TWI577732B - A low dielectric resin composition, a semi-cured film to which the copper foil substrate is used, and a copper foil substrate Circuit board - Google Patents
A low dielectric resin composition, a semi-cured film to which the copper foil substrate is used, and a copper foil substrate Circuit board Download PDFInfo
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本發明係關於一種低介電樹脂組合物，尤指一種應用於印刷電路板的低介電樹脂組合物。 The present invention relates to a low dielectric resin composition, and more particularly to a low dielectric resin composition for use in a printed circuit board.
為適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的環保趨勢，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。歐盟的有害物質限用指令(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元件。印刷電路板(Printed Circuit Board,PCB)為電子電機產品的基礎，無鹵素以對印刷電路板為首先重點管制物件，國際組織對於印刷電路板的鹵素含量已有嚴格要求，其中國際電子電機委員會(IEC)61249-2-21規範要求溴、氯化物的含量必須低於900ppm，且總鹵素含量必須低於1500ppm；日本電子迴路工業會(JPCA)則規定溴化物與氯化物的含量限制均為900ppm；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的聚氯乙烯及溴系阻燃劑，以符合兼具無鉛及無鹵素的綠色電子。因此，材料的無鹵化成為目前業者的重點開發項目。 In order to adapt to the world's environmental protection 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 European 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 zero components. Printed Circuit Board (PCB) is the basis of electronic motor products. Halogen-free is the first key control item for printed circuit boards. International organizations have strict requirements on the halogen content of printed circuit boards, including the International Electro-Electrical Committee ( The IEC) 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) stipulates that the bromide and chloride content limits are 900 ppm. The greening policy promoted by Greenpeace at this stage requires all manufacturers to completely eliminate the PVC and bromine 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.
新時代的電子產品趨向輕薄短小，並適合高頻傳輸，因此電路板的配線走向高密度化，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，電路板的基板材料必須兼具較低的介電常數(dielectric constant,Dk)以及介電損耗(又稱損失因數，dissipation factor,Dt)。同時，為了在高溫、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，故廣泛用於電子零元件及電機機械的銅箔基板或密封材。就防止火災的安全性角度而言，要求材料具有阻燃性，一般是以無阻燃性的環氧樹脂，配合外加阻燃劑的方式達到阻燃的效果，例如，在環氧樹脂中藉由導入鹵素，尤其是溴，而賦予阻燃性，提高環氧基的反應性。然而，近來的電子產品，傾向於輕量化、小型化、電路微細化，在如此的要求下，比重大的鹵化物在輕量化的觀點上並不理想。另外，在高溫下經長時間使用後，可能會引起鹵化物的解離，而有微細配線腐蝕的危險。再者使用過後的廢棄電子零元件，在燃燒後會產生鹵化物等有害化合物，對環境也不友好。 In the new era, electronic products tend to be light and thin, and are suitable for high-frequency transmission. Therefore, the wiring of the circuit board is becoming higher density, and the material selection of the circuit board is more stringent. 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 low dielectric constant (Dk) and a dielectric loss (also called a loss factor). Dissipation factor, Dt). At the same time, in order to maintain the normal electronic components in high temperature and high humidity environments Operational functions, the 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 foil substrate or a sealing material for an electronic component and a motor machine. In terms of safety against fire, the material is required to have flame retardancy. Generally, it is a flame retardant epoxy resin, and a flame retardant is added in combination with a flame retardant, for example, in an epoxy resin. The introduction of a halogen, especially bromine, imparts flame retardancy and improves the reactivity of the epoxy group. However, recent electronic products tend to be lightweight, miniaturized, and circuit miniaturized. Under such requirements, a relatively large halide is not preferable in terms of weight reduction. In addition, after a long period of use at a high temperature, the dissociation of the halide may occur, and there is a risk of corrosion of the fine wiring. In addition, the used electronic components after use will produce harmful compounds such as halides after combustion, and are not environmentally friendly.
CN 102134431 B專利(簡稱CN431)揭露一種使用雙環戊二烯酚醛樹脂的熱固性樹脂組合物，其可製作低介電常數的樹脂清漆，可應用於印刷電路積層板，該樹脂組合物包含：(A)雙環戊二烯-酚性樹脂；(B)一種或多種的雙環戊二烯環氧樹脂；或(C)一種新型雙環戊二烯-二氫苯并樹脂；或(B)與(C)的混合樹脂；與(D)難燃劑、固化劑、固化促進劑及溶劑所構成。該樹脂組合物中的成分(A)、成分(B)與成分(C)都含有具飽和多環狀的雙環戊二烯結構，可降低樹脂清漆的偶極矩、介電常數、介電損失與吸濕性；而添加的溴系或磷系的難燃劑，使組合物具有高熱安定性的特性。然而，CN431所製作的基板的介電損失因數，無法達到在10GHz測量出的Df小於0.009(一般在1GHz測量出的Df為0.009的材料，其在10GHz測量出的Df約略等於0.012)的介電損耗特性要求。 CN 102134431 B (CN431 for short) discloses a thermosetting resin composition using a biscyclopentadiene phenol resin which can be used to produce a low dielectric constant resin varnish which can be applied to a printed circuit laminate, the resin composition comprising: (A a dicyclopentadiene-phenolic resin; (B) one or more dicyclopentadiene epoxy resins; or (C) a novel dicyclopentadiene-dihydrobenzo resin; or (B) and (C) a mixed resin; and (D) a flame retardant, a curing agent, a curing accelerator, and a solvent. The component (A), the component (B) and the component (C) in the resin composition both contain a saturated polycyclic dicyclopentadiene structure, which can reduce the dipole moment, dielectric constant and dielectric loss of the resin varnish. And a bromine- or phosphorus-based flame retardant added to impart a high thermal stability property to the composition. However, the dielectric loss factor of the substrate fabricated by CN431 cannot reach the dielectric measured at 10 GHz with a Df of less than 0.009 (typically a material with a Df of 0.009 at 1 GHz, and a Df measured at 10 GHz is approximately equal to 0.012). Loss characteristics requirements.
銅箔基板及印刷電路板就電氣性質而言，主要需考慮的包括材料的介電常數以及介電損耗。一般而言，由於基板的訊號傳送速度與基板材料的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，故介電損耗較小的材料所能提供的傳輸品質也較為良好。 Copper foil substrates and printed circuit boards, in terms of electrical properties, mainly include dielectric constants and dielectric losses of materials. 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，如何開發出在10GHz測量下仍具有低介電常數以及低介電損耗的材料，並將其應用於高頻印刷電路板的製造，乃是現階段印刷電路板材料供應商亟欲解決的問題。 Therefore, how to develop materials with low dielectric constant and low dielectric loss under 10 GHz measurement and apply them to the manufacture of high-frequency printed circuit boards is the current solution for printed circuit board materials. problem.
鑒於上述現有技術的缺憾，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累積的經驗，研發出一種低介電樹脂組合物。 In view of the above-mentioned shortcomings of the prior art, the inventors felt that they have not perfected their efforts, exhausted their mental and careful research and overcoming, and developed a low dielectric resin composition based on their years of accumulated experience in the industry.
本發明的主要目的在於提供一種低介電樹脂組合物，其藉著包含特定的組成份，使其應用於製作電路基板而使該電路基板可達到高玻璃轉化溫度、低介電特性(Df<0.006在10GHz量測頻率下)、高耐熱性等良好特性；本發明揭露的低介電樹脂組合物，藉由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的目的。 SUMMARY OF THE INVENTION A primary object of the present invention is to provide a low dielectric resin composition which can be applied to a circuit substrate by using a specific composition component to achieve high glass transition temperature and low dielectric properties (Df< Good characteristics such as 0.006 at 10 GHz measurement frequency), high heat resistance, etc. The low dielectric resin composition disclosed in the present invention can be applied to a copper foil substrate and a printed circuit board by forming a semi-cured film or a resin film. the goal of.
為實現上述目的，本發明提供了一種低介電樹脂組合物，其包含：(A)乙烯苄基聚苯醚樹脂(vinyl benzyl poly-phenyl ether resin)；以及(B)雙環戊二烯-乙烯苄基苯醚樹脂(dicyclopentadiene-vinyl benzyl phenyl ether resin)。 To achieve the above object, the present invention provides a low dielectric resin composition comprising: (A) a vinyl benzyl poly-phenyl ether resin; and (B) dicyclopentadiene-ethylene Dicyclopentadiene-vinyl benzyl phenyl ether resin.
上述的組合物，其中該(A)乙烯苄基聚苯醚樹脂包含下述式(1)所示的結構：
其中，R1、R2為氫原子，R3、R4、R5、R6及R7相同或不同，代表氫原子、鹵素原子、烷基基團或鹵素取代的烷基基團；-(O-X-O)-代表通式(2)或通式(3)的其中一個；
其中，R8、R9、R14及R15相同或不同，代表鹵素原子、具有6個或者更少碳原子的烷基基團或苯基；R10、R11、R12及R13相同或不同，代表氫原子、鹵素原子、具有6個或者更少碳原子的烷基基團或苯基；
其中，R16、R17、R22及R23相同或不同，代表鹵素原子、具有6個或者更少碳原子的烷基基團或苯基；R18、R19、R20和R21相同或不同，代表鹵素原子、具有6個或者更少碳原子的烷基基團或苯基，A是具有20個或更少碳原子的線型、支鏈或環狀烴；-(Y-O)-代表通式(4)；
其中，R24和R25相同或不同，代表鹵素原子、具有6個或者更少碳原子的烷基基團或苯基；R26和R27相同或不同，代表氫原子、鹵素原子、具有6個或更少碳原子的烷基基團或苯基；Z代表具有1個碳原子的有機基團，該基團可以包含氧原子、氮原子、硫原子和/或鹵素原子，例如Z可為亞甲基(-CH2-)；a及b分別是1至30的整數，c及d皆為1。 Wherein R 24 and R 25 are the same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; R 26 and R 27 are the same or different and represent a hydrogen atom, a halogen atom, and have 6 An alkyl group of one or less carbon atoms or a phenyl group; Z represents an organic group having 1 carbon atom, and the group may contain an oxygen atom, a nitrogen atom, a sulfur atom and/or a halogen atom, for example, Z may be Methylene (-CH 2 -); a and b are each an integer from 1 to 30, and both c and d are 1.
根據本發明的一個實施例，該(A)乙烯苄基聚苯醚樹脂較佳係選自下述式(5)、式(6)及式(7)所示結構中的一個或其組合。 According to an embodiment of the present invention, the (A) vinylbenzyl polyphenylene ether resin is preferably selected from one or a combination of the structures represented by the following formulas (5), (6) and (7).
其中，R8、R9、R14、R15、R16、R17、R22及R23相同或不同，代表鹵素原子、具有6個或者更少碳原子的烷基基團或苯基；R10、R11、R12、R13、R18、R19、R20和R21相同或不同，代表鹵素原子、具有6個或者更少碳原子的烷基基團或苯基；其中，R24和R25相同或不同，代表鹵素原子、具有6個或者更少碳原子的烷基基團或苯基；R26和R27相同或不同，代表氫原子、鹵素原子、具有6個或更少碳原子的烷基基團或苯基；a及b分別獨立為1至30的任一整數。 Wherein R 8 , R 9 , R 14 , R 15 , R 16 , R 17 , R 22 and R 23 are the same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; R 10 , R 11 , R 12 , R 13 , R 18 , R 19 , R 20 and R 21 are the same or different and each represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; R 24 and R 25 are the same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; R 26 and R 27 are the same or different and represent a hydrogen atom, a halogen atom, have 6 or An alkyl group having less carbon atoms or a phenyl group; a and b are each independently an integer of from 1 to 30.
其中，上述的乙烯苄基聚苯醚樹脂可購自三菱瓦斯化學生產的末端乙烯苄基的聯苯聚苯醚樹脂，其商品名OPE-2st。 Among them, the above vinylbenzyl polyphenylene ether resin is commercially available as a terminal vinylbenzyl biphenyl polyphenylene ether resin produced by Mitsubishi Gas Chemical Co., Ltd. under the trade name of OPE-2st.
本發明所述的乙烯苄基聚苯醚樹脂，相較於雙官能末端羥基的聚苯醚樹脂，具有較低的介電特性，即具有較低的介電常數和介電損耗。 The vinylbenzyl polyphenylene ether resin of the present invention has lower dielectric properties, i.e., lower dielectric constant and dielectric loss than the polyfunctional ether resin having a bifunctional terminal hydroxyl group.
上述的組合物，其中該(B)雙環戊二烯-乙烯苄基苯醚樹脂包含下述式(8)所示的結構：
其中，T為氫、1至20個碳的直鏈烷基、環烷基或芳香基；n為1-10的整數；T較佳為氫或甲烷基。 Wherein T is hydrogen, a linear alkyl group of 1 to 20 carbons, a cycloalkyl group or an aryl group; n is an integer of 1-10; and T is preferably hydrogen or a methyl group.
本發明所述的雙環戊二烯-乙烯苄基苯醚樹脂，可將下述式(9)結構的化合物，藉由其上的羥基與苯乙烯類化合物進行反應，而製得雙環戊二烯-乙烯苄基苯醚樹脂。 The dicyclopentadiene-vinylbenzyl phenyl ether resin of the present invention can be obtained by reacting a compound having the structure of the following formula (9) with a styrene compound to obtain a dicyclopentadiene. - ethylene benzyl phenyl ether resin.
其中，T為氫、1至20個碳的直鏈烷基、環烷基或芳香基；n為1-10的整數；T較佳為氫或甲基。 Wherein T is hydrogen, a linear alkyl group of 1 to 20 carbons, a cycloalkyl group or an aryl group; n is an integer of 1-10; and T is preferably hydrogen or a methyl group.
上述的反應方法，可藉由變換不同的反應物進行反應，而成為多種型式的產物，如該苯乙烯類化合物可選自4-氯-甲基苯乙烯(4-chlro-methyl styrene)、3-氯-甲基苯乙烯(3-chlro-methyl styrene)及2-氯-甲基苯乙烯(2-chlro-methyl styrene)中的一個或其任意組合。 The above reaction method can be carried out by converting different reactants into a plurality of types of products, for example, the styrene compound can be selected from 4-chlro-methyl styrene, 3 One of or any combination of 3-chlro-methyl styrene and 2-chlro-methyl styrene.
上述的反應方法，其較佳在包含下列兩種化合物下進行反應，例如在氫氧化鈉及四丁基碘化胺存在下進行反應，但並不限於這兩種化合物。 The above reaction method preferably carries out the reaction under the following two kinds of compounds, for example, in the presence of sodium hydroxide and tetrabutylammonium iodide, but is not limited to these two compounds.
本發明所述的雙環戊二烯-乙烯苄基苯醚樹脂的合成方法，較佳是由具有羥基的雙環戊二烯-苯酚樹脂與4-氯-甲基苯乙烯，在甲苯溶劑中反應而成雙環戊二烯-乙烯苄基苯醚樹脂，且較佳在氫氧化鈉及四丁基碘化胺兩種化合物 存在下進行反應而成。此外，本發明所述的雙環戊二烯-乙烯苄基苯醚樹脂的製造方法，較佳在反應後經由甲醇清洗，使甲醇清除雜質，如反應物中的含鹵素物質，經反應後會產生鹵化鈉(如：氯化鈉)，即可被甲醇清洗移除，使雙環戊二烯-乙烯苄基苯醚樹脂產物為深褐色的黏稠液態樹脂。 The method for synthesizing the dicyclopentadiene-ethylenebenzyl phenyl ether resin according to the present invention is preferably a reaction of a dicyclopentadiene-phenol resin having a hydroxyl group and 4-chloro-methylstyrene in a toluene solvent. Dicyclopentadiene-vinylbenzyl phenyl ether resin, and preferably two compounds of sodium hydroxide and tetrabutyl iodide It is formed by reacting in the presence. In addition, the method for producing a dicyclopentadiene-vinylbenzyl phenyl ether resin according to the present invention is preferably subjected to methanol cleaning after the reaction to remove impurities such as a halogen-containing substance in the reactant, which may be produced after the reaction. The sodium halide (e.g., sodium chloride) can be removed by washing with methanol to make the dicyclopentadiene-vinylbenzyl phenyl ether resin product a dark brown viscous liquid resin.
本發明所述的雙環戊二烯-乙烯苄基苯醚樹脂，相較於一般酚醛樹脂的優點為具有乙烯基官能基，可與其它具有苯乙烯基官能基的化合物反應。此外，雙環戊二烯-乙烯苄基苯醚樹脂相較於一般傳統的酚醛樹脂、具有羥基的酚醛樹脂或雙環戊二烯-苯酚樹脂，當添加於基板的樹脂組合物中，具有較好的介電特性。 The dicyclopentadiene-vinylbenzyl phenyl ether resin of the present invention has the advantage of having a vinyl functional group compared to a general phenolic resin and reacting with other compounds having a styryl functional group. Further, the dicyclopentadiene-vinylbenzyl phenyl ether resin has better properties as compared with a conventional phenol resin, a phenol resin having a hydroxyl group or a dicyclopentadiene-phenol resin when added to a resin composition of a substrate. Dielectric properties.
本發明所述的低介電樹脂組合物，其中以100重量份的(A)乙烯苄基聚苯醚樹脂為基準，該(B)雙環戊二烯-乙烯苄基苯醚樹脂為10至500重量份，較佳為25至400重量份，更佳為25至50重量份。 The low dielectric resin composition of the present invention, wherein the (B) dicyclopentadiene-vinylbenzyl phenyl ether resin is 10 to 500 based on 100 parts by weight of the (A) ethylene benzyl polyphenylene ether resin. The parts by weight are preferably 25 to 400 parts by weight, more preferably 25 to 50 parts by weight.
本發明所述的低介電樹脂組合物，藉由雙環戊二烯-乙烯苄基苯醚樹脂與乙烯苄基聚苯醚樹脂交聯反應，因反應過程中不會產生羥基官能基，因此，本發明的樹脂組合物所製作的基板具有較好(較低)的介電常數及介電損耗，可以向電路板業界提供具有較好介電特性的基板。 The low dielectric resin composition of the present invention is crosslinked by a dicyclopentadiene-vinylbenzyl phenyl ether resin and an ethylene benzyl polyphenylene ether resin, since no hydroxyl functional group is generated during the reaction. The substrate produced by the resin composition of the present invention has a better (lower) dielectric constant and dielectric loss, and can provide a substrate having better dielectric properties to the circuit board industry.
本發明所述的低介電樹脂組合物，進一步包含：(C)二烯類聚合物，其中以100重量份的(A)乙烯苄基聚苯醚樹脂為基準，添加比例為5至100重量份，較佳為10至50重量份。所述二烯類聚合物可進一步降低基板的介電特性，且並無特別限制。其中，二烯類聚合物例如：苯乙烯-丁二烯共聚物、聚丁二烯均聚物、氫化二烯-丁二烯-苯乙烯共聚物(如H-1052，售自旭化成)、馬來酸酐化二烯-丁二烯-苯乙烯共聚物、苯乙烯-丁二烯-苯乙烯共聚物、苯乙烯-異戊二烯-苯乙烯共聚物、苯乙烯-丁二烯-二乙烯基苯共聚物(如Ricon®257，售自Sartomer)或馬來酸酐化苯乙烯-丁二烯共聚物。 The low dielectric resin composition of the present invention further comprises: (C) a diene polymer in which a ratio of 5 to 100 is added based on 100 parts by weight of the (A) ethylene benzyl polyphenylene ether resin. It is preferably 10 to 50 parts by weight. The diene-based polymer can further reduce the dielectric properties of the substrate, and is not particularly limited. Among them, diene polymers such as styrene-butadiene copolymer, polybutadiene homopolymer, hydrogenated diene-butadiene-styrene copolymer (such as H-1052, sold by Asahi Kasei), horse Anhydride-diene-butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinyl A benzene copolymer (such as Ricon® 257, sold from Sartomer) or a maleated styrene-butadiene copolymer.
本發明所述的低介電樹脂組合物，進一步包含：(D)石油樹脂(Hydrocarbon resin)，其中以100重量份的(A)乙烯苄基聚苯醚樹脂為基準，添加比例為1至100重量份，較佳為5至20重量份。 The low dielectric resin composition of the present invention further comprises: (D) a petroleum resin (Hydrocarbon resin) in which the ratio is from 1 to 100 based on 100 parts by weight of the (A) ethylene benzyl polyphenylene ether resin. The parts by weight are preferably 5 to 20 parts by weight.
本發明所述的石油樹脂例如為具有下述式(10)或式(11)所示結構的甲基苯乙烯共聚物：
所述石油樹脂如購自EASTMAN的C5脂肪族樹脂(C5 Aliphatic Resins)、氫化C5脂肪族樹脂(Hydrogenated C5 Aliphatic Resins)、C9芳烴樹脂(C9 Aromatic Resins)、純單體C9芳烴樹脂(Pure Monomer C9 Aromatic Resins)、氫化C9芳烴樹脂(Hydrogenated C9 Aromatic Resins)及C5/C9脂肪族/芳烴樹脂(C5/C9 Aliphatic/Aromatic Resins)。實驗中發現添加石油樹脂可改善(提高)樹脂組合物的流動性，故包含本樹脂組合物的半固化膠片在製作多層電路板過程中，樹脂的流動性增加，利於填孔過程。 The petroleum resin such as C5 Aliphatic Resins from EASTMAN, Hydrogenated C5 Aliphatic Resins, C9 Aromatic Resins, Pure Monomer C9 Aromatic Resin (Pure Monomer C9) Aromatic Resins), Hydrogenated C9 Aromatic Resins and C5/C9 Aliphatic/Aromatic Resins. It has been found in the experiment that the addition of the petroleum resin improves (improves) the fluidity of the resin composition, so that the semi-cured film containing the resin composition increases the fluidity of the resin during the process of producing the multilayer circuit board, which facilitates the hole filling process.
本發明所述的低介電樹脂組合物，進一步包含：(E)環型烯烴共聚物(cyclic olefin copolymer)，其中以100重量份的(A)乙烯苄基聚苯醚樹脂為基準，添加比例為1至100重量份，較佳為5至20重量份，其可進一步降低基板的介電特性(Dk及Df)。 The low dielectric resin composition of the present invention further comprises: (E) a cyclic olefin copolymer in which a ratio is added based on 100 parts by weight of the (A) ethylene benzyl polyphenylene ether resin. It is 1 to 100 parts by weight, preferably 5 to 20 parts by weight, which can further lower the dielectric properties (Dk and Df) of the substrate.
本發明所述的環型烯烴共聚物具有下述式(12)所示結構：
所述環型烯烴共聚物如購自Polyplastic的Topas 5013、Topas 6013、Topas 6017及Topas 6015。 The cyclic olefin copolymers are, for example, Topas 5013, Topas 6013, Topas 6017 and Topas 6015 available from Polyplastic.
本發明所述的低介電樹脂組合物，為了提高基板特性，可進一步添加選自下列物質組中的至少一種或其改質物：氰酸酯樹脂、馬來醯亞胺樹脂、異氰酸酯樹脂、苯乙烯樹脂、聚丁二烯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚酯樹脂及三烯丙基異氰脲酸酯(TAIC)及三聚氰酸三烯丙基酯(TAC)。 In the low dielectric resin composition of the present invention, in order to improve the substrate characteristics, at least one selected from the group consisting of a cyanate resin, a maleic imide resin, an isocyanate resin, and a benzene may be further added. Vinyl resin, polybutadiene resin, polyamide resin, polyimide resin, polyester resin and triallyl isocyanurate (TAIC) and triallyl cyanurate (TAC).
本發明所述的低介電樹脂組合物，較佳添加氰酸酯樹脂及馬來醯亞胺樹脂，除了可提高交聯性外，更可增加玻璃化溫度、耐熱性及與銅箔的接著力。 The low dielectric resin composition of the present invention preferably comprises a cyanate resin and a maleic imide resin, in addition to improving crosslinkability, and further increasing the glass transition temperature, heat resistance and adhesion to the copper foil. force.
所述氰酸酯樹脂並無特別限制，已知使用的氰酸酯樹脂均可，如具有(Ar-O-C≡N)結構的化合物，其中Ar可為經取代或未經取代的苯、聯苯、萘、酚醛(phenol novolac)、雙酚A(bisphenol A)、雙酚A酚醛(bisphenol A novolac)、雙酚F(bisphenol F)、雙酚F酚醛(bisphenol F novolac)或酚酞(phenolphthalein)。此外，上述Ar可進一步與經取代或未經取代的雙環戊二烯(dicyclopentadienyl,DCPD)鍵結。 The cyanate resin is not particularly limited, and any of the cyanate resins known to be used may be, for example, a compound having an (Ar-OC≡N) structure in which Ar may be substituted or unsubstituted benzene or biphenyl. , naphthalene, phenol novolac, bisphenol A, bisphenol A novolac, bisphenol F, bisphenol F novolac or phenolphthalein. Further, the above Ar may be further bonded to a substituted or unsubstituted dicyclopentadienyl (DCPD).
根據本發明的一個實施例，氰酸酯樹脂較佳選自下列結構構成的組中的一種：
其中X1、X2各自獨立為至少一個R、Ar’、SO2或O；R是選自-C(CH3)2-、-CH(CH3)-、-CH2-及包含雙環戊二烯基的基團；Ar’是選自苯、聯苯、萘、酚醛、雙酚A、環芴、氫化雙酚A、雙酚A酚醛、雙酚F及雙酚F酚醛官能基；n為大於或等於1的整數；及Y為脂肪族官能基或芳香族官能基。 Wherein X 1 and X 2 are each independently at least one R, Ar', SO 2 or O; R is selected from -C(CH 3 ) 2 -, -CH(CH 3 )-, -CH 2 - and contains dicyclopentan a dienyl group; Ar' is selected from the group consisting of benzene, biphenyl, naphthalene, phenolic aldehyde, bisphenol A, cyclic hydrazine, hydrogenated bisphenol A, bisphenol A phenolic, bisphenol F, and bisphenol F phenolic functional group; An integer greater than or equal to 1; and Y is an aliphatic functional group or an aromatic functional group.
前述“脂肪族官能基”指C1-C30的烷類、烯類、炔類、環烷類、環烯類及其衍生物。前述“芳香族官能基”指C1-C14具有苯環的化合物，如苯、萘、蒽及其衍生物等。 The aforementioned "aliphatic functional group" means a C1-C30 alkane, an alkene, an alkyne, a cycloalkane, a cycloalkene, and a derivative thereof. The aforementioned "aromatic functional group" means a compound having a benzene ring of C1-C14, such as benzene, naphthalene, anthracene, and derivatives thereof.
所述氰酸酯樹脂的實例例如但不限於：商品名為Primaset PT-15、PT-30S、PT-60S、CT-90、BADCY、BA-100-10T、BA-200、BA-230S、BA-3000S、BTP-2500、BTP-6020S、DT-4000、DT-7000、Methylcy、ME-240S等由Lonza公司生產的氰酸酯樹脂。 Examples of the cyanate resin are, for example but not limited to, the trade names Primaset PT-15, PT-30S, PT-60S, CT-90, BADCY, BA-100-10T, BA-200, BA-230S, BA. -3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, Methylcy, ME-240S, etc. Cyanate resin produced by Lonza.
所述馬來醯亞胺樹脂並無特別限制，已知使用的馬來醯亞胺樹脂均可，該馬來醯亞胺樹脂較佳選自下列物質組中的至少一種：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)、間亞苯基雙馬來醯亞胺(m-phenylene bismaleimide)、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-亞苯基 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 maleic imine resin is not particularly limited, and any of the maleimide resins known to be used may be used. The maleimide resin is preferably selected from at least one of the group consisting of 4, 4'- Diphenylmethane of phenylmethane Bismaleimide), bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl Methyl bismaleimide (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide), 4-methyl-1,3-phenylene 4-methyl-1,3-phenylene bismaleimide and 1,6-bismaleimide-(2,2,4-trimethyl)hexane (1,6-bismaleimide- (2,2,4-trimethyl)hexane).
本發明所述的樹脂組合物還可選擇性包含阻燃劑(flame retardant)無機填充物(inorganic filler)、硬化促進劑(curing accelerator)、表面活性劑(surfactant)、矽烷偶合劑(silane coupling agent)、增韌劑(toughening agent)或溶劑(solvent)等添加物。 The resin composition of the present invention may further optionally comprise a flame retardant inorganic filler, a curing accelerator, a surfactant, a silane coupling agent. Additives such as toughening agents or solvents.
本發明所述的低介電樹脂組合物，可進一步包含阻燃劑，使其基板達到UL94 V-0難燃等級。阻燃劑並無特別限制，本發明所屬技術領域具有通常知識者所知的阻燃劑皆可使用。通常使用無鹵阻燃劑、含溴阻燃劑、含氮阻燃劑或含磷阻燃劑。 The low dielectric resin composition of the present invention may further comprise a flame retardant such that the substrate reaches a UL94 V-0 flame retardant rating. The flame retardant is not particularly limited, and any flame retardant known to those skilled in the art can be used. Halogen-free flame retardants, bromine-containing flame retardants, nitrogen-containing flame retardants or phosphorus-containing flame retardants are commonly used.
所述阻燃劑的實例例如但不限於：雙酚聯苯磷酸鹽(bisphenol diphenyl phosphate)、聚磷酸銨(ammonium poly phosphate)、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、磷酸三甲酯(trimethyl phosphate,TMP)、甲基膦酸二甲酯(dimethyl methyl phosphonate,DMMP)、間苯二酚雙二甲苯基磷酸鹽(resorcinol dixylenylphosphate,RDXP，如PX-200)、磷氮基化合物(磷腈(phosphazene)，如購自大塚化學的產品SPB-100、SPH-100、SPE-100或購自伏見製藥的產品FP-110,FP-300)、甲基膦酸間亞苯基酯(m-phenylene methylphosphonate,PMP)、聚磷酸三聚氰胺(melamine polyphosphate，如購自BASF公司的產品Melapur 200)、三聚氰胺氰尿酸酯(melamine cyanurate)、二乙基磷酸鋁(aluminum diethylphosphinate,OP-935，售自Clariant)及三-羥乙基異氰尿酸酯(tri-hydroxy ethyl isocyanurate)等。此外，無鹵阻燃劑也可為9,10-二氫-9-氧雜-10-磷菲-10-氧化物 (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,DOPO)、含DOPO酚樹脂(如DOPO-HQ、DOPO-PN、DOPO-BPN)、含DOPO環氧樹脂、含DOPO-HQ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。 Examples of such flame retardants are, for example but not limited to, bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone bis -(diphenyl phosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP) , tris (isopropyl chloride) phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol dixylenyl phosphate (resorcinol dixylenylphosphate) , RDXP, such as PX-200), phosphorus-nitrogen compound (phosphazene), such as SPB-100, SPH-100, SPE-100 from Otsuka Chemical or FP-110 from Fushi Pharmaceutical, FP -300), m-phenylene methylphosphonate (PMP), melamine polyphosphate (such as Melapur 200 from BASF), melamine cyanurate, Aluminum diethylphosphinate (OP-935, sold from Clariant) and tris-hydroxyethyl Cyanurate (tri-hydroxy ethyl isocyanurate) and the like. In addition, the halogen-free flame retardant can also be 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO), DOPO-containing phenolic resin (such as DOPO-HQ, DOPO-PN, DOPO-BPN), DOPO-containing epoxy resin, DOPO-containing HQ epoxy resin or the like, wherein DOPO-BPN may be a bisphenol phenolic compound such as DOPO-BPAN, DOPO-BPFN, DOPO-BPSN.
根據本發明的實施例，適用於本發明的樹脂組合物中的阻燃劑，較佳選自以下阻燃劑中的至少一種：乙基-雙(四溴苯鄰二甲醯亞胺)(如購自Albemarle的SAYTEX BT-93)及乙烷-1,2雙(五溴苯)(如購自Albemarle的SAYTEX 8010)，間苯二酚雙二甲苯基磷酸鹽(resorcinol dixylenylphosphate,RDXP，如PX-200)、磷氮基化合物(磷腈(phosphazene)，如購自大塚化學的產品SPB-100、SPH-100、SPE-100或購自伏見製藥的產品FP-110,FP-300)、甲基膦酸間亞苯基酯(m-phenylene methylphosphonate,PMP)、聚磷酸三聚氰胺(melamine polyphosphate，如購自BASF公司的產品Melapur 200)。 According to an embodiment of the present invention, the flame retardant suitable for use in the resin composition of the present invention is preferably selected from at least one of the following flame retardants: ethyl-bis(tetrabromophenenyldimethylimine) ( For example, SAYTEX BT-93 from Albemarle and ethane-1,2 bis(pentabromobenzene) (such as SAYTEX 8010 from Albemarle), resorcinol dixylenylphosphate (RDXP). PX-200), a phosphorus-nitrogen compound (phosphazene, such as SPB-100, SPH-100, SPE-100 or FP-110 from Fushi Pharmaceuticals, FP-300) M-phenylene methylphosphonate (PMP), melamine polyphosphate (such as Melapur 200 from BASF).
本發明所述的低介電樹脂組合物，可進一步添加無機填充物，其主要作用在於增加樹脂組合物的熱傳導性，改善其熱膨脹性及機械強度等特性，且無機填充物較佳係均勻分佈於該樹脂組合物中。 The low dielectric resin composition of the present invention may further contain an inorganic filler, the main function of which is to increase the thermal conductivity of the resin composition, to improve characteristics such as thermal expansion and mechanical strength, and the inorganic filler is preferably uniformly distributed. In the resin composition.
所述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、煆燒滑石、滑石、氮化矽、莫萊石、煆燒高嶺土、黏土、鹼式硫酸鎂晶須、莫萊石晶須、硫酸鋇、氫氧化鎂晶須、氧化鎂晶須、氧化鈣晶須、納米碳管、納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的粉體粒子。且無機填充物可為球型、纖維狀、板狀、粒狀、片狀或針須狀，並可選擇性經由矽烷偶合劑預處理。 The inorganic filler may comprise cerium oxide (molten state, non-molten state, porous or hollow type), aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, Aluminum lanthanum carbide, tantalum carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond powder, diamond powder, graphite, magnesium carbonate, potassium titanate, ceramic fiber, mica, boehmite (AlOOH), Zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, strontium talc, talc, tantalum nitride, mullite, calcined kaolin, clay, basic magnesium sulfate whisker, mullite whisker, barium sulfate, Magnesium hydroxide whiskers, magnesium oxide whiskers, calcium oxide whiskers, carbon nanotubes, nano-sized cerium oxide and related inorganic powders, or powder particles modified with an organic core outer shell as an insulator. The inorganic filler may be in the form of spheres, fibers, plates, granules, flakes or whiskers, and may be optionally pretreated via a decane coupling agent.
此外，本發明所述的樹脂組合物還可選擇性包含硬化促進劑、介面活性劑、矽烷偶合劑、增韌劑或溶劑等添加物。添加硬化促進劑的主要作用在於增加所述樹脂組合物的反應速率。添加介面活性劑的主要目的在於改善無機填充物在所述樹脂組合物中的均勻分散性，避免無機填充物凝聚。添加增韌劑的主要目的在於改善所述樹脂組合物的韌性。添加溶劑的主要目的在於改變所述樹脂組合物的固含量，並調整該樹脂組合物的黏度。 Further, the resin composition of the present invention may optionally further contain an additive such as a hardening accelerator, a surfactant, a decane coupling agent, a toughening agent or a solvent. The main function of adding a hardening accelerator is to increase the reaction rate of the resin composition. The main purpose of adding the surfactant is to improve the uniform dispersibility of the inorganic filler in the resin composition and to avoid aggregation of the inorganic filler. The main purpose of adding a toughening agent is to improve the toughness of the resin composition. The main purpose of adding a solvent is to change the solid content of the resin composition and adjust the viscosity of the resin composition.
所述硬化促進劑可包含路易士鹼或路易士酸等催化劑(catalyst)。其中，路易士鹼可包含咪唑(imidazole)、三氟化硼胺複合物、乙基三苯基氯化鏻(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,2E4MZ)、三苯基膦(triphenylphosphine,TPP)與4-二甲基胺基吡啶(4-dimethylaminopyridine,DMAP)中的一個或多個。路易士酸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 hardening accelerator may include 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 (2E4MZ), triphenylphosphine (TPP) and 4-dimethyl One or more of 4-dimethylaminopyridine (DMAP). The Lewis acid may include 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.
所述硬化促進劑較佳包含可產生自由基的過氧化物硬化促進劑，例如包括但不限於：過氧化二異丙苯(dicumylperoxide)、叔丁基過氧化苯甲酸酯(tert-butyl peroxybenzoate)及雙(叔丁基過氧異丙基)苯(di(tert-butylperoxyisopropyl)benzene,BIPB)。根據本發明的一個實施例，適用於本發明的樹脂組合物中的硬化促進劑較佳為2,5-二甲基-2,5-二(叔丁基過氧基)-3-己炔(2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3，購自日本油脂)。 The hardening accelerator preferably comprises a peroxide hardening accelerator which generates a radical, such as but not limited to: dicumylperoxide, tert-butyl peroxybenzoate And bis(tert-butylperoxyisopropyl)benzene (BIPB). According to an embodiment of the present invention, the hardening accelerator suitable for use in the resin composition of the present invention is preferably 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne. (2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, purchased from Japanese fats and oils).
所述矽烷偶合劑可包含矽烷化合物(silane)及矽氧烷化合物(siloxane)，依官能基種類又可分為胺基矽烷化合物(amino silane)、胺基矽氧烷化合物(amino siloxane)、環氧基矽烷化合物(epoxy silane)及環氧基矽氧烷化合物(epoxy siloxane)。 The decane coupling agent may include a silane compound and a siloxane compound, and may be further classified into an amino silane, an amino siloxane, and a ring depending on the functional group. An epoxy silane and an epoxy siloxane.
所述增韌劑選自：橡膠(rubber)樹脂、端羧基聚丁二烯丙烯腈(carboxyl-terminated butadiene acrylonitrile rubber,CTBN)、核殼聚合物(core-shell rubber)等添加物。 The toughening agent is selected from the group consisting of rubber resin, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), and core-shell rubber.
所述溶劑可包含甲醇、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、丙二醇甲基醚等溶劑或其混合溶劑。 The solvent may comprise methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxy ethyl A solvent such as an acid ester, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide or propylene glycol methyl ether or a mixed solvent thereof.
本發明的又一目的為提供一種半固化膠片(prepreg)，其具有高玻璃轉化溫度、低介電特性及高耐熱性等特性。據此，本發明所揭露的半固化膠片可包含補強材及前述樹脂組合物，其中該樹脂組合物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，補強材可為纖維材料、織布及不織布，如玻璃纖維布等，其可增加該半固化膠片機械強度。此外，該補強材可選擇性經由矽烷偶合劑進行預處理。 It is still another object of the present invention to provide a prepreg having characteristics such as high glass transition temperature, low dielectric properties, and high heat resistance. Accordingly, the prepreg film disclosed in the present invention may comprise a reinforcing material and the foregoing resin composition, wherein the resin composition is attached to the reinforcing material by impregnation or the like, and is heated to a semi-cured state by high temperature. 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 can increase the mechanical strength of the prepreg film. In addition, the reinforcing material can be selectively pretreated via a decane coupling agent.
前述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，其中樹脂組合物若含有溶劑，則該溶劑會於高溫加熱過程中揮發移除。 The prepreg film can be cured by high temperature heating or heating under high temperature and high pressure to form a cured film or a solid insulating layer. If the resin composition contains a solvent, the solvent is volatilized and removed during high temperature heating.
本發明的另一目的在提供一種樹脂膜(film)，其具有高玻璃轉化溫度、低介電特性及高耐熱性等特性。該樹脂膜包含上述的樹脂組合物。該樹脂膜可塗佈於PET膜(polyester film)、PI膜(polyimide film)上，或是塗佈於銅箔上(resin coated copper,RCC)再經過烘烤加熱而成。 Another object of the present invention is to provide a resin film having characteristics such as high glass transition temperature, low dielectric properties, and high heat resistance. This resin film contains the above resin composition. The resin film can be applied on a PET film, a polyimide film, or a resin coated copper (RCC) and then baked and heated.
本發明的又一目的為提供一種積層板(laminate)，如銅箔基板(copper clad laminate)，其具有高玻璃轉化溫度、低介電特性及高耐熱性等特性，且特別適用於高速度高頻率訊號傳輸電路板。據此，本發明提供一種積層板，其包含兩個或兩個以上金屬箔及至少一個絕緣層。其中，金屬箔例如為銅箔， 可進一步包含鋁、鎳、鉑、銀、金等至少一種金屬合金；絕緣層由前述半固化膠片或是樹脂膜於高溫高壓下固化而成，如將前述半固化膠片疊合於兩個金屬箔間且於高溫與高壓下進行壓合而成。 It is still another object of the present invention to provide a laminate, such as a copper clad laminate, which has high glass transition temperature, low dielectric properties, and high heat resistance, and is particularly suitable for high speed and high speed. Frequency signal transmission board. Accordingly, the present invention provides a laminate comprising two or more metal foils and at least one insulating layer. Wherein, the metal foil is, for example, a copper foil, Further comprising at least one metal alloy such as aluminum, nickel, platinum, silver, gold, etc.; the insulating layer is formed by curing the above-mentioned semi-cured film or resin film under high temperature and high pressure, such as laminating the aforementioned prepreg film on two metal foils It is formed by pressing at high temperature and high pressure.
本發明所述積層板進一步經過製作線路等過程加工後，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 laminated board of the present invention is further processed by a process such as a circuit to form a circuit board, and the circuit board is engaged with the electronic component and operated under a severe environment such as high temperature and high humidity without affecting the quality thereof.
據上，本發明的又一目的為提供一種印刷電路板，其具有高玻璃轉化溫度、低介電特性及高耐熱性等特性，且適用於高速度高頻率訊號傳輸。其中，該電路板包含至少一個前述積層板，且該電路板可由已知過程製作而成。 Accordingly, it is still another object of the present invention to provide a printed circuit board having high glass transition temperature, low dielectric properties, and high heat resistance, and is suitable for high speed and high frequency signal transmission. Wherein, the circuit board comprises at least one of the aforementioned laminated boards, and the circuit board can be fabricated by a known process.
為進一步揭露本發明，以使本發明所屬技術領域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。然而應注意的是，以下實施例僅用以對本發明做進一步的說明，並非用以限制本發明的實施範圍，且任何本發明所屬技術領域具有通常知識者在不違背本發明的精神下所完成的修飾及變化，均屬於本發明的範圍。 The invention will be further described in the following examples in order to explain the invention. However, it should be noted that the following examples are only intended to illustrate the invention and are not intended to limit the scope of the invention, and any one of ordinary skill in the art to which the invention pertains can be practiced without departing from the spirit of the invention. Modifications and variations are within the scope of the invention.
第1圖顯示具有羥基的雙環戊二烯酚醛樹脂(化合物A)的FTIR光譜圖。 Fig. 1 shows an FTIR spectrum of a dicyclopentadiene phenol resin (Compound A) having a hydroxyl group.
第2圖顯示雙環戊二烯-乙烯苄基苯醚樹脂(化合物B)的FTIR光譜圖。 Fig. 2 shows an FTIR spectrum of a dicyclopentadiene-vinylbenzyl phenyl ether resin (Compound B).
第3圖為具有羥基的雙環戊二烯酚醛樹脂(化合物A)及雙環戊二烯-乙烯苄基苯醚樹脂(化合物B)的FTIR光譜比較圖。 Fig. 3 is a FTIR spectrum comparison chart of a biscyclopentadiene phenol resin (compound A) having a hydroxyl group and a dicyclopentadiene-vinylbenzyl phenyl ether resin (compound B).
為充分瞭解本發明的目的、特徵及功效，茲藉由下述具體的實施例，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.
製造例1Manufacturing example 1
將80克(0.1莫爾)PD-9110(數均分子量Mn=800g/mol，如結構式13,n=1~10的正整數)與64克(0.42莫爾)4-氯-甲基苯乙烯(CMS-P)及100克甲苯投入反應槽裝置中，將溫度設定於50~80℃並開始攪拌反應6小時，加入16.8克(0.42莫爾)氫氧化鈉與11克(0.03莫爾)四丁基碘化胺並持續拌反應4小時，後以甲醇及蒸餾水清洗得到雙環戊二烯-乙烯苄基苯醚樹脂，產物為深褐色黏稠液態。 80 g (0.1 mole) of PD-9110 (number average molecular weight Mn = 800 g / mol, such as structural formula 13, n = 10 ~ positive integer) and 64 grams (0.42 mole) of 4-chloro-methylbenzene Ethylene (CMS-P) and 100 g of toluene were placed in a reaction tank apparatus, the temperature was set at 50-80 ° C and stirring reaction was started for 6 hours, and 16.8 g (0.42 mol) of sodium hydroxide and 11 g (0.03 mol) were added. The tetrabutyl iodide amine was continuously mixed for 4 hours, and then washed with methanol and distilled water to obtain a dicyclopentadiene-ethylenebenzyl phenyl ether resin, and the product was a dark brown viscous liquid.
式(13)，其中n=1~10的正整數。 Formula (13), wherein n = 1 to 10 is a positive integer.
上述合成的雙環戊二烯-乙烯苄基苯醚樹脂的檢測方法，可使用FTIR進行檢測，如第1圖、第2圖及第3圖所示。第1圖顯示具有羥基的雙環戊二烯酚醛樹脂(化合物A)的FTIR光譜圖，於3300~3400cm-1出現代表羥基(OH官能基)的波峰。而第2圖顯示雙環戊二烯-乙烯苄基苯醚樹脂(化合物B)的FTIR光譜圖，明顯可見第2圖中於3300~3400cm-1代表羥基(OH官能基)的波峰明顯減少至只剩微量，且於1600~1700cm-1出現代表乙烯官能基(碳碳雙鍵)的波峰，可證實本發明已合成雙環戊二烯-乙烯苄基苯醚樹脂。 The method for detecting the above-mentioned synthesized dicyclopentadiene-vinylbenzyl phenyl ether resin can be detected by FTIR as shown in Fig. 1, Fig. 2, and Fig. 3. Fig. 1 shows an FTIR spectrum of a biscyclopentadiene phenol resin (Compound A) having a hydroxyl group, and a peak representing a hydroxyl group (OH functional group) appears at 3300 to 3400 cm -1 . Figure 2 shows the FTIR spectrum of the dicyclopentadiene-vinylbenzyl phenyl ether resin (Compound B). It is obvious that the peak of the hydroxyl group (OH functional group) at 3300~3400 cm -1 in Figure 2 is significantly reduced to only A trace amount is present, and a peak representing an ethylene functional group (carbon-carbon double bond) appears at 1600 to 1700 cm -1 , and it has been confirmed that the present invention has synthesized a dicyclopentadiene-vinylbenzyl phenyl ether resin.
之後將製造例1合成的雙環戊二烯-乙烯苄基苯醚樹脂，用於實施例中，並與使用具有羥基的雙環戊二烯酚醛樹脂的比較例進行比較。 Thereafter, the dicyclopentadiene-vinylbenzyl phenyl ether resin synthesized in Production Example 1 was used in the examples and compared with a comparative example using a biscyclopentadiene phenol resin having a hydroxyl group.
實施例1至11(E1-E11)Embodiments 1 to 11 (E1-E11)
依表一所示的各組成份及比例，均勻混合形成各樹脂組合物。 Each of the resin compositions was uniformly mixed according to the respective components and ratios shown in Table 1.
比較例1至6(C1-C6)Comparative Examples 1 to 6 (C1-C6)
依表三所示的各組成份及比例，均勻混合形成各樹脂組合物。 Each of the resin compositions was uniformly mixed according to the respective components and ratios shown in Table 3.
上述製造例、實施例及比較例使用的化學品名如下。 The names of the chemicals used in the above production examples, examples and comparative examples are as follows.
PD-9110：具有羥基的雙環戊二烯酚醛樹脂，購自長春樹脂。 PD-9110: a dicyclopentadiene phenolic resin having a hydroxyl group, available from Changchun resin.
SA-90：雙官能末端羥基的雙酚A聚苯醚樹脂，購自Sabic公司。 SA-90: Bisphenol A polyphenylene ether resin having a difunctional terminal hydroxyl group available from Sabic Corporation.
SA-9000：末端甲基聚丙烯酸酯的雙酚A聚苯醚樹脂，購自Sabic公司。 SA-9000: Bisphenol A polyphenylene ether resin with terminal methyl polyacrylate available from Sabic.
OPE-2st：末端乙烯苄基的聯苯聚苯醚樹脂，購自三菱瓦斯化學。 OPE-2st: a biphenyl polyphenylene ether resin having a terminal vinyl group, purchased from Mitsubishi Gas Chemical.
Ricon257：苯乙烯-丁二烯-二乙烯基苯共聚物，購自Cray Valley公司。 Ricon 257: a styrene-butadiene-divinylbenzene copolymer available from Cray Valley.
H-1052：氫化二烯-丁二烯-苯乙烯共聚物，購自旭化成。 H-1052: hydrogenated diene-butadiene-styrene copolymer available from Asahi Kasei.
BA-230S：雙酚A氰酸酯樹脂，購自Lonza公司。 BA-230S: bisphenol A cyanate resin available from Lonza Corporation.
BTP-6020S：氰酸酯樹脂，購自Lonza公司。 BTP-6020S: Cyanate resin, available from Lonza Corporation.
C5、C9：石油樹脂，購自EASTMAN公司。 C5, C9: petroleum resin, purchased from EASTMAN.
BMI-2300：苯甲烷馬來醯亞胺，購自大和化成。 BMI-2300: Benzene methane quinone imine, purchased from Daiwa Chemical.
BMI-1700：4,4’-二苯甲烷雙馬來醯亞胺，購自大和化成。 BMI-1700: 4,4'-diphenylmethane bismaleimide, purchased from Daiwa Chemical.
25B：2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne(2,5-二甲基-2,5-二(叔丁基過氧基)-3-己炔)，購自日本油脂。 25B: 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne(2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne) , purchased from Japanese fats.
SPB-100：磷腈化合物，購自大塚化學。 SPB-100: phosphazene compound, purchased from Otsuka Chemical.
Saytex 8010：乙烷-1,2雙(五溴苯)，購自Albemarle公司。 Saytex 8010: Ethane-1,2 bis(pentabromobenzene) available from Albemarle.
PX-202：間苯二酚雙二甲苯基磷酸鹽，購自日本大八化學公司。 PX-202: resorcinol bis-xylyl phosphate, purchased from Japan Daiba Chemical Co., Ltd.
TAIC：三烯丙基異氰脲酸酯，購自Evonik Industries公司。 TAIC: triallyl isocyanurate available from Evonik Industries.
熔融態二氧化矽：Fused silica，購自矽比科。 Molten cerium oxide: Fused silica, purchased from the genus.
將上述實施例1至11及比較例1至6的樹脂組合物，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，使樹脂組合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 resin compositions of the above Examples 1 to 11 and Comparative Examples 1 to 6 were uniformly mixed in a stirred tank, placed in a dipping tank, and the glass fiber cloth was passed through the above-mentioned impregnation tank to adhere the resin composition to the resin composition. The glass fiber cloth is heated and baked into a semi-cured state to obtain a semi-cured film.
將上述分批製得的半固化膠片，取同一批的半固化膠片四張及兩張18μm銅箔，依銅箔、四片半固化膠片、銅箔的順序進行疊合，再於真空條件下經由210℃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的絕緣層。 The semi-cured film obtained in batches above is taken from the same batch of semi-cured film four sheets and two 18 μm copper foils, laminated in the order of copper foil, four-ply semi-cured film and copper foil, and then under vacuum conditions. A copper foil substrate was formed by pressing at 210 ° 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的不含銅基板做物性測量，物性測量項目包含：玻璃轉化溫度(Tg，DMA儀器(動態熱機械分析儀器)測量)、耐熱性(T288，TMA熱機械分析儀器測量，以含銅基板測量288℃下受熱不爆板的時間)、含銅基板浸錫測試(solder dip，S/D，288℃，10秒，測耐熱回數)、不含銅基板PCT(高壓鍋蒸煮試驗)吸濕後浸錫測試(pressure cooking at 121℃(在121℃高壓蒸煮)，3小時後，測solder dip 288℃(在288℃浸錫測試)，20秒觀看有無爆板)、銅箔與基板間拉力(peeling strength(剝離強度，以萬能拉力機測量)，P/S,half ounce copper foil(半盎司銅箔)，銅箔與基板間拉力越高越好)、介電常數(dielectric constant,Dk，Dk值越低越好，以AET微波誘電分析儀測量不含銅基板Dk值)、介電損耗(dissipation factor,Df，Df值越低越好，以AET微波誘電分析儀測量不含銅基板Df值)、耐燃性(flaming test(燃燒試驗)，UL94，其中等級排列V-0優於V-1優於V-2)。 The copper-containing substrate after etching the copper-containing foil substrate and the copper foil was separately measured for physical properties, and the physical property measurement items included: glass transition temperature (Tg, DMA instrument (dynamic thermomechanical analysis instrument) measurement), heat resistance (T288, TMA) Thermomechanical analysis instrument measurement, measuring the temperature of the non-explosive plate at 288 °C with a copper-containing substrate), copper-plated substrate immersion tin test (solder dip, S/D, 288 ° C, 10 seconds, measured heat-resistance count), excluding Copper substrate PCT (pressure cooker cooking test) moisture immersion tin test (pressure cooking at 121 ° C (at 121 ° C high pressure cooking), after 3 hours, measured solder dip 288 ° C (at 288 ° C immersion tin test), 20 seconds to see if there is Explosion), tensile strength between copper foil and substrate (peeling strength, measured by universal tension machine), P/S, half ounce copper foil (half ounce copper foil), the higher the tensile force between copper foil and substrate, the better) Dielectric constant (Dk, the lower the Dk value, the better, the Ak microwave inductive analyzer measures the Dk value of the copper-free substrate), the dielectric loss (dissipation factor, Df, the lower the Df value, the better, to AET Microwave induction analyzer measures Df value without copper substrate), flame resistance (flaming test) Test), UL94, wherein a ranking V-0 V-1 better than V-2).
其中實施例1至11的樹脂組合物製作的基板，其物性測量結果列表於表二中，比較例1至6的樹脂組合物製作的基板，其物性測量結果列於表四中。由表二及表四，綜合比較實施例1至11及比較例1至6可發現，本發明的低介電樹脂組合物藉由包含特定的組成份，以使可達到高玻璃轉化溫度、低介電特性(Df<0.006於10GHz量測頻率下)、高耐熱性以及良好難燃性等電路基板特性。比較例1至6的結果顯示所製作的基板的玻璃轉化溫度明顯較低，且介電特性及耐熱性也較差。 The physical property measurement results of the substrates prepared in the resin compositions of Examples 1 to 11 are shown in Table 2, and the physical property measurement results of the substrates prepared in the resin compositions of Comparative Examples 1 to 6 are shown in Table 4. From Tables 2 and 4, comparing Comparative Examples 1 to 11 and Comparative Examples 1 to 6, it can be found that the low dielectric resin composition of the present invention can achieve a high glass transition temperature and low by including a specific composition component. Circuit board characteristics such as dielectric characteristics (Df < 0.006 at a measurement frequency of 10 GHz), high heat resistance, and good flame retardancy. The results of Comparative Examples 1 to 6 show that the substrate produced has a significantly lower glass transition temperature and is inferior in dielectric properties and heat resistance.
由實施例1至3可發現，雙環戊二烯-乙烯苄基苯醚樹脂相對於乙烯苄基聚苯醚樹脂的含量提升，可提升基板的玻璃轉化溫度以及對銅箔拉力。 From Examples 1 to 3, it was found that the content of the dicyclopentadiene-vinylbenzyl phenyl ether resin was increased relative to the ethylene benzyl polyphenylene ether resin, and the glass transition temperature of the substrate and the pulling force against the copper foil were improved.
由實施例4及5可發現，加入苯乙烯-丁二烯共聚物，可進一步降低基板的介電損耗，得到更好的介電特性，此外額外加入馬來醯亞胺樹脂可進一步提升基板耐熱性(T288)。 It can be found from Examples 4 and 5 that the addition of the styrene-butadiene copolymer can further reduce the dielectric loss of the substrate and obtain better dielectric properties, and further addition of the maleic imine resin can further improve the heat resistance of the substrate. Sex (T288).
由實施例6及7可發現，加入石油樹脂C5或C9，並不影響基板特性，但在印刷電路板的多層板製作時，可有效改善樹脂填孔流動性。 It can be found from Examples 6 and 7 that the addition of the petroleum resin C5 or C9 does not affect the substrate characteristics, but the resin filling hole fluidity can be effectively improved when the multilayer board of the printed circuit board is produced.
由實施例8及9可發現，加入氰酸酯樹脂可進一步提升基板的對銅箔拉力及基板耐熱性(T288)。 It can be found from Examples 8 and 9 that the addition of the cyanate resin further enhances the copper foil pulling force and the substrate heat resistance (T288) of the substrate.
由實施例10可發現，加入適量的磷系阻燃劑可提升基板耐燃性，達到UL94 V-0的耐燃等級，由實施例11可發現，加入適量的溴系阻燃劑可提升基板耐燃性，也可達到UL94 V-0的耐燃等級。 It can be found from Example 10 that the addition of an appropriate amount of the phosphorus-based flame retardant can improve the flame resistance of the substrate and achieve the flame resistance of UL94 V-0. It can be found from Example 11 that the addition of an appropriate amount of the bromine-based flame retardant can improve the flame resistance of the substrate. It can also achieve the flame resistance rating of UL94 V-0.
比較實施例1至3及比較例1至3，可以發現雙環戊二烯-乙烯苄基苯醚樹脂與乙烯苄基聚苯醚樹脂組合所製作的基板，相較於具有羥基的雙環戊二烯-苯酚樹脂與聚苯醚樹脂組合所製作的基板，前者具有較好的耐熱性、介電特性及銅箔拉力。因為雙環戊二烯-乙烯苄基苯醚樹脂具有烯鍵反應官能基，可以與同為乙烯或者苯乙烯樹脂反應(如OPE-2st)；而羥基的雙環戊二烯-苯酚樹脂，難以與乙烯或者苯乙烯樹脂反應，導致基板特性不好。 Comparing Examples 1 to 3 and Comparative Examples 1 to 3, it was found that a substrate prepared by combining a dicyclopentadiene-vinylbenzyl phenyl ether resin and an ethylene benzyl polyphenylene ether resin is compared with a dicyclopentadiene having a hydroxyl group. A substrate produced by combining a phenol resin and a polyphenylene ether resin, the former having good heat resistance, dielectric properties, and copper foil tensile force. Because the biscyclopentadiene-vinylbenzyl phenyl ether resin has an ethylenic reaction functional group, it can react with the same ethylene or styrene resin (such as OPE-2st); while the hydroxy dicyclopentadiene-phenol resin is difficult to react with ethylene. Or the styrene resin reacts, resulting in poor substrate properties.
進一步比較實施例1與比較例1，可證實上述推論，即因具有羥基的雙環戊二烯-苯酚樹脂無法與乙烯苄基聚苯醚樹脂反應，致使基板耐熱性(T288及S/D)及介電特性不好。此外，比較例3的測試結果具有很差的Dk及Df值，因其使用具有羥基的雙環戊二烯-苯酚樹脂及末端羥基的聚苯醚樹脂，導致基板含羥基官能基含量上升，而使基板具有很差的Tg、介電特性及吸濕耐熱性。 Further comparing Example 1 with Comparative Example 1, it was confirmed that the above-mentioned inference that the dicyclopentadiene-phenol resin having a hydroxyl group could not react with the ethylene benzyl polyphenylene ether resin, resulting in heat resistance (T288 and S/D) of the substrate and The dielectric properties are not good. In addition, the test results of Comparative Example 3 have poor Dk and Df values because the use of a dicyclopentadiene-phenol resin having a hydroxyl group and a polyphenylene ether resin having a terminal hydroxyl group results in an increase in the content of the hydroxyl group-containing substrate of the substrate. The substrate has poor Tg, dielectric properties, and moisture absorption heat resistance.
因此，由上述實施例及比較例的測試結果，可以發現本發明的低介電樹脂組合物藉由包含特定的組成份，以使可達到高玻璃轉化溫度、低介電特性及高耐熱性等電路基板特性。 Therefore, from the test results of the above examples and comparative examples, it can be found that the low dielectric resin composition of the present invention can achieve high glass transition temperature, low dielectric properties, high heat resistance, etc. by including a specific composition component. Circuit board characteristics.
如上所述，本發明完全符合專利三要素：新穎性、進步性和產業利用性。就新穎性和進步性而言，本發明的低介電樹脂組合物藉由包含特定的組成份，從而可達到高玻璃轉化溫度、低介電特性及高耐熱性等電路基板特性；就產業利用性而言，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 elements of the patent: novelty, advancement, and industrial applicability. In terms of novelty and advancement, the low dielectric resin composition of the present invention can achieve circuit board characteristics such as high glass transition temperature, low dielectric property, and high heat resistance by including a specific composition component; Sexually, the products derived from the present invention can fully satisfy the needs of the current market.
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，該等實施例僅用於描繪本發明，而不應理解為限制本發明的範圍。應注意的是，凡是與該等實施例等效的變化與置換，均應設為涵蓋於本發明之範疇內。因此，本發明的保護範圍應當以申請專利範圍所界定的範圍為准。 The invention has been described above in terms of the preferred embodiments, and it is 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 all variations and permutations equivalent to the embodiments are intended to be within the scope of the invention. Therefore, the scope of protection of the present invention should be determined by the scope defined by the scope of the patent application.
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| TWI546319B (en) | 2015-09-25 | 2016-08-21 | 台光電子材料股份有限公司 | Phosphorus-containing polyphenylene oxide resin, its preparation method, prepolymer of phosphorus-containing polyphenylene oxide, resin composition, and its application |
| JP6675183B2 (en) * | 2015-11-30 | 2020-04-01 | ナミックス株式会社 | Thermosetting resin composition, thermosetting resin film, printed wiring board, and semiconductor device |
| CN106928446B (en) * | 2015-12-30 | 2019-08-13 | 台光电子材料(昆山)有限公司 | Modify polyphenylene oxide resin, preparation method and resin combination |
| TW201800437A (en) * | 2016-03-01 | 2018-01-01 | 新日鐵住金化學股份有限公司 | Poly(vinylbenzyl)ether compound, curable resin composition containing this and cured article |
| US10023672B2 (en) * | 2016-05-24 | 2018-07-17 | Elite Material Co., Ltd. | Polyphenylene oxide prepolymer, method of making the same, resin composition and product made therefrom |
| CN108148332A (en) * | 2016-12-02 | 2018-06-12 | 臻鼎科技股份有限公司 | The film and circuit board of resin combination and the application resin combination |
| WO2018105070A1 (en) | 2016-12-07 | 2018-06-14 | 日立化成株式会社 | Resin varnish, prepreg, laminate, and printed wiring board |
| CN109305894B (en) * | 2017-07-26 | 2022-07-19 | 郑州大学 | Low-polarity resin and preparation method and application thereof |
| CN109305896B (en) * | 2017-07-26 | 2022-07-19 | 郑州大学 | Low-polarity resin and preparation method and application thereof |
| KR102165971B1 (en) * | 2018-01-09 | 2020-10-15 | 미츠비시 가스 가가쿠 가부시키가이샤 | Resin composition, prepreg, metal foil coated laminate, resin composite sheet, and printed wiring board |
| WO2023027060A1 (en) * | 2021-08-27 | 2023-03-02 | 三菱瓦斯化学株式会社 | Resin composition, and curable film and laminated plate containing same |
| TWI785916B (en) * | 2021-12-03 | 2022-12-01 | 財團法人工業技術研究院 | Resin compound and resin composition containing the same |
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