1283237 玖、發明說明： 【發明所屬之技術領域】 本發明係關於低介電常數玻璃纖維，特別是關於用於 高密度印刷線路板補強材料，且具有良好纖維成型性的低 介電常數玻璃纖維。 【先前技術】1283237 玖, DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to low dielectric constant glass fibers, and more particularly to low dielectric constant glass fibers for high density printed wiring board reinforcing materials having good fiber formability. . [Prior Art]
資訊、通訊、以及消費性電子（Computer，Information, communication, and consumer electronics (Computer,
Communication, and Consumer Electronics，3C)無疑地已 成為全球工業中成長最快速的產業。3C產業中，印刷線路 板（Printed Circuit Board， PCB)扮演著極為重要的角 色，同時也是不可或缺的重要零組件。PCB主要是被應用 於提供電子零組件安裝與插接時主要的支撐體，並藉由電 路設計，達成中繼傳輸的目的。Communication, and Consumer Electronics, 3C) has undoubtedly become the fastest growing industry in the global industry. In the 3C industry, Printed Circuit Board (PCB) plays an extremely important role and is also an indispensable important component. The PCB is mainly used to provide the main support for the installation and plugging of electronic components, and to achieve relay transmission by circuit design.
PC B製作過程中，藉著電路設計將連接電子零組件之 線路繪製成配線圖形，再將此圖案製作成膠片，然後在銅 箔層板上經過圖形顯像、鑽孔、電鍍、蝕刻等加工過程， 如此製作成所需的成品。當PCB安裝與插接電子零組件 後，即可應用在電腦主機板、顯示卡、通訊板等產品中。 PCB主要由絕緣層和導電層這兩部分所組成。絕緣層是將 補強材料如玻璃纖維布在粘結材料樹脂溶液中浸潰、烘乾 6 1283237 後層壓而成。導電層則是將銅箔壓製在樹脂層上而成。 玻璃纖維之產品若依形態而區分，有玻璃紗（G 1 a s s Yarn) ，玻璃布（Glass Cloth) ，紗束（Roving) ’ 編紗束（Woven Roving)，切股（Chopped Strand)，切股 範（Chopped Strand Mat)，表面薦（Fiberglass Tissue)， 連續鼓（Continuous Strand Mat)或玻璃纖維粉（Milled Fiber )等。若依玻璃組成與物化性質而區分，則有無鹼玻 璃（E玻璃）、耐酸/鹼玻璃、低介電常數玻璃與高強度玻 璃等。其中應用在前述PCB之玻璃纖維布，而為業界所熟 知者是屬於無鹼玻璃之E玻璃。 在討論E玻璃所產生的問題前，必須先了解造成能量 損耗的因素。在一定頻率的交流電壓作用下，玻璃會因極 化或吸收，使交流電中的部份能量轉變為熱量而散失此 外，玻璃產生上述能量損耗的機制包括電導損失、鬆弛損 失、結構損失、和共振損失等。而此能量損耗的方程式為： Q = UItan5 其中，Q :能量損耗，U :電壓，I :電流，tan5:介電正 切。由此方程式可知，能量損耗與玻璃的介電正切成比例。 另外，當PCB信號高密度化，即線寬與間距逐漸縮小之際， 間接也造成了連線電阻以及連線間電容的增加，因此產生 了阻容遲滯（RC-delay)效應。阻容遲滯在元件性能上有許 多負面影響，諸如使得訊號傳遞速度降低、傳輸噪音（cross talknoise)增加及功率消耗上升等。其中，阻容遲滯所造 7 1283237 成的訊號傳遞速度的降低，是影響PCB品質降低的主要因 素之一。解決阻容遲滯最直接的方法是降低電阻與電容， 所以，目前研究方向朝向藉著降低介電常數，進而降低電 容，同時避免產生阻容遲滯。 然而，由於E玻璃在室溫下，頻率1MHz時，其介電 常數為6.7，而介電正切為12 X 1(Γ4。所以，基於此過高 的介電常數和介電正切，若將Ε玻璃作為PCB之玻璃纖維 布時，不但會產生會過大的能量損耗，同時也無法避免阻 容遲滯的發生，所以，這對信號高密度化與高速處理化的 要求顯有不足。因此，業界無不期待比Ε玻璃具有更低的 介電常數與介電正玻璃的誕生。 目前，市場上已出現一種D玻璃，其在室溫下，頻率 1MHz時，其介電常數為4.3，而介電正切為10χ1(Γ4。雖 然，此D玻璃比起Ε玻璃已確實具有更低的介電常數與介 電正玻璃，但是，由於D玻璃高溫熔解困難，容易在抽絲 時出現熔解不完全的筋紋或氣泡，造成纖維斷裂或缺陷， 使抽絲纖維成型效率降低。再者，D玻璃抽絲溫度過高（抽 絲溫度一般定義為玻璃膏黏度為103poise時的溫度），達 1 4 1 0 °C ，不但使抽絲作業困難，也同樣減短了抽絲裝置的 壽命。所以，D玻璃仍非業界真正所期待的玻璃。 在進一步討論其他先前技術的缺陷前，須先簡述玻璃 8 1283237 製造的過程。玻璃纖維之製造涉及玻璃的熔解、紡絲與加 工等三個工程。在紡絲工程中的抽絲階段，一般係透過白 金或其合金所製成的抽絲盒（Bushing)將玻璃膏抽成纖維。 此外，玻璃液相溫度（Liquid temperature， Tl)則是影 響抽絲階段成敗的主要因素之一。TL之定義為玻璃能產生 失透或結晶之最高溫度，意即，當玻璃溫度高於Tl時，即 使經長時間之熱處理，也不致產生失透或結晶現象。反之， 當玻璃溫度長時間低於Tl，即有可能產生失透或結晶現 象，使抽絲纖維成型效率降低，玻璃品質劣化。 $In the process of PC B production, the circuit connecting the electronic components is drawn into a wiring pattern by circuit design, and then the pattern is made into a film, and then subjected to graphic development, drilling, plating, etching, etc. on the copper foil layer board. The process is thus made into the desired finished product. When the PCB is installed and plugged in electronic components, it can be applied to products such as computer motherboards, display cards, and communication boards. The PCB is mainly composed of two parts, an insulating layer and a conductive layer. The insulating layer is formed by laminating a reinforcing material such as a glass fiber cloth in a binder resin solution and drying the film 6 1283237. The conductive layer is formed by pressing a copper foil on a resin layer. Glass fiber products are distinguished by form, such as glass yarn (G 1 ass Yarn), glass cloth (Glass Cloth), yarn bundle (Roving), Woven Roving, Chopped Strand, and stock cutting. Chopped Strand Mat, Fiberglass Tissue, Continuous Strand Mat or Milled Fiber. If it is distinguished by the composition of the glass and the physical and chemical properties, there are alkali-free glass (E glass), acid/alkali glass, low dielectric constant glass, and high-strength glass. Among them, the glass fiber cloth used in the aforementioned PCB is known as E glass which is an alkali-free glass. Before discussing the problems caused by E-glass, it is necessary to understand the factors that cause energy loss. Under the action of a certain frequency of alternating voltage, the glass will be converted into heat by the polarization or absorption, and the mechanism of the above energy loss including the conductance loss, relaxation loss, structural loss, and resonance Loss and so on. The equation for this energy loss is: Q = UItan5 where Q: energy loss, U: voltage, I: current, tan5: dielectric tangent. From this equation, the energy loss is proportional to the dielectric tangent of the glass. In addition, when the PCB signal is densified, that is, when the line width and the pitch are gradually reduced, the connection resistance and the capacitance between the lines are indirectly increased, so that the RC-delay effect is generated. Resistor delay has many negative effects on component performance, such as reduced signal transmission speed, increased cross talk noise, and increased power consumption. Among them, the reduction of the signal transmission speed of 7 1283237 caused by the RC is one of the main factors affecting the degradation of PCB quality. The most straightforward way to solve the lag is to reduce the resistance and capacitance. Therefore, the current research direction is to reduce the dielectric constant, thereby reducing the capacitance while avoiding the RC. However, since E glass has a dielectric constant of 6.7 at a frequency of 1 MHz at room temperature and a dielectric tangent of 12 X 1 (Γ4, therefore, based on this excessive dielectric constant and dielectric tangent, if Ε When glass is used as the glass fiber cloth of PCB, not only will there be excessive energy loss, but also the occurrence of resistance delay hysteresis cannot be avoided. Therefore, the requirements for high-density and high-speed processing of signals are insufficient. It is not expected to have a lower dielectric constant and a dielectric positive glass than bismuth glass. At present, there is a D glass on the market which has a dielectric constant of 4.3 at room temperature and a frequency of 1 MHz. The tangent is 10χ1 (Γ4. Although this D glass does have a lower dielectric constant and dielectric positive glass than the bismuth glass, it is easy to melt incompletely during the spinning because of the difficulty in melting the D glass at high temperature. Patterns or bubbles, causing fiber breakage or defects, reducing the forming efficiency of the drawn fiber. Moreover, the D glass drawing temperature is too high (the spinning temperature is generally defined as the temperature at which the glass paste viscosity is 103 poise), up to 1 4 1 0 °C, However, it is difficult to make the spinning operation, and the life of the spinning device is also shortened. Therefore, D glass is still not the glass that the industry really expects. Before further discussing the defects of other prior art, the glass 8 1283237 must be briefly described. Process. The manufacture of glass fiber involves three projects of melting, spinning and processing of glass. In the spinning stage of spinning engineering, the glass paste is generally made by using a platinum box or its alloy. In addition, the liquid temperature (Tl) is one of the main factors affecting the success or failure of the spinning stage. TL is defined as the highest temperature at which glass can devitrify or crystallize, that is, when the glass temperature When it is higher than Tl, even if it is heat treated for a long time, it will not cause devitrification or crystallization. Conversely, when the glass temperature is lower than Tl for a long time, it may cause devitrification or crystallization, which will reduce the molding efficiency of the spinning fiber. Glass quality is deteriorating. $
因此，為了在抽絲盒進行抽絲作業，玻璃膏必須長時 間維持在抽絲溫度附近，所以，如果Tl不夠低的話，在抽 絲過程中，將容易引發玻璃失透或結晶，造成玻璃於抽絲 時纖維斷裂，不利於連續生產，甚或使玻璃纖維之品質劣 化，因此希望玻璃之Tl能盡量降低，實務上希望低於抽絲 溫度3 0 °C或更低。 然而，在日本特開2 0 0 3 - 1 3 7 5 9 0號公報、特開平 11-292567號公報、及美國第6309990號專利中，雖然揭 示了多種可保持低介電常數與低介電正切的玻璃，惟此等 玻璃之玻璃液相溫度（Tl)偏高，因此，均須藉著調整其 配方，改善Tl偏高的問題。 9 1283237 【發明内容】 本發明之主要目的在提供一種低介電常數玻璃纖 維，藉著重新調整習知技術的配方，而提供具有相同低介 電常數與低介電正切，但Tl較低且具有良好纖維抽絲成型 性的玻璃。 本發明之另一目的在提供一種低介電常數玻璃纖 維，藉此提供其玻璃液相溫度（Tl )低於抽絲溫度，至少3 0 °c ，甚至更低的玻璃。 本發明人等為達到上述目的，經過精心研究，結果發 現，玻璃纖維組成中，以莫耳百分比計分別為：4 5 %至6 5 % 之氧化矽8丨〇2、4%至15%之氧化鋁人12〇3、8%至22%之氧化 硼B2〇3、2%至12%之氧化鎂MgO、7%至22%之氧化鈣CaO、 0.5%至3%之氧化鈦Ti〇2、0%至2%之氟F2、氧化鋰Li2〇與 氧化鈉N a 2 0與氧化鉀K 2 0之總和介於0 %至1 %之間，此等 組成可製成具有低介電常數與低介電正切特性的，且玻璃 液相溫度較低的，具有良好成型性的玻璃。該玻璃纖維， 舉其中一例，在室溫下，頻率1MHz時，介電常數為5. 0 以下，介電正切為1 0 X 1 (Γ4以下，玻璃液相溫度低於抽 絲溫度3 0 °C。 本發明的玻璃纖維，以莫耳百分比計，其組成更好是 10 1283237 50%至60%之氧化矽Si〇2、6%至12%之氧化鋁Al2〇3、10%至 1 8%之氧化硼β2〇3、4%至9%之氧化鎂MgO、9%至20%之氧化 鈣CaO、（L 5%至3%之氧化鈦Ti〇2、0%至2%之氟F2、氧化鋰 Li2〇與氧化鈉Na2〇與氧化鉀K2〇之總和介於0%至1%之間。 關於本發明之優點與精神可以藉由以下的發明詳述 及所附圖式得到進一步的瞭解。Therefore, in order to perform the spinning operation in the spinning box, the glass paste must be maintained near the spinning temperature for a long time, so if Tl is not low enough, in the spinning process, the glass will be easily devitrified or crystallized, resulting in glass. When the fiber is broken during spinning, it is not conducive to continuous production, or even deteriorates the quality of the glass fiber. Therefore, it is desirable that the T1 of the glass can be minimized, and it is practically desirable to lower the spinning temperature by 30 ° C or lower. However, in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Tangent glass, but the glass liquid temperature (Tl) of these glass is high, so it is necessary to adjust the formulation to improve the problem of high Tl. 9 1283237 SUMMARY OF THE INVENTION A primary object of the present invention is to provide a low dielectric constant glass fiber that provides the same low dielectric constant and low dielectric tangent by re-adjusting the formulation of the prior art, but with a low Tl and Glass with good fiber drawability. Another object of the present invention is to provide a low dielectric constant glass fiber, thereby providing a glass having a glass liquidus temperature (Tl) lower than the spinning temperature, at least 30 ° C, or even lower. In order to achieve the above object, the inventors of the present invention have conducted intensive studies and found that, in the glass fiber composition, the percentage of moles is: 45% to 65% of cerium oxide 8丨〇2, 4% to 15%, respectively. Alumina 12〇3, 8% to 22% boron oxide B2〇3, 2% to 12% magnesium oxide MgO, 7% to 22% calcium oxide CaO, 0.5% to 3% titanium oxide Ti〇2 0% to 2% of fluorine F2, lithium oxide Li2〇 and the sum of sodium oxide N a 2 0 and potassium oxide K 2 0 are between 0% and 1%, and these compositions can be made to have a low dielectric constant A glass having good dielectric properties with low dielectric tangent characteristics and low glass liquidus temperature. For the glass fiber, for example, at room temperature, at a frequency of 1 MHz, the dielectric constant is 5.0 or less, and the dielectric tangent is 1 0 X 1 (Γ4 or less, the glass liquidus temperature is lower than the spinning temperature of 30 °). C. The glass fiber of the present invention, in terms of percentage of moles, preferably has a composition of 10 1283237 50% to 60% of yttrium oxide Si 〇 2, 6% to 12% of alumina Al 2 〇 3, 10% to 1 8 % of boron oxide β2〇3, 4% to 9% of magnesium oxide MgO, 9% to 20% of calcium oxide CaO, (L 5% to 3% of titanium oxide Ti〇2, 0% to 2% of fluorine F2 The sum of lithium oxide Li2〇 and sodium oxide Na2〇 and potassium oxide K2〇 is between 0% and 1%. The advantages and spirit of the present invention can be further obtained by the following detailed description of the invention and the accompanying drawings. To understanding.
【實施方式】 本發明所提供的低介電常數玻璃纖維，其配合為：4 5% 至65%之氧化矽（5丨〇2)、4%至15%之氧化鋁（人12〇3)、8%至 22%之氧化硼（Β2〇3)、2%至12%之氧化鎂（MgO)、7%至22%之 氧化鈣（CaO)、0.5%至3%之氧化鈦（Ti〇2)、0%至2%之氟 (F2)、氧化鋰（Li2〇)與氧化鈉（Na2〇)與氧化鉀（K2〇)之總和 介於0%至1%之間。又以，50%至60%之氧化矽、6%至12% 之氧化鋁、10 %至18%之氧化硼、4%至9%之氧化鎂、9%至 φ 2 0 %之氧化鈣、〇 · 5 %至3 %之氧化鈦、0 %至2 %之氟、氧化鋰 與氧化鈉與氧化鉀之總和介於0¾至1%之間，為最佳的配 方。以下將詳細地說明此配方中上下限定義的由來。 氧化矽為玻璃組成的主體，若氧化矽含量少於4 5 %，所製 作出的玻璃介電常數過高。若氧化矽含量多於65%，將導 致玻璃的熔解溫度太高，抽絲困難，且玻璃液相溫度偏高。 因此氧化矽限定為45%至65%，更好是50%至60%。 11 1283237 氧化鋁用來提高玻璃結構之強度，若氧 則玻璃液相溫度偏高。若氧化鋁含量多 璃黏度太高，抽絲困難。因此氧化鋁限 好是6 %至1 2 %。 氧化硼的作用為助熔劑，主要係用 玻璃膏之黏度，若氧化硼含量少於8%， 充分發揮，且介電常數和介電正切過高 於22%，由於氧化硼的揮發，不易製成 氧化硼限定為8%至22%，更好是10 %至 氧化鎂的作用亦為助熔劑，若氧化 助熔效果即無法充分發揮。若氧化鎂含 常數和介電正切過高，且玻璃液相溫度 限定為2%至12%，更好是4%至9%。 氧化鈣的作用亦為助熔劑，若氧化 助熔效果即無法充分發揮。若氧化鈣含 常數和介電正切過高。因此氧化鈣限定 是9%至20% 。 氧化鈦可降低熔製玻璃時玻璃膏之 電正切，若氧化鈦含量少於0.5%，其上 發揮。若氧化鈦含量多於3%，其玻璃液 化鋁含量少於4%， 於1 5%，將導致玻 定為4%至1 5%，更 以降低熔製玻璃時 其助熔效果即無法 。若氧化蝴含量多 均質的玻璃。因此 18%。 鎂含量少於2%，其 量多於12%，介電 偏高。因此氧化鎂 鈣含量少於79έ，其 量多於22%，介電 為7%至22%，更好 黏度，也能降低介 述效果即無法充分 相溫度偏高。因此 12 1283237 氧化鈦限定為Ο . 5 %至3 %。 氟可降低熔製玻璃時玻璃膏之黏度，也能降低介電常 數和介電正切，若氟含量多於2%’其玻璃液相溫度偏南。 因此氟限定為0%至2%。 氧化裡、氧化鈉和氧化钟的作用都是助溶劑，主要用 以降低熔製玻璃時玻璃膏之黏度，若氧化鋰、氧化鈉和氧 化鉀之總和多於1 %，則介電正切過高。因此氧化鋰與氧化 鈉與氧化鉀之總和限定為0 %至1 %。 以上之配方為本發明精心調配研究之結果，為達到玻 璃之品質，於融製玻璃時必須有壹套特殊之方法，如使用 密閉式融爐防止配方中原料的揮發，適度攪拌使玻璃均質 化，降低玻璃液相溫度，此乃玻璃融製及抽絲操作技術， 此並不包括於本發明所揭露的玻璃組成内。 .此外，依據專利審查基準第二章第四節關於選擇發明 的審查建議指出，選擇發明，係指選擇已知上位概念發明 之下位概念而作為構成要件之發明。一般所謂選擇發明， 皆常見於化學及材料技術領域之發明。就選擇發明所選擇 已知上位概念發明之下位概念之技術内容而言，已知發明 並未有具體之揭示，且其所選擇之技術内容無論為已知發 明所未揭示之異質物或同質物，其說明書内所記載達成的 13 1283237 功效，即使在已知發明之文獻内有記載，只要其較已知發 明者具有非顯而易知之突出功效，此選擇發明即非能輕易 完成者。 因此，本發明所揭露的低介電常數玻璃纖維，雖然其 配方中的組成元素均與習知技術相同，但由於每個組成元 素的比例並不相同，y旦卻可以因此產生出具有相同低介電 常數與低介電正切，但Tl較低且具有良好纖維抽絲成型性 的玻璃，同時，也提供其玻璃液相溫度（τ L)低於抽絲溫度， 至少3 0 °C ，甚至更低的玻璃。所以，本發明實屬非能輕易 完成者。以下，將以實際的實驗數據證明，本發明所產生 的突出功效，進而證明本發明確實為非輕易完成者。 請參閱第1A〜1C圖表，第1A〜1C圖表為基於指定的配方所 製作出的玻璃之實驗數據。按照第1A〜1C圖表各組中所指 定的配方，在均勻混合各元素後，放在白金坩堝内，再以 電爐1500〜1550 °C之溫度，熔解6至8小時。熔解過程中， 並以白金攪拌棒攪拌2-3小時，以促進玻璃中各組成成份 之均勻性。然後，將玻璃膏倒入金屬模板中冷卻成型為板 狀。此時，針對各玻璃樣品進行檢測，可分別得到介電常 數、介電正切、抽絲溫度及玻璃液相溫度等特性值，並分 別表列在第1A〜1C圖表之對應攔位上。 上述所進行的檢測，主要係依下列方法進行檢測： (1 )介電常數、介電正切檢測：將板狀玻璃樣品經研磨、拋 14 1283237 光後，製成直徑45mm，厚度2mm的圓片狀試樣，夾入專用 治具後，以Hewlett Packard公司製，精密電阻電容電感 鍊（HP 4284A Precision LCR Meter)，在室溫下，頻率 1 Μ Η z時，測定樣品之介電常數與介電正切。 (2 )抽絲溫度（單位：°C )檢測：參照美國材料試驗協會 (American Society for Testing and Materials，以下簡 稱ASTM)所訂定之編號C965-96檢測標準，將玻璃放在坩 堝中熔融後，放入鉑合金轉子，測量轉子之轉速與扭力的 關係，導出玻璃在高溫下溫度與黏度的對應曲線後，得到 玻璃膏黏度為103p〇ise時的對應溫度。 (3)玻璃液相溫度（單位：°C )檢測：係參照ASTM C829 - 81，將小於850//m之玻璃屑放入白金皿中，置於梯 度爐2 4小時後，以顯微鏡測量玻璃之結晶情形，判定其液 相溫度而得。 如第1A和1B圖表所示，各組實施例的玻璃纖維的組 成配方，為依據本發明所揭露的配方比例，其介電常數均 為5.0以下，且介電正切均為10 X 104以下。更具體的 說，實施例的玻璃纖維，介電常數為4. 5〜4. 8，介電正切 為7〜9 X 1(Γ4。因此，本發明所提供的低介電常數玻璃纖 維，不但，具有和D玻璃大致相近的低介電常數和低介電 正切。同時，也可由第1Α〜1Β圖表所顯示的玻璃液相溫度 低於抽絲溫度之幅度可知，均達成本發明的目的，意即玻 璃液相溫度（Tl)低於抽絲溫度，至少30°C ，甚至更低。在 15 1283237 第1 C圖表中，例1、例2、例3之玻璃織維係分別相當於 日本特開平1 1 - 2 9 2 5 6 7號公報、美國第6 3 0 9 9 9 0號專利、 日本特開2 0 0 3 - 1 3 7 5 9 0號公報記載之玻璃纖維，而例4、 例5則為某些組成未滿足本發明組成範圍之玻璃纖維。 於第1C圖表中各實施例的玻璃織維，雖也有較低的介電常 數和低介電正切，但均無法滿足玻璃液相溫度低於抽絲溫 度3 0 °C或更低的要求。由此習知的玻璃纖維其成型性均較 本發明的玻璃纖維低劣。[Embodiment] The low dielectric constant glass fiber provided by the present invention is compounded by: 45% to 65% of cerium oxide (5丨〇2), 4% to 15% of aluminum oxide (human 12〇3). 8% to 22% of boron oxide (Β2〇3), 2% to 12% of magnesium oxide (MgO), 7% to 22% of calcium oxide (CaO), and 0.5% to 3% of titanium oxide (Ti〇 2) The sum of 0% to 2% of fluorine (F2), lithium oxide (Li2〇) and sodium oxide (Na2〇) and potassium oxide (K2〇) is between 0% and 1%. Further, 50% to 60% of cerium oxide, 6% to 12% of alumina, 10% to 18% of boron oxide, 4% to 9% of magnesium oxide, 9% to φ20% of calcium oxide, 〇· 5 % to 3% of titanium oxide, 0% to 2% of fluorine, lithium oxide and the sum of sodium oxide and potassium oxide are between 03⁄4 and 1%, which is the best formula. The origin of the definition of the upper and lower limits in this recipe will be explained in detail below. Cerium oxide is the main component of the glass. If the cerium oxide content is less than 45%, the dielectric constant of the glass is too high. If the cerium oxide content is more than 65%, the melting temperature of the glass is too high, the spinning is difficult, and the glass liquid temperature is high. Therefore, cerium oxide is limited to 45% to 65%, more preferably 50% to 60%. 11 1283237 Alumina is used to increase the strength of the glass structure. If oxygen is used, the glass liquid temperature is high. If the alumina content is too high, the spinning is difficult. Therefore, the alumina limit is 6% to 12%. The role of boron oxide is flux, mainly using the viscosity of glass paste. If the boron oxide content is less than 8%, the full play, and the dielectric constant and dielectric tangent are higher than 22%, due to the volatilization of boron oxide, it is difficult to manufacture. The boron oxide is limited to 8% to 22%, more preferably 10% to magnesium oxide, and is also a flux, and if the oxidative fluxing effect is not fully exerted. If the magnesium oxide has a constant and the dielectric tangent is too high, and the glass liquidus temperature is limited to 2% to 12%, more preferably 4% to 9%. The role of calcium oxide is also a flux, and if the oxidative fluxing effect is not fully exerted. If the calcium oxide contains a constant and the dielectric tangent is too high. Therefore, the calcium oxide is limited to 9% to 20%. Titanium oxide can reduce the electric tangent of the glass paste when the glass is melted, and if the content of titanium oxide is less than 0.5%, it is exerted thereon. If the content of titanium oxide is more than 3%, the content of liquefied aluminum in the glass is less than 4%, and at 15%, the glass is set to 4% to 15%, and the melting effect of the molten glass is not improved. If the oxidized butterfly content is more homogeneous, the glass. So 18%. The magnesium content is less than 2%, the amount is more than 12%, and the dielectric is high. Therefore, the magnesium oxide content of calcium oxide is less than 79 έ, the amount is more than 22%, the dielectric is 7% to 22%, the viscosity is better, and the effect is also lowered, that is, the temperature is not sufficiently high. Therefore 12 1283237 titanium oxide is limited to Ο 5 % to 3%. Fluorine can reduce the viscosity of the glass paste when melting glass, and can also reduce the dielectric constant and dielectric tangent. If the fluorine content is more than 2%, the glass liquid temperature is southerly. Therefore fluorine is limited to 0% to 2%. Oxidation, sodium oxide and oxidation clock are all auxiliary solvents, mainly used to reduce the viscosity of the glass paste when melting glass. If the sum of lithium oxide, sodium oxide and potassium oxide is more than 1%, the dielectric tangent is too high. . Therefore, the sum of lithium oxide and sodium oxide and potassium oxide is limited to 0% to 1%. The above formula is the result of careful study of the invention. In order to achieve the quality of the glass, it is necessary to have a special method for melting the glass, such as using a closed melting furnace to prevent volatilization of the raw materials in the formulation, and moderate agitation to homogenize the glass. The glass liquidus temperature is lowered, which is a glass melting and spinning operation technique, and is not included in the glass composition disclosed in the present invention. In addition, according to the review of the selection of inventions in Section 4 of Chapter 2 of the Patent Examination Benchmark, the choice of invention refers to the invention of selecting the subordinate concept of the known superior concept invention as the constituent element. The so-called selective inventions are common in the fields of chemistry and materials technology. In view of the technical content of selecting the underlying concept of the known superior concept invention, the invention is not specifically disclosed, and the selected technical content is a heterogeneous substance or homomorphism not disclosed by the known invention. The efficacy of 13 1283237 achieved in the specification, even if it is described in the literature of known inventions, is not easily accomplished as long as it has a prominent effect that is not readily apparent to known inventors. Therefore, the low dielectric constant glass fiber disclosed in the present invention, although the composition elements in the formulation are the same as the prior art, since the ratio of each constituent element is not the same, the y den can be produced to have the same low A glass having a dielectric constant and a low dielectric tangent, but having a low Tl and good fiber drawability, and also a glass liquidus temperature (τ L) lower than the spinning temperature, at least 30 ° C, or even Lower glass. Therefore, the present invention is not easily accomplished. Hereinafter, the outstanding experimental results produced by the present invention will be demonstrated by actual experimental data, thereby further demonstrating that the present invention is indeed not easily accomplished. Please refer to the 1A to 1C charts, and the 1A to 1C charts are experimental data of the glass produced based on the specified recipe. According to the formulas specified in the respective groups of Figures 1A to 1C, after uniformly mixing the respective elements, they are placed in a platinum crucible, and then melted for 6 to 8 hours at an electric furnace at a temperature of 1500 to 1550 °C. During the melting process, it was stirred with a platinum stir bar for 2-3 hours to promote the uniformity of the components in the glass. Then, the glass paste was poured into a metal template to be cooled and formed into a plate shape. At this time, for each glass sample, characteristic values such as dielectric constant, dielectric tangent, spinning temperature, and glass liquid phase temperature are obtained, and are listed in the corresponding blocks of the 1A to 1C charts, respectively. The above-mentioned tests are mainly carried out according to the following methods: (1) Dielectric constant, dielectric tangent detection: After the plate glass sample is polished and thrown 14 1283237 light, a wafer having a diameter of 45 mm and a thickness of 2 mm is prepared. The sample was clamped into a special fixture, and the dielectric constant of the sample was measured at a temperature of 1 Μ Η z at a room temperature of 1 Μ Η z using a precision resistor-capacitor inductor chain (HP 4284A Precision LCR Meter) manufactured by Hewlett Packard. Electric tangent. (2) Threading temperature (unit: °C) detection: refer to the test number of C965-96 set by American Society for Testing and Materials (ASTM), after the glass is melted in the crucible, The platinum alloy rotor is placed, and the relationship between the rotational speed of the rotor and the torsion is measured, and the corresponding temperature of the glass at a high temperature is obtained, and the corresponding temperature when the viscosity of the glass paste is 103 p〇ise is obtained. (3) Glass liquidus temperature (unit: °C) detection: according to ASTM C829-81, put glass shards of less than 850//m into a white gold dish, placed in a gradient furnace for 24 hours, and measure the glass with a microscope. In the case of crystallization, it is determined by the liquidus temperature. As shown in the graphs of Figs. 1A and 1B, the composition of the glass fibers of each of the examples is a formulation ratio according to the present invention, and the dielectric constant is 5.0 or less, and the dielectric tangent is 10 X 104 or less. More specifically, the glass fiber of the embodiment has a dielectric constant of 4. 5 to 4. 8. The dielectric tangent is 7 to 9 X 1 (Γ4. Therefore, the low dielectric constant glass fiber provided by the present invention is not only It has a low dielectric constant and a low dielectric tangent which are substantially similar to D glass. At the same time, it can be understood that the glass liquidus temperature shown by the first Α1 to 1 Β graph is lower than the range of the spinning temperature, and the object of the present invention is achieved. That is, the glass liquidus temperature (Tl) is lower than the spinning temperature, at least 30 ° C, or even lower. In the 1 C chart of 15 1283237, the glass woven systems of Examples 1, 2, and 3 are equivalent to Japan, respectively. Japanese Laid-Open Patent Publication No. 1 1 - 2 9 2 5 6 7 , US Patent No. 6 3 0 9 9 0, and Japanese Patent Laid-Open Publication No. WO 03-133075, and Example 4 Example 5 is a glass fiber having a composition that does not satisfy the composition range of the present invention. The glass weave of each embodiment in the 1C chart has a lower dielectric constant and a low dielectric tangent, but cannot satisfy the glass. The liquidus temperature is lower than the spinning temperature of 30 ° C or lower. Thus, the well-known glass fibers are more moldable. The glass fibers of the present invention are inferior.
藉由以上較佳具體實施例之詳述，係希望能更加清楚 描述本發明之特徵與精神，而並非以上述所揭露的較佳具 體實施例來對本發明之範疇加以限制》相反地，其目的是 希望能涵蓋各種改變及具相等性的安排於本發明所欲申請 之專利範圍的範疇内。 【圖式簡單說明】 第1A〜1C圖表為基於指定的配方所製作出的玻璃 之實驗數據。 【圖式符號說明】 【露ΠΓ 7TV\ 16The features and spirit of the present invention are more clearly described in the above detailed description of the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. It is intended that the various modifications and equivalents are intended to be included within the scope of the invention as claimed. [Simple description of the drawings] The 1A to 1C charts are experimental data of glass produced based on a specified recipe. [Illustration of schema symbols] [露ΠΓ 7TV\ 16