Polyimide and composition and preparation method thereof

Abstract

The invention provides a polyimide composition as well as a preparation method and application thereof. The polyimide composition comprises polyimide resin 1 with a repetitive unit as shown in a formula (I) and polyimide precursor resin 2 with a repetitive unit as shown in a formula (II), wherein at least one of R1, R2, R3 and R4 is a polar group, or at least one of R5 and R6 is provided with a polar group, and one end or two ends of a molecular chain of the polyimide precursor resin 2 are terminated by a group containing a carbon-carbon unsaturated bond. The composition disclosed by the invention can be completely cured at a relatively low temperature (such as 280 DEG C or below), and a cured film has low thermal expansion coefficient, high mechanical property, good toughness and interface adhesion.

Description

Technical Field

[0001] This invention relates to the field of microelectronic device materials, and more particularly to a polyimide resin composition suitable for low-temperature curing processes, its preparation method, and a polyimide film with excellent comprehensive properties made from the composition. Background Technology

[0002] Polyimide (PI) film possesses unique properties such as high strength, high toughness, wear resistance, high temperature resistance, and corrosion resistance, making it suitable for designs that are lightweight, thin, short, and small. It is a competitive high-temperature insulating material. After more than 40 years of development, it has become one of the important raw materials for electronic and electrical products. In the electronics field, it is widely used in flexible printed circuit boards, semiconductor packaging, photovoltaic (solar) energy, and liquid crystal displays, while in the electrical field, it is mainly used in aerospace, military, machinery, and automotive industries.

[0003] Polyimide (PI) films have wide applications in the field of microelectronic devices: 1) as dielectric layers for interlayer insulation; 2) as buffer layers to reduce stress and improve yield; 3) as protective layers to reduce the impact of the environment on devices and to shield alpha particles, reducing or eliminating soft errors; 4) in the semiconductor industry, polyimide is used as a high-temperature adhesive. In the production of digital semiconductor materials and MEMS system chips, the good mechanical ductility and tensile strength of the polyimide layer help improve the adhesion between the polyimide layer and the deposited metal layer; 5) the high-temperature resistance and chemical stability of polyimide also serve to isolate the metal layer from various external environments.

[0004] The PI industry requires high technology and high investment, and its market is characterized by exclusivity. International chemical giants such as DuPont of the United States, Kaneka Chemical of Japan, and SKC of South Korea monopolize a considerable portion of the global PI market.

[0005] In recent years, the new applications of PI film in industries such as high-end FPC, LED, electronic communications, and optoelectronic displays have led to an increasing demand for new PI materials, and polyimide film is playing an increasingly important role in industrial development. With the ever-changing demands of mobile electronic devices, the development of PI products is driven by higher requirements for physical properties, such as improvements in high solids content, low-temperature curing effect, tensile strength, modulus, and dimensional stability. Summary of the Invention

[0006] The present invention provides a polyimide resin composition capable of complete curing at a low temperature (e.g., 280°C or below), and the cured film having a low coefficient of thermal expansion, high mechanical properties, good toughness and interfacial adhesion, a method for preparing the composition, and a polyimide film obtained therefrom.

[0007] The first aspect of this application is to provide a polyimide composition comprising a polyimide resin 1 and a polyimide precursor resin 2, wherein the resin 1 has repeating units as shown in formula (I): (I); R1, R2, R3, and R4 are each independently H or monovalent organic groups; R5 and R6 are each independently single bonds and divalent organic groups, or R5 and R6 independently form fused ring structures with the benzene rings at their two ends; and at least one of R1, R2, R3, and R4 is a polar group, or at least one of R5 and R6 has a polar group. The polyimide precursor resin 2 has repeating units as shown in structural formula (II), and one or both ends of the molecular chain are capped with groups containing carbon-carbon unsaturated bonds: (II); R7 and R8 are each independently a divalent organic group; Where m and n are positive numbers.

[0008] R5 and R6 can be combinations of one or more selected independently from single bonds, -O-, -S-, -CO-, -COO-, -CONH-, -NH-, -SO2-, -C=N-, alkylene groups R, and alkylene groups R substituted with polar groups.

[0009] Preferably, the "hydrocarbon" in "hydrocarbon-independent R, or hydrocarbon-independent R with polar group substitution" can be selected from C1-C4 chain aliphatic hydrocarbons (preferably C1-C3 chain aliphatic hydrocarbons, more preferably C1-C2 chain aliphatic hydrocarbons), C3-C10 cyclic aliphatic hydrocarbons (preferably C4-C8 cyclic aliphatic hydrocarbons, such as C3 cyclic aliphatic hydrocarbons, C4 cyclic aliphatic hydrocarbons, C5 cyclic aliphatic hydrocarbons, C6 cyclic aliphatic hydrocarbons, more preferably, cyclic aliphatic hydrocarbons can be one or more of fused rings, spiro rings, bridged rings, and bicyclic rings), and C5-C15 aromatic hydrocarbons (preferably C5-C12 aromatic hydrocarbons, such as C6 aromatic hydrocarbons, C7 aromatic hydrocarbons, C8 aromatic hydrocarbons, C10 aromatic hydrocarbons, etc.). For example, "hydrocarbon" can be methane, ethane, n-propane, isopropane, cyclopropane, cyclobutane, cyclohexane, cyclopentane, benzene, naphthalene, etc.

[0010] More preferably, the "hydroalkylene group R" may be selected from -CH2-, -CH2-CH2-, -CH(CH3)-, -C(CH3)2-, -CH2-CH2-CH2-, -CH2-CH(CH3)-, -CH2-CH2-CH2-CH2-, -CH2-CH(CH3)-CH2-, -CH2-CH2-CH(CH3)-, -CH(CH3)-CH(CH3)-, -C(CH3)2-CH2-, , , , , , , , , , , , , , , , , , , , , One or more combinations thereof.

[0011] Preferably, the "polar group-substituted alkylene group R" means that the H atom of the alkylene group R is replaced by a polar group, or that the polar group is located between the two C atoms of the alkylene group R. For example, the "polar group-substituted alkylene group R" can be: 1) alkylene group R substituted with polar groups such as -OH, -NO2, -SH, -Cl, -Br, -F, -COOH, -CHO, -CN, -SO3H, -NH2, etc.; or 2) alkylene group R with polar groups such as -O-, -S-, -SO2-, -COO-, -CO-, -CONH-, -C=N- located between the two C atoms of the alkylene group R, for example, it can be one or more of the following: forming a chain group containing heteroatoms, a cyclic group containing heteroatoms. Combinations, such as forming one or more of -COC-, -C-NH-C-, -CSC-, cyclic lactone groups, cyclic lactam groups, tetrahydrofuran groups, tetrahydropyran groups, dioxane groups, hexahydropiperidine groups, methylhexahydropiperidine groups, high-piperidine groups, N-methylhexahydropiperidine groups, pyrrole groups, pyridine groups, quinoline groups, isoquinoline groups, pyrimidine groups, triazine groups, imidazoline groups, tetrahydrothiophene groups, thiocyclohexyl groups, triazole groups, thiazole groups, imidazoline groups, and purine groups. For example, the "polar group-substituted alkylene group R" can be: -R-OH, -R-Cl, -RF, -R-CHO, -R-COOH, -R-CN, -R-NH2, -R-SO3H, -C(CF3)2-, -R-CONH2, , , , , , , , , , , , , , , , , , , , , One or more combinations thereof.

[0012] Preferably, R5 and R6 can be independent common bonds of the benzene rings, connecting the two benzene rings to form a fused ring, or R5 and R6 can be independent cyclic structures, connected to the two benzene rings to form a fused ring or a fused ring. For example, the fused ring or fused ring can be: , , , , , , , , , , , , , One or more combinations thereof. More preferably, R5 and R6 further contain the polar group, thereby forming a fused ring or fused ring with polar group substitution.

[0013] Preferably, at least one of R5 and R6 contains one or more polar groups. Preferably, the polar group may be located on the side group or main chain of R5 and / or R6. For example, the polar group may be one or more of the following groups, or a combination of one or more organic groups containing any of the following groups: -OH, -NO2, -SH, -CN, -Cl, -Br, -F, -COOH, -SO3H, -NH2, -CHO, -CONH2, -O-, -S-, -SO2-, -COO-, -CO-, -CONH-, -C=N-, etc.

[0014] R8 contains or is selected from a chain structure, particularly preferably a chain structure of C4-C18 (preferably C5-C15, such as C6, C7, C8, C9, C10, C11, C12). More preferably, the chain structure of R8 can be composed of C and H atoms, or it can contain heteroatoms. More preferably, the heteroatoms contained in R8 can be one or more combinations of Si, O, N, P, S, and halogen atoms. More preferably, the heteroatoms contained in R8 can be located on the main chain (e.g., between two C atoms) or on the side group (e.g., all or part of the heteroatoms as side groups), for example forming one or more combinations of -O-, -NH-, -Si-, -S-, -CO-, -COO-, -CONH-, -C=N-, -Cl, -Br, -F, -OH, -NO2, -SH, -COOH, -CN, -SO3H, -CHO, -CONH2, and -NH2.

[0015] For example, R8 can be -(CH2)4-, -(CH2)5-, -(CH2)6-, or -(CH2). a -SiR 11 R 12 -(CH2) b -、-(CH2) a -NR 11 -(CH2) b -、-(CH2) a -O-SiR 11 R 12 -O-(CH2) b -、 (x is preferably a positive integer ≥ 4), and one or more of -CH2-CH2-O-CH2-CH2-O-CH2-CH2-. Wherein, R 11 R 12 Each group is independently H or a monovalent organic group, and is preferably H or a C1-C10 hydrocarbon group, such as alkyl groups of C1-C6 (e.g., C1, C2, C3, C4, C5), cycloalkyl groups of C3-C8 (e.g., C2, C3, C4, C5, C6), and aromatic groups of C5-C10 (e.g., C6, C7, C8, C9, C10). Wherein, a and b are positive numbers, and are preferably 0-5, such as being independently selected from 1, 2, 3, 4, and 5.

[0016] Wherein, R7 is a tetravalent organic group, and preferably a tetravalent organic group containing a benzene ring, such as a combination of one or more selected from benzene, biphenyl, and fused ring structures. Specific examples may include: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , wait.

[0017] R1, R2, R3, and R4 are each independently selected from one or more combinations of H, polar groups, and hydrocarbon groups substituted with polar groups. More preferably, at least one of R1, R2, R3, and R4 is a polar group. More preferably, the polar group can be one or more combinations selected from -OH, -NO2, -SH, -Cl, -Br, -F, -COOH, -SO3H, -NH2, -CHO, -CN, and -COONH2.

[0018] Preferably, a "polar group-substituted hydrocarbon group" means that one or more H atoms in the hydrocarbon group Q are replaced by a polar group, and / or the polar group is located on the main chain of the hydrocarbon group Q.

[0019] Preferably, the hydrocarbon group Q can be one or more of a straight-chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and is more preferably one or more of a C1-C6 straight-chain aliphatic hydrocarbon group, a C3-C10 cyclic aliphatic hydrocarbon group, or a C5-C15 aromatic hydrocarbon group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, cyclopentyl, cyclopropyl, phenyl, benzyl, naphthyl, methylphenyl, etc.

[0020] Preferably, the "polar group-substituted hydrocarbon group" means that the H of the hydrocarbon group Q is replaced by a polar group. For example, one or more H of the hydrocarbon group Q is replaced by one or more of -OH, -NO2, -SH, -Cl, -Br, -F, -COOH, -SO3H, -NH2, -CHO, -CN, -COONH2; preferably, the "polar group-substituted hydrocarbon group" is one or more of -QF, -Q-Cl, -Q-Br, -Q-OH, -Q-SH, -Q-COOH, -Q-COONH2, -Q-NH2, -Q-CHO, -Q-CN, -Q-SO3H. For example, the "polar group-substituted hydrocarbon group" is -CH2F, -CHF2, -CF3, -C(CF3)3, -CH2Cl, -CHCl2, -CCl3, -CH2OH, -CH2-COOH, -CH2-CN, -CH2-NH2, -CH2-CHO, -CH2-CF3, -CHOH-CH2-CH2OH, -CH(CH2OH)2. , , , , , , , , , , , , , , , , One or more combinations thereof.

[0021] Preferably, the "polar group-substituted hydrocarbon group" can be a polar group located between the two C atoms of the hydrocarbon group Q, and / or between the hydrocarbon group Q and the benzene ring connected to the hydrocarbon group Q. For example, it can be a heteroatom located between the two C atoms of the hydrocarbon group (such as a straight-chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group), or between the hydrocarbon group Q and the benzene ring connected to the hydrocarbon group Q, forming -COC-, -C-CO-C-, -C-COO-C-, -CC=N-, -C-CONH-C-, -C-NH-C-, -CSC-, -C-SO2-C-. For example, the "polar group-substituted hydrocarbon group" can be: -CH2-O-CH3, -CH2-S-CH3, -CH2-SO2-CH3, -CH2-CO-CH3, -CH2-CO-O-CH3, -CH2-O-CO-CH3, -CH2-CO-NH2-CH3, -CH2-NH2-CO-CH3, -CH2-O-CF3, -CH2-NH-CH3, -CH2-N(CH3)2, -CH2-N(CH2-CH3)2, -CH2-N(CH2-CH3)(CH3), , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , One or more combinations thereof.

[0022] In a preferred embodiment, the "group containing carbon-carbon unsaturated bonds" refers to non-conjugated unsaturated bonds, preferably one or more of C=C and C≡C, for example, a combination of one or more of olefin groups and alkyne groups.

[0023] The olefin may be one or more of a chain olefin group or a cyclic olefin group.

[0024] The olefin may be one or more of a monoolefin group, a diene group, or a more polyolefin group.

[0025] The alkyne may be one or more of a chain alkyne group or a cyclic alkyne group.

[0026] The alkyne can be one or more of a combination of monoalkyne groups, dialkyne groups, and more polyalkyne groups.

[0027] More preferably, the "group containing a carbon-carbon unsaturated bond" can be one or more of the following: olefinic group, alkyneic group, substituent-substituted olefinic group, and substituent-substituted alkyneic group. Preferably, the substituent can be located on a side group or on the main chain; for example, the substituent can be one or more of the following: -OH, -NO2, -SH, -Cl, -Br, -F, -COOH, -SO3H, -NH2, -CHO, -CN, -COONH2, -O-, -S-, -CO-, -COO-, -C=N-, -CO-NH-, -NH-, and -SO2-.

[0028] In a more preferred embodiment, the group containing a carbon-carbon unsaturated bond can be CH2=CH-, CH2=CH-CH2-, CH2=CH-CH-CH-, CH2=C(CH3)-, CH(CH3)=CH-, CH2=CHC(CH3)2-O-, CH(CH3)=C(CH3)-, CH3-CH=CH-CH2-, CH≡C-, CH3-C≡C-, CH(CH3)=CH-CO-, CH(CH3)=CH- COO-CH2CH2-NH-, CH(CH3)=CH-COO-, CH(CH3)=CH-O-, CH(CH3)=CH-CH2-NH-, CH2=CH-CO-, CH2=CH-COO-, CH2=CH-CH2-NH-, CH2=CH-COO-CH2CH2-NH-, CH2=CH-O-, CH2=CH-C(=CH2)-, CH2=CH-CH2-O-, CH3-CH=CH- CH2-O-, CH3CH2CH2CH2CH2CH(CH=CH2)-O-, CH2(OH)CH=CHCH2-O-, CH3CH=C(CH3)-COO-, HOOC-CH2C(=CH2 )-COO-, HOOC-CH=CH-COO-, CH2=CH-CH2-O-CH2CH2-O-, CH2=C(CH3)-CH2-O-CH2CH2-O-, CH3CH2CH2-OOC- CH=CH-COO-, CH2=CH-OOC-CH=CH-COO-, CH2=CH-OOC-CH2CH2-COO-, CH2=C(CH3)-CH2-O-CH2CH2-, CH2=CH -CH2-O-CH2CH2-, C(CH3)2=CHCH2CH2C(CH3)=CHCH2-O-, CH2=CH-CH2OCH2CH2-O-, HO-CH2-CH=CH-CH2-O-, , , , , , , , , , , , , , , , , , One or more of them. Among them, R 31It can be one or more combinations of H, monovalent polar groups, and monovalent nonpolar groups, such as: R 31 It can be H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, benzyl, methoxy, ethoxy, halogen atom, -SH, -OH, -SO3H, -CHO, -CN, -COOH, -CONH2, -NH2, -NO2 or combinations thereof, examples of such combinations include aminomethyl, aminoethyl, chloromethyl, hydroxymethyl, hydroxyethyl, carboxymethyl, carboxyethyl, carboxypropyl, chlorophenyl, fluorophenyl, methyl chloride, methyl fluoride, CH3-O-CO-CH2-, CH3CH2-O-CO-CH2-, etc.

[0029] In a preferred embodiment, the polyimide composition may further include a curing agent.

[0030] Preferably, the curing agent can be a peroxide initiator, a persulfide initiator, an azo initiator, a redox initiator, a coordination polymerization initiator, etc. , One or more combinations of R; where R 32 R 33 R 34 R 36 R 37 R 38 The substituents are, respectively, H, a halogen atom, a C1-C10 chain monovalent substituent, a C3-C15 cyclic monovalent non-aromatic substituent, and a C5-C20 monovalent aromatic substituent. Preferably, they can be hydrocarbon groups or substituents containing heteroatoms. In a preferred embodiment, R 32 R 33 R 34 The individual components are H, methyl, ethyl, vinyl, n-propyl, isopropyl, allyl, cyclohexyl, cyclopentyl, phenyl, naphthyl, benzyl, methylphenyl, norbornyl, norbornyl, m-dimethylphenyl, (3,5-di-tert-butyl-4-hydroxy)phenyl, hydroxyphenyl, tert-butylphenyl, allylphenyl, vinylphenyl, carboxymethyl, hydroxymethyl, chloromethyl, carboxyethyl, hydroxyethyl, methoxy, ethoxy, acryloyloxy, methacryloyloxy, acryloyloxymethyl, acryloyloxyethyl, methacryloyloxymethyl, methoxysilyl, ethoxysilyl, methoxysilanepropyl, 1-chloro-2-hydroxypropyl, 2,3-dibromopropyl, epoxypropyl, epoxyethyl, etc.; R 35 It can be one or more combinations of H, monovalent polar groups, and monovalent nonpolar groups, such as: R 35It can be H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, benzyl, methoxy, ethoxy, halogen atom, -SH, -OH, -SO3H, -CHO, -CN, -COOH, -CONH2, -NH2, -NO2 or combinations thereof, examples of such combinations include aminomethyl, aminoethyl, chloromethyl, hydroxymethyl, hydroxyethyl, carboxymethyl, carboxyethyl, carboxypropyl, chlorophenyl, fluorophenyl, methyl chloride, methyl fluoride, CH3-O-CO-CH2-, CH3CH2-O-CO-CH2-, etc.

[0031] In a preferred embodiment, the curing agent may also contain carbon-carbon unsaturated bonds, particularly preferably non-conjugated carbon-carbon unsaturated bonds, and preferably any one or more combinations of carbon-carbon unsaturated bonds described in the context of this invention.

[0032] In a preferred embodiment, the curing agent may be benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butyl valerate peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxide, dicyclohexyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, azobisisopropylimidazoline, benzoyl peroxide / sucrose, tert-butyl hydroperoxide / sodium thiosulfate, tert-butyl hydroperoxide / sodium metabisulfite, or benzoyl peroxide / N,N-dimethylaniline. Ammonium persulfate / sodium bisulfite, potassium persulfate / sodium bisulfite, hydrogen peroxide / tartaric acid, hydrogen peroxide / sodium formaldehyde sulfoxylate, ammonium persulfate / ferrous sulfate, hydrogen peroxide / ferrous sulfate, benzoyl peroxide / N,N-diethylaniline, benzoyl peroxide / ferrous pyrophosphate, potassium persulfate / silver nitrate, persulfate / thiol, cumene hydrogen peroxide / ferrous chloride, potassium persulfate / ferrous chloride, hydrogen peroxide / ferrous chloride, cumene hydrogen peroxide / tetraethyleneimine, Ziegler-Natta catalyst, metallocene catalyst, non-metallocene catalyst, dibromoisocyanuric acid, trichloroisocyanuric acid, sodium dichloroisocyanurate, triglycidyl isocyanurate, tri(2-hydroxyethyl)isocyanurate, di(carboxyethyl)isocyanurate, tri(methoxysilanepropyl)isocyanurate, tri(2-acryloyloxyethyl)isocyanurate, tri(2,3-dibromopropyl)isocyanurate Ester, Triallyl Isocyanurate, Tris(methylallyl) Isocyanurate, Diallyl Isocyanurate, Tripropyl Isocyanurate, Tris(1'-chloro-2'-hydroxy-propyl) Isocyanurate, Bis(2-carboxyethyl) Isocyanurate, Tris(2,3-epoxypropyl) Isocyanurate, Tris[(3,5-di-tert-butyl-4-hydroxy)phenyl] Isocyanurate, Imidazole, N-methylimidazole, N-ethylimidazole, 2-methyl Imidazole, 4-methylimidazole, 5-methylimidazole, 2-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1,2-dimethylimidazole, 2,4-dimethylimidazole, 4,5-dimethylimidazole, 2,4,5-trimethylimidazole, 2-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 2-phenylimidazole, 4-phenylimidazole, 5-phenylimidazole, 2-acetylimidazole, 4-carboxyimidazole, 1-vinylimidazole, 2,4-Diphenylimidazolium, 4-Methyl-diphenylimidazolium, 2-Methyl-4-ethylimidazolium, 4-Methyl-2-ethylimidazolium, 2-propyl-4-methylimidazolium, 2-aminoethylimidazolium, 4-aminoethylimidazolium, 5-aminoethylimidazolium, 2-hydroxyethylimidazolium, 4-hydroxyethylimidazolium, 5-hydroxyethylimidazolium, L-histidine, 4-methyl-2-aminoethylimidazolium, 2-methyl-4-aminoethylimidazolium, 1-methyl-L-histidine, 2-chloromethyl-4-methylimidazolium, 2-aldehyde-4-methylimidazolium, 4-methyl-2-ethylimidazolium, 2-isobutyl-4-isopropylimidazolium, 2,4-diisopropylimidazolium, 4,5-dinitrileimidazolium, 2,4-diisobutylimidazolium, 2,2-bis(4,5-dimethylimidazolium), 2-methyl-4-carboxyimidazole, 1- The following are one or more of the following: methyl-4-Cl-imidazolium, 4-amino-5-carboxyimidazole, 1-methyl-4-nitro-2-hydroxymethylimidazole, (4-amino-5-imidazolyl)formamide, 1,2-dimethyl-4-nitroimidazole, 2-methyl-4-nitroimidazole, (2-methyl-5-nitroimidazole-1-yl)-ethanol, (2-methyl-5-nitroimidazole-1-yl)-propanol, 3-(4-imidazolyl)acrylic acid, N,N'-carbonyldiimidazole, diethyl imidazolium-4,5-dicarboxylate, 1-(2-hydroxyethyl)imidazole, 2-(2-chlorophenyl)-4,5-diphenylimidazole, 2-(2-methoxyphenyl)-4,5-diphenylimidazole, 4-(imidazol-1-yl)aniline, 1-(4-nitrophenyl)imidazole, and 1-p-methylbenzenesulfonylimidazole.

[0033] In a preferred embodiment, the polyimide composition further includes a solvent, preferably capable of dissolving resin 1 and resin 2, and more preferably, the solvent may be one or more of alcohols, ethers, ketones, aldehydes, esters, hydrocarbons, halogenated hydrocarbons, and heterocyclic compounds, such as N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, methyl lactate, propyl lactate, isopropyl lactate, dimethyl sulfoxide, and N,N-dimethylformamide.

[0034] In a preferred embodiment, the weight average molecular weight of resin 1 is preferably 8,000-60,000, more preferably 10,000-50,000, more preferably 15,000-40,000, and even more preferably 20,000-35,000.

[0035] In a preferred embodiment, the weight average molecular weight of the resin is preferably 50,000-200,000, more preferably 60,000-180,000, even more preferably 80,000-150,000, and even more preferably 100,000-120,000.

[0036] In a preferred embodiment, the molecular weight of resin 1 is ≤ the molecular weight of resin 2.

[0037] In a preferred embodiment, the mass ratio of resin 1 to resin 2 is (1-99):(1-99), more preferably (3-97):(3-97), more preferably (5-95):(5-95), and even more preferably (10-90):(10-90).

[0038] In a preferred embodiment, based on the total weight of resin 1 and resin 2, the weight fraction of resin 2 is preferably 1-99%, more preferably 3-87%, more preferably 5-95%, more preferably 10-90%, more preferably 15-85%, more preferably 20-80%, such as 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, etc.

[0039] In a preferred embodiment, the solid content of the polyimide composition is preferably 5-30 wt%, more preferably 8-28 wt%, and even more preferably 10-25 wt%, such as 15 wt% or 20 wt%.

[0040] The present invention also provides a method for preparing the polyimide composition, comprising: providing resin 1 and resin 2, wherein resin 1 and resin 2 may form a mixture or exist independently.

[0041] Preferably, both resin 1 and resin 2 are dissolved in a solvent to form a mixture.

[0042] More preferably, resin 1 is first dissolved in a solvent to form a first mixture, and then resin 2 is added to the first mixture; or, resin 1 and resin 2 are dissolved independently in their respective solvents and then mixed.

[0043] In a preferred embodiment, the method of providing resin 2 includes: (IV) The anhydride of structural formula (IV) reacts with diamine NH2-R8-NH2 to obtain resin 2.

[0044] In a preferred embodiment, the method of providing resin 2 includes: The anhydride of structure (IV) reacts with diamine NH2-R8-NH2 to obtain a polymer, which is then capped by adding a compound containing carbon-carbon unsaturated bonds as a capping agent.

[0045] More preferably, the capping agent can be one or more of A-OH, A-COOH, and A-NH2, wherein A is the group containing a carbon-carbon unsaturated bond.

[0046] In a preferred embodiment, the method for preparing the polyimide composition further includes providing a curing agent; more preferably, after resin 1 and resin 2 are mixed to form a mixture, the curing agent is added to the mixture.

[0047] The present invention also provides a method for preparing a film, preferably a method for preparing a polyimide film, comprising: curing the above-described polyimide composition into the film.

[0048] In a preferred embodiment, the curing temperature is preferably 150-280℃, more preferably 180-260℃, and even more preferably 200-250℃.

[0049] In the above description of this invention, "polar group" refers to a group with uneven charge distribution in a chemical bond.

[0050] The present invention has the following beneficial effects: 1) Excellent comprehensive performance: Through the ingenious combination of rigid resin and flexible crosslinkable resin, the cured film forms an interpenetrating network structure, achieving a balance between low thermal expansion coefficient and high mechanical strength / toughness, and good dimensional stability.

[0051] 2) Low-temperature curing: The second polyimide precursor resin of the present invention can be cross-linked at a lower temperature. The composition of the present invention can be fully cured at 150-280°C, especially below 280°C, which greatly expands its application potential in heat-sensitive devices.

[0052] 3) Good processability and adhesion: The composition of this invention exhibits good solubility and storage stability in common organic solvents, and has a wide film-forming process window. The polar groups in resin (A) and the dense network formed during curing contribute to improving the adhesion strength between the film and metal, inorganic dielectric layers, or organic underlayers.

[0053] 4) High reliability: The fully imidized structure and dense three-dimensional cross-linked network of this invention endow the film with excellent heat resistance, chemical stability and electrical insulation properties, meeting the requirements of high-end microelectronic applications. Detailed Implementation

[0054] To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention will be further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0055] It should be noted that the terms "first," "second," etc., in the specification and claims of this invention are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be used interchangeably where appropriate. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or apparatus that comprises a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.

[0056] Examples of reactants used in the following embodiments are as follows: Synthesis Example 1: Synthesis of the first polyimide (resin A-1): Acid anhydride A002: Biphenyl tetracarboxylic anhydride (BPDA)

[0057] Diamine E004: 3,3'-Dihydroxybenzidine

[0058] Diamine E008: 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP)

[0059] End-capping agent: SSZ-061: 3-Aminophenylpropynyl ether

[0060] Under nitrogen protection, 440.3 g of NMP was added to a reaction flask equipped with a stirrer, thermometer, and nitrogen inlet tube, followed by 62.3 g of BPDA (A002) and 2.5 g of 3,3'-dihydroxybenzidine (E004). The temperature was raised to 55 °C, and 62.0 g of BAPP (E008) was rapidly added with stirring. After reacting at 55 °C for 1 hour, the temperature was raised to 190 °C, and the reaction was continued with stirring for 4 hours to carry out one-step thermal imidization.

[0061] After the reaction was complete, the temperature was lowered to 40°C, and 3.3 g of 3-aminophenylpropynyl ether (SSZ-061) was added as a capping agent. The mixture was stirred at 40°C for another hour. The reaction solution was then added dropwise to 12 L of deionized water to precipitate the polymer. The precipitate was filtered, and the filter cake was washed several times with deionized water. The resulting solid was dried in a vacuum oven at 60°C for at least 48 hours to obtain a pale yellow powdery resin A-1. GPC analysis showed that its weight-average molecular weight (Mw) was approximately 25,000.

[0062] Synthesis Example 2, Synthesis of the second polyimide precursor (resin B-1): Biphenyl tetracarboxylic anhydride (BPDA)

[0063] PMDA (pyromellitic anhydride):

[0064] Diamine SiDA: Bis(3-aminopropyl)polydimethylsiloxane (number-average molecular weight approximately 1000), with the following general formula: (a is a positive number) End-capping agent allylamine: CH2=CH-CH2-NH2 Under nitrogen protection, 120 g of NMP was added to the reaction flask, and the temperature was raised to 60 °C. 13.0 g of PMDA and 0.9 g of SiDA were added, and the mixture was stirred and dissolved for 30 minutes. Then, 9.3 g of PMDA and 12.6 g of BPDA were added in batches, controlling the addition rate to keep the temperature below 70 °C. After the addition was complete, the reaction was continued at 60 °C with stirring for 120 minutes to obtain a polyamic acid solution.

[0065] Then, 4.3 g of allylamine (CH2=CH-CH2-NH2) was added to the solution, and the end-capping reaction was carried out at room temperature for 20 minutes to obtain a solution of resin B-1. GPC testing (using polystyrene as a standard) showed that its weight-average molecular weight (Mw) was approximately 105,000. FT-IR monitoring showed that its imidization rate was less than 5% (mainly in the form of polyamic acid).

[0066] Synthesis Example 3: Synthesis of the second polyimide precursor (resin B-2): Biphenyl tetracarboxylic anhydride (BPDA)

[0067] PMDA (pyromellitic anhydride):

[0068] 1,8-Octadiamine: NH2-(CH2)8-NH2 End-capping agent allylamine: CH2=CH-CH2-NH2 Under nitrogen protection, 120 g of NMP was added to the reaction flask, and the temperature was raised to 60 °C. 13.0 g of PMDA and 0.5 g of 1,8-octanediamine were added, and the mixture was stirred and dissolved for 30 minutes. Then, 9.5 g of PMDA and 12.5 g of BPDA were added in portions, controlling the addition rate to keep the temperature below 70 °C. After the addition was complete, the reaction was continued at 60 °C with stirring for 120 minutes to obtain a polyamic acid solution.

[0069] Then, 4.5 g of allylamine (CH2=CH-CH2-NH2) was added to the solution, and the end-capping reaction was carried out at room temperature for 20 minutes to obtain a solution of resin B-2. GPC testing (using polystyrene as a standard) showed that its weight-average molecular weight (Mw) was approximately 98,000. FT-IR monitoring showed that its imidization rate was less than 5% (mainly in the form of polyamic acid).

[0070] Synthesis Example 4: Synthesis of the second polyimide precursor (resin C-1): Biphenyl tetracarboxylic anhydride (BPDA)

[0071] PMDA (pyromellitic anhydride):

[0072] Diamine SiDA: Bis(3-aminopropyl)polydimethylsiloxane (number-average molecular weight approximately 1000), with the following general formula: (a is a positive number) Under nitrogen protection, 120 g of NMP was added to the reaction flask, and the temperature was raised to 60 °C. 13.0 g of PMDA and 0.9 g of SiDA were added, and the mixture was stirred and dissolved for 30 minutes. Then, 9.3 g of PMDA and 12.6 g of BPDA were added in batches, controlling the addition rate to keep the temperature below 70 °C. After the addition was complete, the reaction was continued at 60 °C with stirring for 120 minutes to obtain a polyamic acid (resin C-1) solution.

[0073] Example 1, Polyimide Composition 1: 90g of resin A-1, 10g of resin B-1 (provided in the form of a solution of resin B-1 in Synthesis Example 2, the weight of which is based on resin B-1), and 1.5g of triallyl isocyanurate (TAIC).

[0074] Resin A-1 was dissolved in NMP to prepare a solution with a solid content of 20 wt%. The solution of resin B-1 from Synthesis Example 2 was added and stirred to mix. Then, a curing agent was added and the mixture was stirred and mixed again. The total solid content of the composition was adjusted to 20 wt% with NMP to obtain the composition.

[0075] Example 2, Polyimide Composition 2: 85g of resin A-1, 15g of resin B-1 (provided in the form of a solution of resin B-1 in Synthesis Example 2, the weight of which is based on resin B-1), and 2.0g of triallyl isocyanurate (TAIC).

[0076] The composition was prepared according to the steps in Example 1.

[0077] Example 3, Polyimide Composition 3: 90g resin A-1, 10g resin B-2 (provided in the form of a solution of resin B-2 in Synthesis Example 3, the weight of which is based on resin B-2), and 1.5g triallyl isocyanurate (TAIC).

[0078] Resin A-1 was dissolved in NMP to prepare a solution with a solid content of 20 wt%. The solution of resin B-2 from Synthesis Example 3 was added and stirred to mix. Then, a curing agent was added and the mixture was stirred to continue mixing. The total solid content of the composition was adjusted to 20 wt% using NMP.

[0079] Example 4, Polyimide Composition 4: 90g of resin A-1, 10g of resin B-1 (provided in the form of a solution of resin B-1 in Synthesis Example 2, the weight of which is based on resin B-1), and 3.0g of 1,3,5-tris(2-hydroxyethyl)isocyanurate (THEIC).

[0080] The composition was prepared according to the steps in Example 1.

[0081] Example 5, Polyimide Composition 5: 80g of resin A-1, 20g of resin B-1 (provided in the form of a solution of resin B-1 in Synthesis Example 2, the weight of which is based on resin B-1), and 3.0g of triallyl isocyanurate (TAIC).

[0082] The composition was prepared according to the steps in Example 1.

[0083] Comparative Example 1, Polyimide Composition 6: 100g of resin A-1.

[0084] Comparative Example 2, Polyimide Composition 7: 90g of resin A-1 and 10g of resin C-1 (provided in the form of a solution of resin C-1 in Synthesis Example 4, the weight of which is based on resin C-1).

[0085] Resin A-1 was dissolved in NMP to prepare a solution with a solid content of 20 wt%. The solution of resin C-1 from Synthesis Example 4 was added and stirred to mix. Then, a curing agent was added and the mixture was stirred to continue mixing. The total solid content of the composition was adjusted to 20 wt% using NMP.

[0086] Comparative Example 3, Polyimide Composition 8: 90g of resin A-1, 10g of resin B-1 (provided in the form of a solution of resin B-1 in Synthesis Example 2, the weight of which is based on resin B-1), and 2.0g of dicumyl peroxide (DCP).

[0087] The composition was prepared according to the steps in Example 1.

[0088] Table 1. Components (g) and notes for Examples 1-5 and Comparative Examples 1-3

[0089] Preparation and performance testing of polyimide films The above-mentioned composition solutions were spin-coated onto a clean glass substrate or silicon wafer, pretreated on a hot plate at 100°C for 5 minutes, and then cured in a circulating hot air oven in a stepped manner: 150°C / 30 min + 200°C / 30 min + 250°C / 60 min (Examples 1-5, Comparative Examples 2-3), or 150°C / 30 min + 200°C / 30 min + 350°C / 60 min (Comparative Example 1, which requires high-temperature complete imidization due to the absence of low-temperature crosslinking components).

[0090] Curing was performed under a nitrogen atmosphere. After curing, the film was peeled off from the substrate, and the following performance tests were conducted. The test results are summarized in Tables 2 and 3: 1) Curing characteristics: The lowest crosslinking exothermic peak temperature was determined by differential scanning calorimetry (DSC) (for systems containing unsaturated bonds). The degree of imidization completion was assessed by thermogravimetric analysis (TGA) combined with Fourier transform infrared spectroscopy (FT-IR) (>95% was considered complete).

[0091] 2) Thermal properties: The average coefficient of thermal expansion (CTE) and glass transition temperature (Tg) within the range of 50-200℃ were determined using a thermomechanical analyzer (TMA).

[0092] 3) Mechanical properties: Tensile strength, elastic modulus and elongation at break were tested using a universal testing machine according to ASTM D882 standard.

[0093] 4) Adhesion: Apply the composition to a silicon wafer with copper foil or SiO2, cure it under the above conditions, and perform a cross-cut test (according to ASTM D3359) to evaluate the adhesion grade (0 is the worst, 5 is the best).

[0094] Table 2. Performance test results of polyimide films in Examples 1-5

[0095] Table 3. Performance test results of polyimide films in comparative examples 1-3

[0096] Results Analysis As shown in Table 2: 1) Low-temperature curing effect: All examples achieved high imidization (>98%) at 250°C, while Comparative Example 1 (pure rigid PI) required 350°C. This confirms the significant low-temperature curing advantage of the compositions of the present invention.

[0097] 2) Dimensional stability and heat resistance: The CTE (28-38 ppm / ℃) of all embodiments was significantly lower than that of Comparative Example 2 (no crosslinking, 40 ppm / ℃) and Comparative Example 1 (pure rigid resin, but the molecular chain arrangement may differ under high-temperature processing, 45 ppm / ℃), indicating that the synergistic effect of the rigid resin and the crosslinked network effectively reduced the CTE. Moreover, the Tg of all embodiments was higher than 280℃, maintaining excellent heat resistance.

[0098] 3) Balance of Mechanical Properties: All embodiments exhibited a good balance of mechanical properties. Compared to Comparative Example 1 (with high rigidity but brittleness, elongation of only 8%), all embodiments showed a significant increase in elongation (22-45%), while the strength decrease was not significant (165-185 MPa vs 210 MPa). Compared to Comparative Example 2 (with flexible chains but no crosslinking), all embodiments, due to the presence of crosslinking networks, generally exhibited higher tensile strength and modulus, resulting in superior mechanical properties.

[0099] 4) Adhesion: All embodiments achieved an adhesion rating of 4-5 on copper and SiO2 substrates, significantly better than the comparative examples. This is attributed to the polar groups in the resin and the dense, strong cross-linked network formed during curing.

[0100] 5) Influence of Curing Agent: Example 4 uses THEIC, which has a similar effect on promoting imidization as TAIC. However, because it does not contain allyl groups, the crosslinking density may be slightly lower than that of TAIC, resulting in a slightly lower elongation at break, but the CTE and modulus are still quite good. Comparative Example 3 uses the conventional peroxide DCP, which leads to a lower imidization rate (92%), and its overall performance (especially elongation and adhesion) is inferior to Examples 1, 3, and 4 with the same resin ratio.

[0101] In summary, the polyimide resin composition of the present invention achieves low-temperature curing below 280°C by designing rigid, flexible, crosslinkable and catalytic curing units at the molecular level, and successfully obtains a polyimide film with low CTE, high strength, high toughness and high adhesion, perfectly solving the contradiction between low-temperature curing and high performance in the prior art.

[0102] The specific embodiments of the present invention have been described in detail above, but they are merely examples, and the present invention is not limited to the specific embodiments described above. For those skilled in the art, any equivalent modifications and substitutions to the present invention are also within the scope of the present invention. Therefore, all equivalent transformations and modifications made without departing from the spirit and scope of the present invention should be covered within the scope of the present invention.

Claims

1. A polyimide composition, characterized in that, It includes polyimide resin 1 and polyimide precursor resin 2, wherein resin 1 has repeating units as shown in formula (I): （I） ； R1, R2, R3, and R4 are each independently H or monovalent organic groups; R5 and R6 are each independently single bonds and divalent organic groups, or R5 and R6 independently form fused ring structures with the benzene rings at their two ends; and at least one of R1, R2, R3, and R4 is a polar group, or at least one of R5 and R6 has a polar group. The polyimide precursor resin 2 has repeating units as shown in structural formula (II), and one or both ends of the molecular chain are capped with groups containing carbon-carbon unsaturated bonds: (II); R7 and R8 are each independently a divalent organic group; Where m and n are positive numbers.

2. The composition according to claim 1, characterized in that, R5 and R6 can be independently selected from one or more combinations of single bonds, -O-, -S-, -CO-, -COO-, -CONH-, -NH-, -SO2-, -C=N-, alkylene groups R, and alkylene groups R substituted with polar groups; or, R5 and R6 can independently serve as common bonds of the benzene ring, connecting the two benzene rings at both ends to form a fused ring; or R5 and R6 can independently be cyclic structures, and connect with the two benzene rings at both ends to form a fused ring or a fused ring; and / or R8 is a C4-C18 chain structure; R7 is a tetravalent organic group containing a benzene ring; and / or R1, R2, R3, and R4 are each independently selected from one or more combinations of: H, polar groups, and hydrocarbon groups substituted with polar groups; and / or The "group containing a carbon-carbon unsaturated bond" is one or more of the following: olefinic group, alkyneic group, substituent-substituted olefinic group, and substituent-substituted alkyneic group.

3. The composition according to claim 2, characterized in that, At least one of R1, R2, R3, and R4 is a polar group.

4. The composition according to claim 2, characterized in that, The groups containing carbon-carbon unsaturated bonds are CH2=CH-, CH2=CH-CH2-, CH2=CH-CH-CH-, CH2=C(CH3)-, CH(CH3)=CH-, CH2=CHC(CH3)2-O-, CH(CH3)=C(CH3)-, CH3-CH=CH-CH2-, CH≡C-, CH3-C≡C-, CH(CH3)=CH-CO-, CH(CH3)=CH-COO-CH2CH2 -NH-, CH(CH3)=CH-COO-, CH(CH3)=CH-O-, CH(CH3)=CH-CH2-NH-, CH2=CH-CO-, CH2=CH-COO-, CH2=CH-C H2-NH-, CH2=CH-COO-CH2CH2-NH-, CH2=CH-O-, CH2=CH-C(=CH2)-, CH2=CH-CH2-O-, CH3-CH=CH-CH2-O-, CH3CH2CH2CH2CH2CH(CH=CH2)-O-, CH2(OH)CH=CHCH2-O-, CH3CH=C(CH3)-COO-, HOOC-CH2C(=CH2)-COO -, HOOC-CH=CH-COO-, CH2=CH-CH2-O-CH2CH2-O-, CH2=C(CH3)-CH2-O-CH2CH2-O-, CH3CH2CH2-OOC-CH=C H-COO-, CH2=CH-OOC-CH=CH-COO-, CH2=CH-OOC-CH2CH2-COO-, CH2=C(CH3)-CH2-O-CH2CH2-, CH2=CH-C H2-O-CH2CH2-, C(CH3)2=CHCH2CH2C(CH3)=CHCH2-O-, CH2=CH-CH2OCH2CH2-O-, HO-CH2-CH=CH-CH2-O-, , , , , , , , , , , , , , , , , , One or more of them; wherein, R 31 It is a combination of one or more of H, a monovalent polar group, and a monovalent nonpolar group.

5. The composition according to claim 1, characterized in that, The polyimide composition further includes a curing agent, which is a peroxide initiator, a persulfide initiator, an azo initiator, a redox initiator, or a coordination polymerization initiator. , One or more combinations of R; where R 32 R 33 R 34 R 36 R 37 R 38 The substituents are, independently, H, halogen atoms, C1-C10 chain monovalent substituents, C3-C15 cyclic monovalent non-aromatic substituents, and C5-C20 monovalent aromatic substituents; R 35 It is a combination of one or more of H, a monovalent polar group, and a monovalent nonpolar group.

6. The composition according to claim 5, characterized in that, The curing agent contains non-conjugated carbon-carbon unsaturated bonds.

7. The composition according to claim 5, characterized in that, The curing agent is selected from benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butyl benzoate, tert-butyl valerate peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxide, dicyclohexyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, azobisisopropylimidazoline, benzoyl peroxide / sucrose, tert-butyl hydroperoxide / sodium metabisulfite, tert-butyl hydroperoxide / sodium metabisulfite, benzoyl peroxide / N,N-dimethylaniline, ammonium persulfate / sodium bisulfite, potassium persulfate / sodium bisulfite, hydrogen peroxide / tartaric acid, hydrogen peroxide / sodium bisulfite. White block, ammonium persulfate / ferrous sulfate, hydrogen peroxide / ferrous sulfate, benzoyl peroxide / N,N-diethylaniline, benzoyl peroxide / ferrous pyrophosphate, potassium persulfate / silver nitrate, persulfate / thiol, cumene hydrogen peroxide / ferrous chloride, potassium persulfate / ferrous chloride, hydrogen peroxide / ferrous chloride, cumene hydrogen peroxide / tetraethyleneimine, Ziegler-Natta catalyst, metallocene catalyst, non-metallocene catalyst, dibromoisocyanuric acid, trichloroisocyanuric acid, sodium dichloroisocyanurate, triglycidyl isocyanurate, tri(2-hydroxyethyl)isocyanurate, di(carboxyethyl)isocyanurate, tri(methoxysilanepropyl)isocyanurate, tri(2-acryloyloxyethyl)isocyanurate, tri(2,3-dibromoisocyanurate) Tris(methylallyl) isocyanurate, triallyl isocyanurate, tris(methylallyl) isocyanurate, diallyl isocyanurate, tripropyl isocyanurate, tris(1'-chloro-2'-hydroxy-propyl) isocyanurate, bis(2-carboxyethyl) isocyanurate, tris(2,3-epoxypropyl) isocyanurate, tris[(3,5-di-tert-butyl-4-hydroxy)phenyl] isocyanurate, imidazole, N-methylimidazolium, N-ethylimidazolium, 2-methylimidazolium, 4-methylimidazolium, 5-methylimidazolium, 2-ethylimidazolium, 4-ethylimidazolium, 5-ethylimidazolium, 1,2-dimethylimidazolium, 2,4-dimethylimidazolium, 4,5-dimethylimidazolium, 2,4,5-trimethylimidazolium, 2-ethylimidazolium, 4-ethylimidazolium, 5-ethylimidazolium Imidazole, 2-phenylimidazole, 4-phenylimidazole, 5-phenylimidazole, 2-acetylimidazole, 4-carboxyimidazole, 1-vinylimidazole, 2,4-diphenylimidazole, 4-methyl-diphenylimidazole, 2-methyl-4-ethylimidazole, 4-methyl-2-ethylimidazole, 2-propyl-4-methylimidazole, 2-aminoethylimidazole, 4-aminoethylimidazole, 5-aminoethylimidazole, 2-hydroxyethylimidazole, 4-hydroxyethylimidazole, 5-hydroxyethylimidazole, L-histidine, 4-methyl-2-aminoethylimidazole, 2-methyl-4-aminoethylimidazole, 1-methyl-L-histidine, 2-chloromethyl-4-methylimidazole, 2-aldehyde-4-methylimidazole, 4-methyl-2-ethylimidazole, 2-isobutyl-4-isopropylimidazole, 2,4-Diisopropylimidazolium, 4,5-diacenic imidazolium, 2,4-diisobutylimidazolium, 2,2-bis(4,5-dimethylimidazolium), 2-methyl-4-carboxyimidazolium, 1-methyl-4-Cl-imidazolium, 4-amino-5-carboxyimidazolium, 1-methyl-4-nitro-2-hydroxymethylimidazolium, (4-amino-5-imidazolyl)formamide, 1,2-dimethyl-4-nitroimidazolium, 2-methyl-4-nitroimidazolium, (2-methyl-5-nitroimidazol-1-yl) The following are included in the list of one or more: ethanol, (2-methyl-5-nitroimidazole-1-yl)propanol, 3-(4-imidazolyl)acrylic acid, N,N'-carbonyldiimidazole, diethyl imidazolium-4,5-dicarboxylate, 1-(2-hydroxyethyl)imidazole, 2-(2-chlorophenyl)-4,5-diphenylimidazole, 2-(2-methoxyphenyl)-4,5-diphenylimidazole, 4-(imidazol-1-yl)aniline, 1-(4-nitrophenyl)imidazole, and 1-p-methylbenzenesulfonylimidazole.

8. The composition according to claim 1, characterized in that, The weight average molecular weight of resin 1 is 8000-60000; and / or The average molecular weight of the resin is 50,000-200,000.

9. A method for preparing the composition according to any one of claims 1-8, characterized in that the step... include: Provide resin 1 and resin 2; First, resin 1 is dissolved in a solvent to form a first mixture, and then resin 2 is added to the first mixture; or, resin 1 and resin 2 are dissolved independently in their respective solvents and then mixed.

10. A method for preparing a thin film, characterized in that, The polyimide composition of claim 1 is cured into the film.

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