A photosensitive resin composition and its application

Abstract

The present invention relates to the field of photosensitive technology, and in particular to a photosensitive resin composition and its application. The photosensitive resin composition provided by the present invention comprises: a resin having a structure shown in Formula I, a phenolic hydroxyl compound and a photosensitizer; wherein M has a structure shown in Formula II; R 1 , R 2 and R 3 R is independently selected from a divalent to hexavalent organic group of C2 to C20; 4 and R 5 independently selected from hydrogen, alkali metal ions, ammonium ions or organic groups containing 1 to 20 carbon atoms; o is selected from integers of 3 to 100,000; n and m are independently selected from integers of 0 to 2; p is selected from integers of 0 to 8, q is selected from integers of 0 to 4, and p+q>0. The photosensitive resin composition of the present invention can be used to obtain a sheet and a cured film with excellent light transmittance.

Description

Technical Field

[0001] The present invention relates to the field of photosensitive technology, and in particular to a photosensitive resin composition and application thereof. Background Art

[0002] Since heat-resistant resins such as polyimide, polybenzoxazole, and polyamide-imide have excellent heat resistance and electrical insulation, photosensitive resin compositions containing these heat-resistant resins can be used to protect the surface of semiconductor devices such as LSI, interlayer insulating layers, organic devices, and insulating layers of OLED display devices, and device flat layers of TFT substrates. In recent years, with the continuous progress of electronic devices becoming thinner and shorter, display devices becoming more sophisticated, and semiconductor devices becoming smaller and more integrated, various technical problems have arisen in insulating film or protective film materials. One of the problems is light transmittance. If the light transmittance is low, the sensitivity and accuracy of the touch sensor will be reduced.

[0003] Japanese patent JP2003043686A provides a photosensitive resin precursor composition. The light transmittance of the material obtained by using the photosensitive resin precursor composition is poor, and the sensitivity and accuracy of the touch sensor obtained need to be improved. Summary of the invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a photosensitive resin composition and application thereof. The photosensitive resin composition of the present invention can be used to obtain a material with better light transmittance.

[0005] The present invention provides a photosensitive resin composition, comprising: a resin having a structure shown in Formula I, a phenolic hydroxyl compound and a photosensitizer;

[0006]

[0007] Wherein, M has the structure shown in Formula II;

[0008] R 1 , R 2 and R 3 R is independently selected from a divalent to hexavalent organic group of C2 to C20; 4 and R 5 independently selected from hydrogen, alkali metal ions, ammonium ions or organic groups containing 1 to 20 carbon atoms;

[0009] o is an integer selected from 3 to 100000;

[0010] n and m are independently selected from integers from 0 to 2;

[0011] p is selected from an integer of 0 to 8, q is selected from an integer of 0 to 4, and p+q>0.

[0012] In certain embodiments of the present invention, the C2-C20 divalent to hexavalent organic group includes: 2 to 4 aromatic rings bonded together by one or more of a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a methylene bond, a propylene bond, an ester bond, a sulfone bond and a carbonyl bond.

[0013] In certain embodiments of the present invention, M is selected from one of the structures shown below:

[0014]

[0015] In certain embodiments of the present invention, the resin having the structure shown in Formula I has one of the structures shown in Formula (1) to Formula (5):

[0016]

[0017] In certain embodiments of the present invention, the phenolic hydroxyl compound comprises Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTPB-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTPB-CP, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPG-26X, BisPC-OCHP, Bis26X-OCHP, B isPG-26X, BisOCHP-OC, Bis236T-OCHP, BisRS-26X, BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, BIR-BIPC-F and TEP-BIP-A; preferably one or more of Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP and BIR-BIPC-F.

[0018] In certain embodiments of the present invention, the ratio of the phenolic hydroxyl compound to the resin having the structure represented by Formula I is 1 to 50:100.

[0019] In certain embodiments of the present invention, the photosensitizer includes a quinone diazo compound or a photopolymerization initiator.

[0020] In certain embodiments of the present invention, the quinone diazo compound is obtained by esterification bonding between naphthoquinonediazine sulfonic acid and a compound having a phenolic hydroxyl group. The present invention has no particular limitation on the esterification bonding method, and any esterification bonding method known to those skilled in the art can be used.

[0021] In certain embodiments of the present invention, the phenolic hydroxyl compound includes one or more of Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, BisRS-26X, BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, methylene bisphenol and BisP-AP.

[0022] In certain embodiments of the present invention, the molecular weight of the quinone diazo compound is 300 to 1300, preferably 350 to 1100. When the molecular weight of the quinone diazo compound is higher than 1300, the esterified quinone diazo compound is not sufficiently thermally decomposed in the subsequent heat treatment, which may lead to the problem of decreased heat resistance, mechanical properties and adhesion of the obtained film.

[0023] In certain embodiments of the present invention, the mass ratio of the quinone diazo compound to the resin having the structure represented by formula I is 1 to 50:100.

[0024] In certain embodiments of the present invention, the photopolymerization initiator includes two or more of benzyl ketone-based photopolymerization initiator, α-hydroxyketone photopolymerization initiator, α-aminoketone photopolymerization initiator, acylphosphine oxide photopolymerization initiator, oxime ester photopolymerization initiator, acridine photopolymerization initiator, titanium metal photopolymerization initiator, benzophenone photopolymerization initiator, acetophenone photopolymerization initiator, aromatic ketone ester photopolymerization initiator and benzoate ester photopolymerization initiator; preferably, it includes α-aminoketone type photoinitiator, acylphosphine oxide type photoinitiator and oxime ester type photoinitiator.

[0025] In some embodiments of the present invention, the α-amino ketone type photoinitiator includes one or more of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octyl-9H-carbazole.

[0026] In certain embodiments of the present invention, the acylphosphine oxide type photoinitiator includes one or more of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide.

[0027] In some embodiments of the present invention, the oxime ester type photoinitiator includes 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)-oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)-oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)-oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl)oxime, One or more of 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methoxy]benzoyl]-9H-carbazole-3-yl]ethyl-1-(O-acetyl)oxime and 1-(9-ethyl-6-nitro-9H-carbazole-3-yl)-1-[2-methyl-4-(1-methoxyprop-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime.

[0028] In certain embodiments of the present invention, the mass ratio of the photopolymerization initiator to the resin having the structure represented by Formula I is 0.1 to 25:100, preferably 1 to 15:100.

[0029] The present invention further limits the mass ratio of the photopolymerization initiator to the resin containing the structure shown in Formula I, which can effectively improve the sensitivity, increase the resolution and reduce the cone angle.

[0030] In some embodiments of the present invention, the photosensitive resin composition further comprises an imidazole compound. In some embodiments of the present invention, the imidazole compound comprises one or more of 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, imidazole and benzimidazole; preferably 1,2-dimethylimidazole and 1-methylimidazole. In some embodiments, the boiling point of 1,2-dimethylimidazole at 1 atmosphere is 205°C; the boiling point of 1-methylimidazole at 1 atmosphere is 198°C; the boiling point of 2-methylimidazole at 1 atmosphere is 268°C; the boiling point of imidazole at 1 atmosphere is 256°C.

[0031] In certain embodiments of the present invention, the mass ratio of the imidazole compound to the resin having the structure represented by Formula I is 0.1 to 10:1, preferably 0.1 to 5:1.

[0032] The present invention further adds an imidazole compound to obtain a polyimide having a small thickness direction phase difference while maintaining high transparency. That is, according to the present invention, a polyimide having a small thickness direction retardation while maintaining high transparency can be obtained from a polyimide precursor having the same composition. Further limiting the mass ratio of the imidazole compound to the resin having the structure shown in Formula I can reduce the amount of exhaust during heat curing.

[0033] In the present invention, when an imidazole compound having a boiling point lower than 340° C. at 1 atmosphere is used, the obtained photosensitive resin composition has a light transmittance of 73% or more at a wavelength of 400 nm in a film having a thickness of 1 μm.

[0034] In some embodiments of the present invention, the photosensitive resin composition further comprises a solvent. By adding a solvent, the coating property of the photosensitive resin composition can be further improved. In some embodiments of the present invention, the solvent comprises a polar aprotic solvent, which can be γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol, monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ... Glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene ether, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, 2-hydroxy-2 -Ethyl methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate , isoamyl acetate, propyl valerate, n-butyl ester, ethyl butyrate, n-propyl butyrate, butyrate isobutyric acid, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, aromatic compounds (such as toluene and / or xylene), amides (for example, hydrocarbons, one or more of N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide).

[0035] The present invention has no special restrictions on the content of the solvent. In certain embodiments of the present invention, the mass ratio of the sum of the mass of the resin, phenolic hydroxyl compound, photosensitizer and imidazole compound having the structure shown in Formula I to the mass ratio of the solvent is 100:100-3000; preferably 150-2000. In certain embodiments of the present invention, the solvent with a boiling point of 180°C or above accounts for less than 20% of the total volume of the solvent, and more preferably less than 10%. By reducing the volume ratio of the solvent with a boiling point of 180°C or above to less than 20%, the outgassing after thermal curing can be reduced, further improving the long-term reliability of OLED devices and semiconductor devices.

[0036] In certain embodiments of the present invention, the photosensitive resin composition is prepared according to the following method:

[0037] A resin having a structure shown in formula I, a phenolic hydroxy compound and a photosensitizer are mixed and dissolved to obtain a photosensitive resin composition.

[0038] In certain embodiments of the present invention, after the dissolution, filtering is also included. The filtering is used to remove dust and particles. In certain embodiments of the present invention, the pore size of the filter used for the filtering includes but is not limited to 0.5μm, 0.2μm, 0.1μm, 0.07μm, 0.05μm or 0.02μm. In certain embodiments of the present invention, the filter material used for the filtering includes one or more of polypropylene (PP), polyethylene (PE), nylon (NY) and polytetrafluoroethylene (PTFE), preferably polyethylene and nylon.

[0039] The present invention also provides a resin sheet, the raw materials for preparing which include the photosensitive resin composition described above.

[0040] In certain embodiments of the present invention, the resin sheet is obtained by coating and curing the photosensitive resin composition described above. In certain embodiments of the present invention, the coating method of the photosensitive resin composition includes spin coating, slit coating, dip coating, spray coating or printing; preferably slit coating. The film thickness of the coating varies depending on the solid content concentration and viscosity of the photosensitive resin composition, but it is usually coated in a manner that the film thickness after drying is 0.1 to 10 μm, preferably 0.3 to 5 μm.

[0041] In some embodiments of the present invention, the coating further includes drying. The drying method may be an oven, a heating plate or infrared rays. The drying temperature is 50-150° C. and the drying time is greater than 1 minute.

[0042] When the coating film has photosensitivity, a pattern can be formed. For example, the photosensitive coating film can be exposed to chemical rays through a mask with the desired pattern, and then developed to form the desired pattern. The chemical rays used for exposure include ultraviolet rays, visible light, electron beams and X-rays. In the present invention, it is preferred to use i-rays (365nm), h-rays (405nm) and g-rays (436nm) of a mercury lamp. In the case of positive photosensitivity, the exposed part is dissolved in a developer. In the case of negative photosensitivity, the exposed part will solidify and become insoluble in the developer. After exposure, the exposed part of the positive film or the non-exposed part of the negative film is removed with a developer to form the desired pattern. The developer includes one or more of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylamine and dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethyldiamine, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, gamma-polar solvent, butyrolactone, dimethylacrylamide, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone. The developing method can be sprayed, paddled, immersed, ultrasonic or other methods. The pattern formed by the development is preferably rinsed with distilled water. In some embodiments, one or more of ethanol, isopropanol, ethyl lactate and propylene glycol monomethyl ether acetate can be rinsed in distilled water.

[0043] In certain embodiments of the present invention, from the viewpoint of further reducing the amount of outgassing produced by the cured film, a heat curing temperature of 200°C or more is preferred, and more preferably 230°C or more is preferred. On the other hand, from the viewpoint of improving the film toughness of the cured film, a temperature below 450°C is preferred, and below 400°C is more preferred. Within this temperature range, the temperature can be increased in stages or continuously. In view of further reducing the outgassing amount, the heat curing time is preferably more than 30 minutes. In addition, in view of improving the toughness of the cured film, it is preferably within 3 hours. For example, a heat treatment method of 150°C and 250°C for 30 minutes each, or a heat treatment method of heating from room temperature to 300°C for 2 hours, while increasing the temperature linearly.

[0044] In some embodiments of the present invention, the resin sheet has a light transmittance of more than 73% in a thin film with a thickness of 1 μm and a wavelength of 400 nm in terms of accuracy and sensitivity of the touch sensor.

[0045] The present invention also provides a semiconductor device, comprising the photosensitive resin composition or the resin sheet described above.

[0046] The photosensitive resin composition and resin sheet of the present invention can be used for the surface protection layer and interlayer insulating layer of semiconductor devices, and can also be used for the insulating layer of organic electroluminescent (hereinafter referred to as "EL") devices, and thin film transistors (hereinafter referred to as TFT). They are suitable for the planarization layer of TFT (transistor) substrates, the wiring protection insulating layer of circuit boards, the on-chip microlenses of solid-state image sensors, and the planarization layers of various displays and solid-state image sensors. For example, as the next generation of memory, the surface protection layer and interlayer layer of MRAM, polymer ferroelectric RAM (PFRAM) and phase change RAM (PCRAM, OUM) with low heat resistance, as well as the surface protection layer and interlayer layer of OUM are adopted. It is suitable as an insulating layer. It can also be used as an insulating layer of a display device including a first electrode formed on a substrate and a second electrode arranged opposite to the first electrode, such as LCD, ECD, ELD, and a display device using an organic electric field device. The following is explained by taking OLED display devices, semiconductor devices, and semiconductor electronic components as examples.

[0047] OLED Display:

[0048] The resin sheet (cured film) of the present invention can be appropriately used for a planarization layer and / or an insulating layer in an OLED display device having a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate. OLED light-emitting materials are easily degraded by moisture, which may cause adverse effects such as a decrease in the area ratio of the light-emitting portion to the area ratio of the light-emitting pixel, but the cured film of the present invention has a low water absorption rate and therefore has stable driving and light-emitting characteristics.

[0049] Taking an active matrix display device as an example, the display device has a TFT and wiring located on the side of the TFT, and is connected to the TFT on a substrate such as glass or various plastics. A planarization layer is provided on the TFT to cover the uneven areas, and a display element is also provided on the planarization layer. The display element and the wiring are connected through contact holes formed in the planarization layer.

[0050] When the resin sheet (cured film) of the present invention is used as the above-mentioned planarization layer, the film thickness is preferably 1.0 to 5.0 μm, and more preferably 2.0 μm or more. By setting the planarization layer within the above range, the planarity and wiring of the dense TFT can be improved due to the high fineness. Once the planarization layer becomes thicker, the outgassing increases and the luminous reliability of the organic EL display device decreases. Since the cured film of the present invention has less outgassing, high luminous reliability can be obtained. In addition, since TFTs and wiring can be configured with high clarity in the film thickness direction, it is preferred that the planarization layer is multilayered.

[0051] Figure 1A cross-sectional view of a TFT substrate provided for an embodiment of the present invention, wherein 1: insulating layer, 2: contact hole, 3: ITO (transparent electrode), 4: substrate, 5: wiring, 6: TFT (thin film transistor), 7: TFT insulating layer, 8: planarization layer.

[0052] On the substrate 4, bottom-gate or top-gate TFTs (thin film transistors) 6 are arranged in a matrix manner to form a TFT insulating layer 7 covering the TFT 1. On the TFT insulating layer 7, there is also a wiring 5 connected to the TFT 6. In addition, a planarization layer 8 is provided on the TFT insulating layer 7, and the wiring 5 is embedded in the TFT insulating layer 7. In the planarization layer 8, a contact hole 2 is provided on the planarization layer 8, and the wiring 5 is connected through the contact hole 2. Through the contact hole 2, an ITO (transparent electrode) 3 is formed on the planarization layer 8. Here, ITO 3 serves as an electrode of a display element (such as an OLED device). And an insulating layer 1 covering the periphery of ITO 3 is formed. The OLED device can be a top emission type that emits light from the back side of the substrate 4, or a bottom emission type that emits light from the side of the substrate 4. In this way, an active matrix OLED display device that generates a drive by connecting each OLED element with TFT 6 is obtained.

[0053] In summary, the TFT insulating layer 7, the planarizing layer 8 and / or the insulating layer 1 can be formed by making the resin composition or the resin sheet of the present invention into a photosensitive resin film and sequentially exposing, developing and heat treating. The organic EL display device can be obtained by the manufacturing method having these steps.

[0054] Semiconductor electronic components-equipment:

[0055] The photosensitive resin composition or resin sheet (cured film) of the present invention can be suitably used for an interlayer insulating layer and / or a surface protective layer in a semiconductor electronic component and a semiconductor device having electrodes, metal wiring, an interlayer insulating layer and / or a surface protective layer on a substrate. Since the cured film of the present invention has excellent mechanical properties, the stress from the encapsulation resin can be relieved during installation, and damage to the low-k layer can be suppressed, so that a highly reliable semiconductor device can be provided.

[0056] Figure 2 An enlarged cross-sectional view of a pad portion of a semiconductor device with bumps provided for an embodiment of the present invention, wherein 9: passivation layer, 10: scribe groove, 11: aluminum pad, 12: silicon wafer, 13: metal wiring (Al, Cu, etc.), 14: metal (Cr, Ti, etc.) layer, 15: barrier metal, 16: insulating film, 17: insulating layer, 18: solder bump.

[0057] A passivation layer 9 with aluminum pads 11 for input / output and through holes is formed on a silicon wafer 12. In addition, an insulating layer 17 is formed on the passivation layer 9, and a metal layer 14 composed of Cr, Ti, etc. is formed to connect the aluminum pads 11, and a metal wiring 13 composed of Al, Cu, etc. is formed by electrolytic plating, etc. The pads are insulated by etching the metal layer 14 located near the solder bump 18. A barrier metal 15 and a solder bump 18 are formed on the insulating pad. After the insulating film 16 is processed, a scribe groove 10 is formed.

[0058] Next, a method for manufacturing a semiconductor device will be described using drawings. Figure 3 This is a manufacturing example of a semiconductor device with solder bumps provided by an embodiment of the present invention. In which, 9: passivation layer, 10: scribe groove, 11: aluminum pad, 12: silicon wafer, 13: metal wiring (Al, Cu, etc.), 14: metal (Cr, Ti, etc.) layer, 15: barrier metal, 16: insulating film, 17: insulating layer, 18: solder bumps.

[0059] In the process of 3-1, the resin composition of the present invention is applied to the silicon wafer 12, an aluminum pad 11 and a passivation layer 9 are formed thereon, and a patterned insulating layer 17 is formed by a photolithography process. Then, in the process of 3-2, a metal layer 14 is formed by a sputtering method. In the process of 3-3, a metal wiring 13 is deposited on the metal layer 14 by an electroplating method. Next, in the process of 3-4, the resin composition of the present invention is applied, and in the process of 3-5, a pattern of an insulating film 16 is formed by a photolithography process. In this process, the resin composition containing the insulating film 16 is processed into a thick film at the scribe groove 10. Further wiring (so-called rewiring) can be performed on the insulating film 16. In the case of forming a multilayer wiring structure with two or more layers, the above process can be repeated to form a multilayer wiring structure, wherein the rewiring of two or more layers can be separated by an interlayer insulating layer composed of a cured film of the present invention. There is no upper limit to the number of layers of the multilayer wiring structure, but 10 layers or less are generally used. In the process of 3-6, a barrier metal 15 is formed, and in the process of 3-7, a solder bump 18 is formed. Then, by cutting along the final scribe line 10 and cutting each chip, a semiconductor device with solder bumps can be obtained.

[0060] The present invention provides a photosensitive resin composition. The photosensitive resin composition of the present invention can be used to obtain a sheet material and a cured film with relatively good light transmittance. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1 A cross-sectional view of a TFT substrate provided for one embodiment of the present invention;

[0062] Figure 2An enlarged cross-sectional view of a pad portion of a semiconductor device having a bump provided for one embodiment of the present invention;

[0063] Figure 3 The present invention is a manufacturing example of a semiconductor device having solder bumps provided by one embodiment of the present invention. DETAILED DESCRIPTION

[0064] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0065] The evaluation method of the effect in the embodiment is as follows:

[0066] (1) Preparation of coating

[0067] A solution containing a photosensitive resin precursor, a quinonediazide compound, a compound having a phenolic hydroxyl group, etc. was applied on a 5 cm×5 cm glass substrate, and then pre-baked at 120° C. for 3 minutes using a hot plate (Azowan EC-7050) to obtain a coating film.

[0068] (2) Film thickness measurement method

[0069] The measurement was performed using a field emission scanning electron microscope (EX-30).

[0070] (3) Exposure

[0071] The mask having the pattern was set on an exposure machine (SMA-150GA-TR), and i-line exposure was performed by changing the exposure time (intensity was 365 nm).

[0072] (4) Development Using a MIKASA AD-1200 developer, a 2.38% tetramethylammonium hydroxide aqueous solution was sprayed at 50 rpm for 10 seconds, then allowed to stand at 0 rpm for 60 seconds, rinsed with water at 400 rpm, shaken at 3000 rpm for 10 seconds, and finally dried.

[0073] (5) Sensitivity calculation

[0074] After exposure and development, the exposure time for forming a 50 μm line and space pattern (1L / 1S) with a width of 1:1 (hereinafter referred to as the optimal exposure time) was determined.

[0075] (6) Calculate light transmittance by ultraviolet absorption

[0076] A solution containing a photosensitive resin precursor, a quinone diazo compound, a phenolic hydroxyl compound, etc. is coated on a 5 cm × 5 cm glass substrate, and then a heating plate (Azowan EC-7050) is used. Then, pre-bake at 120°C for 3 minutes to obtain a coating film. Then, the coating film is cured at 250°C for 30 minutes in a Koyo oven (INH-21CD-S manufactured by Koyo Co., Ltd.) to obtain a resin sheet with a film thickness of 1 μm. The ultraviolet absorption rate of the resin sheet is measured, and the transmittance (T) is calculated from the absorbance (A) at a wavelength of 365 nm using the following formula according to the Lambert-Beer law.

[0077] T = exp(-A) × 100

[0078] In addition, the ultraviolet absorbance was measured using a Beijing Puxi TU-1810 UV-visible spectrophotometer.

[0079] Example 1

[0080]

[0081] 1. Under nitrogen protection system, weigh 4,4'-(perfluoropropane-2,2-diyl)bis(2-aminophenol) (82mmol, 30g), tetrabutylammonium fluoride (82mmol, 21.4g) were added to the reaction system, and 600mL of tetrahydrofuran solution was added. Under nitrogen protection, the mixture was stirred at 80°C for 24h. The reaction was complete on TLC plate. Then the mixture was cooled to room temperature. The reaction solution was vortexed until no liquid flowed out. The reaction product after spin drying was added to 200mL of acetone. Under nitrogen protection, the mixture was stirred at 50°C for 5 hours. The temperature was lowered to 25°C, filtered under reduced pressure, and dried under vacuum at 50°C to obtain 2-amino-4-(2-(3-amino-4-fluorophenyl)-1,1,1,3,3,3-hexafluoropropane-2-yl)phenol (24g, yield was 80%).

[0082] HPLC purity: greater than 99%;

[0083] Mass spectrum: calculated value is 368.25; tested value is 368.20;

[0084] 2. Under nitrogen protection, weigh the intermediate 2-amino-4-(2-(3-amino-4-fluorophenyl)-1,1,1,3,3,3-hexafluoropropane-2-yl)phenol (65.2mmol, 24g), dissolve it in a reaction system of 200mL acetone and propylene oxide (391.2mmol, 22.7g) solution, cool the reaction system temperature to -15°C, and drop 3-nitrobenzoyl chloride (143.4mmol, 24g) into the reaction system. After the addition of a solution prepared by dissolving 1,4-difluoro-2-(4-hydroxy-3-(3-nitrobenzamido)phenyl)propan-2-yl)phenyl)-3-nitrobenzamide (36.9 g, yield 85%) was completed, the temperature was continued to stir for 4 h at -15 °C, the temperature of the reaction system was raised to 25 °C, the reaction was filtered under reduced pressure, and vacuum dried at 50 °C to obtain N-(2-fluoro-5-(1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-(3-nitrobenzamido)phenyl)propan-2-yl)phenyl)-3-nitrobenzamide (36.9 g, yield 85%);

[0085] HPLC purity: greater than 99.5%;

[0086] Mass spectrum: calculated value is 666.46; tested value is 666.50;

[0087] 3. Under the protection of hydrogen, weigh the intermediate N-(2-fluoro-5-(1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-(3-nitrobenzamido)phenyl)propan-2-yl)phenyl)-3-nitrobenzamide (55.4mmol, 36.9g), add it to the stainless steel autoclave reaction system, add 370mL ethylene glycol methyl ether, add 7g 5% palladium carbon, introduce hydrogen into it, and carry out reduction reaction under stirring at a temperature of 25°C. After 2h, the balloon does not shrink further, the reaction is complete, filter, remove the palladium carbon catalyst, use a rotary evaporator to rotate the filtrate until no liquid flows out, and vacuum dry it at 50°C to obtain diamine compound E-001 (33g, yield 90%), and the obtained solid is directly used for the reaction;

[0088] HPLC purity: greater than 99%;

[0089] Mass spectrum: calculated value: 606.50; tested value: 606.40.

[0090] Example 2

[0091]

[0092] 1. Under nitrogen protection system, weigh 4,4'-(perfluoropropane-2,2-diyl)bis(2-aminophenol) (82mmol, 30g), tetrabutylammonium fluoride (205mmol, 53.5g) and add them to the reaction system, add 600mL tetrahydrofuran, stir at 80°C for 24h under nitrogen protection, the reaction is complete on TLC plate, the reaction system is cooled to 25°C, the reaction solution is spun with a rotary evaporator until no liquid flows out, the reaction product after spin drying is added to 200mL acetone, stirred at 50°C for 4h under nitrogen protection, filtered under reduced pressure, and dried under vacuum at 50°C to obtain 5,5'-(perfluoropropane-2,2-diyl)bis(2-fluoroaniline) (27.3g, yield 90%);

[0093] HPLC purity: greater than 99%;

[0094] Mass spectrum: calculated value is 370.25; tested value is 370.20;

[0095] 2. Under nitrogen protection system, weigh 5,5'-(perfluoropropane-2,2-diyl)bis(2-fluoroaniline) (74mmol, 27.3g), dissolve it in a reaction system of 150mL acetone and propylene oxide (444mmol, 25.7g), cool the reaction system temperature to -15°C, and dropwise add a solution prepared by dissolving 3-nitrobenzoyl chloride (162.8mmol, 30g) in 100mL acetone into the reaction system. After the addition is completed, stir at -15°C for 4h, raise the temperature of the reaction system naturally to 25°C, filter under reduced pressure, and dry under vacuum at 50°C to obtain N,N'-((perfluoropropane-2,2-diyl)bis(6-fluoro-3,1-phenylene))bis(3-nitrobenzamide) (39.5g, yield 80%);

[0096] HPLC purity: greater than 99.5%;

[0097] Mass spectrum: calculated value is 668.46; tested value is 668.50;

[0098] 3. Under the protection of hydrogen, weigh the intermediate N, N'-((perfluoropropane-2,2-diyl)bis(6-fluoro-3,1-phenylene))bis(3-nitrobenzamide) (59mmol, 39.5g), add it to the stainless steel autoclave reaction system, add 400mL ethylene glycol methyl ether, add 7.5g 5% palladium carbon, introduce hydrogen into it, and carry out reduction reaction at a temperature of 25°C. After 2h, the balloon did not shrink further, and the reaction was completed. Filter under reduced pressure to remove the palladium carbon catalyst, use a rotary evaporator to rotate the filtrate until no liquid flows out, and vacuum dry it at 50°C to obtain diamine compound E-002 (30.5g, yield 85%), and the obtained solid is directly used for the reaction;

[0099] HPLC purity: greater than 99%;

[0100] Mass spectrum: calculated value: 608.49; tested value: 608.50.

[0101] Example 3

[0102]

[0103] 1. Under nitrogen protection, weigh 4,4'-(propane-2,2-diyl)bis(2-aminophenol) (116.1mmol, 30g), tetrabutylammonium fluoride (116.1mmol, 30.4g) and add them to the reaction system, add 600mL of tetrahydrofuran, stir at 80°C for 24h under nitrogen protection, and the reaction is complete on TLC plate. The temperature of the reaction system is lowered to 25°C, and the reaction solution is rotated with a rotary evaporator until no liquid flows out. The reaction product after spin drying is added to 200mL of acetone, and stirred at 50°C for 5h under nitrogen protection. The temperature of the reaction system is lowered to 25°C, filtered under reduced pressure, and dried in a vacuum at 50°C to obtain 2-amino-4-(2-(3-amino-4-fluorophenyl)propan-2-yl)phenol (22.7g, yield 75%);

[0104] HPLC purity: greater than 99%;

[0105] Mass spectrum: calculated value is 260.31; tested value is 260.30;

[0106] 2. Under nitrogen protection, weigh 2-amino-4-(2-(3-amino-4-fluorophenyl)propan-2-yl)phenol (87.2mmol, 22.7g), dissolve it in a reaction system of 200mL acetone and propylene oxide (523.2mmol, 30.4g), cool the reaction system temperature to -15°C, and add dropwise a solution prepared by dissolving 3-nitrobenzoyl chloride (191.84mmol, 35.6g) in 100mL acetone to the reaction system. After the addition is completed, stir the reaction system at -15°C for 4h, raise the temperature of the reaction system naturally to 25°C, filter under reduced pressure, and dry under vacuum at 50°C to obtain N-(5-(2-(4-fluoro-3-(3-nitrobenzamido)phenyl)propan-2-yl)-2-hydroxyphenyl)-3-nitrobenzamide (40.4g, yield 83%);

[0107] HPLC purity: greater than 99.5%;

[0108] Mass spectrum: calculated value is 558.52; tested value is 558.50;

[0109] 3. Under the protection of hydrogen, weigh N-(5-(2-(4-fluoro-3-(3-nitrobenzamido)phenyl)propan-2-yl)-2-hydroxyphenyl)-3-nitrobenzamide (72.3mmol, 40.4g) and add it to the stainless steel autoclave reaction system, add 400mL ethylene glycol methyl ether, add 8g 5% palladium carbon, introduce hydrogen into the reaction system, and carry out reduction reaction at a temperature of 25°C. After 2h, the balloon did not shrink further, and the reaction was completed. Filter under reduced pressure to remove the palladium carbon catalyst, use a rotary evaporator to rotate the filtrate until no liquid flows out, and vacuum dry at 50°C to obtain diamine compound E-003 (31g, yield 86%), and the obtained solid is directly used for the reaction;

[0110] HPLC purity: greater than 99%;

[0111] Mass spectrum: calculated value: 498.56; tested value: 498.50.

[0112] Example 4

[0113]

[0114] 1. Under nitrogen protection system, weigh 4,4'-(propane-2,2-diyl)bis(2-aminophenol) (116.1mmol, 30g), tetrabutylammonium fluoride (290.25mmol, 75.9g) and add them to the reaction system, add 600mL tetrahydrofuran solution, stir at 80°C for 24h under nitrogen protection, the reaction is complete on TLC plate, the temperature of the reaction body is lowered to 25°C, the reaction liquid is spun on a rotary evaporator until no liquid flows out, the reaction product after spin drying is added to 200mL acetone, stirred at 50°C for 4h under nitrogen protection, filtered under reduced pressure, and dried under vacuum at 50°C to obtain 5,5'-(propane-2,2-diyl)bis(2-fluoroaniline) (22.3g, yield is 73%);

[0115] HPLC purity: greater than 99%;

[0116] Mass spectrum: calculated value is 262.30; tested value is 262.30;

[0117] 2. Under nitrogen protection system, weigh 5,5'-(propane-2,2-diyl)bis(2-fluoroaniline) (85mmol, 22.3g), dissolve it in a reaction system of 150mL acetone and propylene oxide (510mmol, 29.6g), cool the reaction system temperature to -15°C, and dropwise add a solution prepared by dissolving 3-nitrobenzoyl chloride (187mmol, 34.7g) in 100mL acetone into the reaction system. After the addition is completed, stir at -15°C for 4h, raise the temperature of the reaction system to room temperature naturally, filter under reduced pressure, and dry under vacuum at 50°C to obtain N,N'-(propane-2,2-diylbis(6-fluoro-3,1-phenylene))bis(3-nitrobenzamide) (41g, yield 86%);

[0118] HPLC purity: greater than 99.5%;

[0119] Mass spectrum: calculated value is 668.46; tested value is 668.50;

[0120] 3. Under the protection of hydrogen, weigh N, N'-(propane-2,2-diylbis(6-fluoro-3,1-phenylene))bis(3-nitrobenzamide) (73.1mmol, 41g) and add it to the stainless steel autoclave reaction system, add 450mL ethylene glycol methyl ether, add 8.5g 5% palladium carbon, introduce hydrogen into it, and carry out reduction reaction at a temperature of 25°C. After 2h, the balloon does not shrink further, the reaction is completed, and the palladium carbon catalyst is removed by vacuum filtration. The filtrate is rotated with a rotary evaporator until no liquid flows out, and vacuum dried at 50°C to obtain diamine compound E-004 (30g, yield 82%), and the obtained solid is directly used for the reaction;

[0121] HPLC purity: greater than 99%;

[0122] Mass spectrum: calculated value: 500.55; tested value: 500.50.

[0123] Comparative Example 1

[0124]

[0125] 1. Under the protection of nitrogen system, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (30g, 82mmol) was dissolved in a system of acetone (100ml) and propylene oxide (17.4g, 0.3mol), and the temperature of the reaction system was cooled to -15°C. A solution prepared by dissolving 20.4g (0.11mol) of 3-nitrobenzoyl chloride in 100mL of acetone was added dropwise to the reaction system. After the addition was completed, the reaction system was stirred at -15°C for 4 hours, and the temperature of the reaction system was naturally raised to 25°C. The solution was concentrated by rotary evaporator, and the obtained solid was recrystallized from a mixed solution of 60ml tetrathiofuran and 180ml ethanol, and filtered under reduced pressure to obtain N,N'-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(3-nitrobenzamide) (43.6g, yield 89%);

[0126] HPLC purity: greater than 99%;

[0127] Mass spectrum: calculated value is 664.47; tested value is 664.50;

[0128] 2. Under the protection of hydrogen, weigh N, N'-((perfluoropropane-2,2-diyl)bis(6-hydroxy-3,1-phenylene))bis(3-nitrobenzamide) (45.1mmol, 30g) and add it to the stainless steel autoclave reaction system, add 300mL ethylene glycol methyl ether, add 6g 5% palladium carbon, introduce hydrogen into it, and carry out reduction reaction at a temperature of 25°C. After 2h, the balloon does not shrink further, the reaction is completed, and the palladium carbon catalyst is removed by vacuum filtration. The filtrate is spun on a rotary evaporator until no liquid flows out, and vacuum dried at 50°C to obtain diamine compound E-005 (23.7g, yield 87%). The obtained solid is directly used for the reaction;

[0129] HPLC purity: greater than 99%;

[0130] Mass spectrum: calculated value: 604.51; tested value: 604.50.

[0131] Example 5

[0132] Synthesis of quinone diazo compounds (d-1)

[0133] 21.22 g (0.05 mol) of TrisP-PA (manufactured by Honshu Chemical Industry) and 36.27 g (0.135 mol) of 5-naphthoquinonediazidesulfonyl chloride were dissolved in 450 g of 1,4-dioxane at room temperature. 15.18 g of triethylamine and 50 g of 1,4-dioxane were added dropwise and mixed so that the temperature in the system did not exceed 35°C. After the addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by reduced pressure filtration. The precipitate was dried with a vacuum dryer to obtain a quinone diazo compound (d-1) represented by the following formula.

[0134]

[0135] Example 6

[0136] Under dry nitrogen, 10.3 g (0.017 mol) of the hydroxyl-containing diamine compound (E-001) obtained in Example 1 was dissolved in 50 g of NMP. 6.2 g (0.02 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and 0.3 g (0.001 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane ((SiDA)) were added together with 21 g of NMP, and the resulting mixture was reacted at 50°C for 2 hours, 0.4 g (0.004 mol) of 3-aminophenol (MAP) was added as a capping agent, and the mixture was stirred at 50°C for 2 hours, and then 29.4 g (0.2 mol) of N,N-dimethylformamido diethyl acetal was added. Dilute with 5 g of NMP and add dropwise over 10 minutes. After the addition, the mixture was stirred at 50°C for 3 hours. After the reaction was completed, , pour the solution into 2L of water, and filter and collect the precipitate of the photosensitive polyimide precursor. Dry the photosensitive polyimide precursor in a vacuum dryer at 80°C for 40 hours to obtain a photosensitive polyimide precursor A. Next, add 10.0g of photosensitive polyimide precursor A, 2.0g of quinone diazo compound (d-1), 1.2g of compound Bis-Z with phenolic hydroxyl group (manufactured by Honshu Chemical Industry Co., Ltd.), and 0.1g of 1-methylimidazole to 30g of GBL to obtain a slurry A-1 of photosensitive resin component. The obtained slurry is prepared into a coating 2-1 as described above, and then a resin sheet 2-1 is prepared by exposure, development, sensitivity, and heat curing, and the transmittance is evaluated. The results are shown in Table 1.

[0137] Example 7

[0138] Imidazole-free:

[0139] 10.0 g of the photosensitive polyimide precursor A obtained in Example 6, 2.0 g of the quinone diazo compound (d-1), and 1.2 g of a compound having a phenolic hydroxyl group, Bis-Z (manufactured by Honshu Chemical Industry Co., Ltd.), were added to 30 g of GBL to obtain a slurry A-2 of a photosensitive resin component. As described above, the obtained slurry was used to prepare a coating film 1-2, which was exposed and developed, and the slurry and the resin were cured by heating to prepare a resin sheet 1-2, and the transmittance was evaluated. The results are shown in Table 1.

[0140] Example 8

[0141] 10.0 g of the photosensitive polyimide precursor A obtained in Example 6, 1.5 g of a quinone diazo compound (d-1), 0.5 g of 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1.2 g of Bis-Z (manufactured by Honshu Chemical Industry Co., Ltd.) having a phenolic hydroxyl group, and 0.1 g of 1-methylimidazole were added to 30 g of GBL to obtain a photosensitive resin component slurry A-3. As described above, using the obtained slurry, a coating film 1-3 was prepared, exposure and development were performed, the slurry and the resin were cured by heating to prepare a resin sheet 1-3, and the transmittance was evaluated. The results are shown in Table 1.

[0142] Example 9

[0143] Under dry nitrogen, 10.3 g (0.017 mol) of the hydroxyl-containing diamine compound (E-001) obtained in Example 1 was dissolved in 50 g of NMP. 8.9 g (0.02 mol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 0.3 g (0.001 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) were added together with 21 g of NMP, and the resulting mixture was reacted at 50°C for 2 hours. 0.4 g (0.004 mol) of 3-aminophenol (MAP) was added as a capping agent, and after the mixture was stirred at 50°C for 2 hours, 29.4 g (0.2 mol) of N,N-dimethylformamide diethyl acetal was diluted with 5 g of NMP and added dropwise over 10 minutes. After the addition, the mixture was stirred at 50°C for 3 hours. After the reaction is completed, the solution is poured into 2L of water, and the precipitate of the photosensitive polyimide precursor is filtered and collected. The photosensitive polyimide precursor is dried in a vacuum dryer at 80°C for 40 hours to obtain a photosensitive polyimide precursor B. Next, 10.0g of photosensitive polyimide precursor B, 2.0g of quinone diazo compound (d-1), 1.2g of compound Bis-Z with phenolic hydroxyl group (manufactured by Honshu Chemical Industry Co., Ltd.), and 0.1g of 1-methylimidazole are added to 30g of GBL to obtain a slurry B-1 of the photosensitive resin component. The obtained slurry is prepared into a coating 2-1 as described above, and then a resin sheet 2-1 is prepared by exposure, development, sensitivity, and heat curing, and the transmittance is evaluated. The results are shown in Table 1.

[0144] Example 10

[0145] 10.0 g of the photosensitive polyimide precursor B obtained in Example 9, 1.5 g of a quinone diazo compound (d-1), 0.5 g of 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1.2 g of Bis-Z (manufactured by Honshu Chemical Industry Co., Ltd.) having a phenolic hydroxyl group, and 0.1 g of 1-methylimidazole were added to 30 g of GBL to obtain a photosensitive resin component slurry A-3. As described above, using the obtained slurry, a coating film 2-2 was prepared, exposure and development were performed, the slurry and the resin were cured by heating to prepare a resin sheet 2-2, and the transmittance was evaluated. The results are shown in Table 1.

[0146] Embodiment 11

[0147] Under dry nitrogen, 10.4 g (0.017 mol) of the hydroxyl-containing diamine compound (E-002) obtained in Example 2 was dissolved in 50 g of NMP. 6.2 g (0.02 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and 0.3 g (0.001 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) were added to 21 g of NMP, and the resulting mixture was reacted at 50° C. for 2 hours, 0.4 g (0.004 mol) of 3-aminophenol (MAP) was added as a capping agent, and the mixture was stirred at 50° C. for 2 hours, and then 29.4 g (0.2 mol) of N,N-dimethylformamido diethyl acetal was added, and 5 g of NMP was diluted and added dropwise within 10 minutes. After the addition, the mixture was stirred at 50°C for 3 hours. After the reaction was completed, the solution was poured into 2L of water, and the precipitate of the photosensitive polyimide precursor was filtered and collected. The photosensitive polyimide precursor was dried in a vacuum dryer at 80°C for 40 hours to obtain a photosensitive polyimide precursor C. Next, 10.0g of photosensitive polyimide precursor C, 2.0g of quinone diazo compound (d-1), 1.2g of compound Bis-Z with phenolic hydroxyl group (manufactured by Honshu Chemical Industry Co., Ltd.), and 0.1g of 1-methylimidazole were added to 30g of GBL to obtain a slurry C-1 of the photosensitive resin component. The obtained slurry was prepared into a coating 3-1 as described above, and then a resin sheet 3-1 was prepared by exposure, development, sensitivity, and heating curing, and the transmittance was evaluated. The results are shown in Table 1.

[0148] Example 12

[0149] Under dry nitrogen, 10.4 g (0.017 mol) of the hydroxyl-containing diamine compound (E-002) obtained in Example 2 was dissolved in 50 g of NMP. 8.9 g (0.02 mol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 0.3 g (0.001 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) were added together with 21 g of NMP, and the resulting mixture was reacted at 50°C for 2 hours. 0.4 g (0.004 mol) of 3-aminophenol (MAP) was added as a capping agent, and the mixture was stirred at 50°C for 2 hours, and then 5 g of 29.4g (0.2mol) of N,N-dimethylformamide diethyl acetal was diluted with NMP and added dropwise within 10 minutes. After the addition, the mixture was stirred at 50°C for 3 hours. After the reaction was completed, the solution was poured into 2L of water, and the precipitate of the photosensitive polyimide precursor was filtered and collected. The photosensitive polyimide precursor was dried in a vacuum dryer at 80°C for 40 hours to obtain a photosensitive polyimide precursor D. Next, 10.0g of photosensitive polyimide precursor D, 2.0g of quinone diazo compound (d-1), 1.2g of compound Bis-Z with phenolic hydroxyl group (manufactured by Honshu Chemical Industry Co., Ltd.), and 0.1g of 1-methylimidazole were added to 30g of GBL to obtain a slurry D-1 of a photosensitive resin component. The obtained slurry was prepared as described above to prepare a coating 4-1, and then a resin sheet 4-1 was prepared by exposure, development, sensitivity, and heat curing, and the transmittance was evaluated. The results are shown in Table 1.

[0150] Embodiment 13

[0151] Under a dry nitrogen stream, 8.5 g (0.017 mol) of the hydroxyl-containing diamine compound (E-003) obtained in Example 3 was dissolved in 50 g of NMP. 6.2 g (0.02 mol) of 3,3',4,4'-diphenyl ether tetracarbon dianhydride (ODPA) and 0.3 g (0.001 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) were added to NMP (21 g), and the mixture was reacted at 50° C. for 2 hours. 0.4 g (0.004 mol) of 3-aminophenol (MAP) was added thereto as a capping agent, and the mixture was stirred at 50° C. for 2 hours, and then 29.4 g (0.2 mol) of N, N-dimethylformamido diethyl acetal was added, diluted with 5 g of NMP, and added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50° C. for 3 hours. After the reaction is completed, the solution is poured into 2L of water, and the precipitate of the photosensitive polyimide precursor is filtered and collected. The photosensitive polyimide precursor is dried in a vacuum dryer at 80°C for 40 hours to obtain photosensitive polyimide precursor E. Subsequently, 10.0g of photosensitive polyimide precursor E, 2.0g of quinone diazo compound (d-1), 1.2g of compound Bis-Z with phenolic hydroxyl group (produced by Honshu Chemical Industry Co., Ltd.), and 0.1g of 1-methylimidazole are added to 30g of GBL to obtain slurry E-1 of the photosensitive resin composition. The obtained slurry is prepared into coating 5-1 as described above, and then the resin sheet 5-1 is prepared by exposure, development, sensitivity, and heating curing, and the transmittance is evaluated. The results are shown in Table 1.

[0152] Embodiment 14

[0153] Under dry nitrogen, 8.5 g (0.017 mol) of the hydroxyl-containing diamine compound (E-003) obtained in Example 3 was dissolved in 50 g of NMP. 8.9 g (0.02 mol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 1,3-bis(3-aminopropyl) tetramethylcysteine ​​were dissolved in 50 g of NMP. 0.3 g (0.001 mol) of siloxane (SiDA) was added together with 21 g of NMP and reacted at 50°C for 2 hours. 0.4 g (0.004 mol) of 3-aminophenol (MAP) was added as a capping agent, and after stirring at 50°C for 2 hours, 29.4 g (0.2 mol) of N,N-dimethylformamide diethyl acetal was diluted with 5 g of NMP, and the diluted solution was added dropwise over 10 minutes. After the dripping was completed, the solution was stirred at 50°C for 3 hours. After the reaction is completed, the solution is introduced into 2L of water, and the precipitate of the photosensitive polyimide precursor is collected by filtration. The photosensitive polyimide precursor is dried in a vacuum dryer at 80°C for 40 hours to obtain a photosensitive polyimide precursor F. Then, 10.0g of photosensitive polyimide precursor F, 2.0g of quinone diazo compound (d-1), 1.2g of compound Bis-Z with phenolic hydroxyl group (produced by Honshu Chemical Industry Co., Ltd.), and 0.1g of 1-methylimidazole are added to 30g of GBL to obtain a slurry F-1 of a photosensitive resin composition. The obtained slurry is prepared as described above to prepare a coating 6-1, and then a resin sheet 6-1 is prepared by exposure, development, sensitivity, and heat curing, and the transmittance is evaluated. The results are shown in Table 1.

[0154] Embodiment 15

[0155] Under dry nitrogen, 8.5 g (0.017 mol) of the hydroxyl-containing diamine compound (E-004) obtained in Example 4 was dissolved in 50 g of NMP. 6.2 g (0.02 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and 0.3 g (0.001 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) were added together with 21 g of NMP and reacted at 50° C. for 2 hours. 0.4 g (0.004 mol) of 3-aminophenol (MAP) was added as a capping agent, and after stirring at 50° C. for 2 hours, 5 g of 29.4g (0.2mol) of N,N-dimethylformamide diethyl acetal was diluted with NMP, and the diluted solution was added dropwise within 10 minutes. After the dripping was completed, the solution was stirred at 50°C for 3 hours. After the reaction was completed, 2L of water was added to the solution, and the precipitate of the photosensitive polyimide precursor was collected by filtration. The photosensitive polyimide precursor was dried in a vacuum dryer at 80°C for 40 hours to obtain a photosensitive polyimide precursor G. Then, 10.0 grams of photosensitive polyimide precursor G, 2.0g of quinone diazo compound (d-1), 1.2g of compound Bis-Z with phenolic hydroxyl group (produced by Honshu Chemical Industry Co., Ltd.), and 0.1g of 1-methylimidazole were added to 30g of GBL to obtain a slurry G-1 of a photosensitive resin composition. The obtained slurry was prepared as described above to prepare a coating 7-1, and then a resin sheet 7-1 was prepared by exposure, development, sensitivity, and heat curing, and the transmittance was evaluated. The results are shown in Table 1.

[0156] Example 16

[0157] Under dry nitrogen, 8.5 g (0.017 mol) of the hydroxyl-containing diamine compound (E-004) obtained in Example 4 was dissolved in 50 g of NMP. 8.9 g (0.02 mol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 1,3-bis(3-aminopropyl)tetramethylcysteine ​​were dissolved in 50 g of NMP. 0.3 g (0.001 mol) of synthetic siloxane (SiDA) was added together with 21 g of NMP and reacted at 50°C for 2 hours. Then 0.4 g (0.004 mol) of 3-aminophenol (MAP) was added as a capping agent. After stirring at 50°C for 2 hours, 29.4 g (0.2 mol) of N,N-dimethylformamide diethyl acetal was diluted with 5 g of NMP, and the diluted solution was added dropwise over 10 minutes. After the dripping was completed, the solution was stirred at 50°C for 3 hours. After the reaction is completed, the solution is added to 2L of water, and the precipitate of the photosensitive polyimide precursor is collected by filtration. The photosensitive polyimide precursor is dried in a vacuum dryer at 80°C for 40 hours to obtain a photosensitive polyimide precursor H. Then, 10.0g of the photosensitive polyimide precursor H, 2.0g of a quinone diazo compound (d-1), 1.2g of a compound Bis-Z with a phenolic hydroxyl group (manufactured by Honshu Chemical Industry Co., Ltd.), and 0.1g of 1-methylimidazole are added to 30g of GBL to obtain a slurry H-1 of a photosensitive resin composition. The obtained slurry is prepared as described above to prepare a coating 8-1, and then a resin sheet 8-1 is prepared by exposure, development, sensitivity, and heat curing, and the transmittance is evaluated. The results are shown in Table 1.

[0158] Comparative Example 2

[0159] Under dry nitrogen, 10.3 g (0.017 mol) of the hydroxyl-containing diamine compound (E-005) obtained in Comparative Example 1 was dissolved in 50 g of NMP. 6.2 g (0.02 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and 0.3 g (0.001 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) were added together with 21 g of NMP, and reacted at 50° C. for 2 hours. 0.4 g (0.004 mol) of 3-aminophenol (MAP) was added as a capping agent, and after stirring at 50° C. for 2 hours, 29.4 g (0.2 mol) of N,N-dimethylformamide diethyl ether was diluted with 5 g of NMP. Acetal, and add the diluted solution dropwise within 10 minutes. After the dripping is completed, the solution is stirred at 50°C for 3 hours. After the reaction is completed, 2L of water is added to the solution, and the precipitate of the photosensitive polyimide precursor is collected by filtration. The photosensitive polyimide precursor is dried in a vacuum dryer at 80°C for 40 hours to obtain a photosensitive polyimide precursor I. Then, 10.0g of photosensitive polyimide precursor I, 2.0g of quinone diazo compound (d-1), 1.2g of compound Bis-Z with phenolic hydroxyl group (produced by Honshu Chemical Industry Co., Ltd.), and 0.1g of 1-methylimidazole are added to 30g of GBL to obtain a slurry I-1 of the photosensitive resin composition. The obtained slurry is prepared into a coating 9-1 as described above, and then a resin sheet 9-1 is prepared by exposure, development, sensitivity, and heating curing, and the transmittance is evaluated. The results are shown in Table 1.

[0160] Comparative Example 3

[0161] Under dry nitrogen, 10.3 g (0.017 mol) of the hydroxyl-containing diamine compound (E-005) obtained in Comparative Example 1 was dissolved in 50 g of NMP. 8.9 g (0.02 mol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 1,3-bis(3-aminopropyl) tetramethylcysteine ​​were dissolved in 5 g of NMP. Then 0.3 g (0.001 mol) of siloxane (SiDA) was added to the mixture and reacted at 50°C for 2 hours. 0.4 g (0.004 mol) of 3-aminophenol (MAP) was added as a capping agent. After stirring at 50°C for 2 hours, 29.4 g (0.2 mol) of N,N-dimethylformamide diethyl acetal was diluted with 5 g of NMP, and the diluted solution was added dropwise within 10 minutes. After the dripping was completed, the solution was stirred at 50°C for 3 hours. After the reaction is completed, add 2L of water to the solution and filter to collect the precipitate of the photosensitive polyimide precursor. Dry the photosensitive polyimide precursor in a vacuum dryer at 80°C for 40 hours to obtain a photosensitive polyimide precursor J. Then, add 10.0g of the photosensitive polyimide precursor J, 2.0g of a quinone diazo compound (d-1), 1.2g of a compound with a phenolic hydroxyl group Bis-Z (manufactured by Honshu Chemical Industry Co., Ltd.), and 1-0.1g of methylimidazole to 30g of GBL to obtain a slurry J-1 of a photosensitive resin composition. The obtained slurry is used to prepare a coating film 10-1 as described above, and then a resin sheet 10-1 is prepared by exposure, development, sensitivity, and heat curing, and the transmittance is evaluated. The results are shown in Table 1.

[0162] Comparative Example 4

[0163] 0.0 g of the photosensitive polyimide precursor J1 obtained in Comparative Example 3, 1.5 g of a quinone diazo compound (d-1), 0.5 g of 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime and 1.2 g of a compound with a phenolic hydroxyl group, Bis-Z (manufactured by Honshu Chemical Industry Co., Ltd.), were added to 30 g of GBL to obtain a resin component slurry J-2. The obtained slurry was used to prepare a coating film 10-2 as described above, and then a resin sheet 10-2 was prepared by exposure, development, sensitivity, and heat curing, and the transmittance was evaluated. The results are shown in Table 1.

[0164] Table 1 Preparation parameters and effect data of the resin sheets obtained in Examples 6 to 16 and Comparative Examples 2 to 4

[0165]

[0166]

[0167] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A photosensitive resin composition comprising: A resin containing a structure shown in formula I, a phenolic hydroxyl compound and a photosensitizer; Wherein, M has one of the structures shown below; R 1 and R 3 R is independently selected from a divalent to tetravalent organic group of C2 to C20; 4 and R 5 independently selected from hydrogen, alkali metal ions, ammonium ions or organic groups containing 1 to 20 carbon atoms; o is an integer selected from 3 to 100000; n and m are independently selected from integers of 0-2.

2. The photosensitive resin composition according to claim 1, characterized in that: C2 to C20 divalent to tetravalent organic groups include: 2 to 4 aromatic rings are bonded together by one or more of a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a methylene bond, an propylene bond, an ester bond, a sulfone bond and a carbonyl bond.

3. The photosensitive resin composition according to claim 1, characterized in that: The diamine compound forming the resin having the structure represented by Formula I has one of the structures represented by Formula (1) to Formula (4):

4. The photosensitive resin composition according to claim 1, characterized in that: The phenolic hydroxyl compound includes one or more of Bis-Z, BisP-CP, BisOCHP-Z, BisP-MZ, BisP-EZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BisRS-26X, BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, BIR-BIPC-F and TEP-BIP-A; The mass ratio of the phenolic hydroxy compound to the resin containing the structure shown in formula I is 1 to 50:

100.

5. The photosensitive resin composition according to claim 1, characterized in that: The photosensitizer includes a quinone diazo compound or a photopolymerization initiator; The molecular weight of the quinone diazo compound is 300 to 1300; The mass ratio of the quinone diazo compound to the resin having the structure represented by formula I is 1 to 50:100; The photopolymerization initiator includes an α-amino ketone type photoinitiator, an acylphosphine oxide type photoinitiator and an oxime ester type photoinitiator; The mass ratio of the photopolymerization initiator to the resin containing the structure represented by formula I is 0.1 to 25:

100.

6. The photosensitive resin composition according to claim 1, characterized in that: Also includes: Imidazole compounds; The imidazole compound includes one or more of 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, imidazole and benzimidazole; The mass ratio of the imidazole compound to the resin having the structure represented by formula I is 0.1 to 10:1; The photosensitive resin composition further includes a solvent; The solvent with a boiling point above 180°C accounts for less than 20% of the total volume of the solvent; The mass ratio of the total mass of the resin having the structure shown in formula I, the phenolic hydroxyl compound, the photosensitizer and the imidazole compound to the mass of the solvent is 100:100-3000.

7. A resin sheet, wherein the raw materials for preparing the sheet include the photosensitive resin composition according to any one of claims 1 to 6. 8 . A semiconductor device comprising the photosensitive resin composition according to claim 1 or the resin sheet according to claim 7 . 9 . An organic electroluminescent device, comprising the photosensitive resin composition according to claim 1 or the resin sheet according to claim 7 .

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