Low-dielectric glass fiber composition and glass fiber, electronic cloth and composite material thereof

Abstract

The invention provides a low-dielectric glass fiber composition as well as glass fibers, electronic cloth and a composite material thereof. Wherein the glass fiber composition is prepared from the following components in percentage by weight: 24 to 59 percent of SiO2, 18 to 27 percent of B2O3, 12 to 18 percent of Al2O3, 1.5 to 6.0 percent of CaO, 0 to 4.0 percent of MgO, 1.0 to 8.0 percent of P2O5 and 1.0 to 10.0 percent of CeO2; the weight percentage content of P2O5 + CeO2 ranges from 3.0% to 18.0%, and the weight percentage ratio of C1 = (P2O5 + CeO2) / B2O3 ranges from 0.12 to 1.0. The glass fiber composition has the characteristics of low dielectric and low loss under a high-frequency condition; meanwhile, the devitrification and phase separation tendency of the glass can be reduced, the forming efficiency of the glass fibers can be improved, and continuous production of the high-performance low-dielectric glass fibers can be guaranteed. By adopting the glass fiber composition, the low-dielectric glass fiber with excellent dielectric property and good processability can be obtained, and the glass fiber composition is suitable for the field of high-frequency microwaves. Compared with quartz glass and D glass, the preparation method has the advantages that the dielectric property is ensured, the production difficulty can be greatly reduced, the comprehensive performance is excellent, and the practicability is higher.

Description

Technical Field

[0001] This application relates to a glass fiber composition, and more particularly to a low-dielectric glass fiber composition suitable for high-frequency, low-dielectric applications, as well as the glass fiber, electronic cloth, and composite materials thereof. Background Technology

[0002] With the advent of the highly information-driven era, the development of electronic components has entered a new stage of high integration and reliability, and the demand for copper clad laminates (CCL) and printed circuit boards (PCB) will further expand. As a primary material for copper-clad laminates and printed circuit boards, glass fiber requires lower dielectric constants and dielectric losses, as well as higher dimensional stability, i.e., a low coefficient of thermal expansion (CTE), to achieve high characteristic impedance or matched impedance, reducing interference and crosstalk in signal transmission, thereby ensuring PCB reliability and lifespan. Accordingly, the research and development of low-dielectric glass fiber has become a hot topic in the glass fiber industry. With the continuous growth of consumer electronics and the expansion of artificial intelligence, the market demand for low-dielectric glass fiber is experiencing explosive growth. From 2024 to 2025, market demand is projected to increase by more than 100%. To date, the market demand for low-dielectric glass fiber electronic cloth is approximately 120 million meters per year.

[0003] According to the development history of low-dielectric glass fibers, early traditional low-dielectric glass fibers, such as D-glass fiber, had the following main components by weight fraction: 20-25% B2O3, 72-76% SiO2, 0-5% Al2O3, and 2-4% Na2O + K2O. While D-glass fiber has good dielectric properties, its melting and clarifying performance is poor, easily producing veins and bubbles. It also suffers from numerous fiber breakages during the drawing process, resulting in poor workability and hindering large-scale production. Furthermore, D-glass fiber exhibits poor water resistance and CAF resistance, which is detrimental to subsequent processing and use. To address these issues, major glass fiber companies have conducted extensive research and improvement studies.

[0004] Currently, the main components of mainstream low-dielectric glass fibers are the RO-B2O3-SiO2-Al2O3 system, with other components including Fe2O3, TiO2, SrO, Li2O, ZrO2, and F2. Although continuous production is feasible, it is difficult to further reduce dielectric loss while maintaining production requirements. Therefore, related technologies are continuously being developed.

[0005] Chinese patent CN113754295B discloses a low-dielectric modified glass fiber, with the following weight percentages of components: SiO2 51-61 parts, B2O3 15-30 parts, Al2O3 11-21 parts, ZnO 1-4 parts, MgO / CaO 0-10 parts, and functional oxides 1.02-1.525 parts. This patent does not contain P2O5 and has a relatively low CeO2 content, resulting in less than outstanding overall dielectric and manufacturing performance.

[0006] Chinese patent CN113135666B discloses a low-dielectric glass fiber, which, by weight percentage, comprises the following components: 50-58% SiO2, 20-28% B2O3, 10-16% Al2O3, 0.2-1.5% TiO2, 1-4% CaO, 1-4% MgO, and 0-1% CeO2. This patent does not contain P2O5, and the CeO2 content is relatively low, resulting in less than outstanding overall dielectric and manufacturing performance. Summary of the Invention

[0007] This application addresses the shortcomings of existing low-dielectric glass fiber technologies and, considering the characteristics of glass fiber manufacturing processes, provides a low-dielectric glass fiber composition, as well as its glass fibers, electronic cloth, and composite materials. The glass fiber composition exhibits low dielectric constant and low loss characteristics, yielding glass fibers with low dielectric constant, low dielectric loss, and excellent production performance, making it highly suitable for high-frequency microwave applications.

[0008] To achieve the above objectives, this application rationally controls the contents of SiO2, B2O3, Al2O3, CaO, and MgO, introduces appropriate amounts of P2O5 and CeO2, and scientifically sets the range of the total amount of P2O5+CeO2 and the mass ratio of P2O5+CeO2 to B2O3; simultaneously, it controls the contents of alkali metal oxides, TiO2, Fe2O3, and F2. Furthermore, ZnO, La2O3, SnO2, ZrO2, and Cr2O3 can be selectively introduced. These measures not only achieve lower glass dielectric constant and dielectric loss under 10GHz frequency (i.e., high-frequency microwave conditions), but also control the glass melting and molding temperature, reduce the tendency of glass crystallization and phase separation, which is beneficial to improving the forming efficiency of glass fibers and ensuring the continuous production of high-performance, low-dielectric glass fibers. Compared to quartz glass and D-glass, the glass fiber composition of this application significantly reduces production difficulty while ensuring dielectric properties, exhibits excellent overall performance, and is more practical.

[0009] The specific technical solution adopted in this application is as follows: According to one aspect of this application, a low-dielectric glass fiber composition is provided, the glass fiber composition comprising the following components, the contents of each component being expressed as a weight percentage: SiO2 46~59%, B2O3 18~27%, Al2O3 12~18%, CaO 1.5~6.0%, MgO 0~4.0%, P2O5 1.0~8.0%, CeO2 1.0~10.0%; wherein, the weight percentage content of P2O5+CeO2 ranges from 3.0~18.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.12~1.0.

[0010] In a glass network, from a dielectric mechanism perspective, when an external electric field is applied, the glass dielectric generates induced charges, 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 dielectric polarization and structural relaxation. Relaxation occurs because various resistances to the motion of electric dipole moments in the glass network cause the electric displacement vector in the network to lag behind the electric field by an angle. This angle is called the dielectric loss angle, which is also the ratio of the imaginary part to the real part of the generalized dielectric constant, i.e., the dielectric loss.

[0011] This application rationally sets the component content range in a SiO2, B2O3, Al2O3, CaO, and MgO glass system, and innovatively incorporates high contents of P2O5 and CeO2, while scientifically setting the total amount of P2O5+CeO2 and the ratio range of the mass percentage of P2O5+CeO2 to B2O3. By controlling the dielectric polarization and structural relaxation of the glass network, the melting and molding temperature of the glass is improved while ensuring its dielectric properties, and the tendency of crystallization and phase separation is reduced. 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, and these devitrification behaviors have an adverse effect on the forming of glass fibers, hindering the continuous drawing of glass fibers.

[0012] SiO2 is the main oxide forming the glass framework and plays a stabilizing role among the components. In this application, to obtain better glass dielectric properties and melting effect, it is desirable that the SiO2 content not be too high. When the SiO2 content is too high, although some dielectric properties can be guaranteed, the viscosity of the glass is too high, making glass fiber production difficult; conversely, when the SiO2 content is too low, the skeletal effect of the glass network is 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 46-59%, preferably 48-56%, and more preferably 48.5-54%. In some embodiments, the weight percentage content of SiO2 is in the range of 48-52%.

[0013] B2O3 is also a major oxide forming the glass skeleton. Compared to SiO2, B2O3 is more conducive to melting; however, if 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 18-27%, preferably 19.5-26%. In some embodiments, the weight percentage content of B2O3 is in the range of 20-27%.

[0014] Al₂O₃ is an intermediate oxide that plays a crucial role in preventing phase separation and controlling the dielectric properties of glass. It is generally believed that when the alumina content is too low, the glass is prone to phase separation, but when its content is too high, the viscosity of the glass also increases. Therefore, in the glass fiber composition of this application, the weight percentage content of Al₂O₃ is limited to 12-18%, preferably 13-16%. In some embodiments, the weight percentage content of Al₂O₃ is in the range of 12-16%.

[0015] Both CaO and MgO are alkaline earth metal oxides, both of which can lower the melting temperature of glass, with CaO having a more pronounced effect. If the MgO content is too high and the CaO content is too low, the overall glass network breaking effect is small, and the glass system is prone to phase separation or crystallization devitrification. To ensure the dielectric properties and melting of the glass, this application limits the weight percentage content of CaO to 1.5-6.0% and the MgO content to 0-4.0%. Preferably, the weight percentage content of CaO is 2.5-5.0%, and preferably the weight percentage content of MgO is 0-2.0%. In some embodiments, the weight percentage content of CaO is 3.0-5.0%. In some embodiments, the weight percentage content of MgO is 0-1.1%. In some embodiments, the glass fiber composition of this application does not contain MgO.

[0016] P2O5 is also an oxide that forms the glass framework. When Si and P coexist in the glass network, both should not be present in excessively high amounts simultaneously to avoid excessively high glass viscosity or easy phase separation. Furthermore, phosphate glasses have poorer corrosion resistance than silicate glasses; therefore, when controlling the SiO2 content in the glass, the P2O5 content should be further limited. Thus, in the glass fiber composition of this application, the weight percentage content of P2O5 is limited to 1.0% to 8.0%, preferably 2.0% to 7.0%.

[0017] CeO2 (cerium oxide) is an oxidizing agent that decomposes at high temperatures to release oxygen and is generally used as a clarifying agent in glass. However, in this application, CeO2 not only serves a clarifying function, but it has also been found to promote the reduction of dielectric constant, dielectric loss, and control of glass melt viscosity. However, when the CeO2 content is too high, although the viscosity of the glass melt decreases, the dielectric properties are poor. Therefore, the weight percentage content of CeO2 is limited to 1.0% to 10.0%, preferably 2.0% to 8.0%. In some embodiments, the weight percentage content of CeO2 ranges from 1.5% to 8.0%. To ensure the dielectric and manufacturing performance of the glass fiber in this application, the total amount of P2O5+CeO2 is limited. Experiments have shown that both excessively high and excessively low total amounts of P2O5+CeO2 cannot guarantee the dielectric properties of the glass. Therefore, this application limits the total amount of P2O5+CeO2 to a range of 3.0% to 18.0%, preferably 3.5% to 14.0%. In some embodiments, the total amount of P2O5+CeO2 ranges from 3.5% to 10.5%.

[0018] To ensure the dielectric and manufacturing performance of the glass fiber in this application, the ratio C1 of the total amount of P2O5+CeO2 to the mass percentage of B2O3 is limited. If C1 is too high, the glass network system will be unstable; if C1 is too low, the dielectric performance cannot be guaranteed. Therefore, this application limits the weight percentage ratio C1 = (P2O5+CeO2) / B2O3 to a range of 0.12~1.0, preferably 0.13~0.70. In some embodiments, C1 ranges from 0.13 to 0.75.

[0019] In the glass industry, alkali metal oxides are commonly used as additives in the glass network to control its high-temperature viscosity. However, in electronic-grade glass fibers, excessive amounts of alkali metal oxides can reduce the electrical insulation and dielectric properties of the glass. Therefore, in the glass fiber composition of this application, the alkali metal oxide R2O (Na2O + K2O + Li2O) is limited to a total weight percentage of 0-0.5%, preferably 0-0.1%. In some embodiments, the weight percentage content of R2O is 0-0.05%. In some embodiments, the glass fiber composition of this application does not contain alkali metal oxides, i.e., the total weight percentage of Na2O + K2O + Li2O is 0.

[0020] 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 0-1.0%, preferably 0-0.5%, and more preferably 0-0.1%. In some embodiments, the glass fiber composition of this application does not contain TiO2.

[0021] The glass fiber composition of this application may also contain Fe2O3. Fe2O3 is beneficial for glass melting and improves the crystallization properties of glass. Excessive content can affect the dielectric properties of the glass fiber and also 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 0-0.1%. In some embodiments, the weight percentage content of Fe2O3 is 0-0.05%. In some embodiments, the glass fiber composition of this application does not contain Fe2O3.

[0022] 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 can play 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 can be introduced into the glass fiber composition of this application. When introducing F2, the weight percentage content of F2 is limited to a range of 0~2.5%, preferably 0.1~2.5%. In some embodiments, the weight percentage content of F2 ranges from 0~1.0%. In some embodiments, the weight percentage content of F2 ranges from 0.5~1.0%.

[0023] Based on the main scheme, this application may also introduce appropriate amounts of ZnO and La2O3 to further control dielectric properties and production performance. In the glass fiber composition of this application, the weight percentage content of ZnO+La2O3 is limited to 0~2.0%, preferably 0.4~2.0%. In some embodiments, the glass fiber composition of this application does not contain ZnO and La2O3.

[0024] Based on the main scheme, SnO2 can also be introduced in this application to improve the clarifying ability of the glass melt. In the glass fiber composition of this application, the weight percentage content of SnO2 is limited to 0~0.6%.

[0025] Based on the main scheme, this application may also introduce appropriate amounts of ZrO2 and Cr2O3, both of which are major components of kiln refractory materials, and their content is generally not too high. Therefore, in the glass composition of this application, the weight percentage content of ZrO2+Cr2O3 is limited to 0~1.5%.

[0026] In this application, the main components of the glass fiber composition are SiO2, B2O3, Al2O3, CaO, MgO, P2O5, and CeO2. In some embodiments, the sum of the weight percentages of the main components is greater than or equal to 97.0%. In some embodiments, the sum of the weight percentages of the main components is greater than or equal to 97.5%. In some embodiments, when the glass fiber composition does not contain ZnO and La2O3, the sum of the weight percentages of the main components is greater than or equal to 98.5%.

[0027] According to another aspect of this application, a glass fiber is provided, said glass fiber being made from the aforementioned low-dielectric glass fiber composition.

[0028] Furthermore, the glass fiber is made from the aforementioned low-dielectric glass fiber composition by conventional methods.

[0029] According to the glass fiber of this application, the dielectric constant is ≤4.6, the dielectric loss is ≤3.5‰, and the forming temperature is ≤1430℃ at 10GHz. In some preferred embodiments, the dielectric constant is ≤4.35, the dielectric loss is ≤2.7‰, and the forming temperature is ≤1390℃. In some more preferred embodiments, the dielectric constant is ≤4.22, the dielectric loss is ≤1.8‰, and the forming temperature is ≤1380℃. For the feasibility of glass fiber production, a forming temperature of 1400℃ or below is generally required. Higher temperatures require matching furnace processes, and a larger forming range ΔT is better. Under specific processes, ΔT can be controlled above 20℃. In some embodiments, the glass fiber of this application has a forming temperature between 1250-1400℃ and a ΔT range of 10-100℃. In some embodiments, the forming temperature is between 1255-1380℃ and a ΔT range of 40-85℃.

[0030] According to a third aspect of this application, an electronic cloth is provided, the electronic cloth comprising the aforementioned glass fibers. Simultaneously, a composite material is provided, the composite material comprising the aforementioned glass fibers.

[0031] Compared with existing technologies, this application innovatively incorporates high contents of P2O5 and CeO2 in SiO2, B2O3, Al2O3, CaO, and MgO glass systems, and scientifically sets two ranges for the total amount of P2O5+CeO2 and the mass ratio C1 of P2O5+CeO2 to B2O3. By controlling the dielectric polarization and structural relaxation of the glass network, the melting and molding temperature of the glass is improved while ensuring its dielectric properties, and the tendency of crystallization and phase separation is reduced.

[0032] Building upon this foundation, low levels of alkali metal oxides and fluorine are introduced, along with controlled amounts of TiO2 and Fe2O3. Other additives such as ZnO, La2O3, SnO2, ZrO2, and Cr2O3 can also be introduced to further control the overall performance. These measures not only control the polarization and relaxation of the glass network, resulting in lower glass dielectric constants and losses, but also improve the glass melting and forming temperature, reduce crystallization and phase separation tendencies, and enhance the forming efficiency of glass fibers. Compared to traditional D-glass, this application exhibits better melting performance and is more suitable for large-scale production. Detailed Implementation

[0033] 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.

[0034] In this application, the glass fiber composition comprises the following components, the content of each component expressed as a weight percentage: SiO2 46~59%, B2O3 18~27%, Al2O3 12~18%, CaO 1.5~6.0%, MgO 0~4.0%, P2O5 1.0~8.0%, CeO2 1.0~10.0%; the weight percentage content of P2O5+CeO2 ranges from 3.0~18.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.12~1.0. Using this glass fiber composition, low-dielectric glass fibers with excellent dielectric properties and good processing performance can be obtained, making it suitable for high-frequency microwave applications.

[0035] The glass fiber composition may further contain TiO2, with a weight percentage ranging from 0 to 1.0%. The glass fiber composition may further contain F2, with a weight percentage ranging from 0 to 2.5%. The glass fiber composition may further contain Fe2O3, with a weight percentage ranging from 0 to 0.5%. The glass fiber composition may further contain ZnO and La2O3, with the weight percentage of ZnO + La2O3 ranging from 0 to 2.0%. The glass fiber composition may further contain R2O (i.e., the sum of alkali metal oxides Li2O, Na2O, and K2O) with a weight percentage ranging from 0 to 0.5%. The glass fiber composition may further contain SnO2, with a weight percentage ranging from 0 to 0.6%. The glass fiber composition may further contain ZrO2 and Cr2O3, with the weight percentage of ZrO2 + Cr2O3 ranging from 0 to 1.5%.

[0036] Below are examples of preferred value ranges for each component of the glass fiber composition according to this application.

[0037] Preferred Example 1 The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage: SiO2 48~56% B2O3 19.5~26% Al2O3 13~16% CaO 2.5~5.0% MgO 0~2.0% P2O5 2.0~7.0% CeO2 2.0~8.0% Alkali metal oxides 0~0.5% Fe2O3 0~0.5% TiO20~1.0% F20.1~2.5%; The weight percentage content of P2O5+CeO2 ranges from 3.5% to 14.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.13 to 0.70.

[0038] Preferred Example 2 The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage: SiO2 48~56% B2O3 19.5~26% Al2O3 13~16% CaO 2.5~5.0% MgO 0~2.0% P2O5 2.0~7.0% CeO2 2.0~8.0% Alkali metal oxides 0~0.5% Fe2O3 0~0.5% TiO20~1.0% F20.1~2.5% ZnO 0~1.0% La2O30~2.0% ZnO + La2O 30~2.0%; The weight percentage content of P2O5+CeO2 ranges from 3.5% to 14.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.13 to 0.70.

[0039] Preferred Example 3 The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage: SiO2 48.5~54% B2O3 19.5~26% Al2O3 13~16% CaO 2.5~5.0% MgO 0~1.5% P2O5 2.0~7.0% CeO2 2.0~8.0% Alkali metal oxides 0~0.1% Fe2O3 0~0.1% TiO20~0.1% F20.1~2.5%; The weight percentage content of P2O5+CeO2 ranges from 3.5% to 13.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.13 to 0.55.

[0040] Preferred Example 4 The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage: SiO2 48.5~54% B2O3 19.5~26% Al2O3 13~16% CaO 2.5~5.0% MgO 0~1.5% P2O5 2.0~7.0% CeO2 2.0~8.0% Alkali metal oxides 0~0.1% Fe2O3 0~0.1% TiO20~0.5% F20.1~1.0% ZnO 0~1.0% La2O30~2.0% ZnO + La2O 30~2.0%; The weight percentage content of P2O5+CeO2 ranges from 3.5% to 10.5%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.13 to 0.55.

[0041] Preferred Example 5 The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage: SiO2 48.5~51.8% B2O3 22~27% Al2O3 14.5~16% CaO 2.5~4.0% MgO 0.1~0.5% P2O5 2.3~7.0% CeO2 1.5~4.0% Alkali metal oxides 0~0.05% Fe2O3 0~0.04% TiO20~0.01% F20.5~0.7% ZnO + La2O 30~2.0%; The weight percentage content of P2O5+CeO2 ranges from 3.8% to 10.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.13 to 0.50.

[0042] Preferred Example 6 The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage: SiO2 48~52% B2O3 20~27% Al2O3 12~16% CaO 3.0~5.0% MgO 0~1.1% P2O5 2.0~7.0% CeO2 1.5~8.0% Alkali metal oxides 0~0.05% Fe2O3 0~0.1% TiO20~1% F20~1.0% ZnO + La2O 30~2.0% SnO20~0.6% ZrO2+Cr2O30~1.5%; The weight percentage content of P2O5+CeO2 ranges from 5.0% to 10.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.20% to 0.50.

[0043] Preferred Example 7 The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage: SiO2 48~56% B2O3 19.5~27% Al2O3 13~16% CaO 2.5~5.0% MgO 0~2.0% P2O5 2.0~7.0% CeO2 2.0~8.0% Alkali metal oxides 0~0.5% Fe2O3 0~0.5% TiO20~1.0% F20.1~2.5% ZnO 0~1.0% La2O30~2.0% ZnO + La2O 30~2.0% SnO20~0.6% ZrO2+Cr2O30~1.5%; The weight percentage content of P2O5+CeO2 ranges from 3.5% to 14.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.13 to 0.70.

[0044] Preferred Example 8 The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage: SiO2 48.5~54% B2O3 19.5~27% Al2O3 13~16% CaO 2.5~5.0% MgO 0~1.5% P2O5 2.0~7.0% CeO2 2.0~8.0% Alkali metal oxides 0~0.1% Fe2O3 0~0.1% TiO20~0.1% F20.1~2.5% ZnO 0~1.0% La2O30~2.0% ZnO + La2O 30~2.0% SnO20~0.6% ZrO2+Cr2O30~1.5%; The weight percentage content of P2O5+CeO2 ranges from 3.5% to 13.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.13 to 0.55.

[0045] Preferred Example 9 The glass fiber composition according to this application contains the following components, the content of each component being expressed as a weight percentage: SiO2 48.5~52% B2O3 19.5~26% Al2O3 13~16% CaO 2.5~5.0% MgO 0~1.5% P2O5 2.0~5.0% CeO2 1.5~6.0% Alkali metal oxides 0~0.1% Fe2O3 0~0.05% TiO20~0.01% F20.1~1.0% ZnO 0~1.0% La2O30~2.0% ZnO + La2O 30~2.0% SnO20~0.6% ZrO2+Cr2O30~1.5%; The weight percentage content of P2O5+CeO2 ranges from 3.5% to 10.5%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.13 to 0.55.

[0046] 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.

[0047] The following basic parameters are used in the test: 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.

[0048] 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.

[0049] 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.

[0050] 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. 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.

[0051] The performance parameters of the glass fiber compositions of this application are further compared with those of the comparative embodiments in a table format below. The content of each glass fiber composition is expressed as a weight percentage.

[0052] Tables 1-3 list some specific embodiments of this application, numbered S1-S20. Table 4 shows comparative examples K01-K07; wherein, K01 is a typical E-glass comparative example, K02 is a typical D-glass comparative example, K03 is a low P2O5 formulation, K04 is a low CeO2 formulation, K05 is a high alkali metal oxide and high F2 formulation, K06 is a high alkali metal and high TiO2 formulation, and K07 is a high MgO, low boron, P2O5, and CeO2-containing formulation. The glass fiber composition in the tables is expressed as a weight percentage.

[0053] Table 1

[0054] Table 2

[0055] Table 3

[0056] Table 4

[0057] As shown in Tables 1-4, the glass fibers produced by the glass fiber compositions of the various embodiments of this application exhibit superior dielectric properties and production performance at high frequencies of 10 GHz compared to the comparative examples. In some preferred embodiments, the dielectric properties have achieved further breakthroughs compared to the prior art; for example, a dielectric constant ≤ 4.3 and a dielectric loss ≤ 1.9‰ can be achieved.

[0058] Among them, Examples S01, S09, S10, S16, S17, and S19-S26 exhibit the best overall performance, simultaneously achieving good dielectric and production performance. Compared to the conventional E glass (K01) of the comparative examples, this application has a lower dielectric constant and dielectric loss; and compared to the conventional D glass (K02), this application has better melting performance and is more suitable for large-scale tank furnace production. The K05 glass formulation cannot form a uniform glass when melted in a high-temperature electric furnace because the F2 content is too high, and the significant opacifying ability of F2 prevents the formation of a uniform glass.

[0059] Further analysis of the examples and comparative examples reveals that, compared to existing glass fiber technologies, this application controls the content of SiO2, B2O3, Al2O3, CaO, and MgO, introduces appropriate amounts of P2O5 and CeO2, and scientifically sets the range of the total amount of P2O5+CeO2 and the mass ratio C1 of P2O5+CeO2 to B2O3; simultaneously, it controls the content of alkali metal oxides, TiO2, Fe2O3, and F2, and can selectively introduce ZnO, La2O3, SnO2, ZrO2, and Cr2O3. These measures not only achieve lower glass dielectric constant and dielectric loss under 10GHz frequency (i.e., high-frequency microwave conditions), but also control the glass melting and molding temperature, reduce the tendency of glass crystallization and phase separation, which is beneficial to improving the molding efficiency of glass fibers and ensuring the continuous production of high-performance, low-dielectric glass fibers. Compared to quartz glass and D glass, this application significantly reduces production difficulty while ensuring dielectric properties, exhibits excellent overall performance, and is more practical.

[0060] 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.

[0061] 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.

Claims

1. A low-dielectric 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: SiO2 46~59% B2O3 18~27% Al2O3 12~18% CaO 1.5~6.0% MgO 0~4.0% P2O5 1.0~8.0% CeO2 1.0~10.0%; The weight percentage content of P2O5+CeO2 ranges from 3.0% to 18.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.12 to 1.

0.

2. The low-dielectric 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 1.0%.

3. The low-dielectric 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 2.5%.

4. The low-dielectric glass fiber composition according to claim 1, characterized in that, The weight percentage content of P2O5+CeO2 ranges from 3.5% to 14.0%.

5. The low-dielectric glass fiber composition according to claim 1, characterized in that, The weight percentage ratio C1 = (P2O5 + CeO2) / B2O3 ranges from 0.13 to 0.

70.

6. The low-dielectric glass fiber composition according to claim 1, characterized in that, The glass fiber composition further comprises ZnO and La2O3, with the weight percentage content of ZnO+La2O3 ranging from 0 to 2.0%.

7. The low-dielectric 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: SiO2 48~56% B2O3 19.5~26% Al2O3 13~16% CaO 2.5~5.0% MgO 0~2.0% P2O5 2.0~7.0% CeO2 2.0~8.0% Alkali metal oxides 0~0.5% Fe2O3 0~0.5% TiO20~1.0% F20.1~2.5%； The weight percentage content of P2O5+CeO2 ranges from 3.5% to 14.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.13 to 0.

70.

8. The low-dielectric 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: SiO2 48~56% B2O3 19.5~26% Al2O3 13~16% CaO 2.5~5.0% MgO 0~2.0% P2O5 2.0~7.0% CeO2 2.0~8.0% Alkali metal oxides 0~0.5% Fe2O3 0~0.5% TiO20~1.0% F2 0.1~2.5% ZnO + La2O 30.4~2.0%; The weight percentage content of P2O5+CeO2 ranges from 3.5% to 14.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.13 to 0.

70.

9. The low-dielectric 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: SiO2 48.5~54% B2O3 19.5~26% Al2O3 13~16% CaO 2.5~5.0% MgO 0~1.5% P2O5 2.0~7.0% CeO2 2.0~8.0% Alkali metal oxides 0~0.1% Fe2O3 0~0.1% TiO20~0.1% F20.1~2.5%； The weight percentage content of P2O5+CeO2 ranges from 3.5% to 13.0%, and the weight percentage ratio C1=(P2O5+CeO2) / B2O3 ranges from 0.13 to 0.

65.

10. The low-dielectric 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: SiO2 48.5~54% B2O3 19.5~26% Al2O3 13~16% CaO 2.5~5.0% MgO 0~1.5% P2O5 2.0~7.0% CeO2 2.0~8.0% Alkali metal oxides 0~0.1% Fe2O3 0~0.1% TiO20~0.5% F2 0.1~2.5% ZnO + La2O3 0.4~2.0%; The total weight percentage of P2O5+CeO2 ranges from 3.5% to 13.0%, and the weight percentage ratio C1 = (P2O5+CeO2) / B2O3 ranges from 0.13 to 0.

65.

11. The low-dielectric glass fiber composition according to claim 1, characterized in that, The glass fiber composition further comprises SnO2, wherein the weight percentage content of SnO2 ranges from 0 to 0.6%.

12. The low-dielectric glass fiber composition according to claim 1, characterized in that, The glass fiber composition further comprises ZrO2 and Cr2O3, wherein the weight percentage content of ZrO2+Cr2O3 ranges from 0 to 1.5%.

13. A type of glass fiber, characterized in that, The glass fiber is made of the low dielectric glass fiber composition as described in any one of claims 1 to 12.

14. An electronic cloth, characterized in that, The electronic cloth contains the glass fiber as described in claim 13.

15. A composite material, characterized in that, The composite material contains the glass fiber as described in claim 13.

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