A negative photosensitive polyimide precursor resin, a preparation method and applications thereof, and a negative photosensitive resin composition and applications

Abstract

The application provides a negative photosensitive polyimide precursor resin, a preparation method and application thereof, a negative photosensitive resin composition and application, and belongs to the technical field of photosensitive polyimides. The negative photosensitive polyimide precursor resin contains a fluorene structure, a fluorine group and a urea group structure, can effectively improve the heat resistance and transparency of polyimide, and has a moderate thermal expansion coefficient. The negative photosensitive resin composition formed by using the negative photosensitive polyimide precursor resin can form a fine pattern and can obtain high resolution, high adhesion, high heat resistance and a moderate thermal expansion coefficient.

Description

Technical Field

[0001] This invention relates to the field of photosensitive polyimide technology, and more particularly to a negative photosensitive polyimide precursor resin, its preparation method and application, and a negative photosensitive resin composition and its application. Background Technology

[0002] Polyimide has excellent mechanical, thermal and insulating properties, so it is widely used in semiconductor packaging, flexible circuit boards and display panels. Among them, photosensitive polyimide is widely used in passivation films, surface protective films and interlayer insulating films of semiconductor integrated circuits.

[0003] With the miniaturization and high performance of electronic devices such as mobile communications and computers, as well as the rapid reduction in the size of high-frequency communication and integrated circuit packages and the pin pitch of devices, the requirements for miniaturization and thinning of semiconductor devices have become increasingly stringent. To avoid warping and interface cracking of the package plane caused by thermal stress, on the one hand, the polyimide material is required to have a suitable coefficient of thermal expansion (CTE). On the other hand, excessively high process temperatures should be avoided, as this would amplify the interface stress caused by the difference in the coefficient of thermal expansion between the package material and the copper conductor. In other words, the curing temperature of the polyimide material needs to be reduced as much as possible.

[0004] Therefore, to solve the above problems, photosensitive resins are required to have a suitable coefficient of thermal expansion, better adhesion, higher resolution, and heat resistance. Summary of the Invention

[0005] The purpose of this invention is to provide a negative photosensitive polyimide precursor resin, its preparation method and application, a negative photosensitive resin composition and its application, wherein the formed photosensitive resin composition has moderate CTE, high adhesion, high resolution and high heat resistance.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a method for preparing a negative photosensitive polyimide precursor resin, comprising the following steps:

[0008] The dianhydride monomer, esterification reagent, catalyst and first organic solvent are mixed and esterification reaction is carried out to obtain diacid diester;

[0009] The diacid diester, diamine monomer, dehydrating agent, and second organic solvent are mixed and subjected to an amidation reaction. Then, a capping agent is added to cap the resin, resulting in a negative photosensitive polyimide precursor resin.

[0010] The diamine monomers include fluorene-containing diamine monomers, fluorinated diamine monomers, and ureido-containing diamine monomers.

[0011] Preferably, the dianhydride monomer includes one or more of aromatic acid dianhydrides, dianhydrides containing a siloxane skeleton, aliphatic acid dianhydrides, and alicyclic acid dianhydrides.

[0012] Preferably, the molar ratio of the fluorene-containing diamine monomer, the fluorinated diamine monomer, the ureido-containing diamine monomer, and the total diamine monomer is 0.05~0.5:0.15~0.5:0.05~0.5:1; and the molar ratio of the total diamine monomer to the dianhydride monomer is 1:0.8~1.2.

[0013] Preferably, the esterification reagent includes one or more of alcohol reagents and ester reagents; the molar ratio of the esterification reagent to the dianhydride monomer is 1.0~2.0:1.

[0014] Preferably, the esterification reaction is carried out at a temperature of 10~60℃ for 10~24h; the amidation reaction is carried out at a temperature of -10~30℃ for 8~15h.

[0015] Preferably, the capping agent is one or more of monoamine compounds, acid anhydride compounds, monocarboxylic acid compounds, monoacyl chloride compounds, and monoactive ester compounds; the molar ratio of the capping agent to the total diamine monomer is 0.01~0.5:1.

[0016] The present invention provides a negative photosensitive polyimide precursor resin prepared by the preparation method described in the above technical solution.

[0017] This invention provides the application of the negative photosensitive polyimide precursor resin described above in negative photosensitive resins.

[0018] This invention provides a negative photosensitive resin composition, comprising the following components by weight percentage:

[0019] Polyamate resin 15-40%; acrylic structural monomer 10-30%; photoinitiator 5-20%; thermal crosslinking agent 5-20%; additives 1-10%; solvent 30-50%;

[0020] The polyamic acid ester resin is the negative photosensitive polyimide precursor resin described in the above technical solution or the negative photosensitive polyimide precursor resin prepared by the preparation method described in the above technical solution.

[0021] This invention provides the application of the negative photosensitive resin composition described above in photosensitive polyimide.

[0022] This invention utilizes a diacid diester generated from a dianhydride monomer and an esterification reagent to react with diamine monomers (containing fluorene diamine monomers, fluorinated diamine monomers, and urea-containing diamine monomers as diamine monomers) to prepare a negative photosensitive polyimide precursor resin. The prepared negative photosensitive polyimide precursor resin simultaneously contains fluorene, fluorine, and urea structures. Due to the large number and size of benzene rings in the fluorene structure, it improves thermal performance while also preventing the molecular weight from becoming too densely packed, thus enhancing transparency. The fluorine groups can reduce the formation of CTC (charge-transfer complex) and also improve transparency. The urea structure contains amide bonds, which can improve its adhesion to the substrate. Therefore, the negative photosensitive polyimide precursor resin can effectively improve the heat resistance and transparency of polyimide and has a moderate coefficient of thermal expansion.

[0023] Furthermore, the negative photosensitive polyimide precursor resin is a polyamic acid ester resin, which can reduce the degradation rate of the negative photosensitive resin composition through the action of polyamic acid ester (esterification reaction reduces the number of carboxyl groups, reducing the degradation caused by carboxyl groups), and improve the storage time.

[0024] This invention can improve the different properties of precursor resins by adjusting the content of diamine monomer structure, so that the negative photosensitive polyimide precursor resin has a moderate coefficient of thermal expansion (CTE), and different esterification reagent groups can be used to enhance the different properties of the precursor resin.

[0025] The negative photosensitive resin composition formed using the aforementioned negative photosensitive polyimide precursor resin can form fine patterns and achieve high resolution, high adhesion, high heat resistance, and a moderate coefficient of thermal expansion.

[0026] This invention prepares a negative photosensitive polyimide precursor resin through the reaction of fluorene-containing molecular chain blocks, fluorine-containing molecular chain blocks, and urea-containing molecular chain blocks. The film formed by coating the prepared photosensitive resin composition onto the substrate surface has moderate CTE, high heat resistance, high adhesion, and high resolution; the CTE value is 10~25ppm / ℃ in the range of 50~250℃; the Td1 can reach 410℃ under heat treatment conditions of 250℃ / 1h; the adhesion can reach 4b under heat treatment conditions of 230℃ / 30min, and the adhesion can reach 5b under heat treatment conditions of 230℃ / 1h, 250℃ / 30min, and 250℃ / 1h. Attached Figure Description

[0027] Figure 1 The image shows the development effect of the photosensitive composition prepared in Example 8;

[0028] Figure 2 Thermogravimetric analysis diagram of the photosensitive composition prepared in Example 8;

[0029] Figure 3The image shows a cross-cut pattern of the photosensitive composition prepared in Example 8. Detailed Implementation

[0030] This invention provides a method for preparing a negative photosensitive polyimide precursor resin, comprising the following steps:

[0031] The dianhydride monomer, esterification reagent, catalyst and first organic solvent are mixed and esterification reaction is carried out to obtain diacid diester;

[0032] The diacid diester, diamine monomer, dehydrating agent, and second organic solvent are mixed and subjected to an amidation reaction. Then, a capping agent is added to cap the resin, resulting in a negative photosensitive polyimide precursor resin.

[0033] The diamine monomers include fluorene-containing diamine monomers, fluorinated diamine monomers, and ureido-containing diamine monomers.

[0034] The present invention involves mixing dianhydride monomer, esterification reagent, catalyst and first organic solvent to carry out esterification reaction to obtain diacid diester.

[0035] In this invention, the dianhydride monomer preferably includes one or more of aromatic acid dianhydrides, dianhydrides containing a siloxane skeleton, aliphatic acid dianhydrides, and alicyclic acid dianhydrides.

[0036] In this invention, the aromatic acid dianhydride preferably includes 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, pyrolithic dianhydride, 2,3,3',4'-oxyphthalic dianhydride, 2,3,2',3'-oxyphthalic dianhydride, 3,3',4,4'-triphenyltetracarboxylic dianhydride, 3,3',4,4'-oxyphthalic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'- Tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,4-(3,4-dicarboxyphenoxy)phenyl dianhydride, p-phenylene bis(trimethylbenzene monoester anhydride), 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis(4-(3,4-dicarboxyphenoxy)phenyl)fluorene dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2'-bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 2,2 -One or more of bis(4-(3,4-dicarboxybenzoyloxy)phenyl)hexafluoropropane dianhydride, 1,6-difluoropyrolithic dianhydride, 1-trifluoromethylpyrolithic dianhydride, and 1,6-ditrifluoromethylpyrolithic dianhydride; the dianhydride containing the siloxane skeleton preferably includes one or more of 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride and 3,3'-((1,1,3,3-tetramethyl-1,3-disiloxanediyldi-3,1-propanediyl)bis(dihydro-2,5-furandione).

[0037] The aliphatic acid dianhydride is preferably 1,2,3,4-butanetetracarboxylic acid dianhydride or 1,2,3,4-pentanetetracarboxylic acid dianhydride; the alicyclic acid dianhydride preferably includes: 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride. Anhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cycloheptanetetracarboxylic anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic anhydride, 3,4-dicarboxy-1-cyclohexylsuccinic anhydride, 2,3,5-tricarboxy-cyclopentylacetic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthylsuccinic anhydride, bis... Cyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5, One or more of the following: 6-tetracarboxylic dianhydride, bicyclo[2,2,1]heptanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecanthane-1,2,8,9-tetracarboxylic dianhydride, and 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride.

[0038] When the dianhydride monomers are two or more of the above-mentioned types, the present invention does not impose any special limitations on the ratio of different types of dianhydride monomers, and can be adjusted according to actual needs.

[0039] In this invention, the esterification reagent preferably includes one or more of alcohols and esters; the esterification reagent is preferably any one or at least two of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, hexanol, cyclohexanol, vinylcyclohexanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, cyclohexyl methacrylate, 2-ethoxyethyl methacrylate, and glycidyl methacrylate; more preferably, glycidyl methacrylate or 2-hydroxypropyl methacrylate. When the esterification reagent is two or more of the above, this invention does not have a special limitation on the ratio of different types of esterification reagents, and can be adjusted according to actual needs.

[0040] In this invention, the molar ratio of the esterification reagent to the dianhydride monomer is preferably 1.0~2.0:1, more preferably 1.18~1.5:1.

[0041] In this invention, the catalyst is preferably 1,8-diazobisspirocyclic [5.4.0]undec-7-ene; the molar ratio of the catalyst to the dianhydride monomer is preferably 0.1~0.3:1, more preferably 0.16~0.2:1.

[0042] In this invention, the first organic solvent preferably includes one or more of the following: N-methylpyrrolidone, γ-butyrolactone, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ethyl ether. When the first organic solvent is two or more of the above, this invention does not have a special limitation on the ratio of different types of solvents, and any ratio is acceptable. This invention does not have a special limitation on the amount of the organic solvent used; it can be adjusted according to actual needs to ensure the smooth progress of the reaction.

[0043] In this invention, the dianhydride monomer is dissolved in a first organic solvent, and then an esterification reagent and a catalyst are added to carry out an esterification reaction; the temperature of the esterification reaction is preferably 10~60℃, more preferably 25~30℃, and the time is preferably 10~24h, more preferably 12~18h; the esterification reaction is preferably carried out in a nitrogen atmosphere.

[0044] After the esterification reaction is completed, the present invention preferably requires no post-processing to obtain a diacid diester.

[0045] After obtaining the diacid diester, the present invention mixes the diacid diester, diamine monomer, dehydrating agent and second organic solvent, performs an amidation reaction, adds a capping agent, and performs capping to obtain a negative photosensitive polyimide precursor resin.

[0046] In this invention, the diamine monomer includes fluorene-containing diamine monomers, fluorinated diamine monomers, and ureido-containing diamine monomers;

[0047] The fluorene-containing diamine monomer is preferably... , , or ;

[0048] The fluorinated diamine monomers used in this invention are preferably 3,5-difluorophenyl-1,2-diamine, 4,5-difluoro-1,2-phenylenediamine, 2-(trifluoromethyl)-1,4-phenylene diamine, 4-trifluoromethyl o-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-... -bis(trifluoromethyl)-4,4'-diaminophenyl ether, N,N'-(2,2'-bis(trifluoromethyl)-[1,1'-diphenyl]-4,4'-diyl)bis(4-aminobenzamide), 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, 2,2-bis[4-hydroxyphenyl-3-(4-amino)benzamido]hexafluoropropane or 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene;

[0049] The urea-containing diamine monomer is preferably 1,3-di(4-aminophenyl)urea, 1,1'-(1,4-phenylene)diurea, 3-(4-aminophenyl)-1-phenylurea, 3-[4-(1-aminoethyl)phenyl]-1-phenylurea, 1-(2-((3-(2-cyanophenoxy)-2-hydroxypropyl)amino)ethyl)-3-phenylurea, m-urea-aniline, (4-aminophenyl)urea, 3,3'-diaminodiphenylurea, 1,3-bis(3-aminophenyl)urea, N,N''-1,3-phenylenebisurea, or N,N'',N'''-1,3,5-phenyltriacryltriurea.

[0050] In this invention, the molar ratio of the fluorene-containing diamine monomer, the fluorinated diamine monomer, the ureido-containing diamine monomer, and the total diamine monomer is preferably 0.05~0.5:0.15~0.5:0.05~0.5:1, more preferably 0.33:0.42:0.25:1; the molar ratio of the total diamine monomer to the dianhydride monomer is preferably 1:0.8~1.2, more preferably 1:0.8~1.06.

[0051] In this invention, the dehydrating agent is preferably N,N'-dicyclohexylcarbodiimide (DCC); the molar ratio of the dehydrating agent to the dianhydride monomer is preferably 1.1 to 1.7:1, more preferably 1.5:1.

[0052] In this invention, the second organic solvent is preferably the same type as the first organic solvent; the amount of the second organic solvent is not particularly limited and can be adjusted according to actual needs.

[0053] In this invention, the dehydrating agent is dissolved in a portion of the second organic solvent and added dropwise to the diacid diester. After stirring for 1 hour, the diamine monomer is dissolved in the remaining second organic solvent, and the resulting product is added dropwise to the stirred mixture to carry out the amidation reaction.

[0054] In this invention, the temperature of the amidation reaction is preferably -10 to 30°C, more preferably 0 to 20°C, and the time is preferably 8 to 15 hours, more preferably 10 to 12 hours.

[0055] In this invention, the capping agent is preferably added 8 hours after the amidation reaction; the capping time is preferably 2 hours.

[0056] In this invention, the capping agent is preferably one or more of monoamine compounds, acid anhydride compounds, monocarboxylic acid compounds, monoacyl chloride compounds, and monoactive ester compounds;

[0057] The monoamine compound is preferably:

[0058] , , , , and One or two of them.

[0059] The anhydride compound preferably includes maleic anhydride or itaconic anhydride; the monocarboxylic acid compound preferably includes 3-carboxyphenol or 4-carboxyphenol; the monoacyl chloride compound preferably includes acetyl chloride or benzoyl chloride; and the monoactive ester preferably includes phenolic benzoate or phenolic acetate.

[0060] In this invention, the molar ratio of the capping agent to the total diamine monomer is preferably 0.01~0.5:1, more preferably 0.05~0.3:1, and even more preferably 0.08~0.1:1.

[0061] After the end-capping is completed, the present invention preferably drops the obtained product into water to precipitate, filters and collects the precipitate, and performs vacuum drying to obtain negative photosensitive polyimide precursor resin; the vacuum drying temperature is preferably 40~100℃, more preferably 50~80℃, and the time is preferably 8~72h, more preferably 12~48h.

[0062] The present invention provides a negative photosensitive polyimide precursor resin prepared by the preparation method described in the above technical solution.

[0063] In this invention, the preferred structural formula of the negative photosensitive polyimide precursor resin is:

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071] .

[0072] This invention provides the application of the negative photosensitive polyimide precursor resin described in the above technical solution or the negative photosensitive polyimide precursor resin prepared by the preparation method described in the above technical solution in negative photosensitive resin.

[0073] This invention provides a negative photosensitive resin composition, comprising the following components by weight percentage:

[0074] Polyamate resin 15-40%; acrylic structural monomer 10-30%; photoinitiator 5-20%; thermal crosslinking agent 5-20%; additives 1-10%; solvent 30-50%;

[0075] The polyamic acid ester resin is the negative photosensitive polyimide precursor resin described in the above technical solution or the negative photosensitive polyimide precursor resin prepared by the preparation method described in the above technical solution.

[0076] The negative photosensitive resin composition provided by the present invention comprises 15-40% polyamic acid ester resin, preferably 16-30%, by weight percentage.

[0077] The negative photosensitive resin composition provided by the present invention comprises 10-30% acrylic structural monomer, more preferably 10-20%, by weight percentage.

[0078] In this invention, the acrylic acid-containing structural monomer includes:

[0079] , , , or ;

[0080] X1, X2, X3, X4 and X5 are independently straight-chain alkyl, branched alkyl, cycloalkyl or cycloalkenyl containing 1 to 20 carbon atoms, and are more preferably isobornyl, cyclopentene, decane, polyethylene glycol, bisphenol A, isocyanuric acid or glycerol oxide containing 1 to 10 carbon atoms.

[0081] In this invention, the acrylic-containing monomer is preferably one or more of the following monomers: dicyclopentenyl acrylate, dicyclopentenyl ethoxyacrylate, glycidyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentyl methacrylate, tricyclodecanediethanol diacrylate, 1,6-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, tricyclodecanediethanol dimethacrylate, 1,6-hexanediol dimethacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol triacrylate, propoxylated glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and caprolactone-modified dipentaerythritol hexaacrylate.

[0082] The negative photosensitive resin composition provided by the present invention comprises, by weight percentage, 5-20% photoinitiator, preferably 5-15%, more preferably 10%. In the present invention, the photoinitiator is preferably one or more of benzophenone derivatives, benzoyl derivatives, oximes, benzoin derivatives, acetophenone derivatives, thioxanone derivatives, N-arylglycine derivatives, peroxides, and aromatic biimidazoles. The benzophenone derivatives are preferably benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, or fluorenone; the benzoyl derivatives are preferably benzoyl, benzoyl dimethyl ketal, or benzoyl-β-methoxyethyl acetal; the oximes are preferably... The derivatives are 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenyltriketone-2-(O-ethoxycarbonyl)oxime, or 1-phenyl-3-ethoxytriketone-2-(O-benzoyl)oxime; the benzoin derivatives are preferably benzoin or benzoin methyl ether; the acetophenone derivatives are preferably 2... 2'-Diethoxyacetophenone, 2-hydroxy-2-methylacetophenone, or 1-hydroxycyclohexylphenyl ketone; the thioxanthone derivatives are preferably thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, or diethylthioxanthone; the N-arylglycine derivatives are preferably α-(n-octanesulfonyloxyimino)-4-methoxybenzylcyanine or N-phenylglycine; the peroxide derivatives are preferably benzoyl perchlorate; the aromatic biimidazole derivatives are preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole.

[0083] The present invention preferably uses oxime photoinitiators, which can achieve better development performance.

[0084] The photoinitiator described in this invention generates free radicals upon exposure to ultraviolet light, undergoing a cross-linking reaction that renders it insoluble in the developing solution.

[0085] The negative photosensitive resin composition provided by the present invention comprises 5-20% thermal crosslinking agent, preferably 9-15%, by weight percentage. In this invention, the thermal crosslinking agent is preferably an epoxy compound, an alkoxy compound, or a hydroxymethyl compound; the epoxy compound is preferably a compound containing two or more epoxy groups in one molecule; more preferably, it is a bisphenol A type epoxy resin, a bisphenol A type oxetane resin, a bisphenol F type epoxy resin, a bisphenol F type oxetane resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, or polymethyl (glycidyloxypropyl)siloxane; more preferably, it is the EPICLON or EXA series products of Nippon Ink Chemical Industry Co., Ltd., the Epikote series of bisphenol A type epoxy compounds of Yuka Shell Epoxy Co. Ltd., or the EP series products of ADEKA Co. Ltd.; the alkoxy compound is preferably a compound containing two or more alkoxy groups in one molecule; the hydroxymethyl compound is preferably a compound with 2 to 8 hydroxymethyl functional groups, more preferably the DML, TriML, DMOM, HMOM, or TMOM series of Honshu Chemical, or the MX or MW series of Sanwa Chemical.

[0086] The negative photosensitive resin composition provided by the present invention comprises 1-10% additives, more preferably 4.7-8%, by weight percentage. The additives preferably include leveling agents, defoamers, and catalysts; the leveling agent is preferably an acrylic leveling agent, a silicone leveling agent, or a fluorinated leveling agent; the defoamer is preferably BYK-A530 defoamer, BYK-A550 defoamer, or Airex-920 defoamer; the catalyst is preferably one or two of 1,8-diazabicycloundecene, N,N'-diisopropylcarbodiimide, and N,N'-dicyclohexylcarbodiimide.

[0087] The mass ratio of the leveling agent, defoamer, and polyamic acid ester resin is preferably 1~2:1~2:10, more preferably 1.2~1.8:1.2~1.8:10, and even more preferably 1.4~1.6:1.2~1.6:10; the molar ratio of the catalyst to the dianhydride monomer is preferably 0.1~0.3:1, more preferably 0.1~0.2:1.

[0088] The negative photosensitive resin composition provided by the present invention comprises 30-50% to 40-50% solvent by weight percentage. In the present invention, the solvent is preferably N-methylpyrrolidone (NMP) or N,N-dimethylacetamide (DMAc).

[0089] In this invention, the preferred method for preparing the negative photosensitive resin composition is to add the negative photosensitive polyimide precursor resin and the remaining components together to a solvent and mix them evenly in a Class 1000 cleanroom equipped with a yellow light source, and then filter the mixture using a filter membrane. The mixing temperature is preferably 20-30°C, more preferably 22-28°C, and even more preferably 25°C. The mixing time is preferably 1-24 hours, more preferably 2-18 hours, and even more preferably 10-16 hours. The pore size of the filter membrane is preferably 0.45 μm, and the material is preferably PP.

[0090] This invention provides the application of the negative photosensitive resin composition described above in photosensitive polyimide. The method of application is not particularly limited by this invention; any method well-known in the art can be used.

[0091] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0092] The structures and abbreviations of the compounds used in the following examples are as follows:

[0093] Fluorene diamine monomer a1: ;

[0094] Fluorene diamine monomer a2: ;

[0095] Fluorene diamine monomer a3: ;

[0096] Fluorene diamine monomer a4: ;

[0097] Fluorinated diamine monomer b1: 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane;

[0098] Contains ureidodiamine monomer C1: 1,3-bis(4-aminophenyl)urea;

[0099] Contains ureidodiamine monomer C2: 1,1'-(1,4-phenylene)diurea;

[0100] End-capping agent monomer d1: 4-aminoindazole

[0101] End-capping agent monomer d2: 3-aminoquinoline

[0102] End-capping agent monomer d3: 2-aminobenzimidazole

[0103] End-capping agent monomer d4: 2-phenyl-2H-benzo[D][1,2,3]triazole-5-amine

[0104] Photoinitiator e: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime;

[0105] Thermal crosslinking agent f: HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.);

[0106] Acrylic monomer g1: glycidyl methacrylate

[0107] Acrylic monomer g2: Tricyclodecanediethanol dimethacrylate

[0108] Acrylic monomer g3: Tris(2-hydroxyethyl)isocyanurate triacrylate

[0109] Acrylic monomer g4: Pentaerythritol tetraacrylate ethoxylate

[0110] Dihydride monomer ODPA: 4,4'-O-diphthalic anhydride;

[0111] Solvent NMP: N-methylpyrrolidone.

[0112] Example 1

[0113] 0.127 mol of dianhydride monomer ODPA and 70 g of N-methylpyrrolidone (NMP) were added to a 500 mL flask and dissolved. Then, 0.15 mol of glycidyl methacrylate and 0.02 mol of 1,8-diazobisspirocyclic [5.4.0]undecyl-7-ene were added. The mixture was stirred at room temperature (25 °C) under nitrogen atmosphere for 18 h to carry out the esterification reaction and obtain the reaction solution.

[0114] The reaction solution was cooled to 0°C in an ice bath. 0.19 mol of N,N'-dicyclohexylcarbodiimide (DCC) was dissolved in 65 g of NMP and added dropwise to the above reaction solution, with stirring for 1 h. 0.04 mol of fluorene-containing diamine monomer a1, 0.05 mol of fluorinated diamine monomer b1, and 0.03 mol of ureoyl diamine monomer c1 were dissolved in 69 g of NMP and added dropwise to the above reaction solution. The amidation reaction was carried out at 0°C with stirring for 8 h. 0.01 mol of end-capping monomer d1 was added, and the reaction continued for 2 h. The resulting reaction solution was added dropwise to distilled water to precipitate the precipitate. The precipitate was collected by filtration and vacuum dried at 50°C for 48 h to obtain the polyimide precursor resin, with the following structural formula:

[0115] ;

[0116] The number-average molecular weight Mn was determined to be 42533 by GPC.

[0117] In a Class 1000 cleanroom equipped with a yellow light source, 10g of the dried polyimide precursor resin, 6g of photoinitiator e, 5.4g of crosslinking agent f, 6g of acrylic monomer resin g1, 1.6g of silicone leveling agent BYK348, and 1.2g of defoamer BYKA530 were dissolved in 30g of NMP and stirred at 25°C for 2 hours. The mixture was then filtered through a PP membrane with a pore size of 0.45μm to obtain the photosensitive resin composition.

[0118] Example 2

[0119] In Example 1, 0.04 mol of fluorene-containing diamine monomer a1 was replaced with 0.04 mol of fluorene-containing diamine monomer a2, while other conditions remained unchanged, to obtain a photosensitive resin composition;

[0120] The polyimide precursor resin has the following structural formula:

[0121] ;

[0122] The number-average molecular weight Mn, as measured by GPC, was 43462.

[0123] Example 3

[0124] In Example 1, 0.04 mol of fluorene-containing diamine monomer a1 was replaced with 0.04 mol of fluorene-containing diamine monomer a3, while other conditions remained unchanged, to obtain a photosensitive resin composition;

[0125] The polyimide precursor resin has the following structural formula:

[0126] ;

[0127] The number-average molecular weight Mn, as measured by GPC, was 41725.

[0128] Example 4

[0129] In Example 1, 0.04 mol of fluorene-containing diamine monomer a1 was replaced with 0.04 mol of fluorene-containing diamine monomer a4, while other conditions remained unchanged, to obtain a photosensitive resin composition;

[0130] The polyimide precursor resin has the following structural formula:

[0131] ;

[0132] The number-average molecular weight Mn, as determined by GPC, was 40593.

[0133] Example 5

[0134] In Example 2, 0.01 mol of the capped diamine monomer d1 was replaced with 0.01 mol of the capped monomer d2, while other conditions remained unchanged, to obtain the photosensitive resin composition.

[0135] The polyimide precursor resin has the following structural formula:

[0136] ;

[0137] The number-average molecular weight Mn was determined to be 42285 by GPC.

[0138] Example 6

[0139] In Example 2, 0.01 mol of the terminal diamine monomer d1 was replaced with 0.01 mol of the terminal monomer d3, while other conditions remained unchanged, to obtain the photosensitive resin composition.

[0140] The polyimide precursor resin has the following structural formula:

[0141] ;

[0142] The number-average molecular weight Mn, as measured by GPC, was 42446.

[0143] Example 7

[0144] In Example 2, 0.01 mol of the terminal diamine monomer d1 was replaced with 0.01 mol of the terminal monomer d4, while other conditions remained unchanged, to obtain the photosensitive resin composition.

[0145] The polyimide precursor resin has the following structural formula:

[0146] ;

[0147] The number-average molecular weight Mn, as measured by GPC, was 41253.

[0148] Example 8

[0149] In Example 2, 0.03 mol of urea-containing diamine monomer c1 was replaced with 0.03 mol of urea-containing diamine monomer c2, while other conditions remained unchanged, to obtain a photosensitive resin composition.

[0150] The polyimide precursor resin has the following structural formula:

[0151] ;

[0152] The number-average molecular weight Mn, as measured by GPC, is 45625.

[0153] Comparative Example 1

[0154] In Example 8, 6g of acrylic monomer resin g1 was replaced with 6g of acrylic monomer resin g2, while other conditions remained unchanged, to obtain a photosensitive resin composition.

[0155] Comparative Example 2

[0156] In Example 8, 6g of acrylic monomer resin g1 was replaced with 6g of acrylic monomer resin g3, while other conditions remained unchanged, to obtain a photosensitive resin composition.

[0157] Comparative Example 3

[0158] In Example 8, 6g of acrylic monomer resin g1 was replaced with 6g of acrylic monomer resin g4, while other conditions remained unchanged, to obtain a photosensitive resin composition.

[0159] Comparative Example 4

[0160] In Example 8, the 0.03 mol of urea-containing diamine monomer C2 was replaced with 0.025 mol of urea-containing diamine monomer C2, while other conditions remained unchanged, to obtain a photosensitive resin composition.

[0161] Comparative Example 5

[0162] In Example 8, the 0.03 mol of urea-containing diamine monomer C2 was replaced with 0.035 mol of urea-containing diamine monomer C2, while other conditions remained unchanged, to obtain a photosensitive resin composition.

[0163] Comparative Example 6

[0164] In Example 8, 0.04 mol of fluorene-containing diamine monomer a2 was replaced with 0.05 mol of fluorene-containing diamine monomer a2, while other conditions remained unchanged, to obtain a photosensitive resin composition.

[0165] Comparative Example 7

[0166] In Example 8, the esterification reaction temperature was adjusted to 50°C and the reaction time was adjusted to 10 h; the amidation reaction time was adjusted to 30°C and the reaction time was adjusted to 8 h, while other conditions remained unchanged, to obtain a photosensitive resin composition.

[0167] Comparative Example 8

[0168] In Example 8, the esterification reaction temperature was adjusted to 10°C and the reaction time was adjusted to 24 h; the amidation reaction time was adjusted to 0°C and the reaction time was adjusted to 15 h, while other conditions remained unchanged, to obtain a photosensitive resin composition.

[0169] Performance testing

[0170] 1) Resolution detection

[0171] A 10 μm thick negative photosensitive resin composition was spin-coated onto a silicon wafer, and then pre-baked on a hot plate at 120°C for 3 min; ultraviolet light (i.e., wavelength 365 nm, intensity 30 mW / cm²) was then used. 2 Exposure was performed at an energy of 200 mJ / cm². 2The film was developed in cyclopentanone solvent for 2 min and rinsed with PMA solvent; finally, it was cured in an oven at 230℃~250℃ under nitrogen protection. The cured film pattern was observed using an optical microscope, and the results are shown in Table 1.

[0172] 2) Thermal performance testing

[0173] The cured film was cut into rectangles 5 mm wide and 15 mm long. Thermomechanical analysis was performed on the samples using a thermomechanical analyzer and the tensile load method. The heating rate was set to 5 °C / min, and the coefficient of thermal expansion in the planar direction (ppm / °C) within the range of 25–200 °C was calculated. The results are shown in Table 1.

[0174] 3) In addition, the glass transition temperature Tg and the 1%wt thermal decomposition temperature (Td1) of the sample were detected using a thermogravimetric analyzer. The results are shown in Table 1.

[0175] 4) Adhesion testing

[0176] Using a cross-cut tester (BYK-Gardner A-5125), a grid of 10 rows and 10 columns was cut into the resin film. A peel test was then performed using tape (special transparent 3M tape) in accordance with the national standard GB / T 9286-1998 Cross-cut test for paint and varnish films. The number of squares peeled off was recorded. The results are shown in Table 1.

[0177] Table 1 Performance data of the photosensitive resin compositions prepared in Examples 1-8 and Comparative Examples 1-8

[0178]

[0179] As can be seen from Examples 1-4 and Comparative Example 6 in Table 1, the use of spirofluorene-structured diamine monomers has a slightly higher resolution than that of general structured diamine monomers, and has a moderate CTE, a higher Tg, and a 1%wt thermal decomposition temperature; increasing the amount of spirofluorene diamine slightly increases Tg and decreases resolution.

[0180] As can be seen from Examples 5-7, the use of amino-end-capping agents with a benzotriazole structure can improve adhesion and thermal properties.

[0181] As can be seen from Example 8 and Comparative Examples 1-5, using an acrylic monomer resin with a g3 structure can improve resolution; reducing the urea diamine content decreases resolution and worsens adhesion; increasing the urea diamine content increases resolution and improves adhesion.

[0182] Comparative Examples 7 and 8 show that the appropriate reaction temperature is crucial. Increasing the temperature during the esterification stage may cause the double bonds to break, resulting in incomplete esterification. Decreasing the temperature during the esterification stage may slow down the reaction and prolong the reaction time. Increasing the temperature during the synthesis stage may decrease the molecular weight, resulting in excessive solubility. Decreasing the temperature may result in excessive molecular weight, resulting in poor solubility.

[0183] In summary, the addition of spirofluorene diamine, urea groups, and end-capping agents can give the resin a suitable CTE, thereby improving its thermal properties and adhesion.

[0184] Figure 1 The image shows the development effect of the photosensitive composition prepared in Example 8; Figure 1 It can be seen that the image resolution is clear, the adhesion is good, and there is no penetration or uncleanliness.

[0185] Figure 2 Thermogravimetric analysis (TGA) curve of the photosensitive composition prepared in Example 8; by Figure 2 It can be seen that the glass transition temperature is relatively high, reaching 365℃; the 1% thermal decomposition temperature reaches 400℃.

[0186] Figure 3 A cross-cut pattern of the photosensitive composition prepared in Example 8; by Figure 3 It can be seen that the scratches are smooth and neat, with no pulling or peeling, indicating good adhesion.

[0187] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a negatively photosensitive polyimide precursor resin, characterized in that, Includes the following steps: The dianhydride monomer, esterification reagent, catalyst and first organic solvent are mixed and esterification reaction is carried out to obtain diacid diester; The diacid diester, diamine monomer, dehydrating agent, and second organic solvent are mixed and subjected to an amidation reaction. Then, a capping agent is added to cap the resin, resulting in a negative photosensitive polyimide precursor resin. The dianhydride monomer is 4,4'-oxobisphthalic anhydride; The esterification reagent is glycidyl methacrylate, tricyclodecanediethanol dimethacrylate. Tris(2-hydroxyethyl) isocyanurate triacrylate or pentaerythritol ethoxylate tetraacrylate; The diamine monomer is a fluorene-containing diamine monomer, a fluorinated diamine monomer, or a ureido-containing diamine monomer; The fluorene-containing diamine monomer is 、 、 or ; The fluorinated diamine monomer is 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane; The ureidodiamine monomer is 1,3-bis(4-aminophenyl)urea or 1,1'-(1,4-phenylene)diurea; The capping agent is 4-aminoindazole, 3-aminoquinoline, 2-aminobenzimidazole or 2-phenyl-2H-benzo[D][1,2,3]triazole-5-amine; The molar ratio of the fluorene-containing diamine monomer, the fluorinated diamine monomer, the ureido-containing diamine monomer, and the total diamine monomer is 0.05~0.5:0.15~0.5:0.05~0.5:1; The molar ratio of the esterification reagent to the dianhydride monomer is 1.0~2.0:1; The esterification reaction is carried out at a temperature of 25-30°C for 12-18 hours. The molar ratio of the capping agent to the total diamine monomer is 0.01 to 0.5:

1.

2. The preparation method according to claim 1, characterized in that, The molar ratio of total diamine monomer to dianhydride monomer is 1:0.8~1.

2.

3. The preparation method according to claim 1, characterized in that, The amidation reaction is carried out at a temperature of -10 to 30°C for 8 to 15 hours.

4. The negative photosensitive polyimide precursor resin prepared by the preparation method according to any one of claims 1 to 3.

5. The application of the negative photosensitive polyimide precursor resin according to claim 4 in negative photosensitive resins.

6. A negative photosensitive resin composition, characterized in that, It comprises the following components by weight percentage: Polyamate resin 15-40%; acrylic structural monomer 10-30%; photoinitiator 5-20%; thermal crosslinking agent 5-20%; additives 1-10%; solvent 30-50%; The polyamic acid ester resin is the negative photosensitive polyimide precursor resin according to claim 4.

7. The use of the negative photosensitive resin composition of claim 6 in photosensitive polyimide.

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