Negative photosensitive resin composition and preparation method and application thereof

Abstract

The invention discloses a negative photosensitive resin composition and a preparation method and application thereof. The negative photosensitive resin composition comprises polyimide precursor resin, a cross-linking agent, a photoinitiator, a coupling agent and a solvent. The composition disclosed by the invention has relatively high light transmittance and resolution ratio after being cured into a film, and has relatively low thermal expansion coefficient, excellent mechanical property and chemical resistance after being cured. The method can be used in the high-tech field with high resolution, low expansion coefficient and high tensile strength requirements.

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 type of organic polymer material containing an imide ring. It has good chemical stability, electrical insulation and mechanical properties. It is the main polymer for the insulation layer, protective layer and circuit packaging of the new generation of integrated circuit multilayer wiring and multi-chip components. The highly rigid and conjugated aromatic heterocyclic structure in the main chain of traditional polyimide makes polyimide difficult to melt process and has poor solubility. The easy formation of charge transfer complexes in its molecules leads to a characteristic yellow or brown appearance, which seriously affects and limits the application of polyimide.

[0003] In order to obtain highly transparent polyimide materials, researchers usually introduce bulky substituents, fluorine-containing groups, asymmetric structures, alicyclic structures and non-coplanar structures into the molecular chain to improve the light transmittance of PI. However, the existing colorless and transparent PI materials still have obvious defects in heat resistance and dimensional stability, which are difficult to meet application needs. How to reduce the coefficient of thermal expansion (CTE) of polyimide materials and improve the dimensional stability of the materials is an important research direction for 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 inorganic particles with low thermal expansion coefficient to the polyimide for blending to form a composite film. In patent CN110156991A, naphthalene diamine and naphthalene dianhydride are used as raw materials, and the purpose of reducing the thermal expansion coefficient is achieved by selecting a suitable raw material ratio and controlling suitable reaction conditions. 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 rigid main chain polyimide, and low thermal expansion coefficient SiO2 / is added for in-situ blending 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] The present 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, the transmittance of the polyimide film is not affected, and it can be used for insulating films and packaging materials for precision electronic devices.

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

[0008] Component a: cross-linking 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 of 2 to 4, indicating that the Y structure selects 2 to 4 access points from the 4 access points in the X structure for connection;

[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] Optionally, Cy represents a divalent group of an aliphatic heterocycle including azetidine, azopentane, and azohexane, and the nitrogen atom is substituted by 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 shown in Formula A-1 to Formula A-12;

[0032]

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

[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 the structure X and n 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] Among them, 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:(1-1.5).

[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 to 30° C., and the time of the second reaction stage is 1 to 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 treatment, 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 compound having the structure shown in 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 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 tetramethyl Acrylates, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-diacryloxy-2-hydroxypropane, 1,3-dimethacryloxy-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-1,2-dipiperidinyl 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] Optionally, 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 '-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 compound of the structure 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-acryloxyethanol, 1-acryloxy-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-methacrylamideethanol, 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 at least one selected from benzophenone, 4,4-bis(diethylamino)benzophenone, and 3,3,4,4-tetra(tert-butylperoxycarbonyl)benzophenone.

[0069] Optionally, the coumarin compound is selected from benzylidene compounds such as 3,5-bis(diethylaminobenzylidene)-N-methyl-4-piperidone, 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone; 7-diethylamino-3-nonyl coumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3-(1-methylbenzimidazolyl) coumarin, and at least one of 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-benzoyl oxime) (trade name: OXE-01, manufactured by BASF), and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(0-acetyl oxime) (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-epoxypropyloxy)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, tetramethyl urea, 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 described above is provided, the preparation method comprising:

[0080] The mixture containing component a, component b, component c, component d and component e is stirred uniformly 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 polycondensation 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 is preferably 3 to 20 times the total amount of the polymer solution by mass.

[0089] 6) After washing and drying the solid resin, a polyimide precursor resin is obtained. The washing is carried out by washing with the poor solvent used for precipitation in step 5), and 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 can be obtained. The number of washings is preferably 2 to 6 times. 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 consistent with 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 liquid can in principle satisfy the conditions that the monomers are fully dissolved and the generated polymers do not precipitate. If the monomer concentration is too high, the polymer will precipitate; and 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 liquid.

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

[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, thereby obtaining 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 in the present application contains a fluorene group and a double bond structure in its structure. When added to a photosensitive resin composition, the film made from the photosensitive resin composition has high resolution, low thermal expansion coefficient, excellent mechanical properties and chemical resistance, and does not affect the light transmittance of the polyimide film. It can be used to prepare transparent protective films and insulating layers of liquid crystal display devices, chip protection passivation films in advanced microelectronics manufacturing and packaging, interlayer insulating films for multi-layer circuit interconnection, and stress buffer protective layer films. 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 The 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), cooled to 0°C, and 100 mL of THF solution containing 3-butene-1-amine (14.22 g, 0.2 mol) was added dropwise to the above solution. After the addition was completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h, and the reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 100 ml of pure water were added for extraction, the water layer was separated and removed, and the above operation was repeated 3 times. Finally, the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated with a rotary evaporator to obtain a white solid A-1, 34.10 g, 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), cooled to 0°C, and 100 mL of THF solution containing 3-butene-1-amine (14.22 g, 0.2 mol) was added dropwise to the above solution. After the addition was completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h. The reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 100 ml of pure water were added for extraction, the water layer was separated and removed, and the above operation was repeated 3 times. Finally, the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated with a rotary evaporator to obtain a white solid A-2, 35.01 g, 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), cooled to 0°C, and 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 completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h, and the reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 100 ml of pure water were added for extraction, the water layer was separated and removed, and the above operation was repeated 3 times. Finally, the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated with a rotary evaporator to obtain a white solid A-3, 41.71 g, 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), cooled to 0°C, and 100 mL of THF solution containing 4-vinylpiperidine (22.24 g, 0.2 mol) was added dropwise to the above solution. After the addition was completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h. The reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 100 ml of pure water were added for extraction, the water layer was separated and removed, and the above operation was repeated 3 times. Finally, the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated with a rotary evaporator to obtain a white solid A-4, 40.64 g, 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), cooled to 0°C, and 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 completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h. The reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 200 ml of pure water were added for extraction, the water layer was separated and removed, and the above operation was repeated 3 times. Finally, the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated using a rotary evaporator to obtain a white solid A-5, 46.83 g, 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), cooled to 0°C, and 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 completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h, and the reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 200 ml of pure water were added for extraction, and the water layer was removed by separation. The above operation was repeated 3 times, and finally the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated by a rotary evaporator to obtain a white solid A-6, 48.71 g, 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-mouth 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), cooled to 0°C, and 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 completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h, and the reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 200 ml of pure water were added for extraction, and the water layer was removed by separation. The above operation was repeated 3 times, and finally the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated by a rotary evaporator to obtain a white solid A-7, 46.73 g, 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), cooled to 0°C, and 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 completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h. The reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 200 ml of pure water were added for extraction, the water layer was separated and removed, and the above operation was repeated 3 times. Finally, the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated using a rotary evaporator to obtain a white solid A-8, 53.16 g, 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), cooled to 0°C, and 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 completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h, and the reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 200 ml of pure water were added for extraction, and the water layer was removed by separation. The above operation was repeated 3 times, and finally the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated by a rotary evaporator to obtain a white solid A-9, 61.00 g, 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), cooled to 0°C, and 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 completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h, and the reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 200 ml of pure water were added for extraction, and the water layer was separated and removed. The above operation was repeated 3 times, and finally the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated using a rotary evaporator to obtain a white solid A-10, 63.07 g, 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), cooled to 0°C, and 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 completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h, and the reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 200 ml of pure water were added for extraction, and the water layer was removed by separation. The above operation was repeated 3 times, and finally the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated by a rotary evaporator to obtain a white solid A-11, 61.37 g, 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 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), cooled to 0°C, and 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 completed, the mixture was stirred at 0°C for 3 h, then heated to 25°C for 3 h, and finally heated to 65°C for 3 h, and the reaction was completed. After the temperature was cooled to room temperature, the reaction solution was transferred to a separating funnel, 100 g of toluene and 200 ml of pure water were added for extraction, and the water layer was removed by separation. The above operation was repeated 3 times, and finally the organic phase was dried with MgSO4 to remove water and filtered to obtain a clear filtrate, which was concentrated by a rotary evaporator to obtain a white solid A-12, 69.16 g, 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, weigh 22.44g (0.1mol) of 4,4'-diamino-2,2'-dimethylbicyclohexane and add it into a 500mL three-necked flask, then add 100g NMP and 27.69g (0.35mol) pyridine in turn, stir to dissolve, cool the reaction system to below 0°C, then slowly drop the reaction solution B, and control the temperature of the reaction system below 0°C during the addition process; after the addition is completed, continue the reaction at 0°C for 3h, and the reaction is completed; pour the polymer solution into 3L deionized water, precipitate a white polymer precipitate, filter, wash three times with deionized water, and vacuum dry at 80°C for 48h to obtain the polyimide precursor resin S-1.

[0166] The weight average molecular weight (M) of each resin was measured by gel permeation chromatography (standard polystyrene conversion). w ), and the 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 is 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, filter 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 contents 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, the other contents 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 contents were the same as those in Example 1.

[0175] Example 5

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

[0177] Example 6

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

[0179] Example 7

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

[0181] Example 8

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

[0183] Example 9

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

[0185] Example 10

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

[0187] Embodiment 11

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

[0189] Example 12

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

[0191] Embodiment 13

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

[0193] Embodiment 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] Embodiment 15

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

[0199] Embodiment 17

[0200] Except that the photoinitiator was replaced with 0.25 g of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) (OXE-01) and 0.25 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), the other steps were the same as in Example 1.

[0201] Embodiment 18

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

[0203] Embodiment 19

[0204] Except that the crosslinking agent 1 was replaced by 2.5 g A-12 and 2.5 g pentaerythritol tetraacrylate, the other steps were the same as 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-acryloxypropoxy)phenyl]fluorene, that is, the compound of the structure represented by formula (4), the rest is the same as in Example 1.

[0207]

[0208] Comparative Example 2

[0209] Except that the crosslinking 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 is changed to pentaerythritol tetraacrylate, the other steps are the same as those in Example 1.

[0213] Comparative Example 4

[0214] Except that no cross-linking agent is added to the system, the rest is the same as Example 1.

[0215] The film forming property, 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 composition obtained in the above examples and comparative examples was uniformly coated on a silicon wafer using a coating machine, and the wafer was placed on a heating table (HT-300 experimental electric heating plate, Guangzhou Gedan Instrument Co., Ltd.) at 105° C. for 3 minutes for soft baking. A photomask 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 temperature of 400 mJ / cm 2After 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 with an optical microscope (MX63-F, Olympus) at a magnification of 20 times, and the minimum size of the through-hole pattern was taken as the resolution.

[0218] 2. Light transmittance

[0219] The transmittance of the cured film of the resin composition was tested by 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 by TMA (TA, TMA450) at a heating rate of 5° C. / min.

[0222] 4. Mechanical properties

[0223] The cured film of the resin composition was cut into strips with a length of 20 mm and a width of 3 mm, and the tensile strength of the film was tested by DMA (TA, DMA850). The tensile rate was 3 N / min, and 5 strips were collected in each group. The highest value and the lowest value were removed, and the remaining 3 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 heating plate, Guangzhou Gedaner Co., Ltd.) for 5 minutes of soft baking to obtain a resin film with a film thickness of 15μm. 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 protection, and then heated to 200°C after 30 minutes, and treated at 200°C for 1 hour, and then directly 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, even the film 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 crosslinking agent 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 for 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 light transmittance of the polyimide film. It can be used for insulating film and packaging film materials of precision electronic devices.

[0237] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the 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: cross-linking 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 of 2 to 4, indicating that the Y structure selects 2 to 4 access points from the 4 access points in the X structure for connection; 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; n1 is an integer from 2 to 200; 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; 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.

2. The negative photosensitive resin composition according to claim 1, characterized in that The cross-linking agent is selected from at least one of the structures shown in Formula A-1 to Formula A-12; 3. The negative photosensitive resin composition according to claim 1, characterized in that: 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 the structure X and n 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; Among them, 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 amount of R 10 The molar amount of Preferably, the catalyst is selected from at least one of KHCO3, NaHCO3, K2CO3, Na2CO3, and N,N-diisopropylethylamine; Preferably, the organic solvent is selected from at least one of tetrahydrofuran, acetone, toluene, N,N-dimethylformamide and xylene.

5. The negative photosensitive resin composition according to claim 3, characterized in that: In the fluorene structure-containing compound, R 10 The molar ratio with the catalyst is 1:(1-1.5); Preferably, the mass ratio of the fluorene structure-containing compound to the organic solvent is 1:(2-10).

6. The negative photosensitive resin composition according to claim 3, characterized in that: 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 to 30° C., and the time of the second reaction stage is 1 to 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.

7. The negative photosensitive resin composition according to claim 1, characterized in that: The mass ratio of the polyimide precursor resin to the cross-linking agent is 100:(20-150); Preferably, the mass ratio of the polyimide precursor resin to the photoinitiator is 100:(0.1-20); Preferably, the mass ratio of the polyimide precursor resin to the coupling agent is 100:(0.2-10); Preferably, the mass ratio of the polyimide precursor resin to the solvent is 100:(80-5000).

8. The negative photosensitive resin composition according to claim 1, characterized in that: The R3 is derived from tetracarboxylic dianhydride; Preferably, the R4 is derived from a diamine; Preferably, the compound having the structure represented by formula III is derived from an alcohol containing an unsaturated double bond.

9. The method for preparing the negative photosensitive resin composition according to claim 1, characterized in that: The preparation method comprises: The mixture containing component a, component b, component c, component d and component e is stirred evenly 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.

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

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