Negative photosensitive resin composition, preparation method and application

Abstract

This application discloses a negative-type photosensitive resin composition, preparation method, and application thereof. The negative-type photosensitive resin composition comprises a polyimide precursor resin, a crosslinker, a photoinitiator, a coupling agent, and a solvent. After curing to form a film, the composition disclosed herein exhibits high transmittance and resolution, a low thermal expansion coefficient, excellent mechanical properties, and chemical resistance. It can be used in high-tech fields requiring high resolution, a low thermal expansion coefficient, and high tensile strength.

Description

Technical Field

[0001] The present application relates to a negative photosensitive resin composition, a preparation method and an application thereof, and belongs to the technical field of electronic device packaging materials. Background Art

[0002] Polyimide (PI) is a class of organic polymer materials containing imide rings. It possesses excellent chemical stability, electrical insulation, and mechanical properties, making it a key polymer used in the insulation, protective layers, and circuit packaging of multi-layer wiring and multi-chip assemblies in the new generation of integrated circuits. However, the highly rigid and conjugated aromatic heterocyclic ring structure of traditional polyimide backbones makes them difficult to melt process and exhibits poor solubility. Furthermore, the susceptibility to charge transfer complexes within the molecule leads to a characteristic yellow or brown appearance, severely limiting their application.

[0003] To achieve highly transparent polyimide materials, researchers typically improve PI transmittance by introducing bulky substituents, fluorinated groups, asymmetric structures, alicyclic structures, and non-coplanar structures into the molecular chain. However, existing colorless, transparent PI materials still suffer from significant deficiencies in heat resistance and dimensional stability, making them difficult to meet application requirements. Reducing the coefficient of thermal expansion (CTE) of polyimide materials and improving their dimensional stability are key research areas in the development of transparent polyimide materials.

[0004] In the prior art, the main method for reducing the thermal expansion coefficient of polyimide materials is to introduce rigid structural units into the molecular structure, and to add low-expansion-coefficient inorganic particles to the polyimide for blending to form a composite film. Patent CN110156991A adopts naphthalene diamine and naphthalene dianhydride as raw materials, and by selecting a suitable raw material ratio and controlling suitable reaction conditions, the purpose of reducing the thermal expansion coefficient is achieved. Patent CN110372895A discloses a low-thermal-expansion-coefficient SiO2 / polyimide composite film and its preparation method. Rigid pyromellitic dianhydride and 2-(4-aminophenyl)-5-amino-benzoxazole monomer are used to synthesize a rigid main-chain polyimide, and low-expansion-coefficient SiO2 / is added and in-situ blended to obtain a low-thermal-expansion-coefficient SiO2 / polyimide composite film. Although the thermal expansion coefficient of the film can be reduced, the transparency of the film is affected. Summary of the Invention

[0005] In order to reduce the expansion coefficient of polyimide without affecting the transmittance and mechanical properties of the polyimide film, the present application provides a cross-linking agent containing a fluorene structure. The negative photosensitive resin composition film containing the cross-linking agent has high resolution, low thermal expansion coefficient, excellent mechanical properties and chemical resistance, and does not affect the transmittance of the polyimide film. It can be used for chip protection passivation films, insulating films, buffer protective layers, etc. in advanced microelectronics manufacturing and packaging.

[0006] This application designs and synthesizes a cross-linking agent by simultaneously introducing double bonds and fluorene structures into the structure. The introduction of the fluorene structure can improve the rigidity of the overall structure. The cross-linking agent shown in Formula I is added to the resin composition. The resulting polyimide film has a low thermal expansion coefficient and excellent mechanical properties. At the same time, it does not affect the transmittance of the polyimide film and can be used for insulating films and packaging materials of precision electronic devices.

[0007] According to a first aspect of the present application, a negative photosensitive resin composition is provided, which is formed by combining the components of the following formula, wherein the negative photosensitive resin composition includes the following components:

[0008] Component a: crosslinking agent;

[0009] Component b: polyimide precursor resin;

[0010] Component c: photoinitiator;

[0011] Component d: coupling agent;

[0012] Component e: solvent;

[0013] The cross-linking agent has a structure shown in Formula I;

[0014]

[0015] The X structure includes the structure shown in Formula I-1, Formula I-2, Formula I-3 or Formula I-4, wherein * represents an access point;

[0016]

[0017]

[0018] The Y structure includes the structure shown in Formula I-5 or Formula I-6, wherein * represents an access point;

[0019]

[0020] Wherein, Cy is selected from one of azetidine, azopentane, and azohexane;

[0021] R1 and R2 are independently selected from C1 to C4 alkyl groups;

[0022] n is a positive integer from 2 to 4, indicating that the Y structure can connect to any 2 to 4 of the 4 access points in the X structure.

[0023] The polyimide precursor resin has a structure shown in Formula II:

[0024]

[0025] In formula II, R3 is a tetravalent organic group having 2 to 16 carbon atoms; R4 is a divalent organic group having 2 to 20 carbon atoms;

[0026] n1 is an integer from 2 to 200;

[0027] R5 and R6 are independently selected from a hydrogen atom, a monovalent organic group having a structure represented by formula III, and a saturated aliphatic group having 1 to 4 carbon atoms;

[0028]

[0029] In formula III, R7, R8, and R9 are independently selected from a hydrogen atom or an organic group having 1 to 3 carbon atoms, m is an integer of 2 to 10, and * represents an insertion site.

[0030] Alternatively, Cy represents a divalent group of an aliphatic heterocycle including azetidine, azopentane, or azohexane, and the nitrogen atom is substituted with a carbon atom at any position on the aliphatic heterocycle. R1 and R2 represent an alkyl group having 1 to 4 carbon atoms, and * represents an attachment point.

[0031] Optionally, the cross-linking agent is selected from at least one of the structures represented by Formula A-1 to Formula A-12;

[0032]

[0033] Optionally, the preparation method of the cross-linking agent includes:

[0034] reacting a mixture of a fluorene structure-containing compound, a compound represented by formula V, a catalyst, and an organic solvent to obtain the cross-linking agent;

[0035] The fluorene structure-containing compound has a structure shown in Formula IV:

[0036]

[0037] In formula IV, the structure X and n are the same as those in claim 1, and R 10 At least one selected from fluorine, chlorine, and bromine;

[0038] The compound represented by formula V includes the structure represented by formula V-1 or formula V-2;

[0039]

[0040] Here, Cy, R1, and R2 are the same as Cy, R1, and R2 in claim 1.

[0041] Optionally, the molar ratio of the fluorene structure-containing compound to the compound represented by formula V is 1:1.0-1.1, wherein the molar amount of the fluorene structure-containing compound is based on the molar ratio of R10 The molar amount of

[0042] Optionally, the catalyst is selected from at least one of KHCO3, NaHCO3, K2CO3, Na2CO3, and N,N-diisopropylethylamine.

[0043] Optionally, the organic solvent is selected from at least one of tetrahydrofuran, acetone, toluene, N,N-dimethylformamide, and xylene.

[0044] Optionally, R 10 The molar ratio of the catalyst to the catalyst is 1: (1 to 1.5).

[0045] Optionally, the mass ratio of the fluorene structure-containing compound to the organic solvent is 1:(2-10).

[0046] Optionally, the reaction includes a first reaction stage, a second reaction stage and a third reaction stage;

[0047] The temperature of the first reaction stage is -5 to 0°C, and the time of the first reaction stage is 1 to 5 hours;

[0048] The temperature of the second reaction stage is 20-30°C, and the time of the second reaction stage is 1-5 hours;

[0049] The temperature of the third reaction stage is 60-80° C., and the time of the third reaction stage is 1-5 hours.

[0050] Optionally, the reaction is followed by a purification process, which includes extraction, drying, filtration, and concentration.

[0051] Optionally, the mass ratio of the polyimide precursor resin to the cross-linking agent is 100:(20-150).

[0052] Optionally, the mass ratio of the polyimide precursor resin to the photoinitiator is 100:(0.1-20).

[0053] Optionally, the mass ratio of the polyimide precursor resin to the coupling agent is 100:(0.2-10).

[0054] Optionally, the mass ratio of the polyimide precursor resin to the solvent is 100:(80-5000).

[0055] Optionally, the R3 is derived from tetracarboxylic dianhydride.

[0056] Optionally, the R4 is derived from a diamine.

[0057] Optionally, the structural compound represented by formula III is derived from an alcohol containing an unsaturated double bond.

[0058] Optionally, the cross-linking agent further includes other cross-linking agents, and the other cross-linking agents include at least one of a carbon-carbon double bond cross-linking agent and a thermal cross-linking agent.

[0059] Optionally, the carbon-carbon double bond crosslinking agent is selected from diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, p-vinylbenzene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isobutyl acrylate, Octyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate Acrylates, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, N-hydroxymethylacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, At least one of 1,2-dimethoxy-2-piperidinyl acrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, propoxylated bisphenol A diacrylate, propoxylated bisphenol A methacrylate, propoxylated ethoxylated bisphenol A diacrylate, propoxyethoxylated bisphenol A dimethacrylate, N-vinyl caprolactam, polyethylene glycol diacrylate, 2-isocyanatoethyl methacrylate, 9,9-bis(4-allyloxyphenyl)fluorene, 9,9-bis[4-(2-hydroxy-3-acryloyloxypropoxy)phenyl]fluorene, and 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene.

[0060] Optionally, the thermal crosslinking agent is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD ​​epoxy resin, dimethylol urea, dimethylol ethylene urea, dimethylol propylene urea, trimethylol melamine, and hexamethylol melamine.

[0061] Optionally, in the polyimide precursor resin having the structure shown in Formula II, R3 is derived from tetracarboxylic dianhydride.

[0062] Optionally, the tetracarboxylic dianhydride is selected from at least one of pyromellitic dianhydride, 4,4'-oxydiphthalic anhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane.

[0063] Optionally, in the polyimide precursor resin having the structure shown in Formula II, R4 is derived from diamine.

[0064] Alternatively, the diamine is selected from p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4 At least one of 1,4-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, 2,2-bis(4-aminophenyl)benzene, 1,4-bis(3-aminopropyldimethylsilyl)benzene, and 4,4'-diamino-2,2'-dimethylbicyclohexane.

[0065] Optionally, the structural compound represented by formula III is derived from alcohols having an unsaturated double bond.

[0066] Optionally, the alcohol with unsaturated double bonds is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acrylamideethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-methyl At least one of acryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0067] Optionally, the photoinitiator is selected from at least one of benzophenone compounds, benzyl compounds, coumarin compounds, anthraquinone compounds, benzoin compounds, thioxanthone compounds, thiol compounds, glycine compounds, oxime compounds, α-aminoalkylphenone compounds, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name: BAPO, manufactured by Wuhan Yuancheng Technology).

[0068] Optionally, the benzophenone compound is selected from at least one of benzophenone, 4,4-bis(diethylamino)benzophenone, and 3,3,4,4-tetra(tert-butylperoxycarbonyl)benzophenone.

[0069] Optionally, the coumarin compound is selected from at least one of 3,5-bis(diethylaminobenzylidene)-N-methyl-4-piperidone, 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone and the like; 7-diethylamino-3-nonyl coumarin, 4,6-dimethyl-3-ethylamino coumarin, 3,3-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3-(1-methylbenzimidazolyl) coumarin and 3-(2-benzothiazolyl)-7-diethylaminocoumarin.

[0070] Optionally, the anthraquinone compound is selected from anthraquinone compounds such as 2-tert-butylanthraquinone, 2-ethylanthraquinone, and 1,2-benzanthraquinone.

[0071] Optionally, the benzoin compound is selected from at least one of benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.

[0072] Optionally, the thioxanthone compound is selected from at least one of 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-isopropylthioxanthone.

[0073] Optionally, the mercapto compound is selected from at least one of ethylene glycol di(3-mercaptopropionate), 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole;

[0074] Optionally, the glycine compound is selected from at least one of N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-(p-chlorophenyl)glycine, and N-(4-cyanophenyl)glycine.

[0075] Optionally, the oxime compound is selected from at least one of 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-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (trade name: OXE-01, manufactured by BASF), and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyloxime) (trade name: OXE-02, manufactured by BASF).

[0076] Optionally, the α-aminoalkylphenone compound is selected from at least one of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one.

[0077] Optionally, the coupling agent is selected from at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis(γ-aminopropyl)tetramethylsiloxane, bis(γ-aminobutyl)tetramethylsiloxane, bis(γ-aminopropyl)tetraphenylsiloxane, bis(γ-aminopropyl)tetraphenylpolysiloxane, bis(γ-aminopropyl)tetraphenylsiloxane, bis(γ-aminobutyl)tetraphenylpolysiloxane, 3-(2,3-epoxypropoxy)propyltriethoxysilane, vinyltriethoxysilane, and vinyltrimethoxysilane.

[0078] Optionally, the solvent is selected from at least one of N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, and butyl acetate.

[0079] According to a second aspect of the present application, a method for preparing the negative photosensitive resin composition is provided, the method comprising:

[0080] stirring a mixture containing component a, component b, component c, component d, and component e to obtain the negative photosensitive resin composition;

[0081] The component a, component b, component c, component d, and component e are consistent with the component a, component b, component c, component d, and component e described above.

[0082] According to a third aspect of the present application, there is provided a use of the negative photosensitive resin composition described above in a chip protection passivation film, an insulating film, and a buffer protection layer in advanced microelectronics manufacturing and packaging.

[0083] In the present application, a method for preparing a polyamic acid ester resin comprises the following steps:

[0084] 1) Tetracarboxylic dianhydride reacts with an alcohol compound to form a diacid diester, wherein the alcohol compound is a compound having a structure shown in Formula III and is derived from an alcohol having an unsaturated double bond.

[0085] 2) the diacid diester reacts with an acyl chloride reagent to form a corresponding diacid chloride diester, wherein the acyl chloride reagent is preferably at least one of SOCl2, PCl3, PCl5, oxalyl chloride or COCl2.

[0086] 3) dissolving diamine in a solvent to form a homogeneous diamine solution; wherein the molar ratio of diamine to the dianhydride in step 1) is preferably 0.8 to 1.2; and the mass percentage concentration of the diamine solution is preferably 10 to 30 wt%.

[0087] 4) The diacid chloride diester solution and the diamine solution are subjected to a condensation reaction to form a polyamic acid ester solution. Preferably, the diamine solution prepared in step 3) is added dropwise to the diacid chloride diester solution obtained in step 2) at a temperature below 10° C. and reacted at room temperature for 5 to 24 hours to form a polyamic acid ester solution.

[0088] 5) The polyamic acid ester solution is mixed with a poor solvent to precipitate a solid resin; the poor solvent may be deionized water, methanol, ethanol, hexane, butyl cellosolve, toluene, etc., preferably deionized water, methanol, and / or ethanol. The amount of the poor solvent used is preferably 3 to 20 times the mass of the total amount of the polymer solution.

[0089] 6) The solid resin is washed and dried to obtain a polyimide precursor resin. The washing is performed using the poor solvent used for precipitation in step 5). The amount of the poor solvent used for washing is preferably 1 to 6 times the mass of the polymer. The more times the polymer is washed, the less impurities are obtained. The number of washings is preferably 2 to 6. After washing, the polymer is preferably dried under vacuum at 20 to 70°C to obtain a polyimide precursor solid resin.

[0090]

[0091] Furthermore, the organic solvent I in steps 1) and 3) is the same as the above-mentioned solvent.

[0092] Furthermore, the polyimide precursor solid resin obtained in step 6) can be crushed according to application requirements.

[0093] In the present application, the concentration of monomers (including dianhydrides, diester diacids, and diamines) in the polycondensation reaction solution should, in principle, be sufficient to allow the monomers to fully dissolve and prevent the resulting polymer from precipitating. If the monomer concentration is too high, the polymer will precipitate; if the concentration is too low, the molecular weight of the polymer will not increase. Therefore, the monomer concentration of the present invention can be 5 to 35 wt%, preferably 10 to 30 wt%, relative to the total mass of the reaction solution.

[0094] In this application, a method for preparing a negative photosensitive resin composition is provided, which adopts the following technical solution:

[0095] The preparation method of the negative photosensitive resin composition is:

[0096] The polyimide precursor resin, the crosslinking agent, the photoinitiator, the coupling agent and 100 to 1000 parts by mass of the solvent are mixed and stirred until a uniform solution is formed to obtain a photosensitive resin composition solution.

[0097] The preparation process is preferably completed in a Class 1000 clean room equipped with a yellow light source, especially when the formulated amount of polyimide precursor resin, crosslinking agent, photoinitiator, and coupling agent are added to the organic solvent in sequence at room temperature, the effect is best.

[0098] The beneficial effects of this application include:

[0099] The crosslinking agent provided herein contains a fluorene group and a double bond structure. When added to a photosensitive resin composition, the resulting film exhibits high resolution, a low thermal expansion coefficient, excellent mechanical properties, and chemical resistance, while maintaining the light transmittance of the polyimide film. The crosslinking agent can be used to prepare transparent protective films and insulating layers for liquid crystal displays, chip protection passivation films for advanced microelectronics manufacturing and packaging, and interlayer insulating films and stress buffer protective layers for multilayer circuit interconnects. DETAILED DESCRIPTION

[0100] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0101] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0102] A DD2 600M superconducting Fourier transform nuclear magnetic resonance spectrometer (Anglient, USA) was used with tetramethylsilane (TMS) with a mass fraction of 0.0003 as the internal standard. 1 Characterization was performed in H spectroscopy mode.

[0103] Preparation Example 1 Preparation of crosslinking agent A-1

[0104] In a four-necked reaction flask with a stirrer and a thermometer, compound 1 (47.43 g, 0.1 mol) and NaHCO3 (16.80 g, 0.2 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 100 mL of a THF solution containing 3-butene-1-amine (14.22 g, 0.2 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 100 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated on a rotary evaporator to obtain 34.10 g of A-1 as a white solid with a yield of 75%.

[0105]

[0106] A-1 NMR information is as follows:

[0107] 1HNMR(DMSO): δ: 2.19(m,4H),3.21(m,4H),4.88(d,2H),5.13(d,2H),5.82(m,4H) ,6.65(d,2H),6.82(s,2H),7.28(m,4H),7.45(d,2H),7.80(d,2H),7.89(d,2H).

[0108] Preparation Example 2 Preparation of crosslinking agent A-2

[0109] In a four-necked reaction flask with a stirrer and a thermometer, compound 2 (47.43 g, 0.1 mol) and NaHCO3 (16.80 g, 0.2 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 100 mL of a THF solution containing 3-butene-1-amine (14.22 g, 0.2 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 100 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated on a rotary evaporator to obtain 35.01 g of white solid A-2 with a yield of 77%.

[0110]

[0111] A-2 NMR information is as follows:

[0112] 1 HNMR(DMSO): δ: 2.19(m,4H),3.21(m,4H),4.88(d,2H),5.13(d,2H),5.82(m,4H),6 .60(d,2H),6.77(s,2H),7.27-7.33(m,4H),7.50(d,2H),7.79(d,2H),7.89(d,2H).

[0113] Preparation Example 3 Preparation of crosslinking agent A-3

[0114] In a four-necked reaction flask with a stirrer and a thermometer, compound 1 (47.43 g, 0.1 mol) and NaHCO3 (16.80 g, 0.2 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 100 mL of a THF solution containing 4-vinylpiperidine (22.24 g, 0.2 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 100 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate. The filtrate was concentrated on a rotary evaporator to obtain 41.71 g of white solid A-3 with a yield of 78%.

[0115]

[0116] A-3 NMR information is as follows:

[0117] 1 HNMR(DMSO): δ: 1.38(m,4H),1.62(m,4H),2.18(m,2H),3.04-3.14(m,8H),5.03-5.07(d,4H) ,5.70(m,2H),6.71(d,2H),6.88(s,2H),7.28(m,4H),7.45(d,2H),7.72(d,2H),7.89(d,2H).

[0118] Preparation Example 4 Preparation of Crosslinking Agent A-4

[0119] In a four-necked reaction flask with a stirrer and a thermometer, compound 2 (47.43 g, 0.1 mol) and NaHCO3 (16.80 g, 0.2 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 100 mL of a THF solution containing 4-vinylpiperidine (22.24 g, 0.2 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 100 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate. The filtrate was concentrated on a rotary evaporator to obtain 40.64 g of A-4 as a white solid with a yield of 76%.

[0120]

[0121] A-4 NMR information is as follows:

[0122] 1 HNMR(DMSO): δ: 1.38(m,4H),1.62(m,4H),2.18(m,2H),3.04-3.14(m,8H),5.03-5.07(d,4H),5. 70(m,2H),6.66(d,2H),6.83(s,2H),7.27-7.33(m,4H),7.50(d,2H),7.71(d,2H),7.89(d,2H).

[0123] Preparation Example 5 Preparation of crosslinking agent A-5

[0124] In a four-necked reaction flask with a stirrer and a thermometer, compound 3 (63.20 g, 0.1 mol) and NaHCO3 (33.60 g, 0.4 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 200 mL of a THF solution containing 3-butene-1-amine (28.45 g, 0.4 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 200 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated on a rotary evaporator to obtain 46.83 g of white solid A-5 with a yield of 79%.

[0125]

[0126] A-5 NMR information is as follows:

[0127] 1 HNMR(DMSO): δ: 2.19(m,8H),3.21(m,8H),4.88(d,4H),5.13(d,4H),5.82(m,8H),6.60(d,4H),6.77(s,4H),7.79(d,4H).

[0128] Preparation Example 6 Preparation of Crosslinking Agent A-6

[0129] In a four-necked reaction flask with a stirrer and a thermometer, compound 4 (64.80 g, 0.1 mol) and NaHCO3 (33.60 g, 0.4 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 200 mL of a THF solution containing 3-butene-1-amine (28.45 g, 0.4 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 200 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated on a rotary evaporator to obtain 48.71 g of A-6 as a white solid with a yield of 80%.

[0130]

[0131] A-6 NMR information is as follows:

[0132] 1 HNMR(DMSO): δ: 2.19(m,8H),3.21(m,8H),4.88(d,4H),5.13(d,4H),5.82(m,8H) ,6.23(d,2H),6.34(s,2H),6.65(d,2H),6.82(s,2H),7.04(d,2H),7.80(d,2H).

[0133] Preparation Example 7 Preparation of Crosslinking Agent A-7

[0134] In a four-necked reaction flask with a stirrer and a thermometer, compound 5 (64.60 g, 0.1 mol) and NaHCO3 (33.60 g, 0.4 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 200 mL of a THF solution containing 3-butene-1-amine (28.45 g, 0.4 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 200 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated on a rotary evaporator to obtain 46.73 g of white solid A-7 with a yield of 77%.

[0135]

[0136] A-7 NMR information is as follows:

[0137] 1 HNMR(DMSO): δ: 2.19(m,8H),3.21(m,8H),4.63(s,2H),4.88(d,4H),5.13(d,4H),5.82(m,8H),6.65(d,4H),6.82(s,4H),7.80(d,4H).

[0138] Preparation Example 8 Preparation of Crosslinking Agent A-8

[0139] In a four-necked reaction flask with a stirrer and a thermometer, compound 6 (71.21 g, 0.1 mol) and NaHCO3 (33.60 g, 0.4 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 200 mL of a THF solution containing 3-butene-1-amine (28.45 g, 0.4 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 200 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate. The filtrate was concentrated on a rotary evaporator to obtain 53.16 g of A-8 as a white solid with a yield of 79%.

[0140]

[0141] A-8 NMR information is as follows:

[0142] 1 HNMR(DMSO): δ: 2.19(m,8H),2.42(s,8H),3.21(m,8H),4.88(d,4H),5.13(d,4H),5.82(m,8H),6.65(d,4H),6.82(s,4H),7.80(d,4H).

[0143] Preparation Example 9 Preparation of Crosslinking Agent A-9

[0144] In a four-necked reaction flask with a stirrer and a thermometer, compound 3 (63.20 g, 0.1 mol) and NaHCO3 (33.60 g, 0.4 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 200 mL of a THF solution containing 4-vinylpiperidine (44.48 g, 0.4 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 200 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate. The filtrate was concentrated on a rotary evaporator to obtain 61.00 g of A-9 as a white solid with a yield of 81%.

[0145]

[0146] A-9 NMR information is as follows:

[0147] 1 HNMR(DMSO): δ: 1.38(m,8H),1.62(m,8H),2.18(m,4H),3.04-3.14(m,16H ),5.03-5.07(d,8H),5.70(m,4H),6.66(d,4H),6.83(s,4H),7.71(d,4H).

[0148] Preparation Example 10 Preparation of Crosslinking Agent A-10

[0149] In a four-necked reaction flask with a stirrer and a thermometer, compound 4 (64.80 g, 0.1 mol) and NaHCO3 (33.60 g, 0.4 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 200 mL of a THF solution containing 4-vinylpiperidine (44.48 g, 0.4 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 200 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate. The filtrate was concentrated on a rotary evaporator to obtain 63.07 g of A-10 as a white solid with a yield of 82%.

[0150]

[0151] A-10 NMR information is as follows:

[0152] 1 HNMR(DMSO): δ: 1.38(m,8H),1.62(m,8H),2.18(m,4H),3.04-3.14(m,16H),5.03-5.07(d,8H) ,5.70(m,4H),6.23(s,2H),6.39(d,2H),6.71(d,2H),6.88(s,2H),6.96(d,2H),7.72(d,2H).

[0153] Preparation Example 11 Preparation of Crosslinking Agent A-11

[0154] In a four-necked reaction flask with a stirrer and a thermometer, compound 5 (64.60 g, 0.1 mol) and NaHCO3 (33.60 g, 0.4 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 200 mL of a THF solution containing 4-vinylpiperidine (44.48 g, 0.4 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 200 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate. The filtrate was concentrated on a rotary evaporator to obtain 61.37 g of A-11 as a white solid with a yield of 80%.

[0155]

[0156] A-11 NMR information is as follows:

[0157] 1 HNMR(DMSO): δ: 1.38(m,8H),1.62(m,8H),2.18(m,4H),3.04-3.14(m,16H),4.63 (s,2H),5.03-5.07(d,8H),5.70(m,4H),6.71(d,4H),6.88(s,4H),7.72(d,4H).

[0158] Preparation Example 12 Preparation of crosslinking agent A-12

[0159] In a four-necked reaction flask with a stirrer and thermometer, compound 6 (71.21 g, 0.1 mol) and NaHCO3 (33.60 g, 0.4 mol) were added to 200 mL of tetrahydrofuran (THF) and cooled to 0°C. 200 mL of a THF solution containing 4-vinylpiperidine (44.48 g, 0.4 mol) was added dropwise to the above solution. After the addition was complete, the mixture was stirred at 0°C for 3 h, then heated to 25°C and stirred for 3 h, and finally heated to 65°C and stirred for 3 h. The reaction was completed. After the temperature cooled to room temperature, the reaction solution was transferred to a separatory funnel, 100 g of toluene and 200 ml of pure water were added for extraction. The aqueous layer was separated and the above operation was repeated 3 times. Finally, the organic phase was dried over MgSO4 to remove water and filtered to obtain a clear filtrate. The filtrate was concentrated on a rotary evaporator to obtain 69.16 g of A-12 as a white solid with a yield of 83%.

[0160]

[0161] A-12 NMR information is as follows:

[0162] 1 HNMR(DMSO): δ: 1.38(m,8H),1.62(m,8H),2.18(m,4H),2.42(s,8H),3.04-3.14( m,16H),5.03-5.07(d,8H),5.70(m,4H),6.71(d,4H),6.88(s,4H),7.72(d,4H).

[0163] Synthesis Example 1 Synthesis of polyimide precursor resin S-1

[0164] Under nitrogen flow, 31.02 g (0.1 mol) of 4,4'-oxydiphthalic anhydride, 0.07 g (0.0007 mol) of triethylamine, 26.29 g (0.202 mol) of hydroxyethyl methacrylate, and 100 g of N-methylpyrrolidine (NMP) were added to a 500 mL three-necked flask in sequence, stirred to dissolve, and reacted at 25°C for 24 h; then 24.03 g (0.202 mol) of SOCl2 was added dropwise, and the temperature of the reaction system was controlled below 0°C during the addition process; after the addition was completed, the reaction was continued at 0°C for 3 h to obtain reaction solution B.

[0165] Under nitrogen flow, 22.44 g (0.1 mol) of 4,4'-diamino-2,2'-dimethylbicyclohexane was weighed and added to a 500 mL three-necked flask, and then 100 g of NMP and 27.69 g (0.35 mol) of pyridine were added in sequence, stirred and dissolved, the reaction system was cooled to below 0°C, and then the reaction solution B was slowly added dropwise, and the temperature of the reaction system was controlled to be below 0°C during the addition process; after the addition was completed, the reaction was continued at 0°C for 3 h, and the reaction was terminated; the polymer solution was poured into 3 L of deionized water, a white polymer precipitate was precipitated, filtered, washed three times with deionized water, and vacuum dried at 80°C for 48 h to obtain a polyimide precursor resin S-1.

[0166] The weight average molecular weight (M) of each resin was measured by gel permeation chromatography (based on standard polystyrene). w ), and a GPC system of Shimadzu Corporation of Japan was used for the measurement. The weight average molecular weight (Mw) of the polyimide precursor resin obtained in Synthesis Example 1 was 20,000 to 30,000.

[0167] Example 1

[0168] In a three-necked flask equipped with a stirrer, 10.0 g of polyimide precursor resin S-1 was dissolved in 20 g of N-methylpyrrolidone (NMP). After sufficient dissolution, 5 g of crosslinker A-1, 0.5 g of photoinitiator 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) (OXE-01), and 0.5 g of vinyltrimethoxysilane were added. After sufficient dissolution, the mixture was filtered using a 1.0 μm filter membrane to obtain a photosensitive resin composition P-1.

[0169] Example 2

[0170] Except that the cross-linking agent A-1 was changed from 5 g to 2 g, the other steps were the same as those in Example 1.

[0171] Example 3

[0172] Except that the cross-linking agent A-1 was changed from 5 g to 10 g, other ingredients were the same as those in Example 1.

[0173] Example 4

[0174] Except that the cross-linking agent A-1 was changed from 5 g to 15 g, the other steps were the same as those in Example 1.

[0175] Example 5

[0176] Except that the cross-linking agent A-1 was replaced by A-2, the other steps were the same as those in Example 1.

[0177] Example 6

[0178] Except that the cross-linking agent A-1 was replaced by A-3, the other steps were the same as those in Example 1.

[0179] Example 7

[0180] Except that the cross-linking agent A-1 was replaced by A-4, the other steps were the same as those in Example 1.

[0181] Example 8

[0182] Except that the cross-linking agent A-1 was replaced by A-5, the other steps were the same as those in Example 1.

[0183] Example 9

[0184] Except that the cross-linking agent A-1 was replaced by A-6, the other steps were the same as those in Example 1.

[0185] Example 10

[0186] Except that the cross-linking agent A-1 was replaced by A-7, the other steps were the same as those in Example 1.

[0187] Example 11

[0188] Except that the cross-linking agent A-1 was replaced by A-8, the other steps were the same as those in Example 1.

[0189] Example 12

[0190] Except that the cross-linking agent A-1 was replaced by A-9, the other steps were the same as those in Example 1.

[0191] Example 13

[0192] Except that the cross-linking agent A-1 was replaced by A-10, other procedures were the same as in Example 1.

[0193] Example 14

[0194] Except that the cross-linking agent A-1 was replaced by A-11, the other steps were the same as those in Example 1.

[0195] Example 15

[0196] Except that the cross-linking agent A-1 was replaced by A-12, the other steps were the same as those in Example 1.

[0197] Example 16

[0198] Except that the photoinitiator was replaced with phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), other processes were the same as those in Example 1.

[0199] Example 17

[0200] The same procedures as in Example 1 were followed except that the photoinitiator was replaced with 0.25 g of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (OXE-01) and 0.25 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO).

[0201] Example 18

[0202] Except that the cross-linking agent A-1 was replaced by 2.5 g A-8 and 2.5 g A-12, the other steps were the same as those in Example 1.

[0203] Example 19

[0204] Except that the cross-linking agent 1 was replaced by 2.5 g of A-12 and 2.5 g of pentaerythritol tetraacrylate, the other steps were the same as those in Example 1.

[0205] Comparative Example 1

[0206] Except that the crosslinking agent A-1 is replaced by 9,9-bis[4-(2-hydroxy-3-acryloyloxypropoxy)phenyl]fluorene, that is, the compound having the structure represented by formula (4), the rest is the same as in Example 1.

[0207]

[0208] Comparative Example 2

[0209] Except that the cross-linking agent A-1 is replaced by 9,9-bis(4-allyloxyphenyl)fluorene, that is, the compound with the structure shown in formula (5), the rest is the same as Example 1.

[0210]

[0211] Comparative Example 3

[0212] Except that the crosslinking agent A-1 was changed to pentaerythritol tetraacrylate, other processes were the same as those in Example 1.

[0213] Comparative Example 4

[0214] Except that no cross-linking agent was added to the system, other aspects were the same as those in Example 1.

[0215] The film forming properties, light transmittance, coefficient of thermal expansion (CTE), mechanical properties, and chemical resistance of the resin composition prepared above were tested. The test results are shown in Table 1. The method is as follows:

[0216] 1. Resolution

[0217] The photosensitive polyamic acid resin compositions obtained in the above examples and comparative examples were uniformly coated on a silicon wafer using a coating machine, and then placed on a heating table (HT-300 experimental hot plate, Guangzhou Gedan Instrument Co., Ltd.) at 105°C for 3 minutes for soft baking. A mask with a circular through-hole pattern was set on an i-line exposure machine (BG401A, China Electronics Technology Corporation) and the exposure was carried out at a rate of 400 mJ / cm 2The film was exposed to an exposure dose of 10 μm. After exposure, the film was developed with cyclopentanone for 90 seconds, then rinsed with pure water and dried to obtain a pattern with a film thickness of 10 μm. The pattern was observed using an optical microscope (MX63-F, Olympus) at a magnification of 20x, and the minimum size of the resolvable through-hole pattern was defined as the resolution.

[0218] 2. Light transmittance

[0219] The transmittance of the cured film of the resin composition was tested using UV (UV-2600), and the transmittance of the film was tested at 450 nm.

[0220] 3. Coefficient of thermal expansion (CTE)

[0221] The cured film of the resin composition was cut into strips with a length of 20 mm and a width of 3 mm. The thermal expansion coefficient of the film was tested using TMA (TA, TMA450) at a heating rate of 5° C. / min.

[0222] 4. Mechanical properties

[0223] Cut the cured resin composition film into 20 mm long and 3 mm wide strips. DMA (TA, DMA850) was used to test the tensile strength of the film. The tensile rate was 3 N / min. Five strips were measured in each group. The highest and lowest values ​​were removed, and the remaining three values ​​were averaged to obtain the tensile strength.

[0224] 5. Chemical resistance

[0225] The resin composition sample was evenly coated on a silicon wafer and then placed on a heating table at 105°C (HT-300 experimental electric hot plate, Guangzhou Gedaner Co., Ltd.) for 5 minutes of soft baking to obtain a resin film with a film thickness of 15 μm. The film was then placed in a vacuum oxygen-free oven (MOLZK-32D1) and heat-treated at 150°C for 30 minutes under nitrogen atmosphere. The temperature was then raised to 200°C after 30 minutes and treated at 200°C for 1 hour. It was then naturally cooled to below 50°C in the oven to finally obtain a cured film. The cured film was immersed in a 10wt% sodium hydroxide (NaOH) aqueous solution, a 10% sulfuric acid aqueous solution, and N-methylpyrrolidone (NMP) at 50°C for 30 minutes respectively to observe whether there were cracks. The crack condition of the film was evaluated according to the following standards:

[0226] “None”: no cracks;

[0227] “Minor”: Minor cracks can be observed;

[0228] “Severe”: A large number of cracks, or even the membrane breaks into pieces.

[0229] Table 1

[0230]

[0231]

[0232] By comparing the data of Examples 1-15 and Comparative Examples 1-4 in Table 1, it can be seen that the resin composition containing the crosslinking agent of the present invention has excellent resolution, and the prepared cured film of the resin composition has high light transmittance, low thermal expansion coefficient, high tensile strength and excellent chemical resistance.

[0233] By comparing Examples 1-4 and Comparative Examples 1-4, it can be seen that the mass ratio of the polyimide precursor resin to the fluorene-containing crosslinking agent of the present invention in the range of 100:(20-150) can reduce the thermal expansion coefficient of the cured film of the resin composition and improve the mechanical properties of the cured film of the resin composition.

[0234] By comparing Example 17 with Examples 1-16, 18 and Comparative Examples 1-4, it can be seen that when the crosslinker A-12 of the present invention is combined with the photoinitiator OXE-01 and BAPO, the resolution of the resin composition is optimal, while the transmittance, thermal expansion coefficient and chemical resistance are optimal, the tensile strength is high, and the overall performance is optimal.

[0235] By comparing Example 19 with Example 1, it can be seen that the crosslinking agent of the present invention can be used together with other crosslinking agents, and the prepared cured film of the resin composition has high light transmittance, low thermal expansion coefficient, high tensile strength and excellent chemical resistance.

[0236] In summary, the fluorene-containing crosslinking agent of the present invention can be used in a resin composition. The polyimide film obtained after thermal curing of the resin composition containing the crosslinking agent has a low thermal expansion coefficient, excellent resolution, mechanical properties and chemical resistance, and does not affect the transmittance of the polyimide film. It can be used as an insulating film and packaging film material for precision electronic devices.

[0237] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A negative photosensitive resin composition, characterized in that The negative photosensitive resin composition is formed by combining the components of the following formula, and includes the following components: Component a: crosslinking agent; Component b: polyimide precursor resin; Component c: photoinitiator; Component d: coupling agent; Component e: solvent; The cross-linking agent has a structure shown in Formula I; The X structure includes the structure shown in Formula I-1, Formula I-2, Formula I-3 or Formula I-4, wherein * represents an access point; The Y structure includes the structure shown in Formula I-5 or Formula I-6, wherein * represents an access point; Wherein, Cy is selected from one of azetidine, azopentane, and azohexane; R1 and R2 are independently selected from C1 to C4 alkyl groups; n is a positive integer from 2 to 4, indicating that the Y structure can connect to any 2 to 4 of the 4 access points in the X structure. The polyimide precursor resin has a structure shown in Formula II: In formula II, R3 is a tetravalent organic group having 2 to 16 carbon atoms; R4 is a divalent organic group having 2 to 20 carbon atoms; The R3 is derived from tetracarboxylic dianhydride; the R4 is derived from diamine; n1 is an integer from 2 to 200; R5 and R6 are independently selected from a monovalent organic group having a structure represented by formula III; The structural compound represented by formula III is derived from an alcohol containing an unsaturated double bond; in formula III, R7, R8, and R9 are independently selected from hydrogen atoms or organic groups having 1 to 3 carbon atoms, m is an integer from 2 to 10, and * represents an accession site.

2. The negative photosensitive resin composition according to claim 1, wherein The cross-linking agent is selected from at least one of the structures represented by formula A-1 to formula A-12; 3. The negative photosensitive resin composition according to claim 1, wherein The preparation method of the cross-linking agent comprises: reacting a mixture of a fluorene structure-containing compound, a compound represented by formula V, a catalyst, and an organic solvent to obtain the cross-linking agent; The fluorene structure-containing compound has a structure shown in Formula IV: In formula IV, the structure X and n are the same as those in claim 1, and R 10 At least one selected from fluorine, chlorine, and bromine; The compound represented by formula V includes the structure represented by formula V-1 or formula V-2; Here, Cy, R1, and R2 are the same as Cy, R1, and R2 in claim 1.

4. The negative photosensitive resin composition according to claim 3, characterized in that The molar ratio of the fluorene structure-containing compound to the compound represented by formula V is 1:1.0-1.1, wherein the molar amount of the fluorene structure-containing compound is based on the molar ratio of R in the fluorene structure. 10 The molar amount of 5. The negative photosensitive resin composition according to claim 3, wherein The catalyst is selected from at least one of KHCO3, NaHCO3, K2CO3, Na2CO3, and N,N-diisopropylethylamine.

6. The negative photosensitive resin composition according to claim 3, wherein The organic solvent is selected from at least one of tetrahydrofuran, acetone, toluene, N,N-dimethylformamide and xylene.

7. The negative photosensitive resin composition according to claim 3, wherein In the fluorene structure-containing compound, R 10 The molar ratio of the catalyst to the catalyst is 1: (1 to 1.5).

8. The negative photosensitive resin composition according to claim 3, wherein The mass ratio of the fluorene structure-containing compound to the organic solvent is 1:(2-10).

9. The negative photosensitive resin composition according to claim 3, wherein The reaction includes a first reaction stage, a second reaction stage and a third reaction stage; The temperature of the first reaction stage is -5 to 0°C, and the time of the first reaction stage is 1 to 5 hours; The temperature of the second reaction stage is 20-30°C, and the time of the second reaction stage is 1-5 hours; The temperature of the third reaction stage is 60-80° C., and the time of the third reaction stage is 1-5 hours.

10. The negative photosensitive resin composition according to claim 1, wherein The mass ratio of the polyimide precursor resin to the cross-linking agent is 100:(20-150).

11. The negative photosensitive resin composition according to claim 1, wherein The mass ratio of the polyimide precursor resin to the photoinitiator is 100:(0.1-20).

12. The negative photosensitive resin composition according to claim 1, wherein The mass ratio of the polyimide precursor resin to the coupling agent is 100:(0.2-10).

13. The negative photosensitive resin composition according to claim 1, wherein The mass ratio of the polyimide precursor resin to the solvent is 100:(80-5000).

14. The method for preparing the negative photosensitive resin composition according to claim 1, wherein: The preparation method comprises: The mixture containing component a, component b, component c, component d, and component e is stirred uniformly and filtered to obtain the negative photosensitive resin composition; The component a, component b, component c, component d, and component e are consistent with the component a, component b, component c, component d, and component e in claim 1.

15. Use of the negative photosensitive resin composition according to claim 1 in chip protection passivation films, insulating films, and buffer protection layers in advanced microelectronics manufacturing and packaging.

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