Oxide-based glass composition having low permittivity, and glass fiber using same

Abstract

The present invention relates to an oxide-based glass composition having low permittivity and dielectric loss. The oxide-based glass composition according to the present invention can provide a PCB glass material and glass fiber having low permittivity and low dielectric loss, and has a low softening temperature and excellent fining characteristics, and thus can solve various problems of a conventional technology.

Description

Low dielectric constant oxide glass composition and glass fiber using the same

[0001] The present invention relates to an oxide-based glass composition and glass fibers using the same, and more particularly, to an oxide-based glass composition having low dielectric properties, low viscosity, and easy microbubble removal, and glass fibers using the same.

[0002] Multilayer printed circuit boards (PCBs) are a key component used in the development of high-performance IT devices. Driven by the growth of ultra-high-speed communications, autonomous vehicles, and artificial intelligence markets, demand for multilayer PCBs used in the development of high-performance signal processing boards is rapidly increasing.

[0003] CCL (Copper Clad Laminate) used in PCB development is largely composed of inorganic materials such as glass fiber, organic materials such as resin, filler, and copper foil. Glass fiber is used as the skeleton of the prepreg that makes up the CCL and plays an important role in ensuring that it has sufficient mechanical and thermal properties required.

[0004] In particular, as communication technology has recently become faster and larger in capacity, it is important to secure materials with low dielectric loss characteristics in the high-frequency signal band for substrate materials (CCL) used in communication equipment, base station radars, antennas, server boards, etc. To this end, it is essential to secure technology for glass fiber materials with low dielectric constant (ε) and dielectric dissipation factor (tanδ) that make up CCL.

[0005]

[0006] For example, conventional E-glass used in low-speed PCBs is made of glass materials with a composition of SiO2 54.3 wt%, B2O3 6 wt%, Al2O3 14 wt%, MgO+CaO 22.7 wt%, Li2O+Na2O+K2O 1.0 wt%, and FeO20.3 wt%. Such E-glass has a high permittivity in the range of 6.5-7.0 at 1 MHz and a high dielectric loss in the range of 0.005-0.008, making it difficult to use in high-frequency bands higher than 1 GHz due to high energy loss.

[0007] Therefore, in order to secure the dielectric properties of CCL required for ultra-high-speed communications of 5G and higher, the existing general glass fiber (E-glass) material for electronic devices has limitations, and it is necessary to secure a glass material with mechanical and thermal properties similar to existing materials but lower permittivity and dielectric loss characteristics, and glass technology using such a material. In order to secure the dielectric properties of CCL required for ultra-high-speed communications of 5G and higher, it is desirable to secure glass material technology with sufficiently low permittivity and dielectric loss characteristics in the high-frequency band of 10 GHz or higher. Recently, ultra-high-speed communications technology of 28 GHz or higher has been commercialized to increase data transmission capacity. Therefore, it is necessary to verify and secure low-k glass technology for glass fiber used in printed circuit boards that has sufficient dielectric properties and physical properties in the ultra-high frequency band of 1 to 10 GHz and even tens of GHz or more.

[0008] To date, extensive research has been conducted on glass compositions with low dielectric properties for use in PCBs, and various low-k glass compositions have been proposed. For example, low-k glass typically contains 60–68 wt% SiO2, 7–12 wt% B2O3, and 9–14 wt% Al2O3. These glass compositions contain a high concentration of SiO2, which can increase viscosity and hinder glass fiber spinning. Adding alkaline ions to lower viscosity can also lead to other problems, such as deteriorating dielectric properties.

[0009] Another example is a low-k glass with a composition range of SiO2 50-60 wt%, B2O3 15-25 wt%, Al2O3 10-18 wt%, and CaO+MgO 5-12 wt%. In the case of such a composition, the large amount of B2O3 contained may cause various problems such as reduced water resistance, increased bubble generation, and reduced mechanical strength, which entails the difficulty of using additional additives or optimizing the composition.

[0010]

[0011] In order to be used as a low-k glass material for glass fiber used in PCBs, various properties such as dielectric properties, viscosity, microbubble properties, and thermal stability must be secured.

[0012] To be more specific, glass fiber materials for PCBs must exhibit low signal transmission loss. To achieve this, the glass material must have sufficiently low permittivity and dielectric loss. Glass fiber materials for PCBs typically have a permittivity of 4.9 or lower and a dielectric loss of 0.005 or lower.

[0013] Additionally, the low-k glass material used in PCBs must be capable of being manufactured into glass fibers with diameters ranging from several microns to tens of microns through a radiation process. To achieve this, the glass must have sufficiently low viscosity and be free of microbubbles.

[0014] If the viscosity of the glass is not sufficiently low, the temperature must be increased, which shortens the life of the bushing module made of platinum and makes it difficult to control the diameter of the glass fiber and achieve high-speed spinning. In addition, it is necessary to easily remove air bubbles (or microbubbles) present in the glass. Air bubbles present in the glass cause the glass fiber to break during the spinning process. In the past, substances with a fining effect such as As2S3, Sb2O3, and Na2SO4 were used to remove air bubbles in the glass. However, the use of these substances can cause the dielectric properties of the glass to deteriorate or cause toxicity. In addition, the glass must have sufficient thermal stability for smooth glass fiber spinning. If the thermal stability of the glass is low, crystallization (devitrification) occurs in the glass fiber during the spinning process, which can cause the glass fiber to break or the bushing hole to become clogged, making continuous glass fiber production impossible.

[0015] The present invention aims to solve the problems of the prior art by presenting a glass material and glass fiber technology having low dielectric properties as well as excellent viscosity, microbubble properties, and thermal stability.

[0016] The present invention is intended to solve various problems of the prior art, and provides an oxide-based glass composition having low viscosity, easy radiation, excellent microbubble characteristics, and low dielectric constant and dielectric loss, and a glass fiber technology using the same.

[0017] The present invention can provide a low-k glass composition characterized by having a glass component including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and tellurium oxide (TeO2).

[0018] The above glass composition may additionally include one or two or more selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), and strontium oxide (SrO).

[0019] The above glass composition may additionally include one or two or more selected from the group consisting of lithium oxide (Li2O), sodium (Na2O), and potassium oxide (K2O).

[0020] The above glass composition may additionally include one or two or more selected from the group consisting of phosphorus pentoxide (P2O5), titanium oxide (TiO2), and fluorine (F2).

[0021] The above glass composition may additionally include one or two or more selected from the group consisting of zinc oxide (ZnO), gallium oxide (Ga2O3), and indium oxide (In2O3).

[0022] The present invention provides a low-k glass composition characterized by having a glass component including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and germanium oxide (GeO2).

[0023] The above glass composition may additionally include one or two or more selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), and strontium oxide (SrO).

[0024] The above glass composition may additionally include one or two or more selected from the group consisting of lithium oxide (Li2O), sodium (Na2O), and potassium oxide (K2O).

[0025] The above glass composition may additionally include one or two or more selected from the group consisting of phosphorus pentoxide (P2O5), titanium oxide (TiO2), and fluorine (F2).

[0026] The above glass composition may additionally include zinc oxide (ZnO), gallium oxide (Ga2O3), and indium oxide (In2O3).

[0027] In addition, the present invention provides a low-k glass composition characterized by having a glass component including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), tellurium oxide (TeO2), and germanium oxide (GeO2).

[0028] The above glass composition may additionally include one or two or more selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), and strontium oxide (SrO).

[0029] The above glass composition may additionally include one or two or more selected from the group consisting of lithium oxide (Li2O), sodium (Na2O), and potassium oxide (K2O).

[0030]

[0031] The above glass composition may additionally include one or two or more selected from the group consisting of phosphorus pentoxide (P2O5), titanium oxide (TiO2), and fluorine (F2).

[0032] The above glass composition may additionally include one or two or more selected from the group consisting of zinc oxide (ZnO), gallium oxide (Ga2O3), and indium oxide (In2O3).

[0033] In addition, the present invention can provide a glass fiber formed from a low-k glass composition having a glass component including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and tellurium oxide (TeO2).

[0034] In addition, the present invention can provide a glass fiber formed from a low-k glass composition having a glass component including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and germanium oxide (GeO2).

[0035] In addition, the present invention can provide a glass fiber formed from a low-k glass composition having a glass component including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), tellurium oxide (TeO2), and germanium oxide (GeO2).

[0036] According to the present invention, the glass composition exhibits low viscosity, facilitating radiation, excellent microbubble properties, and low dielectric constant and dielectric loss. The glass composition according to the present invention can be utilized as glass fiber for printed circuit boards requiring low dielectric properties, high mechanical strength, and low thermal expansion properties.

[0037] FIG. 1 shows an SEM image of a low-k glass fiber made through a glass fiber spinning process using glass having a glass composition of 25 (Table 2) according to one embodiment of the present invention.

[0038] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings. However, the following embodiments are provided to enable those of ordinary skill in the art to fully understand the present invention, and may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

[0039] When it is said in the detailed description or claims of an invention that one component "includes" another component, this is not to be construed as being limited to that component alone, unless specifically stated to the contrary, and should be understood to mean that it may further include other components.

[0040]

[0041] A low-k glass composition according to a preferred embodiment of the present invention has glass components including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and tellurium oxide (TeO2).

[0042] The above glass composition may additionally include one or two or more selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), and strontium oxide (SrO).

[0043] The above glass composition may additionally include one or two or more selected from the group consisting of lithium oxide (Li2O), sodium (Na2O), and potassium oxide (K2O).

[0044] The above glass composition may additionally include one or two or more selected from the group consisting of phosphorus pentoxide (P2O5), titanium oxide (TiO2), and fluorine (F2).

[0045] The above glass composition may additionally include one or two or more selected from the group consisting of zinc oxide (ZnO), gallium oxide (Ga2O3), and indium oxide (In2O3).

[0046] A low-k glass composition according to another preferred embodiment of the present invention has glass components including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and germanium oxide (GeO2).

[0047] The above glass composition may additionally include one or two or more selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), and strontium oxide (SrO).

[0048] The above glass composition may additionally include one or two or more selected from the group consisting of lithium oxide (Li2O), sodium (Na2O), and potassium oxide (K2O).

[0049] The above glass composition may additionally include one or two or more selected from the group consisting of phosphorus pentoxide (P2O5), titanium oxide (TiO2), and fluorine (F2).

[0050] The above glass composition may additionally include one or two or more selected from the group consisting of zinc oxide (ZnO), gallium oxide (Ga2O3), and indium oxide (In2O3).

[0051] According to another preferred embodiment of the present invention, a low-k glass composition has glass components including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), tellurium oxide (TeO2), and germanium oxide (GeO2).

[0052] The above glass composition may additionally include one or two or more selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), and strontium oxide (SrO).

[0053] The above glass composition may additionally include one or two or more selected from the group consisting of lithium oxide (Li2O), sodium (Na2O), and potassium oxide (K2O).

[0054] The above glass composition may additionally include one or two or more selected from the group consisting of phosphorus pentoxide (P2O5), titanium oxide (TiO2), and fluorine (F2).

[0055] The above glass composition may additionally include one or two or more selected from the group consisting of zinc oxide (ZnO), gallium oxide (Ga2O3), and indium oxide (In2O3).

[0056] A glass fiber according to a preferred embodiment of the present invention is a glass fiber formed from a low-k glass composition having glass components including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and tellurium oxide (TeO2).

[0057] According to another preferred embodiment of the present invention, a glass fiber is a glass fiber formed from a low-k glass composition having glass components including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and germanium oxide (GeO2).

[0058] According to another preferred embodiment of the present invention, a glass fiber is a glass fiber formed from a low-k glass composition having glass components including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), tellurium oxide (TeO2), and germanium oxide (GeO2).

[0059]

[0060] In the case of oxide glass compositions with low dielectric properties, the silica content is generally increased and the content of alkaline earth components such as aluminum oxide, MgO, and CaO is decreased in order to lower the permittivity and dielectric loss, so compared to general PCB glass compositions such as E-glass, the viscosity may be high, making it difficult to spin glass fibers. This may cause a problem.

[0061]

[0062] The glass composition and glass fiber technology using the same according to the present invention aims to solve the problems of the prior art by using tellurium oxide (TeO2) or germanium oxide (GeO2) as a glass component. Hereinafter, a low-k glass composition according to a preferred embodiment of the present invention will be described in more detail.

[0063]

[0064] An oxide-based glass composition having low dielectric properties according to one embodiment of the present invention includes silica (SiO2); boron trioxide (B2O3); aluminum oxide (Al2O3); and tellurium oxide (TeO2).

[0065] The above silica (SiO2) is an essential glass former component that forms the glass network. As a glass component, silica (SiO2) is an important component that ensures vitrification, thermal stability, excellent mechanical properties, and low thermal expansion properties of glass, and that glass has low dielectric constant and dielectric dissipation factor characteristics.

[0066] More specifically, if the content of the silica (SiO2) component is too low, the dielectric constant of the glass may increase and the mechanical strength of the glass may decrease. In addition, if the content of the silica (SiO2) component is too high, the viscosity of the glass may increase, making it difficult to homogenize during the melting process and making it difficult to create glass fibers during the spinning process.

[0067] The above boron trioxide (B2O3) is an important component that lowers the viscosity of glass, facilitating the melting process of glass, enabling the glass fiber spinning process at low temperatures, and ensuring that the glass composition has low permittivity and dielectric loss characteristics.

[0068] More specifically, when the content of the boron trioxide (B2O3) component is too low, it is difficult to secure sufficiently low dielectric constant and dielectric loss characteristics, and the desired viscosity of the glass composition including the silica (SiO2) may increase, which may cause problems such as difficulty in melting and glass fiber spinning. On the other hand, when the content of the boron trioxide (B2O3) component is too high, the glass's resistance to moisture may weaken, bubbles may be generated during the spinning process, mechanical strength may be weakened, and the thermal expansion coefficient of the glass may increase.

[0069] The above aluminum oxide (Al2O3) is a glass intermediate that increases the stability of glass, facilitates vitrification, and prevents crystallization, devitrification, and phase separation of glass during the glass melting and glass fiber spinning processes. In addition, the above aluminum oxide (Al2O3) can control the viscosity of glass within an appropriate range and improve mechanical strength.

[0070] More specifically, if the content of the aluminum oxide (Al2O3) is too low, the glass stability may be low, crystallization (devitrification) and phase separation may easily occur, and it may be difficult to secure sufficient mechanical strength. On the other hand, if the content of the aluminum oxide (Al2O3) is too high, the dielectric constant may increase, the thermal stability of the glass may deteriorate again, and the viscosity of the glass in a molten state may become too high, making it difficult to spin glass fibers.

[0071] The tellurium oxide (TeO2) used in accordance with the present invention is a component that has the function of lowering the viscosity of glass, thereby facilitating the spinning of glass fibers. In addition, tellurium oxide (TeO2) has a fining effect, and is a component that has the function of removing microbubbles generated in the glass during the glass melting process. In the prior art, substances such as As2S3, Sb2O3, and Na2SO4 have been used to remove microbubbles. These components have the disadvantage of being toxic or increasing the dielectric loss or permittivity of the glass. On the other hand, the tellurium oxide (TeO2) according to the present invention has the effect of controlling viscosity and removing microbubbles, and has the advantage of lowering or not significantly increasing the permittivity and dielectric loss. Therefore, the tellurium oxide (TeO2) added in accordance with the present invention can further have the effect of improving thermal and dielectric properties compared to glass to which germanium oxide is not added.

[0072]

[0073] According to another embodiment of the present invention, an oxide-based glass composition having low dielectric properties includes silica (SiO2); boron trioxide (B2O3); aluminum oxide (Al2O3); and germanium oxide (GeO2).

[0074] According to the present invention, the germanium oxide (GeO2) contained in the glass is a component that lowers the viscosity of the glass and facilitates glass fiber spinning. In addition, germanium oxide (GeO2) has a fining effect, and can remove microbubbles that are generated in the glass during the glass melting process. Germanium oxide (GeO2) has the characteristic of giving the glass a network structure like silica as a glass forming agent. Germanium oxide (GeO2), which is a component of the oxide-based glass composition having low dielectric properties according to the present invention, has the effect of controlling the viscosity of the glass and fining effects, and at the same time, has the effect of lowering or not significantly increasing the permittivity and dielectric loss. Therefore, the germanium oxide (GeO2) added according to the present invention can further have the effect of improving thermal and dielectric properties compared to glass to which germanium oxide is not added.

[0075]

[0076] According to another embodiment of the present invention, an oxide-based glass composition having low dielectric properties includes silica (SiO2); boron trioxide (B2O3); aluminum oxide (Al2O3); tellurium oxide (TeO2) and germanium oxide (GeO2).

[0077] For the purpose of the present invention, tellurium oxide and germanium oxide can be simultaneously contained in an oxide-based glass composition having low dielectric properties. In the oxide-based composition having the low dielectric properties, tellurium oxide can effectively produce a clarification effect that reduces the viscosity of the glass and removes microbubbles. On the other hand, if a glass composition containing silica as a main component contains tellurium oxide exceeding a certain amount, a problem may arise in the stability of the glass. On the other hand, germanium oxide (GeO2) is a glass network component with a structure similar to silica (SiO2) and has superior glass stability compared to tellurium oxide. Therefore, by simultaneously containing tellurium oxide (TeO2) and germanium oxide (GeO2) in the glass, it can have the advantage of exhibiting glass clarification and microbubble removal effects while simultaneously ensuring glass stability.

[0078]

[0079] A glass fiber according to a preferred embodiment of the present invention is a glass fiber formed using the low-k glass composition described above.

[0080] A glass fiber according to a preferred embodiment of the present invention is a glass fiber formed from a low-k glass composition having glass components including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and tellurium oxide (TeO2).

[0081] According to another preferred embodiment of the present invention, a glass fiber is a glass fiber formed from a low-k glass composition having glass components including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and germanium oxide (GeO2).

[0082] According to another preferred embodiment of the present invention, a glass fiber is a glass fiber formed from a low-k glass composition having glass components including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), tellurium oxide (TeO2), and germanium oxide (GeO2).

[0083]

[0084] Hereinafter, embodiments according to the present invention are specifically presented, and the present invention is not limited to the embodiments presented below.

[0085]

[0086] <Example 1>

[0087] After preparing raw materials having a glass component according to the present invention, a ball mill process was performed at 150 rpm for 12 hours (hr) to mix and grind the mixture to prepare a mixture. The prepared mixture was heated in an electric furnace at a melting temperature of 1550°C for 3 hours (hr) to vitrify the mixture, and then the melt was heated to 650°C. o After casting into a brass mold preheated to C, the glass was maintained near the glass transition temperature for 4 hours (hr) to relieve residual stress, and then slowly cooled to room temperature (25 ℃) to produce low-k glass.

[0088] The composition of the glass manufactured by the glass melting process according to Example 1 is SiO2: 55.0 mol%, B2O3: 27.2 mol%, Al2O3: 8.0 mol%, MgO: 1.0 mol%, CaO: 8.0 mol%, Na2O: 0.3 mol%, TeO2: 0.5 mol%. The glass manufactured according to Example 1 showed excellent dielectric properties with a 1 GHz permittivity of 4.84 and a dielectric loss of 0.0047. In addition, the permittivity and dielectric loss at 28 GHz were 4.88 and 0.0046, respectively, showing very excellent properties. In addition, the softening temperature of the glass analyzed by thermo-mechanical analysis (TMA) equipment was 747 o It showed excellent properties as C. This is because the softening temperature of commercial low-k glass (~850 o C) has the advantage of being much lower than that of commercial glass. The softening temperature is 100 oThe decrease in C indicates that the bonding structure of the glass changes due to the inclusion of TeO2, and accordingly, the viscosity characteristics of the glass are greatly improved.

[0089]

[0090] <Example 2>

[0091] Low-k glass was produced using a glass melting process under similar conditions to Example 1.

[0092] The composition of the glass produced by the glass melting process according to Example 2 is SiO2: 55.0 mol%, B2O3: 27.0 mol%, Al2O3: 8.0 mol%, MgO: 1.0 mol%, CaO: 8.0 mol%, Na2O: 0.5 mol%, GeO2: 0.5 mol%. The 1 GHz dielectric constant of the glass produced according to Example 2 was 4.78, and the dielectric loss was 0.0053, showing excellent dielectric properties.

[0093]

[0094] <Example 3>

[0095] Low-k glass was produced using a glass melting process under similar conditions to Example 1.

[0096] The composition of the glass manufactured by the glass melting process according to Example 3 is SiO2: 55.0 mol%, B2O3: 27.0 mol%, Al2O3: 8.0 mol%, MgO: 1.0 mol%, CaO: 8.0 mol%, TeO2: 0.5 mol%, GeO2: 0.5 mol%. The 1 GHz dielectric constant of the glass manufactured according to Example 3 was 4.71, and the dielectric loss was 0.0025, showing excellent dielectric properties. It shows that the glass composition containing both tellurium oxide and germanium oxide can induce better dielectric properties than the glass composition containing only tellurium oxide or germanium oxide.

[0097]

[0098] Table 1 below shows the component ratio (mol%) of the glass composition and the properties of the glass composition according to an embodiment of the present invention.

[0099] Glass composition numbers 1, 2, and 3 represent the composition and properties of the glasses according to Examples 1, 2, and 3, respectively. O, △, and X, indicated as bubble properties in the table, represent a large number of bubbles, a small number of bubbles, and almost no bubbles, respectively.

[0100] NoSiO2B2O3Al2O3MgOCaONa2OZnOGeO2TeO2CTE(ppm / o C)Tdg( o C)Tds( o C) Density (g / cm) 3)Dk@1GHzDf@1GHzDk@28GHzDf@28GHzBubble characteristicsRemarks155.027.28.01.08.00.3--0.54.206417472.3114.840.00474.880.0046X255.027.08.01.08.00.5-0.5----2.3004.780.0053X355.027.08.01.08.0--0.50.5---2.3124.710.0025X458.022.09.01.010.0-------2.3284.9070.0047OComparative example558.0 21.09.01.010.00.5--0.5---2.3574.9080.0086X658.021.09.01.010.00.5-0.5----2.3494.9120.0095X762.022.06.01.06.03.0---3.896137292.2864.7350.0207OComparative Example862.022.06.01.06.03.0-0.5-3.976067142.2904.7500.0203X962.022.06.01.06.03.0--0.54.096016692.2974.7 450.0194X1061.022.08.0-8.01.0---3.786447662.2874.8180.0093OComparative Example 1161.022.08.0-8.01.0-0.5-3.606457482.2974.8120.0086X1261.022.08.0-8.01.0--0.53.896327502.3044.8010.0079X1364.022.04.0--10.0------2.258--△Comparative Example 1464.022.04.0--9.0--1.0---2.273--X1564 .022.04.0--9.0-1.0----2.263--X1664.022.04.0-1.09.0---5.395476322.2665.1970.03△Comparative Example1764.022.04.0-1.08.0-1.0----2.262--X1864.022.04.0-1.08.0--1.0---2.272--X1964.022.04.0-1.08.5--0.55.565426192.271--X2064.022.04.0-1.08.00.5-0.55.635375842.276--X

[0101]

[0102] As another embodiment of the present invention, glass compositions 5 and 6 each contain 58.0 mol% of SiO2, 21 mol% of B2O3, 9.0 mol% of Al2O3, 1.0 mol% of MgO, 10.0 mol% of CaO, 0.5 mol% of Na2O, 0.5 mol% of TeO2, and 0.5 mol% of GeO2, respectively, and the characteristics of these glass compositions are compared with those of the comparative example (glass composition no. 4). It was confirmed that the density and dielectric constant (Dk@1GHz) of glass compositions 5 and 6 did not increase significantly compared to the comparative example glass that did not contain Na2O, even though they contained 0.5 mol% of Na2O compared to the comparative example. In addition, it was confirmed that the number of microbubbles contained in the glass was significantly reduced by the inclusion of GeO2 and TeO2.

[0103] As another example, glass compositions 8 and 9 show the properties of glass compositions containing 62.0 mol% of SiO2, 22 mol% of B2O3, 6.0 mol% of Al2O3, 1.0 mol% of MgO, 6.0 mol% of CaO, 3.0 mol% of Na2O, 0.5 mol% of TeO2, and 0.5 mol% of GeO2, respectively, compared to the comparative example (glass composition no. 7). It was confirmed that glass compositions 8 and 9 improved the viscosity and microbubble properties by containing GeO2 and TeO2, respectively, compared to the comparative example, and maintained the density and permittivity (Dk@1GHz) at similar levels to the comparative example glass. The reason that glass compositions 7, 8, and 9 have relatively high dielectric loss (Dk@1GHz= ~0.02) is because the Na2O content is high at 3 mol%. Therefore, it can be seen that too much Na2O can be used to secure viscosity reduction and glass stability, and that it is necessary to secure glass components and matrix composition technology that can replace these functions.

[0104] As another example, glass compositions 11 and 12 are glass compositions containing 61.0 mol% of SiO2, 22 mol% of B2O3, 8.0 mol% of Al2O3, 8.0 mol% of CaO, 1.0 mol% of Na2O, and 0.5 mol% of GeO2 and 0.5 mol% of TeO2, respectively, and do not contain MgO, and their characteristics are compared with those of the comparative example (glass composition no. 10). In glass compositions 11 and 12, it can be seen that the viscosity and microbubble characteristics are improved and the dielectric constant (Dk@1GHz) is lowered compared to the comparative example glass by containing GeO2 and TeO2, respectively. In addition, it was confirmed that the inclusion of GeO2 and TeO2 has the effect of slightly lowering the dielectric loss (Df@1GHz). The relatively high dielectric loss (Dk@1GHz= 0.0079-0.0093) in glass compositions 10, 11, and 12 is due to the high Na2O content of 1 mol%. Therefore, it indicates that too much Na2O may be used in low-k glasses.

[0105] As another example, glass compositions 14 and 15 contain 64.0 mol% of SiO2, 22 mol% of B2O3, 4.0 mol% of Al2O3, 9.0 mol% of Na2O, and 1.0 mol% of GeO2 and 1.0 mol% of TeO2, respectively, and show the characteristics of a glass composition that does not contain MgO and CaO, compared to a comparative example (glass composition no. 13). It was confirmed that in glass compositions 14 and 15, the viscosity and microbubble characteristics were improved and the density was maintained at a similar level by containing GeO2 and TeO2, respectively, compared to the comparative example.

[0106] As another example, glass compositions 17 and 18 contain 64.0 mol% of SiO2, 22 mol% of B2O3, 4.0 mol% of Al2O3, 1.0 mol% of CaO, 8.0 mol% of Na2O, and 1.0 mol% of GeO2 and 1.0 mol% of TeO2, respectively, and show the characteristics of glass compositions that do not contain MgO, compared to a comparative example (glass composition no. 16). In glass compositions 17 and 18, it was confirmed that the viscosity and microbubble characteristics were improved and the density was lowered or maintained at a similar level to that of the comparative example glass by containing GeO2 and TeO2, respectively.

[0107] Next, as other examples, glass compositions 19 and 20 contain SiO2 64.0 mol%, B2O3 22 mol%, Al2O3 4.0 mol%, CaO 1.0 mol%, and Na2O 8.5 mol% + TeO2 0.5 mol% and Na2O 8.0 mol% + TeO2 0.5 mol% + ZnO 1.0 mol%, respectively, and do not contain MgO, and the characteristics of the glass compositions are shown in comparison with the comparative example (glass composition number 16). In glass compositions 11 and 12, it can be confirmed that the viscosity and microbubble characteristics are greatly improved compared to the comparative example by containing GeO2 and TeO2, respectively, and the density is not greatly increased compared to the comparative example glass.

[0108]

[0109] Table 2 below shows the component ratio (mol%) of the glass composition and the properties of the glass composition according to another embodiment of the present invention.

[0110] In Table 2, O, △, and X, which are indicated as bubble characteristics, indicate that there are a large number of bubbles, a small number of bubbles, and almost no bubbles, respectively.

[0111] NoSiO2B2O3Al2O3MgOCaONa2OSnO2GeO2TeO2CTE(ppm / o C)Tdg( o C)Tds( oC) Density (g / cm) 3)Dk@1GHzDf@1GHzDk@28GHzDf@28GHzBubble characteristicsRemarks2155.0027.28.01.08.00.3-0.5-4.356487122.3114.910.00514.840.00418X2257.0025.28.01.08.00.3-0.5----2.3254.790.0051X2358.6022.09.01.09.0-0.4--3.577047992.3584.890.0080△Comparative example2458.3522.09.01.09.0-0.40.25-3.536817882.3594 .880.0058X2558.1022.09.01.09.0-0.40.5-3.646837852.3664.870.006 7X2657.8522.09.01.09.0-0.40.75-3.836807852.3694.860.0068X2757. 6022.09.01.09.0-0.41.0-3.556867792.3724.840.0058X2857.3522.09. 01.09.0-0.41.25-3.756837762.3744.830.0066X2957.1022.09.01.09.0- 0.41.5-3.806797532.3804.810.0065X3058.7522.09.01.09.0---0.254. 026697812.3324.850.0012X3158.5022.09.01.09.0---0.54.176687802. 3374.810.0010X3258.2522.09.01.09.0---0.754.036647742.3444.770. 0015X3358.0022.09.01.09.0---1.03.966667242.3514.740.0011X3458.9 022.09.01.09.00.1------2.329--△Comparative example 3558.8022.09.01.09.00.1--0.1---2.312--X3658.7022.09.01.09.00.1--0.2---2.318--X3758.3022.09. 01.09.00.1-0.50.1---2.323--X3858.2022.09.01.09.00.1-0.50.2---2 .323--X3958.5022.09.01.09.0--0.5----2.316--X4057.5022.09.01.09.0--1.5----2.328--X.

[0112] As an example, glass composition 21 shows the characteristics of a glass composition containing 55.0 mol% of SiO2, 27.2 mol% of B2O3, 8.0 mol% of Al2O3, 1.0 mol% of MgO, 8.0 mol% of CaO, 0.3 mol% of Na2O, and 0.5 mol% of GeO2. It was confirmed that glass composition 21 has relatively excellent dielectric properties, with a low density of about 2.311 and a permittivity and dielectric loss of 4.91 and 0.0051 at 1 GHz, and 4.84 and 0.00418 at 28 GHz, respectively.

[0113] As an example, glass composition 22 shows the characteristics of a glass composition containing SiO2 57.0 mol%, B2O3 25.2 mol%, Al2O3 8.0 mol%, MgO 1.0 mol%, CaO 8.0 mol%, Na2O 0.3 mol%, and GeO2 0.5 mol%. Glass composition 22 was confirmed to have excellent dielectric properties, with a low density of approximately 2.325 and a permittivity and dielectric loss at 1 GHz of 4.79 and 0.0051, respectively.

[0114] As an example, glass compositions 24-29 show the properties of glass compositions containing 58.35-57.10 mol% of SiO2, 22.0 mol% of B2O3, 9.0 mol% of Al2O3, 1.0 mol% of MgO, 9.0 mol% of CaO, 0.4 mol% of SnO2, and 0.25-1.5 mol% of GeO2, compared to a comparative example (glass composition No. 23). As shown in the table, as the content of GeO2 increases from 0.25 to 1.5 mol%, the density increases from 2.359 to 2.380 g / cm. 3It can be seen that the dielectric constant (Dk@1GHz) gradually increases from 4.88 to 4.81, compared to 4.89 of the comparative glass. In particular, the dielectric loss (Df@1GHz) was 0.0058-0.0068, which was lower than that of the comparative glass. These results indicate that GeO2 is effective in improving the dielectric properties of glass. In addition, as the GeO2 content increases, the softening temperature of the glass is also lower than that of the comparative glass, from 788 to 753. o It can be confirmed that C continuously decreases, and it can be seen that the viscosity of the glass is lowered by including GeO2, which enables radiation at a relatively low temperature, thereby ensuring ease of radiation. The coefficient of thermal expansion (CTE) is also 3.53-3.83 ppm / o It can be confirmed that C has very excellent characteristics.

[0115] As an example, glass compositions 30-33 show the characteristics of glass compositions containing 58.75-58.00 mol% of SiO2, 22.0 mol% of B2O3, 9.0 mol% of Al2O3, 1.0 mol% of MgO, 9.0 mol% of CaO, and 0.25-1.0 mol% of TeO2, compared to a comparative example (glass composition No. 23). As shown in the table, as the content of TeO2 increases from 0.25 to 1.0 mol%, the density increases from 2.332 to 2.351 g / cm. 3 It can be seen that the dielectric constant (Dk@1GHz) gradually increases. On the other hand, it was confirmed that the dielectric constant (Dk@1GHz) continuously decreases from 4.85 to 4.74 compared to 4.89 of the comparative glass. These results indicate that TeO2 is effective in greatly improving the dielectric constant of the glass. In particular, it can be confirmed that the dielectric loss (Df@1GHz) is 0.0011-0.0015, which is significantly lower than the dielectric loss of the comparative glass (glass composition number 23) of 0.0080. In addition, the softening temperature is also much lower than that of the comparative glass, 781-724o As C, it is significantly reduced compared to the comparative glass that does not contain TeO2, and the coefficient of thermal expansion is also 4.17-3.96 ppm / o It can be confirmed that C has very excellent characteristics.

[0116] As an example, glass compositions 35-36 show the properties of glass compositions containing 58.80-58.70 mol% of SiO2, 22.0 mol% of B2O3, 9.0 mol% of Al2O3, 1.0 mol% of MgO, 9.0 mol% of CaO, and 0.1-0.2 mol% of TeO2, compared to a comparative example (glass composition number 34). As shown in the table, it can be seen that the density decreases compared to the comparative example glass when TeO2 is contained.

[0117] As an example, glass composition 37-40 shows the properties of glass compositions containing 58.50-57.50 mol% of SiO2, 22.0 mol% of B2O3, 9.0 mol% of Al2O3, 1.0 mol% of MgO, 9.0 mol% of CaO, and 0.5 mol% of GeO2 + 0.1 mol% of TeO2, 0.5 mol% of GeO2 + 0.2 mol% of TeO2, 0.5 mol% of GeO2, or 1.5 mol% of GeO2, compared to a comparative example (glass composition No. 34). As shown in the table, in all examples, it can be seen that the density is relatively lower compared to the comparative example glass when GeO2 and TeO2 are contained.

[0118]

[0119] <Example 4>

[0120] As an example, glass having the glass composition 25 of Table 2 was manufactured through a glass melting process, and used at a radiation temperature of 1380 oLow-k glass fiber was spun in C. In a test spinning experiment, it was possible to spin continuously for more than 3 hours at a spinning speed of more than 250 m / min, and no crystallization phenomenon occurred in the glass melt maintained at a high melting temperature for a long time during the spinning process.

[0121] Fig. 1 shows SEM images of radiated glass fibers. Fig. 1-a) is an SEM image of glass fibers made using glass having a glass composition 25 of the above Example Table 2. Figs. 1-b) to 1-d) show enlarged SEM images of different parts of Fig. 1-a). Referring to Figs. 1-a) to 1-d), the SEM images show the surface condition of the glass fibers without any defects. As a result of measuring the diameter of the glass fibers at various parts, it was confirmed that the diameter of the glass fibers was uniform at about 9.6 micrometers.

[0122]

[0123]

[0124] Therefore, the results presented in Tables 1 and 2 and FIG. 1 show that the oxide-based glass composition according to the present invention has excellent properties and characteristics required for manufacturing low-k glass fiber.

[0125]

[0126] Above, the preferred embodiments of the present invention have been described in detail, but the present invention is not limited to the above embodiments, and various modifications are possible by those skilled in the art.

Claims

1. A low-k glass composition characterized by having a glass component including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and tellurium oxide (TeO2).

2. In paragraph 1, A low-dielectric glass composition, wherein the glass component further comprises one or two or more selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), and strontium oxide (SrO).

3. In paragraph 1, A low-dielectric glass composition, wherein the glass component further comprises one or two or more selected from the group consisting of lithium oxide (Li2O), sodium (Na2O), and potassium oxide (K2O).

4. A low-k glass composition in the first paragraph, wherein the glass component further comprises one or two or more selected from the group consisting of phosphorus pentoxide (P2O5), titanium oxide (TiO2), and fluorine (F2).

5. A low-k glass composition according to claim 1, wherein the glass component further comprises zinc oxide (ZnO), gallium oxide (Ga2O3), and indium oxide (In2O3).

6. A low-k glass composition characterized by having a glass component including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and germanium oxide (GeO2).

7. A low-k glass composition in claim 6, wherein the glass component further comprises one or two or more selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), and strontium oxide (SrO).

8. A low-k glass composition in claim 6, wherein the glass component further comprises one or two or more selected from the group consisting of lithium oxide (Li2O), sodium (Na2O), and potassium oxide (K2O).

9. A low-k glass composition in the 6th paragraph, wherein the glass component further comprises one or two or more selected from the group consisting of phosphorus pentoxide (P2O5), titanium oxide (TiO2), and fluorine (F2).

10. A low-k glass composition in claim 6, wherein the glass component further comprises one or two or more selected from the group consisting of zinc oxide (ZnO), gallium oxide (Ga2O3), and indium oxide (In2O3).

11. A low-k glass composition characterized by having a glass component including silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), tellurium oxide (TeO2), and germanium oxide (GeO2).

12. A low-k glass composition according to claim 11, wherein the glass component further comprises one or two or more selected from the group consisting of magnesium oxide (MgO), calcium oxide (CaO), and strontium oxide (SrO).

13. A low-k glass composition according to claim 11, wherein the glass component further comprises one or two or more selected from the group consisting of lithium oxide (Li2O), sodium (Na2O), and potassium oxide (K2O).

14. A low-k glass composition according to claim 11, wherein the glass component further comprises one or two or more selected from the group consisting of phosphorus pentoxide (P2O5), titanium oxide (TiO2), and fluorine (F2).

15. A low-k glass composition in claim 11, wherein the glass component further comprises one or two or more selected from the group consisting of zinc oxide (ZnO), gallium oxide (Ga2O3), and indium oxide (In2O3).

16. A glass fiber formed from a low-k glass composition having a glass component comprising silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and tellurium oxide (TeO2).

17. A glass fiber formed from a low-k glass composition having a glass component comprising silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), and germanium oxide (GeO2).

18. A glass fiber formed from a low-k glass composition having a glass component comprising silica (SiO2), boron trioxide (B2O3), aluminum oxide (Al2O3), tellurium oxide (TeO2), and germanium oxide (GeO2).

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