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KR-102964639-B1 - Active ester with high heat-resistance and low dielectric constant containing bismaleimide structure and Manufacturing method thereof

KR102964639B1KR 102964639 B1KR102964639 B1KR 102964639B1KR-102964639-B1

Abstract

The present invention relates to a curing agent and a method for manufacturing the same. More specifically, it relates to a reactive active ester compound used as a curing agent for an epoxy-based curable resin having low dielectric constant, low dielectric loss, excellent bonding strength, and thermal properties, which is used together with an epoxy resin applied to copper clad laminates (CCL), printed circuit boards (PCB), sealants for electronic components, adhesives, etc., and an invention for manufacturing the same.

Inventors

  • 최형욱
  • 유상운
  • 이종두
  • 이난영
  • 김인아

Assignees

  • 주식회사 나노코

Dates

Publication Date
20260513
Application Date
20231208

Claims (16)

  1. A low-dielectric reactive active ester comprising a bismaleimide structure characterized by comprising a compound represented by the following chemical formula 1; [Chemical Formula 1] X in Chemical Formula 1 is is, and Y is and A is or is, and Z is a phenylene group or And, R1 is a C1 - C5 straight-chain alkyl group or a C3 - C5 branched-chain alkyl group, R2 to R5 are each independently a hydrogen atom or a C1 - C3 straight-chain alkyl group, R6 and R7 are each a hydrogen atom or a methyl group, R8 to R11 are hydrogen atom or a methyl group, R12 is a carbon atom, an unsubstituted aromatic hydrocarbon (aromatic ring) or an aromatic hydrocarbon substituted with an alkyl group, R13 and R14 are independently a hydrogen atom or a methyl group, R15 to R18 are independently a hydrogen atom, a methyl group or an ethyl group, n is 2 to 20, m is 2 to 20, a is 0 to 3, and * indicates a bonding site.
  2. In paragraph 1, A is and Z is A low-dielectric reactive active ester comprising a bismaleimide structure, characterized in that R1 is a straight-chain C1 to C5 alkyl group, R2 to R5 are each independently a hydrogen atom or a methyl group, R6 and R7 are each a hydrogen atom or a methyl group, R12 is a carbon atom, an unsubstituted aromatic hydrocarbon (aromatic ring) or an aromatic hydrocarbon substituted with an alkyl group, R13 and R14 are independently a hydrogen atom or a methyl group, R15 to R18 are a hydrogen atom, a methyl group, or an ethyl group, n is 2 to 20, and m is 2 to 20.
  3. A low dielectric reactive active ester comprising a bismaleimide structure, characterized in that, in claim 2, it has a softening point of 180 to 230°C, a weight-average molecular weight of 8,000 to 26,000, and an ester equivalent of 900 to 980 g/eq.
  4. In paragraph 1, A is A low-dielectric reactive active ester comprising a bismaleimide structure, characterized in that R1 is a C1 - C5 straight-chain alkyl group, R2 to R5 are each independently a hydrogen atom or a methyl group, R6 and R7 are each a hydrogen atom or a methyl group, R12 is an unsubstituted aromatic hydrocarbon or an aromatic hydrocarbon substituted with an alkyl group, R13 and R14 are independently a hydrogen atom or a methyl group, R15 to R18 are independently a hydrogen atom, a methyl group, or an ethyl group, n is 2 to 20, m is 2 to 20, and a is 0 to 3.
  5. A low dielectric reactive active ester comprising a bismaleimide structure, characterized in that, in claim 4, it has a softening point of 170 to 220°C, a weight-average molecular weight of 10,000 to 30,000, and an ester equivalent of 930 to 1,000 g/eq.
  6. Step 1: A mixed solution of an ester resin, a compound represented by the following chemical formula 5 or a compound represented by the following chemical formula 6, and a solvent is heated while stirring; Step 2, adding a reaction catalyst to the heated solution and performing the heating and main reaction; Step 3, after the main reaction is completed, cooling, adding distilled water to the cooled reaction solution, stirring, and then settling to remove the water layer; and A process comprising the fourth step of raising the reaction solution from which the water layer has been removed to 150°C using an oil-water separator to remove residual moisture, thereby obtaining a solution containing a compound represented by the following chemical formula 1; A method for preparing a low dielectric reactive active ester comprising a bismaleimide structure, characterized in that the above ester resin comprises an ester compound represented by the following chemical formula 4 and a solvent; [Chemical Formula 4] In Chemical Formula 4, X is is, and Y is and, R1 is a C1 – C5 straight-chain alkyl group or a C3 – C5 branched-chain alkyl group, R2 to R5 are each independently a hydrogen atom or a C1 – C3 straight-chain alkyl group, R6 and R7 are each a hydrogen atom or a methyl group, R8 to R11 are hydrogen atoms or methyl groups, n is 2–20, m is 2–20, and * indicates a bonding site, [Chemical Formula 1] R1 , X, and Y of Chemical Formula 1 are identical to those of Chemical Formula 4, and R2 to R5 of X and R6 and R7 of Y are of Chemical Formula 4. It is identical to R 2 to R 7 , and A is or is, and Z is a phenylene group or R12 is a carbon atom, an unsubstituted aromatic hydrocarbon (aromatic ring) or an aromatic hydrocarbon substituted with an alkyl group, R13 and R14 are independently a hydrogen atom or a methyl group, R15 to R18 are a hydrogen atom, a methyl group, or an ethyl group, and are independently a hydrogen atom, a methyl group, or an ethyl group, n and m are the same as in Formula 4, a is 0 to 3, and * indicates a bonding site. [Chemical Formula 5] In Chemical Formula 5, Z is a phenylene group or and, R12 is a carbon atom, an unsubstituted aromatic hydrocarbon (aromatic ring) or an aromatic hydrocarbon substituted with an alkyl group, R13 and R14 are independently a hydrogen atom or a methyl group, and R15 to R18 are independently a hydrogen atom, a methyl group or an ethyl group, and [Chemical Formula 6] In chemical formula 6, a is 0 to 3.
  7. A method for preparing a low dielectric reactive ester comprising a bismaleimide structure, wherein, in claim 6, the first step is characterized by mixing 18.0 to 40.0 parts by weight of a compound represented by the following chemical formula 5 or a compound represented by the following chemical formula 6 with respect to 100 parts by weight of the ester resin.
  8. A method for producing a low dielectric reactive active ester comprising a bismaleimide structure, characterized in that, in claim 6, the main reaction temperature of the second step is 90 to 120℃.
  9. In claim 6, the ester compound represented by the above chemical formula 4 is, Step 1-1: In which a mixed solution of polyphenylene oxide and maleic anhydride represented by the following chemical formula 2 mixed in a solvent is heated while stirring; Step 1-2, which involves adding a reaction catalyst to a heated solution, raising the temperature to the reflux temperature, and performing a first-order reflux reaction; Step 1-3, in which an anhydride represented by the following chemical formula 3 and a reaction catalyst are added dropwise to the reflux reaction solution in which the first reflux reaction has been performed, and then a second reflux reaction is performed; Steps 1-4, after the reflux reaction is completed, cooling, adding distilled water to the reflux reaction solution, stirring, and then settling to remove the aqueous layer; and Step 1-5 of raising the temperature of the reflux reaction solution from which the aqueous layer has been removed to 200 to 230°C to remove the solvent and obtaining an ester represented by Chemical Formula 4; A method for producing a low dielectric reactive active ester comprising a bismaleimide structure, characterized by being produced by performing a process including the above steps; [Chemical Formula 2] In Chemical Formula 2, Y is and, each of R2 to R5 is independently a hydrogen atom or a C1 to C3 straight-chain alkyl group, each of R6 and R7 is a hydrogen atom or a methyl group, R8 to R11 is a hydrogen atom or a methyl group, n is 2 to 20, m is 2 to 20, and , [Chemical Formula 3] In Chemical Formula 3, R1 is a straight-chain C1 – C5 alkyl group or a branched-chain C3 – C5 alkyl group.
  10. In claim 9, the above-mentioned mixed solution of step 1-1 is, A method for preparing a low dielectric reactive active ester comprising a bismaleimide structure, characterized by comprising 4.0 to 15.0 parts by weight of the maleic anhydride and 100 to 150 parts by weight of the solvent, based on 100 parts by weight of the polyphenylene oxide.
  11. A method for preparing a low dielectric reactive active ester containing a bismaleimide structure, characterized in that, in claim 9, the reflux reaction temperature of the first reflux reaction in step 1-2 and the second reflux reaction in step 1-3 is 80 to 150℃.
  12. A method for producing a low dielectric reactive active ester comprising a bismaleimide structure, characterized in that, in claim 6 or 9, the reaction catalyst comprises one or more selected from 4-dimethylaminopyridine, pyrrolidinylpyridine, 2-halopyridine salt, triethylamine, and diethylamine.
  13. A method for producing a low dielectric reactive ester containing a bismaleimide structure, characterized in that, in claim 9, the anhydride represented by Chemical Formula 3 of steps 1-3 is added in an amount of 15.0 to 30.0 parts by weight per 100 parts by weight of the polyphenylene oxide of step 1.
  14. In paragraph 6, the yield of the obtained active ester is 80% or more and the purity is 70 to 99%, The above yield was measured based on the following Equation 1, and A method for preparing a low-dielectric reactive active ester containing a bismaleimide structure, characterized in that the purity is measured using HPLC (High Performance Liquid Chromatography). [Equation 1] Yield (%) = (Reaction product yield / Reactant input amount) × 100%
  15. A prepreg comprising a cured product of a varnish comprising: an epoxy resin; a curing agent comprising an active ester selected from any one of claims 1 to 5; and an accelerator.
  16. In paragraph 15, the glass transition temperature (Tg) is 205°C to 230°C when measured using a dynamic mechanical analyzer (DMA), and A prepreg characterized by the dielectric constant (D k ) being 3.30 or less and the dielectric loss (D f ) being 0.010 or less when measuring the dielectric constant and dielectric loss of the cured product having a thickness of 0.8 to 1.0 mm using an impedance analyzer (Agilent E4991B ) at a measurement frequency of 1 GHz and a measurement temperature of 25℃ to 27℃.

Description

Active ester with high heat resistance and low dielectric constant containing bismaleimide structure and Manufacturing method thereof The present invention relates to a novel reactive ester structure used in conjunction with an epoxy resin applied to copper clad laminates (CCL), printed circuit boards (PCB), sealants for electronic components, adhesives, etc., and a method for manufacturing the same. The invention relates to an active ester as a curing agent compound capable of simultaneously performing the roles of a radical curing agent and an epoxy curing agent by possessing a highly reactive double bond within the substituent of the active ester, while also enhancing heat resistance and low dielectric properties, and a method for manufacturing the same. As the amount of information in electronic devices using printed circuit boards becomes vast, the size of components becomes smaller, and as speed and density increase, circuit line widths shrink and more components are mounted per unit area, generating significant heat when transmitting high-speed signals. This heat causes problems such as deformation of the board due to differences in CTE between component materials. Furthermore, as the use of Pb is completely banned due to environmental regulations such as RoHS, soldering temperatures have risen by 20 to 40°C, requiring materials to have characteristics such as lead-free properties and high heat resistance with a high glass transition temperature ( Tg ). In addition, in the high-frequency range of 10–28 GHz used in mobile devices, stations, routers, and data servers for 5G communication, significantly more heat is generated, requiring high heat resistance performance. Furthermore, low dielectric constant and dielectric loss are required to prevent loss of transmitted information. The materials primarily used for printed circuit boards utilize epoxy resin and novolak-type curing agents. Generally, the heat resistance of epoxy resin can be improved by increasing the crosslinking density between the resin and the curing agent; however, when novolak-based curing agents are used, there is a limit to the improvement in the heat resistance performance of the cured material itself. Furthermore, due to the material's high hygroscopicity and the formation of alcohol structures after curing, there are problems with deteriorating electrical properties such as dielectric constant and dielectric loss. In addition, styrene-maleic anhydride (SMA) resin exhibits characteristics of low dielectric constant and dielectric loss, but has poor heat resistance and thus has a problem with a high coefficient of thermal expansion. Recently used high-frequency printed circuit boards have significantly improved dielectric performance by utilizing resins in which vinyl group structures are introduced at the ends of polyphenylene ether resins; however, their high unit cost makes them economically disadvantageous, and their poor heat resistance has limited their application as high-frequency printed circuit boards. To improve this, we attempted to improve heat resistance and adhesive performance by using bismaleimide, which possesses excellent heat resistance, but since mixing with polyphenylene ether did not occur, it is difficult to manufacture prepreg and CCL using both materials simultaneously. Therefore, there is an urgent need to develop cured materials with new chemical structures that improve both heat resistance and electrical performance, while also being economically superior. The present invention will be described in more detail below. The present invention aims to provide a curing agent capable of satisfying low dielectric properties while improving the heat resistance of such existing epoxy-based curable resins, and relates to a new reactive active ester (ester compound) capable of performing radical polymerization and epoxy polymerization in parallel by possessing a vinyl group capable of satisfying these properties of the present invention. The reactive active ester of the present invention comprises a compound represented by the following chemical formula 1. [Chemical Formula 1] X in Chemical Formula 1 is is, and Y is am. A of Chemical Formula 1 is or is, and Z is a phenylene group or am. And, R1 of Chemical Formula 1 is a C1 - C5 straight-chain alkyl group or a C3 - C5 branched-chain alkyl group, preferably a C1 - C5 straight-chain alkyl group, and more preferably a C1 - C3 straight-chain alkyl group. In addition, each of R2 to R5 in Formula 1 is independently a hydrogen atom or a C1 to C3 straight-chain alkyl group, preferably a hydrogen atom or a methyl group. Also, each of R6 and R7 in Formula 1 is a hydrogen atom or a methyl group, and each of R8 to R11 is independently a hydrogen atom or a methyl group. In addition, the R 12 of A is a carbon atom, an unsubstituted aromatic hydrocarbon, an aromatic hydrocarbon substituted with an alkyl group, or an aralkyl aromatic hydrocarbon, preferably an unsubstituted arom