Glass fiber composition, and glass fiber and composite material having low dielectric properties prepared therefrom

Abstract

Disclosed in the present application are a glass fiber composition, and a glass fiber and composite material having low dielectric properties prepared therefrom. The glass fiber composition comprises the following components in weight percentage: 48%-57% of SiO2, 19%-29% of B2O3, 10%-14% of Al2O3, 0.5%-5.0% of CaO, 0%-2.0% of MgO, 0.5%-6.0% of ZnO, 0.05%-4.0% of La2O3, 0.01%-0.45% of the total amount of Na2O + K2O + Li2O, and 0%-0.5% of Fe2O3, wherein the sum of the weight percentages of all the components is greater than or equal to 99.0%, the weight percentage ratio C1 = ZnO / (CaO + MgO) is in a range of 0.25-2.5, and the weight percentage ratio C2 = La2O3 / ZnO is in a range of 0.008-4. By using the glass fiber composition, the glass fiber having a low dielectric constant, low dielectric loss, moderate viscosity, and a wide fiber-forming range can be obtained.

Description

A glass fiber composition and the glass fiber and composite material thereof having low dielectric properties

[0001] This application claims priority to Chinese Patent Application No. 202510233572.2, filed on February 28, 2025, entitled "A glass fiber composition and glass fiber and composite material made therefrom having low dielectric properties", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to a glass fiber composition and glass fibers and composite materials made from the composition, particularly to glass fibers with high-frequency and low dielectric properties, which are especially suitable for the fields of copper clad laminates and printed circuit boards. Background Technology

[0003] The "14th Five-Year Plan for National Economic and Social Development and the Outline of Long-Term Goals for 2035" released by the State Council at the end of 2020 clearly stated: Systematically plan new infrastructure and accelerate the construction of 5G mobile communication, industrial internet, and big data centers. With the arrival of the highly information-driven era, electronic device development has entered a new stage of high integration and lightweighting, further expanding the demand for copper clad laminates (CCL) and printed circuit boards (PCBs). Low-dielectric glass fiber, as an important component of electronic glass fiber cloth, CCL, and PCB, has a promising market prospect due to its ability to meet the high-frequency and high-speed parameter requirements of 5G and 6G communication. Its core performance characteristics are low dielectric constant and low dielectric loss, with lower being better. However, traditional electronic glass (alkali-free glass, abbreviated as E glass) cannot meet the needs of high-end CCL and PCB.

[0004] Against this backdrop, researchers both domestically and internationally have been continuously developing in this field. However, existing research findings often have some shortcomings in practical applications. It is well known that quartz glass possesses excellent low dielectric properties, with a dielectric constant of approximately 3.74 and a loss of approximately 0.2‰ at a high frequency of 10GHz, essentially representing the low-loss limit for glass materials. However, its melting and fiber drawing requirements are too stringent, making mass production difficult. Therefore, D-glass was developed. Its main composition is a SiO2+B2O3 system, with an dielectric constant below 4.5 and excellent dielectric loss performance. However, D-glass also has significant drawbacks; it remains difficult to melt and clarify, hindering fiber drawing and shaping. In existing patented technologies, the glass composition system is basically Si2O+B2O3+Al2O3+CaO+MgO. Its dielectric constant is ≤4.8 and dielectric loss is ≤4.0‰ under high frequency conditions of 10GHz. The high temperature viscosity and forming range of the glass are moderate. However, although it has the feasibility of continuous production, it is difficult to break through the dielectric loss to below 2.5‰ under the condition of ensuring production requirements.

[0005] As a result, the relevant technologies were developed.

[0006] In patent CN118176170A, the mass contents of each component are as follows: SiO2 36-48%, B2O3 18-32%, Al2O3 12-24%, P2O5 2.5-8.9%, and CaO+MgO 5.0-13.0%.

[0007] In patent CN116670091A, the mass contents of each component are as follows: SiO2 50-61%, B2O3 16-27%, Al2O3 7-14%, P2O5 0.2-4.0%, TiO2 0.5-5%, CaO 0.1-5.0%, MgO 0-4.0%, and F2+Cl2 0-2.0%.

[0008] In patent CN103482876A, the mass content of each component is as follows: SiO2 48%–53%, Al2O3 13%–16%, B2O3 19%–25%, P2O5 0.5%–2%, CaO 5.0%–8.5%, La2O3 0.5%–8%, ZnO 0.5%–2.5%, TiO2 0.5%–2%, Na2O, K2O, and Li2O less than 1%, SO3 less than 0.45%, and Fe2O3 less than 0.45%. Summary of the Invention

[0009] In view of the shortcomings of existing low-dielectric glass fiber technology, and in combination with the characteristics of glass fiber production process, this application provides a glass fiber composition and glass fibers with low dielectric properties made therefrom. The glass fiber composition can produce glass fibers with low dielectric constant, low dielectric loss, moderate viscosity and a wide fiber forming range.

[0010] To achieve the above objectives, this application controls the contents of SiO2, B2O3, Al2O3, CaO, and MgO, selectively introduces low amounts of alkali metal oxides, introduces appropriate amounts of ZnO and La2O3, and rationally sets the ranges for the ratios of ZnO / (CaO+MgO) and La2O3 / ZnO. These measures not only achieve lower glass dielectric constant and dielectric loss at 10GHz high frequencies, but also improve the glass melting and forming temperature, reduce the tendency of glass crystallization and phase separation, and are beneficial to improving the forming efficiency of glass fibers. Compared with quartz glass and D glass, this application significantly reduces production difficulty while ensuring dielectric properties, exhibits superior overall performance, and is more practical.

[0011] The specific technical solution adopted in this application is as follows:

[0012] This application provides a glass fiber composition and glass fibers with low dielectric properties made therefrom. The glass fiber composition comprises the following components, the contents of which are expressed as weight percentages: SiO2 48-57%, B2O3 19-29%, Al2O3 10-14%, CaO 0.5-5.0%, MgO 0-2.0%, ZnO 0.5-6.0%, La2O3 0.05-4.0%, the total amount of Na2O+K2O+Li2O 0.01-0.45%, and Fe2O3 0-0.5%. The sum of the weight percentages of all components is greater than or equal to 99.0%, the weight percentage ratio C1 = ZnO / (CaO+MgO) with a value of 0.25-2.5, and the weight percentage ratio C2 = La2O3 / ZnO with a value of 0.008-4.

[0013] In a glass network, the glass dielectric generates induced charges when an external electric field is applied, weakening the electric field. The ratio of the original applied electric field to the final electric field in the dielectric is the dielectric constant. When the glass dielectric is suddenly subjected to an electric field, it often takes a period of time for the polarization to reach its final value, resulting in energy loss. This phenomenon is called structural relaxation. Therefore, the essential characteristics of the glass dielectric constant and dielectric loss are the dielectric polarization and structural relaxation of the glass.

[0014] This application, based on the general CaO-B2O3-SiO2-Al2O3 glass system, controls the content of MgO and alkali metals, and simultaneously introduces ZnO and La2O3. It rationally sets the ratios of ZnO to CaO, MgO, and La2O3 to ZnO, while ensuring the amount of Al2O3 and SiO2. By controlling the dielectric polarization and structural relaxation of the glass network, it improves the melting and molding temperature of the glass while maintaining its dielectric properties, and reduces the tendency of crystallization and phase separation. Here, crystallization refers to the precipitation of crystals in amorphous glass, while phase separation refers to the formation of two or more amorphous states in a homogeneous amorphous glass, causing inhomogeneity. Apparently, both crystallization and phase separation cause devitrification in the glass, which adversely affects the forming of glass fibers and hinders continuous fiber drawing.

[0015] SiO2 is the main oxide forming the glass framework and plays a stabilizing role among the components. In order to obtain better glass dielectric properties and melting effect, this application prefers that the SiO2 content not be too high. If the SiO2 content is too high, although some dielectric properties can be guaranteed, the viscosity of the glass will be too high, making glass fiber production difficult. Conversely, if the SiO2 content is too low, the skeletal effect of the glass network will be reduced, which is detrimental to the dielectric properties of the glass. Therefore, in the glass fiber composition of this application, the weight percentage content of SiO2 is limited to 48-57%, preferably 48-56%, and more preferably 48-54%.

[0016] B2O3 is also a major oxide forming the glass skeleton. Compared to SiO2, B2O3 is more conducive to melting; however, when its content is too high, the glass becomes unstable, leading to phase separation. This phase separation affects the drawing performance of glass fibers. The essence of this phase separation is the competition between B and Si, two glass-forming elements, for oxygen ion groups; a balance between the two is the optimal combination. Therefore, in the glass fiber composition of this application, the weight percentage content of B2O3 is limited to 19-29%, preferably 19.5-27%, and more preferably 21-26%.

[0017] Al₂O₃ is an intermediate oxide that plays a crucial role in preventing phase separation in glass. It is generally believed that glass is prone to phase separation when the alumina content is below 10%, but excessively high content leads to high viscosity. Therefore, in the glass fiber composition of this application, the weight percentage content of Al₂O₃ is limited to 10-14%. In some embodiments, it is 10-13%.

[0018] CaO and MgO are alkaline earth metal oxides that can lower the melting temperature of glass, with CaO having a more pronounced effect. To ensure the dielectric properties and melting process of the glass, this application limits the weight percentage content of CaO to 0.5–5.0% and the MgO content to 0–2.0%. Preferably, the weight percentage content of CaO is 0.9–4.0%, more preferably 2.0–4.0%. In some embodiments, the weight percentage content of MgO is 0–1.5%. In some embodiments, the glass fiber composition of this application does not contain MgO.

[0019] In glass networks, ZnO typically exists as zinc-oxygen octahedrons as the network's outer oxide. When there is sufficient free oxygen in the glass, zinc-oxygen tetrahedra can form and enter the glass's structural network, making the glass structure more stable. Generally, the ZnO content in glass does not exceed 5% to 6%; excessive ZnO can make the glass prone to crystallization. Furthermore, ZnO can lower the melting temperature of glass. Therefore, in the glass fiber composition of this application, the weight percentage content of ZnO is limited to 0.5% to 6.0%, preferably 1.5% to 6.0%, more preferably 1.5% to 5.5%, and even more preferably 2% to 5%.

[0020] To ensure the dielectric and manufacturing performance of the glass fiber in this application, the weight percentage ratio C1 is limited to ZnO / (CaO+MgO), and the value of C1 is controlled between 0.25 and 2.5. If the value of C1 is too high, the influence of ZnO will be greater than that of CaO+MgO, leading to phase separation or crystallization in the glass, and it will also be detrimental to the dielectric properties. Here, Zn, Ca, and Mg atoms all exhibit a +2 valence, but Zn differs from Ca and Mg in that its polarization ability is not as strong. The glass network system needs to control its dielectric properties and devitrification behavior, and C1 is a direct manifestation of this control result. If the value of C1 is too low, the effect of ZnO will be insignificant, the structural stability of the glass will decrease, and thus affect the overall performance of the glass. Preferably, the value of C1 is between 0.25 and 2.3.

[0021] In electronic-grade glass fiber technology, the rare earth oxide La2O3 is rarely introduced. Experiments have shown that introducing La2O3 into the glass fiber composition of this application, and limiting the weight percentage content of La2O3 to 0.05%–4.0%, results in superior dielectric and melt properties of the glass. However, excessively high La2O3 content can negatively impact the dielectric properties of the glass. Therefore, the La2O3 content is limited to 0.05%–4.0%. In some embodiments, the La2O3 content is 0.05%–3.5%. In some embodiments, the La2O3 content is 1.3%–4.0%.

[0022] To further ensure the dielectric and manufacturing performance of this application, the weight percentage ratio C2 = La2O3 / ZnO is limited to 0.008–4. If the value of C2 is too high, the effect of La2O3 will overshadow ZnO, reducing the overall synergistic effect and leading to dielectric performance deviation; if the value of C2 is too low, the effect of La2O3 is not significant, reducing the ability to control phase separation and crystallization. Preferably, the value of C2 is 0.008–2, more preferably 0.008–1.5.

[0023] In the glass industry, alkali metal oxides or alkaline earth metal oxides are commonly used as network excipients. However, in electronic-grade glass fibers, excessive amounts of alkali metal oxides or alkaline earth metal oxides can reduce the electrical insulation and dielectric properties of the glass, while excessively low amounts can lead to excessively high viscosity. Therefore, in the glass fiber composition of this application, the total weight percentage of alkali metals Na₂O + K₂O + Li₂O is limited to 0.01–0.45%, preferably 0.01–0.30%, and more preferably 0.01–0.25%. In some embodiments, the total weight percentage of Na₂O + K₂O + Li₂O is 0.01–0.20%.

[0024] Fe2O3 is beneficial for glass melting and improves the crystallization properties of glass. However, excessive content can affect the dielectric properties of glass fibers and corrode the platinum materials in the furnace. In the glass fiber composition of this application, the weight percentage content of Fe2O3 is limited to 0-0.5%, preferably 0-0.3%. In some embodiments, the glass fiber composition of this application does not contain Fe2O3.

[0025] In this application, the total weight percentage of the main components of the glass fiber composition, namely SiO2, B2O3, Al2O3, CaO, MgO, ZnO, La2O3, Na2O, K2O, Li2O, and Fe2O3, is greater than or equal to 99.0%, preferably greater than or equal to 99.2%, and even more preferably greater than or equal to 99.5%.

[0026] Based on the main scheme, this application may also introduce an appropriate amount of F2. Extensive experiments have shown that an appropriate amount of F2 plays a significant role in fluxing, reducing molding temperature and liquidus temperature, and is easily removed during waste gas treatment. Experiments have found that the presence of an appropriate amount of F2 in glass is beneficial for reducing the dielectric constant of the glass. Therefore, an appropriate amount of F2 may be introduced into the glass fiber composition of this application. When introducing F2, the weight percentage content of F2 is limited to 0–1.6%, preferably 0–1.5%, and more preferably 0–0.5%.

[0027] The glass fiber composition of this application may also contain TiO2. TiO2 has a certain fluxing effect, but excessive content will cause the glass fiber to exhibit ion coloring, affecting the application of low-dielectric glass fiber. Therefore, in the glass fiber composition of this application, the weight percentage content of TiO2 is limited to 0-0.4%, preferably 0-0.3%. In some embodiments, the glass fiber composition of this application does not contain TiO2.

[0028] In some embodiments, when the glass fiber composition of this application incorporates 0-0.4% TiO2 and / or 0-1.6% F2, the total weight percentage of all components, i.e., the total weight percentage of SiO2, B2O3, Al2O3, CaO, MgO, ZnO, La2O3, Na2O, K2O, Li2O, Fe2O3, TiO2, and F2, is greater than or equal to 99.3%; in some embodiments, it is greater than or equal to 99.5%; and in some embodiments, it is greater than or equal to 99.8%.

[0029] In order to control production costs, glass density and improve environmental friendliness, the glass fiber composition of this application does not contain P2O5.

[0030] According to another aspect of this application, a glass fiber with low dielectric properties is provided, said glass fiber with low dielectric properties being made from the above-described glass fiber composition, specifically, said glass fiber with low dielectric properties being made from the above-described glass fiber composition by conventional methods.

[0031] According to the glass fiber of this application, the dielectric constant is ≤4.5 and the dielectric loss is ≤2.7‰ at 10GHz. In some embodiments, the dielectric constant is ≤4.4 and the dielectric loss is ≤2.2‰.

[0032] For low-dielectric glass fibers, the forming temperature is generally required to be between 1200-1400℃, preferably controlled between 1290℃ and 1380℃. Higher temperatures require matching furnace processes. The forming range ΔT is generally required to exceed 50℃, the larger the better; under specific processes, ΔT can be controlled above 30℃. In some embodiments, the glass fiber according to this application has a forming temperature between 1335-1380℃, with a ΔT range of 37-148℃. In some embodiments, the forming temperature is between 1349-1375℃, with a ΔT range of 60-125℃.

[0033] According to a third aspect of this application, a composite material is provided, the composite material comprising the glass fiber described above.

[0034] Compared with existing technologies, this application introduces appropriate amounts of ZnO and La2O3, controls the MgO content, and ensures the amounts of Al2O3, SiO2, and B2O3, while introducing low amounts of alkali metal oxides and selectively introducing fluorine. Based on the reasonable setting of the content of each component, the proportions of ZnO to CaO, MgO, and La2O3 to ZnO are also rationally determined. These measures not only control the polarization and relaxation of the glass network, resulting in a lower glass dielectric constant and lower glass dielectric loss, but also improve the glass melting and forming temperature, reduce the tendency of glass crystallization and phase separation, and are beneficial to improving the forming efficiency of glass fibers. Compared with traditional E glass, this application has a lower dielectric constant and dielectric loss; compared with traditional D glass, this application has better melting performance and is more suitable for large-scale tank furnace production. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of this application can be arbitrarily combined with each other.

[0036] In this application, the glass fiber composition comprises the following components, the content of each component expressed as a weight percentage: SiO2 48-57%, B2O3 19-29%, Al2O3 10-14%, CaO 0.5-5.0%, MgO 0-2.0%, ZnO 0.5-6.0%, La2O3 0.05-4.0%, the total amount of Na2O+K2O+Li2O 0.01-0.45%, and Fe2O3 0-0.5%. The sum of the weight percentages of all components is greater than or equal to 99.0%, the weight percentage ratio C1 = ZnO / (CaO+MgO), with a value of C1 of 0.25-2.5, and the weight percentage ratio C2 = La2O3 / ZnO, with a value of C2 of 0.008-4. The glass fiber composition may also contain 0 to 0.4% TiO2 by weight and 0 to 1.6% F2 by weight.

[0037] Below are examples of preferred value ranges for each component of the glass fiber composition according to this application.

[0038] Preferred Example 1

[0039] The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage:

[0040] The total weight percentage of the above components is greater than or equal to 99.3%, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2; the glass fiber composition does not contain P2O5.

[0041] Preferred Example 2

[0042] The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage:

[0043] Wherein, the sum of the weight percentages of the above components is greater than or equal to 99.3%, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, and the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2.

[0044] Preferred Example 3

[0045] The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage:

[0046] Wherein, the sum of the weight percentages of the above components is greater than or equal to 99.5%, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, and the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2.

[0047] Preferred Example 4

[0048] The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage:

[0049] Wherein, the sum of the weight percentages of the above components is greater than or equal to 99.5%, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, and the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2.

[0050] Preferred Example 5

[0051] The glass fiber composition according to this application contains the following components. The content of each component is expressed as a weight percentage:

[0052] Among them, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, and the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2.

[0053] Preferred Example 6

[0054] The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage:

[0055] The total weight percentage of the above components is greater than or equal to 99.5%, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.3, and the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 1.5.

[0056] Preferred Example 7

[0057] The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage:

[0058] Wherein, the sum of the weight percentages of the above components is greater than or equal to 99.8%, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, and the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2.

[0059] Preferred Example 8

[0060] The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage:

[0061] Wherein, the sum of the weight percentages of the above components is greater than or equal to 99.0%; the weight percentage ratio C1 = ZnO / (CaO+MgO), with C1 ranging from 0.417 to 2.0, and the weight percentage ratio C2 = La2O3 / ZnO, with C2 ranging from 0.26 to 1.5; the glass fiber composition does not contain P2O5.

[0062] Preferred Example 9

[0063] The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage:

[0064] The total weight percentage of the above components is greater than or equal to 99.3%, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2; the glass fiber composition does not contain P2O5.

[0065] Preferred Example 10

[0066] The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage:

[0067] The total weight percentage of the above components is greater than or equal to 99.8%, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2; the glass fiber composition does not contain P2O5.

[0068] This application utilizes a high-temperature electric furnace in a laboratory to melt glass samples. First, various raw materials are prepared into a batch according to the designed formula. After the batch is thoroughly mixed, it is melted into a homogeneous molten glass in a high-temperature electric furnace. The molten glass is then poured into glass blocks of a specified shape as required, annealed, and after cooling, cut into glass sheets of a specified shape. Relevant performance parameters are then tested.

[0069] The following basic parameters are selected for the test:

[0070] The dielectric constant and dielectric loss at 10 GHz were determined using the resonant cavity method. The glass required for sample preparation was melted, annealed, cut, and polished.

[0071] The forming temperature corresponds to the glass melt at a viscosity of 10. 3 The temperature at which the glass block is heated during sample preparation is determined by placing the glass block in an alumina crucible, heating it, and then measuring the temperature corresponding to the desired viscosity using temperature control and viscosity curves. This temperature is the molding temperature.

[0072] The liquidus temperature is the upper limit temperature for glass crystallization and phase separation. During sample preparation, the glass is placed in a clay crucible, and the liquidus temperature is read by observing the temperature distribution of the gradient temperature furnace and the crystallization and phase separation boundary.

[0073] ΔT is the difference between the forming temperature and the liquidus temperature, characterizing the temperature range for glass fiber drawing. A larger ΔT is more advantageous for the operation.

[0074] The above basic parameters and their measurement methods are well known to those skilled in the art and are measured using industry-standard testing methods.

[0075] The performance parameters of the glass fiber compositions of this application are further compared with those of the comparative examples in a table format below. The content of each glass fiber composition is expressed as a weight percentage. It should be noted that the total content of the components in the examples is slightly less than 100%, which can be understood as residual amounts being trace impurities or small amounts of components that cannot be analyzed.

[0076] Tables 1-3 list some specific embodiments of this application, numbered S1-S15, and Tables 4-5 show comparative embodiments K1-K9. K1 contains neither ZnO nor La2O3, K2 contains ZnO but not La2O3, K3 contains La2O3 but not ZnO, K4 is a typical E-glass comparative embodiment, K5 is a typical D-glass comparative embodiment, K6-K8 are comparative embodiments with different ratios of ZnO and La2O3, and K9 is a comparative embodiment containing P2O5. The glass fiber composition in the tables is expressed as a weight percentage.

[0077] Table 1

[0078] Table 2

[0079] Table 3

[0080] Table 4

[0081] Table 5

[0082] The K7 glass formulation cannot form a uniform glass when melted in a high-temperature electric furnace because the Al2O3 content is too low and the network lacks oxygen atoms and groups, which leads to phase separation in the glass.

[0083] As shown in Tables 1-5, the glass fiber prepared by the glass fiber composition described in this application has excellent dielectric properties at a high frequency of 10 GHz compared with the comparative embodiments. Specifically, the dielectric constant is ≤4.5 and the dielectric loss is ≤2.7‰. In addition, the glass fiber composition has moderate viscosity and a wide fiber forming range, making it suitable for large-scale tank furnace production.

[0084] Among them, embodiments S1, S7-S9, and S12 exhibit superior overall performance. Compared to the conventional E-glass of the comparative embodiments, this application has a lower dielectric constant and dielectric loss; and compared to conventional D-glass, this application has better melting performance and is more suitable for large-scale tank furnace production.

[0085] Further analysis of the embodiments and comparative embodiments shows that: in the general CaO-B2O3-SiO2- Based on the Al2O3 glass system, the content of MgO and alkali metals is controlled. Introducing ZnO alone reduces the dielectric loss of the glass, but introduces certain risks to the forming range, leading to a decrease in the ΔT value. Introducing La2O3 alone has little effect on reducing the dielectric constant and dielectric loss of the glass, and may even have adverse effects. However, simultaneously introducing appropriate amounts of ZnO and La2O3 can improve the forming range of the glass while maintaining a low dielectric constant and low dielectric loss, and the viscosity and temperature are also moderate. Therefore, the formulation has good practicality and can be promoted for mass production in kilns. Furthermore, when Fe2O3, TiO2, and F2 are controlled at certain levels, they have no adverse effects on the dielectric properties, viscosity temperature, and forming range of the glass.

[0086] The glass fiber composition according to this application can be combined with one or more organic and / or inorganic materials to prepare composite materials with excellent performance, such as copper clad laminates (CCL) and printed circuit boards (PCB).

[0087] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

[0088] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit it. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application. Industrial applicability

[0089] The glass fiber composition of this application controls the content of SiO2, B2O3, Al2O3, CaO, and MgO, selectively introduces low amounts of alkali metal oxides, and introduces appropriate amounts of ZnO and La2O3, while rationally setting the range of ZnO / (CaO+MgO) and La2O3 / ZnO ratios. This not only achieves lower glass dielectric constant and dielectric loss at high frequencies up to 10GHz, but also improves the glass melting and forming temperature, expands the fiber forming range, reduces the tendency of glass crystallization and phase separation, and is beneficial to improving the forming efficiency of glass fibers. Compared to quartz glass and D glass, this application significantly reduces production difficulty while ensuring dielectric properties, exhibits superior overall performance, and is more practical and suitable for large-scale tank furnace production.

Claims

1. A glass fiber composition, characterized in that, The glass fiber composition comprises the following components, the content of which is expressed as a weight percentage as follows: The total weight percentage of the above components is greater than or equal to 99.0%; the weight percentage ratio C1 = ZnO / (CaO+MgO), with a value of 0.25 to 2.5; and the weight percentage ratio C2 = La2O3 / ZnO, with a value of 0.008 to 4.

2. The glass fiber composition according to claim 1, characterized in that, The glass fiber composition further comprises TiO2, wherein the weight percentage content of TiO2 ranges from 0 to 0.4%.

3. The glass fiber composition according to claim 1, characterized in that, The glass fiber composition further comprises F2, wherein the weight percentage content of F2 ranges from 0 to 1.6%.

4. The glass fiber composition according to claim 1, characterized in that, The weight percentage ratio C1 = ZnO / (CaO+MgO) ranges from 0.25 to 2.

3.

5. The glass fiber composition according to claim 1, characterized in that, The weight percentage ratio C2 = La2O3 / ZnO ranges from 0.008 to 2.

6. The glass fiber composition according to claim 1, characterized in that, The glass fiber composition contains the following components, the content of which is expressed as a weight percentage as follows: Among them, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, and the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2.

7. The glass fiber composition according to claim 1, characterized in that, The glass fiber composition contains the following components, the content of which is expressed as a weight percentage as follows: Wherein, the sum of the weight percentages of the above components is greater than or equal to 99.2%, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, and the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2.

8. The glass fiber composition according to claim 1, characterized in that, The glass fiber composition contains the following components, the content of which is expressed as a weight percentage as follows: Among them, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, and the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2.

9. The glass fiber composition according to claim 1, characterized in that, The glass fiber composition contains the following components, the content of which is expressed as a weight percentage as follows: Among them, the weight percentage ratio C1 = ZnO / (CaO+MgO), the range of C1 is 0.25 to 2.5, and the weight percentage ratio C2 = La2O3 / ZnO, the range of C2 is 0.008 to 2.

10. The glass fiber composition according to claim 1, characterized in that, The glass fiber composition does not contain P2O5.

11. A type of glass fiber, characterized in that, The glass fiber is made from the glass fiber composition as described in any one of claims 1 to 10.

12. A composite material, characterized in that, The composite material includes the glass fiber as described in claim 11.

Images