1231729 玖、發明說明： 【發明所屬之技術領域】 本發明係關於提升印刷電路板性質的基板材料組成與製造方法， 特別是其具有高玻璃移轉溫度（glass transition temperature)、良好的抗 熱性與耐熱衝擊性及具有抗玻纖漏電（anti-Conductive Anodic Filament，anti-CAF)特性，並可應用於無鉛銲錫製程中。 【先前技術】 印刷電路板的基版通常都是使用多層複合的方式組合而成，包括 一熱固性(thermoset)的高分子材料和一適當的補強材料（reinf〇rcing material)。高分子單體（monomer)與聚合所需原料混合後，塗佈於補 強材料上，通常為一玻璃纖維布，再以加熱或其他方式加以固化作成 高分子基板。此高分子材料通常為一環氧樹脂（ep〇xy resin)材料。高 分子基板的機械強度與耐熱性都必須具有一定的水準以適用各種不 同的製程與操作環境。 近年來，由於環保的意識抬頭，對於電子產品的環保要求越來越 重視。對於印刷電路板的製程與材料也要求具有環保的做法。在一般 的銲錫製程中，由原來的錫鉛製程逐漸要求轉變為無鉛製程。因此， 知接製程的加工溫度亦由原來的22〇。〇升高至250〜270°C之間。對於 作為印刷電路板内層的基板之耐熱要求也相對必須提高。 壞氧樹脂的玻璃移轉溫度為一個顯示基板之熱性質與機械性質的 數值。所謂賴雜溫度係高分子由較硬的麵態變化成較軟的橡膠 1231729 態之溫度。在環氧樹脂的直鏈結構中含有軟鏈段（sof^segment)與硬鏈 段（hard-segemnt)。軟鏈段由環氧化合物所形成，而硬鏈段則由硬化劑 所形成。軟鏈段的長度愈短，硬化後環氧樹脂的玻璃移轉溫度愈高。 一般使用於FR-4的雙官能基環氧樹脂之玻璃移轉溫度大約為12(rc或 更高，玻璃移轉溫度愈高，在常溫下的機械性質愈好，亦表示其耐熱 性愈好，可抵抗較高的作業環境溫度。但是，玻璃移轉溫度如果太高 也會造成基板性質變脆，加工性變差。因此玻璃移轉溫度必須在某一 適當範圍内，基板的耐熱性與加工性則皆可兼顧。 【發明内容】 本發明係提升印刷電路板性質的基板材料組成與製造方法，其中 組成的重量比例為： (1) 含鹵素之環氧化合物（epoxy)l〇〇份，為一高分子聚合用單體。 (2) 二氰二胺（Dicyandiamide，Dicy)硬化劑 2·2〜3.5 份，以 100 份的含 齒素之$衣氧化合物為基準’作為聚合反應的聚合劑（curing agent)。 (3) 三級胺催化劑〇·〇ι〜ι·〇份，以100份的含鹵素之環氧化合物為基 準，為聚合反應的催化劑，可降低進行聚合反應的溫度。 (4) 酚醛環氧化合物(CresolNovolacEpoχy，CNE)3〜30份，以100份的 含鹵素之環氧化合物為基準，同樣作為聚合單體用。 本發明主要係藉由添加合適的無齒素之環氧化合物CNE於高分子 材料中，來提高高分子材料的玻璃移轉溫度、基板的抗熱性及耐熱衝 1231729 擊性及具有抗玻纖漏電特性。CNE為一具有三個聚合官能基的環氧化 口物，與聚合劑固化後形成一網狀結構。由於網狀高分子結構比直鏈 形結構之強度要來的高，因此添加CNEw環氧樹脂之玻璃移轉溫度提 升大約3〜lOt，基板的耐熱性、耐熱衝擊性與抗玻纖漏電特性亦獲得 改善。另一方面，由於整個高分子結構強度變高，基板的z軸膨脹係 數（coefficient of thermal expansion)也會變小。 CNE為一不含鹵素的環氧化合物，因此可降低基板的鹵素含量， 減少對環境的傷害影響。 環氧樹脂組成的混合方法為加入含齒素之環氧化合物於攪拌器 内，一邊攪拌一邊加入硬化劑，再加入催化劑，均勻混合後加入CNE , 最後利用稀釋劑調整漿料至適當粘度狀態。利用塗佈或含浸方式將環 氧樹脂漿料塗覆至補強材料上形成一高分子膠片（gel film)，經由加熱 聚合硬化形成一高分子基板。 茲配合下列實施例之詳細說明及專利申請範圍，將上述及本創作 之其他目的與優點詳述於後。 【實施方式】 本發明係提升印刷電路板性質的基板材料組成與製造方法，此材 料組成具有提高玻璃移轉溫度的功能、改善所製造出來的基板之抗熱 性、耐熱衝擊性、降低Z袖膨脹係數及抗玻纖漏電特性等優點。傳統 上，作為主要原料的環氧化合物都含有齒素成分。本發明的實施例中 即為含 >臭的ί哀氧化合物’其〉臭含為15〜25%，環氧當量（Ερ〇χγ 12317291231729 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a substrate material composition and manufacturing method for improving the properties of a printed circuit board, in particular, it has a high glass transition temperature, good heat resistance and Thermal shock resistance and anti-Conductive Anodic Filament (anti-CAF) characteristics, and can be used in lead-free solder process. [Prior art] The base plates of printed circuit boards are usually combined using a multilayer composite method, which includes a thermoset polymer material and an appropriate reinforcing material. After the polymer monomer (monomer) is mixed with the raw materials required for polymerization, it is coated on a reinforcing material, usually a glass fiber cloth, and then cured by heating or other methods to form a polymer substrate. The polymer material is usually an epoxy resin material. The mechanical strength and heat resistance of the high molecular substrate must have a certain level in order to be suitable for a variety of different processes and operating environments. In recent years, due to the rising awareness of environmental protection, more and more attention has been paid to the environmental protection requirements of electronic products. The process and materials of printed circuit boards also require environmentally friendly practices. In the general soldering process, the original tin-lead process is gradually required to change to a lead-free process. Therefore, it is known that the processing temperature of the joining process is also from the original 22 °. 〇Raise between 250 ~ 270 ° C. The heat resistance requirements of the substrate as the inner layer of the printed circuit board must be relatively increased. The glass transition temperature of a bad oxygen resin is a value showing the thermal and mechanical properties of a substrate. The so-called miscellaneous temperature is the temperature at which the polymer changes from a harder surface state to a softer rubber 1231729 state. The linear structure of epoxy resin contains soft segments (sof ^ segment) and hard segments (hard-segemnt). The soft segment is formed by an epoxy compound, and the hard segment is formed by a hardener. The shorter the length of the soft segment, the higher the glass transition temperature of the epoxy resin after hardening. Generally, the glass transition temperature of the bifunctional epoxy resin used in FR-4 is about 12 (rc or higher, the higher the glass transition temperature, the better the mechanical properties at room temperature, and the better its heat resistance. , Can resist higher working environment temperature. However, if the glass transition temperature is too high, it will cause the substrate to become brittle and processability worse. Therefore, the glass transition temperature must be within a certain range, and the substrate's heat resistance and The processability can be taken into account. [Summary of the Invention] The present invention is a substrate material composition and manufacturing method for improving the properties of a printed circuit board, wherein the composition weight ratio is: (1) 100 parts of halogen-containing epoxy compound (epoxy) Is a monomer for high-molecular polymerization. (2) Dicyandiamide (Dicy) hardener 2.2-2 to 3.5 parts, based on 100 parts of tooth-containing $ coating oxygen compounds as the reference ' Polymerization agent (curing agent) (3) tertiary amine catalyst 〇〇〇〜〜ι · 〇 part, based on 100 parts of halogen-containing epoxy compounds as a catalyst for the polymerization reaction, can reduce the temperature of the polymerization reaction (4) Phenolic ring 3 to 30 parts of compound (CresolNovolacEpoxy, CNE), based on 100 parts of halogen-containing epoxy compounds, also used as polymerized monomers. The present invention is mainly based on the addition of suitable toothless element epoxy compounds CNE In molecular materials, to improve the glass transition temperature of polymer materials, heat resistance and thermal shock resistance of the substrate 1231729 and resistance to glass fiber leakage. CNE is an epoxide with three polymerized functional groups, and polymerized After the agent is cured, a network structure is formed. Since the network polymer structure has a higher strength than the linear structure, the glass transition temperature of the CNEw epoxy resin is increased by about 3 ~ 10t, and the heat resistance and heat resistance of the substrate are increased. The impact resistance and the resistance to glass fiber leakage have also been improved. On the other hand, as the strength of the entire polymer structure becomes higher, the coefficient of thermal expansion of the substrate becomes smaller. CNE is a halogen-free ring Oxygen compounds, which can reduce the halogen content of the substrate and reduce the impact on the environment. The epoxy resin composition is mixed by adding an epoxy compound containing tooth element to In the mixer, add the hardener while stirring, then add the catalyst, add CNE after uniform mixing, and finally adjust the slurry to a suitable viscosity state with a diluent. Apply the epoxy resin slurry to the reinforcing material by coating or impregnation. A polymer film (gel film) is formed thereon, and a polymer substrate is formed by heat polymerization and hardening. With the detailed description of the following embodiments and the scope of patent applications, the above and other objects and advantages of this creation will be detailed later. Embodiments The present invention relates to a substrate material composition and a manufacturing method for improving the properties of a printed circuit board. The material composition has the function of increasing the glass transition temperature, improving the heat resistance, thermal shock resistance of the manufactured substrate, and reducing the Z-sleeve expansion coefficient. And anti-glass fiber leakage characteristics. Traditionally, epoxy compounds, which are the main raw materials, have a tooth element component. In the embodiment of the present invention, the compound contains a odorous oxal compound, which has an odor content of 15 to 25% and an epoxy equivalent (Eρ〇χγ 1231729).
Equivalent Weight，EEW)為 250〜750g/eq，水解氯含量小於 500ppm， 使用量為100份。環氧化合物中含有溴的成分，其作用為當基板暴露 於火焰與高溫時，會放出溴元素以延遲燃燒形成難燃物，因而使基板 具有良好的焊接耐熱性及防止氣泡產生。當環氧當量高於75〇g/eq時， 環氧樹脂漿料與玻璃纖維布的濕潤狀態會變差，環氧樹脂無法與補強 材料作一緊密結合。當環氧當量低於250g/eq時，高分子膠片會有流膠 (resin flow)過大的現象，作成基板後的尺寸變異性會升高。水解氣含量 若大於500ppm時，則會影響聚合硬化反應之進行。 與環氧化合物進行聚合反應的硬化劑為二氰二胺硬化劑。二氰二 胺的分子量為83g/moL，其分子結構中含有兩個一級胺、一個二級胺與 一個三級胺。二氰二胺在室溫為一穩定物質，不會進行反應，其進行 反應溫度須在170°C以上，因此可長時間儲放。二氰二胺的反應使用量 為每100份含溴環氧化合物添加2.2〜3.5份，若低於2.2份，則聚合反 應的硬化程度不足，若高於3·5份，則會出現硬化劑析出之現象。 聚合反應的催化劑為一種三級胺催化劑，如二甲基咪嗤 (2-Methyl-Imidazole ’ 2MI)、二乙基四甲基咪嗤 (2-Ethyl-4-Methyl-Imidazole ， 2E4MI)、二苯基味吨 (2-Phenyl-Imidazole，2PI)及二甲基苯基胺（Benyl Di-Methyl-Amine， BDMA)。三級胺催化劑的作用在降低聚合的反應溫度，從原來的i7(y>c 降低至120°C左右即發生聚合反應。三級胺的使用量為每100份含溴環 氧化合物添加0.01〜1.0份，若低於0.01份，則反應速率太慢，無催化 1231729 劑的效果，若高於1·〇份，則反應速率太快，影響製程。 CNE為不含齒素的環氧化合物，其環氧當量（Ep〇Xy EqUivaient Weight ’ EEW)為100〜5〇〇g/eq，水解氣含量小於5〇〇ppm。CN£的使用 置為每100份含溴環氧化合物添加3〜3〇份，若低於3份，則顯現不出 添加CNE的效果，若高於30份，則會形成高分子膠片流膠過大及玻 璃移轉溫度過高，造成基板性質變脆的現象。 第一圖為添加CNE於環氧樹脂中的傅立葉轉換紅外光圖譜 (FTIR)，其中CNE之特性吸收峰為··環氧基915cm-1，苯環1600、1580、 1500、1480cm-1，甲基3000cm-1 及醚基 1130cm-1。 上述的材料必須以稀釋劑均勻分散並調整環氧樹脂漿料的粘度， 才可塗佈於補強材料上。本發明的實施例之補強材料皆為玻璃纖維 布。稀釋劑可為丙酮（acet〇ne)、曱乙酮（Methyl Ethyl Ketone，MEK)、 % 己酮（cyclohexanol)、一 甲基氧二丙醇（Propylene-glycol Methyl-ether»PM) ^ 一 甲基氧二丙醇甲 δ旨（Propylene-glycol Methyl-ether Acteate，PMA)與二甲基曱酿胺（DimethylFormamide , DMF) 〇 本發明的實施例皆利用滚筒塗佈機將漿料塗佈於玻璃纖維布上， 硬化乾燥後即為一高分子基板。玻璃移轉溫度的測試儀器分為兩種， 一種為微分掃描熱卡儀（Differential Scanning Calorimeter，DSC)，另一 為熱機械分析儀（Thermal Mechanical Analyzer，TMA)，熱機械分析儀 並可同時量測Z轴膨脹係數。玻璃移轉溫度的測試規範為電子電路互 1231729 聯與封裝學會（The Institute for Interconnecting and Packaging Electronic Circuits，IPC)之 IPC_TM-650.2.425C 及 24C 號檢測方法。Z 轴膨脹係 數的測試規範為IPC-TM-650.2.4.41號檢測方法。耐熱性的測試規範為 ΙΡ(ΜΓΜ-650·2·4·24·1號檢測方法。熱衝擊試驗為將試片放入2大氣壓、 121 C之高溫高濕的環境下1或2小時，再放入288°C的錫爐中20秒後 拉起，重複此浸入拉起之動作5次。抗玻纖漏電特性測試是以日本工 業標準（Japan Industrial Standard，JIS)之 JIS-Z3284 的規範。測試方法 為基板在溫度85°C，相對溼度為85%的環境下，通入100V之直流電， 檢測在孔對孔（孔距〇.7mm，孔徑0.3mm)及線對線（線長1〇〇/zm，線 距100/zm)測試項目的電阻值小於1〇8 〇hm之時間。 實施例一： 將100份的環氧樹脂（Dow 539)、2·6份的二氰二胺硬化劑及〇 〇8 份的二甲基咪嗤催化劑，於室溫下使用攪拌器混合6〇分鐘，再加入cne 10份及稀釋劑（Acetone) 8份。將上述的材料於室溫下攪拌12〇分鐘， 利用滾筒塗佈機將漿料塗佈於細玻璃纖維布上，乾燥後即為一基板。 實施例一之基板的熱性質檢測數據如表一所示，對照組為不含 CNE之基板。 表一，實施例一之基板的熱性質檢測結果。 項目 實驗組（添加CNE) 對照組（未添加CNE) 玻璃移轉 溫度-DSC (°C) 142 ----—_______ 132 1231729 玻璃移轉 溫度-TMA (°C) 135 126 Z軸膨脹係數 (25 〜260〇C) (%) 4.0 4.5 耐熱性 (min) 23 14 熱衝擊試驗 (1小時） PASS PASS 熱衝擊試驗 (2小時） PASS FAIL 抗玻纖漏電 測試 (小時） 孔對孔 >2000 >1000 ------ 線對線 >2000 >1000 由表一可知，添加適當的CNE ’玻璃移轉溫度提高大約l〇°C ’ Z 轴膨脹係數降低0.5% ’对熱性、对衝擊性及抗玻纖漏電特性都獲得改 善0 實施例二： 將100份的環氧樹脂（AER4100)、3.1份的二氰二胺硬化劑及0.15 份的二甲基咪唑催化劑，於室溫下使用攪拌器混合60分鐘，再加入CNE 20份及稀釋劑（Acetone) 13份。將上述的材料於室溫下授拌12〇分鐘， 利用滾筒塗佈機將漿料塗佈於玻璃纖維布上，乾燥後即為一基板。 實施例二之基板的熱性質檢測數據如表二所示，對照組為不含 CNE之基板。 表二，實施例二之基板的熱性質檢測結果。 實驗組（添加CNE) 對照組（未添加CNE) 12 1231729 玻璃移轉 溫度-DSC (°C) 178 170 玻璃移轉 溫度-TMA (°C) 171 165 z轴膨脹係數 (25 〜260〇C) (%) 2.8 3.0 耐熱性 (min) 18 7 熱衝擊試驗 (1小時） PASS FAIL 熱衝擊試驗 (2小時） PASS FAIL 抗玻纖漏電 測試 (小時） 孔對孔 >2000 >1000 線對線 >2000 >1000 由表二可知，添加適當的CNE，玻璃移轉溫度提高大約7°C ’ Z轴 膨脹係數降低0.2%，耐熱性、耐衝擊性及抗玻纖漏電特性都獲得改善。 由本發明之實施利可知，高分子基板的玻璃移轉溫度與環氧化合 物的種類有關係，CNE添加量之多寡關係玻璃移轉溫度可提升多少及 耐熱性質的改善，並提高抗玻纖漏電特性。添加CNE確實可改善基板 的耐熱性質。CNE添加量過多會導致基板性質變脆，太少則耐熱衝擊 性無法獲得滿意改善。 —唯’以上所述者，僅為本創作之較佳實施例而已，當不能以此限 疋本創作實施之相。即大凡依本創作中請料_所作之均 與修飾’皆應仍屬本創作專利涵蓋之範圍内 【圖式簡單說明】 13 1231729 第一圖為添加CNE於環氧樹脂中的傅力葉轉換紅外光圖譜。Equivalent Weight (EEW) is 250 ~ 750g / eq, hydrolyzed chlorine content is less than 500ppm, and the amount used is 100 parts. The epoxy compound contains a bromine component. When the substrate is exposed to flame and high temperature, it will release bromine element to delay combustion and form a flame retardant. Therefore, the substrate has good soldering heat resistance and prevents bubbles from being generated. When the epoxy equivalent is higher than 75.0 g / eq, the wet state of the epoxy resin slurry and the glass fiber cloth will be deteriorated, and the epoxy resin cannot be closely combined with the reinforcing material. When the epoxy equivalent is less than 250 g / eq, the polymer film may have excessive resin flow, and the dimensional variability after forming a substrate may increase. If the content of hydrolysis gas is more than 500 ppm, it will affect the progress of the polymerization and hardening reaction. A hardening agent which polymerizes with an epoxy compound is a dicyandiamine hardening agent. Dicyandiamine has a molecular weight of 83 g / moL and its molecular structure contains two primary amines, one secondary amine and one tertiary amine. Dicyandiamine is a stable substance at room temperature and will not react. The reaction temperature must be above 170 ° C, so it can be stored for a long time. The amount of dicyandiamine used is 2.2 to 3.5 parts per 100 parts of the bromine-containing epoxy compound. If it is less than 2.2 parts, the degree of hardening of the polymerization reaction is insufficient. If it is higher than 3.5 parts, a hardener will appear. The phenomenon of precipitation. The polymerization catalyst is a tertiary amine catalyst, such as 2-Methyl-Imidazole '2MI, 2-Ethyl-4-Methyl-Imidazole, 2E4MI, Phenyl-Imidazole (2PI) and Benyl Di-Methyl-Amine (BDMA). The role of the tertiary amine catalyst is to reduce the polymerization reaction temperature. From the original i7 (y &c; c) to about 120 ° C, the polymerization reaction occurs. The amount of tertiary amine used is 0.01 to 100 parts of bromine-containing epoxy compound 1.0 part, if it is less than 0.01 part, the reaction rate is too slow, and there is no effect of catalyzing 1231729 agent; if it is more than 1.0 part, the reaction rate is too fast, which affects the process. Its epoxy equivalent (EpOxy EqUivaient Weight 'EEW) is 100 ~ 500g / eq, and the content of hydrolyzed gas is less than 5000ppm. The use of CN £ is set to add 3 ~ 3 per 100 parts of bromine-containing epoxy compound 〇part, if it is less than 3 parts, the effect of adding CNE will not appear, and if it is more than 30 parts, the polymer film will flow too much and the glass transition temperature will be too high, which will cause the substrate to become brittle. A picture shows the Fourier transform infrared spectroscopy (FTIR) of adding CNE to epoxy resin. Among them, the characteristic absorption peaks of CNE are: epoxy 915cm-1, benzene ring 1600, 1580, 1500, 1480cm-1, methyl 3000cm-1 and ether group 1130cm-1. The above materials must be evenly dispersed and adjusted with diluent. The viscosity of the epoxy resin slurry can be applied to the reinforcing material. The reinforcing materials in the embodiments of the present invention are all glass fiber cloths. The diluent can be acetone, Methyl Ethyl Ketone, MEK),% cyclohexanol, Propylene-glycol Methyl-ether »PM) ^ Propylene-glycol Methyl-ether Acteate (PMA) and DimethylFormamide (DMF) 〇 In the examples of the present invention, the slurry is coated on a glass fiber cloth by a roller coater, and after curing and drying, it is a polymer substrate. Testing of glass transition temperature There are two types of instruments, one is a Differential Scanning Calorimeter (DSC), and the other is a Thermal Mechanical Analyzer (TMA). The thermomechanical analyzer can also measure the Z-axis expansion coefficient at the same time. The test specification for the glass transition temperature is IPC_TM-650.2.425C and 24C of the Institute for Interconnecting and Packaging Electronic Circuits (IPC) 1231729. Test specification number .Z axis expansion coefficient of IPC-TM-650.2.4.41 number detection. The test specification for heat resistance is IP (ΜΓΜ-650 · 2 · 4 · 24 · 1 test method. The thermal shock test is to place the test piece in a high temperature and high humidity environment of 2 atmospheres and 121 C for 1 or 2 hours, and then Put it in a tin furnace at 288 ° C for 20 seconds and pull it up. Repeat the immersion and pull-up operation 5 times. The glass fiber leakage resistance test is based on the JIS-Z3284 of Japan Industrial Standard (JIS). The test method is that the substrate is under a temperature of 85 ° C and a relative humidity of 85%, and a direct current of 100V is passed. The hole-to-hole (hole distance 0.7mm, hole diameter 0.3mm) and wire-to-wire (wire length 1) are tested. 〇 / zm, line spacing 100 / zm) The time when the resistance value of the test item is less than 108 hm. Example 1: 100 parts of epoxy resin (Dow 539) and 2. 6 parts of dicyandiamine are hardened Agent and 008 parts of dimethyl imidium catalyst, mixed with a stirrer at room temperature for 60 minutes, and then added 10 parts of cne and 8 parts of diluent (Acetone). The above materials were stirred at room temperature for 12 〇 minutes, the slurry was coated on a fine glass fiber cloth by a roller coater, and it was a substrate after drying. The thermal property test data is shown in Table 1. The control group is a substrate without CNE. Table 1. The thermal property test results of the substrate in Example 1. Project experiment group (with CNE added) Control group (without CNE added) Glass transfer Temperature-DSC (° C) 142 --------______ 132 1231729 Glass transition temperature-TMA (° C) 135 126 Z-axis expansion coefficient (25 to 260 ° C) (%) 4.0 4.5 Heat resistance (min) 23 14 Thermal shock test (1 hour) PASS PASS Thermal shock test (2 hours) PASS FAIL Resistance to glass fiber leakage test (hours) Hole-to-hole > 2000 > 1000 ------ Wire-to-wire > 2000 > 1000 It can be known from Table 1 that with the addition of appropriate CNE, the glass transition temperature is increased by about 10 ° C, and the Z-axis expansion coefficient is reduced by 0.5%. The thermal resistance, impact resistance, and resistance to glass fiber leakage are improved. Example 2: 100 parts of epoxy resin (AER4100), 3.1 parts of dicyandiamine hardener and 0.15 parts of dimethylimidazole catalyst were mixed at room temperature using a stirrer for 60 minutes, and then 20 parts of CNE and a diluent ( Acetone) 13. Serving the above materials for 12 minutes at room temperature, using a roller The slurry cloth coated on a glass fiber cloth, drying a substrate after thermal properties of the detected data according to a second embodiment of the substrate as shown in Table, in the control group as two of the CNE-free substrate. Table 2. Test results of thermal properties of the substrate in Example 2. Experimental group (with CNE added) Control group (without CNE added) 12 1231729 Glass transition temperature-DSC (° C) 178 170 Glass transition temperature-TMA (° C) 171 165 Z-axis expansion coefficient (25 to 260 ° C) (%) 2.8 3.0 Heat resistance (min) 18 7 Thermal shock test (1 hour) PASS FAIL Thermal shock test (2 hours) PASS FAIL Resistance to glass fiber leakage test (hours) Hole to hole > 2000 > 1000 Wire to wire > 2000 > 1000 As can be seen from Table 2, with the addition of appropriate CNE, the glass transition temperature is increased by about 7 ° C. The Z-axis expansion coefficient is reduced by 0.2%, and the heat resistance, impact resistance, and resistance to glass fiber leakage are improved. According to the implementation of the present invention, it can be known that the glass transition temperature of the polymer substrate is related to the type of epoxy compound, and the amount of CNE added depends on how much the glass transition temperature can be improved and the heat resistance improved, and the glass fiber leakage resistance characteristics are improved. . The addition of CNE does improve the thermal resistance of the substrate. Too much CNE will cause the substrate to become brittle, and too little CNE will not provide satisfactory improvement in thermal shock resistance. —The above is only the preferred embodiment of this creation. It should not be limited to the implementation of this creation. That is to say, all the materials and modifications made by Dafan according to this creation should still fall within the scope of this creation patent. [Schematic description] 13 1231729 The first picture is the Fourier transform infrared light with the addition of CNE in epoxy resin. Atlas.