Electronic-grade low-dielectric glass fiber composition, glass fiber and preparation method thereof

Abstract

The invention belongs to the technical field of glass fibers, and provides an electronic-grade low-dielectric glass fiber composition which comprises the following components in percentage by mass: 54-60% of SiO2; 12% to 18% of Al2O3; 15 to 20% of CaO; 0.2% to 3.5% of MgO; 0.5% to 5.5% of B2O3; 0 to 2.0% of F; 0% to 0.4% of Na2O + K2O; 0 to 0.5 percent of Fe2O3 (ferric oxide); 0.1 to 3% of TiO2; from 0 to 3.5% of Y2O3; 0% to 3.5% of La2O3; and 0 to 3.0% of CeO2. The dielectric constant of the glass fiber is smaller than or equal to 6.0, the dielectric loss is smaller than or equal to 0.005 (under the frequency of 10GHz), the forming temperature does not exceed 1280 DEG C, the forming interval is larger than 50 DEG C, and the glass fiber can be produced in batches on a ten-thousand-ton tank furnace.

Description

Technical Field

[0001] This invention relates to the field of glass fiber technology, and in particular to an electronic-grade low-dielectric glass fiber composition, glass fiber, and a method for preparing the same. Background Technology

[0002] With the rapid development of the electronics and information industry, printed circuit boards (PCBs) are evolving towards higher density, multilayering, and higher frequency, which places higher demands on the dielectric properties of PCBs. The PCB substrate is mainly composed of glass fiber and epoxy resin, with glass fiber having the highest volume proportion and the greatest impact on the overall dielectric properties of the circuit board. Currently, most PCBs use E-glass, which has advantages such as good processability, good water resistance, and low price. However, its dielectric constant (Dk) is relatively high (approximately 6.7), and its dielectric loss (Df) is relatively large, typically greater than 60 × 10⁻⁶ at 10 GHz frequencies. -4 It is becoming increasingly difficult to meet the demands of high density and high-speed information processing.

[0003] To reduce the dielectric properties of glass fibers, low-dielectric glass fibers have been developed, such as D-glass, NE-glass (Nittobo), and L-glass (AGY). Although these low-dielectric glass fibers have significantly reduced dielectric constant and dielectric loss, they all use a high B2O3 (mass content exceeding 20%) and low R2O (mass content less than 0.1%) formulation, resulting in high glass melting temperature, poor compositional uniformity, easy generation of veins and bubbles, and difficulties in fiber drawing. They are poor in both productivity and workability, making it difficult to achieve large-scale mass production and meet the rapidly expanding market demand.

[0004] Chinese patent CN202210726068.2 discloses a low-dielectric glass fiber composition comprising the following components in the indicated mass percentages: SiO2 50-58.5%, Al2O3 8-16%, B2O3 17-26%, CaO 0-1.0%, ZnO 0-5.0%, BaO 0.5-6.0%, SrO 0.5-3.0%, TiO2 0.1-5.0%, F2 0.1-1.8%, and Na2O+K2O+Li2O 0.05-0.5%. To achieve low dielectric constant and dielectric loss, this invention not only contains a high content of B2O3 but also replaces CaO and MgO with BaO and SrO. However, the production difficulty and cost remain unresolved, hindering large-scale mass production.

[0005] Chinese patent CN201880038357.5 discloses a glass composition for glass fibers with low dielectric constant and low dielectric loss tangent. The composition comprises 52.0–59.5% SiO2, 17.5–25.5% B2O3, 9.0–14.0% Al2O3, 0.5–6.0% SrO, 1.0–5.0% MgO, 1.0–5.0% CaO, and F2 and Cl2 in a total content ranging from 0.1–2.5% by mass. This invention also employs a high-content B2O3 technology route, while also adding SrO, F2, and Cl2. This results in very high production control difficulty and production costs, and it is not suitable for large-scale mass production.

[0006] Therefore, developing a new type of electronic-grade low-dielectric-loss glass fiber with low dielectric constant, low dielectric loss, good manufacturability, and mass production capability has become an urgent problem for the electronics industry in the 5G era. Summary of the Invention

[0007] In view of this, the technical problem to be solved by the present invention is to provide a glass fiber composition, which has the characteristics of low dielectric constant and low dielectric loss.

[0008] This invention provides an electronic-grade low-dielectric glass fiber composition comprising the following components by weight percentage:

[0009] 54-60% SiO2;

[0010] 12-18% Al2O3;

[0011] 15-20% CaO;

[0012] 0.2~3.5% MgO;

[0013] 0.5~5.5% B2O3;

[0014] 0~2.0% F;

[0015] 0~0.4% Na₂O + K₂O;

[0016] 0~0.5% Fe2O3;

[0017] 0.1~3% TiO2;

[0018] 0~3.5% Y2O3;

[0019] 0~3.5% La2O3;

[0020] 0~3.0% CeO2.

[0021] The dielectric properties of glass are mainly related to the atomic polarization within the glass. When electrons or ions in the glass are subjected to an external electric field, they undergo displacement polarization or orientation polarization. The higher the degree of polarization, the greater the dielectric constant of the glass. Simultaneously, due to polarization, some electrical energy is converted into heat energy and lost; the higher the polarization, the greater the dielectric loss. Therefore, increasing the density of the glass network structure, reducing the content of mobile ions, and adding network ions with stronger electric fields all help to reduce the degree of glass polarization, thereby reducing the dielectric constant and dielectric loss. Existing low-dielectric glass fibers typically achieve lower dielectric constants and dielectric losses by significantly increasing the B2O3 content (above 20%) and reducing the alkaline earth metal oxide (RO) content (CaO+MgO less than 10%). However, excessively high B2O3 content not only significantly increases the glass fiber melting temperature and production difficulty (forming temperature above 1330℃, only small-batch production via crucible method or electric melting furnace), but also makes it difficult to solve the problem of large fluctuations in glass composition and the easy generation of secondary bubbles caused by the easy volatilization of B2O3 at high temperatures (the ultrafine electronic cloth used in printed circuit boards is very sensitive to the glass bubble content and composition fluctuations, and the requirements are very stringent). Therefore, the current market production of low-dielectric glass fibers is very limited, and the price is also very high.

[0022] This invention relates to a glass fiber based on a SiO2-Al2O3-RO glass system. The glass formulation, through designing a high SiO2 content, a medium RO content, and a small amount of B2O3, effectively improves the fiber-forming properties, enabling the large-scale production of ultrafine electronic yarns in large-scale tank furnaces. Simultaneously, the introduction of a certain amount of highly coordinated, high-field-strength TiO2 / CeO2 / Y2O3 / La2O3 into the glass fiber composition further strengthens the network structure and reduces atomic polarization tendency, resulting in a dielectric constant and dielectric loss that are more than 10% lower than ordinary E glass. The inventors also discovered that K2O and Na2O are easily polarized ions that significantly affect the dielectric properties of the glass; therefore, their content and proportion are strictly controlled in this invention, and the glass is essentially free of BaO, ZnO, PbO, and other components.

[0023] This invention, through the above-mentioned glass composition design and precise control of the content and proportion of each component, yields a glass with low dielectric constant (Dk≤6.0, 10GHz) and low dielectric loss (Df≤50×10⁻⁶). -4 The composition of this invention also exhibits excellent fiber-forming properties, with a forming temperature not exceeding 1280°C and a crystallization upper limit temperature not exceeding 1200°C, enabling large-scale production of ultrafine electronic yarns in existing large-scale tank furnaces.

[0024] In the composition of this invention, silicon dioxide (SiO2) is the main oxide forming the glass network structure, which plays a role in regulating the glass drawing properties, reducing the glass dielectric constant and dielectric loss, and imparting certain mechanical strength and chemical stability to the glass. Within a certain range, the higher the SiO2 content in the glass, the better the mechanical strength of the glass, and the lower the glass dielectric constant and dielectric loss. However, at the same time, the melting temperature and fiber forming temperature of the glass are also higher, and the production difficulty is greater. In this invention, the SiO2 mass percentage is limited to 54-60%, preferably 55.2-60%, and more preferably 56.5-59.1%.

[0025] The electronic-grade low-dielectric glass fiber composition provided by this invention comprises 54-60 wt% SiO2; specifically, it can be 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, or 60 wt%.

[0026] Al2O3 is also one of the main oxides constituting the glass network structure. At a certain content, it enters the glass network structure in the form of aluminum-oxygen tetrahedra, which helps to improve the structural stability of glass fibers and reduce the dielectric constant and dielectric loss of glass fibers. However, if the Al2O3 content is too high, the glass crystallization temperature will increase significantly, which is not conducive to the stable drawing and forming of glass fibers. The mass percentage of Al2O3 in the composition of the present invention is limited to 12-18%, preferably 13-17%, and more preferably 13.2-16.4%.

[0027] The electronic-grade low-dielectric glass fiber composition provided by the present invention comprises 12-18 wt% Al2O3; specifically, it can be 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, or 18wt%.

[0028] CaO, an alkaline earth metal oxide, plays a crucial role in the stable production of ultrafine glass fibers by reducing high-temperature viscosity, regulating glass fiber properties, and improving the crystallization tendency of silicate glasses. However, Ca... 2+ Due to their large ionic radius, CaO is prone to ionic polarization in electromagnetic fields, and high CaO content is detrimental to the dielectric constant and dielectric loss of glass. Therefore, in this invention, the CaO content is controlled at 15-20%, preferably 15-19.2% by mass, and more preferably 16.2-18.8%.

[0029] The electronic-grade low-dielectric glass fiber composition provided by the present invention comprises 15-20 wt% CaO; specifically, it can be 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt%.

[0030] Similar to CaO, MgO belongs to the alkaline earth metal oxides, but MgO has a greater influence on the tendency of glass crystallization. Typically, the mass percentage of MgO in electronic yarn does not exceed 4%. In this invention, the MgO content is controlled at 0.2-3.5%, preferably 0.2-3.0%, and more preferably 0.5-2.4%.

[0031] The electronic-grade low-dielectric glass fiber composition provided by this invention comprises 0.2~3.5 wt% MgO; specifically, it can be 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2.0wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3.0wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, and 3.5wt%.

[0032] The composition of this invention incorporates B2O3. In an alkali-free glass system, a small amount of B2O3 enters the glass network structure in the form of boron-oxygen tetrahedra, thereby reducing the high-temperature viscosity of the glass and improving its dielectric properties. Simultaneously, controlling the B2O3 content can regulate the surface tension during glass fiber drawing, contributing to the stable forming of ultrafine glass fibers. The B2O3 mass percentage in the glass fibers of this invention is 0.5% to 5.5%, preferably 0.8% to 5%, and more preferably 0.8% to 4.8%.

[0033] The electronic-grade low-dielectric glass fiber composition provided by this invention comprises 0.5~5.5 wt% B2O3; specifically, it can be 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%. wt%, 2.8wt%, 2.9wt%, 3.0wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt%, 4.0wt%, 4.1wt %, 4.2wt%, 4.3wt%, 4.4wt%, 4.5wt%, 4.6wt%, 4.7wt%, 4.8wt%, 4.9wt%, 5.0wt%, 5.1wt%, 5.2wt%, 5.3wt%, 5.4wt%, 5.5wt%.

[0034] According to the present invention, the CaO+MgO content is 16~22wt%, specifically 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, or 22wt%.

[0035] The content of CeO2+Y2O3+La2O3 is 0~3.8 wt%, specifically 0.0wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2.0wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3.0wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, and 3.8wt%.

[0036] The ratio of TiO2 + Y2O3 + La2O3 is 0.5~4 wt%. Specifically, it can be 0.5wt%, 0.7wt%, 0.9wt%, 1.1wt%, 1.3wt%, 1.5wt%, 1.7wt%, 1.9wt%, 2.1wt%, 2.3wt%, 2.5wt%, 2.7wt%, 2.9wt%, 3.1wt%, 3.3wt%, 3.5wt%, 3.7wt%, and 3.9wt%.

[0037] As a preferred embodiment, the CaO+MgO content is 18~20.3%, the CeO2+Y2O3+La2O3 content is 1.1~3.5%, and the TiO2+Y2O3+La2O3 ratio is 1.5~3.5%.

[0038] Na₂O and K₂O, as alkali metal oxides, both act as fluxes and reduce the difficulty of drawing glass in glass. However, increasing the alkali content has a significant negative impact on the dielectric properties of the glass. Therefore, in the composition of this invention, the sum of the contents of Na₂O and K₂O is limited to 0-0.4%, preferably 0-0.3%, and more preferably 0-0.2%.

[0039] TiO2, La2O3, Y2O3, and CeO2 are all highly coordinated, high-field-strength oxides that can improve the aggregation of the glass network, reduce displacement polarization effects, and decrease glass conductivity loss, structural loss, and relaxation loss. Therefore, adding a certain amount of TiO2, La2O3, Y2O3, and CeO2 to the glass composition can effectively reduce the glass dielectric constant and dielectric loss. Meanwhile, the inventors discovered that excessively high levels of any one of these components (TiO2, La2O3, Y2O3, and CeO2) can lead to a severe tendency for glass crystallization. However, by controlling the introduction of multiple components, a synergistic effect can be achieved, reaching an optimal balance between reducing the glass dielectric properties and controlling the glass crystallization tendency. In this invention, the content of TiO2 is limited to 0.1-3%, the content of Y2O3 to 0-3.5%, the content of La2O3 to 0-3.5%, the content of CeO2 to 0-3%, the combined value of TiO2, La2O3, and Y2O3 to 0-3.8%, and the combined value of CeO2, La2O3, and Y2O3 to 0-3.8%. Preferably, the content of TiO2 is 0.1-2.4%, the content of Y2O3 is 0.5-3%, the content of La2O3 is 0.3-3%, the content of CeO2 is 0.2-2%, the combined value of TiO2, La2O3, and Y2O3 is 1.5-3.5%, and the combined value of CeO2, La2O3, and Y2O3 is 1.1-3.5%. More preferably, the TiO2 content is 0.1-2.4%, the Y2O3 content is 0.5-2.5%, the La2O3 content is 0.3-2%, the CeO2 content is 0.2-1.8%, the combined value of TiO2, La2O3 and Y2O3 is 1.5-3.2%, and the combined value of CeO2, La2O3 and Y2O3 is 1.4-3.3%.

[0040] Fe2O3 is generally not added to glass fibers, as a high content can cause the glass to turn yellow or green. In this invention, Fe2O3 exists only as a mineral raw material impurity, and its content is controlled at 0-0.6%, more preferably 0-0.4%.

[0041] In a preferred embodiment of the present invention, the electronic-grade low-dielectric glass fiber composition comprises:

[0042] The composition consists of 55.2-60% SiO2; 13-17% Al2O3; 15-19.2% CaO; 0.5-3.0% MgO; 0.8-5.0% B2O3; 0.2-2.0% F; 0-0.5% Fe2O3; 0-0.4% Na2O + K2O; 0.1-2.4% TiO2; 0.2-2.0% CeO2; 0.5-3.0% Y2O3; and 0.3-3.0% La2O3. The CaO + MgO content is 18-20.3%, the CeO2 + Y2O3 + La2O3 content is 1.1-3.5%, and the TiO2 + Y2O3 + La2O3 ratio is 1.5-3.5%.

[0043] In a preferred embodiment of the present invention, the electronic-grade low-dielectric glass fiber composition comprises:

[0044] The composition is as follows: 56.5-59.5% SiO2; 13.2-16.4% Al2O3; 16.2-18.8% CaO; 0.5-2.4% MgO; 0.8-4.8% B2O3; 0.2-1.5% F; 0-0.4% Fe2O3; 0-0.3% Na2O + K2O; 0.1-2.4% TiO2; 0.2-1.8% CeO2; 0.5-2.5% Y2O3; 0.3-2.0% La2O3; with CaO + MgO content of 18.6-19.7%, CeO2 + Y2O3 + La2O3 content of 1.4-3.3%, and TiO2 + Y2O3 + La2O3 ratio of 1.5-3.2%.

[0045] This invention provides a glass fiber prepared from the glass fiber composition described in any one of the above technical solutions.

[0046] The glass fiber described in this invention has a dielectric constant ≤ 6.0 and a dielectric loss ≤ 0.005.

[0047] The present invention provides a method for preparing glass fiber, comprising: forming the glass fiber composition described in any one of the above technical solutions into a fiber by a drawing process.

[0048] Glass fiber can be prepared using the well-known tank furnace method or electric melting furnace method. Specifically, the tank furnace method or electric melting furnace method involves: calculating the required raw material addition ratios based on the actual glass formulation; quantitatively feeding various raw materials into a mixing silo according to this ratio, ensuring thorough and uniform mixing to obtain a qualified batch; conveying the batch to the kiln head silo of the tank furnace or electric melting furnace, where it is uniformly fed into the furnace by a feeder; the batch being heated, melted, clarified, and homogenized at 1500-1600℃ in the tank furnace to form a qualified molten glass, i.e., a liquid composition; the molten glass being cooled to approximately 1250℃ through a working channel, and then passed through a platinum baffle (4... Glass fibers (00-6000 holes) flow out to form glass filaments; the glass filaments are rapidly drawn into glass fibers of a set diameter (3-24um) under the high-speed traction of the drawing machine, and after spray cooling, coating with sizing agent, and bundling, they are wound into a filament cake by the drawing machine; then, through warping, twisting, weaving and other processes, they are made into electronic cloth of various specifications; or they are dried in a drying oven, unwound and packaged to obtain continuous glass fiber yarn; or the wound filament cake is sent to the chopped strand production line to be cut into chopped strands of the required length, and after granulation, drying, screening and other processes, chopped glass fiber yarn is obtained.

[0049] This invention provides a composite material comprising a resin and the glass fiber described in the above-described technical solution;

[0050] The resin includes thermosetting resin or thermoplastic resin.

[0051] In this invention, the thermosetting resin includes epoxy resin, unsaturated polyester resin or polyurethane resin; the thermoplastic resin includes polycarbonate (PC), polypropylene (PP), polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polystyrene (PS), polyphenylene sulfide (PPS), polyoxymethylene (POM) or polymethyl methacrylate (PMMA).

[0052] The present invention provides a circuit board material comprising the glass fiber described in the above technical solution.

[0053] The electronic-grade low-dielectric glass fiber composition provided by this invention comprises the following components by mass percentage: 54-60% SiO2; 12-18% Al2O3; 15-20% CaO; 0.2-3.5% MgO; 0.5-5.5% B2O3; 0-2.0% F; 0-0.4% Na2O + K2O; 0-0.5% Fe2O3; 0.1-3% TiO2; 0-3.5% Y2O3; 0-3.5% La2O3; and 0-3.0% CeO2. This glass fiber has a dielectric constant ≤6.0, a dielectric loss ≤0.005 (at 10GHz), a molding temperature not exceeding 1280℃, a molding range greater than 50℃, and can be mass-produced in a 10,000-ton-class furnace.

[0054] The electronic-grade low dielectric loss glass fiber composition and composite material of the present invention have the following advantages compared with the prior art:

[0055] (1) Lower dielectric constant and dielectric loss: The dielectric constant of the glass fiber of the present invention is ≤6.0 and the dielectric loss is ≤0.005 (at 10GHz frequency), which is more than 10% lower than that of ordinary E glass fiber. Therefore, the printed circuit board made of the glass fiber of the present invention has better dielectric performance and can better meet the needs of high frequency and high speed communication.

[0056] (2) More stable electrical properties: By adding a small amount of high field strength ions to the glass composition and controlling the ratio of TiO2+Y2O3+La2O3, the glass of the present invention can achieve a lower dielectric constant and dielectric loss with only a lower content of B2O3. At the same time, it effectively overcomes the problem of poor composition uniformity and difficulty in stable control of product electrical properties caused by excessive B2O3 content in existing LDK glass.

[0057] (3) Lower production difficulty: The glass fiber forming temperature (temperature when the viscosity is 1000 poise) of the present invention does not exceed 1280℃ and the crystallization temperature is lower than 1200℃, which is comparable to the production difficulty of ordinary glass fiber. Stable mass production of ultrafine electronic yarn can be achieved on existing 10,000-ton-level pool furnaces. Detailed Implementation

[0058] This invention provides an electronic-grade low-dielectric glass fiber composition, glass fiber, and a method for preparing the same. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired results. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and fall within the scope of this invention. The methods and applications of this invention have been described through preferred embodiments. Those skilled in the art can clearly modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0059] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.

[0060] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.

[0061] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0062] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items.

[0063] It should be understood that the order of the steps or the order in which certain actions are performed is not important as long as the invention remains operational. Furthermore, two or more steps or actions can be performed simultaneously.

[0064] The use of any and all instances or exemplary language such as “e.g.” or “including” in this document is merely intended to better illustrate the invention and is not intended to limit the scope of the invention unless the claims are made. No language in this specification should be construed as indicating that any unclaimed element is essential to the practice of the invention.

[0065] Furthermore, the numerical ranges and parameters used to define the present invention are approximate values, and the relevant values ​​in the specific embodiments have been presented as precisely as possible. However, any value inevitably contains standard deviations due to individual test methods. Therefore, unless explicitly stated otherwise, it should be understood that all ranges, quantities, values, and percentages used in this disclosure are modified with the word "approximately". Here, "approximately" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a specific value or range.

[0066] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0067] The embodiments and comparative examples of this invention describe some examples, in which the embodiments illustrate certain implementations of the invention. However, this does not mean that the effects of the invention can only be achieved in these examples.

[0068] To further illustrate the present invention, the following detailed description, in conjunction with embodiments, describes an electronic-grade low-dielectric glass fiber composition, glass fiber, and its preparation method provided by the present invention.

[0069] Examples 1-23

[0070] The examples were prepared according to the following method:

[0071] The required proportions of raw materials (quartz powder, kaolin, boron anhydride, quicklime, lightly calcined powder, fluorite, cerium oxide, yttrium oxide, lanthanum oxide) are calculated based on the actual glass formula. Each raw material is precisely weighed according to this proportion and transported to the mixing silo for thorough and uniform mixing to obtain a qualified batch. The batch is then transported to the kiln head silo of the experimental electric melting furnace and fed into the furnace at a uniform speed by a feeder. The batch is heated, melted, clarified, and homogenized at 1500-1600℃ in the tank furnace to form a qualified glass melt. The uniform glass melt is cooled to approximately 1250℃ through the working channel and then flows out through a platinum perforator (800 holes) to form glass fibers. These glass fibers are rapidly drawn into glass fibers of a set diameter (7µm) under high-speed traction by a drawing machine. After spray cooling, coating with a sizing agent, and bundling, they are wound into a fiber cake by the drawing machine and dried to obtain a glass fiber sample. The forming temperature and crystallization limit temperature of the glass samples were tested using a high-temperature viscometer and a crystallization gradient furnace. The dielectric constant and dielectric loss of the glass samples were tested using the split resonant cavity method.

[0072] Tables 1, 2, and 3 show the formulation composition and properties of glass fibers in Examples 1-22 of the present invention. The composition of the comparative examples is referenced from pages 53-54 of the "Complete Book of Glass Fibers and Mineral Wool". The values ​​are mass percentages. Due to factors such as detection errors, trace impurities not being analyzed and included, and decimal places, the total percentage content of the components listed in the tables may not all reach 100%.

[0073] Where T logη=3 This indicates the temperature at which the glass viscosity reaches 1000 poise, equivalent to the temperature of the molten glass during glass fiber forming; it is also known as the "glass fiber forming temperature". 液 It represents the glass liquidus temperature, which is the temperature at which the glass crystallization rate is 0. It is equivalent to the upper limit of the glass crystallization temperature and is often simply referred to as the "glass fiber crystallization temperature".

[0074] The high-temperature viscosity of the glass fiber was measured using a Brookfield high-temperature viscometer manufactured by ORTON, the glass liquidus temperature was measured using an Orton Model gradient furnace, and the dielectric constant and dielectric loss of the glass were determined according to GB / T 7265.1 standard. Table 1

[0075]

[0076] Table 2

[0077]

[0078] Table 3

[0079]

[0080] Table 4

[0081]

[0082] As shown in Tables 1-3, the glass fiber of the present invention has a lower dielectric constant and dielectric loss (glass fiber dielectric constant ≤ 6.0, dielectric loss ≤ 0.005, at 10GHz frequency) and lower molding difficulty. The molding temperature does not exceed 1280℃, and the molding range is greater than 50℃. It can be mass-produced in a 10,000-ton-level pool furnace.

[0083] As can be seen from Comparison Examples 1 and 4 in Table 4, E glass and boron-free and fluorine-free ECR glass have poor dielectric properties due to their high alkali and CaO content. Comparison Example 2 shows that the Na2O and K2O content has a significant impact on the dielectric constant and dielectric loss of the glass. Comparison Example 3 shows that increasing the MgO content to replace CaO has a certain positive effect on dielectric properties, but it also significantly increases the glass crystallization temperature and increases the difficulty of production.

[0084] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An electronic-grade low-dielectric glass fiber composition, characterized in that, Including the following components by weight percentage: 54-60% SiO2; 12-18% Al2O3; 15-20% CaO; 0.2~3.5% MgO; 0.5~5.5% B2O3; 0~2.0% F; 0~0.4% Na₂O + K₂O; 0~0.5% Fe2O3; 0.1~3% TiO2; 0~3.5% Y2O3; 0~3.5% La2O3; 0~3.0% CeO2.

2. The composition according to claim 1, characterized in that, The CaO+MgO content is 16~22%, the CeO2+Y2O3+La2O3 content is 0-3.8%, and the TiO2+Y2O3+La2O3 ratio is 0.5~4%.

3. The composition according to claim 1, characterized in that, The electronic-grade low-dielectric glass fiber composition comprises: The composition consists of 55.2-60% SiO2; 13-17% Al2O3; 15-19.2% CaO; 0.5-3.0% MgO; 0.8-5.0% B2O3; 0.2-2.0% F; 0-0.5% Fe2O3; 0-0.4% Na2O + K2O; 0.1-2.4% TiO2; 0.2-2.0% CeO2; 0.5-3.0% Y2O3; and 0.3-3.0% La2O3. The CaO + MgO content is 18-20.3%, the CeO2 + Y2O3 + La2O3 content is 1.1-3.5%, and the TiO2 + Y2O3 + La2O3 ratio is 1.5-3.5%.

4. The composition according to claim 3, characterized in that, The electronic-grade low-dielectric glass fiber composition comprises: The composition is as follows: 56.5-59.1% SiO2; 13.2-16.4% Al2O3; 16.2-18.8% CaO; 0.5-2.4% MgO; 0.8-4.8% B2O3; 0.2-1.5% F; 0-0.4% Fe2O3; 0-0.3% Na2O + K2O; 0.1-2.4% TiO2; 0.2-1.8% CeO2; 0.5-2.5% Y2O3; 0.3-2.0% La2O3; with CaO + MgO content of 18.6-19.7%, CeO2 + Y2O3 + La2O3 content of 1.4-3.3%, and TiO2 + Y2O3 + La2O3 ratio of 1.5-3.2%.

5. A type of glass fiber, characterized in that, It is prepared from the glass fiber composition according to any one of claims 1 to 4.

6. The glass fiber according to claim 5, characterized in that, The dielectric constant of the glass fiber is ≤6.0, and the dielectric loss is ≤0.

005.

7. A method for preparing glass fiber, characterized in that, include: The glass fiber composition according to any one of claims 1 to 4 is formed by a drawing process.

8. A composite material, characterized in that, Includes resin and the glass fiber as described in claim 5; The resin includes thermosetting resin or thermoplastic resin.

9. The composite material according to claim 8, characterized in that, The Thermosetting resins include epoxy resins, unsaturated polyester resins, or polyurethane resins; Thermoplastic resins include polycarbonate, polypropylene, polyamide, polybutylene terephthalate, polyethylene terephthalate, polystyrene, polyphenylene sulfide, polyoxymethylene, or polymethyl methacrylate.

10. A circuit board, characterized in that, The raw material includes the glass fiber as described in claim 5.

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