CN115850596A - Transparent photosensitive polyimide resin and preparation method and application thereof - Google Patents
Transparent photosensitive polyimide resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN115850596A CN115850596A CN202211372852.4A CN202211372852A CN115850596A CN 115850596 A CN115850596 A CN 115850596A CN 202211372852 A CN202211372852 A CN 202211372852A CN 115850596 A CN115850596 A CN 115850596A
- Authority
- CN
- China
- Prior art keywords
- dianhydride
- fluorine
- photosensitive polyimide
- temperature
- methyl
- 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.)
- Pending
Links
Images
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a transparent photosensitive polyimide resin and a preparation method and application thereof, belonging to the technical field of polyimide. The invention adopts hydroxyl-containing (methyl) acrylate, organic base, rigid aromatic dianhydride, fluorine-containing aromatic diamine and rigid aromatic diamine to prepare a photosensitive resin precursor, and then the photosensitive resin precursor is mixed with photosensitive auxiliary agent, solvent and the like to obtain the transparent photosensitive polyimide resin. The polyimide resin prepared by the invention has excellent photoetching process performance, and meanwhile, a polyimide layer film formed by a photoetching pattern after high-temperature curing has the characteristics of high transparency, high heat resistance, high toughness, low dielectric loss and the like.
Description
Technical Field
The invention relates to the technical field of polyimide, in particular to a transparent photosensitive polyimide resin and a preparation method and application thereof.
Background
Photosensitive Polyimide (PSPI) has the excellent comprehensive performance of Polyimide and the photoetching process performance of photoresist, is widely applied to the fields of microelectronic manufacturing and packaging, planar display and the like, and mainly comprises a chip surface passivation layer, an a-particle shielding layer, a buffer inner coating layer, an interlayer insulating medium layer of a multilayer circuit and the like. The PSPI material is divided into a negative type and a positive type, wherein the negative PSPI material is formed by introducing a photosensitive group into a main chain structure of a polyimide precursor resin, and firstly forming photosensitive polyamic acid ester (Poly (amic ester), PAE) resin; then, the Negative photosensitive polyimide resin is uniformly mixed with a photosensitive auxiliary agent, a crosslinking agent, a solvent and the like to form a Negative photosensitive polyimide (n-PSPI). Spin-coating n-PSPI solution on the surface of a substrate such as a silicon wafer, and forming a negative stereolithography pattern after prebaking, exposing, developing and rinsing; and carrying out imidization reaction on the developed substrate such as a silicon wafer at a high temperature to obtain the polyimide negative photoetching pattern. The polyimide layer film which is obtained by high-temperature curing and forms the photoetching pattern has excellent heat resistance, mechanical property, electrical insulation property, dielectric property, corrosion resistance, high dimensional stability and the like. Because the main chain structure of the photosensitive PAE resin contains photosensitive crosslinking groups such as (methyl) acrylate and the like, the crosslinking groups such as the (methyl) acrylate and the like generate photochemical crosslinking reaction under the action of ultraviolet light, the solubility in a developing solution is greatly reduced, and the PSPI material is endowed with excellent photoetching process performance.
However, the polyimide film formed by the n-PSPI material after photoetching and high-temperature curing is a yellowish brown non-transparent film. This is mainly attributed to the fact that a great amount of imide rings and conjugated aromatic rings exist in the main chain structure of the polyimide film resin formed by conversion in the high-temperature curing process, strong intra-and inter-chain Charge Transfer Complexation (CTC) is easily formed, and the film material has strong light absorption in the visible light region, resulting in yellow or yellow brown color. In recent years, colorless and transparent polyimide resins are urgently needed for technical development in the fields of flat panel displays, optical devices and the like, and PSPI materials are required to have not only excellent photoetching manufacturability and comprehensive mechanical, heat-resistant and electrical properties, but also excellent transparency of polyimide film formed after photoetching and high-temperature curing.
Guojianwei et al (CN 112979949A) disclose a transparent photosensitive polyimide resin and a preparation method thereof. Carrying out polycondensation reaction on an aromatic diamine monomer (BAFP) containing fluorine atoms and modified by pyridine rings and an aromatic diacid chloride diester monomer containing methacrylate groups in an organic solution to obtain photosensitive PAE resin; and uniformly mixing the photosensitive PAE resin with a photosensitive auxiliary agent, an active diluent and an organic solvent to obtain the transparent photosensitive PSPI resin. The light transmittance of the polyimide layer film obtained by photosensitive and high-temperature curing at the ultraviolet wavelength of 420nm is more than or equal to 80 percent, the temperature of the film with 10 percent of thermal weight loss is 360-390 ℃, and the polyimide layer film has good photosensitive property. However, the thermal stability of the resist is still to be improved, and the resist cannot be used for forming a resist pattern.
Chineseme et al (CN 110804181A) disclose a transparent photosensitive polyimide resin and a preparation method thereof. Carrying out polycondensation reaction on a diamine monomer with a strong electronegative group structure and an aliphatic ring structure and an aromatic dianhydride monomer in a solvent solution to form polyamic acid resin; after imidization, a resin side chain is grafted with a photosensitive group containing spiropyran, so that the modified transparent photosensitive polyimide resin is obtained, can change color under the irradiation of ultraviolet rays, and has the characteristic of visually observing a photoinduced modified area. However, the above resins cannot produce a photolithographic pattern.
Disclosure of Invention
The polyimide resin prepared by the invention has excellent photoetching process performance, and meanwhile, a polyimide layer film formed by a photoetching pattern after high-temperature curing has the characteristics of high transparency, high heat resistance, high toughness, high electrical insulation, low dielectric loss and the like.
The invention firstly provides a preparation method of transparent photosensitive polyimide resin, which comprises the following steps:
(1) Dissolving a mixture of hydroxyl-containing (meth) acrylate, organic base, rigid aromatic dianhydride and fluorine-containing aromatic dianhydride in an organic solvent, and performing esterification reaction to form a (meth) acrylate group-containing aromatic diacid diester mixture solution; further reacting the mixture under the action of an acyl chlorination reagent to form a mixture solution of aromatic diester diacid chloride containing a (methyl) acrylate group;
(2) Slowly dripping the aromatic diester diacid chloride mixture solution containing the (methyl) acrylate group into an organic solution containing fluorine-containing aromatic diamine and rigid aromatic diamine at the temperature of 0-15 ℃, and then reacting at room temperature to generate a photosensitive polyamic acid ester resin solution; precipitating the photosensitive polyamic acid ester resin solution in a poor solvent, filtering, washing and drying to obtain a photosensitive polyamic acid ester resin solid;
(3) And dissolving the photosensitive polyamic acid ester resin solid, a photosensitive auxiliary agent, a cross-linking agent and a polymerization inhibitor in an organic solvent, and reacting to obtain the transparent photosensitive polyimide resin.
In the above-mentioned production method, in the step (1), the hydroxyl group-containing (meth) acrylate is at least one of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1-acryloyloxy-3-propanol, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-methacrylamidoglycol, 1-methacryloyloxy-3-propanol, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropylacrylate, and 2-hydroxy-3-cyclohexyloxypropylmethacrylate;
the organic base is at least one of triethylamine, pyridine, 2-methylpyridine, 3-methylpyridine, isoquinoline, piperidine and 3-methyl-piperidine;
the rigid aromatic dianhydride is pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3', at least one of 4' -biphenyltetracarboxylic dianhydride, 3',4' -benzophenonetetracarboxylic dianhydride, and 3,3',4' -diphenylsulfonetetracarboxylic dianhydride;
the fluorine-containing aromatic dianhydride is at least one of 4,4'- (hexafluoroisopropylidene) diphenyl anhydride, 4' - (trifluoromethylphenylisopropyl) diphenyl anhydride, 1, 4-bis (trifluoromethyl) -2,3,5, 6-benzenetetracarboxylic dianhydride, 4'- (4, 4' -hexafluoroisopropyldiphenoxy) bis (phthalic anhydride), 4'- (trifluoromethyl-m-trifluoromethylphenyl-isopropyl) diphenyl anhydride, 4' - (trifluoromethyl-m, m-bistrifluoromethylphenyl-isopropyl) diphenyl anhydride and 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic dianhydride;
in the step (1), the organic solvent is at least one of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, acetone, cyclohexanone, ethyl acetate, tetrahydrofuran, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether;
the acyl chlorination reagent is SOCl 2 、PCl 3 、PCl 5 Oxalyl chloride and COCl 2 At least one of (1).
In the above production method, in the step (1), the ratio of the number of moles of the hydroxyl group-containing (meth) acrylate to the total number of moles of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 2;
the molar ratio of the fluorine-containing aromatic dianhydride to the rigid aromatic dianhydride is 1; specifically, 1 can be 1;
the ratio of the mole number of the organic base to the total mole number of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 1-5, preferably 2-4; more preferably 2;
the mass ratio of the organic solvent to the total mass of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 1 to 10, preferably 2 to 8;
the ratio of the number of moles of the acylating chlorination reagent to the total number of moles of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 2.
<xnotran> , (2) , 2,2'- -4,4' - ,2,2 '- -4,4' - ,3,3'- -5,5' - ,1,4- (2- -4- ) ,1,3- (2- -4- ) ,4,4'- (2- -4- ) ,2,2- [4- (4- ) ] ,2,2- [4- (2- -4- ) ] ,3- -4,4' - ,2,2 '- ( ) -4,4' - , N, N '- (2,2' - ( ) - [1,1'- ] -4,4' - ) (4- ), 3- , , ,4,4'- 4,4' - ; </xnotran>
The rigid aromatic diamine is 4,4 '-diaminodiphenyl ether, 1, 4-p-phenylenediamine, 4' -biphenyldiamine, 2 '-dimethyl-4, 4' -diaminobiphenyl 2,2 '-diethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, 2', at least one of 3,3' -tetramethyl-4, 4 '-diaminobiphenyl and 3,3',5 '-tetramethyl-4, 4' -diaminodiphenylmethane;
the organic solvent of the organic solution is at least one of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, acetone, cyclohexanone, ethyl acetate, tetrahydrofuran, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether;
the poor solvent is at least one of water, ethanol, methanol, hexane and toluene; preferably at least one of deionized water, ethanol and methanol; specifically deionized water;
the total molar number of the fluorine-containing aromatic diamine and the rigid aromatic diamine: the total molar ratio of the fluorine-containing aromatic dianhydride to the rigid aromatic dianhydride is 100 to 90-110;
the molar ratio of the fluorine-containing aromatic diamine to the rigid aromatic diamine is 1 to 10, preferably 1.1 to 5; specifically, 1 can be 1;
the ratio of the mass of the organic solvent to the total mass of the fluorine-containing aromatic diamine and the rigid aromatic diamine is 1 to 10, preferably 5 to 10;
the mass ratio of the poor solvent to the photosensitive polyamic acid resin solution is 3 to 20.
In the above-mentioned preparation method, in the step (3), the photo-sensitizer is at least one of benzophenone, dibenzyl ketone, 4-benzoyl-4 '-methylbenzophenone, 2' -diethoxy acetophenone, 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methyl thioxanthone, benzil dimethyl ketal, 1-phenyl-1, 2-butanedione-2- (0-methoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (0-benzoyl) oxime, and N-phenylglycine;
the photocrosslinking agent is at least one of ethylene glycol diethyl ether methacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, cyclohexane dimethacrylate and 1, 4-butanediol dimethacrylate;
the polymerization inhibitor is at least one of hydroquinone, N-nitrosodiphenylamine, N-phenylnaphthylamine, p-tert-butylcatechol, phenothiazine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanone diamine tetraacetic acid, glycol ether diamine tetraacetic acid, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 5-nitroso-8-hydroxyquinoline and 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol;
the organic solvent in the step (3) is at least one of N-methyl-2-pyrrolidone (NMP), N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), gamma-butyrolactone (GBL), acetone, ethyl acetate, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol and tert-butanol;
in the step (3), the mass ratio of the photosensitive polyamic acid ester resin solid to the photosensitive auxiliary agent is 1;
the mass ratio of the photosensitive polyamic acid ester resin solid to the crosslinking agent is 1;
the mass ratio of the photosensitive polyamic acid ester resin solid to the polymerization inhibitor is 1;
the mass ratio of the photosensitive polyamic acid ester resin solid to the organic solvent is 1.
In the preparation method, in the step (1), the temperature of the esterification reaction is room temperature; the esterification reaction time is 6-12 h;
the further reaction under the action of the acyl chlorination reagent is carried out for 2 to 6 hours at the temperature of 0 to 10 ℃ and then for 4 to 6 hours at room temperature;
in the step (2), the room temperature reaction time is 6-12 h;
in the step (3), the reaction temperature is room temperature; the reaction time is 2-4 h.
Specifically, the reaction is carried out under stirring.
In the above preparation methods, the room temperature is well known to those skilled in the art, i.e., no additional heating is required, typically 15 to 35 ℃.
The invention further provides the transparent photosensitive polyimide resin prepared by the preparation method.
The application of the transparent photosensitive polyimide resin in preparing the transparent photosensitive polyimide film also belongs to the protection scope of the invention.
In the above application, the transparent photosensitive polyimide film is a film having a stereolithography pattern.
Finally, the present invention provides a transparent photosensitive polyimide film, which is prepared by a method comprising the steps of:
and (3) coating the transparent photosensitive polyimide resin, photoetching a pattern, and curing at a high temperature to obtain the transparent photosensitive polyimide film.
Specifically, the high-temperature curing temperature is 280-350 ℃; the high-temperature curing time is 0.5-4 h.
The preparation method of the transparent photosensitive polyimide film specifically comprises the following steps: the transparent photosensitive polyimide resin film is coated, subjected to ultraviolet exposure, development and rinsing, and then cured at high temperature to obtain the transparent photosensitive polyimide film.
The ultraviolet exposure condition is 10-1000 mJ/cm 2 ；
The developing time is 10-200 s;
the high-temperature curing condition is that the curing is carried out for 0.5 to 4 hours at the temperature of between 280 and 350 ℃;
the step of drying is also included before the ultraviolet exposure; specifically, the drying is carried out for 10-500 s at the temperature of 100 +/-30 ℃.
The light transmittance of the transparent photosensitive polyimide film at the ultraviolet wavelength of 450nm is more than or equal to 83 percent, the light transmittance at the wavelength of 550nm is more than or equal to 90 percent, the temperature of 5 percent of thermal weight loss of the film is 506-522 ℃, and the Tg is more than or equal to 330 ℃; the elongation at break of the film can reach 49.1 percent; tan delta can reach 0.0033 under 10 GHz.
The transparent photosensitive polyimide resin prepared by the invention has excellent photoetching process performance, and the resolution of a photoetching three-dimensional pattern formed after ultraviolet exposure, development and rinsing can reach 10 mu m; meanwhile, a polyimide layer film formed by high-temperature curing of the photoetching pattern has excellent transparency and comprehensive performance, the light transmittance at the ultraviolet wavelength of 450nm is more than or equal to 83 percent, the light transmittance at the ultraviolet wavelength of 550nm is more than or equal to 90 percent, the polyimide layer film also has excellent thermal stability and heat resistance, the temperature of 5 percent of thermal weight loss of the film is 506-522 ℃, and the Tg is more than or equal to 330 ℃; good mechanical property, the elongation at break of the film can reach 49.1%; and good dielectric property, and Tan delta can reach 0.0033 at 10 GHz.
Drawings
FIG. 1 is a UV-Vis spectrum of a transparent photosensitive polyimide film prepared in example 1;
FIG. 2 is a TGA curve of a transparent photosensitive polyimide film prepared in example 1;
FIG. 3 is a DMA curve of a transparent photosensitive polyimide film prepared in example 1;
fig. 4 is a photolithographic pattern of the transparent photosensitive polyimide film prepared in example 1.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
The experimental procedures in the following examples are conventional unless otherwise specified.
The quantitative tests in the following examples, all set up three replicates and the results averaged.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
To a 500mL three necked round bottom flask equipped with mechanical stirring, thermometer and nitrogen blanket was added 26.03g of 2-hydroxyethyl methacrylate (HEMA), 15.82g of pyridine, 7.36g (0.025 mole) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA), 33.32g (0.075 mole) of 4,4' - (hexafluoroisopropylene) diphenylanhydride (6 FDA) and 200g of N-methyl-2-pyrrolidone (NMP) in that order, and stirred at room temperature for 6h to form the corresponding aromatic diacid dimethacrylate mixture. The product is reacted with 23.79g SOCl at 0 DEG C 2 Reacting for 2h at room temperature for 4h to generate the corresponding aromatic-diacid chloride dimethacrylate mixture.
In a 1L three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer and a nitrogen gas guard, 28.82g (0.09 mol) of 2,2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl (TFDB), 2.00g (0.01 mol) of 4,4 '-diaminodiphenyl ether (4, 4' -ODA) solid powder and 280g of N-methyl-2-pyrrolidone (NMP) were sequentially added, and stirred until the solid powder was completely dissolved, to obtain an aromatic diamine mixed solution; cooling the mixed solution of aromatic diamine to below 10 ℃ by adopting an ice water bath, and slowly dropwise adding the prepared mixture of aromatic-diacid chloride dimethacrylate into the mixed solution of aromatic diamine; then, reacting for 10 hours at room temperature; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, washing and drying in vacuum to obtain the photosensitive Polyamide Acid Ester (PAE) resin.
Dissolving 40g of the photosensitive PAE resin in 40g of NMP in an ultraclean room provided with a yellow light lamp to form a homogeneous solution; then, 0.4g of 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 3.2g of ethylene glycol diethy ether methacrylate (4 EM), and 0.2g of N-nitrosodiphenylamine were added in this order, and stirred at room temperature for 3 hours to form a transparent photosensitive polyimide resin (PSPI) solution.
Spin-coating the above transparent photosensitive polyimide resin solution on the surface of 6 inch wafer, baking at 110 deg.C for 4min, placing mask on the surface, and irradiating with ultraviolet lamp (i and g rays) at 200mJ/cm 2 Exposure energy of 30s; developing for 60s by using a cyclopentanone/NMP (mass ratio of 1). Curing the film in a high-temperature blowing nitrogen-filled oven at 350 ℃/1h to obtain the transparent photosensitive polyimide film three-dimensional graph. The resolution ratio of a high-temperature cured PI film round hole (with the thickness of 5 mu m) is 10 mu m; the light transmittance at the ultraviolet wavelength of 450nm is 90.5 percent, and the light transmittance at the wavelength of 550nm is 92.5 percent; tg of 344 ℃; the temperature of 5 percent of thermal weight loss is 515 ℃; elongation at break of 49.1%; tan. Delta. At 10GHz was 0.0041.
The ultraviolet-visible spectrum of the obtained transparent photosensitive polyimide film is shown in figure 1; the TGA curve is shown in FIG. 2; the DMA curves are shown in FIG. 3; the lithographic pattern is shown in FIG. 4.
Example 2
In a 500mL three necked round bottom flask equipped with mechanical stirring, thermometer and nitrogen blanket, 26.03g of 2-hydroxyethyl methacrylate (HEMA), 15.82g of pyridine, 14.71g (0.05 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA), 26.01g (0.05 mol) of 4,4' - (trifluoromethyl-m-trifluoromethylphenyl-isopropyl) phthalic anhydride (6 FBA) and 200g of N-methyl-2-pyrrolidone (NMP) were added in sequence and stirred at room temperature for 6h to form the corresponding aromatic diacid dimethacrylate mixture. The product is reacted with 23.79g SOCl at 0 DEG C 2 Reacting for 2h at room temperature for 4h to generate corresponding aromaA family-diacid chloride dimethacrylate mixture.
In a 1L three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer and a nitrogen gas guard, 25.62g (0.08 mol) of 2,2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl (TFDB), 4.00g (0.02 mol) of 4,4 '-diaminodiphenyl ether (4, 4' -ODA) solid powder and 280g of N-methyl-2-pyrrolidone (NMP) were sequentially added, and stirred until the solid powder was completely dissolved, to obtain an aromatic diamine mixed solution; cooling the mixed solution of aromatic diamine to below 10 ℃ by adopting an ice water bath, and slowly dropwise adding the prepared mixture of aromatic-diacid chloride dimethacrylate into the mixed solution of aromatic diamine; then, reacting for 10 hours at room temperature; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, washing and drying in vacuum to obtain the photosensitive Polyamide Acid Ester (PAE) resin.
Dissolving 40g of the photosensitive PAE resin in 50g of NMP in an ultraclean room provided with a yellow light lamp to form a homogeneous solution; then, 0.4g of 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 3.2g of ethylene glycol diethy ether methacrylate (4 EM), and 0.2g of N-nitrosodiphenylamine were added in this order, and stirred at room temperature for 3 hours to form a transparent photosensitive polyimide resin (PSPI) solution.
Spin-coating the above transparent photosensitive polyimide resin solution on the surface of 6 inch wafer, baking at 110 deg.C for 4min, placing mask on the surface, and irradiating with ultraviolet lamp (i and g lines) at 200mJ/cm 2 Is exposed for 30s at an exposure energy of (1); developing for 60s by using a cyclopentanone/NMP (mass ratio of 1). Curing the film in a high-temperature blowing nitrogen-filled oven at 350 ℃/1h to obtain the transparent photosensitive polyimide film three-dimensional graph. The resolution of a high-temperature cured PI film round hole (with the thickness of 5 mu m) is 14 mu m; the light transmittance at the ultraviolet wavelength of 450nm is 86.4 percent, and the light transmittance at the wavelength of 550nm is 91.9 percent; tg of 340 ℃; the temperature of 5 percent of thermal weight loss is 519 ℃; elongation at break of 22.5%; tan. Delta. At 10GHz was 0.0033.
Example 3
In a 500mL three-necked round-bottomed flask equipped with mechanical stirring, a thermometer and a nitrogen blanket26.03g of 2-hydroxyethyl methacrylate (HEMA), 15.82g of pyridine, 22.07g (0.075 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA), 11.31g (0.025 mol) of 4,4' - (trifluoromethylphenylisopropyl) diphenyl anhydride (3 FDA) and 200g of N-methyl-2-pyrrolidone (NMP) were added in portions and stirred at room temperature for 6h to give the corresponding aromatic diacid dimethacrylate mixture. The product is reacted with 23.79g SOCl at 0 DEG C 2 Reacting for 2h at room temperature for 4h to generate the corresponding aromatic-diacid chloride dimethacrylate mixture.
In a 1L three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer and a nitrogen gas guard, 17.13g (0.04 mol) of 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene (6 FAPB), 15.26g (0.06 mol) of 3,3', 5' -tetramethyl-4, 4' -diaminodiphenylmethane (TMMDA) solid powder and 280g of N-methyl-2-pyrrolidone (NMP) were sequentially added, and stirred until the solid powder was completely dissolved, to obtain an aromatic diamine mixed solution; cooling the mixed solution of aromatic diamine to below 10 ℃ by adopting an ice water bath, and slowly dropwise adding the prepared mixture of aromatic-diacid chloride dimethacrylate into the mixed solution of aromatic diamine; then, reacting for 10 hours at room temperature; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, washing and drying in vacuum to obtain the photosensitive Polyamide Acid Ester (PAE) resin.
Dissolving 40g of the photosensitive PAE resin in 55g of NMP in an ultraclean room provided with a yellow light lamp to form a homogeneous solution; then, 0.4g of 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 3.2g of ethylene glycol diethy ether methacrylate (4 EM), and 0.2g of N-nitrosodiphenylamine were added in this order, and stirred at room temperature for 3 hours to form a transparent photosensitive polyimide resin (PSPI) solution.
Spin-coating the above transparent photosensitive polyimide resin solution on the surface of 6 inch wafer, baking at 110 deg.C for 4min, placing mask on the surface, and irradiating with ultraviolet lamp (i and g lines) at 200mJ/cm 2 Is exposed for 30s at an exposure energy of (1); developing for 60s by using a cyclopentanone/NMP (mass ratio of 1). Curing at 350 deg.C/1 h in a high temperature blowing nitrogen-filled oven to obtain a transparent filmAnd (3) forming a bright photosensitive polyimide film three-dimensional pattern. The resolution ratio of a high-temperature cured PI film round hole (with the thickness of 5 mu m) is 15 mu m; the light transmittance at the ultraviolet wavelength of 450nm is 85.4 percent, and the light transmittance at the wavelength of 550nm is 91.0 percent; tg of 353 ℃; the temperature of 5 percent of thermal weight loss is 522 ℃; elongation at break was 12.6%; tan delta at 10GHz was 0.0062.
Example 4
In a 500mL three necked round bottom flask equipped with mechanical stirring, thermometer and nitrogen blanket, 26.03g of 2-hydroxyethyl methacrylate (HEMA), 15.82g of pyridine, 2.94g (0.01 mole) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA), 39.98g (0.09 mole) of 4,4' - (hexafluoroisopropylene) diphenylanhydride (6 FDA) and 200g of N-methyl-2-pyrrolidone (NMP) were added sequentially and stirred at room temperature for 6h to form the corresponding aromatic diacid dimethacrylate mixture. The product is reacted with 23.79g SOCl at 0 DEG C 2 Reacting for 2 hours at room temperature for 4 hours to generate a corresponding aromatic-diacid chloride dimethacrylate mixture.
In a 1L three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer and a nitrogen gas guard, 28.82g (0.09 mol) of 2,2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl (TFDB), 2.12g (0.01 mol) of 2,2 '-dimethyl-4, 4' -diaminobiphenyl (M-toidine) solid powder and 280g of N-methyl-2-pyrrolidone (NMP) were sequentially added, and stirred until the solid powder was completely dissolved, to obtain an aromatic diamine mixed solution; cooling the mixed solution of aromatic diamine to below 10 ℃ by adopting an ice water bath, and slowly dropwise adding the prepared mixture of aromatic-diacid chloride dimethacrylate into the mixed solution of aromatic diamine; then, reacting for 10 hours at room temperature; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, washing and drying in vacuum to obtain the photosensitive Polyamide Acid Ester (PAE) resin.
Dissolving 40g of the photosensitive PAE resin in 35g of NMP in an ultraclean room provided with a yellow light lamp to form a homogeneous solution; then, 0.4g of 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 3.2g of ethylene glycol diethy ether methacrylate (4 EM), and 0.2g of N-nitrosodiphenylamine were added in this order, and stirred at room temperature for 3 hours to form a transparent photosensitive polyimide resin (PSPI) solution.
Spin-coating the above transparent photosensitive polyimide resin solution on the surface of 6 inch wafer, baking at 110 deg.C for 4min, placing mask on the surface, and irradiating with ultraviolet lamp (i and g lines) at 200mJ/cm 2 Exposure energy of 30s; developing for 60s by using a cyclopentanone/NMP (mass ratio of 1). Curing the film in a high-temperature blowing nitrogen-filled oven at 350 ℃/1h to obtain the transparent photosensitive polyimide film three-dimensional graph. The resolution ratio of a high-temperature cured PI film round hole (with the thickness of 5 mu m) is 13 mu m; the light transmittance at the ultraviolet wavelength of 450nm is 90.7 percent, and the light transmittance at the wavelength of 550nm is 95.7 percent; tg of 335 ℃; the temperature of 5 percent of thermal weight loss is 510 ℃; elongation at break of 37.6%; tan. Delta. At 10GHz was 0.0066.
Example 5
To a 500mL three necked round bottom flask equipped with mechanical stirring, thermometer and nitrogen blanket, 26.03g of 2-hydroxyethyl methacrylate (HEMA), 15.82g of pyridine, 5.45g (0.025 mole) pyromellitic dianhydride (PMDA), 33.32g (0.075 mole) of 4,4' - (hexafluoroisopropylidene) diphenylanhydride (6 FDA) and 200g of N-methyl-2-pyrrolidone (NMP) were added sequentially and stirred at room temperature for 6h to form the corresponding aromatic diacid dimethacrylate mixture. The product is reacted with 23.79g SOCl at 0 DEG C 2 Reacting for 2h at room temperature for 4h to generate the corresponding aromatic-diacid chloride dimethacrylate mixture.
In a 1L three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer and a nitrogen gas guard, 28.82g (0.09 mol) of 2,2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl (TFDB), 2.00g (0.01 mol) of 4,4 '-diaminodiphenyl ether (4, 4' -ODA) solid powder and 280g of N-methyl-2-pyrrolidone (NMP) were sequentially added, and stirred until the solid powder was completely dissolved, to obtain an aromatic diamine mixed solution; cooling the mixed solution of aromatic diamine to below 10 ℃ by adopting an ice water bath, and slowly dropwise adding the prepared mixture of aromatic-diacid chloride dimethacrylate into the mixed solution of aromatic diamine; then, reacting for 10 hours at room temperature; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, washing and drying in vacuum to obtain the photosensitive Polyamide Acid Ester (PAE) resin.
Dissolving 40g of the photosensitive PAE resin in 40g of NMP in an ultraclean room provided with a yellow light lamp to form a homogeneous solution; then, 0.4g of 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 3.2g of ethylene glycol diethy ether methacrylate (4 EM), and 0.2g of N-nitrosodiphenylamine were added in this order, and stirred at room temperature for 3 hours to form a transparent photosensitive polyimide resin (PSPI) solution.
Spin-coating the above transparent photosensitive polyimide resin solution on the surface of 6 inch wafer, baking at 110 deg.C for 4min, placing mask on the surface, and irradiating with ultraviolet lamp (i and g lines) at 200mJ/cm 2 Exposure energy of 30s; developing for 60s by using a cyclopentanone/NMP (mass ratio of 1). Curing the film in a high-temperature blowing nitrogen-filled oven at 350 ℃/1h to obtain the transparent photosensitive polyimide film three-dimensional graph. The resolution ratio of a high-temperature cured PI film round hole (with the thickness of 5 mu m) is 15 mu m; the light transmittance at the ultraviolet wavelength of 450nm is 86.4 percent, and the light transmittance at the wavelength of 550nm is 90.9 percent; tg of 330 ℃; the temperature of 5 percent of thermal weight loss is 506 ℃; elongation at break of 20.1%; tan. Delta. At 10GHz was 0.0058.
Example 6
In a 500mL three necked round bottom flask equipped with mechanical stirring, thermometer and nitrogen blanket, 26.03g of 2-hydroxyethyl methacrylate (HEMA), 15.82g of pyridine, 13.09g (0.06 mol) of pyromellitic dianhydride (PMDA), 23.53g (0.04 mol) of 4,4' - (trifluoromethyl-meta, meta-bistrifluoromethylphenyl-isopropyl) phthalic anhydride (9 FDA) and 200g of N-methyl-2-pyrrolidone (NMP) were sequentially added and stirred at room temperature for 6h to form the corresponding aromatic diacid dimethacrylate mixture. The product is reacted with 23.79g SOCl at 0 DEG C 2 Reacting for 2h at room temperature for 4h to generate the corresponding aromatic-diacid chloride dimethacrylate mixture.
In a 1L three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer and a nitrogen gas guard, 12.81g (0.04 mol) of 2,2' -bistrifluoromethyl-4, 4' -diaminobiphenyl (TFDB), 15.26g (0.06 mol) of 3,3', 5' -tetramethyl-4, 4' -diaminodiphenylmethane (TMMDA) solid powder and 280g of N-methyl-2-pyrrolidone (NMP) were sequentially added, and stirred until the solid powder was completely dissolved, to obtain an aromatic diamine mixed solution; cooling the mixed solution of aromatic diamine to below 10 ℃ by adopting an ice water bath, and slowly dropwise adding the prepared mixture of aromatic-diacid chloride dimethacrylate into the mixed solution of aromatic diamine; then, reacting for 10 hours at room temperature; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, washing and drying in vacuum to obtain the photosensitive Polyamide Acid Ester (PAE) resin.
Dissolving 40g of the photosensitive PAE resin in 50g of NMP in an ultraclean room provided with a yellow light lamp to form a homogeneous solution; then, 0.4g of 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 3.2g of ethylene glycol diethy ether methacrylate (4 EM), and 0.2g of N-nitrosodiphenylamine were added in this order, and stirred at room temperature for 3 hours to form a transparent photosensitive polyimide resin (PSPI) solution.
Spin-coating the above transparent photosensitive polyimide resin solution on the surface of 6 inch wafer, baking at 110 deg.C for 4min, placing mask on the surface, and irradiating with ultraviolet lamp (i and g rays) at 200mJ/cm 2 Exposure energy of 30s; developing for 60s by using a cyclopentanone/NMP (mass ratio of 1). Curing the film in a high-temperature blowing nitrogen-filled oven at 350 ℃/1h to obtain the transparent photosensitive polyimide film three-dimensional graph. The resolution ratio of a high-temperature cured PI film round hole (with the thickness of 5 mu m) is 10 mu m; the light transmittance at the ultraviolet wavelength of 450nm is 86.7 percent, and the light transmittance at the wavelength of 550nm is 91.3 percent; tg of 332 ℃; the temperature of 5 percent of thermal weight loss is 512 ℃; elongation at break of 26.9%; tan. Delta. At 10GHz was 0.0083.
Example 7
In a 500mL three necked round bottom flask equipped with mechanical stirring, thermometer and nitrogen blanket, 26.03g of 2-hydroxyethyl methacrylate (HEMA), 15.82g of pyridine, 10.91g (0.05 mole) pyromellitic dianhydride (PMDA), 22.21g (0.05 mole) of 4,4' - (hexafluoroisopropylidene) diphenylanhydride (6 FDA) and 200g of N-methyl-2-pyrrolidone (NMP) were added sequentially and stirred at room temperature for 6h to form the corresponding aromatic diacid dimethacrylate mixture. At 0 deg.C, mixing the aboveThe product was reacted with 23.79g SOCl 2 Reacting for 2h at room temperature for 4h to generate the corresponding aromatic-diacid chloride dimethacrylate mixture.
In a 1L three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer and a nitrogen gas guard, 35.31g (0.07 mol) of 4,4 '-bis (2-trifluoromethyl-4-aminophenoxy) biphenyl (6 FBAB), 7.63g (0.03 mol) of 3,3',5 '-tetramethyl-4, 4' -diaminodiphenylmethane (TMMDA) solid powder and 280g of N-methyl-2-pyrrolidone (NMP) were sequentially added, and stirred until the solid powder was completely dissolved, to obtain an aromatic diamine mixed solution; cooling the mixed solution of aromatic diamine to below 10 ℃ by adopting an ice water bath, and slowly dropwise adding the prepared mixture of aromatic-diacid chloride dimethacrylate into the mixed solution of aromatic diamine; then, reacting for 10 hours at room temperature; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, washing and drying in vacuum to obtain the photosensitive Polyamide Acid Ester (PAE) resin.
In an ultra-clean room equipped with a yellow light lamp, 40g of the photosensitive PAE resin was dissolved in 47g of NMP to form a homogeneous solution; then, 0.4g of 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 3.2g of ethylene glycol diethy ether methacrylate (4 EM), and 0.2g of N-nitrosodiphenylamine were added in this order, and stirred at room temperature for 3 hours to form a transparent photosensitive polyimide resin (PSPI) solution.
Spin-coating the above transparent photosensitive polyimide resin solution on the surface of 6 inch wafer, baking at 110 deg.C for 4min, placing mask on the surface, and irradiating with ultraviolet lamp (i and g lines) at 200mJ/cm 2 Exposure energy of 30s; developing for 60s by using a cyclopentanone/NMP (mass ratio of 1). Curing the film in a high-temperature blowing nitrogen-filled oven at 350 ℃/1h to obtain the transparent photosensitive polyimide film three-dimensional graph. The resolution ratio of a high-temperature cured PI film round hole (with the thickness of 5 mu m) is 10 mu m; the light transmittance at the ultraviolet wavelength of 450nm is 89.8 percent, and the light transmittance at the wavelength of 550nm is 90.7 percent; tg of 336 ℃; the temperature with 5 percent of thermal weight loss is 509 ℃; elongation at break 35.2%; tan. Delta. At 10GHz was 0.0082.
Example 8
In a 500mL three necked round bottom flask equipped with mechanical stirring, thermometer and nitrogen blanket, 26.03g of 2-hydroxyethyl methacrylate (HEMA), 15.82g of pyridine, 2.94g (0.01 mole) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA), 39.98g (0.09 mole) of 4,4' - (hexafluoroisopropylene) diphenylanhydride (6 FDA) and 200g of N-methyl-2-pyrrolidone (NMP) were added sequentially and stirred at room temperature for 6h to form the corresponding aromatic diacid dimethacrylate mixture. The product is reacted with 23.79g SOCl at 0 DEG C 2 Reacting for 2h at room temperature for 4h to generate the corresponding aromatic-diacid chloride dimethacrylate mixture.
In a 1L three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer and a nitrogen gas guard, 28.82g (0.09 mol) of 2,2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl (TFDB), 2.00g (0.01 mol) of 4,4 '-diaminodiphenyl ether (4, 4' -ODA) solid powder and 280g of N-methyl-2-pyrrolidone (NMP) were sequentially added, and stirred until the solid powder was completely dissolved, to obtain an aromatic diamine mixed solution; cooling the mixed solution of aromatic diamine to below 10 ℃ by adopting an ice water bath, and slowly dropwise adding the prepared aromatic-diacid chloride dimethacrylate mixture into the mixed solution of aromatic diamine; then, reacting for 10 hours at room temperature; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, washing and drying in vacuum to obtain the photosensitive Polyamide Acid Ester (PAE) resin.
Dissolving 40g of the photosensitive PAE resin in 40g of NMP in an ultraclean room provided with a yellow light lamp to form a homogeneous solution; then, 0.4g of 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 3.2g of ethylene glycol diethy ether methacrylate (4 EM), and 0.2g of N-nitrosodiphenylamine were added in this order, and stirred at room temperature for 3 hours to form a transparent photosensitive polyimide resin (PSPI) solution.
Spin-coating the above transparent photosensitive polyimide resin solution on the surface of 6 inch wafer, baking at 110 deg.C for 4min, placing mask on the surface, and irradiating with ultraviolet lamp (i and g lines) at 200mJ/cm 2 Exposure energy of 30s; developing for 60s by using a cyclopentanone/NMP (mass ratio of 1)And (5) performing stereo lithography. Curing the film in a high-temperature blowing nitrogen-filled oven at 350 ℃/1h to obtain the transparent photosensitive polyimide film three-dimensional graph. The resolution ratio of a high-temperature cured PI film round hole (with the thickness of 5 mu m) is 12 mu m; the light transmittance at the ultraviolet wavelength of 450nm is 83.8 percent, and the light transmittance at the wavelength of 550nm is 91.1 percent; tg of 338 ℃; the temperature with 5 percent of thermal weight loss is 512 ℃; elongation at break 29.1%; tan. Delta. At 10GHz was 0.0086.
Comparative example 1
In a 500mL three necked round bottom flask equipped with mechanical stirring, thermometer and nitrogen blanket, 26.03g of 2-hydroxyethyl methacrylate (HEMA), 15.82g of pyridine, 29.42g (0.1 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA) and 200g of N-methyl-2-pyrrolidone (NMP) were added in sequence and stirred at room temperature for 6h to form the corresponding aromatic diacid dimethacrylate mixture. The product is reacted with 23.79g SOCl at 0 DEG C 2 Reacting for 2h at room temperature for 4h to generate the corresponding aromatic-diacid chloride dimethacrylate mixture.
In a 1L three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer and a nitrogen gas guard, 32.02g (0.1 mol) of 2,2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl (TFDB) solid powder and 280g of N-methyl-2-pyrrolidone (NMP) were sequentially added, and stirred until the solid powder was completely dissolved, to obtain an aromatic diamine mixed solution; cooling the mixed solution of aromatic diamine to below 10 ℃ by adopting an ice water bath, and slowly dropwise adding the prepared mixture of aromatic-diacid chloride dimethacrylate into the mixed solution of aromatic diamine; then, reacting for 10 hours at room temperature; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, washing and drying in vacuum to obtain the photosensitive Polyamide Acid Ester (PAE) resin.
Dissolving 40g of the photosensitive PAE resin in 60g of NMP in an ultraclean room provided with a yellow light lamp to form a homogeneous solution; then, 0.4g of 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 3.2g of ethylene glycol diethy ether methacrylate (4 EM), and 0.2g of N-nitrosodiphenylamine were added in this order, and stirred at room temperature for 3 hours to form a transparent photosensitive polyimide resin (PSPI) solution.
Mixing the above transparent photosensitive polyimide resinSpin coating the lipid solution on the surface of 6 inch wafer, baking at 110 deg.C for 4min, placing mask on the surface, and irradiating with ultraviolet lamp (i and g lines) at 200mJ/cm 2 Is exposed for 30s at an exposure energy of (1); developing for 60s by using a cyclopentanone/NMP (mass ratio of 1). Curing the film in a high-temperature blowing nitrogen-filled oven at 350 ℃/1h to obtain the transparent photosensitive polyimide film three-dimensional graph. The resolution ratio of a high-temperature cured PI film round hole (with the thickness of 5 mu m) is 15 mu m; the light transmittance at the ultraviolet wavelength of 450nm is 88.5 percent, and the light transmittance at the wavelength of 550nm is 90.5 percent; tg of 355 ℃; the temperature of 5 percent of thermal weight loss is 524 ℃; elongation at break 8.4%; tan. Delta. At 10GHz was 0.0076.
Comparative example 2
In a 500mL three necked round bottom flask equipped with mechanical stirring, thermometer and nitrogen blanket, 26.03g of 2-hydroxyethyl methacrylate (HEMA), 15.82g of pyridine, 44.42g (0.1 mol) of 4,4' - (hexafluoroisopropyl) diphenylanhydride (6 FDA) and 200g of N-methyl-2-pyrrolidone (NMP) were added sequentially and stirred at room temperature for 6h to form the corresponding aromatic diacid dimethacrylate mixture. The product is reacted with 23.79g SOCl at 0 deg.C 2 Reacting for 2h at room temperature for 4h to generate the corresponding aromatic-diacid chloride dimethacrylate mixture.
In a 1L three-neck round-bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 25.44g (0.1 mol) of 3,3', 5' -tetramethyl-4, 4' -diaminodiphenylmethane (TMMDA) solid powder and 280g of N-methyl-2-pyrrolidone (NMP) are sequentially added and stirred until the solid powder is completely dissolved, so as to obtain an aromatic diamine mixed solution; cooling the mixed solution of aromatic diamine to below 10 ℃ by adopting an ice water bath, and slowly dropwise adding the prepared mixture of aromatic-diacid chloride dimethacrylate into the mixed solution of aromatic diamine; then, reacting for 10 hours at room temperature; and pouring the reaction solution into 5L of deionized water, separating out a solid, filtering, washing and drying in vacuum to obtain the photosensitive Polyamide Acid Ester (PAE) resin.
Dissolving 40g of the photosensitive PAE resin in 50g of NMP in an ultraclean room provided with a yellow light lamp to form a homogeneous solution; then, 0.4g of 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 3.2g of ethylene glycol diethy ether methacrylate (4 EM), and 0.2g of N-nitrosodiphenylamine were added in this order, and stirred at room temperature for 3 hours to form a transparent photosensitive polyimide resin (PSPI) solution.
Spin-coating the above transparent photosensitive polyimide resin solution on the surface of 6 inch wafer, baking at 110 deg.C for 4min, placing mask on the surface, and irradiating with ultraviolet lamp (i and g lines) at 200mJ/cm 2 Exposure energy of 30s; developing for 60s by using a cyclopentanone/NMP (mass ratio of 1). Curing the film in a high-temperature blowing nitrogen-filled oven at 350 ℃/1h to obtain the transparent photosensitive polyimide film three-dimensional graph. The resolution ratio of a high-temperature cured PI film round hole (with the thickness of 5 mu m) is 15 mu m; the light transmittance at the ultraviolet wavelength of 450nm is 84.5 percent, and the light transmittance at the wavelength of 550nm is 90.5 percent; tg of 340 ℃; the temperature of 5 percent of thermal weight loss is 514 ℃; elongation at break was 9.2%; tan. Delta. At 10GHz was 0.0072.
TABLE 1 Main Properties of transparent photosensitive polyimide prepared in examples and comparative examples
As can be seen from the data in Table 1, the transparent photosensitive polyimide film prepared by the embodiments of the present invention has not only excellent photolithography performance, but also resolution of a circular hole (thickness of 5 μm) of 10 μm; the film has excellent transparency, the light transmittance at the ultraviolet wavelength of 450nm is more than or equal to 83 percent, the light transmittance at the ultraviolet wavelength of 550nm is more than or equal to 90 percent, the film also has excellent thermal stability and heat resistance, the temperature of the thermal weight loss of the film is 5 percent between 506 and 522 ℃, and the Tg is more than or equal to 330 ℃; good mechanical property, the elongation at break of the film can reach 49.1%; and good dielectric property, and Tan delta can reach 0.0033 at 10 GHz.
Compared with a comparative example, the photosensitive precursor PAE resin prepared by only adopting the rigid aromatic diamine monomer or the rigid aromatic dianhydride monomer can still obtain a transparent photosensitive polyimide film with excellent photoetching performance, transparency, thermal stability, heat resistance and dielectric property from the prepared negative PSPI material; however, the toughness of the high-temperature cured film is poor, and the elongation at break is less than or equal to 10 percent, so that the high-temperature cured film is difficult to be practically applied.
Claims (10)
1. A method for preparing a transparent photosensitive polyimide resin, comprising the steps of:
(1) Dissolving a mixture of hydroxyl-containing (meth) acrylate, organic base, rigid aromatic dianhydride and fluorine-containing aromatic dianhydride in an organic solvent, and carrying out esterification reaction to form a mixture solution of (meth) acrylate-group-containing aromatic diacid diester; further reacting the mixture under the action of an acyl chlorination reagent to form a mixture solution of aromatic diester diacid chloride containing a (methyl) acrylate group;
(2) Slowly dripping the aromatic diester diacid chloride mixture solution containing the (methyl) acrylate group into an organic solution containing fluorine-containing aromatic diamine and rigid aromatic diamine at the temperature of between 0 and 15 ℃, and reacting at room temperature to generate a photosensitive polyamic acid ester resin solution; precipitating the photosensitive polyamic acid ester resin solution in a poor solvent, filtering, washing and drying to obtain a photosensitive polyamic acid ester resin solid;
(3) And dissolving the photosensitive polyamic acid ester resin solid, a photosensitive auxiliary agent, a cross-linking agent and a polymerization inhibitor in an organic solvent, and reacting to obtain the transparent photosensitive polyimide resin.
2. The method of claim 1, wherein: in the step (1), the hydroxyl group-containing (meth) acrylate is at least one of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1-acryloyloxy-3-propanol, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-methacrylamidoglycol, 1-methacryloyloxy-3-propanol, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropylacrylate and 2-hydroxy-3-cyclohexyloxypropylmethacrylate;
the organic base is at least one of triethylamine, pyridine, 2-methylpyridine, 3-methylpyridine, isoquinoline, piperidine and 3-methyl-piperidine;
the rigid aromatic dianhydride is pyromellitic dianhydride, 3',4' -biphenyltetracarboxylic dianhydride, 2, 3', at least one of 4' -biphenyltetracarboxylic dianhydride, 3',4' -benzophenonetetracarboxylic dianhydride, and 3,3',4' -diphenylsulfonetetracarboxylic dianhydride;
the fluorine-containing aromatic dianhydride is at least one of 4,4'- (hexafluoroisopropylidene) diphenyl anhydride, 4' - (trifluoromethylphenylisopropyl) diphenyl anhydride, 1, 4-bis (trifluoromethyl) -2,3,5, 6-benzenetetracarboxylic dianhydride, 4'- (4, 4' -hexafluoroisopropyldiphenoxy) bis (phthalic anhydride), 4'- (trifluoromethyl-m-trifluoromethylphenyl-isopropyl) diphenyl anhydride, 4' - (trifluoromethyl-m, m-bistrifluoromethylphenyl-isopropyl) diphenyl anhydride and 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic dianhydride;
in the step (1), the organic solvent is at least one of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, acetone, cyclohexanone, ethyl acetate, tetrahydrofuran, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether;
the acyl chlorination reagent is SOCl 2 、PCl 3 、PCl 5 Oxalyl chloride and COCl 2 At least one of (1).
3. The production method according to claim 1 or 2, characterized in that: in the step (1), the ratio of the number of moles of the hydroxyl group-containing (meth) acrylate to the total number of moles of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 2;
the molar ratio of the fluorine-containing aromatic dianhydride to the rigid aromatic dianhydride is 1;
the ratio of the mole number of the organic base to the total mole number of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 1 to 5, preferably 2 to 4;
the mass ratio of the organic solvent to the total mass of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 1 to 10, preferably 2 to 8;
the ratio of the number of moles of the acylating chlorination reagent to the total number of moles of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 2.
4. The production method according to any one of claims 1 to 3, characterized in that: <xnotran> (2) , 2,2'- -4,4' - ,2,2 '- -4,4' - ,3,3'- -5,5' - ,1,4- (2- -4- ) ,1,3- (2- -4- ) ,4,4'- (2- -4- ) ,2,2- [4- (4- ) ] ,2,2- [4- (2- -4- ) ] ,3- -4,4' - ,2,2 '- ( ) -4,4' - , N, N '- (2,2' - ( ) - [1,1'- ] -4,4' - ) (4- ), 3- , , ,4,4'- 4,4' - ; </xnotran>
The rigid aromatic diamine is 4,4 '-diaminodiphenyl ether, 1, 4-p-phenylenediamine, 4' -biphenyldiamine, 2 '-dimethyl-4, 4' -diaminobiphenyl 2,2 '-diethyl-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, 2', at least one of 3,3' -tetramethyl-4, 4 '-diaminobiphenyl and 3,3',5 '-tetramethyl-4, 4' -diaminodiphenylmethane;
the organic solvent of the organic solution is at least one of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, acetone, cyclohexanone, ethyl acetate, tetrahydrofuran, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether;
the poor solvent is at least one of water, ethanol, methanol, hexane and toluene; preferably at least one of deionized water, ethanol and methanol;
the total molar number of the fluorine-containing aromatic diamine and the rigid aromatic diamine is as follows: the total molar ratio of the fluorine-containing aromatic dianhydride to the rigid aromatic dianhydride is 100 to 20;
the molar ratio of the fluorine-containing aromatic diamine to the rigid aromatic diamine is 1;
the ratio of the mass of the organic solvent to the total mass of the fluorine-containing aromatic diamine and the rigid aromatic diamine is 1 to 10, preferably 5 to 10;
the mass ratio of the poor solvent to the photosensitive polyamic acid resin solution is 3 to 20.
5. The production method according to any one of claims 1 to 4, characterized in that: in the step (3), the photo-sensitive assistant is at least one of benzophenone, dibenzyl ketone, 4-benzoyl-4 '-methyl benzophenone, 2' -diethoxy acetophenone, 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methyl thioxanthone, benzil dimethyl ketal, 1-phenyl-1, 2-butanedione-2- (0-methoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (0-benzoyl) oxime, and N-phenylglycine;
the photocrosslinking agent is at least one of ethylene glycol diethyl ether methacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, cyclohexane dimethacrylate and 1, 4-butanediol dimethacrylate;
the polymerization inhibitor is at least one of hydroquinone, N-nitrosodiphenylamine, N-phenylnaphthylamine, p-tert-butylcatechol, phenothiazine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanone diamine tetraacetic acid, glycol ether diamine tetraacetic acid, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 5-nitroso-8-hydroxyquinoline and 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol;
the organic solvent in the step (3) is at least one of N-methyl-2-pyrrolidone (NMP), N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), gamma-butyrolactone (GBL), acetone, ethyl acetate, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol and tert-butanol;
in the step (3), the mass ratio of the photosensitive polyamic acid ester resin solid to the photosensitive assistant is 1;
the mass ratio of the photosensitive polyamic acid ester resin solid to the crosslinking agent is 1;
the mass ratio of the photosensitive polyamic acid ester resin solid to the polymerization inhibitor is 1;
the mass ratio of the photosensitive polyamic acid ester resin solid to the organic solvent is 1.
6. The production method according to any one of claims 1 to 5, characterized in that: in the step (1), the temperature of the esterification reaction is room temperature; the esterification reaction time is 6-12 h;
the further reaction condition under the action of the acyl chlorination reagent is that the reaction is carried out for 2 to 6 hours at the temperature of between 0 and 10 ℃ and then for 4 to 6 hours at room temperature;
in the step (2), the room temperature reaction time is 6-12 h;
in the step (3), the reaction temperature is room temperature; the reaction time is 2-4 h.
7. A transparent photosensitive polyimide resin produced by the production method described in any one of claims 1 to 6.
8. Use of the transparent photosensitive polyimide resin according to claim 7 for preparing a transparent photosensitive polyimide film.
9. Use according to claim 8, characterized in that: the transparent photosensitive polyimide film is a film with a stereo photoetching pattern.
10. A transparent photosensitive polyimide film characterized in that: the transparent photosensitive polyimide film is prepared by the method comprising the following steps:
coating the transparent photosensitive polyimide resin of claim 7, then performing photoetching on the pattern, and curing at a high temperature to obtain the transparent photosensitive polyimide film;
specifically, the high-temperature curing temperature is 280-350 ℃; the time of high-temperature curing is 0.5 to 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211372852.4A CN115850596A (en) | 2022-11-03 | 2022-11-03 | Transparent photosensitive polyimide resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211372852.4A CN115850596A (en) | 2022-11-03 | 2022-11-03 | Transparent photosensitive polyimide resin and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115850596A true CN115850596A (en) | 2023-03-28 |
Family
ID=85662473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211372852.4A Pending CN115850596A (en) | 2022-11-03 | 2022-11-03 | Transparent photosensitive polyimide resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115850596A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117186403A (en) * | 2023-09-01 | 2023-12-08 | 明士(北京)新材料开发有限公司 | Negative photosensitive resin, resin composition, and preparation method and application thereof |
| CN117402351A (en) * | 2023-12-14 | 2024-01-16 | 山东广垠新材料有限公司 | Photo-induced cross-linking/de-cross-linking nylon material, and preparation method and application thereof |
-
2022
- 2022-11-03 CN CN202211372852.4A patent/CN115850596A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117186403A (en) * | 2023-09-01 | 2023-12-08 | 明士(北京)新材料开发有限公司 | Negative photosensitive resin, resin composition, and preparation method and application thereof |
| CN117186403B (en) * | 2023-09-01 | 2024-04-02 | 明士(北京)新材料开发有限公司 | Negative photosensitive resin, resin composition, and preparation method and application thereof |
| CN117402351A (en) * | 2023-12-14 | 2024-01-16 | 山东广垠新材料有限公司 | Photo-induced cross-linking/de-cross-linking nylon material, and preparation method and application thereof |
| CN117402351B (en) * | 2023-12-14 | 2024-02-13 | 山东广垠新材料有限公司 | Photo-induced cross-linking/de-cross-linking nylon material, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5593548B2 (en) | POLYIMIDE POLYMER, COPOLYMER THEREOF, AND POSITIVE PHOTOSENSITIVE RESIN COMPOSITION CONTAINING THE SAME | |
| TWI491987B (en) | A negative photosensitive resin composition, a hardened embossed pattern, and a semiconductor device | |
| CN115850596A (en) | Transparent photosensitive polyimide resin and preparation method and application thereof | |
| JP4930883B2 (en) | Photosensitive resin composition and circuit board using the same | |
| JP3526829B2 (en) | Polyamic acid ester | |
| JP2007264028A (en) | Photosensitive resin composition and metal-resin complex using same | |
| KR100291376B1 (en) | Photosensitive resin composition | |
| WO2004008252A1 (en) | Highly heat-resistant, negative-type photosensitive resin composition | |
| CN114280887A (en) | Negative photosensitive solid glue film developed by alkaline water system and preparation method thereof | |
| CN114995060A (en) | Negative photosensitive resin composition capable of being cured at low temperature and preparation method and application thereof | |
| CN115160569A (en) | Photosensitive polyamic acid ester resin, resin composition and electronic component | |
| JP2011013602A (en) | Photosensitive resin composition, method for producing resist pattern, and hard disk suspension | |
| KR101888620B1 (en) | polyamic acids resin composition comprising polyfunctional photo-crosslinkable monomer and photosensitive polyimides resin composition manufactured therefrom | |
| US6096480A (en) | Photosensitive polyimidosiloxane compositions and insulating films made thereof | |
| JP4592999B2 (en) | Novel terminal-modified polyamic acid and photosensitive resin composition containing the same | |
| KR100230505B1 (en) | Photosensitive polyimidosiloxanes and compositions and insulating films made thereof | |
| CN116802559A (en) | Photosensitive resin composition, cured film, electronic component, antenna element, semiconductor package, and compound | |
| JP5721459B2 (en) | Photosensitive resin composition, cured product using the same, and multilayer material | |
| JP2006071783A (en) | Photosensitive resin composition and method for producing fine pattern using the same | |
| JP2006083307A (en) | Photosensitive polyimide-siloxane and its composition | |
| JP2003121997A (en) | Negative photosensitive resin composition | |
| CN117186403B (en) | Negative photosensitive resin, resin composition, and preparation method and application thereof | |
| KR102152075B1 (en) | Polyimide-based compound and composition including the same | |
| CN116836388B (en) | Positive photosensitive resin, resin composition, preparation method and application thereof | |
| KR102254505B1 (en) | Polyimide-based compound and photosensitive composition including the same |
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 |