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JP-2026514529-A - Polyimide oligomer, method for preparing the same, and cured product having low dielectric properties prepared thereby

JP2026514529AJP 2026514529 AJP2026514529 AJP 2026514529AJP-2026514529-A

Abstract

The present invention provides a polyimide oligomer, a method for preparing the same, and a cured product having low dielectric properties prepared thereby. The polyimide oligomer of the present invention has the structure shown in formula (I) or formula (II), where the symbols in formulas (I) and (II) are as defined in the specification. By combining a dimeric diamine with a specific monomer and adjusting the ratio, a radical-curable polyimide oligomer can be obtained, and the cured material has good thermal properties and excellent low dielectric properties, making it suitable for industrial applications in high-frequency circuit boards. [Chemical formula 1]

Inventors

  • ワン，メン‐ウェイ
  • ファン，ユン‐ウェン
  • カオ，ジュン‐チー
  • ライ，ペイ‐チェン

Assignees

  • 上緯創新育成股▲ふん▼有限公司

Dates

Publication Date
20260511
Application Date
20230510

Claims (15)

  1. A polyimide oligomer having the structure shown in formula (I) or formula (II), However, X is independently either a hydrogen atom or a methyl group, and R1 is a cycloalkane having a total of 5 to 20 carbon atoms and a structure with 5 or more carbon atoms, as shown in formula (A), formula (B), or formula (C). Each R2 is independently a saturated or unsaturated hydrocarbon group having 36 carbon atoms, and each A is independently a benzene ring, biphenyl, naphthalene ring, cycloalkanes having 4 to 6 carbon atoms, or a structure represented by formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), formula (g), formula (h), or formula (i). A polyimide oligomer characterized in that n is any number between 0 and 10, and m/p is any number between 0.5 and 5.
  2. The cycloalkanes having five or more carbon atoms are defined by formula (D), formula (E), or formula (F). The polyimide oligomer according to claim 1, characterized by comprising the structure shown in (1).
  3. R2 is formula (G), formula (H), formula (I), or formula (J) The polyimide oligomer according to claim 1, characterized by having the structure shown in (1).
  4. Equation (I-1) or Equation (II-1) The polyimide oligomer according to claim 1, characterized by having the structure shown in (1).
  5. A method for preparing a polyimide oligomer according to claim 1, The first dissolution step involves dissolving a diacid anhydride and a monoacid anhydride having an unsaturated double bond in a first solvent to form an acid anhydride solution. The second dissolution step involves mixing a dimeric diamine with a bifunctional aliphatic amine having a rigid cyclic structure and dissolving it in a second solvent to form a diamine solution. The mixing step involves adding the diamine solution to the acid anhydride solution and reacting it at the polymerization temperature to form a mixed solution. The addition step involves adding xylene to the mixed solution and carrying out the reaction and distillation at the reaction distillation temperature to obtain the polyimide oligomer. A method for preparing a polyimide oligomer, characterized by containing [a specific substance].
  6. The method for preparing a polyimide oligomer according to claim 5, characterized in that the first solvent and the second solvent are selected from the group consisting of N,N-dimethylacetamide, N-methylpyrrolidone, dimethylformamide, anisole, dimethyl sulfoxide, cyclohexanone, and resorcinol.
  7. The method for preparing a polyimide oligomer according to claim 5, characterized in that the polymerization temperature is 0°C to 90°C.
  8. The method for preparing a polyimide oligomer according to claim 5, characterized in that the reaction distillation temperature is 130°C to 170°C.
  9. The method for preparing a polyimide oligomer according to claim 5, characterized in that the molar ratio of the dimeric diamine to the bifunctional aliphatic amine is 1:0.4 to 1:3.
  10. The method for preparing a polyimide oligomer according to claim 5, characterized in that the molar ratio of the diamine obtained by adding the bifunctional aliphatic amine to the dimeric diamine to the diacid anhydride is 1.2:1 to 1.8:1.
  11. A cured product having low dielectric properties, characterized by being obtained by adding a radical initiator to a polyimide oligomer according to any one of claims 1 to 4 and firing it at a curing temperature.
  12. The cured product having low dielectric properties according to claim 11, characterized in that the radical initiator is a peroxide, an azo initiator, or a mixture thereof.
  13. The cured product having low dielectric properties according to claim 11, characterized in that the amount of radical initiator added is 0.3% to 2% by weight of the polyimide oligomer content.
  14. The cured product having low dielectric properties according to claim 11, characterized in that the curing temperature is 160°C to 240°C.
  15. The cured product having low dielectric properties according to claim 14, characterized in that the curing temperature is 180°C, 200°C, or 220°C.

Description

This invention relates to oligomers, methods for preparing the same, and cured products thereof, and more particularly to polyimide oligomers derived from dimeric diamines, methods for preparing the same, and cured products having low dielectric properties prepared thereby. Currently, with the rise of cloud technologies such as the internet and data centers, radical curing systems are attracting significant attention in the application of printed circuit board materials. Noryl SA9000, sold by SABIC, is a polyphenylene ether oligomer with difunctional acrylic groups at its ends. Its low molecular weight gives it good organic solubility and excellent workability in the impregnation process. Therefore, Noryl SA9000 acquires its basic properties through radical curing of the terminal acrylic groups. Furthermore, due to the non-polar structure of the polyphenylene ether itself, and the absence of polar matrix formation after radical curing, the cured material exhibits superior electrical properties. As a result, Noryl SA9000 is becoming one of the mainstream materials for high-grade printed circuit boards. However, the preparation process of Noryl SA9000 is difficult to purify and generates a large amount of wastewater. From an environmental protection perspective, developing a usable material with good electrical properties and minimal process pollution would contribute to both the advancement of printed circuit board materials and environmental protection. In recent years, with increasing awareness of environmental protection and carbon reduction, many studies have focused on applied research involving special bio-based diamines. For example, dimeric diamines are mixed with the aromatic diamine monomer m-tolidine and polymerized with 4,4'-bisphenol A dihydroanhydride (BPADA) to obtain high-molecular-weight polyimide (PI), or dimeric diamines and dihydroanhydrides are reacted to prepare polyimide oligomers or polymers with reactive functional groups at their ends. The dimeric diamine itself has a large, branched diamine structure and a large free volume, so its introduction into materials is expected to result in low dielectric properties. As a result, the measured electrical properties of the above-mentioned polyimide materials are excellent, but there is still considerable room for improvement in heat resistance. To make the above and other objectives, features, advantages, and embodiments of the present invention clearer and easier to understand, the accompanying drawings are described below. This is a process flow diagram showing a method for preparing a polyimide oligomer according to one embodiment of the present invention. The embodiments of the present invention will be described in more detail below. However, these embodiments represent applications of various inventive concepts and can be specifically implemented in various different specific scopes. Specific embodiments are provided for illustrative purposes only and are not limited to the scope of disclosure. In this invention, the structure of a compound may be represented by a skeletal formula. In this notation, carbon atoms, hydrogen atoms, and carbon-hydrogen bonds may be omitted. However, if functional groups are explicitly depicted in the structural formula, those depicted shall be used as the basis. In this invention, for brevity and fluency, the phrase "the polyimide oligomer has the structure shown in formula (I)" may sometimes be expressed as "the polyimide oligomer shown in formula (I)" or "polyimide oligomer (I)," and the same applies to the representation of other compounds or base groups. In this invention, unless otherwise specified, the grouping of a fundamental element may or may not be substituted. For example, "alkyl group" may or may not be substituted. <Polyimide oligomer> The present invention provides a polyimide oligomer having a structure represented by formula (I) or formula (II), However, X is independently either a hydrogen atom or a methyl group, and R1 is a cycloalkane having a total of 5 to 20 carbon atoms and a structure with 5 or more carbon atoms, as shown in formula (A), formula (B), or formula (C). Each R2 is independently a saturated or unsaturated hydrocarbon group having 36 carbon atoms. Each A is independently a benzene ring, biphenyl, naphthalene ring, cycloalkanes having 4 to 6 carbon atoms, or a structure represented by formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), formula (g), formula (h), or formula (i). However, n is any number between 0 and 10, and m/p is any number between 0.5 and 5. More specifically, cycloalkanes having five or more carbon atoms may include the structures shown in formula (D), formula (E), or formula (F). However, the present invention is not limited to these. Furthermore, R2 may have the structure shown in formula (G), formula (H), formula (I), or formula (J). For example, in a polyimide oligomer represented by formula (I) or formula (II), if X is