WO2021108955A1 - 一种高频低损耗绝缘胶膜材料及其制备方法 - Google Patents

一种高频低损耗绝缘胶膜材料及其制备方法 Download PDF

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WO2021108955A1
WO2021108955A1 PCT/CN2019/122423 CN2019122423W WO2021108955A1 WO 2021108955 A1 WO2021108955 A1 WO 2021108955A1 CN 2019122423 W CN2019122423 W CN 2019122423W WO 2021108955 A1 WO2021108955 A1 WO 2021108955A1
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epoxy resin
film material
material according
insulating film
accelerator
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PCT/CN2019/122423
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English (en)
French (fr)
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罗遂斌
孙蓉
于淑会
高春波
阮盼盼
徐鹏鹏
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中国科学院深圳先进技术研究院
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon

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  • the present invention belongs to the technical field of electronic packaging materials. More specifically, the present invention relates to a high-frequency low-loss insulating adhesive film material for semiconductor system-level packaging.
  • the present invention provides an insulating adhesive film material with low dielectric loss at high frequency. After thermal curing, the insulating adhesive film material has a dielectric loss of less than 0.005 in the high frequency range of 1GHz to 20GHz, and is suitable for High-frequency semiconductor packaging field.
  • the present invention provides a low-dielectric loss insulating film material that can be used in the field of high-frequency semiconductor packaging.
  • One aspect of the present invention provides a high-frequency low-loss insulating adhesive film material, which is made of electronic paste prepared with raw materials containing the following ingredients, in parts by mass,
  • the other types of epoxy resins are selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, o-cresol novolac epoxy resin, polyfunctional epoxy resin, and alicyclic epoxy resin.
  • epoxy resin resorcinol epoxy resin, polyurethane modified epoxy resin, rubber modified epoxy resin, biphenyl epoxy resin, and dicyclopentadiene epoxy resin;
  • the curing accelerator is selected from imidazole curing accelerators, alcohol curing accelerators or a combination of the two.
  • the total amount of the other types of epoxy resins accounts for less than 50% of the total mass of the epoxy resins, preferably 40% to 45%.
  • the naphthalene ring structure epoxy resin contains at least 2 or more epoxy groups in the molecular chain of the naphthalene ring structure epoxy resin, preferably selected from epoxy resin HP4700, HP9900, HP4032, HP4032D, HP4032SS, HP4032H, HP4710, HP5000, ESN475V.
  • epoxy resins are selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin and a composition of multifunctional epoxy resin.
  • the bisphenol A epoxy resin is selected from JER828 type epoxy resin, E51 type epoxy resin, E44 type epoxy resin, E20 type epoxy resin and E12 type epoxy resin.
  • the bisphenol F epoxy resin is selected from JER807 type epoxy resin, EPIKOTE 862 type epoxy resin, EPICLON830 type epoxy resin, EPICLON830S type epoxy resin, EPICLON835 type epoxy resin, CYDF-170 , GEFR170, NPEF-170 and CYDF-180 in one or a combination.
  • the multifunctional epoxy resin is selected from ERDM-404L multifunctional epoxy resin, TDE-85 multifunctional epoxy resin, AG-80 multifunctional epoxy resin, AFG-90 and more. Functional epoxy resin.
  • the polyester resin curing agent is selected from EXB-9451, EXB-9460, HPC-8000, HPC-8000H, HPC-8000L, EPICLON HPC-8000-65T produced by DIC , EXB-9460B, DC808, YLH1026, YLH1030, YLH1048 produced by Mitsubishi Chemical.
  • the added amount of the polyester resin curing agent is 15% to 50% by weight of the total mass of the epoxy resin, preferably 20% to 35%.
  • it is less than 15wt%, it will affect the degree of curing of the cured product, reduce the temperature resistance of the cured product, and increase its thermal expansion coefficient, dielectric constant, and dielectric loss.
  • it is higher than 50wt%, there are more short molecular segments in the molecules of the cured product, which increases the polarization effect of the cured product under high frequency, which is not conducive to obtaining low dielectric loss.
  • the imidazole curing agent accelerator is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole , 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-methylimidazole-trimeric isocyanate, 2-phenylimidazole-trimeric isocyanate , 2,4-Diamino-6(2'-methylimidazole-(1'))ethyl-S-triazine trimer isocyanate, 2-phenyl-4,5-dihydroxymethylimidazole , 2-Phenyl-4-methyl-5-hydroxymethylimidazo
  • the added amount of the imidazole curing accelerator is 0.1 wt% to 0.5 wt% of the mass of the epoxy resin.
  • the curing temperature is high and the curing rate is slow.
  • the epoxy resin mixture has a short storage time.
  • the alcohol curing agent accelerator is selected from the group consisting of dimethylaminoethanol, 2-[2-(N,N-dimethylamino)ethoxy]ethanol, 2- ⁇ 2 -[2-(N,N-Dimethylamino)ethoxy]ethoxy ⁇ ethanol and other alcohol accelerators.
  • the added amount of this type of curing accelerator is 0.025% to 0.1% by weight of the total mass of the epoxy resin, preferably 0.025% to 0.05% by weight.
  • the addition amount of imidazole accelerator is 0.1wt% to 0.5wt% of the total mass of epoxy resin
  • the addition amount of alcohol accelerator is epoxy 0.05wt% to 0.1wt% of the total mass of the resin.
  • the inorganic filler is ceramic filler particles with a dielectric loss of less than 1 ⁇ 10 -3 , preferably spherical silica, alumina, magnesium oxide-silica composition, etc. One or more of.
  • the inorganic filler is preferably spherical particles with a particle size of 100 nm to 10 ⁇ m, preferably 200 nm to 5 ⁇ m, and more preferably 300 nm to 2 ⁇ m.
  • the inorganic filler is treated with a filler surface treatment agent, and the filler surface treatment agent is a coupling agent.
  • the coupling agent is a silane coupling agent, more preferably, N-( 2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane , N-(2-Aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, phenyltriethoxysilane Silane, phenyltrimethoxysilane, anilinemethyltriethoxysilane, anilinemethyltriethoxysilane, phenyltrimethoxysilane, phen
  • the coupling agent may be a titanate coupling agent, more preferably, isopropyl tris(dioctyl pyrophosphate acyloxy) titanate, isopropyl triisostearate titanate, isopropyl di Oleic acid acyloxy (dioctyl phosphate acyloxy) titanate, isopropyl tris (dioctyl phosphate acyloxy) titanate, isopropyl trioleic acyloxy titanate, isopropyl Tris(dioctyl pyrophosphate acyloxy) titanate, bis(dioctyl pyrophosphate) ethylene titanate, tetraisopropyl bis(dioctyl pyrophosphate acyloxy) titanic acid ester.
  • a titanate coupling agent more preferably, isopropyl tris(dioctyl pyrophosphate acyloxy) titan
  • the amount of filler surface treatment agent used is 0.5 wt% to 2 wt% of the total mass of the inorganic filler.
  • the solvent is selected from organic solvents, preferably methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, propylene glycol methyl ether acetate, and N,N-dimethylformamide.
  • the edge glue film material is made of electronic paste prepared with raw materials containing the following ingredients, in parts by mass,
  • the edge glue film material is made of electronic paste prepared with raw materials containing the following ingredients, in parts by mass,
  • the edge glue film material is made of electronic paste prepared with raw materials containing the following ingredients, in parts by mass,
  • the edge glue film material is made of electronic paste prepared with raw materials containing the following ingredients, in parts by mass,
  • the electronic paste further contains a defoamer, a leveling agent, a toughening agent, and a flame retardant.
  • Another aspect of the present invention provides a method for preparing a high-frequency low-loss insulating adhesive film material, which includes the following steps:
  • step 3 heating and curing temperature is 150-250°C.
  • step 2) the hot-pressing compounding temperature is 70-100°C.
  • the dielectric loss of the insulating adhesive film material in the frequency range of 1 GHz to 20 GHz is less than 0.005.
  • the insulating adhesive film material can be used as a dielectric material or an underfill material and can be applied to semiconductor packaging fields such as printed circuit boards, packaging substrates, and packaging substrates.
  • Figure 1 is a schematic diagram of the structure of high-frequency and low-loss insulating film materials, in which 1-1 is a protective film material, 1-2 is a high-dielectric insulating polymer composite, and 1-3 is a supporting film material.
  • Figure 2 is a schematic diagram of the structure of an insulating polymer composite in a high-dielectric insulating adhesive film material, in which 2-1 dielectric filler particles and 2-2 are high molecular polymers.
  • Fig. 3 is a schematic diagram of the process of preparing the high-dielectric insulating film material of the present invention.
  • This embodiment provides a high-frequency and low-loss insulating adhesive film material suitable for semiconductor packaging that can be used as a dielectric material or an underfill material, which is prepared by the following steps:
  • the thickness of the insulating polymer composite film is controlled according to the solid content of the electronic paste and the distance between the doctor blade and the PET film.
  • the thickness of the film after drying is controlled to 30 ⁇ m.
  • the drying process uses a segmented oven, and the temperature of the oven is heated in stages. , Starting from the coating end, the temperature of the oven is set to 60°C, 80°C, 100°C, 110°C, 120°C.
  • the insulating adhesive film is heated to 200° C. and cured for 2 hours to obtain a cured sheet material, and the high-frequency dielectric properties of the cured sheet material are tested using a resonance cavity.

Abstract

本发明公开一种在高频下具有低介电损耗的绝缘胶膜材料及其制备方法。该绝缘胶膜材料由包含以下成分的原料配制的电子浆料制成,以质量份计,萘环结构环氧树脂30-70 其他类型环氧树脂20-50 聚酯树脂固化剂15-35 固化剂促进剂0.01-0.5 无机填料100-300 填料表面处理剂1-9 溶剂50-150 所述的固化促进剂选自咪唑类固化促进剂,醇类固化促进剂或者二者的组合物。

Description

一种高频低损耗绝缘胶膜材料及其制备方法 技术领域
本发明属于电子封装材料技术领域,更具体地,本发明涉及一种应用于半导体系统级封装用的高频低损耗绝缘胶膜材料。
背景技术
随着电子信息技术的发展,特别是近年来以可穿戴电子、智能手机、超薄电脑、无人驾驶、物联网技术和5G通讯技术为主的快速发展,对电子系统的小型化、轻薄化、多功能、高性能等方面提出了越来越高的要求。绝缘电介质材料是电子封装技术的一种重要材料。其高频特性对电子封装器件信号的传输具有很大的影响。环氧树脂基于其良好的耐热性、耐化学腐蚀性、易加工、价格低廉等优势在印刷线路板中具有非常多的应用,常规的基材如FR-4都是采用环氧树脂作为聚合物基体制备的。一般地,环氧树脂复合材料经热固化后因存在较多的羟基导致在高频(1GHz~20GHz)条件下产生较大的介电损耗,为0.04~0.06,不利于高频应用。
基于此,本发明提供一种在高频下具有低介电损耗的绝缘胶膜材料,该绝缘胶膜材料经热固化后在高频1GHz~20GHz频率范围内的介电损耗小于0.005,适用于高频半导体封装领域。
发明内容
为了克服现有技术的缺陷,本发明提供一种可用于高频半导体封装领域的低介电损耗绝缘胶膜材料。
为了实现上述发明目的,本发明采取了以下技术方案。
本发明一个方面提供了一种高频低损耗绝缘胶膜材料,该绝缘胶膜材料由包含以下成分的原料配制的电子浆料制成,以质量份计,
Figure PCTCN2019122423-appb-000001
Figure PCTCN2019122423-appb-000002
其特征在于,所述其他类型环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、酚醛型环氧树脂、邻甲酚醛环氧树脂、多官能度环氧树脂、脂环族环氧树脂、间苯二酚环氧树脂、聚氨酯改性环氧树脂、橡胶改性环氧树脂、联苯环氧树脂、双环戊二烯环氧树脂中的一种或多种;
所述的固化促进剂选自咪唑类固化促进剂,醇类固化促进剂或者二者的组合物。
在本发明的技术方案中,所述其他类型环氧树脂总量占环氧树脂总质量的50%以下,优选为40%~45%。
在本发明的技术方案中,所述萘环结构环氧树脂为含萘环结构环氧树脂分子链中至少含有2个或2个以上环氧基团,优选地,选自环氧树脂HP4700、HP9900、HP4032、HP4032D、HP4032SS、HP4032H、HP4710、HP5000、ESN475V。
在本发明的技术方案中,其他类型环氧树脂选自双酚A环氧树脂、双酚F环氧树脂以及多官能度环氧树脂的组合物。
在本发明的技术方案中,双酚A环氧树脂选自JER828型环氧树脂、E51型环氧树脂、E44型环氧树脂、E20型环氧树脂和E12型环氧树脂。
在本发明的技术方案中,双酚F环氧树脂选自JER807型环氧树脂、EPIKOTE 862型环氧树脂、EPICLON830型环氧树脂、EPICLON830S型环氧树脂、EPICLON835型环氧树脂、CYDF-170、GEFR170、NPEF-170和CYDF-180中的一种或多种的组合。
在本发明的技术方案中,多官能度环氧树脂选自ERDM-404L多官能度环氧树脂、TDE-85多官能度环氧树脂、AG-80多官能度环氧树脂、AFG-90多官能度环氧树脂。
在本发明的技术方案中,所述的聚酯树脂固化剂选自迪爱生公司生产的EXB-9451,EXB-9460、HPC-8000、HPC-8000H、HPC-8000L、EPICLON HPC-8000-65T,EXB-9460B,三菱化学生产的DC808、YLH1026、YLH1030、YLH1048。
在本发明的技术方案中,所述的聚酯树脂固化剂加入量为环氧树脂总质量的15wt%~50wt%,优选为20%-35%。低于15wt%时,将影响固化物的固化程度,降低固化物的耐温性,增加其热膨胀系数和介电常数、介电损耗。高于50wt%时,固化物中分子中存在较多的短分子链段,增加固化物在高频下的极化效应,不利于获得低的介电损耗。
在本发明的技术方案中,所述的咪唑类固化剂促进剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1,2-二甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-苯基咪唑、2-甲基咪唑- 三聚异氰酸盐、2-苯基咪唑-三聚异氰酸盐、2,4-二氨基-6(2’-甲基咪唑-(1’))乙基-S-三嗪三聚异氰酸盐、2-苯基-4,5-二羟基甲基咪唑、2-苯基-4-甲基-5-羟基甲基咪唑、1-氰乙基-2-苯基-4,5-二氰乙基甲基咪唑、1-β-胺乙基-2-甲基咪唑、1-β-胺乙基-2-乙基咪唑、2-苯基-4-苄基-5-羟基甲基咪唑、2E4MZ、FXR-1061、PN23J。
在本发明的技术方案中,所述的咪唑固化促进剂加入量为环氧树脂质量的0.1wt%~0.5wt%。低于0.01wt%时,固化温度高,固化速率慢。高于1wt%时,环氧树脂混合物储存时间短。
在本发明的技术方案中,所述的醇类固化剂促进剂选自二甲基氨基乙醇、2-[2-(N,N-二甲基氨基)乙氧基]乙醇、2-{2-[2-(N,N-二甲基氨基)乙氧基]乙氧基}乙醇等醇类促进剂。该类固化促进剂的加入量为环氧树脂总质量的0.025wt%~0.1wt%,优选0.025wt%~0.05wt%。
更优的技术方案,同时使用咪唑固化促进剂和醇类固化促进剂,咪唑促进剂的添加量为环氧树脂总质量的0.1wt%~0.5wt%,醇类促进剂的添加量为环氧树脂总质量的0.05wt%~0.1wt%。
在本发明的技术方案中,所述的无机填料为具有介电损耗小于1×10 -3陶瓷填料粒子,优选地,为球形二氧化硅、氧化铝、氧化镁-二氧化硅组合物等中的一种或多种。
在本发明的技术方案中,所述的无机填料优选为球形粒子,粒径为100nm~10μm,优选为200nm~5μm,更优选为300nm~2μm。
在本发明的技术方案中,所述的无机填料经过填料表面处理剂进行处理,填料表面处理剂为偶联剂,优选地,偶联剂为硅烷偶联剂,更优选地,为N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、N-(2-氨乙基)-3-氨丙基三乙氧基硅烷、3-氨丙基甲基二甲氧基硅烷、N-(2-氨乙基)-3-氨丙基甲基二甲氧基硅烷、3-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷、苯基三乙氧基硅烷、苯基三甲氧基硅烷、苯胺甲基三乙氧基硅烷、苯胺甲基三乙氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、3-(2,3-环氧丙氧)丙基甲基二乙氧基硅烷、3-(2,3-环氧丙氧)丙基甲基二甲氧基硅烷、3-(2,3-环氧丙氧)丙基三乙氧基硅烷、十三氟辛基三乙氧基硅烷、十三氟辛基三甲氧基硅烷、十七氟癸基三乙氧基硅烷、十七氟癸基三甲氧基硅烷、乙烯基三异丙氧基硅烷、乙烯基三异丙烯氧基硅烷、双-[3-(三甲氧基硅)-丙基]-胺、苯基三(异丙稀氧基)硅烷、N-正丁基-3-氨丙基三乙氧基硅烷、N-正丁基-3-氨丙基三甲氧基硅烷。偶联剂可为钛酸酯偶联剂,更优选地,为异丙基三(二辛基焦磷酸酰氧基)钛酸酯、三异硬脂酸钛酸异丙酯、异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯、异丙基三(二辛基磷酸酰氧基)钛酸酯、异丙基三油酸酰氧基钛酸酯、异丙基三(二辛基焦磷酸酰氧基)钛酸 酯、双(二辛氧基焦磷酸酯基)乙撑钛酸酯、四异丙基二(二辛基亚磷酸酰氧基)钛酸酯。
在本发明的技术方案中,填料表面处理剂使用量为无机填料总质量的0.5wt%-2wt%。
在本发明的技术方案中,所述的溶剂选自有机溶剂,优选为丁酮、甲基异丁基甲酮、甲苯、二甲苯、丙二醇甲醚醋酸酯、N,N-二甲基甲酰胺。
在本发明的一个具体技术方案中,缘胶膜材料由包含以下成分的原料配制的电子浆料制成,以质量份计,
Figure PCTCN2019122423-appb-000003
在本发明的一个具体技术方案中,缘胶膜材料由包含以下成分的原料配制的电子浆料制成,以质量份计,
Figure PCTCN2019122423-appb-000004
在本发明的一个具体技术方案中,缘胶膜材料由包含以下成分的原料配制的电子浆料制成,以质量份计,
Figure PCTCN2019122423-appb-000005
在本发明的一个具体技术方案中,缘胶膜材料由包含以下成分的原料配制的电子浆料制成,以质量份计,
Figure PCTCN2019122423-appb-000006
在本发明的技术方案中,所述电子浆料中还包含消泡剂、流平剂、增韧剂、阻燃剂。
本发明另一个方面提供了一种高频低损耗绝缘胶膜材料的制备方法,其包括如下步骤:
1)制备电子浆料,将上述电子浆料原料进行共混形成电子浆料;
2)将电子浆料涂覆于离型膜表面,经烘烤去除溶剂后,在薄膜表面贴上塑料保护膜并热压复合;
3)加热固化,得到三层结构的绝缘胶膜材料。
在上述制备方法中,步骤3)加热固化温度为150-250℃。
在上述制备方法中,步骤2)热压复合温度为70-100℃。
在本发明的技术方案中,所述绝缘胶膜材料在1GHz~20GHz频率范围内的介电损耗小于0.005。
在本发明的技术方案中,该绝缘胶膜材料可作为介质材料或底部填充材料可应用与印刷线路板、封装基板、封装载板等半导体封装领域。
附图说明
图1为高频低损耗绝缘胶膜材料的结构示意图,其中1-1为保护膜材料,1-2为高介电绝缘聚合物复合物,1-3为支撑薄膜材料。
图2为高介电绝缘胶膜材料中绝缘聚合物复合物的结构示意图,其中2-1介电填料粒子,2-2为高分子聚合物。
图3为制备本发明高介电绝缘胶膜材料的流程示意图。
具体实施方式
为了使本发明的上述目的、特征和优点能够更加明显易懂,下面结合附图对本发明的具体实施方式做详细的说明,但不能理解为对本发明的可实施范围的限定。
了使本发明的上述目的、特征和优点能够更加明显易懂,下面结合附图对本发明的具体实施方式做详细的说明,但不能理解为对本发明的可实施范围的限定。
本实施例提供了一种适用于用于半导体封装的、可作为介质材料或底部填充材料高频低损耗绝缘胶膜材料,其是通过以下步骤制备的:
实施例
制备方法
1)将原料按配比一起置于球磨罐中,在600rpm的转速下球磨10小时后,在经过60-120min超声得到绝缘聚合物复合物的电子浆料。
2)使用刮刀涂布方式将上述电子浆料涂覆于厚度38μm PET离型膜表面。
3)依据电子浆料的固含量和刮刀与PET薄膜之间的间距控制绝缘聚合物复合物薄膜的厚度,干燥后的薄膜厚度控制为30μm,干燥过程使用分段烘箱,烘箱的温度采用阶段升温,从涂覆端开始,烘箱的温度设置为60℃、80℃、100℃、110℃、120℃。
4)干燥后的绝缘聚合物复合物薄膜与厚度18μm的OPP薄膜进行热压复合,热压过程中,加热辊的温度设置为80℃。经过热压后得到具有三层结构的绝缘胶膜材料。
5)将绝缘胶膜升温至200℃固化2小时得到固化片材料,使用谐振腔测试固化片材料的高频介电性能。
Figure PCTCN2019122423-appb-000007
Figure PCTCN2019122423-appb-000008
Figure PCTCN2019122423-appb-000009
Figure PCTCN2019122423-appb-000010
Figure PCTCN2019122423-appb-000011
Figure PCTCN2019122423-appb-000012

Claims (20)

  1. 一种绝缘胶膜材料,该绝缘胶膜材料由包含以下成分的原料配制的电子浆料制成,以质量份计,
    Figure PCTCN2019122423-appb-100001
    其特征在于,所述其他类型环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、酚醛型环氧树脂、邻甲酚醛环氧树脂、多官能度环氧树脂、脂环族环氧树脂、间苯二酚环氧树脂、聚氨酯改性环氧树脂、橡胶改性环氧树脂、联苯环氧树脂、双环戊二烯环氧树脂中的一种或多种;
    所述的固化促进剂选自咪唑类固化促进剂,醇类固化促进剂或者二者的组合物。
  2. 根据权利要求1所述的一种绝缘胶膜材料,所述萘环结构环氧树脂为含萘环结构环氧树脂分子链中至少含有2个或2个以上环氧基团,优选地,选自环氧树脂HP4700、HP9900、HP4032、HP4032D、HP4032SS、HP4032H、HP4710、HP5000、ESN475V。
  3. 根据权利要求1所述的一种绝缘胶膜材料,其他类型环氧树脂选自双酚A环氧树脂、双酚F环氧树脂以及多官能度环氧树脂的组合物。
  4. 根据权利要求3所述的一种绝缘胶膜材料,双酚A环氧树脂选自JER828型环氧树脂、E51型环氧树脂、E44型环氧树脂、E20型环氧树脂和E12型环氧树脂。
  5. 据权利要求3所述的一种绝缘胶膜材料,双酚F环氧树脂选自JER807型环氧树脂、EPIKOTE 862型环氧树脂、EPICLON830型环氧树脂、EPICLON830S型环氧树脂、EPICLON835型环氧树脂、CYDF-170、GEFR170、NPEF-170和CYDF-180中的一种或多种的组合。
  6. 据权利要求3所述的一种绝缘胶膜材料,多官能度环氧树脂选自ERDM-404L多官能度环氧树脂、TDE-85多官能度环氧树脂、AG-80多官能度环氧树脂、AFG-90多官能度环氧树脂。
  7. 根据权利要求1所述的一种绝缘胶膜材料,所述的聚酯树脂固化剂加入量为环氧树脂总质量的15wt%~50wt%。
  8. 根据权利要求1所述的一种绝缘胶膜材料,所述的聚酯树脂固化剂选自迪爱生公司生产的EXB-9451,EXB-9460、HPC-8000、HPC-8000H、HPC-8000L、EPICLON HPC-8000-65T,EXB-9460B,三菱化学生产的DC808、YLH1026、YLH1030、YLH1048。
  9. 根据权利要求1所述的一种绝缘胶膜材料,所述的咪唑类固化剂促进剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1,2-二甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-苯基咪唑、2-甲基咪唑-三聚异氰酸盐、2-苯基咪唑-三聚异氰酸盐、2,4-二氨基-6(2’-甲基咪唑-(1’))乙基-S-三嗪三聚异氰酸盐、2-苯基-4,5-二羟基甲基咪唑、2-苯基-4-甲基-5-羟基甲基咪唑、1-氰乙基-2-苯基-4,5-二氰乙基甲基咪唑、1-β-胺乙基-2-甲基咪唑、1-β-胺乙基-2-乙基咪唑、2-苯基-4-苄基-5-羟基甲基咪唑、2E4MZ、FXR-1061、PN23J。
  10. 根据权利要求1所述的一种绝缘胶膜材料,所述的醇类固化剂促进剂选自二甲基氨基乙醇、2-[2-(N,N-二甲基氨基)乙氧基]乙醇、2-{2-[2-(N,N-二甲基氨基)乙氧基]乙氧基}乙醇。
  11. 根据权利要求1所述的一种绝缘胶膜材料,单独使用咪唑促进剂时,咪唑促进剂的加入量为环氧树脂总质量的0.025wt%~0.1wt%。
  12. 根据权利要求1所述的一种绝缘胶膜材料,单独使用醇类固化剂促进剂时,醇类固化剂促进剂的加入量为环氧树脂总质量的0.025wt%~0.1wt%。
  13. 根据权利要求1所述的一种绝缘胶膜材料,同时使用咪唑固化促进剂和醇类固化促进剂时,咪唑促进剂的添加量为环氧树脂总质量的0.1wt%~0.5wt%,醇类促进剂的添加量为环氧树脂总质量的0.05wt%~0.1wt%。
  14. 根据权利要求1所述的一种绝缘胶膜材料,所述的无机填料为具有介电损耗小于1×10 -3陶瓷填料粒子,所述的无机填料经过填料表面处理剂进行处理,填料表面处理剂为偶联剂,优选地,偶联剂为硅烷偶联剂,更优选地,为N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、 N-(2-氨乙基)-3-氨丙基三乙氧基硅烷、3-氨丙基甲基二甲氧基硅烷、N-(2-氨乙基)-3-氨丙基甲基二甲氧基硅烷、3-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷、苯基三乙氧基硅烷、苯基三甲氧基硅烷、苯胺甲基三乙氧基硅烷、苯胺甲基三乙氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、3-(2,3-环氧丙氧)丙基甲基二乙氧基硅烷、3-(2,3-环氧丙氧)丙基甲基二甲氧基硅烷、3-(2,3-环氧丙氧)丙基三乙氧基硅烷、十三氟辛基三乙氧基硅烷、十三氟辛基三甲氧基硅烷、十七氟癸基三乙氧基硅烷、十七氟癸基三甲氧基硅烷、乙烯基三异丙氧基硅烷、乙烯基三异丙烯氧基硅烷、双-[3-(三甲氧基硅)-丙基]-胺、苯基三(异丙稀氧基)硅烷、N-正丁基-3-氨丙基三乙氧基硅烷、N-正丁基-3-氨丙基三甲氧基硅烷。偶联剂可为钛酸酯偶联剂,更优选地,为异丙基三(二辛基焦磷酸酰氧基)钛酸酯、三异硬脂酸钛酸异丙酯、异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯、异丙基三(二辛基磷酸酰氧基)钛酸酯、异丙基三油酸酰氧基钛酸酯、异丙基三(二辛基焦磷酸酰氧基)钛酸酯、双(二辛氧基焦磷酸酯基)乙撑钛酸酯、四异丙基二(二辛基亚磷酸酰氧基)钛酸酯。
  15. 根据权利要求1所述的一种绝缘胶膜材料,所述的溶剂选自有机溶剂,优选为丁酮、甲基异丁基甲酮、甲苯、二甲苯、丙二醇甲醚醋酸酯、N,N-二甲基甲酰胺。
  16. 根据权利要求1-8任一项所述的缘胶膜材料,其由包含以下成分的原料配制的电子浆料制成,以质量份计,
    Figure PCTCN2019122423-appb-100002
  17. 根据权利要求1所述的缘胶膜材料,其由包含以下成分的原料配制的电子浆料制成,以质量份计,
    Figure PCTCN2019122423-appb-100003
    Figure PCTCN2019122423-appb-100004
  18. 根据权利要求1所述的缘胶膜材料由包含以下成分的原料配制的电子浆料制成,以质量份计,
    Figure PCTCN2019122423-appb-100005
  19. 根据权利要求1所述的缘胶膜材料,其由包含以下成分的原料配制的电子浆料制成,以质量份计,
    Figure PCTCN2019122423-appb-100006
  20. 根据权利要求1-19任一项所述绝缘胶膜材料的制备方法,其包括如下步骤:
    1)制备电子浆料,将电子浆料的原料进行共混形成电子浆料;
    2)将电子浆料涂覆于离型膜表面,经烘烤去除溶剂后,在薄膜表面贴上塑料保护膜并热压复合;
    3)加热固化,得到三层结构的绝缘胶膜材料;
    优选地,步骤3)加热固化温度为150-250℃;
    优选地,步骤2)热压复合温度为70-100℃。
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