A resin precursor composition and a polyimide resin film containing the same and application thereof

Abstract

The present invention discloses a resin precursor composition and a polyimide resin film containing the same and application thereof, belonging to the field of semiconductor technology. The present invention specifically discloses a polyimide resin film with photosensitive properties, which is formed by combining polyamide, polyimide and a variety of compounds and then curing at high temperature. The resin film is suitable for interlayer insulating films, surface protective films of semiconductor elements, and insulating layers and planarizing layers of organic electroluminescent display elements, etc. It is a polyimide resin film with excellent heat resistance and mechanical properties. At the same time, the resin film has high adhesion to a metal substrate and small thermal shrinkage.

Description

Technical Field

[0001] The invention relates to the field of semiconductor technology, in particular to a resin precursor composition and a polyimide resin film containing the same. Background Art

[0002] In recent years, with the miniaturization, high integration and high functionality of electronic devices, the performance requirements for materials have become increasingly higher. Unlike traditional photoresists, photosensitive polyimide resin films will remain permanently in electronic components after heating, so the heat resistance, mechanical properties, dielectric properties and reliability of the resin film are particularly high. At the same time, according to different needs, the resin film is also required to have good flexibility, high adhesion to components and low thermal shrinkage.

[0003] In addition, as the industry's requirements for materials become increasingly higher, high-performance polyimide and polybenzoxazole resins obtained by low-temperature (below 250°C) curing are being studied and valued. However, in general, it is difficult to obtain fully cyclized polyimide and polybenzoxazole resins by low-temperature curing, resulting in poor heat resistance and mechanical properties of the film, and low adhesion to the component substrate.

[0004] The existing patent reports a positive photosensitive resin composition, which introduces aliphatic chains into the main chain structure of polyimide, so that the imidization rate in the polyimide resin structure reaches more than 80%, and reduces the curing temperature by increasing the cyclization ratio. However, the same problems occur, such as poor polymer solubility, difficulty in coating, inability to form patterns after development, and insufficient processability, which also leads to large internal stress during later curing. Summary of the invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a resin precursor composition.

[0006] It should be noted that polyimide, polyamide and polybenzoxazole resins are widely used in electronic appliances due to their excellent heat resistance, mechanical properties and electrical insulation, such as interlayer insulation films and surface protection films of semiconductor components, and insulation layers and planarization layers of organic electroluminescent display components. With the continuous development of semiconductor components, the performance requirements for microelectronic components are constantly increasing. In order to simplify the process procedures, photosensitive polyimide, polyamide and polybenzoxazole resin materials are becoming more and more popular.

[0007] Positive photosensitive polyimide resin has its own unique advantages over negative resin. For example, its imaging process uses alkaline aqueous solution to dissolve the exposed area for development, avoiding the erosion of the non-exposed area by organic developer, high graphic resolution, and small film shrinkage. In addition, alkaline aqueous developer has good environmental compatibility and is more environmentally friendly. These advantages make it highly used in mechanical production.

[0008] The present invention starts from optimizing the structure of a polymer and provides a polymer, wherein the structure of the polymer includes polyamic acid, polyamide ester, polyimide, polybenzoxazole, polyamide and polyhydroxyamide, etc. A positive photosensitive polyimide resin precursor composition is formed by combining the polymer with a variety of compounds, and then cured at a low temperature (below 250°C) to obtain a polyimide resin film with excellent heat resistance and mechanical properties. At the same time, the resin film has high adhesion to a metal substrate and small thermal shrinkage.

[0009] To achieve the above objectives, the embodiments of the present invention provide the following technical solutions:

[0010] A resin precursor composition, comprising component A, component B1 and component B2; the total amount of component B1 and component B2 is 10-40wt% of component A, and the mass ratio of component B1 to component B2 is 40:1-10:1;

[0011] Wherein, component A is a polymer comprising structures represented by formula (1) and formula (2);

[0012] Formula (1) is

[0013] Formula (2) is

[0014] Wherein, X is selected from a tetracarboxylic acid residue containing 1 to 10 aromatic rings and containing one or more of O, S, N or F heteroatoms; Y1 is selected from a diamine residue containing 1 to 10 aromatic rings and containing one or more of O, S, N or F heteroatoms; R1, R2, R3 and R4 are independently selected from a hydrogen atom or an organic group having 1 to 20 carbon atoms; p is represented by an integer of 1 to 10, m1 and m2 are integers of 3 to 10000, n1 and n2 are integers of 1 to 2000, and the ratio of m1+m2 to n1+n2 is between 3 and 10;

[0015] In formula (1) and formula (2), Y2 is selected from amide fatty chain diamines having 5 to 15 carbon atoms, and its structure is shown in formula (3). The content of Y2 is selected from 10% to 30% of the total molar amount of Y1 and Y2;

[0016] Formula (3) is

[0017] Wherein, R5 and R7 are independently selected from 1 to 6 methylene groups, R6 is independently selected from a fatty chain group having 0 to 8 carbon atoms and may contain one or more heteroatoms of O, N or S, s independently represents an integer of 0 to 4, and t independently represents an integer of 0 to 3;

[0018] Component B1 is an aromatic ester thermal crosslinking agent containing phenolic hydroxyl groups, and its structure is shown in formula (4);

[0019] Formula (4) is

[0020] wherein R8 is independently selected from an organic group containing 2 to 30 carbon atoms, R9 is independently selected from an organic group containing 1 to 10 carbon atoms, u is independently selected from an integer of 1 to 4, v is independently selected from an integer of 1 to 16, and u+v>2;

[0021] Component B2 is an unsaturated bond type thermal crosslinking agent containing alkoxy and vinyl groups, and its structure is shown in formula (5);

[0022] Formula (5) is

[0023] Among them, R 10 Independently selected from organic groups containing alkoxy groups and having 2 to 30 carbon atoms, which may contain N or S heteroatoms, and w is independently selected from integers of 1 to 10. Preferably, the component A is mainly copolymerized from polyamic acid, polyamide ester and polyimide, and also includes a resin composition of polybenzoxazole, polyamide, polyhydroxyamide and other copolymers.

[0024] And, X is selected from a tetracarboxylic acid residue containing 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 aromatic rings; in terms of heat resistance, X is preferably selected from an aromatic ring group having a rigid structure or a benzamide structure in which the hydroxyl group and the amino group are located at the ortho position and can be cyclized to benzoxazole after heat treatment; and in terms of interaction with metal elements and intermolecular crosslinking, X preferably contains one or more of O, S, N or F heteroatoms.

[0025] Furthermore, X is selected from one or more of the compound structures represented by the following formulas X-1 to X-14:

[0026]

[0027]

[0028] In formula X-1 to formula X-14, the left and right ends Indicates the connection location.

[0029] In some preferred embodiments, X can be selected from the following structures:

[0030]

[0031] Furthermore, Y1 can be selected from diamine residues with 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 aromatic rings; considering heat resistance, Y1 is preferably selected from aromatic ring groups with a rigid structure or a benzamide structure in which the hydroxyl group and the amino group are located in the ortho position and can be cyclized to benzoxazole after heat treatment; considering heat resistance and good flexibility, Y1 is preferably selected from a polyamide structure; considering the interaction with metal elements and intermolecular crosslinking, Y1 preferably contains one or more of O, S, N or F heteroatoms.

[0032] Furthermore, in formula (1) and formula (2), in order to increase the solubility and photosensitivity of the alkaline aqueous solution, Y1-(OH) p must contain a hydroxyl group, and the value of p can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;

[0033] And, Y1-(OH) p It can be selected from one or more compounds represented by formula Y1-1 to formula Y1-12:

[0034]

[0035] In the above formula Y1-1 to formula Y1-12, the left and right ends Indicates the connection location.

[0036] In some preferred embodiments, Y1-(OH) p You can choose from:

[0037]

[0038] And, Y2 is an aliphatic chain diamine. From the perspective of closing the ring of part of the polyamic acid, polyamide ester or polyamide in which the hydroxyl group and the amino group are located in the ortho position in the polymer of component A when heated to reduce the curing temperature and increase the flexibility of the polymer, Y2 is preferably an aliphatic chain with 5 or more C atoms; from the perspective of controlling the imide and oxazole ring structures in the polymer, increasing heat resistance, processability, adhesion to metal components and intermolecular crosslinking, Y2 is preferably an aliphatic chain structure with 20 or less C atoms and containing one or more of O, N or F atoms;

[0039] Specifically, the content of Y2 is selected from 10% to 30% by mole of the total mole of Y1 and Y2.

[0040] Furthermore, Y2 can be selected from one or more compounds represented by formula Y2-1 to formula Y2-16:

[0041]

[0042]

[0043] In some preferred embodiments, Y2 can be selected from:

[0044]

[0045] Preferably, the structure of the above-mentioned component A preferably contains a group with F atoms. It should be noted that F atoms have strong electronegativity and can increase the hydrophobicity of the resin film. In addition, F atoms have large steric hindrance and can increase the light transmittance of the polyimide resin film and increase the photosensitivity of the resin film. Preferably, the F atom content accounts for 8% to 16% by weight of the polymer. Too high a content will lead to reduced heat resistance and solubility in alkaline aqueous solutions of the polymer.

[0046] In the present application, R1, R2, R3 and R4 can be independently selected from a hydrogen atom or an organic group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.

[0047] When R1, R2, R3 or R4 is hydrogen, the corresponding functional group is a carboxyl group; when R1, R2, R3 or R4 is an alkyl group, the corresponding functional group is an ester group, wherein the alkyl group is preferably a methyl group, an ethyl group or an isopropyl group, that is, R8, R9, R 11 or R 12 Preferably, they are independently methyl, ethyl or isopropyl. In the present application, the ratio of carboxyl groups to be esterified is controlled by controlling the content of the esterifying agent. In addition, different contents of the esterifying agent lead to different acidity and alkalinity of the system, and the imidization cyclization rates of the polyamic acid and polyamide ester in the component A polymer are also different.

[0048] In order to achieve the best ring formation ratio, preferably, the molar mass of the esterifying agent is selected from 2 to 4 times the molar amount of X. The corresponding esterification rate, i.e., the total molar amount of ester groups / the total molar amount of (R1+R2+R3+R4), is 60% to 90%, for example, 60%, 65%, 70%, 75%, 80%, 85% or 90%, etc., or any other value within the range of 60% to 90%.

[0049] For reference, the esterifying agent for esterifying the carboxyl group into the ester group in the present application is not particularly limited and may be selected from:

[0050] From the perspective of esterification effect, an esterifying agent with a smaller molecular weight is preferred. Therefore, the esterifying agent preferably contains a chain alkyl substituent, such as the following structure:

[0051]

[0052] Above, by adjusting the content of the copolymerized fatty chain Y2 and the esterifying agent, the polyamic acid and polyamide ester in the component A polymer are partially cyclized into polyimide rings, and the polybenzamide of the ortho-hydroxyl and amino groups is partially cyclized into polybenzoxazole rings after heating, and the ratio of the cyclization of the two is represented by the imidization rate and the polyhydroxyamide ring closure rate, respectively. In this application, in order to reduce the curing temperature without affecting the coating and processability, the imidization rate is preferably 5% to 50%, more preferably 10% to 40%. In order to have high heat resistance and flexibility, and a small heat shrinkage rate, the polyhydroxyamide ring closure rate is preferably 1% to 20%, more preferably 3% to 15%.

[0053] In the present application, a small amount of aliphatic chain diamine having a siloxane structure can be copolymerized to improve the adhesion between the resin film and the silicon substrate without reducing the heat resistance. The molar mass of the aliphatic chain siloxane diamine relative to the molar mass of X is preferably 2% to 10% by mole.

[0054] In some optional embodiments, the fatty chain siloxane diamine can be selected from one or more of the following:

[0055]

[0056] Furthermore, in order to control the molecular weight and processability, a capping group is added to component A, that is, in the polymer formed by the random arrangement of multiple repeating units, the ends of the structural units at both ends are capped by the capping group; through the above-mentioned capping treatment, the molecular weight of the polymer can be controlled, the stability of the polymer molecular chain can be improved, and the storage safety of the photosensitive polyimide resin precursor can be enhanced.

[0057] For reference, in the present application, one or more of monoamine compounds, acid anhydrides and monocarboxylic acid compounds can be used as end-capping agents for end-capping, preferably monoamine compounds.

[0058] In some optional embodiments, the capping group formed by using a monoamine compound as a capping agent can be selected from the following structures:

[0059]

[0060] For reference, the content of the above-mentioned end-capping agent is not particularly limited. In some embodiments, it can be 0.5-20wt% of the content of component A, such as 0.5wt%, 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt% or 20wt%, etc., or any other value within the range of 0.5-20wt%. Preferably, it is 0.8-15wt%, and more preferably 1-10wt%.

[0061] In the present application, the solvent used to synthesize component A is not particularly limited, as long as it can dissolve the raw material diamine and acid dianhydride, and is preferably a high-boiling point polar aprotic organic solvent.

[0062] For reference, the above-mentioned high boiling point polar aprotic organic solvent may illustratively include amide solvents, cyclic esters, carbonates, acetophenone, tetrahydrofuran, propylene glycol methyl ether acetate or dimethyl sulfoxide.

[0063] Among them, the amide solvent may include at least one of N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylformamide, N,N-dimethylacetamide and N,N-dimethylisobutyramide. The cyclic ester solvent may include at least one of γ-butyrolactone, γ-valerolactone, γ-caprolactone, δ-valerolactone and α-methyl-γ-butyrolactone. The carbonate solvent may include at least one of ethylene carbonate and propylene carbonate.

[0064] The synthesis of component A in the present application can be carried out by the following method, but is not limited to this method.

[0065] First, the raw material diamine and carboxylic acid dianhydride are respectively put into a solvent (a high boiling point polar aprotic organic solvent). According to the easy hydrolysis side reaction of the anhydride, the diamine can be added to the solvent first, and then the anhydride is added. Then, the reaction is stirred at 0 to 80 ° C for 1 to 8 hours. According to the polymerization temperature in this application, the polymerization degree of the reaction is controlled and the reasonable cyclization rate is achieved in the polymer. The preferred polymerization temperature is 20 to 70 ° C. Then, the end-capping agent is added, the reaction is stirred for 1 to 3 hours, and then the esterification agent is added, and the reaction is stirred for 10 minutes to 5 hours to obtain a resin containing polyamic acid, polyamide ester, polyimide, polyhydroxy amino acid, polyhydroxyamine ester, polybenzoxazole and other copolymers. Finally, the obtained solution is put into methanol or water to precipitate solids. The unreacted monomers and oligomer components are removed through this process. Finally, the target polymer, i.e., component A, is obtained by drying at 50 to 100 ° C, preferably 60 to 80 ° C.

[0066] In the present application, considering the dissolution uniformity, the weight average molecular weight of the polymer of component A is preferably 5,000 to 200,000, more preferably 6,000 to 150,000, and even more preferably 8,000 to 100,000.

[0067] Preferably, B1 is selected from the structures shown in formula B1-1 to B1-8:

[0068]

[0069] In some preferred embodiments, B1 can be selected from:

[0070]

[0071] Preferably, B2 is selected from the structures shown in formula B2-1 to formula B2-8:

[0072]

[0073] In some preferred embodiments, B2 can be selected from:

[0074]

[0075] For reference, the total amount of the above-mentioned component B1 and component B2 is 10-40wt% of component A, such as 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt% or 40wt%, etc., and can also be any other value within the range of 10-40wt%. In some preferred embodiments, the total amount of component B1 and component B2 is 12-40wt% of component A, and more preferably 15-30wt%.

[0076] Preferably, the mass ratio of component B1 to component B2 can be 40:1 to 10:1, such as 40:1, 35:1, 30:1, 25:1, 20:1, 15:1 or 10:1, or any other value within the range of 40:1 to 10:1. Preferably, the mass ratio of component B1 to component B2 is 35:1 to 5:1, more preferably 30:1 to 10:1.

[0077] As mentioned above, the polyimide resin precursor composition of the present application normally adds an aromatic ester thermal crosslinking agent containing a phenolic hydroxyl group, and the addition of this crosslinking agent can not only crosslink itself, but also crosslink with the polymer molecular chain of component A. Secondly, an unsaturated bond type thermal crosslinking agent containing an alkoxy group and a vinyl group is added, which can make up for the insufficient crosslinking degree of the aromatic ester thermal crosslinking agent with a single phenolic hydroxyl group, and inhibit the thermal shrinkage caused by the cyclodehydration of the polymer caused by curing.

[0078] In addition, the resin precursor composition further comprises component C, component D, component E, component F and component G; the amount of component C is 10-50wt% of component A, the amount of component D is 1-30wt% of component A, the amount of component E is 1-50wt% of component A, the amount of component F is 0.1-10wt% of component A, and the amount of component G is 100-2000wt% of component A; wherein,

[0079] Component C is a photosensitizer. For reference, as a positive photosensitive resin, component C is preferably a photoacid generator, which illustratively but not limitatively includes at least one of quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts and iodonium salts; more preferably, the photoacid generator is a photoacid generator containing a quinonediazide compound; further preferably, it is an ester compound formed by bonding a polyhydroxy compound with the sulfonic acid of diazidequinone, wherein the long-term reliability of the organic light-emitting device is more favorable.

[0080] Wherein, component C can be selected from one or more of the following structures:

[0081]

[0082]

[0083] Wherein, Q is independently selected from or H, the curved line segment indicates the connection location;

[0084] Component D is a low molecular weight phenolic hydroxyl compound as a reference. The amount of component C can be 10 to 50 wt% of component A, such as 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%, etc., or it can be any other value within the range of 10 to 50 wt%, preferably 20 to 40 wt%. In this way, a good contrast between the exposure area and the non-exposure area can be obtained, thereby achieving high sensitivity.

[0085] Furthermore, in order to achieve high sensitivity in the present application, component D can be added to the resin precursor composition without affecting the heat resistance of the resin film and the thermal shrinkage of the film. Component D is a low molecular weight phenolic hydroxyl compound. By adding component D, the alkali solubility of the polymer can be better improved, thereby shortening the development time and improving the sensitivity and resolution;

[0086] In some optional embodiments, component D can be selected from one or more of the following structures:

[0087]

[0088]

[0089] Among them, from the viewpoint of heat resistance of phenolic hydroxy compounds, bisphenol compounds are preferred. The amount of component D can be 1 to 30 wt% of component A, such as 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%, and based on the requirement for film thermal shrinkage, more preferably 1 to 20 wt%.

[0090] Furthermore, the resin precursor composition of the present application may also contain other additives, for example, it may also include component E, and component E is a surfactant. By adding a surfactant, the wettability and adhesion to the substrate can be improved, and the coating property can be increased.

[0091] For reference, the surfactant may illustratively but not limitatively include at least one of ethanol, isopropyl alcohol, acetone, cyclohexanone, ethyl lactate, and propylene glycol methyl ether acetate.

[0092] For reference, the amount of component E can be 1 to 50 wt% of component A, such as 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%, etc., or it can be any other value within the range of 1 to 50 wt%, preferably 5 to 30 wt%.

[0093] Furthermore, the resin precursor composition also contains component F, which is an adhesion improver. The addition of component F can improve the adhesion with the substrate.

[0094] For reference, component F can be selected from a silane coupling agent, which illustratively but not limitatively can include at least one of trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxyepoxysilane, trimethoxyaminopropylsilane, trimethoxy-3-epoxypropylpropoxysilane, trimethoxy-3-aminopropylsilane, and triethoxy-3-aminopropylsilane.

[0095] For reference, the amount of component F can be 0.1 to 10 wt% of component A, such as 0.1 wt%, 0.5 wt%, 1 wt%, 5 wt% or 10 wt%, etc., or it can be any other value within the range of 0.1 to 10 wt%. In order not to affect the preservation of the resin slurry, the heat resistance and mechanical properties of the resin film, it is preferably 0.1 to 5 wt%.

[0096] In addition, the resin precursor composition may further include component G, which is a solvent and can improve the coating properties of the slurry.

[0097] In the present application, component G is preferably a high boiling point polar solvent, which can exemplarily but not limitatively include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tetrahydrofuran, dioxane, methyl ethyl ketone, acetone, diisobutyl ketone, cyclohexanone, At least one of 2-heptanone, 3-heptanone, diacetone alcohol, ethylene glycol methyl ether ethyl acetate, ethylene glycol ethyl ether ethyl acetate, diethylene glycol methyl ether ethyl acetate, diethylene glycol ethyl ether ethyl acetate, propylene glycol methyl ether ethyl acetate, propylene glycol ethyl ether ethyl acetate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, ethyl butyrate, n-propyl butyrate, n-butyl butyrate, methyl acetoacetate, ethyl acetoacetate or xylene.

[0098] For reference, the amount of component G is not particularly limited, and the composition can be dissolved to form a slurry. In some embodiments, the amount of component G can be 100-2000wt% of component A, such as 100wt%, 200wt%, 500wt%, 800wt%, 1000wt%, 1500wt% or 2000wt%, etc., or any other value within the range of 100-2000wt%. Preferably, the amount of component G is 100-1800wt% of component A, more preferably 150-1500wt%.

[0099] Accordingly, the present application also provides a method for preparing the above-mentioned resin precursor composition, comprising the following steps:

[0100] For reference, component A may be mixed with component G first, then mixed with component B1, component B, component C and component D, and finally mixed with component E and other additives.

[0101] In the present application, the resin composition slurry is prepared as follows: at room temperature, the obtained target polymer (component A) is first added to the solvent (component G) and stirred until completely dissolved, and then the thermal crosslinking agent (component B1) and (component B2), the photosensitizer (component C) and the phenolic hydroxyl compound (component D) are added to the solution and stirred until completely dissolved, and then the surfactant (component E) and the fit improver (component F) are added to the solution and stirred until uniform; according to the needs of other performance indicators, some other additives can also be added to finally obtain a slurry, that is, a resin composition slurry (Varnish, abbreviated as V in the embodiment).

[0102] In view of the stability of the slurry, the solid content of the resin precursor composition is preferably 5 to 50 wt%, more preferably 6 to 40%, and further preferably 7 to 30%. In view of the coating performance, the viscosity of the resin precursor composition is preferably 0.1 to 10000 cp, more preferably 0.5 to 8000 cp, and further preferably 1 to 6000 cp.

[0103] In addition, the present application also provides a polyimide resin film, the raw materials for preparing the polyimide resin film contain the above-mentioned resin precursor composition slurry.

[0104] The polyimide resin film has good heat resistance, mechanical properties and photosensitivity, and the cured resin film has good adhesion to the metal substrate and a small thermal shrinkage rate.

[0105] For example, please refer to:

[0106] Preferably, the thermal shrinkage rate of the polyimide resin film provided in the present application is below 25%, and has low thermal shrinkage; the thermal decomposition temperature T 1％ Above 280℃, it exhibits excellent heat resistance; Young's modulus is in the range of 2.5-3.4GPa, elongation at break is between 15% and 30%, showing excellent flexibility; residual film rate is in the range of 80%-90%, and sensitivity value is 400mJ / cm 2 The resin film has good adhesion to metal.

[0107] Accordingly, the present application provides a method for preparing the above-mentioned polyimide resin film, comprising the following steps: exposing and developing a pre-baked film made from a slurry of a resin precursor composition, and then performing a curing treatment.

[0108] The pre-baked film is obtained by coating a slurry of the resin precursor composition on a substrate and pre-baking it.

[0109] For reference, the substrate may illustratively but not limitatively include silicon wafer, ceramic, glass, quartz or ITO, etc.

[0110] The coating methods include slit coating, spin coating, dip coating, spray coating or printing.

[0111] The pre-drying temperature can be 50-150°C, such as 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, etc., or any other value within the range of 50-150°C, preferably 80-150°C. The pre-drying time can be 1 min-1h, such as 1 min, 2 min, 5 min, 10 min, 20 min, 30 min, 40 min, 50 min or 1h, etc., or any other value within the range of 1 min-1h. Pre-drying can be carried out by a heating plate, an oven or an infrared method.

[0112] The thickness of the pre-baked film varies depending on the solid content and viscosity of the resin composition. In some embodiments, the thickness of the pre-baked film can be 0.1 to 12 μm, such as 0.1 μm, 0.5 μm, 1 μm, 2 μm, 5 μm, 8 μm, 10 μm or 12 μm, or any other value within the range of 0.1 to 12 μm, preferably 0.3 to 10 μm.

[0113] The present application does not specifically limit the exposure and development method, and can be carried out in accordance with the exposure and development method of conventional photosensitive resin films in the art. The photosensitive resin slurry provided in the present application is a positive photosensitive material, and light rays are exposed to it through a mask with a specific pattern, and the exposed part is then removed by a developer, thus obtaining a resin pre-baked film with a desired pattern.

[0114] For reference, the light rays used for exposure may include ultraviolet rays, visible light, electron beams, or X-rays, and preferably, i-line (365 nm), h-line (405 nm), or g-line (436 nm) of a mercury lamp is used.

[0115] The developer used for exposure is an alkaline water-based solution, wherein the alkaline substance may include at least one of tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. The advantage of the above developer is that it is environmentally friendly and suitable for industrial applications.

[0116] For reference, the temperature of the heat treatment can be 100-350°C, such as 100°C, 150°C, 200°C, 250°C, 300°C or 350°C, etc., or any other value within the range of 100-350°C. In the present application, an amide-containing fatty chain diamine is added. In some preferred embodiments, the temperature of the heat treatment is 120-300°C, more preferably 200-250°C. At 200-250°C, the gas discharged from the resin film after the heat treatment can be reduced, and the light transmittance and toughness of the resin film can be improved. The heat treatment time is not less than 30min, such as 30min, 40min, 50min, 60min, 100min or 150min, etc. The heating rate of the heat treatment can be 2 to 10°C / min, such as 2°C / min, 3°C / min, 4°C / min, 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min or 10°C / min, or any other value within the range of 2 to 10°C / min. The heat treatment curing method can use a heating plate, an oven or infrared rays, or a combination of multiple methods.

[0117] In some specific embodiments, the temperature may be raised to 210° C. at a rate of 2.5° C. / min and the heat treatment may be performed for 100 minutes.

[0118] In addition, the present application also provides the use of the above-mentioned polyimide resin film in a surface protection film (including a passivation film) of a semiconductor or an interlayer insulating film on a semiconductor element circuit.

[0119] Preferably, the polyimide resin film can be used to prepare an insulating layer or a planarization layer in an organic electroluminescent display device.

[0120] Compared with the prior art, the beneficial effects of the technical solution disclosed in the present invention are:

[0121] 1) The introduction of polyamide and fatty chain structure in the component (A) polymer of the present application can also increase the flexibility of the resin film, increase the elongation, and reduce the internal stress during the heat treatment process.

[0122] 2) The present invention adds an esterifying agent to the polymer to control the acidity and alkalinity of the polymerization process, appropriately increase the imidization rate, reduce the curing temperature of the resin composition, and improve the adhesion between the formed cured film and the metal substrate.

[0123] 3) The present invention controls the imidization rate by introducing the length and proportion of the fatty chain and adjusting the acidity and alkalinity during the polymer synthesis process, so that the reaction solution has a suitable viscosity, good coating and processability.

[0124] 4) Compared with long alkyl chains and long alkoxy chains, the present invention introduces amide fatty chains of heteroatoms such as O, N or S with lone pairs of electrons, which are easier to form coordination bonds with metals and improve the adhesion with metal substrates.

[0125] 5) Although the introduction of aliphatic chains into the polymer can increase the ratio of polyhydroxyamides with ortho-hydroxyl groups and amino groups to polybenzoxazoles during heat treatment, and thus improve heat resistance, the higher the cyclization ratio, the higher the dehydration rate. In this application, a crosslinking agent containing alkoxy and vinyl unsaturated bonds is added to increase the degree of crosslinking, thereby suppressing thermal shrinkage caused by cyclization dehydration. DETAILED DESCRIPTION

[0126] The technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0127] The evaluation methods of the embodiments and comparative examples are as follows:

[0128] 1. Film thickness test:

[0129] The thickness of the photosensitive polyimide resin film and the prebaked film was measured using a film thickness meter (field emission scanning electron microscope EX-30).

[0130] 2. Determination of polymer esterification rate:

[0131] 500mL of the polymer solution obtained by polymerization was dropped into 5L of pure water, stirred continuously, and a white solid was precipitated. The solid polymer was obtained by vacuum filtration and dried in a vacuum drying oven (Yamato DKN612, Japan) at 80°C for 48h. The dried polymer was dissolved in dimethyl sulfoxide (DMSO) and tested by a nuclear magnetic spectrometer (Bruker AVANCE) to determine the chemical shift of H on the ester group and carboxyl group in the nuclear magnetic spectrum, calculate the corresponding peak area, and calculate the proportion of ester groups in the polymer by conversion.

[0132] 3. Determination of polymer imidization rate:

[0133] At room temperature, the solid component A polymer was dissolved in GBL to form a slurry, and the slurry was applied to a 6-inch silicon wafer by spin coating. The silicon wafer was then transferred to a hot plate (Azov EC-7050) and treated at 120°C for 3 minutes to obtain a polymer pre-baked film with a thickness of 5 μm. The pre-baked film was divided into two halves, one of which was placed in a high-temperature clean furnace (Azov HPM-2G). Under a nitrogen flow and an oxygen concentration of 20 ppm, the temperature was raised from room temperature to 210°C at a rate of 2.5°C / min, and heat treated at 210°C for 1 hour. The temperature in the furnace was naturally cooled to below 50°C to obtain a cured film of the polymer. The infrared absorption spectra of the polymer pre-baked film and the cured film were measured using a Fourier transform infrared spectrometer (Shimadzu IRAffinity-1S, Japan). From the obtained infrared spectrum, the 1377 cm -1 The CN stretching vibration peak near the film is then calculated to determine the intensities of the corresponding peaks of the two films, and the ratio of the peak intensity of the prebaked film to the peak intensity of the polyimide resin film is taken as the imidization rate of the polymer.

[0134] 4. Determination of closed-loop rate of polyhydroxyamide:

[0135] As in the evaluation method 3, the polymer slurry of component A was made into a 5μm polymer pre-baked film. The pre-baked film was evenly divided into two halves, one half was placed on a heating plate at 210°C and heat treated for 10 minutes to obtain a cured film (referred to as film F1), and the other half was placed on a heating plate at 320°C and heat treated for 10 minutes to obtain a cured film (referred to as film F2). The infrared absorption spectra of cured films F1 and F2 were measured using a Fourier transform infrared spectrometer (Shimadzu IRAffinity-1S, Japan). The 1570cm -1 The C=N stretching vibration peak near the two films was then calculated to determine the intensities of the corresponding peaks. The ratio of the peak intensity of the cured film F1 to the peak intensity of the cured film F2 was taken as the ring closure rate of the polyhydroxyamide in the polymer.

[0136] 5. Determination of residual film rate

[0137] The resin composition slurry was applied to a 6-inch silicon wafer by spin coating, and then the silicon wafer was transferred to a heating plate (Azowan EC-7050), and treated at 120°C for 3 minutes to obtain a pre-baked film with a thickness of 10 μm. The pre-baked film was exposed using an exposure machine (SMA-150GA-TR) i line (365nm). After exposure, a developing device (AD-1200MIKASA) was used to develop for 90 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution as a developing solution, and then washed with pure water to obtain a developed film with a pattern. The ratio of the film thickness of the developed film to the film thickness of the pre-baked film was taken as the residual film rate (residual film rate = film thickness of the developed film / film thickness of the pre-baked film × 100%). Considering high photosensitivity and resolution, the measured residual film rate value is considered to be poor if it is below 80% or above 90%, is considered to be good if it is in the range of 80% to 85%, and is considered to be better if it is in the range of 85% to 90%.

[0138] 6. Determination of pattern processability

[0139] The resin composition slurry is applied to a 6-inch silicon wafer by spin coating, and then the silicon wafer is transferred to a hot plate and treated at 120°C for 3 minutes to obtain a pre-baked film with a thickness of 10 μm. The pre-baked film is exposed using an exposure machine i-line (365nm). After exposure, a developing device is used to develop the film for 90 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution as a developing solution, and then the film is washed with pure water to obtain a developed film. The case where a developed film with a specific pattern can be obtained is considered to have good processability, and the case where the solubility in the developer is low and the pattern cannot be formed, and the case where the solubility is high and the pattern flows, are considered to have poor processability.

[0140] 7. Determination of photosensitivity:

[0141] The pre-baked film is exposed using the i-line (365nm) of the exposure machine. After exposure, the film is developed using a 2.38% tetramethylammonium hydroxide aqueous solution as a developing solution using a developing device, and the process is repeated twice. The film is then washed with pure water and blown dry. The lowest exposure when the exposed part is completely dissolved is taken as the sensitivity. The measured sensitivity value is considered bad if it is higher than 400mJ / cm2, good if it is in the range of 200-400mJ / cm2, and better if it is lower than 200mJ / cm2.

[0142] 8. Determination of thermal shrinkage

[0143] The pre-baked film was placed in an oxygen-free clean oven (Glenier GN120XF, China), and heated to 210°C at a rate of 2.5°C / min under a nitrogen flow (oxygen concentration is less than 20ppm), and maintained at 210°C for 1h to form a cured film. The thickness of the pre-baked film and the thickness of the cured film after heat treatment were measured using a film thickness meter. The calculation formula for the shrinkage rate can be expressed as: Shrinkage rate (%) = (pre-baked film thickness - cured film thickness) ÷ pre-baked film thickness × 100. The measured shrinkage rate (%) value above 25 is considered bad, the value within the range of 20 to 25 is considered good, and the value below 20 is considered better.

[0144] 9. Determination of thermal decomposition temperature (T 1％ ):

[0145] A 10 mg polyimide resin film sample was prepared. The sample was heated to 150°C at a heating rate of 10°C / min and maintained for 30 min in the first stage under a nitrogen flow using a thermogravimetric analyzer (NETZSCH TG209F1, Germany). The temperature was lowered to 50°C in the second stage. The temperature was heated from 50°C to 700°C at a heating rate of 10°C / min in the third stage. The temperature corresponding to 1% weight loss was determined from the measured weight-temperature curve as the corresponding thermal decomposition temperature. The measured thermal decomposition temperature T 1％ A value below 280°C is considered bad, a value within the range of 280°C to 300°C is considered good, and a value above 300°C is considered better.

[0146] 10. Determination of tensile modulus and elongation at break of film:

[0147] Prepare a 10μm thick polyimide resin film sample and make it into a rectangular film with a size of 80mm×10mm. Use a tensile testing machine (RTH-20-RACK1310, Japan) to stretch the film sample at a stretching speed of 50mm / min at 23℃ / 45%RH indoors. The clamp spacing is 50mm. Prepare 10 specimens for each batch of samples. After stretching, obtain the stress-strain curve, and obtain the tensile modulus and elongation at break results. The result is the average of 5 good data. Considering both heat resistance and tensile properties, the measured tensile modulus value lower than 2.5GPa or higher than 3.4GPa is considered bad, and the value in the range of 2.5GPa to 3.4GPa is considered good. The measured elongation at break value lower than 20% or higher than 40% is considered bad, and the value in the range of 20% to 40% is considered good.

[0148] 11. Determination of adhesion with metallic copper

[0149] Sputtering copper with a thickness of 2 μm on a silicon wafer to form a copper sputtering substrate. Spin coating the resin composition slurry on the copper substrate, using a heating plate (Azowan EC-7050), after treatment at 120°C for 3 minutes, a pre-baked film with a thickness of 8 μm was obtained. The pre-baked film was placed in an oxygen-free clean oven (China Glenier GN120XF), and heated to 210°C at a rate of 2.5°C / min under a nitrogen flow (oxygen concentration less than 20ppm), and maintained at 210°C for 1 hour to form a cured film. Use a single-edged blade and a grid plate to cut out 10*10 squares with a spacing of 2mm on the cured film, put it into a blast oven, and store it at 150℃ for 500h. After the storage, use a soft brush to clean the surface of the cured film, unroll the Sellotape tape, and use your fingers to smooth the tape-adhered cured film in the direction parallel to the scribe line. Finally, within 0.5-1.0s, tear off the tape at an angle close to 60° and peel off 100 grids. The adhesion between the metal copper and the resin cured film is evaluated based on the number of grids peeled off. If the number of grids peeled off is less than 20, it is considered bad and rated C, if the number is in the range of 10-20, it is considered good and rated B, and if the number is less than 10, it is considered better and rated A.

[0150] The following will describe the embodiments / synthesis examples in conjunction with the technical solution, and the specific contents are as follows:

[0151] Aromatic tetracarboxylic dianhydride raw material preparation example 1: Synthesis example 1①

[0152] Synthesis Example 1①: Synthesis Formula (X-12)

[0153]

[0154] At room temperature, 36.63g (0.1mol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 57.07g (0.5mol) of allyl glycidyl ether and 300g of N-methylpyrrolidone (NMP) were added to a 1L three-necked flask, nitrogen was replaced, stirring was started to completely dissolve, the temperature was lowered to -15°C, and then 46.33g (0.22mol) of 1,2,4-trimellitic anhydride chloride NMP (100g) solution was slowly added to the reaction flask, and after the addition was completed, the temperature was kept at -15°C for 6h and then naturally warmed to room temperature. The next day, the reaction solution was concentrated until no liquid flowed out, 2L of anhydrous ethanol was added thereto, stirred for 2h, and a white solid was obtained by filtration, that is, aromatic ring tetracarboxylic dianhydride (X-12) was obtained.

[0155] Example 2 for preparing hydroxyl-containing aromatic diamine raw materials: Synthesis examples 2①~2④

[0156] Synthesis example 2①: Synthesis formula Y1-1

[0157] Step S1:

[0158]

[0159] At room temperature, add 2-amino-5-nitrophenol (CAS No.: 121-88-0) 15.4g (0.1mol), propylene oxide 20.91g (0.36mol) and 120ml acetone to a 1L three-necked reaction bottle, stir at room temperature until completely dissolved, and cool the reaction system to -15°C. Then, slowly drop 3-fluoro-4-nitrobenzoyl chloride (CAS No.: 157665-51-5) 120ml acetone solution, after the dropwise addition, continue the reaction at -15°C for 5h, and then naturally warm to room temperature. The obtained reaction solution is filtered under reduced pressure to obtain an off-white solid, which is placed in a vacuum oven at 60°C and dried for 20h (24.41g, yield 76%).

[0160] Step S2:

[0161]

[0162] 9.64g (0.03mol) of the off-white solid obtained above, 2.58g of 5% palladium carbon and 170ml of ethylene glycol methyl ether were added to a 500ml autoclave, and hydrogen was replaced, pressurized with hydrogen to make the pressure inside the autoclave reach 10kgf / cm2, heated to 35°C, and stirred for 2h. After the reaction was completed, the pressure was slowly released, and the reaction solution was filtered under reduced pressure to obtain a transparent solution. Ethanol and petroleum ether were added to the solution, stirred for 12h to precipitate solids, filtered under reduced pressure to obtain a white solid, and the solid was placed in a vacuum oven at 50°C and dried for 20h to obtain hydroxyl-containing aromatic diamine Y1-1 (4.70g, yield 60%).

[0163] Synthesis example 2②: Synthesis formula (Y1-9)

[0164] Step S1:

[0165]

[0166] At room temperature, add 13.93g (0.06mol) of 5,5-oxybis(2-aminophenol) (CAS No.: 20817-05-4), 20.91g (0.36mol) of propylene oxide and 120ml of acetone to a 1L three-necked reaction bottle, stir at room temperature until completely dissolved, and cool the reaction system to -15°C. Then, slowly drop 120ml of acetone solution of 24.49g (0.132mol) of m-nitrobenzoyl chloride (CAS No.: 121-90-4), and after the dropwise addition, continue the reaction at -15°C for 5h, and then naturally warm to room temperature. Filter the obtained reaction solution under reduced pressure to obtain an off-white solid, and dry the solid in a vacuum oven at 60°C for 20h (22.60g, yield 71%).

[0167] Step S2:

[0168]

[0169] The above obtained off-white solid 15.91g (0.03mol), 5% palladium carbon 2.58g and 170ml ethylene glycol methyl ether were added to a 500ml autoclave, and hydrogen was replaced, and the pressure in the autoclave was pressurized with hydrogen to reach 10kgf / cm2, and the temperature was raised to 35°C and stirred for 2h. After the reaction was completed, the pressure was slowly released, and the reaction solution was filtered under reduced pressure to obtain a transparent solution. Ethanol and petroleum ether were added to the solution, and the solid was precipitated by stirring for 12h, and the solid was filtered under reduced pressure to obtain a white solid. The solid was placed in a vacuum oven and dried at 50°C for 20h to obtain bis(3-hydroxy-4-(2-amino)benzamide)diphenyl ether (Y1-9) (7.90g, yield 56%).

[0170] Synthesis example 2③: Synthesis formula (Y1-10)

[0171] Step S1:

[0172]

[0173] At room temperature, add 22g (0.06mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (CAS No.: 83558-87-6), 20.91g (0.36mol) of propylene oxide and 120ml of acetone to a 1L three-necked reaction bottle, stir at room temperature until completely dissolved, and cool the reaction system to -15°C. Then, slowly drop 24.49g (0.132mol) of m-nitrobenzoyl chloride in 120ml of acetone. After the dropwise addition, continue the reaction at -15°C for 5h, and then naturally warm to room temperature. Filter the obtained reaction solution under reduced pressure to obtain an off-white solid, and dry the solid in a vacuum oven at 60°C for 20h (27.91g, yield 70%).

[0174] Step S2:

[0175]

[0176] The above-obtained off-white solid 19.93g (0.03mol), 5% palladium carbon 2.58g and 170ml ethylene glycol methyl ether were added to a 500ml high-pressure reactor, and hydrogen was replaced, and the pressure in the reactor was pressurized with hydrogen to reach 10kgf / cm2, and the temperature was raised to 35°C and stirred for 2h. After the reaction was completed, the pressure was slowly released, and the reaction solution was filtered under reduced pressure to obtain a transparent solution. Ethanol and petroleum ether were added to the solution, and the solid was precipitated by stirring for 12h, and the solid was filtered under reduced pressure to obtain a white solid. The solid was placed in a vacuum oven and dried at 50°C for 20h to obtain 2,2-bis(3-(3-amino)benzamide-4-hydroxyphenyl)hexafluoropropane (Y1-10) (9.97g, yield 55%).

[0177] Synthesis Example 2④: Synthesis of Hydroxyl-Containing Aromatic Diamine (Y1-10a)

[0178]

[0179] The synthesis process is the same as that of Synthesis Example 2③, except that the synthetic raw material 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 22g (0.06mol) is replaced with 2,2-bis(3-aminophenyl)hexafluoropropane 20.06g (0.06mol), and finally hydroxyl-containing aromatic diamine (Y1-10a) (9.27g, yield 54%) is obtained.

[0180] Preparation Example 3 of Amide-containing Fatty Chain Diamine Raw Materials: Synthesis Examples 3①~3④

[0181] Synthesis Example 3①: Synthesis of amide-containing fatty chain diamine Y2-5

[0182] Step S1:

[0183]

[0184]

[0185] Under nitrogen protection at room temperature, add 11.9g (0.10mol) of 3-nitropropionic acid (CAS No.: 504-88-1) and 100ml of dichloromethane to a 500ml three-necked reaction bottle, start stirring, and cool the reaction system to 0°C. Then, slowly drop a solution of 16.22g (0.10mol) of N,N'-carbonyldiimidazole (CAS No.: 530-62-1) in dichloromethane (100ml) into the system. After the addition is complete, keep the temperature at 0°C for 30min. Add 3.71g (0.05mol) of 1,3-propylenediamine (CAS No.: 109-76-2) into the system, keep stirring for 30min, then naturally warm to room temperature and react overnight. The next day, the reaction solution was filtered under reduced pressure, the filtrate was dried to obtain an off-white solid, which was purified and separated by column chromatography and distilled under reduced pressure to obtain a white solid N,N'-(propane-1,3-diyl)bis(3-nitropropionamide) (12.43 g, yield 90%).

[0186] Step S2:

[0187]

[0188] The above-obtained white solid 8.29g (0.03mol), 5% palladium carbon 2.58g and 160ml tetrahydrofuran were added to a 500ml high-pressure reactor, and hydrogen was replaced, and the pressure in the reactor was pressurized with hydrogen to reach 10kgf / cm2, and the temperature was raised to 35°C and stirred for 2h. After the reaction was completed, the pressure was slowly released, and the reaction solution was filtered under reduced pressure to obtain a transparent solution. Ethanol and petroleum ether were added to the solution, and the solid was precipitated by stirring for 12h, and the solid was filtered under reduced pressure to obtain a white solid. The solid was placed in a vacuum oven and dried at 50°C for 20h to obtain the product N, N'-(propane-1,3-diyl)bis(3-aminopropionamide) (Y2-5) (4.67g, yield 72%).

[0189] Synthesis Example 3②: Synthesis of amide-containing fatty chain diamine Y2-7

[0190] Step S1:

[0191]

[0192] Under nitrogen protection at room temperature, add 11.9g (0.10mol) of 3-nitropropionic acid and 100ml of dichloromethane to a 500ml three-necked reaction bottle, start stirring, and cool the reaction system to 0°C. Then, slowly drop a solution of 16.22g (0.10mol) of N,N'-carbonyldiimidazole in dichloromethane (100ml) into the system. After the addition is complete, keep the temperature at 0°C for 30min. Add 5.21g (0.05mol) of 2,2-oxybis(ethylamine) (CAS No.: 2752-17-2) into the system, keep stirring for 30min, then naturally warm to room temperature and react overnight. The next day, the reaction solution was filtered under reduced pressure, the filtrate was dried to obtain an off-white solid, which was purified and separated by column chromatography and distilled under reduced pressure to obtain a white solid N,N'-(oxybis(ethane-2,1-diyl))bis(3-nitropropionamide) (13.94 g, yield 91%).

[0193] Step S2:

[0194]

[0195] Add 9.19g (0.03mol) of the white solid obtained above, 2.58g of 5% palladium carbon and 160ml of tetrahydrofuran into a 500ml high-pressure reactor, replace the hydrogen, pressurize with hydrogen to make the pressure inside the reactor reach 10kgf / cm2, heat to 35°C, and stir for 2h. After the reaction is completed, slowly release the pressure, filter the reaction solution under reduced pressure to obtain a transparent solution. Add ethanol and petroleum ether to the solution, stir for 12h to precipitate solid, filter under reduced pressure to obtain a white solid, put the solid into a vacuum oven at 50°C and dry for 20h to obtain the product N,N'-(oxybis(ethane-2,1-diyl))bis(3-aminopropionamide) (Y2-7) (5.25g, yield 71%).

[0196] Synthesis Example 3③: Synthesis of amide-containing fatty chain diamine Y2-10

[0197] Step S1:

[0198]

[0199] Under nitrogen protection at room temperature, add 11.9g (0.10mol) of 3-nitropropionic acid and 100ml of dichloromethane to a 500ml three-necked reaction bottle, start stirring, and cool the reaction system to 0°C. Then, slowly drop a solution of 16.22g (0.10mol) of N,N'-carbonyldiimidazole in dichloromethane (100ml) into the system. After the addition is complete, keep the temperature at 0°C for 30min. Add 7.41g (0.05mol) of 1,2-bis(2-aminoethoxy)ethane (CAS No.: 929-59-9) into the system, keep stirring for 30min, then naturally warm to room temperature and react overnight. The next day, the reaction solution was filtered under reduced pressure, the filtrate was dried to obtain an off-white solid, which was purified and separated by column chromatography and distilled under reduced pressure to obtain a white solid N,N'-(ethane-1,2-dioxy)bis(ethane-1,2-diyl)bis(3-nitropropionamide) (15.76 g, yield 90%).

[0200] Step S2:

[0201]

[0202] Add 10.51g (0.03mol) of the white solid obtained above, 2.58g of 5% palladium carbon and 160ml of tetrahydrofuran into a 500ml high-pressure reactor, replace the hydrogen, pressurize with hydrogen to make the pressure inside the reactor reach 10kgf / cm2, heat to 35°C, and stir for 2h. After the reaction is completed, slowly release the pressure, filter the reaction solution under reduced pressure to obtain a transparent solution. Add ethanol and petroleum ether to the solution, stir for 12h to precipitate solids, filter under reduced pressure to obtain white crystals, put the solids into a vacuum oven at 50°C and dry for 20h to obtain the product amide-containing fatty chain diamine (Y2-10) (6.01g, yield 69%).

[0203] Synthesis Example 3④: Synthesis of amide-containing fatty chain diamine Y2-a

[0204] Step S1:

[0205]

[0206] This synthesis process is the same as the operation of step S1 in synthesis example 3①, except that 3.71 g (0.05 mol) of the synthetic raw material 1,3-propylenediamine is replaced with 11.02 g (0.05 mol) of diethylene glycol di(3-aminopropyl) ether (CAS No.: 4246-51-9) to obtain brown liquid N,N-(((oxybis(ethane-2,1-diyl))dioxybis(propane-3,1-diyl)bis(3-nitropropionamide) (16.48 g, yield 78%).

[0207] Step S2:

[0208]

[0209] This process is the same as the operation of step S2 in Synthesis Example 3①, except that the synthetic raw material N,N'-(propane-1,3-diyl)bis(3-nitropropionamide) is changed to N,N-(((oxybis(ethane-2,1-diyl))dioxybis(propane-3,1-diyl)bis(3-nitropropionamide) 12.67 g (0.03 mol), and finally an amide-containing fatty chain diamine (Y2-a) (7.18 g, yield 66%) is obtained.

[0210] Photosensitizer Preparation Example 4: Synthesis Examples 4①~4②

[0211] Synthesis Example 4①: Synthesis of Quinonediazide Compound C-1

[0212]

[0213] At room temperature, 15.32g (0.05mol) of 1,1,1-tri(4-hydroxyphenyl)ethane, 37.61g (0.14mol) of 5-naphthoquinone azide sulfonyl chloride and 450g of 1,4-dioxane were added to a 1L reaction bottle, stirring was started, nitrogen was replaced, and stirring was performed until completely dissolved. A mixture of triethylamine (14.19g, 0.14mol) and 1,4-dioxane (45g) was slowly dripped therein. After the addition was completed, the temperature was raised to 35°C and the reaction was continued for 4h. After the reaction was completed, the mixture was filtered under reduced pressure, the filtrate was dripped into 3L of water, and the precipitated solid was filtered and collected. Finally, the precipitate was washed twice with 10L of pure water, and dried in a vacuum drying oven at 50°C for 24h to obtain quinone diazide compound C-1.

[0214] Among them, Q1, Q2, and Q3 are Or H, the molar ratio of the two in the compound is 3:1.

[0215] Synthesis Example 4②: Synthesis of Quinonediazide Compound C-3

[0216]

[0217] At room temperature, 20.23 g (0.05 mol) of 1,1,2-tris(3,5-dimethyl-4-hydroxyphenyl)propane, 37.61 g (0.14 mol) of 5-naphthoquinone azide sulfonyl chloride and 450 g of 1,4-dioxane were added to a 1L reaction bottle, stirring was started, nitrogen was replaced, and stirring was performed until completely dissolved. A mixture of triethylamine (14.19 g, 0.14 mol) and 1,4-dioxane (45 g) was slowly dripped therein. After the addition was completed, the temperature was raised to 35°C and the reaction was continued for 4 hours. After the reaction was completed, the mixture was filtered under reduced pressure, the filtrate was dripped into 3L of water, and the precipitated solid was filtered and collected. Finally, the precipitate was washed twice with 10L of pure water, and dried in a vacuum drying oven at 50°C for 24 hours to obtain quinone diazide compound C-3.

[0218] Among them, Q4, Q5, and Q6 are Or H, the molar ratio of the two in the compound is 3:1.

[0219] Preparation Example 5 of Component A: Synthesis Example 5①~5

[0220] Synthesis Example 5①: Synthesis of Polymer A-1

[0221] Under dry nitrogen, the hydroxyl-containing aromatic diamine compound 2,2-bis(3-(3-amino)benzamido-4-hydroxyphenyl)hexafluoropropane (Y1-10) (24.18 g, 0.04 mol) obtained in Synthesis Example 2③, the amide-containing fatty chain diamine (Y2-7) (2.46 g, 0.01 mol) in Synthesis Example 3② and 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) (0.50 g, 2.00 mmol) were dissolved in 200 g of solvent N-methylpyrrolidone (NMP) and added into a 1 L reaction bottle. At 50°C, add aromatic cyclic acid dianhydride p-phenylene-diphenyltrimethylol dianhydride (X-7) (CAS No.: 2770-49-2) (27.5 g, 0.06 mol), keep stirring for 2 hours, add end-capping agent 3-aminophenol (MAP) (CAS No.: 591-27-5) (1.09 g, 0.01 mol), stir for 2 hours, then add esterification agent N, N-dimethylformamide dimethyl acetal (DMFDMA) (CAS No.: 4637-24-5) (17.88 g, 0.15 mol), stir at 50°C for 3 hours. After the reaction is completed, cool to room temperature, slowly pour the reaction solution into 2L of pure water, precipitate a white solid, collect the solid by vacuum filtration, wash twice with pure water, and dry in a vacuum drying oven at 80°C for 72 hours to obtain 53 g of polymer (A-1).

[0222] Synthesis Example 5②: Synthesis of polymer A-2

[0223] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the raw material 2,2-bis(3-(3-amino)benzamido-4-hydroxyphenyl)hexafluoropropane (Y1-10) (24.18 g, 0.04 mol) was changed to bis(3-hydroxy-4-(2-amino)benzamido)diphenyl ether (Y1-9) (18.82 g, 0.04 mol) in Synthesis Example 2②, and p-phenylene-diphenyltrimethylol dianhydride (X-7) (27.5 g, 0.06 mol) was changed to hexafluorodianhydride (CAS No.: 1107-00-2) (26.65 g, 0.06 mol), and finally 48 g of polymer (A-2) was obtained.

[0224] Synthesis Example 5③: Synthesis of polymer A-3

[0225] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the raw material 2,2-bis(3-(3-amino)benzamido-4-hydroxyphenyl)hexafluoropropane (Y1-10) (24.18 g, 0.04 mol) was replaced by the hydroxyl-containing aromatic diamine (Y1-1) (10.45 g, 0.04 mol) in Synthesis Example 2①, and p-phenylene-diphenyltrimethylol dianhydride (X-7) (27.5 g, 0.06 mol) was replaced by the aromatic ring tetracarboxylic dianhydride (X-12) (42.87 g, 0.06 mol) obtained in Synthesis Example 1①, and finally 55 g of polymer (A-3) was obtained.

[0226] Synthesis Example 5④: Synthesis of polymer A-4

[0227] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the raw material amide-containing fatty chain diamine (Y2-7) (2.46 g, 0.01 mol) was replaced with the amide-containing fatty chain diamine (Y2-5) (2.16 g, 0.01 mol) obtained in Synthesis Example 3①, and finally 53 g of polymer (A-4) was obtained.

[0228] Synthesis Example 5⑤: Synthesis of Polymer A-5

[0229] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the raw material amide-containing fatty chain diamine (Y2-7) (2.46 g, 0.01 mol) was replaced with the amide-containing fatty chain diamine (Y2-10) (2.90 g, 0.01 mol) obtained in Synthesis Example 3①, and finally 54 g of polymer (A-5) was obtained.

[0230] Synthesis Example 5⑥: Synthesis of Polymer A-6

[0231] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the amount of the raw material hydroxyl-containing aromatic diamine compound 2,2-bis(3-(3-amino)benzamido-4-hydroxyphenyl)hexafluoropropane (Y1-10) was changed to 27.20 g (0.045 mol), and the amount of the amide-containing fatty chain diamine (Y2-7) was changed to 1.23 g (0.005 mol), and finally 55 g of polymer (A-6) was obtained.

[0232] Synthesis Example 5⑦: Synthesis of polymer A-7

[0233] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the amount of the raw material hydroxyl-containing aromatic diamine compound 2,2-bis(3-(3-amino)benzamido-4-hydroxyphenyl)hexafluoropropane (Y1-10) was changed to 21.16 g (0.035 mol), and the amount of the amide-containing fatty chain diamine (Y2-7) was changed to 3.69 g (0.015 mol), and finally 51 g of polymer (A-7) was obtained.

[0234] Synthesis Example 5⑧: Synthesis of Polymer A-8

[0235] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the amount of the raw material esterification agent N,N-dimethylformamide dimethyl acetal was changed to 11.92g (0.10mol), and finally 49g of polymer (A-8) was obtained.

[0236] Synthesis Example 5⑨: Synthesis of Polymer A-9

[0237] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the amount of the raw material esterification agent N,N-dimethylformamide dimethyl acetal was changed to 23.84g (0.20mol), and finally 56g of polymer (A-9) was obtained.

[0238] Synthesis Example 5⑩: Synthesis of Polymer A-10

[0239] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the raw esterifying agent N,N-dimethylformamide dimethyl acetal (17.88 g, 0.15 mol) was changed to N,N-dimethylformamide diethyl acetal (DMFDEA) (22.08 g, 0.15 mol), and finally 55 g of polymer (A-10) was obtained.

[0240] Synthesis example 5 Synthetic polymer A-11

[0241] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the raw material 2,2-bis(3-(3-amino)benzamido-4-hydroxyphenyl)hexafluoropropane (Y1-10) (24.18 g, 0.04 mol) was replaced with bis(3-hydroxy-4-(2-amino)benzamido)diphenyl ether (Y1-9) (18.82 g, 0.04 mol) in Synthesis Example 2②, and finally 48 g of polymer (A-11) was obtained.

[0242] Synthesis example 5 Synthetic polymer A-12

[0243] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the raw material 2,2-bis(3-(3-amino)benzamido-4-hydroxyphenyl)hexafluoropropane (Y1-10) (24.18 g, 0.04 mol) was replaced with the hydroxyl-containing aromatic diamine (Y1-10a) (22.90 g, 0.04 mol) in Synthesis Example 2④, and finally 52 g of polymer (A-12) was obtained.

[0244] Synthesis example 5 Synthetic polymer A-13

[0245] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the amount of raw material 2,2-bis(3-(3-amino)benzamido-4-hydroxyphenyl)hexafluoropropane (Y1-10) was changed to 30.23 g (0.05 mol), and amide-containing fatty chain diamine was not added, and finally 55 g of polymer (A-13) was obtained.

[0246] Synthesis example 5 Synthetic polymer A-14

[0247] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the raw material amide-containing fatty chain diamine (Y2-7) was changed to 2.00 g (0.01 mol) of 1,12-diaminododecane (CAS No.: 2783-17-7), and finally 43 g of polymer (A-14) was obtained.

[0248] Synthesis example 5 Synthetic polymer A-15

[0249] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that the raw material amide-containing fatty chain diamine (Y2-7) (2.46 g, 0.01 mol) was replaced with the amide-containing fatty chain diamine (Y2-a) (3.62 g, 0.01 mol) obtained in Synthesis Example 3①, and finally 54 g of polymer (A-15) was obtained.

[0250] Synthesis example 5 Synthetic polymer A-16

[0251] The synthesis was carried out according to the synthesis method of Synthesis Example 5①, except that no esterifying agent was added, and finally 58g of polymer (A-16) was obtained.

[0252] Synthesis Example 5①~5 The synthesis ratio of the polymer of component A is shown in Table 1.

[0253] Table 1

[0254]

[0255]

[0256] Example 1

[0257] Step S1: Determine the esterification rate, imidization rate and polyhydroxy ring closure rate of the solid polymer (A-1) using the above-mentioned evaluation method.

[0258] Step S2: Preparing a positive photosensitive resin precursor composition

[0259] At room temperature, 10 g of polymer (A-1) was added to 50 g of γ-butyrolactone (GBL), and stirred until completely dissolved. Then, 2.0 g of thermal crosslinking agent (B1-4) (CAS No.: 672926-26-0), 0.12 g of thermal crosslinking agent (B2-4) (CAS No.: 29570-58-9), 1.3 g of photosensitizer quinone diazide compound (C-1), 1.7 g of photosensitizer quinone diazide compound (C-3) and 0.3 g of phenolic hydroxy compound 1,1,1-tri(4-hydroxyphenyl)ethane (CAS No.: 27955-94-8) was stirred thoroughly until completely dissolved, and then 5 g of surfactant propylene glycol methyl ether acetate (CAS No.: 108-65-6) and 0.2 g of fit improver trimethoxyvinylsilane (CAS No.: 2768-02-7) were added to the solution and stirred thoroughly for 1 hour to obtain a resin composition slurry (V-1).

[0260] Step S3: Preparing a photosensitive polyimide resin film

[0261] The obtained slurry (V-1) was applied to a 6-inch silicon wafer by spin coating, and then dried at 120°C for 5 minutes to obtain a silicon wafer assembly with a 10μm thick pre-baked film. Next, the i-line (365nm) of a mercury lamp was used to expose it through a mask, and then a developing device was used to remove the exposed part using a tetramethylammonium hydroxide developer to obtain a resin pre-baked film with a specific pattern. The residual film rate, processability and sensitivity of this pre-baked film were measured using the evaluation method described above.

[0262] The resin pre-baked film was placed in a high-temperature clean furnace, heated to 210°C at a heating rate of 2.5°C / min, and maintained at 210°C for 1 hour. After the temperature in the furnace dropped to below 50°C, the cured film was taken out to obtain a photosensitive polyimide resin cured film (F-1). The thermal shrinkage rate and thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0263] Example 2

[0264] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-2). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-2) were measured; second, a resin composition slurry (V-2) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-2), and its residual film rate, processability and sensitivity were measured; finally, the photosensitive polyimide resin cured film (F-2) was obtained using the pre-baked film, and its thermal shrinkage rate and thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0265] Example 3

[0266] The process of Example 1 was followed, except that polymer (A-1) was replaced by polymer (A-3), the amount of thermal crosslinking agent (B1-4) added in step S2 was changed to 1.97 g, and the amount of thermal crosslinking agent (B2-4) added was changed to 0.15 g. First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-3) were measured; secondly, a resin composition slurry (V-3) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-3), and its residual film rate, processability and sensitivity were measured; finally, the photosensitive polyimide resin cured film (F-3) was obtained using the pre-baked film, and its thermal shrinkage rate and thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0267] Example 4

[0268] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-4). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-4) were measured; second, a resin composition slurry (V-4) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-4), and its residual film rate, processability and photosensitivity were measured; finally, the photosensitive polyimide resin cured film (F-4) was obtained using the pre-baked film, and its thermal shrinkage rate and thermal decomposition temperature (T 1％), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0269] Example 5

[0270] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-5). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-5) were measured; second, a resin composition slurry (V-5) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-5), and its residual film rate, processability and photosensitivity were measured; finally, the photosensitive polyimide resin cured film (F-5) was obtained using the pre-baked film, and its thermal shrinkage rate and thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0271] Example 6

[0272] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-6). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-6) were measured; second, a resin composition slurry (V-6) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-6), and its residual film rate, processability and sensitivity were measured; finally, the photosensitive polyimide resin cured film (F-6) was obtained using the pre-baked film, and its thermal shrinkage rate and thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0273] Example 7

[0274] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-7). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-7) were measured; second, a resin composition slurry (V-7) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-7), and its residual film rate, processability and sensitivity were measured; finally, the photosensitive polyimide resin cured film (F-7) was obtained using the pre-baked film, and its thermal shrinkage rate, thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0275] Example 8

[0276] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-8). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-8) were measured; second, a resin composition slurry (V-8) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-8), and its residual film rate, processability and sensitivity were measured; finally, the photosensitive polyimide resin cured film (F-8) was obtained using the pre-baked film, and its thermal shrinkage rate and thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0277] Example 9

[0278] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-9). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-9) were measured; second, a resin composition slurry (V-9) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-9), and its residual film rate, processability and sensitivity were measured; finally, the photosensitive polyimide resin cured film (F-9) was obtained using the pre-baked film, and its thermal shrinkage rate and thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0279] Example 10

[0280] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-10). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-10) were measured; second, a resin composition slurry (V-10) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-10), and its residual film rate, processability and sensitivity were measured; finally, a photosensitive polyimide resin cured film (F-10) was obtained using the pre-baked film, and its thermal shrinkage rate and thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0281] Embodiment 11

[0282] The process of Example 1 was followed, except that the amount of the thermal crosslinking agent (B1-4) added in step S2 was changed to 1.92 g, and the amount of the thermal crosslinking agent (B2-4) added was changed to 0.2 g. The various substances were mixed to obtain a resin composition slurry (V-11), and a resin pre-baked film with a specific pattern was obtained using the slurry (V-11), and its residual film rate, processability and sensitivity were measured; finally, the pre-baked film was used to obtain a photosensitive polyimide resin cured film (F-11), and its thermal shrinkage rate and thermal decomposition temperature (T 1％), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0283] Comparative Example 1

[0284] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-11). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-11) were measured; second, a resin composition slurry (V-12) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-12), and its residual film rate, processability and sensitivity were measured; finally, the photosensitive polyimide resin cured film (F-12) was obtained using the pre-baked film, and its thermal shrinkage rate and thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0285] Comparative Example 2

[0286] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-12). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-12) were measured; second, a resin composition slurry (V-13) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-13), and its residual film rate, processability and photosensitivity were measured; finally, the pre-baked film was used to obtain a photosensitive polyimide resin cured film (F-13), and its thermal shrinkage rate, thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0287] Comparative Example 3

[0288] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-13). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-13) were measured; second, a resin composition slurry (V-14) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-14), and its residual film rate, processability and sensitivity were measured; finally, the photosensitive polyimide resin cured film (F-14) was obtained using the pre-baked film, and its thermal shrinkage rate, thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0289] Comparative Example 4

[0290] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-14). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-14) were measured; second, a resin composition slurry (V-15) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-15), and its residual film rate, processability and sensitivity were measured; finally, the photosensitive polyimide resin cured film (F-15) was obtained using the pre-baked film, and its thermal shrinkage rate, thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0291] Comparative Example 5

[0292] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-15). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-15) were measured; second, a resin composition slurry (V-16) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-16), and its residual film rate, processability and sensitivity were measured; finally, the pre-baked film was used to obtain a photosensitive polyimide resin cured film (F-16), and its thermal shrinkage rate, thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0293] Comparative Example 6

[0294] The process of Example 1 was followed, except that the polymer (A-1) was replaced by the polymer (A-16). First, the esterification rate, imidization rate and polyhydroxyl ring closure rate of the solid polymer (A-16) were measured; second, a resin composition slurry (V-17) was obtained, and a resin pre-baked film with a specific pattern was obtained using the slurry (V-17), and its residual film rate, processability and sensitivity were measured; finally, the photosensitive polyimide resin cured film (F-17) was obtained using the pre-baked film, and its thermal shrinkage rate, thermal decomposition temperature (T 1％ ), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0295] Comparative Example 7

[0296] The process of Example 1 was followed, except that the amount of the thermal crosslinking agent (B1-4) added in step S2 was changed to 2.12 g, and no thermal crosslinking agent (B2-4) was added. The various substances were mixed to obtain a resin composition slurry (V-18), and a resin pre-baked film with a specific pattern was obtained using the slurry (V-18), and its residual film rate, processability and sensitivity were measured; finally, the pre-baked film was used to obtain a photosensitive polyimide resin cured film (F-18), and its thermal shrinkage rate and thermal decomposition temperature (T 1％), tensile modulus and elongation at break as well as adhesion indicators with metals.

[0297] The amounts of individual raw materials used and the polymer properties of component A in Examples 1 to 11 and Comparative Examples 1 to 7 are shown in Table 2.

[0298] Table 2

[0299]

[0300]

[0301] The performance test results of the polyimide resin films obtained in Examples 1 to 11 and Comparative Examples 1 to 7 are shown in Table 3.

[0302] Table 3

[0303]

[0304]

[0305] It can be seen from the test results in Table 3 that the thermal shrinkage of the polyimide resin film obtained in Examples 1 to 11 of the present invention is below 25%, and has a relatively low thermal shrinkage; the thermal decomposition temperature T 1％ Above 280℃, it exhibits excellent heat resistance; Young's modulus is in the range of 2.5-3.4GPa, elongation at break is between 16% and 29%, exhibiting excellent tensile properties; residual film rate is in the range of 80%-90%, and sensitivity value is 400mJ / cm 2 The resin film has good adhesion to metal.

[0306] Moreover, by comparing Example 1, Examples 4 to 7 and Comparative Example 5, it can be seen that the more the proportion of the introduced chain amide diamine is, the longer it is, the greater the polyhydroxyl ring closure rate is, the higher the ring closure dehydration rate is, and the heat shrinkage rate of the resin film is increased. At the same time, the proportion of aromatic rings is relatively reduced, the heat resistance is reduced, and the elongation at break is increased.

[0307] Furthermore, by comparing Example 1, Examples 8 to 10 and Comparative Example 6, it can be seen that the esterification agent in the system can increase the imidization rate, and the polyimide ring can increase the adhesion between the resin film and the metal.

[0308] In addition, by comparing Example 1 with Comparative Example 1, it can be seen that the photosensitivity of the resin film is reduced when F atoms are not introduced into the main chain structure, which indicates that the introduction of an appropriate amount of F atom structure into the copolymerization can form a certain steric hindrance, reduce the interaction between chain segments, and is beneficial to improving the imaging performance of the resin film.

[0309] From the comparison between Example 1 and Comparative Example 2, it can be seen that the photosensitivity decreases rapidly when no hydroxyl group is introduced into the main chain structure, indicating that the presence of hydroxyl group greatly promotes the dissolution of the pre-baked film into the developer. Secondly, when the structure does not contain hydroxyl group, the heat resistance and adhesion to metal of the resin film are both reduced. It is believed that the polybenzamide lacking ortho-hydroxyl group and amino group cannot be cyclized into polybenzoxazole when heated, and the hydroxyl group can increase the cross-linking effect between chain segments.

[0310] By comparing Example 1 and Comparative Example 3, it can be seen that without adding a diamine containing a fatty chain, the curing temperature of 210°C is not sufficient to completely imidize the resin film, and the overall performance such as residual film rate, thermodynamic properties, tensile properties and adhesion to metal are not good.

[0311] By comparing Example 1 and Comparative Example 4, it can be seen that the same molar amount of alkane diamine as that of Example 1 is copolymerized in Comparative Example 4. Although the elongation is slightly increased, due to the lack of heteroatoms (such as O, N, etc.), the intermolecular force and the force between the molecular chain and the metal are small, and the heat resistance and the adhesion to the metal are affected.

[0312] By comparing Example 1 and Comparative Example 7, it can be obtained that the introduction of unsaturated bond-type thermal crosslinking agent B2 containing alkoxy and vinyl groups can improve the degree of crosslinking, increase the heat resistance and flexibility of the resin film, and also inhibit the thermal shrinkage caused by closed-loop dehydration, thereby improving the adhesion to the substrate.

[0313] In summary, it can be seen from the above test results that the polyimide resin precursor composition provided by the present invention, which contains at least four components (A), (B1), (B2), and (C), has good coating and processability mainly through the control of components (A), (B1), and (B2), and the photosensitive polyimide resin film obtained by low-temperature curing thereof has good imaging performance. In addition, the introduction of heteroatoms with lone pairs of electrons (such as O, F, N, S), the combination of aromatic groups and fatty chain groups, and the addition of specific cross-linking agents make the resin film also have good heat resistance and tensile properties, small heat shrinkage, and good adhesion to metal substrates.

[0314] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A resin precursor composition, characterized in that The resin precursor composition comprises component A, component B1 and component B2; the total amount of component B1 and component B2 is 10-40wt% of component A, and the mass ratio of component B1 to component B2 is 40:1-10:1; component A comprises polyamic acid, polyamide ester, polyimide, polybenzoxazole, polyamide and polyhydroxyamide; Wherein, component A is a polymer comprising structures represented by formula (1) and formula (2); Formula (1) is Formula (2) is wherein X is selected from a tetracarboxylic acid residue containing 1 to 10 aromatic rings and containing one or more of O, S, N or F heteroatoms; Y1 is selected from a diamine residue containing 1 to 10 aromatic rings and containing one or more of O, S, N or F heteroatoms; R1, R2, R3 and R4 are independently selected from a hydrogen atom or an organic group having 1 to 20 carbon atoms; p is an integer of 1 to 10, m1 and m2 are integers of 3 to 10000, n1 and n2 are integers of 1 to 2000, and the ratio of m1+m2 to n1+n2 is between 3 and 10; In formula (1) and formula (2), Y2 is an amide fatty chain diamine residue selected from 5 to 15 carbon atoms, and its structure is shown in formula (3). The content of Y2 is 10% to 30% of the total molar amount of Y1 and Y2; Formula (3) is Indicates the connection location wherein R5 and R7 are independently selected from 1 to 6 methylene groups, R6 is independently selected from a fatty chain group having 0 to 8 carbon atoms and containing one or more heteroatoms of O, N or S, s is independently an integer of 0 to 4, and t is independently an integer of 0 to 3; Component B1 is an aromatic ester thermal crosslinking agent containing phenolic hydroxyl groups, and its structure is shown in formula (4); Formula (4) is wherein R8 is independently selected from an organic group containing 2 to 30 carbon atoms, R9 is independently selected from an organic group containing 1 to 10 carbon atoms, u is independently selected from an integer of 1 to 4, v is independently selected from an integer of 1 to 16, and u+v>2; Component B2 is an unsaturated bond type thermal crosslinking agent containing alkoxy and vinyl groups, and its structure is shown in formula (5); Formula (5) is Among them, R 10 They are independently selected from organic groups containing an alkoxy group and having 2 to 30 carbon atoms, and contain N or S heteroatoms, and w is independently selected from integers of 1 to 10.

2. A resin precursor composition according to claim 1, characterized in that: X is selected from one or more of the compound structures represented by the following formulas X-1 to X-14: In formula X-1 to formula X-14, the left and right ends Indicates the connection location.

3. A resin precursor composition according to claim 1, characterized in that: Y1-(OH) p One or more selected from the compounds represented by formula Y1-1 to formula Y1-12: In the above formula Y1-1 to formula Y1-12, the left and right ends Indicates the connection location.

4. A resin precursor composition according to claim 1, characterized in that: Y2 is selected from one or more residues of compounds represented by formula Y2-1 to formula Y2-16:

5. A resin precursor composition according to claim 1, characterized in that: B1 is selected from the structures shown in formula B1-1 to formula B1-8:

6. A resin precursor composition according to claim 1, characterized in that: B2 is selected from the structures shown in formula B2-1 to formula B2-8:

7. A resin precursor composition according to claim 1, characterized in that: The resin precursor composition further comprises component C, component D, component E, component F and component G; the amount of component C is 10-50wt% of component A, the amount of component D is 1-30wt% of component A, the amount of component E is 1-50wt% of component A, the amount of component F is 0.1-10wt% of component A, and the amount of component G is 100-2000wt% of component A; wherein, Component C is a photoacid generator, which includes at least one of a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt and an iodonium salt; Component D is a low molecular weight phenolic hydroxyl compound; Component E is a surfactant, including at least one of ethanol, isopropanol, acetone, cyclohexanone, ethyl lactate, and propylene glycol methyl ether acetate; Component F is a silane coupling agent, including at least one of trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxyepoxysilane, trimethoxyaminopropylsilane, trimethoxy-3-epoxypropylpropoxysilane, trimethoxy-3-aminopropylsilane, and triethoxy-3-aminopropylsilane; Component G is a high boiling point polar solvent.

8. A resin precursor composition according to claim 7, characterized in that: Component C is selected from one or more of the following structures: Wherein, Q is independently selected from or H, the curved line segment indicates the connection location; Component D is selected from one or more of the following structures: And, the high boiling point polar solvent includes N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tetrahydrofuran, dioxane, methyl ethyl ketone, acetone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone , diacetone alcohol, ethylene glycol methyl ether ethyl acetate, ethylene glycol ethyl ether ethyl acetate, diethylene glycol methyl ether ethyl acetate, diethylene glycol ethyl ether ethyl acetate, propylene glycol methyl ether ethyl acetate, propylene glycol ethyl ether ethyl acetate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, ethyl butyrate, n-propyl butyrate, n-butyl butyrate, methyl acetoacetate, ethyl acetoacetate or xylene.

9. A polyimide resin film, characterized in that: The invention comprises the resin precursor composition as claimed in claim 1.

10. Use of the polyimide resin film according to claim 9 in the semiconductor field.

11. The use according to claim 10, characterized in that: Also includes: The polyimide resin film is used in interlayer insulating films and surface protective films of semiconductor elements, and insulating layers and planarizing layers of organic electroluminescent display elements.

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