[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN118108661B - 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

Info

Publication number
CN118108661B
CN118108661B CN202410111699.2A CN202410111699A CN118108661B CN 118108661 B CN118108661 B CN 118108661B CN 202410111699 A CN202410111699 A CN 202410111699A CN 118108661 B CN118108661 B CN 118108661B
Authority
CN
China
Prior art keywords
diamine monomer
reaction
monomer
azacyclic
diamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202410111699.2A
Other languages
Chinese (zh)
Other versions
CN118108661A (en
Inventor
王珂
盛泽东
李铭新
虞连亭
孙洪阳
陈存浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bomi Technology Co ltd
Original Assignee
Bomi Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bomi Technology Co ltd filed Critical Bomi Technology Co ltd
Priority to CN202410111699.2A priority Critical patent/CN118108661B/en
Publication of CN118108661A publication Critical patent/CN118108661A/en
Application granted granted Critical
Publication of CN118108661B publication Critical patent/CN118108661B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G73/22—Polybenzoxazoles
    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (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. The diamine monomer with the nitrogen heterocycle and benzocyclobutene structure has a structural formula shown in the following formula (I): the diamine monomer containing an o-hydroxyanilino group can be used for preparing a polybenzoxazole precursor resin, and further, a photosensitive resin composition excellent in photosensitivity can be prepared, and a cured film can be prepared from the photosensitive resin composition, and since a benzocyclobutene structure is crosslinked upon thermal curing, film forming property, solvent resistance, mechanical properties and thermal stability of the cured film can be improved. The presence of the heterocyclic N atom can lower the dielectric constant of the cured film while inhibiting 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
In recent years, polybenzoxazole (PBO) has been attracting attention due to its excellent heat resistance, mechanical properties, chemical resistance and low water absorption, and is generally used as an insulating material for electronic components, a passivation film, a surface protective film, an interlayer insulating film, and the like for semiconductor devices. By applying, exposing, developing and curing the photosensitive polybenzoxazole resin composition, not only a fine pattern but also a relief pattern coating film having high heat resistance can be formed. With the development of aerospace and national defense military equipment, the performance requirements of the high-end field on PBO materials are higher and higher.
In order to improve the heat resistance and mechanical strength of the cured film, a thermal crosslinking agent, for example, a thermal crosslinking agent containing an alkoxymethyl group, a hydroxymethyl group, an epoxy group, an unsaturated group, or the like, is generally introduced, and the thermal crosslinking agent is condensed with a resin and the same kind of molecules to form a crosslinked structure, but if the resin itself lacks crosslinkability, even if the thermal crosslinking agent is added, it is not possible to ensure sufficient mechanical properties and thermal stability of the cured film, and it is difficult to achieve both low stress and the like. The dielectric constant of the conventional PBO is generally 2.9 to 3.3, but in order to cope with the trend of miniaturization, high density and multi-functionalization of electronic products, the dielectric constant performance thereof needs to be further reduced. In addition, the resin easily reacts with the substrate such as copper and copper alloy, and corrodes the substrate, resulting in problems of poor adhesion of the cured film to the substrate, discoloration of the substrate, poor reliability, and the like.
When the PBO 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. However, the PBO materials in the prior art cannot meet the above performance requirements at the same time, so that development of PBO materials having excellent film forming properties, mechanical properties, thermal stability and dielectric properties is becoming 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 contains an o-hydroxyanilino group and can be used for preparing a polybenzoxazole precursor resin, and thus a photosensitive resin composition excellent in photosensitivity, from which a cured film can be prepared, and which can improve film forming property, solvent resistance, mechanical properties and thermal stability of the cured film due to crosslinking of the benzocyclobutene structure upon thermal curing. The presence of the heterocyclic N atom can lower the dielectric constant of the cured film while inhibiting 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 I is reacted to obtain an intermediate product X, wherein the reaction formula is as follows:
(2) Under the protection of inactive gas, reacting the mixture II of the intermediate product X and the 2-methoxyaniline under the condition of concentrated HCl to obtain an intermediate product Y, wherein the reaction formula is as follows:
(3) And (3) reacting the intermediate product Y under the condition of concentrated HBr 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 i 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 time of the reaction I is 20-30 h. Preferably, in the step (1), the temperature of the reaction I is 135-145 ℃ and the reaction time is 22-26h.
Optionally, the inert gas is nitrogen or other inert gas.
Optionally, in the step (2), the molar ratio of the intermediate product X to the 2-methoxyaniline is 1:1-3.
Specifically, in the step (2), the molar ratio of the intermediate product X to the 2-methoxyaniline is 1:2.
Optionally, in the step (2), the temperature of the reaction II is 80-150 ℃, and the time of the reaction II is 5-8h.
Preferably, in step (2), the temperature of reaction II is from 100 to 150 ℃.
Optionally, in step (3), the concentrated HBr is present in a concentration of 45 to 55wt%.
Optionally, in the step (3), heating is performed to a reflux state during the reaction III, and the time of the reaction III is 8-15 h.
The intermediate product Y is heated and refluxed under the environment of concentrated hydrobromic acid (HBr), and ether bonds are broken to generate hydroxyl.
In yet another aspect, the present application provides a polybenzoxazole precursor resin having a structural formula shown in the following formula (III):
Wherein in formula (III), X is derived from the residual fraction of the diacid chloride monomer after removal of the end groups of the acid chloride;
Y is derived from the residual part of the diamine monomer after the terminal amine group is removed;
The diamine monomer comprises a diamine monomer A and a diamine monomer B;
The diamine monomer A is the diamine monomer with an azacyclic ring and benzocyclobutene structure;
the diamine monomer B is a diamine monomer which does not have a structure shown in a formula (I).
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 monomer A comprises 1 to 50%, preferably 10 to 30% of the total molar amount of diamine monomer.
Optionally, the diamine monomer B is selected from one or more of bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene.
Alternatively, the diacid chloride monomer is selected from one or more of isophthaloyl dichloride, terephthaloyl dichloride, 2, 6-naphthalene dicarboxylic acid dichloride, 4' -diacid-dichloride diphenyl ether, and 2, 2-bis (4-chloroformylphenoxy) propane.
Alternatively, the polybenzoxazole precursor resin has a weight average molecular weight of 2 to 2.3 ten thousand.
In still another aspect, the present application provides a method for preparing the polybenzoxazole precursor resin, including: reacting a mixture III of an organic solvent II, a diamine monomer and a diacid chloride monomer to obtain the polybenzoxazole precursor resin;
The diamine monomer comprises a diamine monomer A and a diamine monomer B;
The diamine monomer A is the diamine monomer with an azacyclic ring and benzocyclobutene structure;
the diamine monomer B is a diamine monomer which does not have a structure shown in a formula (I).
Optionally, the organic solvent II comprises anhydrous N-methyl pyrrolidone.
Optionally, the temperature of the reaction IV is 20-30 ℃, and the time of the reaction IV is 20-48 h.
Further, the reaction IV is carried out under the protection of inactive gas.
Optionally, the inert gas is nitrogen or other inert gas.
Optionally, the molar ratio of diamine monomer to diacid chloride monomer is 1 (1-1.5).
Preferably, the molar ratio of diamine monomer to diacid chloride monomer is 1 (1-1.1).
Optionally, the preparation method of the polybenzoxazole precursor resin comprises the following steps: dissolving metered diamine monomer in anhydrous N-methyl pyrrolidone (NMP), adding a solution dissolved with diacid chloride monomer at a low temperature of 0-5 ℃, continuously stirring at the temperature for reaction for 30-60 min, continuously stirring at a room temperature of 20-25 ℃ for reaction for 20-48 h to obtain polybenzoxazole precursor resin solution, and pouring the solution into a methanol-water solution to precipitate a polymer to obtain the polybenzoxazole precursor resin.
In still another aspect, the present application provides a photosensitive resin composition comprising the above polybenzoxazole precursor resin, 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 polybenzoxazole precursor resin to the sensitizer is 100 (5-40); preferably, the weight ratio of polybenzoxazole precursor resin to 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 polybenzoxazole precursor resin to solvent is 100 (100-2000); preferably, the weight ratio of polybenzoxazole precursor resin to 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 polybenzoxazole precursor resin 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 IV of the polybenzoxazole precursor resin, the photosensitive agent, the silane coupling agent and the solvent to obtain the photosensitive resin composition.
Optionally, the mixture IV further comprises an acrylic surfactant.
Alternatively, the viscosity of the photosensitive resin composition is 500 to 5000cP, preferably 1500 to 2000cP.
Optionally, the method for preparing the photosensitive resin composition includes: and dissolving the polybenzoxazole precursor resin in a solvent, adding a photosensitive agent, adding a silane coupling agent after dissolving, stirring until the mixture is completely dispersed, and performing pressure filtration to obtain the photosensitive resin composition.
In yet another aspect, the present application provides a polybenzoxazole film prepared from the photosensitive resin composition described above.
The polybenzoxazole film of the application is used as a semiconductor interlayer insulating film, a semiconductor protective film and an etching protective film.
In another aspect, the present application provides a method for preparing a polybenzoxazole film, including: and (3) coating the photosensitive resin composition on a substrate, and drying, exposing, developing and curing to obtain the polybenzoxazole film.
In the above-mentioned method for producing a polybenzoxazole film, the coated substrate is not particularly limited, and those skilled in the art may make routine selections, and alternatively, the coated substrate is selected from any one or more of a silicon wafer, an aluminum sheet, a silver sheet, a copper alloy sheet, and a ceramic sheet, preferably, a four-inch copper substrate.
The specific coating method of the present application is also not particularly limited, and alternatively, the coating method is selected from one or more of spray coating, spin coating, doctor blade, and the film thickness may vary during the actual coating operation due to the coating method, rotation speed, viscosity, composition, and the like. The coating method is preferably spin coating.
In the above-mentioned method for producing a polybenzoxazole film, the drying method may be a baking operation, and specifically, baking may be performed by using an oven, a heating stage, an infrared lamp or the like, preferably, baking by using a heating stage. Optionally, the drying temperature is 80-150deg.C, the drying time is 1-10min, preferably, the drying temperature is 100-130deg.C, and the drying time is 2-5min. After the drying operation was completed, the thickness of the photosensitive resin film was measured after naturally cooling to 25 ℃.
In the above-mentioned method for producing a polybenzoxazole film, the exposure step is performed by exposing the dried photosensitive resin film layer to light through a patterned mask plate by an exposure apparatus. Typical active rays include ultraviolet rays, X-rays, electron beams, etc., and in the present invention, exposure treatment using a mercury lamp is preferable, wherein the exposure treatment includes three light sources of i-line (365 nm), h-line (405 nm), g-line (436 nm).
In the preparation method of the polybenzoxazole film, the developing solution is adopted to dissolve and form a pattern to complete the development. Alternatively, the developing solution is selected from the group consisting of N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, methanol, ethanol, isopropanol, ethyl lactate, butyl acetate, propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone, isobutyl ketone, aqueous tetramethylammonium hydroxide, and the like. Rinsing with rinsing liquid after development. Common rinse solutions are: deionized water, ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate.
Optionally, the specific operation of developing is: pouring developing solution and rinsing solution into the two glass culture dishes respectively, controlling the temperature of the developing solution to be 25+/-1 ℃, immersing the exposed resin film into the developing solution, starting timing immediately, finishing development after the developed part is completely exposed out of the substrate, stopping timing, and recording the time required by the whole process.
In the above-mentioned process for producing a polybenzoxazole film, the curing temperature is 300 to 400℃and preferably 350 ℃. The pattern obtained after the development and rinsing is subjected to thermal imidization to be converted into a cured film. The heating treatment is usually carried out by a stepwise heating, and a continuous heating at different temperatures for a certain period of time or a certain temperature range. For example, a heat treatment method in which the temperature is 150℃and 250℃and 350℃is carried out for 30 minutes, a method in which the temperature is continuously raised from room temperature to 350℃or the like is carried out. Inert gases such as nitrogen and argon are often used for curing. As a specific application example, firstly controlling the oxygen content in the oven cavity to be reduced to below 50ppm, then starting to heat to 150 ℃ and keeping the temperature for 30 minutes, then heating to 250 ℃ and keeping the temperature for 30 minutes, then heating to 350 ℃ and keeping the temperature for 1 hour, and cooling to room temperature, thus finally obtaining the cured relief pattern.
The polybenzoxazole film formed by the photosensitive resin composition provided by the application has high heat resistance and high mechanical strength, and can be used for surface protection films, interlayer dielectrics or insulating layers of semiconductor elements and insulating layers for protecting circuit board circuits. An electronic device such as a surface protective layer and an interlayer insulating layer obtained by using the photosensitive resin composition provided by the present application includes, for example: magnetoresistive memory, polymer memory, phase change memory, etc.
In yet another aspect, the present application provides a semiconductor device comprising a polybenzoxazole film.
The semiconductor element of the present application preferably comprises a polybenzoxazole film with a cured relief pattern.
The application has the beneficial effects that:
The present application provides a diamine monomer having an azacyclic and benzocyclobutene structure, which contains an o-hydroxyanilino group and can be used for preparing a polybenzoxazole precursor resin, thereby preparing a photosensitive resin composition having excellent photosensitivity, and a cured film can be prepared from the photosensitive resin composition, and since the benzocyclobutene structure is crosslinked upon thermal curing, film forming property, solvent resistance, mechanical properties and thermal stability of the cured film can be improved. The presence of the heterocyclic N atom can lower the dielectric constant of the cured film while inhibiting discoloration of the copper or copper alloy substrate.
Drawings
FIG. 1 is a graph showing the thermal weight loss of polybenzoxazole films obtained by high temperature curing of example 1 and comparative example 1.
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;
2-Methoxyaniline (3.08 g,25.0 mmol) was placed in a 200mL flask, heated to 100℃with stirring, a mixed solution of intermediate X1 (3.77 g,12.5 mmol) and 0.66g of concentrated hydrochloric acid was slowly added dropwise, and after the addition was completed, the reaction was continued at 100℃for 5 hours, and then cooled to 70 ℃. The reaction mixture was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying with sodium sulfate, and concentrating under reduced pressure to obtain intermediate Y1.
Intermediate Y1 (6.36 g,12.0 mmol), 40mL acetic acid, 40mL hydrobromic acid (47%) were placed in a 200mL flask and heated to reflux with stirring. After reaction at reflux for 8 hours, cool to room temperature. The reaction solution was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying over sodium sulfate, and concentrating under reduced pressure to obtain diamine monomer A1.
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;
2-Methoxyaniline (3.08 g,25.0 mmol) was placed in a 200mL flask, heated to 100deg.C with stirring, a mixed solution of intermediate X2 (4.64 g,12.5 mmol) and 0.66g concentrated hydrochloric acid was slowly added dropwise, and after the addition was completed, the reaction was continued at 100deg.C for 5 hours, and then cooled to 70deg.C. The reaction mixture was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying with sodium sulfate, and concentrating under reduced pressure to obtain intermediate Y2.
Intermediate Y2 (7.20 g,12.0 mmol), 40mL acetic acid, 40mL hydrobromic acid (47%) were placed in a 200mL flask and heated to reflux with stirring. After reaction at reflux for 8 hours, cool to room temperature. The reaction solution was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying over sodium sulfate, and concentrating under reduced pressure to obtain diamine monomer A2.
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 ℃;
2-Methoxyaniline (3.08 g,25.0 mmol) was placed in a 200mL flask, heated to 100deg.C with stirring, a mixed solution of intermediate X3 (3.92 g,12.5 mmol) and 0.66g concentrated hydrochloric acid was slowly added dropwise, and after the addition was completed, the reaction was continued at 100deg.C for 5 hours, and then cooled to 70deg.C. The reaction mixture was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying with sodium sulfate, and concentrating under reduced pressure to obtain intermediate Y3.
Intermediate Y3 (6.50 g,12.0 mmol), 40mL acetic acid, 40mL hydrobromic acid (47%) were placed in a 200mL flask and heated to reflux with stirring. After reaction at reflux for 8 hours, cool to room temperature. The reaction solution was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying over sodium sulfate, and concentrating under reduced pressure to obtain diamine monomer A3.
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;
2-Methoxyaniline (3.08 g,25.0 mmol) was placed in a 200mL flask, heated to 100deg.C with stirring, a mixed solution of intermediate X4 (3.29 g,12.5 mmol) and 0.66g concentrated hydrochloric acid was slowly added dropwise, and after the addition was completed, the reaction was continued at 100deg.C for 5 hours, and then cooled to 70deg.C. The reaction mixture was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying with sodium sulfate, and concentrating under reduced pressure to obtain intermediate Y4.
Intermediate Y4 (5.90 g,12.0 mmol), 40mL acetic acid, 40mL hydrobromic acid (47%) were placed in a 200mL flask and heated to reflux with stirring. After reaction at reflux for 8 hours, cool to room temperature. The reaction solution was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying over sodium sulfate, and concentrating under reduced pressure to obtain diamine monomer A4.
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;
2-Methoxyaniline (3.08 g,25.0 mmol) was placed in a 200mL flask, heated to 100deg.C with stirring, a mixed solution of intermediate X5 (3.84 g,12.5 mmol) and 0.66g concentrated hydrochloric acid was slowly added dropwise, and after the addition was completed, the reaction was continued at 100deg.C for 5 hours, and then cooled to 70deg.C. The reaction mixture was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying with sodium sulfate, and concentrating under reduced pressure to obtain intermediate Y5.
Intermediate Y5 (6.43 g,12.0 mmol), 40mL acetic acid, 40mL hydrobromic acid (47%) were placed in a 200mL flask and heated to reflux with stirring. After reaction at reflux for 8 hours, cool to room temperature. The reaction solution was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying over sodium sulfate, and concentrating under reduced pressure to obtain diamine monomer A5.
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;
2-Methoxyaniline (3.08 g,25.0 mmol) was placed in a 200mL flask, heated to 100deg.C with stirring, a mixed solution of intermediate X6 (3.84 g,12.5 mmol) and 0.66g concentrated hydrochloric acid was slowly added dropwise, and after the addition was completed, the reaction was continued at 100deg.C for 5 hours, and then cooled to 70deg.C. The reaction mixture was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying with sodium sulfate, and concentrating under reduced pressure to obtain intermediate Y6.
Intermediate Y6 (6.43 g,12.0 mmol), 40mL acetic acid, 40mL hydrobromic acid (47%) were placed in a 200mL flask and heated to reflux with stirring. After reaction at reflux for 8 hours, cool to room temperature. The reaction solution was neutralized with a 20% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. Washing with pure water, drying over sodium sulfate, and concentrating under reduced pressure to obtain diamine monomer A6.
Example 1
100G of N-methylpyrrolidone (NMP), 12.36g (33.75 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP) and 5.64g (11.25 mmol) of diamine monomer A were successively added to a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen stream, and dissolved by stirring, and at this temperature, 14.61g (49.5 mmol) of 4,4' -diphenylether dicarboxylic acid chloride was added over 10 minutes and the reaction was continued for 30 minutes. And (3) returning the system to the room temperature of 25 ℃, and continuing to stir and react for 24 hours to obtain the polybenzoxazole precursor solution. The solution was poured into a methanol-water solution to precipitate a polymer, and the precipitate was placed in a vacuum oven and dried at 80℃for 72hr to obtain a polybenzoxazole precursor resin.
The molecular weight of the polybenzoxazole precursor resin was determined by gel permeation chromatography (GPC, shimadzu LC-20 AD) in terms of standard polystyrene with N-methylpyrrolidone as eluent at 40℃in the column oven. The polybenzoxazole precursor resin was found to have a weight average molecular weight (Mw) of 2 to 2.3 ten thousand.
In a three-necked flask equipped with stirring, 10.0g of the synthesized polybenzoxazole precursor resin 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 P-1.
Example 2
A photosensitive resin composition P-2 was obtained in the same manner as in example 1 except that 5.64g (11.25 mmol) of the diamine monomer A1 was replaced with 6.43g (11.25 mmol) of the diamine monomer A2.
Example 3
A photosensitive resin composition P-3 was obtained in the same manner as in example 1 except that 5.64g (11.25 mmol) of the diamine monomer A1 was replaced with 5.78g (11.25 mmol) of the diamine monomer A3.
Example 4
A photosensitive resin composition P-4 was obtained in the same manner as in example 1 except that 5.64g (11.25 mmol) of the diamine monomer A1 was replaced with 5.21g (11.25 mmol) of the diamine monomer A4.
Example 5
A photosensitive resin composition P-5 was obtained in the same manner as in example 1 except that 5.64g (11.25 mmol) of the diamine monomer A1 was replaced with 5.71g (11.25 mmol) of the diamine monomer A5.
Example 6
A photosensitive resin composition P-6 was obtained in the same manner as in example 1 except that 5.64g (11.25 mmol) of the diamine monomer A1 was replaced with 5.71g (11.25 mmol) of the diamine monomer A6.
Example 7
A photosensitive resin composition P-7 was obtained in the same manner as in example 1 except that 5.64g (11.25 mmol) of the diamine monomer A1 was replaced with 4.57g (9.00 mmol) of the diamine monomer A6 and 12.36g (33.75 mmol) of the 6FAP was replaced with 13.19g (36.00 mmol) of the 6 FAP.
Example 8
A photosensitive resin composition P-8 was obtained in the same manner as in example 1 except that 5.64g (11.25 mmol) of the diamine monomer A1 was replaced with 6.85g (13.50 mmol) of the diamine monomer A6 and 12.36g (33.75 mmol) of the 6FAP was replaced with 11.54g (31.5 mmol) of the 6 FAP.
Example 9
A photosensitive resin composition P-9 was obtained in the same manner as in example 1 except that 5.64g (11.25 mmol) of the diamine monomer A1 was replaced with 2.82g (5.625 mmol) of the diamine monomer A1 and 2.89g (5.625 mmol) of the diamine monomer A3.
Example 10
A photosensitive resin composition P-10 was obtained in the same manner as in example 1 except that 5.64g (11.25 mmol) of the diamine monomer A1 was replaced with 3.22g (5.625 mmol) of the diamine monomer A2 and 2.86g (5.625 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 5.64g (11.25 mmol) of the diamine monomer A1 was replaced with 2.61g (5.625 mmol) of the diamine monomer A4 and 2.86g (5.625 mmol) of the diamine monomer A6.
Comparative example 1
100G of N-methylpyrrolidone (NMP), 16.48g (45 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP) and a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer were successively charged under a nitrogen stream, dissolved by stirring, placed at a low temperature of 0 to 5℃and 14.61g (49.5 mmol) of 4,4' -diphenylether dicarboxylic acid chloride was added at this temperature for 10 minutes and the reaction was continued for 30 minutes. And (3) returning the system to the room temperature of 25 ℃, and continuing to stir and react for 24 hours to obtain the polybenzoxazole precursor solution. The solution was poured into a methanol-water solution to precipitate a polymer, and the precipitate was placed in a vacuum oven and dried at 80℃for 72hr to obtain a polybenzoxazole precursor resin.
The molecular weight of the polybenzoxazole precursor resin was determined by gel permeation chromatography (GPC, shimadzu LC-20 AD) in terms of standard polystyrene with N-methylpyrrolidone as eluent at 40℃in the column oven. The polybenzoxazole precursor resin was found to have a weight average molecular weight (Mw) of 2 to 2.3 ten thousand.
In a three-necked flask equipped with stirring, 10.0g of the synthesized polybenzoxazole precursor resin 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 carried out with a 1.0 μm PTFE filter membrane to obtain a photosensitive resin composition Q-1.
The photosensitive resin composition prepared above was tested for photosensitivity, film forming property, thermal stability, stretching mildness, dielectric property and copper discoloration by the following methods:
(1) Photosensitivity test
Coating the resin composition glue solution on a 4-inch substrate by using a spin coater, and placing the substrate on a heating table for soft drying at 120 ℃ for 3min to obtain a resin film with the film thickness of 7-8 mu m. A film thickness of a was measured by a step-down machine (P-7, KLA-Tencor, U.S.A.), the above-mentioned silicon wafer was placed on an exposure machine (BG-401A, manufactured by forty-five research institute of China electronics and technology group Co., ltd.), a mask was placed thereon, 365nm light (i-line) was selected, and the photosensitive resin film was exposed to light with an energy of 250mJ/cm 2. The exposed silicon wafer is put into alkaline developer (2.38% TMAH, 25+ -1deg.C) for development, the time for the recorded pattern to fully show (substrate exposed) is T 1, and the time for the non-exposure area coating adhesive to fully dissolve is T 2.
The dissolution rate of the exposed area was calculated by the following formula (unit: μm/s):
exposure area dissolution rate = a/T 1
The dissolution rate of the non-exposed areas was calculated by the following formula (unit: μm/s):
Non-exposed area dissolution rate = a/T 2
Contrast = dissolution rate of exposed areas/dissolution rate of unexposed areas, contrast greater than 5 can meet photosensitive application requirements.
(2) Film Forming test
The resin composition was applied to a4 inch silicon substrate using a spin coater and soft-baked at 120℃for 3 minutes on a heated stage 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: heating to 150 ℃ and keeping the temperature for 30 minutes, heating to 250 ℃ and keeping the temperature for 30 minutes, heating to 350 ℃ and keeping the temperature for 1 hour, and cooling to room temperature to obtain the resin cured film.
And (3) placing the silicon wafer with the resin cured 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 thermal stability of the cured film was measured using a temperature of 5% thermal weight loss (decomposition temperature at 5% weight reduction, i.e., T 5wt％). The temperature was measured by a thermogravimetric analyzer (TA company, Q50 series, USA) under a nitrogen atmosphere at a heating rate of 10 ℃/min and a temperature range of (30-650).
(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 polybenzoxazole film was measured by using Agilent vector network analyzer E5071C using the resonant cavity method at a test frequency of 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": the copper substrate was visually confirmed to be severely discolored.
The test results are shown in table 1:
TABLE 1
As is clear from the data in Table 1, the diamine monomer having an azacyclic ring and benzocyclobutene structure of the present application is used for preparing a polybenzoxazole precursor and used in a photosensitive resin composition, and a polybenzoxazole film excellent in film forming property, heat resistance and mechanical properties can be prepared by high temperature curing, and at the same time, the dielectric constant of the film is reduced, and discoloration of a copper base material is suppressed. In addition, after the exposure process, the solubility difference of the exposed part and the unexposed part of the photosensitive resin composition in an alkaline developing solution is large, the photosensitive resin composition has excellent contrast, clear patterns and meets the photosensitive application requirement.
FIG. 1 is a graph showing the thermal weight loss of the polybenzoxazole films obtained by curing example 1 and comparative example 1 at high temperature, and it can be seen from the graph that the mass retention rate of the polybenzoxazole film of example 1 is significantly better than that of comparative example 1.
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 (21)

1. Diamine monomer having an azacyclic and benzocyclobutene structure, characterized by having a structural formula represented by the following formula (I):
Wherein,
W is selected from any one of the groups represented by formula (II), wherein the dotted line represents an access site;
2. a process for the preparation of diamine monomer having an azacyclic and benzocyclobutene structure as claimed in claim 1, characterized by 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 I is reacted to obtain an intermediate product X, wherein the reaction formula is as follows:
(2) Under the protection of inactive gas, reacting the mixture II of the intermediate product X and the 2-methoxyaniline under the condition of concentrated HCl to obtain an intermediate product Y, wherein the reaction formula is as follows:
(3) And (3) reacting the intermediate product Y under the condition of concentrated HBr to obtain the diamine monomer, wherein the reaction formula is as follows:
Wherein,
W is selected from any one of the groups represented by formula (II), wherein the dotted line represents an access site;
3. The process for producing a diamine monomer having an azacyclic and benzocyclobutene structure as claimed in claim 2, wherein,
The hydroxyl-containing aldehyde compound is selected from one or more of the compounds shown in the following structures:
4. The method for producing diamine monomer having an azacyclic and benzocyclobutene structure as claimed in claim 2, wherein in the step (1), the organic solvent I is N, N-dimethylformamide.
5. The method for producing diamine monomer having an azacyclic and benzocyclobutene structure as claimed in claim 2, wherein in the step (1), the base is potassium carbonate.
6. The method for producing a diamine monomer having an azacyclic and benzocyclobutene structure according to claim 2, wherein in the step (1), the molar ratio of the hydroxyl group-containing aldehyde compound to 4-bromobenzocyclobutene is 1:0.9 to 1.1.
7. The method for producing a diamine monomer having an azacyclic and benzocyclobutene structure according to claim 2, wherein in the step (2), the molar ratio of the intermediate product X to 2-methoxyaniline is 1:1 to 3.
8. The process for producing a diamine monomer having an azacyclic and benzocyclobutene structure as claimed in claim 2, wherein in the step (1), the temperature of the reaction I is 130 to 150℃and the time of the reaction I is 20 to 30 hours.
9. The process for producing a diamine monomer having an azacyclic and benzocyclobutene structure as claimed in claim 2, wherein in the step (2), the temperature of the reaction II is 80 to 150℃and the time of the reaction II is 5 to 8 hours.
10. The process for producing a diamine monomer having an azacyclic and benzocyclobutene structure as claimed in claim 2, wherein in the step (3), the reaction III is heated to a reflux state for 8 to 15 hours.
11. A polybenzoxazole precursor resin characterized by having a structural formula represented by the following formula (III):
Wherein in formula (III), X is derived from the residual fraction of the diacid chloride monomer after removal of the end groups of the acid chloride;
Y is derived from the residual part of the diamine monomer after the terminal amine group is removed;
The weight average molecular weight of the polybenzoxazole precursor resin is 2 to 2.3 ten thousand;
The diamine monomer is diamine monomer A and diamine monomer B;
the diamine monomer A is the diamine monomer with an azacyclic ring and benzocyclobutene structure as described in claim 1;
the diamine monomer B is a diamine monomer which does not have a structure shown in a formula (I).
12. The polybenzoxazole precursor resin according to claim 11 wherein the diamine monomer B is selected from one or more of bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene.
13. The polybenzoxazole precursor resin according to claim 11 wherein the diacid chloride monomer is selected from one or more of isophthaloyl dichloride, terephthaloyl dichloride, 2, 6-naphthaloyl dichloride, 4' -diacid chloride diphenyl ether, 2-bis (4-chloroformylphenoxy) propane.
14. The polybenzoxazole precursor resin according to claim 11 wherein the diamine monomer a accounts for 1 to 50% of the total molar amount of diamine monomers.
15. The polybenzoxazole precursor resin according to claim 11 wherein the diamine monomer a accounts for 10 to 30% of the total molar amount of diamine monomers.
16. A method for producing the polybenzoxazole precursor resin according to any one of claims 11 to 15, including: reacting a mixture III of an organic solvent II, a diamine monomer and a diacid chloride monomer to obtain the polybenzoxazole precursor resin;
The diamine monomer is diamine monomer A and diamine monomer B;
the diamine monomer A is the diamine monomer of claim 1;
The diamine monomer B is a diamine monomer which does not have a structure shown in a formula (I);
the organic solvent II is anhydrous N-methyl pyrrolidone.
17. A process according to claim 16, wherein the molar ratio of diamine monomer to diacid chloride monomer is 1 (1) to 1.5.
18. A process according to claim 16, wherein the reaction iv is carried out at a temperature of 20 to 30 ℃ for a period of 20 to 48 hours.
19. A photosensitive resin composition comprising the polybenzoxazole precursor resin according to any one of claims 11 to 15, a photosensitive agent, a silane coupling agent and a solvent.
20. A polybenzoxazole film is characterized in that, the film is prepared from the photosensitive resin composition of claim 19.
21. A semiconductor device comprising the polybenzoxazole film according to claim 20.
CN202410111699.2A 2024-01-25 2024-01-25 Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof Active CN118108661B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202410111699.2A CN118108661B (en) 2024-01-25 2024-01-25 Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202410111699.2A CN118108661B (en) 2024-01-25 2024-01-25 Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN118108661A CN118108661A (en) 2024-05-31
CN118108661B true CN118108661B (en) 2024-09-20

Family

ID=91213322

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202410111699.2A Active CN118108661B (en) 2024-01-25 2024-01-25 Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN118108661B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105777519A (en) * 2014-12-19 2016-07-20 中国科学院上海有机化学研究所 Bisphenol or dual amine containing benzocyclobutene structure unit, preparation and application thereof
CN107200845A (en) * 2017-06-14 2017-09-26 中国科学院上海有机化学研究所 A kind of high glass-transition temperature and low thermal expansion coefficient polyimide and its preparation method and application

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102336910B (en) * 2010-07-14 2015-04-08 株式会社Lg化学 Low temperature curable polyimide resin and method of preparing the same
KR20140118621A (en) * 2013-03-29 2014-10-08 코오롱인더스트리 주식회사 Positive-type photoresist composition, insulating film and OLED comprising the same
CN114315686B (en) * 2021-09-23 2022-09-06 波米科技有限公司 Alkynyl-containing diamine, preparation method thereof and application thereof in preparation of photosensitive resin composition
CN115639724B (en) * 2022-10-26 2023-08-08 波米科技有限公司 Preparation method and application of photosensitive resin composition
CN116333354B (en) * 2023-02-23 2024-07-12 深圳大学 Benzocyclobutene-based intrinsic crosslinked polyimide film and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105777519A (en) * 2014-12-19 2016-07-20 中国科学院上海有机化学研究所 Bisphenol or dual amine containing benzocyclobutene structure unit, preparation and application thereof
CN107200845A (en) * 2017-06-14 2017-09-26 中国科学院上海有机化学研究所 A kind of high glass-transition temperature and low thermal expansion coefficient polyimide and its preparation method and application

Also Published As

Publication number Publication date
CN118108661A (en) 2024-05-31

Similar Documents

Publication Publication Date Title
TWI761897B (en) Negative photosensitive resin composition, method for producing polyimide, method for producing hardened relief pattern, and semiconductor device
CN114315686B (en) Alkynyl-containing diamine, preparation method thereof and application thereof in preparation of photosensitive resin composition
WO2007034604A1 (en) Negative photosensitive resin composition, method of pattern forming and electronic part
JP2006313237A (en) Positive photosensitive resin composition, method for manufacturing pattern, and electronic component
JP5054158B2 (en) Positive photosensitive composition
CN115826360A (en) Photosensitive polyimide composition, method for producing pattern, cured product, and electronic component
JP5267415B2 (en) Resin composition and use thereof
JP4541944B2 (en) Photosensitive polyimide resin composition
CN118108661B (en) Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof
CN116841122B (en) Photosensitive resin composition and preparation method and application thereof
JP5099979B2 (en) Negative photosensitive resin composition, pattern manufacturing method, and electronic component
CN115974762B (en) Diamine monomer with bulky alkynyl side group, polybenzoxazole precursor, photosensitive resin composition and application thereof
KR101025395B1 (en) Negative photosensitive resin composition, method of pattern forming and electronic part
JP4672135B2 (en) Alkoxysilane compound and photosensitive resin composition
TW202039638A (en) Negative photosensitive resin composition, manufacturing method of polyimide and manufacturing method of cured protruded pattern wherein the negative photosensitive resin composition includes a polyimide precursor, a photopolymerization initiator, a silane coupling agent and an organic solvent
JPH11102069A (en) Positive photosensitive resin composition
CN117304225B (en) Alkynyl-containing compound, positive photosensitive resin composition, and preparation methods and applications thereof
TW201715301A (en) Photosensitive resin composition, photosensitive sheet, semiconductor device, and method for manufacturing semiconductor device
JP2005336125A (en) Photo acid generator and actinic ray-sensitive polymer composition using the same
JP2005062405A (en) Alkali-soluble photosensitive resin composition and method for forming resin layer
CN118125972B (en) Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof
KR20140073278A (en) High-tranparent POSS photosensitive varnish
CN116880123B (en) Polybenzoxazole photosensitive resin composition and preparation method and application thereof
JPH11143070A (en) Positive photosensitive resin composition
JP4622282B2 (en) Positive photosensitive resin composition, semiconductor device and display element

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant