TW201012771A - Glass fiber composition and printed circuit board made from the glass fiber composition - Google Patents

Abstract

Disclosed are glass fibers having a dielectric constant less than or equal to 6 and glass viscosity of 1000 poise at a temperature no greater than 2250 DEG F (1232.2 DEG C ). The glass fibers include between 45 Wt% and 65 Wt% of SiO2; between 15 Wt% and 25 Wt% of B2O3; between 8 Wt% and 16 Wt% of Al2O3; less than or equal to 10 Wt% of CaO; less than or equal to 10 Wt% of MgO; less than or equal to 3 Wt% of Na2O; less than or equal to 2 Wt% of K2O; less than or equal to 2 Wt% of Li2O; less than or equal to 5 Wt% of TiO2; less than or equal to 2 Wt% of F2; and less than or equal to 1 Wt% of Fe2O3. The glass fibers can have less than or equal to five hollow glass fibers per cubic centimeter of glass and are intended for use in a printed circuit board.

Description

201012771 VI. INSTRUCTIONS: [Reference to related cases] This application claims the US Provisional Patent Application No. 61/083,706, entitled "Gla_ss Fiber Composition", filed on July 25, 2008. The priority of this application is hereby incorporated by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to glass fibers having a low dielectric constant, and more particularly to glass fibers having a low dielectric constant for use in reinforcing printed circuit boards. [Prior Art] At present, the so-called "E glass" is widely used in the form of glass fiber to reinforce a printed circuit board. E-glass is defined in the specification ASTM-D578 "Standard Specification for Glass Fiber Strands" and IPC-4412A "Specification for Finished Fabric Woven from 'E' Glass for Printed Boards", which includes between 5 Wt% and 10 Wt%. Boron oxide (B2〇3); calcium oxide (CaO) between 16 Wt% and 25 Wt%; alumina between 12 Wt% and 16 Wt% (A1203); between 52 Wt% and Cerium oxide (Si02) between 56 Wt%; magnesium oxide (MgO) between 0 Wt% and 5 Wt%; sodium oxide (Na20) between 0 Wt% and 2 Wt%; Potassium oxide (K20) between 0 Wt% and 2 Wt%; titanium dioxide (Ti02) between 0 Wt% and 0.8 Wt%; ferric oxide between 0.05 Wt% and 0.4 Wt% (Fe203); and fluorine (F2) between 0 Wt% and 1 Wt%. 201012771 Here, the percentage of all ingredients used to form the glass is expressed in weight percent (i.e., wt%). As electronic circuitry is expected to operate at increased clock speeds, printed circuit boards have become a limiting factor in device design. The signal propagation speed is determined by the combination of circuit size and laminate dielectric constant (Dk). The laminate Dk is determined by the individual Dk of the material used to form the laminate, including resin and glass reinforcement. In general, glass fibers are a major contributor to laminate Dk. Lu needs fiberglass with reduced Dk to meet the demand for high-speed computing equipment. A summary of the glass process used in printed circuit board (PCB) reinforcement by Eng (Dlass Fiber Glass Reinforcements Within Circuit, D. Eng -, September, 2001, The Board Authority)

Board Composites") given. The authors describe glass melting, glass fiber forming, twisting, warping, sizing, weaving, burning, and processing processes that involve the pretreatment steps of making glass spheres or glass shavings. The authors also agree that there is a need for glass with low Dk and current commercial offerings that include higher glass melting temperatures, higher energy costs and shorter glass melting and fiberglass forming equipment life. The third revision of the book "The Manufacturing' Technology of Continuos Glass Fibres" by Lowenstein KL, published by Elsevier Publishing in 1993 (hereafter referred to as "Lowenstein") details the manufacture of glass yarns, including melting, Glass fiber forming and twisting is considered a standard work in this industry. Lowenstein contains key details of equipment design and operation, standards for fiberglass, and examples of low-temperature 201012771 electrical constant glass composites and properties. An alternative glass fiber composite containing "D" and "S" can be utilized, and Eng and I^owenstein mention that they also have a low D. These glasses have very high melting temperatures and high viscosities, such as Y〇k〇. It is difficult to eliminate air bubbles in the melting of the glass as mentioned in U.S. Patent No. 4,824,806. Similarly, glass fibers made from these glass composites are unable to achieve a glass fiber diameter of less than 9 microns due to handling difficulties, which limits their use in high density printed circuit boards.

U.S. Patent No. 4,762,809 to Imai describes improved water resistance and heat resistance as compared to D glass while verifying low Dk. The Imai patent discloses a glass composition similar to D glass, but which contains 215% by weight of B2〇3 and up to 5% of alkali metal (R2〇 = Na20 + K20 + Li2〇). A high vermiculite content of greater than 70% results in a high melting temperature of greater than 2800 °F. - Similarly, high vermiculite content makes it difficult to drill a printed circuit board substrate reinforced with this glass. Y Compared with D glass, Yokoi et al.'s specialists verify low Dk and good water resistance by increasing the alkaline earth metal (CaO + MgO) and alumina levels, sometimes introducing Ζη〇 while reducing the alkali metal level. This glass showed no improvement in productivity compared to d glass, but had a higher melting temperature than .E: glass.

The Yokoi et al. patent states that the result of high viscosity and high melting temperature is that it is difficult to obtain a homogeneous glass without bubbles. The bubble in the glass melt during the formation of the glass fiber was previously observed in the E glass, and the inventors of U.S. Patent No. 4,542,106 to Spr. U.S. The concern of E glass variability. If these are small bubbles, they pass through the glass fiber forming process and result in hollow glass fibers. If it is a large bubble, it will cause the process to be interrupted. In either case, the bubbles and the resulting hollow glass fibers must be avoided in the production of glass fibers, the weaving from these glass fibers, and the laminates or composites used for printed circuit boards or electrical insulation containing these glass fibers. . The shortcomings of insulating glass fibers in printed circuit board laminates have been demonstrated in many medical journals and professional publications such as: (1) K. R0gers, C. Hillman and M. Pecht, "Hollow Fibers Can Accelerate Conductive Filament Formation" , ASM International ^ Failure Failure Analysis, Volume 1, Issue 4 'Page 57-60, August 2001; (2) K. Rogers, P. Driessche, C. Hillman, and M. Pecht "Do Ϋοιι Know That Your Laminates May Contain Hollow Fibers", Printed Circuit Fabrication, Vol. 22, No. 4, pp. 34_38, April 1999, and (3) A. Shukla, T. Dishongh., M. Pecht, and D. Jennings, "Hollow Fibers in Woven Laminates" Printed Circuit Manufacturing, Vol. 20, pp. i, p. 3〇_32 'January 1997. The method of hollow glass fiber is determined in Sproull's specialization, and the acceptable upper limit is $10,000 per cubic centimeter of glass. This is within the limits of the insulating glass fiber limits established by manufacturers of different printed circuit board materials.

A glass having a low dielectric 201012771 constant comprising an alkali metal content between 〇wt% and 〇5 wt%, between 20 wt% and 30 wt%, is disclosed in U.S. Patent No. 5,958,8, the entire disclosure of which is incorporated herein by reference. The B2〇3 content and the Ti〇2 content between 0.5 Wt% and 5 Wt%. U.S. Patent No. 6,309,990 to Tamura et al. discloses an increase in alkali metal content between 〇 Wt/ο and 1.0 Wt%, and I. The amount of 3 is reduced to between 15 Wt% and 30 Wt/〇 while still containing Ti02 between 〇.5^% and 5 Wt%. ❹

The Mori et al. patent states that the lower limit of ία is 2〇 wt% to avoid dielectric ditangential; the upper limits of CaO and Mg〇 are 5 stomachs, respectively. And 4 Wt/o to avoid 咼 dielectric constant and high dielectric tangent; and R2 〇 upper limit of 0.5 (four) to avoid high dielectric tangent and poor water resistance. The Ta_a et al. patent states that the lower limit of B2〇3 is 15 Wt% to avoid high dielectric constant and high dielectric tangent; the upper limit of Mg〇 is 5 Wt% to avoid high dielectric constant, high dielectric tangent and reduction The water resistance; the upper limit of Ca 为 is Η Wt% 'to avoid high dielectric constant and high dielectric tangent; and the upper limit of palpitations is 1.0 Wt%, otherwise Dk will be too high and poor water resistance. It is expected that the increase in the limits of alkaline earth metals (Ca0 and Mg〇) and alkali metals (Na2〇, κ山^LkO) will lower the melting temperature, reduce the incidence of hollow glass fibers, and improve workability. Patent spear according to M〇d et al.

Glass fiberglass made from the teachings of the Tamura et al. patent is manufactured by Nmo Boseki and sold under the trade name NE Glass. The glass exhibits a low Dk' which is not as low as D glass but lower than s. Glass fiberglass made according to the teachings of Mon et al. and the teachings of Tamura et al. is still difficult to melt, requiring high temperatures and leaving bubbles in the glass fill 201012771. In the electronics industry, NE glass is known to exhibit hollow glass fibers, and the inventors have observed that it is far beyond the limits established by the Spr〇ull patent. It is recognized in the Tamura et al. patent that "s〇me slight difficulty in worability and productivity j 〇 [Summary] discloses a glass fiber which is composed of the following as required: between 45 Wt% and 65 Wt% SiO2; B2〇3 between φ 15 Wt% and 25 Wt%; Al2〇3 between 8 Wt·· and 16 Wt%; CaO less than or equal to 10 Wt°/〇; MgO less than or equal to 10 Wt%; Na20 less than or equal to 3 Wt%; K20 less than or equal to 2 Wt%; LhO less than or equal to 2 Wt%; Ti02 less than or equal to 5 Wt%; less than or equal to 2 Wt % F2; and less than or equal to 1 Wt% of Fe203, wherein the glass fiber has a dielectric constant of less than or equal to 6 and a glass viscosity of 1000 poise at a temperature of not more than 2250 °F (1232.2 °C). a glass fiber, which is more suitably formed as follows: SiO 2 between 48 Wt ° / 〇 and 62 Wt %; B 2 〇 3 between 17 Wt% and 23 Wt%; between 9 Wt Al2〇3 between % and 15 Wt%; CaO between 2 Wt% and 10 Wt%; MgO between 2 Wt% and 8 Wt%; Na20 less than or equal to 2 Wt%; less than or equal to l Wt % K20 ; less than or Li20 equal to 1 Wt%; Ti02 less than or equal to 2 Wt%; F2 less than or equal to 1.5 Wt%; and Fe2〇3 less than or equal to 0.8 Wt%, wherein the glass fiber is not more than 225 〇.17 (1232.2 The temperature at °(:) has a dielectric constant of less than or equal to 6 and a glass adhesion of 100012771 degrees. Also, a glass fiber is disclosed which is most preferably composed of the following: between 52 Wt% and 56 Wt%. Q02; B2〇3 between 18 Wt% and 22 Wt%; ai2o3 between 10 Wt% and 14 Wt°/〇; CaO between 4 Wt% and 8 Wt%; 2 Wt% and 6 Wt% of MgO; less than or equal to 2 Wt% of Na20; less than or equal to 1 Wt°/〇 of K20; less than or equal to 1 Wt°/〇 of Li20; less than or equal to 0.5 Wt% of Ti02; F2 less than or equal to 1 Wt%; and less than or equal to 0.4 Wt% - Fe203 ' wherein the glass fiber has a dielectric constant (Dk) of less than or equal to 6 at a temperature not greater than 2250 °F (2 °C) And 1 berth of glass viscosity. The aforementioned glass fibers each contain not more than 5 hollow glass fibers per cubic centimeter of glass fibers as required. Each of the foregoing glass fibers may further comprise one or more of the following components in an amount of up to 5 Wt%: BaO; BeO; CaF2; CdO; Μη203; ❹P2〇5; PbO; S03; Sb203; SrO; ZnO; and Zr02. Also disclosed is a printed circuit board comprising one or more plies, wherein each ply comprises glass fibers supported by a resin having a dielectric of less than or equal to 6 at a temperature of no greater than 22507 (1232.2 ° C) Electrical constant (Dk) and glass viscosity of 1 Torr. The glass fibers constituting the printed circuit board are constructed as follows: SiO 2 between 45 Wt% and 65 Wt%; b2 〇 3 between 15 Wt ° / 〇 and 25 Wt %; Al2〇3 between 8 Wt% and 16 Wt%; Ca〇 less than or equal to 1〇Wt〇/〇; MgO less than or equal to wt% 201012771; Na20 less than or equal to 3 wt%; less than or equal to 2 Wt % of K20; less than or equal to 2 wt% of Li20; less than or equal to 5 Wt% of TiO 2 ; less than or equal to 2 wt%; and less than or equal to 1 wt% of Fe 203. The glass fibers constituting the printed circuit board are further composed of: SiO 2 between 48 Wt% and 62 Wt%; b2 〇 3 between 17 Wt% and 23 Wt%; _ A12〇3 between Wt% and 15 Wt%; CaO between 2 Wt% and 1〇wt%; MgO between 2 Wt〇/〇 and 8 Wt0/〇; Na20 less than or equal to 2 wt% ; less than or equal to 1 wt% of K20; less than or equal to i wt% of Li20; less than or equal to 2 Wt% of Ti02; less than or equal to 15 wt% of F2; and less than or equal to 〇.8 Wt% of Fe2〇3 0 The glass fiber constituting the printed circuit board is most preferably composed of: SiO 2 between 52 Wt% and 56 Wt%; B2 〇 3 between 18 Wt% and 22 Wt%; 〇Al2〇3 between 1〇Wt% and 14wt%; CaO between 4 Wt% and 8 Wt%; MgO between 2 Wt% and 6 Wt%; Na20 less than or equal to 2 Wt%; less than Or equal to 1 Wt% of K20; less than or equal to 1 Wt°/. Li20; less than or equal to 0.5 Wt% of Ti〇2; less than or equal to 1 Wt% of F2; and less than or equal to 0.4 Wt% of Fe2〇3°. The glass fiber constituting the printed circuit board may include one or more The following ingredients amounted to 5 Wt%: BaO; Be〇; CaF2; CdO; Mn2〇3; P2〇5; PbO; S〇3; Sb203; SrO; ZnO; and Zr02. The printed circuit board can further be wrapped in glass fibers per cubic centimeter. 11 201012771 contains no more than 5 hollow glass fibers β. [Embodiment] Shuming glazed fiber is used for supplementing (four) brushed circuit boards. The glass fibers have a low dielectric constant, a low dielectric tangent, and a low glass fiber forming temperature. The inventors have observed that the glass (four) dimension exhibits a low haze temperature, a low viscosity, and a reduced bubble in (iv) together with a corresponding reduction in hollow glass fibers and superior productivity. • The inventors have observed that the amount of different glass components must be carefully selected to achieve the desired balance of electrical, chemical, mechanical and thermal properties. To date, restrictions on the acceptability of glass fibers and the contribution of different glass components to these properties have not been properly established. The four properties have been selected as a measure of the performance of the glass fiber composition according to the present invention formed from the glass component shown in the following Table ι. • These metrics include: dielectric constant (Dk); dissipative factor or dielectric tangent (DfK high temperature viscosity (HTV) or viscosity equal to 1 Torr (〇F/〇c); (F/0C). The liquidus temperature is the maximum temperature at which the crystal and the melt coexist under thermal equilibrium. In view of the aforementioned performance metrics, the contribution of the glass composition to the four properties is evaluated @ acceptable level. For this purpose, consider the table j The composition of the two commercial E glass, NE glass and experimental glass examples, and for each of the glass of the table, is determined by the corresponding estimates of Dk, Df, high temperature viscosity (Ητν) and liquidus temperature in Table π. Compared with the published data, the table [the hunger and the evaluation of each glass is reasonable. Similarly, the actual glass fiber forming temperature is greater than HTV, which helps to produce glass fibers with a diameter of 5 microns. This is also quite obvious when HTV and liquidus temperatures are used because glass fibers cannot be formed commercially below liquidus temperature.

Samples of the two prepared E glasses and experimental glasses prepared at Dk and 0 at 10 GHz will now be referred to Table III below and continue to be referred to Tables I and II. Example In Glass Fiber Example #1, the relatively high weight percentage (Wt%) of vermiculite (si〇2), boron (Β2〇3), and titanium (Ti〇2) is selected to combine relatively low Wt%. Alumina to reduce Dk(R) glass fiber Example #1 has superior electrical properties as shown in Table η, as well as superior electrical properties as shown in Table 。. It should be understood that for each of the glass fibers listed in the two tables, the intensity difference level of the Df values in Tables II and m is due to the frequency used to measure Dk, ie the table and table (1) I〇ghz. Historically, 1 MHz was used to determine the frequency of the Dk value of fiberglass. However, today's printed circuit boards (PCBs) are increasingly used for components operating at GHz frequencies. For the exemplary operational values, the measurements of Dk and Df in Table III are performed at 1〇(}112. Salt is considered to be the htv phase calculated for the glass fiber of Example #1, high, and the glass fiber is prepared. It will crystallize. In the continuation of the example described below, the Wt% of vermiculite (Si〇2) is chosen to be closer to the glass fiber in the table [^^1^#2 t Si〇2 ^ per-example Difficulties encountered in making PCBs. 13 201012771 In glass fiber examples #2 and #3, sodium oxide (NaA) was reduced based on the Wt% of NazO, LisO and F2 used to produce the glass fibers of Example #1. The Wt% of lithium oxide (LisO) and fluorine (F2) will be compared to the HTV of the glass fiber of the example #2 and #3 of the glass fiber HTV of the example. Increasing the Wt% of sodium oxide (NazO) and fluorine (F2) based on the wt% of Na20 and F2 used to produce the NE glass of Tables I and II will reduce the glass of Examples #2 and #3 with respect to the HTV of NE glass. Fiber HTV. As shown in Tables π and III, the glass fibers of Examples #2 and #3 have superior electrical properties and superior electrical properties. However, the glass fibers of Examples #2 and #3 are liquid. The temperature is higher than the liquidus temperature of the glass fiber of Example #1. As shown in the glass fiber example #4, the oxidation of the glass fiber examples #丨, #2, and #3, based on the Wt% of CaO, MgO, and TiO2, is added. (ca〇) and Wt% of magnesium oxide (MgO) simultaneously reduce the wt% of titanium dioxide (Ti〇2). The glass fiber of example #4 is produced, which has more glass fibers than the examples #1, #2, and #3. Low liquidus temperature. φ In each glass fiber example, the Wt% of each component is carefully selected to maintain an optimal balance of electrical properties (Dk and Df), HTV, and liquidus temperature. In Example #5, 'Wt% of the composition of the glass fiber used to form Example #4 is adjusted to adjust the Wt% of the different components, especially the Wt% of CaO and MgO, Further improvements in Dk, HTV and liquidus temperatures. Finally, in Glass Fiber Example #6, Wt% of these same components in the glass fibers of Example #5, Wt of CaO, MgO, Na20, K20, Li20 and F2. The change in / is caused by changes in Dk, Df, HTV, and liquidus temperatures shown in Tables π and III. In Examples #ι至#5, the electrical properties of the glass 14 201012771 sample were measured and expressed in the table. Reported 0 times, based on the assessment of the nature of the repeated estimates and the measured properties of the table 111, the present month surprised to learn the glass composition (for example, in the case of unrestricted 'example #1 to The glass composition of #6 may exhibit a melting and glass fiber forming property similar to that of glass, while verifying superior electrical properties. The inventors believe that 'so far, the combination of such glass fiber forming properties and electrical properties is in this technology. It is not yet known. Lu 15 201012771

Table i Glass composition (wt%) E glass E glass NE Fan Fan Fan Fan Fan component glass glass example Example #1 #璃#1 #2 #3 #4 #5 #6 二氧化55.07 53.20 55.2 60. 52.8 52.8 52.6 54.9 55.5 矽7 00 0 5 9 9 8 18.4 20. 18.8 18.9 20.4 19.9 19.6 Boron oxide 5.53 8.38 5 00 0 7 9 3 9 15.0 5.0 15.9 15.8 12.1 11.8 11.8 Alumina 13.74 14.58 9 0 0 7 3 0 5 Calcium oxide 5.0 20.99 16.76 4.20 0 4.50 3.99 7.15 5.92 6.04 Magnesium oxide 4.0 2.47 4.84 4.38 0 4.00 3.96 5.09 4.20 4.06 Sodium oxide 1.38 .33 .05 .75 .45 0.68 .60 1.60 1.80 Potassium oxide .09 .23 .00 .00 •00 .61 .84 .16 .22 Lithium oxide •00 •00 .14 .75 .45 .10 .12 .19 .25 Dioxide .50 .28 1.99 4.0 2.80 2.69 .37 .40 .41 Titanium 0 Fluorine .02 .62 •02 .50 .30 .29 •53 .79 • 18 Trioxide .234 .335 .092 .01 .015 .017 •017 .017 .054 One Mb One Iron 5 16 201012771

Table II Estimated Properties at 1 MHz E-glass E-glass NE Fan Fan Fan Fan Fan Fan Properties Glass Glass Example Example #1 #2 璃#1 #2 #3 #4 #5 #6 Dk 6.85 6.39 5.02 4.42 5.09 5.16 5.33 4.68 5.03 Df x 8.35 12.12 10.57 14.69 6.17 5.74 7.29 5.10 4,65 104 2395 2172 2088 2034 1966 1951 HTV 1945/ 2122/ 2449/ / / / / / / (°F/° 1062. 1161. 1342. 1312. 1188 1142 1112 1074 1066 C) 8 1 8 8 .9 .2 .2 .4 .1 Liquid phase 2074/ 2131 / 2251 / 2114 / 2248 2238 2110 2095 2090 Temperature 1134. 1166. 1232. 1156. / / / / / (°F/° 1231 1225 1154 1146 1143 4 1 8 7 C) .1 .6 .4 .1 .3 Table III Measurement properties at 10 GHz (measurement #1) Sample examples of E-glass E-glass examples Example Example Example Nature Glass #1 璃#2 #1 #2 #3 #4 #5 #6 Dk 6.85 6.29 5.07 5.04 5.08 5.12 5.08 5.17 Df .0094 .0059 .0047 .0052 .0053 .0053 .0074 .0064 17 201012771 Measurement properties at 10 GHz (measurement #2) E-glass E-glass properties #1 璃#2 Sample example #1 #2 Example m Example #4 Example #5 Example #6 Dk 6.82 6.28 5.07 5.09 5.08 5.12 5.0 8 Df .0079 .0051 .0044 .0045 .0056 •0055 .0075 In Tables I, II, and III, “Ex :” = Example To determine the glass melting condition similar to E glass, consider

The melting temperature of 2,588 °F (1420 °C) as disclosed in U.S. Patent No. 2,334,961 to Schoenlaub, and 2,350 °F and 2450.1 (1288. Melting temperature between 1343 ° C. For the melting of a batch of borosilicate glass in a crucible, the general practice is to melt the two feeds and then maintain the resulting melt at 2470 ° F (1354 ° C). 14 hours. After the laboratory melting of Examples #1 to #6 above, five batches of different Example #5 glasses totaling more than 6000 pounds were prepared. In each example, the batch was 2500 in a clay crucible. Melt at °F (1371 ° C), then at 2500 ° F (1371 ° C) for 16 hours. Then take the molten glass from the crucible g and quench it in water. Rapid cooling causes the glass to crack into glass chips, It can be remelted in a standard glass ball melt bushing. The glass flakes are then placed in a standard glass ball melt bushing under process conditions similar to those used for melting and forming E glass fiber as described in Lowenstein, pages 115-121. Remelting and forming glass fibers. Due to the formation of glass 201012771 glass fiber The process is well known in the art, and for the sake of simplicity, such processes will not be described here. Although a small reduction is noted in the production of the fiber of Example #5 compared to the production of E glass. The glass flow rate and production efficiency still verify the commercial viability of the standard glass fiber forming process to form the surface fiber of Example #5. In the production of the glass woven glass sample of Example #5, the inventor was surprised that any sample The bubbles and hollow glass fibers are picked up. The fabric is then woven from these glass fibers, injected into a commercially available, steep target resin, and pressed into a laminate of the type used to make pcB. The same tree with a resin content of 68% by weight, t, together with a glass made of E glass, NE glass and sample #5: woven fabric, made together under 1 〇 GH.z The measured electrical properties are shown in the following hV. 19 201012771 Table IV Electrical Properties of the Laminates E Glass NE Glass Samples at 10 GHz and 68% Resin Content #5 Dk 3.30 3.00 2.97 Df 0.0090 0.0080 0.0079 Shown, experience It was found that the electrical properties of the PCB laminates made using the glass fibers of Example #5 are equivalent to the laminates made using existing high performance glass fibers and resins. At the same time, it has been verified that the above example #5 The melting of the glass fibers and the glass fiber forming temperature are comparable to those of the E glass, which has a corresponding improvement in productivity and completely eliminates bubbles and hollow glass fibers. The scope of each component of each of the exemplary glass compositions shown in Table I is not to be construed as limiting the invention. More specifically, it is desirable to include each component of Table I of the glass composition according to the present invention. The range may include: Si〇2 between 45 Wt% and 65 Wt%; Be3 between 15 arms (9) and ΜWt%; ai2〇3 between 8 goods (9) and 16 wt%; Between 〇wt〇/. Ca〇 between and ίο Wt%; Mg0 between 〇 wt% and 1〇 Wt%; between 〇 and 3

Na2〇\K2〇 between tWt%* 2 wt%; Li20 between 〇 and 20 201012771 2 Wt%; Ti〇2 between 〇Wt% and 5 Wt%; F2. between Wt/i and 2 Wt%; and Fe2〇3 between 0 Wt% and 1 contains more of each component of the surface composition of the glass composition according to the present invention. The range may include: Si〇2 between 48 wt% and 62 Wt%; b2〇3 between I? wt% and 23 Wt%; ai2o3 between 9 wt% and 15 wm; φ Ca0 between 2 Wt% and 10 Wt%, MgO between 2 Wt% and 8 Wt%; between 〇Wt. /. And 2

Na20 between Wt%; κ20 between 〇wt% and 1 Wt%; Li20 between 0 Wt% and 1 wt%; Ti02 between 0 Wt% and 2 Wt%; F2 between wt% and 1.5 Wt%; and Fe2〇3 between 〇Wt% and 0.8 Wt%. Finally, the most desirable range of each component of Table I comprising the glass composition according to the present invention may comprise: between 12 Wt% and 56 Wt% of SiO 2 ; between 18 Wt% and 22 Wt% Between B2〇3; Al2〇3 between #10 wt% and 14 wt%; CaO between 4 Wt%# 8 Wt%; between 2 Wt% and 6 Wt% MgO; Na2〇 between 0 Wt〇/〇 and 2 Wt%; K20 between 〇wt% and 1 Wt%; Li20 between 0 Wt% and 1 Wt%; between 0 Ti〇2 between Wt% and 0.5 Wt0/〇; F2 between 〇wt% and 1 Wt%; and Fe2〇3 between 0 Wt% and 0.4 Wt%. Although it is known in the art of glass fiber production to list the constituents based on the oxides of the elements, the ingredients can be added to the glass batch in several different forms. For example, lithium may be added without limitation, and it is also known in the art of glass fiber production that one or more other compounds may be added to improve the properties of the glass. For example, U.S. Patent No. 2,33, 463, to steinbock, discloses the addition of Ba,

Sr〇, Mn2〇3, Zn〇 and/or Cd〇 to glass compositions of the type shown by the watchmakers improve heat resistance, moisture resistance and chemical resistance. In addition, it has also been observed that the addition of Ba or SrO reduces the tendency of devitrification of the glass composition of the type shown in Table I. U.S. Patent No. 2,685,527 to U. The von Wranau et al. patent (discussed above) discloses glass compositions of the type shown in Table I, including the addition of Ba, CaFz, PbO, ZnO and/or ZrCh, exhibiting low melting and fiber forming temperatures, corrosion resistance , U.S. Patent Nos. 3,183,1,4, and 3,189,4*71, which are incorporated by reference to the disclosure of the disclosure. The material will improve the tensile strength and modulus. U.S. Patent No. 4,582,748 to the disclosure of U.S. Pat. The Yokoi et al. patent (discussed above) discloses that the addition of Zn 〇 also reduces the dielectric constant of the glass composition of the type shown in Table 。. The use of trace amounts of S〇3 in glass compositions of the type shown in Table 会 improves the water resistance and devitrification resistance of U.S. Patent No. 4,628, filed on Jan. It is expected that one of the foregoing compounds or a combination thereof may be added in an amount of up to 5% by weight to improve the properties of the glass. Finally, the International Patent Application Publication No. 22 201012771 WO/2002/094728 discloses that replacing P02 with P2〇5 in the glass composition of the type shown in Table I reduces the dielectric constant of the glass. The invention has been described with reference to the preferred embodiments. Once you have read and understood the detailed description above, those with ordinary skills in this technology will come up with obvious modifications and changes. For example, all Wt% between two Wt% contains the two Wt%, for example, between 17 Wt% and 23 Wt%, including 17 Wt% and 23 Wt%. It is intended that the present invention be construed as covering all such modifications and changes, [Simple description of the diagram] None [Key component symbol description] None 23

Claims (1)

201012771 VII. Patent application scope: u A broken glass fiber' consists of: si02 between 45 Wt% and 65 Wt%; b2〇3 between 15 Wt% and 25 Wt%; Al2〇3 between 8 Wt% and 16 Wt%; CaO less than or equal to 10 Wt%; MgO less than or equal to 1〇Wt%; φ less than or equal to 3 Wt% of Na20; less than or equal to 2 Wt% K20 ; Li20 less than or equal to 2 Wt%; Ti02 less than or equal to 5 Wt°/〇; F2 less than or equal to 2 Wt%; and Fe2〇1 less than or equal to 1 Wt%, wherein the glass fiber is not greater than 225 0°? (1232.2. <:) has a dielectric constant of less than or equal to 6 and a glass viscosity of 1 Torr. 2. The glass fiber of claim 1 wherein the glass fiber comprises no more than five hollow glass fibers per cubic centimeter of glass fiber. 24 1 The glass fiber according to claim 1 which further comprises at least one of the following, in an amount of 5 Wt%: BaO; BeO; 201012771 CaF2; CdO; Mn2〇3; P2O5; Pb〇; 〇3; Sb2〇3; SrO; ZnO; and Zr〇2 〇4. A glass fiber consisting of: si〇2 between 48 Wt% and 62 Wt%; between 17 Wt% and 23 B2〇3 between Wt%; ai2〇3 between 9 Wt% and 15 Wt%; Ca〇 between 2 Wt% and 1〇wt%. Between 2 Wt% and 8 Wt% Between the Mg〇; less than or equal to 2 Wt% of Na2〇; less than or equal to 1 Wt°/. Κ2ο ; less than or equal to 1 Wt°/. Li2〇; — Ti02 less than or equal to 2 Wt%; * Less than or equal to 1.5 Wt°/. F2; and Fe2〇3 less than or equal to 0.8 Wt0/〇, wherein the glass fiber has a dielectric constant of less than or equal to 6 and a wave of 1000 poise at a temperature of Φ not more than 2250 °F (1232.2 °C) Glass viscosity. 5 · The glass fiber according to item 4 of the research patent scope further contains not more than five hollow glass fibers per cubic centimeter of glass fiber. 6. The glass fiber of claim 4, further comprising at least one of the following: an amount of 5 wt%: Baa; Be〇; 25 201012771 CaF2; CdO; Mn2〇3; P205; Pb〇 ;s〇3.sb2〇3; Sr〇. ZnO; and Zr〇2 〇7. A glass fiber consisting of: si〇2 between 52 Wt% and 56 Wt%; between 1 8 B2〇3 between Wt% and 22 Wt%; a12〇3 between 10 Wt% and 14 Wt%; Ca〇 between 4 Wt% and 8 Wt%; reference between 2 Wt% Mg〇 between 6 Wt%; Na2〇 less than or equal to 2 Wt%; K2〇 less than or equal to 1 Wt%; Li2〇 less than or equal to i Wt%; ^ Less than or equal to 0.5 Wt°/. Ti〇2; • F2 less than or equal to 1 Wi°/〇; and Fe2〇3 less than or equal to 0.4 wt%, wherein the glass fiber has a temperature of not more than 225〇$(1232.2.(:) a dielectric constant (Dk) of less than or equal to 6 and a glass viscosity of 1 berth. 8. The glass fiber of claim 7 further comprising no more than five per cubic centimeter of glass fiber. The glass fiber bundle according to claim 7, which further comprises at least one of the following, in an amount of up to 5 Wt%: BaO; BeO; 26 201012771 Sr〇; CaF2; CdO; Mn203 P205; PbO; S03; Sb2〇3; ZnO; and ZrO, 〇10. A printed circuit board comprising one or more laminates, wherein each of the laminates comprises glass fibers supported by a resin, the glass fibers The dielectric viscosity is greater than 2250. (1232.2. The temperature at 〇 has a glass constant of less than or equal to 6 electrical constants (Dk) and 1 Torr. ❹ ❹ 11. The printed circuit according to claim 10 a board in which the glass fiber is composed of the following: SiO 2 between 45 Wt% and 65 Wt%; B203 between 15 Wt% and 25 Wt%; Al2〇3 between 8 Wt% and 16 Wt%; less than or equal to 1〇Wt % CaO ; - less than or equal to 1 〇 Wt% of MgO; less than or equal to 3 Wt% of Na2 〇; less than or equal to 2 Wt% of K20; less than or equal to 2 Wt% of Li20; less than or equal to 5 Wt% Ti02; F2 less than or equal to 2 wt%; and Fe203 less than or equal to 丨Wt%. 12. Printed circuit board mine as described in claim 10, 维 Λ quot "ΤΓ 7:,! Ze J» The glass fiber is composed of the following: 27 201012771 SiO 2 between 48 Wt% and 62 Wt%; B203 between 17 Wt% and 23 Wt%; between 9 Wt°/〇 and 15 Wt A1203 between %; CaO between 2 Wt°/〇 and 10 Wt%; MgO between 2 Wt% and 8 Wt%; Na20 less than or equal to 2 Wt%; less than or equal to 1 Wt % κ2ο ; Li20 less than or equal to 1 Wt%; Ti02 less than or equal to 2 Wt°/〇; F2 less than or equal to 1.5 Wt%; and Fe203 less than or equal to 0.8 Wt%. 13. The printed circuit board of claim 10, wherein the glass fiber is comprised of: SiO 2 between 52 Wt% and 56 Wt%; between 18 Wt% and 22 Wt% B203; A1203 between 10 Wt% and 14 Wt%; CaO between 4 Wt% and 8 Wt%; MgO between 2 Wt% and 6 Wt%; less than or equal to 2 Wt % Na20; κ2ο less than or equal to 1 Wt%; Li20 less than or equal to 1 Wt°/〇; Ti02 less than or equal to 0.5 Wt%; F2 less than or equal to 1 Wt%; and 28 201012771 less than or equal to 0.4 Wt . /. Fe203. 14. The printed circuit board of claim 10, wherein the glass fiber comprises one or more of the following components in an amount of up to 5 Wt%: BaO; BeO; CaF2; CdO; Mn203; P205; PbO; S03; Sb203; SrO; ZnO; and Zr02. 15. The printed circuit board of claim 10, which comprises no more than 5 hollow glass fibers per cubic centimeter of glass fibers. 201012771 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Reference 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: