TW200536801A - Low-dielectric-constant fiberglass - Google Patents

Abstract

A Low-Dielectric-Constant Fiberglass having a glass composition by mole%, 45%~65% of SiO2, 4%~15% of Al2O3, 8%~22% of B2O3, 2%~12% of MgO, 7%~22% of CaO, 0.5%~3% of TiO2, 0%~2% of F2, 0%-1% of Li2O+Na2O+K2O, and the glass has low Liquid Temperature. The Fiberglass of the present invention has a low dielectric constant and a low dielectric tangent, is excellent in fiber forming process. The Fiberglass is suitable for reinforcing Printed Circuit Board (PCB) for high-density circuits.

Description

200536801 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to low dielectric constant glass fibers, and particularly to low dielectric constant glass fibers which are used in high-density printed circuit board reinforcement materials and have good fiber moldability. . [Prior art]

Information, communications, and consumer electronics (Computer,

Communication, and Consumer Electronics (3C) has undoubtedly become the fastest growing industry in the global industry. In the 3C industry, the printed circuit board (PCB) plays an extremely important role, and it is also an indispensable and important component. The PCB is mainly used to provide the main support for the installation and insertion of electronic components, and the circuit design is used to achieve the purpose of relay transmission.

During the PCB manufacturing process, the circuit connecting electronic components is drawn into a wiring pattern by circuit design, and then this pattern is made into a film. Then, the copper foil layer is subjected to graphics development, drilling, plating, etching and other processing processes. In this way, the required finished product is produced. After the PCB is installed and plugged in electronic components, it can be used in computer motherboards, graphics cards, communication boards and other products. The PCB is mainly composed of two parts, an insulating layer and a conductive layer. The insulating layer is made by impregnating a reinforcing material such as glass fiber cloth in a resin solution of the bonding material, drying it, and then laminating it. The conductive layer is made by pressing copper foil on the resin layer. If glass fiber products are differentiated according to their forms, they include glass yarn (G 1 ass Yarn), glass cloth (G 1 ass C 1 oth), and yarn bundle (Roving ) 'Woven Roving, Chopped Strand' Chopped Strand Mat, Fiberglass Tissue Continuous Strand Mat or Milled Fiber, etc. According to the composition and physical and chemical properties of glass, there are alkali-free glass (E-glass), acid-resistant / alkali-resistant glass, low dielectric constant glass, and high-strength glass. Among them, the glass fiber cloth used in the aforementioned PCB is well known in the industry as the 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 an AC voltage at a certain frequency, glass will be lost due to polarization or absorption, so that part of the energy in the alternating current is converted into heat. In addition, the mechanism for the above-mentioned energy loss of glass includes conductivity loss, relaxation loss, structural loss, and resonance. Loss, etc. The equation of this energy loss is: Q = UI tan 5 where Q: energy loss, U: voltage, I: current, tan (5: dielectric tangent. From this equation, we can know that energy loss is related to the dielectric tangent of glass In addition, when the PCB signal becomes denser, that is, when the line width and the pitch are gradually reduced, the connection resistance and the capacitance between the connections are indirectly increased, so the RC-delay effect is generated. Resistance-capacitance hysteresis has many negative effects on component performance, such as reducing signal transmission speed, increasing cross talk noise, and increasing power consumption. Among them, the reduction in signal-transmission speed caused by resistance-capacitance delay 200536801 is an impact One of the main factors for the degradation of PCB quality. The most direct way to solve the resistance-capacitance hysteresis is to reduce the resistance and capacitance. Therefore, the current research direction is to reduce the capacitance by reducing the dielectric constant, while avoiding the resistance-capacitance hysteresis. At room temperature, E glass has a dielectric constant of 6.7 and a dielectric tangent of 12x 104 at room temperature. Therefore, based on this, the dielectric constant and the dielectric constant are too high. Electrical tangent, if E glass is used as the glass fiber cloth of PCB, not only will it cause excessive energy loss, but also it will not be able to avoid the occurrence of resistance-capacitance hysteresis. Therefore, the requirements for higher signal density and higher speed processing are obvious Insufficient. Therefore, the industry all expects a lower dielectric constant than E glass and the birth of dielectric positive glass. At present, a type of D glass has appeared on the market. At room temperature, the dielectric constant is 1MHz. It is 4.3, and the dielectric tangent is IOχΙΟ4. Although this D glass does have a lower dielectric constant and dielectric positivity than E glass, it is difficult to fuse D glass when it is drawn at high temperature. Incomplete ribs or bubbles cause fiber breakage or defects, which reduces the efficiency of drawing fiber formation. Furthermore, the D glass drawing temperature is too high (the drawing temperature is generally defined as the temperature at which the viscosity of the glass paste is 103 poise). 1 4 1 0 ° C, not only makes the drawing operation difficult, but also shortens the life of the drawing device. Therefore, D glass is still not the glass that the industry really expects. In the further discussion of other first Prior art defects, a glass must first briefly 8200536801

The manufacturing process. The manufacture of glass fiber involves three processes, such as melting, spinning and processing of glass. In the spinning stage of the spinning process, glass paste is generally drawn into fibers through a spinning box made of platinum or its alloys. In addition, the glass liquid temperature (Liquid temperature, Tl) is one of the main factors affecting the success of the spinning stage. Tl is defined as the highest temperature at which glass can produce devitrification or crystallization, that is, when the temperature of the glass is higher than Tl, devitrification or crystallization will not occur even after a long period of heat treatment. Conversely, when the temperature of the glass is lower than Tl for a long time, it may cause devitrification or crystallization, which will reduce the forming efficiency of the drawn fiber and deteriorate the glass quality. Therefore, in order to maintain the drawing temperature during the drawing process, the fiber breaks easily, which is not conducive to chemical conversion. Therefore, it is desirable that the temperature of the glass is 30 ° C or lower. The wire box is subjected to wire drawing operations. Therefore, if Tl does not devitrify or crystallize the glass, continuous production or even glass Tl can be reduced as much as possible. In practice, the glass paste must be low enough for a long time. The quality of fiber is lower than that of silk

However, in Japanese Patent Application Laid-Open Nos. 003-3-3 7 590, Japanese Patent Application Laid-Open No. 11-292567, and U.S. Patent No. 6309990, various kinds of low-k and low-k dielectric materials are disclosed. Tangent glass, but the glass liquidus temperature (Tl) of these glasses is relatively high, therefore, by adjusting its formula, the problem of high Tl must be improved. 9 200536801 [Summary of the invention] The main purpose of the present invention is to provide a low dielectric constant glass fiber. By readjusting the formula of the conventional technology, it can provide the same low dielectric constant and low dielectric tangent, but the Tl is low 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 whose glass liquidus temperature (T L) is lower than the drawing temperature, at least 30 t, or even lower. In order to achieve the above purpose, the inventors have conducted careful research and found that the glass fiber composition, in terms of mole percentages, is: 45% to 65% of silicon oxide S i 0 2, 4% to 15% Alumina A 1 2 0 3, 8% to 22% oxidized m BeOS, 2% to 12% oxygen > dagger town MgO, 7% to 22% oxygen 4 dagger 1 bow CaO, 0.5% to 3% titanium oxide Ti02, 0% to 2% fluorine F2, lithium oxide Li2〇, sodium oxide Na2〇 and potassium oxide K2〇 sum between 0% to 1%, these compositions can be made Glass with low dielectric constant and low dielectric tangent characteristics, and low glass liquidus temperature, with good moldability. The glass fiber, for example, has a dielectric constant of 5.0 or less and a dielectric tangent of 1 0 X 1 0_ 4 or less at a frequency of 1 MHz at room temperature. C. The glass fiber of the present invention, in terms of mole percentage, has a better composition of 10 200536801 50% to 60% silicon oxide Si02, 6% to 12% aluminum oxide Al203, 10% to 18%. Boron oxide B203, 4% to 9% magnesium oxide MgO, 9% to 20% calcium oxide 0.30, 0.5% to 3% titanium oxide 1 ^ 02, 0% to 2% fluorine? 2. The sum of lithium oxide L i 2 0 and sodium oxide Na 2 0 and potassium oxide K2 0 is between 0% and 1%. The advantages and spirit of the present invention can be further understood through the following detailed description of the invention and the accompanying drawings.

[Embodiment] The low-dielectric-constant glass fiber provided by the present invention is formulated with 45% to 65% silicon oxide (5.02), 4% to 15% alumina (human 1203), 8% to 22% boron oxide (820.3), 2% to 12% magnesium oxide (»^ 0), 7% to 22% calcium oxide (CaO), and 0.5% to 3% 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)

Between 0% and 1%. In addition, 50% to 60% silicon oxide, 6% to 12% alumina, 10% to 18% boron oxide, 4% to 9% magnesium oxide, 9% to 20% calcium oxide, 0.5% The best formula is the sum of 3% of titanium oxide, 0% to 2¾ of fluorine, lithium oxide, sodium oxide and potassium oxide in the range of 0% to 1%. The origin of the upper and lower limit definitions in this recipe will be explained in detail below. Silicon oxide is the main body of glass. If the silicon oxide content is less than 45%, the dielectric constant of the glass produced is too high. If the content of silicon oxide is more than 65%, the melting temperature of the glass will be too high, the drawing will be difficult, and the liquidus temperature of the glass will be too high. Therefore, the silicon oxide is limited to 45¾ to 65%, more preferably 50% to 60%. 11 200536801 Alumina is used to increase the strength of the glass structure. If oxygen, the liquidus temperature of the glass is high. If the content of alumina is too high, the viscosity of the glass is too high, which makes drawing difficult. Therefore, the alumina limit is preferably 6% to 12 ° / 〇. The role of boron oxide as a flux is mainly based on the viscosity of glass paste. If the content of boron oxide is less than 8%, it will be fully utilized, and the dielectric constant and dielectric tangent will be higher than 22%. Due to the volatilization of boron oxide, it is not easy to make. The formation of boron oxide is limited to 8% to 22%, and more preferably 10% to the role of oxidation ball is also a co-solvent, if the effect of oxidative flux cannot be fully exerted. If magnesia contains a constant and a high dielectric tangent, 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, if the effect of oxidative flux cannot be fully exerted. If the calcium oxide contains a constant and the dielectric tangent is too high. Therefore, the limit of calcium oxide is 9% to 20%. Titanium oxide can reduce the electrical tangent of glass paste when melting glass. If the content of titanium oxide is less than 0.5%, it will play a role. If the content of titanium oxide is more than 3%, the content of liquefied aluminum in the glass is less than 4%, and the content of 15% will lead to a glass content of 4% to 15%, which will further reduce the effect of melting when melting glass. If the content of oxidized butterfly is much cold glass. Therefore, the content of 18% ° Mg is less than 2%, the amount is more than 12%, and the dielectric is high. Therefore, the content of magnesium oxide is less than 7%, the amount is more than 22%, and the dielectric is 7% to 22%. It has better viscosity and can reduce the effect of the description. Therefore, 12 200536801 titanium oxide is limited to 0.5% to 3%. Fluorine can reduce the viscosity of glass paste when melting glass. It can also reduce the dielectric and dielectric tangent. If the fluorine content is more than 2%, the glass liquidus temperature is good. Therefore, fluorine is limited to 0% to 2%. The functions of oxidation chain, sodium oxide and oxidation unloading are all co-solvents, mainly to reduce the viscosity of glass paste when melting glass. If the total of lithium oxide and sodium oxide potassium oxide is more than 1%, the dielectric tangent is too high. Therefore, the sum of lithium oxide, sodium and potassium oxide is limited to 0% to 1%. The above formula is the result of careful preparation research of the present invention. In order to achieve the quality of glass, there must be a special method when melting glass, such as a closed furnace to prevent volatilization of raw materials in the formula, and moderate stirring to make the glass vitrify and reduce The liquidus temperature of the glass, which is the glass melting and drawing operation technique, is not included in the glass composition disclosed in the present invention. In addition, according to the review recommendations on section 4 of Chapter 2 of the Patent Examination Benchmark, the selection of inventions refers to the selection of inventions that constitute the essential elements by selecting known lower-level concepts. The so-called selective hair is commonly found in inventions in the fields of chemistry and materials technology. As far as the technical content of the lower-level concept of the known invention of the selected invention is concerned, it is known that there is no specific disclosure, and whether the selected technical content is a heterogeneous substance or a homogeneous substance that has not been disclosed, the specification The recorded electricity is always high. To oxidize spring to glass with oxygen and use homogenization,

According to the invention, it is 13 200536801 that the effect of the invention is selected. Even if it is recorded in the literature of the known invention, as long as it has a non-obvious and easy-to-know outstanding effect than the known inventor, this choice of invention is not easily completed. . Therefore, although the low-dielectric-constant glass fiber disclosed in the present invention has the same constituent elements in the formula as the conventional technology, the proportion of each constituent element is not the same, but it can produce the same low-dielectric Glass with a low dielectric constant and a low dielectric tangent, but with a low Tl and good fiber drawability. At the same time, it also provides a glass liquid temperature (Tl) that is lower than the draw temperature, at least 30 ° C, or even lower. Glass. Therefore, the present invention is not easily accomplished. In the following, actual experimental data will be used to demonstrate the outstanding efficacy of the present invention, and further prove that the present invention is indeed a non-easy to complete. Please refer to the graphs 1A to 1C. The graphs 1A to 1C are the experimental data of the glass made based on the specified formula. According to the formula specified in each group of the charts of 1A to 1C, after uniformly mixing the elements, put it in a platinum crucible, and then melt it at an electric furnace at a temperature of 1500 to 1550 ° C for 6 to 8 hours. During the melting process, stir with a platinum stirring rod for 2-3 hours to promote the uniformity of each component in the glass. Then, the glass paste is poured into a metal template and cooled to form a plate. At this time, for each glass sample, characteristic values such as dielectric constant, dielectric tangent, wire drawing temperature, and glass liquid phase temperature can be obtained, and listed in the corresponding columns on the 1st A to 1C charts. . The above tests are mainly performed in accordance with the following methods: (1) Dielectric constant and dielectric tangent detection: After grinding and polishing the plate-shaped glass sample 14 200536801, it is made into a disc with a diameter of 45mm and a thickness of 2mm. The sample is sandwiched into a special jig, and a precision resistance capacitor inductance meter (HP 4284A Precision LCR Meter) made by Hewlett Packard Company is used to measure the dielectric constant and dielectric constant of the sample at room temperature at a frequency of 1 μΗz. Electric tangent. (2) Wire drawing temperature (unit: ° C) detection: refer to the testing standard No. C965-96 set by the American Society for Testing and Materials (hereinafter referred to as ASTM), and after melting the glass in a crucible, Put a platinum alloy rotor, measure the relationship between the rotation speed and the torque of the rotor, and derive the corresponding curve of the temperature and viscosity of the glass at high temperature, and then obtain the corresponding temperature when the viscosity of the glass paste is 103 poise. (3) Glass liquid temperature (unit · ° C) detection: refer to AST C829-81, put glass shavings less than 850 // m into a platinum dish, place it in a gradient oven for 24 hours, and then use a microscope It is obtained by measuring the crystallization of glass and determining its liquidus temperature. As shown in the graphs of FIGS. 1A and 1B, the composition formulas of the glass fibers of the examples of each group are the proportions of the formulas disclosed in accordance with the present invention. The dielectric constants are all 5.0 or less, and the dielectric tangents are 10 X 10 4 or less. . More specifically, the glass fiber of the embodiment has a dielectric constant of 4.5 to 4.8 and a dielectric tangent of 7 to 9 x 104. Therefore, the low dielectric constant glass fiber provided by the present invention not only has a low dielectric constant and a low dielectric tangent which are substantially similar to those of D glass. At the same time, it can also be seen from the magnitude of the glass liquid phase temperature lower than the drawing temperature that the graphs 1A ~ 1B show, all of which achieve the purpose of the invention, which means that the glass liquid temperature (Tl) is lower than the drawing temperature, at least 30 ° C, even lower. In the chart of 15200536801 1C, the glass fibers of Examples 1, 2, and 3 correspond to Japanese Patent Laid-Open No. 11-292567, US Patent No. 6309990, and Japanese Patent Laid-Open No. 2 0 0 3-1 3 7 5 The glass fibers described in the 90th publication, while Examples 4 and 5 are glass fibers whose composition does not satisfy the composition range of the present invention. Although the glass fibers of the respective examples in the 1C chart also have a low dielectric constant and a low dielectric tangent, they cannot meet the requirements that the liquidus temperature of the glass is 30 ° C or lower than the drawing temperature. The conventional glass fibers are inferior in formability to the glass fibers of the present invention.

With the above detailed description of the preferred embodiments, it is hoped that the features and spirit of the present invention may be more clearly described, rather than limiting the scope of the present invention with the preferred specific embodiments disclosed above. On the contrary, it is intended to cover various changes and equivalent arrangements within the scope of the patents to be applied for in the present invention. [Brief description of the circle type] The graphs 1A to 1C are experimental data of glass made based on the specified formula. [Illustration of Symbols]

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Claims (1)

200536801 The scope of patent application: 1. A low-dielectric-constant glass fiber, which is used to make printed circuit boards, which is characterized in that each component is expressed in mole percentages, including: 45% to 65% silicon oxide S i 0 2, 4% to 15% alumina Al203, 8% to 22% boron oxide 6203, 2% to 12% magnesium oxide MgO, 7% to 22% calcium oxide CaO, 0.5% To 3% of titanium oxide Ti02, 0% to 2% of fluorine F2, lithium oxide Li2〇 and sodium oxide Na2〇 and potassium oxide K2O The sum is between 0% and 1%. 2. The low-dielectric-constant glass fiber described in item 1 of the scope of the patent application, each component having a better effect is measured in mole percentages, including: 50% to 60% silicon oxide Si02, 6% to 12% alumina Al203, 10% to 18% boron oxide B 2 0 3 ^ 4% to 9% magnesium oxide MgO, 9% to 20% calcium oxide CaO, 0.5% to 3% oxidation The total of Ti02, 0% to 2% of fluorine F2, lithium oxide Li2O, sodium oxide Na2O, and potassium oxide K2O is between 0% and 1%. 3. The low-dielectric-constant glass fiber as described in item 1 of the scope of the patent application, wherein at room temperature and a frequency of 1 MHz, the dielectric constant is 5.0 or less, and the dielectric tangent is 10 X 10 4 or less. 4. The low-dielectric-constant glass fiber as described in item 1 of the scope of the patent application, wherein the glass liquid phase temperature is lower than the drawing temperature 17 200536801 3 0 ° C or lower. 5. The low dielectric constant glass fiber as described in the second item of the patent application scope, wherein at room temperature, the frequency is 1MHz, the dielectric constant is 4.5 ~ 4.8, and the dielectric tangent is 7 ~ 9 X 10 -4. 6. The low-dielectric-constant glass fiber according to item 2 of the scope of the patent application, wherein the glass liquid phase temperature is lower than the drawing temperature by 30 ° C or lower. 18