Glass composition for glass fiber, glass fiber, glass fiber fabric, and glass fiber reinforced resin composition

Abstract

The present invention provides a glass composition for glass fiber having a 1000 poise temperature reduced. A glass fiber having excellent water resistance and excellent dielectric properties in a high frequency region can be obtained using the glass composition for glass fiber. The glass composition for glass fiber contains SiO2 in a range of 50.00 to 61.00 mass% relative to the total amount of the glass composition for glass fiber, B2O3 in a range of 16.00 to 27.00 mass%, Al2O3 in a range of 7.00 to 14.00 mass%, P2O5 in a range of 0.20 to 4.00 mass%, TiO2 in a range of 0.50 to 5.00 mass%, CaO in a range of 0.10 to 5.00 mass%, MgO in a range of 0 to 4.00 mass%, and F2 and Cl2 in a total amount in a range of 0 to 2.00 mass%, and the content rate S of SiO2, the content rate A of Al2O3, the content rate P of P2O5, the content rate T of TiO2, the content rate C of CaO, and the content rate M of MgO satisfy the following formula (1): 3.65 ≤ (S / A) 2 × (P × T) 1 / 2 / (C + M) 3 ≤ 8.25 … (1).

Description

Technical Field

[0001] This invention relates to glass compositions for glass fibers, glass fibers, glass fiber fabrics, and glass fiber reinforced resin compositions. Background Technology

[0002] Glass fibers are manufactured by melting glass raw materials, which are formulated into a glass composition for glass fibers with a desired composition, in a glass melting furnace to produce molten glass (the melt of the glass composition for glass fibers). The molten glass is then ejected from a container (sleeve) having a nozzle plate with several to thousands of nozzle chips. The molten glass is then stretched and cooled and solidified at high speed by high-speed winding to form fibers (hereinafter, this operation is sometimes referred to as "spinning"). The sleeve is, for example, made of a precious metal such as platinum.

[0003] In the past, fiberglass has been widely used in various applications because it can improve the strength of resin molded products, which are used for housings or accessories of electronic devices such as servers, smartphones, and laptops.

[0004] Typically, glass absorbs energy as heat from alternating current. Therefore, when the aforementioned resin molded articles are used in the housings or accessories of the aforementioned electronic devices, there is a problem that the resin molded articles will generate heat.

[0005] Here, the dielectric loss absorbed by the glass is proportional to the dielectric constant and dielectric loss tangent determined by the composition and structure of the glass, and can be expressed by the following equation (A).

[0006] W = kfv 2 ×ε 1 / 2 ×tanδ…(A)

[0007] Here, W represents dielectric loss energy, k represents a constant, f represents frequency, and v represents the frequency. 2 Let ε represent the potential gradient, ε represent the dielectric constant, and tanδ represent the dielectric loss tangent. According to equation (A), the larger the dielectric constant and dielectric loss tangent, and the higher the frequency, the greater the dielectric loss, and therefore the greater the heat generation of the above-mentioned resin molded product.

[0008] In recent years, due to the increasing frequency of the alternating current used in the aforementioned electronic devices (f in equation (A) above), it has been required that the glass fibers used in the housings or components of these electronic devices have lower dielectric constants and dielectric loss tangents in order to reduce dielectric loss energy. In particular, since the dielectric loss tangent has a greater impact on equation (A) than the dielectric constant to the power of 1 / 2, a low dielectric loss tangent is required.

[0009] In view of the above, the applicant has proposed a glass composition for glass fibers that has a low dielectric constant and a low dielectric loss tangent, suppresses phase separation, and further reduces viscosity at high temperatures. This glass composition for glass fibers contains SiO2 in the range of 52.0 to 59.5% by mass, B2O3 in the range of 17.5 to 25.5% by mass, Al2O3 in the range of 9.0 to 14.0% by mass, SrO in the range of 0.5 to 6.0% by mass, MgO in the range of 1.0 to 5.0% by mass, CaO in the range of 1.0 to 5.0% by mass, and F2 and Cl2 in the range of 0.1 to 2.5% by mass (see Patent Document 1).

[0010] Existing technical documents

[0011] Patent documents

[0012] Patent Document 1: Japanese Patent No. 6468409 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] On the other hand, there is a particular demand for a glass composition for glass fibers that has a lower dielectric constant and dielectric loss tangent in the high-frequency region of around 10 GHz. In order to achieve the above-mentioned problem, it is considered to reduce the content of Al2O3 and alkaline earth metal oxides (CaO, MgO and SrO) in the glass composition for glass fibers relative to the total amount of the glass composition for glass fibers, thereby correspondingly increasing the content of SiO2 and B2O3.

[0015] However, when the content of SiO2 in the glass composition for glass fiber increases relative to the total amount of the glass composition for glass fiber, the 1000 poise temperature increases, the viscosity of the glass also increases, making it difficult to mix. As a result, there are problems such as difficulty in melting homogeneous glass and premature deterioration of the sleeve during spinning.

[0016] To solve the above problems, the following technical solution is considered: In the above glass composition for glass fiber, P2O5 is used to replace a portion of the content of SiO2 relative to the total amount of the glass composition for glass fiber. As a result, while maintaining excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in the high frequency region, the temperature can be reduced by 1000 poise.

[0017] However, in the glass composition for glass fibers described above, if P2O5 is used to replace a portion of the content of SiO2 relative to the total amount of the glass composition for glass fibers, the water resistance of the glass fibers obtained using the glass composition for glass fibers decreases, and there are problems such as the deterioration of dielectric properties and a significant reduction in the strength of the glass fibers due to foreign matter precipitated on the surface of the glass fibers caused by the hydrolysis of the glass.

[0018] The present invention aims to solve the above-mentioned problems and provides a glass composition for glass fibers with a reduced temperature of 1000 poise. This glass composition for glass fibers can achieve excellent water resistance and excellent dielectric properties in the high-frequency region.

[0019] Methods for solving problems

[0020] To achieve the above objectives, the glass composition for glass fibers of the present invention is characterized in that it contains: SiO2 in the range of 50.00 to 61.00% by mass relative to the total amount of the glass composition for glass fibers, B2O3 in the range of 16.00 to 27.00% by mass, Al2O3 in the range of 7.00 to 14.00% by mass, P2O5 in the range of 0.20 to 4.00% by mass, TiO2 in the range of 0.50 to 5.00% by mass, and O The following formula (1) is provided: CaO in the range of 0.10–5.00% by mass, MgO in the range of 0–4.00% by mass, and F2 and Cl2 in the range of 0–2.00% by mass. The content of SiO2 (mass%) S, Al2O3 (mass%) A, P2O5 (mass%) P, TiO2 (mass%) T, CaO (mass%) C, and MgO (mass%) M satisfies the following formula (1).

[0021] 3.65≤(S / A) 2 ×(P×T) 1 / 2 / (C+M) 3 ≤8.25…(1)

[0022] The glass composition for glass fibers of the present invention contains SiO2, B2O3, Al2O3, P2O5, TiO2, CaO, MgO, F2, and Cl2 within the above-mentioned range. The content of SiO2 (mass%) S, Al2O3 (mass%) A, P2O5 (mass%) P, TiO2 (mass%) T, CaO (mass%) C, and MgO (mass%) M satisfies formula (1). Thus, it is possible to have a reduced temperature of 1000 poise, and glass fibers with excellent dielectric properties such as excellent water resistance, low dielectric constant and low dielectric loss tangent in the high-frequency region can be obtained using this glass composition for glass fibers.

[0023] It should be noted that the glass fiber obtained using the glass composition of the present invention has a low dielectric constant, meaning that the dielectric constant is 4.1 or less at the measurement frequency of 10 GHz, and has a low dielectric loss tangent, meaning that the dielectric loss tangent is 0.0011 or less at the measurement frequency of 10 GHz.

[0024] Furthermore, the glass fibers obtained using the glass composition for glass fibers of the present invention exhibit excellent water resistance, meaning that when evaluated by the following water resistance evaluation method, the mass reduction rate is less than 2.0%, and the glass fiber components hardly dissolve in water.

[0025] In the method for evaluating water resistance, firstly, glass raw materials are mixed to form a glass batch with a specified glass fiber composition. This glass batch is placed in a platinum crucible with a diameter of 80 mm and heated at 1550°C for 4 hours, followed by further heating at 1650°C for 2 hours to melt it. Next, the homogeneous glass shavings obtained from the crucible are placed in a small cylindrical platinum sleeve with a circular nozzle at the bottom of the container and heated to a specified temperature to melt it. Then, the molten glass ejected from the nozzle is wound onto a stainless steel sleeve at a specified speed, thereby stretching the molten glass while cooling and solidifying it to obtain glass fibers with a circular cross-section and a fiber diameter of 13 μm. Next, approximately 1 g (test glass fiber) of the obtained glass fiber is collected from the sleeve, dried at 120°C for 1 hour, and its mass (mass before operation) is measured. Next, the glass fiber for testing was left to stand in 100 ml of distilled water at 80°C for 24 hours. The glass fiber was then obtained using a metal mesh with approximately 150 μm openings, washed with distilled water, and dried at 120°C for 1 hour. The mass (mass after operation) was then measured. Based on the pre-operation and post-operation masses, the mass reduction rate (100 × (1 - (post-operation mass / pre-operation mass))) was calculated.

[0026] Furthermore, the glass composition for glass fiber of the present invention having a reduced 1000 poise temperature means that the 1000 poise temperature is 1500°C or below.

[0027] Furthermore, in the glass composition for glass fiber of the present invention, the above-mentioned S, A, P, T, C and M preferably satisfy the following formula (2), more preferably satisfy the following formula (3), and even more preferably satisfy the following formula (4).

[0028] 4.51≤(S / A) 2 ×(P×T) 1 / 2 / (C+M) 3 ≤7.32…(2)

[0029] 4.87≤(S / A) 2 ×(P×T) 1 / 2 / (C+M) 3 ≤7.20…(3)

[0030] 5.96≤(S / A) 2 ×(P×T) 1 / 2 / (C+M) 3 ≤7.16…(4)

[0031] Furthermore, the present invention is also a glass fiber characterized by being composed of any of the aforementioned glass fiber compositions. Additionally, the present invention is also a glass fiber fabric characterized by containing the glass fiber. Further, the present invention is also a glass fiber reinforced resin composition characterized by containing the glass fiber.

[0032] The glass fibers of the present invention can be obtained, for example, by melting the glass composition for glass fibers described above, ejecting the obtained molten material from a sleeve having a nozzle plate having 1 to 8000 nozzle heads or holes, winding it at high speed, thereby stretching the molten material while cooling and solidifying it to form fibers. Therefore, the glass fibers of the present invention have the same glass composition as the glass composition for glass fibers described above. Detailed Implementation

[0033] The embodiments of the present invention will now be described in more detail.

[0034] The glass composition for glass fiber of this embodiment contains: SiO2 in the range of 50.00 to 61.00% by mass, B2O3 in the range of 16.00 to 27.00% by mass, Al2O3 in the range of 7.00 to 14.00% by mass, P2O5 in the range of 0.20 to 4.00% by mass, TiO2 in the range of 0.50 to 5.00% by mass, CaO in the range of 0.10 to 5.00% by mass, MgO in the range of 0 to 4.00% by mass, and F2 and Cl2 in the range of 0 to 2.00% by mass, wherein the content of SiO2 (mass%) S, the content of Al2O3 (mass%) A, the content of P2O5 (mass%) P, the content of TiO2 (mass%) T, the content of CaO (mass%) C, and the content of MgO (mass%) M satisfy the following formula (1).

[0035] 3.65≤(S / A) 2 ×(P×T) 1 / 2 / (C+M) 3 ≤8.25…(1)

[0036] The glass composition for glass fiber of this embodiment contains SiO2, B2O3, Al2O3, P2O5, TiO2, CaO, MgO, F2, and Cl2 within the above-mentioned range. The content of SiO2 (mass%) S, Al2O3 (mass%) A, P2O5 (mass%) P, TiO2 (mass%) T, CaO (mass%) C, and MgO (mass%) M satisfies formula (1). As a result, it is possible to have a reduced temperature of 1000 poise of less than 1500°C. Furthermore, it is possible to obtain glass fibers with excellent water resistance, a low dielectric constant of 4.1 or less in the high-frequency region of the measurement frequency of 10 GHz, and a low dielectric loss tangent of 0.0011 or less.

[0037] Here, in equation (1), "S / A" is the ratio of the SiO2 content to the Al2O3 content. The smaller the value, the higher the Al2O3 content, which tends to deteriorate the dielectric properties of the glass fiber. On the other hand, a larger "S / A" means a higher SiO2 content, which helps to improve the dielectric properties of the glass fiber, but tends to increase the 1000 poise temperature of the glass composition for glass fiber.

[0038] "P×T" is the product of P2O5 and TiO2, which are intermediate oxides. The larger the value, the better the dielectric properties of the glass fiber, but the worse the water resistance of the glass fiber. On the other hand, the smaller the "P×T", the higher the viscosity of the molten glass, and the higher the 1000 poise temperature of the glass composition for glass fiber.

[0039] "C+M" refers to the total content of alkaline earth metal oxides, namely CaO and MgO, which significantly affect the dielectric properties of glass fibers. A higher "C+M" value tends to result in poorer dielectric properties of the glass fibers. Conversely, a lower "C+M" value tends to result in a higher 1000 poise temperature for the glass composition used with glass fibers.

[0040] Therefore, Equation (1) integrates these tendencies and can be inferred to reflect the dielectric properties of glass fiber, the water resistance of glass fiber, and the uniformity of the 1000 poise temperature of the glass composition for glass fiber.

[0041] In the glass composition for glass fibers of this embodiment, if the content of SiO2 relative to the total amount of the glass composition for glass fibers is less than 50.00% by mass, the mechanical strength of the glass fibers obtained using this glass composition is significantly reduced, and the function of the glass fibers as reinforcing materials in the glass fiber reinforcing resin composition is impaired. Furthermore, the glass fibers are prone to deterioration in acidic environments. On the other hand, if the content of SiO2 relative to the total amount of the glass composition for glass fibers exceeds 61.00% by mass, the viscosity at high temperatures increases, thus raising the melting temperature of the glass raw materials. From a manufacturing cost perspective, this is not suitable for industrial glass fiber manufacturing.

[0042] In the glass composition for glass fiber of this embodiment, the content of SiO2 relative to the total amount of the glass composition for glass fiber is preferably in the range of 52.10 to 59.90% by mass, more preferably in the range of 54.10 to 59.70% by mass, further preferably in the range of 56.10 to 59.60% by mass, particularly preferably in the range of 57.60 to 59.50% by mass, and most preferably in the range of 58.10 to 59.40% by mass.

[0043] In the glass composition for glass fibers of this embodiment, if the content of B2O3 relative to the total amount of the glass composition for glass fibers is less than 16.00% by mass, the dielectric loss tangent of the glass fibers obtained using this glass composition cannot be sufficiently reduced. On the other hand, if the content of B2O3 relative to the total amount of the glass composition for glass fibers exceeds 27.00% by mass, the glass fibers obtained using this glass composition will experience phase separation, and the chemical durability of the glass fibers may be reduced.

[0044] In the glass composition for glass fiber of this embodiment, the content of B2O3 relative to the total amount of the glass composition for glass fiber is preferably in the range of 19.60 to 24.90% by mass, more preferably in the range of 20.10 to 24.50% by mass, even more preferably in the range of 20.60 to 24.00% by mass, particularly preferably in the range of 21.10 to 23.50% by mass, and most preferably in the range of 21.50 to 23.00% by mass.

[0045] The glass composition for glass fibers in this embodiment maintains a low viscosity of the molten glass obtained by using the glass composition for glass fibers by making the content of B2O3 at 19.60% by mass or more relative to the total amount of the glass composition for glass fibers, thereby reducing manufacturing costs and making it suitable for industrial glass fiber manufacturing.

[0046] In the glass composition for glass fibers of this embodiment, the content of B2O3 is 24.90% by mass or less relative to the total amount of the glass composition for glass fibers, which can reduce the volatile components emitted when manufacturing glass fibers by melting glass using this glass composition for glass fibers. In addition, the furnace body wear of the glass melting furnace for melting this glass composition for glass fibers can be reduced, and the furnace body life is extended, thus reducing manufacturing costs.

[0047] In the glass composition for glass fibers of this embodiment, if the content of Al2O3 relative to the total amount of the glass composition for glass fibers is less than 7.00% by mass, the glass fibers obtained using this glass composition will experience phase separation, which may lead to a decrease in the chemical durability of the glass fibers. On the other hand, if the content of Al2O3 relative to the total amount of the glass composition for glass fibers exceeds 14.00% by mass, the dielectric loss tangent of the glass fibers obtained using this glass composition cannot be sufficiently reduced.

[0048] In the glass composition for glass fiber of this embodiment, the content of Al2O3 relative to the total amount of the glass composition for glass fiber is preferably in the range of 8.00 to 13.50% by mass, more preferably in the range of 9.00 to 13.00% by mass, even more preferably in the range of 9.60 to 12.80% by mass, particularly preferably in the range of 10.10 to 12.40% by mass, especially preferably in the range of 10.30 to 11.90% by mass, extremely preferably in the range of 10.50 to 11.50% by mass, and most preferably in the range of 10.60 to 10.90% by mass.

[0049] In the glass composition for glass fiber of this embodiment, by making the content of Al2O3 relative to the total amount of the glass composition for glass fiber 13.00% by mass or less, the liquid phase temperature is greatly reduced and the operating temperature range is widened, thus enabling stable spinning.

[0050] In the glass composition for glass fibers of this embodiment, if the content of P2O5 relative to the total amount of the glass composition for glass fibers is less than 0.20% by mass, it is difficult to simultaneously achieve a reduction in the dielectric loss tangent of the glass fibers obtained using this glass composition and a reduction in the 1000 poise temperature of the glass composition for glass fibers. On the other hand, if the content of P2O5 relative to the total amount of the glass composition for glass fibers exceeds 4.00% by mass, it is impossible to suppress phase separation in the glass fibers obtained using this glass composition, resulting in poor water resistance.

[0051] In the glass composition for glass fiber of this embodiment, the content of P2O5 relative to the total amount of the glass composition for glass fiber is preferably in the range of 0.30 to 3.50% by mass, more preferably in the range of 0.50 to 3.20% by mass, even more preferably in the range of 0.70 to 2.90% by mass, particularly preferably in the range of 0.90 to 2.70% by mass, and most preferably in the range of 1.00 to 2.50% by mass.

[0052] In the glass composition for glass fibers of this embodiment, when the content of TiO2 relative to the total amount of the glass composition for glass fibers is less than 0.50% by mass, the viscosity at high temperatures increases. Therefore, the melting temperature of the glass raw materials increases, which is not suitable for industrial glass fiber manufacturing from the viewpoint of manufacturing cost. On the other hand, when the content of TiO2 relative to the total amount of the glass composition for glass fibers exceeds 5.00% by mass, the dielectric loss tangent of the glass fibers obtained using this glass composition cannot be sufficiently reduced. In addition, the liquidus temperature of the glass composition for glass fibers increases significantly, making it impossible to manufacture stable glass fibers.

[0053] In the glass composition for glass fiber of this embodiment, the content of TiO2 relative to the total amount of the glass composition for glass fiber is preferably in the range of 0.60 to 4.90% by mass, more preferably in the range of 1.00 to 4.50% by mass, even more preferably in the range of 1.50 to 4.00% by mass, particularly preferably in the range of 1.60 to 3.50% by mass, especially preferably in the range of 1.70 to 3.40% by mass, particularly preferably in the range of 1.80 to 3.30% by mass, and most preferably in the range of 2.10 to 3.20% by mass.

[0054] In the glass composition for glass fibers of this embodiment, if the content of CaO relative to the total amount of the glass composition for glass fibers is less than 0.10% by mass, it is difficult to suppress the crystallization of the glass, and the liquidus temperature of the glass composition for glass fibers increases significantly. Therefore, the operating temperature range cannot be adequately ensured. On the other hand, if the content of CaO relative to the total amount of the glass composition for glass fibers exceeds 5.00% by mass, it is not possible to adequately reduce the dielectric loss tangent of the glass fibers obtained using this glass composition for glass fibers.

[0055] In the glass composition for glass fiber of this embodiment, the content of CaO relative to the total amount of the glass composition for glass fiber is preferably in the range of 0.50 to 4.50% by mass, more preferably in the range of 0.70 to 4.00% by mass, further preferably in the range of 0.90 to 3.50% by mass, particularly preferably in the range of 1.10 to 3.00% by mass, extremely preferably in the range of 1.30 to 2.70% by mass, and most preferably in the range of 1.50 to 2.50% by mass.

[0056] In the glass composition for glass fibers of this embodiment, if the content of MgO relative to the total amount of the glass composition for glass fibers exceeds 4.00% by mass, ripples will be generated in the melt of the glass composition for glass fibers, which may lead to easy breakage of the glass fibers during spinning.

[0057] In the glass composition for glass fiber of this embodiment, the content of MgO relative to the total amount of the glass composition for glass fiber is preferably less than 3.00% by mass, more preferably less than 2.00% by mass, further preferably less than 1.50% by mass, particularly preferably less than 1.00% by mass, especially preferably less than 0.95% by mass, and most preferably less than 0.50% by mass.

[0058] In the glass composition for glass fiber of this embodiment, if the total content of F2 and Cl2 relative to the total amount of the glass composition for glass fiber exceeds 2.00% by mass, the chemical durability of the glass fiber obtained using the glass composition for glass fiber decreases.

[0059] In the glass composition for glass fiber of this embodiment, the total content of F2 and Cl2 relative to the total amount of the glass composition for glass fiber is preferably in the range of 0.10 to 1.80% by mass, more preferably in the range of 0.30 to 1.60% by mass, and even more preferably in the range of 0.50 to 1.50% by mass.

[0060] In the glass composition for glass fiber of this embodiment, the total content of F2 and Cl2 relative to the total amount of the glass composition for glass fiber is 0.30% by mass or more, thereby further reducing the dielectric constant of the glass fiber obtained using the glass composition for glass fiber.

[0061] In the glass composition for glass fiber of this embodiment, the total content of F2 and Cl2 relative to the total amount of the glass composition for glass fiber is 1.60% by mass or less. Thus, when manufacturing glass fibers using this glass composition for glass fiber, the generation of volatiles from F2 and Cl2 can be suppressed, and the deterioration of the environment around the furnace body of the glass melting furnace in which the glass composition for glass fiber is melted can be prevented.

[0062] Furthermore, the glass composition for glass fibers in this embodiment may contain SrO in an amount ranging from 0 to 6.00% by mass relative to the total amount of the glass composition for glass fibers. When the glass composition for glass fibers in this embodiment contains SrO, if the SrO content exceeds 6.00% by mass, the dielectric properties of the glass fibers obtained using this glass composition deteriorate, and the target dielectric properties cannot be met.

[0063] When the glass composition for glass fiber in this embodiment contains SrO, the content of SrO relative to the total amount of the glass composition for glass fiber is preferably in the range of 4.00% by mass or less, more preferably in the range of 3.00% by mass or less, even more preferably in the range of 2.00% by mass or less, particularly preferably in the range of less than 1.00% by mass, extremely preferably in the range of less than 0.50% by mass, and most preferably in the range of less than 0.45% by mass.

[0064] Furthermore, the glass composition for glass fibers in this embodiment may contain Na₂O, K₂O, and Li₂O in a total content of less than 1.00% by mass relative to the total amount of the glass composition for glass fibers. When the glass composition for glass fibers in this embodiment contains Na₂O, K₂O, and Li₂O, if their total content exceeds 1.00% by mass, the dielectric properties of the glass fibers obtained using this glass composition deteriorate significantly, and the target dielectric properties cannot be achieved.

[0065] In the case where the glass composition for glass fiber in this embodiment contains Na2O, K2O and Li2O, the total content of Na2O, K2O and Li2O relative to the total amount of the glass composition for glass fiber is preferably less than 0.80% by mass, more preferably less than 0.50% by mass, further preferably less than 0.20% by mass, particularly preferably less than 0.10% by mass, and most preferably less than 0.05% by mass.

[0066] Furthermore, the glass composition for glass fibers in this embodiment may contain ZnO in a content ranging from 0% to 3.00% by mass relative to the total amount of the glass composition for glass fibers. When the glass composition for glass fibers in this embodiment contains ZnO, if the ZnO content exceeds 3.00% by mass, the glass fibers obtained using this glass composition are prone to devitrification during spinning, making stable glass fiber manufacturing impossible. Additionally, the dielectric properties of the glass fibers deteriorate.

[0067] When the glass composition for glass fiber in this embodiment contains ZnO, the content of ZnO relative to the total amount of the glass composition for glass fiber is preferably in the range of 2.50% by mass or less, more preferably in the range of 1.50% by mass or less, and even more preferably in the range of 0.50% by mass or less.

[0068] Furthermore, the glass composition for glass fibers in this embodiment may contain MnO2 in the range of 0 to 3.00% by mass relative to the total amount of the glass composition for glass fibers. When the glass composition for glass fibers in this embodiment contains MnO2, if the content of MnO2 exceeds 3.00% by mass, the dielectric properties of the glass fibers obtained using this glass composition deteriorate, and the desired dielectric properties cannot be obtained.

[0069] In the case where the glass composition for glass fiber in this embodiment contains MnO2, the content of MnO2 relative to the total amount of the glass composition for glass fiber is preferably in the range of 2.50% by mass or less, more preferably in the range of 1.50% by mass or less, and even more preferably in the range of 0.50% by mass or less.

[0070] Furthermore, the glass composition for glass fibers in this embodiment may contain Fe2O3 in a concentration of 0% by mass or more and 1.00% by mass or less relative to the total amount of the glass composition for glass fibers. When the glass composition for glass fibers in this embodiment contains Fe2O3, from the viewpoint of suppressing bubbles contained in the glass fibers, it is effective that the Fe2O3 concentration is in a concentration of 0.10% by mass or more and 0.60% by mass or less.

[0071] Furthermore, the glass composition for glass fibers in this embodiment may contain SnO2 in a concentration of 0% by mass or more and 1.00% by mass or less relative to the total amount of the glass composition for glass fibers. When the glass composition for glass fibers in this embodiment contains SnO2, from the viewpoint of suppressing bubbles contained in the glass fibers, it is effective that the SnO2 concentration is in a concentration of 0.10% by mass or more and 0.60% by mass or less.

[0072] Furthermore, the glass composition for glass fibers in this embodiment may also contain ZrO2 as long as the content of ZrO2 relative to the total amount of the glass composition for glass fibers is less than 0.50% by mass. When the glass composition for glass fibers in this embodiment contains ZrO2, if the content of ZrO2 relative to the total amount of the glass composition for glass fibers is 0.50% by mass or more, the glass fibers obtained using this glass composition are prone to devitrification during spinning, making stable glass fiber manufacturing impossible.

[0073] When the glass composition for glass fiber in this embodiment contains ZrO2, the content of ZrO2 relative to the total amount of the glass composition for glass fiber is preferably less than 0.45% by mass, more preferably less than 0.40% by mass, even more preferably less than 0.20% by mass, particularly preferably less than 0.10% by mass, and most preferably less than 0.05% by mass.

[0074] Furthermore, the glass composition for glass fibers in this embodiment can also contain Cr2O3 as long as the content of Cr2O3 relative to the total amount of the glass composition for glass fibers is less than 0.05% by mass. When the glass composition for glass fibers in this embodiment contains Cr2O3, if the content of Cr2O3 relative to the total amount of the glass composition for glass fibers is 0.05% by mass or more, the glass fibers obtained using this glass composition are prone to devitrification during spinning, making stable glass fiber manufacturing impossible.

[0075] Furthermore, in the glass composition for glass fibers of this embodiment, as impurities derived from raw materials, oxides of Ba, Co, Ni, Cu, Mo, W, Ce, Y, La, Bi, Gd, Pr, Sc, or Yb may be present in an amount less than 1.00% by mass relative to the total amount of the glass composition for glass fibers. Particularly when the glass composition for glass fibers of this embodiment contains BaO, CeO2, Y2O3, La2O3, Bi2O3, Gd2O3, Pr2O3, Sc2O3, or Yb2O3 as impurities, their respective contents are preferably less than 0.40% by mass, more preferably less than 0.20% by mass, further preferably less than 0.10% by mass, particularly preferably less than 0.05% by mass, and most preferably less than 0.01% by mass.

[0076] Furthermore, in the glass composition for glass fiber in this embodiment, the above-mentioned S, A, P, T, C and M preferably satisfy the following formula (1-1), more preferably satisfy the following formula (1-2), even more preferably satisfy the following formula (1-3), particularly preferably satisfy the following formula (2), extremely preferably satisfy the following formula (3), and most preferably satisfy the following formula (4).

[0077] 3.86≤(S / A) 2 ×(P×T) 1 / 2 / (C+M) 3 ≤7.32…(1-1)

[0078] 4.00≤(S / A) 2 ×(P×T) 1 / 2 / (C+M) 3 ≤7.32…(1-2)

[0079] 4.25≤(S / A) 2 ×(P×T) 1 / 2 / (C+M) 3 ≤7.32…(1-3)

[0080] 4.51≤(S / A)2 ×(P×T) 1 / 2 / (C+M) 3 ≤7.32…(2)

[0081] 4.87≤(S / A) 2 ×(P×T) 1 / 2 / (C+M) 3 ≤7.20…(3)

[0082] 5.96≤(S / A) 2 ×(P×T) 1 / 2 / (C+M) 3 ≤7.16…(4)

[0083] By making the glass composition for glass fiber of this embodiment satisfy formula (2), it is possible to have a temperature of 1000 poise that is reduced by itself to below 1500°C, and by using this glass composition for glass fiber, it is possible to obtain glass fiber with excellent water resistance and extremely excellent dielectric properties such as a low dielectric constant of 4.0 or less and a low dielectric loss tangent of 0.0010 or less in the high-frequency region of the measurement frequency of 10 GHz.

[0084] Furthermore, by making the glass composition for glass fiber of this embodiment satisfy formula (3), it is possible to have excellent glass fiber manufacturability with a self-reduced temperature of 1000 poise below 1500°C and an operating temperature range of 150°C or more. Moreover, it is possible to obtain glass fiber with excellent water resistance and extremely excellent dielectric properties such as a low dielectric constant of 4.0 or less and a low dielectric loss tangent of 0.0010 or less in the high-frequency region of the measurement frequency of 10 GHz.

[0085] Furthermore, by making the glass composition for glass fiber of this embodiment satisfy formula (4), it is possible to have extremely excellent glass fiber manufacturability with a self-reduced temperature of 1000 poise below 1500°C and an operating temperature range of 200°C or more. Moreover, by using this glass composition for glass fiber, it is possible to obtain glass fiber with excellent water resistance, a low dielectric constant of 4.0 or less in the high-frequency region of the measurement frequency of 10 GHz, and a low dielectric loss tangent of 0.0010 or less.

[0086] It should be noted that, in the glass composition for glass fiber of this embodiment, the content of each of the above components can be determined by using an ICP emission spectrophotometer to measure Li as a light element, and by using a wavelength dispersive fluorescence X-ray analyzer to measure other elements.

[0087] The determination method is as follows: First, the glass batch prepared by mixing glass raw materials is placed in a platinum crucible and kept at 1550°C for 4 hours in an electric furnace, and then further kept at 1650°C for 2 hours while stirring to melt it, thereby obtaining homogeneous molten glass. Alternatively, glass fibers are placed in a platinum crucible and kept at 1550°C for 6 hours in an electric furnace while stirring to melt it, thereby obtaining homogeneous molten glass.

[0088] When organic matter is attached to the surface of glass fiber, or when glass fiber is mainly contained in organic matter (resin) as a reinforcing material, the organic matter is removed by heating in a muffle furnace at a temperature of 300 to 650°C for about 0.5 to 24 hours before using the glass fiber.

[0089] Next, the molten glass obtained is poured onto a carbon plate to form glass shavings, which are then crushed and powdered. The resulting glass powder is then heated and decomposed with acid, and Li, as a light element, is quantitatively analyzed using an ICP-based fluorescence spectrophotometer. After the glass powder is formed into a disc shape using a press, other elements are quantitatively analyzed using a wavelength dispersive X-ray fluorescence spectrophotometer. Specifically, the quantitative analysis using the wavelength dispersive X-ray fluorescence spectrophotometer is based on a standard curve sample prepared according to the results determined by the basic parameter method, and analysis is performed using the standard curve method. It should be noted that the content of each component in the standard curve sample can be quantitatively analyzed using an ICP-based fluorescence spectrophotometer. These quantitative analysis results can be converted to oxides to calculate the content and total amount of each component, and the content rate of each component can be determined based on these values.

[0090] The glass composition for glass fiber in this embodiment can be obtained by melting a glass raw material (glass batch) that has been prepared in the manner described above after melting and solidification, and then cooling and solidifying it.

[0091] When forming the glass fiber of this embodiment using the glass composition for glass fiber, firstly, the glass raw material prepared in the above manner is supplied to a glass melting furnace and melted at a temperature in the temperature range of 1000 poise or higher, specifically in the range of 1400°C to 1700°C. Then, the molten glass melted to the specified temperature is ejected from 1 to 8000 nozzles or holes controlled at a predetermined temperature, and is stretched and cooled while being wound at high speed, and then solidified to form glass fiber.

[0092] Here, the glass monofibers (glass filaments) ejected from a single nozzle or aperture and cooled and cured typically have a circular cross-sectional shape and a diameter ranging from 3.0 to 35.0 μm. In applications requiring low dielectric properties, the glass filaments preferably have a diameter ranging from 3.0 to 6.0 μm, and more preferably a diameter ranging from 3.0 to 4.5 μm.

[0093] On the other hand, when the nozzle head has a non-circular shape and has a protrusion or cutout for quenching the molten glass, glass filaments with non-circular (e.g., elliptical, oblong) cross-sectional shapes can be obtained by controlling the temperature conditions. When the glass filament has an elliptical or oblong cross-sectional shape, the ratio of the major axis to the minor axis (major axis / minor axis) of the cross-sectional shape is, for example, in the range of 2.0 to 10.0, and the fiber diameter when the cross-sectional area is converted to a perfect circle (converted fiber diameter) is in the range of 3.0 to 35.0 μm.

[0094] The glass fibers in this embodiment are typically in the shape of a glass fiber bundle (glass filament) formed by bundling 10 to 8000 of the aforementioned glass filaments, and have a weight in the range of 1 to 10000 tex (g / km). It should be noted that glass filaments ejected from multiple nozzles or orifices may sometimes be bundled into a single glass fiber bundle, or sometimes into multiple glass fiber bundles.

[0095] The glass fiber in this embodiment can take various forms, such as yarn, fabric, braided fabric, nonwoven fabric (including chopped strand mat and multi-axis nonwoven fabric), chopped strand, roving, powder, etc., obtained by further processing the glass filament.

[0096] To improve the bundleability of glass filaments, enhance the adhesion between glass fibers and resins, and improve the uniform dispersion of glass fibers in mixtures of glass fibers with resins or inorganic materials, the surface of the glass fibers in this embodiment can be coated with an organic material. Examples of such organic materials include: starch, polyurethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (especially carboxylic acid-modified polypropylene), copolymers of (poly)carboxylic acid (especially maleic acid) and unsaturated monomers, etc.

[0097] In addition to these resins, the glass fibers of this embodiment may also be coated with a resin composition containing silane coupling agents, lubricants, surfactants, etc. Alternatively, the glass fibers of this embodiment may not contain the aforementioned resins, but may be coated with a treatment agent composition containing silane coupling agents, surfactants, etc. Based on the mass of the glass fibers of this embodiment in their uncoated state by the resin composition or treatment agent composition, such resin compositions or treatment agent compositions coat the glass fibers in a proportion ranging from 0.03% to 2.0% by mass.

[0098] It should be noted that the coating of glass fibers with organic matter can be performed, for example, by applying a resin solution or resin composition solution to the glass fibers using a known method such as a roller coater during the glass fiber manufacturing process, and then drying the glass fibers coated with the resin solution or resin composition solution. Alternatively, the coating of glass fibers with organic matter can also be performed by immersing the glass fibers of this embodiment, in the form of a fabric, in a treatment agent composition solution, and then drying the glass fibers coated with the treatment agent composition.

[0099] Examples of silane coupling agents include: aminosilanes, chlorosilanes, mercaptosilanes, vinylsilanes, and (meth)acrylate silanes.

[0100] Examples of aminosilanes include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinepropyltrimethoxysilane.

[0101] Examples of chlorosilanes include γ-chloropropyltrimethoxysilane.

[0102] Examples of epoxy silanes include (β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-epoxypropoxypropyltrimethoxysilane.

[0103] Examples of mercaptosilanes include γ-mercaptotrimethoxysilane.

[0104] Examples of vinyl silanes include vinyltrimethoxysilane and N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane.

[0105] Examples of (meth)acrylic silanes include γ-methacryloyloxypropyltrimethoxysilane.

[0106] In this embodiment, the above-mentioned silane coupling agent can be used alone, or two or more of the above-mentioned silane coupling agents can be used in combination.

[0107] Examples of lubricants include: modified silicone oil, animal oils and their hydrogenated derivatives, vegetable oils and their hydrogenated derivatives, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids and higher saturated alcohols, polyethyleneimine, polyalkyl polyamine alkyl linolenic acid derivatives, fatty acid amides, and quaternary ammonium salts.

[0108] Examples of animal fats include beef tallow.

[0109] Examples of vegetable oils include soybean oil, coconut oil, rapeseed oil, palm oil, and castor oil.

[0110] Examples of animal-derived waxes include beeswax and wool.

[0111] Examples of plant-based waxes include candelilla wax and carnauba wax.

[0112] Examples of mineral waxes include paraffin wax and lignite wax.

[0113] Examples of stearates, such as lauryl stearate, are condensations of higher saturated fatty acids and higher saturated alcohols.

[0114] Examples of fatty acid amides include dehydration condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine with fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid.

[0115] Examples of quaternary ammonium salts include alkyl trimethyl ammonium salts such as lauryltrimethylammonium chloride.

[0116] In this embodiment, the above-mentioned lubricant can be used alone, or two or more of the above-mentioned lubricants can be used in combination.

[0117] Examples of surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In this embodiment, the above-mentioned surfactants can be used alone, or two or more of the above-mentioned surfactants can be used in combination.

[0118] Examples of nonionic surfactants include ethylene oxide propylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene-polyoxypropylene-block copolymers, alkyl polyoxyethylene-polyoxypropylene-block copolymer ethers, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid monoesters, polyoxyethylene fatty acid diesters, polyoxyethylene sorbitan fatty acid esters, glycerol fatty acid ester ethylene oxide adducts, polyoxyethylene stearyl ethers, hydrogenated castor oil ethylene oxide adducts, alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, glycerol fatty acid esters, polyglycerol fatty acid esters, pentaerythritol fatty acid esters, sorbitol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyol alkyl ethers, fatty acid alkanolamides, acetylenol, ethylene oxide adducts of acetylenol, and ethylene oxide adducts of acetylenol.

[0119] Examples of cationic surfactants include: alkyl dimethyl benzyl ammonium chloride, alkyl trimethyl ammonium chloride, alkyl dimethyl ethyl ammonium ethyl sulfate, higher alkylamine salts (acetates or hydrochlorides, etc.), ethylene oxide adducts of higher alkylamines, condensates of higher fatty acids and polyalkylene polyamines, ester salts of higher fatty acids and alkanolamines, salts of higher fatty acid amides, imidazoline-type cationic surfactants, and alkylpyridine salts.

[0120] Examples of anionic surfactants include higher alcohol sulfates, higher alkyl ether sulfates, α-olefin sulfates, alkylbenzene sulfonates, α-olefin sulfonates, reaction products of fatty acid halides and N-methyl taurine, dialkyl sulfosuccinates, higher alcohol phosphates, and phosphates of higher alcohol ethylene oxide adducts.

[0121] Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as alkali metal salts of alkylaminopropionic acid, betaine-type amphoteric surfactants such as alkyl dimethyl betaine, and imidazoline-type amphoteric surfactants.

[0122] The glass fiber fabric of this embodiment includes the glass fiber of this embodiment described above. Specifically, the glass fiber fabric of this embodiment can be produced by weaving the glass fiber of this embodiment as at least part of the warp or weft yarns using a known loom. Examples of such looms include: air-jet looms, water-jet looms, shuttle looms, rapier looms, etc.

[0123] Furthermore, examples of weaving methods for the aforementioned looms include plain weave, satin weave, square weave, and twill weave, but from a manufacturing efficiency perspective, plain weave is preferred. The glass fiber fabric of this embodiment preferably uses the aforementioned glass fiber as both warp and weft yarns.

[0124] In the glass fiber fabric of this embodiment, it is preferable that the glass fiber of this embodiment is a bundle of 35 to 400 glass filaments with a diameter in the range of 3.0 to 9.0 μm and a mass in the range of 0.9 to 69.0 tex (g / km) with a twist rate in the range of 0 to 1.0 times / 25 mm.

[0125] In the glass fiber fabric of this embodiment, when the glass fiber of this embodiment is used as the warp or weft yarn, it is preferable that the warp yarn density is in the range of 40 to 120 threads / 25 mm and the weft yarn density is in the range of 40 to 120 threads / 25 mm.

[0126] The glass fiber fabric of this embodiment can also undergo degreasing, surface treatment, and fiber opening treatment after weaving.

[0127] As a degreasing treatment, the following treatment can be cited: placing glass fiber fabric in a heating furnace with an atmosphere temperature in the range of 350°C to 400°C for a period of 40 to 80 hours, and heating and decomposing the organic matter attached to the glass fiber.

[0128] As a surface treatment, the following treatment can be used: impregnating the glass fiber fabric in a solution containing the above-mentioned silane coupling agent or a solution containing the above-mentioned silane coupling agent and the above-mentioned surfactant, and after removing excess water, heating and drying it at a temperature in the range of 80 to 180°C for a time in the range of 1 to 30 minutes.

[0129] As a fiber opening process, examples include the following: fiber opening using water pressure, fiber opening using high-frequency vibration with liquid as the medium, fiber opening using fluid pressure with surface pressure, and fiber opening using roller pressure, while applying a tension of 30 to 200 N to the warp yarns of the glass fiber fabric, thereby widening the line width of the warp and weft yarns.

[0130] The glass fiber fabric in this embodiment preferably has a strength of 7.0–190.0 g / m². 2 The unit area mass ranges from 8.0 to 200.0 μm, with a thickness ranging from 8.0 to 200.0 μm.

[0131] In this embodiment, the warp yarn width of the glass fiber fabric is preferably in the range of 110 to 600 μm, and the weft yarn width is preferably in the range of 110 to 600 μm.

[0132] The glass fiber fabric of this embodiment may also include a surfactant containing the aforementioned silane coupling agent or a surface treatment layer containing the aforementioned silane coupling agent and the aforementioned surfactant. When the glass fiber fabric of this embodiment includes the surface treatment layer, the surface treatment layer may, for example, have a mass percentage in the range of 0.03 to 1.50% relative to the total amount of the glass fiber fabric including the surface treatment layer.

[0133] The glass fiber reinforced resin composition of this embodiment includes the glass fiber described in this embodiment. Specifically, in a glass fiber reinforced resin composition comprising a thermoplastic resin or thermosetting resin, glass fiber, and other additives, the glass fiber reinforced resin composition of this embodiment contains glass fiber in the range of 10 to 90% by mass relative to the total amount of the glass fiber reinforced resin composition. Furthermore, the glass fiber reinforced resin composition of this embodiment contains resin in the range of 90 to 10% by mass relative to the total amount of the glass fiber reinforced resin composition, and contains other additives in the range of 0 to 40% by mass.

[0134] Examples of the aforementioned thermoplastic resins include: polyethylene, polypropylene, polystyrene, styrene / maleic anhydride resin, styrene / maleimide resin, polyacrylonitrile, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, chlorinated polyethylene / acrylonitrile / styrene (ACS) resin, acrylonitrile / ethylene / styrene (AES) resin, acrylonitrile / styrene / methyl acrylate (ASA) resin, styrene / acrylonitrile (SAN) resin, methacrylic acid resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polypropylene terephthalate (PP). Glycol esters (PTT), polycarbonate, polysulfides, polyethersulfone (PES), polyphenylene sulfone (PPSU), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyaryl ether ketone, liquid crystal polymers (LCP), fluoropolymers, polyetherimide (PEI), polyarylate (PAR), polysulfone (PSF), polyamide-imide (PAI), polyaminobismaleimide (PABM), thermoplastic polyimide (TPI), polyethylene naphthalate (PEN), ethylene / vinyl acetate (EVA) resin, ionomer (IO) resin, polybutadiene, styrene / butadiene resin, polybutene, polymethylpentene, olefin / vinyl alcohol resin, cyclic olefin resin, cellulose resin, polylactic acid, etc.

[0135] Specifically, examples of polyethylene include: high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene.

[0136] Examples of polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures of the above polypropylenes.

[0137] Examples of polystyrene include general-purpose polystyrene (GPPS), which is atactic polystyrene with a random stereostructure; impact-resistant polystyrene (HIPS), which incorporates rubber components into GPPS; and syndiotactic polystyrene, which has a syndiotactic structure.

[0138] Examples of methacrylic resins include polymers formed by polymerizing one of the following methacrylic resins: acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and vinyl fatty acid esters; and polymers formed by copolymerizing two or more of the above-mentioned methacrylic resins.

[0139] Examples of polyvinyl chloride include: homopolymers of vinyl chloride polymerized using existing known methods such as emulsion polymerization, suspension polymerization, micro-suspension polymerization, and bulk polymerization; copolymers of vinyl chloride monomers that can copolymerize with vinyl chloride monomers; and graft copolymers of polymers to which vinyl chloride monomers have been grafted.

[0140] Examples of polyamides include: polycaprolactam (Nylon 6), polyhexamethylene adipamide (Nylon 66), polytetramethylene adipamide (Nylon 46), polyhexamethylene sebacate (Nylon 410), polypentamethylene adipamide (Nylon 56), polypentamethylene sebacate (Nylon 510), polyhexamethylene sebacate (Nylon 610), polyhexamethylene dodecylamide (Nylon 612), polydematyl adipamide (Nylon 106), and polydematyl methyl sebacate. Dimethyl phthalamide (Nylon 1010), polydecylidene dodecylamide (Nylon 1012), polyundecylamide (Nylon 11), polyhexamethylene adipamide (Nylon 116), polydodecylamide (Nylon 12), polyxylene adipamide (Nylon D6), polyxylene sebacic acid amide (Nylon MXD10), poly(m-phenylene adipamide) (Nylon MXD6), poly(p-xylene adipamide) (Nylon PXD6), poly(terephthalamide) (Nylon 4T), polypentaphthalamide Methyl terephthalamide (Nylon 5T), polyhexamethylene terephthalamide (Nylon 6T), polyhexamethylene isophthalamide (Nylon 6I), polynonamethylene terephthalamide (Nylon 9T), polyterephthaloylmethyl terephthalamide (Nylon 10T), polyhexamethylene terephthalamide (Nylon 11T), polydodecyl terephthalamide (Nylon 12T), polytetramethylene polyphthalamide (Nylon 4I), polybis(3-methyl-4-amino) The composition may include one or more of the following components: poly(3-methyl-4-aminohexyl)methane terephthalamide (Nylon PACMT), poly(3-methyl-4-aminohexyl)methane isophthalamide (Nylon PACMI), poly(3-methyl-4-aminohexyl)methane dodecylamide (Nylon PACM12), poly(3-methyl-4-aminohexyl)methane tetradecylamide (Nylon PACM14), copolymers of two or more of the above components, or mixtures of the above components and the above copolymers.

[0141] Examples of polyacetals include homopolymers with oxymethylene units as the main repeating units, and copolymers mainly composed of oxymethylene units and containing oxyalkylene units with 2 to 8 adjacent carbon atoms in the main chain.

[0142] Examples of polyethylene terephthalate include polymers obtained by polycondensation of ethylene glycol with terephthalic acid or its derivatives.

[0143] Examples of polybutylene terephthalate include polymers obtained by polycondensation of 1,4-butanediol with terephthalic acid or its derivatives.

[0144] Examples of polypropylene terephthalate include polymers obtained by polycondensation of 1,3-propanediol with terephthalic acid or its derivatives.

[0145] Examples of polycarbonates include polymers obtained by transesterification, which involves reacting a dihydroxy aryl compound with a carbonate such as diphenyl carbonate in a molten state, and polymers obtained by phosgene reaction, which involves reacting a dihydroxy aryl compound with phosgene.

[0146] Examples of polyaryl sulfides include linear polyphenylene sulfides, cross-linked polyphenylene sulfides that are polymerized by curing after polymerization, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone.

[0147] Examples of polyphenylene ethers include: poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4'-methylphenyl)-1,4-phenylene ether], poly(2-bromo-6-phenyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2-phenyl-1... Poly(2-chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly(2-chloro-6-ethyl-1,4-phenylene ether), poly(2-chloro-6-bromo-1,4-phenylene ether), poly(2,6-dipropyl-1,4-phenylene ether), poly(2-methyl-6-isopropyl-1,4-phenylene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dibromo-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether), etc.

[0148] Examples of modified polyphenylene ethers include: polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polystyrene; polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene copolymer; polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / maleic anhydride copolymer; polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polyamide; polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene / acrylonitrile copolymer; modified polyphenylene ethers in which functional groups such as amino, epoxy, carboxyl, and styrene groups are introduced at the polymer chain ends of the above-mentioned polyphenylene ethers; and modified polyphenylene ethers in which functional groups such as amino, epoxy, carboxyl, styrene, and methacryloyl groups are introduced into the side chains of the polymer chains of the above-mentioned polyphenylene ethers.

[0149] Examples of polyaryl ether ketones include: polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyether ether ketone ketone (PEEKK).

[0150] Examples of liquid crystal polymers (LCPs) include (co)polymers composed of one or more structural units selected from the following components: aromatic hydroxy carbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, aliphatic dicarbonyl units, etc., which are thermotropic liquid crystal polyesters.

[0151] Examples of fluoropolymers include: polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyethylene fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).

[0152] Examples of ionomer (IO) resins include copolymers of olefins or styrene with unsaturated carboxylic acids, where a portion of the carboxyl group is neutralized with metal ions.

[0153] Examples of olefin / vinyl alcohol resins include: ethylene / vinyl alcohol copolymers, propylene / vinyl alcohol copolymers, ethylene / vinyl acetate copolymer saponifications, and propylene / vinyl acetate copolymer saponifications.

[0154] Examples of cyclic olefin resins include: monocyclic resins such as cyclohexene, polycyclic resins such as tetracyclic cyclic olefins, and polymers of cyclic olefin monomers.

[0155] Examples of polylactic acid include: poly-L-lactic acid as a homopolymer of the L-body, poly-D-lactic acid as a homopolymer of the D-body, or stereocomposite polylactic acid as a mixture thereof.

[0156] Examples of cellulose resins include: methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0157] In addition, examples of the aforementioned thermosetting resins include: unsaturated polyester resins, vinyl ester resins, epoxy (EP) resins, melamine (MF) resins, phenolic resins (PF), polyurethane resins (PU), polyisocyanates, polyisocyanurates, polyimide (PI), urea (UF) resins, silicone (SI) resins, furan (FR) resins, benzoguanamine (BR) resins, alkyd resins, xylene resins, bismaleimide triazine (BT) resins, diallyl phthalate resins (PDAP), etc.

[0158] Specifically, as an example of an unsaturated polyester resin, a resin obtained by esterifying an aliphatic unsaturated dicarboxylic acid with an aliphatic diol can be cited.

[0159] Examples of vinyl ester resins include: divinyl ester resins and phenolic varnish-based vinyl ester resins.

[0160] Examples of epoxy resins include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylene diisopropylidene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylene diisopropylidene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexylene diphenol type epoxy resin), phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, and tetraphenolic ethane type phenolic resin. Aldehyde-based varnish epoxy resins, phenolic varnish epoxy resins with fused ring aromatic hydrocarbon structures, biphenyl-based epoxy resins, xylene-based epoxy resins or phenylarylene-based epoxy resins and other aralkyl-based epoxy resins, naphthylene ether-based epoxy resins, naphthol-based epoxy resins, naphthalene glycol-based epoxy resins, difunctional or tetrafunctional naphthalene epoxy resins, binatyl-based epoxy resins, naphthalene aralkyl-based epoxy resins, anthracene-based epoxy resins, phenoxy-based epoxy resins, dicyclopentadiene-based epoxy resins, norbornene-based epoxy resins, adamantane-based epoxy resins, fluorene-based epoxy resins, etc.

[0161] Examples of melamine resins include polymers formed by the condensation polymerization of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

[0162] Examples of phenolic resins include: phenolic varnish resin, cresol varnish resin, bisphenol A varnish resin and other phenolic varnish type phenolic resins, hydroxymethyl methyl phenolic resin, dimethylene ether methyl phenolic resin and other methyl phenolic resins, or arylalkylene phenolic resins, etc., or a combination of two or more resins.

[0163] Examples of urea-formaldehyde resins include those obtained by the condensation of urea and formaldehyde.

[0164] The above-mentioned thermoplastic resin or thermosetting resin can be used alone or in combination of two or more resins.

[0165] The glass fiber reinforced resin composition of this embodiment is intended for applications requiring low dielectric properties. Therefore, epoxy resin, modified polyphenylene ether, polybutylene terephthalate, polypropylene, fluoropolymer, and liquid crystal polymer (LCP) are preferred as the resins described above.

[0166] Other additives mentioned above include: reinforcing fibers other than glass fibers, fillers other than glass fibers, flame retardants, ultraviolet absorbers, heat stabilizers, antioxidants, antistatic agents, flow modifiers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, pigments, etc.

[0167] Other reinforcing fibers besides glass fiber include carbon fiber and metal fiber.

[0168] Examples of fillers other than glass fibers include glass powder, talc, and mica.

[0169] The glass fiber reinforced resin composition of this embodiment can be a prepreg prepared by impregnating the glass fiber fabric of this embodiment with the resin by a method known to the public and then semi-curing it.

[0170] The glass fiber reinforced resin composition of this embodiment can be molded using known molding methods such as injection molding, injection compression molding, two-color molding, blow molding, foaming molding (including supercritical fluid molding), insert molding, in-mold coating molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, compression molding, blow molding, stamping, melt molding, hand lay-up molding, spraying, resin transfer molding, sheet molding compound molding, bulk molding compound molding, pultrusion molding, and filament winding to obtain various glass fiber reinforced resin molded articles. Alternatively, glass fiber reinforced resin molded articles can also be obtained by curing the aforementioned prepreg.

[0171] Examples of uses for such molded products include: electronic device housings, electronic components, vehicle exterior parts, vehicle interior parts, vehicle engine peripheral parts, muffler-related parts, high-pressure tanks, etc.

[0172] Examples of electronic components include printed wiring boards.

[0173] Examples of exterior vehicle components include bumpers, mudguards, hoods, air deflectors, and wheel covers.

[0174] Examples of interior vehicle components include door trim and headliner materials.

[0175] As peripheral components of a vehicle engine, examples include the oil pan, hood, intake manifold, and exhaust manifold.

[0176] As components related to mufflers, examples include muffler parts, etc.

[0177] It should be noted that the glass fiber of this embodiment can be used not only in the glass fiber reinforced resin composition of this embodiment, but also as a reinforcing material for inorganic materials such as gypsum and cement. For example, when used as a reinforcing material for gypsum, especially gypsum board with a thickness in the range of 4 to 60 mm, the gypsum contains glass fiber having the above composition range in the range of 0.1 to 4.0% by mass relative to the total mass of the gypsum.

[0178] Next, embodiments and comparative examples of the present invention are shown.

[0179] Example

[0180] First, glass raw materials are mixed to obtain glass batches, such that the glass composition after melting and solidification will be the compositions of Examples 1 to 8 and Comparative Examples 1 to 5 shown in Table 1.

[0181] Next, glass batches corresponding to the glass fiber glass compositions of Examples 1-8 or Comparative Examples 1-5 were placed in a platinum crucible with a diameter of 80 mm. After heating at 1550°C for 4 hours, the batches were further heated at 1650°C for 2 hours to melt them. The melted glass batches were then removed from the crucible, yielding homogeneous glass blocks and glass shavings. The resulting glass blocks and shavings were then annealed at 620°C for 8 hours to obtain test pieces.

[0182] The dielectric constant and dielectric loss tangent of the obtained test pieces were then evaluated using the methods shown below. Additionally, water resistance was evaluated using glass shavings obtained during the test piece fabrication process, using the methods shown below. Furthermore, the 1000 poise temperature and liquidus temperature were measured using glass shavings obtained during the test piece fabrication process, and the operating temperature range was calculated using these values. The results are shown in Table 1.

[0183] [Evaluation method for water resistance]

[0184] The glass shavings obtained as described above are placed into a small cylindrical platinum sleeve with a circular nozzle at the bottom of the container. After being heated to a specified temperature and melted, the molten glass ejected from the nozzle is wound onto a stainless steel collet at a specified speed, thereby stretching and cooling it to solidify, resulting in glass fibers with a perfectly circular cross-section and a fiber diameter of 13 μm. Approximately 1 g of the obtained glass fibers (test glass fibers) is collected from the collet and dried at 120°C for 1 hour, and the mass is measured (mass before operation). Next, the test glass fibers are placed in 100 ml of distilled water at 80°C for 24 hours. Then, the test glass fibers are obtained using a metal mesh with approximately 150 μm openings, washed with distilled water, dried at 120°C for 1 hour, and the mass is measured (mass after operation).

[0185] Based on the pre-operation and post-operation quality, the mass reduction rate (100 × (1 - (post-operation quality / pre-operation quality)))) is calculated. A mass reduction rate of less than 2.0% and with almost no dissolution of glass fiber components in water is designated as OK; a mass reduction rate exceeding 2.0% and with significant dissolution of glass fiber components in water is designated as NG.

[0186] [Methods for measuring dielectric constant and dielectric loss tangent]

[0187] A polishing test piece was prepared, measuring 80 mm × 3 mm (1 mm thickness). The prepared polishing test piece was then oven-dried and stored indoors at 23°C and 60% humidity for 24 hours. Next, according to JIS C 2565:1992, the dielectric constant (dielectric constant Dk) and dielectric loss tangent (dissipation rate Df) of the obtained polishing test piece at 10 GHz were measured using a cavity resonator method dielectric constant measuring apparatus (manufactured by AET Corporation, trade name: ADM01Oc1).

[0188] [Method for determining 1000 poise temperature]

[0189] The 1000 poise temperature was determined as follows: using a high-temperature electric furnace equipped with a rotational viscometer (manufactured by Shibaura Systems Co., Ltd.), glass shavings were melted in a platinum crucible, and while the melting temperature was varied, the viscosity of the molten glass was continuously measured using a rotational Brinell viscometer, and the temperature corresponding to a rotational viscosity of 1000 poise was determined.

[0190] [Methods for determining liquid phase temperature]

[0191] Glass shavings were crushed, and 40g of glass particles with a diameter ranging from 0.5 to 1.5 mm were placed in a platinum dish measuring 180 mm × 20 mm × 15 mm. The dish was then heated in a tubular electric furnace with a temperature gradient ranging from 1000 to 1550 °C for at least 8 hours. After heating, the dish was removed from the furnace and observed using a polarizing microscope to determine the location where crystallization (devitrification) originating from the glass began to precipitate. The temperature inside the tubular electric furnace was measured using a type B thermocouple to determine the temperature at which the crystallization began, and this temperature was taken as the liquidus temperature.

[0192] [Calculation method for operating temperature range]

[0193] The operating temperature range is calculated using the difference between the 1000 poise temperature and the liquid phase temperature.

[0194] [Table 1]

[0195] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 <![CDATA[SiO2 (mass %: S)]]> 58.90 56.30 56.20 57.30 56.90 56.60 56.40 56.90 <![CDATA[B2O3 (mass%)]]> 22.20 22.80 22.90 22.50 22.90 22.80 22.90 22.90 <![CDATA[Al2O3 (mass %: A)]]> 10.80 12.00 12.00 11.90 12.00 11.40 12.00 12.00 <![CDATA[P2O5 (% by mass: P)]]> 2.10 2.10 3.60 2.20 1.60 2.10 1.00 1.60 <![CDATA[TiO2 (mass %: T)]]> 3.10 3.10 1.60 3.20 3.10 3.60 4.20 2.60 CaO (mass %: C) 2.20 2.20 2.20 2.20 2.20 2.60 2.20 2.20 MgO (mass %: M) 0 0 0 0 0 0 0 0 <![CDATA[F2 (mass%)]]> 0.70 1.50 1.50 0.70 1.30 0.90 1.30 1.30 <![CDATA[Cl2 (mass%)]]> 0 0 0 0 0 0 0 0 <![CDATA[F2 + Cl2 (mass%)]]> 0.70 1.50 1.50 0.70 1.30 0.90 1.30 1.30 <![CDATA[Na2O+K2O+Li2O]]> 0 0 0 0 0 0 0 0 SrO (mass%) 0 0 0 0 0 0 0 0 <![CDATA[MnO2 (mass%)]]> 0 0 0 0 0 0 0 0.50 <![CDATA[ZrO2 (wt%)]]> 0 0 0 0 0 0 0 0.0 total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 <![CDATA[(S / A) 2 ×(P×T)(1 2) / (C+M) 3 ]]> 7.13 5.27 4.94 5.78 4.70 3.86 4.25 4.31 Water resistance OK OK OK OK OK OK OK OK Temperature at 1000 poise (°C) 1463 1424 1446 1449 1416 1436 1395 1414 Liquid phase temperature (°C) 1208 1270 1275 1270 1300 1289 1332 1292 Operating temperature range (°C) 255 154 171 179 116 147 63 122 Dielectric constant 4.0 4.0 4.0 4.0 4.0 4.1 4.1 4.1 Dielectric loss tangent 0.0010 0.0010 0.0010 0.0010 0.0010 0.0011 0.0011 0.0011

[0196] [Table 2]

[0197] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 <![CDATA[SiO2 (mass %: S)]]> 60.10 55.30 52.50 59.60 62.20 <![CDATA[B2O3 (mass%)]]> 22.30 22.90 26.20 20.20 22.30 <![CDATA[Al2O3 (mass %: A)]]> 8.40 13.00 1210 11.60 8.30 <![CDATA[P2O5 (mass %: P)]]> 2.00 1.00 3.40 0.30 0 <![CDATA[TiO2 (mass %: T)]]> 2.90 4.20 3.40 4.10 3.10 CaO (mass %: C) 3.30 2.30 1.90 3.70 3.10 MgO (mass %: M) 0 0 0 0 0 <![CDATA[F2 (mass%)]]> 1.00 1.30 0.50 0.50 1.00 <![CDATA[Cl2 (mass%)]]> 0 0 0 0 0 <![CDATA[F2 + Cl2 (mass%)]]> 1.00 1.30 0.50 0.50 1.00 <![CDATA[Na2O+K2O+Li2O]]> 0 0 0 0 0 SrO (mass%) 0 0 0 0 0 <![CDATA[MnO2 (mass%)]]> 0 0 0 0 0 <![CDATA[ZrO2 (mass%)]]> 0 0 0 0 0 total 100.00 100.00 100.00 100.00 100.00 <![CDATA[(S / A) 2 ×(P×T) (1 / 2) / (C+M) 3 ]]> 3.43 3.05 9.33 0.58 0.00 Water resistance OK OK NG OK OK Temperature at 1000 poise (°C) 1507 1376 1414 1443 1504 Liquid phase temperature (°C) 1100 1334 1239 1215 1120 Operating temperature range (°C) 407 42 175 228 384 Dielectric constant 4.0 4.2 4.0 4.1 4.0 Dielectric loss tangent 0.0010 0.0011 0.0010 0.0012 0.0009

[0198] As shown in Table 1, the glass compositions for glass fibers according to Examples 1 to 8 below can reduce their 1000 poise temperature to less than 1500°C, and glass fibers with excellent water resistance and excellent dielectric properties, such as a dielectric constant of 4.1 or less and a dielectric loss tangent of 0.0011 or less, can be obtained using these glass compositions for glass fibers. In Examples 1 to 8, the glass composition for glass fiber contains 50.00 to 61.00% by mass of SiO2, 16.00 to 27.00% by mass of B2O3, 7.00 to 14.00% by mass of Al2O3, 0.20 to 4.00% by mass of P2O5, 0.50 to 5.00% by mass of TiO2, 0.10 to 5.00% by mass of CaO, 0 to 4.00% by mass of MgO, and a total of 0 to 2.00% by mass of F2 and Cl2. The content of SiO2 (mass%) S, the content of Al2O3 (mass%) A, the content of P2O5 (mass%) P, the content of TiO2 (mass%) T, the content of CaO (mass%) C, and the content of MgO (mass%) M satisfy Equation (1).

[0199] On the other hand, it is evident from Table 2 that the glass compositions for glass fibers according to Comparative Examples 1, 2, and 4 below have a 1000 poise temperature exceeding 1500°C, or the dielectric constant of the glass fibers obtained using the glass compositions for glass fibers exceeds 4.1, or the dielectric loss tangent exceeds 0.0011; the glass composition for glass fibers according to Comparative Example 3, whose S, A, P, T, C, and M exceed the range of Formula (1), cannot obtain sufficient water resistance. In Comparative Examples 1, 2, and 4, although the glass composition contained SiO2 in the range of 50.00 to 61.00% by mass, B2O3 in the range of 16.00 to 27.00% by mass, Al2O3 in the range of 7.00 to 14.00% by mass, P2O5 in the range of 0.20 to 4.00% by mass, TiO2 in the range of 0.50 to 5.00% by mass, CaO in the range of 0.10 to 5.00% by mass, MgO in the range of 0 to 4.00% by mass, and F2 and Cl2 in the range of 0 to 2.00% by mass, the S, A, P, T, C, and M were less than the range of Formula (1).

[0200] Furthermore, it is evident that the glass composition for glass fiber according to Comparative Example 5 below has a 1000 poise temperature exceeding 1500°C. In Comparative Example 5, it contains more than 61.00% by mass of SiO2 relative to the total amount of the glass composition for glass fiber, and the content of P2O5 is less than 0.20% by mass. The aforementioned S, A, P, T, C and M are less than the range of Formula (1).

Claims

1. A glass composition for glass fibers, characterized by, containing Si02 in a range of 50.00 to 61.00 mass%, B203 in a range of 16.00 to 27.00 mass%, Al203 in a range of 7.00 to 14.00 mass%, P205 in a range of 0.20 to 2.90 mass%, Ti02 in a range of 0.50 to 5.00 mass%, CaO in a range of 0.10 to 5.00 mass%, MgO in a range of 0 to 4.00 mass%, and F2 and Cl2 in a total amount in a range of 0 to 2.00 mass%, relative to the total amount of the glass composition for glass fibers, the content (mass%) of Si02 (S), the content (mass%) of Al203 (A), the content (mass%) of P205 (P), the content (mass%) of Ti02 (T), the content (mass%) of CaO (C), and the content (mass%) of MgO (M) satisfy the following formula (1): 3.65 ≤ (S / A) 2 × (P x T) 1 / 2 / (C + M) 3 ≤ 8.25... (1).

2. The glass composition for glass fibers according to claim 1, characterized by, the S, the A, the P, the T, the C, and the M satisfy the following formula (2):

4. 51 ≤ (S / A) 2 × (P x T) 1 / 2 / (C + M) 3 ≤ 7.32 … (2).

3. The glass composition for glass fibers according to claim 1 or 2, characterized by, the S, the A, the P, the T, the C, and the M satisfy the following formula (3): 4.87 ≤ (S / A) 2 × (P x T) 1 / 2 / (C + M) 3 ≤ 7.20... (3).

4. The glass composition for glass fibers according to any one of claims 1 to 3, characterized by, the S, the A, the P, the T, the C, and the M satisfy the following formula (4): 5.96 ≤ (S / A) 2 × (P x T) 1 / 2 / (C + M) 3 ≤ 7.16 … (4).

5. A glass fiber, characterized by, comprising the glass composition for glass fibers according to any one of claims 1 to 4.

6. A glass fiber fabric, characterized by, comprising the glass fiber according to claim 5.

7. A glass fiber reinforced resin composition, characterized by, comprising the glass fiber according to claim 5.