TWI435909B - Epoxy resin composition and the application of its low dielectric constant insulation material - Google Patents
Epoxy resin composition and the application of its low dielectric constant insulation material Download PDFInfo
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本發明係關於一種環氧樹脂組成物，尤指一種應用於銅箔基板及印刷電路板之環氧樹脂組成物。The present invention relates to an epoxy resin composition, and more particularly to an epoxy resin composition applied to a copper foil substrate and a printed circuit board.
為因應世界環保潮流及綠色法規，無鹵素(Halogen-free)為當前全球電子產業之環保趨勢，世界各國及相關電子大廠陸續對其電子產品，制定無鹵素電子產品的量產時程表。歐盟之有害物質限用指令(Restriction of Hazardous Substances,RoHS)實施後，包含鉛、鎘、汞、六價鉻、聚溴聯苯與聚溴二苯醚等物質，已不得用於製造電子產品或其零組件。印刷電路板(Printed Circuit Board,PCB)為電子電機產品之基礎，無鹵素以對印刷電路板為首先重點管制對象，國際組織對於印刷電路板之鹵素含量已有嚴格要求，其中國際電工委員會(IEC) 61249-2-21規範要求溴、氯化物之含量必須低於900 ppm，且總鹵素含量必須低於1500 ppm；日本電子迴路工業會(JPCA)則規範溴化物與氯化物之含量限制均為900 ppm；而綠色和平組織現階段大力推動的綠化政策，要求所有的製造商完全排除其電子產品中之聚氯乙烯及溴系阻燃劑，以符合兼具無鉛及無鹵素之綠色電子。因此，材料的無鹵化成為目前業者的重點開發項目。In response to the world's environmental trends and green regulations, Halogen-free is the current environmental trend of the global electronics industry. Countries around the world and related electronics manufacturers have successively developed mass production schedules for halogen-free electronic products for their electronic products. After the implementation of the Restriction of Hazardous Substances (RoHS), substances including lead, cadmium, mercury, hexavalent chromium, polybrominated biphenyls and polybrominated diphenyl ethers have not been used in the manufacture of electronic products or Its components. Printed Circuit Board (PCB) is the basis of electronic motor products. Halogen-free is the first key control object for printed circuit boards. International organizations have strict requirements on the halogen content of printed circuit boards, including the International Electrotechnical Commission (IEC). The 61249-2-21 specification requires that the bromine and chloride content must be less than 900 ppm and the total halogen content must be less than 1500 ppm; the Japanese Electronic Circuit Industry Association (JPCA) regulates the bromide and chloride content limits. 900 ppm; Greenpeace’s greening policy, which is currently being promoted, requires all manufacturers to completely eliminate the PVC and brominated flame retardants in their electronic products to meet the lead-free and halogen-free green electronics. Therefore, the halogen-free material has become a key development project for the current industry.
新世代的電子產品趨向輕薄短小，並適合高頻傳輸，因此電路板之配線走向高密度化，電路板的材料選用走向更嚴謹的需求。高頻電子元件與電路板接合，為了維持傳輸速率及保持傳輸訊號完整性，電路板之基板材料必須兼具較低的介電常數(dielectric constant,Dk)及介電損耗(又稱損失因子，dissipation factor,Df)。同時，為了於高溫、高濕度環境下依然維持電子元件正常運作功能，電路板也必須兼具耐熱、難燃及低吸水性的特性。環氧樹脂由於接著性、耐熱性、成形性優異，故廣泛使用於電子零組件及電機機械之覆銅箔積層板或密封材。為了提升電路板之耐熱難燃性、低介電損耗、低吸濕性、高交聯密度、高玻璃轉化溫度、高接合性及適當之熱膨脹性，環氧樹脂、硬化劑及補強材的材料選擇成了主要影響因素。The new generation of electronic products tend to be light and thin, and suitable for high-frequency transmission, so the wiring of the circuit board is becoming higher density, and the material selection of the circuit board is moving toward more stringent requirements. The high-frequency electronic components are bonded to the circuit board. In order to maintain the transmission rate and maintain the integrity of the transmission signal, the substrate material of the circuit board must have a lower dielectric constant (Dk) and a dielectric loss (also referred to as a loss factor). Dissipation factor, Df). At the same time, in order to maintain the normal operation of electronic components in high temperature and high humidity environments, the circuit board must also have the characteristics of heat resistance, flame retardancy and low water absorption. Since epoxy resin is excellent in adhesiveness, heat resistance, and moldability, it is widely used for a copper-clad laminate or a sealing material for an electronic component and a motor machine. Epoxy resin, hardener and reinforcing material for improving the heat resistance and flame retardancy of the board, low dielectric loss, low moisture absorption, high crosslink density, high glass transition temperature, high bondability and proper thermal expansion. Choice has become the main factor.
隨著通訊與寬頻應用技術的快速進展，以及雲端運算的普及與高速傳輸的應用擴大，現有傳統印刷電路板中所使用的材料(如FR-4等級者)已無法滿足進階的應用，特別是高頻印刷電路板的需求。基本上，欲達到高頻印刷電路板高頻率及高速度之電訊傳送特性，同時又避免在傳送過程中造成資料的損失或干擾，所使用的基板材料最好具有符合製程技術與市場應用所需要之電氣性質、耐熱性、吸水性、機械性質、尺寸安定性、耐化學性等。就電氣性質而言，主要需考量者包括材料的介電常數以及介電損耗。一般而言，由於基板之訊號傳送速度與基板材料之介電常數的平方根成反比，故基板材料的介電常數通常越小越好；另一方面，由於介電損耗越小代表訊號傳遞的損失越少，故介電損耗較小之材料所能提供之傳輸品質也較為良好。With the rapid advancement of communication and broadband application technologies, as well as the popularity of cloud computing and the expansion of high-speed transmission applications, materials used in conventional printed circuit boards (such as FR-4 grades) have been unable to meet advanced applications, especially It is the demand for high frequency printed circuit boards. Basically, in order to achieve high-frequency and high-speed telecommunication transmission characteristics of high-frequency printed circuit boards, and at the same time avoid loss or interference of data during transmission, the substrate materials used should preferably meet the needs of process technology and market applications. Electrical properties, heat resistance, water absorption, mechanical properties, dimensional stability, chemical resistance, etc. In terms of electrical properties, the main considerations include the dielectric constant of the material and the dielectric loss. In general, since the signal transmission speed of the substrate is inversely proportional to the square root of the dielectric constant of the substrate material, the dielectric constant of the substrate material is generally as small as possible; on the other hand, the smaller the dielectric loss represents the loss of signal transmission. The less the material, the lower the dielectric loss, the better the transmission quality.
因此，如何開發出具有低介電常數、低介電損耗、高玻璃轉移溫度及無鹵素之材料，並將其應用於高頻印刷電路板之製造，乃是現階段印刷電路板材料供應商亟欲解決之問題。Therefore, how to develop materials with low dielectric constant, low dielectric loss, high glass transition temperature and halogen-free materials, and apply them to the manufacture of high-frequency printed circuit boards, is the supplier of printed circuit board materials at this stage亟The problem to be solved.
有鑑於上述習知技術之缺憾，發明人有感其未臻於完善，遂竭其心智悉心研究克服，憑其從事該項產業多年之累積經驗，進而研發出一種環氧樹脂組成物，以期達到低介電常數、低介電損耗、高玻璃轉移溫度及無鹵素之目的。In view of the shortcomings of the above-mentioned prior art, the inventor feels that he has not perfected it, exhausted his mind and researched and overcome it, and based on his accumulated experience in the industry for many years, he developed an epoxy resin composition in order to achieve Low dielectric constant, low dielectric loss, high glass transition temperature and halogen-free purpose.
本發明之主要目的在提供一種環氧樹脂組成物，其藉著包含特定之組成份及比例，以使可達到低介電常數、低介電損耗、高玻璃轉移溫度及無鹵素，進而達到可應用於銅箔基板及印刷電路板之目的。The main object of the present invention is to provide an epoxy resin composition which can achieve a low dielectric constant, a low dielectric loss, a high glass transition temperature and a halogen-free content by including a specific composition and ratio. It is applied to copper foil substrates and printed circuit boards.
為達上述目的，本發明提供一種環氧樹脂組成物，其包含：(A)100重量份之環氧樹脂；(B)20至100重量份之含聚苯醚(polyphenylene oxide)結構的氰酸酯(cyanate ester)樹脂；(C)10至50重量份之苯乙烯馬來酸酐(styrene-maleic anhydride,SMA)共聚物；(D)5至50重量份之馬來醯亞胺(maleimide)樹脂；以及選擇性包含下列成分之至少一者：(E)無機填充物、(F)觸媒、(G)酚醛樹脂、(H)阻燃劑及(I)密著劑。In order to achieve the above object, the present invention provides an epoxy resin composition comprising: (A) 100 parts by weight of an epoxy resin; (B) 20 to 100 parts by weight of a cyanic acid having a polyphenylene oxide structure. Cyanate ester resin; (C) 10 to 50 parts by weight of styrene-maleic anhydride (SMA) copolymer; (D) 5 to 50 parts by weight of maleimide resin And optionally comprising at least one of the following: (E) an inorganic filler, (F) a catalyst, (G) a phenolic resin, (H) a flame retardant, and (I) an adhesive.
上述之組成物，其中該(E)無機填充物之添加量為10至150重量份。The above composition wherein the (E) inorganic filler is added in an amount of 10 to 150 parts by weight.
上述之組成物，其中該(F)觸媒之添加量為0.2至25重量份。The above composition wherein the (F) catalyst is added in an amount of from 0.2 to 25 parts by weight.
上述之組成物，其中該(G)酚醛樹脂之添加量為0.5至20重量份。The above composition wherein the (G) phenol resin is added in an amount of from 0.5 to 20 parts by weight.
上述之組成物，其中該(H)阻燃劑之添加量為10至250重量份。The above composition wherein the (H) flame retardant is added in an amount of 10 to 250 parts by weight.
上述之組成物，其中該(I)密著劑之添加量為0.5至5重量份。The above composition wherein the (I) binder is added in an amount of from 0.5 to 5 parts by weight.
上述之組成物，其中該成分(A)環氧樹脂可選擇自雙酚A(bisphenol A)環氧樹脂、雙酚F(bisphenol F)環氧樹脂、雙酚S(bisphenol S)環氧樹脂、雙酚AD(bisphenol AD)環氧樹脂、酚醛(phenol novolac)環氧樹脂、雙酚A酚醛(bisphenol A novolac)環氧樹脂、鄰甲酚(o-cresol novolac)環氧樹脂、三官能基(trifunctional)環氧樹脂、四官能基(tetrafunctional)環氧樹脂、多官能基(multifunctional)環氧樹脂、二環戊二烯環氧樹脂(dicyclopentadiene(DCPD) epoxy resin)、含磷環氧樹脂、對二甲苯環氧樹脂(p-xylene epoxy resin)、萘型(naphthalene)環氧樹脂、苯并哌喃型(benzopyran)環氧樹脂、聯苯酚醛(biphenyl novolac)環氧樹脂、酚基苯烷基酚醛(phenol aralkyl novolac)環氧樹脂或其組合。本發明之環氧樹脂組成物中，該成分(A)環氧樹脂較佳係至少包含一種異氰酸酯改質之環氧樹脂(isocyanate modified epoxy resin)。The above composition, wherein the component (A) epoxy resin may be selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, Bisphenol AD (bisphenol AD) epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin, trifunctional ( Trifunctional) epoxy resin, tetrafunctional epoxy resin, multifunctional epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, pair P-xylene epoxy resin, naphthalene epoxy resin, benzopyran epoxy resin, biphenyl novolac epoxy resin, phenolic phenylalkyl group Phenolic aralkyl novolac epoxy resin or a combination thereof. In the epoxy resin composition of the present invention, the component (A) epoxy resin preferably contains at least one isocyanate modified epoxy resin.
上述之組成物，其中該(B)含聚苯醚結構的氰酸酯係具有下列結構式：The above composition, wherein the (C) polycphenyl ether-containing cyanate ester has the following structural formula:
其中X6 係共價鍵、-SO2 -、-C(CH3 )2 -、-CH(CH3 )-或-CH2 -；Z5 至Z12 各自獨立係氫或甲基；W為-O-C≡N；n為大於或等於1之整數。Wherein X 6 is a covalent bond, -SO 2 -, -C(CH 3 ) 2 -, -CH(CH 3 )- or -CH 2 -; and Z 5 to Z 12 are each independently hydrogen or methyl; -OC≡N; n is an integer greater than or equal to 1.
更具體來說，該(B)含聚苯醚結構的氰酸酯樹脂較佳係選自下列群組之至少一者：More specifically, the (B) polyphenylene ether-containing cyanate resin is preferably selected from at least one of the following groups:
其中，n為大於或等於1之正整數。Where n is a positive integer greater than or equal to 1.
上述之組成物，其中該(C)苯乙烯馬來酸酐(SMA)共聚物之苯乙烯(S)與馬來酸酐(MA)比例可為1/1、2/1、3/1、4/1、6/1或8/1之其一者或其組合，如商品名SMA-1000、SMA-2000、SMA-3000、EF-30、EF-40、EF-60及EF-80等之苯乙烯馬來酸酐共聚物。The above composition wherein the ratio of styrene (S) to maleic anhydride (MA) of the (C) styrene maleic anhydride (SMA) copolymer may be 1/1, 2/1, 3/1, 4/ 1, 6/1 or 8/1 of one or a combination thereof, such as benzene such as SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60 and EF-80 Ethylene maleic anhydride copolymer.
上述之組成物，其中該(D)馬來醯亞胺樹脂係選自下列群組中之至少一者：4,4’-二苯甲烷雙馬來醯亞胺(4,4’-diphenylmethane bismaleimide)、苯甲烷馬來醯亞胺寡聚物(oligomer of phenylmethane maleimide)、m-伸苯基雙馬來醯亞胺(m-phenylenebismaleimide)、雙酚A二苯基醚雙馬來醯亞胺(bisphenol A diphenyl ether bismaleimide)、3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷雙馬來醯亞胺(3,3’-dimethyl-5,5’-diethyl-4,4’-diphenylmethane bismaleimide)、4-甲基-1,3-伸苯基雙馬來醯亞胺(4-methyl-1,3-phenylene bismaleimide)及1,6-雙馬來醯亞胺-(2,2,4-三甲基)已烷(1,6-bismaleimide-(2,2,4-trimethyl) hexane)。The above composition, wherein the (D) maleic imine resin is selected from at least one of the group consisting of 4,4'-diphenylmethane bismaleimide (4,4'-diphenylmethane bismaleimide) ), oligomer of phenylmethane maleimide, m-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide ( Bisphenol A diphenyl ether bismaleimide), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (3,3'-dimethyl-5, 5'-diethyl-4,4'-diphenylmethane bismaleimide), 4-methyl-1,3-phenylene bismaleimide and 1,6-double 1,2-Bismaleimide-(2,2,4-trimethyl)hexane.
上述之組成物，其中該(E)無機填充物可包含二氧化矽(熔融態、非熔融態、多孔質或中空型)、氧化鋁、氫氧化鋁、氧化鎂、氫氧化鎂、碳酸鈣、氮化鋁、氮化硼、碳化鋁矽、碳化矽、碳酸鈉、二氧化鈦、氧化鋅、氧化鋯、石英、鑽石粉、類鑽石粉、石墨、碳酸鎂、鈦酸鉀、陶瓷纖維、雲母、勃姆石(boehmite,AlOOH)、鉬酸鋅、鉬酸銨、硼酸鋅、磷酸鈣、煅燒滑石、滑石、氮化矽、莫萊石、段燒高嶺土、黏土、鹼式硫酸鎂晶鬚、莫萊石晶鬚、硫酸鋇、氫氧化鎂晶鬚、氧化鎂晶鬚、氧化鈣晶鬚、奈米碳管、奈米級二氧化矽與其相關無機粉體、或具有有機核外層殼為絕緣體修飾之粉體粒子。The above composition, wherein the (E) inorganic filler may comprise cerium oxide (molten state, non-molten state, porous or hollow type), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, Aluminum nitride, boron nitride, aluminum carbide tantalum, tantalum carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond powder, diamond powder, graphite, magnesium carbonate, potassium titanate, ceramic fiber, mica, bo Boehmite (AlOOH), zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, calcined talc, talc, tantalum nitride, molys, kaolin, clay, basic magnesium sulfate whisker, Morai Stone whiskers, barium sulfate, magnesium hydroxide whiskers, magnesium oxide whiskers, calcium oxide whiskers, carbon nanotubes, nano-sized cerium oxide and related inorganic powders, or organic core outer shells are modified by insulators Powder particles.
該無機填充物可為球型、纖維狀、板狀、粒狀、片狀或針鬚狀，並可選擇性經由矽烷偶合劑預處理。無機填充物可為粒徑100 μm以下之顆粒粉末，且較佳為粒徑1 nm至20 μm之顆粒粉末，最佳為粒徑1 μm以下之奈米尺寸顆粒粉末；針鬚狀無機填充物可為直徑50 μm以下且長度1至200 μm之粉末。The inorganic filler may be in the form of a sphere, a fiber, a plate, a granule, a sheet or a whisker, and may be optionally pretreated via a decane coupling agent. The inorganic filler may be a particle powder having a particle diameter of 100 μm or less, and preferably a particle powder having a particle diameter of 1 nm to 20 μm, preferably a nanometer-sized particle powder having a particle diameter of 1 μm or less; an whisker-like inorganic filler; It can be a powder having a diameter of 50 μm or less and a length of 1 to 200 μm.
上述之組成物，其中該(F)觸媒係可包含路易士鹼或路易士酸等催化劑。其中，路易士鹼可包含咪唑(imidazole)、三氟化硼胺複合物、氯化乙基三苯基鏻(ethyltriphenyl phosphonium chloride)、2-甲基咪唑(2-methylimidazole,2MI)、2-苯基咪唑(2-phenyl-1H-imidazole,2PZ)、2-乙基-4-甲基咪唑(2-ethyl-4-methylimidazole,2E4MI)、三苯基膦(triphenylphosphine,TPP)與4-二甲基胺基吡啶(4-dimethylaminopyridine,DMAP)中之一者或多者。路易士酸係可包含金屬鹽類化合物，如錳、鐵、鈷、鎳、銅、鋅等金屬鹽化合物，如辛酸鋅、辛酸鈷等金屬催化劑。The above composition, wherein the (F) catalyst system may comprise a catalyst such as Lewis base or Lewis acid. Among them, the Lewis base may comprise imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-benzene. 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP) and 4-dimethyl One or more of 4-dimethylaminopyridine (DMAP). The Lewis acid system may contain a metal salt compound such as a metal salt compound such as manganese, iron, cobalt, nickel, copper or zinc, such as a metal catalyst such as zinc octoate or cobalt octoate.
上述之組成物，其中該(G)酚醛樹脂可為胺基三嗪酚醛(amino triazine novolac)樹脂、雙酚A酚醛樹脂或聯苯酚醛樹脂等。In the above composition, the (G) phenol resin may be an amino triazine novolac resin, a bisphenol A phenol resin or a biphenol aldehyde resin.
上述之組成物，其中該(H)阻燃劑可為磷酸鹽化合物或含氮磷酸鹽化合物，但並不以此為限。更具體來說，阻燃劑較佳係包含以下化合物中之至少一種：雙酚聯苯磷酸鹽(bisphenol diphenyl phosphate)、聚磷酸銨(ammonium polyphosphate)、對苯二酚-雙-(聯苯基磷酸鹽)(hydroquinone bis-(diphenyl phosphate))、雙酚A-雙-(聯苯基磷酸鹽)(bisphenol A bis-(diphenylphosphate))、三(2-羧乙基)膦(tri(2-carboxyethyl)phosphine,TCEP)、三(異丙基氯)磷酸鹽、三甲基磷酸鹽(trimethyl phosphate,TMP)、二甲基-甲基磷酸鹽(dimethyl methyl phosphonate,DMMP)、間苯二酚雙二甲苯基磷酸鹽(resorcinol dixylenylphosphate,RDXP(如PX-200))、聚磷酸三聚氰胺(melamine polyphosphate)、偶磷氮化合物、9,10-二氫-9-氧雜-10-磷菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,DOPO)及其衍生物或樹脂、三聚氰胺氰尿酸酯(melamine cyanurate)及三-羥乙基異氰尿酸酯(tri-hydroxy ethyl isocyanurate)等，但並不以此為限。舉例來說，阻燃性化合物可為DOPO化合物、DOPO樹脂(如DOPO-HQ、DOPO-PN、DOPO-BPN)、DOPO鍵結之環氧樹脂等，其中DOPO-BPN可為DOPO-BPAN、DOPO-BPFN、DOPO-BPSN等雙酚酚醛化合物。The above composition, wherein the (H) flame retardant may be a phosphate compound or a nitrogen-containing phosphate compound, but is not limited thereto. More specifically, the flame retardant preferably comprises at least one of the following compounds: bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone-bis-(biphenyl) Hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenylphosphate), tris(2-carboxyethyl)phosphine (tri(2-) Carboxyethyl)phosphine, TCEP), tris(isopropyl chloride) phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol double Resorcinol dixylenylphosphate (RDXP (such as PX-200)), melamine polyphosphate, azo phosphate, 9,10-dihydro-9-oxa-10-phosphaphene-10- Oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO) and its derivatives or resins, melamine cyanurate and tris-hydroxyethyl isocyanurate (tri-hydroxy ethyl isocyanurate), etc., but not limited to this. For example, the flame retardant compound may be a DOPO compound, a DOPO resin (such as DOPO-HQ, DOPO-PN, DOPO-BPN), a DOPO bonded epoxy resin, etc., wherein the DOPO-BPN may be DOPO-BPAN, DOPO. a bisphenol phenolic compound such as BPFN or DOPO-BPSN.
上述之組成物，其中該(I)密著劑係2,4,6-三巰基-s-三嗪(2,4,6-trimercapto-s-triazine,TSH)上述之組成物，其進一步包含選自下列群組中之至少一者：硬化促進劑、增韌劑、阻燃劑、分散劑、有機矽彈性體及溶劑。The above composition, wherein the (I) binder is a composition of 2,4,6-trimercapto-s-triazine (TSH), which further comprises It is selected from at least one of the group consisting of a hardening accelerator, a toughening agent, a flame retardant, a dispersing agent, an organic cerium elastomer, and a solvent.
本發明中作為溶解環氧樹脂組成物之有機溶劑，係可包含甲醇、乙醇、乙二醇單甲醚、丙酮、丁酮(甲基乙基酮)、甲基異丁基酮、環己酮、甲苯、二甲苯、甲氧基乙基乙酸酯、乙氧基乙基乙酸酯、丙氧基乙基乙酸酯、乙酸乙酯、二甲基甲醯胺、二甲基乙醯胺、丙二醇甲基醚等溶劑或其混合溶劑。The organic solvent for dissolving the epoxy resin composition in the present invention may include methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone. , toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide A solvent such as propylene glycol methyl ether or a mixed solvent thereof.
本發明之再一目的在於揭露一半固化膠片(prepreg)，其具有低介電常數與低介電損耗、耐熱難燃性、低吸濕性及不含鹵素等特性。據此，本發明所揭露之半固化膠片可包含一補強材及前述之環氧樹脂組成物，其中該環氧樹脂組成物係以含浸等方式附著於該補強材上，並經由高溫加熱形成半固化態。其中，補強材係可為纖維材料、織布及不織布，如玻璃纖維布等，其係可增加該半固化膠片之機械強度。此外，該補強材可選擇性經由矽烷偶合劑或矽氧烷偶合劑進行預處理，如經矽烷偶合劑預處理之玻璃纖維布。Still another object of the present invention is to disclose a semi-cured film having a low dielectric constant and low dielectric loss, heat and flame retardancy, low moisture absorption, and halogen-free properties. Accordingly, the prepreg film disclosed in the present invention may comprise a reinforcing material and the epoxy resin composition described above, wherein the epoxy resin composition is attached to the reinforcing material by impregnation or the like, and is formed by heating at a high temperature. Cured state. Among them, the reinforcing material may be a fiber material, a woven fabric and a non-woven fabric, such as a glass fiber cloth, etc., which may increase the mechanical strength of the prepreg film. In addition, the reinforcing material may be optionally pretreated with a decane coupling agent or a decane coupling agent, such as a glass fiber cloth pretreated with a decane coupling agent.
前述之半固化膠片經由高溫加熱或高溫且高壓下加熱可固化形成固化膠片或是固態絕緣層，其中環氧樹脂組成物若含有溶劑，則該溶劑會於高溫加熱程序中揮發移除。The aforementioned prepreg film can be cured by high temperature heating or high temperature and high pressure to form a cured film or a solid insulating layer. If the epoxy resin composition contains a solvent, the solvent is volatilized and removed in a high temperature heating process.
本發明之又一目的在於揭露一種銅箔基板(copper clad laminate)，其具有低介電特性、耐熱難燃性、低吸濕性及不含鹵素等特性，且特別適用於高速度高頻率訊號傳輸之電路板。據此，本發明提供一種銅箔基板，其包含兩個或兩個以上之銅箔及至少一絕緣層。其中，銅箔可進一步包含銅與鋁、鎳、鉑、銀、金等至少一種金屬之合金；絕緣層係由前述之半固化膠片於高溫高壓下固化而成，如將前述半固化膠片疊合於兩個銅箔之間且於高溫與高壓下進行壓合而成。Another object of the present invention is to disclose a copper clad laminate having low dielectric properties, heat and flame retardancy, low hygroscopicity and halogen-free properties, and is particularly suitable for high-speed and high-frequency signals. The board of the transmission. Accordingly, the present invention provides a copper foil substrate comprising two or more copper foils and at least one insulating layer. The copper foil may further comprise an alloy of copper and at least one metal such as aluminum, nickel, platinum, silver, gold, etc.; the insulating layer is formed by curing the above-mentioned semi-cured film under high temperature and high pressure, such as laminating the aforementioned prepreg film. It is formed by pressing between two copper foils under high temperature and high pressure.
本發明所述之銅箔基板至少具有以下優點之一：低介電常數與低介電損耗、優良的耐熱性及難燃性、低吸濕性、較高的熱傳導率及不含鹵素之環保性。該銅箔基板進一步經由製作線路等製程加工後，可形成一電路板，且該電路板與電子元件接合後於高溫、高濕度等嚴苛環境下操作而並不影響其品質。The copper foil substrate of the present invention has at least one of the following advantages: low dielectric constant and low dielectric loss, excellent heat resistance and flame retardancy, low moisture absorption, high thermal conductivity, and halogen-free environmental protection. Sex. After the copper foil substrate is further processed by a manufacturing process or the like, a circuit board can be formed, and the circuit board is bonded to the electronic component and operated in a severe environment such as high temperature and high humidity without affecting the quality.
本發明之再一目的在於揭露一種印刷電路板(printed circuit board)，其具有低介電特性、耐熱難燃性、低吸濕性及不含鹵素等特性，且適用於高速度高頻率之訊號傳輸。其中，該電路板係包含至少一個前述之銅箔基板，且該電路板係可由習知之製程製作而成。A further object of the present invention is to disclose a printed circuit board having low dielectric properties, heat and flame resistance, low hygroscopicity, and halogen-free characteristics, and is suitable for high-speed and high-frequency signals. transmission. Wherein, the circuit board comprises at least one of the foregoing copper foil substrates, and the circuit board can be fabricated by a conventional process.
為進一步揭露本發明，以使本發明所屬技術領域者具有通常知識者可據以實施，以下謹以數個實施例進一步說明本發明。然應注意者，以下實施例僅係用以對本發明做進一步之說明，並非用以限制本發明之實施範圍，且任何本發明所屬技術領域者具有通常知識者在不違背本發明之精神下所得以達成之修飾及變化，均屬於本發明之範圍。The present invention will be further described in the following examples, in which the present invention may be practiced by those of ordinary skill in the art. It is to be understood that the following examples are merely illustrative of the invention and are not intended to limit the scope of the invention, and that Modifications and variations are possible within the scope of the invention.
為充分瞭解本發明之目的、特徵及功效，茲藉由下述具體之實施例，對本發明做一詳細說明，說明如後：In order to fully understand the objects, features and effects of the present invention, the present invention will be described in detail by the following specific embodiments.
實施例1Example 1
40g含聚苯醚結構的氰酸酯樹脂(BTP-6020S)溶解於160g的甲苯，製備成20%的甲苯溶液。於1000 ml反應瓶中依序加入100g異氰酸酯改質之環氧樹脂(Dow 97103)、20g苯乙烯馬來酸酐共聚物(EF-80)、15g雙馬來醯亞胺樹脂(BMI-5100)、90g中空二氧化矽(B-6C)、10g熔融二氧化矽(SC-2050MB)、0.02g辛酸鋅、8g酚醛樹脂(HE-601C)、40g含磷阻燃劑(OP-935)、1g橡膠改質之反應性聚醯胺樹脂(rubber modified reactive polyamide resin,BPAM)及0.2g觸媒(2E4MI)。然後將200g含BTP-6020S的甲苯溶液加入前述反應瓶中，製備完成分散的環氧樹脂組成物。40 g of a polyphenylene ether-containing cyanate resin (BTP-6020S) was dissolved in 160 g of toluene to prepare a 20% toluene solution. 100 g of isocyanate-modified epoxy resin (Dow 97103), 20 g of styrene maleic anhydride copolymer (EF-80), and 15 g of bismaleimide resin (BMI-5100) were sequentially added to a 1000 ml reaction flask. 90g hollow cerium oxide (B-6C), 10g molten cerium oxide (SC-2050MB), 0.02g zinc octoate, 8g phenolic resin (HE-601C), 40g phosphorus-containing flame retardant (OP-935), 1g rubber Modified reactive polypropylene resin (BPAM) and 0.2 g catalyst (2E4MI). Then, 200 g of a toluene solution containing BTP-6020S was added to the aforementioned reaction flask to prepare a dispersed epoxy resin composition.
實施例2Example 2
40g含聚苯醚結構的氰酸酯樹脂(BTP-6020S)溶解於160g的二甲基乙醯胺(DMAC)，製備成20%的DMAC溶液。於1000 ml反應瓶中依序加入50g聯苯型環氧樹脂(NC-3000H)、50g異氰酸酯改質之環氧樹脂(Dow 97103)、26g苯乙烯馬來酸酐共聚物(EF-60)、30g雙馬來醯亞胺樹脂(BMI-2300)、90g中空二氧化矽(B-6C)、10g熔融二氧化矽(SC-2050MB)、0.02g辛酸鋅、8g酚醛樹脂(HE-200C)、45g含磷阻燃劑(SPB-100)、1.5g橡膠改質之反應性聚醯胺樹脂(BPAM)、0.2g觸媒(2E4MI)。然後將200g含BTP-6020S之DMAC溶液加入前述反應瓶中，製備完成分散的環氧樹脂組成物。40 g of a polyphenylene ether-containing cyanate resin (BTP-6020S) was dissolved in 160 g of dimethylacetamide (DMAC) to prepare a 20% DMAC solution. 50 g of biphenyl type epoxy resin (NC-3000H), 50 g of isocyanate modified epoxy resin (Dow 97103), 26 g of styrene maleic anhydride copolymer (EF-60), 30 g were sequentially added to a 1000 ml reaction flask. Bismaleimide resin (BMI-2300), 90g hollow cerium oxide (B-6C), 10g molten cerium oxide (SC-2050MB), 0.02g zinc octoate, 8g phenolic resin (HE-200C), 45g Phosphorus-containing flame retardant (SPB-100), 1.5 g of rubber modified reactive polyamine resin (BPAM), and 0.2 g of catalyst (2E4MI). Then, 200 g of a DMAC solution containing BTP-6020S was placed in the aforementioned reaction flask to prepare a dispersed epoxy resin composition.
比較例1Comparative example 1
40g乙烯橡膠(Ricon 250)溶解於160g的甲苯，製備成20%的甲苯溶液。於1000 ml反應瓶中依序加入100g聯苯型環氧樹脂(NC-3000H)、26g苯乙烯馬來酸酐共聚物(EF-60)、30g氮氧雜環化合物(benzoxazine)、90g氫氧化鋁(CL-303M)、10g滑石粉(KS-1000)、4g過氧化物劑(DCP)、0.5g二氰基二醯胺(DICY)、8g二胺基二苯碸(DDS)、25g含磷阻燃劑(OP-935)、0.5g密著劑(TSH)、0.2g觸媒(2E4MI)。然後將200g含乙烯橡膠之甲苯溶液加入前述反應瓶中，製備完成分散的環氧樹脂組成物。40 g of ethylene rubber (Ricon 250) was dissolved in 160 g of toluene to prepare a 20% toluene solution. 100 g of biphenyl type epoxy resin (NC-3000H), 26 g of styrene maleic anhydride copolymer (EF-60), 30 g of benzoxazine, and 90 g of aluminum hydroxide were sequentially added to a 1000 ml reaction flask. (CL-303M), 10g talc (KS-1000), 4g peroxide (DCP), 0.5g dicyanodiamine (DICY), 8g diaminodiphenyl hydrazine (DDS), 25g phosphorus Flame retardant (OP-935), 0.5 g of adhesive (TSH), 0.2 g of catalyst (2E4MI). Then, 200 g of a toluene solution containing ethylene rubber was added to the aforementioned reaction flask to prepare a dispersed epoxy resin composition.
比較例2Comparative example 2
40g羧基化丁腈橡膠溶解於160g的甲基異丁基酮(MIBK)，製備成20%的MIBK溶液。於1000 ml反應瓶中依序加入100g含磷環氧樹脂、26g酚醛樹脂、90g氫氧化鋁(CL-303M)、10g滑石粉(KS-1000)、0.2g觸媒(2E4MI)。然後將200g含羧基化丁腈橡膠之MIBK溶液加入前述反應瓶中，製備完成分散的環氧樹脂組成物。40 g of carboxylated nitrile rubber was dissolved in 160 g of methyl isobutyl ketone (MIBK) to prepare a 20% MIBK solution. 100 g of a phosphorus-containing epoxy resin, 26 g of a phenol resin, 90 g of aluminum hydroxide (CL-303M), 10 g of talc (KS-1000), and 0.2 g of a catalyst (2E4MI) were sequentially added to a 1000 ml reaction flask. Then, 200 g of a MIBK solution containing a carboxylated nitrile rubber was added to the aforementioned reaction flask to prepare a dispersed epoxy resin composition.
將實施例1、2與比較例1、2所製成之環氧樹脂組成物，分批於攪拌槽中混合均勻後置入一含浸槽中，再將玻璃纖維布通過上述含浸槽，使樹脂組成物附著於玻璃纖維布，再進行加熱烘烤成半固化態而得半固化膠片。The epoxy resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were uniformly mixed in a stirred tank and placed in an impregnation tank, and then the glass fiber cloth was passed through the above-mentioned impregnation tank to make the resin. The composition is attached to a glass fiber cloth, and then baked and baked to a semi-cured state to obtain a semi-cured film.
將上述分批製得的半固化膠片，取同一批之半固化膠片四張及兩張18 μm銅箔，依銅箔、四片半固化膠片、銅箔之順序進行疊合，再於真空條件下經由220℃壓合2小時形成銅箔基板，其中四片半固化膠片固化形成兩銅箔間之絕緣層。The semi-cured film prepared in batches above is taken from the same batch of semi-cured film four sheets and two 18 μm copper foils, which are laminated in the order of copper foil, four-ply semi-cured film and copper foil, and then vacuumed. A copper foil substrate was formed by pressing at 220 ° C for 2 hours, in which four sheets of semi-cured film were cured to form an insulating layer between the two copper foils.
分別將上述含銅箔基板及銅箔蝕刻後之不含銅基板做物性量測，物性量測項目包含以厚度為25 μm之試片進行剝離強度、熱膨脹係數(CTE)、玻璃轉換溫度(Tg)、介電常數(Dk)、介電損耗(Df)及耐熱性(Dip 288℃/10s)之測試，結果詳見表一。The copper-containing substrate after etching the copper-containing foil substrate and the copper foil was measured for physical properties, and the physical property measurement item included peeling strength, thermal expansion coefficient (CTE), and glass transition temperature (Tg) of a test piece having a thickness of 25 μm. ), dielectric constant (Dk), dielectric loss (Df) and heat resistance (Dip 288 ° C / 10s) test, the results are shown in Table 1.
比較實施例1、2與比較例1、2，本發明之環氧樹脂組成物中添加含聚苯醚結構的氰酸酯樹脂，可有效增加玻璃轉換溫度(Tg)，且降低熱膨脹係數(CTE)。比較實施例1與2及比較例1與2，添加含聚苯醚結構的氰酸酯樹脂，其降低環氧樹脂組成物之介電常數的效果，比無添加聚苯醚結構的氰酸酯樹脂的效果為佳。另比較比較例1與比較例2，密著劑之使用可增加接著劑的剝離強度。Comparing Examples 1, 2 and Comparative Examples 1 and 2, the addition of a polyphenylene ether-containing cyanate resin to the epoxy resin composition of the present invention can effectively increase the glass transition temperature (Tg) and lower the coefficient of thermal expansion (CTE). ). Comparing Examples 1 and 2 and Comparative Examples 1 and 2, a cyanate resin containing a polyphenylene ether structure was added, which lowers the dielectric constant of the epoxy resin composition, and is cyanate ester having no polyphenylene ether structure added thereto. The effect of the resin is better. In addition, in Comparative Example 1 and Comparative Example 2, the use of the adhesive increased the peel strength of the adhesive.
由上述可知，本發明實施例中的環氧樹脂組成物，具有較較高的玻璃轉換溫度以及較低的熱膨脹係數，因而具有較佳的熱穩定性，可用於高溫的製程上。由於玻璃轉換溫度的提高，對環氧樹脂組成物的耐熱性與儲存安定性都有極大的助益，可避免因實際使用時所產生之熱與工作循環溫度，而影響環氧樹脂組成物之效能。在介電性質上，實施例中的環氧樹脂組成物具有較低的介電常數與介電損耗，可用於改善環氧樹脂組成物的介電性質以及降低能量傳遞的損耗。It can be seen from the above that the epoxy resin composition in the embodiment of the present invention has a relatively high glass transition temperature and a low coefficient of thermal expansion, and thus has better thermal stability and can be used in a high temperature process. Due to the increase of the glass transition temperature, the heat resistance and storage stability of the epoxy resin composition are greatly improved, and the heat and the working cycle temperature generated by the actual use can be avoided, and the epoxy resin composition is affected. efficacy. In terms of dielectric properties, the epoxy resin composition of the examples has a lower dielectric constant and dielectric loss and can be used to improve the dielectric properties of the epoxy resin composition and reduce the loss of energy transfer.
如上所述，本發明完全符合專利三要件：新穎性、進步性和產業上的可利用性。以新穎性和進步性而言，本發明之環氧樹脂組成物，其藉著包含特定之組成份及比例，以使可達到低介電常數、低介電損耗、高玻璃轉移溫度及無鹵素，可製作成半固化膠片或樹脂膜，進而達到可應用於銅箔基板及印刷電路板之目的；就產業上的可利用性而言，利用本發明所衍生的產品，當可充分滿足目前市場的需求。As described above, the present invention fully complies with the three requirements of the patent: novelty, advancement, and industrial applicability. In terms of novelty and advancement, the epoxy resin composition of the present invention can achieve low dielectric constant, low dielectric loss, high glass transition temperature and halogen-free by including specific component parts and ratios. It can be made into a semi-cured film or a resin film to achieve the purpose of being applied to a copper foil substrate and a printed circuit board; in terms of industrial availability, the products derived from the present invention can fully satisfy the current market. Demand.
本發明在上文中已以較佳實施例揭露，然熟習本項技術者應理解的是，該實施例僅用於描繪本發明，而不應解讀為限制本發明之範圍。應注意的是，舉凡與該實施例等效之變化與置換，均應設為涵蓋於本發明之範疇內。因此，本發明之保護範圍當以下文之申請專利範圍所界定者為準。The invention has been described above in terms of the preferred embodiments, and it should be understood by those skilled in the art that the present invention is not intended to limit the scope of the invention. It should be noted that variations and permutations equivalent to those of the embodiments are intended to be included within the scope of the present invention. Therefore, the scope of the invention is defined by the scope of the following claims.
Claims (16)
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| TW100141260A TWI435909B (en) | 2011-11-11 | 2011-11-11 | Epoxy resin composition and the application of its low dielectric constant insulation material |
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| CN103724945B (en) * | 2013-12-31 | 2016-09-07 | 广东生益科技股份有限公司 | A kind of halogen-free epoxy resin composition and application thereof |
| TWI795183B (en) * | 2022-01-21 | 2023-03-01 | 聯茂電子股份有限公司 | Halogen-free epoxy resin composition |
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