A photosensitive polyimide coating adhesive and its preparation method and application

Abstract

The present application discloses a photosensitive polyimide coating adhesive and its preparation method and application. The photosensitive polyimide coating adhesive comprises (A) resin, (B) photosensitizer, (C) porphyrin compound, (D) silane coupling agent, and (E) solvent; the photosensitive polyimide coating adhesive provided by the present application uses a polyimide resin terminated with a cyclobutene compound and a porphyrin compound containing a cyclobutene structure as additives, which can undergo a cross-linking reaction during the thermal curing process to improve the thermal stability and electrical resistance of the cured film of the coating adhesive. Introducing a photosensitive diamine monomer into the molecular chain of polyamide ester can improve the photosensitivity of the photosensitive polyimide coating adhesive.

Description

Technical Field

[0001] The present application relates to a photosensitive polyimide coating adhesive and a preparation method and application thereof, belonging to the field of photosensitive materials. Background Art

[0002] Polyimide (PI) is one of the most widely used polymer materials in the semiconductor and microelectronics industries. Due to the rigid and aromatic structure of cyclic imide on the PI skeleton, PI has good thermal stability, excellent mechanical properties, electrical properties and chemical properties, and is widely used in electronics, optics, aerospace, optoelectronic devices and other fields. With the lightweight, high-performance and multifunctional electronic products, the requirements for PI are getting higher and higher.

[0003] In order to improve the photosensitivity of PI, a lot of research has been done both at home and abroad. US4093461 proposed a photosensitive PI earlier, which is prepared by PI and o-naphthoquinone diazide in proportion. With o-naphthoquinone diazide as a photosensitizer, the photosensitive PI is a mixture of photosensitizer and PI, in which there is no chemical bond between the photosensitive group of the photosensitizer and PI, and the solubility of PI in the exposed area and the non-exposed area is not much different.

[0004] In order to improve the mechanical properties and thermal stability of polyimide, a lot of research has been done. There are currently two main methods: First, adding nanofillers such as graphene and carbon nanotubes to prepare composite materials to improve the mechanical properties and thermal stability of the material, but it will affect its electrical properties and is not suitable for polyimide for semiconductor materials. Second, the molecular structure of polyimide is modified, mainly including end-capping agents containing reactive groups, monomers containing cross-linking groups, etc. Patent document CN202010043741.3 prepares a high-temperature resistant acetylene-terminated polyimide material by adding end-capping agent 3-ethynylaniline, but it cannot adjust the degree of cross-linking according to demand. Patent document CN 111116950A adds diamine POSS, acetylene-containing diamine and fluorine-containing diamine to a phenolic solvent, and then adds rigid dianhydride and twisted dianhydride, and then adds acetylene-containing monoamine, and imidization prepares a high-performance polyimide film. Summary of the invention

[0005] In order to simultaneously improve the photosensitivity, thermal stability, and electrical resistance of a polyimide coating adhesive, the present application provides a photosensitive polyimide coating adhesive and a preparation method thereof.

[0006] According to one aspect of the present application, a photosensitive polyimide coating adhesive is provided, wherein the photosensitive polyimide coating adhesive comprises (A) a resin, (B) a photosensitizer, (C) a porphyrin compound, (D) a silane coupling agent, and (E) a solvent;

[0007] The resin (A) is selected from compounds having a structure represented by formula (1) and / or formula (2);

[0008]

[0009] Wherein, p1 is selected from an integer between 2 and 200, p2 is selected from an integer between 2 and 50, and the ratio of p1 to p2 is 100:2 to 20; i1 is selected from an integer between 2 and 200, i2 is selected from an integer between 2 and 50, and the ratio of i1 to i2 is 100:2 to 20;

[0010] Optionally, the ratio of i1 to i2 is 100:5-15;

[0011] Optionally, the ratio of i1 to i2 is any value among 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, 100:20, or any range value between two of them.

[0012] Optionally, the ratio of p1 to p2 is 100:5-15;

[0013] Optionally, the quantitative ratio of p1 to p2 is any value among 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, 100:20, or any range value between two of them.

[0014] R1 and R2 are each independently selected from a saturated aliphatic group having 1 to 10 carbon atoms, a hydrogen atom or an organic group having a structure represented by formula (3);

[0015]

[0016] R3, R4, and R5 are each independently selected from a hydrogen atom or an organic group having 1 to 3 carbon atoms; m is selected from an integer of 2 to 200;

[0017] X1 and X2 are independently selected from tetravalent organic groups having 4 to 40 carbon atoms; Y1 and Y2 are independently selected from divalent organic groups having 2 to 40 carbon atoms; and Z is selected from a group having a structure represented by formula (4):

[0018]

[0019] The weight average molecular weight of the resin (A) is 5,000 to 40,000, calculated as a polystyrene conversion value based on gel permeation chromatography (GPC);

[0020] Optionally, the weight average molecular weight of the resin (A) is 10,000 to 30,000;

[0021] Optionally, the weight average molecular weight of the resin (A) is 20,000 to 25,000;

[0022] The photosensitizer is selected from at least one of acetophenone compounds, biimidazole compounds, triazine compounds, oxime compounds, diazoquinone compounds, onium salts, halogen-containing compounds, and polyhydroxy compounds;

[0023] The (C) porphyrin compound is selected from compounds having a structure of formula (5);

[0024]

[0025] Wherein, P1, P2, P3, and P4 are independently selected from a group having a structure shown in formula (4);

[0026] The (D) silane coupling agent is at least one selected from the group consisting of urea-based silane coupling agents, epoxy-based silane coupling agents, mercapto-based silane coupling agents, vinyl-based silane coupling agents, and triazole-based silane coupling agents;

[0027] The (E) solvent is selected from at least one of N-methylpyrrolidone, γ-butyrolactone, tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ether;

[0028] The mass ratio of the (A) resin to the (B) photosensitizer is 100:0.1-30;

[0029] Optionally, the mass ratio of the (A) resin to the (B) photosensitizer is 100:0.5-25;

[0030] Optionally, the mass ratio of the (A) resin to the (B) photosensitizer is 100:0.5-20;

[0031] The mass ratio of the (A) resin to the (C) porphyrin compound is 100:1-20;

[0032] Optionally, the mass ratio of the (A) resin to the (C) porphyrin compound is 100:2-15;

[0033] Optionally, the mass ratio of the (A) resin to the (C) porphyrin compound is 100:5-10;

[0034] The mass ratio of the (A) resin to the (D) silane coupling agent is 100:0.1-5;

[0035] Optionally, the mass ratio of the (A) resin to the (D) silane coupling agent is 100:1-5;

[0036] The mass ratio of the resin (A) to the solvent (E) is 100:80-5000;

[0037] Optionally, the mass ratio of the (A) resin to the (E) solvent is 100:100-1000;

[0038] Optionally, the mass ratio of the (A) resin to the (E) solvent is 100:150-400.

[0039] The viscosity of the photosensitive polyimide coating adhesive is 10 to 10000 cP.

[0040] Optionally, the viscosity of the photosensitive polyimide coating adhesive is 500 to 5000 cP;

[0041] Optionally, the viscosity of the photosensitive polyimide coating adhesive is 1000-4000 cP.

[0042] The R1 and R2 are each independently selected from a saturated aliphatic group having 1 to 4 carbon atoms;

[0043] Optionally, R1 and R2 are each independently selected from at least one of ethyl, methyl, hydroxyethyl methacrylate, and n-butyl;

[0044] X1 and X2 are independently selected from groups having structures shown in formula (6) a to j;

[0045]

[0046] Y1 is independently selected from the group having the structure shown in formula (7) a~p;

[0047]

[0048]

[0049] Y2 is a photosensitive diamine monomer having a structure of formula (8);

[0050]

[0051] Wherein, R6 is selected from hydrogen atom, substituted or unsubstituted C1~C 20 Alkyl, substituted or unsubstituted C1~C 20 Alkoxy, substituted or unsubstituted C6~C 30 The aromatic group;

[0052] Optionally, the R6 is selected from any one of the structures: H, -CH3, -CF3, -OCF3;

[0053] Q is selected from 5-naphthoquinonediazidesulfonic acid or 4-naphthoquinonediazidesulfonic acid;

[0054] n is an integer between 1 and 5; * represents the access site;

[0055] The photosensitizer is selected from 1-(4-phenylthio-phenyl)-octane-1,2-dione-2-oxime-0-benzoate, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, dibenzil ketone, 4-benzoyl-4'-methyldiphenyl ketone, fluorenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid, 2-oxirane-2-{4-[2,4 -bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxy-p-cresol, 2,6-diacetoxymethyl-p-cresol, tetrahydroxybenzophenone, NT-300 (esterification reaction product of 2,3,4-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid), 4NT-350, 4NT-300 (esterification reaction product of 2,3,4,4-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid), TPPA series products (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan);

[0056] The (D) silane coupling agent is selected from 3-ureidopropyltriethoxysilane (Nanjing Xuanhao New Material Technology, XH-1160), 3-ureidopropyltrimethoxysilane (Nanjing Demonte, DMT-116), 1-propyl-1-(triethoxysilyl)methylurea (Nanjing Xuanhao New Material Technology, XH-712), (3-glycidoxypropyl)trimethoxysilane (KH-560), (8-glycidoxyoctyl)trimethoxysilane (Japan Shin-Etsu Chemical, KBM-4803), (3-glycidoxypropyl)trimethoxysilane (Japan Shin-Etsu Chemical, KBM-403), 3-(triethoxysilylthio)propyltrimethoxysilane (Japan Shin-Etsu Chemical, X-12-1056ES), 3-(trimethoxysilane)trimethoxysilane (Japan Shin-Etsu Chemical, X-12-1056ES), 3-(trimethoxysilane)trimethoxysilane (Japan Shin-Etsu Chemical, X-12-1056ES), 3-(trimethoxysilane)trimethoxysilane (Japan Shin-Etsu Chemical, X-12-1056ES), 3-(triethoxysilylthio)propyltrimethoxysilane (Japan Shin-Etsu Chemical, X-12-1056ES), 3-(trimethoxysilane)trimethoxysilane (Japan Shin-Etsu Chemical, X-12-1056ES), 3-(trimethoxysilane)trimethoxysilane (Japan 1-propanethiol (Momentive High-Tech Materials, A-189), γ-thiopropyltriethoxysilane (Nanjing Xuanhao New Materials Technology, KH-580), 3-(triethoxysilylthio)propyltrimethoxysilane (Shin-Etsu Chemical, X-12-1056ES), 3-(trimethoxysilyl)-1-propanethiol (Momentive High-Tech Materials, A-189), γ-thiopropyltriethoxysilane (Nanjing Xuanhao New Materials Technology, KH-580), vinyltriethoxysilane (Nanjing Demonte, KH-151), p-vinylphenyltrimethoxysilane (Shin-Etsu Chemical, KBM-1403), at least one of the compounds having the structures shown in formula (9) a to f and the compounds having the structures shown in formula (10) a to k;

[0057]

[0058]

[0059]

[0060] The urea-based silane coupling agent of formula (9) was prepared by referring to patent CN111825884B.

[0061] The preparation method of the nitrogen-containing heterocyclic silane coupling agent in formula (10) can refer to patent CN114456205B.

[0062] According to another aspect of the present application, a method for preparing the above-mentioned photosensitive polyimide coating adhesive is provided, comprising the following steps:

[0063] The raw materials containing (A) resin, (B) photosensitizer, (C) porphyrin compound, (D) silane coupling agent and (E) solvent are mixed and filtered to obtain the photosensitive polyimide coating adhesive.

[0064] The filtration is performed using a filter with a pore size of 0.1 to 5 μm.

[0065] (A) The resin is obtained by the following steps: the whole is a polycondensation reaction;

[0066] Mixing a common diamine monomer, a photosensitive diamine monomer, a dianhydride monomer and a non-protonic solvent, performing reaction I, adding a capping agent, performing reaction II, adding an esterification agent, performing reaction III, precipitating, washing and drying to obtain the resin (A);

[0067] The common diamine monomer is selected from at least one of the compounds having the structures shown in formula (11) a to p:

[0068]

[0069] The photosensitive diamine monomer has a structure shown in formula (12):

[0070]

[0071] Wherein, R6 is selected from hydrogen atom, substituted or unsubstituted C1~C 20 Alkyl, substituted or unsubstituted C1~C 20 Alkoxy, substituted or unsubstituted C6~C 30 The aromatic group;

[0072] Preferably, the R6 is selected from any one of the structures: H, -CH3, -CF3, -OCF3;

[0073] Q is selected from 5-naphthoquinonediazidesulfonic acid or 4-naphthoquinonediazidesulfonic acid;

[0074] n is an integer between 1 and 5;

[0075] The photosensitive diamine monomer is prepared according to the preparation method of patent CN114634429B;

[0076] The dianhydride monomer is selected from at least one of the compounds having the structure shown in formula (13):

[0077]

[0078] The aprotic solvent is selected from at least one of N-methylpyrrolidone, γ-butyrolactone, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ether;

[0079] The end-capping agent is selected from a compound having a structure shown in formula (14);

[0080]

[0081] The esterification agent is selected from at least one of methanol, ethanol, n-butanol, hydroxyethyl methacrylate, N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal and 4-nitrobenzyl alcohol.

[0082] The molar ratio of the common diamine monomer to the photosensitive diamine monomer is 100:5-20;

[0083] Optionally, the molar ratio of the common diamine monomer to the photosensitive diamine monomer is 100:10-15;

[0084] The total molar ratio of the common diamine monomer and the photosensitive diamine monomer to the total molar ratio of the dianhydride monomer is 100:80-100;

[0085] Optionally, the total molar ratio of the common diamine monomer and the photosensitive diamine monomer to the total molar ratio of the dianhydride monomer is 100:90-95;

[0086] The mass ratio of the common diamine monomer to the aprotic solvent is 1:3-20;

[0087] The ratio of the total molar amount of the common diamine monomer and the photosensitive diamine monomer to the total molar amount of the end-capping agent and the dianhydride monomer is 1:1;

[0088] The molar ratio of the esterification agent to the dianhydride monomer is 1 to 5:1;

[0089] Optionally, the molar ratio of the esterification agent to the dianhydride monomer is 1.5 to 3:1;

[0090] The temperature of the reaction I is 10 to 100°C;

[0091] The reaction time is 3 to 24 hours;

[0092] The temperature of the reaction II is 10 to 100°C;

[0093] The time of the reaction II is 3 to 24 hours;

[0094] The temperature of the reaction III is 30-80°C;

[0095] The time of the reaction III is 2 to 24 hours.

[0096] The precipitation is carried out by adding the mixture into water.

[0097] The (C) porphyrin compound is obtained by the following steps:

[0098] Under a nitrogen atmosphere, a compound having a structure of formula (14) and a compound having a structure of formula (12) are mixed with a non-protonic polar solvent to undergo an amidation reaction, and the solvent is removed by distillation under reduced pressure to obtain the porphyrin compound (C);

[0099]

[0100] The aprotic polar solvent is selected from at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and γ-butyrolactone.

[0101] The molar ratio of the compound having the structure of formula (14) to the compound having the structure of formula (15) is 3.9 to 4.1:1;

[0102] The mass ratio of the compound having the structure of formula (14) to the aprotic polar solvent is 1:3-10;

[0103] The temperature of the amidation reaction is 20 to 50° C.

[0104] The amidation reaction time is 5 to 10 hours.

[0105] According to another aspect of the present application, a photosensitive resin film is provided, which is made of the above-mentioned photosensitive polyimide coating adhesive.

[0106] Optionally, the photosensitive resin film is formed by using the above-mentioned photosensitive polyimide coating adhesive through the following method:

[0107] The photosensitive resin composition is coated on the substrate. A suitable substrate is selected according to the reagent requirements. Common substrates include, but are not limited to, copper sheets, copper alloy sheets, silicon sheets, ceramic sheets, aluminum sheets, glass sheets, ITO glass, etc. As coating methods, spray coating, spin coating, and ink scraper coating methods can be cited. The coating film thickness will also be different due to different coating methods, rotation speeds, viscosities, composition components, etc. In the present invention, a 4-inch silicon wafer is preferably used as the substrate for the coating film, and the coating is preferably performed by spin coating, and the thickness of the cured film on the silicon wafer is controlled to be 10 to 20 μm.

[0108] Subsequently, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin film. The drying method is usually an oven, a heating table, an infrared lamp, etc. In the present invention, a heating table is preferably used, and the drying is preferably carried out at a temperature of 50 to 150° C. for 1 minute to 1 hour, and the thickness of the photosensitive resin film is measured after natural cooling to 25° C. In the present invention, it is preferably dried at a temperature of 100 to 130° C. for 2 to 5 minutes.

[0109] Next, the photosensitive resin film is exposed to ultraviolet rays, X-rays, electron beams, etc. through a photomask or mask with a pattern or directly under a mask having a desired pattern on the resin film formed above. Common active rays include ultraviolet rays, X-rays, electron beams, etc. In the present invention, a mercury lamp is preferably used, which includes i-line (365nm), h-line (405nm), and g-line (436nm).

[0110] Thereafter, in order to improve the sensitivity, etc., a post-exposure bake and / or a pre-development bake may be performed based on any temperature and practical combination as required. The baking conditions are a temperature of 40 to 120° C. and a time of 10 to 240 seconds, and are not limited to this range as long as the properties of the photosensitive resin composition of the present invention are not affected.

[0111] After exposure, a pattern is formed by removing the unexposed part using a developer. Common developers include: N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol, isopropanol, ethyl lactate, butyl acetate, propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone, isobutyl ketone, etc. After development, it is preferably rinsed with ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate, etc. For example, a developer and a rinse solution are poured into two glass culture dishes respectively. The developer temperature is controlled to be 25±1°C, the exposed resin film is immersed in the developer, and the timing is started immediately. After the unexposed part is completely exposed to the copper substrate, the development is completed, the timing is stopped, and the time required for the whole process is recorded.

[0112] Finally, the resin pattern obtained after development is thermally imidized at 200-500°C to convert it into a cured film. This heat treatment usually selects staged temperature increase and maintains a certain time at different temperatures or selects a certain temperature range for continuous temperature increase. For example, a heat treatment method is performed at 180°C, 240°C, and 350°C for 30 minutes respectively, or a method of linearly increasing the temperature from 25°C to 400°C over 2 hours.

[0113] The beneficial effects of this application include:

[0114] (1) The photosensitive polyimide coating adhesive provided in the present application uses a polyimide resin terminated with a cyclobutene compound and a porphyrin compound containing a cyclobutene structure as additives, which can undergo a cross-linking reaction during the thermal curing process to improve the thermal stability and electrical resistance of the cured film of the coating adhesive.

[0115] (2) The present application introduces a photosensitive diamine monomer into the molecular chain of polyamide ester, which can improve the photosensitivity of the photosensitive polyimide coating adhesive. BRIEF DESCRIPTION OF THE DRAWINGS

[0116] Figure 1This is a spectrum of the porphyrin structure compound B-1 characterized by hydrogen nuclear magnetic resonance spectrum in Preparation Example 1 of the present application. DETAILED DESCRIPTION

[0117] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0118] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0119] The chemical formulas and abbreviations of the chemical substances in the examples of the present application are as follows:

[0120] Porphyrin diamine:

[0121]

[0122] Silane coupling agents containing urea and imide structures:

[0123]

[0124] Triazole silane coupling agent:

[0125]

[0126] 4-Aminobenzocyclobutene:

[0127]

[0128] ODPA: 4,4-oxydiphthalic anhydride

[0129]

[0130] 6FDA: 4,4'-(Hexafluoroisopropylene) diphthalic anhydride

[0131]

[0132] HFHA: 2,2-bis[4-hydroxy-3-(3-amino)benzamido]hexafluoropropane

[0133]

[0134] BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0135]

[0136] SIDA:

[0137]

[0138] Preparation Example 1: Preparation of Capping Agent

[0139] 23.83 g (0.2 mol) of 4-aminobenzocyclobutene and 100 g of NMP were placed in a 500 ml three-necked flask, and 38.43 g (0.2 mol) of trimellitic anhydride was added under nitrogen atmosphere, and the mixture was reacted at 40° C. for 12 h.

[0140] After the above reaction is completed, the reaction solution is cooled to 0-5°C and stirred at 60°C for 4 hours. After cooling to room temperature, the solvent is removed by rotary evaporation to obtain benzocyclobutene F-1 containing acyl chloride.

[0141]

[0142] Benzocyclobutene containing acyl chloride was characterized by hydrogen nuclear magnetic resonance spectroscopy. The hydrogen spectrum information is as follows:

[0143] δ: 8.56(d,1H), 8.26(s,1H), 8.02(d,1H), 7.73(s,1H), 7.31(d,1H), 7.25(d,1H), 2.84(m,2H), 2.72(m,2H).

[0144] Preparation Example 2: Preparation of porphyrin compounds

[0145] Under nitrogen protection, add 67.48g (0.1mol) D-1 and 150g N-methylpyrrolidone (NMP) to a 250ml three-necked flask and mix well. Add 124.41g (0.4mol) F-1 to the above solution and react for 8 hours at 25°C; after the reaction is completed, add 63.20g (0.8mol) pyridine, stir well, add 81.68g (0.8mol) acetic anhydride, and react for 20 hours at 25°C. After the reaction is completed, the above reaction solution is subjected to reduced pressure distillation to remove the solvent to obtain compound B-1 containing a porphyrin structure.

[0146]

[0147] The porphyrin compound B-1 was characterized by hydrogen nuclear magnetic resonance spectroscopy. Figure 1 Preparation Example 3: Preparation of Photosensitive Diamine Monomer

[0148] Add 4-hydroxy-3-trifluoromethylbenzaldehyde (38.02g, 0.2mol), triethylamine (25.30, 0.25mol) and DMAC (200g) to a three-necked flask and stir to dissolve; cool the reaction system, and when the internal temperature is between -10℃ and -5℃, add a mixed solution of 2-diazo-1-naphthol-5-sulfonyl chloride (113.69g, 0.42mol) and DMAc (300g) to the solution, and stir to react after the addition is complete. Add hydrochloric acid (20g) to the mixture and stir for 10min. Separate the triethylamine hydrochloride formed by filtration; quickly pour the obtained filtrate into a 0.1% hydrochloric acid aqueous solution (1700ml) maintained at 20-25℃. Stir well to obtain a yellowish solid, filter, and wash the filter cake with deionized water several times until the ion content of the washing liquid is below 50ppm. Finally, rinse the filter cake with anhydrous ethanol and dry it under reduced pressure at 40℃.

[0149] The above product (59.06 g, 0.1 mol), aniline hydrochloride (51.80 g, 0.4 mol) and aniline (93.20 g, 1 mol) were added into a 500 ml three-necked flask, heated at 100 °C for 2 h under a nitrogen atmosphere, then heated to 160 °C and stirred for 6 h, cooled to room temperature, and the excess aniline was distilled off under reduced pressure at 80 °C. 2 mol.L-1 hydrochloric acid was added to dissolve and filter, and the filtrate was neutralized with 2 mol.L-1 sodium hydroxide to obtain an off-white solid, which was washed with water, recrystallized twice with ethanol / water, and dried in vacuo at 80 °C to obtain the product photosensitive monomer A-1.

[0150]

[0151] Preparation Example 4: Preparation of photosensitive diamine monomer

[0152] Add 4-hydroxy-3-trifluoromethoxybenzaldehyde (41.22g, 0.2mol), triethylamine (25.30, 0.25mol) and DMAC (200g) to a three-necked flask and stir to dissolve; cool the reaction system, and when the internal temperature is between -10℃ and -5℃, add a mixed solution of 2-diazo-1-naphthol-5-sulfonyl chloride (113.69g, 0.42mol) and DMAc (300g) to the solution, and stir to react after the addition is complete. Add hydrochloric acid (20g) to the mixture and stir for 10min. Separate the triethylamine hydrochloride formed by filtration; quickly pour the obtained filtrate into a 0.1% hydrochloric acid aqueous solution (1700ml) maintained at 20-25℃. Stir thoroughly to obtain a yellowish solid, filter, and wash the filter cake with deionized water for several times until the ion content of the washing liquid is below 50ppm. Finally, the filter cake was rinsed with anhydrous ethanol and dried under reduced pressure at 40 °C.

[0153] The above product (66.66 g, 0.1 mol), aniline hydrochloride (51.80 g, 0.4 mol) and aniline (93.20 g, 1 mol) were added into a 500 ml three-necked flask, heated at 100 °C for 2 h under a nitrogen atmosphere, then heated to 160 °C and stirred for 6 h, cooled to room temperature, and the excess aniline was distilled off under reduced pressure at 80 °C. 2 mol.L-1 hydrochloric acid was added to dissolve and filter, and the filtrate was neutralized with 2 mol.L-1 sodium hydroxide to obtain an off-white solid, which was washed with water, recrystallized twice with ethanol / water, and dried in vacuo at 80 °C to obtain the product photosensitive monomer A-2.

[0154]

[0155] Preparation Example 5: Preparation of photosensitive diamine monomer

[0156] Add 4-hydroxy-3-trifluoromethoxybenzaldehyde (41.22g, 0.2mol), triethylamine (25.30, 0.25mol) and DMAC (200g) to a three-necked flask and stir to dissolve; cool the reaction system, and when the internal temperature is between -10℃ and -5℃, add a mixed solution of 2-diazo-1-naphthol-4-sulfonyl chloride (113.69g, 0.42mol) and DMAc (300g) to the solution, and stir to react after the addition is complete. Add hydrochloric acid (20g) to the mixture and stir for 10min. Separate the triethylamine hydrochloride formed by filtration; quickly pour the obtained filtrate into a 0.1% hydrochloric acid aqueous solution (1700ml) maintained at 20-25℃. Stir thoroughly to obtain a yellowish solid, filter, and wash the filter cake with deionized water several times until the ion content of the washing liquid is below 50ppm. Finally, the filter cake was rinsed with anhydrous ethanol and dried under reduced pressure at 40 °C.

[0157] The above product (66.66 g, 0.1 mol), aniline hydrochloride (51.80 g, 0.4 mol) and aniline (93.20 g, 1 mol) were added into a 500 ml three-necked flask, heated at 100 °C for 2 h under a nitrogen atmosphere, then heated to 160 °C and stirred for 6 h, cooled to room temperature, and the excess aniline was distilled off under reduced pressure at 80 °C. 2 mol.L-1 hydrochloric acid was added to dissolve and filter, and the filtrate was neutralized with 2 mol.L-1 sodium hydroxide to obtain an off-white solid, which was washed with water, recrystallized twice with ethanol / water, and dried in vacuo at 80 °C to obtain the product photosensitive monomer A-3.

[0158]

[0159] The test results of the photosensitive diamine monomer are shown in Table 1.

[0160] The photosensitive diamine monomers prepared in the above-mentioned Preparation Examples 3 to 5 were qualitatively analyzed by infrared spectrometer, and the purity of the photosensitive diamine monomers prepared in the above-mentioned Preparation Examples 3 to 5 was measured by liquid chromatography.

[0161] Specific test method:

[0162] (1) Infrared spectrum test

[0163] The photosensitive diamine monomer samples synthesized in the above-mentioned preparation examples were tested by using an infrared spectrometer (Shimadzu, IRAffinity-1S) using a KBr pellet method to detect whether the photosensitive diamine monomer was successfully prepared.

[0164] (2) Liquid chromatography test

[0165] The purity of the synthesized photosensitive diamine monomer was tested using a liquid chromatograph (Shimadzu, LC-2030).

[0166] Chromatographic column: C18; wavelength: 254nm; column oven: 40℃; mobile phase: water: acetonitrile = 40:60; flow rate: 1.0ml / min.

[0167] Method for judging the synthetic photosensitive diamine monomer: If the infrared spectrum is at 3400cm -1 ~3500cm -1 The asymmetric stretching vibration and symmetric stretching vibration absorption peaks of NH2 appear at 1370cm -1 and 1180cm -1 There is a strong absorption peak of sulfonyl group S=O near 2100cm -1 The asymmetric stretching vibration absorption peak of -N=N azide group appears on the left and right, indicating that the photosensitive diamine monomer has been successfully synthesized. In addition, the monomer containing trifluoromethyl group has an absorption peak at 1350cm -1 ~1100cm -1 The stretching vibration absorption peak of the CF bond will appear. If there is no obvious impurity peak in the liquid chromatogram and the purity measured by the integration method is greater than 97%, it can be considered that the photosensitive diamine monomer has been successfully synthesized.

[0168] From the test results in Table 1, it can be seen that the above Preparation Examples 3-5 all successfully synthesized photosensitive diamine monomers, and the purity was greater than 97%, and the highest purity could reach 97.8%.

[0169] Table 1 Structural formula and test results of photosensitive diamine monomers prepared in Preparation Examples 3-5

[0170]

[0171]

[0172] Preparation Examples 6 to 16: Preparation of Precursor Resins

[0173] In the preparation and synthesis process of each precursor resin, the types and proportions of dianhydride, diamine or end-capping agent used are different, as shown in Table 2. The types of photosensitive diamine monomers respectively represent the photosensitive diamine monomers prepared by the corresponding preparation examples in the above preparation examples 3-5.

[0174] The preparation method of the above-mentioned sensitive precursor resin specifically comprises the following steps:

[0175] (1) Preparation of dianhydride solution: In a 500 ml three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, add dianhydride compound and 100 g N-methylpyrrolidone (NMP) in the amounts shown in Table 2 in sequence under nitrogen flow, and stir at room temperature to fully dissolve the substances to obtain a dianhydride solution;

[0176] (2) Preparation of diamine solution: Add diamine compound and 100 g N-methylpyrrolidone in the amounts shown in Table 2 to another three-necked flask equipped with a stirrer, stir to fully dissolve the substances, and obtain a diamine solution;

[0177] (3) Polycondensation reaction:

[0178] The diamine solution obtained in step (2) is added to the dianhydride solution obtained in step (1), and after the addition is complete, the mixture is reacted at room temperature for 1 hour, and then at 40° C. for 6 hours;

[0179] (4) After the above reaction is completed, add the end-capping agent according to the amount added in Table 2, and react at 50°C for 4 hours;

[0180] (5) Then, a solution obtained by diluting 23.83 (0.2 mol) of N,N-dimethylformamide dimethyl acetal with 45 g of NMP was added dropwise, and after the addition was completed, the mixture was reacted at 50° C. for 8 h to obtain a reaction solution;

[0181] The reaction solution was poured into 3L of deionized water to precipitate the polymer and obtain a white precipitate. After filtering, the white precipitate was washed three times with deionized water and dried in a vacuum oven at 80°C for 72 hours to obtain a precursor resin.

[0182] Table 2 Preparation process of precursor resin in Preparation Examples 6-16

[0183]

[0184] The molecular weight of the precursor resin was determined by gel permeation chromatography (GPC, Shimadzu LC-20AD) by conversion to standard polystyrene. The molecular weight data of the precursor resins PAE-1 to PAE-11 are shown in Table 3:

[0185] Table 3. Precursor resin molecular weight data

[0186] Precursor resin Weight average molecular weight Mw Molecular weight distribution PDI Preparation Example 6 PAE-1 22368 1.89 Preparation Example 7 PAE-2 23472 1.91 Preparation Example 8 PAE-3 23127 1.90 Preparation Example 9 PAE-4 21259 1.87 Preparation Example 10 PAE-5 21865 1.89 Preparation Example 11 PAE-6 21768 1.89 Preparation Example 12 PAE-7 20962 1.85 Preparation Example 13 PAE-8 23152 1.91 Preparation Example 14 PAE-9 23011 1.91 Preparation Example 15 PAE-10 22010 1.89 Preparation Example 16 PAE-11 22429 1.89

[0187] Examples 1 to 9, Comparative Examples 1 to 5: Preparation of photosensitive polyimide coating adhesive

[0188] Examples 1-9 and Comparative Examples 1-5 respectively provide a photosensitive polyimide coating adhesive, and the types and addition amounts of the precursor resin, photosensitizer, porphyrin compound, silane coupling agent, and solvent are specifically shown in Table 4.

[0189] The preparation method of the photosensitive polyimide coating adhesive specifically comprises the following steps:

[0190] Add the precursor resin and N-methylpyrrolidone (NMP) solvent into a three-necked flask and stir; after the precursor resin is fully dissolved, add the photosensitizer, porphyrin compound and silane coupling agent in sequence, and after fully dissolved, filter with a 1.0 μm filter membrane to obtain a photosensitive polyimide coating adhesive.

[0191] Table 4 Resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 5

[0192]

[0193]

[0194] The following tests were performed on a photosensitive polyimide coating adhesive provided in Examples 1 to 9 and Comparative Examples 1 to 5, respectively. The test results are shown in Table 5.

[0195] The following tests were performed using the photosensitive resin compositions prepared in Examples 1 to 9 and the polyamide ester compositions prepared in Comparative Examples 1 to 5 as test samples.

[0196] 1. Detection method

[0197] (1) Dissolution rate of exposed and non-exposed areas

[0198] The test sample was coated onto a 4-inch silicon wafer, and then soft-baked at 120° C. for 3 min using a heating stage (NDK-2K, Japan) to obtain a resin film with a thickness of 10 to 20 μm.

[0199] The film thickness was measured by a step profiler (P-7, KLA-Tencor, USA), and was recorded as a. The silicon wafer was then placed on an exposure machine (BG-401A, produced by the 45th Institute of China Electronics Technology Group Corporation), a mask was placed on it, 365nm light (i-line) was selected, and 250mJ / cm 2 The resin film is exposed with energy of.

[0200] The exposed silicon wafer was placed in an alkaline developer (2.38% TMAH aqueous solution) for development, and the temperature was controlled at 25°C ± 1°C. The development time for the 50μm lines and spaces pattern (1L / 1S) to form a 1:1 width was recorded as T1, and the time for the resin film to fall off in the non-exposed area was T2.

[0201] The formula for calculating the dissolution rate of the exposed area is as follows:

[0202] Dissolution rate of exposed area = T1 / a.

[0203] The calculation formula for the dissolution rate of the non-exposed area is as follows:

[0204] Dissolution rate of exposed area = T2 / a.

[0205] (2) Heat resistance

[0206] The resin composition sample was evenly coated on a silicon wafer using a coating machine, and then placed on a heating table (HT-300 experimental electric heating plate, Guangzhou Gedan Instrument Co., Ltd.) at 120°C for 3 minutes for soft baking to obtain a resin film with a thickness of 10 to 20 μm. The film was then placed in a vacuum oxygen-free oven (MOLZK-32D1) and heat-treated at 170°C for 30 minutes under nitrogen atmosphere, and then heated to 320°C after 1 hour, and treated at 320°C for 1 hour, and then naturally cooled to below 50°C in the oven to finally obtain a cured film.

[0207] The temperature at which the weight of the cured film decreases by 5% (i.e., T 5wt The heat resistance of the resin was evaluated by using a thermogravimetric analyzer (TA, USA, Q50 series) with a heating rate of 10°C / min and a temperature range of 30-650°C.

[0208] (3) Breakdown voltage

[0209] The breakdown voltage test is carried out with reference to the national standard GB / T 1408.2-2006.

[0210] 2. Test results

[0211] The test results are shown in Table 5.

[0212] Table 5 Test results of Examples 1 to 9 and Comparative Examples 1 to 5

[0213]

[0214]

[0215] As shown in Table 5, it can be seen from Example 1 and Comparative Example 5 that the coating adhesive prepared by adding the porphyrin compound of the present invention shows a higher 5% thermal weight loss temperature and a higher breakdown voltage than the coating adhesive without adding the porphyrin compound. It can be seen from the comparison between Example 1 and Comparative Example 2 that the coating adhesive composed of the cyclobutene-terminated resin and the porphyrin compound can show better thermal stability and electrical resistance, mainly because the cyclobutene at the end group can undergo a cross-linking cyclization reaction with the cyclobutene in the porphyrin compound during the thermal curing process. It can be seen from the comparison between Examples 1-3 and Comparative Example 1 that the coating adhesive prepared by adding the resin with the photosensitive diamine monomer shows a lower dissolution rate in the exposure area and better photosensitivity. It can be seen from the above comparison results that the photosensitive polyimide coating adhesive prepared by the resin containing the photosensitive diamine monomer, the cyclobutene-terminated resin, and the porphyrin compound provided in the present application can show excellent heat resistance, electrical resistance and photosensitivity.

[0216] 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 photosensitive polyimide coating adhesive, characterized in that: The photosensitive polyimide coating adhesive comprises (A) a resin, (B) a photosensitizer, (C) a porphyrin compound, (D) a silane coupling agent, and (E) a solvent; The resin (A) is selected from compounds having a structure represented by formula (1) and / or formula (2); Wherein, p1 is selected from an integer between 2 and 200, p2 is selected from an integer between 2 and 50, and the ratio of p1 to p2 is 100:2 to 20; i1 is selected from an integer between 2 and 200, i2 is selected from an integer between 2 and 50, and the ratio of i1 to i2 is 100:2 to 20; R1 and R2 are each independently selected from a saturated aliphatic group having 1 to 10 carbon atoms, a hydrogen atom or an organic group having a structure represented by formula (3); R3, R4, and R5 are each independently selected from a hydrogen atom or an organic group having 1 to 3 carbon atoms; m is an integer selected from 2 to 200; X1 and X2 are independently selected from tetravalent organic groups having 4 to 40 carbon atoms; Y1 and Y2 are independently selected from divalent organic groups having 2 to 40 carbon atoms; Z is selected from a group having a structure represented by formula (4): The weight average molecular weight of the resin (A) is 5,000 to 40,000, calculated as a polystyrene conversion value based on gel permeation chromatography; The (B) photosensitizer is at least one selected from acetophenone compounds, biimidazole compounds, triazine compounds, oxime compounds, diazoquinone compounds, onium salts, halogen-containing compounds, and polyhydroxy compounds; The (C) porphyrin compound is selected from compounds having a structure of formula (5); Wherein, P1, P2, P3, and P4 are independently selected from a group having a structure shown in formula (4); The (D) silane coupling agent is at least one selected from the group consisting of urea-based silane coupling agents, epoxy-based silane coupling agents, mercapto-based silane coupling agents, vinyl-based silane coupling agents, and triazole-based silane coupling agents; The (E) solvent is selected from at least one of N-methylpyrrolidone, γ-butyrolactone, tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ether.

2. The photosensitive polyimide coating adhesive according to claim 1, characterized in that: The mass ratio of the (A) resin to the (B) photosensitizer is 100:0.1-30; Preferably, the mass ratio of the (A) resin to the (B) photosensitizer is 100:0.5-25; Preferably, the mass ratio of the (A) resin to the (B) photosensitizer is 100:0.5-20; The mass ratio of the (A) resin to the (C) porphyrin compound is 100:1-20; Preferably, the mass ratio of the (A) resin to the (C) porphyrin compound is 100:2-15; Preferably, the mass ratio of the (A) resin to the (C) porphyrin compound is 100:5-10; The mass ratio of the (A) resin to the (D) silane coupling agent is 100:0.1-5; Preferably, the mass ratio of the (A) resin to the (D) silane coupling agent is 100:1-5; The mass ratio of the resin (A) to the solvent (E) is 100:80-5000; The mass ratio of the (A) resin to the (E) solvent is 100:100-1000; Preferably, the mass ratio of the (A) resin to the (E) solvent is 100:150-400; The weight average molecular weight of the resin (A) is 10,000 to 30,000; Preferably, the weight average molecular weight of the resin (A) is 20,000-25,000.

3. The photosensitive polyimide coating adhesive according to claim 1, characterized in that: The R1 and R2 are each independently selected from a saturated aliphatic group having 1 to 4 carbon atoms; Preferably, R1 and R2 are each independently selected from at least one of ethyl, methyl, hydroxyethyl methacrylate, and n-butyl; The ratio of i1 to i2 is 100:5-15; X1 and X2 are independently selected from groups having structures shown in formula (6) a to j; Y1 is independently selected from the group having the structure shown in formula (7) a~p; Y2 is a photosensitive diamine monomer having a structure of formula (8); Wherein, R6 is selected from hydrogen atom, substituted or unsubstituted C1~C 20 Alkyl, substituted or unsubstituted C1~C 20 Alkoxy, substituted or unsubstituted C6~C 30 The aromatic group; Preferably, the R6 is selected from any one of the structures: H, -CH3, -CF3, -OCF3; Q is selected from 5-naphthoquinonediazidesulfonic acid or 4-naphthoquinonediazidesulfonic acid; n is an integer between 1 and 5; * indicates access site; The (B) photosensitive agent is selected from 1-(4-phenylthio-phenyl)-octane-1,2-dione-2-oxime-0-benzoate, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, dibenzil ketone, 4-benzoyl-4'-methyldiphenyl ketone, fluorenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid, 1,1,1,3,3,3-hexadecene, Fluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionate, 2-oxiranyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxy-p-cresol, 2,6-diacetoxymethyl-p-cresol, tetrahydroxybenzophenone, NT-300, 4NT-350, 4NT-300, at least one of the TPPA series products; The (D) silane coupling agent is selected from at least one of 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 1-propyl-1-(triethoxysilyl)methylurea, (3-glycidoxypropyl)trimethoxysilane, (8-glycidoxyoctyl)trimethoxysilane, (3-glycidoxypropyl)trimethoxysilane, 3-(triethoxysilylthio)propyltrimethoxysilane, 3-(trimethoxysilyl)-1-propanethiol, γ-thiopropyltriethoxysilane, 3-(triethoxysilylthio)propyltrimethoxysilane, 3-(trimethoxysilyl)-1-propanethiol, γ-thiopropyltriethoxysilane, vinyltriethoxysilane, p-vinylphenyltrimethoxysilane, compounds having structures represented by formula (9) a to f, and compounds having structures represented by formula (10) a to k; 4. The photosensitive polyimide coating adhesive according to claim 1, characterized in that: The viscosity of the photosensitive polyimide coating adhesive is 10 to 10000 cP; Preferably, the viscosity of the photosensitive polyimide coating adhesive is 500 to 5000 cP; Preferably, the viscosity of the photosensitive polyimide coating adhesive is 1000-4000 cP.

5. A method for preparing the photosensitive polyimide coating adhesive according to any one of claims 1 to 4, characterized in that: The following steps are involved: The raw materials containing (A) resin, (B) photosensitizer, (C) porphyrin compound, (D) silane coupling agent and (E) solvent are mixed and filtered to obtain the photosensitive polyimide coating adhesive.

6. The preparation method according to claim 5, characterized in that: (A) The resin is obtained by the following steps: Mixing a common diamine monomer, a photosensitive diamine monomer, a dianhydride monomer and a non-protonic solvent, performing reaction I, adding a capping agent, performing reaction II, adding an esterification agent, performing reaction III, precipitating, washing and drying to obtain the resin (A); The common diamine monomer is selected from at least one of the compounds having the structures shown in formula (11) a to p: The photosensitive diamine monomer has a structure shown in formula (12): Wherein, R6 is selected from hydrogen atom, substituted or unsubstituted C1~C 20 Alkyl, substituted or unsubstituted C1~C 20 Alkoxy, substituted or unsubstituted C6~C 30 The aromatic group; Preferably, R6 is selected from one of H, -CH3, -CF3, and -OCF3; Q is selected from 5-naphthoquinonediazidesulfonic acid or 4-naphthoquinonediazidesulfonic acid; n is an integer between 1 and 5; The dianhydride monomer is selected from at least one of the compounds having the structure shown in formula (13): The aprotic solvent is selected from at least one of N-methylpyrrolidone, γ-butyrolactone, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; The end-capping agent is selected from a compound having a structure shown in formula (14); The esterification agent is selected from at least one of methanol, ethanol, n-butanol, hydroxyethyl methacrylate, N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal and 4-nitrobenzyl alcohol.

7. The preparation method according to claim 6, characterized in that: The molar ratio of the common diamine monomer to the photosensitive diamine monomer is 100:5-20; Preferably, the molar ratio of the common diamine monomer to the photosensitive diamine monomer is 100:10-15; The total molar ratio of the common diamine monomer and the photosensitive diamine monomer to the total molar ratio of the dianhydride monomer is 100:80-100; Preferably, the total molar ratio of the common diamine monomer and the photosensitive diamine monomer to the total molar ratio of the dianhydride monomer is 100:90-95; The mass ratio of the common diamine monomer to the aprotic solvent is 1:3-20; The ratio of the total molar amount of the common diamine monomer and the photosensitive diamine monomer to the total molar amount of the end-capping agent and the dianhydride monomer is 1:1; The molar ratio of the esterification agent to the dianhydride monomer is 1 to 5:1; Preferably, the molar ratio of the esterification agent to the dianhydride monomer is 1.5 to 3:1; The temperature of the reaction I is 10 to 100°C; The reaction time is 3 to 24 hours; The temperature of the reaction II is 10 to 100°C; The reaction time of II is 3 to 24 hours; The temperature of the reaction III is 30 to 80°C; The time of the reaction III is 2 to 24 hours.

8. The preparation method according to claim 5, characterized in that: The (C) porphyrin compound is obtained by the following steps: Under a nitrogen atmosphere, a compound having a structure of formula (14) and a compound having a structure of formula (15) are mixed with a non-protonic polar solvent to undergo an amidation reaction to obtain the porphyrin compound (C); The aprotic polar solvent is selected from at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and γ-butyrolactone.

9. The preparation method according to claim 8, characterized in that: The molar ratio of the compound having the structure of formula (14) to the compound having the structure of formula (15) is 3.9 to 4.1:1; The mass ratio of the compound having the structure of formula (14) to the aprotic polar solvent is 1:3-10; The temperature of the amidation reaction is 20 to 50° C. The amidation reaction time is 5 to 10 hours.

10. A photosensitive resin film, characterized in that: The photosensitive polyimide coating adhesive according to any one of claims 1 to 4 is used as the material.

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