Photosensitive polyimide resin composition, and preparation method therefor and use thereof

Abstract

Provided are a photosensitive polyimide resin composition, and a preparation method therefor and the use thereof. The composition comprises a photosensitive polyamic acid ester resin, a low-temperature curing accelerator and an alkali-soluble polyfunctional photosensitive epoxy resin, wherein the preparation of the photosensitive polyamic acid ester resin comprises: reacting a dianhydride and a diamine, using a monoanhydride as an end-capping agent to obtain polyamic acid, dehydrating same to obtain a polyisoimide, and then grafting same with a photosensitive group. The composition has a high glass transition temperature, high heat resistance, and a CTE that matches copper.

Description

A photosensitive polyimide resin composition and its preparation method and application Technical Field

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

[0002] Printed circuit boards (PCBs) are important electronic components that provide electrical connections between electronic components. Typically, electronic components are soldered to the soldering areas of the circuit pattern through methods such as reflow soldering. Circuits in non-soldering areas are covered with a layer of photosensitive solder mask ink to prevent them from being covered by solder. Furthermore, the photosensitive solder mask ink layer acts as a protective layer, preventing corrosion and disconnection of circuits, reducing contamination caused by copper dissolution in welds, and preventing problems such as cold solder joints. Furthermore, the coating provides excellent electrical insulation properties, effectively preventing faults such as short circuits between circuits.

[0003] With the advancement of high-frequency, high-speed communication technology, PCB substrates are increasingly moving towards high precision and refinement, placing increasingly stringent demands on the performance of solder mask layers. PCBs used for high-frequency, high-speed communications typically undergo a lead-tin soldering process at temperatures exceeding 260°C, requiring the photosensitive solder mask to possess high heat resistance (high glass transition temperature and thermal decomposition temperature). For high-reliability circuit boards, failures such as peeling, cracking, and even shedding during the TCT (Temperature Cycle Test) process are common due to a CTE mismatch between the solder mask and the substrate. To improve device reliability, the cured solder mask must also have a thermal expansion coefficient (CTE) that matches that of the PCB to prevent failure during use.

[0004] However, the photosensitive solder mask inks that are currently widely used in the market are mainly photosensitive resin compositions containing photopolymerization initiators and carboxyl groups, with epoxy resins as the main resin. Among them, epoxy resins are usually modified with acrylic acid to graft 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 below 160°C), CTE that does not match copper (generally above 30ppm / °C) and low elongation at break (generally below 3%), the heat resistance of the cured film is insufficient, and it is easy to bubble or lose oil during soldering. It is easy to cause circuit cracking and other failure phenomena under a wide range of temperature cycles, and cannot meet the demanding application requirements of electrical circuit boards.

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

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

[0007] Summary of the Invention

[0008] In response to the shortcomings of the prior art, the present invention provides an alkaline-developable photosensitive polyimide resin composition, its preparation method, and its application. The present invention controls the molecular weight of the photosensitive polyimide resin by adjusting the amount of a capping agent, thereby adjusting the composition's development performance. Furthermore, thanks to the high glass transition temperature and high heat resistance of the synthesized photosensitive polyimide resin, the final composition exhibits excellent development performance, a high glass transition temperature, and high heat resistance. Furthermore, the present invention adds a curing accelerator, making the photosensitive polyimide suitable for use in conventional epoxy resin curing processes. By regulating the rigidity and flexibility of the polyimide molecular chain, the CTE of the composition is reduced, enabling compatibility with printed circuit boards (PCBs).

[0009] To achieve the above object, the technical solution adopted by the present invention is:

[0010] In one aspect, 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 mass of an alkali-soluble multifunctional photosensitive epoxy resin, 3 to 25 parts by mass of a photopolymerization initiator, 10 to 30 parts by mass of a photopolymerizable monomer, 15 to 45 parts by mass of a thermosetting component, and 10 to 80 parts by mass 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;

[0011] The preparation method of the photosensitive polyamic acid ester resin comprises the following steps:

[0012] (1) reacting dianhydride and diamine in a polar organic solvent, and using monoanhydride as a capping agent to obtain polyamic acid (PAA);

[0013] (2) reacting the polyamic acid to form polyisoimide under the action of a dehydrating agent;

[0014] (3) Esterification reaction is carried out between polyisoimide and 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.

[0015] 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;

[0016] 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 sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminodiphenyl sulfone, 4,4'-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-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[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.

[0017] 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, bis(5-amino-2-hydroxyphenyl)methane hydrochloride, 3,3'-dihydroxybenzidine and 2,4-diamino-6-hydroxypyrimidine;

[0018] Preferably, the monoacid anhydride 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;

[0019] Preferably, the dianhydride is selected from pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic 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-diphenylsulfone tetracarboxylic dianhydride, 4,4'-terephthalic 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 diphenyl sulfide dianhydride;

[0020] 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;

[0021] Preferably, the molar ratio of the dianhydride to the diamine is 0.8 to 1:1;

[0022] Preferably, the molar ratio of the end-capping agent to the diamine is 0.1 to 0.6:1;

[0023] Preferably, the reaction is carried out in an inert atmosphere;

[0024] Preferably, the reaction is carried out under stirring conditions;

[0025] Preferably, the reaction time is 5 to 24 hours;

[0026] In certain specific embodiments, the specific operation of step (1) is: in an inert atmosphere, dissolving diamine in a polar organic solvent, adding monoanhydride and dianhydride, stirring and reacting to obtain a polyamic acid (PAA) solution.

[0027] 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;

[0028] Preferably, the acid anhydride is selected from at least one of acetic anhydride, phthalic anhydride and trifluoroacetic anhydride;

[0029] Preferably, the tertiary amine is selected from at least one of pyridine and triethylamine;

[0030] Preferably, the molar ratio of the acid anhydride to the tertiary amine is 1 to 1.2:1;

[0031] Preferably, the molar ratio of the acid anhydride to the diamine in step (1) is 2 to 5:1;

[0032] Preferably, the reaction temperature is ≤10°C;

[0033] Preferably, the reaction time is 0.5 to 4 hours;

[0034] 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.

[0035] As a preferred embodiment, in step (3), the compound containing a photosensitive group is selected from 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- At least one of butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol trialnoate, 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;

[0036] Preferably, the molar ratio of the compound containing a photosensitive group to the diamine is 1.5 to 3.5:1;

[0037] Preferably, the temperature of the esterification reaction is 45 to 80°C;

[0038] Preferably, the esterification reaction time is 12 to 36 hours;

[0039] In certain 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.

[0040] 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;

[0041] 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;

[0042] Preferably, the number average molecular weight of the alkali-soluble multifunctional photosensitive epoxy resin is 2,000 to 100,000, more preferably 5,000 to 30,000;

[0043] 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 at least one of 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 epoxy compounds of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups;

[0044] In certain specific embodiments, the method for preparing the alkali-soluble multifunctional photosensitive epoxy resin comprises the following steps: esterifying (a) a multifunctional epoxy compound and (b) an unsaturated monocarboxylic acid, and then reacting the obtained ester with (c) a saturated / unsaturated polyacid anhydride;

[0045] 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. These can be used alone or in any combination.

[0046] Examples of the (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 anhydrides such as trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride; and other acid anhydride derivatives such as 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexenyl-1,2-dicarboxylic anhydride. The above-mentioned anhydrides may be used alone or in any combination. In view of the properties of the cured resin film, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and succinic anhydride are preferred.

[0047] 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.

[0048] 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, specifically 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, 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.

[0049] 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 benzophenone, anthraquinone-based photopolymerization initiators, such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, etc.; thioxanthone-based photopolymerization initiators, such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.; ketal-based photopolymerization initiators, such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; benzophenone-based photopolymerization initiators, such as benzophenone, 4,4'-bisdiethylaminobenzophenone, etc. The above-mentioned photopolymerization initiators can be used alone or in combination, and oxime ester-based photopolymerization initiators are preferred.

[0050] 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.

[0051] As a preferred embodiment, the heat curing component is epoxy resin;

[0052] 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-xylenol dimer diglycidyl ether, alicyclic epoxy resin and xylene epoxy resin.

[0053] 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;

[0054] 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, without particular limitation.

[0055] In the technical solution 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 solvents can be used alone or in any combination.

[0056] 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.

[0057] 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 auxiliary, 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.

[0058] In another aspect, the present invention provides a method for preparing the photosensitive polyamic acid ester resin composition, comprising the following steps:

[0059] 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;

[0060] S2) adding the remaining components into the mixed system obtained in step S1), and mixing to obtain the photosensitive polyamic acid ester resin composition.

[0061] In certain 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.

[0062] In another aspect, the present invention provides a photosensitive polyimide resin composition obtained by imidizing the photosensitive polyamic acid ester resin composition.

[0063] 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;

[0064] 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;

[0065] Preferably, the curing is carried out under heating conditions;

[0066] Preferably, the heating temperature is 50-120°C, more preferably 55-90°C;

[0067] Preferably, the heating time is 1 to 60 minutes, more preferably 2 to 30 minutes;

[0068] In certain specific embodiments, the photosensitive dry film further comprises a protective film covering the surface of the photosensitive film and a carrier film supporting the photosensitive film; the thickness of the carrier film and the protective film is preferably 5-100 μm, 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;

[0069] In the technical solution of the present invention, the preparation method of the photosensitive dry film includes the following steps: 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. to coat the photosensitive polyamic acid ester resin on a carrier film, and then laminating a protective film after drying.

[0070] Preferably, the drying is hot air drying or far infrared / near infrared drying machine;

[0071] Preferably, the drying temperature is 50-120°C, more preferably 55-90°C;

[0072] Preferably, the drying time is 1 to 60 minutes, more preferably 2 to 30 minutes.

[0073] On the other hand, the present invention provides uses of the above-mentioned photosensitive polyamic acid ester resin composition and photosensitive polyimide resin composition in semiconductor packaging, preferably, uses in preparing photosensitive solder resist inks, preparing circuit boards, and preparing FC-BGA substrates.

[0074] The above technical solution has the following advantages or beneficial effects:

[0075] As PCB substrates develop towards high precision and refinement, the performance requirements for solder mask layers are getting higher and higher. The currently common photosensitive solder mask ink coating has a low glass transition temperature and insufficient heat resistance after curing, and is prone to blistering or oil loss during soldering, which cannot meet the stringent application requirements of electrical circuit boards. At the same time, in order to improve reliability, the solder mask formed after curing by the solder mask coating 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 a low-temperature curing agent, while reducing the CTE of the composition from 35.5ppm / °C to 16.6ppm / °C (the CTE of copper is about 17ppm / °C), which can well meet the soldering process's need for heat resistance of the solder mask ink cured film, and can significantly reduce the risk of mismatched thermal expansion coefficients, improve the reliability of the circuit, and has good application prospects in flip-chip ball grid array (FCBGA) packaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] FIG1 is a graph showing the change in loss tangent of dry films prepared from the photosensitive polyamic acid ester resin compositions according to the embodiments of the present invention and the comparative examples as a function of temperature. DETAILED DESCRIPTION

[0077] The following embodiments are merely some of the embodiments of the present invention, rather than all of them. Therefore, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the claimed invention, but rather merely represents selected embodiments of the present invention. All other embodiments derived by those skilled in the art based on the embodiments of the present invention without creative effort are intended to fall within the scope of protection of the present invention.

[0078] 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, unless otherwise specified, are all conventional methods in the art.

[0079] Preparation Example 1:

[0080] (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;

[0081] (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 them. Under a nitrogen atmosphere, 4.04 g of phthalic anhydride (PA) was added, and then 100 g of N-methylpyrrolidone was added to dilute the mixture. After PA was completely dissolved, 40.63 g of bisphenol A dianhydride was added in two portions and stirred for 12 h to obtain a polyamic acid solution.

[0082] (3) In an ice bath, 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 complete, the reaction was continued for 1.5 h to convert the polyamic acid solution into a polyisoimide solution.

[0083] (4) Heat the oil bath to 50° C. and add 26.290 g of hydroxyethyl methacrylate to carry out esterification reaction; after reacting for 24 hours, a photosensitive polyamic acid ester solution is obtained;

[0084] (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 placed in a vacuum oven to dry for 36 hours to constant weight to obtain photosensitive polyamic acid ester resin-1.

[0085] Preparation Example 2

[0086] 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 "21.98g2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 6.00g4,4'-diaminodiphenyl ether" in step (2) is replaced by "15.50g2,2-bis(3-amino-4-hydroxyphenyl)propane, 5.53g4,4'-diaminobiphenyl", and the dianhydride "40.63gbisphenol A dianhydride" in step (2) is replaced by "23.73g4,4'-oxydiphthalic anhydride" to prepare photosensitive polyamic acid ester resin-2.

[0087] Preparation Example 3

[0088] 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.

[0089] Preparation Example 4

[0090] 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 hexafluorodianhydride" to prepare photosensitive polyamic acid ester resin-4.

[0091] Preparation Example 5

[0092] 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 an 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. 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, the acid value of the reactant was measured until the acid value reached 0.8mg KOH / g, the temperature was lowered to 60°C, and then 75g tetrahydrophthalic anhydride was added and reacted 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.

[0093] Example 1

[0094] Dissolving photosensitive polyamic acid ester resin-1 and alkali-soluble multifunctional photosensitive resin A in diethylene glycol ethyl ether acetate at a solid content of 65%, mechanically stirring for 2 hours, and filtering to obtain a photosensitive polyamic acid ester resin glue and a photosensitive epoxy resin glue;

[0095] 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, and stir at 800rpm for 2h under mechanical stirring; after mixing evenly, mix again on a three-roll mill to finally prepare a photosensitive polyamic acid ester resin composition.

[0096] 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.

[0097] Example 2

[0098] 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.

[0099] Example 3

[0100] 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.

[0101] Example 4

[0102] 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.

[0103] Example 5

[0104] 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.

[0105] Example 6

[0106] 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.

[0107] Comparative Example 1

[0108] The difference between this comparative example and Example 1 is that the amount of 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, thereby obtaining a composition containing only the alkali-soluble multifunctional photosensitive resin A.

[0109] Effect embodiment

[0110] The compositions of the examples and comparative examples were coated or spin-coated to prepare films having a thickness of approximately 25 μm. The films were 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. The relevant properties were then tested. The results are shown in Table 1.

[0111] Table 1

[0112] The glass transition temperature, Young's modulus, elongation at break, and strength at break reported in Table 1 were measured using a dynamic mechanical analyzer (DMA850, manufactured by TA Instruments, USA). The test was conducted at a heating rate of 5°C / min over a temperature range from room temperature to 300°C. The test curves are shown in Figure 1. In Table 1, the glass transition temperature is plotted as the temperature corresponding to the maximum loss tangent value.

[0113] In Table 1, the thermal expansion coefficients in different temperature ranges were measured by a thermomechanical analyzer (TMA402, manufactured by NETZSCH, Germany). The heating rate during the test was 10°C / min, and the test range was from room temperature to 270°C.

[0114] 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 that matches 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 lithographic pattern reaches 40μm<resolution<60μm, which is judged as excellent, 60μm<resolution<90μm is judged as good, and 90μm<resolution<100μm is judged as passing. Compared with Comparative Example 1, the development time is also greatly shortened.

[0115] 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 principles 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, Comprising: A photosensitive polyamic acid ester resin, a low-temperature curing accelerator, 100 parts by mass of an alkali-soluble polyfunctional photosensitive epoxy resin, 3 to 25 parts by mass of a photoinitiator, 10 to 30 parts by mass of a photopolymerizable monomer, 15 to 45 parts by mass of a thermosetting component, and 10 to 80 parts by mass 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 polyfunctional 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: (1) Reacting a dianhydride and a diamine in a polar organic solvent and using a monoanhydride as a capping agent to obtain polyamic acid (PAA); (2) Under the action of a dehydrating agent, reacting the polyamic acid to polyimide; (3) Performing an esterification reaction on the polyimide and a compound containing a photosensitive group to graft the photosensitive group onto the polyimide molecular chain to obtain the photosensitive polyamic acid ester.

2. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that, In step (1), the diamine is a diamine containing a hydroxyl group and a diamine without a hydroxyl group; the molar ratio of the diamine containing a hydroxyl group to the diamine without a hydroxyl group is 1.9 to 5:1; The diamine containing a hydroxyl group 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-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; The monoanhydride is selected from at least one 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; The dianhydride is selected from at least one of pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride, 4,4'-oxybisphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3,4,4-diphenylsulfonetetracarboxylic dianhydride, 4,4'-phenylenedioxybisphthalic anhydride, hexafluorodiacid anhydride, 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-bisbenzotrimellitate dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-(ethyne-1,2-diyl)diphthalic anhydride, and diphenyl sulfide dianhydride; The polar organic solvent is selected from at least one of N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylformamide, tetrahydrofuran, m-cresol, γ-butyrolactone, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoric triamide, and chloroform; The molar ratio of the dianhydride to the diamine is 0.8 - 1:1; The molar ratio of the end-capping agent to the diamine is 0.1 - 0.6:1; The reaction is carried out in an inert atmosphere; The reaction is carried out under stirring conditions; The reaction time is 5 - 24 h.

3. The photosensitive polyamic acid ester resin composition according to claim 1, wherein In step (2), the dehydrating agent is selected from at least one 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 is selected from at least one of acetic anhydride, phthalic anhydride, and trifluoroacetic anhydride; The tertiary amine is selected from at least one of pyridine and triethylamine; The molar ratio of the acid anhydride to the tertiary amine is 1 - 1.2:1; The molar ratio of the acid anhydride to the diamine in step (1) is 2 - 5:1; The reaction temperature ≤ 10°C; The reaction time is 0.5 - 4 h.

4. The photosensitive polyamic acid ester resin composition according to claim 1, wherein, In step (3), the compound containing a photosensitive group is selected from at least one 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, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylene bisacrylamide, N,N-dimethylacrylamide, and N-hydroxymethylacrylamide; The molar ratio of the compound containing a photosensitive group to the diamine is 1.5 - 3.5:1; The temperature of the esterification reaction is 45 - 80°C; The time of the esterification reaction is 12 - 36 h.

5. The photosensitive polyamic acid ester resin composition according to claim 1, wherein The alkali-soluble polyfunctional photosensitive epoxy resin is a polyfunctional epoxy resin containing a photosensitive group and an alkali-soluble group in 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; The acid value of the alkali-soluble polyfunctional photosensitive epoxy resin is 40 - 200 mg KOH / g; The number-average molecular weight of the alkali-soluble polyfunctional photosensitive epoxy resin is 2000 - 100000.

6. The photosensitive polyamic acid ester resin composition according to claim 5, wherein The acid value of the alkali-soluble polyfunctional photosensitive epoxy resin is 50 - 180 mg KOH / g; The number-average molecular weight of the alkali-soluble polyfunctional photosensitive epoxy resin is 5,000 to 30,000.

7. The photosensitive polyamic acid ester resin composition according to claim 1, wherein 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 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, and polydipentaerythritol hexa(meth)acrylate.

8. The photosensitive polyamic acid ester resin composition according to claim 1, wherein The thermosetting component is an epoxy resin; the epoxy resin is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, dimethylxylenol type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, soluble and fusible phenolic epoxy resin, cresol-soluble epoxy resin, triphenolmethane type epoxy resin, N-glycidyl type epoxy resin, isocyanuric acid triglycidyl ester, 2,6-dimethylphenol dimer diglycidyl ether, alicyclic epoxy resin, and xylene type epoxy resin.

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

10. The method for preparing the photosensitive polyamic acid ester resin composition according to claim 1, characterized in that, It includes the following steps: S1) Dissolve the photosensitive polyamic acid ester resin in a solvent to prepare a glue solution, and add a low-temperature curing accelerator to dissolve it. S2) Add the remaining components to the mixed system obtained in step S1), and after mixing, the photosensitive polyamic acid ester resin composition is obtained.

11. A photosensitive polyimide resin composition obtained by imidizing the photosensitive polyamic acid ester resin composition according to claim 1.

12. Use of the photosensitive polyimide resin composition according to claim 11 in semiconductor packaging, characterized in that, Uses in preparing photosensitive solder resist ink, preparing printed circuit boards, and preparing FC-BGA substrates.

13. A photosensitive dry film includes a photosensitive film cured from the photosensitive polyamic acid ester resin composition according to claim 1.

14. The photosensitive polyamic acid ester resin composition according to claim 13, wherein, The thickness of the photosensitive film is 5 to 200 μm; The curing is carried out under heating conditions; The temperature of the heating is 50 to 120 °C; The time of the heating is 1 to 60 minutes.

15. The photosensitive polyamic acid ester resin composition according to claim 1, characterized in that, Uses in preparing photosensitive solder resist ink, preparing printed circuit boards, and preparing FC-BGA substrates.

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