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. The glass fiber composition comprises the following components in percentage by weight: 50.0 to 58.0 percent of SiO2, 10.0 to 16.9 percent of Al2O3, 19.0 to 27.3 percent of B2O3, 2.3 to 6.6 percent of CaO, 0.2 to 4.0 percent of MgO, 0.01 to 1.0 percent of SrO, 0.01 to 0.3 percent of Na2O, 0.01 to 0.45 percent of K2O, 0.01 to 0.5 percent of Fe2O3, 0.01 to 0.49 percent of TiO2, 0.01 to 1.7 percent of F2, 0 to 1.4 percent of ZrO2, 0.12 to 1.8 percent of F2 + K2O, 0.05 to 2.0 percent of F2 + SrO, 0.03 to 0.49 percent of Na2O + K2O, greater than or equal to 0.6 percent of K2O / Na2O, greater than or equal to 0.5 percent of F2 / K2O, 3.0 to 9.8 percent of CaO + MgO + SrO and 72.0 to 84.0 the range of C2 = (F2 + K2O) / Na2O is greater than or equal to 1.4, the range of C3 = (F2 + K2O) / (Na2O + TiO2) is greater than or equal to 0.5, the range of C4 = (MgO + SrO) / CaO is greater than or equal to 0.05, and the range of C5 = (SiO2 + B2O3) / (CaO + MgO + Al2O3 + TiO2) is greater than or equal to 3.0; and the glass fiber composition does not contain lithium oxide. The glass fiber composition has the characteristics of low dielectric, low loss and low density, can improve the glass modulus, reduce the glass forming temperature, devitrification temperature and rate, can also reduce the surface tension and clarification difficulty of molten glass, has more cost advantages, and is suitable for large-scale production of low-dielectric glass fibers.

Description

Technical Field

[0001] The present application relates to a glass fiber composition, and in particular to a low-dielectric glass fiber composition for the electronics industry, and glass fibers, electronic cloth, and composite materials thereof. Background Art

[0002] Electronic-grade glass fiber is a functional substrate for electronic circuits, and its main application areas include communications, computers, AI intelligence, IC packaging, automotive electronics, etc. The "electronic-grade glass fiber-electronic cloth-copper clad laminate-printed circuit board (PCB)" industry chain is the core application of electronic-grade glass fiber. In order to meet the dielectric properties of printed circuit boards, electronic-grade glass fiber is required to have good dielectric properties. With the vigorous development of the global electronic circuit industry, electronic products are constantly developing towards being thin, light, short, high-frequency and high-speed. This poses a new challenge to printed circuit boards. The electronic-grade glass fiber used as the substrate is required to have lower dielectric properties, such as a dielectric constant below 5.0. The dielectric constant of traditional E-glass fiber is generally 6.5-7.0, which can no longer meet these requirements. Therefore, it is imperative to develop a glass fiber with a lower dielectric constant and dielectric loss than E-glass fiber.

[0003] D-glass fiber is a typical low-dielectric glass fiber, boasting significantly superior dielectric properties to traditional E-glass fiber, meeting the requirements of high-frequency and high-speed applications. Its main components, by weight, range from 72-76% SiO2, 20-25% B2O3, 0-5% Al2O3, and 2-4% Na2O+K2O. While D-glass fiber has a dielectric constant below 4.5, it presents significant challenges in melting and drawing. For example, the drawing temperature exceeds 1400°C, making large-scale kiln production difficult. Furthermore, the fiber's mechanical properties and water resistance are poor, hindering subsequent processing and use. Furthermore, it suffers from high raw material costs. Researchers have made significant efforts to address these shortcomings.

[0004] Japanese Patent JP10120437A discloses a low-dielectric glass fiber composition comprising, by weight, 50-56% SiO2, 10-18% Al2O3, 18-25% B2O3, greater than 10% and ≤17% CaO, 0-4% MgO, 0-1.0% Li2O+Na2O+K2O, and 0-2% F2. Due to the high calcium oxide content, this composition exhibits a relatively high dielectric constant, although the molding temperature is relatively low. Most examples have a dielectric constant between 5 and 5.5.

[0005] Chinese patent CN102976620A discloses a low-dielectric glass fiber composition containing, by weight, 60.4-65% SiO2, 10-14% Al2O3, 22-26% B2O3, and 0.5-2% Li2O. The high silicon oxide and lithium oxide content in this composition results in high molding temperatures and raw material costs, resulting in a low cost-performance ratio and hindering large-scale production.

[0006] Chinese patent CN110171929A discloses a low-dielectric glass fiber composition, primarily containing, by weight, 55.0-58.0% SiO2, 13.5-15.0% Al2O3, 19.0-21.0% B2O3, 3.0-3.3% ZrO2, 3.0-5.0% CaO, and 2.5-4.5% MgO. The composition's excessive zirconium oxide content results in high molding temperatures, making glass melting and clarification difficult, hindering large-scale production. Furthermore, the high cost of the zirconium raw material results in a low cost-performance ratio. Summary of the Invention

[0007] The present application aims to address the above-described problems by providing a low-dielectric glass fiber composition, glass fiber, electronic cloth, and composite material thereof. The composition has the properties of low dielectric, low loss, and low density, and can improve the modulus and water resistance of glass, lower the molding temperature of glass, effectively reduce the devitrification temperature and rate of glass, and expand the glass fiber molding range. It can also reduce the surface tension of molten glass and the difficulty of clarification, which is conducive to reducing the difficulty of glass fiber production and improving the quality of molten glass. It also has a greater cost advantage and is suitable for large-scale production of low-dielectric glass fibers.

[0008] According to one aspect of the present application, a low dielectric glass fiber composition is provided, wherein the glass fiber composition comprises the following components, and the content of each component is expressed in weight percentage as follows:

[0009]

[0010] The total content of the above components is greater than or equal to 98.7%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.63, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 1.4, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.5, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.0; the glass fiber composition does not contain lithium oxide.

[0011] The low dielectric glass fiber composition contains the following components, and the content of each component is expressed in weight percentage as follows:

[0012]

[0013]

[0014] The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.65, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 1.7, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.65, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

[0015] The weight percentage ratio C1=SiO2 / (CaO+Al2O3) is further limited to a range of 2.65-4.2.

[0016] The weight percentage ratio C2=(F2+K2O) / Na2O is further limited to a range greater than or equal to 2.0.

[0017] The weight percentage ratio C3=(F2+K2O) / (Na2O+TiO2) is further limited to a range greater than or equal to 0.75.

[0018] The weight percentage ratio C5=(SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is further limited to a range greater than or equal to 3.1.

[0019] The content range of F2+K2O is further limited to 0.3-1.7% by weight.

[0020] The low dielectric glass fiber composition contains the following components, and the content of each component is expressed in weight percentage as follows:

[0021]

[0022] The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.65, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 2.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.65, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

[0023] The low dielectric glass fiber composition contains the following components, and the content of each component is expressed in weight percentage as follows:

[0024]

[0025] The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of 2.65-4.2, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 2.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.75, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

[0026] The weight percentage ratio of K2O / Na2O is further limited to be greater than or equal to 1.2.

[0027] The weight percentage range of CaO+MgO+SrO is further limited to 3.5-7.9%.

[0028] The low dielectric glass fiber composition contains the following components, and the content of each component is expressed in weight percentage as follows:

[0029]

[0030]

[0031] The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of 2.75-4.0, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 2.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.75, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.1, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

[0032] The low dielectric glass fiber composition contains the following components, and the content of each component is expressed in weight percentage as follows:

[0033]

[0034] The total content of the above components is greater than or equal to 99.3%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of 2.75-4.0, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of 2.0-40.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.75, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.13, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

[0035] Wherein, the low dielectric glass fiber composition further comprises one or more of SO3, P2O5, ZnO, CeO2, La2O3, and Y2O3 with a total weight percentage of less than 1%.

[0036] Wherein, the low dielectric glass fiber composition further comprises SO3 in an amount of 0.005-0.45% by weight.

[0037] Wherein, the low dielectric glass fiber composition further comprises P2O5 in a weight percentage content of 0-0.2%.

[0038] It is further specified that the composition does not contain rare earth oxides.

[0039] Wherein, it is further specified that the composition does not contain SnO2.

[0040] Wherein, it is further specified that the composition does not contain ZnO.

[0041] The low dielectric glass fiber composition contains the following components, and the content of each component is expressed in weight percentage as follows:

[0042]

[0043] The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.65, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 2.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.65, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.1, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

[0044] Among them, it is further limited that the total content of SiO2, Al2O3, B2O3, CaO, MgO, SrO, Na2O, K2O, Fe2O3, TiO2, F2, and ZrO2 in the glass fiber composition is greater than or equal to 99.3%.

[0045] The low-dielectric glass fiber composition has a glass dielectric constant of 4.75 or less, a glass dielectric loss of 3.5‰ or less, and a glass forming temperature of 1349°C or less at room temperature and a frequency of 10 GHz.

[0046] Wherein, the glass devitrification temperature of the low dielectric glass fiber composition is below 1100°C.

[0047] According to another aspect of the present application, a glass fiber is provided. The glass fiber is made of the low-dielectric glass fiber composition described above.

[0048] According to a third aspect of the present application, an electronic cloth is provided, the electronic cloth containing the aforementioned glass fiber. Simultaneously, a composite material is provided, the composite material including the aforementioned glass fiber.

[0049] The main innovations of the low dielectric glass fiber composition of the present application are: appropriately increasing the content of SiO2, B2O3, and F2 and controlling the total amount of SiO2+B2O3, effectively reducing the Na2O content, the total amount of alkali metal oxides and controlling the potassium-sodium ratio, appropriately reducing the total amount of alkaline earth metal oxides and introducing an appropriate amount of SrO, focusing on designing the total amount and ratio of F2+K2O, the total amount and ratio of F2+SrO, and accurately controlling the ratios such as C1=SiO2 / (CaO+Al2O3), C2=(F2+K2O) / Na2O, C3=(F2+K2O) / (Na2O+TiO2), C4=(MgO+SrO) / CaO, and C5=(SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2). By controlling the above-mentioned glass composition and proportion, on the one hand, the synergistic effect between silicon, boron, aluminum ions and oxygen, fluorine ions can be improved, and the total amount and proportion of network extracellular ions such as alkali metals and alkaline earth metals can be controlled to obtain a better glass structure stacking effect, thereby reducing the glass dielectric constant, dielectric loss and density, and obtaining good glass modulus and water resistance; on the other hand, it can also reduce the molding temperature of the glass, effectively reduce the devitrification temperature and rate of the glass, expand the glass fiber molding range, and reduce the surface tension of the glass liquid and the difficulty of clarification, which is conducive to reducing the difficulty of glass fiber production and improving the quality of the glass liquid. It has more cost advantages and is suitable for large-scale production of low-dielectric glass fiber.

[0050] Specifically, the low dielectric glass fiber composition according to the present application contains the following components, and the content of each component is expressed in weight percentage as follows:

[0051]

[0052] The total content of the above components is greater than or equal to 98.7%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.63, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 1.4, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.5, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.0; the glass fiber composition does not contain lithium oxide.

[0053] The functions and contents of the various components in the glass fiber composition are described as follows:

[0054] SiO2 is a glass network former oxide, the main body that forms the glass skeleton, and the basis of the glass's electrical insulation properties. In the glass fiber composition of the present application, the weight percentage range of SiO2 is limited to 50.0-58.0%. In order to ensure that the glass has good dielectric and mechanical properties, the silicon oxide content is not less than 50.0%; in order to prevent the glass from having high viscosity and difficulty in clarification, the silicon oxide content should not be higher than 58.0%. Preferably, the weight percentage range of SiO2 can be limited to 50.5-57.5%. Preferably, the weight percentage range of SiO2 can be limited to 51.0-57.0%. More preferably, the weight percentage range of SiO2 can be limited to 51.0-56.5%.

[0055] B2O3 is also a glass network forming oxide, which can improve the dielectric properties of glass and has a good high-temperature fluxing effect. At the same time, under different conditions, boron can exist as [BO3] triangles and / or [BO4] tetrahedrons. Under high-temperature melting conditions, it is generally difficult to form [BO4] tetrahedrons, and it mainly exists as [BO3] triangles. This is the main reason why B2O3 can reduce high-temperature viscosity; at low temperatures, under certain conditions, B 3+ It has a tendency to capture free oxygen to form boron oxide tetrahedrons, which plays a role in filling the network. Moreover, the volume of [BO4] tetrahedron is smaller than that of [SiO4] tetrahedron, which makes the glass structure tend to be compact, which is conducive to reducing electrical conductivity and dielectric constant. At the same time, in order to ensure that the glass has good mechanical properties and corrosion resistance, the amount of B2O3 introduced should not be too high. In the glass fiber composition of the present application, the weight percentage content range of B2O3 is limited to 19.0-27.3%. Preferably, the weight percentage content range of B2O3 can be limited to 19.9-27.3%. Preferably, the weight percentage content range of B2O3 can be limited to 19.9-26.9%. More preferably, the weight percentage content range of B2O3 can be limited to 20.4-26.9%.

[0056] Al2O3 is an intermediate oxide in the glass network and an important oxide in forming the glass skeleton. It plays an important role in preventing glass devitrification (phase separation / crystallization) and water resistance. Combined with SiO2, it can play a substantial role in the modulus properties of glass. However, in glass systems with high boron content, due to the 3+ The ability to combine with oxygen ions is better than Al 3+ Stronger, in large quantities B 3+ Under the influence of ions, it becomes more difficult to form [AlO4] tetrahedron in glass. 3+The Al2O3 content is preferably in an octahedral configuration. Furthermore, to prevent excessive difficulty in melting and refining the glass, the amount of Al2O3 introduced should not be too high. In the glass fiber composition of the present application, the Al2O3 content is limited to a weight percentage range of 10.0-16.9%. Preferably, the Al2O3 content is limited to a weight percentage range of 10.5-16.5%. More preferably, the Al2O3 content is limited to a weight percentage range of 11.0-16.0%.

[0057] Experiments have found that by controlling the content and total amount of SiO2 and B2O3, not only good dielectric properties and suitable molding temperature can be obtained, but also the glass density can be reduced, the risk of glass devitrification can be improved, and it is conducive to large-scale production. In the glass fiber composition of the present application, the weight percentage content of SiO2+B2O3 is limited to 72.0-84.0%. Preferably, the weight percentage content of SiO2+B2O3 can be limited to 73.0-84.0%. More preferably, the weight percentage content of SiO2+B2O3 can be limited to 73.0-83.0%. In some embodiments, the weight percentage content of SiO2+B2O3 is 72.0-83.0%.

[0058] Na₂O is an oxide outside the glass network and acts as a glass flux. It can act as a network breaker, reduce glass viscosity, improve glass melting, and effectively provide free oxygen. However, it can also reduce the dielectric properties, mechanical properties, and chemical stability of the glass. Alkali metal oxides significantly affect the electrical properties of glass. As the amount of alkali metal oxide increases, the monovalent alkali metal ions in the glass increase, as does the number of more easily polarized non-bridging oxygen ions. This increases the glass's conductivity and dielectric constant. Na₂O has a greater impact on the electrical properties of glass than other alkali metal oxides, which is related to its greater ability to provide highly polarizable non-bridging oxygen ions. Therefore, the amount of Na₂O incorporated into the present glass composition system must be kept low. In the glass fiber composition of this application, the weight percentage range of Na₂O is limited to 0.01-0.3%. Preferably, the weight percentage range of Na₂O can be limited to 0.01-0.25%. More preferably, the weight percentage range of Na₂O can be limited to 0.02-0.2%.

[0059] K2O is an oxide outside the glass network and can also act as a network breaker, reducing glass viscosity. It can also significantly reduce the surface tension of the glass liquid, which is beneficial for glass clarification and homogenization. When used in combination with Na2O at a certain ratio, it produces a mixed alkali effect, which easily achieves a better ion stacking effect. They may also block each other's movement channels, which is beneficial for reducing the dielectric constant and dielectric loss. However, excessive K2O content can also affect the dielectric properties and chemical stability of the glass, so the amount introduced should not be too high. In the glass fiber composition of the present application, the weight percentage range of K2O is limited to 0.01-0.45%. Preferably, the weight percentage range of K2O can be limited to 0.02-0.4%. More preferably, the weight percentage range of K2O can be limited to 0.04-0.35%. In the glass fiber composition of the present application, the weight percentage ratio of K2O / Na2O is limited to ≥0.6. Preferably, the weight percentage range of K2O / Na2O can be limited to ≥0.75. Preferably, the weight percentage ratio of K2O / Na2O can be limited to a range of ≥1.0. More preferably, the weight percentage ratio of K2O / Na2O can be limited to a range of ≥1.2. In some embodiments, the weight percentage ratio of K2O / Na2O is in the range of 1.2-4.4. In the glass fiber composition of the present application, the weight percentage content of Na2O+KO is limited to a range of 0.03-0.49%. Preferably, the weight percentage content of Na2O+KO can be limited to a range of 0.03-0.45%. More preferably, the weight percentage content of Na2O+KO is in the range of 0.06-0.4%.

[0060] Li2O is an oxide outside the glass network and is an expensive alkali metal oxide relative to Na2O and K2O. Considering the adverse effects of Li2O on cost and dielectric properties, the glass fiber composition of the present application does not contain Li2O.

[0061] F2 is a good fluxing agent and clarifying agent that can effectively reduce the surface tension of glass liquid, help clarify the glass and eliminate bubbles, and also reduce the viscosity and liquidus temperature of the glass. At the same time, studies have shown that an appropriate amount of F2 in glass is beneficial for reducing the dielectric constant and dielectric loss of the glass. In the glass fiber composition of the present application, the weight percentage content range of F2 is limited to 0.01-1.7%. Preferably, the weight percentage content range of F2 is 0.05-1.7%. Preferably, the weight percentage content range of F2 is 0.15-1.5%. More preferably, the weight percentage content range of F2 is 0.3-1.5%. In some embodiments, the weight percentage content range of F2 is 0.1-0.9%.

[0062] On the basis of ensuring the dielectric properties of the glass, in order to effectively reduce the surface tension of the glass liquid, improve glass clarification, reduce glass bubbles, and at the same time reduce glass viscosity and molding difficulty. In the glass fiber composition of the present application, the weight percentage content range of F2+K2O is limited to 0.12-1.8%. Preferably, the weight percentage content range of F2+K2O can be limited to 0.15-1.8%. Preferably, the weight percentage content range of F2+K2O can be limited to 0.2-1.8%. Preferably, the weight percentage content range of F2+K2O can be limited to 0.3-1.7%. More preferably, the weight percentage content range of F2+K2O can be limited to 0.51-1.6%. In some embodiments, the weight percentage content range of F2+K2O is 0.3-1.1%. In the glass fiber composition of the present application, the weight percentage ratio F2 / K2O is limited to a range of ≥0.5. Preferably, the weight percentage ratio F2 / K2O can be limited to a range of ≥1.0. Preferably, the weight percentage ratio F2 / K2O can be limited to a range of ≥1.2. More preferably, the weight percentage ratio F2 / K2O can be limited to a range of ≥1.5. In some embodiments, the weight percentage ratio F2 / K2O ranges from 0.5 to 11.0.

[0063] CaO is an oxide outside the glass network, and plays a substantial role in reducing glass viscosity, improving chemical stability, controlling glass crystallization and material properties. The inventors have found through research that in a glass system with a low alkali metal content and a small amount of free oxygen, calcium ions can provide a large amount of free oxygen while filling the network gaps, allowing more boron and aluminum ions to form tetrahedral coordination, thereby strengthening the glass structure. However, too high a calcium oxide content is not conducive to obtaining lower dielectric properties. In the glass fiber composition of the present application, the weight percentage content range of CaO is limited to 2.3-6.6%. Preferably, the weight percentage content range of CaO can be limited to 2.5-6.4%. Preferably, the weight percentage content range of CaO can be limited to 3.0-6.4%. More preferably, the weight percentage content range of CaO can be limited to 3.3-5.9%.

[0064] MgO is an intermediate oxide in the glass network, and plays a substantial role in improving the glass modulus, reducing the glass viscosity, controlling the glass crystallization and material properties. The Mg-O bond has a certain covalent nature, but the ionic nature is dominant. In a glass system with insufficient "free oxygen", it mainly plays an "accumulation" role, which is beneficial to reducing the conductivity and dielectric constant of the glass. At the same time, Mg 2+ The ionic radius is smaller than that of Na + and K + , the ion field strength is significantly greater than that of Na + and K +, it is firmly bonded to the oxygen ions in the glass and can effectively suppress the migration ability of alkali metal ions. In the glass system of the present application, magnesium ions are usually located outside the glass skeleton network in the form of [MgO6] octahedrons, which can provide a considerable amount of free oxygen while filling the network gaps. At the same time, magnesium ions and calcium ions have different effects on the properties of glass materials. Mixing them can obtain better glass materials, which is beneficial to improving the molding efficiency of the fiber. In the glass fiber composition of the present application, the weight percentage range of MgO is limited to 0.2-4.0%. Preferably, the weight percentage range of MgO can be limited to 0.3-3.9%. More preferably, the weight percentage range of MgO can be limited to 0.5-3.6%.

[0065] SrO is an oxide outside the glass network, which is beneficial to controlling glass crystallization and reducing glass conductivity and dielectric loss. 2+ , Ca 2+ 、Sr 2+ The ion radius becomes larger in sequence, and the ion field strength is also different. More alkaline earth metal ions of different radii participate in the substitution. By rationally controlling the content, total amount and ratio of multiple alkaline earth metal oxides, it is easier to form a tight glass structure stack, which is beneficial to reduce the glass conductivity and make the dielectric loss, crystallization performance and forming performance of the glass more excellent. In the glass fiber composition of the present application, the weight percentage content range of SrO is limited to 0.01-1.0%. Preferably, the weight percentage content range of SrO can be limited to 0.01-0.8%. The weight percentage content range of SrO can be limited to 0.02-0.6%. More preferably, the weight percentage content range of SrO can be limited to 0.02-0.49%.

[0066] In order to reduce the devitrification temperature and rate of glass, improve the dielectric properties of glass, and reduce the difficulty of glass fiber molding. In the glass fiber composition of the present application, the weight percentage range of F2 + SrO is limited to 0.05-2.0%. Preferably, the weight percentage range of F2 + SrO can be limited to 0.1-2.0%. Preferably, the weight percentage range of F2 + SrO can be limited to 0.2-2.0%. More preferably, the weight percentage range of F2 + SrO can be limited to 0.3-1.8%.

[0067] In order to reduce the forming temperature and devitrification temperature of glass and improve the dielectric properties of glass. In the glass fiber composition of the present application, the weight percentage content range of CaO+MgO+SrO is limited to 3.0-9.8%. Preferably, the weight percentage content range of CaO+MgO+SrO can be limited to 3.3-9.4%. Preferably, the weight percentage content range of CaO+MgO+SrO can be limited to 3.3-8.9%. The weight percentage content range of CaO+MgO+SrO can be limited to 3.5-8.5%. More preferably, the weight percentage content range of CaO+MgO+SrO can be limited to 3.5-7.9%.

[0068] Fe2O3 facilitates glass melting and improves glass crystallization. However, because ferric and ferrous ions have a coloring effect, their inclusion rate should be limited. Therefore, in the glass fiber composition of the present application, the Fe2O3 content is limited to a weight percentage range of 0.01-0.5%. Preferably, the Fe2O3 content can be limited to a weight percentage range of 0.01-0.45%. More preferably, the Fe2O3 content can be limited to a weight percentage range of 0.02-0.42%.

[0069] TiO2 can reduce the viscosity of high temperature glass and also has a certain fluxing effect. However, due to the coloring effect of titanium ions combined with iron ions, it will affect the appearance of glass fiber products. 4+ It also does not contribute to reducing the dielectric properties of the glass, so the content should not be too high. Therefore, in the glass fiber composition of the present application, the weight percentage range of TiO2 is limited to 0.01-0.49%. Preferably, the weight percentage range of TiO2 can be limited to 0.01-0.45%. More preferably, the weight percentage range of TiO2 can be limited to 0.03-0.45%.

[0070] ZrO2 can improve the chemical stability and heat resistance of glass, but it is difficult to melt and has high costs. In the glass fiber composition of the present application, the weight percentage range of ZrO2 is limited to 0-1.4%. Preferably, the weight percentage range of ZrO2 can be limited to 0-1.0%. In some embodiments, the weight percentage range of ZrO2 is 0-0.6%.

[0071] In order to ensure the electrical insulation and dielectric properties of the glass, and effectively control the devitrification properties of the glass. In the glass fiber composition of the present application, the range of the weight percentage ratio C1=SiO2 / (CaO+Al2O3) is limited to be greater than or equal to 2.63. Preferably, the range of the weight percentage ratio C1=SiO2 / (CaO+Al2O3) can be limited to be greater than or equal to 2.65. Preferably, the range of the weight percentage ratio C1=SiO2 / (CaO+Al2O3) can be limited to 2.65-4.2. Preferably, the range of the weight percentage ratio C1=SiO2 / (CaO+Al2O3) can be limited to 2.66-4.0. More preferably, the range of the weight percentage ratio C1=SiO2 / (CaO+Al2O3) can be limited to 2.75-4.0.

[0072] In order to effectively reduce the surface tension of the glass liquid, improve glass clarification, reduce glass bubbles, and take into account the dielectric properties and molding properties of the glass. In the glass fiber composition of the present application, the range of the weight percentage ratio C2=(F2+K2O) / Na2O is limited to be greater than or equal to 1.4. Preferably, the range of the weight percentage ratio C2=(F2+K2O) / Na2O can be limited to be greater than or equal to 1.7. Preferably, the range of the weight percentage ratio C2=(F2+K2O) / Na2O can be limited to be greater than or equal to 2.0. Preferably, the range of the weight percentage ratio C2=(F2+K2O) / Na2O can be limited to 2.0-40.0. More preferably, the range of the weight percentage ratio C2=(F2+K2O) / Na2O can be limited to 2.7-35.0.

[0073] In order to reduce the surface tension of the glass liquid, improve the clarity of the glass, effectively control the color of the glass, and take into account the dielectric properties and cost of the glass. In the glass fiber composition of the present application, the range of the weight percentage ratio C3 = (F2 + K2O) / (Na2O + TiO2) is limited to be greater than or equal to 0.5. Preferably, the range of the weight percentage ratio C3 = (F2 + K2O) / (Na2O + TiO2) can be limited to be greater than or equal to 0.65. Preferably, the range of the weight percentage ratio C3 = (F2 + K2O) / (Na2O + TiO2) can be limited to be greater than or equal to 0.75. More preferably, the range of the weight percentage ratio C3 = (F2 + K2O) / (Na2O + TiO2) can be limited to 0.75-15.0.

[0074] In order to effectively control the devitrification of glass, ensure the mechanical properties of glass, and take into account the reduction of the dielectric constant and dielectric loss of glass. In the glass fiber composition of the present application, the range of the weight percentage ratio C4=(MgO+SrO) / CaO is limited to be greater than or equal to 0.05. Preferably, the range of the weight percentage ratio C4=(MgO+SrO) / CaO can be limited to be greater than or equal to 0.1. Preferably, the range of the weight percentage ratio C4=(MgO+SrO) / CaO can be limited to be greater than or equal to 0.13. Preferably, the range of the weight percentage ratio C4=(MgO+SrO) / CaO can be limited to 0.13-2.0. More preferably, the range of the weight percentage ratio C4=(MgO+SrO) / CaO can be limited to 0.15-1.0.

[0075] In order to effectively reduce the dielectric properties of glass, improve glass devitrification, and take into account the glass melting clarification performance and mechanical properties. In the glass fiber composition of the present application, the range of the weight percentage ratio C5=(SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is limited to be greater than or equal to 3.0. Preferably, the range of the weight percentage ratio C5=(SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) can be limited to be greater than or equal to 3.1. Preferably, the range of the weight percentage ratio C5=(SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) can be limited to 3.1-5.2. More preferably, the range of the weight percentage ratio C5=(SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) can be limited to 3.2-4.8.

[0076] The above components are the main components of this application, and their total weight percentage content is limited to greater than or equal to 98.7%. Further, the total weight percentage content of the main components can be limited to greater than or equal to 99.0%. Further, the total weight percentage content of the main components can be limited to greater than or equal to 99.3%. Further, the total weight percentage content of the main components can be limited to greater than or equal to 99.5%.

[0077] In addition to the above-mentioned main components, the glass fiber composition of the present application may also contain a small amount of other components, with a total weight percentage of less than or equal to 1.3%. Furthermore, the glass fiber composition of the present application may contain other components with a weight percentage range of less than or equal to 1.0%. Furthermore, the glass fiber composition of the present application may contain other components with a weight percentage range of less than or equal to 0.7%. Furthermore, in some embodiments, the glass fiber composition of the present application may also contain one or more of SO3, P2O5, ZnO, CeO2, La2O3, and Y2O3 with a total weight percentage content of less than 1.0%. Furthermore, in some embodiments, the glass fiber composition of the present application may also contain one or more of SO3, P2O5, ZnO, CeO2, La2O3, and Y2O3 with a total weight percentage content of less than 0.5%. Furthermore, in some embodiments, the glass fiber composition of the present application may also contain SO3 with a weight percentage content of 0.005-0.45%. Furthermore, in some embodiments, the glass fiber composition of the present application may further include less than 0.5% by weight of SO3+P2O5. Furthermore, in some embodiments, the glass fiber composition of the present application may further include 0-0.2% by weight of P2O5.

[0078] Furthermore, in order to control production costs and glass density, the glass fiber composition of the present application may not contain rare earth oxides.

[0079] Furthermore, the glass fiber composition of the present application may not contain SnO2.

[0080] Furthermore, the glass fiber composition of the present application may not contain P2O5.

[0081] Furthermore, the glass fiber composition of the present application may not contain ZnO.

[0082] Furthermore, the glass fiber composition of the present application may not contain SnO2 and ZnO.

[0083] Furthermore, at room temperature and a frequency of 10 GHz, the glass dielectric constant of the glass fiber composition of the present application can be controlled to be below 4.8, and the glass dielectric loss is below 3.7‰. Preferably, the glass dielectric constant of the composition is 4.75 or below, and the glass dielectric loss is 3.5‰ or below. Preferably, the glass dielectric constant of the composition is 4.7 or below, and the glass dielectric loss is 3.0‰ or below. More preferably, the glass dielectric constant of the composition is 4.7 or below, and the glass dielectric loss is 2.8‰ or below.

[0084] Furthermore, the glass density of the glass fiber composition of the present application can be controlled to be less than or equal to 2.40 g / cm 3 Preferably, the glass density of the composition is less than or equal to 2.35 g / cm 3 More preferably, the glass density of the composition is less than or equal to 2.33 g / cm 3 .

[0085] In order to reduce the difficulty of glass clarification and improve bubble removal efficiency, the glass forming temperature of the glass fiber composition of the present application can be controlled to be less than or equal to 1360°C. Preferably, the glass forming temperature of the composition is less than or equal to 1349°C. Preferably, the glass forming temperature of the composition is less than or equal to 1339°C. More preferably, the glass forming temperature of the composition is less than or equal to 1329°C.

[0086] Furthermore, the glass devitrification temperature of the glass fiber composition of the present application can be controlled to be less than or equal to 1250°C. Preferably, the glass devitrification temperature of the composition is less than or equal to 1150°C. Preferably, the glass devitrification temperature of the composition is less than or equal to 1100°C. More preferably, the glass devitrification temperature of the composition is less than or equal to 1080°C.

[0087] Furthermore, at room temperature and a frequency of 10 GHz, the glass dielectric constant of the glass fiber composition of the present application can be controlled to be 4.75 or less, the glass dielectric loss is 3.5‰ or less, and the glass forming temperature is below 1349°C. Preferably, the glass dielectric constant of the composition can be controlled to be below 4.7, the glass dielectric loss is below 3.0‰, and the glass forming temperature is below 1349°C.

[0088] In the glass fiber composition of the present application, the beneficial effects of selecting the above-mentioned ranges of the content of each component will be described through specific experimental data given in the examples. DETAILED DESCRIPTION

[0089] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application. It should be noted that, in the absence of conflict, the embodiments in the present application and the features in the embodiments can be combined with each other in any way.

[0090] The basic idea of ​​the present application is that the contents of the components of the glass fiber composition are expressed in weight percentage as follows: SiO2 is 50.0-58.0%, Al2O3 is 10.0-16.9%, B2O3 is 19.0-27.3%, CaO is 2.3-6.6%, MgO is 0.2-4.0%, SrO is 0.01-1.0%, Na2O is 0.01-0.3%, and K2O is 0.01-0. 45%, Fe2O3 is 0.01-0.5%, TiO2 is 0.01-0.49%, F2 is 0.01-1.7%, ZrO2 is 0-1.4%, F2+K2O is 0.12-1.8%, F2+SrO is 0.05-2.0%, Na2O+K2O is 0.03-0.49%, the K2O / Na2O ratio range is greater than or equal to 0.6, the F2 / K2O ratio range is The glass fiber composition is greater than or equal to 0.5, CaO+MgO+SrO is 3.0-9.8%, SiO2+B2O3 is 72.0-84.0%, and the total content of the above components is greater than or equal to 98.7%, the weight percentage ratio C1=SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.63, the weight percentage ratio C2=(F2+K2O) / Na2O is in the range of greater than or equal to 1.4, the weight percentage ratio C3=(F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.5, the weight percentage ratio C4=(MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5=(SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.0; at the same time, the glass fiber composition does not contain lithium oxide. The glass fiber composition has the characteristics of low dielectric, low loss, and low density. It can improve the modulus and water resistance of glass, reduce the molding temperature of glass, effectively reduce the devitrification temperature and rate of glass, expand the molding range of glass fiber, and reduce the surface tension of glass liquid and the difficulty of clarification. It is beneficial to reduce the difficulty of glass fiber production and improve the quality of glass liquid. It has more advantages in terms of cost and is suitable for large-scale production of low-dielectric glass fiber.

[0091] The following are examples of preferred value ranges for the various components included in the glass fiber composition according to the present application.

[0092] Preferred Example 1

[0093] The low dielectric glass fiber composition according to the present application contains the following components, and the content of each component is expressed in weight percentage as follows:

[0094]

[0095]

[0096] The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.65, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 2.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.65, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

[0097] Preferred Example 2

[0098] The low dielectric glass fiber composition according to the present application contains the following components, and the content of each component is expressed in weight percentage as follows:

[0099]

[0100] The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of 2.75-4.0, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 2.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.75, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.1, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

[0101] Preferred Example 3

[0102] The low dielectric glass fiber composition according to the present application contains the following components, and the content of each component is expressed in weight percentage as follows:

[0103]

[0104] The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.65, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 2.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.65, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.1, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

[0105] Preferred Example 4

[0106] The low dielectric glass fiber composition according to the present application contains the following components, and the content of each component is expressed in weight percentage as follows:

[0107]

[0108]

[0109] The total content of the above components is greater than or equal to 98.7%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.63, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 1.4, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.5, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.0; the glass fiber composition does not contain lithium oxide, SnO2, ZnO and rare earth oxides.

[0110] Preferred Example 5

[0111] The low dielectric glass fiber composition according to the present application contains the following components, and the content of each component is expressed in weight percentage as follows:

[0112]

[0113] The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.65, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 1.7, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.65, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide, SnO2, ZnO and rare earth oxides.

[0114] Preferred Example 6

[0115] The low dielectric glass fiber composition according to the present application contains the following components, and the content of each component is expressed in weight percentage as follows:

[0116]

[0117]

[0118] The total content of the above components is greater than or equal to 98.7%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) ranges from 2.63 to 4.2, the weight percentage ratio C2 = (F2+K2O) / Na2O ranges from 1.4 to 40.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) ranges from 0.5 to 15.0, the weight percentage ratio C4 = (MgO+SrO) / CaO ranges from 0.05 to 2.0, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) ranges from 3.0 to 5.2; the glass fiber composition does not contain lithium oxide, SnO2, ZnO and rare earth oxides.

[0119] Preferred Example 7

[0120] The low dielectric glass fiber composition according to the present application contains the following components, and the content of each component is expressed in weight percentage as follows:

[0121]

[0122] The total content of the above components is greater than or equal to 99.3%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) ranges from 2.65 to 3.27, the weight percentage ratio C2 = (F2+K2O) / Na2O ranges from 3.3 to 28, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) ranges from 0.75 to 7.31, the weight percentage ratio C4 = (MgO+SrO) / CaO ranges from 0.05 to 0.89, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) ranges from 3.1 to 4.57; the glass fiber composition does not contain lithium oxide, SnO2, ZnO and rare earth oxides.

[0123] The specific content values ​​of SiO2, Al2O3, B2O3, CaO, MgO, SrO, Na2O, K2O, Fe2O3, TiO2, etc. in the glass fiber composition of the present application are selected as examples and compared with the performance parameters of three comparative examples B1, B2 and B3. Seven performance parameters are selected for comparison:

[0124] (1) Molding temperature, corresponding to the glass melt with a viscosity of 10 3 The temperature at anchor.

[0125] (2) Devitrification temperature, which corresponds to the temperature at which the glass medium loses its transparency due to the unevenness of tiny areas inside the glass medium when the glass melt is cooled. The causes of glass devitrification generally include glass crystallization and phase separation. The test method for this item is consistent with that for liquidus temperature.

[0126] (3) △S value, the difference between the forming temperature and the devitrification temperature, represents the temperature range of wire drawing. The larger the forming range, the more conducive it is to wire drawing.

[0127] (4) Glass modulus, which characterizes the ability of glass to resist elastic deformation, is tested according to ASTM E1876 standard for the elastic modulus of glass blocks.

[0128] (5) Glass density: This characterizes the specific gravity and lightweight level of glass. Glass density is tested according to ASTM C693.

[0129] (6) Dielectric constant: This characterizes the polarization ability of a glass dielectric in an electric field. The smaller the dielectric constant, the faster the electrical signal travels through the dielectric. This value is measured using the resonant cavity method at room temperature and a frequency of 10 GHz.

[0130] (7) Dielectric loss: This characterizes the energy loss of a glass dielectric in an electric field. The lower the dielectric loss, the lower the transmission loss of the electrical signal in the dielectric. This measurement was performed using the resonant cavity method at room temperature and a frequency of 10 GHz.

[0131] The above seven parameters and their determination methods are well known to those skilled in the art. Therefore, the above parameters can be used to effectively illustrate the performance of the glass fiber composition of the present application.

[0132] The experimental process is as follows: Each component can be obtained from appropriate raw materials, which are then mixed in proportion to achieve the desired final weight percentage. The mixed materials are then melted and clarified. The molten glass is then drawn through a nozzle on a drain plate to form glass fibers. The glass fibers are then drawn and wound onto the rotating head of a drawing machine to form raw fiber cakes or yarn balls. Of course, these glass fibers can be further processed using conventional methods to meet the desired requirements.

[0133] The following table further compares the performance parameters of the glass fiber compositions of the present application's examples and comparative examples. The glass fiber composition contents are expressed in weight percentages. It should be noted that the total component content of the examples is slightly less than 100%, which can be understood as residual amounts of trace impurities or small amounts of components that could not be analyzed.

[0134] Table 1A

[0135]

[0136]

[0137] Table 1B

[0138]

[0139]

[0140] Table 1C

[0141]

[0142] Table 1D

[0143]

[0144]

[0145] It can be seen from the specific values ​​in the above table that compared with the traditional E glass fiber composition (Comparative Example B1), the low dielectric glass fiber composition of the present application has the following advantages: (1) a much lower dielectric constant and dielectric loss; (2) a lower density and lightweight level; (3) a wider molding range.

[0146] Compared with the conventional D glass fiber composition (Comparative Example B2), the low dielectric glass fiber composition of the present application has the following advantages: (1) a much lower molding temperature and devitrification temperature; (2) a much lower total alkali metal content; (3) a higher glass modulus; and (4) excellent dielectric constant and dielectric loss.

[0147] Compared with a typical low-dielectric glass fiber composition (Comparative Example B3), the low-dielectric glass fiber composition of the present application has the following advantages: (1) a lower dielectric constant and dielectric loss; (2) a wider molding range; and (3) a lower devitrification temperature.

[0148] It can be seen from this that the technical solution of the present application is different from traditional E glass fiber compositions, traditional D glass fiber compositions and typical low-dielectric glass fiber compositions, and has made substantial progress in dielectric constant, dielectric loss, molding temperature, devitrification temperature, molding range, glass modulus, glass density, etc. It has excellent comprehensive performance, is easy to achieve large-scale production, and has achieved unexpected technical effects.

[0149] The low-dielectric glass fiber composition according to the present application can be made into low-dielectric glass fibers having the above-mentioned excellent properties; and the low-dielectric glass fibers can be made into electronic cloth.

[0150] The low-dielectric glass fiber composition and glass fiber of the present application can be combined with one or more organic and / or inorganic materials to prepare composite materials with excellent performance, for example, glass fiber reinforced substrates, typical applications of which include copper-clad laminates, packaging materials, electrical insulation materials, electronic device materials, etc.

[0151] Finally, it should be noted that in this document, the terms "comprises," "comprising," or any other variations thereof are intended to encompass non-exclusive inclusion, such that a process, method, article, or apparatus comprising a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus. In the absence of further limitations, an element defined by the phrase "comprising a..." does not preclude the presence of additional identical elements in the process, method, article, or apparatus comprising the element.

[0152] The above embodiments are intended only to illustrate the technical solutions of the present application and are not intended to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they may still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein with equivalents; and such modifications or replacements do not deviate from the spirit and scope of the technical solutions of the various embodiments of the present application.

Claims

1. A low dielectric glass fiber composition, characterized in that The glass fiber composition contains the following components, and the content of each component is expressed as follows in weight percentage: The total content of the above components is greater than or equal to 98.7%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.63, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 1.4, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.5, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.0; the glass fiber composition does not contain lithium oxide.

2. The low dielectric glass fiber composition according to claim 1, characterized in that The glass fiber composition contains the following components, and the content of each component is expressed as follows in weight percentage: The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.65, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 1.7, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.65, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

3. The low dielectric glass fiber composition according to claim 1 or 2, characterized in that: The weight percentage ratio C1=SiO2 / (CaO+Al2O3) ranges from 2.65 to 4.

2.

4. The low dielectric glass fiber composition according to claim 1 or 2, characterized in that: The weight percentage ratio C2=(F2+K2O) / Na2O is in the range of greater than or equal to 2.

0.

5. The low dielectric glass fiber composition according to claim 1 or 2, characterized in that: The weight percentage ratio C3=(F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.

75.

6. The low dielectric glass fiber composition according to claim 1, characterized in that The weight percentage ratio C5=(SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.

1.

7. The low dielectric glass fiber composition according to claim 1, characterized in that The weight percentage content of F2+K2O is in the range of 0.3-1.7%.

8. The low dielectric glass fiber composition according to claim 1, characterized in that The glass fiber composition contains the following components, and the content of each component is expressed as follows in weight percentage: The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.65, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 2.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.65, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

9. The low dielectric glass fiber composition according to claim 1, characterized in that The glass fiber composition contains the following components, and the content of each component is expressed as follows in weight percentage: The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of 2.65-4.2, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 2.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.75, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.05, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

10. The low dielectric glass fiber composition according to claim 1, characterized in that The weight percentage ratio of K2O / Na2O is greater than or equal to 1.

2.

11. The low dielectric glass fiber composition according to claim 1, characterized in that The weight percentage content of CaO+MgO+SrO is in the range of 3.5-7.9%.

12. The low dielectric glass fiber composition according to claim 1, characterized in that The glass fiber composition contains the following components, and the content of each component is expressed as follows in weight percentage: The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of 2.75-4.0, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 2.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.75, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.1, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

13. The low dielectric glass fiber composition according to claim 1, characterized in that: The glass fiber composition contains the following components, and the content of each component is expressed as follows in weight percentage: The total content of the above components is greater than or equal to 99.3%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of 2.75-4.0, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of 2.0-40.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.75, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.13, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

14. The low dielectric glass fiber composition according to claim 1, characterized in that It also contains one or more of SO3, P2O5, ZnO, CeO2, La2O3, and Y2O3 with a total weight percentage of less than 1.0%.

15. The low dielectric glass fiber composition according to claim 1, characterized in that It also contains SO3 in a weight percentage of 0.005-0.45%.

16. The low dielectric glass fiber composition according to claim 1, characterized in that It also contains P2O5 in a weight percentage of 0-0.2%.

17. The low dielectric glass fiber composition according to claim 1, characterized in that The low dielectric glass fiber composition does not contain rare earth oxides.

18. The low dielectric glass fiber composition according to claim 1, characterized in that The low dielectric glass fiber composition does not contain SnO2.

19. The low dielectric glass fiber composition according to claim 1, characterized in that The low dielectric glass fiber composition does not contain ZnO.

20. The low dielectric glass fiber composition according to claim 1, characterized in that The glass fiber composition contains the following components, and the content of each component is expressed as follows in weight percentage: The total content of the above components is greater than or equal to 99.0%, the weight percentage ratio C1 = SiO2 / (CaO+Al2O3) is in the range of greater than or equal to 2.65, the weight percentage ratio C2 = (F2+K2O) / Na2O is in the range of greater than or equal to 2.0, the weight percentage ratio C3 = (F2+K2O) / (Na2O+TiO2) is in the range of greater than or equal to 0.65, the weight percentage ratio C4 = (MgO+SrO) / CaO is in the range of greater than or equal to 0.1, and the weight percentage ratio C5 = (SiO2+B2O3) / (CaO+MgO+Al2O3+TiO2) is in the range of greater than or equal to 3.1; the glass fiber composition does not contain lithium oxide.

21. The low dielectric glass fiber composition according to claim 1, characterized in that The total content of SiO2, Al2O3, B2O3, CaO, MgO, SrO, Na2O, K2O, Fe2O3, TiO2, F2 and ZrO2 in the glass fiber composition is greater than or equal to 99.3%.

22. The low dielectric glass fiber composition according to claim 1, characterized in that At room temperature and a frequency of 10 GHz, the glass dielectric constant of the glass fiber composition is 4.75 or less, the glass dielectric loss is 3.5‰ or less, and the glass forming temperature is below 1349°C.

23. The low dielectric glass fiber composition according to claim 1, characterized in that The glass devitrification temperature of the glass fiber composition is below 1100°C.

24. A glass fiber, characterized in that The glass fiber is made of the low dielectric glass fiber composition according to any one of claims 1 to 23.

25. An electronic cloth, characterized in that: The electronic cloth contains the glass fiber according to claim 24.

26. A composite material, characterized in that The composite material contains the glass fiber according to claim 24.

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