CN114836033B - Resin precursor composition, resin film thereof, preparation method and application - Google Patents

Resin precursor composition, resin film thereof, preparation method and application Download PDF

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CN114836033B
CN114836033B CN202210378725.9A CN202210378725A CN114836033B CN 114836033 B CN114836033 B CN 114836033B CN 202210378725 A CN202210378725 A CN 202210378725A CN 114836033 B CN114836033 B CN 114836033B
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component
precursor composition
resin precursor
composition according
ether
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CN114836033A (en
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王钊
王辉
李建行
贺金新
王华彬
李荣生
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Jilin Optical and Electronic Materials Co Ltd
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Jilin Optical and Electronic Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a resin precursor composition, a resin film thereof, a preparation method and application thereof, and belongs to the technical field of photoelectric materials. The composition comprises a component A and a component B 1 And component B 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the component A is a resin composition of polyamide acid or polyamide ester; component B 1 Is thatA cross-linking agent as shown; component B 2 Is thatThe cross-linking agent shown. The polyimide resin precursor composition can enable the polyimide resin film to have a thermal shrinkage rate of 25% or less, a thermal expansion coefficient of 45 or less, a glass transition temperature of 280 ℃ or more, and a thermal decomposition temperature T 1％ Above 320 ℃, T 5％ The tensile strength is higher than 150MPa, the Young modulus is higher than 3.4GPa, the elongation at break is higher than 10%, and the sensitivity value is 500mJ/cm 2 The resolution value is below 10 μm; so that the corresponding polyimide resin film has good thermal performance, mechanical performance and imaging performance.

Description

Resin precursor composition, resin film thereof, preparation method and application
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a resin precursor composition, a resin film thereof, a preparation method and application.
Background
Polyimide (PI) has been widely used as protective layer, insulating layer and packaging material in microelectronics because of its excellent thermal stability, size and chemical stability, while photosensitive polyimide (PSPI) has increased photosensitive characteristics on the basis of maintaining excellent PI properties, and can simplify photolithography process, becoming the subject of continuous development and research by people, and becoming the mainstream product in the photosensitive polyimide market.
With miniaturization, higher functionality and higher integration of electronic devices, performance requirements for microelectronic devices are increasing, and resins such as polyimide, polybenzoxazole, polybenzoxazine and polyamide have been found to be excellent in heat resistance, electrical insulation and the like, and photosensitive resin compositions containing such resins have been applied to insulating layers or planarizing layers of organic electroluminescent display devices.
The positive PSPI imaging has the advantages that the exposure area is dissolved by using an alkaline aqueous solution for development, the erosion of the organic developer to the non-exposure area is avoided, the pattern resolution is high, and the shrinkage rate of the film is small. And secondly, the alkaline aqueous solution developer has good environmental compatibility and is more environment-friendly. The image forming performance of the positive type PSPI resin film is related to the difference in the dissolution rate of the developer in the exposed region and the non-exposed region, and it is known and well-known that a diazonaphthoquinone composition is added to a polyamic acid, a diazonaphthoquinone composition is added to a hydroxyl group-containing polyamic acid, a carboxyl group in a polyamic acid is esterified to an ester group, a diazonaphthoquinone composition is added to a hydroxyl group-containing soluble polyimide, and the like.
The addition of diazonaphthoquinone composition or the introduction of ester group to polyamide acid can inhibit the solubility of polymer in exposed area to alkaline aqueous solution, but the inhibition effect is high, and in most cases, pattern with high resolution is not easy to obtain, and photosensitivity is lowered, so that in order to control the solubility of polymer in alkaline developer, phenolic hydroxyl compound is added to polyimide precursor composition, photosensitivity is improved, but there are also problems of large shrinkage rate of film after curing, heat resistance and mechanical property lowering, etc.
In view of this, the present application has been made.
Disclosure of Invention
It is an object of the present application to provide a resin precursor composition to overcome the above-mentioned problems.
The second object of the present application is to provide a method for producing the above resin precursor composition.
The third object of the present application is to provide a polyimide resin film produced from the above resin precursor composition.
The fourth object of the present application is to provide a method for producing the polyimide resin film.
The fifth object of the present application is to provide an application of the polyimide resin film.
The application can be realized as follows:
in a first aspect, the present application provides a resin precursor composition comprising component A, component B 1 And component B 2 ；
Wherein, the component A is a resin composition of polyamide acid or polyamide ester;
component B 1 A benzoxazine-based crosslinking agent represented by the formula (1);
component B 2 A benzoxazine-based crosslinking agent having a hydroxyl group or a carboxyl group represented by the formula (2);
formula (1) is
The structural formula (2) is
Wherein R in formula (1) 1 Independently selected from linear siloxane groups, R 2 Independently selected from hydrogen or cyano or vinyl or allyl or ethynyl; r in formula (2) 3 And R is 5 Independently selected from 1 to 6 aromatic or aliphatic rings and not forming a ring between adjacent rings, s and t are independently selected from integers of 0 to 2, s and t are not zero at the same time, and u and v are independently selected fromWherein u and v are not zero at the same time and o is independently selected from integers of 0 to 20; r is R 4 Independently selected from hydrogen or an organic group of 1 to 20C atoms.
In an alternative embodiment, component A is of the structure shown in formula (4);
the structural formula (4) is
Wherein R is 6 Selected from tetracarboxylic acid residues with 1-6 aromatic rings, R 7 Selected from diamine residues with 1-6 aromatic rings; r is R 8 、R 9 、R 11 And R is 12 Independently selected from hydrogen atoms or organic groups having 1 to 20 carbon atoms; r is R 10 An organic group selected from the group consisting of 1 to 20 Si-O units; w is an integer of 1-10, m is an integer of 5-1000, n is an integer of 1-200, and the ratio of m to n is between 5-30.
In a second aspect, the present application provides a method for preparing a resin precursor composition according to any one of the preceding embodiments, comprising the steps of: the components were mixed.
In a third aspect, the present application provides a polyimide resin film, the polyimide resin film comprising the resin precursor composition of any one of the foregoing embodiments as a raw material for its production.
In a fourth aspect, the present application provides a method for producing a polyimide resin film according to the foregoing embodiment, comprising the steps of: the pre-baked film made from the slurry of the resin precursor composition is subjected to exposure development, followed by heat treatment curing.
In a fifth aspect, the present application provides use of a polyimide resin film as in the foregoing embodiments in a surface protective film of a semiconductor or an interlayer insulating film on a semiconductor element circuit.
The beneficial effects of the application include:
the polyimide resin precursor composition of the application is added with the siloxane modified benzoxazine cross-linking agent with good heat resistance, no phenolic hydroxyl compound is added, and the benzoxazine compound undergoes ring opening addition reaction during high-temperature curingCrosslinking, without degassing caused by curing; secondly, the cross-linking agent with the benzoxazine structure is free from low-molecular compound residues after being solidified, and the shrinkage caused by heat is small, so that the generation of warping can be restrained; the original high heat resistance of the benzoxazine is reserved by the benzoxazine modified by the siloxane, the brittleness of the benzoxazine is improved, and the toughness of the polyimide resin film is improved; when acid groups (such as hydroxyl, carboxyl and the like) exist, the acid groups are introduced into benzoxazine molecules, so that H is provided for the system in the heating ring-opening addition process + As a catalyst, the ring-opening curing temperature is reduced, the crosslinking degree is increased, and the ring-opening crosslinking reaction is more complete; at the same time, the introduction of unsaturated substituents also increases the crosslink density.
The corresponding polyimide resin film has good thermal performance, mechanical performance, imaging performance and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The resin precursor composition, the resin film, the preparation method and the application thereof provided by the application are specifically described below.
The application provides a resin precursor composition, which comprises a component A and a component B 1 And component B 2 ；
Wherein, the component A is a resin composition of polyamide acid or polyamide ester;
component B 1 A benzoxazine-based crosslinking agent represented by the formula (1);
component B 2 A benzoxazine-based crosslinking agent having a hydroxyl group or a carboxyl group represented by the formula (2);
formula (1) is
The structural formula (2) is
Wherein R in formula (1) 1 Independently selected from linear siloxane groups, R 2 Independently selected from hydrogen or cyano or vinyl or allyl or ethynyl; r in formula (2) 3 And R is 5 Independently selected from 1-6 aromatic rings or aliphatic rings, wherein adjacent rings can not form a ring, s and t are independently selected from integers of 0-2, s and t are not zero at the same time, u and v are independently selected from integers of 0-3, u and v are not zero at the same time, and o is independently selected from integers of 0-20; r is R 4 Independently selected from hydrogen or an organic group of 1 to 20C atoms.
As for the component a, it has a structure represented by formula (4);
the structural formula (4) is
Wherein R is 6 Selected from tetracarboxylic acid residues with 1-6 aromatic rings, R 7 Selected from diamine residues with 1-6 aromatic rings; r is R 8 、R 9 、R 11 And R is 12 Independently selected from hydrogen atoms or organic groups having 1 to 20 carbon atoms; r is R 10 An organic group selected from the group consisting of 1 to 20 Si-O repeating units; w is an integer of 1-10, m is an integer of 5-1000, n is an integer of 1-200, and the ratio of m to n is between 5-30.
Referring to ground, R 6 May be selected from tetracarboxylic acid residues having 1, 2, 3, 4, 5 or 6 aromatic rings. R is R 6 May contain at least one of methyl, methylene, ether, phenolic hydroxyl, benzyl, carbonyl, amide, trifluoromethyl and sulfone groups.
In some alternative embodiments, R 6 Can be selected from the formula R 6 -1 to R 6 -15 shows the structure:
r is as described above 6 -1 to R 6 -15, left and right endsWhere represents the connection location.
In some preferred embodiments, R 6 May be selected from the following structures:
in the present application, R 7 May be selected from diamine residues with 1, 2, 3, 4, 5 or 6 aromatic rings.
In formula (4), R 7 -(OH) w Optionally containing a hydroxyl group, and possibly at least one of a methyl group, a methylene group, an ether group, a benzyl group, a carbonyl group, an amide group, a trifluoromethyl group, and a sulfone group. w may take the value of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
In some alternative embodiments, R 7 -(OH) w Can be selected from the formula R 7 -1 to R 7 -16:
r is as described above 7 -1 to R 7 -16, left and right endsThe position represents the connection position;
in some preferred embodiments, R 7 -(OH) w Can be selected from:
preferably, the structure of component A is preferably a group having an F atom. The polyimide resin film has a high electronegativity of the F atoms, and can be increased in light transmittance, and the presence of the F atoms can improve the hydrophobicity of the surface of the resin film to some extent.
In the present application, R 8 、R 9 、R 11 And R is 12 May be independently selected from hydrogen atoms or organic groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.
When R is 8 、R 9 、R 11 Or R is 12 When hydrogen, the corresponding functional group is carboxyl; when R is 8 、R 9 、R 11 Or R is 12 When alkyl, the corresponding functional group is an ester group, wherein the alkyl is preferably methyl, ethyl or isopropyl. I.e. R 8 、R 9 、R 11 Or R is 12 Preferably independently methyl, ethyl or isopropyl.
As the esterifying agent for esterifying carboxyl groups to ester groups in the present application, there are no particular restrictions, but N, N-dimethylformamide dimethyl acetal (DMFDMA), N-dimethylformamide diethyl acetal, N-dimethylformamide dipropylacetal, N-dimethylformamide diisobutyl acetal, N, at least one of N-diethylformamide dimethyl acetal, N-dipropylformamide dimethyl acetal, N-diisobutylformamide dimethyl acetal, N-dimethylacetamide diethyl acetal and N, N-dimethylformamide dibenzyl acetal.
In the present application, R 10 An organic group containing 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 si—o repeating units may be selected. Further, R 10 The composition also contains aliphatic groups.
In some alternative embodiments, R 10 Can be selected from the formula R 10 -1 to R 10 -8 in the structure shown inOne less:
r is as described above 10 -1 to R 10 In the 8-structure, the curved segments represent the connection locations.
In the formula (4) of the present application, m and n are molar amounts of the respective repeating units, that is, m corresponds to a structural unit entirely composed of an aromatic ring, and n corresponds to a structural unit having a certain aliphatic group.
The value of m may be, for example, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000, or any other integer in the range of 5 to 1000.
The value of n may be 1, 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 120, 150, 180, 200, or the like, or any other integer in the range of 1 to 200.
The ratio of m to n is between 5 and 30, and may be exemplified by 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, etc., or may be any other value between 5 and 30.
In an alternative embodiment, the total molar amount of ester groups/(R) in the repeating units of formula (4) 8 +R 9 +R 11 +R 12 ) The total molar amount may be 50% to 80%, for example, 50%, 55%, 60%, 65%, 70%, 75% or 80%, or any other value within the range of 50% to 80%.
It is emphasized that in the application, the introduction of the ester group reduces the proportion of carboxyl, and the dissolution rate of the polymer to the alkaline aqueous solution can be adjusted; meanwhile, the content of certain ester groups is controlled, so that the content of carboxylic acid in the polymer is higher if the content of ester groups is too low, the dissolution rate of an alkaline aqueous solution is too high, the resolution of the polyimide resin film is reduced, and the dissolution of the alkaline aqueous solution is not facilitated if the content of ester groups is too high, so that the photosensitivity of a polyimide resin film product is finally reduced.
The application controls the dissolution rate of the polymer in the alkaline aqueous solution by adjusting the proportion of the ester group in the polymer to replace the added phenolic hydroxyl compound, so as to avoid the problems of large shrinkage rate, heat resistance, mechanical property reduction and the like of the cured film caused by the phenolic hydroxyl compound.
Further, the two ends of the component A are also connected with end capping groups, namely, in the polymer formed by random arrangement of a plurality of repeating units, the end parts of the structural units at the two ends are capped by the end capping groups; by the end-capping treatment, the molecular weight of the polymer can be controlled, the stability of a polymer molecular chain can be improved, and the preservation safety of the photosensitive polyimide resin precursor can be enhanced.
By way of reference, in the present application, one or more of a monoamine compound, an acid anhydride and a monocarboxylic acid compound may be used as a capping agent for capping, preferably a monoamine compound.
In some alternative embodiments, the capping group formed with the monoamine compound as the capping agent may be selected from the following structures:
in the above structure, the curved line section indicates the connection position.
For reference, the content of the above-mentioned end-capping agent is not particularly limited, and in some embodiments, it may be 0.5 to 20wt%, such as 0.5wt%, 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, or 20wt%, etc., of the content of component a, and may be any other value in the range of 0.5 to 20 wt%. Preferably 0.8 to 15wt%, more preferably 1 to 10wt%.
In the present application, the solvent used for synthesizing the component a is not particularly limited, and may be any solvent capable of dissolving the starting diamines and acid dianhydrides, and is preferably a high-boiling polar aprotic organic solvent.
By way of reference, the above-mentioned high boiling polar aprotic organic solvents may include, for example, amide solvents, cyclic esters, carbonates, acetophenones, tetrahydrofuran, propylene glycol methyl ether acetate or dimethyl sulfoxide.
Wherein the amide solvent may include at least one of N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, N-dimethylformamide, N-dimethylacetamide and N, N-dimethylisobutyramide. The cyclic ester solvent may include at least one of gamma-butyrolactone, gamma-valerolactone, gamma-caprolactone, delta-valerolactone, and alpha-methyl-gamma-butyrolactone. The carbonate-based solvent may include at least one of ethylene carbonate and propylene carbonate.
As component B 1 In the formula (1), R is 1 Selected from structures represented by formula (3);
the structural formula (3) is
Wherein p is independently selected from integers from 1 to 10 and q is independently selected from integers from 1 to 6.
By way of reference, p may take the value 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.q may take the value of 1, 2, 3, 4, 5 or 6.
In some alternative embodiments, component B 1 Selected from B 1 -1 to B 1 -20 at least one of the structures shown:
in some preferred embodiments, component B 1 At least one selected from the following structures:
the thermal crosslinking agent component B 1 Is modified by flexible long chain of siloxaneThe benzoxazine compound is subjected to ring-opening addition reaction to crosslink when cured at high temperature, so that degassing caused by curing is not generated, shrinkage caused by heat of the benzoxazine structural crosslinking agent is small, and warping can be restrained; secondly, the benzoxazine modified by the siloxane keeps the original high heat resistance and increases the toughness of the polyimide resin film.
In the present application, R in formula (2) 3 And R is 5 Independently selected from 1, 2, 3, 4, 5 or 6 aromatic or aliphatic rings and not ring-forming between adjacent rings. R is R 3 And R is 5 May be the same or different.
s and t are independently selected from 0, 1 or 2, and s and t are not zero at the same time.
u, v are independently selected from 0, 1, 2 or 3, u and v are not zero at the same time.
o may have a value of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.
R 4 May be independently selected from hydrogen or an organic group of 1 to 20C atoms. Wherein the number of C atoms may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.
In some alternative embodiments, component B 2 Can be selected from formula B 2 -1 to B 2 -16 at least one of the structures shown in:
/>
in some preferred embodiments, component B 2 At least one selected from the following structures:
the thermal cross-linking agent component B2 is a benzoxazine cross-linking agent with hydroxyl or carboxyl groups, and when an acid group is introduced into a benzoxazine compound molecule, the curing temperature of the benzoxazine during ring opening can be reduced, so that the cross-linking temperature is less than 300 ℃. Meanwhile, the cured film participates in the crosslinking reaction after curing, small molecular groups cannot be remained, and compared with phenolic hydroxyl compounds, the shrinkage rate of the cured film can be reduced.
The total amount of the above-mentioned component B1 and component B2 may be 10 to 50% by weight, such as 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight or 50% by weight, etc., of the component A, and may be any other value within the range of 10 to 50% by weight.
In some preferred embodiments, the total amount of component B1 and component B2 is 12 to 40wt%, more preferably 15 to 30wt% of component A.
Preferably, the mass ratio of the component B1 to the component B2 may be 40:1 to 2:1, such as 40:1, 35:1, 30:1, 25:1, 20:1, 15:1, 10:1, 8:1, 5:1 or 2:1, and the like, and may be any other value within the range of 40:1 to 2:1. Preferably, the mass ratio of the component B1 to the component B2 is 35:1-3.5:1, more preferably 30:1-3:1.
Illustratively, taking single-molecule thermal crosslinking agents B1-8 and B2-2 as examples, the addition crosslinking reaction process is as follows:
wherein the wavy line->The position is the connection position between molecules, and can be connected with B 1 -8, or may be linked to B 2 -2.
The addition crosslinking reaction of the remaining crosslinking agent is the same and is not described herein.
On the other hand, the polyimide resin precursor composition of the application is added with the siloxane modified benzoxazine cross-linking agent with good heat resistance, no phenolic hydroxyl compound is added, and during high-temperature curing, the benzoxazine compound carries out ring-opening addition reaction to crosslink, so that degassing caused by curing is not generated; secondly, the cross-linking agent with the benzoxazine structure is free from low-molecular compound residues after being solidified, and the shrinkage caused by heat is small, so that the generation of warping can be restrained; the original high heat resistance of the benzoxazine is reserved by the benzoxazine modified by the siloxane, the brittleness of the benzoxazine is improved, and the toughness of the polyimide resin film is improved; when acid groups (such as hydroxyl, carboxyl and the like) exist, the acid groups are introduced into benzoxazine molecules, so that H is provided for the system in the heating ring-opening addition process + As a catalyst, the ring-opening curing temperature is reduced, the crosslinking degree is increased, and the ring-opening crosslinking reaction is more complete; at the same time, the introduction of unsaturated substituents also increases the crosslink density.
According to the above-mentioned crosslinking process, first, the benzoxazine molecule undergoes ring-opening addition only under heating, and is crosslinked and cured. Second, compared to other added small molecular phenolic hydroxyl compounds, benzoxazine molecules do not generate small molecular compounds during the ring opening process, so that the volume shrinkage before and after curing is almost zero. Thirdly, from the viewpoint of the benzoxazine structure after molecular solidification, a large number of hydroxyl groups are contained in the structure, so that a large number of hydrogen bonds are formed in the molecule and among the molecules, the hydrogen bonds can inhibit the interaction between the compound and water molecules, the water absorption rate of the material is reduced, and the material has certain low dielectric property. Fourth, the bond length of Si-O bond is longer, bond energy is higher, and the siloxane chain has good flexibility, and the benzoxazine material modified by the siloxane chain can not only improve the toughness, but also can not lose the thermodynamic property of the material.
Further, the resin precursor composition provided by the application can further comprise a component C, wherein the component C is a photosensitizer.
Component C may be a photoacid generator and may include, by way of example and not limitation, at least one of a quinone diazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, and an iodonium salt.
More preferably, the photoacid generator is a quinone diazide compound-containing photoacid generator; further preferred are ester compounds formed by bonding polyhydroxy compounds with sulfonic acids of diazidoquinones to further facilitate long-term reliability of organic light emitting devices.
In some alternative embodiments, component C may be selected from at least one of the following structures:
wherein Q is independently selected fromOr H, the curved segment indicates the connection location.
For reference, the component C may be used in an amount of 10 to 50wt%, such as 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% or 50wt%, etc., of the component A, or may be any other value in the range of 10 to 50wt%, preferably 20 to 40wt%.
Further, the resin precursor composition may contain additives other than the above-mentioned components, for example, it may further include a component D, which is a surfactant. By adding the surfactant, wettability and adhesiveness to the substrate can be improved.
For reference, the surfactant may include at least one of ethanol, isopropanol, acetone, cyclohexanone, ethyl lactate, propylene glycol methyl ether acetate, by way of example and not limitation.
For reference, component D may be used in an amount of 10 to 70wt%, such as 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt% or 70wt%, etc. of component A, or any other value in the range of 10 to 70wt%, preferably 20 to 60wt%.
In addition, the resin precursor composition may further include a component E, which is a solvent, which may improve the coatability of the slurry.
In the present application, component E is preferably a high boiling point polar solvent and may include, by way of example and not limitation, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, gamma-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 acetate, diethylene glycol methyl ether ethyl acetate, diethylene glycol ethyl ether acetate, propylene glycol methyl ether ethyl acetate, propylene glycol ethyl ether acetate, ethyl ether lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, methyl 3-hydroxy-3-methyl butyrate, 3-methoxybutyl acetate, and at least one of toluene-3-methoxybutyl acetate.
For reference, the amount of component E is not particularly limited, and the composition may be dissolved to form a slurry.
In some embodiments, component E may be used in an amount of 1-15 times, such as 1-2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times, or 15 times, etc., as well as any other value in the range of 1-15 times, as compared to component A. Preferably, component E is used in an amount of 1.2 to 12 times, more preferably 1.3 to 10 times that of component A.
Correspondingly, the application also provides a preparation method of the resin precursor composition, which comprises the following steps: the components were mixed.
For reference, component A may be mixed with component E first,then with component B 1 Component B 2 And component C, and then with component D.
Specifically, reference may be made exemplarily to:
s1, synthesizing a component A: firstly, respectively adding raw materials diamine and acid dianhydride into a solvent (preferably a high-boiling-point polar aprotic organic solvent), stirring and reacting for 1-8 hours at the temperature of 0-80 ℃, then adding a blocking agent, stirring and reacting for 1-3 hours to form a polymer with target molecular weight, then adding an esterifying agent, stirring and reacting for 10 min-5 hours, finally adding the obtained solution into water, precipitating solids, and drying to obtain the target polymer (component A).
In the present application, the weight average molecular weight of the polymer (a) is preferably 5000 to 200000, more preferably 6000 to 150000, even more preferably 8000 to 100000, from the viewpoint of dissolution uniformity.
S2, preparing resin composition slurry: the resulting target polymer (component A) is first added to a solvent (component E, preferably a high boiling polar solvent) and stirred until complete dissolution, to give a solution, and the thermal crosslinking agent (component B) 1 ) And (component B) 2 ) Adding the photosensitizer (component C) into the solution, stirring until the photosensitizer is completely dissolved, and adding the surfactant (component D) into the solution; depending on the requirements of other performance indexes, other additives can be added, and finally, the slurry, namely the resin composition, is obtained.
The solid content in the resin precursor composition is preferably 5 to 50% by weight, more preferably 6 to 40% by weight, and even more preferably 7 to 30% by weight, from the viewpoint of the stability of the slurry. From the viewpoint of coating properties, the viscosity of the resin precursor composition is preferably 0.1 to 10000cp, more preferably 0.5 to 8000cp, and even more preferably 1 to 6000cp.
In addition, the application also provides a polyimide resin film, and the preparation raw material of the polyimide resin film contains the resin precursor composition.
The polyimide resin film has good heat resistance, mechanical properties and imaging properties, and, after curing, the film has a small shrinkage.
Preferably, the polyimide resin provided by the applicationThe film has a heat shrinkage rate of 25% or less and a low heat shrinkage; the thermal expansion coefficient is below 45, which is beneficial to reducing interface stress; the glass transition temperature is above 280 ℃, and the glass transition temperature shows good thermal performance and high crosslinking degree; thermal decomposition temperature T 1％ Above 320 ℃, T 5％ Exhibits excellent thermodynamic properties above 370 ℃; the tensile strength is higher than 150MPa, the Young modulus is higher than 3.4GPa, the elongation at break is higher than 10%, and the excellent tensile property is shown; the sensitivity value is 500mJ/cm 2 Hereinafter, the resolution value is 10 μm or less, and excellent imaging performance is exhibited.
Correspondingly, the application provides a preparation method of the polyimide resin film, which comprises the following steps: the pre-baked film made from the slurry of the resin precursor composition is subjected to exposure development, followed by heat treatment curing.
Wherein, the pre-baking film is obtained by coating slurry of a resin precursor composition on a substrate and pre-baking.
By way of example, but not limitation, the substrate may include a silicon wafer, ceramic, glass, quartz, or ITO.
The coating method includes a slit coating method, a spin coating method, a dip coating method, a spray coating method, or a printing method.
The pre-drying temperature may be 50 to 150 ℃, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, or the like, or any other value within the range of 50 to 150 ℃, preferably 80 to 150 ℃. The pre-drying time can be 1min-1h, such as 1min, 2min, 5min, 10min, 20min, 30min, 40min, 50min or 1h, or any other value within 1min-1 h. The pre-drying can be performed by a heating plate, an oven or an infrared method.
The film thickness of the pre-baked film varies depending on the solid content and viscosity in the resin composition. In some embodiments, the thickness of the pre-baked film may be 0.1 to 10 μm, such as 0.1 μm, 0.2 μm, 0.5 μm, 1 μm, 2 μm, 5 μm, 8 μm, or 10 μm, etc., but may be any other value in the range of 0.1 to 10 μm, preferably 0.3 to 8 μm.
The method of exposure and development in the present application is not particularly limited, and may be carried out according to a conventional exposure and development method for a photosensitive resin film in the art. The photosensitive resin slurry provided by the application is a positive photosensitive compound, light rays are used for exposing the photosensitive compound through a mask plate with a specific pattern, and the exposed part is removed through a developing solution, so that the resin pre-baking film with the required pattern is obtained.
By reference, the light rays used for exposure may include ultraviolet rays, visible rays, electron beams, X-rays, or the like, and an i-line (365 nm), an h-line (405 nm), or a g-line (436 nm) of a mercury lamp is preferably used.
The developing solution 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 developer has the advantages of being environment-friendly and suitable for industrial application.
The temperature of the heat treatment may be 100 to 350 ℃, such as 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, or the like, or any other value within the range of 100 to 350 ℃. In some preferred embodiments, the heat treatment is performed at a temperature of 120 to 300 ℃, more preferably 200 to 300 ℃, and at 200 to 300 ℃ can reduce the gas exhausted from the resin film after the heat treatment and improve the light transmittance and toughness of the resin film. The heat treatment time is not less than 30 mm, such as 30min, 40min, 50min, 60min, 100min or 150 min. The heating rate of the heat treatment may be 2 to 10 ℃ per minute, such as 2 ℃ per minute, 3 ℃ per minute, 4 ℃ per minute, 5 ℃ per minute, 6 ℃ per minute, 7 ℃ per minute, 8 ℃ per minute, 9 ℃ per minute or 10 ℃ per minute, etc., or any other value within the range of 2 to 10 ℃ per minute. The heat treatment curing method may be a heating plate, an oven or infrared rays, or a combination of various methods may be used.
In some specific embodiments, the temperature may be raised to 300 ℃ at 2.5 ℃/min, and the heat treatment is maintained for 1 hour.
In addition, the application also provides application of the polyimide resin film in a surface protection film (comprising a passivation film) of a semiconductor or an interlayer insulating film on a semiconductor element circuit.
Preferably, the polyimide resin film described above may be used to prepare an insulating layer or a planarization layer in an organic electroluminescent display device.
The features and capabilities of the present application are described in further detail below in connection with the examples.
In the following examples and comparative examples, the evaluation methods were as follows:
1. film thickness test:
the thicknesses of the photosensitive polyimide resin film and the pre-baked film were measured using a film thickness meter (field emission scanning electron microscope EX-30).
2. Measurement of shrinkage:
the pre-baked film was put into an anaerobic clean oven (chinese gurnies GN120 XF), heated to 300 ℃ at a heating rate of 2.5 ℃/min under a nitrogen flow (oxygen concentration is less than 20 ppm), and heat-treated at 300 ℃ for 1 hour to prepare a cured film. And measuring the film thickness of the pre-baked film and the film thickness of the cured film after heat treatment respectively by using a film thickness meter. The calculation formula for shrinkage can be expressed as: shrinkage (%) = (pre-baked film thickness-cured film thickness)/(pre-baked film thickness×100). The measured shrinkage (%) was regarded as not good at 25 or more, as good at 20 to 25, and as better at 20 or less.
3. Determination of Coefficient of Thermal Expansion (CTE) and glass transition temperature (Tg):
a polyimide resin film sample 10 μm thick was prepared, and a rectangle of 13mm×4mm was fabricated, and a thermal mechanical expansion analyzer (TMA 4000, perkin Elmer) was used to test the sample at a jig pitch of 10mm, the first stage was heated to 150 ℃ at a heating rate of 10 ℃/min, held for 30min, the second stage was cooled to 25 ℃ at a heating rate of 5 ℃/min, and the third stage was heated from 25 ℃ to 350 ℃ at a heating rate of 5 ℃/min, and then naturally cooled to room temperature, whereby a displacement-dependent temperature change curve was obtained, and the Coefficient of Thermal Expansion (CTE) and glass transition temperature (Tg) of the sample were analyzed from the curve. A value of the linear thermal expansion coefficient measured at 45 ppm/DEG C or more is regarded as poor, a value in the range of 35 to 45 ppm/DEG C is regarded as good, and a value of 35 ppm/DEG C or less is regarded as more good. The glass transition temperature Tg represents the molecular chain segment movement performance, and the larger the Tg value is, the smaller the molecular chain segment movement is, which means that the better the crosslinking degree is, and on the contrary, the poor the crosslinking degree is. The measured glass transition temperature Tg values were considered to be poor below 280℃and values were considered to be good in the range of 280℃to 300℃and values above 300℃were considered to be better.
4. Measurement of thermal decomposition temperature (T) 1％ 、T 5％ )：
A 10mg polyimide resin film sample was prepared, and the sample piece was heated from 50 to 700 ℃ at a heating rate of 10 ℃/min in the first stage to 150 ℃ for 30min, cooled to 50 ℃ in the second stage, and heated from 50 to 700 ℃ at a heating rate of 10 ℃/min in the third stage using a thermogravimetric analyzer (germany anti-TG 209F 1) under a nitrogen flow. From the measured weight-temperature curves, the temperatures corresponding to the 1% and 5% weight losses were determined as the respective thermal decomposition temperatures. The measured thermal decomposition temperature T 1％ Values below 320℃are considered to be poor, values in the range 320℃to 330℃are considered to be good, and values above 330℃are considered to be better. Likewise, the measured thermal decomposition temperature T 5％ Values below 370 ℃ are considered to be poor, values in the range of 370 ℃ to 390 ℃ are considered to be good, and values above 390 ℃ are considered to be even better.
5. Film tensile properties determination:
a10 μm thick polyimide resin film sample was prepared, a rectangular film having a size of 80mm X10 mm was produced, the film sample was stretched with a tensile tester (RTH-20-RACK 1310, japan) at a clamp pitch of 50mm, a stress-strain curve was obtained by stretching, and three tensile property indexes of tensile strength, tensile modulus and elongation at break were obtained. Values of measured tensile strength below 150MPa are considered to be poor, values in the range of 150MPa to 170MPa are considered to be good, and values above 170MPa are considered to be better. Values of the tensile modulus measured below 3.3GPa are considered to be poor, values in the range of 3.3GPa to 3.8GPa are considered to be good, and values above 3.8GPa are considered to be even better. Values below 10% are considered to be poor, values in the range of 10% to 12% are considered to be good, and values above 12% are considered to be better.
6. Determination of resolution:
a mask plate with a specific pattern is arranged on an i line of an exposure machine (SMA-150 GA-TR) at the speed of 800mJ/cm 2 Exposure is performed by the exposure amount of (2). After exposure, use ofDeveloping equipment (AD-1200 MIKASA), developing with 2.38% tetramethyl ammonium hydroxide aqueous solution, repeating for two times, cleaning with purified water, and blow drying to obtain resin pre-baked film with positive pattern. The pattern on the polyimide film was observed with an optical microscope, and the minimum size of the resolvable line and gap was taken as the resolution. Measured resolution values above 10 μm are considered to be poor, values in the range 5-10 μm are considered to be good, and values below 5 μm are considered to be better.
Preparation example 1 of aromatic ring tetracarboxylic dianhydride raw material: synthesis examples 1(1) to 1(2).
Synthesis example 1(1): synthetic (R) 6 -10)：
23.22g (0.1 mol) of 3,3 '-diamino-4, 4' -dihydroxydiphenyl ether, 57.07g (0.5 mol) of allyl glycidyl ether and 300g of N-methyl pyrrolidone (NMP) are added into a 1L three-mouth bottle at normal temperature, nitrogen is replaced, stirring is started to completely dissolve the mixture, the temperature is reduced to minus 15 ℃, then 46.33g (0.22 mol) of NMP (100 g) solution of 1, 2.4-trimellitic anhydride acyl chloride is slowly added into a reaction bottle, after the dripping is finished, the reaction is carried out for 4 hours at minus 15 ℃, and then the temperature is naturally raised to room temperature. The next day, the reaction solution was concentrated until no liquid flowed out, 1.6L of absolute ethanol was added thereto, stirred for 2 hours, and a white solid was obtained by filtration, thereby obtaining aromatic tetracarboxylic dianhydride (R 6 -10)。
Synthesis example 1(2): synthetic (R) 6 -11)：
At normal temperature, 36.63g (0.1 mol) of 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 57.07g (0.5 mol) 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 dissolve completely, the temperature was lowered to-15℃and then 46.33g (0) of 1,2, 4-trimellitic anhydride acid chloride was slowly added dropwise to the flask22 mol) of NMP (100 g) was left to react at-15℃for 6h after the addition, and then warmed to room temperature naturally. The next day, the reaction solution was concentrated until no liquid flowed out, 2L of absolute ethanol was added thereto, stirred for 2 hours, and a white solid was obtained by filtration to obtain aromatic tetracarboxylic dianhydride (R) 6 -11)。
Preparation example 2 of hydroxyl-containing aromatic diamine raw material: synthesis examples 2(1) to 2(5).
Synthesis example 2(1): synthetic (R) 7 -11a)：
Step S1:
22g (0.06 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 20.91g (0.36 mol) of propylene oxide and 120ml of acetone were charged into a 1L three-port reaction flask at room temperature, stirred at room temperature until completely dissolved, and the reaction system was cooled to-15 ℃. Then, a solution of m-nitrobenzoyl chloride (24.49 g, 0.132 mol) in acetone (120 ml) was slowly added dropwise thereto, and after completion of the dropwise addition, the reaction was continued at-15℃for 5 hours, and then naturally warmed to room temperature. The resulting reaction solution was filtered under reduced pressure to give an off-white solid, which was dried in a vacuum oven at 60℃for 20 hours (27.91 g, yield 70%).
Step S2:
19.93g (0.03 mol) of the off-white solid obtained above, 2.58g of 5% palladium on carbon and 170ml of ethylene glycol methyl ether were charged into a 500ml autoclave, and hydrogen was replaced and the autoclave was pressurized with hydrogen to bring the internal pressure of the autoclave to 10kgf/cm 2 Heating to 35 ℃, and stirring 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. Adding ethanol and petroleum ether into the solution, stirring for 12h to separate out solid, filtering under reduced pressure to obtain white solid, and drying the solid in a vacuum oven at 50 ℃ for 20h to obtain 2, 2-bis (3- (3-amino) benzamido-4-hydroxyphenyl) hexafluoropropaneR 7 11 a) (9.97 g, 55% yield).
Synthesis example 2(2): synthetic (R) 7 -11b)：
Step S1:
22g (0.06 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 20.91g (0.36 mol) of propylene oxide and 120ml of acetone were charged into a 1L three-port reaction flask at room temperature, stirred at room temperature until completely dissolved, and the reaction system was cooled to-15 ℃. Then, a solution of 24.49g (0.132 mol) of p-nitrobenzoyl chloride in 120ml of acetone was slowly added dropwise thereto, and after completion of the dropwise addition, the reaction was continued for 5 hours at-15℃and then naturally warmed to room temperature. The resulting reaction solution was filtered under reduced pressure to give an off-white solid, which was dried in a vacuum oven at 60℃for 20 hours (29.9 g, yield 75%).
Step S2:
the off-white solid obtained above, 20g (0.03 mol), 2.58g of 5% palladium on carbon and 170ml of ethylene glycol methyl ether, were charged into a 500ml autoclave, and hydrogen was replaced and the autoclave was pressurized with hydrogen to bring the internal pressure of the autoclave to 10kgf/cm 2 Heating to 35 ℃, and stirring 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. Adding ethanol and petroleum ether into the solution, stirring for 12h to separate out solid, filtering under reduced pressure to obtain white solid, and drying the solid in a vacuum oven at 50deg.C for 20h to obtain N, N-bis (4-amino-2-hydroxyphenyl) terephthalamide (R) 7 11 b) (10.5 g, 57% yield).
Synthesis example 2(3): synthetic (R) 7 -15)：
Step S1:
15.4g (0.1 mol) of 2-amino-5-nitrophenol, 20.91g (0.36 mol) of propylene oxide and 120ml of acetone are added into a 1L three-port reaction flask at normal temperature, stirred at normal temperature until the mixture is completely dissolved, and the reaction system is cooled to-15 ℃. Then, a solution of terephthaloyl chloride 12.19g (0.06 mol) in acetone 120ml was slowly dropped thereinto, and after the completion of the dropping, the reaction was continued for 5 hours at-15℃and then naturally warmed to room temperature. The resulting reaction solution was filtered under reduced pressure to give an off-white solid, which was dried in a vacuum oven at 60℃for 20 hours (33.3 g, yield 76%).
Step S2:
13.15g (0.03 mol) of the off-white solid obtained above, 2.58g of 5% palladium on carbon and 170ml of ethylene glycol methyl ether were charged into a 500ml autoclave, and hydrogen was replaced, and the autoclave was pressurized with hydrogen to an internal pressure of 10kgf/cm2, heated to 35℃and stirred for 2 hours. After the reaction was completed, the pressure was slowly released, and the reaction solution was filtered under reduced pressure to obtain a transparent solution. Adding ethanol and petroleum ether into the solution, stirring for 12h to separate out solid, filtering under reduced pressure to obtain white solid, and drying the solid in a vacuum oven at 50deg.C for 20h to obtain N, N-bis (4-amino-2-hydroxyphenyl) terephthalamide (R) 7 -15) (6.81 g, 60% yield).
Synthesis example 2(4): synthesis of hydroxy-containing aromatic diamine (R) 7 -11c)：
The synthesis procedure was the same as that of Synthesis example 2(1, except that 22g (0.06 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as a synthesis raw material was changed to 20.06g (0.06 mol) of 2, 2-bis (3-aminophenyl) hexafluoropropane, to finally obtain a hydroxyl group-containing aromatic diamine (R 7 11 c) (9 g, 53% yield).
Synthesis example 2(5): synthesis of hydroxy-containing aromatic diamine (R) 7 -10a)：
The synthesis procedure was the same as that of Synthesis example 2(1, except that 22g (0.06 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as a synthesis raw material was changed to 13.93g (0.06 mol) of 2, 2-bis (3-amino-4-hydroxy) diphenyl ether, to finally obtain a hydroxyl-containing aromatic diamine (R 7 11 c) (8.9 g, 54% yield).
Thermal crosslinker raw material preparation example 3: synthesis examples 3(1) to 3(8).
Synthesis example 3(1): synthetic (B) 1 -2)：
Under the protection of normal temperature nitrogen, adding 37% formaldehyde (0.1 mol) aqueous solution (8.12 g) into a 1L three-port reaction bottle, adding 200ml toluene, placing the three-port bottle into an ice-water bath, starting stirring for 30min to ensure constant temperature in the bottle, slowly dripping 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane (0.025 mol,6.21 g) toluene (80 ml) into the bottle by using a constant pressure dropping funnel, controlling the temperature of the system below 10 ℃, stirring for 20min after the dripping is finished, and finally adding phenol (0.05 mol,4.71 g) into the reaction bottle, heating to reflux, and keeping reflux for 24h.
After the reaction, the reaction solution was evaporated to dryness by using a rotary evaporator, then dissolved in 500ml of diethyl ether, washed with deionized water until the organic phase became colorless, dried over anhydrous sodium sulfate, and then subjected to rotary evaporation until it was completely dried to obtain a pale brown viscous liquid as a thermal crosslinking agent (B) 1 -2) (9.09 g, 75% yield).
Synthesis example 3(2): synthetic (B) 1 -4)：
Under the protection of normal temperature nitrogen, adding 37% formaldehyde (0.1 mol) aqueous solution (8.12 g) into a 1L three-port reaction bottle, adding 200ml toluene, placing the three-port bottle into an ice-water bath, starting stirring for 30min to ensure constant temperature in the bottle, slowly dripping 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane (0.025 mol,6.21 g) toluene (80 ml) into the bottle by using a constant pressure dropping funnel, controlling the temperature of the system to be below 10 ℃, stirring for 20min after the dripping is finished, and finally adding p-cyano phenol (CAS: 767-00-0) (0.05 mol,5.96 g) into the reaction bottle, heating to reflux, and keeping reflux for 24h.
After the reaction, the reaction solution was evaporated to dryness by using a rotary evaporator, then dissolved in 500ml of diethyl ether, washed with deionized water until the organic phase became colorless, dried over anhydrous sodium sulfate, and then subjected to rotary evaporation until it was completely dried to obtain a pale brown viscous liquid as a thermal crosslinking agent (B) 1 -4) (9.76 g, 73% yield).
Synthesis example 3(3): synthetic (B) 1 -6)：
The synthesis procedure was the same as in Synthesis example 3(2) except that the starting p-cyanophenol was changed to 4-vinylphenol (CAS: 2628-17-3) (0.05 mol,6.01 g) to give a pale brown viscous liquid as a thermal crosslinking agent (B) 1 -6) (9.40 g, yield 70%).
Synthesis example 3(4): synthetic formula (B1-8):
the synthesis procedure was the same as in Synthesis example 3(2) except that the starting p-cyanophenol was changed to 4-ethynylphenol (CAS: 2200-91-1) (0.05 mol,5.91 g) to give a pale brown viscous liquid as a thermal crosslinking agent (B) 1 -8) (8.92 g, 67% yield).
Synthesis example 3(5): synthetic formula (B1-10):
the synthesis procedure was the same as in Synthesis example 3(2) except that the starting p-cyanophenol was changed to 4-ethynylphenol (CAS: 501-92-8) (0.05 mol,6.71 g) to give a pale brown viscous liquid as a thermal crosslinking agent (B) 1 -8) (10.03 g, 71% yield).
Synthesis example 3(6): synthetic formula (B2-1):
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under the protection of normal temperature nitrogen, adding 37% formaldehyde (0.1 mol) aqueous solution (8.12 g) into a 1L three-port reaction bottle, adding 200ml toluene, placing the three-port bottle into an ice-water bath, starting stirring for 30min to ensure constant temperature in the bottle, slowly dripping toluene (80 ml) solution of 4- (aminomethyl) benzoic acid (0.05 mol,7.56 g) into the bottle by using a constant pressure dropping funnel, controlling the temperature of the system to be lower than 10 ℃, stirring for 20min after the dripping, finally adding phenol (0.05 mol,4.71 g) into the reaction bottle, heating to reflux, and keeping reflux for 24h.
After the reaction, evaporating the reaction solution to dryness by using a rotary evaporator, adding 500ml of diethyl ether for dissolution, washing with deionized water until the organic phase is colorless, drying the organic phase with anhydrous sodium sulfate, performing rotary evaporation, screwing until the organic phase is completely dried to obtain a white solid, and drying the solid in a vacuum oven at 60 ℃ for 20 hours to obtain a thermal cross-linking agent (B) 2 -1) (10.23 g, 76% yield).
Synthesis example 3(7): synthetic (B) 2 -2)：
Under the protection of normal temperature nitrogen, adding 37% formaldehyde (0.1 mol) aqueous solution (8.12 g) into a 1L three-port reaction bottle, adding 200ml toluene, placing the three-port bottle into an ice-water bath, starting stirring for 30min to ensure constant temperature in the bottle, slowly dripping 4- (aminomethyl) phenol (0.05 mol,6.16 g) toluene (80 ml) solution into the bottle by using a constant-pressure dropping funnel, controlling the temperature of the system below 10 ℃, stirring for 20min after the dripping, finally adding phenol (0.05 mol,4.71 g) into the reaction bottle, heating to reflux, and keeping reflux for 24h.
After the reaction, evaporating the reaction solution to dryness by using a rotary evaporator, adding 500ml of diethyl ether for dissolution, washing with deionized water until the organic phase is colorless, drying the organic phase with anhydrous sodium sulfate, performing rotary evaporation, screwing until the organic phase is completely dried to obtain a white solid, and drying the solid in a vacuum oven at 60 ℃ for 20 hours to obtain a thermal cross-linking agent (B) 2 -2) (9.41 g, 78% yield).
Synthesis example 3(8): synthetic crosslinker B3-1:
step S1:
200g of aqueous pure water solution of sodium hydroxide (20 g,0.5 mol) was added to a 2L three-necked flask at room temperature (25 ℃ C.), and the mixture was stirred slowly, and 1, 1-tris (4-hydroxyphenyl) ethane (30.64 g,0.1 mol) was then added slowly, and stirred to dissolve completely, and then 37% aqueous formaldehyde solution (175 g) was added dropwise to the flask at an acceleration of 1 drop/2 s, and stirred at 25 ℃ C. For 22 hours after completion of the dropwise addition. The next day, 15% dilute sulfuric acid aqueous solution (162 g) was slowly added dropwise thereto at room temperature, stirring was maintained for 36 hours after the completion of the addition, white solid was precipitated, filtered, and washed with 300ml of purified water to obtain a white solid, and the product was dried in a vacuum drying oven at 50℃for 48 hours.
Step S2:
the white solid obtained above was dissolved in 100mL of ethanol at room temperature, and 0.5g of concentrated sulfuric acid was slowly added dropwise thereto, followed by stirring for 24 hours. Then, 5g of anion exchange resin was added to the solution, stirred for 2 hours, and a clear filtrate was obtained by filtration, the filtrate was concentrated until no liquid was eluted, 150mL of ethyl lactate was added, and stirred So that it is completely and uniformly dissolved. The solution is stirred at room temperature for 36 hours, white crystals are precipitated, the solid is obtained by filtration, and the thermal cross-linking agent 1, 1-tris (4-hydroxy-2, 5-di (ethoxymethylphenyl)) ethane (B) is obtained after drying for 24 hours by a vacuum drying oven at 50 DEG C 3 -1)。
Photosensitizer preparation example 4: synthesis examples 4(1) to 4(2).
Synthesis example 4(1): synthesis of quinone diazide C-1:
15.32g (0.05 mol) of 1, 1-tris (4-hydroxyphenyl) ethane, 37.61g (0.14 mol) of 5-naphthoquinone azide sulfonyl chloride and 450g of 1, 4-dioxane were added to a 1L reaction flask at room temperature, and stirring was started to replace nitrogen gas and stirred until complete dissolution. A mixture of triethylamine (14.19 g,0.14 mol) and 1, 4-dioxane (45 g) was slowly added dropwise thereto. After the dripping is finished, the temperature is raised to 35 ℃ and the reaction is carried out for 4 hours. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, the filtrate was dropped into 3L of water, and the precipitated solid was collected by filtration. And finally, repeatedly washing the precipitate with 10L of purified water for 2 times, and drying the precipitate in a vacuum drying oven at 50 ℃ for 24 hours to obtain the naphthoquinone diazide compound C-1 in the formula.
Wherein Q is 1 、Q 2 、Q 3 Is thatOr H, the molar ratio of the two compounds is 3:1.
Synthesis example 4(2): synthesis of quinone diazide C-2:
19.53g (0.05 mol) of 1, 1-tris (3, 5-dimethyl-4-hydroxyphenyl) ethane, 37.61g (0.14 mol) of 5-naphthoquinone azide sulfonyl chloride and 450g of 1, 4-dioxane were added to a 1L reaction flask at room temperature, and stirring was started to replace nitrogen gas and stirred until complete dissolution. A mixture of triethylamine (14.19 g,0.14 mol) and 1, 4-dioxane (45 g) was slowly added dropwise thereto. After the dripping is finished, the temperature is raised to 35 ℃ and the reaction is carried out for 4 hours. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, the filtrate was dropped into 3L of water, and the precipitated solid was collected by filtration. Finally, the precipitate was repeatedly washed with 10L of purified water for 2 times, and dried in a vacuum drying oven at 50℃for 24 hours to obtain naphthoquinone diazide compound C-2 as shown below.
Wherein Q is 4 、Q 5 、Q 6 Is thatOr H, the molar ratio of the two compounds is 3:1.
Example 1
Step S1: a polyamic acid resin composition is prepared.
The hydroxyl group-containing diamine compound 2, 2-bis (3- (3-amino) benzamide-4-hydroxyphenyl) hexafluoropropane (R) obtained in Synthesis example 2(1) was reacted under dry nitrogen 7 11 a) (30.23 g,0.05 mol) and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (SiDA) (0.62 g,2.50 mmol) were dissolved in 200g solvent N-methylpyrrolidone (NMP) and added to a 1L reaction flask. At 50℃with the aromatic tetracarboxylic dianhydride (R) obtained in Synthesis example 1(1) 6 -10) (34.83 g,0.06 mol) kept stirring for 2h, 3-aminophenol (MAP) as end-capping agent (CAS No.: 591-27-5) (1.09 g,0.01 mol), stirred for 2h, then esterifying agent N, N-dimethylformamide dimethyl acetal (DMFDMA) (CAS number: 4637-24-5) (14.72 g,0.10 mol), stirred at 50℃for 3h. After the completion of the reaction, the temperature was lowered to room temperature, the reaction solution was slowly poured into 2L of purified water to precipitate a white solid, the solid was collected by filtration under reduced pressure, washed with purified water 2 times, and then dried in a vacuum oven at 60℃for 72 hours to give 60g of polymer (A-1).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
10g of polymer (A-1) was added to 100g of gamma-butyrolactone (GBL), followed by addition of thermal crosslinking agent (B) 1 8) 2.0g of thermal crosslinking agent (B) 2 -2) 0.4g, 1.5g of photosensitizer quinone diazide (C-1), 1.5g of photosensitizer quinone diazide (C-2) and 50g of propylene glycol methyl ether acetate, and stirring thoroughly for 1hA slurry (P-1) was obtained.
Step S3: a photosensitive polyimide resin film was prepared.
The obtained slurry (P-1) was applied to a 6 inch silicon wafer by spin coating, and then dried at 120℃for 5 minutes to obtain a 1 μm thick pre-baked film silicon wafer assembly. Next, the i-line (365 nm) using a mercury lamp was exposed through a mask plate, and then the exposed portion was removed using a tetramethylammonium hydroxide developer using a developing device, to obtain a resin pre-baked film with a specific pattern. The sensitivity and resolution of the pre-baked film were determined using the evaluation methods described above. And (3) placing the resin pre-baked film into a high-temperature clean furnace, heating to 150 ℃ and 200 ℃ at a heating rate of 2.5 ℃/min, keeping each temperature for 10min, heating to 300 ℃, keeping the temperature for 300 ℃ for heat treatment for 1h, and cooling to below 50 ℃ to obtain the photosensitive polyimide resin film (F-1).
Example 2
Step S1: a polyamic acid resin composition is prepared.
According to the embodiment 1, except that the aromatic tetracarboxylic dianhydride (R 6 -10) the aromatic ring tetracarboxylic dianhydride (R) obtained in Synthesis example 1(2) 6 11) (42.87 g,0.06 mol), and 68g of the polymer (A-2) was finally obtained.
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using the polymer (A-2), a slurry (P-2) was obtained in the same manner as in example 1.
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-2), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-2).
Example 3
Step S1: a polyamic acid resin composition is prepared.
According to the embodiment 1, except that the aromatic tetracarboxylic dianhydride (R 6 -10) conversion to p-phenylene-bis-trimellitate dianhydride (R) 6 -8) (CAS number: 2770-49-2) (27.5 g,0.06 mol)59g of the polymer (A-3) was finally obtained.
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using the polymer (A-3), a slurry (P-3) was obtained in the same manner as in example 1.
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-3), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-3).
Example 4
Step S1: a polyamic acid resin composition is prepared.
Implemented as in example 1, except that the hydroxyl-containing diamine compound 2, 2-bis (3- (3-amino) benzamide-4-hydroxyphenyl) hexafluoropropane (R 7 -11 a) Synthesis example 2(2) with R 7 11b (30.23 g,0.05 mol), finally 64g of polymer (A-4) were obtained.
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using the polymer (A-4), a slurry (P-4) was obtained in the same manner as in example 1.
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-4), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-4).
Example 5
Step S1: a polyamic acid resin composition is prepared.
Implemented as in example 1, except that the hydroxyl group-containing diamine compound 2, 2-bis (3- (3-amino) benzamide-4-hydroxyphenyl) hexafluoropropane (R7-11 a) was changed to R7-15 (18.92 g,0.05 mol) in Synthesis example 2(3), and the aromatic ring tetracarboxylic dianhydride (R6-10) was changed to R obtained in Synthesis example 1(2) 6 11 (42.87 g,0.06 mol), and finally 57g of the polymer (A-5) were obtained.
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using the polymer (A-5), a slurry (P-5) was obtained in the same manner as in example 1.
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-5), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-5).
Example 6
Implemented as in example 1, except that the hydroxyl-containing diamine compound 2, 2-bis (3- (3-amino) benzamide-4-hydroxyphenyl) hexafluoropropane (R 7 -11 a) is changed to 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (R) 7 -1) (CAS: 83558-87-6) (18.31 g,0.05 mol) of an aromatic tetracarboxylic dianhydride (R) 6 -10) conversion to p-phenylene-bis-trimellitate dianhydride (R) 6 -8) (27.5 g,0.06 mol) to finally obtain 41g of the polymer (A-3).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using the polymer (A-6), a slurry (P-6) was obtained in the same manner as in example 1.
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-6), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-6).
Example 7
Step S1: a polyamic acid resin composition is prepared.
The procedure was carried out as in example 1 to finally obtain polymer (A-1).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-1), the procedure of example 1 was followed, except that a thermal crosslinking agent (B 1 -8) is changed to (B) 1 -2) 2.0g, giving a slurry (P-7).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-7), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-7).
Example 8
Step S1: a polyamic acid resin composition is prepared.
The procedure was carried out as in example 1 to finally obtain polymer (A-1).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-1), the procedure of example 1 was followed, except that a thermal crosslinking agent (B 1 -8) is changed to (B) 1 -4) 2.0g, giving a slurry (P-8).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-8), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-8).
Example 9
Step S1: a polyamic acid resin composition is prepared.
The procedure was carried out as in example 1 to finally obtain polymer (A-1).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-1), the procedure of example 1 was followed, except that a thermal crosslinking agent (B 1 -8) is changed to (B) 1 -6) 2.0g, giving a slurry (P-9).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-9), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-9).
Example 10
Step S1: a polyamic acid resin composition is prepared.
The procedure was carried out as in example 1 to finally obtain polymer (A-1).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-1), the procedure of example 1 was followed, except that a thermal crosslinking agent (B 1 -8) is changed to (B) 1 -10) 2.0g, to give a slurry (P-10).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-10), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-10).
Example 11
Step S1: a polyamic acid resin composition is prepared.
The procedure was carried out as in example 1 to finally obtain polymer (A-1).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-1), the procedure of example 1 was followed, except that a thermal crosslinking agent (B 1 The amount of-8) was changed to 2.34g, and the thermal crosslinking agent (B) 2 The amount of-2) was changed to 0.06g, to obtain a slurry (P-11).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-11), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain a photosensitive polyimide resin film (F-11).
Example 12
Step S1: a polyamic acid resin composition is prepared.
The procedure was carried out as in example 1 to finally obtain polymer (A-1).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-1), the procedure of example 1 was followed, except that a thermal crosslinking agent (B 1 The amount of-8) was changed to 1.8g, and the thermal crosslinking agent (B) 2 The amount of-2) was changed to 0.6g, to obtain a slurry (P-12).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-12), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-12).
Example 13
Step S1: a polyamic acid resin composition is prepared.
Implemented as in example 1, except that the hydroxyl-containing diamine compound 2, 2-bis (3- (3-amino) benzamide-4-hydroxyphenyl) hexafluoropropane (R 7 -11 a) Synthesis example 2(2) with R 7 11b (30.23 g,0.05 mol) of aromatic tetracarboxylic dianhydride (R) 6 -10) the aromatic ring tetracarboxylic dianhydride (R) obtained in Synthesis example 1(2) 6 11) (42.87 g,0.06 mol), and finally 65g of the polymer (A-7) were obtained.
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-7), the procedure of example 1 was followed, except that a thermal crosslinking agent (B 1 -8) is changed to (B) 1 -6) 2.0g of a thermal crosslinking agent (B) 2 -2) is changed to (B) 2 -1) 0.4g, giving a slurry (P-13).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-13), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain a photosensitive polyimide resin film (F-13).
Example 14
Step S1: a polyamic acid resin composition is prepared.
The procedure was carried out as in example 5 to finally obtain polymer (A-5).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-5), the procedure of example 1 was followed, except that a thermal crosslinking agent (B 1 -8) is changed to (B) 1 -10) 2.0g of a thermal crosslinking agent (B) 2 -2) is changed to (B) 2 -1) 0.4g, giving a slurry (P-14).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-14), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-14).
Comparative example 1
Step S1: a polyamic acid resin composition is prepared.
Implemented as in example 3, except that the hydroxyl-containing diamine compound 2, 2-bis (3- (3-amino) benzamide-4-hydroxyphenyl) hexafluoropropane (R 7 -11 a) is changed to R 7 11c (28.63 g,0.05 mol), finally giving 55g of polymer (A-8).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using the polymer (A-8), a slurry (P-15) was obtained in the same manner as in example 1.
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-15), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-15).
Comparative example 2
Step S1: a polyamic acid resin composition is prepared.
Implemented as in example 1, except that the hydroxyl-containing diamine compound 2, 2-bis (3- (3-amino) benzamide-4-hydroxyphenyl) hexafluoropropane (R 7 -11 a) is changed to R 7 10a (23.52 g,0.05 mol) to give 52g of a polymer (A-9).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using the polymer (A-9), a slurry (P-16) was obtained in the same manner as in example 1.
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-16), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-16).
Comparative example 3
Step S1: a polyamic acid resin composition is prepared.
The procedure was carried out as in example 1 to finally obtain polymer (A-1).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-1), the procedure of example 1 was followed, except that a thermal crosslinking agent (B 1 -8) and (B) 2 -2) changing to the usual thermal crosslinking agent (B) 3 -1) 2.4g, giving a slurry (P-17).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-17), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain a photosensitive polyimide resin film (F-17).
Comparative example 4
Step S1: a polyamic acid resin composition is prepared.
The procedure was carried out as in example 1 to finally obtain polymer (A-1).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-1), the procedure of example 1 was followed, except that a thermal crosslinking agent (B 1 -9) changing to a thermal crosslinker 3, 4-dihydro-1, 3-benzoxazine (B) which has not been modified by a long chain of siloxanes 3 -2) 2.0g, giving a slurry (P-18).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-18), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain a photosensitive polyimide resin film (F-18).
Comparative example 5
Step S1: a polyamic acid resin composition is prepared.
The procedure was carried out as in example 1 to finally obtain polymer (A-1).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-1), the procedure of example 1 was followed, except that only the thermal crosslinking agent (B 1 -8) 2.4g, giving a slurry (P-19).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-19), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain a photosensitive polyimide resin film (F-19).
Comparative example 6
Step S1: a polyamic acid resin composition is prepared.
The procedure was carried out as in example 1 to finally obtain polymer (A-1).
Step S2: a photosensitive polyimide resin precursor composition is prepared.
Using Polymer (A-1), the procedure of example 1 was followed, except that a thermal crosslinking agent (B 1 The amount of-8) was changed to 1.2g, and the thermal crosslinking agent (B) 2 The amount of-2) was changed to 1.2g, to obtain a slurry (P-20).
Step S3: a photosensitive polyimide resin film was prepared.
Using the slurry (P-20), a resin pre-baked film having a specific pattern was obtained in the same manner as in example 1. And curing the pre-baked film at high temperature to obtain the photosensitive polyimide resin film (F-20).
The amounts of the individual raw materials and the products of examples 1 to 14 and comparative examples 1 to 6 are shown in Table 1.
TABLE 1 amounts of individual raw materials and products in examples 1 to 14 and comparative examples 1 to 6
/>
The polyimide resin films obtained in examples 1 to 14 and comparative examples 1 to 6 were measured for sensitivity and resolution by the evaluation method described aboveRate, shrinkage, coefficient of thermal expansion, glass transition temperature, thermal decomposition temperature (T) 1％ And T 5％ ) And tensile properties, the test results of which are shown in Table 2.
TABLE 2 Properties of polyimide resin films obtained in examples 1 to 14 and comparative examples 1 to 6
As can be seen from the test results in Table 2, the polyimide resin films obtained in examples 1 to 14 of the present application exhibited lower heat shrinkability with shrinkage of 25% or less; the thermal expansion coefficient is below 45, which is beneficial to reducing interface stress; the glass transition temperature is above 280 ℃, and the glass transition temperature shows good thermal performance and high crosslinking degree; thermal decomposition temperature T 1％ Above 320 ℃, T 5％ Exhibits excellent thermodynamic properties above 370 ℃; the tensile strength is higher than 150MPa, the Young modulus is higher than 3.4GPa, the elongation at break is higher than 10%, and the excellent tensile property is shown; the sensitivity value is 500mJ/cm 2 Hereinafter, the resolution value is 10 μm or less, and excellent imaging performance is exhibited.
Comparison of example 1 and examples 7 to 10 can result in: the benzoxazine modified by long-chain siloxane is used as a cross-linking agent, and the resin film has low shrinkage rate and good thermodynamic property and mechanical property. In addition, the degree of crosslinking varies depending on the substituents on the crosslinking agent, and the data shows that: the ethynyl substituted cross-linking agent was best crosslinked, followed by allyl, vinyl, and cyano groups, with the cross-linking agent of example 7 not substituted with the above groups, and having a smaller degree of cross-linking.
From the comparison of example 3 and comparative example 1, it is possible to obtain: hydroxyl groups are not introduced into the main chain structure, the sensitivity and the resolution are both increased rapidly, the imaging performance is reduced, and the existence of the hydroxyl groups is proved to promote the dissolution of the pre-baked film to the developing solution greatly.
From the comparison of example 1, example 13 and comparative example 2, it can be obtained: f atoms are not introduced into the main chain structure, the photosensitivity of the resin film is reduced, and the structure with F atoms is introduced into the copolymerization, so that the imaging performance of the resin film is improved, and the thermodynamic performance of the film is reduced due to the excessively large introduction amount of F atoms.
From the comparison of example 1 and comparative example 3, it is possible to obtain: compared with the conventional crosslinking agent, the modified benzoxazine crosslinking agent has better curing and crosslinking effects and lower shrinkage, and improves the thermal performance and tensile performance of the cured film.
From the comparison of example 1 and comparative example 4, it is possible to obtain: the cross-linking agent which is not modified by the siloxane long-chain structure and the substituent is insufficient in cross-linking degree, higher in resolution and higher in brittleness of the cured film.
From the comparison of example 1 and comparative example 5 and comparative example 6, it can be obtained: without addition of crosslinker B 2 When the shrinkage and resolution increase, the tensile strength is low, indicating poor crosslinking, crosslinking agent B 2 Can promote the crosslinking reaction. However, when crosslinking agent B 2 When the aromatic group is excessively added, brittleness of the resin film increases, mechanical properties decrease, and photosensitivity decreases.
From the test results, the photosensitive polyimide resin film obtained by curing the polyimide resin precursor composition provided by the application can effectively reduce the thermal shrinkage of the film under the condition of good imaging performance, and meanwhile, the benzoxazine modified by siloxane has higher crosslinking degree, so that the heat resistance and mechanical performance of the resin film can be improved.
In summary, the technical scheme provided by the application has at least the following beneficial effects:
(1) The benzoxazine cross-linking agent B modified by siloxane long-chain structure 1 The polymer can keep good thermal performance, and the defect that benzoxazine has brittleness can be improved, so that the crosslinking degree and toughness are improved; secondly, the introduction of substituents such as ethynyl, allyl, vinyl, cyano and the like increases the crosslinking degree of the crosslinking agent during curing and improves the heat property of the filmEnergy and mechanical properties.
(2) The application introduces the cross-linking agent B with acid groups 2 Can reduce the cross-linking agent B 1 The curing crosslinking temperature (less than 300 ℃) of the (B) is further increased, the crosslinking degree is further increased, the dissolution of an alkaline aqueous solution developer is promoted, the photosensitivity and the resolution are improved, and the crosslinking agent B is the most important 2 Will be cured at high temperature with crosslinker B 1 The crosslinking is carried out, and the defect that the compound is easy to scatter during curing like a small molecular phenolic hydroxyl compound, and the shrinkage rate after curing is large is avoided.
(3) The photosensitive polyimide resin polymer disclosed by the application is matched with a certain thermal crosslinking agent, a photosensitizer and other additives, so that not only can the original good photosensitivity and resolution be maintained, but also a polyimide resin film with excellent thermal stability and mechanical property can be obtained.
The above is only a preferred embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (76)

1. A resin precursor composition comprising a component A and a component B 1 And component B 2 ；
Wherein, the component A is polyamide acid or polyamide ester;
the component B 1 A benzoxazine-based crosslinking agent represented by the formula (1);
the component B 2 A benzoxazine-based crosslinking agent having a hydroxyl group or a carboxyl group represented by the formula (2);
formula (1) is ；
The structural formula (2) is；
Wherein R in formula (1) 1 Selected from structures represented by formula (3); the structural formula (3) isThe method comprises the steps of carrying out a first treatment on the surface of the Wherein p is independently selected from integers of 1 to 10, and q is independently selected from integers of 1 to 6; r is R 2 Independently selected from hydrogen or cyano or vinyl or allyl or ethynyl; r in formula (2) 3 And R is 5 Independently selected from 1-6 aromatic rings or aliphatic rings, wherein adjacent rings cannot form a ring, s and t are independently selected from integers of 0-2, s and t are not zero at the same time, u and v are independently selected from integers of 0-3, u and v are not zero at the same time, and o is independently selected from integers of 0-20; r is R 4 Independently selected from hydrogen or an organic group of 1 to 20C atoms.
2. The resin precursor composition according to claim 1, wherein the component a has a structure represented by formula (4);
the structural formula (4) is ；
Wherein R is 6 Selected from tetracarboxylic acid residues with 1-6 aromatic rings, R 7 Selected from diamine residues with 1-6 aromatic rings; r is R 8 、R 9 、R 11 And R is 12 Independently selected from hydrogen atoms or organic groups with 1-20 carbon atoms; r is R 10 An organic group selected from the group consisting of 1 to 20 Si-O repeating units; w is an integer of 1 to 10, m is an integer of 5 to 1000, n is an integer of 1 to 200, and the ratio of m to n is 5 to 30.
3. The resin precursor composition according to claim 2, wherein R 8 、R 9 、R 11 Or R is 12 Independently methyl, ethyl or isopropyl.
4. The resin precursor composition according to claim 2, wherein in the repeating unit represented by the formula (4), the total moles of ester groupsMolar quantity/(R) 8 +R 9 +R 11 +R 12 ) The total molar amount is 50% -80%.
5. The resin precursor composition according to claim 2, wherein the structure of component a has a group of F atoms.
6. The resin precursor composition according to claim 2, wherein the weight average molecular weight of component a is 5000-200000.
7. The resin precursor composition according to claim 6, wherein the weight average molecular weight of the component a is 6000 to 150000.
8. The resin precursor composition according to claim 7, wherein the weight average molecular weight of component a is 8000-100000.
9. The resin precursor composition according to claim 2, wherein R 6 The catalyst contains at least one of methyl, methylene, ether, phenolic hydroxyl, benzyl, carbonyl, amido, trifluoromethyl and sulfonyl.
10. The resin precursor composition according to claim 9, wherein R 6 Selected from R 6 -1-R 6 -15 shows the structure:
、/>、 />、/> 、 、 />、/>、 、/>、 、/>、 、/> 、、/>；
r is as described above 6 -1-R 6 In-15, left and right ends'"where the connection is indicated.
11. The resin precursor composition according to claim 10, wherein R 6 Selected from the following structures:
、 />or (b)；
And/or R 7 -(OH) w Contains hydroxyl groups.
12. The resin precursor composition according to claim 11, wherein R 7 -(OH) w And at least one of methyl, methylene, ether, benzyl, carbonyl, amide, trifluoromethyl and sulfonyl groups.
13. The resin precursor composition according to claim 12, wherein R 7 -(OH) w Selected from R 7 -1-R 7 -16:
、 /> 、/>、 />、 、/>、/>、、/> 、、/> 、、 /> 、、/> 、 ；
r is as described above 7 -1-R 7 In-16, left and right ends'"where the connection is indicated.
14. The resin precursor composition according to claim 13, wherein R 7 -(OH) w Selected from:
、/> 、or->；
And/or R 10 Selected from organic groups having 1 to 20 Si-O units.
15. The resin precursor composition according to claim 14, wherein R 10 The composition also contains aliphatic groups.
16. The resin precursor composition according to claim 15, wherein R 10 Selected from R 10 -1-R 10 -8 at least one of the structures shown in:
、 /> 、/>、 、/>、 />、 、/>；
r is as described above 10 -1-R 10 -8 knotIn this configuration, the curved segments represent the connection locations.
17. The resin precursor composition of claim 16, wherein component a is further capped with a capping agent.
18. The resin precursor composition according to claim 17, wherein the capping is performed using one or more of a monoamine compound, an acid anhydride and a monocarboxylic acid compound as a capping agent.
19. The resin precursor composition according to claim 18, wherein the capping is performed using a monoamine compound as a capping agent.
20. The resin precursor composition according to claim 19, wherein the blocking group formed with the monoamine compound as the blocking agent is selected from the following structures:
、 />、/>、/>、/> 、、/>、/>、/>、/> 、、/>、/>or->；
In the above structure, the curved line section indicates the connection position.
21. The resin precursor composition according to claim 20, wherein the content of the end-capping agent is 0.5 to 20wt% of the content of the component a.
22. The resin precursor composition according to claim 21, wherein the content of the end-capping agent is 0.8 to 5wt% of the content of the component a.
23. The resin precursor composition according to claim 21, wherein the content of the end-capping agent is 1 to 10wt% of the content of the component a.
24. The resin precursor composition according to claim 1, wherein the component B 1 Selected from B 1 -1-B 1 -20 at least one of the structures shown:
、/> 、、 />、 、/>、、 />、 、 />、 、/>、 、 /> 、、 />、 、/>、 、 />。
25. the resin precursor composition of claim 24, wherein component B 1 At least one selected from the following structures:
、 />、、/>、；
and/or the component B 2 Selected from B 2 -1-B 2 -16 at least one of the structures shown in:
、/> 、 /> 、 、/>、/> 、、/>、/>、、 /> 、/>、 、/>、/>、。
26. root of Chinese characterThe resin precursor composition of claim 25, wherein component B 2 At least one selected from the following structures:
、/>。
27. the resin precursor composition of claim 26, wherein component B 1 With said component B 2 The total amount of (a) is 10 to 50wt% of the component A.
28. The resin precursor composition of claim 27, wherein component B 1 With said component B 2 The total amount of (C) is 12-40 wt% of the component A.
29. The resin precursor composition of claim 28, wherein component B 1 With said component B 2 The total amount of (C) is 15-30wt% of the component A.
30. The resin precursor composition according to claim 29, wherein component B 1 With said component B 2 The mass ratio of (2) is 40:1-2:1.
31. The resin precursor composition of claim 30, wherein component B 1 With said component B 2 The mass ratio of (2) is 35:1-3.5:1.
32. The resin precursor composition of claim 30, wherein component B 1 With said component B 2 The mass ratio of (2) is 30:1-3:1.
33. The resin precursor composition according to any one of claims 1 to 32, wherein the resin precursor composition further comprises component C;
the component C is a photosensitizer.
34. The resin precursor composition of claim 33, wherein component C is a photoacid generator.
35. The resin precursor composition according to claim 34, wherein the photoacid generator comprises at least one of a quinone diazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, and an iodonium salt.
36. The resin precursor composition according to claim 35, wherein the photoacid generator is a quinone diazide compound-containing photoacid generator.
37. The resin precursor composition according to claim 36, wherein the photoacid generator is an ester compound formed by bonding a polyhydroxy compound with a sulfonic acid of a diazidoquinone.
38. The resin precursor composition according to claim 37, wherein component C is selected from at least one of the following structures:
、 />；
wherein Q is independently selected fromOr H, the curved segment indicates the connection location.
39. The resin precursor composition according to claim 38, wherein the amount of component C is 10 to 50wt% of the component a.
40. The resin precursor composition according to claim 39, wherein the amount of component C is 20 to 40wt% of component A.
41. The resin precursor composition of claim 33, further comprising component D, wherein component D is a surfactant.
42. The resin precursor composition of claim 41, wherein the surfactant comprises at least one of ethanol, isopropanol, acetone, cyclohexanone, ethyl lactate, propylene glycol methyl ether acetate.
43. The resin precursor composition according to claim 42, wherein the component D is used in an amount of 10 to 70wt% based on the component A.
44. The resin precursor composition according to claim 43, wherein the component D is used in an amount of 20 to 60wt% based on the component A.
45. The resin precursor composition of claim 41, wherein the resin precursor composition further comprises component E, wherein component E is a solvent.
46. The resin precursor composition according to claim 45, wherein component E is a high boiling point polar solvent.
47. The resin precursor composition of claim 46, wherein the high boiling polar solvent comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, gamma-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 acetate, diethylene glycol methyl ether ethyl acetate, diethylene glycol ethyl acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether ethyl acetate, propylene glycol ethyl ether acetate, 2-hydroxy ethyl propionate, 3-methoxy ethyl 3-methyl propionate, 3-methoxy butyl 3-methoxy ethyl propionate, 3-methoxy ethyl 3-methyl propionate, and 3-methoxy butyl 3-ethoxy propionate.
48. The resin precursor composition according to claim 47, wherein the amount of component E is 1 to 15 times that of component A.
49. The resin precursor composition according to claim 48, wherein the component E is used in an amount of 1.2 to 12 times that of the component A.
50. The resin precursor composition according to claim 49, wherein the amount of the component E is 1.3 to 10 times that of the component A.
51. The method for producing a resin precursor composition according to any one of claims 1 to 50, comprising the steps of: the components were mixed.
52. The method of claim 51, wherein the resin precursor composition has a solids content of 5 to 50wt%.
53. The process of claim 52 wherein the resin precursor composition has a solids content of 6 to 40wt%.
54. The method of claim 53, wherein the resin precursor composition has a solids content of 7 to 30wt%.
55. The method of claim 52, wherein the resin precursor composition has a viscosity of 0.1 to 10000cp.
56. The method of claim 55, wherein the resin precursor composition has a viscosity of 0.5 to 8000cp.
57. The method of claim 56, wherein said resin precursor composition has a viscosity of 1 to 6000cp.
58. A polyimide resin film, which is prepared from the resin precursor composition according to any one of claims 1 to 50.
59. The method for producing a polyimide resin film according to claim 58, comprising the steps of: the pre-baked film prepared from the slurry of the resin precursor composition is subjected to exposure development, followed by heat treatment curing.
60. The method of claim 59, wherein the pre-baked film is obtained by applying a slurry of the resin precursor composition to a substrate and pre-baking.
61. The method of claim 60, wherein the substrate comprises a silicon wafer, ceramic, glass, quartz, or ITO.
62. The method of claim 60, wherein the coating comprises a slit coating, a spin coating, a dip coating, a spray coating, or a printing.
63. The method of claim 60, wherein the pre-drying temperature is 50-150 ℃.
64. The method of claim 63, wherein the pre-baking temperature is 80-150 ℃.
65. The method of claim 60, wherein the pre-drying time is 1 min-1 h.
66. The method of claim 59, wherein the pre-baked film has a thickness of 0.1 to 10. Mu.m.
67. The method of claim 66, wherein the pre-baked film has a thickness of 0.3 μm to 8 μm.
68. The method of claim 58, wherein the light rays used for exposure comprise ultraviolet rays, visible rays, electron beams or X-rays.
69. The method according to claim 58, wherein the developing solution for exposure is an aqueous base solution of an alkaline substance, wherein the alkaline substance comprises at least one of tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
70. The method of claim 60, wherein the temperature of the heat treatment is 100-350 ℃.
71. The method of claim 70, wherein the heat treatment is performed at a temperature of 120-300 ℃.
72. The method of claim 71, wherein the heat treatment is performed at a temperature of 200-300 ℃.
73. The method of claim 60, wherein the heat treatment is performed for a period of not less than 30 minutes.
74. The method of claim 59, wherein the heating rate of the heat treatment is 2-10deg.C/min.
75. The use of a polyimide resin film according to claim 58 as a surface protective film of a semiconductor or an interlayer insulating film on a semiconductor element circuit.
76. The use according to claim 75, wherein the polyimide resin film is used for the preparation of an insulating layer or a planarizing layer in an organic electroluminescent display device.
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