reaction with a compound containing a photosensitive group, so that the photosensitive group is grafted onto the molecular chain of the polyisoimide to obtain the photosensitive polyamic acid ester; In step (1), the diamine is a hydroxyl-containing diamine and a hydroxyl-free diamine; the molar ratio of the hydroxyl-containing diamine to the hydroxyl-free diamine is 1.9-5:1; the molar ratio of the end-capping agent to the diamine is 0.1-0.6:1; The molar ratio of the compound containing the photosensitive group to the diamine is 1.5-3.5:

1.

2. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: In step (1), the hydroxyl-containing diamine is selected from at least one of 2,5-diamino-4,6-dihydroxypyrimidine hydrochloride, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,5-diaminobenzene-1,4-diphenol dihydrochloride, 3,3-diamino-4,4'-biphenyldiol, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,4-diamino-6-hydroxymethylpteridine, 4,6-diaminoresorcinol dihydrochloride, di(5-amino-2-hydroxyphenyl)methane hydrochloride, 3,3'-dihydroxybenzidine and 2,4-diamino-6-hydroxypyrimidine.

3. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: In step (1), the monoanhydride is selected from at least one 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.

4. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: In step (1), the dianhydride is selected from pyromellitic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride, 4,4'-dioxydiphthalic anhydride, hexafluoro At least one of dianhydride, 1,2-ethylenebis[1,3-dihydro-1,3-dioxoisobenzofuran-5-carboxylate], bisphenol A dianhydride, glycerol bis(anhydrotrimellitate) acetate, 2,3,3',4'-biphenyltetracarboxylic dianhydride, p-phenylene-bis(trimellitate) dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-(acetylene-1,2-diyl) diphthalic anhydride and diphenyl sulfide dianhydride.

5. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: In step (1), the polar organic solvent is selected from at least one of N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylformamide, tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethyl urea, dimethyl sulfoxide, hexamethylphosphoric acid triamide and chloroform.

6. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: In step (1), the molar ratio of the dianhydride to the diamine is 0.8-1:

1.

7. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: The reaction in step (1) is carried out in an inert atmosphere.

8. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: The reaction in step (1) is carried out under stirring conditions.

9. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that The reaction time in step (1) is 5 to 24 h.

10. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: In step (2), the dehydrating agent is selected from at least one of anhydride-tertiary amine dehydrating agent, thionyl chloride-tertiary amine dehydrating agent and acetyl chloride-tertiary amine dehydrating agent.

11. The photosensitive polyamic acid ester resin composition according to claim 10, characterized in that: The acid anhydride in the acid anhydride-tertiary amine dehydrating agent is selected from at least one of acetic anhydride, phthalic anhydride and trifluoroacetic anhydride.

12. The photosensitive polyamic acid ester resin composition according to claim 10, characterized in that: In step (2), the tertiary amine is selected from at least one of pyridine and triethylamine.

13. The photosensitive polyamic acid ester resin composition according to claim 10, characterized in that: The molar ratio of the acid anhydride to the tertiary amine in the acid anhydride-tertiary amine dehydrating agent is 1-1.2:

1.

14. The photosensitive polyamic acid ester resin composition according to claim 10, characterized in that: The molar ratio of the acid anhydride in the acid anhydride-tertiary amine dehydrating agent to the diamine in step (1) is 2-5:

1.

15. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: The reaction temperature in step (2) is ≤10°C.

16. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that In step (2), the reaction time in step (2) is 0.5 to 4 h.

17. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: In step (3), the photosensitive group-containing compound is selected from 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, At least one of 1,6-hexanediol dimethacrylate, pentaerythritol trialsenoate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, 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.

18. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: In step (3), the temperature of the esterification reaction is 45-80°C.

19. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that In step (3), the esterification reaction time is 12 to 36 hours.

20. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: The alkali-soluble multifunctional photosensitive epoxy resin is a multifunctional epoxy resin containing a photosensitive group and an alkali-soluble group on the molecular chain; the photosensitive group is selected from at least one of a carbonyl group, a carboxyl group, a peroxide group and a carbon-carbon double bond; the alkali-soluble group is selected from at least one of a carboxyl group, an acid anhydride and an ester group.

21. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that The acid value of the alkali-soluble multifunctional photosensitive epoxy resin is 40-200 mg KOH / g.

22. The photosensitive polyamic acid ester resin composition according to claim 21, characterized in that The acid value of the alkali-soluble multifunctional photosensitive epoxy resin is 50-180 mg KOH / g.

23. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: The number average molecular weight of the alkali-soluble multifunctional photosensitive epoxy resin is 2,000 to 100,000.

24. The photosensitive polyamic acid ester resin composition according to claim 23, characterized in that: The number average molecular weight of the alkali-soluble multifunctional photosensitive epoxy resin is 5000-30000.

25. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: The photopolymerizable monomer is selected from at least one of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, neopentyl glycol diethoxy / propoxy di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and polydipentaerythritol hexa(meth)acrylate.

26. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that: The inorganic filler is selected from at least one of barium sulfate, barium titanate, calcium oxide, talc, silicon dioxide, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, titanium oxide, mica powder and kaolin.

27. The photosensitive polyamic acid ester resin composition according to claim 26, characterized in that: The inorganic filler is at least one of barium sulfate, silicon dioxide, aluminum oxide, aluminum hydroxide and calcium carbonate.

28. Use of the photosensitive polyamic acid ester resin composition according to any one of claims 1 to 27 in semiconductor packaging.

29. The use according to claim 28, characterized in that Used in the preparation of photosensitive solder resist ink and circuit board preparation.

30. The use according to claim 29, characterized in that Use in preparing FC-BGA substrate.

31. The method for preparing the photosensitive polyamic acid ester resin composition according to any one of claims 1 to 27, characterized in that: The following steps are involved: S1) dissolving a photosensitive polyamic acid ester resin in a solvent to prepare a glue solution, and adding a low-temperature curing accelerator to dissolve; S2) Adding the remaining components into the mixed system obtained in step S1) to obtain the photosensitive polyamic acid ester resin composition after mixing.

32. A photosensitive polyimide resin composition, characterized in that: The invention is obtained by imidizing the photosensitive polyamic acid ester resin composition according to any one of claims 1 to 27.

33. Use of the photosensitive polyimide resin composition according to claim 32 in semiconductor packaging.

34. The use according to claim 33, characterized in that Used in the preparation of photosensitive solder resist ink and circuit board preparation.

35. The use according to claim 34, characterized in that Use in preparing FC-BGA substrate.

36. A photosensitive dry film, characterized in that: The invention comprises a photosensitive film obtained by curing the photosensitive polyamic acid ester resin composition according to any one of claims 1 to 27.

37. The photosensitive dry film according to claim 36, characterized in that The thickness of the photosensitive film is 5-200 μm.

38. The photosensitive dry film according to claim 37, characterized in that The thickness of the photosensitive film is 15-60 μm.

39. The photosensitive dry film according to claim 38, characterized in that The thickness of the photosensitive film is 20-50 μm.

40. The photosensitive dry film according to claim 36, characterized in that The curing is carried out under heating conditions.

41. The photosensitive dry film according to claim 40, characterized in that The heating temperature is 50-120°C.

42. The photosensitive dry film according to claim 41, characterized in that The heating temperature is 55-90°C.

43. The photosensitive dry film according to claim 40, characterized in that: The heating time is 1 to 60 minutes.

44. The photosensitive dry film according to claim 43, characterized in that The heating time is 2 to 30 minutes.

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