High-heat-resistance low-dielectric-loss resin as well as preparation method and application thereof

Abstract

The invention discloses high-heat-resistance low-dielectric-loss resin as well as a preparation method and application thereof, and relates to the technical field of resin materials. The high-heat-resistance and low-dielectric-loss resin is prepared through the curing reaction of the alicyclic epoxy resin and the active ester; the core of the method is that alicyclic epoxy resin is subjected to curing reaction with active ester by utilizing the characteristics of small molecular weight, high crosslinking density and no glyceryl ether structure, so that the defects of large molecular weight, low crosslinking density, low Tg, low cost and the like of resin formed by bisphenol A type epoxy resin, phenolic aldehyde type epoxy resin and the active ester in the prior art are effectively overcome. And electrical defects caused by a glyceryl ether-containing structure of part of resin are overcome. The prepared high-heat-resistance low-dielectric-loss resin has high heat resistance and excellent electrical performance, the manufacturing process is simple and easy to operate, and the high-heat-resistance low-dielectric-loss resin can be applied to the electronic field of copper-clad plates and the like and has wide application prospects.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of resin materials, in particular to a high-heat-resistant low-dielectric-loss resin and a preparation method and application thereof. BACKGROUND

[0002] In the field of resin materials, the existing technology is mostly based on bisphenol A type, phenolic type, dicyclopentadiene type or biphenyl epoxy resin and active ester for curing reaction. However, this curing system has the problems of large molecular weight, low crosslinking density, and low glass transition temperature (Tg) formed, and needs to be combined with different types of resins for crosslinking and curing to meet the Tg requirement.

[0003] The active ester curing agent has the following structure:

[0004]

[0005] X is a biphenyl or aromatic ring compound.

[0006] The commonly used epoxy resin curing agent has the following structure:

[0007]

[0008] The BNE (bisphenol A phenolic epoxy resin) and CNE (o-cresol novolac epoxy resin) have sufficient Tg, and have glycerol ether structure, and have defects in electrical properties.

[0009]

[0010] The DCPD (dicyclopentadiene phenol epoxy resin) has good electrical properties, but the Tg is insufficient, and the PNE (phenolic epoxy resin) also has glycerol ether structure, and has defects in electrical properties and Tg.

[0011] At the same time, the commonly used epoxy resin curing agents, such as BNE and CNE, have glycerol ether structure, resulting in defects in electrical properties; the DCPD has good electrical properties, but the Tg is insufficient; and the PNE also has glycerol ether structure, and has defects in electrical properties and Tg, which limits the application of related resin materials in high requirement fields.

[0012] To solve the above problems, the present application provides a high-heat-resistant low-dielectric-loss resin and a preparation method and application thereof. SUMMARY

[0013] The present application aims to provide a high-heat-resistant low-dielectric-loss resin and a preparation method and application thereof to solve the problems in the prior art.

[0014] To achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0015] A preparation method of a high-heat-resistant low-dielectric-loss resin, comprising the following steps:

[0016] Mixing the alicyclic epoxy resin with the active ester resin, adding the filler and the promoter, stirring, to obtain the high heat resistance low dielectric loss resin.

[0017] Further, the active ester is a DCPD type active ester resin.

[0018] Further, the alicyclic epoxy resin is selected from one of EHPE3150, 2021P, tetramethylcyclotetrasiloxane alicyclic epoxy resin.

[0019] Further, the reaction principle for preparing the tetramethylcyclotetrasiloxane alicyclic epoxy resin is as follows:

[0020]

[0021] The tetramethylcyclotetrasiloxane alicyclic epoxy resin is prepared by the following process:

[0022] In a three-necked flask, 1,3,5,7-tetramethylcyclotetrasiloxane, 3,4-cyclohexyl oxirane-1 chloropropane and sodium hydroxide are added, a thermometer, a serpentine reflux tube and a stirrer are inserted, the stirrer is turned on, the heating bag is heated to 50-60℃, and the reaction is carried out for 6-8h; then the reflux tube is removed and replaced with a distillation tube, a vacuum pump is turned on, and the temperature is raised to 30-35℃; after the water is distilled off, NaCl is filtered out with 2-3μm filter paper, to obtain the tetramethylcyclotetrasiloxane alicyclic epoxy resin.

[0023] Further, the mass ratio of 1,3,5,7-tetramethylcyclotetrasiloxane, 3,4-cyclohexyl oxirane-1 chloropropane and sodium hydroxide is (1.5-2):4:1.

[0024] Further, the filler is selected from silicon dioxide; and the promoter is selected from DMAP.

[0025] Further, the filler can also be modified silicon dioxide, which is prepared by the following process:

[0026] (1) Nanosilica pretreatment

[0027] Gas phase silicon dioxide with a particle size of 50-100nm is placed in a muffle furnace and calcined at 500-600℃ for 1-2h; after cooling to room temperature, vacuum drying at 60-70℃ for 10-12h, adding to a mixture of anhydrous ethanol and concentrated hydrochloric acid, stirring at a rate of 600-800r / min, oil bath heating to 60-70℃ for reflux reaction for 3-4h; after the reaction is completed, centrifugal separation, washing with anhydrous ethanol until neutral, vacuum drying at 60-70℃ for 8-10h, to obtain pretreated silicon dioxide.

[0028] (2) Dopamine modification

[0029] The pretreated silicon dioxide is added into a 2-3 g / L dopamine hydrochloride solution (pH 8.5) at a solid-liquid ratio of 1:(20-25), and stirred at 300-400 r / min at 30-35℃ for 20-24 h. After the reaction is completed, the product is collected by centrifugation, washed with deionized water for 3-5 times, and vacuum dried at 50-60℃ for 8-10 h to obtain dopamine-modified silicon dioxide.

[0030] (3) Fluorine-containing silane grafting

[0031] The dopamine-modified silicon dioxide is added into a four-necked flask under nitrogen protection, toluene is added as a solvent, perfluorooctyltriethoxysilane and dibutyltin dilaurate catalyst are sequentially added, and stirred at a speed of 500-600 r / min. The oil bath is heated to 100-110℃ to reflux for 10-12 h. After the reaction is completed, the temperature is cooled to room temperature, n-hexane is added to precipitate the product, and the product is washed with toluene / n-hexane (volume ratio 1:1) for 3-5 times after filtration. Vacuum drying is performed at 70-80℃ for 10-12 h to obtain fluorine-modified silicon dioxide. The solid-liquid ratio of dopamine-modified silicon dioxide and toluene is 1:(20-25). The mass ratio of dopamine-modified silicon dioxide, perfluorooctyltriethoxysilane and dibutyltin dilaurate catalyst is (20-23):4:1.

[0032] (4) Rare earth ion chelation

[0033] The fluorine-modified silicon dioxide is added into a 0.5-0.8 mol / L cerium nitrate hexahydrate ethanol solution at a solid-liquid ratio of 1:(50-55), and stirred at a speed of 200-300 r / min at 45-50℃ for 4-6 h. After the reaction is completed, the product is separated by centrifugation, washed with ethanol until no nitrate ions are present, and vacuum dried at 70-80℃ for 6-8 h to obtain modified silicon dioxide.

[0034] The application of a high-heat-resistant low-dielectric-loss resin is applied to the preparation of a copper-clad plate.

[0035] Further, the copper-clad plate is prepared by the following process:

[0036] The glass fiber cloth is soaked in the high-heat-resistant low-dielectric-loss resin, and the resin is attached to the glass fiber. The resin content is controlled to be 50%, and the pre-preg is prepared after drying. Then, the copper-clad plate is obtained by stacking the copper foil-pre-preg-copper foil in a layered structure and curing by high-temperature vacuum pressing.

[0037] Further, the glass fiber cloth is E-Glass glass cloth 2116.

[0038] The copper foil is 1 oz HTE copper foil with a thickness of 35 μm.

[0039] Compared with the prior art, the application has the beneficial effects that:

[0040] 1、The high-heat-resistant low-dielectric-loss resin and its preparation method and application described in the application have the advantages that the operation is simple, the cycloaliphatic epoxy resin is directly cured with the active ester resin to form a high-heat-resistant low-dielectric-loss resin by virtue of the characteristics of small molecular weight and high crosslinking density, the cycloaliphatic epoxy resin has excellent electrical properties and good heat resistance due to its unique chemical structure, and the cycloaliphatic epoxy resin has no glycerol ether structure and high crosslinking density, thereby improving the Tg and electrical properties of the high-heat-resistant low-dielectric-loss resin.

[0041] 2、The high-heat-resistant low-dielectric-loss resin and its preparation method and application described in the application have the advantages that the system of the cycloaliphatic epoxy resin has a low CTE (linear expansion coefficient) of 2.3, which is lower than that of the DCPD type, PN type and CNE type systems, thereby reducing the size fluctuation caused by temperature change; at the same time, the PCT (high-voltage accelerated aging test) weathering time is greater than 60h, which is much higher than the 10h of the traditional DCPD system, and the moisture and heat aging resistance is significantly improved, so the application is suitable for electronic devices in a humid and high-temperature environment.

[0042] 3、The high-heat-resistant low-dielectric-loss resin and its preparation method and application described in the application have the advantages that the peeling strength of the copper foil and the prepreg is better than that of the existing DCPD system, the interface is more firmly combined, and the delamination risk is reduced; and the water absorption (ABS) is lower than that of the DCPD system, the moisture resistance is better, and the stability of the material for long-term use is further ensured.

[0043] 4、The high-heat-resistant low-dielectric-loss resin and its preparation method and application described in the application have the advantages that modified silica is used as a filler, the modified silica is subjected to multi-scale modification through a four-step composite process, the pretreatment increases the hydroxyl groups through acid etching to provide a binding site for dopamine coating; the dopamine layer connects the silica and the fluorine-containing silane (covalent bond) and the cerium ion (coordination bond) through the catechol group to realize the "bridge effect"; the fluorine-containing silane introduces a low-polarity fluorine group (to reduce dielectric loss), and the cerium ion improves the heat resistance of the filler by virtue of the high thermal stability of the rare earth element, and finally the modified silica filler can reduce the dielectric loss of the resin system to below 0.002 and improve the glass transition temperature to above 220℃. DETAILED DESCRIPTION

[0044] The technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0045] In the following detailed description:

[0046] The following examples are laboratory scale experiments, which can be scaled up proportionally.

[0047] E-Glass Cloth: Type 2116, basis weight 104 g / m 2 , purchased from South Asia Plastic;

[0048] 1 oz HTE Copper Foil: Thickness 35 pm, purchased from South Asia Plastic;

[0049] DCPD type epoxy resin: Type HP-7200, EEW: 247, purchased from DIC, Japan;

[0050] PN type epoxy resin: Type PN-438A, EEW: 200, purchased from South Asia Plastic;

[0051] CNE type epoxy resin: Type CN-703, EEW: 208, purchased from South Asia Plastic;

[0052] Cycloaliphatic epoxy resin: Type EHPE3150, EEW: 177, purchased from Daicel, Japan;

[0053] Cycloaliphatic epoxy resin: Type CELLOXIDE 2021P, EEW: 130, purchased from Daicel, Japan;

[0054] DCPD type active ester resin: Type HPC-8000, AEW: 230, purchased from DIC, Japan;

[0055] Tetramethylcyclotetrasiloxane cycloaliphatic epoxy resin: self-made;

[0056] Silica filler: Type SS15, D50 3 pm, purchased from Sibelco;

[0057] Promoter: DMAP (4-dimethylaminopyridine), purchased from Sigma-aldrich;

[0058] VNA Vector Network Analyzer: Keysight PNA-X N5245B, purchased from Malaysia;

[0059] SPDR: QWED, purchased from Poland;

[0060] PCT: Hirayama HF260, purchased from Japan;

[0061] TMA: Hitachi TMA-7100, purchased from Japan.

[0062] Example 1: A method for preparing a high heat resistance and low dielectric loss resin and its application, comprising the following steps:

[0063] Put 177 g of alicyclic epoxy resin EHPE3150 into a beaker, add 230 g of DCPD type active ester HPC-8000, start the stirrer and mix for 30 min, then add 134.31 g of silica filler SS15 and 0.407 g of promoter DMAP, stir for 1 h, to obtain a high-heat-resistant low-dielectric-loss resin;

[0064] E-Glass glass cloth 2116 is soaked in the high-heat-resistant low-dielectric-loss resin, so that the resin adheres to the glass fiber, the resin content is controlled to be 50%, and after being taken out, it is dried at 171 ℃ to prepare a prepreg; then, a copper-clad plate is obtained by stacking in a layered structure of "1 oz copper foil-prepreg-1 oz copper foil", and pressing in a high-temperature vacuum press at 200 ℃ and 25 kg / cm 2 under the condition of 2, so that it is cured and formed.

[0065] Embodiment 2: A preparation method and application of a high-heat-resistant low-dielectric-loss resin, comprising the following steps:

[0066] Put 130 g of alicyclic epoxy resin CELLOXIDE 2021P into a beaker, add 230 g of DCPD type active ester HPC-8000, start the stirrer and mix for 30 min, then add 118.8 g of silica filler SS15 and 0.36 g of promoter DMAP, stir for 1 h, to obtain a high-heat-resistant low-dielectric-loss resin;

[0067] E-Glass glass cloth 2116 is soaked in the high-heat-resistant low-dielectric-loss resin, so that the resin adheres to the glass fiber, the resin content is controlled to be 50%, and after being taken out, it is dried at 171 ℃ to prepare a prepreg; then, a copper-clad plate is obtained by stacking in a layered structure of "1 oz copper foil-prepreg-1 oz copper foil", and pressing in a high-temperature vacuum press at 200 ℃ and 25 kg / cm

[0068] Embodiment 3: A preparation method and application of a high-heat-resistant low-dielectric-loss resin, comprising the following steps:

[0069] Put 737 g of alicyclic epoxy resin tetramethylcyclosiloxane alicyclic epoxy resin into a beaker, add 230 g of DCPD type active ester HPC-8000, start the stirrer and mix for 30 min, then add 319.11 g of silica filler SS15 and 0.967 g of promoter DMAP, stir for 1 h, to obtain a high-heat-resistant low-dielectric-loss resin;

[0070] E-Glass glass cloth 2116 is soaked in high-heat-resistant and low-dielectric-loss resin to make the resin adhere to the glass fiber, and the resin content is controlled to be 50%. After being taken out, it is dried at 171°C to prepare a prepreg. Then, it is stacked in a layered structure of "1 oz copper foil-prepreg-1 oz copper foil", and is placed into a high-temperature vacuum press to be compressed at 200°C and 25 kg / cm2, so that it is cured and formed to obtain a copper-clad plate.

[0071] Tetramethylcyclotetrasiloxane alicyclic epoxy resin is prepared by the following process:

[0072] In a 1L three-necked flask, 1 mole (240g) of 1,3,5,7-tetramethylcyclotetrasiloxane, 4 moles (640g) of 3,4-cyclohexyl oxirane-1 chloropropane and 4 moles (160g) of sodium hydroxide are added, a thermometer, a serpentine reflux tube and a stirrer are inserted, the stirrer is started, the heating bag is warmed to 50°C, and the reaction is carried out for 8h. Then the reflux tube is removed and replaced with a distillation tube, a vacuum pump is started, and the temperature is raised to 30°C. Water is distilled off, and then NaCl is filtered off with 3μm filter paper to obtain tetramethylcyclotetrasiloxane alicyclic epoxy resin.

[0073] Example 4: Based on Example 1, the silica filler is adjusted to modified silica, and the difference from Example 1 is only that:

[0074] Modified silica is prepared by the following process:

[0075] (1) Nanosilica pretreatment

[0076] Fumed silica with a particle size of 50nm is calcined in a muffle furnace at 500°C for 2h. After cooling to room temperature, it is vacuum dried at 60°C for 12h, and then added to a mixture of anhydrous ethanol and concentrated hydrochloric acid. The mixture is stirred at a speed of 600r / min, and the oil bath is warmed to 60°C for reflux reaction for 4h. After the reaction is completed, the product is centrifuged and washed with anhydrous ethanol until neutral. The product is vacuum dried at 60°C for 10h to obtain pretreated silica.

[0077] (2) Dopamine modification

[0078] The pretreated silica is added to a 2g / L dopamine hydrochloride solution (pH 8.5) at a solid-liquid ratio of 1:20, and stirred at a speed of 300r / min at 30°C for 20h. After the reaction is completed, the product is collected by centrifugation, washed with deionized water for 3 times, and vacuum dried at 50°C for 10h to obtain dopamine-modified silica.

[0079] (3) Fluorine-containing silane grafting

[0080] Dopamine modified silica was added into a four-necked flask under nitrogen protection, toluene was added as solvent, perfluorooctyltriethoxysilane and dibutyltin dilaurate catalyst were added in turn, stirring at a speed of 500 r / min, oil bath was heated to 100°C to reflux for 12 h, after the reaction was completed, it was cooled to room temperature, n-hexane was added to precipitate the product, after filtration, the product was washed with toluene / n-hexane mixture (volume ratio 1:1) for 3 times, and vacuum dried at 70°C for 12 h to obtain fluorine-modified silica; the solid-liquid ratio of dopamine-modified silica and toluene was 1:20; the mass ratio of dopamine-modified silica, perfluorooctyltriethoxysilane and dibutyltin dilaurate catalyst was 20:4:1;

[0081] (4) Rare earth ion chelation

[0082] The fluorine-modified silica was added into a 0.5 mol / L cerium nitrate hexahydrate ethanol solution at a solid-liquid ratio of 1:50, stirred at a speed of 200 r / min at 45°C for 6 h, after the reaction was completed, centrifugal separation was performed, ethanol was used for washing until no nitrate ions were present, and vacuum drying was performed at 70°C for 6 h to obtain modified silica.

[0083] Example 5: Based on Example 1, the silica filler was adjusted to modified silica, and the difference from Example 1 was only that:

[0084] The modified silica was prepared by the following process:

[0085] (1) Nanosilica pretreatment

[0086] Fumed silica with a particle size of 80 nm was placed in a muffle furnace and calcined at 550°C for 1.5 h, after cooling to room temperature, vacuum drying was performed at 65°C for 11 h, then the fumed silica was added into a mixture of anhydrous ethanol and concentrated hydrochloric acid, stirring at a speed of 700 r / min, oil bath was heated to 65°C to reflux for 3.5 h, after the reaction was completed, centrifugal separation was performed, deionized water was used for washing until neutral, and vacuum drying was performed at 65°C for 9 h to obtain pretreated silica.

[0087] (2) Dopamine modification

[0088] The pretreated silica was added into a 2.5 g / L dopamine hydrochloride solution (pH 8.5) at a solid-liquid ratio of 1:22, stirring at a speed of 350 r / min at 32°C for 22 h, after the reaction was completed, the product was collected by centrifugal separation, deionized water was used for washing 4 times, and vacuum drying was performed at 55°C for 9 h to obtain dopamine-modified silica.

[0089] (3) Fluorine-containing silane grafting

[0090] Dopamine modified silica was added into a four-necked flask under nitrogen protection, toluene was added as solvent, perfluorooctyltriethoxysilane and dibutyltin dilaurate catalyst were added in turn, stirring at a speed of 550 r / min, oil bath was heated to 105°C to reflux for 11 h, after the reaction was completed, it was cooled to room temperature, n-hexane was added to precipitate the product, after filtration, the product was washed with toluene / n-hexane mixture (volume ratio 1:1) for 4 times, and vacuum dried at 75°C for 11 h to obtain fluorine-modified silica; the solid-liquid ratio of dopamine-modified silica and toluene was 1:22; the mass ratio of dopamine-modified silica, perfluorooctyltriethoxysilane and dibutyltin dilaurate catalyst was 21:4:1;

[0091] (4) Rare earth ion chelation

[0092] The fluorine-modified silica was added into a 0.6 mol / L cerium nitrate hexahydrate ethanol solution at a solid-liquid ratio of 1:52, and stirred at a speed of 250 r / min at 48°C for 5 h, after the reaction was completed, centrifugal separation was performed, and ethanol was used for washing until there was no nitrate ion, and then vacuum drying was performed at 75°C for 7 h to obtain modified silica.

[0093] Example 6: Based on example 1, the silica filler was adjusted to modified silica, and the difference from example 1 was only that:

[0094] The modified silica was prepared by the following process:

[0095] (1) Nanosilica pretreatment

[0096] The fumed silica with a particle size of 100 nm was placed in a muffle furnace and calcined at 600°C for 1 h, after cooling to room temperature, vacuum drying was performed at 70°C for 10 h, then the fumed silica was added into a mixture of anhydrous ethanol and concentrated hydrochloric acid, stirring at a speed of 800 r / min, oil bath was heated to 70°C to reflux for 3 h, after the reaction was completed, centrifugal separation was performed, and anhydrous ethanol was used for washing until neutral, and then vacuum drying was performed at 70°C for 8 h to obtain pretreated silica.

[0097] (2) Dopamine modification

[0098] The pretreated silica was added into a 3 g / L dopamine hydrochloride solution (pH 8.5) at a solid-liquid ratio of 1:25, and stirred at a speed of 400 r / min at 35°C for 20 h, after the reaction was completed, the product was collected by centrifugal separation, and deionized water was used for washing for 5 times, and then vacuum drying was performed at 60°C for 8 h to obtain dopamine-modified silica.

[0099] (3) Fluorine-containing silane grafting

[0100] Dopamine modified silica was added into a four-necked flask under nitrogen protection, toluene was added as solvent, perfluorooctyltriethoxysilane and dibutyltin dilaurate catalyst were added in turn, stirring at a speed of 600 r / min, oil bath was heated to 110℃ to reflux for 10h, after the reaction was completed, it was cooled to room temperature, n-hexane was added to precipitate the product, after filtration, the product was washed with toluene / n-hexane mixture (volume ratio 1:1) for 5 times, and vacuum dried at 80℃ for 10h to obtain fluorine modified silica; the solid-liquid ratio of dopamine modified silica and toluene was 1:25; the mass ratio of dopamine modified silica, perfluorooctyltriethoxysilane and dibutyltin dilaurate catalyst was 23:4:1;

[0101] (4) Rare earth ion chelation

[0102] The fluorine modified silica was added into a 0.8 mol / L cerium nitrate hexahydrate ethanol solution at a solid-liquid ratio of 1:55, stirred at a speed of 300 r / min at 50℃ for 6h, after the reaction was completed, centrifugal separation was performed, washed with ethanol until no nitrate ions were present, and vacuum dried at 80℃ for 6h to obtain modified silica.

[0103] Comparative Example 1: A preparation method and application of a high heat-resistant low dielectric loss resin, comprising the following steps:

[0104] Put 247g of DCPD type epoxy resin HP-7200 into a beaker, add 230g of DCPD type active ester HPC-8000, start the stirrer and mix for 30min, then add 157.41g of silica filler SS15 and 0.477g of accelerator DMAP, stir for 1h to obtain a high heat-resistant low dielectric loss resin;

[0105] Soak E-Glass glass cloth 2116 in the high heat-resistant low dielectric loss resin, so that the resin adheres to the glass fiber, control the resin content to be 50%, take it out and dry at 171℃ to prepare a prepreg; then stack according to the layered structure of “1oz copper foil-prepreg-1oz copper foil”, put it into a high temperature vacuum press, press at 200℃ and 25kg / cm2 to make it cure and form a copper-clad plate.

[0106] Comparative Example 2: A preparation method and application of a high heat-resistant low dielectric loss resin, comprising the following steps:

[0107] Put 200g of PN type epoxy resin PN-438A into a beaker, add 230g of DCPD type active ester HPC-8000, start the stirrer and mix for 30min, then add 141.9g of silica filler SS15 and 0.43g of accelerator DMAP, stir for 1h to obtain a high heat-resistant low dielectric loss resin;

[0108] E-Glass glass cloth 2116 is soaked in the high-heat-resistant low-dielectric-loss resin, so that the resin is attached to the glass fiber, and the resin content is controlled to be 50%. After being taken out, it is dried at 171°C to prepare a prepreg. Then, it is stacked in a layered structure of "1 oz copper foil-prepreg-1 oz copper foil", and is placed into a high-temperature vacuum press to be pressed at 200°C and 25 kg / cm2, so that it is cured to form a copper-clad plate.

[0109] Comparative Example 3: A preparation method and application of a high-heat-resistant low-dielectric-loss resin, comprising the following steps:

[0110] 208 g of CNE type epoxy resin CN-703 is placed in a beaker, 230 g of DCPD type active ester HPC-8000 is added, and after mixing for 30 min by starting a stirrer, 144.54 g of silica filler SS15 and 0.438 g of promoter DMAP are added, and stirring is performed for 1 h to obtain a high-heat-resistant low-dielectric-loss resin.

[0111] E-Glass glass cloth 2116 is soaked in the high-heat-resistant low-dielectric-loss resin, so that the resin is attached to the glass fiber, and the resin content is controlled to be 50%. After being taken out, it is dried at 171°C to prepare a prepreg. Then, it is stacked in a layered structure of "1 oz copper foil-prepreg-1 oz copper foil", and is placed into a high-temperature vacuum press to be pressed at 200°C and 25 kg / cm2, so that it is cured to form a copper-clad plate.

[0112] Comparative Example 4: A preparation method and application of a high-heat-resistant low-dielectric-loss resin, comprising the following steps:

[0113] 123 g of DCPD type epoxy resin HP-7200 and 100 g of PN type epoxy resin PN-438A are placed in a beaker, 230 g of DCPD type active ester HPC-8000 is added, and after mixing for 30 min by starting a stirrer, 149.49 g of silica filler SS15 and 0.453 g of promoter DMAP are added, and stirring is performed for 1 h to obtain a high-heat-resistant low-dielectric-loss resin.

[0114] E-Glass glass cloth 2116 is soaked in the high-heat-resistant low-dielectric-loss resin, so that the resin is attached to the glass fiber, and the resin content is controlled to be 50%. After being taken out, it is dried at 171°C to prepare a prepreg. Then, it is stacked in a layered structure of "1 oz copper foil-prepreg-1 oz copper foil", and is placed into a high-temperature vacuum press to be pressed at 200°C and 25 kg / cm2, so that it is cured to form a copper-clad plate.

[0115] Comparative Example 5: A preparation method and application of a high-heat-resistant low-dielectric-loss resin, comprising the following steps:

[0116] Put 123 g of DCPD type epoxy resin HP-7200 and 104 g of CNE type epoxy resin CN-703 into a beaker, add 230 g of DCPD type active ester HPC-8000, start the stirrer and mix for 30 min, then add 150.81 g of silica filler SS15 and 0.457 g of promoter DMAP, stir for 1 h, to obtain a high-heat-resistant low-dielectric-loss resin;

[0117] Soak E-Glass glass cloth 2116 in the high-heat-resistant low-dielectric-loss resin, so that the resin adheres to the glass fiber, control the resin content to be 50%, take it out and dry it at 171°C to make a prepreg; then stack it according to the layered structure of "1 oz copper foil-prepreg-1 oz copper foil", put it into a high-temperature vacuum press, press it at 200°C and 25 kg / cm2, so that it is cured and formed into a copper-clad plate.

[0118] Comparative Example 6: The difference from Example 4 is only that step (3) of fluorosilane grafting is omitted.

[0119] Comparative Example 7: The difference from Example 4 is only that step (4) of rare earth ion chelation is omitted.

[0120] Experiment: Take the copper-clad plates obtained in Examples 1-6 and Comparative Examples 1-7, make samples, and detect their properties respectively and record the detection results, and the test results are shown in Table 1:

[0121] TMA-Tg (glass transition temperature): using a thermal mechanical analyzer (TMA, model Hitachi TMA-7100), under nitrogen atmosphere, at a heating rate of 10°C / min from room temperature to 300°C, recording the temperature at which the resin matrix undergoes glass transition;

[0122] CTE (linear expansion coefficient): obtained synchronously by TMA test, calculating the average linear expansion coefficient before glass transition (usually 50-150°C), unit: ppm / °C;

[0123] T288 (288°C hot delamination time): referring to the IPC-TM-650 standard, placing the sample in a 288°C molten solder, recording the time when the sample delaminates or bubbles, characterizing the heat shock resistance;

[0124] Peeling (copper foil peeling strength): using a tensile testing machine, according to the IPC-TM-650 standard, peeling 1 oz copper foil at a rate of 50 mm / min, testing the average peeling force of copper foil and prepreg, unit: N;

[0125] DK (dielectric constant), Df (dielectric loss): The dielectric properties DK and dielectric loss Df of the sample were tested at a frequency of 10 GHz using a VNA vector network analyzer (Keysight PNA-X N5245B) in combination with an SPDR (QWED) test fixture;

[0126] PCT (high voltage accelerated aging test): A high voltage accelerated aging oven (Hirayama HF260) was used to age the sample under the conditions of 121°C, 2 atm, and 100% relative humidity, and the time for the sample to delaminate or significantly decrease in electrical performance was recorded in hours;

[0127] ABS (water absorption rate): After drying the sample at 105°C to a constant weight and weighing (W1), the sample was immersed in 25°C deionized water for 24 hours, then taken out and dried, and weighed (W2). The water absorption rate was calculated according to the formula (W2-W1) / W1 x 100%.

[0128] Table 1 Sample test results

[0129]

[0130] Conclusion: From the data comparison, it can be seen that the TMA-Tg of the copper-clad plate prepared by using the alicyclic epoxy resin in Examples 1-3 is significantly improved, the CTE is reduced, the PCT weathering time is prolonged, the copper foil peel strength is improved, the water absorption rate is reduced, and the dielectric properties are more excellent, compared with Comparative Examples 1-5 (DCPD / PNE / CNE type epoxy resin). The problems of low Tg and poor heat resistance of the traditional DCPD system are solved, and the electrical defects caused by the glycerol ether structure are overcome.

[0131] Examples 4-6 use modified silica fillers, compared with Example 1 (unmodified silica), the CTE is further reduced, the copper foil peel strength is improved, the dielectric loss Df is reduced, and the water absorption rate is reduced, which shows the optimization effect of modified silica on interface bonding, dielectric properties, and heat resistance and stability.

[0132] Comparative Example 6 is based on Example 4, and step (3) of fluorine-containing silane grafting is cancelled. The copper-clad plate prepared has slightly poorer performance than Example 4, which shows that the low-polarity fluorine group introduced by fluorine-containing silane grafting is the core of reducing dielectric loss, and its strong reactivity with the resin (epoxy group) is crucial for improving interface bonding force, heat resistance, and moisture resistance.

[0133] Comparative Example 7 is based on Example 4, and step (4) of rare earth ion chelation is cancelled. The copper-clad plate prepared has slightly poorer performance than Example 4, which shows that the chelation of rare earth ions (cerium ions) can improve the heat resistance of the filler through its high thermal stability, and at the same time, enhance the interface interaction with the resin, which is a key link to maintain high Tg, low Df, and low water absorption rate.

[0134] In conclusion, the resin is prepared by the curing reaction of alicyclic epoxy resin and active ester, combined with modified silica filler, the resin is used for preparing copper-clad plate, and the prepared copper-clad plate has high heat resistance (Tg≥200℃), low dielectric loss (Df<0.008), excellent mechanical properties and moisture resistance, and is suitable for high-frequency electronic field.

[0135] It will be obvious to a person skilled in the art that, without departing from the scope of the present application, the application can be implemented in other specific forms. The examples are therefore to be considered as being illustrative and not restrictive, the scope of the application being indicated by the claims appended hereto rather than by the description given above, and all changes falling within the meaning and range of equivalency of the claims are therefore to be embraced therein.

Claims

1. A method for preparing a high heat-resistant, low dielectric loss resin, characterized in that: Includes the following steps: Alicyclic epoxy resin and reactive ester resin are mixed, filler and accelerator are added, and the mixture is stirred to obtain a resin with high heat resistance and low dielectric loss.

2. The method for preparing a high heat-resistant and low dielectric loss resin according to claim 1, characterized in that: The active ester is a DCPD type active ester resin.

3. The method for preparing a high heat-resistant, low dielectric loss resin according to claim 1, characterized in that: The alicyclic epoxy resin is selected from one of EHPE3150, 2021P, and tetramethylcyclotetrasiloxane alicyclic epoxy resins.

4. The method for preparing a high heat-resistant and low dielectric loss resin according to claim 3, characterized in that: The methylcyclotetrasiloxane alicyclic epoxy resin is prepared by the following process: 1,3,5,7-Tetramethylcyclotetrasiloxane, 3,4-cyclohexylethylene oxide-1-chloropropane and sodium hydroxide were mixed, and the mixture was stirred, heated, distilled and filtered to obtain tetramethylcyclotetrasiloxane alicyclic epoxy resin.

5. The method for preparing a high heat-resistant and low dielectric loss resin according to claim 1, characterized in that: The filler is made of silicon dioxide.

6. The method for preparing a high heat-resistant and low dielectric loss resin according to claim 5, characterized in that: The accelerator used is DMAP.

7. The method for preparing a high heat-resistant and low dielectric loss resin according to claim 1, characterized in that: The filler can also be modified silica.

8. The method for preparing a high heat-resistant and low dielectric loss resin according to claim 7, characterized in that: The modified silica is obtained by the following process: (1) Pretreatment of nano-silica Fumed silica was placed in a muffle furnace, calcined, and vacuum dried. Then it was added to a mixture of anhydrous ethanol and concentrated hydrochloric acid. After stirring, oil bath heating reaction, centrifugation, washing with anhydrous ethanol, and vacuum drying, pretreated silica was obtained. (2) Dopamine modification Pretreated silica was added to a dopamine hydrochloride solution, and the reaction was carried out by stirring, centrifugation was performed to collect the product, the product was washed with deionized water and dried under vacuum to obtain dopamine-modified silica. (3) Grafting of fluorinated silanes Under nitrogen protection, dopamine-modified silica was added to a four-necked flask, toluene was added as a solvent, and perfluorooctyltriethoxysilane and dibutyltin dilaurate catalyst were added in sequence. After stirring and heating in an oil bath, the mixture was cooled to room temperature, n-hexane was added to precipitate the product, and after filtration, washing and vacuum drying, fluorine-modified silica was obtained. (4) Rare earth ion chelation Fluorine-modified silica was added to an ethanol solution of cerium nitrate hexahydrate, and after stirring, centrifugation, washing, and vacuum drying, modified silica was obtained.

9. An application of a high heat-resistant, low dielectric loss resin, characterized in that: It is prepared by the preparation method according to any one of claims 1-8.

10. The application of the high heat resistance and low dielectric loss resin according to claim 9, characterized in that: This is applied to the preparation of copper-clad laminates, which are obtained by the following process: Take fiberglass cloth and immerse it in a high heat-resistant and low dielectric loss resin to allow the resin to adhere to the fiberglass. Control the resin content to be 50%. After drying, take it out to make a prepreg. Then, stack the layers in a "copper foil-prepreg-copper foil" layered structure and press them together under high temperature and vacuum to cure and form a copper-clad laminate.

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