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CN-122010815-A - Fluorine-containing bismaleimide alkali-soluble resin, preparation method thereof, photoresist and application

CN122010815ACN 122010815 ACN122010815 ACN 122010815ACN-122010815-A

Abstract

The invention belongs to the technical field of bismaleimide resin modification, and particularly relates to fluorine-containing bismaleimide alkali-soluble resin, a preparation method thereof, photoresist and application thereof. The invention provides a low dielectric fluorine-containing bismaleimide monomer generated by imidization reaction of maleic anhydride and fluorine-containing ether bond diamine, and also provides fluorine-containing bismaleimide alkali-soluble resin which is obtained by blending reaction of fluorine-containing bismaleimide monomer, cyanate, polyphenyl ether, polar solvent and photoinitiator in parts by weight. The fluorine-containing bismaleimide alkali-soluble resin is suitable for low dielectric medium layers or photoresist functional components in OLED capacitive touch devices, and solves the problems of insufficient dielectric property, unstable comprehensive performance and poor process compatibility with devices of the existing materials.

Inventors

  • GAO TONG
  • LEI TING
  • GUO QIANQIAN
  • MENG JINGRU

Assignees

  • 西安思摩威新材料有限公司

Dates

Publication Date
20260512
Application Date
20251231

Claims (10)

  1. 1. The low-dielectric fluorine-containing bismaleimide monomer is characterized in that the fluorine-containing bismaleimide monomer is formed by imidizing maleic anhydride and fluorine-containing ether bond diamine, and the structural general formula of the fluorine-containing bismaleimide monomer is shown as the following formula (1): (1) Wherein R 1 、R 2 is the same or different and is selected from one or more of H, C 1～6 alkyl and fluorine substituted C 1～6 alkyl, R 3 、R 4 is the same or different and is selected from perfluoro substituted C 1～6 alkyl or phenyl.
  2. 2. The low dielectric fluorine-containing bismaleimide monomer of claim 1 wherein the molar ratio of maleic anhydride to fluoroether linkage-containing diamine is 2:1; The structural general formula of the maleic anhydride is shown as the following formula (2): (2) Wherein R 1 、R 2 is the same or different and is independently selected from one or more of H, C 1～6 alkyl and fluorine substituted C 1～6 alkyl; the structural general formula of the fluorine-containing ether bond diamine is shown as the following formula (3): (3) Wherein R 3 、R 4 , which are the same or different, are each independently selected from perfluoro substituted C 1～6 alkyl or phenyl.
  3. 3. The low dielectric fluorine-containing bismaleimide monomer of claim 2 wherein the maleic anhydride comprises the structure: (2-1) (2-2) (2-3) (2-4) (2-5) (2-6) (2-7) (2-8) (2-9) Formula (2-10).
  4. 4. The low dielectric fluorine-containing bismaleimide monomer according to claim 2 wherein the fluorine-containing ether linkage diamine comprises the following structure: (3-1) (3-2) Formula (3-3).
  5. 5. The low-dielectric fluorine-containing bismaleimide alkali-soluble resin is characterized in that the low-dielectric fluorine-containing bismaleimide alkali-soluble resin is obtained by a blending reaction of the following components based on the low-dielectric fluorine-containing bismaleimide monomer according to any one of claims 1 to 4, and the low-dielectric fluorine-containing bismaleimide alkali-soluble resin comprises the following components in parts by weight based on 100 parts by weight of the total weight of the components: 10-25 parts of fluorine-containing bismaleimide monomer, 5-20 parts of cyanate ester, 5-15 parts of polyphenyl ether, 45-65 parts of polar solvent and 0.1-2 parts of initiator.
  6. 6. The low dielectric fluorine-containing bismaleimide alkali soluble resin according to claim 5 wherein said cyanate ester comprises any of bisphenol a cyanate, bisphenol E cyanate, phenolic cyanate; The polar solvent comprises any one of propylene glycol methyl ether acetate, N-methyl pyrrolidone, N-dimethylformamide and dimethyl sulfoxide; the initiator comprises any one of azodiisobutyronitrile, azodiisoheptonitrile and dicumyl peroxide.
  7. 7. A method for preparing a low dielectric fluorine-containing bismaleimide alkali-soluble resin, characterized in that it is used for preparing the fluorine-containing bismaleimide alkali-soluble resin according to claim 5 or 6, comprising the steps of: Step 1, adding maleic anhydride, diamine containing fluoroether bond and polar solvent into a reaction container, stirring at room temperature under the protection of inert gas for reaction, then heating to a set temperature, and reacting at constant temperature to obtain a solution of fluorine-containing bismaleimide monomer; step 2, when the solution obtained in the step 1 is at a set temperature, adding cyanate into the solution, and stirring until the cyanate is completely dissolved to obtain a transparent solution; and 3, when the transparent solution obtained in the step 2 is at a set temperature, adding polyphenyl ether and an initiator into the transparent solution, and reacting to obtain the low-dielectric fluorine-containing bismaleimide alkali-soluble resin.
  8. 8. The preparation method of the fluorine-containing bismaleimide alkali-soluble resin according to claim 7 is characterized in that in the step 1, stirring reaction is carried out for 2-4 hours at room temperature, heating is carried out to 80-150 ℃, and constant-temperature reaction is carried out for 2-3 hours; In the step 2, the set temperature of the solution is 80-110 ℃; in the step 3, the temperature of the transparent solution is set to be 120-140 ℃ and the reaction is carried out for 0.5-3 hours.
  9. 9. The low dielectric photoresist is characterized by comprising, by weight, 8-15 parts of a fluorine-containing bismaleimide alkali-soluble resin, 4-8 parts of a reactive diluent, 3-6 parts of an alkali-soluble acrylate monomer, 1.5-3 parts of a photoinitiator and 25-75 parts of a solvent, wherein the fluorine-containing bismaleimide alkali-soluble resin is the fluorine-containing bismaleimide alkali-soluble resin according to claim 5 or 6 or the fluorine-containing bismaleimide alkali-soluble resin prepared by the preparation method according to claim 7 or 8.
  10. 10. Use of a low dielectric fluorine-containing bismaleimide alkali soluble resin characterized in that the fluorine-containing bismaleimide alkali soluble resin according to claim 5 or 6 or the fluorine-containing bismaleimide alkali soluble resin prepared by the preparation method according to claim 7 or 8 is used for preparing an OLED capacitance touch device.

Description

Fluorine-containing bismaleimide alkali-soluble resin, preparation method thereof, photoresist and application Technical Field The invention belongs to the technical field of bismaleimide resin modification, and particularly relates to fluorine-containing bismaleimide alkali-soluble resin, a preparation method thereof, photoresist and application thereof. Background An Organic Light-emitting diode (EmittingDiode, OLED) is a device for generating electroluminescence by utilizing a multi-layer Organic film structure, has the advantages of easy preparation, low driving voltage, high brightness, low power consumption, quick response, high definition, quick luminous efficiency, wide viewing angle, light weight, thinness, flexibility and the like, and meets the new requirements of consumers on display technology. In the construction of OLED devices, capacitive touch devices have stringent requirements on the dielectric constant of the material. The larger the display screen area is, the lower dielectric constant is required for the touch device material, so that the touch performance of the device is improved. At present, silicon nitride is often used as a medium in a touch device, but the higher dielectric constant of the silicon nitride reduces the touch sensitivity in use, and the larger the area of a display screen is, the more remarkable the influence is. Accordingly, the industry is seeking to use low dielectric constant transparent photoresist materials in place of silicon nitride. Bismaleimide resins are attracting attention in applications replacing silicon nitride materials due to their excellent properties such as wet heat resistance, mechanical properties, chemical resistance, and excellent dielectric properties. However, the dielectric properties of the bismaleimide resin cannot meet the requirements of the current technical development, and the conventional bismaleimide resin does not contain carboxyl groups, has no alkali solubility and cannot be used as a photoresist resin, so that the bismaleimide resin needs to be modified to further reduce the dielectric constant and improve the alkali solubility. Regarding the dielectric constant, the modification methods commonly used at present are (1) blending modification with resins with excellent dielectric properties such as polytetrafluoroethylene, polyphenylene oxide, cyanate ester and the like, and (2) introducing a nanovoid structure. However, the optimization of the dielectric performance by the modification method still cannot meet the touch sensitivity of the display screen, and the modification method also causes unstable performance, poor compatibility with the device process, increased moisture absorption risk and damage to long-term reliability. In view of this, the present invention has been made. Disclosure of Invention The invention aims to overcome the defects of the prior art, and provides fluorine-containing bismaleimide alkali-soluble resin with low dielectric constant and excellent comprehensive performance, a preparation method, photoresist and application thereof, the fluorine-containing bismaleimide alkali-soluble resin is suitable for low dielectric medium layers or photoresist functional components in OLED capacitive touch devices, and solves the problems of insufficient dielectric property, unstable comprehensive performance and poor process compatibility with devices of the existing materials. In order to achieve the above purpose, the present invention adopts the following technical scheme: In a first aspect, the invention provides a low dielectric fluorine-containing bismaleimide monomer, which is formed by imidization reaction of maleic anhydride and fluorine-containing ether bond diamine, and has a structural general formula shown in the following formula (1): (1) Wherein R 1、R2 is the same or different and is selected from one or more of H, C 1～6 alkyl and fluorine substituted C 1～6 alkyl, R 3、R4 is the same or different and is selected from perfluoro substituted C 1～6 alkyl or phenyl. Further, the molar ratio of the maleic anhydride to the diamine containing fluorine ether bond is 2:1; The structural general formula of the maleic anhydride is shown as the following formula (2): (2) Wherein R 1、R2 is the same or different and is independently selected from one or more of H, C 1～6 alkyl and fluorine substituted C 1～6 alkyl; the structural general formula of the fluorine-containing ether bond diamine is shown as the following formula (3): (3) Wherein R 3、R4, which are the same or different, are each independently selected from perfluoro substituted C 1～6 alkyl or phenyl. Preferably, R 3、R4 is selected from perfluoroethyl groups which are better than perfluoromethyl groups, and when the perfluoroethyl groups are selected, the dielectric constant of the resin is reduced by 0.1-0.2 compared with the perfluoromethyl groups. Further, the maleic anhydride comprises the following structure: (2-1) (2-2)(2-3)(2-4)(2-5)(2-6)(2-7)(2-8)