Glass compositions for glass fibers, glass fibers, glass fiber fabrics, and glass fiber reinforced resin compositions

Abstract

A glass composition for glass fiber is provided, which can provide glass fiber having excellent water resistance and excellent dielectric properties in the high frequency range, and has a reduced 1000 poise temperature. [Solution] The glass composition for glass fiber contains, based on the total amount, 50.00 to 61.00 mass% of SiO2, 16.00 to 27.00 mass% of B2O3, 7.00 to 14.00 mass% of Al2O3, 0.20 to 4.00 mass% of P2O5, 0.50 to 5.00 mass% of TiO2, 0.10 to 5.00 mass% of CaO, 0 to 4.00 mass% of MgO, and a total of 0 to 2.00 mass% of F2 and Cl2.

Description

Technical Field

[0001] The present invention relates to a glass composition for glass fibers, glass fibers, glass fiber fabrics, and glass fiber-reinforced resin compositions.

Background Art

[0002] Glass fibers are produced as follows: glass raw materials formulated to obtain a glass composition for glass fibers having a desired composition are melted in a glass melting furnace to obtain molten glass (a melt of the glass composition for glass fibers); the molten glass is discharged from a container (bushing) having a nozzle plate formed with several to thousands of nozzle tips, wound at a high speed, stretched while being cooled, and solidified into a fibrous form (hereinafter, this operation may be referred to as "spinning"). The bushing is formed of, for example, a noble metal such as platinum.

[0003] Conventionally, glass fibers have been widely used in various applications to improve the strength of resin molded products, and such resin molded products are used as housings or components of electronic devices such as servers, smartphones, and notebook personal computers.

[0004] In general, glass absorbs energy as heat from alternating current, so when the resin molded product is used as a housing or component of the aforementioned electronic device, there is a problem that the resin molded product generates heat.

[0005] Here, the dielectric loss energy absorbed by glass is proportional to the permittivity and dielectric loss tangent determined by the components and structure of the glass, and is represented by the following formula (A). W=kfv 2 ×ε 1 / 2 ×tanδ ···(A)

[0006] where W is dielectric loss energy, k is a constant, f is frequency, v 2 is potential gradient, ε is permittivity, and tanδ is dielectric loss tangent. From formula (A), it can be seen that the larger the permittivity and dielectric loss tangent, and the higher the frequency, the larger the dielectric loss, and the greater the heat generation of the resin molded product.

[0007] In recent years, due to the increasing frequency of the alternating current used in the aforementioned electronic devices (f in equation (A) above), there is a need for glass fibers used in the housing or components of such electronic devices to have lower dielectric constants and lower dielectric loss tangents in order to reduce dielectric loss energy. In particular, a low dielectric loss tangent is required because it has a greater impact on equation (A) than the dielectric constant which is raised to the power of 1 / 2.

[0008] In view of these circumstances, the applicant has proposed a glass composition for glass fibers that has a low dielectric constant and low dielectric loss tangent, suppresses the generation of phase separation, and further reduces viscosity at high temperatures, comprising, in a total amount of glass fiber composition, 52.0 to 59.5 mass% of SiO2, 17.5 to 25.5 mass% of B2O3, 9.0 to 14.0 mass% of Al2O3, 0.5 to 6.0 mass% of SrO, 1.0 to 5.0 mass% of MgO, 1.0 to 5.0 mass% of CaO, and a total of 0.1 to 2.5 mass% of F2 and Cl2 (see Patent Document 1). [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Patent No. 6468409 [Overview of the project] [Problems that the invention aims to solve]

[0010] On the other hand, there is a need for glass compositions for glass fibers that can produce glass fibers with lower dielectric constants and lower dielectric loss tangents, especially in the high-frequency range of around 10 GHz. To achieve this goal, it is conceivable to reduce the content of Al2O3 and alkaline earth metal oxides (CaO, MgO, and SrO) relative to the total amount of the glass composition for glass fibers, and increase the content of SiO2 and B2O3 accordingly.

[0011] However, in the glass composition for glass fibers, when the SiO2 content relative to the total amount of the glass composition for glass fibers increases, the 1000 poise temperature increases, the viscosity of the glass also increases, making it difficult to mix, which makes it difficult to melt homogeneous glass, and also causes a significant and rapid deterioration of the bushing during spinning.

[0012] To solve the aforementioned problem, it is conceivable that in the glass composition for glass fibers, a portion of the SiO2 content relative to the total amount of the glass composition for glass fibers may be replaced with P2O5, thereby reducing the 1000 poise temperature while maintaining excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in the high-frequency range.

[0013] However, if a portion of the SiO2 content in the glass fiber composition is replaced with P2O5, there are disadvantages such as a decrease in the water resistance of the glass fibers obtained from the glass fiber composition, deterioration of dielectric properties due to foreign matter precipitated on the surface of the glass fibers due to glass hydrolysis, and a significant decrease in the strength of the glass fibers.

[0014] The present invention aims to resolve these inconveniences and provide a glass composition for glass fibers that has excellent water resistance and excellent dielectric properties in the high-frequency range, and that itself has a reduced poise temperature of 1000. [Means for solving the problem]

[0015] To achieve this objective, the glass fiber composition of the present invention contains, based on the total amount of the glass fiber composition, 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, and 0.20% 3.20 P2O5 in the mass% range, and 0.50~ 4.00TiO2 in the mass% range, CaO in the 0.10-5.00 mass% range, MgO in the 0-4.00 mass% range, and in total 0.10 Contains F2 and Cl2 in the range of ~2.00 mass% Furthermore, the 1000 poise temperature is 1500°C or less. It is characterized by the following:

[0016] The glass fiber composition of the present invention contains SiO2, B2O3, Al2O3, P2O5, TiO2, CaO, MgO, F2, and Cl2 in the above-mentioned ranges. Furthermore, the 1000 poise temperature is 1500°C or less. This makes it possible to obtain glass fibers that possess excellent water resistance and excellent dielectric properties such as low dielectric constant and low dielectric loss tangent in the high-frequency range, and that themselves have a reduced poise temperature of 1000.

[0017] In this context, the glass fibers obtained from the glass composition for glass fibers of the present invention are said to have a low dielectric constant, meaning that the dielectric constant is 4.1 or less at a measurement frequency of 10 GHz, and the glass fibers are said to have a low dielectric loss tangent, meaning that the dielectric loss tangent is 0.0011 or less at a measurement frequency of 10 GHz.

[0018] Furthermore, the statement that the glass fibers obtained from the glass composition for glass fibers of the present invention exhibit excellent water resistance means that, when evaluated by the following water resistance evaluation method, the mass loss rate is 2.0% or less, and that the components of the glass fibers hardly dissolve even in water.

[0019] In the water resistance evaluation method, first, a glass batch obtained by mixing glass raw materials so as to have a predetermined glass composition for glass fibers is placed in a platinum crucible with a diameter of 80 mm, heated at a temperature of 1550° C. for 4 hours, and further heated at a temperature of 1650° C. for 2 hours to melt. Next, the homogeneous glass cullet obtained after being taken out from the crucible is placed in a small cylindrical platinum bushing having one circular nozzle tip at the bottom of the container, and heated to a predetermined temperature to melt. Thereafter, the molten glass discharged from the nozzle tip is wound around a stainless steel collet at a predetermined speed, so as to be cooled and solidified while being drawn, thereby obtaining a glass fiber having a perfect circular cross-section and a fiber diameter of 13 µm. Next, about 1 g of the obtained glass fiber (test glass fiber) is collected from the collet, dried at a temperature of 120° C. for 1 hour, and the mass (mass before operation) is measured. Subsequently, after the test glass fiber is left standing in 100 ml of distilled water at a temperature of 80° C. for 24 hours, the test glass fiber is collected on a wire mesh with openings of approximately 150 µm, washed with distilled water, dried at a temperature of 120° C. for 1 hour, and the mass (mass after operation) is measured. Then, the mass reduction rate (100×(1-(mass after operation / mass before operation))) is calculated from the mass before operation and the mass after operation.

[0020] Furthermore, that the glass composition for glass fibers of the present invention has a reduced 1000 poise temperature means that the 1000 poise temperature is 1500° C. or lower.

[0021] The present invention also relates to Record a glass fiber characterized by being formed of the glass composition for glass fibers. The present invention also relates to a glass fiber fabric characterized by comprising said glass fiber. Furthermore, the present invention also relates to a glass fiber reinforced resin composition characterized by comprising said glass fiber.

[0022] The glass fiber of the present invention can be obtained, for example, by melting the aforementioned glass composition for glass fiber of the present invention, discharging the obtained melt from a bushing having a nozzle plate formed with 1 to 8000 nozzle tips or pores, winding it at a high speed to stretch it while cooling it, and solidifying it to form a fibrous shape. Therefore, the glass fiber of the present invention has the same glass composition as the aforementioned glass composition for glass fiber of the present invention. Mode for Carrying Out the Invention

[0023] Next, embodiments of the present invention will be described in more detail.

[0024] The glass composition for glass fiber of the present embodiment comprises, based on the total mass of the glass composition for glass fiber, SiO2 in a range of 50.00 to 61.00 mass%, B2O3 in a range of 16.00 to 27.00 mass%, Al2O3 in a range of 7.00 to 14.00 mass%, 0.20 to 3.20 mass% of P2O5, and 0.50 to 4.00 mass% of TiO2, 0.10 to 5.00 mass% of CaO, 0 to 4.00 mass% of MgO, and in total 0.10 to 2.00 mass% of F2 and Cl2 Furthermore, the 1000 poise temperature is 1500°C or less.

[0025] The glass composition for glass fiber of the present embodiment contains SiO2, B2O3, Al2O3, P2O5, TiO2, CaO, MgO, F2 and Cl2 within the above ranges Including a 1000 poise temperature of 1500°C or less, Glass fiber having excellent water resistance and excellent dielectric properties including a low dielectric constant of 4.1 or less and a low dielectric loss tangent of 0.0011 or less in a high frequency region at a measurement frequency of 10 GHz can be obtained, and the glass composition itself can have a reduced 1000 poise temperature of 1500°C below with the reduced 1000 poise temperature.

[0030] In this embodiment, if the SiO2 content of the glass fiber composition is less than 50.00% by mass relative to the total amount of the glass fiber composition, the mechanical strength of the glass fibers obtained from the glass fiber composition will decrease significantly, and the function of the glass fibers as a reinforcing material in the glass fiber reinforced resin composition will be impaired. Furthermore, the glass fibers will be more susceptible to degradation when exposed to an acidic environment. On the other hand, if the SiO2 content of the glass fiber composition exceeds 61.00% by mass relative to the total amount of the glass fiber composition, the viscosity at high temperatures will increase, requiring a higher melting temperature for the glass raw materials, making it unsuitable for industrial glass fiber production from the viewpoint of manufacturing costs.

[0031] The glass fiber composition of this embodiment has an SiO2 content of 52.10 to 59.90% by mass, more preferably 54.10 to 59.70% by mass, even more preferably 56.10 to 59.60% by mass, particularly preferably 57.60 to 59.50% by mass, and most preferably 58.10 to 59.40% by mass, based on the total amount of the glass fiber composition.

[0032] In this embodiment, if the B2O3 content of the glass fiber composition is less than 16.00% by mass relative to the total amount of the glass fiber composition, the dielectric loss tangent of the glass fibers obtained from the glass fiber composition cannot be sufficiently reduced. On the other hand, if the B2O3 content is greater than 27.00% by mass relative to the total amount of the glass fiber composition, phase separation may occur in the glass fibers obtained from the glass fiber composition, potentially reducing the chemical durability of the glass fibers.

[0033] The glass fiber composition of this embodiment has a B2O3 content of preferably 19.60 to 24.90% by mass, more preferably 20.10 to 24.50% by mass, even more preferably 20.60 to 24.00% by mass, particularly preferably 21.10 to 23.50% by mass, and most preferably 21.50 to 23.00% by mass, relative to the total amount of the glass fiber composition.

[0034] In this embodiment, the glass composition for glass fibers has a B2O3 content of 19.60% by mass or more relative to the total amount of the glass composition for glass fibers. This keeps the viscosity of the molten glass obtained from the glass composition for glass fibers low, reducing manufacturing costs and making it more suitable for industrial glass fiber production.

[0035] In this embodiment, the glass composition for glass fibers has a B2O3 content of 24.90% by mass or less relative to the total amount of the glass composition for glass fibers, which reduces the amount of volatile components released when glass fibers are manufactured from the glass composition via molten glass. Furthermore, it reduces wear and tear on the furnace body of the glass melting furnace used to melt the glass composition for glass fibers, extending the lifespan of the furnace body and thus reducing manufacturing costs.

[0036] In this embodiment, if the Al2O3 content of the glass fiber composition is less than 7.00% by mass relative to the total amount of the glass fiber composition, phase separation may occur in the glass fibers obtained from the glass fiber composition, potentially reducing the chemical durability of the glass fibers. On the other hand, if the Al2O3 content is greater than 14.00% by mass relative to the total amount of the glass fiber composition, the dielectric loss tangent of the glass fibers obtained from the glass fiber composition cannot be sufficiently reduced.

[0037] The glass fiber composition of this embodiment has an Al2O3 content of 8.00 to 13.50 mass%, more preferably 9.00 to 13.00 mass%, even more preferably 9.60 to 12.80 mass%, particularly preferably 10.10 to 12.40 mass%, especially preferably 10.30 to 11.90 mass%, particularly preferably 10.50 to 11.50 mass%, and most preferably 10.60 to 10.90 mass% relative to the total amount of the glass fiber composition.

[0038] In this embodiment, the glass fiber composition has an Al2O3 content of 13.00% by mass or less relative to the total amount of the glass fiber composition. This significantly reduces the liquidus temperature and widens the working temperature range, enabling stable spinning.

[0039] In this embodiment, if the P2O5 content of the glass fiber composition is less than 0.20% by mass relative to the total amount of the glass fiber composition, it becomes difficult to achieve both a reduction in the dielectric loss tangent of the glass fibers obtained from the glass fiber composition and a reduction in the 1000 poise temperature of the glass fiber composition. On the other hand, if the P2O5 content is greater than 4.00% by mass relative to the total amount of the glass fiber composition, the phase separation of the glass fibers obtained from the glass fiber composition cannot be suppressed, and the water resistance deteriorates.

[0040] The glass composition for glass fibers of this embodiment has a P2O5 content of preferably 0.30 to 3.50% by mass, more preferably 0.50 to 3.20% by mass, even more preferably 0.70 to 2.90% by mass, particularly preferably 0.90 to 2.70% by mass, and most preferably 1.00 to 2.50% by mass, relative to the total amount of the glass composition for glass fibers.

[0041] In this embodiment, if the TiO2 content of the glass fiber composition is less than 0.50% by mass relative to the total amount of the glass fiber composition, the viscosity at high temperatures increases, which raises the melting temperature of the glass raw materials, making it unsuitable for industrial glass fiber production from the viewpoint of manufacturing costs. On the other hand, if the TiO2 content relative to the total amount of the glass fiber composition is 4.00 If the amount exceeds mass%, the dielectric loss tangent of the glass fibers obtained from the glass fiber composition cannot be sufficiently reduced, and the liquidus temperature of the glass fiber composition increases significantly, making it impossible to manufacture stable glass fibers.

[0042] The glass fiber composition of this embodiment has a TiO2 content of preferably 0.60 to 4.90% by mass, more preferably 1.00 to 4.50% by mass, even more preferably 1.50 to 4.00% by mass, particularly preferably 1.60 to 3.50% by mass, especially preferably 1.70 to 3.40% by mass, particularly preferably 1.80 to 3.30% by mass, and most preferably 2.10 to 3.20% by mass, based on the total amount of the glass fiber composition.

[0043] In this embodiment, if the CaO content of the glass fiber composition is less than 0.10% by mass relative to the total amount of the glass fiber composition, it is difficult to suppress the crystallization of the glass, and the liquidus temperature of the glass fiber composition increases significantly, making it impossible to secure a sufficient working temperature range. On the other hand, if the CaO content is more than 5.00% by mass relative to the total amount of the glass fiber composition, it is not possible to sufficiently reduce the dielectric loss tangent of the glass fibers obtained from the glass fiber composition.

[0044] The glass fiber composition of this embodiment has a CaO content of preferably 0.50 to 4.50% by mass, more preferably 0.70 to 4.00% by mass, even more preferably 0.90 to 3.50% by mass, particularly preferably 1.10 to 3.00% by mass, especially preferably 1.30 to 2.70% by mass, and most preferably 1.50 to 2.50% by mass, based on the total amount of the glass fiber composition.

[0045] In this embodiment, if the MgO content of the glass fiber composition exceeds 4.00% by mass relative to the total amount of the glass fiber composition, striations may occur in the molten glass fiber composition, which may make it easier for glass fibers to break during spinning.

[0046] The glass fiber composition of this embodiment has an MgO content of less than 3.00% by mass, more preferably less than 2.00% by mass, even more 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, based on the total amount of the glass fiber composition.

[0047] In this embodiment, if the combined content of F2 and Cl2 in the glass fiber composition exceeds 2.00% by mass relative to the total amount of the glass fiber composition, the chemical durability of the glass fibers obtained from the glass fiber composition decreases.

[0048] The glass fiber composition of this embodiment has a total content of F2 and Cl2 relative to the total amount of the glass fiber composition. 、0 The range is 0.10 to 1.80 mass%. , good The mass is preferably in the range of 0.30 to 1.60 mass%, and more preferably in the range of 0.50 to 1.50 mass%.

[0049] In this embodiment, the glass composition for glass fibers has a total content of F2 and Cl2 of 0.30% by mass or more relative to the total amount of the glass composition for glass fibers, which further reduces the dielectric constant of the glass fibers obtained from the glass composition for glass fibers.

[0050] In this embodiment, the glass composition for glass fibers has a total content of F2 and Cl2 of 1.60% by mass or less relative to the total amount of the glass composition for glass fibers. This suppresses the generation of volatile substances derived from F2 and Cl2 when glass fibers are manufactured from the glass composition for glass fibers, and prevents deterioration of the surrounding environment of the furnace body of the glass melting furnace in which the glass composition for glass fibers is melted.

[0051] Furthermore, the glass fiber composition of this embodiment may contain SrO in an amount of 0 to 6.00% by mass relative to the total amount of the glass fiber composition. If the glass fiber composition of this embodiment contains SrO, and the SrO content exceeds 6.00% by mass, the dielectric properties of the glass fibers obtained from the glass fiber composition will deteriorate and will not meet the target dielectric properties.

[0052] In the glass fiber composition of this embodiment, if SrO is included, the SrO content relative to the total amount of the glass fiber composition 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, especially preferably in the range of less than 0.50% by mass, and most preferably in the range of less than 0.45% by mass.

[0053] Furthermore, the glass fiber composition of this embodiment may contain Na2O, K2O, and Li2O in a total amount of less than 1.00% by mass relative to the total amount of the glass fiber composition. If the glass fiber composition of this embodiment contains Na2O, K2O, and Li2O, and the total content of these exceeds 1.00% by mass, the dielectric properties of the glass fibers obtained from the glass fiber composition will deteriorate significantly, and the target dielectric properties cannot be achieved.

[0054] When the glass fiber composition of this embodiment contains Na2O, K2O, and Li2O, the total content of these substances relative to the total amount of the glass fiber composition is preferably in the range of less than 0.80% by mass, more preferably in the range of less than 0.50% by mass, even more preferably in the range of less than 0.20% by mass, particularly preferably in the range of less than 0.10% by mass, and most preferably in the range of less than 0.05% by mass.

[0055] Furthermore, the glass fiber composition of this embodiment may contain ZnO in an amount of 0 to 3.00% by mass relative to the total amount of the glass fiber composition. If the glass fiber composition of this embodiment contains ZnO, and the ZnO content exceeds 3.00% by mass, devitrified substances are more likely to occur during the spinning of glass fibers obtained from the glass fiber composition, making stable glass fiber production impossible and worsening the dielectric properties of the glass fibers.

[0056] When the glass fiber composition of this embodiment contains ZnO, the ZnO content relative to the total amount of the glass fiber composition 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.

[0057] Furthermore, the glass fiber composition of this embodiment may contain MnO2 in an amount of 0 to 3.00% by mass relative to the total amount of the glass fiber composition. If the glass fiber composition of this embodiment contains MnO2, and the MnO2 content exceeds 3.00% by mass, the dielectric properties of the glass fibers obtained from the glass fiber composition will deteriorate, and the desired dielectric properties cannot be obtained.

[0058] When the glass fiber composition of this embodiment contains MnO2, the MnO2 content relative to the total amount of the glass fiber composition 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.

[0059] Furthermore, the glass fiber composition of this embodiment may contain Fe2O3 in an amount of 0% to 1.00% by mass relative to the total amount of the glass fiber composition. When the glass fiber composition of this embodiment contains Fe2O3, it is effective for the Fe2O3 content to be in the range of 0.10% to 0.60% by mass from the viewpoint of suppressing air bubbles contained in the glass fibers.

[0060] Furthermore, the glass fiber composition of this embodiment may contain SnO2 in an amount of 0% to 1.00% by mass relative to the total amount of the glass fiber composition. When the glass fiber composition of this embodiment contains SnO2, from the viewpoint of suppressing air bubbles contained in the glass fibers, it is effective for the SnO2 content to be in the range of 0.10% to 0.60% by mass.

[0061] Furthermore, the glass fiber composition of this embodiment may contain ZrO2, provided that the amount is less than 0.50% by mass of the total amount of the glass fiber composition. If the glass fiber composition of this embodiment contains ZrO2, and the ZrO2 content is 0.50% by mass or more of the total amount of the glass fiber composition, devitrified substances are more likely to occur during the spinning of glass fibers obtained from the glass fiber composition, making it impossible to manufacture stable glass fibers.

[0062] When the glass fiber composition of this embodiment contains ZrO2, the ZrO2 content relative to the total amount of the glass fiber composition is preferably in the range of less than 0.45% by mass, more preferably in the range of less than 0.40% by mass, even more preferably in the range of less than 0.20% by mass, particularly preferably in the range of less than 0.10% by mass, and most preferably in the range of less than 0.05% by mass.

[0063] Furthermore, the glass fiber composition of this embodiment may contain Cr2O3, provided that the amount is less than 0.05% by mass of the total amount of the glass fiber composition. If the glass fiber composition of this embodiment contains Cr2O3, and the Cr2O3 content is 0.05% by mass or more of the total amount of the glass fiber composition, devitrified substances are more likely to occur during the spinning of glass fibers obtained from the glass fiber composition, making it impossible to manufacture stable glass fibers.

[0064] Furthermore, the glass fiber composition of this embodiment may contain oxides of Ba, Co, Ni, Cu, Mo, W, Ce, Y, La, Bi, Gd, Pr, Sc, or Yb as impurities originating from the raw materials, in a total amount of less than 1.00% by mass relative to the total amount of the glass fiber composition. In particular, when the glass fiber composition of this embodiment contains BaO, CeO2, Y2O3, La2O3, Bi2O3, Gd2O3, Pr2O3, Sc2O3, or Yb2O3 as impurities, their respective content is preferably in the range of less than 0.40% by mass, more preferably in the range of less than 0.20% by mass, even more preferably in the range of less than 0.10% by mass, particularly preferably in the range of less than 0.05% by mass, and most preferably in the range of less than 0.01% by mass.

[0069] In the glass fiber composition of this embodiment, the content of each component can be measured using an ICP emission spectrometer for the light element Li, and using a wavelength-dispersive X-ray fluorescence spectrometer for the other elements.

[0070] The measurement method involves first mixing glass raw materials to create a glass batch, placing it in a platinum crucible, and holding it in an electric furnace at 1550°C for 4 hours. Then, it is further held at 1650°C for 2 hours while stirring to melt the mixture and obtain homogeneous molten glass. Alternatively, glass fibers are placed in a platinum crucible and held in an electric furnace at 1550°C for 6 hours while stirring to melt the mixture and obtain homogeneous molten glass.

[0071] If organic matter is attached to the surface of the glass fibers, or if the glass fibers are mainly included as a reinforcing material in the organic matter (resin), the organic matter should be removed before use, for example, by heating in a muffle furnace at a temperature of 300 to 650°C for about 0.5 to 24 hours.

[0072] Next, the obtained molten glass is poured onto a carbon plate to produce glass cullet, which is then crushed and powdered to obtain glass powder. For the light element Li, the obtained glass powder is heated and decomposed with acid, and then quantitatively analyzed using an ICP emission spectrometer. For the other elements, the glass powder is formed into a disc shape using a press, and then quantitatively analyzed using a wavelength-dispersive X-ray fluorescence spectrometer. Specifically, quantitative analysis using a wavelength-dispersive X-ray fluorescence spectrometer can be performed by preparing calibration curve samples based on the results measured by the fundamental parameter method, and then analyzing them using the calibration curve method. The content of each component in the calibration curve sample can be quantitatively analyzed using an ICP emission spectrometer. These quantitative analysis results can be converted to oxides to calculate the content and total amount of each component, and from these values, the content of each component described above can be determined.

[0073] The glass fiber composition of this embodiment can be obtained by melting a glass raw material (glass batch) that has been prepared to have the aforementioned composition after melting and solidifying, and then cooling and solidifying it.

[0074] When forming the glass fibers of this embodiment from the glass composition for glass fibers of this embodiment, first, the glass raw material prepared as described above is supplied to a glass melting furnace, and the temperature range of 1000 poise temperature or higher, specifically, 1500℃ The glass is melted at a temperature in the range of ~1700℃. Then, the molten glass, which has been melted at the aforementioned temperature, is extruded from 1 to 8000 nozzle tips or holes controlled to a predetermined temperature, and cooled and solidified while being stretched by winding it up at high speed, thereby forming glass fibers.

[0075] Here, a single glass fiber (glass filament) extruded from a nozzle tip or hole and cooled and solidified typically has a circular cross-sectional shape and a diameter in the range of 3.0 to 35.0 μm. For applications requiring low dielectric properties, the glass filament preferably has a diameter in the range of 3.0 to 6.0 μm, and more preferably in the range of 3.0 to 4.5 μm.

[0076] On the other hand, if the nozzle tip has a non-circular shape and includes protrusions or notches for rapidly cooling the molten glass, a glass filament having a non-circular (e.g., elliptical, oblong) cross-sectional shape 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 of the cross-sectional shape (major axis / minor axis) 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.

[0077] The glass fibers in this embodiment typically take the form of a glass fiber bundle (glass strand) in which 10 to 8,000 glass filaments are bundled together, and have a weight in the range of 1 to 10,000 tex (g / km). Note that glass filaments extruded from multiple nozzle tips or holes may be bundled into a single glass fiber bundle or into multiple glass fiber bundles.

[0078] The glass fibers of this embodiment can take various forms, such as yarn, woven fabric, knitted fabric, nonwoven fabric (including chopped strand mats and multiaxial nonwoven fabrics), chopped strands, roving, and powder, obtained by further processing the glass strands.

[0079] The glass fibers of this embodiment may have their surface coated with an organic substance for purposes such as improving the bundling properties of the glass filaments, improving the adhesion between the glass fibers and the resin, and improving the uniform dispersion of the glass fibers in a mixture of glass fibers and resin or an inorganic material. Examples of such organic substances include starch, urethane resin, epoxy resin, vinyl acetate resin, acrylic resin, modified polypropylene (especially carboxylic acid-modified polypropylene), and copolymers of (poly)carboxylic acids (especially maleic acid) and unsaturated monomers.

[0080] Furthermore, the glass fibers of this embodiment may be coated with a resin composition containing a silane coupling agent, lubricant, surfactant, etc., in addition to these resins. Alternatively, the glass fibers of this embodiment may be coated with a treatment agent composition that does not contain the above-mentioned resins, but contains a silane coupling agent, surfactant, etc. Such a resin composition or treatment agent composition coats the glass fibers in a proportion ranging from 0.03 to 2.0% by mass, based on the mass of the glass fibers of this embodiment in an uncoated state.

[0081] Furthermore, the coating of glass fibers with organic matter can be carried out, for example, in the glass fiber manufacturing process by applying a resin solution or resin composition solution to the glass fibers using a known method such as a roller-type applicator, and then drying the glass fibers to which the resin solution or resin composition solution has been applied. Alternatively, the coating of glass fibers with organic matter can also be carried out by immersing the glass fibers of this embodiment, which are in the form of a woven fabric, in a treatment agent composition solution, and then drying the glass fibers to which the treatment agent composition has been applied.

[0082] Examples of silane coupling agents include aminosilane, chlorsilane, mercaptosilane, vinylsilane, and (meth)acrylsilane.

[0083] Examples of aminosilanes include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane.

[0084] Examples of chlorsilanes include γ-chloropropyltrimethoxysilane.

[0085] Examples of epoxysilanes include (β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0086] Examples of mercaptosilanes include γ-mercaptotrimethoxysilane.

[0087] Examples of vinylsilanes include vinyltrimethoxysilane and N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane.

[0088] Examples of (meth)acrylosisilanes include γ-methacryloxypropyltrimethoxysilane.

[0089] In this embodiment, the silane coupling agent may be used alone, or two or more may be used in combination.

[0090] Examples of lubricants include modified silicone oils, animal oils and their hydrogenated counterparts, vegetable oils and their hydrogenated counterparts, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids and higher saturated alcohols, polyethyleneimines, polyalkylpolyamine alkylamide derivatives, fatty acid amides, and quaternary ammonium salts.

[0091] Examples of animal fats include beef tallow.

[0092] Examples of vegetable oils include soybean oil, coconut oil, rapeseed oil, palm oil, and castor oil.

[0093] Examples of animal-derived waxes include beeswax and lanolin.

[0094] Examples of plant-based waxes include candelilla wax and carnauba wax.

[0095] Examples of mineral-based waxes include paraffin wax and montan wax.

[0096] Examples of condensates of higher saturated fatty acids and higher saturated alcohols include stearic acid esters such as lauryl stearate.

[0097] 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.

[0098] Examples of quaternary ammonium salts include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.

[0099] In this embodiment, the lubricant may be used alone, or two or more may be used in combination.

[0100] Examples of surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In this embodiment, the surfactants may be used individually or in combination of two or more types.

[0101] Examples of nonionic surfactants include ethylene oxide propylene oxide alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene-polyoxypropylene-block copolymer, alkyl polyoxyethylene-polyoxypropylene-block copolymer ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid monoester, polyoxyethylene fatty acid diester, polyoxyethylene sorbitan fatty acid ester, glycerol fatty acid ester ethylene oxide adduct, polyoxyethylene castor oil ether, hydrogenated castor oil ethylene oxide adduct, alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, glycerol fatty acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyhydric alcohol alkyl ether, fatty acid alkanolamide, acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, and ethylene oxide adduct of acetylene alcohol.

[0102] Examples of cationic surfactants include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethyl sulfate, higher alkylamine salts (such as acetates and hydrochlorides), ethylene oxide adducts to higher alkylamines, condensates of higher fatty acids and polyalkylene polyamines, salts of esters of higher fatty acids and alkanolamines, salts of higher fatty acid amides, imidazoline-type cationic surfactants, and alkylpyridinium salts.

[0103] Examples of anionic surfactants include higher alcohol sulfates, higher alkyl ether sulfates, α-olefin sulfates, alkylbenzene sulfons, α-olefin sulfons, reaction products of fatty acid halides and N-methyl taurine, dialkyl sulfosuccinates, higher alcohol phosphates, and phosphate salts of higher alcohol ethylene oxide adducts.

[0104] Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as alkali metal alkylaminopropionates, betaine-type amphoteric surfactants such as alkyldimethylbetaine, and imidazoline-type amphoteric surfactants.

[0105] The glass fiber fabric of this embodiment includes the glass fibers of this embodiment described above. Specifically, the glass fiber fabric of this embodiment can be obtained by weaving the glass fibers of this embodiment described above, at least as part of the warp or weft threads, using a loom that is known in itself. Examples of such looms include jet looms such as air jet or water jet looms, shuttle looms, rapier looms, and the like.

[0106] Furthermore, examples of weaving methods using the loom include plain weave, satin weave, twill weave, etc., and plain weave is preferred from the viewpoint of manufacturing efficiency. In the glass fiber fabric of this embodiment, it is preferable to use the glass fibers of this embodiment described above as the warp and weft threads.

[0107] In the glass fiber fabric of this embodiment, it is preferable that the glass fibers of this embodiment consist of glass filaments having a diameter in the range of 3.0 to 9.0 μm, bundled in the range of 35 to 400 strands, with a twist in the range of 0 to 1.0 turns / 25 mm, and a mass in the range of 0.9 to 69.0 tex (g / km).

[0108] In the glass fiber fabric of this embodiment, when the glass fibers of this embodiment described above are used as warp or weft threads, the warp weave density is preferably in the range of 40 to 120 threads / 25 mm, and the weft weave density is preferably in the range of 40 to 120 threads / 25 mm.

[0109] The glass fiber fabric of this embodiment may undergo de-oiling treatment, surface treatment, and fiber opening treatment after weaving.

[0110] As a de-oiling treatment, one method involves placing the glass fiber fabric in a heating furnace with an ambient temperature in the range of 350°C to 400°C for a period of 40 to 80 hours to thermally decompose any organic matter adhering to the glass fibers.

[0111] As a surface treatment, one example is to immerse the glass fiber fabric in the silane coupling agent, or in a solution containing the silane coupling agent and the surfactant, squeeze out the excess water, and then heat-dry it at a temperature in the range of 80 to 180°C for a time in the range of 1 to 30 minutes.

[0112] Examples of fiber opening processes include applying tension in the range of 30 to 200 N to the warp threads of a glass fiber fabric while opening the fibers by water flow pressure, opening the fibers by high-frequency vibration using a liquid as a medium, opening the fibers by the pressure of a fluid with surface pressure, and opening the fibers by pressing with a roll, thereby widening the width of the warp and weft threads.

[0113] The glass fiber fabric of this embodiment has a density of 7.0 to 190.0 g / m². 2 It is preferable that the mass per unit area is in the range of 8.0 to 200.0 μm and the thickness is in the range of 8.0 to 200.0 μm.

[0114] In this embodiment, the warp thread width of the glass fiber fabric is preferably in the range of 110 to 600 μm, and the weft thread width is preferably in the range of 110 to 600 μm.

[0115] The glass fiber fabric of this embodiment may include a surface treatment layer containing the silane coupling agent, or the silane coupling agent and the surfactant. When the glass fiber fabric of this embodiment includes the surface treatment layer, the surface treatment layer may have a mass in the range of, for example, 0.03 to 1.50% by mass relative to the total amount of the glass fiber fabric including the surface treatment layer.

[0116] The glass fiber reinforced resin composition of this embodiment contains the glass fibers of this embodiment as described above. Specifically, the glass fiber reinforced resin composition of this embodiment is a glass fiber reinforced resin composition containing a thermoplastic resin or thermosetting resin, glass fibers, and other additives, and contains glass fibers in an amount 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 an amount of 90 to 10% by mass relative to the total amount of the glass fiber reinforced resin composition, and other additives in an amount of 0 to 40% by mass.

[0117] Here, the 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 resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and polycarbonate. Examples include polyphosphates, polyarylene sulfides, polyethersulfones (PES), polyphenylsulfones (PPSU), polyphenylene ethers (PPE), modified polyphenylene ethers (m-PPE), polyarylether ketones, liquid crystal polymers (LCP), fluororesins, polyetherimides (PEI), polyarylates (PAR), polysulfones (PSF), polyamideimides (PAI), polyaminobismaleimides (PABM), thermoplastic polyimides (TPI), polyethylene naphthalates (PEN), ethylene / vinyl acetate (EVA) resins, ionomer (IO) resins, polybutadiene, styrene / butadiene resins, polybutylene, polymethylpentene, olefin / vinyl alcohol resins, cyclic olefin resins, cellulose resins, and polylactic acid.

[0118] 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.

[0119] Examples of polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.

[0120] Examples of polystyrene include general-purpose polystyrene (GPPS), which is atactic polystyrene having an atactic structure; high-impact polystyrene (HIPS), which is GPPS with added rubber components; and syndiotactic polystyrene, which has a syndiotactic structure.

[0121] Examples of methacrylic resins include polymers obtained by homopolymerizing one of the following: acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and fatty acid vinyl esters, or polymers obtained by copolymerizing two or more of these.

[0122] Examples of polyvinyl chloride include vinyl chloride homopolymers polymerized by conventionally known methods such as emulsion polymerization, suspension polymerization, microsuspension polymerization, and bulk polymerization, copolymers of vinyl chloride monomer and copolymerizable monomers, and graft copolymers obtained by graft polymerization of vinyl chloride monomer onto a polymer.

[0123] Examples of polyamides include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sevacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sevacamide (nylon 510), polyhexamethylene sevacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (nylon 106), and polydecamethylene. Polyethylene sevacamide (Nylon 1010), Polydecamethylene dodecamide (Nylon 1012), Polyundecaneamide (Nylon 11), Polyundecamethylene adipamide (Nylon 116), Polydodecaneamide (Nylon 12), Polyxylene adipamide (Nylon XD6), Polyxylene sevacamide (Nylon XD10), Polymetaxylylene adipamide (Nylon MXD6), Polyparaxylylene adipamide (Nylon PXD6), Polytetramethylene terephthalamide (Nylon 4T), polypentamethylene terephthalamide (nylon 5T), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), polyundecamethylene terephthalamide (nylon 11T), polydodecamethylene terephthalamide (nylon 12T), polytetramethylene isophthalamide (nylon 4I), polybis( Examples include copolymers or mixtures thereof, consisting of one or more of the following components: 3-methyl-4-aminohexyl)methaneterephthalamide (nylon PACMT), polybis(3-methyl-4-aminohexyl)methaneisophthalamide (nylon PACMI), polybis(3-methyl-4-aminohexyl)methanendodecamido (nylon PACM12), polybis(3-methyl-4-aminohexyl)methanetetradecamide (nylon PACM14).

[0124] Examples of polyacetals include homopolymers in which oxymethylene units are the main repeating units, and copolymers that mainly consist of oxymethylene units and contain oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain.

[0125] Examples of polyethylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with ethylene glycol.

[0126] Examples of polybutylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,4-butanediol.

[0127] Examples of polytrimethylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,3-propanediol.

[0128] Examples of polycarbonates include polymers obtained by a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate in a molten state, or polymers obtained by a phosgene method in which a dihydroxyaryl compound is reacted with phosgene.

[0129] Examples of polyarylene sulfides include linear polyphenylene sulfides, cross-linked polyphenylene sulfides with high molecular weight obtained by curing reactions after polymerization, polyphenylene sulfide sulfones, polyphenylene sulfide ethers, and polyphenylene sulfide ketones.

[0130] 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), and poly(2-phenyl-1,4-phenylene Examples include 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-di-n-propyl-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), and poly(2,6-dimethyl-1,4-phenylene ether).

[0131] 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, polyphenylene ethers in which functional groups such as amino groups, epoxy groups, carboxyl groups, and styryl groups are introduced at the polymer chain ends, and polyphenylene ethers in which functional groups such as amino groups, epoxy groups, carboxyl groups, styryl groups, and methacrylic groups are introduced at the polymer chain side chains.

[0132] Examples of polyaryl ether ketones include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyether ether ketone ketone (PEEKK).

[0133] Examples of liquid crystal polymers (LCPs) include (co)polymers consisting of one or more structural units selected from the group consisting of aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, aliphatic dicarbonyl units, etc., which are thermotropic liquid crystal polyesters.

[0134] Examples of fluororesins include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluoroethylene propylene resin (FEP), fluoroethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).

[0135] Examples of ionomer (IO) resins include polymers obtained by copolymerizing olefins or styrene with unsaturated carboxylic acids, in which some of the carboxyl groups are neutralized with metal ions.

[0136] Examples of olefin / vinyl alcohol resins include ethylene / vinyl alcohol copolymers, propylene / vinyl alcohol copolymers, ethylene / vinyl acetate copolymer saponifies, and propylene / vinyl acetate copolymer saponifies.

[0137] Examples of cyclic olefin resins include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclopentadiene, and polymers of cyclic olefin monomers.

[0138] Examples of polylactic acid include poly-L-lactic acid, which is a homopolymer of the L-isomer; poly-D-lactic acid, which is a homopolymer of the D-isomer; and stereocomplex-type polylactic acid, which is a mixture thereof.

[0139] Examples of cellulose resins include methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0140] Furthermore, examples of thermosetting resins include unsaturated polyester resins, vinyl ester resins, epoxy (EP) resins, melamine (MF) resins, phenolic (PF) resins, urethane (PU) resins, polyisocyanates, polyisocyanurates, polyimide (PI), urea (UF) resins, silicone (SI) resins, furan (FR) resins, benzoguanamine (BR) resins, alkyd resins, xylene resins, bismalade triazine (BT) resins, diallyl phthalate (PDAP) resins, and the like.

[0141] Specifically, examples of unsaturated polyester resins include resins that can be obtained by esterifying an aliphatic unsaturated dicarboxylic acid with an aliphatic diol.

[0142] Examples of vinyl ester resins include bis-based vinyl ester resins and novolac-based vinyl ester resins.

[0143] 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-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexydiene bisphenol type epoxy resin), phenol novolac type epoxy resin, cresol novolac type epoxy resin, and tetraphenol group ethane type novolac type epoxy resin. Examples include epoxy resins, novolac-type epoxy resins having a condensed ring aromatic hydrocarbon structure, biphenyl-type epoxy resins, aralkyl-type epoxy resins such as xylylene-type epoxy resins and phenylaralkyl-type epoxy resins, naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalenediol-type epoxy resins, bifunctional or tetrafunctional epoxy-type naphthalene resins, binaphthyl-type epoxy resins, naphthalenearalkyl-type epoxy resins, anthracene-type epoxy resins, phenoxy-type epoxy resins, dicyclopentadiene-type epoxy resins, norbornene-type epoxy resins, adamantane-type epoxy resins, and fluorene-type epoxy resins.

[0144] Examples of melamine resins include polymers formed by the polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

[0145] Examples of phenolic resins include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, and bisphenol A type novolac resin; resol-type phenolic resins such as methylol-type resol resin and dimethylene ether-type resol resin; and arylalkylene-type phenolic resins. One of these, or a combination of two or more, may be used.

[0146] Examples of urea resins include those obtained by the condensation of urea and formaldehyde.

[0147] The thermoplastic resin or thermosetting resin may be used alone or in combination of two or more types.

[0148] Since the glass fiber reinforced resin composition of this embodiment is used in applications where low dielectric properties are required, the resin is preferably epoxy resin, modified polyphenylene ether, polybutylene terephthalate, polypropylene, fluororesin, or liquid crystal polymer (LCP).

[0149] Other additives include reinforcing fibers other than glass fibers, fillers other than glass fibers, flame retardants, ultraviolet absorbers, heat stabilizers, antioxidants, antistatic agents, flow improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, pigments, and the like.

[0150] Examples of reinforcing fibers other than glass fibers include carbon fibers and metal fibers.

[0151] Other fillers besides glass fibers include, for example, glass powder, talc, and mica.

[0152] The glass fiber reinforced resin composition of this embodiment may be a prepreg obtained by impregnating the glass fiber fabric of this embodiment with the resin using a method known to that effect and then semi-curing it.

[0153] 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, hollow molding, foam molding (including supercritical fluid), insert molding, in-mold coating molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, blow molding, stamping, infusion, hand lay-up, spray-up, resin transfer molding, sheet molding compound, bulk molding compound, pultrusion, and filament winding to obtain various glass fiber reinforced resin molded products. Furthermore, glass fiber reinforced resin molded products can also be obtained by curing the prepreg.

[0154] Applications for such molded products include, for example, electronic equipment housings, electronic components, vehicle exterior components, vehicle interior components, vehicle engine components, muffler-related components, and high-pressure tanks.

[0155] Examples of electronic components include printed circuit boards.

[0156] Examples of vehicle exterior components include bumpers, fenders, hoods, air dams, and wheel covers.

[0157] Examples of vehicle interior components include door trims and ceiling materials.

[0158] Examples of components around a vehicle engine include the oil pan, engine cover, intake manifold, and exhaust manifold.

[0159] Examples of muffler-related components include sound-absorbing components.

[0160] Furthermore, the glass fibers of this embodiment can be suitably used not only as a 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, particularly gypsum board having a thickness in the range of 4 to 60 mm, glass fibers having the glass composition in the above range can be included in an amount of 0.1 to 4.0% by mass relative to the total mass of the gypsum.

[0161] Examples and comparative examples of the present invention are shown below. [Examples]

[0162] First, the glass composition after melting and solidifying is shown in Table 1. 、2 Glass raw materials were mixed to obtain glass batches, resulting in the compositions shown in Examples 1-8 and Comparative Examples 1-5.

[0163] Next, Examples 1-8 or Comparative Examples 1 A glass batch corresponding to the glass composition for glass fibers was placed in an 80 mm diameter platinum crucible and heated at 1550°C for 4 hours, then further heated at 1650°C for 2 hours to melt it. It was then removed from the crucible to obtain homogeneous glass bulk and glass cullet. Next, the obtained glass bulk and glass cullet were annealed at 620°C for 8 hours to obtain test specimens.

[0164] The dielectric constant and dielectric loss tangent of the obtained test specimens were evaluated using the method described below. Furthermore, the water resistance was evaluated using the glass cullet obtained during the test specimen preparation process, using the method described below. Additionally, the 1000 poise temperature and liquidus temperature were measured using the glass cullet obtained during the test specimen preparation process, using the method described below, and the working temperature range was calculated from these values. The results are shown in Table 1. 、2 This will be shown.

[0165] [Method for evaluating water resistance] The glass cullet obtained as described above was placed in a small cylindrical platinum bushing having a circular nozzle tip at the bottom of the container, heated to a predetermined temperature to melt, and then the molten glass extruded from the nozzle tip was wound onto a stainless steel collet at a predetermined speed, stretched and cooled to solidify, thereby obtaining 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) was taken from the collet, dried at 120°C for 1 hour, and its mass (mass before operation) was measured. Next, the test glass fibers were left to stand in 100 ml of distilled water at 80°C for 24 hours. After that, the test glass fibers were placed on a wire mesh with holes of approximately 150 μm, washed with distilled water, dried at 120°C for 1 hour, and its mass (mass after operation) was measured.

[0166] The mass reduction rate (100 × (1 - (mass after operation / mass before operation))) was calculated from the mass before and after operation. A mass reduction rate of 2.0% or less, where almost no glass fiber components leached out in water, was considered OK, while a mass reduction rate exceeding 2.0%, where a large amount of glass fiber components leached out in water, was considered NG.

[0167] [Method for measuring dielectric constant and dielectric loss tangent] The test specimens were polished to create polished specimens measuring 80 mm x 3 mm (1 mm thick). The resulting polished specimens were then completely dried and stored for 24 hours in a room at 23°C and 60% humidity. Subsequently, the dielectric constant (dielectric constant Dk) and dielectric loss tangent (dissipation rate Df) at 10 GHz were measured on the resulting polished specimens using a cavity resonator dielectric constant measuring device (manufactured by AET Co., Ltd., product name: ADMS01Oc1) in accordance with JIS C 2565:1992.

[0168] [Method for measuring 1000 poise temperature] Using a high-temperature electric furnace equipped with a rotational viscometer (manufactured by Shibaura Systems Co., Ltd.), glass cullet was melted in a platinum crucible. The viscosity of the molten glass was continuously measured using a rotational Brookfield viscometer while varying the melting temperature. The 1000 poise temperature was determined by measuring the temperature corresponding to when the rotational viscosity reached 1000 poise.

[0169] [Method for measuring liquidus temperature] Glass cullet was crushed, and 40 g of glass particles with a particle size in the range of 0.5 to 1.5 mm were placed in a platinum boat measuring 180 mm x 20 mm x 15 mm. After heating in a tubular electric furnace with a temperature gradient in the range of 1000 to 1550°C for more than 8 hours, the boat was removed from the tubular electric furnace and observed with a polarizing microscope to identify the position where glass-derived crystals (devitrification) began to precipitate. The temperature inside the tubular electric furnace was measured using a B thermocouple, and the temperature at the position where the crystals began to precipitate was determined and defined as the liquidus temperature.

[0170] [Method for calculating the working temperature range] The operating temperature range was calculated based on the difference between the 1000 poise temperature and the liquidus temperature.

[0171] [Table 1]

[0172] [Table 2]

[0173] Table 1 shows that, relative to the total amount of glass fiber composition, SiO2 is in the range of 50.00 to 61.00% by mass, B2O3 is in the range of 16.00 to 27.00% by mass, Al2O3 is in the range of 7.00 to 14.00% by mass, and 0.20% 3.20 P2O5 in the mass% range, and 0.50~ 4.00 TiO2 in the mass% range, CaO in the 0.10-5.00 mass% range, MgO in the 0-4.00 mass% range, and in total 0.10 Contains F2 and Cl2 in the range of ~2.00 mass% Furthermore, the 1000 poise temperature is 1500°C or less.The glass compositions for glass fibers of Examples 1 to 8 demonstrate that it is possible to obtain 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 in the high-frequency range of 10 GHz, and that their own 1000 poise temperature can be reduced to less than 1500°C.

[0175] Furthermore, the glass fiber composition contains more than 61.00% by mass of SiO2 and has a P2O5 content of less than 0.20% by mass. be In the case of the glass fiber composition of Comparative Example 5, it is clear that its own 1000 poise temperature is over 1500°C.

Claims

1. Based on the total amount of the glass composition for glass fiber, SiO in an amount of 50.00 to 61.00% by mass ２ ２ , B ２ O ３ ２ , Al in an amount of 7.00 to 14.00% by mass ２ O ３ ２ , P in an amount of 0.20 to 3.20% by mass ２ O ５ ２ , TiO in an amount of 0.50 to 4.00% by mass ２ , 0.10 to 5.00% by mass of CaO, 0 to 4.00% by mass of MgO, and F in a total amount of 0.10 to 2.00% by mass ２ ２ and Cl ２ , and comprises A glass composition for glass fibers, characterized in that its 1000 poise temperature is 1500°C or less.

2. A glass fiber characterized by comprising the glass composition for glass fibers described in claim 1.

3. A glass fiber fabric characterized by containing the glass fibers described in claim 2.

4. A glass fiber reinforced resin composition characterized by containing the glass fibers described in claim 2.

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