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CN118125972A - Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof - Google Patents

Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof Download PDF

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Publication number
CN118125972A
CN118125972A CN202410110794.0A CN202410110794A CN118125972A CN 118125972 A CN118125972 A CN 118125972A CN 202410110794 A CN202410110794 A CN 202410110794A CN 118125972 A CN118125972 A CN 118125972A
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diamine monomer
diamine
bis
dianhydride
reaction
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CN118125972B (en
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盛泽东
王珂
李铭新
孙洪阳
虞连亭
公聪聪
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Bomi Technology Co ltd
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Bomi Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/28—Radicals substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The application discloses a diamine monomer with an azacyclic ring and benzocyclobutene structure, and a preparation method and application thereof, and belongs to the field of functional polymer materials. Diamine monomer with nitrogen heterocycle and benzocyclobutene structure has the structural formula shown in the following formula (I): Wherein in the formula (I), W is an organic group containing nitrogen heterocycle. It is combined with other diamine monomers, introduced into a resin precursor, and thus a photosensitive resin composition is prepared. The diamine monomer contains an azacyclo structure, so that the dehydration cyclization reaction of a resin precursor can be promoted, the curing temperature is further reduced, the problem of insufficient imidization of the resin during low-temperature curing is solved, and meanwhile, the benzocyclobutene structure can be subjected to ring opening crosslinking under the low-temperature condition of 250 ℃, so that the film forming performance, mechanical performance and thermal stability of a cured film under the low-temperature condition are improved. In addition, the presence of the heterocyclic N atom can also reduce the dielectric constant of the cured film and inhibit discoloration of the copper or copper alloy substrate.

Description

Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof
Technical Field
The application relates to a diamine monomer with an azacyclic ring and benzocyclobutene structure, and a preparation method and application thereof, belonging to the field of functional polymer materials.
Background
Polyimide (PI) is one of the most widely used polymer materials in the semiconductor and microelectronic industries because of its excellent heat resistance, mechanical properties, and electrical properties. With the light weight, high performance and multifunction of electronic products, there is a higher demand for photosensitive polyimide (PSPI) packaging materials.
At present, the dielectric constant of some common PSPI materials is higher (generally more than 3), and the performance requirements of low dielectric constant and low dielectric loss of the new generation of communication technology cannot be met. On the other hand, an excessively high process temperature amplifies the interfacial stress between the encapsulation material and the substrate due to the difference in thermal expansion coefficient, thereby lowering the curing temperature of the polyimide material as much as possible. To achieve low temperature cure, soft groups are typically introduced into the repeating units of the polymer, such as: alkyl groups, alkylene glycol groups, siloxane bonds, and the like. However, polyimide obtained by introducing a soft group into a molecular chain is difficult to have sufficient mechanical properties and excellent thermal properties; preparing soluble polyimide or polyisoimide to realize low-temperature curing of resin, but the solubility is often poor and the application is limited; the problem of insufficient resin ring closure during low-temperature curing is solved by adding compounds containing imidazole rings, triazole rings, thiazole rings and the like, but small molecular substances are easy to thermally decompose, so that the effect is influenced or side effects are generated on other properties. The thermal crosslinking agent containing alkoxymethyl, hydroxymethyl, epoxy, unsaturated group and the like is added to perform condensation reaction with the resin and the same molecule to form a crosslinked structure, thereby improving the heat resistance and mechanical strength of the resin cured film. However, if the resin itself lacks crosslinking properties, the cured film cannot be ensured to have sufficient mechanical properties and chemical resistance even if a thermal crosslinking agent is added, and there is a problem that it is difficult to achieve both low stress and the like. When the PSPI material is used for a semiconductor or the like, the cured film remains as a permanent film in the device, and thus, the overall performance of the cured film is important.
The PSPI materials in the prior patents cannot meet the performance requirements at the same time, and development of low-temperature curing PSPI materials with excellent film forming property, mechanical property, thermal stability and dielectric property is urgent.
Disclosure of Invention
According to one aspect of the present application, there is provided a diamine monomer having an azacyclic and benzocyclobutene structure, which is incorporated into a resin precursor in combination with other diamine monomers, to thereby prepare a photosensitive resin composition. The diamine monomer contains an azacyclo structure, so that the dehydration cyclization reaction of a resin precursor can be promoted, the curing temperature is further reduced, the problem of insufficient imidization of the resin during low-temperature curing is solved, and meanwhile, the benzocyclobutene structure can be cured and crosslinked at low temperature, so that the film forming property, solvent resistance, mechanical property and thermal stability of a cured film at low temperature are improved. In addition, the presence of the heterocyclic N atom can also reduce the dielectric constant of the cured film and inhibit discoloration of the copper or copper alloy substrate.
The diamine monomer with the nitrogen heterocycle and benzocyclobutene structure has the structural formula shown in the following formula (I):
wherein in the formula (I), W is an organic group containing nitrogen heterocycle.
Optionally, in the formula (I), the nitrogen heterocycle is selected from any one of pyridine, benzothiazole, carbazole, indole, piperidine and thiazole.
Optionally, W is selected from any one of the groups represented by formula (ii), wherein the dashed line represents an access site;
in another aspect, the present application provides a method for preparing a diamine monomer having an azacyclic and benzocyclobutene structure, comprising the following synthetic steps:
(1) Under the protection of inactive gas, the mixture I of aldehyde compound containing hydroxyl, 4-bromobenzocyclobutene, alkali and organic solvent is reacted to obtain an intermediate product X, wherein the reaction formula is as follows:
(2) Under the protection of inactive gas, reacting a mixture II of an intermediate product X, aniline hydrochloride and aniline to obtain the diamine monomer, wherein the reaction formula is as follows:
Wherein W is an organic group containing a nitrogen heterocycle.
Optionally, the nitrogen heterocycle is selected from any one of pyridine, benzothiazole, carbazole, indole, piperidine and thiazole.
Optionally, W is selected from any one of the groups represented by formula (ii), wherein the dashed line represents an access site;
Optionally, the hydroxyl-containing aldehyde compound is selected from one or more of the compounds shown in the following structures:
in the preparation method, the raw materials are all common raw materials in the field and can be purchased commercially or prepared according to the method disclosed in the prior art.
Optionally, in step (1), the hydroxyl-containing aldehyde compound is selected from one or more of the following: 2-hydroxy-5- (pyridin-4-yl) benzaldehyde, 5-methyl-3- (2-benzothiazolyl) -2-hydroxybenzaldehyde, 1-hydroxy-9H-carbazole-3-carbaldehyde, 5-hydroxyindole-3-carbaldehyde, 4- (4-hydroxypiperidin-1-yl) benzaldehyde, 2- (4-hydroxyphenyl) thiazole-4-carbaldehyde.
Optionally, in step (1), the organic solvent comprises N, N-dimethylformamide.
Optionally, in step (1), the base comprises potassium carbonate.
Optionally, in the step (1), the molar ratio of the hydroxyl-containing aldehyde compound to the 4-bromobenzocyclobutene is 1:0.9-1.1.
Optionally, in the step (1), the temperature of the reaction I is 130-150 ℃ and the reaction time is 20-30 h. Preferably, in the step (1), the temperature of the reaction I is 135-145 ℃ and the reaction time is 22-26 h.
Optionally, the inert gas is nitrogen or other inert gas.
Optionally, in step (2), the molar ratio of intermediate X, aniline hydrochloride and aniline is 1:3 to 5: 8-12.
Specifically, in step (2), the molar ratio of intermediate X, aniline hydrochloride and aniline is 1:4:10.
Optionally, in the step (2), the temperature of the reaction II is 150-180 ℃ and the time is 5-8 h.
Specifically, in the step (2), the temperature of the reaction II is 160 ℃ and the time is 6 hours.
Optionally, the preparation method of the mixture II comprises the following steps: under the protection of inactive gas, the intermediate product X, aniline hydrochloride and aniline are mixed and dissolved at 90-120 ℃.
In yet another aspect, the present application provides a resin precursor obtained by reacting a mixture III comprising dianhydride monomer and diamine monomer;
the diamine monomer comprises the diamine with an azacyclic ring and benzocyclobutene structure;
the diamine monomer also includes a diamine monomer having no nitrogen heterocycle and benzocyclobutene structure.
The dianhydride monomer may be selected from prior art reports. Alternatively, the dianhydride monomer is selected from pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2,3',3,4' -diphenyl ether tetracarboxylic dianhydride, 3,4,3',4' -benzophenone tetracarboxylic dianhydride, 3', one or more of 4,4' -diphenyl sulfone tetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 4'- (hexafluoroisopropylidene) dicarboxylic anhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 4' - (hexafluoroisopropylidene) isophthalic anhydride, and the like.
For diamine monomers not having an azacyclic and benzocyclobutene structure, one can choose from prior art reports and, alternatively, the diamine monomer without nitrogen heterocycle and benzocyclobutene structure is selected from 2, 2-bis [ 4-hydroxy-3- (3-amino) benzamido ] hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (3-aminophenyl) hexafluoropropane, 9-bis (3-amino-4-hydroxyphenyl) fluorene, 2-bis (3-amino-4-hydroxyphenyl) propane, 4 '-diaminodiphenyl ether 3,4' -diaminodiphenyl ether, 1, 3-bis (3-aminophenoxy) benzene, biphenyldiamine, p-phenylenediamine, 3 '-dihydroxybenzidine, 2' -bis (3-amino-4-hydroxyphenyl) propane one or more of 2,2 '-bis (3-amino-4-hydroxyphenyl) diphenyl sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane, 2' -bis [4- (4-aminophenoxyphenyl) ] propane, and the like.
The diamine monomer with the nitrogen heterocycle and benzocyclobutene structure contains the crosslinkable benzocyclobutene, so that excessive crosslinking of the resin is easily caused by the excessive content of the diamine monomer in the resin, and the comprehensive usability of the resin is affected. Alternatively, the diamine having an azacyclic and benzocyclobutene structure is present in an amount of 1 to 50%, preferably 10 to 30% of the total molar amount of diamine monomers.
Alternatively, the resin precursor is polyimide or a precursor thereof, preferably a polyimide precursor.
Alternatively, the polyimide precursor is a polyamic acid or polyamic acid ester.
In yet another aspect, the present application provides a method for preparing the resin precursor,
When the resin precursor is a polyamic acid, it comprises: and (3) reacting the mixture III comprising the dianhydride monomer and the diamine monomer to obtain a polyamic acid solution.
When the resin precursor is a polyamic acid ester, comprising the steps of:
reacting a mixture III comprising dianhydride monomers and diamine monomers to obtain polyamide acid solution;
(II) reacting IV with the mixture IV comprising the polyamic acid obtained in the step (I) and an esterification reagent to obtain a polyamic acid ester solution.
Alternatively, the temperature of reaction III is 20-80℃for 1-24 hours.
In step (II), the polyamic acid is heated in an esterification reagent, during which the carboxylic acid functionality in the polyamic acid is converted to carboxylate groups by the esterification reaction.
Optionally, in the step (II), the temperature of the reaction IV is 40-100 ℃ and the time is 1-12 h.
Alternatively, the esterification rate of the polyamic acid is 40 to 90%.
Optionally, in the step (ii), the esterifying reagent is selected from any one or more of alcohol compounds such as methanol, ethanol, and N-butanol, acetal compounds such as N, N-dimethylformamide dimethyl methylal (DMFDMA), and N, N-dimethylformamide dimethyl acetal (DMADEA).
Optionally, the molar ratio of the polyamic acid to the esterification agent is 1:1 to 10.
In order to improve the stability of the resin, a blocking agent may be introduced during the synthesis as needed. Optionally, the mixture III further comprises a capping agent selected from any one or more of monoamines, monoanhydrides, monocarboxylic acids, monoacylchloride compounds, monoacylester compounds.
The type and amount of the capping agent selected may be adjusted as desired. The capping agents are generally used in a manner that can be divided into: adding a blocking agent and diamine and dianhydride simultaneously; adding a blocking agent after the diamine reacts with the dianhydride; the diamine or dianhydride is added after reacting the capping agent with the dianhydride or diamine.
Optionally, after reaction IV, water or methanol solution is added, precipitation, filtration, water washing and drying are performed. The film characteristics after heat curing can be improved by removing the unreacted monomer, dimer, trimer and other oligomer components.
In yet another aspect, the present application provides a photosensitive resin composition comprising the above resin precursor, a photosensitive agent, a silane coupling agent, and a solvent.
Alternatively, the sensitizer may be selected from the prior art. In the positive resin composition, a quinone diazide compound, a sulfonate compound formed from naphthoquinone diazide sulfonyl chloride and a low-molecular polyhydric phenol compound is preferable. The diazonaphthoquinone compound has a dissolution inhibiting effect on the resin before exposure, and can generate indenic acid in the ultraviolet exposure region after exposure, and the solubility of the exposed portion in an alkaline aqueous solution is increased, so that the exposed portion can be removed, leaving an unexposed portion, and finally the desired pattern can be obtained. Among them, the difference in dissolution rate of the exposed portion and the unexposed portion in an alkaline developer is a key to obtaining an excellent pattern.
Preferably, the sensitizer is a commercially available quinone diazide compound such as NT-300 (the esterification reaction product of 2,3, 4-tetrahydroxybenzophenone with 6-diazo-5, 6-dihydroxy-5-oxo-1-naphthalenesulfonic acid), 4NT-300 (the esterification reaction product of 2,3, 4-tetrahydroxybenzophenone with 6-diazo-5, 6-dihydroxy-5-oxo-1-naphthalenesulfonic acid), HP-190 (the esterification reaction product of tris (4-hydroxyphenyl) ethane and 6-diazo-5, 6-dihydroxy-5-oxo-1-naphthalenesulfonic acid) (manufactured by Toyo-Kabushiki Kaisha).
The use of two or more kinds of the quinone diazide compounds can further increase the dissolution rate ratio of the exposed portion to the unexposed portion, and can further provide a positive photosensitive resin composition having high sensitivity.
For the negative type resin composition, the sensitizer is preferably an oxime ester compound such as: 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime, 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime. After ultraviolet exposure, the sensitizer can trigger the resin to generate a crosslinking reaction to generate an insoluble structure, so that the solubility difference is generated between the exposed part and the unexposed part, and then the target pattern is formed.
Optionally, the weight ratio of the resin precursor to the sensitizer is 100 (5-40); preferably, the weight ratio of the resin precursor and the sensitizer is 100 (10-30).
The silane coupling agent may be selected from the prior art. Optionally, the silane coupling agent is selected from any one or more of p-styryl trimethoxysilane, trimethoxyaminopropyl silane, trimethoxyepoxy silane, trimethoxyvinyl silane and trimethoxymercapto propyl silane.
Optionally, the weight ratio of the silane coupling agent to the resin precursor is 0.01-10:100; preferably 1 to 5:100.
Optionally, the solvent is selected from any one or more of polar aprotic solvents, ethers, ketones, esters, alcohols, aromatic hydrocarbons.
Optionally, the polar aprotic solvent is selected from any one or more of N-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide.
Alternatively, the ketone is selected from any one or more of acetone, methyl ethyl ketone, diisobutyl ketone.
Optionally, the ethers are selected from any one or more of tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether.
Alternatively, the esters are selected from any one or more of ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, methyl lactate.
Optionally, the alcohol is selected from any one or more of diacetone alcohol and 3-methyl-3-methoxybutanol.
Optionally, the aromatic hydrocarbon is toluene and/or xylene.
Optionally, the weight ratio of the resin precursor to the solvent is 100 (100-2000); preferably, the weight ratio of the resin precursor and the solvent is 100 (150-500).
In addition, in order to improve leveling property of the glue solution, prevent bubbles or stripes from being generated during coating and avoid influencing the performance of a cured film, the photosensitive resin composition further comprises an acrylic surfactant.
Alternatively, the acrylic surfactant is selected from any one or more of POLYFLOW No.7, no.36, no.56, no.77, no.90, WS-314 (trade name, co-Rong chemical Co., ltd.), SKB-FLOW SD, SL, P90, 1358, 1392, 1460D, 90D (trade name, korea SKB).
Optionally, the weight ratio of the resin precursor to the acrylic surfactant is 100 (0.01-5).
In still another aspect, the present application provides a method for preparing the photosensitive resin composition, comprising: and (3) stirring and filtering the mixture V of the resin precursor, the photosensitive agent, the silane coupling agent and the solvent to obtain the photosensitive resin composition.
Optionally, the mixture v further comprises an acrylate surfactant.
The composition is coated on a substrate, and the cured film is obtained by heat treatment under the low-temperature condition of 250 ℃, and the cured film has strong adhesion with the substrate and low dielectric constant.
The application has the beneficial effects that:
(1) The application provides a diamine monomer with an azacyclic and benzocyclobutene structure, wherein the azacyclic structure promotes the dehydration cyclization reaction of a resin precursor, so that the curing temperature of a composition is reduced, the problem of insufficient imidization of the resin during low-temperature curing is solved, and meanwhile, the benzocyclobutene structure can be subjected to ring-opening crosslinking under the low-temperature condition of 250 ℃, so that the film forming performance, mechanical performance and heat stability of a cured film under the low-temperature condition are improved. In addition, the presence of the heterocyclic N atom can also reduce the dielectric constant of the cured film and inhibit discoloration of the copper or copper alloy substrate.
(2) The photosensitive resin composition provided by the application is cured at a low temperature of 250 ℃ to obtain a cured film with excellent dielectric property, mechanical property and thermal stability, and is suitable for the application field of low-temperature curing.
Drawings
FIG. 1 is an infrared spectrum of a cured film obtained at 250℃and 350℃respectively in example 1 of the present application;
FIG. 2 is a graph showing the thermal weight loss of polyimide films obtained by curing at 250℃in example 1 and comparative example 1 of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Synthesis example 1 Synthesis of diamine monomer A1
2-Hydroxy-5- (pyridin-4-yl) benzaldehyde (9.96 g,50 mmol), 4-bromobenzocyclobutene (9.15 g,50 mmol) and potassium carbonate (6.91 g,50 mmol) were dissolved in 200mL of N, N-dimethylformamide, nitrogen was introduced under stirring, the reaction was carried out at 140℃for 24 hours, the solvent was distilled off under reduced pressure, washed with deionized water, and dried under vacuum at 80℃to give intermediate X1;
the above-mentioned product (7.53 g,25 mmol), aniline hydrochloride (12.96 g,0.1 mol) and aniline (23.28 g,0.25 mol) were added into a 500ml three-necked flask, mixed and dissolved at 110℃under nitrogen atmosphere, then heated to 160℃to react for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to remove excess aniline, dissolved and filtered by adding 2mol/L hydrochloric acid, the filtrate was neutralized with 2mol/L sodium hydroxide to obtain a solid, the solid was washed with deionized water, recrystallized with ethanol/water, dried under vacuum at 80℃to obtain diamine monomer A1 having the following structural formula:
Synthesis example 2 Synthesis of diamine monomer A2
5-Methyl-3- (2-benzothiazolyl) -2-hydroxybenzaldehyde (13.47 g,50 mmol), 4-bromobenzocyclobutene (9.15 g,50 mmol) and potassium carbonate (6.91 g,50 mmol) are dissolved in 200mL of N, N-dimethylformamide, nitrogen is introduced under stirring, the reaction is carried out for 24 hours at 140 ℃, the solvent is removed by reduced pressure distillation, the mixture is washed by deionized water, and the mixture is dried under vacuum at 80 ℃ to obtain an intermediate product X2;
The above product (9.29 g,25 mmol), aniline hydrochloride (12.96 g,0.1 mol) and aniline (23.28 g,0.25 mol) were added to a 500ml three-necked flask, mixed and dissolved at 110℃under nitrogen atmosphere, then heated to 160℃to react for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to give an excess aniline, dissolved and filtered by adding 2mol/L hydrochloric acid, the filtrate was neutralized with 2mol/L sodium hydroxide to give a solid, the solid was washed with deionized water, recrystallized with ethanol/water, dried under vacuum at 80℃to give diamine monomer A2 having the following structural formula:
Synthesis example 3 Synthesis of diamine monomer A3
1-Hydroxy-9H-carbazole-3-carbaldehyde (10.56 g,50 mmol), 4-bromobenzocyclobutene (9.15 g,50 mmol) and potassium carbonate (6.91 g,50 mmol) are dissolved in 200mL of N, N-dimethylformamide, nitrogen is introduced under stirring, the reaction is carried out for 24 hours at 140 ℃, the solvent is distilled off under reduced pressure, the deionized water is used for cleaning, and the intermediate product X3 is obtained after vacuum drying at 80 ℃;
the above-mentioned product (7.83 g,25 mmol), aniline hydrochloride (12.96 g,0.1 mol) and aniline (23.28 g,0.25 mol) were added into a 500ml three-necked flask, mixed and dissolved at 110℃under nitrogen atmosphere, then heated to 160℃to react for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to remove excess aniline, dissolved and filtered by adding 2mol/L hydrochloric acid, the filtrate was neutralized with 2mol/L sodium hydroxide to obtain a solid, the solid was washed with deionized water, recrystallized with ethanol/water, dried under vacuum at 80℃to obtain diamine monomer A3 having the following structural formula:
Synthesis example 4 Synthesis of diamine monomer A4
5-Hydroxy indole-3-carbaldehyde (8.06 g,50 mmol), 4-bromo-benzocyclobutene (9.15 g,50 mmol) and potassium carbonate (6.91 g,50 mmol) are dissolved in 200mL of N, N-dimethylformamide, nitrogen is introduced under stirring to react for 24 hours at 140 ℃, the solvent is distilled off under reduced pressure, the mixture is washed with deionized water, and the mixture is dried under vacuum at 80 ℃ to obtain an intermediate X4;
The above product (6.58 g,25 mmol), aniline hydrochloride (12.96 g,0.1 mol) and aniline (23.28 g,0.25 mol) were added to a 500ml three-necked flask, mixed and dissolved at 110℃under nitrogen atmosphere, then heated to 160℃to react for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to give an excess aniline, dissolved and filtered by adding 2mol/L hydrochloric acid, the filtrate was neutralized with 2mol/L sodium hydroxide to give a solid, the solid was washed with deionized water, recrystallized with ethanol/water, dried under vacuum at 80℃to give a diamine monomer A4 having the following structural formula:
Synthesis example 5 Synthesis of diamine monomer A5
4- (4-Hydroxy-piperidin-1-yl) benzaldehyde (10.26 g,50 mmol), 4-bromobenzocyclobutene (9.15 g,50 mmol) and potassium carbonate (6.91 g,50 mmol) were dissolved in 200mL of N, N-dimethylformamide, nitrogen was introduced under stirring, the reaction was carried out at 140℃for 24 hours, the solvent was distilled off under reduced pressure, washing with deionized water, and vacuum drying at 80℃was carried out to obtain intermediate X5;
The above-mentioned product (7.68 g,25 mmol), aniline hydrochloride (12.96 g,0.1 mol) and aniline (23.28 g,0.25 mol) were added into a 500ml three-necked flask, mixed and dissolved at 110℃under nitrogen atmosphere, then heated to 160℃to react for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to remove excess aniline, dissolved and filtered by adding 2mol/L hydrochloric acid, the filtrate was neutralized with 2mol/L sodium hydroxide to obtain a solid, the solid was washed with deionized water, recrystallized with ethanol/water, dried under vacuum at 80℃to obtain diamine monomer A5 having the following structural formula:
synthesis example 6 Synthesis of diamine monomer A6
2- (4-Hydroxyphenyl) thiazole-4-carbaldehyde (10.26 g,50 mmol), 4-bromobenzocyclobutene (9.15 g,50 mmol) and potassium carbonate (6.91 g,50 mmol) were dissolved in 200mL of N, N-dimethylformamide, nitrogen was introduced under stirring, the reaction was carried out at 140℃for 24 hours, the solvent was distilled off under reduced pressure, washing was carried out with deionized water, and vacuum drying was carried out at 80℃to obtain intermediate X6;
The above-mentioned product (7.68 g,25 mmol), aniline hydrochloride (12.96 g,0.1 mol) and aniline (23.28 g,0.25 mol) were added into a 500ml three-necked flask, mixed and dissolved at 110℃under nitrogen atmosphere, then heated to 160℃to react for 6 hours, cooled to room temperature, distilled off under reduced pressure at 80℃to remove excess aniline, dissolved and filtered by adding 2mol/L hydrochloric acid, the filtrate was neutralized with 2mol/L sodium hydroxide to obtain a solid, the solid was washed with deionized water, recrystallized with ethanol/water, dried under vacuum at 80℃to obtain diamine monomer A6 having the following structural formula:
Example 1
To a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer were successively added 31.02g (0.1 mol) of 4,4' -oxydiphthalic anhydride (ODPA) and 100g of N-methylpyrrolidone (NMP) under a nitrogen flow, and the mixture was stirred and dissolved to obtain a dianhydride solution. Another three-necked flask equipped with a stirrer was taken, 43.52g (72 mmol) of 2, 2-bis [ 4-hydroxy-3- (3-amino) benzamide ] hexafluoropropane (HFHA), 8.45g (18 mmol) of diamine monomer a and 100g of N-methylpyrrolidone were sequentially added thereto, and stirred and dissolved to obtain a diamine solution. And (3) dropwise adding the diamine solution into the dianhydride solution, reacting for 1h at normal temperature after the dropwise adding is finished, and then reacting for 2h at 50 ℃. After completion of the reaction, 2.18g (0.02 mol) of 3-aminophenol as a blocking agent was added thereto and reacted at 50℃for 2 hours. Thereafter, a solution of 23.83g (0.2 mol) of N, N-dimethylformamide dimethyl acetal diluted with 45.00g of NMP was added dropwise thereto, and the mixture was reacted at 50℃for 3 hours after completion of the addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and the polymer is separated out to obtain white precipitate. Filtering, washing with deionized water for three times, and drying in a vacuum oven at 80deg.C for 72hr to obtain polyamic acid ester.
The molecular weight of the polyamic acid ester was measured by gel permeation chromatography (GPC, shimadzu LC-20 AD) in terms of standard polystyrene, and the eluent was N-methylpyrrolidone, column temperature 40 ℃. The weight average molecular weight (Mw) of the polyamic acid ester was measured to be 1.8 to 2.0 ten thousand.
In a three-necked flask equipped with stirring, 10.0g of the synthesized polyamic acid ester was dissolved in 20g of gamma-butyrolactone (GBL), stirred until complete dissolution, 2.0g of NT-300 (manufactured by Toyo Kagaku Co., ltd.) was added, stirring was continued until complete dissolution, then 0.1g of KBM-1403 (P-styryltrimethoxysilane, japanese Kogyo Co., ltd.) and 0.05g POLYFLOW NO.77 (Kyowa Kagaku Co., ltd.) were added, stirring was continued until complete dispersion was uniform, and pressure filtration was performed with a 1.0 μm PTFE filter membrane, to obtain a photosensitive resin composition P-1.
Example 2
A photosensitive resin composition P-2 was obtained in the same manner as in example 1 except that 8.45g (18 mmol) of the diamine monomer A1 was replaced with 4.23g (9 mmol) of the diamine monomer A1 and 43.52g (72 mmol) of HFHA was replaced with 48.97g (81 mmol) of HFHA.
Example 3
A photosensitive resin composition P-3 was obtained in the same manner as in example 1 except that 8.45g (18 mmol) of the diamine monomer A1 was replaced with 12.67g (27 mmol) of the diamine monomer A1 and 43.52g (72 mmol) of HFHA was replaced with 38.09g (63 mmol) of HFHA.
Example 4
A photosensitive resin composition P-4 was obtained in the same manner as in example 1 except that 8.45gg (18 mmol) of the diamine monomer A1 was replaced with 9.71g (18 mmol) of the diamine monomer A2.
Example 5
A photosensitive resin composition P-5 was obtained in the same manner as in example 1 except that 8.45g (18 mmol) of the diamine monomer A1 was replaced with 8.66g (18 mmol) of the diamine monomer A3.
Example 6
A photosensitive resin composition P-6 was obtained in the same manner as in example 1 except that 8.45g (18 mmol) of the diamine monomer A1 was replaced with 7.76g (18 mmol) of the diamine monomer A4.
Example 7
A photosensitive resin composition P-7 was obtained in the same manner as in example 1 except that 8.45g (18 mmol) of the diamine monomer A1 was replaced with 8.56g (18 mmol) of the diamine monomer A5.
Example 8
A photosensitive resin composition P-8 was obtained in the same manner as in example 1 except that 8.45g (18 mmol) of the diamine monomer A1 was replaced with 8.56g (18 mmol) of the diamine monomer A6.
Example 9
A photosensitive resin composition P-9 was obtained in the same manner as in example 1 except that 8.45g (18 mmol) of the diamine monomer A1 was replaced with 4.23g (9 mmol) of the diamine monomer A1 and 3.88g (9 mmol) of the diamine monomer A4.
Example 10
A photosensitive resin composition P-10 was obtained in the same manner as in example 1 except that 8.45g (18 mmol) of the diamine monomer A2 was replaced with 4.85g (9 mmol) of the diamine monomer A2 and 4.28g (9 mmol) of the diamine monomer A5.
Example 11
A photosensitive resin composition P-11 was obtained in the same manner as in example 1 except that 8.45g (18 mmol) of the diamine monomer A1 was replaced with 4.33g (9 mmol) of the diamine monomer A3 and 4.28g (9 mmol) of the diamine monomer A6.
Comparative example 1
To a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer were successively added 31.02g (0.1 mol) of 4,4' -oxydiphthalic anhydride (ODPA) and 100g of N-methylpyrrolidone (NMP) under a nitrogen flow, and the mixture was stirred and dissolved to obtain a dianhydride solution. Another three-necked flask equipped with a stirrer was taken, 54.41g (0.09 mol) of 2, 2-bis [ 4-hydroxy-3- (3-amino) benzamide ] hexafluoropropane (HFHA) and 100g of N-methylpyrrolidone were sequentially added thereto, and the mixture was stirred and dissolved to obtain a diamine solution. And (3) dropwise adding the diamine solution into the dianhydride solution, reacting for 1h at normal temperature after the dropwise adding is finished, and then reacting for 2h at 50 ℃. After completion of the reaction, 2.18g (0.02 mol) of 3-aminophenol as a blocking agent was added thereto and reacted at 50℃for 2 hours. Thereafter, a solution of 23.83g (0.2 mol) of N, N-dimethylformamide dimethyl acetal diluted with 45.00g of NMP was added dropwise thereto, and the mixture was reacted at 50℃for 3 hours after completion of the addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and the polymer is separated out to obtain white precipitate. Filtering, washing with deionized water for three times, and drying in a vacuum oven at 80deg.C for 72hr to obtain polyamic acid ester.
The molecular weight of the polyamic acid ester was measured by gel permeation chromatography (GPC, shimadzu LC-20 AD) in terms of standard polystyrene, and the eluent was N-methylpyrrolidone, column temperature 40 ℃. The weight average molecular weight (Mw) of the polyamic acid ester was measured to be 1.8 to 2.0 ten thousand.
In a three-necked flask equipped with stirring, 10.0g of the synthesized polyamic acid ester was dissolved in 20g of gamma-butyrolactone (GBL), stirred until complete dissolution, 2.0g of NT-300 (manufactured by Toyo Kagaku Co., ltd.) was added, stirring was continued until complete dissolution, then 0.1g of KBM-1403 (p-styryl trimethoxysilane, japanese Kogyo Co., ltd.) and 0.05g POLYFLOW NO.77 (Kyowa Kagaku Co., ltd.) were added, stirring was continued until complete dispersion was uniform, and pressure filtration was performed with a 1.0 μm PTFE filter membrane, to obtain a photosensitive resin composition Q-1.
Imidization rate, film forming property, thermal stability, mechanical strength, dielectric constant, and copper discoloration of PI films prepared from the photosensitive resin compositions prepared in the above examples and comparative examples were evaluated, and the evaluation results are shown in table 1.
(1) Imidization test
The infrared spectra of the cured films were measured at 250℃and 350℃by the ATR method using an infrared spectrometer (Shimadzu, IRAFFINITY-1S), and the intensity A of the absorption peak of the stretching vibration of the C-N bond near 1380cm -1 and the intensity A of the absorption peak of the benzene ring near 1500cm -1 were recorded.
The calculation formula of the imidization degree alpha is as follows:
Wherein, the infrared spectrograms of the cured films obtained in example 1 at 250 ℃ and 350 ℃ respectively are shown in figure 1.
(2) Film Forming test
The photosensitive resin composition was applied onto a4 inch silicon substrate using a spin coater, and soft-baked at 120℃for 3 minutes on a heating table to obtain a resin film having a film thickness of 10 to 20. Mu.m.
Then, it was placed in a vacuum anaerobic oven (Lemnaceae, technophora Co., ltd., MOLZK-32D 1) for heat treatment. The specific process of the heat treatment is as follows: the method comprises the steps of performing heat treatment at 150 ℃ for 30min, then performing heat treatment at 250 ℃ for 1h by programming, and then cooling to room temperature to obtain the cured film.
And (3) placing the silicon wafer with the solidified film in hydrofluoric acid solution, and carrying out corrosion stripping on the silicon wafer.
The specific evaluation criteria are as follows:
"you": film forming, folding without breaking;
"good": forming a film, and breaking the folded part;
"difference": cannot form a film and is crushed into pieces.
In addition, when the film formability is "poor", the tensile strength and the electrical property cannot be tested.
(3) Heat resistance test
The heat resistance of a material is typically measured by a 5% thermal weight loss temperature.
10Mg of the cured film obtained in the film forming property test (2) above was filled into an aluminum standard container, and measured by a thermogravimetric analyzer (model: TGA55, manufacturer: TA).
Test conditions: the temperature was raised from room temperature to 600℃at a heating rate of 10℃per minute.
Among them, the thermal weight loss graph of the polyimide film obtained by curing the polyimide film at 250℃in example 1 of the present application and comparative example 1 is shown in FIG. 2.
(4) Tensile Strength test
Cutting the cured film obtained in the film forming property test (2) into sample strips (length <3cm, width <8 mm) meeting the test requirements by using a die, and carrying out tensile strength test on the sample strips by using a dynamic thermo-mechanical analyzer (model: DMA850, manufacturer: TA company), wherein the tensile force range is 0-18N, and the speed is: 3N/min; temperature range: 30-400 ℃, the rate is: 3 ℃/min.
(5) Dielectric property test
The cured film was cut to a size of 2cm×2cm. The dielectric constant of the polyimide film is tested by using an Agilent vector network analyzer E5071C by adopting a resonant cavity method, and the test frequency is 1MHz.
(6) Copper discoloration test
The composition was uniformly coated on a copper substrate, and then soft-baked on a heating table at 120℃for 3 minutes to obtain a resin film having a film thickness of 10 to 20. Mu.m, and after leaving at room temperature for 12 hours, the resin film was dissolved in a developer. The discoloration of the copper base material after dissolution of the resin film was evaluated according to the following criteria.
"Best": no discoloration of the copper substrate was confirmed even when observed with a 200-fold optical microscope under visual observation;
"Jia": no discoloration of the copper substrate was visually confirmed, and slight discoloration of the copper substrate was confirmed when observed with a 200-fold optical microscope;
"slightly good": a slight discoloration of the copper substrate was visually confirmed;
"difference": visual confirmation of severe discoloration of copper substrates
The above-prepared composition was evaluated in terms of imidization rate, film forming property, thermal stability, tensile strength, dielectric properties, copper discoloration test and the like as described above, and the results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the diamine monomer with the structure of nitrogen heterocycle and benzocyclobutene in the invention is used in the photosensitive resin composition, shows higher imidization rate at the low temperature of 250 ℃, can prepare a cured film with excellent film forming property, thermal stability and mechanical property, reduces the dielectric constant of the cured film, inhibits the discoloration of a copper substrate, and is suitable for the application field of low-temperature curing.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (10)

1. A diamine monomer having an azacyclic and benzocyclobutene structure, characterized by having a structural formula represented by the following formula (I):
wherein in the formula (I), W is an organic group containing nitrogen heterocycle.
2. The diamine monomer having an azacyclic and benzocyclobutene structure according to claim 1, wherein in the formula (i), the azacyclic ring is selected from any one of pyridine, benzothiazole, carbazole, indole, piperidine, thiazole;
Preferably, W is selected from any one of the groups of formula (ii), wherein the dashed line represents an access site;
3. A process for the preparation of diamine monomers having an azacyclic and benzocyclobutene structure as claimed in claim 1 or 2, characterized by comprising the steps of:
(1) Under the protection of inactive gas, the mixture I of aldehyde compound containing hydroxyl, 4-bromobenzocyclobutene, alkali and organic solvent is reacted to obtain an intermediate product X, wherein the reaction formula is as follows:
(2) Under the protection of inactive gas, reacting a mixture II of an intermediate product X, aniline hydrochloride and aniline to obtain the diamine monomer, wherein the reaction formula is as follows:
Wherein W is an organic group containing a nitrogen heterocycle.
4. The method for producing a diamine monomer having an azacyclic and benzocyclobutene structure according to claim 3, wherein the azacyclic ring is any one selected from the group consisting of pyridine, benzothiazole, carbazole, indole, piperidine and thiazole;
Preferably, W is selected from any one of the groups of formula (ii), wherein the dashed line represents an access site;
preferably, in step (1), the organic solvent comprises N, N-dimethylformamide;
preferably, in step (1), the base comprises potassium carbonate;
Preferably, in the step (1), the molar ratio of the hydroxyl-containing aldehyde compound to the 4-bromobenzocyclobutene is 1:0.9-1.1;
In step (2), the molar ratio of intermediate X, aniline hydrochloride and aniline is 1:3 to 5: 8-12.
5. The process for producing a diamine monomer having an azacyclic and benzocyclobutene structure as claimed in claim 3, wherein in the step (1), the temperature of the reaction I is 130 to 150℃for 20 to 30 hours;
Preferably, in step (2), the temperature of reaction II is 150-180℃and the time is 5-8 hours.
6. A resin precursor is characterized by being obtained by a reaction of a mixture III comprising dianhydride monomers and diamine monomers;
the diamine monomer comprises the diamine having an azacyclic ring and benzocyclobutene structure as described in claim 1 or 2;
the diamine monomer also includes a diamine monomer having no nitrogen heterocycle and benzocyclobutene structure.
7. The resin precursor according to claim 6, wherein, the diamine monomer without nitrogen heterocycle and benzocyclobutene structure is selected from 2, 2-bis [ 4-hydroxy-3- (3-amino) benzamido ] hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (3-aminophenyl) hexafluoropropane, 9-bis (3-amino-4-hydroxyphenyl) fluorene, 2-bis (3-amino-4-hydroxyphenyl) propane, 4 '-diaminodiphenyl ether 3,4' -diaminodiphenyl ether, 1, 3-bis (3-aminophenoxy) benzene, biphenyldiamine, p-phenylenediamine, 3 '-dihydroxybenzidine, 2' -bis (3-amino-4-hydroxyphenyl) propane one or more of 2,2 '-bis (3-amino-4-hydroxyphenyl) diphenyl sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane, 2' -bis [4- (4-aminophenoxyphenyl) ] propane, and the like;
Preferably, the dianhydride monomer is selected from pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2,3',3,4' -diphenyl ether tetracarboxylic dianhydride, 3,4,3',4' -benzophenone tetracarboxylic dianhydride, 3', one or more of 4,4' -diphenyl sulfone tetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 4'- (hexafluoroisopropylidene) dicarboxylic anhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 4' - (hexafluoroisopropylidene) isophthalic anhydride, and the like;
preferably, the content of the diamine with an azacyclic ring and benzocyclobutene structure is 1-50% of the total molar amount of diamine monomers;
Preferably, the content of the diamine with the nitrogen heterocycle and benzocyclobutene structure is 10-30% of the total molar weight of the diamine monomer;
preferably, the resin precursor is polyimide or a precursor thereof;
Preferably, the polyimide precursor is a polyamic acid or polyamic acid ester.
8. The method for producing a resin precursor according to claim 6, wherein,
When the resin precursor is a polyamic acid, it comprises: and (3) reacting the mixture III comprising the dianhydride monomer and the diamine monomer to obtain a polyamic acid solution.
When the resin precursor is a polyamic acid ester, comprising the steps of:
reacting a mixture III comprising dianhydride monomers and diamine monomers to obtain polyamide acid solution;
(II) reacting the mixture IV comprising the polyamic acid obtained in the step (I) and an esterification reagent to obtain a polyamic acid ester solution;
Preferably, the temperature of the reaction III is 20-80 ℃ and the time is 1-24 h;
Preferably, the temperature of the reaction IV is 40-100 ℃ and the time is 1-12 h.
9. A photosensitive resin composition comprising the resin precursor according to claim 6, a photosensitive agent, a silane coupling agent and a solvent.
10. A method for producing the photosensitive resin composition according to claim 9, comprising: and (3) stirring and filtering the mixture V of the resin precursor, the photosensitive agent, the silane coupling agent and the solvent to obtain the photosensitive resin composition.
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