Search

CN-115850596-B - Transparent photosensitive polyimide resin and preparation method and application thereof

CN115850596BCN 115850596 BCN115850596 BCN 115850596BCN-115850596-B

Abstract

The invention discloses a transparent photosensitive polyimide resin, a preparation method and application thereof, and belongs to the technical field of polyimide. The invention adopts hydroxyl-containing (methyl) acrylic ester, organic alkali, rigid aromatic dianhydride, fluorine-containing aromatic diamine and rigid aromatic diamine to prepare photosensitive resin precursor, and then the photosensitive resin precursor is mixed with photosensitive auxiliary agent, solvent and the like to obtain transparent photosensitive polyimide resin. The polyimide resin prepared by the invention has excellent photoetching process performance, and meanwhile, the polyimide layer film formed by high-temperature curing of the photoetching pattern has the characteristics of high transparency, high heat resistance, high strength and toughness, low dielectric loss and the like.

Inventors

  • YANG SHIYONG
  • MA JIAXIN
  • YUAN LILI
  • FAN SHENGNAN
  • YANG HAIXIA

Assignees

  • 中国科学院化学研究所

Dates

Publication Date
20260505
Application Date
20221103

Claims (14)

  1. 1. A preparation method of transparent photosensitive polyimide resin comprises the following steps: (1) Dissolving a mixture of hydroxyl-containing (methyl) acrylic ester, organic alkali, rigid aromatic dianhydride and fluorine-containing aromatic dianhydride in an organic solvent, and carrying out esterification reaction to form an aromatic diacid diester mixture solution containing (methyl) acrylic ester groups; The hydroxyl-containing (methyl) acrylic ester is 2-hydroxyethyl methacrylate; 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 3,3', 4' -biphenyl tetracarboxylic dianhydride; The fluorine-containing aromatic dianhydride is 4,4' - (hexafluoroisopropenyl) diphenyl anhydride, and the molar ratio of the fluorine-containing aromatic dianhydride to the rigid aromatic dianhydride is 1:0.3 or 1:0.1; The ratio of the moles of the hydroxyl group-containing (meth) acrylate to the total moles of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 2:1; (2) Slowly dripping the (methyl) acrylic ester group-containing aromatic diester diacid chloride mixture solution into an organic solution of 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; The fluorine-containing aromatic diamine is 2, 2 '-bistrifluoromethyl-4, 4' -diaminobiphenyl; the rigid aromatic diamine is 4,4' -diaminodiphenyl ether or 2, 2' -dimethyl-4, 4' -diaminobiphenyl; the molar ratio of the fluorine-containing aromatic diamine to the rigid aromatic diamine is 1:0.1; total moles 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 100:90-110; (3) And dissolving the photosensitive polyamic acid ester resin solid, a photosensitive auxiliary agent, a crosslinking agent and a polymerization inhibitor in an organic solvent, and reacting to obtain the transparent photosensitive polyimide resin.
  2. 2. The process according to claim 1, wherein in the step (1), the organic solvent is N Methyl group 2 Pyrrolidone, N Dimethylacetamide, N Dimethylformamide, dimethylsulfoxide, gamma At least one of butyrolactone, acetone, cyclohexanone, ethyl acetate, tetrahydrofuran, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether; The acyl chloride reagent is at least one of SOCl 2 、PCl 3 、PCl 5 , oxalyl chloride and COCl 2 .
  3. 3. The method according to claim 1 or 2, wherein in the step (1), the ratio of the number of moles of the organic base to the total number of moles of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 1 to 5:1; The ratio of the mass of the organic solvent to the total mass of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 1-10:1; the ratio of the moles of the acid chloride reagent to the total moles of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 2:1.
  4. 4. The method according to claim 3, wherein in the step (1), the ratio of the number of moles of the organic base to the total number of moles of the fluorinated aromatic dianhydride and the rigid aromatic dianhydride is 2 to 4:1; the ratio of the mass of the organic solvent to the total mass of the fluorine-containing aromatic dianhydride and the rigid aromatic dianhydride is 2-8:1.
  5. 5. The method according to claim 1 or 2, wherein in the step (2), the organic solvent of the organic solution is N Methyl group 2 Pyrrolidone, N Dimethylacetamide, N Dimethylformamide, dimethylsulfoxide, gamma At least one of 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; 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 1-10:1; the mass ratio of the poor solvent to the photosensitive polyamic acid ester resin solution is 3-20:1.
  6. 6. The method according to claim 5, wherein in the step (2), the poor solvent is at least one of deionized water, ethanol and methanol; 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 5-10:1.
  7. 7. The preparation method according to claim 1 or 2, wherein in the step (3), the photosensitive auxiliary agent is benzophenone, dibenzylmethylketone, or 4 Benzoyl group 4 ' Methylbenzophenone, 2' Diethoxyacetophenone, 2 Hydroxy group 2 Methyl propiophenone, 1 Hydroxycyclohexyl phenyl ketone, thioxanthone, 2 Methyl thioxanthone, benzil dimethyl ketal, 1 Phenyl group 1 ,2 Butanedione 2 (0 Methoxycarbonyl) oxime, 1 Phenyl group 1 ,2 Propylene dione 2 (0 Methoxycarbonyl) oxime, 1 Phenyl group 1 ,2 Propylene dione 2 (0 Ethoxycarbonyl) oxime, 1 Phenyl group 1 ,2 Propylene dione 2 (0 Benzoyl) oxime, and N At least one of phenylglycine; The cross-linking agent is ethylene glycol diethyl ether methacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, cyclohexane dimethacrylate and 1,4 At least one of butylene glycol dimethacrylate; The polymerization inhibitor is hydroquinone, N Nitrosodiphenylamine, N Phenyl-nenamine, p-tert-butylcatechol, phenothiazine, ethylenediamine tetraacetic acid, 1,2 Cyclohexanone diamine tetraacetic acid, glycol ether diamine tetraacetic acid, 1 Nitroso group 2 Naphthol, 2 Nitroso group 1 Naphthol, 5 Nitroso group 8 Hydroxyquinoline and 2 Nitroso group 5 (N Ethyl group N Sulfopropylamino) phenol at least one of (a) and (b); the organic solvent in the step (3) is N Methyl group 2 Pyrrolidone (NMP), N Dimethylacetamide (DMAc), N Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), gamma At least one of butyrolactone (GBL), acetone, ethyl acetate, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol; in the step (3), the mass ratio of the photosensitive polyamic acid ester resin solid to the photosensitive auxiliary agent is 1:0-1:0.5; the mass ratio of the photosensitive polyamide acid ester resin solid to the cross-linking agent is 1:0-1:0.5; the mass ratio of the photosensitive polyamic acid ester resin solid to the polymerization inhibitor is 1:0-1:0.5; The mass ratio of the photosensitive polyamide acid ester resin solid to the organic solvent is 1:0.1-1:100.
  8. 8. The method according to claim 7, wherein in the step (3), the mass ratio of the photosensitive polyamic acid ester resin solid to the photosensitive auxiliary agent is 1:0.01-1:0.2; The mass ratio of the photosensitive polyamide acid ester resin solid to the cross-linking agent is 1:0.01-1:0.3; the mass ratio of the photosensitive polyamide acid ester resin solid to the polymerization inhibitor is 1:0.001-1:0.2; The mass ratio of the photosensitive polyamide acid ester resin solid to the organic solvent is 1:0.5-1:10.
  9. 9. The preparation method according to claim 1 or 2, wherein in the step (1), the temperature of the esterification reaction is room temperature, and the time of the esterification reaction is 6-12 hours; the condition of further reaction under the action of an acyl chloride reagent is that the reaction is carried out for 2 to 6 hours at 0 to 10 ℃ firstly, and then the reaction is carried out for 4 to 6 hours at room temperature; in the step (2), the room temperature reaction time is 6-12 hours; in the step (3), the reaction temperature is room temperature, and the reaction time is 2-4 hours.
  10. 10. The transparent photosensitive polyimide resin produced by the production method according to any one of claims 1 to 9.
  11. 11. Use of the transparent photosensitive polyimide resin according to claim 10 for the preparation of a transparent photosensitive polyimide film.
  12. 12. The method according to claim 11, wherein the transparent photosensitive polyimide film is a film having a stereolithography pattern.
  13. 13. The transparent photosensitive polyimide film is characterized by being prepared by a method comprising the following steps: The transparent photosensitive polyimide film is obtained by using the transparent photosensitive polyimide resin coating film according to claim 10, then carrying out photoetching pattern and high-temperature curing.
  14. 14. The transparent photosensitive polyimide film according to claim 13, wherein the high-temperature curing temperature is 280-350 ℃ and the high-temperature curing time is 0.5-4 hours.

Description

Transparent photosensitive polyimide resin and preparation method and application thereof 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 The photosensitive polyimide (Photosensitive Polyimide, PSPI) has excellent comprehensive performance of polyimide and photoetching patterning process performance of photoresist, and is widely applied to the fields of microelectronic manufacturing and packaging, flat panel 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. PSPI materials are classified into negative and positive types, wherein the negative PSPI material is prepared by introducing photosensitive groups into a main chain structure of polyimide precursor resin, firstly forming photosensitive polyamide acid ester (Poly (amic ester), PAE) resin, and then uniformly mixing the photosensitive polyamide acid ester (Poly (amic ester), PAE) resin with photosensitive auxiliary agents, cross-linking agents, solvents and the like to form negative photosensitive polyimide resin (Negative photosensitive polyimide, n-PSPI). Spin-coating n-PSPI solution on the surface of a substrate such as a silicon wafer, forming a negative stereo lithography pattern after pre-baking, exposing, developing and rinsing, and carrying out imidization reaction on the substrate such as the developed silicon wafer at high temperature to obtain a polyimide negative lithography pattern. The polyimide layer film forming the photoetching pattern obtained by high-temperature curing 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) acrylic ester, the crosslinking groups such as (methyl) acrylic ester generate photochemical crosslinking reaction under the action of ultraviolet light, the solubility in developing solution is greatly reduced, and excellent photoetching process performance of the PSPI material is endowed. However, the polyimide layer film formed by photoetching and high-temperature curing the n-PSPI material is a yellow-brown non-transparent layer film. This is mainly due to the presence of a large number of imide rings and conjugated aromatic rings in the backbone structure of the polyimide film resin converted by the high temperature curing process, which is prone to form strong intra-and inter-chain charge transfer complexation (CHARGE TRANSFER Complex, CTC), with strong light absorption in the visible region, resulting in a yellow or tan color of the film material. In recent years, the technical development in the fields of flat panel display, optical devices and the like is in urgent need of using colorless and transparent polyimide resin, and PSPI materials are required to have excellent photoetching manufacturability, comprehensive mechanical property, heat resistance and electrical property, and meanwhile, polyimide layer films formed after photoetching and high-temperature curing have excellent transparency. Guo Jianwei et al (CN 112979949A) discloses a transparent photosensitive polyimide resin and a method for producing the same. The transparent photosensitive PSPI resin is prepared by carrying out polycondensation reaction on an aromatic diamine monomer (BAFP) modified by fluorine atoms and 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, a reactive diluent and an organic solvent. The polyimide layer film obtained through photosensitive and high-temperature curing has light transmittance of more than or equal to 80% at the ultraviolet wavelength of 420nm, the temperature of 10% of thermal weight loss of the film is 360-390 ℃, and good photosensitive performance is achieved. However, the thermal stability is to be improved, and a photolithographic pattern cannot be prepared. Rong Minzhi et al (CN 110804181A) discloses a transparent photosensitive polyimide resin and a method for producing the same. Diamine monomer with strong electronegative group structure and alicyclic structure and aromatic dianhydride monomer are formed into polyamide acid resin through polycondensation reaction in solvent solution, after imidization, the side chain of the resin is grafted with photosensitive group containing spiropyran to obtain modified transparent photosensitive polyimide resin, which can change color under the irradiation of ultraviolet ray and has the characteristic of visual observation of photo-mo