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KR-102964634-B1 - Active ester for curable agent of epoxy type resin having high heat-resistance and low dielectric constant and Manufacturing method thereof

KR102964634B1KR 102964634 B1KR102964634 B1KR 102964634B1KR-102964634-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
20231127

Claims (13)

  1. A high heat-resistant and low dielectric reactive active ester for epoxy resin curing agents 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, R1 is a straight-chain C1 - C5 alkyl group or a branched-chain C3 - C5 alkyl group, R2 to R5 are each independently a hydrogen atom or a straight-chain C1 - C3 alkyl group, R6 and R7 are each independently a hydrogen atom or a methyl group, R8 to R11 are each independently a hydrogen atom or a methyl group, n is 2 to 20, m is 2 to 20, and * indicates a bonding site.
  2. A high heat-resistant and low dielectric reactive active ester for an epoxy resin curing agent according to claim 1, wherein 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 methyl groups, R8 to R11 are each independently a hydrogen atom or a methyl group, n is 4 to 15, and m is 4 to 15.
  3. A high heat-resistant and low dielectric reactive active ester for epoxy resin curing agents according to claim 1, characterized by a softening point of 160 to 200°C, a weight-average molecular weight of 5,000 to 20,000, and an ester equivalent of 800 to 950 g/eq.
  4. Step 1: 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 2, adding a reaction catalyst to the heated solution, raising the temperature to the reflux temperature, and performing a first-order reflux reaction; Step 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 was performed, and then a second reflux reaction is performed; Step 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 5, heating the reflux reaction solution from which the aqueous layer has been removed to 200 to 230°C to remove the solvent and obtaining a reactive active ester containing a compound represented by the following chemical formula 1; A method for manufacturing a high-heat-resistant and low-dielectric reactive active ester for an epoxy resin curing agent, characterized by performing a process including: [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 independently a hydrogen atom or a methyl group, each of R8 to R11 is independently a hydrogen atom or a methyl group, n is 2 to 20, and m is 2 to 20, and [Chemical Formula 3] In Chemical Formula 3, R1 is a C1 – C5 straight-chain alkyl group or a C3 – C5 branched-chain alkyl group, and [Chemical Formula 1] X in Chemical Formula 1 is is, and Y is And, R1 is a straight-chain C1 - C5 alkyl group or a branched-chain C3 - C5 alkyl group, R2 to R5 are each independently a hydrogen atom or a straight-chain C1 - C3 alkyl group, R6 and R7 are each independently a hydrogen atom or a methyl group, R8 to R11 are each independently a hydrogen atom or a methyl group, n is 2 to 20, m is 2 to 20, and * indicates a bonding site.
  5. In paragraph 4, the above-mentioned mixed solution of step 1 is, A method for preparing a high heat-resistant and low dielectric reactive active ester for an epoxy resin curing agent, 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.
  6. A method for producing a high heat-resistant and low dielectric reactive active ester for an epoxy resin curing agent, characterized in that, in claim 4, the reflux reaction temperature of the 2nd stage primary reflux reaction and the 3rd stage secondary reflux reaction is 80 to 150℃.
  7. A method for producing a high heat-resistant and low dielectric reactive active ester for an epoxy resin curing agent, characterized in that, in claim 4, the reaction catalyst comprises one or more selected from dimethylaminopyridine, pyrrolidinylpyridine, 2-halopyridine salts, triethylamine, and diethylamine.
  8. In paragraph 4, the above primary reflux reaction and secondary reflux reaction are A method for producing a high heat-resistant and low dielectric reactive active ester for an epoxy resin curing agent, characterized by raising the temperature to a reflux reaction temperature and then removing the condensed water generated during the reaction using an oil-water separator.
  9. A method for manufacturing a high heat-resistant and low dielectric reactive active ester for an epoxy resin curing agent, characterized in that, in claim 4, the anhydride represented by Chemical Formula 3 of the third step is added in an amount of 15.0 to 30.0 parts by weight per 100 parts by weight of the polyphenylene oxide of the first step.
  10. In claim 4, the yield of the obtained active ester according to Formula 1 below is 50.0 to 80.0%, and A method for preparing a high-heat-resistant and low-dielectric reactive active ester for epoxy-based curable resins, characterized by having a purity of 70.0 to 99.0% when unreacted substances are measured using HPLC (High Performance Liquid Chromatography); [Equation 1] Yield (%) = (Reaction product yield / Reactant input amount) × 100%
  11. A prepreg characterized by 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 3; and an accelerator.
  12. delete
  13. In claim 11, the glass transition temperature (Tg) is 195°C to 225°C when measured using a dynamic mechanical analyzer (DMA), and A prepreg characterized by the dielectric constant (D k ) being 3.50 or less and the dielectric loss (D f ) being 0.015 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 for curable agent of epoxy-type resin having high heat-resistance and low dielectric constant 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. Specifically, the invention relates to an active ester as a curing agent compound that possesses a vinyl group structure within the active ester, thereby enabling it to simultaneously perform the roles of a radical curing agent and an epoxy curing agent, 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 rise 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 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 independently a hydrogen atom or a methyl group, and each of R8 to R11 is independently a hydrogen atom or a methyl group, preferably a hydrogen atom. Also, n is 2 to 20, preferably 4 to 15, and m is 2 to 20, preferably 4 to 15. The active ester represented by the above chemical formula 1 may have a softening point of 160 to 200°C, a weight-average molecular weight of 5,000 to 20,000, an