TWI699409B - Conductive composition for electromagnetic shielding, electromagnetic shielding layer formed of the same, circuit board laminate comprising the same, and method of forming electromagnetic shielding layer - Google Patents
Conductive composition for electromagnetic shielding, electromagnetic shielding layer formed of the same, circuit board laminate comprising the same, and method of forming electromagnetic shielding layer Download PDFInfo
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Abstract
Description
本發明是有關於一種用於電磁屏蔽的導電組成物、一種由其形成之電磁屏蔽層、一種包含其之電路板積層體以及一種形成電磁屏蔽層的方法。The present invention relates to a conductive composition for electromagnetic shielding, an electromagnetic shielding layer formed therefrom, a circuit board laminate containing the same, and a method of forming an electromagnetic shielding layer.
近來,藉由通訊技術的快速發展,可達成電子裝置的高積體度及高精密度。然而,電子裝置的高積體度及高精密度造成嚴重的電磁干擾問題。舉例而言,電磁波的干擾發生在高度積體電子裝置中緊密設置的相鄰電路之間,因而造成電子裝置的故障,或者自電子裝置發射的電磁波造成與其相鄰的其他精密電子裝置的故障。Recently, with the rapid development of communication technology, high integration and high precision of electronic devices can be achieved. However, the high integration and high precision of electronic devices cause serious electromagnetic interference problems. For example, electromagnetic wave interference occurs between adjacent circuits closely arranged in a highly integrated electronic device, thereby causing failure of the electronic device, or electromagnetic waves emitted from the electronic device cause failure of other precision electronic devices adjacent to it.
此外,由於基於各種研究的關於電磁波的物理危害的爭議越來越多,所述研究顯示出自電子裝置發射的電磁波可藉由熱反應導致的生物組織細胞的溫度升高而削弱免疫功能,或者可對身體產生不利影響(例如基因改變等),因此亟需進行電磁屏蔽。In addition, due to the increasing controversy regarding the physical hazards of electromagnetic waves based on various studies, the studies have shown that electromagnetic waves emitted from electronic devices can weaken the immune function by increasing the temperature of biological tissue cells caused by thermal reactions, or Have adverse effects on the body (such as genetic changes, etc.), so electromagnetic shielding is urgently needed.
目前,電磁屏蔽是藉由無電鍍覆、真空沈積、導電膏等來達成。鍍覆(無電鍍覆)需要高的成本及複雜的製造製程,且可造成環境污染。真空沈積亦需要高的成本且存在長期可靠性方面的問題。因此,已進行了各種研究來開發可藉由噴射而塗佈至屏蔽目標的表面上的導電膏。At present, electromagnetic shielding is achieved by electroless plating, vacuum deposition, conductive paste, etc. Plating (electroless plating) requires high costs and complicated manufacturing processes, and can cause environmental pollution. Vacuum deposition also requires high costs and has long-term reliability issues. Therefore, various studies have been conducted to develop a conductive paste that can be applied to the surface of a shielding target by spraying.
典型的導電膏在1 GHz或小於1 GHz的低頻帶中具有屏蔽效率低的缺點。儘管已進行各種嘗試以藉由提供含有各種組分的導電膏來解決此問題,然而此種導電膏具有藉由增大電阻或可分散性劣化而降低總體電磁屏蔽效率的問題。Typical conductive paste has the disadvantage of low shielding efficiency in the low frequency band of 1 GHz or less. Although various attempts have been made to solve this problem by providing conductive pastes containing various components, such conductive pastes have a problem of reducing overall electromagnetic shielding efficiency by increasing electrical resistance or deteriorating dispersibility.
因此,需要不僅在低頻率範圍內而且在寬的電磁波範圍內具有良好電磁屏蔽效率並且適用於噴射注入的導電膏。Therefore, there is a need for conductive paste that has good electromagnetic shielding efficiency not only in a low frequency range but also in a wide electromagnetic wave range and is suitable for spray injection.
在韓國專利註冊號10-0871603中揭露了背景技術的一個實例。An example of the background art is disclosed in Korean Patent Registration No. 10-0871603.
本發明的一個目的是提供一種用於電磁屏蔽的導電組成物、一種由其形成之電磁屏蔽層、一種包含其之電路板積層體以及一種形成電磁屏蔽層的方法,所述導電組成物不僅在低頻率範圍內而且在寬的電磁波範圍內可確保良好的電磁屏蔽效率。An object of the present invention is to provide a conductive composition for electromagnetic shielding, an electromagnetic shielding layer formed therefrom, a circuit board laminate containing the same, and a method of forming an electromagnetic shielding layer. It can ensure good electromagnetic shielding efficiency in a low frequency range and a wide electromagnetic wave range.
本發明的另一目的是提供一種用於電磁屏蔽的導電組成物、一種由其形成之電磁屏蔽層、一種包含其之電路板積層體以及一種形成電磁屏蔽層的方法,所述導電組成物具有良好的可分散性以提高電磁屏蔽效率且適用於噴射注入。Another object of the present invention is to provide a conductive composition for electromagnetic shielding, an electromagnetic shielding layer formed therefrom, a circuit board laminate containing the same, and a method of forming an electromagnetic shielding layer, the conductive composition having Good dispersibility to improve electromagnetic shielding efficiency and suitable for jet injection.
本發明的以上及其他目的可藉由以下所述的本發明的實施例來達成。The above and other objects of the present invention can be achieved by the embodiments of the present invention described below.
本發明的一個態樣是有關於一種用於電磁屏蔽的導電組成物。One aspect of the present invention relates to a conductive composition for electromagnetic shielding.
在一些實施例中,所述用於電磁屏蔽的導電組成物包含導電粉、環氧樹脂、固化劑以及溶劑,其中所述導電粉包括銀粉及鎳塗佈的碳奈米管。In some embodiments, the conductive composition for electromagnetic shielding includes conductive powder, epoxy resin, curing agent and solvent, wherein the conductive powder includes silver powder and nickel-coated carbon nanotubes.
所述銀粉及所述鎳塗佈的碳奈米管可以60:1至6000:1的重量比存在。The silver powder and the nickel-coated carbon nanotube may be present in a weight ratio of 60:1 to 6000:1.
在所述用於電磁屏蔽的導電組成物中可存在0.01重量%(wt%)至3重量%的量的所述鎳塗佈的碳奈米管。The nickel-coated carbon nanotube may be present in the conductive composition for electromagnetic shielding in an amount of 0.01% by weight (wt%) to 3% by weight.
所述鎳塗佈的碳奈米管可含有5重量%至50重量%的鎳。The nickel-coated carbon nanotube may contain 5% to 50% by weight nickel.
所述碳奈米管可具有0.5微米至20微米的平均粒徑以及1微米至200微米的平均長度。The carbon nanotube may have an average particle size of 0.5 to 20 microns and an average length of 1 to 200 microns.
在所述用於電磁屏蔽的導電組成物中可存在20重量%至80重量%的量的所述銀粉。The silver powder may be present in the conductive composition for electromagnetic shielding in an amount of 20% to 80% by weight.
所述導電粉可更包括金(Au)、鋁(Al)、鈀(Pd)、鎳(Ni)、鉑(Pt)及銅(Cu)中的至少一者。The conductive powder may further include at least one of gold (Au), aluminum (Al), palladium (Pd), nickel (Ni), platinum (Pt), and copper (Cu).
本發明的另一態樣是有關於一種電磁屏蔽層。Another aspect of the present invention relates to an electromagnetic shielding layer.
在一些實施例中,所述電磁屏蔽層可由用於電磁屏蔽的導電組成物形成。In some embodiments, the electromagnetic shielding layer may be formed of a conductive composition for electromagnetic shielding.
所述電磁屏蔽層在30 MHz至1.5 GHz的頻率範圍內可具有50分貝(dB)至100分貝的電磁屏蔽率。The electromagnetic shielding layer may have an electromagnetic shielding rate of 50 decibels (dB) to 100 decibels in a frequency range of 30 MHz to 1.5 GHz.
在10微米的厚度下量測時,所述電磁屏蔽層可具有50毫歐姆/□或小於50毫歐姆/□的片電阻。When measured at a thickness of 10 microns, the electromagnetic shielding layer may have a sheet resistance of 50 milliohms/□ or less than 50 milliohms/□.
本發明的另一態樣是有關於一種電路板積層體。Another aspect of the present invention relates to a circuit board laminate.
在一些實施例中,所述電路板積層體可包括包封層,形成於電路板上;以及電磁屏蔽層,形成於所述包封層上。In some embodiments, the circuit board laminate may include an encapsulation layer formed on the circuit board; and an electromagnetic shielding layer formed on the encapsulation layer.
本發明的再一態樣是有關於一種形成電磁屏蔽層的方法。Another aspect of the present invention relates to a method of forming an electromagnetic shielding layer.
在一些實施例中,所述形成電磁屏蔽層的方法可包括:將用於電磁屏蔽的導電組成物注入待由所述電磁屏蔽層屏蔽的屏蔽目標,然後對所述導電組成物進行固化。In some embodiments, the method of forming an electromagnetic shielding layer may include: injecting a conductive composition for electromagnetic shielding into a shielding target to be shielded by the electromagnetic shielding layer, and then curing the conductive composition.
所述固化可在100℃至250℃的溫度下執行。The curing may be performed at a temperature of 100°C to 250°C.
本發明提供一種用於電磁屏蔽的導電組成物、一種由其形成之電磁屏蔽層、一種包含其之電路板積層體以及一種形成電磁屏蔽層的方法,所述導電組成物不僅在低頻率範圍內而且在寬的電磁波範圍內可確保良好的電磁屏蔽效率,具有良好的可分散性以提高電磁屏蔽效率,且適用於噴射注入。The present invention provides a conductive composition for electromagnetic shielding, an electromagnetic shielding layer formed therefrom, a circuit board laminate containing the same, and a method for forming an electromagnetic shielding layer. The conductive composition is not only in the low frequency range Moreover, it can ensure good electromagnetic shielding efficiency in a wide electromagnetic wave range, has good dispersibility to improve electromagnetic shielding efficiency, and is suitable for injection injection.
以下,將詳細闡述本發明的實施例。應理解,本發明並非僅限於以下實施例,而是可以不同的方式實施。Hereinafter, embodiments of the present invention will be explained in detail. It should be understood that the present invention is not limited to the following embodiments, but can be implemented in different ways.
應理解,提供以下實施例是為了使本揭露完整並使熟習此項技術者透徹地理解本發明。另外,應理解,在不背離本發明的精神及範圍的條件下,熟習此項技術者可作出各種修改、變化及更改。It should be understood that the following embodiments are provided to complete the disclosure and enable those skilled in the art to thoroughly understand the present invention. In addition, it should be understood that those skilled in the art can make various modifications, changes, and alterations without departing from the spirit and scope of the present invention.
除非上下文另外清晰地指明,否則本文所使用的單數形式「一(a、an)」及「所述(the)」旨在亦包括複數形式。此外,當在本說明書中使用用語「包括(comprises、comprising、includes及/或including)」時,是具體指明所述特徵、整數、步驟、操作、元件、組件及/或其群組的存在,但並不排除一或多個其他特徵、整數、步驟、操作、元件、組件及/或其群組的存在或添加。Unless the context clearly indicates otherwise, the singular forms "一 (a, an)" and "the (the)" used herein are intended to also include the plural forms. In addition, when the term "comprises, comprising, includes, and/or including" is used in this specification, it specifically indicates the existence of the features, integers, steps, operations, elements, components, and/or groups thereof, However, the existence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof is not excluded.
本文所使用的表示特定值範圍的「X至Y」意指「大於或等於X且小於或等於Y」。用於電磁屏蔽的導電組成物 As used herein, "X to Y" representing a specific value range means "greater than or equal to X and less than or equal to Y". Conductive composition for electromagnetic shielding
根據本發明一個實施例的用於電磁屏蔽的導電組成物包含導電粉、環氧樹脂、固化劑及溶劑。 (A)導電粉The conductive composition for electromagnetic shielding according to an embodiment of the present invention includes conductive powder, epoxy resin, curing agent and solvent. (A) Conductive powder
在一個實施例中,導電粉包括銀粉及鎳塗佈的碳奈米管。In one embodiment, the conductive powder includes silver powder and nickel-coated carbon nanotubes.
銀粉用於對屏蔽層賦予導電性且可具有20微米或小於20微米、例如0.1微米至20微米、具體而言0.1微米至10微米的平均粒徑D50
。在此平均粒徑範圍內,導電組成物在電阻與耐久性之間具有良好的平衡。另外,銀粉可以薄片形狀來提供以改善電阻及電磁屏蔽效率。The silver powder is used to impart conductivity to the shielding layer and may have an average
在用於電磁屏蔽的導電組成物中,可存在20重量%至80重量%、具體而言25重量%至70重量%、更具體而言30重量%至70重量%的量的銀粉。In the conductive composition for electromagnetic shielding, the silver powder may be present in an amount of 20% to 80% by weight, specifically 25% to 70% by weight, more specifically 30% to 70% by weight.
用於電磁屏蔽的導電組成物中所含有的鎳塗佈的碳奈米管可進一步提高電磁屏蔽效率,尤其是在低頻率範圍(例如,1 GHz或小於1 GHz)內。當導電組成物僅含有鎳粉時,導電組成物具有高的電阻,因而造成在寬頻率範圍內的總體電磁屏蔽效率劣化,且當導電組成物含有未經鎳塗佈的碳奈米管時,導電組成物在低頻率範圍內的電磁屏蔽效率的提高不顯著。另外,使用鎳塗佈的石墨製備的導電組成物具有可分散性劣化及高電阻的問題,且使用石墨烯及碳纖維製備的導電組成物無法提高電磁屏蔽效率。The nickel-coated carbon nanotube contained in the conductive composition for electromagnetic shielding can further improve the electromagnetic shielding efficiency, especially in the low frequency range (for example, 1 GHz or less than 1 GHz). When the conductive composition contains only nickel powder, the conductive composition has high electrical resistance, thereby causing deterioration of the overall electromagnetic shielding efficiency in a wide frequency range, and when the conductive composition contains carbon nanotubes that are not coated with nickel, The improvement of the electromagnetic shielding efficiency of the conductive composition in the low frequency range is not significant. In addition, the conductive composition prepared using nickel-coated graphite has the problems of degraded dispersibility and high resistance, and the conductive composition prepared using graphene and carbon fiber cannot improve the electromagnetic shielding efficiency.
根據本發明的用於電磁屏蔽的導電組成物包含鎳塗佈的碳奈米管,因而在維持在寬頻率範圍內的總體電磁屏蔽效率的同時提高電磁屏蔽效率。The conductive composition for electromagnetic shielding according to the present invention includes nickel-coated carbon nanotubes, thereby improving the electromagnetic shielding efficiency while maintaining the overall electromagnetic shielding efficiency in a wide frequency range.
鎳塗佈的碳奈米管可含有5重量%至50重量%的鎳、具體而言10重量%至50重量的鎳。在鎳的此含量範圍內,用於電磁屏蔽的導電組成物可在維持在寬頻率範圍內的總體電磁屏蔽效率的同時提高電磁屏蔽效率。The nickel-coated carbon nanotube may contain 5 to 50% by weight of nickel, specifically 10 to 50% by weight of nickel. Within this content range of nickel, the conductive composition for electromagnetic shielding can improve the electromagnetic shielding efficiency while maintaining the overall electromagnetic shielding efficiency in a wide frequency range.
碳奈米管可具有0.5微米至20微米、具體而言1微米至10微米的平均粒徑以及1微米至200微米、具體而言5微米至100微米的平均長度。在該些範圍內,鎳塗佈的碳奈米管可在分散之後具有減小的粒徑或減小的長度。在此粒徑範圍內,碳奈米管可具有良好的可分散性且適用於噴射注入。The carbon nanotube may have an average particle size of 0.5 to 20 microns, specifically 1 to 10 microns, and an average length of 1 to 200 microns, specifically 5 to 100 microns. Within these ranges, the nickel-coated carbon nanotubes may have a reduced particle size or a reduced length after dispersion. Within this particle size range, carbon nanotubes can have good dispersibility and are suitable for jet injection.
碳奈米管可包括單壁式碳奈米管(single-walled carbon nanotube,SWCNT)及多壁式碳奈米管(multi-walled carbon nanotube,MWCNT)中的至少一者。The carbon nanotube may include at least one of a single-walled carbon nanotube (SWCNT) and a multi-walled carbon nanotube (MWCNT).
可藉由將重量比為1:1000至1:10、具體而言1:100至1:10的單壁式碳奈米管(SWCNT)及多壁式碳奈米管(MWCNT)混合來製備碳奈米管。在此種情形中,碳奈米管具有良好的可分散性及低的電阻。It can be prepared by mixing single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT) with a weight ratio of 1:1000 to 1:10, specifically 1:100 to 1:10 Carbon nanotubes. In this case, carbon nanotubes have good dispersibility and low electrical resistance.
在用於電磁屏蔽的導電組成物中,可存在0.01重量%至3重量%、具體而言0.01重量%至2重量%、更具體而言0.05重量%至1重量%的量的鎳塗佈的碳奈米管。在此含量範圍內,用於電磁屏蔽的導電組成物可提高在低頻率範圍內的電磁屏蔽效率。In the conductive composition for electromagnetic shielding, there may be an amount of 0.01% to 3% by weight, specifically 0.01% to 2% by weight, more specifically 0.05% to 1% by weight of nickel-coated Carbon nanotubes. Within this content range, the conductive composition used for electromagnetic shielding can improve the electromagnetic shielding efficiency in the low frequency range.
銀粉及鎳塗佈的碳奈米管可以60:1至6,000:1、具體而言90:1至3,000:1、更具體而言90:1至3000:1、90:1至1000:1或100:1至1000:1的重量比存在。在此重量比範圍內,用於電磁屏蔽的導電組成物可在維持在其他頻率範圍內的電磁屏蔽效率的同時提高在低頻率範圍內的電磁屏蔽效率。Carbon nanotubes coated with silver powder and nickel can be 60:1 to 6,000:1, specifically 90:1 to 3,000:1, more specifically 90:1 to 3000:1, 90:1 to 1000:1 or A weight ratio of 100:1 to 1000:1 exists. Within this weight ratio range, the conductive composition used for electromagnetic shielding can improve electromagnetic shielding efficiency in low frequency ranges while maintaining electromagnetic shielding efficiency in other frequency ranges.
在另一實施例中,導電粉可更包括金(Au)、鋁(Al)、鈀(Pd)、鎳(Ni)、鉑(Pt)及銅(Cu)中的至少一者以改善其性質。在用於電磁屏蔽的導電組成物中,另外添加至導電粉的金屬粉可以0.1重量%至50重量%、具體而言1重量%至40重量%、更具體而言10重量%至30重量%的量存在。 (B)環氧樹脂In another embodiment, the conductive powder may further include at least one of gold (Au), aluminum (Al), palladium (Pd), nickel (Ni), platinum (Pt), and copper (Cu) to improve its properties . In the conductive composition for electromagnetic shielding, the metal powder additionally added to the conductive powder may be 0.1% to 50% by weight, specifically 1% to 40% by weight, more specifically 10% to 30% by weight The amount exists. (B) Epoxy resin
環氧樹脂使導電組成物能夠形成電磁屏蔽層。另外,環氧樹脂可對待由電磁屏蔽層屏蔽的屏蔽目標賦予黏合強度。The epoxy resin enables the conductive composition to form an electromagnetic shielding layer. In addition, epoxy resin can impart adhesion strength to the shielding target shielded by the electromagnetic shielding layer.
環氧樹脂可包括以下中的至少一者:丁基縮水甘油醚型環氧樹脂、甲苯基縮水甘油醚型環氧樹脂、苯基縮水甘油醚型環氧樹脂、壬基苯基縮水甘油醚型環氧樹脂、丁基苯基縮水甘油醚型環氧樹脂、2-乙基己基縮水甘油醚型環氧樹脂、雙酚F二縮水甘油醚型環氧樹脂、雙酚A二縮水甘油醚型環氧樹脂、1,6-己二醇二縮水甘油醚型環氧樹脂、1,4-丁二醇二縮水甘油醚型環氧樹脂、脂環族二縮水甘油醚型環氧樹脂、萘型環氧樹脂、二環戊二烯環氧樹脂、矽酮改質的環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A改質的苯酚酚醛清漆型環氧樹脂、添加液態雙馬來醯亞胺的環氧樹脂、三羥甲基丙烷三縮水甘油醚型環氧樹脂、多元脂環族環氧樹脂、異氰脲酸三縮水甘油酯環氧樹脂、添加胺基苯酚的二縮水甘油醚型環氧樹脂、N,N,N',N'-四縮水甘油基-4,4'-亞甲基雙苯胺樹脂、多元氧雜環丁烷樹脂、三-(羥基苯基)乙烷縮水甘油醚型環氧樹脂、固體甲酚酚醛清漆型環氧樹脂及雙馬來醯亞胺環氧樹脂。The epoxy resin may include at least one of the following: butyl glycidyl ether type epoxy resin, cresyl glycidyl ether type epoxy resin, phenyl glycidyl ether type epoxy resin, nonylphenyl glycidyl ether type Epoxy resin, butyl phenyl glycidyl ether type epoxy resin, 2-ethylhexyl glycidyl ether type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, bisphenol A diglycidyl ether type ring Oxygen resin, 1,6-hexanediol diglycidyl ether type epoxy resin, 1,4-butanediol diglycidyl ether type epoxy resin, alicyclic diglycidyl ether type epoxy resin, naphthalene type ring Oxygen resin, dicyclopentadiene epoxy resin, silicone modified epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A modified phenol novolac type epoxy Resin, epoxy resin containing liquid bismaleimide, trimethylolpropane triglycidyl ether type epoxy resin, polyalicyclic epoxy resin, triglycidyl isocyanurate epoxy resin, additive Diglycidyl ether type epoxy resin of aminophenol, N,N,N',N'-tetraglycidyl-4,4'-methylene bisaniline resin, polyoxetane resin, tri- (Hydroxyphenyl) ethane glycidyl ether type epoxy resin, solid cresol novolac type epoxy resin, and bismaleimide epoxy resin.
在一個實施例中,環氧樹脂可包括重量平均分子量(Mw)為1,000至100,000的第一環氧樹脂以及重量平均分子量(Mw)為10至小於1,000的第二環氧樹脂。In one embodiment, the epoxy resin may include a first epoxy resin having a weight average molecular weight (Mw) of 1,000 to 100,000 and a second epoxy resin having a weight average molecular weight (Mw) of 10 to less than 1,000.
在此種情形中,由導電組成物形成的電磁屏蔽膜對於待由電磁屏蔽膜屏蔽的屏蔽目標可具有提高的黏合力且可表現出良好的耐久性。In this case, the electromagnetic shielding film formed of the conductive composition may have improved adhesion to the shielding target to be shielded by the electromagnetic shielding film and may exhibit good durability.
第一環氧樹脂及第二環氧樹脂可以0.25:1至4:1、具體而言0.4:1至2.5:1的重量比存在。在此範圍內,導電組成物可將電磁屏蔽膜的黏合強度最佳化。The first epoxy resin and the second epoxy resin may be present in a weight ratio of 0.25:1 to 4:1, specifically 0.4:1 to 2.5:1. Within this range, the conductive composition can optimize the adhesive strength of the electromagnetic shielding film.
在用於電磁屏蔽的導電組成物中,可存在1重量%至35重量%、具體而言3重量%至32.5重量%的量的環氧樹脂。在此含量範圍內,由導電組成物形成的電磁屏蔽膜可表現出良好的黏合強度及耐久性。 (C)固化劑In the conductive composition for electromagnetic shielding, the epoxy resin may be present in an amount of 1% to 35% by weight, specifically 3% to 32.5% by weight. Within this content range, the electromagnetic shielding film formed of the conductive composition can exhibit good adhesion strength and durability. (C) Curing agent
固化劑可選自任何典型的固化劑,只要所述固化劑使得環氧樹脂能夠完全固化即可。具體而言,固化劑可包括三聚氰胺化合物、咪唑化合物及三苯基膦化合物。該些固化劑可選自市售的產品,例如對於咪唑化合物為PN-23、PN-40(味之素精密技術有限公司(Ajinomoto Precision Technology Co., Ltd.))、2P4MZ、2MA-OK、2MAOK-PW、2P4MHZ、2MZ-H(四國化學有限公司(Shikoku Chemical Co., Ltd))以及TPP-K及TPP-MK(北興化工有限公司(Hokko Chemical Industry Co., Ltd.))。該些固化劑可單獨使用或以其組合形式使用。The curing agent may be selected from any typical curing agent as long as the curing agent enables the epoxy resin to be completely cured. Specifically, the curing agent may include a melamine compound, an imidazole compound, and a triphenylphosphine compound. These curing agents can be selected from commercially available products, for example, for imidazole compounds, PN-23, PN-40 (Ajinomoto Precision Technology Co., Ltd.), 2P4MZ, 2MA-OK, 2MAOK-PW, 2P4MHZ, 2MZ-H (Shikoku Chemical Co., Ltd) and TPP-K and TPP-MK (Hokko Chemical Industry Co., Ltd.). These curing agents can be used alone or in combination.
在用於電磁屏蔽的導電組成物中,可存在0.01重量%至5重量%、具體而言0.1重量%至5重量%的量的固化劑。在此含量範圍內,固化劑使得環氧樹脂能夠充分交聯,且可改善熱阻及儲存穩定性。 (D)溶劑In the conductive composition for electromagnetic shielding, the curing agent may be present in an amount of 0.01% to 5% by weight, specifically 0.1% to 5% by weight. Within this content range, the curing agent enables the epoxy resin to be fully crosslinked, and can improve the thermal resistance and storage stability. (D) Solvent
溶劑可包括選自以下中的至少一者:甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、2-甲基-1-丙醇、1-戊醇、2-戊醇、3-戊醇、3-甲基-1-丁醇、二丙二醇單甲醚、丙二醇單甲醚乙酸酯、乙二醇、二乙二醇、三乙二醇、甘油、2-甲氧基乙醇、2-乙氧基乙醇、2-(2-乙氧基乙氧基)乙醇及2-(2-甲氧基乙氧基)乙醇。The solvent may include at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentanol , 2-pentanol, 3-pentanol, 3-methyl-1-butanol, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol, diethylene glycol, triethylene glycol, glycerin , 2-methoxyethanol, 2-ethoxyethanol, 2-(2-ethoxyethoxy)ethanol and 2-(2-methoxyethoxy)ethanol.
在用於電磁屏蔽的導電組成物中,可存在餘量、具體而言5重量%至60重量%、具體而言20重量%至60重量%的溶劑。舉例而言,除其他組分的量外,可存在餘量的溶劑。In the conductive composition for electromagnetic shielding, there may be a balance, specifically 5 to 60 wt%, specifically 20 to 60 wt% of solvent. For example, there may be a balance of solvent in addition to the amounts of other components.
用於電磁屏蔽的導電組成物可更包含黏結劑樹脂。黏結劑樹脂可包括環氧樹脂、丙烯酸樹脂、胺基甲酸酯樹脂及纖維素樹脂中的至少一者。在用於電磁屏蔽的導電組成物中,可存在1重量%至20重量%、具體而言1重量%至10重量%的量的黏結劑樹脂。The conductive composition used for electromagnetic shielding may further include a binder resin. The binder resin may include at least one of epoxy resin, acrylic resin, urethane resin, and cellulose resin. In the conductive composition for electromagnetic shielding, the binder resin may be present in an amount of 1% to 20% by weight, specifically 1% to 10% by weight.
除上述組分以外,根據本發明的導電組成物可更包含典型的添加劑以改善流動性、製程特性及穩定性。所述添加劑可包括分散劑、觸變劑、塑化劑、黏度穩定劑、消泡劑、顏料、紫外線(ultraviolet,UV)穩定劑、抗氧化劑及偶合劑。該些添加劑可單獨使用或以其組合形式使用。在用於電磁屏蔽的導電組成物中,可存在0.01重量%至5重量%的量的添加劑,但並非僅限於此。電磁屏蔽層 In addition to the above-mentioned components, the conductive composition according to the present invention may further include typical additives to improve fluidity, process characteristics and stability. The additives may include dispersants, thixotropic agents, plasticizers, viscosity stabilizers, defoamers, pigments, ultraviolet (UV) stabilizers, antioxidants, and coupling agents. These additives can be used alone or in combination. In the conductive composition for electromagnetic shielding, the additive may be present in an amount of 0.01% to 5% by weight, but it is not limited to this. Electromagnetic shielding layer
根據本發明一個實施例的電磁屏蔽層可由用於電磁屏蔽的導電組成物形成。具體而言,根據實施例的電磁屏蔽層可使用噴塗機將導電組成物注入屏蔽目標、然後在100℃至250℃下或在150℃至250℃下固化1分鐘至60分鐘來形成。另外,導電組成物的注入量可端視所需厚度來調整。The electromagnetic shielding layer according to an embodiment of the present invention may be formed of a conductive composition for electromagnetic shielding. Specifically, the electromagnetic shielding layer according to the embodiment may be formed by injecting a conductive composition into a shielding target using a sprayer, and then curing at 100°C to 250°C or 150°C to 250°C for 1 minute to 60 minutes. In addition, the injection amount of the conductive composition can be adjusted according to the required thickness.
電磁屏蔽層在30 MHz至1.5 GHz的頻率範圍內可具有50分貝至100分貝、具體而言60分貝至90分貝的電磁屏蔽率。在此種情形中,電磁屏蔽層在低頻率範圍(例如,1 GHz或小於1 GHz)內具有良好的電磁屏蔽效率。The electromagnetic shielding layer may have an electromagnetic shielding rate of 50 decibels to 100 decibels, specifically 60 decibels to 90 decibels in the frequency range of 30 MHz to 1.5 GHz. In this case, the electromagnetic shielding layer has good electromagnetic shielding efficiency in the low frequency range (for example, 1 GHz or less than 1 GHz).
在10微米的厚度下量測時,電磁屏蔽層可具有50毫歐姆/□或小於50毫歐姆/□、例如10毫歐姆/□至50毫歐姆/□、具體而言10毫歐姆/□至40毫歐姆/□的片電阻。電磁屏蔽層可具有10微米或小於10微米、例如1微米至10微米、具體而言3微米至8微米的厚度。在此厚度範圍內,電磁屏蔽層可具有50毫歐姆/□或小於50毫歐姆/□、例如10毫歐姆/□至50毫歐姆/□、具體而言10毫歐姆/□至40毫歐姆/□的片電阻。在此片電阻範圍內,電磁屏蔽層在寬的頻率範圍內表現出良好的屏蔽效率。When measured at a thickness of 10 microns, the electromagnetic shielding layer may have 50 milliohms/□ or less than 50 milliohms/□, for example, 10 milliohms/□ to 50 milliohms/□, specifically 10 milliohms/□ to Sheet resistance of 40 milliohms/□. The electromagnetic shielding layer may have a thickness of 10 microns or less, for example, 1 to 10 microns, specifically 3 to 8 microns. Within this thickness range, the electromagnetic shielding layer may have 50 milliohms/□ or less than 50 milliohms/□, for example, 10 milliohms/□ to 50 milliohms/□, specifically 10 milliohms/□ to 40 milliohms/□ □The sheet resistance. Within this sheet resistance range, the electromagnetic shielding layer shows good shielding efficiency in a wide frequency range.
圖1為根據本發明一個實施例的電路板積層體的示意圖。參照圖1,根據本發明一個實施例的電路板積層體包括電路板10;包封層20,形成於電路板10上;以及電磁屏蔽層30,形成於包封層20上。包封層可由用於包封半導體裝置的任何環氧樹脂組成物形成而無限制。舉例而言,包封層可由包含環氧樹脂、固化劑、固化促進劑、無機填料等的組成物形成。Fig. 1 is a schematic diagram of a circuit board laminate according to an embodiment of the present invention. 1, a circuit board laminate according to an embodiment of the present invention includes a
電磁屏蔽層30可形成於電路板10的至少一個表面上。具體而言,電磁屏蔽層可包括根據本發明另一態樣的電磁屏蔽層。舉例而言,電磁屏蔽層可藉由使用噴塗機將用於電磁屏蔽的導電組成物注入電路板來形成。根據本發明的電磁屏蔽層不僅在低頻率範圍內且在寬的電磁範圍內具有良好的電磁屏蔽效率,並且使得導電顆粒能夠具有良好的可分散性,進而提高電磁屏蔽效率。The
電路板可包括印刷電路板或可撓性電路板。形成電磁屏蔽層的方法 The circuit board may include a printed circuit board or a flexible circuit board. Method of forming electromagnetic shielding layer
根據本發明一個實施例的形成電磁屏蔽層的方法包括:將用於電磁屏蔽的導電組成物注入待由所述電磁屏蔽層屏蔽的屏蔽目標,然後對所述導電組成物進行固化。A method of forming an electromagnetic shielding layer according to an embodiment of the present invention includes: injecting a conductive composition for electromagnetic shielding into a shielding target to be shielded by the electromagnetic shielding layer, and then curing the conductive composition.
注入可藉由噴射注入來執行。噴射注入具有例如成本低、製程簡單及生產率高等優點。Injection can be performed by jet injection. Jet injection has advantages such as low cost, simple process and high productivity.
根據本發明的用於電磁屏蔽的導電組成物具有適用於噴射注入的黏度且確保注入時導電粉的良好分散。The conductive composition for electromagnetic shielding according to the present invention has a viscosity suitable for spray injection and ensures good dispersion of conductive powder during injection.
固化可在100℃至250℃、具體而言110℃至250℃下執行。具體而言,固化可在烘箱中在此固化溫度下執行30分鐘或大於30分鐘。The curing may be performed at 100°C to 250°C, specifically 110°C to 250°C. Specifically, curing can be performed in an oven at this curing temperature for 30 minutes or more.
接下來,將參照一些實例來更詳細地闡述本發明。然而,應注意,提供該些實例僅是用於說明且不應被視為以任何方式限制本發明。將省略對熟習此項技術者顯而易見的細節的說明。實例 Next, the present invention will be explained in more detail with reference to some examples. However, it should be noted that these examples are provided for illustration only and should not be seen as limiting the present invention in any way. A description of details that are obvious to those familiar with this technology will be omitted. Instance
實例及比較例中所用的組分的詳細情況如下。 (A)導電粉 (a-1)銀粉:SF29(D50 :4.2微米,埃姆斯有限公司(AMES Co., Ltd.)) (a-2)鎳塗佈的碳奈米管(鎳含量:20重量%,平均粒徑:13微米,平均長度:20微米,錦湖石化有限公司(Kumho Petrochemical Co., Ltd.)) (a-3)鎳粉:T255(威爾公司(Vale Inco.)) (a-4)省略鎳塗層的碳奈米管:K-諾斯(Nanos)100P,(錦湖石化有限公司) (a-5)石墨:MSG-15P(BTR新能源材料有限公司(BTR New Energy Materials Inc.)) (a-6)石墨烯:在N-甲基吡咯啶酮中的多層石墨烯油墨(默克普羅有限公司(Mexplorer Co., Ltd.)) (B)環氧樹脂 (b-1)環氧樹脂:E4275(Mw = 60,000,三菱化學有限公司(Mitsubishi Chemical Co., Ltd.)) (b-2)環氧樹脂:YD-115CA(Mw = 400,國都化學有限公司(Kukdo Chemical Co., Ltd.)) (C)固化劑:2P4MHZ-PW(四國化學有限公司) (D)溶劑 (d-1)丙二醇單甲醚乙酸酯(三春化學有限公司(Samchun Chemical Co., Ltd.)) (d-2)二丙二醇單甲醚(三春化學有限公司)實例 1 至實例 2 以及比較例 1 至比較例 4 The details of the components used in the examples and comparative examples are as follows. (A) Conductive powder (a-1) Silver powder: SF29 (D 50 : 4.2 microns, AMES Co., Ltd.) (a-2) Nickel-coated carbon nanotubes (nickel content : 20% by weight, average particle size: 13 microns, average length: 20 microns, Kumho Petrochemical Co., Ltd.) (a-3) Nickel powder: T255 (Vale Inco. )) (a-4) Carbon nanotubes without nickel coating: K-North (Nanos) 100P, (Kumho Petrochemical Co., Ltd.) (a-5) Graphite: MSG-15P (BTR New Energy Materials Co., Ltd.) (BTR New Energy Materials Inc.)) (a-6) Graphene: Multilayer graphene ink in N-methylpyrrolidone (Mexplorer Co., Ltd.) (B) Ring Oxygen resin (b-1) epoxy resin: E4275 (Mw = 60,000, Mitsubishi Chemical Co., Ltd.) (b-2) epoxy resin: YD-115CA (Mw = 400, Guodu (Kukdo Chemical Co., Ltd.) (C) Curing agent: 2P4MHZ-PW (Shikoku Chemical Co., Ltd.) (D) Solvent (d-1) Propylene glycol monomethyl ether acetate (Sanchun Chemical Co., Ltd.) (Samchun Chemical Co., Ltd.)) (d-2) Dipropylene glycol monomethyl ether (Sanchun Chemical Co., Ltd.) Examples 1 to 2 and Comparative Examples 1 to 4
將上述組分在混合器中以表1所列的量均勻地混合。然後,使用噴塗機將混合物注入至環氧模製化合物(epoxy molding compound,EMC)上並在200℃下固化了10分鐘以形成10微米厚的電磁屏蔽層。 <表1>
針對以下性質對電磁屏蔽層中的每一者進行了評價,且評價結果示於表2中。性質評價 Each of the electromagnetic shielding layers was evaluated for the following properties, and the evaluation results are shown in Table 2. Property evaluation
(1)片電阻(單位:毫歐姆/□):藉由4點探針方法量測了在10微米的厚度下的片電阻,且量測結果示於表2中。(1) Sheet resistance (unit: milliohm/□): The sheet resistance at a thickness of 10 microns was measured by the 4-point probe method, and the measurement results are shown in Table 2.
(2)電磁屏蔽率(單位:分貝(dB)):根據韓國標準(KoreaStandard,KS)C 0304:1998使用網路分析儀E5071C及屏蔽效果測試夾具EM-2107A量測了電磁屏蔽率。 表2
如表2所示,由根據本發明的用於電磁屏蔽的導電組成物形成的電磁屏蔽層具有良好的電阻且在寬的頻率範圍內,尤其在低頻率範圍(例如,1 GHz或小於1 GHz)內具有進一步提高的電磁屏蔽效率。As shown in Table 2, the electromagnetic shielding layer formed of the conductive composition for electromagnetic shielding according to the present invention has good resistance and is in a wide frequency range, especially in a low frequency range (for example, 1 GHz or less than 1 GHz). ) Has further improved electromagnetic shielding efficiency.
相反地,由不利用鎳塗佈的碳奈米管製備的比較例1至比較例4的導電組成物形成的電磁屏蔽層在總體頻率範圍(30 MHz至1 GHz)內具有降低的電磁屏蔽效率。In contrast, the electromagnetic shielding layer formed of the conductive composition of Comparative Example 1 to Comparative Example 4 prepared without using nickel-coated carbon nanotubes has reduced electromagnetic shielding efficiency in the overall frequency range (30 MHz to 1 GHz) .
具體而言,由僅包含鎳粉的比較例1的導電組成物形成的電磁屏蔽層因電阻增大而遭遇在總體頻率範圍(30 MHz至1 GHz)內的電磁屏蔽率降低,且由不利用鎳塗佈的碳奈米管製備的比較例2的導電組成物形成的電磁屏蔽層在低頻率範圍內表現出不顯著的電磁屏蔽效率的提高。Specifically, the electromagnetic shielding layer formed of the conductive composition of Comparative Example 1 containing only nickel powder suffers from a decrease in the electromagnetic shielding rate in the overall frequency range (30 MHz to 1 GHz) due to an increase in electrical resistance, and is not used The electromagnetic shielding layer formed by the conductive composition of Comparative Example 2 prepared from nickel-coated carbon nanotubes showed an insignificant increase in electromagnetic shielding efficiency in the low frequency range.
此外,由使用石墨製備的比較例3的導電組成物形成的電磁屏蔽層遭遇可分散性劣化且具有高的電阻從而降低電磁屏蔽效率,並且由使用石墨烯製備的比較例4的導電組成物形成的電磁屏蔽層表現出不顯著的電磁屏蔽效率的提高。In addition, the electromagnetic shielding layer formed of the conductive composition of Comparative Example 3 prepared using graphite suffers from deterioration in dispersibility and has high resistance to reduce electromagnetic shielding efficiency, and is formed of the conductive composition of Comparative Example 4 prepared using graphene The electromagnetic shielding layer showed an insignificant increase in electromagnetic shielding efficiency.
儘管本文中已參照圖式及表闡述了一些實施例,然而本發明並不受該些實施例限制,且可以各種方式來達成。此外,熟習此項技術者應理解,在不背離本發明的精神及範圍的條件下,可作出各種修改、變型及更改。因此,給出該些實施例僅用於說明而不應視為以任何方式限制本發明。Although some embodiments have been described herein with reference to the drawings and tables, the present invention is not limited by these embodiments and can be achieved in various ways. In addition, those skilled in the art should understand that various modifications, variations, and alterations can be made without departing from the spirit and scope of the present invention. Therefore, these embodiments are given for illustration only and should not be regarded as limiting the present invention in any way.
10‧‧‧電路板20‧‧‧包封層30‧‧‧電磁屏蔽層10‧‧‧
圖1為根據本發明一個實施例的電路板積層體的示意圖。Fig. 1 is a schematic diagram of a circuit board laminate according to an embodiment of the present invention.
10‧‧‧電路板 10‧‧‧Circuit board
20‧‧‧包封層 20‧‧‧Encapsulation layer
30‧‧‧電磁屏蔽層 30‧‧‧Electromagnetic shielding layer
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TWI405801B (en) * | 2007-10-19 | 2013-08-21 | Nat Univ Tsing Hua | Method of preparation of a mwcnt/polymer composite having electromagnetic interference shielding effectiveness |
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CN102711428A (en) * | 2012-06-21 | 2012-10-03 | 广州方邦电子有限公司 | Ultrathin shielding film with high shielding efficiency and production method thereof |
WO2018028092A1 (en) * | 2016-08-09 | 2018-02-15 | 苏州列治埃盟新材料技术转移有限公司 | Composite material of electroless nickel-plated silicon carbide particles and copper and aluminium, and preparation method therefor |
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