CN114561009B - Preparation method and application of negative photosensitive polyamide acid ester resin and composition thereof - Google Patents

Preparation method and application of negative photosensitive polyamide acid ester resin and composition thereof Download PDF

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CN114561009B
CN114561009B CN202210190302.4A CN202210190302A CN114561009B CN 114561009 B CN114561009 B CN 114561009B CN 202210190302 A CN202210190302 A CN 202210190302A CN 114561009 B CN114561009 B CN 114561009B
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polyamic acid
acid ester
negative photosensitive
ester resin
photosensitive polyamic
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CN114561009A (en
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李铭新
韩兵
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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
    • C08G73/12—Unsaturated polyimide precursors
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0384—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the main chain of the photopolymer

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present application relates to a negative photosensitive polyamic acid ester resin and a composition thereof, wherein the negative photosensitive polyamic acid ester resin has a structure shown in the following formula I:

Description

Preparation method and application of negative photosensitive polyamide acid ester resin and composition thereof
Technical Field
The application relates to negative photosensitive polyamic acid ester resin and a composition thereof, belonging to the field of photosensitive materials.
Background
The photosensitive polyimide material has the advantages of high temperature resistance, low temperature resistance, corrosion resistance, high insulation, low dielectric constant, low dielectric loss, excellent mechanical property and the like, and is widely used for chip surface passivation layer films in the semiconductor manufacturing process, interlayer insulating films of a multi-layer metal interconnection structure, package substrate signal wire distribution of advanced microelectronic packages (BGA, CSP, siP and the like), ball making process of micro solder balls, stress buffering internal coating protective layer films of plastic package circuits, liquid crystal flat panel display manufacturing and the like.
Photosensitive polyimide materials are typically converted from their precursor polyamic acid or polyamic ester resins by thermal imidization. After the negative photosensitive polyamic acid ester resin is exposed by ultraviolet rays (UV, i or g lines), the exposure area generates photo-crosslinking reaction, so that the solubility in the developing solution is greatly reduced, and the non-exposure area is not affected; after development by the developer, the non-exposed areas are completely dissolved and the exposed areas remain, forming a lithographic pattern for metal wiring or via interconnection. With the rapid development of high-frequency and high-speed communication such as 5G, a clear demand is put on a packaging material such as photosensitive polyimide with low dielectric constant and low dielectric loss, so that the loss in the signal transmission process can be reduced. The photosensitive polyimide material synthesized by the prior art is difficult to meet the requirements of semiconductor packaging materials in the 5G era, so that the development of the photosensitive polyimide material with high transparency, high heat resistance, low dielectric constant and low dielectric loss has important significance.
Disclosure of Invention
The application provides a negative photosensitive polyamic acid ester resin and a preparation method thereof, and a negative photosensitive polyamic acid ester resin composition and a preparation method and application thereof. The polyimide film formed by photoinduced drawing and thermosetting the negative photosensitive polyamic acid ester resin composition has the characteristics of high transparency, high heat resistance, low dielectric constant, low dielectric loss and the like, and can meet the requirements of the 5G era on semiconductor packaging materials.
According to a first aspect of the present application, there is provided a negative photosensitive polyamic acid ester resin having a structure represented by the following formula I:
wherein R is 1 Selected from any one of the following structures:
R 2 selected from any one of the following structures:
R 3 、R 4 independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond;
R 5 、R 6 independently selected from hydrogen atoms, methyl groupsAny one of ethyl, propyl and allyl;
R 5 on any one of the carbon atoms of c=c;
n represents an integer of 2 to 200, an integer of 2 to 150, an integer of 2 to 100, or an integer of 2 to 50.
The applicant of the present application found that the negative photosensitive polyamic acid resin structure having the above structure does not contain an aromatic skeleton structure, but the polymer structure contains a large amount of rigid alicyclic structure, so that the film prepared from the polymer has high light transmittance, low dielectric constant and high heat resistance. In addition, the negative photosensitive polyamic acid resin structure is blocked by nadic anhydride series unsaturated aliphatic hydrocarbon, and further generates a crosslinking reaction in the curing process of the negative photosensitive polyamic acid resin composition, so that the chemical resistance and the heat resistance of the polyimide film are further improved.
Optionally, the R 3 And R is 4 Independently selected from one of a hydrogen atom, a saturated aliphatic group having 1 to 4 carbon atoms, and a group represented by the following formula II;
in formula II, R 7 、R 8 、R 9 An organic group independently selected from a hydrogen atom and a carbon number of 1 to 3, m represents an integer of 2 to 10;
and R is 3 、R 4 At least one of which is of a structure shown in a formula II;
the R3 and R4 structures represented by the 1-valent organic group shown in the general formula II are derived from alcohol compounds with carbon-carbon unsaturated double bonds, and the alcohol compounds are preferably alcohols with photopolymerization unsaturated double bonds, for example: 2-hydroxyethyl methacrylate, 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acrylamidoethyl alcohol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-methacryloyloxy-ethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like.
Some of the saturated aliphatic alcohols having 1 to 4 carbon atoms may be incorporated into the above alcohols, for example: methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, etc.
In a second aspect of the present application, there is provided a method for producing the negative photosensitive polyamic acid ester resin.
The preparation method of the negative photosensitive polyamide acid ester resin comprises the following steps:
(1) Obtaining an alicyclic diester dichloride represented by formula III below;
(2) Mixing the alicyclic diester diacid chloride obtained in the step (1) with diamine and a blocking agent, and reacting to obtain a polyamic acid ester resin solution;
(3) Mixing the polyamic acid ester resin solution obtained in the step (2) with a poor solvent to obtain the negative photosensitive polyamic acid ester resin;
the diamine in the step (2) has a structure shown in the following formula IV;
H 2 N-R 2 -NH 2 IV (IV)
Wherein R is 1 、R 2 、R 3 、R 4 And R in claim 1 1 、R 2 、R 3 、R 4 The same applies.
The negative photosensitive polyamic acid ester resin described herein can be obtained after the step (3), but washing and drying are also required after the step (3) in order to obtain a purer resin. Wherein the washing is performed with a poor solvent for 2 to 6 times, and the ratio of the poor solvent used for each washing to the negative photosensitive polyamic acid ester resin to be washed is (1-6): 1 in terms of weight ratio. The drying adopts a vacuum drying method, and the drying temperature is 20-70 ℃.
In the above reaction, the concentration of the dianhydride, diester diacid and diamine in the reactant raw materials may be such that the monomers are sufficiently dissolved and the resulting polymer is not precipitated. If the monomer concentration is too high, the polymer will precipitate; whereas if the concentration is too low, the molecular weight of the polymer does not increase. Thus, the monomer concentration of the present invention may be 5 to 35wt%, preferably 10 to 30wt%, relative to the total mass of the reaction liquid.
Optionally, the end capping agent in the step (2) is at least one selected from substances having structures shown in the following N1 to N9:
optionally, the alicyclic diester diacid chloride of step (1) is prepared in the following manner:
(1-1) A compound R is reacted with an alicyclic tetracarboxylic dianhydride represented by the following formula V 3 -OH and/or R 4 Mixing and reacting-OH to obtain alicyclic diester diacid shown in the following formula VI;
(1-2) mixing the alicyclic diester diacid obtained in the step (1-1) with an acyl chloride reagent, and reacting to obtain the alicyclic diester diacid chloride.
Optionally, in the step (2), the molar ratio of diamine to alicyclic diester diacid chloride is (0.8-1.2): 1;
preferably, in the step (2), the temperature of the reaction is 0-10 ℃, and the total time of the reaction is 5-15 hours;
Further preferably, in the step (3), the poor solvent is at least one selected from the group consisting of water, methanol, ethanol, hexane, butyl cellosolve, and toluene.
Specifically, the preparation method of the alicyclic diester diacid chloride is as follows: the alicyclic tetracarboxylic dianhydride reacts with the unsaturated double bond alcohol ester compound to generate alicyclic diester diacid. And then the obtained alicyclic diester diacid is actually reacted with acyl chloride to obtain the alicyclic diester diacid chloride.
Specifically, an alicyclic diamine is dissolved in an organic solvent to form a homogeneous diamine solution. The mass concentration of the diamine solution is 10-30wt%.
Specifically, the organic solvent is at least one selected from N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma-butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate and butyl acetate.
In a third aspect of the present application, a negative photosensitive polyamic acid ester resin composition is provided.
A negative photosensitive polyamic acid ester resin composition, the composition of which, in parts by mass, is as follows:
The negative photosensitive polyamic acid ester resin is the negative photosensitive polyamic acid ester resin according to claim 1 or 2, or the negative photosensitive polyamic acid ester resin obtained by the production method according to any one of claims 3 to 5.
Wherein the sensitizer is at least one selected from benzophenone, benzophenone derivatives (for example: 4,4 '-bis (dimethylamino) benzophenone, dibenzyl ketone, fluorenone, etc.), acetophenone derivatives (for example: 2,2' -diethoxyacetophenone, 2-hydroxy-2-methylbenzophenone, 1-hydroxycyclohexylphenyl ketone, etc.), thioxanthone derivatives (for example: 2-methyl thioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, etc.), benzil derivatives, benzoin derivatives (for example: benzoin methyl ether, etc.), 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime and 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime. The benzil derivative comprises benzil dimethyl ketal and benzil-beta-methoxyethyl acetic aldehyde.
Preferably, the sensitizer contains at least one of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime and 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime.
When the sensitizer contains the above components, the polyimide film formed has an optimal sensitivity.
The cross-linking auxiliary agent is at least one selected from the group consisting of 2-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, glycidyl methacrylate, ethylene glycol diethyl ether acrylate and polyethylene glycol methacrylate.
The bonding aid is selected from at least one of gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, 3-methacryloxypropyl dimethoxy methylsilane, 3-methacryloxypropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, 3-isocyanatotrimethoxysilane, 3-isocyanatotriethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, vinyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane and 3- (triethoxysilyl) propyl succinic anhydride.
The polymerization inhibitor is at least one selected from hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol and 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol.
The organic solvent is at least one selected from N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma-butyrolactone, ethyl lactate, cyclopentanone, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate and butyl acetate.
In a fourth aspect of the present application, a method of manufacturing a cured relief pattern is provided.
A method of manufacturing a cured relief pattern, the method comprising the steps of:
(1) Mixing the negative photosensitive polyamic acid resin composition to obtain a negative photosensitive polyamic acid resin composition solution;
(2) Coating the solution obtained in the step (1) on the surface of a substrate;
the coating is carried out by a method including a spin coating method, a dip coating method, a spray coating method or a screen printing method.
(3) Heating and evaporating the substrate with the negative photosensitive polyamic acid ester resin composition on the surface obtained in the step (2) to obtain a substrate with a resin coating film;
The evaporation is to evaporate 60 to 90% by weight of the solvent from the negative photosensitive polyamic acid ester resin composition solution, thereby forming a resin coating film.
(4) Covering the resin side of the substrate with the resin coating film obtained in the step (3) with a photomask, and irradiating to obtain an irradiated substance;
the illumination is performed by using an ultraviolet (i-line and/or g-line) exposure device.
(5) Immersing the illuminated substance obtained in the step (4) into a developer, removing the soluble part, and cleaning with a rinsing liquid to obtain a resin pattern which is not completely cured;
the developer is selected from a good solvent of the negative photosensitive resin composition or a combination of a good solvent and a poor solvent. The poor solvent is the same as the poor solvent described above. The good solvent is selected from N-methyl pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-dimethylacetamide, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone and gamma-butyrolactone; the poor solvent is preferably methanol, ethanol, isopropanol, ethyl lactate, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, propylene glycol monomethyl ether or propylene glycol methyl ether acetate. The rinsing liquid is preferably at least one of isopropanol, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate, cyclopentanone and cyclohexanone.
(6) Heating and curing the resin pattern which is not cured completely and is obtained in the step (5) to obtain the cured relief pattern;
the negative photosensitive polyamic acid resin composition according to claim 7 is the negative photosensitive polyamic acid resin composition according to step (1).
Optionally, in the step (3), the evaporating temperature is 80-130 ℃;
the evaporation time is 1min-60min;
the illumination in the step (4) is performed by ultraviolet rays;
the exposure time is 10s-60s;
the wavelength range of the ultraviolet rays is 300-450nm;
preferably, the wavelength of the ultraviolet rays is at least one of 365nm, 405nm and 436 nm; in the step (6), the curing temperature is 150-350 ℃;
the curing time is 30min-300min.
In a fifth aspect of the present invention, there are provided the negative photosensitive polyamic acid ester resin, the negative photosensitive polyamic acid ester resin obtained by the above-described production method, and the use of the negative photosensitive polyamic acid ester resin composition as a protective film or an insulating layer.
The beneficial effects that this application can produce include:
1) The polyimide film obtained by exposing, developing and thermally curing the negative photosensitive polyamic acid ester resin provided by the application has the advantages of high transparency, low dielectric constant, low dielectric loss, excellent thermal stability and the like, and can be applied to preparing transparent protective films and insulating layers of liquid crystal display equipment, chip protection passivation films in advanced microelectronic manufacturing and packaging, interlayer insulating films and stress buffer protective layer films of multi-layer circuit interconnection.
2) In the negative photosensitive polyamic acid ester resin composition provided by the application, the negative photosensitive polyamic acid ester resin is compounded with the photosensitizer, the polymerization inhibitor, the crosslinking auxiliary agent and the bonding auxiliary agent, so that the photosensitivity of the negative photosensitive polyamic acid ester resin composition can be improved, the storage stability of the negative photosensitive polyamic acid ester resin composition can be improved, the mechanical property of a final polyimide film and the bonding force of the final polyimide film and a substrate can be further improved, and the negative photosensitive polyamic acid ester resin composition is mainly applied to preparing transparent protective films and insulating layers of liquid crystal display equipment, chip protective passivation films in advanced microelectronic manufacturing and packaging, interlayer insulating films and stress buffer protective layer films of multi-layer circuit interconnection.
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, the chemical substances in the examples of the present application are abbreviated as follows:
unless otherwise indicated, the starting materials and catalysts in the examples of the present application were purchased commercially, with N1, N5, N7 being purchased from Adamas.
A method for producing a polyimide film using the negative photosensitive polyamic acid resin composition:
uniformly coating the obtained negative photosensitive polyamide acid resin composition on a silicon wafer by using a spin coater, placing the silicon wafer on a heating table (HT-300 experiment electric heating plate, guangzhou Grina instrument Co., ltd.) at 120 ℃ for 3 minutes, and performing soft baking to obtain a resin film with the film thickness of 10-20 mu m, and exposing by using an ultraviolet lamp (i and g lines) under the condition that a mask plate is not placed on the surface of the resin film; spraying and developing with cyclopentanone developer, rinsing with propylene glycol methyl ether acetate, placing the film in a vacuum anaerobic oven (MOLZK-32D 1), heat treating at 170deg.C for 30 min under the protection of nitrogen atmosphere, heating to 320 deg.C for 1 hr, treating at 320 deg.C for 1 hr, and naturally cooling to below 50deg.C in the oven to obtain the final product. The silicon wafer with the film is soaked in 47% HF for 5-10 minutes, and then rinsed with water to obtain a polyimide film with a thickness of 10-12 μm.
The analytical testing method in the examples of the present application is as follows:
(1) Mechanical property test
Cutting polyimide film into strips with length of 90mm and width of 10mm, and testing mechanical properties of the film by using a tensile machine. The test rate was 50mm/min, 7 bars per group, of which 5 highest values were averaged to give tensile strength and elongation at break. If the tensile strength of the prepared polyimide film is more than or equal to 100MPa and the elongation at break is more than or equal to 40%, the polyimide film is evaluated as 'best'; if the tensile strength of the prepared polyimide film is more than or equal to 100MPa and the elongation at break is more than or equal to 20%, the polyimide film is rated as good; if the tensile strength of the prepared polyimide film is less than or equal to 100MPa and the elongation at break is less than or equal to 20%, the polyimide film is rated as 'poor'.
(2) Chemical resistance test
After immersing a polyimide film in a caustic solution (1 wt% potassium hydroxide+39 wt% 3-methoxy-3-methyl-1-butanol+60 wt% dimethyl sulfoxide (DMSO)) at 100 ℃ for 1 hour, the polyimide film was washed with water and air-dried, and then the chemical etching resistance of the polyimide film was evaluated by measuring the film thickness change and observing under an optical microscope: if the thickness of the immersed polyimide layer changes within a range of +/-1% and no cracks or defects are generated, the polyimide layer is evaluated as 'best'; if the thickness of the immersed polyimide layer changes within a range of + -3% and no crack or defect occurs, the polyimide layer is evaluated as "good"; if the thickness of the polyimide layer after immersion varies by more than + -5% or cracks or defects occur, it is evaluated as "bad".
(3) Light transmittance test
Polyimide film transmittance (average transmittance at 380nm to 780 nm) was measured using MCPD-300 manufactured by Otsuka electronics, inc. The transmittance of a film having a thickness of 10 to 12 μm can be calculated from the measured transmittance using the Lambert-Beer (Lambert-Beer) formula, assuming a reflectance of 10%. The calculation formula is as follows.
Log10((T1+10)/100)＝10/L×(Log10((T1’+10)/100))
T1: the transmittance of a polyimide film having a thickness of 10 to 12 μm is assumed to be 10% (%);
t1': measured light transmittance (%);
l: the thickness (μm) of the polyimide film was measured.
If the transmittance of the prepared polyimide film is more than or equal to 85 percent, the polyimide film is judged to be 'best'; if the transmittance of the prepared polyimide film is more than or equal to 80 percent, the polyimide film is rated as 'good'; if the transmittance of the prepared polyimide film was 80% or less, it was rated as "poor".
(4) Dielectric constant, dielectric loss tangent test
The polyimide film was cut into strips 80mm long and 60mm wide, immersed in 47% HF for 5 to 10 minutes, then rinsed with water, and peeled from the silicon wafer as a film sample. The relative dielectric constant and dielectric loss tangent at 10GHz were calculated for the film samples by the resonator perturbation method, and the test method was described in detail below.
The testing method comprises the following steps: disturbance mode Split Cylinder resonator method
Circuit network analyzer: PNA Network analyzer E5224B (Agilent technologies company)
A split cylinder resonator: CR-710
Measuring frequency: about 10GHz
(5) Heat resistance
By measuring the temperature at which the weight of the polyimide film is reduced by 5% (i.e., T 5wt％ ) The heat resistance of the resin was evaluated. Thermal gravimetric analysis (TA company, usa, Q50 series) was used, and the rate of temperature increase was measured: 10 ℃/min and the temperature range is 30-650 ℃.
Synthesis example 1
(1) 192.18g (0.5 mol) of CpODA, 130.8g (1.005 mol) of 2-hydroxyethyl methacrylate (HEMA), 1.1g of hydroquinone and 0.5g of 1, 8-diazabicyclo [5.4.0 ] are placed in a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device]Undec-7-ene (DBU) was dissolved in 500g N-methylpyrrolidone (NMP) and stirred at room temperature for 48h to give the corresponding ester (CpODA-HEMA ester) solution. The above ester solution was cooled in an ice bath, and 120.15g (1.01 mol) SOCl was added dropwise thereto 2 The reaction temperature is kept between 0 and 10 ℃, and the mixture is stirred for 2 hours to generate corresponding acyl chloride solution.
(2) In a three-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP were charged and stirred to dissolve to form a homogeneous transparent solution. The diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 17.24g (0.105 mol) of N1 was further added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to obtain a polyamic acid ester resin (A-1).
Synthesis example 2
(1) Synthesis example 1 (1).
(2) 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 21.44g (0.105 mol) of N5 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-2).
Synthesis example 3
(1) Synthesis example 1 (1).
(2) 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. Then, 20.18g (0.105 mol) of N7 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried in vacuo to give a polyamic acid ester resin (A-3).
Synthesis example 4
(1) Synthesis example 1 (1).
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 17.24g (0.105 mol) of N1 was further added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-4).
Synthesis example 5
(1) Synthesis example 1 (1).
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 21.44g (0.105 mol) of N5 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-5).
Synthesis example 6
(1) Synthesis example 1 (1).
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. Then, 20.18g (0.105 mol) of N7 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-6).
Synthesis example 7
(1) 165.16g (0.5 mol) of BNBDA, 130.8g of HEMA, 1.1g of hydroquinone and 0.5g of DBU were dissolved in 500g of NMP in a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred at room temperature for 48 hours to give a corresponding ester (BNBDA-HEMA ester) solution. The above ester solution was cooled in an ice bath, and 120.15g SOCl was added dropwise thereto 2 The reaction temperature is kept between 0 and 10 ℃, and the mixture is stirred for 2 hours to generate corresponding acyl chloride solution.
(2) In a three-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP were charged and stirred to dissolve to form a homogeneous transparent solution. The diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 17.24g (0.105 mol) of N1 was further added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-7).
Synthesis example 8
(1) The same as in (1) of Synthesis example 7.
(2) 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 21.44g (0.105 mol) of N5 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-8).
Synthesis example 9
(1) The same as in (1) of Synthesis example 7.
(2) 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. Then, 20.18g (0.105 mol) of N7 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-9).
Synthesis example 10
(1) The same as in (1) of Synthesis example 7.
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 17.24g (0.105 mol) of N1 was further added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-10).
Synthesis example 11
(1) The same as in (1) of Synthesis example 7.
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 21.44g (0.105 mol) of N5 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-11).
Synthesis example 12
(1) The same as in (1) of Synthesis example 7.
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. Then, 20.18g (0.105 mol) of N7 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-12).
Synthesis example 13
(1) 164.15g (0.5 mol) of PTTD, 130.8g of HEMA, 1.1g of hydroquinone and 0.5g of DBU were dissolved in 500g of NMP in a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred at room temperature for 48 hours to give a corresponding ester (PTTD-HEMA ester) solution. The above ester solution was cooled in an ice bath, and 120.15g SOCl was added dropwise thereto 2 The reaction temperature is kept between 0 and 10 ℃, and the mixture is stirred for 2 hours to generate corresponding acyl chloride solution.
(2) In a three-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP were charged and stirred to dissolve to form a homogeneous transparent solution. The diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 17.24g (0.105 mol) of N1 was further added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-13).
Synthesis example 14
(1) The same as in (1) of Synthesis example 13.
(2) 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 21.44g (0.105 mol) of N5 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-14).
Synthesis example 15
(1) The same as in (1) of Synthesis example 13.
(2) 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. Then, 20.18g (0.105 mol) of N7 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-15).
Synthesis example 16
(1) The same as in (1) of Synthesis example 13.
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 17.24g (0.105 mol) of N1 was further added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-16).
Synthesis example 17
(1) The same as in (1) of Synthesis example 13.
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 21.44g (0.105 mol) of N5 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-17).
Synthesis example 18
(1) The same as in (1) of Synthesis example 13.
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. Then, 20.18g (0.105 mol) of N7 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-18).
Synthesis example 19
(1) 199.19g (0.5 mol) of Choda, 130.8g of HEMA, 1.1g of hydroquinone and 0.5g of DBU were dissolved in 500g of NMP in a three-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred at room temperature for 48 hours to give a corresponding ester (Choda-HEMA ester) solution. The above ester solution was cooled in an ice bath, and 120.15g SOCl was added dropwise thereto 2 The reaction temperature is kept between 0 and 10 ℃, and the mixture is stirred for 2 hours to generate corresponding acyl chloride solution.
(2) In a three-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP were charged and stirred to dissolve to form a homogeneous transparent solution. The diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 17.24g (0.105 mol) of N1 was further added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-19).
Synthesis example 20
(1) Synthesis example 19 (1) was repeated.
(2) 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 21.44g (0.105 mol) of N5 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-20).
Synthesis example 21
(1) Synthesis example 19 (1) was repeated.
(2) 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. Then, 20.18g (0.105 mol) of N7 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-21).
Synthesis example 22
(1) Synthesis example 19 (1) was repeated.
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 17.24g (0.105 mol) of N1 was further added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-22).
Synthesis example 23
(1) Synthesis example 19 (1) was repeated.
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 21.44g (0.105 mol) of N5 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-23).
Synthesis example 24
(1) Synthesis example 19 (1) was repeated.
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. Then, 20.18g (0.105 mol) of N7 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-24).
Synthesis example 25
(1) Synthesis example 1 (1).
(2) In a three-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP were charged and stirred to dissolve to form a homogeneous transparent solution. The diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-25).
Synthesis example 26
(1) Synthesis example 1 (1).
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-26).
Synthesis example 27
(1) The same as in (1) of Synthesis example 7.
(2) 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-27).
Synthesis example 28
(1) 155.10g (0.5 mol) of ODPA, 130.8g of HEMA, 1.1g of hydroquinone and 0.5g of DBU were dissolved in 500g of NMP in a three-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred at room temperature for 48 hours to give a corresponding ester (ODPA-HEMA ester) solution. The above ester solution was cooled in an ice bath, and 120.15g SOCl was added dropwise thereto 2 The reaction temperature is kept between 0 and 10 ℃, and the mixture is stirred for 2 hours to generate corresponding acyl chloride solution.
(2) 62.8g (0.55 mol) of p-CHDA, 150g of pyridine, 0.35g of hydroquinone and 500g of NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-28).
Synthesis example 29
(1) Synthesis example 28 (1).
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-29).
Synthesis example 30
(1) Synthesis example 28 (1).
(2) 123.41g (0.55 mol) DAC, 150g pyridine, 0.35g hydroquinone and 500g NMP are added into a three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred to be dissolved to form a homogeneous transparent solution; the diamine solution is added into the acyl chloride solution by using a dropping funnel, the reaction temperature is kept between 0 and 10 ℃, and the reaction is continued for 6 hours after the completion of the dropping. 21.44g (0.105 mol) of N1 was added to the reaction mixture, and the reaction was continued for 3 hours. The reaction solution was poured into deionized water, and the precipitated solid was collected by filtration and dried under vacuum to give a polyamic acid ester resin (A-30).
Example 1
Preparation of negative photosensitive resin composition:
in an ultra clean room equipped with a yellow light lamp, 50g of the polyimide precursor resin A-1 (denoted as component A) prepared in the resin synthesis example 1 of the present invention, 1.2g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime (denoted as component B), 0.2. 0.2g N-nitrosodiphenylamine (denoted as component C), 8g of ethylene glycol diethyl ether methacrylate (denoted as component D), and 1.0g of gamma-glycidoxypropyl trimethoxysilane (denoted as component E) were sequentially added to 100g of NMP (denoted as component F), and stirred at room temperature for 3 hours to form a homogeneous solution, namely a negative photosensitive polyamic acid ester resin composition solution.
Examples 2 to 24
The polyimide precursors obtained in synthetic examples 2 to 24 of the resin of the present application were designated as A-2 to A-24, and A-2 to A-24 were mixed with B, C, D, E, F components, respectively, to obtain examples 2 to 24. The amounts of A-2 to A-24 and B, C, D, E, F are shown in Table 1.
Comparative examples 1 to 6
The polyimide precursors obtained in resin synthesis examples 25 to 30 of the present application were designated as A-25 to A-30, and A-25 to A-30 were mixed with B, C, D, E, F components, respectively, to obtain comparative examples 1 to 6. The amounts of A-25 to A-30 and B, C, D, E, F are shown in Table 1.
TABLE 1
The polyimide films obtained in examples 1 to 24 and comparative examples 1 to 6 described herein were subjected to the tests of mechanical properties, chemical resistance, light transmittance, dielectric constant, dielectric loss tangent and heat resistance, respectively, and the test results and evaluations are shown in Table 2.
TABLE 2
As can be seen from the data in Table 2, examples 1 to 24 using the end-capped structural resin have more excellent mechanical properties, chemical resistance and heat resistance than comparative examples 1 to 5 using the uncapped structural resin. In addition, examples 1 to 24 were optimal in light transmittance, and dielectric constant and dielectric loss were also relatively low.
As can be seen from the data in Table 2, the polyimide film prepared from the negative photosensitive resin composition has excellent heat resistance, light transmittance, mechanical property and chemical resistance, reduces the dielectric constant and dielectric loss of the polyimide film, can meet the requirements of the semiconductor packaging material in the 5G era on the packaging materials such as photosensitive polyimide with low dielectric constant and low dielectric loss, and has very wide application prospect.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (13)

1. A negative photosensitive polyamic acid ester resin, characterized in that the negative photosensitive polyamic acid ester resin has a structure represented by the following formula I:
wherein R is 1 Selected from any one of the following structures:
R 2 selected from any one of the following structures:
R 3 、R 4 independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a monovalent organic group having a carbon-carbon unsaturated double bond;
and R is 3 、R 4 At least one of them is a monovalent organic group having a carbon-carbon unsaturated double bond;
R 5 、R 6 independently selected from hydrogen atom, methyl, ethyl, propyl, allylAny one of them;
R 5 on any one of the carbon atoms of c=c;
n represents an integer of 2 to 200.
2. The negative photosensitive polyamic acid ester resin according to claim 1, wherein the R 3 And R is 4 Independently selected from one of saturated aliphatic group having 1-4 carbon atoms and group represented by the following formula II;
in formula II, R 7 、R 8 、R 9 Independently selected from a hydrogen atom, an organic group having 1 to 3 carbon atoms, and m represents an integer of 2 to 10.
3. A method for preparing the negative photosensitive polyamic acid ester resin according to claim 1 or 2, wherein the preparation method comprises the following steps:
(1) Obtaining an alicyclic diester dichloride represented by formula III below;
(2) Mixing the alicyclic diester diacid chloride obtained in the step (1) with diamine and a blocking agent, and reacting to obtain a polyamic acid ester resin solution;
(3) Mixing the polyamic acid ester resin solution obtained in the step (2) with a poor solvent to obtain the negative photosensitive polyamic acid ester resin;
the diamine in the step (2) has a structure shown in the following formula IV;
H 2 N-R 2 -NH 2 IV (IV)
Wherein R is 1 、R 2 、R 3 、R 4 And R in claim 1 1 、R 2 、R 3 、R 4 The same applies.
4. The method according to claim 3, wherein the end-capping agent in the step (2) is at least one selected from the group consisting of substances having structures represented by the following N1 to N9:
5. the process according to claim 3, wherein the alicyclic diester diacid chloride in the step (1) is prepared in the following manner:
(1-1) A compound R is reacted with an alicyclic tetracarboxylic dianhydride represented by the following formula V 3 -OH and/or R 4 Mixing and reacting-OH to obtain alicyclic diester diacid shown in the following formula VI;
(1-2) mixing the alicyclic diester diacid obtained in the step (1-1) with an acyl chloride reagent, and reacting to obtain the alicyclic diester diacid chloride.
6. The process according to claim 3, wherein the molar ratio of the diamine to the alicyclic diester dichloride in the step (2) is (0.8-1.2): 1.
7. A process according to claim 3, wherein in step (2), the reaction is carried out at a temperature of 0 to 10 ℃ for a total time of 5 to 15 hours.
8. The method according to claim 3, wherein in the step (3), the poor solvent is at least one selected from the group consisting of water, methanol, ethanol, hexane, butyl cellosolve and toluene.
9. A negative photosensitive polyamic acid ester resin composition, characterized in that the composition of the composition is as follows, in parts by mass:
the negative photosensitive polyamic acid ester resin is the negative photosensitive polyamic acid ester resin according to claim 1 or 2 or the negative photosensitive polyamic acid ester resin obtained by the production method according to any one of claims 3 to 5.
10. A method of manufacturing a cured relief pattern, the method comprising the steps of:
(1) Mixing the negative photosensitive polyamic acid resin composition to obtain a negative photosensitive polyamic acid resin composition solution;
(2) Coating the solution obtained in the step (1) on the surface of a substrate;
(3) Heating and evaporating the substrate with the negative photosensitive polyamic acid ester resin composition on the surface obtained in the step (2) to obtain a substrate with a resin coating film;
(4) Covering the resin side of the substrate with the resin coating film obtained in the step (3) with a photomask, and irradiating to obtain an irradiated substance;
(5) Immersing the illuminated substance obtained in the step (4) into a developer, removing the soluble part, and cleaning with a rinsing liquid to obtain a resin pattern which is not completely cured;
(6) Heating and curing the resin pattern which is not cured completely and is obtained in the step (5) to obtain the cured relief pattern;
the negative photosensitive polyamic acid resin composition according to claim 9 is the negative photosensitive polyamic acid resin composition according to step (1).
11. The method of claim 10, wherein in step (3), the temperature of evaporation is 80 ℃ to 130 ℃;
The evaporation time is 1min-60min;
the illumination in the step (4) is performed by ultraviolet rays;
the exposure time is 10s-60s;
the wavelength range of the ultraviolet rays is 300-450nm.
12. The method according to claim 11, wherein the ultraviolet light has at least one of 365nm, 405nm, and 436 nm;
in the step (6), the curing temperature is 150-350 ℃;
the curing time is 30min-300min.
13. Use of the negative photosensitive polyamic acid ester resin according to claim 1 or 2 or the negative photosensitive polyamic acid ester resin obtained by the production process according to any one of claims 3 to 8 or the negative photosensitive polyamic acid ester resin composition according to claim 9 as a protective film or an insulating layer.
CN202210190302.4A 2022-02-28 2022-02-28 Preparation method and application of negative photosensitive polyamide acid ester resin and composition thereof Active CN114561009B (en)

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