WO2025217841A1 - 一种负型感光性聚酰亚胺前体及其组合物 - Google Patents

一种负型感光性聚酰亚胺前体及其组合物

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Publication number
WO2025217841A1
WO2025217841A1 PCT/CN2024/088382 CN2024088382W WO2025217841A1 WO 2025217841 A1 WO2025217841 A1 WO 2025217841A1 CN 2024088382 W CN2024088382 W CN 2024088382W WO 2025217841 A1 WO2025217841 A1 WO 2025217841A1
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WIPO (PCT)
Prior art keywords
polyimide precursor
negative photosensitive
photosensitive polyimide
resin composition
parts
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PCT/CN2024/088382
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English (en)
French (fr)
Inventor
李�杰
单良
周选智
韦春兰
孙蓉
张国平
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Shenzhen Institute of Advanced Electronic Materials
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Shenzhen Institute of Advanced Electronic Materials
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Priority to PCT/CN2024/088382 priority Critical patent/WO2025217841A1/zh
Publication of WO2025217841A1 publication Critical patent/WO2025217841A1/zh
Pending legal-status Critical Current
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to the technical field of electronic packaging, and in particular to a negative photosensitive polyimide precursor and a composition thereof.
  • Photosensitive polyimide (PSPI) materials are widely used for surface passivation of integrated circuit chips and surface rewiring processes for wafer-level and panel-level packaging. They are essential key materials in wafer-level advanced packaging processes.
  • Traditional PSPI materials typically require a curing temperature above 350°C to achieve excellent performance.
  • Low-temperature-curing PSPI materials often suffer from insufficient imidization, resulting in poor mechanical properties and chemical resistance that fail to meet packaging process requirements.
  • poor adhesion to other materials in the packaging process, particularly electroplated copper can lead to poor device reliability.
  • advanced packaging processes such as high-density fan-out wafer-level packaging are prone to problems such as wafer warpage, stress cracking, and poor compatibility with other packaging materials at higher temperatures. Therefore, to meet the low-stress and low-warpage requirements of advanced packaging processes, the development of low-temperature-curing PSPI is urgent, particularly ultra-low-temperature-curing PSPI materials with a curing temperature below 200°C.
  • the introduction of a photo- or thermal-based base generator can reduce the activation energy of imidization of a polyimide precursor, thereby achieving polyimides with excellent performance under low-temperature processes, such as those in CN112639616A, CN112513219A, CN112639615A, and CN111919172A.
  • the molecular weight of the precursor can be controlled to ensure sufficient mobility of the molecular chain during low-temperature curing, thereby increasing the imidization rate, such as in CN108475020A.
  • CN112334833A introduces polymeric compounds containing carbamate and urea structures
  • CN110741318A and CN113168093A introduce polymeric compounds containing sulfite structures, achieving the combined properties of low-temperature curing, high imidization rate, good chemical resistance, and excellent copper surface adhesion.
  • various copper surface additives are generally introduced, such as CN102375336B and CN112799281A.
  • the polyimide prepared by the above methods usually has little effect on its performance improvement, or still has the problem of high thermal imidization temperature.
  • the present invention provides a negative-type photosensitive polyimide precursor and its composition.
  • the present invention achieves a polyimide ester molecular structure with a relatively low imidization activation energy, thereby addressing the inherent issues of low-temperature curing PSPI, such as poor reliability and chemical resistance, caused by the low imidization rate.
  • the present invention can meet the requirements of ultra-low-temperature curing processes below 200°C.
  • the present invention provides a negative photosensitive polyimide precursor having a structure as shown in formula (I):
  • Z1 is a tetravalent organic group containing an aromatic group
  • Z2 is a divalent organic group containing an aromatic group
  • R1 and R2 are each independently selected from a monovalent organic group of the structure represented by formula (II) and a monovalent alkyl group having 1 to 4 carbon atoms, and m is 2 to 150;
  • R1 in each repeating unit of formula (I) is the same or different groups
  • R2 in each repeating unit of formula (I) is the same or different groups
  • the ratio of the repeating units containing a monovalent organic group represented by formula (II) in formula (I) is 10% to 100% (quantity ratio);
  • R 3 , R 4 and R 5 are each independently selected from a hydrogen atom and an alkyl group having 1 to 3 carbon atoms.
  • the ratio of the monovalent organic group containing the structure represented by formula (II) in formula (I) is 30% to 80%, more preferably 50% to 70%.
  • the method for preparing the negative photosensitive polyimide precursor comprises the following steps:
  • Tetracarboxylic dianhydride containing a Z 1 group, alcohols containing an R 1 group, and alcohols containing an R 2 group are reacted to prepare a partially esterified tetracarboxylic acid; and then the tetracarboxylic acid is subjected to amide polycondensation with a diamine containing a Z 2 group.
  • the tetracarboxylic dianhydride containing the Z1 group is not particularly limited, and specific examples thereof include 4,4'-oxydiphthalic anhydride, pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride).
  • 4,4'-tetracarboxylic dianhydride more preferably pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, and the like.
  • the above may be used alone or in any combination.
  • the above-mentioned tetracarboxylic dianhydride and the above-mentioned alcohol are preferably reacted in a suitable reaction solvent under the action of a basic catalyst such as pyridine.
  • the mixture is stirred at 20-50° C. for 4-10 hours to obtain a partially esterified tetracarboxylic acid.
  • the solvent used in the above reaction is preferably one that completely dissolves the reaction raw materials and/or product, and more preferably one that completely dissolves the photosensitive polyimide precursor.
  • Specific examples of such solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons. These solvents may be used alone or in any combination.
  • a dehydration condensation agent is added to the solution containing the partially esterified tetracarboxylic acid obtained in the above reaction, preferably in an ice bath, and then a diamine containing a Y group or a solution thereof is added to obtain the target negative photosensitive polyimide precursor through amide polycondensation.
  • the dehydration condensation agent is not particularly limited, and specific examples thereof include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. These can be used alone or in any combination.
  • the diamine containing the Z2 group is not particularly limited, and specific examples thereof 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, 2,2'-dimethyl-4,4 '-Diaminobenzidine, 4,4'-diaminobenzidine, 3,4'-diaminobenzidine, 3,3'-diaminobenz
  • the present invention provides a negative photosensitive polyimide precursor composition comprising:
  • silane coupling agent 0.5-5 parts by mass of silane coupling agent
  • the mass fraction of the free radical polymerizable compound is 5 parts, 7 parts, 10 parts, 12 parts, 15 parts, 17 parts, 20 parts or any mass fraction therebetween.
  • the mass fraction of the photopolymerization initiator is 0.5 parts, 1 parts, 2 parts, 3 parts, 4 parts, 5 parts or any mass fraction therebetween;
  • the mass fraction of the silane coupling agent is 0.5 parts, 1 parts, 2 parts, 3 parts, 4 parts, 5 parts or any mass fraction therebetween;
  • the mass fraction of the polymerization inhibitor is 0.01 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part or any mass fraction therebetween;
  • the mass fraction of the bridging agent is 1 part, 2 parts, 3 parts, 4 parts, 5 parts or any mass fraction therebetween;
  • the weight fraction of the antioxidant is 0.5 parts, 1 parts, 2 parts, 3 parts or any weight fraction therebetween;
  • the mass fraction of the adhesion promoter is 0.1 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts or any mass fraction therebetween.
  • the free radical polymerizable compound can be exemplified by tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylic acid, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, Methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate
  • the photopolymerization initiator is selected from oxime ester compounds, benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinophenyl Any one or more of phenoxy-1-propanone, alkyl anthraquinone, benzoin alkyl ether, benzoin, alkyl benzoin and benzyl dimethyl ketal, and more preferably an oxime ester compound.
  • the silane coupling agent is not particularly limited, and is preferably any one or more silane coupling agents containing a urea bond (-NH-CO-NH-);
  • the silane coupling agent is selected from ureapropyl triethoxysilane, ⁇ -aminopropyl dimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyl methyl dimethoxysilane, ⁇ -glycidoxypropyl methyl dimethoxysilane, ⁇ -mercaptopropyl methyl dimethoxysilane, 3-methacryloxypropyl dimethoxymethyl silane, 3-methacryloxypropyl trimethoxysilane, dimethoxymethyl-3-piperidinylpropyl silane, diethoxy-3-glycidoxypropyl methyl silane, N-(3-diethyl)- Any one or more of triethoxysilyl) propyl succinic anhydride, N-[3-(triethoxysilyl)propyl] phthalamic acid, benzophenone-3,3'-bis(N-[3-[3
  • the polymerization inhibitor is not particularly limited, and is preferably any one or more of the phenolic free radical polymerization inhibitors;
  • the polymerization inhibitor is selected from any one or more of hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, preferably 2-nitroso-1-naphthol.
  • the bridging agent is an amino resin
  • the bridging agent is selected from any one or more of glycol urea resin, hydroxyethylene urea resin and melamine resin, and is particularly preferably an alkoxymethylated melamine compound, such as hexamethoxymethyl melamine.
  • the antioxidant is a hindered phenol antioxidant, preferably a compound having a hindered structure of the ortho-carbon atom of the phenolic hydroxyl group, specifically 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hydrazine, 2,2-oxalylamino-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid, 1,3,5 - one or more of tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, pen
  • the bonding aid is an azole compound
  • the bonding agent is selected from 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, phenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.
  • the bonding agent is selected from any one or more of 1H-benzotriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole.
  • the bonding agent can improve the bonding strength between the bonding agent and the metal substrate.
  • it also includes an organic solvent
  • the organic solvent is selected from any one or more of esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and amides;
  • the esters are selected from any one or more of ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkoxyacetates, alkyl 3-alkoxypropionates, alkyl 2-alkoxypropionates, methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate and ethyl 2-
  • the ethers are selected from any one or more of diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate;
  • the ketone is selected from any one or more of methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone and 3-heptanone;
  • the aromatic hydrocarbons are selected from any one or more of toluene, xylene, anisole and limonene;
  • the amides are selected from any one or more of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide.
  • the organic solvent is selected from any one of N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N-dimethylformamide and N,N-dimethylacetamide in consideration of the solubility of each component and the coating property of the resin film. Meaning one or more;
  • the amount of the organic solvent is such that the negative photosensitive polyimide precursor resin composition can obtain a uniformly dispersed glue solution; in certain specific embodiments, in order to simultaneously meet the coating thickness requirements, the amount of the organic solvent is such that the viscosity of the negative photosensitive polyimide precursor resin composition is 20 to 80 poises.
  • the present invention provides a negative photosensitive polyimide resin composition obtained by thermal imidization of the negative photosensitive polyimide precursor resin composition.
  • the thermal imidization temperature is preferably 150-400°C.
  • the negative photosensitive polyimide precursor resin composition can be cured by thermal imidization to obtain a negative photosensitive polyimide resin composition, and can also be used to prepare a patterned negative photosensitive polyimide resin composition by using a mask with a specific pattern.
  • the method for preparing the patterned negative photosensitive polyimide resin composition comprises the following steps:
  • the pattern is subjected to heat treatment to form a solidified pattern.
  • step (1) there is no specific limitation on the coating method, and spin coating, doctor blade coating, screen printing, spray coating, etc. can be used, and then drying can be performed as needed to form a negative photosensitive polyimide precursor resin layer; as a drying method, heating drying in an oven or a hot plate, vacuum drying, etc. can be used; as a substrate, a metal substrate such as Cu, a glass substrate, a semiconductor substrate, a metal oxide insulator ( TiO2 , SiO2 , etc.), a silicon nitride substrate, etc. can be used.
  • the drying is performed under the condition that the polyamic acid ester in the negative photosensitive polyimide precursor resin composition does not generate imide; specifically, the drying is performed at 70-130° C. for 1-10 minutes.
  • step (2) the negative photosensitive polyimide precursor resin layer is exposed through a mask with a specific pattern;
  • the exposure device used can be a parallel exposure machine, a projection exposure machine, a stepper exposure machine, a scanning exposure machine, etc.;
  • the light source used can be ultraviolet light, visible light or radiation, etc.
  • step (3) a developer is used to remove the unexposed portion of the negative photosensitive polyimide precursor resin layer after exposure to form a pattern;
  • the developer used is a good solvent for the negative photosensitive polyimide precursor resin layer or a mixed solvent of a good solvent and a poor solvent;
  • N-methyl-2-pyrrolidone N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, cyclopentanone, cyclohexanone, etc., which can be used alone or in any combination.
  • the poor solvent examples include toluene, xylene, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water. These poor solvents may be used alone or in any combination.
  • the ratio of the good solvent to the poor solvent is determined according to the solubility of the polymer in the resin layer.
  • the method for treating with the developer is not particularly limited, and any conventionally known developing method can be used, for example, a rotary spray method, a stirring method, an immersion method, and the like.
  • the rinsing solution is preferably a solvent different from the developer used.
  • step (4) the pattern obtained by the development is heated to imidize the polyamic acid ester to obtain the corresponding cured polyimide.
  • the temperature of the heat treatment is 150 to 400° C. Within this reaction temperature range, the cross-linking reaction or the dehydration ring-closure reaction can proceed sufficiently.
  • the present invention provides use of the negative photosensitive polyimide precursor or the negative photosensitive polyimide precursor resin composition in electronic packaging.
  • the negative photosensitive polyimide precursor resin composition of the present invention can be used to prepare semiconductor devices through the above method, and can also be used for applications such as interlayer insulation of multilayer circuits and cover coating of flexible copper clad laminates.
  • the present invention provides a special polyimide precursor molecule, polyamic acid ester.
  • This invention introduces a tert-butyl group into the alcohol compound used to esterify the polyimide precursor molecule, achieving an imidization temperature below 200°C.
  • the present invention limits the number of unsaturated groups on the side chains of the polyimide precursor molecule to a certain range, reducing the residual components other than the polyimide main body during the low-temperature curing process, further improving chemical resistance and device reliability.
  • the room temperature in the following examples is 20-30°C.
  • ODPA 4,4'-oxydiphthalic anhydride
  • GBL ⁇ -butyrolactone
  • DCC dicyclohexylcarbodiimide
  • ODA 4,4'-diaminodiphenyl ether
  • the side chain substituent in the structural formula i.e., the proportion of the substituent corresponding to hydroxy tert-butyl methacrylate, is 100%.
  • the molecular weight of the polymer was measured using an ultra-high performance polymer chromatography (APC) instrument and was as follows: M w is 28200, and PDI is 1.93.
  • Polyimide precursor P4 was obtained by replacing the 106 g hydroxy-tert-butyl methacrylate component in Synthesis Example 1 with 84.5 g hydroxy-tert-butyl methacrylate and 10 g tert-butyl alcohol. The remaining components and operating procedures remained the same as those in Synthesis Example 1. In this synthesis example, the ratio of the substituents corresponding to hydroxy-tert-butyl methacrylate and the substituents corresponding to tert-butyl alcohol in the side chain substituents of the polyimide precursor was 8:2. APC analysis revealed a molecular weight of 28030 and a PDI of 1.95.
  • Polyimide precursor P5 was obtained by replacing the 106 g hydroxy-tert-butyl methacrylate component in Synthesis Example 1 with 32 g hydroxy-tert-butyl methacrylate and 35 g tert-butyl alcohol. The remaining components and operating procedures remained the same as those in Synthesis Example 1. In this synthesis example, the ratio of the substituents corresponding to hydroxy-tert-butyl methacrylate and the substituents corresponding to tert-butyl alcohol in the side chain substituents of the polyimide precursor was 3:7. APC analysis revealed a molecular weight of 27410 and a PDI of 1.80.
  • polyimide precursor P6 71 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (mTB) was used in place of the 67 g of ODA component in Synthesis Example 1. The remaining components and operating procedures remained the same as in Synthesis Example 1 to obtain polyimide precursor P6.
  • the structural formula of the main repeating unit in polyimide precursor P6 prepared in this synthesis example is shown below.
  • the proportion of the side chain substituent, i.e., the substituent corresponding to hydroxy-tert-butyl methacrylate, in the structural formula is 100%.
  • APC analysis revealed a molecular weight of 27,230 and a PDI of 1.75.
  • Polyimide precursor P9 was obtained by replacing 106 g of hydroxy-tert-butyl methacrylate in Synthesis Example 1 with 43.5 g of hydroxyethyl methacrylate and 15.4 g of ethanol. The remaining components and operating procedures remained the same as those in Synthesis Example 1. In this synthesis example, the ratio of the substituents corresponding to hydroxyethyl methacrylate and ethanol in the side chain substituents of the polyimide precursor was 5:5. APC analysis revealed a molecular weight of 26,980 and a PDI of 1.93.
  • Alkyl coupling agent ureapropyl triethoxysilane (Si-1), 0.04g polymerization inhibitor 2-nitroso-1-naphthol, 0.2g 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid (AO-1), and 0.04g benzotriazole (MA-1) were shaken and dissolved on a shaker for 24h, and then NMP was further added to adjust the viscosity to about 30 poise. After secondary filtration, a negative photosensitive polyimide precursor resin composition was prepared.
  • a negative photosensitive polyimide precursor resin composition was prepared by spin coating on an 8-inch silicon wafer using a spin coater and pre-baked on a hot plate at 100°C for 240 seconds to form a coating film approximately 10 ⁇ m thick.
  • the coating film was irradiated with an energy of 400 mJ/ cm2 using an i-line projection stepper using a mask with a test pattern.
  • the coating film was then spray-developed using a developer using cyclopentanone as a developer and rinsed with propylene glycol methyl ether acetate to obtain a photoresist pattern.
  • the film was then heated for 2 hours in a nitrogen atmosphere using a temperature-programmed curing oven under the curing conditions listed in Table 2 to obtain a cured film approximately 10 ⁇ m thick with a photoresist pattern.
  • Example 1 20 g of polyimide precursor P1 in Example 1 was replaced by 20 g of polyimide precursor P2, and the remaining components and operation procedures remained the same as those in Example 1.
  • Example 1 20 g of polyimide precursor P1 in Example 1 was replaced by 20 g of polyimide precursor P3, and the remaining components and operation procedures remained the same as those in Example 1.
  • Example 1 20 g of polyimide precursor P1 in Example 1 was replaced by 20 g of polyimide precursor P4, and the remaining components and operation procedures remained the same as those in Example 1.
  • Example 1 20 g of polyimide precursor P1 in Example 1 was replaced by 20 g of polyimide precursor P5, and the remaining components and operation procedures remained the same as those in Example 1.
  • Example 1 20 g of polyimide precursor P1 in Example 1 was replaced by 20 g of polyimide precursor P6, and the remaining components and operation procedures remained the same as those in Example 1.
  • Example 1 20 g of polyimide precursor P1 in Example 1 was replaced by 20 g of polyimide precursor P7, and the remaining components and operation procedures remained the same as those in Example 1.
  • Example 1 The 20 g of polyimide precursor P1 in Example 1 was replaced by a mixture of 10 g of polyimide precursor P1 and 10 g of polyimide precursor P6. The other components and operation procedures remained the same as those in Example 1.
  • Example 1 The 20 g of polyimide precursor P1 in Example 1 was replaced by a mixture of 10 g of polyimide precursor P1 and 10 g of polyimide precursor P7. The remaining components and operation procedures remained the same as those in Example 1.
  • Example 1 The amount of TC-1 in Example 1 was increased from 0.4 g to 0.8 g, and the curing process was changed to 180° C./2 h. The other components and operating procedures remained the same as in Example 1.
  • Example 2 The amount of TC-1 in Example 2 was increased from 0.4 g to 0.8 g, and the curing process was changed to 180° C./2 h. The other components and operating procedures remained the same as in Example 2.
  • Example 3 The amount of TC-1 in Example 3 was increased from 0.4 g to 0.8 g, and the curing process was changed to 180° C./2 h. The other components and operating procedures remained the same as in Example 3.
  • Example 4 The amount of TC-1 in Example 4 was increased from 0.4 g to 0.8 g, and the curing process was changed to 180° C./2 h. The other components and operating procedures remained the same as in Example 4.
  • Example 1 20 g of polyimide precursor P1 in Example 1 was replaced by 20 g of polyimide precursor P8, and the remaining components and operation procedures remained the same as in Example 1.
  • Example 1 20 g of polyimide precursor P1 in Example 1 was replaced by 20 g of polyimide precursor P9, and the remaining components and operation procedures remained the same as those in Example 1.
  • Example 10 20 g of polyimide precursor P1 in Example 10 was replaced by 20 g of polyimide precursor P9, and the remaining components and operating procedures remained the same as in Example 10.
  • the weight-average molecular weight Mw and polymer dispersity index (PDI) of the polymer involved in the present invention are obtained by testing with an ultra-high performance polymer chromatography analyzer.
  • the cured film obtained above was sliced and analyzed using a focused ion beam electron microscope to evaluate its photolithography accuracy and cross-sectional morphology profile, and then the photolithography performance of the negative photosensitive resin composition was evaluated: a photolithography line accuracy of less than 10 ⁇ m was rated as "excellent”, a photolithography line accuracy of 10-20 ⁇ m was rated as "good”, a photolithography line accuracy of 20-50 ⁇ m was rated as “acceptable”, and a photolithography line accuracy greater than 50 ⁇ m was rated as "poor”.
  • the prepared cured film was immersed in a 1% hydrofluoric acid aqueous solution for 10 minutes, then peeled off to obtain a complete cured film. After drying in an oven at 150°C, the film was immersed in a dimethyl sulfoxide solution containing 2.38% tetramethylammonium hydroxide at 50°C for 60 minutes.
  • the chemical resistance of the cured film was evaluated based on its weight loss before and after chemical resistance treatment: a weight loss of less than 5% was rated as "excellent”, a weight loss between 5% and 15% was rated as "good”, a weight loss between 15% and 25% was rated as "acceptable”, and a weight loss greater than 25% was rated as "poor”.
  • a cured film was prepared on a copper substrate using a mask with a specific pattern and the above method 3.
  • the film was placed in a high-temperature and high-humidity accelerated aging test chamber.
  • the test conditions were 130°C and 85% RH for 264 hours.
  • the adhesion of the cured film on the copper surface was evaluated using the 100-grid method: if 100% of the grid did not fall off, it was rated as "excellent”, if the grid shedding rate was within 5%, it was rated as "good”, if the grid shedding rate was within 5%-15%, it was rated as "acceptable”, and if the grid shedding rate was greater than 15%, it was rated as "poor”.
  • the negative photosensitive polyimide precursor prepared by the present invention can obtain a higher imidization rate by thermal imidization at a temperature below 200°C. Moreover, the performance of the cured film prepared at a thermal imidization temperature of 180°C does not decrease significantly compared to that at a thermal imidization temperature of 200°C. Among them, the embodiment with a higher proportion of unsaturated groups on the side chain of the polyimide precursor has the best comprehensive performance after imidization.
  • the embodiment using 4,4'-oxydiphthalic anhydride (ODPA) and 4,4'-diaminodiphenyl ether (ODA) as dianhydride and diamine obtained the best performance.

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Abstract

本发明公开了一种负型感光性聚酰亚胺前体，具有如下所示结构（I）：Z1为4价含有芳香基的有机基团，Z2为2价含有芳香基的有机基团，R1和R2分别独立地选自式(II)所示有机基团、碳原子数1～4的1价烷基中的任意一种，m为2～150；式(I)中含有式(II)所示结构的重复单元的比例为10％～100％；式(II)中，R3、R4和R5分别独立地选自氢原子、碳原子数1～3的烷基。本发明提供的聚酰亚胺前体可实现200℃以下的酰亚胺化温度，从源头上解决酰亚胺化率低带来的可靠性差、耐化学腐蚀性差等问题。

Description

一种负型感光性聚酰亚胺前体及其组合物 技术领域
本发明涉及电子封装技术领域，尤其涉及一种负型感光性聚酰亚胺前体及其组合物。
背景技术
光敏性聚酰亚胺(PSPI)材料广泛用于集成电路芯片表面钝化以及晶圆级封装、面板级封装的表面再布线工艺，是晶圆级先进封装制程中不可或缺的关键材料。传统的PSPI材料通常需要350℃以上的固化温度才能获得优异性能，低温固化的PSPI材料往往会因为亚胺化程度不足导致力学性能较差、耐化学腐蚀性不佳不能满足封装制程要求，此外还会因为与封装制程中其它材料特别是电镀铜的结合力较差导致器件可靠性不佳。然而，高密度扇出型晶圆级封装等先进封装制程在较高的温度下，容易发生晶圆翘曲、应力开裂、其它封装材料适配性不佳等问题。因此，为了满足先进封装工艺对晶圆低应力、低翘曲的需求，开发出低温固化的的PSPI迫在眉睫，尤其是固化温度在200℃以下的超低温固化PSPI材料。
通常而言，引入光/热产碱剂能够降低聚酰亚胺前体酰亚胺化的活化能进而实现低温制程下得到具有优异性能的聚酰亚胺，比如CN112639616A、CN112513219A、CN112639615A、CN111919172A；亦或者控制前体的分子量，使低温固化时分子链获得足够高的运动能力从而提高亚胺化率，比如CN108475020A。再如CN112334833A通过引入含氨基甲酸酯和脲键结构的聚合性化合物，CN110741318A、CN113168093A引入含亚硫酸酯结构的聚合性化合物，来获得低温固化高亚胺化率、耐化性良好、铜面结合力优异的综合性能。此外，为了提高再布线层与铜面的结合力，一般会引入各种铜面助剂，比如CN102375336B、CN112799281A。但上述方法制备的聚酰亚胺通常对其性能提升的效果不明显，或者依然存在热亚胺化温度较高的问题。
发明内容
为了提高PSPI材料的前体树脂光敏性聚酰亚胺酸酯在低温固化制程下的酰亚胺化率，本发明提供了一种负型感光性聚酰亚胺前体及其组合物。本发明通过分子设计得到了酰亚胺化活化能比较低的聚酰亚胺酸酯的分子结构，从而在源头上解决低温固化PSPI由于低酰亚胺化率带来的可靠性差、耐化学腐蚀性差等问题，并可进一步满足200℃以下的超低温固化制程需求。
为实现上述目的，本发明采取的技术方案为：
一方面，本发明提供一种负型感光性聚酰亚胺前体，所述负型感光性聚酰亚胺前体具有如式(I)所示的结构：
式(I)中，Z1为4价含有芳香基的有机基团，Z2为2价含有芳香基的有机基团，R1和R2分别独立地选自式(II)所示结构的1价有机基团、碳原子数1～4的1价烷基中的任意一种，m为2～150；
式(I)的每个重复单元中的R1为相同或不同的基团，式(I)的每个重复单元中的R2为相同或不同的基团，且式(I)中含有式(II)所示结构的1价有机基团的重复单元的比例为10％～100％(数量比例)；
式(II)中，R3、R4和R5分别独立地选自氢原子、碳原子数1～3的烷基。
作为优选地实施方式，式(I)中含有式(II)所示结构的1价有机基团的比例为30％～80％，更优选为50％～70％。
作为优选地实施方式，所述负型感光性聚酰亚胺前体的制备方法包括以下步骤：
将包含Z1基团的四羧酸二酐、含有R1基团的醇类和含有R2基团的醇类反应，制备部分酯化的四羧酸；然后将其与包含Z2基团的二胺进行酰胺缩聚。
作为包含Z1基团的四羧酸二酐没有特别地限制，具体可列举出4,4'-氧双邻苯二甲酸酐、均苯四甲酸酐、二苯醚-3,3',4,4'-四羧酸二酐、二苯甲酮-3,3',4,4'-四羧酸二酐、联苯-3,3',4,4'-四羧酸二酐、二苯基砜-3,3',4,4'-四羧酸二酐、二苯基甲烷-3,3',4,4'-四羧酸二酐、2,2-双(3,4-邻苯二甲酸酐)丙烷、2,2-双(3,4-邻苯二甲酸酐)-1,1,1,3,3,3-六氟丙烷等，优选4,4'-氧双邻苯二甲酸酐、均苯四甲酸酐、二苯醚-3,3',4,4'-四羧酸二酐、二苯甲酮-3,3',4,4'-四羧酸二酐、联苯-3,3',4,4'-四羧酸二酐，更优选为均苯四甲酸酐、二苯醚-3,3',4,4'-四羧酸二酐、联苯-3,3',4,4'-四羧酸二酐等，以上可以单独使用，也可以任意混合使用。
将上述四羧酸二酐和上述醇类优选在吡啶等碱性催化剂的作用下，在适当的反应溶剂中 20～50℃搅拌反应4～10小时，即可得到部分酯化的四羧酸。
作为上述反应中的溶剂，优选为能使反应原料和/或产物完全溶解的溶剂，更优选为能使感光性聚酰亚胺前体也完全溶解的溶剂。作为这样的溶剂，具体可列举出N-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜、四甲基脲、酮类、酯类、内酯类、醚类、卤化烃类、烃类等，以上可以单独使用，也可以任意混合使用。
将上述反应中得到的包含部分酯化的四羧酸的溶液，优选在冰浴条件下，加入脱水缩合剂后，再加入包含Y基团的二胺或其溶液，通过酰胺缩聚即得到目标负型感光性聚酰亚胺前体。
作为上述脱水缩合剂，没有特别地限制，具体可列举出二环己基碳化二亚胺、1-乙氧基羰基-2-乙氧基-1,2-二氢喹啉、1,1-羰基二氧基-二-1,2,3-苯并三唑、N,N'-二琥珀酰亚胺基碳酸酯等，以上可以单独使用，也可以任意混合使用。
作为包含Z2基团的二胺，没有特别地限制，具体可列举出对苯二胺、间苯二胺、4,4'-二氨基二苯醚、3,4'-二氨基二苯醚、3,3'-二氨基二苯醚、4,4'-二氨基二苯基硫醚、3,4'-二氨基二苯基硫醚、3,3'-二氨基二苯基硫醚、4,4'-二氨基二苯基砜、3,4'-二氨基二苯基砜、3,3'-二氨基二苯基砜、2,2'-二甲基-4,4'-二氨基联苯、4,4'-二氨基联苯、3,4'-二氨基联苯、3,3'-二氨基联苯、4,4'-二氨基二苯甲酮、3,4'-二氨基二苯甲酮、3,3'-二氨基二苯甲酮、4,4'-二氨基二苯基甲烷、3,4'-二氨基二苯基甲烷、3,3'-二氨基二苯基甲烷、1,4-双(4-氨基苯氧基)苯、1,3-双(4-氨基苯氧基)苯、1,3-双(3-氨基苯氧基)苯、双[4-(4-氨基苯氧基)苯基]砜、双[4-(3-氨基苯氧基)苯基]砜、4,4-双(4-氨基苯氧基)联苯、4,4-双(3-氨基苯氧基)联苯、双[4-(4-氨基苯氧基)苯基]醚、双[4-(3-氨基苯氧基)苯基]醚、1,4-双(4-氨基苯基)苯、1,3-双(4-氨基苯基)苯、9,10-双(4-氨基苯基)蒽、2,2-双(4-氨基苯基)丙烷、2,2-双(4-氨基苯基)六氟丙烷、2,2-双[4-(4-氨基苯氧基)苯基)丙烷、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷、1,4-双(3-氨基丙基二甲基甲硅烷基)苯、3,3'-二甲基-4,4'-二氨基二苯砜、9,9-双(4-氨基苯基)芴等，以上可以单独使用，也可以任意混合使用。
又一方面，本发明提供一种负型感光性聚酰亚胺前体组合物，包括：
100质量份的上述负型感光性聚酰亚胺前体；
5～20质量份自由基聚合性化合物；
0.5～5质量份光聚合引发剂；
0.5～5质量份硅烷偶联剂；
0.01～1质量份聚合抑制剂；
1～5质量份架桥剂；
0.5～3质量份抗氧化剂；
0.1～2质量份粘接助剂。
在某些具体的实施方式中，基于100质量份所述负型感光性聚酰亚胺前体，所述自由基聚合性化合物的质量份数为5份、7份、10份、12份、15份、17份、20份或它们之间的任意质量份数。
在某些具体的实施方式中，基于100质量份所述负型感光性聚酰亚胺前体，所述光聚合引发剂的质量份数为0.5份、1份、2份、3份、4份、5份或它们之间的任意质量份数；
在某些具体的实施方式中，基于100质量份所述负型感光性聚酰亚胺前体，所述硅烷偶联剂的质量份数为0.5份、1份、2份、3份、4份、5份或它们之间的任意质量份数；
在某些具体的实施方式中，基于100质量份所述负型感光性聚酰亚胺前体，所述聚合抑制剂的质量份数为0.01份、0.1份、0.2份、0.3份、0.4份、0.5份、0.6份、0.7份、0.8份、0.9份、1份或它们之间的任意质量份数；
在某些具体的实施方式中，基于100质量份所述负型感光性聚酰亚胺前体，所述架桥剂的质量份数为1份、2份、3份、4份、5份或它们之间的任意质量份数；
在某些具体的实施方式中，基于100质量份所述负型感光性聚酰亚胺前体，所述抗氧化剂的质量份数为0.5份、1份、2份、3份或它们之间的任意质量份数；
在某些具体的实施方式中，基于100质量份所述负型感光性聚酰亚胺前体，所述粘接助剂的质量份数为0.1份、0.5份、1份、1.5份、2份或它们之间的任意质量份数。
在本发明的技术方案中，所述自由基聚合性化合物可列举出二甲基丙烯酸三缩四乙二醇酯、二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸、三羟甲基丙烷二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四甲基丙烯酸酯、苯乙烯、二乙烯基苯、4-乙烯基甲苯、4-乙烯基吡啶、N-乙烯基吡咯烷酮、甲基丙烯酸2-羟基乙酯、丙烯酸2-羟基乙酯、1,3-丙烯酰氧基-2-羟基丙烷、1,3-甲基丙烯酰氧基-2-羟基丙烷、亚甲基双丙烯酰胺、N,N-二甲基丙烯酰胺、N-羟甲基丙烯酰胺、三烯丙基异氰脲酸酯等，以上列举可以单独使用也可以任意组合使用。
作为优选地实施方式，所述光聚合引发剂选自肟酯化合物、二苯甲酮、N,N'-四甲基-4,4'-二氨基二苯甲酮、2-苄基-2-二甲基氨基-1-(4-吗啉苯基)丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗 啉基-1-丙酮、烷基蒽醌、苯偶姻烷基醚、苯偶姻、烷基苯偶姻和苯偶酰二甲基缩酮中的任意一种或多种，进一步优选为肟酯化合物。
在本发明的技术方案中，所述硅烷偶联剂没有特别地限制，优选为含有脲键(-NH-CO-NH-)的硅烷偶联剂中的任意一种或多种；
具体地，所述硅烷偶联剂选自脲丙基三乙氧基硅烷、γ-氨基丙基二甲氧基硅烷、N-(β-氨基乙基)-γ-氨基丙基甲基二甲氧基硅烷、γ-环氧丙氧基丙基甲基二甲氧基硅烷、γ-巯基丙基甲基二甲氧基硅烷、3-甲基丙烯酰氧基丙基二甲氧基甲基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、二甲氧基甲基-3-哌啶基丙基硅烷、二乙氧基-3-环氧丙氧基丙基甲基硅烷、N-(3-二乙氧基甲基甲硅烷基丙基)琥珀酰亚胺、N-[3-(三乙氧基甲硅烷基)丙基]邻苯二甲酰胺酸、二苯甲酮-3,3'-双(N-[3-三乙氧基甲硅烷基]丙基酰胺)-4,4'-二羧酸、苯-1,4-双(N-[3-三乙氧基甲硅烷基]丙基酰胺)-2,5-二羧酸、3-(三乙氧基甲硅烷基)丙基琥珀酸酐和N-苯基氨基丙基三甲氧基硅烷中的任意一种或多种，优选为脲丙基三乙氧基硅烷。
在本发明的技术方案中，所述聚合抑制剂没有特别地限制，优选为酚类自由基聚合抑制剂中的任意一种或者几种；
具体地，所述聚合抑制剂选自氢醌、N-亚硝基二苯基胺、对叔丁基儿茶酚、吩噻嗪、N-苯基萘基胺、乙二胺四乙酸、1,2-环己烷二胺四乙酸、乙二醇醚二胺四乙酸、2,6-二叔丁基对甲基苯酚、5-亚硝基-8-羟基喹啉、1-亚硝基-2-萘酚、2-亚硝基-1-萘酚、2-亚硝基-5-(N-乙基-N-磺基丙基氨基)苯酚、N-亚硝基-N-苯基羟基胺铵盐和N-亚硝基-N(1-萘基)羟基胺铵盐中的任意一种或多种，优选为2-亚硝基-1-萘酚。
作为优选地实施方式，所述架桥剂为氨基树脂；
在本发明的技术方案中，所述架桥剂选自二醇脲树脂、羟基亚乙基脲树脂和三聚氰胺树脂中的任意一种或多种，特别优选为烷氧基甲基化三聚氰胺化合物，例如六甲氧基甲基三聚氰胺。
作为优选地实施方式，所述抗氧化剂为受阻酚类抗氧化剂，优选为酚羟基的邻位碳原子具有受阻结构的化合物，具体可列举出1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、双(3，5-二叔丁基-4-羟基-苯丙酰)肼、2,2-草酰胺基-双[乙基-3-(3，5-二叔丁基-4-羟基苯基)]丙酸酯、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、β-(3,5-二叔丁基-4-羟基苯基)丙酸十八碳醇酯、N,N’-六亚甲基双(3，5-二叔丁基-4-羟基苯丙酰胺)、2,2'-亚硫基乙二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]等的一种或多种， 特别优选自1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸等，以上列举可以单独使用，也可以任意混合使用。
作为优选地实施方式，所述粘接助剂为唑类化合物；
优选地，所述粘接助剂选自1H-三唑、5-甲基-1H-三唑、5-乙基-1H-三唑、4,5-二甲基-1H-三唑、5-苯基-1H-三唑、苯基三唑、1,5-二甲基三唑、4,5-二乙基-1H-三唑、1H-苯并三唑、羟基苯基苯并三唑、甲苯基三唑、5-甲基-1H-苯并三唑、4-甲基-1H-苯并三唑、1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-氨基-1H-四唑、1-甲基-1H-四唑等。特别优选选自1H-苯并三唑、5-甲基-1H-苯并三唑和4-甲基-1H-苯并三唑中的任意一种或多种；在本发明的技术方案中，所述粘接助剂可以提高与金属基底界面间的粘接强度。
作为优选地实施方式，还包括有机溶剂；
优选地，所述有机溶剂选自酯类、醚类、酮类、芳香族烃类、亚砜类和酰胺类中的任意一种或多种；
优选地，所述酯类选自乙酸乙酯、乙酸正丁酯、乙酸异丁酯、甲酸戊酯、乙酸异戊酯、丙酸丁酯、丁酸异丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁内酯、ε-己内酯、δ-戊内酯、烷氧基乙酸烷基酯、3-烷氧基丙酸烷基酯、2-烷氧基丙酸烷基酯、2-烷氧基-2-甲基丙酸甲酯、2-烷氧基-2-甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙酰乙酸甲酯、乙酰乙酸乙酯、2-氧代丁酸甲酯和2-氧代丁酸乙酯中的任意一种或多种；
优选地，所述醚类选自二乙二醇二甲醚、四氢呋喃、乙二醇单甲醚、乙二醇单乙醚、甲基溶纤剂乙酸酯、乙基溶纤剂乙酸酯、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、丙二醇单甲醚、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯和丙二醇单丙醚乙酸酯中的任意一种或多种；
优选地，所述酮类选自甲基乙基酮、环己酮、环戊酮，2-庚酮和3-庚酮中的任意一种或多种；
优选地，所述芳香族烃类选自甲苯、二甲苯、苯甲醚和柠檬烯中的任意一种或多种；
优选地，所述酰胺类选自N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N,N-二甲基乙酰胺和N,N-二甲基甲酰胺中的任意一种或多种。
优选地，从各成分的溶解性和树脂膜涂布性考虑，所述有机溶剂选自N-甲基-2-吡咯烷酮、γ-丁内酯、乳酸乙酯、丙二醇单甲醚乙酸酯、N,N-二甲基甲酰胺和N,N-二甲基乙酰胺中的任 意一种或多种；
在本发明的技术方案中，所述有机溶剂的用量以使所述负型感光性聚酰亚胺前体树脂组合物能够得到分散均匀的胶液为准；在某些具体的实施方式中，为了同时满足涂胶厚度需求，所述有机溶剂的用量以使所述负型感光性聚酰亚胺前体树脂组合物的粘度为20～80泊为准。
又一方面，本发明提供一种负型感光性聚酰亚胺树脂组合物，由上述负型感光性聚酰亚胺前体树脂组合物热亚胺化得到，所述热亚胺化的温度优选为150～400℃。
在本发明的技术方案中，上述负型感光性聚酰亚胺前体树脂组合物可以通过热亚胺化得到固化的负型感光性聚酰亚胺树脂组合物，还可以通过特定图案的掩模版制备图案化的负型感光性聚酰亚胺树脂组合物。
其中，图案化的负型感光性聚酰亚胺树脂组合物的制备方法包括如下步骤：
(1)将上述负型感光性聚酰亚胺前体树脂组合物涂覆于基板上，在该基板上形成负型感光性聚酰亚胺前体树脂层；
(2)对基板上的负型感光性聚酰亚胺前体树脂层进行曝光；
(3)对曝光后的负型感光性聚酰亚胺前体树脂层进行显影形成图案；
(4)对图案进行加热处理形成固化图案。
步骤(1)中，作为涂覆方式没有具体地限制，可以采用旋涂、刮涂、丝网印刷、喷涂等方式，然后根据需要使其干燥形成负型感光性聚酰亚胺前体树脂层；作为干燥方法，可以使用烘箱或加热板的加热干燥、真空干燥等方式；作为基板，可以使用Cu等金属基板、玻璃基板、半导体基板、金属氧化物绝缘体(TiO2、SiO2等)、氮化硅基板等。
优选地，所述干燥在负型感光性聚酰亚胺前体树脂组合物中的聚酰胺酸酯不发生酰亚胺的条件下进行；具体为70～130℃下干燥1～10分钟。
步骤(2)中，隔着特定图案的掩模版对上述负型感光性聚酰亚胺前体树脂层进行曝光处理；使用的曝光装置可以为平行曝光机、投影曝光机、步进曝光机、扫描曝光机等；使用的光源可以为紫外光、可见光或放射线等。
步骤(3)中，使用显影液将曝光处理后的负型感光性聚酰亚胺前体树脂层中的未曝光部分除去以形成图案；所适用的显影剂为负型感光性聚酰亚胺前体树脂层的良溶剂或良溶剂与不良溶剂的混合溶剂；
作为良溶剂，可列举出N-甲基-2-吡咯烷酮、N-乙酰基-2-吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜、γ-丁内酯、α-乙酰基-γ丁内酯、环戊酮、环己酮等，以上列举可以单一使用，也可以任意混合使用；
作为不良溶剂，可列举出甲苯、二甲苯、甲醇、乙醇、异丙醇、丙二醇单甲醚乙酸酯、丙二醇单甲醚以及水等，以上列举可以单一使用，也可以任意混合使用。
选用负型感光性聚酰亚胺前体树脂层的良溶剂与不良溶剂的混合溶剂作为显影液时，良溶剂与不良溶剂的比例根据树脂层中的聚合物的溶解性确定。
作为显影液处理的方法，没有特别地限制，现有已知的显影法均可使用，例如旋转喷雾法、搅动法、浸渍法等。
显影液处理后，可以进一步冲洗，冲洗液优选与所用显影液不同的溶剂。
步骤(4)中，通过对上述显影得到的图案加热使聚酰胺酸酯亚胺化得到对应的固化聚酰亚胺。
加热处理的温度为150～400℃，在该反应温度内，能够充分进行交联反应或脱水闭环反应。
又一方面，本发明提供上述负型感光性聚酰亚胺前体或上述负型感光性聚酰亚胺前体树脂组合物在电子封装中的用途。
本发明中的负型感光性聚酰亚胺前体树脂组合物可以通过上述方法应用于制备半导体装置，也可以可用于多层电路的层间绝缘、柔性覆铜板的覆盖涂层等用途。
上述技术方案具有如下优点或者有益效果：
为了提高聚酰亚胺前体在低温固化制程下的酰亚胺化率，本发明提供了一种特殊的聚酰亚胺前体分子聚酰胺酸酯，本发明向聚酰亚胺前体分子酯化的醇类化合物中引入叔丁基，实现200℃以下的酰亚胺化温度下，从源头上解决了聚酰亚胺前体分子由于酰亚胺化率较低带来的聚酰亚胺可靠性差、耐化学腐蚀性差等问题，并满足200℃以下的半导体先进封装的超低温固化制程需求。同时本发明将聚酰亚胺前体分子侧链上的不饱和基团的数量限制在一定范围内，降低了低温固化制程下除聚酰亚胺主体以外的组分残留，可进一步提高其耐化学腐蚀性和器件可靠性。
具体实施方式
下述实施例仅仅是本发明的一部分实施例，而不是全部的实施例。因此，以下提供的本发明实施例中的详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明的实施例，本领域技术人员在没有作出创造性劳动的前提下所获得的所有其他实施例，都属于本发明的保护范围。
在本发明中，若非特指，所有的设备和原料等均可从市场购得或是本行业常用的。下述 实施例中的方法，如无特别说明，均为本领域的常规方法。
下述实施例中的室温温度为20～30℃。
【合成例】
合成例1聚酰亚胺前体P1
将103g4,4'-氧双邻苯二甲酸酐(ODPA)分散于溶剂γ-丁内酯(GBL)中，一次性加入106g甲基丙烯酸羟基叔丁酯，再滴加3g吡啶，50摄氏度下反应6h；降至室温后，将137g二环己基碳二亚胺(DCC)溶于GBL中，缓慢滴加进反应体系后搅拌2h；将67g4,4'-二氨基二苯醚(ODA)氮气氛中溶于GBL中，缓慢滴加入反应体系中，滴加完后搅拌9h；整个反应期间如果搅拌困难可以适当加入溶剂冲稀反应体系；反应结束后，加入5mL乙醇淬灭剂反应2h；将淬灭后的反应液压滤，滤液立即加入甲醇中析出块状固体，冷藏12h后溶解于GBL中，将其滴加入水中，过滤干燥得到相应的聚酰亚胺前体P1。本合成例制备的聚酰亚胺前体P1中主要重复单元的结构式如下所示，结构式中的侧链取代基，即甲基丙烯酸羟基叔丁酯对应的取代基的比例为100％；使用超高效聚合物色谱分析仪器(APC)测试得到该聚合物分子量为：Mw为28200，PDI为1.93。
合成例2聚酰亚胺前体P2
用53g甲基丙烯酸羟基叔丁酯和25g叔丁醇代替合成例1中的106g甲基丙烯酸羟基叔丁酯组分，其余组分和操作流程与合成例1保持一致，得到聚酰亚胺前体P2。本合成例中，聚酰亚胺前体侧链取代基中，甲基丙烯酸羟基叔丁酯对应的取代基与叔丁醇对应的取代基的数量比例为5：5；使用APC测试得到该聚合物分子量为：Mw为27500，PDI为1.88。
合成例3聚酰亚胺前体P3
用74g甲基丙烯酸羟基叔丁酯和15g叔丁醇代替合成例1中的106g甲基丙烯酸羟基叔丁酯组分，其余组分和操作流程与合成例1保持一致，得到聚酰亚胺前体P3。本合成例中，聚酰亚胺前体侧链取代基中，甲基丙烯酸羟基叔丁酯对应的取代基与叔丁醇对应的取代基的 数量比例为7：3；使用APC测试得到该聚合物分子量为：Mw为27870，PDI为1.91。
合成例4聚酰亚胺前体P4
用84.5g甲基丙烯酸羟基叔丁酯和10g叔丁醇代替合成例1中的106g甲基丙烯酸羟基叔丁酯组分，其余组分和操作流程与合成例1保持一致，得到聚酰亚胺前体P4。本合成例中，聚酰亚胺前体侧链取代基中，甲基丙烯酸羟基叔丁酯对应的取代基与叔丁醇对应的取代基的数量比例为8：2；使用APC测试得到该聚合物分子量为：Mw为28030，PDI为1.95。
合成例5聚酰亚胺前体P5
用32g甲基丙烯酸羟基叔丁酯和35g叔丁醇代替合成例1中的106g甲基丙烯酸羟基叔丁酯组分，其余组分和操作流程与合成例1保持一致，得到聚酰亚胺前体P5。本合成例中，聚酰亚胺前体侧链取代基中，甲基丙烯酸羟基叔丁酯对应的取代基与叔丁醇对应的取代基的数量比例为3：7；使用APC测试得到该聚合物分子量为：Mw为27410，PDI为1.80。
合成例6聚酰亚胺前体P6
用71g2,2'-二甲基-4,4'-二氨基联苯(mTB)代替合成例1中的67g ODA组分，其余组分和操作流程与合成例1保持一致，得到聚酰亚胺前体P6。本合成例制备的聚酰亚胺前体P6中主要重复单元的结构式如下所示，结构式中的侧链取代基，即甲基丙烯酸羟基叔丁酯对应的取代基的比例为100％；使用APC测试得到该聚合物分子量为：Mw为27230，PDI为1.75。
合成例7聚酰亚胺前体P7
用70.5g3，3’，4，4’-联苯四甲酸二酐(BPDA)代替合成例1中的103g ODPA组分，其余组分和操作流程与合成例1保持一致，得到聚酰亚胺前体P7。本合成例制备的聚酰亚胺前体P7中主要重复单元的结构式如下所示，结构式中的侧链取代基，即甲基丙烯酸羟基叔丁酯对应的取代基的比例为100％；使用APC测试得到该聚合物分子量为：Mw为26890，PDI为1.78。
合成例8聚酰亚胺前体P8
用87g甲基丙烯酸羟乙酯代替合成例1中的106g甲基丙烯酸羟基叔丁酯，其余组分和操作流程与合成例1保持一致，得到聚酰亚胺前体P8。本合成例制备的聚酰亚胺前体P8中主要重复单元的结构式如下所示，结构式中的侧链取代基，即甲基丙烯酸羟乙酯对应的取代基的比例为100％；使用APC测试得到该聚合物分子量为：Mw为27250，PDI为1.87。
合成例9聚酰亚胺前体P9
用43.5g甲基丙烯酸羟乙酯和15.4g乙醇代替合成例1中的106g甲基丙烯酸羟基叔丁酯，其余组分和操作流程与合成例1保持一致，得到聚酰亚胺前体P9。本合成例中，聚酰亚胺前体侧链取代基中，甲基丙烯酸羟乙酯对应的取代基与乙醇对应的取代基的数量比例为5:5；使用APC测试得到该聚合物分子量为：Mw为26980，PDI为1.93。
【实施例】
实施例1
在恒温恒湿(24℃，50％RH)环境下，往100mL棕色胶瓶中依次加入20g聚酰亚胺前体P1、30g N-甲基吡咯烷酮(NMP)溶剂，2.0g自由基聚合性化合物三烯丙基异氰脲酸酯(PC-1)、0.4g六甲氧基甲基三聚氰胺(TC-1)、0.8g光聚合引发剂BASF IRGACURE OXE-01、0.4g硅 烷偶联剂脲丙基三乙氧基硅烷(Si-1)、0.04g聚合抑制剂2-亚硝基-1-萘酚、0.2g 1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸(AO-1)、0.04g苯并三唑(MA-1)，在摇床上摇匀溶解24h后，进一步添加NMP，将粘度调整至约30泊，二级过滤后制成负型感光性聚酰亚胺前体树脂组合物。
制备带有光刻图案的固化膜：
在8英寸硅晶圆上通过匀胶机旋涂制备得到的负型感光性聚酰亚胺前体树脂组合物，在100℃下用热板进行240秒的预烘烤，形成约10μm厚的涂膜。在该涂膜上，使用带测试图案的掩模，用i线投影步进式曝光机照射400mJ/cm2的能量。接着，对该涂膜，使用环戊酮作为显影液，用显影机进行喷雾显影，用丙二醇甲基醚乙酸酯淋洗，从而得到光刻图案。使用升温程序式固化炉，在氮气气氛下，以表2中记载的固化条件加热处理2小时，从而在得到约10μm厚的带有光刻图案的固化膜。
实施例2
将实施例1中的20g聚酰亚胺前体P1替换为20g聚酰亚胺前体P2，其余组分和操作流程与实施例1保持一致。
实施例3
将实施例1中的20g聚酰亚胺前体P1替换为20g聚酰亚胺前体P3，其余组分和操作流程与实施例1保持一致。
实施例4
将实施例1中的20g聚酰亚胺前体P1替换为20g聚酰亚胺前体P4，其余组分和操作流程与实施例1保持一致。
实施例5
将实施例1中的20g聚酰亚胺前体P1替换为20g聚酰亚胺前体P5，其余组分和操作流程与实施例1保持一致。
实施例6
将实施例1中的20g聚酰亚胺前体P1替换为20g聚酰亚胺前体P6，其余组分和操作流程与实施例1保持一致。
实施例7
将实施例1中的20g聚酰亚胺前体P1替换为20g聚酰亚胺前体P7，其余组分和操作流程与实施例1保持一致。
实施例8
将实施例1中的20g聚酰亚胺前体P1替换为10g聚酰亚胺前体P1和10g聚酰亚胺前体P6的混合物，其余组分和操作流程与实施例1保持一致。
实施例9
将实施例1中的20g聚酰亚胺前体P1替换为10g聚酰亚胺前体P1和10g聚酰亚胺前体P7的混合物，其余组分和操作流程与实施例1保持一致。
实施例10
将实施例1中的TC-1的份数从0.4g增加为0.8g，且固化制程改为180℃/2h，其余组分和操作流程与实施例1保持一致。
实施例11
将实施例2中的TC-1的份数从0.4g增加为0.8g，且固化制程改为180℃/2h，其余组分和操作流程与实施例2保持一致。
实施例12
将实施例3中的TC-1的份数从0.4g增加为0.8g，且固化制程改为180℃/2h，其余组分和操作流程与实施例3保持一致。
实施例13
将实施例4中的TC-1的份数从0.4g增加为0.8g，且固化制程改为180℃/2h，其余组分和操作流程与实施例4保持一致。
比较例1
将实施例1中的20g聚酰亚胺前体P1替换为20g聚酰亚胺前体P8，其余组分和操作流程与实施例1保持一致。
比较例2
将实施例1中的20g聚酰亚胺前体P1替换为20g聚酰亚胺前体P9，其余组分和操作流程与实施例1保持一致。
比较例3
将实施例10中的20g聚酰亚胺前体P1替换为20g聚酰亚胺前体P9，其余组分和操作流程与实施例10保持一致。
效果测试
1、重均分子量测试：
本发明所涉及到的聚合物重均分子量Mw和聚合物分散性指数(Polymer dispersity index，PDI)通过超高效聚合物色谱分析仪器测试得到。
2、光刻图案的制备和评价方法：
用聚焦离子束电子显微镜对上述得到的固化膜进行切片分析，评估其光刻精度和截面形貌轮廓，进而对该负型感光性树脂组合物进行光刻性能评价：光刻线条精度小于10μm评为‘优’，光刻线条精度在10-20μm评为‘良’，光刻线条精度在20-50μm评为‘尚可’，光刻线条精度大于50μm评为‘较差’。
3、固化膜的耐化学药品性测试：
将上述制备的固化膜在1％氢氟酸水溶液中浸泡10min后剥离得到完整的固化膜，在烘箱中150℃烘干水分后，在含质量浓度为2.38％的四甲基氢氧化铵的二甲基亚砜溶液中50℃的条件下浸泡处理60min，根据耐化性处理前后固化膜的失重情况对其耐化性进行评估：失重小于5％评为‘优’，失重介于5％-15％评为‘良’，失重介于15％-25％评为‘尚可’，失重大于25％评为‘较差’。
4、固化膜在铜面上的结合力测试：
利用特定图案的掩膜版和上述方法3在铜基材上制备固化膜，放置于高温高湿加速老化试验箱中，测试条件为130℃、85％RH下放置264h，测试后利用百格法对固化膜在铜面上的结合力进行评估：格子100％不脱落评为‘优’，格子脱落率在5％以内评为‘良’，格子脱落率在5％-15％以内评为‘尚可’，格子脱落率大于15％评为‘较差’。
上述实施例和比较例中的负型感光性聚酰亚胺前体树脂组合物各组分的重量、固化条件以及制备得到的固化膜相关性能测试数据见表1-2。
表1

表2

通过表1-2可以看出，本发明制备的负型感光性聚酰亚胺前体在200℃以下的温度下进行热亚胺化，即能获得较高的酰亚胺化率。且，180℃的热亚胺化温度制备的固化膜的性能相较于200℃的热亚胺化温度没有特别显著的下降。其中，聚酰亚胺前体侧链上的不饱和基团的比例较高的实施例，其酰亚胺化后的综合性能最优。采用4,4'-氧双邻苯二甲酸酐(ODPA)、4,4'-二氨基二苯醚(ODA)作为二酐和二胺的实施例获得了最优的性能。
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (15)

  1. 一种负型感光性聚酰亚胺前体，其特征在于，所述负型感光性聚酰亚胺前体具有如式(I)所示的结构：
    式(I)中，Z1为4价含有芳香基的有机基团，Z2为2价含有芳香基的有机基团，R1和R2分别独立地选自式(II)所示结构的1价有机基团、碳原子数1～4的1价烷基中的任意一种，m为2～150；
    式(I)的每个重复单元中的R1为相同或不同的基团，式(I)的每个重复单元中的R2为相同或不同的基团，且式(I)中含有式(II)所示结构的1价有机基团的重复单元的比例为10％～100％；
    式(II)中，R3、R4和R5分别独立地选自氢原子、碳原子数1～3的烷基。
  2. 权利要求1所述的负型感光性聚酰亚胺前体在电子封装中的用途。
  3. 一种负型感光性聚酰亚胺前体树脂组合物，其特征在于，包括：
    100质量份的权利要求1所述的负型感光性聚酰亚胺前体；
    5～20质量份自由基聚合性化合物；
    0.5～5质量份光聚合引发剂；
    0.5～5质量份硅烷偶联剂；
    0.01～1质量份聚合抑制剂；
    1～5质量份架桥剂；
    0.5～3质量份抗氧化剂；
    0.1～2质量份粘接助剂。
  4. 根据权利要求3所述的负型感光性聚酰亚胺前体树脂组合物，其特征在于，所述光聚合引发剂选自肟酯化合物、二苯甲酮、N,N'-四甲基-4,4'-二氨基二苯甲酮、2-苄基-2-二甲基氨基-1-(4-吗啉苯基)丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉基-1-丙酮、烷基蒽醌、苯偶姻烷基 醚、苯偶姻、烷基苯偶姻和苯偶酰二甲基缩酮中的任意一种或多种。
  5. 根据权利要求3所述的负型感光性聚酰亚胺前体树脂组合物，其特征在于，所述架桥剂为氨基树脂。
  6. 根据权利要求4所述的负型感光性聚酰亚胺前体树脂组合物，其特征在于，所述架桥剂选自二醇脲树脂、羟基亚乙基脲树脂、三聚氰胺树脂中的任意一种或多种。
  7. 根据权利要求3所述的负型感光性聚酰亚胺前体树脂组合物，其特征在于，所述抗氧化剂为受阻酚类抗氧化剂。
  8. 根据权利要求7所述的负型感光性聚酰亚胺前体树脂组合物，其特征在于，所述抗氧化剂为酚羟基的邻位碳原子具有受阻结构的化合物。
  9. 根据权利要求3所述的负型感光性聚酰亚胺前体树脂组合物，其特征在于，所述粘接助剂为唑类化合物。
  10. 根据权利要求9所述的负型感光性聚酰亚胺前体树脂组合物，其特征在于，所述粘接助剂选自1H-三唑、5-甲基-1H-三唑、5-乙基-1H-三唑、4,5-二甲基-1H-三唑、5-苯基-1H-三唑、苯基三唑、1,5-二甲基三唑、4,5-二乙基-1H-三唑、1H-苯并三唑、羟基苯基苯并三唑、甲苯基三唑、5-甲基-1H-苯并三唑、4-甲基-1H-苯并三唑、1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-氨基-1H-四唑和1-甲基-1H-四唑中的任意一种或多种。
  11. 根据权利要求3所述的负型感光性聚酰亚胺前体树脂组合物，其特征在于，还包括有机溶剂。
  12. 根据权利要求11所述的负型感光性聚酰亚胺前体树脂组合物，其特征在于，所述有机溶剂选自酯类、醚类、酮类、芳香族烃类、亚砜类和酰胺类中的任意一种或多种。
  13. 权利要求3所述的负型感光性聚酰亚胺前体树脂组合物在电子封装中的用途。
  14. 一种负型感光性聚酰亚胺树脂组合物，其特征在于，由权利要求3所述的负型感光性聚酰亚胺前体树脂组合物热亚胺化得到。
  15. 根据权利要求14所述的负型感光性聚酰亚胺树脂组合物，其特征在于，所述热亚胺化的温度为150～400℃。
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